JP4590345B2 - Non-magnetic one-component developing toner, image forming apparatus using the same, and process cartridge - Google Patents

Description

  The present invention relates to a non-magnetic one-component developing toner, an image forming method and an image forming apparatus using the toner, and a process cartridge.

  In a conventionally known electrophotographic method, the surface of a photoreceptor is charged and exposed to form an electrostatic latent image, and developed with a predetermined colored toner to form a toner image. This toner image is transferred to a transfer paper or the like. The image is transferred to a body and fixed with a heat roll or the like to form an image.

In the prior art, dry development methods employed in electrophotography, electrostatic recording and the like include a method using a two-component developer composed of toner and a carrier and a method using a one-component developer not containing a carrier. is there.
In the former method using the two-component developer, a good and stable image can be obtained. However, on the other hand, carrier deterioration and fluctuation in the mixing ratio of the toner and the carrier are likely to occur. Therefore, it is difficult to obtain images of a constant quality over a long period of time, and there are difficulties in maintaining and managing the apparatus and making it compact.

Therefore, the latter method, that is, the method using a one-component developer, which does not have the above-described drawbacks, has been attracting attention.
In such a system using a one-component developer, toner (developer) is usually transported by at least one toner transport member, and an electrostatic latent image formed on the latent image carrier by the transported toner is used. A means for making a visible image is used. At this time, it is said that the layer thickness of the toner transported on the surface of the toner transport member must be made as thin as possible.
This is because when a one-component developer is used and a toner having a high electrical resistance is applied, it is necessary to charge the toner with a developing device. That is, when the toner layer is thick, only the vicinity of the surface of the toner layer is charged, and the entire toner layer is hardly charged uniformly.

In view of this demand, various methods have been proposed as means for regulating the toner layer thickness on the toner conveying member (toner layer thickness regulating means).
For example, a regulation blade is used, and this blade is placed against a toner conveying member, whereby the toner conveyed on the surface of the toner conveying member is pressed by a pressing member (regulating blade) and the toner layer thickness is controlled. It is.
Further, a method for obtaining a similar effect by bringing a roller into contact with the blade instead of the blade has been proposed.

  In recent years, in view of the progress of downsizing and cost reduction of the fixing device, a so-called oilless fixing device having a configuration in which the fixing oil application mechanism for the fixing device is omitted or the application amount is reduced. In the apparatus having such a configuration, it is necessary to add a release agent (wax) to the toner as an offset prevention measure.

  However, if a large amount of wax is contained in the toner, it will be in a free wax state or the amount of surface wax of the toner will increase, resulting in mechanical / thermal action, which is caused by the wax on the regulating blade and the photoreceptor in the developing machine. As a result, the toner adheres to a member such as a regulating blade, and white spots / white streaks due to these adhering components are likely to occur in a solid image.

  In addition, in the case of a full-color toner, it is necessary to use a binder resin having a low softening point in order to obtain sufficient properties such as translucency, color developability, and glossiness. There is also a problem that toner is agglomerated when stored at a high temperature.

There has also been proposed a technique for improving the characteristics such as translucency, color developability, and glossiness without increasing the amount of wax and adversely affecting other qualities (see, for example, Patent Document 1).
There has also been proposed a technique for improving transferability by increasing the total amount of external additives (see, for example, Patent Document 2). However, when the total amount of the external additive is increased, there is a problem that the toner particles are prevented from being melted at the time of heat-fixing, and excessive free fine particles are interposed to cause a decrease in offset and fixing strength.

JP 2003-270859 A JP-A-6-324525

  As described above, it is a wax-containing toner, that is, a toner used in a so-called oil-less fixing machine, and the toner (developer) is charged by a non-magnetic single component, that is, a contact regulating member such as a doctor blade / roller. There are many points to be improved in the toner used.

In the case of oilless and non-magnetic one component, the toner has a wax that contains a wax to ensure releasability in the fixing machine and to prevent the toner from sticking to the contact regulating member during charging. The premise is that performance must be achieved at a high level.
In order to achieve such a trade-off performance at a high level, it is possible to apply an internal addition method in which the wax is mixed simultaneously with the resin as the toner composition at the time of resin synthesis (monomer stage). preferable.
In order to ensure that the wax state existing in the toner exists as an optimal wax domain in order to ensure the above-mentioned trade-off performance while the wax and the resin are incompatible, it is mixed with the wax after it becomes a resin. This is because it is easier to control.

  As described above, when adding wax during resin synthesis, a narrowly defined wax, that is, a wax having a functional group in a molecular chain, for example, an ester bond between a higher alcohol such as carnauba and a higher fatty acid, an amide wax, etc. If a material having an amide bond is applied, it may be involved in a reaction at the time of resin synthesis. In such a case, it is not possible to sufficiently secure the releasability, which is an essential performance in the wax formulation.

Therefore, it can be said that the wax used for the wax-added resin needs to be a hydrocarbon wax having no functional group.
Hydrocarbon waxes exhibit high releasability, but their polarities (as compared to the above-mentioned narrow sense wax: with functional groups) greatly depart from the binder resin, so the resin and wax are incompatible. Exist in a state that is not mixed with each other. (A typical form is a so-called sea-island structure.)
In the relationship between the wax and the binder resin in the above-described state, in order to achieve the other performance essential as a toner in a high-order and balanced manner, an extremely pinpoint blend / physical property balance is required.

