JP2009069536A - Toner for electrostatic latent image development, image forming method and apparatus using the same, and process cartridge - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner in which charging is made uniform and stabilized, which suppresses stains on a base, to provide an image forming method and an apparatus using the toner, and to provide a process cartridge for the method. <P>SOLUTION: The toner for electrostatic latent image development contains a binder resin and a coloring material, wherein the toner contains a triaryl triazine compound expressed by general formula (1). In the formula, n represents 1, 2 or 3. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an electrostatic latent image toner, an image forming method, an image forming apparatus, and a process cartridge, and is applied to colored fine particles for a paper-like display.

  It is known that a specific triazine compound is used for various purposes in a light-related field in a very broad sense. For example, Japanese Patent Application Laid-Open No. 07-188188 of Patent Document 1 discloses a specific structure having 2 It is described that a 4,6-triphenyl-1,3,5-triazine compound is used as an ultraviolet absorber or an intermediate therefor. Japanese Patent Application Laid-Open No. 08-217810 of Patent Document 2 describes polymerization of a photoresist material. It is described that 2,4,6-tris (trichloromethyl) -s-triazine is used as a disclosure agent, and Japanese Patent Application Laid-Open No. 07-157473 of Patent Document 3 and Japanese Patent Application Laid-Open No. 2006-225322 of Patent Document 4 disclose , 2,4,6-tris (2'-benzothiazole, -benzoxazole or -benzimidazole) -1,3,5-tria of specific structure, respectively Bis [4.6-bis (alkylphenyl) -1,3,5-triazin-2-yl] -naphthalene having a specific structure as an electroluminescent element material However, these techniques are not related in any way to toners for electrostatic latent images, and the compounds are also different from those used in the present invention.

  Japanese Patent Application Laid-Open No. 10-298167 of Patent Document 5 describes that 2-N-benzyl or -phenyl-anilino-1,3,5-triazine is contained in the toner. , 2, 4 and 6 have only one benzylamino group and no aryl substitution at the other positions. In JP-A-52-003433 of Patent Document 6 and JP-A-52-003432 of Patent Document 7, one of the substituents is chloro for the purpose of fixing the dye by steaming. Although the technique using 1,3,5-triazine is described, the use and compound of these techniques are completely different from those of the present invention. Further, Japanese Patent Publication No. 51-001979 of Patent Document 8 aims to improve color reproducibility, and includes an amino group-containing organic photoconductive compound, 2, 4 in a colorless or light-colored photoconductive toner precursor. Although a technique has been described in which a coloring material containing a dichloro-1,3,5-triazinyl group is bonded to form a color by dehydrochlorination, this technique is also completely different from the present invention in use and compound.

JP 07-188188 A Japanese Patent Laid-Open No. 08-217810 JP 07-157473 A JP 2006-225322 A JP-A-10-298167 JP-A-52-003433 JP-A-52-003432 Japanese Patent Publication No. 51-001979

In image formation by electrophotography, it is required to stably maintain the electrostatic charge of the toner.
For example, in the one-component development, there is a problem that a background stain occurs when the charge of the toner cannot be stably maintained.
SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a toner in which charging is uniform and stabilized, and contamination is suppressed, an image forming method and apparatus using the toner, and a process cartridge therefor.

  The above-described problem is characterized in that (1) “containing at least a binder resin and a coloring material, and the toner for developing an electrostatic latent image contains a triaryltriazine compound represented by the following general formula (1): An electrostatic latent image developing toner.

尚、式中Ａｒ＝炭素数６から１０の置換もしくは無置換のアリーレン基
Ｒ＝ハロゲン原子、炭素数１から１２の分岐又は直鎖のアルキル基またはアルコキシル基、−ＣＯＣＨ_３、−ＮＯ_２、−ＣＮ、−Ｏ−ＣＨ_２Ｐｈ又は−Ｘ−Ｐｈでｎ≧２のときＲはそれぞれ同一でも異なっていてもよい。
ｘ＝−Ｏ−、−Ｓ−、−ＣＨ_２−、−ＣＯ−、−ＳＯ_２−、−Ｃ（ＣＨ_３）_２−、−ＮＨ−、−ＣＯＮＨ−、−ＮＨＣＯ−又は−ＣＯＮＨＣＯ−、
ｎ＝１、２、３」、
（２）「該トリアリールトリアジン化合物が上記一般式（１）中、Ａｒ＝炭素数６、ｎ＝１または２で示される構造からなることを特徴とする前記第（１）項に記載の静電潜像現像用トナー」、
（３）「帯電制御剤をさらに含有することを特徴とする前記第（１）項または第（２）項に記載の静電荷潜像現像用トナー」、
（４）「前記一般式（１）のトリアリールトリアジン化合物の含有量が、前記結着樹脂１００質量部に対して、０．１２〜２０質量部であることを特徴とする前記第（１）項乃至第（３）項のいずれかに記載の静電潜像現像用トナー」、
（５）「一成分現像方式に用いられることを特徴とする前記第（１）項乃至第（４）項のいずれかに記載の静電荷潜像現像用トナー」、
（６）「前記第（１）項乃至第（５）項のいずれかに記載の静電荷潜像現像用トナーを用いて画像を形成することを特徴とする画像形成方法」、
（７）「前記第（１）項乃至第（５）項のいずれかに記載の静電荷潜像現像用トナーを用いて画像を形成することを特徴とする画像形成装置」、
（８）「前記画像が、多色画像であることを特徴とする前記第（７）項に記載の画像形成装置」、
（９）「無端型の中間転写手段を有することを特徴とする前記第（７）項または第（８）項に記載の画像形成装置」、
（１０）「感光体と、該感光体及び／又は前記中間転写手段に残存したトナーをクリーニングするクリーニング手段を有し、該クリーニング手段は、クリーニングブレードを有さないことを特徴とする前記第（８）に記載の画像形成装置」、
（１１）「感光体と、該感光体及び／又は前記中間転写手段に残存したトナーをクリーニングするクリーニング手段を有し、該クリーニング手段は、クリーニングブレードを有することを特徴とする前記第（８）項に記載の画像形成装置」、
（１２）「加熱装置を有するローラを用いて画像を定着する定着手段を有することを特徴とする前記第（７）項乃至第（１１）項のいずれかに記載の画像形成装置」
（１３）「加熱装置を有するベルトを用いて画像を定着する定着手段を有することを特徴とする前記第（７）項乃至第（１１）項のいずれかに記載の画像形成装置」、
（１４）「前記定着手段が、定着部材にオイル塗布を必要としない定着手段であることを特徴とする前記第（１２）項又は第（１３）項に記載の画像形成装置」、
（１５）「感光体と、該感光体に形成された静電潜像を、前記第（１）項乃至第（５）項のいずれかに記載の静電荷潜像現像用トナーを用いて現像する現像手段を少なくとも一体に支持し、画像形成装置本体に着脱自在であることを特徴とするプロセスカートリッジ」により達成される。

In the formula, Ar = a substituted or unsubstituted arylene group having 6 to 10 carbon atoms
R = halogen atom, branched or straight chain alkyl group or alkoxyl group having 1 to 12 carbon atoms, —COCH ₃ , —NO ₂ , —CN, —O—CH ₂ Ph or —X—Ph, where n ≧ 2. Each R may be the same or different.
x = —O—, —S—, —CH ₂ —, —CO—, —SO ₂ —, —C (CH ₃ ) ₂ —, —NH—, —CONH—, —NHCO— or —CONHCO—,
n = 1, 2, 3 ",
(2) The static according to item (1), wherein the triaryltriazine compound has a structure represented by Ar = C6, n = 1 or 2 in the general formula (1). Toner for developing electrostatic latent image ",
(3) "The electrostatic latent image developing toner according to item (1) or (2), further including a charge control agent",
(4) The above-mentioned (1), wherein the content of the triaryltriazine compound of the general formula (1) is 0.12 to 20 parts by mass with respect to 100 parts by mass of the binder resin. Item. The electrostatic latent image developing toner according to any one of Items (3) to (3),
(5) “Electrostatic latent image developing toner according to any one of (1) to (4) above, which is used in a one-component developing method”,
(6) “Image forming method comprising forming an image using the electrostatic latent image developing toner according to any one of (1) to (5)”,
(7) “Image forming apparatus for forming an image using the electrostatic latent image developing toner according to any one of (1) to (5)”,
(8) “The image forming apparatus according to (7), wherein the image is a multicolor image”,
(9) “Image forming apparatus according to item (7) or (8), including an endless intermediate transfer unit”,
(10) “The photoconductor and cleaning means for cleaning the toner remaining on the photoconductor and / or the intermediate transfer means”, wherein the cleaning means does not have a cleaning blade. 8) ",
(11) The above (8), characterized in that it has a photosensitive member and a cleaning unit for cleaning the toner remaining on the photosensitive member and / or the intermediate transfer unit, and the cleaning unit has a cleaning blade. The image forming apparatus according to the item ",
(12) “The image forming apparatus according to any one of (7) to (11), including a fixing unit that fixes an image using a roller having a heating device”
(13) “The image forming apparatus according to any one of (7) to (11), including a fixing unit that fixes an image using a belt having a heating device”;
(14) “The image forming apparatus according to (12) or (13), wherein the fixing unit is a fixing unit that does not require oil application to a fixing member”;
(15) “Developing the photosensitive member and the electrostatic latent image formed on the photosensitive member with the electrostatic latent image developing toner according to any one of (1) to (5). This is achieved by a process cartridge that at least integrally supports the developing means that can be attached to and detached from the main body of the image forming apparatus.