  Therefore, in the present invention, the above-mentioned high-dimensional performance balance is devised in the nonmagnetic one-component toner using the wax-added binder resin, and the softening point of the internally added wax and the wax are internally determined. The softening point of the first resin to be added and the softening point of the second resin not to be added internally, including the blending ratio, and the fluidity greatly influenced by the particle diameter are determined by the surface of the wax. In consideration of the exposed state and the conditions for attaching the external additive, the toner was also balanced in a high dimension and produced extremely excellent performance.

In the present invention, consists of a toner base particles and an external additive, the toner base particles, melting point 70 to 90 ° C. the hydrocarbon wax is a 8-15 parts by weight added per 100 parts by weight of the binder resin a first binder resin having a softening point of 120 to 150 ° C. to have a second binder resin having a softening point of 100 to 130 ° C., containing a colorant, the weight ratio of the first binder resin and the second binder resin is The particle diameter (volume average particle diameter) is 5 to 10 μm, and the external additive includes first inorganic fine particles having a BET of 100 to 300 m ² / g, BET of 40 to 100 m ^2. / G of second inorganic fine particles , and the total amount of the external additive is 2.5 to 5.0 parts by weight with respect to 100 parts by weight of the toner base particles. Provide toner

  According to a second aspect of the present invention, there is provided the nonmagnetic one-component developing toner according to the first aspect, wherein the average circularity is in the range of 0.890 to 0.950.

According to a third aspect of the present invention, there is provided an image forming method in which an image is formed by using the nonmagnetic one-component developing toner according to the first or second aspect.
According to a fourth aspect of the present invention, there is provided a roll fixing type image forming apparatus comprising a fixing device having a heating roll and a pressure roll, and the non-magnetic one-component development according to the first or second aspect. An image forming apparatus configured to perform image formation by applying toner.
According to a fifth aspect of the present invention, there is provided the image forming apparatus according to the fourth aspect, wherein the fixing roller is an oil-less fixing that does not require oil application to the heating roll and the pressure roll.
According to a sixth aspect of the present invention, there is provided the image forming apparatus according to the fourth aspect, further comprising an intermediate transfer unit.
According to a seventh aspect of the present invention, there is provided the image forming apparatus according to the fourth aspect, further comprising blade cleaning means.
According to an eighth aspect of the present invention, there is provided the image forming apparatus according to the fourth aspect, wherein the fixing device is constituted by a belt having a heating device.
According to a ninth aspect of the present invention, there is provided a process cartridge in which a photosensitive member and at least one means selected from a charging means, a developing means, and a cleaning means are integrally supported and are detachable from the main body of the image forming apparatus. The developing means holds toner (developer), and the toner (developer) provides a process cartridge which is the non-magnetic one-component developing toner according to claim 1. .

  According to the present invention, when the amount of added wax is increased, heat storage stability and deterioration of fixing separation can be suppressed, and the total amount of external additives in the toner is increased to improve transferability. In addition, a non-magnetic one-component developing toner capable of realizing excellent fixing separation property was obtained. Furthermore, the above excellent effect could be exhibited even when this was applied to a pulverized toner having poor transferability.

  Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following examples.

In the present invention, consists of a toner base particles and an external additive, the toner base particles, melting point 70 to 90 ° C. the hydrocarbon wax is a 8-15 parts by weight added per 100 parts by weight of the binder resin a first binder resin having a softening point of 120 to 150 ° C. to have a second binder resin having a softening point of 100 to 130 ° C., containing a colorant, the weight ratio of the first binder resin and the second binder resin is The particle diameter (volume average particle diameter) is 5 to 10 μm, and the external additive includes first inorganic fine particles having a BET of 100 to 300 m ² / g, BET of 40 to 100 m ^2. / G of second inorganic fine particles , and the total amount of the external additive is 2.5 to 5.0 parts by weight with respect to 100 parts by weight of the toner base particles. Provide toner

The nonmagnetic one-component developing toner of the present invention preferably has an average circularity of 0.890 to 0.950.
Here, the average circularity is a value that can be measured as an average circularity by a flow type particle image analyzer FPIA-2100 manufactured by Sysmex Corporation.
In a specific measurement, analysis was performed using analysis software (FPIA-2100 Data Processing Program for FPIA version 00-10).
First, 0.1 to 0.5 ml of 10 wt% surfactant (alkylbenzene sulfonate Neogen SC-A; Daiichi Kogyo Seiyaku) is added to a glass 100 ml beaker, and 0.1 to 0.5 g of each toner is added. Next, 80 ml of ion-exchanged water was added. The obtained dispersion was subjected to a dispersion treatment for 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.).
The shape and distribution of the toner were measured using the FPIA-2100 until the density of the dispersion was 5000 to 15000 / μl.
In this measurement method, the dispersion concentration is set to 5000 to 15000 / μl from the viewpoint of measurement reproducibility of the average circularity. In order to obtain the dispersion concentration, the conditions of the dispersion, that is, the amount of surfactant to be added and the amount of toner are changed.
The amount of the surfactant varies depending on the hydrophobicity of the toner as in the measurement of the toner particle diameter described above. If it is added in a large amount, noise due to bubbles is generated. If the amount is too small, the toner cannot be sufficiently wetted. It becomes insufficient. Further, the toner addition amount differs from the particle size, and it is necessary to decrease the small particle size and increase the large particle size. When the toner particle size is 3 to 7 μm, the toner amount is 0.1 to 0. By adding 0.5 g, the dispersion concentration can be adjusted to 5000 to 15000 / μl.
It has been confirmed that practical problems arise when the average circularity measurement is outside the predetermined numerical range.
Specifically, if the average circularity is less than 0.890, transfer failure occurs and a problem in image quality is observed. On the other hand, if the average circularity exceeds 0.950, a cleaning failure occurs and a problem in image quality is observed.

First, the binder resin constituting the nonmagnetic one-component developing toner of the present invention will be described.
The material constituting the first binder resin and the second binder resin is not particularly limited, and a conventionally known binder resin for toner can be applied. Specifically, a polyester resin, a (meth) acrylic resin, Styrene- (meth) acrylic copolymer resin, epoxy resin, COC (for example, cyclic olefin resin (for example, TOPAS-COC (manufactured by Ticona))) and the like are mentioned. From the viewpoint of oilless fixing, the first binder It is preferable to use a polyester resin for both the resin and the second binder resin.

Of the polyester resins, a polyester resin obtained by polycondensation of a polyhydric alcohol component and a polyvalent carboxylic acid component is preferable.
Examples of the dihydric alcohol component among the polyhydric alcohol components include, for example, polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3,3) -2,2- Bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2,0) -2,2-bis (4-hydroxyphenyl) propane Bisphenol A alkylene oxide adducts such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol , Dipropylene glycol, polyethylene glycol, polytetramethylene glycol, bisphenol A, hydrogenated bisphenol A, and the like.
Examples of the trivalent or higher alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol. 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, etc. Is mentioned.

Among the polyvalent carboxylic acid components, examples of the divalent carboxylic acid component include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, and succinic acid. Acid, adipic acid, sebacic acid, azelaic acid, malonic acid, n-dodecenyl succinic acid, isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, isooctenyl succinic acid, n-octyl succinic acid Examples include acids, isooctyl succinic acid, anhydrides of these acids, and lower alkyl esters.
Examples of the trivalent or higher carboxylic acid component include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, and 1,2. , 4-Naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4- Examples include cyclohexanetricarboxylic acid, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, emporic trimer acid, anhydrides of these acids, and lower alkyl esters.

In addition, as a polyester resin, using a mixture of a polyester resin raw material monomer, a vinyl resin raw material monomer, and a monomer that reacts with both resin raw material monomers, a polycondensation reaction to obtain a polyester resin in the same container and A resin obtained by performing a radical polymerization reaction for obtaining a vinyl resin in parallel (hereinafter simply referred to as “vinyl polyester resin”) can also be applied.
The “monomer that reacts with the raw material monomers of both resins” is, in other words, a monomer that can be used in both the condensation polymerization reaction and the radical polymerization reaction. That is, this is a monomer having a carboxy group capable of undergoing condensation polymerization and a vinyl group capable of undergoing radical polymerization. Specific examples include fumaric acid, maleic acid, acrylic acid, and methacrylic acid.
Examples of the raw material monomer for the polyester resin include the polyhydric alcohol component and the polyvalent carboxylic acid component described above.
Examples of the raw material monomer for the vinyl resin include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, α-methyl styrene, p-ethyl styrene, 2,4-dimethyl styrene, p-tert-butyl. Styrene such as styrene and p-chlorostyrene or styrene derivatives, ethylenically unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene, methyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, Isobutyl methacrylate, t-butyl methacrylate, n-pentyl methacrylate, isopentyl methacrylate, neopentyl methacrylate, 3- (methyl) butyl methacrylate, hexyl methacrylate, octyl methacrylate, nonyl methacrylate, methacrylic acid Silyl, alkyl methacrylates such as undecyl methacrylate, dodecyl methacrylate, methyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n acrylate -Acrylic alkyl esters such as pentyl, isopentyl acrylate, neopentyl acrylate, 3- (methyl) butyl acrylate, hexyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, etc. Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, acrylonitrile, maleic acid ester, itaconic acid ester, vinyl chloride, vinyl acetate, vinyl benzoate, vinyl methyl ethyl ketone, vinyl Examples thereof include nilhexyl ketone, vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether.
Examples of the polymerization initiator for polymerizing the raw material monomer of the vinyl resin include 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, , 1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azo or diazo polymerization initiators, benzoyl peroxide, dicumylper Examples thereof include peroxide polymerization initiators such as oxide, methyl ethyl ketone peroxide, isopropyl peroxycarbonate, lauroyl peroxide, and the like.

  As the first binder resin and the second binder resin constituting the nonmagnetic one-component developing toner of the present invention, various polyester resins as described above can be applied. In particular, the separability as an oilless fixing toner. From the viewpoint of improving the offset resistance, the following are preferred.

  As a suitable first binder resin, a polyester resin obtained by polycondensation of the above-mentioned polyhydric alcohol component and polyhydric carboxylic acid component, particularly a bisphenol A alkylene oxide adduct as a polyhydric alcohol component, Examples thereof include polyester resins obtained using terephthalic acid and fumaric acid as the divalent carboxylic acid component.

  As a suitable second binder resin, bisphenol A alkylene oxide adduct, terephthalic acid, trimellitic acid and succinic acid are used as a raw material monomer for a vinyl polyester resin, particularly a polyester resin, and styrene is used as a raw material monomer for a vinyl resin. And vinyl polyester resin obtained using fumaric acid as a bireactive monomer using butyl acrylate.