  As is clear from the following detailed and specific invention, the compound represented by the general formula (1) of the present invention is known to have a high electron affinity and a high electron transporting ability (Polymer 56, May). However, it has been found that the use of a specific amount of this compound in the toner and the presence of the compound in the toner makes the charging of the toner uniform, stabilizes, and suppresses soiling. In particular, it is useful in a negatively charged toner, and exhibits an extremely excellent effect that a much higher charged toner can be obtained when used in combination with a conventionally known CCA (charge control agent).

The toner of the present invention includes at least a binder resin, a black colorant, a yellow colorant, a magenta colorant, and a cyan colorant, and a toner containing a specific amount of the compound represented by the general formula (1). In addition to materials, other components such as the CCA, waxy material, fine particle fluidity improver, and antioxidant are optionally contained. The wax component, fine particle fluidity improver and the like may be added internally or externally. The toner of the present invention can be obtained by mixing desired amounts of these toner materials, melting and kneading, and classifying the obtained kneaded product after pulverization or simultaneously with pulverization to obtain a toner base having a desired particle diameter. it can.
In addition to physical production methods such as the above pulverization method, dry granulation method from solvent droplets in which binder resin is dissolved, solidification granulation method by removing aqueous solvent from O / W emulsion, emulsion aggregation method , Suspension polymerization method, partial polymerization method of binder component, for example, a chemical production method such as in-liquid elongation method of polyester resin component as binder precursor, and further, physical production method It can also be produced by a combination of chemical processes.

[Examples of toner materials]
<Binder resin>
The binder resin is not particularly limited and may be appropriately selected depending on the intended purpose. However, binder resins known in the field of full-color toners such as polyester resins, (meth) acrylic resins, styrene- ( (Meth) acrylic copolymer resin, epoxy resin, COC (cyclic olefin resin (for example, TOPAS-COC, manufactured by Ticona)) and the like. From the viewpoint of stress resistance in the developing unit, styrene- It is preferable to use a (meth) acrylic copolymer resin or a polyester resin. You may use these in combination of 2 or more types as needed.

<Colorant>
As the colorant used in the present invention, known dyes and pigments can be used.
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, bengara, red lead, red lead, cadmium red, cadmium mercury red, antimony red, permanent red 4R, para red, phise red, parachlor ortho nitroaniline red, risor fast scarlet G, Reliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment 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 Range, 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, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridiane, emerald green, pigment green B, naphthol green B, Green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone Green, Oxidized Chi Tan, zinc white, lithopone and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

<Wax component>
The toner composition of the present invention preferably contains a wax component.
For example, polyolefin wax (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbon (paraffin wax, sasol wax, etc.); carbonyl group-containing wax, etc. Carbonyl group-containing waxes include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1, 18-octadecanediol distearate, etc.); polyalkanol esters (tristearyl trimellitate, distearyl maleate, etc.); polyalkanoic acid amides (ethylenediamine dibehenylamide, etc.); polyalkylamides (trimellitic acid tristearylamide, etc.) ); And dialkyl ketones (such as distearyl ketone). Among these carbonyl group-containing waxes, polyalkanoic acid esters are preferred.
Among these, in the present invention, wax having low polarity is preferably used. Specific examples include hydrocarbon waxes such as polyethylene wax, polypropylene wax, paraffin wax, sazol wax, microcrystalline wax, and Fischer-Tropsch wax. The wax content in the toner is 3 to 15% by weight, preferably 4 to 12% by weight, and more preferably 5 to 10% by weight with respect to 100% by weight of the resin component. If the amount of wax with respect to the total amount of toner is less than 3%, the releasing effect by the wax may be lost, and the margin for preventing offset may be lost. On the other hand, if it exceeds 15%, the wax melts at a low temperature, so it is easily affected by thermal energy and mechanical energy. It may adhere and cause image noise. Further, when printing is performed on the OHP sheet, the release agent may spread outside the printing area and appear as image noise in the projected image.

<CCA (charge control agent)>
The toner of the present invention may contain a charge control agent as necessary. Known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified quaternary salts). Secondary ammonium salts or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of 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-147 which is a boron complex (Nippon Carlit), copper phthalocyanine, perylene, quinacridone Azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.
The addition amount of the charge control agent (CCA) includes the addition amount of the triazine compound of the general formula (1), the type of the binder resin, the type and amount of other additives used as necessary, and the dispersion method. Although it is determined by the toner manufacturing method including the above, it is not uniquely limited, but 0.08 to 6 parts by mass is preferable with respect to 100 parts by mass of the binder resin, and 0.2 to 3 is preferable. More preferably, 5 parts by mass.

<External additive>
As the external additive for assisting the fluidity, developability and chargeability of the toner base obtained in the present invention, known inorganic fine particles and polymer fine particles can be used.

<Inorganic fine particles>
As the external additive for assisting the fluidity, developability and chargeability of the colored particles obtained in the present invention, inorganic fine particles can be preferably used. The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and particularly preferably 5 nm to 500 nm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The proportion of the inorganic fine particles used is preferably 0.01 to 5% by weight of the toner, and particularly preferably 0.01 to 2.0% by weight. Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

<Polymer fine particles>
Other polymer fine particles such as polystyrene, methacrylic acid ester and acrylic acid ester copolymer obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, polycondensation systems such as silicone, benzoguanamine, and nylon, and thermosetting resins Examples include polymer particles.

<Surface treatment of external additive>
Such a fluidizing agent can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .

[Compound of general formula (1)]
The following are mentioned as a compound of the said General formula (1) in this invention.
That is, 2,4,6-triphenyl-1,3,5-triazine, 2,4,6-tri (β-naphthyl) -1,3,5-triazine, 2,4,6-tri (4-fluoro) Phenyl) -1,3,5-triazine, 2,4,6-tri (4-toluyl) -1,3,5-triazine, 2,4,6-tri (4-n-hexylphenyl) -1, 3,5-triazine, 2,4,6-tri (4-n-dodecylphenyl) -1,3,5-triazine, 2,4,6-tri (4-methoxyphenyl) -1,3,5- Triazine, 2,4,6-tri (4- (2-ethylhexyloxy) phenyl) -1,3,5-triazine, 2,4,6-tri (3,5-fluorophenyl) -1,3,5 -Triazine, 2,4,6-tri (3-nitrophenyl) -1,3,5-triazine, 2,4,6-tri (4-fuacetylphenyl) -1,3,5-triazine, 2, 4,6-tri (4-phenoxyphenyl) -1,3,5-triazine, 2,4,6-tri (4-benzoylphenyl) -1,3,5-triazi 2,4,6-tri (4-phenylsulfonylphenyl) -1,3,5-triazine, 2,4,6-tri (4-phenylisopropenylphenyl) -1,3,5-triazine, 2 , 4,6-tri (3,5-dimethylphenyl) -1,3,5-triazine, 2,4,6-tri (3-methyl-4-fluorophenyl) -1,3,5-triazine, 2 , 4,6-tri (3,4,5-trifluorophenyl) -1,3,5-triazine and the like, but is not limited thereto. Two or more kinds may be used simultaneously.

  The amount of the compound represented by the general formula (1) is the kind of the binder resin, the amount of the additive used as necessary, and the conventionally known CCA which may be added as needed. Although it is determined by the toner production method including the addition amount and the dispersion method and is not uniquely limited, it is preferably 0.12 to 20 parts by mass with respect to 100 parts by mass of the binder resin. 0.2-12 mass parts is more preferable. When the amount is less than 0.12 parts by mass, desired charge rising characteristics may not be obtained. When the amount is more than 20 parts by mass, the toner particles are exposed on the surface of the toner particles, and contamination of the member or fixing property or stress resistance decreases. Will occur. More preferably, the molecular weight is preferably from 300 to 700 so that the effect of Compound 1 can be more easily expressed at 1 to 10 wt%.