In the present invention, a hydrocarbon wax is internally added during the synthesis of the first binder resin.
In order to add the hydrocarbon wax in the first binder resin in advance, when the first binder resin is synthesized, the hydrocarbon wax is added to the monomer for synthesizing the first binder resin. 1 Binder resin is synthesized.
For example, when a polyester resin is used as the first binder resin, the polycondensation reaction is performed in a state where a hydrocarbon wax is added to an acid monomer and an alcohol monomer constituting the polyester resin.
When the first binder resin is a vinyl-based polyester resin, the vinyl-based resin raw material monomer is added dropwise to the polyester resin raw-material monomer with the hydrocarbon-based wax added thereto while stirring and heating the monomer. Then, a polycondensation reaction and a radical polymerization reaction are performed.

Next, the wax will be described.
As the wax, a hydrocarbon wax having a low polarity is used because a material having a low polarity can exhibit a function excellent in releasability from the fixing member roller.
This hydrocarbon wax will be described.
The hydrocarbon wax is a wax composed of only carbon atoms and hydrogen atoms, and does not contain an ester group, an alcohol group, an amide group, or the like.
Specific examples include polyolefin waxes such as polyethylene, polypropylene, copolymers of ethylene and propylene, petroleum waxes such as paraffin wax and microcrystalline wax, and synthetic waxes such as Fischer-Tropsch wax.
Among these, polyethylene wax, paraffin wax, and Fischer-Tropsch wax are particularly preferable, and polyethylene wax and paraffin wax are more preferable.

The melting point of the wax is the endothermic peak of the wax at the time of temperature rise measured by a differential scanning calorimeter (DSC) and needs to be in the range of 70 ° C to 90 ° C.
If the temperature is higher than 90 ° C., the melting of the wax in the fixing process becomes insufficient, and separation from the fixing member cannot be ensured.
On the other hand, when the temperature is lower than 70 ° C., problems such as fusion of toner particles in a high-temperature and high-humidity environment occur, and storage stability deteriorates.
In order to provide a sufficient margin for fixing separation at low temperatures, the melting point of the wax is preferably 70 ° C to 85 ° C, and more preferably in the range of 70 ° C to 80 ° C.

Moreover, it is preferable that the half value width of the endothermic peak of the wax at the time of temperature rise measured by a differential scanning calorimeter (DSC) is 7 ° C. or less.
As described above, since the melting point of a suitable wax in the present invention is relatively low, a wax whose endothermic peak is broad, that is, a wax that melts from a low temperature range, adversely affects the storage stability of the toner. It is.

The content of the wax in the first binder trees in fat of the present invention, with respect to 100 parts by weight of the binder resin, 8-15 parts by weight, preferably 9-13 parts by weight, still more to 10-12 parts by weight preferable.
If the wax content is less than 8 parts by weight, the amount of wax that exudes between the molten toner and the fixing member in the fixing process becomes insufficient, and the adhesive force between the molten toner and the fixing member does not decrease. The member is no longer separated from the fixing member.
On the other hand, when the wax content exceeds 15 parts by weight, the amount of wax exposed on the toner surface increases, and the transfer efficiency from the developing unit to the photoconductor and from the photoconductor to the recording member is reduced due to the deterioration of the fluidity of the toner particles. This is not preferable because not only the image quality is remarkably lowered but also the wax on the surface of the toner is detached to cause contamination of the developing member and the photosensitive member.

Next, the content ratio of the first binder resin and the second binder resin will be described.
The content ratio of the first binder resin (including the weight of the internally added wax) and the second binder resin in the toner particles is 20/80 to 45/55, preferably 30/70 to 40/60 by weight. To do.
When there is too little 1st binder resin, separability and high temperature-resistant offset property will fall.
On the other hand, when there is too much 1st binder resin, glossiness and heat-resistant storage property will fall.
The softening point of the binder resin composed of the first binder resin and the second binder resin having the above weight ratio is 100 to 125 ° C, and particularly preferably 105 to 125 ° C.
In this invention, it is preferable that the softening point of binder resin which consists of 1st binder resin and 2nd binder resin to which the 1st polyolefin wax was internally added is in the said range.

The wax-added first binder resin and second binder resin both have an acid value of preferably 5 to 50 KOHmg / g, and more preferably 10 to 40 KOHmg / g.
In particular, when a polyester-based resin is used as the binder resin, use of a resin having such an acid value can improve the dispersibility of various colorants and the like and obtain a toner having a sufficient charge amount.
The first binder resin preferably contains a component insoluble in tetrahydrofuran (THF) from the viewpoint of high temperature offset resistance.
The content of the THF-insoluble component in the wax-added first binder resin is preferably 0.1 to 15% by weight, particularly preferably 0.2 to 10% by weight, and more preferably 0.3 to 5% by weight.

Next, the colorant will be described.
As the colorant, it is possible to use pigments and dyes that are used as colorants of conventionally known full-color toners.
For example, carbon black, aniline blue, calcoil blue, chrome yellow, ultramarine blue, dupont oil red, quinoline yellow, methylene blue chloride, copper phthalocyanine, malachite green oxalate, lamp black, rose bengal, CI pigment red 48: 1 CI Pigment Red 122, CI Pigment Red 57: 1, CI Pigment Red 184, CI Pigment Yellow 97, CI Pigment Yellow 12, CI Pigment Yellow 17, CI Solvent Yellow 162, CI Pigment Yellow 180 CI Pigment Yellow 185, CI Pigment Blue 15: 1, CI Pigment Blue 15: 3, and the like.
The colorant content in the toner particles is preferably in the range of 2 to 15 parts by weight with respect to 100 parts by weight of the total binder resin.
It is preferable from the viewpoint of dispersibility that the colorant is used in the form of a masterbatch dispersed in a mixed binder resin of the first binder resin and the second binder resin used.
The addition amount of the master batch may be an amount such that the amount of the colorant contained is within the above range.
The colorant content in the masterbatch is preferably 20 to 40% by weight.

To the toner of the present invention, a known charge control agent used in a conventionally known full color toner may be added.
Examples of the charge control agent include nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified quaternary ammonium salts). ), Alkylamide, phosphorus alone or a compound thereof, tungsten alone or a compound thereof, a fluorine-based activator, a salicylic acid metal salt, and a metal salt of a salicylic acid derivative.
Specifically, Bontron 03 of nigrosine dye, Bontron P-51 of quaternary ammonium salt, Bontron S-34 of metal-containing azo dye, E-82 of oxynaphthoic acid metal complex, E- of salicylic acid metal complex 84, E-89 of phenol-based condensate (above, manufactured by Orient Chemical Co., Ltd.), TP-302, TP-415 of quaternary ammonium salt molybdenum complex (made of Hodogaya Chemical Co., Ltd.), quaternary ammonium salt Copy charge PSY VP2038, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (above, manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit) ), Copper phthalocyanine, perylene, quinacridone, azo Pigment, a sulfonic acid group, a carboxyl group, and polymer compounds having a functional group such as quaternary ammonium salts.
Among these, a substance that controls the negative polarity of the toner is particularly preferable.
The amount of charge control agent used is determined by the toner production method including the type of binder resin, the presence or absence of additives used as necessary, and the dispersion method, and is not limited uniquely. However, it is used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin, and more preferably in the range of 0.2 to 5 parts by weight.
When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, the developer fluidity is reduced, and the image density is reduced. Incurs a decline.

Next, the external additive constituting the toner will be described.
In the present invention, in order to assist the fluidity, developability and chargeability of the toner , an external additive is added to the toner base particles, and two kinds of inorganic fine particles are applied as this.
First, as the first inorganic fine particles, is measured specific surface area by the BET method, it was assumed to be 100 m ^2/300 m ² / g, the BET specific surface area of the second inorganic fine particles, 40 m ² / g to It shall be 100 m ² / g.
Specifically, the inorganic fine particles are silicon oxide, zinc oxide, tin oxide, silica sand, titanium oxide, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, Aluminum oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride and the like can be applied.
The total amount of the external additive is preferably in a 2.5 to 5.0 parts by weight for 100 parts by weight of the toner base particles.
When the total amount of the external additive is larger than the above range, fogging, developability, and fixing separation property are deteriorated. On the other hand, when the total amount is smaller than the above range, fluidity, transfer property, and heat resistant storage property are deteriorated. .

A method for producing the toner of the present invention will be described.
The toner of the present invention is prepared by mixing, kneading, pulverizing, and classifying the first binder resin, the second binder resin, and the colorant, into which the above-described hydrocarbon wax is internally added, by a conventional method. The toner base particles (colored resin particles) are obtained and further mixed with an external additive.
The average particle size of the toner base particles is preferably 4 to 10 μm, and more preferably 5 to 10 μm.

The above-described non-magnetic one-component developing toner of the present invention can be applied to image formation using a conventionally known method.
For example, using a roll fixing type image forming apparatus having a fixing device having a heating roll and a pressure roll, image fixing is performed by passing a paper carrying a toner image through the pressure contact portion of the roll. It can be carried out.
Here, the heating roll and the pressure roll constituting the fixing device may be oil-less fixing that does not require oil application.
In addition, the image forming apparatus may include a predetermined intermediate transfer unit and a predetermined blade cleaning unit. The fixing device is constituted by a belt having a heating device.
Further, the toner of the present invention is versatile and can be applied to conventionally known process cartridges. That is, the process cartridge in this case integrally supports at least one unit selected from a photosensitive member and a charging unit, a developing unit, and a cleaning unit, and is detachable from the image forming apparatus main body. The developing means holds toner (developer), and applies the non-magnetic one-component developing toner of the present invention as toner (developer).

Hereinafter, although the specific Example of this invention is given and demonstrated, this invention is not limited to the example shown below.
In the following description, parts represent parts by weight.
(Preparation of first binder resin)
As a vinyl monomer, 600 g of styrene, 110 g of butyl acrylate, 30 g of acrylic acid, and 30 g of dicumyl peroxide as a polymerization initiator were placed in a dropping funnel.
Among polyester monomers, as polyols, 1230 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4 -Hydroxyphenyl) propane 290 g, isododecenyl succinic anhydride 250 g, terephthalic acid 310 g, 1,2,4-benzenetricarboxylic anhydride 180 g, dibutyltin oxide 7 g as esterification catalyst, wax as paraffin wax (melting point 73.3 ° C., differential Applying 340 g (11.0 parts by weight with respect to 100 parts by weight of charged monomer) of 340 g (half-width of endothermic peak at the time of temperature rise measured by a scanning calorimeter is 4 ° C.), thermometer, stainless steel stirrer, flow down Into a 5 liter four-necked flask equipped with a condenser and a nitrogen inlet tube. Under a nitrogen atmosphere in a coater, with stirring at a temperature of 160 ° C., it was added dropwise over one hour a mixture of the vinyl monomer resins and the polymerization initiator from the dropping funnel.
While this was maintained at 160 ° C., the addition polymerization reaction was aged for 2 hours, and then the temperature was raised to 230 ° C. to perform a condensation polymerization reaction.
The degree of polymerization was tracked by the softening point measured using a constant load extrusion capillary rheometer, and when the desired softening point was reached, the reaction was terminated to obtain Resin H1.