  The compound of the general formula (1) can be synthesized by a synthesis method by trimerization of a nitrile compound described in JP-A-7-188188, after ring formation of a nitrile compound and a carboxylic acid chloride described in JP-A-2006-225322. It can be synthesized in accordance with a synthesis method for treatment or a synthesis method described in JP-A-7-157473 in which an aromatic iodide is converted to a Li salt and coupled with cyanuric chloride. Specific synthesis examples will be described in detail later.

[Production of toner]
[Crushing method]
In the production of the toner by the pulverization method of the present invention, a desired amount of the toner material component containing the binder resin and the triazine compound of the general formula (1) is mixed, melt-kneaded, and the obtained kneaded product is obtained. A toner base having a desired particle diameter can be obtained by classification after pulverization or simultaneously with pulverization. In this method, the toner base particles are melted and kneaded, pulverized, classified, etc. How to get. In the case of the pulverization method, for the purpose of increasing the average circularity of the toner, the shape may be controlled by applying a mechanical impact force to the obtained toner base particles. In this case, the mechanical impact force can be applied to the toner base particles using a device such as a hybridizer or mechanofusion.

  First, each material for toner is mixed. As the mixer, a general powder mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. In addition, you may change the rotation speed, rolling speed, time, temperature, etc. of a mixer. Alternatively, a strong load may be applied first, then a relatively weak load, or vice versa. Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Roedige mixer, a Nauter mixer, and a Henschel mixer. The mixture is charged into a melt kneader and melt kneaded. As the melt kneader, for example, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used. For example, a KTK type twin screw extruder manufactured by Kobe Steel, a TEM type extruder manufactured by Toshiba Machine Co., Ltd., a twin screw extruder manufactured by Casey Kay, a PCM type twin screw extruder manufactured by Ikegai Iron Works, a Kneader manufactured by Buss, etc. are suitable. Used. This melt-kneading is preferably performed under appropriate conditions so as not to cause the molecular chains of the binder resin to be broken.

  In the pulverization, the kneaded product obtained by the kneading is pulverized. In this pulverization, it is preferable that the kneaded material is first coarsely pulverized and then finely pulverized. In this case, a method of pulverizing by colliding with a collision plate in a jet stream, pulverizing particles by colliding with each other in a jet stream, or pulverizing with a narrow gap between a mechanically rotating rotor and a stator is preferably used.

In the classification, the pulverized product obtained by the pulverization is classified and adjusted to particles having a predetermined particle diameter. The classification can be performed by removing the fine particle portion by, for example, a cyclone, a decanter, centrifugation, or the like.
After the pulverization and classification are completed, the pulverized product is classified in an air current by centrifugal force or the like to produce a toner having a predetermined particle size.

Further, in order to improve the fluidity, storage stability, developability, and transferability of the toner, inorganic fine particles such as hydrophobic silica fine powder may be further added to and mixed with the toner base particles produced as described above. For mixing the additives, a general powder mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the additive, the additive may be added in the middle or gradually. In this case, you may change the rotation speed, rolling speed, time, temperature, etc. of a mixer. Alternatively, a strong load may be applied first, then a relatively weak load, or vice versa. Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, and a Henschel mixer. Next, the toner is obtained by passing through a sieve of 250 mesh or more to remove coarse particles and aggregated particles.
Here, the toner material contains at least a binder resin, a colorant, and a charge control agent, and further contains a wax and, if necessary, other components.

[Emulsion aggregation method]
In the present invention, in addition to the pulverization method, a dry granulation method from a solvent droplet in which a binder resin is dissolved, a solidification granulation method by removing an aqueous solvent from an O / W emulsion, an emulsion aggregation method, a suspension method, It can also be produced by a turbid polymerization method, a partial polymerization method of a binder component, for example, a chemical production method such as an in-liquid elongation method of a polyester resin component as a binder precursor, of which, as a typical example, Hereinafter, the [emulsion aggregation method], the [suspension polymerization method] and the [resin component elongation method in liquid] such as a polyester resin as a binder precursor will be described.
The toner of the present invention by the emulsion aggregation method contains at least a binder resin, a triazine compound of the general formula (1), a wax, and a coloring material, and is produced by an emulsion aggregation method in an aqueous phase. The binder resin includes a vinyl resin made of a radical polymerizable monomer, and may include other resin components such as a polyester resin. This toner manufacturing method contains at least a binder resin, a triazine compound of the general formula (1), a wax, and a coloring material, and agglomerates each constituent material such as a pigment dispersion, a binder resin latex, and a wax dispersion in an aqueous phase. The toner base particles are obtained through a particle forming step followed by a washing and drying step. A toner produced by this production method comprises an emulsion aggregation method (heating) in a water phase containing a radical polymerizable monomer, a triazine compound of the general formula (1), a wax, a colorant, and a polyester resin which may be optionally added. After the granulation by the fusing step), it is further manufactured through granulation by heating and heat fusing step.
Any vinyl resin made of a radical polymerizable monomer can be used without particular limitation as long as it is a vinyl resin, and several kinds of vinyl copolymer resins may be mixed and used. The weight average molecular weight is preferably 50000 or less, and more preferably 30000 or less. When the weight average molecular weight is more than 50000, the low-temperature fixability may be lowered. The glass transition temperature is preferably 40 to 80 ° C, more preferably 50 to 70 ° C. When the glass transition temperature is higher than 80 ° C., the low-temperature fixability may be deteriorated, and when it is lower than 40 ° C., the heat resistant storage property may be deteriorated.

(Example of radical polymerizable monomer)
The vinyl resin is obtained by copolymerizing vinyl monomers. The vinyl monomers include (1) vinyl hydrocarbons; (aliphatic vinyl hydrocarbons, alicyclic vinyl hydrocarbons, aromatic vinyl resins). Hydrocarbons), (2) carboxyl group-containing vinyl monomers and their salts ((meth) acrylic acid, (anhydrous) maleic acid, monoalkyl maleate, fumaric acid, monoalkyl fumarate, crotonic acid, itaconic acid, itacone Acid monoalkyl, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl, cinnamic acid, etc.), (3) sulfonic acid group-containing vinyl monomers, vinyl sulfate monoesters and their salts, (4) phosphate groups -Containing vinyl monomers and salts thereof, (5) hydroxyl group-containing vinyl monomers, and (6) nitrogen-containing vinyl monomers. (7) Epoxy group-containing vinyl monomer, (8) Vinyl ester, vinyl (thio) ether, vinyl ketone, vinyl sulfone, (9) Other vinyl monomers (isocyanatoethyl (meth) acrylate, m-isopropenyl-α) , Α-dimethylbenzyl isocyanate, alkyloxysilyl group-containing monomers, etc.) and (10) fluorine atom element-containing vinyl monomers.
Moreover, there is no restriction | limiting in particular as a kind of polyester resin used depending on necessity, A well-known thing can be used. Moreover, you may mix and use several types of polyester resins. Further, by using crystalline polyester, it is possible to obtain a toner having excellent low-temperature fixability while maintaining the storage stability of the toner.

[Suspension polymerization method]
In this production method, toner base particles are obtained through a particle forming step by suspension polymerization in water of an oil droplet in which a pigment or wax is dispersed in a polymerizable monomer, followed by a washing and drying step.
In this suspension polymerization method, a polar resin such as polyester can be added. When the toner is directly produced by the suspension polymerization method, if a polar resin is added during the polymerization reaction from the dispersion step to the polymerization step, the balance between the polarity exhibited by the polymerizable monomer composition that becomes toner particles and the aqueous dispersion medium is achieved. Accordingly, it is possible to control so that the added polar resin forms a thin layer on the surface of the toner particles or exists with an inclination toward the center from the surface of the toner particles. At this time, by using a polar resin that interacts with a colorant and magnetic powder (use for obtaining a magnetic toner), it is possible to make the presence state of the colorant in the toner a desirable form. is there.
The addition amount of the polar resin is preferably 1 to 25 parts by mass, more preferably 2 to 15 parts by mass with respect to 100 parts by mass of the binder resin. If the amount is less than 1 part by mass, the presence state of the polar resin in the toner particles becomes non-uniform. Conversely, if the amount exceeds 25 parts by mass, the thin layer of the polar resin formed on the surface of the toner particles becomes thick.