Resins H2 to H12, resin H14, and resin H15 having different softening point temperatures and internal waxes were prepared in the same manner as the resin H1.
Moreover, resin H13 was produced by the same method as the resin H1 without adding wax.

(Production of second binder resin)
As the polyol, 2210 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 850 g of terephthalic acid and 120 g of 1,2,4-benzenetricarboxylic anhydride were used, and dibutyltin was used as the esterification catalyst. Using 0.5 g of oxide, put it in a 5-liter four-necked flask equipped with a thermometer, a stainless steel stirrer, a flow-down condenser and a nitrogen inlet tube, and raise the temperature to 230 ° C. under a nitrogen atmosphere in a mantle heater. Reaction was performed.
The degree of polymerization was monitored by the softening point measured using a constant load extrusion capillary rheometer, and when the desired softening point was reached, the reaction was terminated to obtain Resin L1.

  Resins L2 to L11 having different softening point temperatures were prepared in the same manner as the resin L1.

(Production of toner )
CIPigment Red 57-1 (Kermin 6B (ECR-102) with respect to 100 parts by weight (including the weight of the internally added wax) of the binder resin in which the first binder resin and the second binder resin are in a predetermined ratio. ) Master batch containing 4 parts by weight of Dainichi Seika Kogyo Co., Ltd.) was mixed thoroughly with a Henschel mixer, and the discharge part of the twin-screw extruder kneader (PCM-30: Ikegai Iron Works) was removed. And kneaded to obtain a kneaded product, which was rolled to a thickness of 2 mm with a cooling press roller, cooled with a cooling belt, and then coarsely pulverized with a feather mill.
Thereafter, the mixture is pulverized with a mechanical pulverizer (KTM: manufactured by Kawasaki Heavy Industries, Ltd.) to an average particle size of 10-12 μm, and further pulverized with a jet pulverizer (IDS: manufactured by Nippon Pneumatic Engineering Co., Ltd.), Thereafter, colored resin particles (toner base particles) were obtained by using a rotor type classifier (Teplex type classifier type: 100ATP: manufactured by Hosokawa Micron Corporation) for fine powder classification.
Predetermined first inorganic fine particles and second inorganic fine particles are added in desired amounts (parts by weight) to 100 parts by weight of the colored resin particles, and mixed with a Henschel mixer (circumferential speed 40 m / sec, 60 seconds). The magenta toners of Examples 1 to 17 and Comparative Examples 1 to 15 having a predetermined particle diameter were obtained.
Tables 1 and 2 below show the constituent materials, composition ratios, and volume average particle diameters of the toners of Examples 1 to 17 and Comparative Examples 1 to 15.

[Evaluation of toner]
A method for measuring the particle size distribution of the toner particles will be described.
Examples of the measuring device for the particle size distribution of toner particles using the Coulter counter method include Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter).
First, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution.
As the electrolytic solution, first grade sodium chloride is used, and a solution prepared in an approximately 1% NaCl aqueous solution can be applied. Examples thereof include ISOTON-II (manufactured by Coulter).
Here, 2 to 20 mg of the measurement sample is further added as a solid content.
The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measuring device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as the aperture. Calculate volume distribution and number distribution.
From the obtained distribution, the weight average particle diameter (Dv) and the number average particle diameter (Dp) of the toner are obtained.
A method for measuring the toner particle diameter (volume average particle diameter) will be specifically described.
As a measuring device, Coulter Multisizer II (manufactured by Coulter, Inc.) was used.
First, 2.0 ml of alkylbenzene sulfonate as a dispersant was added to 125 ml of an electrolytic aqueous solution. As the electrolytic solution, 1% NaCl aqueous solution (ISOTON-II (manufactured by Coulter)) was used.
Here, 5 mg of a measurement sample was further added as a solid content.
The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment for 2 minutes with an ultrasonic disperser, and the volume distribution is measured by measuring the volume and number of toner particles or toner using the 100 μm aperture as the aperture. And the number distribution was calculated, and the volume average particle diameter of the target toner was determined from this.
As a channel, it is less than 2.00 to less than 2.52 μm, less than 2.52 to 3.17 μm, less than 3.17 to 4.00 μm, less than 4.00 to 5.04 μm, less than 5.04 to 6.35 μm, 6 .35 to less than 8.00 μm, less than 8.00 to 10.08 μm, less than 10.08 to 12.70 μm, less than 12.70 to 16.00 μm, less than 16.00 to less than 20.20 μm, 20.20 to 25.25. Uses 13 channels of less than 40 μm, 25.40 to 32.00 μm, 32.00 to less than 40.30 μm, and targets particles having a particle size of 2.00 μm to less than 40.30 μm.