  Specific examples of the polar resin include polyester resins, epoxy resins, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, and styrene-maleic acid copolymers. In particular, a polyester resin having a peak molecular weight of 3000 to 10,000 is preferable because it can improve the fluidity, negative triboelectric charging characteristics, and transparency of toner particles.

In order to increase the mechanical strength of the toner particles and to control the molecular weight of the toner particles, a crosslinking agent can be preferably used during the synthesis of the binder resin.
As a crosslinking agent, as a bifunctional crosslinking agent, divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 Each of diacrylate, dipropylene glycol diacrylate, polypropylene glycol diacrylate, polyester type diacrylate (MANDA Nippon Kayaku), and the above Those obtained by changing the acrylate dimethacrylate.

As polyfunctional crosslinking agents, pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate and its methacrylate, 2, 2
-Bis (4-methacryloxy, polyethoxyphenyl) propane, diallyl phthalate,
Examples include triallyl cyanurate, triallyl isocyanurate, and triallyl trimellitate.
These crosslinking agents are preferably used in an amount of 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, with respect to 100 parts by mass of the monomer.

When the toner of the present invention is produced by a suspension polymerization method, as a polymerization initiator, specifically,
2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2 ′
An azo or diazo polymerization initiator such as azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide,
Peroxide polymerization initiators such as 2,4-dichlorobenzoyl peroxide and lauroyl peroxide are used. Although the usage-amount of these polymerization initiators changes with the target degree of polymerization, generally 5-20 mass parts is used with respect to 100 mass parts of polymerizable vinylic monomers. The kind of the polymerization initiator varies slightly depending on the polymerization method, but is used alone or in combination with reference to the 10-hour half-life temperature.

  In the case of the suspension polymerization method, known inorganic and organic dispersants can be used as the dispersant used when preparing the aqueous dispersion medium. Specifically, as the inorganic dispersant, for example, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, Examples include calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, and alumina. Examples of organic dispersants that can be used include polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, carboxymethylcellulose sodium salt, and starch.

Commercially available nonionic, anionic and cationic surfactants can also be used. For example, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pendadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate can be used.
In the case of the suspension polymerization method, as the dispersant used for preparing the aqueous dispersion medium, an inorganic, poorly water-soluble dispersant is preferable, and a poorly water-soluble inorganic dispersant that is soluble in an acid is preferably used. Moreover, in this invention, when preparing a water-based dispersion medium using a slightly water-soluble inorganic dispersing agent, these dispersing agents are 0.2-2. It is preferable to use it in such a ratio that it becomes 0 parts by mass. In the present invention, it is preferable to prepare an aqueous dispersion medium using 300 to 3,000 parts by mass of water with respect to 100 parts by mass of the polymerizable monomer composition.

  In the present invention, when preparing an aqueous dispersion medium in which a poorly water-soluble inorganic dispersant is dispersed, a commercially available dispersant may be used as it is, but a dispersant particle having a fine uniform particle size is obtained. Therefore, it may be prepared by producing a poorly water-soluble inorganic dispersant as described above in a liquid medium such as water under high-speed stirring. For example, when tricalcium phosphate is used as a dispersant, a preferred dispersant can be obtained by mixing aqueous sodium phosphate solution and aqueous calcium chloride solution at high speed to form fine particles of tricalcium phosphate. .

A specific method for obtaining the toner of the present invention is a so-called suspension polymerization method in which a polymerizable monomer composition containing at least a polymerizable monomer and a colorant is subjected to suspension polymerization in an aqueous dispersion.
In the present invention, it is preferable that each toner material is uniformly present in the toner particles. For this purpose, the toner material is sufficiently contained in the polymerizable monomer composition in the process of producing the toner. Need to be distributed.
In order to sufficiently disperse the toner material, it is necessary to sufficiently shear the polymerizable monomer composition in the dispersion step of the polymerizable monomer composition. For this purpose, the polymerizable monomer composition preferably has a certain degree of viscosity. Examples of the method for increasing the viscosity of the polymerizable monomer composition include dissolving a resin in the polymerizable monomer composition in advance and partially polymerizing the polymerizable monomer.
In the dispersion step, when shearing is applied to the polymerizable monomer composition, a part of the shear energy is converted into heat energy, and thus cooling is necessary as necessary. When the heat generation is large and the cooling is insufficient, the temperature of the polymerizable monomer composition rises, so that the viscosity decreases, and the polymerizable monomer composition does not have sufficient shearing force. Will be insufficiently distributed.

  In addition, when the shear energy applied when the polymerizable monomer composition is dispersed is too large, the toner material and the pigment are excessively dispersed (overdispersion), and the dispersion state may be rapidly unstable. As a result, these dispersoids are aggregated, resulting in insufficient characteristics and a decrease in the coloring degree of the toner. Therefore, overdispersion is not preferable.

The disperser used for the dispersion treatment of the polymerizable monomer composition is not particularly limited, but preferably
Examples thereof include pressure dispersers such as ultrasonic dispersers, mechanical homogenizers, Manton Gorin, CLEAR MIX, CLEAR SS5 and pressure homogenizers, and medium dispersers such as attritors, sand grinders, Getzman mills, and diamond fine mills.

  The pigment (particles) used in the present invention may be surface-modified. As an example of a pigment surface modification method, a pigment is dispersed in a solvent, a surface modifier is added to the dispersion, and the system is reacted by raising the temperature. After completion of the reaction, the pigment is separated by filtration, washed and filtered with the same solvent, and dried to obtain the pigment treated with the surface modifier.

[Method of extending resin components in liquid]
This toner production method typically includes an oil phase containing at least a colorant, a modified polyester (X) having an isocyanate group, and a triazine compound of the general formula (1) in an aqueous medium containing a surfactant. And granulating toner particles containing at least a modified polyester (Z) having a urea group and the unmodified polyester (Y). In this method, an unmodified polyester (Y) having no isocyanate group and having a specific acid value (for example, an acid value of 15 mg / KOH or more) can be preferably used. Moreover, a low molecular weight polyamine and a polyol can be used as an elongation agent and / or a crosslinking agent of the isocyanate group-containing polyester (X). Until now, it has been considered that a polymerized toner is good as a toner for developing an electrostatic latent image for obtaining a high-quality image having excellent fixability. Among them, the ester extension polymerization toner can use a polyester and can have a crosslinked structure in the toner, so that a toner having particularly excellent fixability can be obtained. Further, in order to further improve the fixability, the cross-linked resin skeleton in the toner has a flexible structure, and an unmodified polyester resin having an appropriate polarity is used as an isocyanate group-containing polyester extender and / or cross-linker. Low molecular weight polyamines and polyols are not used or limited, and a portion of the isocyanate at the prepolymer end can be converted to amine by water, and the resulting amine can be reacted with the remaining isocyanate. Compared with the case of using polyamines and polyols, the urea binding site can be reduced to about half.
On the other hand, as for the unmodified polyester resin having an appropriate polarity, in the ester extension polymerization toner, the unmodified polyester is a relatively low molecular weight polyester having almost no cross-linking structure. Since it has a ring function, it has a high acid value in order to have an affinity for paper quality.

  In the production of an ester extension polymerization method toner, an isocyanate-modified polyester having an isocyanate group at the molecular chain end, an unmodified polyester having no isocyanate group, a polyamine compound, and other materials (colorant, release agent, charging) Prepare an oil phase in which a control agent, a viscosity modifier, etc.) are dissolved / dispersed in an organic solvent, and an aqueous phase containing a polymer dispersant such as a low molecular weight activator or organic resin fine particles. Then, the oil phase and the aqueous phase are mixed and stirred (emulsification step), and the oil phase is dispersed in the aqueous phase, so that the isocyanate group and the amine group are reacted while the oil phase particles are obtained, and extension by urea bond is performed. To obtain toner particles. Since it is important that the unmodified polyester is melted at the time of fixing and impregnated into paper or the like, a low molecular weight polyester resin is often used.

  Here, it is considered that the polyamine compound helps dispersion in the aqueous phase in addition to the extension reaction. This can be inferred from the fact that if the emulsification step is carried out without adding the polyamine compound, the particles become enlarged or the emulsified state becomes unstable and the particles cannot be obtained. In particular, when the acid value of the unmodified polyester resin is high, it is very difficult to stabilize the emulsification, and granulation cannot be achieved only by increasing the amount of the low-molecular-weight active agent or the high-molecular dispersant.

Therefore, when the idea is further advanced, the polyamine compound escapes partly into the aqueous phase and has the function of controlling the pH of the aqueous phase, the pH should be controlled with an inorganic base such as sodium hydroxide or potassium hydroxide. Thus, it becomes possible to replace the function of stabilizing the dispersion that has been carried out by the polyamine compound so far, the emulsified state can be stabilized, and a toner having a desired particle diameter can be obtained.
In the toner in this case, since the heat resistant storage performance of the main component of the binder resin depends on the glass transition point of the unmodified polyester resin (Y), the glass transition point of the unmodified polyester resin (Y) is 35 ° C. to 35 ° C. It is preferable to design at 65 ° C. That is, if it is less than 35 ° C., the heat-resistant storage stability is insufficient, and if it exceeds 65 ° C., it adversely affects low-temperature fixing.

Next, materials constituting the toner will be described.
<Unmodified polyester resin>
There is no restriction | limiting in particular as a kind of unmodified polyester resin used for this invention, Any well-known thing can be used.
Examples of the unmodified polyester resin include polycondensates of the following polyol (1) and polycarboxylic acid (2).

<About polyol>
Examples of the polyol (1) include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol, triethylene glycol, Ethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, 4,4′-dihydroxybiphenyls such as bisphenol S, 3,3′-difluoro-4,4′-dihydroxybiphenyl, and the like; bis (3-fluoro-4-hydroxypheny ) Methane, 1-phenyl-1,1-bis (3-fluoro-4-hydroxyphenyl) ethane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 2,2-bis (3,5 -Difluoro-4-hydroxyphenyl) propane (also known as: tetrafluorobisphenol A), 2,2-bis (3-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, etc. Phenyl) alkanes; bis (4-hydroxyphenyl) ethers such as bis (3-fluoro-4-hydroxyphenyl) ether); alkylene oxides of the above alicyclic diols (ethylene oxide, propylene oxide, butylene oxide, etc.) Adducts: alkylene oxides of the above bisphenols (ethylene oxide) Propylene oxide, and the like butylene oxide, etc.) adducts.
Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use.
In addition, trihydric or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (trisphenol PA, phenol novolac, cresol novolac, etc.) ); Alkylene oxide adducts of the above trihydric or higher polyphenols.
In addition, the said polyol can be used individually by 1 type or in combination of 2 or more types, It is not limited to the above.

<Polycarboxylic acid>
Examples of the polycarboxylic acid (2) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, Naphthalenedicarboxylic acid, 3-fluoroisophthalic acid, 2-fluoroisophthalic acid, 2-fluoroterephthalic acid, 2,4,5,6-tetrafluoroisophthalic acid, 2,3,5,6-tetrafluoroterephthalic acid, 5- Trifluoromethylisophthalic acid, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 2,2-bis (3-carboxyphenyl) hexafluoropropane 2,2′-bis (trifluoromethyl) -4,4′- Phenyldicarboxylic acid, 3,3′-bis (trifluoromethyl) -4,4′-biphenyldicarboxylic acid, 2,2′-bis (trifluoromethyl) -3,3′-biphenyldicarboxylic acid, hexafluoroisopropylidene Dendiphthalic anhydride, etc.).
Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Further, polyvalent polycarboxylic acids having 3 or more valences are aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.), and acid anhydrides or lower alkyl esters (methyl esters, ethyl esters) described above. , Isopropyl ester, etc.) may be used to react with polyol (1).
In addition, the said polycarboxylic acid can be used individually by 1 type or in combination of 2 or more types, It is not limited to the above.

<Ratio of polyol and polycarboxylic acid>
The ratio of the polyol (1) to the polycarboxylic acid (2) is usually 2/1 to 1/1, preferably 1. 5/1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.
(Molecular weight of polyester resin)
The peak molecular weight is usually 1000 to 30000, preferably 1500 to 10000, more preferably 2000 to 8000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 30000, low-temperature fixability will deteriorate.

<Isocyanate-modified polyester>
The isocyanate-modified polyester (X) used in the present invention is a polycondensate of the polycarboxylic acid (2) as the polyol (Ao) and the polycarboxylic acid (Ac) as the polyol (Ao) and has an active hydrogen group. Examples include those obtained by further reacting polyester (A) with polyisocyanate. Examples of the active hydrogen group possessed by the polyester include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are preferred.
<Polyisocyanate>
Polyisocyanates include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic diisocyanates ( Tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; the polyisocyanates blocked with phenol derivatives, oximes, caprolactam, etc. And combinations of two or more of these.

<Ratio of isocyanate group to hydroxyl group>
The ratio of the polyisocyanate is usually 5/1 to 1/1, preferably 4 /, as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester (A) having a hydroxyl group. 1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. When the molar ratio of [NCO] is less than 1, the crosslinking density in the isocyanate-modified polyester (X) after the elongation and / or crosslinking reaction is lowered, and the offset resistance is deteriorated. The content of the polyisocyanate component in the isocyanate-modified polyester (X) is usually 0.5 to 40% by weight, preferably 1 to 30% by weight, and more preferably 2 to 20% by weight. If it is less than 0.5% by weight, the offset resistance deteriorates. On the other hand, if it exceeds 40% by weight, the low-temperature fixability deteriorates.
The number of isocyanate groups contained per molecule in the isocyanate-modified polyester (X) is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. If it is less than 1 per molecule, the molecular weight of the isocyanate-modified polyester (X) after chain extension and / or crosslinking becomes low, and offset resistance deteriorates.

<Colorant masterbatch>
The coloring agent to be used can also be used as a master batch combined with a resin. As the binder resin to be kneaded together with the production of the masterbatch or the masterbatch, in addition to the above-mentioned modified and unmodified polyester resins, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and substituted polymers thereof; Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer Styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α- Chloromethyl methacrylate copolymer, Tylene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid Styrene copolymers such as acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, poly Acrylic resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, etc. can be used alone or in combination. The

<Master batch production method>
This master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force to obtain a master batch. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. Also, a so-called flushing method called watering paste containing water of a colorant is mixed and kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove moisture and organic solvent components. Since it can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.
Moreover, as a mold release agent used for this invention, a well-known thing can be used like the case of the said grinding | pulverization method.
As the external additive for assisting the fluidity, developability and chargeability of the obtained toner base, known inorganic fine particles and polymer fine particles can be used as in the pulverization method.

<Cleaning aid>
Examples of the cleaning property improver for removing the developer after transfer remaining on the photoreceptor or the primary transfer medium include, for example, zinc stearate, calcium stearate, fatty acid metal salts such as stearic acid, such as polymethyl methacrylate fine particles, polystyrene fine particles, etc. And polymer fine particles produced by soap-free emulsion polymerization. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

<Granulation of core particles>
<Organic solvent>
The organic solvent for dissolving or dispersing the polyester resin, the colorant and the release agent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal of the solvent later. Examples of such organic solvents include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, Ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more. Particularly preferred are ester solvents such as methyl acetate and ethyl acetate, aromatic solvents such as toluene and xylene, and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform and carbon tetrachloride. The polyester resin, the colorant and the release agent may be dissolved or dispersed at the same time. Usually, each of them is dissolved or dispersed alone, and the organic solvents used at that time may be different or the same. The same is preferable considering the above.

<Dissolution or dispersion of polyester resin>
The polyester resin is preferably dissolved or dispersed in a resin concentration of about 40% to 80%. If the concentration is too high, it will be difficult to dissolve or disperse, and the viscosity will be too high to handle. On the other hand, if the density is too low, the amount of toner produced decreases. When mixing a polyester resin with a modified polyester resin having an isocyanate group at the terminal, it may be mixed in the same solution or dispersion, or separately dissolved or dispersed, but the respective solubility and Considering the viscosity, it is preferable to prepare separate solutions or dispersions.

<Dissolution or dispersion of colorant>
The colorant may be dissolved or dispersed alone, or may be mixed in the solution or dispersion of the polyester resin. If necessary, a dispersion aid or a polyester resin may be added, or the master batch may be used.

<Dissolution or dispersion of release agent>
When the wax is dissolved or dispersed as a release agent, if an organic solvent in which the wax does not dissolve is used, it is used as a dispersion, but the dispersion is prepared by a general method. That is, an organic solvent and wax may be mixed and dispersed with a disperser such as a bead mill. Further, after mixing the organic solvent and the wax, it is sometimes possible to shorten the dispersion time by once heating to the melting point of the wax, cooling with stirring and then dispersing with a disperser such as a bead mill. In addition, a plurality of waxes may be mixed and used, or a dispersion aid or a polyester resin may be added.