[Evaluation of softening point (Tm)]
Using a flow tester (CFT-500 / manufactured by Shimadzu Corporation), 1.5 g of a measurement sample was weighed, and using a die of H1.0 mm × φ1.0 mm, the heating rate was 3.0 ° C./min, and the preheating time was 180. Measurement was performed under the conditions of seconds, a load of 30 kg, and a measurement temperature range of 80 to 140 ° C., and the temperature at which the above sample flowed out 1/2 was taken as the softening point.

(Evaluation of fixing separation)
A two-component developer prepared by mixing and stirring 5 parts of toner and 95 parts of a silicone resin coated carrier is placed in a modified machine from which the Ricoh ipsio CX7500 fixing machine is removed, and this is transferred to a transfer paper (Ricoh type 6200Y eye paper). ) Was adjusted so that 1.1 ± 0.1 mg / cm ² of toner was developed with a solid image having a vertical end margin of 3 mm, and 6 unfixed transfer sheets were output.
Only the fixing part of Ricoh ipsio CX2500 was taken out, and the fixing belt temperature and the belt linear velocity were modified to the desired values, and the belt linear velocity was set to 125 mm / sec. The transfer paper was fixed in the range of 140 ° C. to 190 ° C. at 10 ° C. increments from the end margin of 3 mm.
Evaluation was performed based on the following criteria based on the number of sheets that could be normally fixed without the transfer paper being wrapped around the fixing belt or being clogged like a bellows at the exit of the fixing machine.
A: Six sheets were successfully fixed.
○: The number of sheets successfully fixed is 5.
Δ: 3 to 4 sheets successfully fixed.
X: The number of sheets successfully fixed is 2 or less.
“◎” and “◯” were evaluated as satisfactory in practical use, and passed.

[Evaluation of fixing strength]
A two-component developer prepared by mixing and stirring 5 parts of toner and 95 parts of a silicone resin coated carrier is placed in a modified machine with the Ricoh ipsio CX7500 fixing machine removed, and this is transferred to a transfer paper (Ricoh type 6200Y eye paper). In addition, an adjustment was made so that 1.1 ± 0.1 mg / cm ² of toner was developed with a solid image having a vertical end margin of 100 mm, and unfixed transfer paper was output.
Only the fixing part of Ricoh's ipsio CX2500 was taken out, and the fixing belt temperature and belt linear velocity were modified to the desired values, and the belt linear velocity was set to 125 mm / sec and the fixing belt temperature was set to 140 ° C. After fixing the transfer paper, a drawing tester AD-401 manufactured by Ueshima Seisakusho was used, and the sapphire was run with the sapphire needle 125 μR, the needle rotation diameter of 8 mm, and the load of 1 g on the evaluation image. The running surface of the tip of the needle point was visually observed to evaluate the occurrence of scratches (running traces) according to the following rank.
A: No trace (line) traveled is recognized.
○: Slight lines are recognized.
Δ: The line is slightly observed when observed from directly above the image, but is not clearly observed when observed from an oblique angle of 45 degrees.
X: A line is clearly recognized when observed from directly above the image.
“◎” and “◯” were evaluated as satisfactory in practical use, and passed.

[Glossiness evaluation]
Only the fixing part of Ricoh's ipsio CX2500 was taken out, and the fixing belt temperature and belt linear velocity were modified to the desired values, and the belt linear velocity was set to 125 mm / sec and the fixing belt temperature was set to 160 ° C. Then, fixing of the unfixed transfer paper output by the same method as the evaluation of the fixing strength described above was performed.
The glossiness of the image after fixing was measured at an incident angle of 60 ° with a gloss meter manufactured by Nippon Denshoku Industries Co., Ltd. As a full color image used in an office, moderate gloss was preferred, and about 5 to 15% was evaluated as preferable.

[Evaluation of fixed fixing of regulated blade]
Using Ricoh's ipsio CX3000, a predetermined print pattern with a printing rate of 6% was printed on the developing roller of the developer after continuous copying (after endurance) of 2000 sheets in an N / N environment (23 ° C., 45%) The copied image was visually observed and evaluated.
Judgment criteria are as follows.
A: No streak or unevenness occurred on the developing roller.
○: Although some streaks or unevenness occurred on the developing roller, there were no vertical streaks on the copied image, and there was no practical problem.
X: A lot of streaks or unevenness occurred on the developing roller, and vertical streak-like omission occurred on the copied image, causing a problem in practical use.
“◎” and “◯” were evaluated as satisfactory in practical use, and passed.

[Filming evaluation]
Using a Ricoh ipsio CX3000, a predetermined print pattern with a printing rate of 6% was continuously printed in an N / N environment (23 ° C., 45%). After continuous printing (after endurance) in an N / N environment, the photosensitive member and the intermediate transfer belt were visually observed and evaluated.
Judgment criteria are as follows.
A: There was no filming on the photosensitive member and the intermediate transfer member, and there was no problem at all.
○: Filming was observed on one of the photosensitive member and the intermediate transfer member, but it was not visible on the copied image, and there was no practical problem.
X: Filming occurred on the photoreceptor and / or the intermediate transfer member, which could be confirmed on the image, and there was a problem in practical use.
“◎” and “◯” were evaluated as satisfactory in practical use, and passed.