<Aqueous medium>
As an aqueous medium to be used, water alone may be used, but a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.), and the like. The amount of the aqueous medium used relative to 100 parts by weight of the toner composition is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight. If the amount is less than 50 parts by weight, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle diameter cannot be obtained. Moreover, when it exceeds 2000 weight part, it is not economical.

<Inorganic base>
As the inorganic base used for the purpose of adjusting the pH of the aqueous medium (when the amine as a hydrolysis product is produced by restricting the use of a low molecular amine or a hydroxy compound as an extender), a known inorganic base is used. Can be used. Specifically, hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide; lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, magnesium carbonate, carbonate Carbonates such as calcium; hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate, magnesium hydrogen carbonate, calcium hydrogen carbonate; and any mixtures thereof. The pH of the aqueous medium is adjusted to 9 or more. More specifically, it is adjusted by a resin, a colorant and a release agent which are dissolved or dispersed in an organic solvent.
The pH can also be adjusted with a water-soluble amine compound. However, the toner produced using this tends to have a low charging performance.

<Inorganic dispersant and organic resin fine particles>
When the dissolved or dispersed toner composition is dispersed in the aqueous medium, by dispersing the inorganic dispersant or the organic resin fine particles in the aqueous medium in advance, the particle size distribution is sharpened and the dispersion is reduced. It is preferable in terms of stability. As the inorganic dispersant, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like are used. As the resin forming the organic resin fine particles, any resin can be used as long as it can form an aqueous dispersion, and it may be a thermoplastic resin or a thermosetting resin. Includes vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, polycarbonate resins, and the like. These resins may be used in combination of two or more. Of these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferable from the viewpoint that an aqueous dispersion of fine spherical resin particles is easily obtained.

<Method of dispersing organic resin fine particles in water>
The method of making the resin into an aqueous dispersion of fine organic resin particles is not particularly limited, and examples thereof include the following (a) to (h).
(A) In the case of a vinyl resin, a method of directly producing an aqueous dispersion of resin fine particles by a polymerization reaction such as a suspension polymerization method, an emulsion polymerization method, a seed polymerization method or a dispersion polymerization method using a monomer as a starting material .
(B) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., a precursor (monomer, oligomer, etc.) or a solvent solution thereof is dispersed in an aqueous medium in the presence of a suitable dispersant, A method of producing an aqueous dispersion of resin fine particles by heating and then adding a curing agent to cure.
(C) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, and epoxy resin, a precursor (monomer, oligomer, etc.) or a solvent solution thereof (preferably liquid) may be liquefied by heating. .) A method in which a suitable emulsifier is dissolved therein, and then water is added to perform phase inversion emulsification.
(D) A resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) can be used as a mechanical rotary type or jet type resin. A method in which resin fine particles are obtained by pulverization using a fine pulverizer and then classification, and then dispersed in water in the presence of an appropriate dispersant.
(E) A resin solution obtained by dissolving a resin prepared in advance in a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent, A method in which resin fine particles are obtained by spraying in the form of a mist and then dispersed in water in the presence of an appropriate dispersant.
(F) A solvent is added to a resin solution obtained by dissolving a resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent. The resin fine particles are precipitated by cooling the resin solution previously dissolved in a solvent by heating, and then the solvent is removed to obtain resin fine particles, which are then dispersed in water in the presence of a suitable dispersant. Method.
(G) A resin solution obtained by dissolving a resin prepared in advance in a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent, A method of dispersing in an aqueous medium in the presence of a suitable dispersant and removing the solvent by heating or decompression.
(H) In a resin solution in which a resin prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is dissolved in a solvent. A method of phase inversion emulsification by adding water after dissolving an appropriate emulsifier.

<Surfactant>
Further, a surfactant or the like can be used as necessary in order to emulsify and disperse the oily phase containing the toner composition in the aqueous medium. As surfactants, anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, Quaternary ammonium salt type cationic surfactants such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride, fatty acid amide derivative, polyhydric alcohol Nonionic surfactants such as derivatives, for example, amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine It is.
Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Examples of the anionic surfactant having a fluoroalkyl group preferably used include fluoroalkylcarboxylic acids having 2 to 10 carbon atoms, and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [ω-fluoroalkyl (C6 -C11) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) ) Carboxylic acid and metal salt, perfluoroalkyl carboxylic acid (C7 to C13) and its metal salt, perfluoroalkyl (C4 to C12) sulfonic acid and its metal salt, perfluorooctane sulfonic acid diethanolamide, N-propyl-N -(2-hydroxyethyl) par Fluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Can be mentioned. In addition, examples of the cationic surfactant include aliphatic quaternary ammonium salts such as aliphatic primary, secondary or secondary amine acids having a fluoroalkyl group, and perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts. Benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt and the like.

<Protective colloid>
Further, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Bodies such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-acrylate Chloro-2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N -Of methyl alcohol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or compounds containing vinyl alcohol and carboxyl group Esters such as vinyl acetate, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole , Homopolymers or copolymers such as those having a nitrogen atom such as ethyleneimine or its heterocyclic ring, polyoxyethylene, polyoxypropylene, Oxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonylphenyl Polyoxyethylenes such as esters, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used. In addition, when an acid such as calcium phosphate salt or an alkali-soluble substance is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and then washing with water. To do. It can also be removed by operations such as enzymatic degradation. When a dispersant is used, the dispersant can remain on the surface of the toner particles, but it is preferable to remove it by washing from the charged surface of the toner.

<Method of dispersion>
The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 20 to 80 ° C.

<Desolation>
In order to remove the organic solvent from the obtained emulsified dispersion, a known method can be used. For example, a method can be employed in which the entire system is gradually heated under normal pressure or reduced pressure to completely evaporate and remove the organic solvent in the droplets.

<Extension or / and cross-linking reaction>
In the extension reaction and / or cross-linking reaction of the isocyanate-modified polyester, an oil phase in which an isocyanate-modified polyester, an unmodified polyester resin, a triazine compound of the general formula (1), a colorant, and a wax are dissolved or dispersed is added to an aqueous medium. Although it starts from time, you may provide the process of performing these reactions separately in a manufacturing process. The conditions for the reaction step are appropriately selected depending on the activity and concentration of the isocyanate group. The reaction time is usually 1 minute to 40 hours, preferably 1 to 24 hours. The reaction temperature is usually 0 to 150 ° C., preferably 20 to 98 ° C.

<Washing and drying process>
A known technique is used for washing and drying the toner particles dispersed in the aqueous medium.
That is, after solid-liquid separation with a centrifugal separator, a filter press, etc., the obtained toner cake is redispersed in ion exchange water at room temperature to about 40 ° C., and pH adjusted with acid or alkali as necessary, After removing the impurities and surfactants by repeating the process of solid-liquid separation again and again, the toner powder is obtained by drying with an air dryer, circulating dryer, vacuum dryer, vibration fluid dryer, etc. . At this time, the fine particle component of the toner may be removed by centrifugation or the like, and a desired particle size distribution can be obtained using a known classifier after drying, if necessary.

<External processing>
The obtained dried toner powder is mixed with different kinds of particles such as charge control fine particles and fluidizing agent fine particles, or fixed and fused on the surface by applying a mechanical impact force to the mixed powder. It is possible to prevent the dissociation of the foreign particles from the surface of the resulting composite particle. Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture in a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) has been modified to reduce the pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron Examples include a system (manufactured by Kawasaki Heavy Industries, Ltd.) and an automatic mortar.

[Image Forming Method, Image Forming Apparatus, Process Cartridge]
<Image forming apparatus, process cartridge>
The image forming apparatus of the present invention forms an image using the toner of the present invention. The toner of the present invention can be used as either a one-component developer or a two-component developer, but is preferably used as a one-component developer. The image forming apparatus of the present invention preferably has an endless intermediate transfer unit. Further, the image forming apparatus of the present invention includes a photoreceptor, a photoreceptor and / or
Alternatively, it is preferable to have a cleaning unit for cleaning the toner remaining on the intermediate transfer unit. At this time, the cleaning means may or may not have a cleaning blade. The image forming apparatus of the present invention preferably includes a fixing unit that fixes an image using a roller having a heating device or a belt having a heating device. Further, the image forming apparatus of the present invention preferably has a fixing unit that does not require oil application to the fixing member. Furthermore, it is preferable to include other means appropriately selected as necessary, for example, static elimination means, recycling means, control means, and the like.

  In the image forming apparatus of the present invention, the photosensitive member and the constituent elements such as the developing unit and the cleaning unit may be configured as a process cartridge, and the process cartridge may be configured to be detachable from the image forming apparatus body. Further, at least one of a charging unit, an exposure unit, a developing unit, a transfer unit, a separating unit, and a cleaning unit is supported together with a photosensitive member to form a process cartridge, and a single unit that is detachable from the image forming apparatus main body. It is good also as a structure which can be attached or detached using guide means, such as a rail of a forming apparatus main body.