[Transfer missing]
Using a Ricoh ipsio CX3000, write a plurality of thin line latent images on the photosensitive drum, stop the image forming process during the primary transfer, remove the transfer belt unit from the copier, and visually check the image on the transfer belt. In addition, it was observed with an optical microscope to evaluate the occurrence of voids in thin line images.
In addition, the unfixed and fixed images on the recording paper were observed visually and with an optical microscope to evaluate the occurrence of a thin line image.
A: No void occurred on the transfer belt or the unfixed image.
○: Some omissions occur on the unfixed image, but they are not observed after fixing.
(Triangle | delta): The void | missing has generate | occur | produced to some dot shape after fixing.
X: A void occurred after fixing.

[Evaluation of heat-resistant storage stability]
The toner was stored at 50 ° C. for 8 hours, and then sieved with a 42 mesh sieve for 2 minutes. The residual ratio on the wire mesh was used as an index for heat resistant storage stability.
The heat resistant storage stability was evaluated in the following four stages.
A: Less than 10% B: 10-20%
Δ: 20-30%
×: 30% or more

  Table 3 below shows the evaluation results for the fixing separation property, fixing strength, glossiness, regulation blade fixing and fixing, filming, transfer loss, and heat-resistant storage stability in Examples 1 to 17 and Comparative Examples 1 to 15. Show.

As is clear from the evaluation results of Table 3 above, in Examples 1 to 17 which are non-magnetic one-component developing toners according to the present invention, good evaluations were obtained in any of the above cases.
On the other hand, in Comparative Example 1, since the softening point of the first binder was lower than the numerical range of the present invention, the evaluation of the fixing separation property and the heat resistant storage property was deteriorated.
In Comparative Example 2, since the softening point of the first binder was higher than the numerical value range of the present invention, the evaluation of fixing strength and glossiness deteriorated.
In Comparative Example 3, since the amount of the internally added wax was smaller than the numerical value range of the present invention, the evaluation of the fixing separation property was deteriorated.
In Comparative Example 4, since the amount of the internally added wax was larger than the numerical range of the present invention, evaluation of blade fixing and fixing, filming, and heat-resistant storage stability deteriorated.
In Comparative Examples 5 and 6, since no wax was internally added to the first binder, the evaluation of fixing separation property, fixing strength, blade fixing and filming was significantly deteriorated.
In Comparative Example 7, since the softening point of the second binder was lower than the numerical range of the present invention, the evaluation of the fixing separation property and the heat resistant storage property was deteriorated.
In Comparative Example 8, since the softening point of the second binder was higher than the numerical value range of the present invention, the evaluation of fixing strength and glossiness deteriorated.
In Comparative Example 9, since the composition ratio between the first binder and the second binder was outside the numerical range of the present invention, the evaluation of the fixing separation property was deteriorated.
In Comparative Example 10, since the first binder was excessive in the composition ratio of the first binder and the second binder, the evaluation of heat resistant storage stability was deteriorated.
In Comparative Example 11, the evaluation of blade fixing and filming deteriorated because the BET value of the first inorganic fine particles of the external additive was small.
In Comparative Example 12, since the BET value of the second inorganic fine particles was large, the evaluation of fixing separation property and transfer loss was deteriorated.
In Comparative Examples 13 and 14, the evaluation of fixing separation and filming deteriorated.
In Comparative Example 15, since the particle size of the toner was too small, the evaluation of the fixing separation property was deteriorated.

Claims (9)

In the non-magnetic one-component developing toner comprising toner base particles and an external additive,
The toner base particles, a first binder resin in softening point 120 to 150 ° C., which is added 8-15 parts by weight of the hydrocarbon-based wax is 100 parts by weight of the binder resin of melting point 70 to 90 ° C., a softening point It contains a 100 to 130 ° C. a second binder resin, a colorant, the weight ratio of the first binder resin and the second binder resin is 20 / 80-45 / 5 5, and the particle diameter (volume Average particle diameter) is 5 to 10 μm,
The external additive may include a first inorganic fine particles BET100~300m ² / g, consists of a second inorganic fine particles BET40~100m ² / g, and external additive total amount, the toner base particles 100 parts by weight 2.5 to 5.0 parts by weight,
And a non-magnetic one-component developing toner.   The toner for non-magnetic one-component development according to claim 1, wherein the average circularity is 0.890 to 0.950.   An image forming method comprising performing image formation using the non-magnetic one-component developing toner according to claim 1. A roll fixing type image forming apparatus comprising a fixing device including a heating roll and a pressure roll,
An image forming apparatus, wherein the non-magnetic one-component developing toner according to claim 1 is applied to form an image.   The image forming apparatus according to claim 4, wherein the image forming apparatus is an oilless fixing that does not require oil application to the heating roll and the pressure roll constituting the fixing device.   The image forming apparatus according to claim 4, further comprising an intermediate transfer unit.   The image forming apparatus according to claim 4, further comprising a blade cleaning unit.   The image forming apparatus according to claim 4, wherein the fixing device includes a belt provided with a heating device. A process cartridge that integrally supports at least one member selected from a photosensitive member, a charging unit, a developing unit, and a cleaning unit, and is detachable from an image forming apparatus main body;
The process cartridge according to claim 1, wherein the developing unit holds toner (developer), and the toner (developer) is the non-magnetic one-component developing toner according to claim 1.