  FIG. 1 shows an example of an image forming apparatus of the present invention. In this image forming apparatus, a latent image carrier (1) that is driven to rotate in the clockwise direction in FIG. 1 is housed in a main body housing (not shown), and around the latent image carrier (1). In addition, a charging device (2), an exposure device (3), a developing device (4), a cleaning member (7), an intermediate transfer member (8), a transfer roller (11), a charge removing means (not shown), and the like are provided. .

  The image forming apparatus includes a paper feed cassette (not shown) that stores a plurality of recording papers (9) as an example of a recording medium, and the recording paper (9) in the paper feed cassette is a paper feed (not shown). After the timing is adjusted by a pair of registration rollers (not shown) one by one by the rollers, the rollers are sent out between a transfer roller (11) as a transfer means and an intermediate transfer belt (8).

  In this image forming apparatus, the latent image carrier (1) is rotated clockwise in FIG. 1 to uniformly charge the latent image carrier (1) with the charging device (2), and then the exposure device ( 3) The laser beam modulated with the image data is irradiated to form an electrostatic latent image on the latent image carrier 1, and the latent image carrier (1) on which the electrostatic latent image is formed is developed by the developing device (4). Develop with toner attached. Next, a transfer bias is applied from the latent image carrier (1) on which the toner image is formed by the developing device (4) to the intermediate transfer member (8) to transfer the toner image onto the intermediate transfer member (8). The toner image is transferred to the recording medium (9) by conveying the recording medium (9) between the intermediate transfer member (8) and the transfer roller (11). Further, the recording medium (9) onto which the toner image has been transferred is conveyed to a fixing means (not shown).

  The fixing unit includes a fixing roller heated to a predetermined fixing temperature by a built-in heater, and a pressure roller pressed against the fixing roller with a predetermined pressure, and heats the recording paper conveyed from the transfer roller (11). After pressurizing and fixing the toner image on the recording paper on the recording paper, it is discharged onto a paper discharge tray (not shown).

  On the other hand, the image forming apparatus further rotates the latent image carrier (1) having the toner image transferred to the recording paper by the transfer roller (11), and remains on the surface of the latent image carrier (1) by the cleaning member 7. After the toner is scraped off and removed, the charge is removed by a charge removal device (not shown). The image forming apparatus uniformly charges the latent image carrier (1) neutralized by the static eliminator with the charging device (2), and then performs the next image formation in the same manner as described above.

Hereinafter, each member suitably used for the image forming apparatus of the present invention will be described in detail.
The photoconductor is not particularly limited as to the material, shape, structure, size, and the like, and can be appropriately selected from known ones. Preferred examples of the shape include a drum shape and a belt shape. Examples of the material include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors such as polysilane and phthalopolymethine. Among these, amorphous silicon and organic photoreceptors are preferable from the viewpoint of long life.

  The electrostatic latent image can be formed on the photosensitive member by, for example, charging the surface of the photosensitive member and then performing imagewise exposure, and can be performed by an electrostatic latent image forming unit. The electrostatic latent image forming unit includes, for example, at least a charging unit that charges the surface of the photoconductor and an exposure unit that exposes the surface of the photoconductor imagewise.

Charging can be performed, for example, by applying a voltage to the surface of the photoreceptor using a charging unit.
The charging means is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the charging means includes a conductive or semiconductive roller, a brush, a film, a rubber blade, etc., which is known per se. Non-contact charger using corona discharge such as a charger, corotron and scorotron.

  As the shape of the charging means, in addition to the roller, a form such as a magnetic brush or a fur brush may be adopted, and can be selected according to the specification and form of the electrophotographic apparatus. In the case of using a magnetic brush, the magnetic brush is composed of, for example, various ferrite particles such as Zn-Cu ferrite as a charging member, and a non-magnetic conductive sleeve for supporting the same, and a magnet roll included therein. . In addition, when using a brush, for example, as a material of the fur brush, a fur treated with carbon, copper sulfide, metal or metal oxide is used, and this is wound around a metal or other conductive core. It is configured by pasting.

  The charging unit is not limited to the contact type charger as described above, but it is preferable to use a contact type charger because an image forming apparatus in which ozone generated from the charger is reduced can be obtained. .

  The exposure can be performed, for example, by exposing the surface of the photoreceptor imagewise using an exposure unit. The exposure means is not particularly limited as long as the surface of the photoreceptor charged by the charging means can be exposed like an image to be formed, and can be appropriately selected according to the purpose. 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 are listed.

  The development can be performed, for example, by developing the electrostatic latent image using the toner of the present invention, and can be performed by a developing unit. The developing means is not particularly limited as long as it can be developed using, for example, the toner of the present invention, and can be appropriately selected from known ones. Preferable examples include those having at least a developing unit capable of applying toner to an image in a contact or non-contact manner.

  The developing means includes a developing roller that carries toner on a peripheral surface, rotates in contact with the photosensitive member, supplies toner to an electrostatic latent image formed on the photosensitive member, and performs development. An embodiment having a thin layer forming member that contacts the surface and thins the toner on the developing roller is preferable.

  The developing means may be of a dry development type, may be of a wet development type, may be a single color developer, or may be a multicolor developer. For example, a toner having a stirrer that frictionally stirs toner to be charged and a rotatable magnet roller is preferable.

  As the developing roller, either a metal roller or an elastic roller is preferably used. There is no restriction | limiting in particular as a metal roller, Although it can select suitably according to the objective, For example, an aluminum roller etc. are mentioned. By subjecting the metal roller to blasting, a developing roller having an arbitrary surface friction coefficient can be produced relatively easily. Specifically, by treating the aluminum roller with glass bead blasting, the roller surface can be roughened, and an appropriate toner adhesion amount can be obtained on the developing roller.

As the elastic roller, a roller coated with an elastic rubber layer is used, and a surface coat layer made of a material that is easily charged to a polarity opposite to that of the toner is provided on the surface. The elastic rubber layer is set to a hardness of 60 degrees or less according to JIS-A in order to prevent toner deterioration due to pressure concentration at the contact portion with the layer regulating member. The surface roughness (Ra) is set to 0.3 to 2.0 μm, and a necessary amount of toner is held on the surface. Further, since a developing bias for forming an electric field between the developing roller and the photosensitive member is applied to the developing roller, the elastic rubber layer is set to a resistance value of 10 ³ to 10 ¹⁰ Ω. The developing roller rotates in the clockwise direction, and conveys the toner held on the surface to a position facing the layer regulating member and the photosensitive member.

  The layer regulating member is provided at a position lower than the contact position between the supply roller and the developing roller. The layer regulating member is made of a metal leaf spring material such as stainless steel (SUS) or phosphor bronze, and the free end is brought into contact with the surface of the developing roller with a pressing force of 10 to 40 N / m. The toner that has passed through is thinned and charged by frictional charging. Further, in order to assist frictional charging, the layer regulating member is applied with a regulating bias having a value offset in the same direction as the toner charging polarity with respect to the developing bias.

  The rubber elastic body constituting the surface of the developing roller is not particularly limited and may be appropriately selected depending on the intended purpose.For example, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, Examples thereof include acrylic rubber, epichlorohydrin rubber, urethane rubber, silicone rubber, or a blend of two or more thereof. Among these, a blend rubber of epichlorohydrin rubber and acrylonitrile-butadiene copolymer rubber is particularly preferable.

  The developing roller is manufactured, for example, by covering the outer periphery of the conductive shaft with a rubber elastic body. The conductive shaft is made of a metal such as stainless steel (SUS), for example.

  The transfer can be performed, for example, by charging the photoreceptor, and can be performed by a transfer unit. The transfer unit preferably includes a primary transfer unit that forms a transfer image by transferring a toner image onto an intermediate transfer member, and a secondary transfer unit that transfers the transfer image onto a recording medium. At this time, two or more colors, preferably full color toner is used as the toner, and a primary transfer means for transferring the toner image onto the intermediate transfer member to form a composite transfer image; and the composite transfer image on the recording medium. An embodiment having secondary transfer means for transferring is more preferable.

  The intermediate transfer member is not particularly limited, and can be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

  The transfer means (primary transfer means, secondary transfer means) preferably has at least a transfer device that peels and charges the toner image formed on the photoreceptor toward the recording medium. There may be one transfer means, or two or more transfer means. Examples of the transfer means 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 typically plain paper, but is not particularly limited as long as it can transfer an unfixed image after development, and can be appropriately selected according to the purpose. PET bases and the like can also be used.

  The fixing can be performed, for example, on the toner image transferred to the recording medium using a fixing unit, and may be performed each time the toner image of each color is transferred to the recording medium. The toner images may be stacked at the same time in a stacked state.

  The fixing unit is not particularly limited and may be appropriately selected depending on the intended purpose. However, a known heating and pressing unit is preferable. 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. In addition, as for the heating temperature by a heating-pressing means, 80-200 degreeC is preferable.

  A soft roller type fixing device having a fluorine-based surface layer composition as shown in FIG. 2 may be used. This is because the heating roller (22) has an elastic body layer (14) made of silicone rubber and a PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer) surface layer (15) on an aluminum core bar (13). The heater (16) is provided inside the aluminum cored bar. The pressure roller (12) has an elastic layer (18) made of silicone rubber and a PFA surface layer (19) on an aluminum cored bar (17). The paper (21) on which the unfixed image (20) is printed is passed as shown in the figure.

  In the present invention, for example, a known optical fixing device may be used together with or instead of the fixing unit depending on the purpose.

  The neutralization can be performed, for example, by applying a neutralization bias to the photosensitive member, and can be suitably performed by a neutralization unit. The neutralizing means is not particularly limited as long as it can apply a neutralizing bias to the photoconductor, and can be appropriately selected from known neutralizers. For example, a neutralizing lamp is preferable.

  Cleaning can be suitably performed, for example, by removing the toner remaining on the photoreceptor by a cleaning means. The cleaning means is not particularly limited and may be any one selected from known cleaners as long as it can remove the toner remaining on the photosensitive member. For example, a magnetic brush cleaner, an electrostatic brush cleaner, or a magnetic roller can be selected. A cleaner, a blade cleaner, a brush cleaner, a web cleaner and the like are preferable.

  The recycling can be suitably performed, for example, by transporting the toner removed by the cleaning unit to the developing unit by the recycling unit. There is no restriction | limiting in particular as a recycle means, A well-known conveyance means etc. are mentioned.

  Control can be suitably performed by controlling each means by a control means, for example. The control means is not particularly limited as long as 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.

  According to the image forming apparatus, the image forming method, and the process cartridge of the present invention, an excellent image can be obtained by using the electrostatic latent image developing toner that has excellent fixability and does not deteriorate due to stress in the developing process. Can be provided.

<Multicolor image forming apparatus>
FIG. 3 is a schematic diagram showing an example of a multicolor image forming apparatus to which the present invention is applied. FIG. 3 shows a tandem type full-color image forming apparatus.
In FIG. 3, the image forming apparatus accommodates an electrostatic latent image carrier (2) rotated in the clockwise direction in FIG. 3 in a main body housing (not shown). ), A charging unit (3), a writing unit (4), a developing unit (5), an intermediate transfer unit (6), a paper transfer unit (7), and the like are arranged. Although not shown, the image forming apparatus includes a paper feeding cassette that stores a plurality of recording papers. The recording paper P in the paper feeding cassette is timed by a pair of registration rollers (not shown) one by one by a paper feeding roller (not shown). After the adjustment, the sheet is sent out between the intermediate transfer portion (6) and the electrostatic latent image carrier (2).
The image forming apparatus rotates the electrostatic latent image carrier (2) in the clockwise direction in FIG. 3 to uniformly charge the electrostatic latent image carrier (2) by the charging unit (3), and then performs writing. An electrostatic latent image is formed on the electrostatic latent image carrier (2) by irradiating a laser modulated with image data by the unit (4), and the electrostatic latent image carrier (2) on which the electrostatic latent image is formed The toner is attached to the developing portion (5) and developed. In the image forming apparatus, toner is attached by the developing unit (5), and the toner image is transferred from the electrostatic latent image carrier (2) to the intermediate transfer member by the intermediate transfer unit (6). This is performed for each of four colors, cyan (C), magenta (M), yellow (Y), and black (K), to form a full-color toner image.

  Next, FIG. 4 is a schematic view showing an example of a revolver type full-color image forming apparatus. In this image forming apparatus, a plurality of colors of toner are sequentially developed on one electrostatic latent image carrier by switching the operation of the developing device. Then, the color toner image on the intermediate transfer member is transferred to the recording paper (P) by the paper transfer unit (7), and the recording paper (P) to which the toner image is transferred is conveyed to the fixing unit (10). Get.

On the other hand, the image forming apparatus further rotates the electrostatic latent image carrier (2) having the toner image transferred to the recording paper by the intermediate transfer unit (6), and the cleaning unit (13) performs the electrostatic latent image carrier surface. The toner remaining on the toner is removed by scraping with a blade, and then the charge is removed by the charge removing section (8). The image forming apparatus uniformly charges the electrostatic latent image carrier (2) neutralized by the neutralization unit (8) by the charging unit (3), and then performs the next image formation as described above. The cleaning unit (13) is not limited to scraping off the residual toner on the electrostatic latent image carrier (2) with a blade. For example, the cleaning unit (13) may remain on the electrostatic latent image carrier (2) with a fur brush. The toner may be scraped off.

  In the image forming method and the image forming apparatus of the present invention, since the toner of the present invention is used as the developer, the chargeability is uniform and stabilized, and a good image with suppressed background stain can be obtained.

<Process cartridge>
The process cartridge of the present invention can develop an electrostatic latent image carrier carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using the toner of the present invention. A developing means for forming a visual image, and further having other means such as a charging means, a developing means, a transfer means, a cleaning means, a static elimination means, which are appropriately selected as necessary. The image forming apparatus main body is detachable.
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 mounted on various electrophotographic apparatuses, facsimiles, and printers, and is preferably detachably mounted on the image forming apparatus of the present invention described later.

For example, as shown in FIG. 5, the process cartridge includes a photoconductor (201), and includes a charging unit (202), a developing unit (204), a transfer unit (208), and a cleaning unit (207). Other means are provided as necessary. In FIG. 5, (203) indicates exposure by the exposure means, and (205) indicates a recording medium. As the photoconductor (201), the same one as the image forming apparatus can be used. An arbitrary charging member is used for the charging means (202).
Next, the image forming process using the process cartridge shown in the figure will be described. The photoconductor (201) is charged by the charging means (202) while being rotated in the direction of the arrow, and exposure by the exposure means (not shown) (203). As a result, an electrostatic latent image corresponding to the exposure image is formed on the surface. The electrostatic latent image is developed with toner by the developing means (204), and the toner development is transferred to the recording medium (205) by the transfer means (208) and printed out. Next, the surface of the photoconductor after the image transfer is cleaned by a cleaning unit (207), and is further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

Hereinafter, the present invention will be described more specifically and in detail based on examples.
[Synthesis example of chemical formula (1) shown in Table 1]
The synthesis of the chemical formula (1) shown in Table 1 is similar to the trimerization of the nitrile compound described in JP-A-7-188188 (Ciba-Geigy). Obtained by reacting at 250 ° C. for 5-10 hours. In the case of Compound 5, 3-benzyloxybenzonitrile obtained by reacting 3-hydroxybenzonitrile and benzyl bromide in DMAc in the presence of potassium carbonate at 80 to 100 ° C. is obtained in the same manner as Compound 1 above. It was.

[Examples of pulverized toner (Examples 1 to 7, Comparative Example 1)]
A toner material containing at least one of a binder resin, a black colorant, a yellow colorant, a magenta colorant, and a cyan colorant, a compound represented by the chemical formula (1), and the like are mixed and kneaded. After the obtained kneaded product is pulverized, a toner base having a desired particle diameter is obtained by classification, and examples of toners using this are shown below.

[Example 1]
<Synthesis of Binder Resin A>
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 charged into a dropping funnel. Next, in a 5-liter four-necked flask equipped with a thermometer, a stainless steel stirrer, a flow-down condenser, and a nitrogen introduction tube, polyoxypropylene-2,2-bis as a polyol among polyester monomers. 1230 g of (4-hydroxyphenyl) propane, 290 g of polyoxyethylene-2,2-bis (4-hydroxyphenyl) propane, 250 g of isododecenyl succinic anhydride, 310 g of terephthalic acid, 180 g of 1,2,4-benzenetricarboxylic anhydride, ester 340 g (100 parts by weight of charged monomer) 7 g of dibutyltin oxide as the catalyst for the conversion, and paraffin wax (melting point: 73.3 ° C., half-value width of the endothermic peak at the time of temperature rise measured by the differential scanning calorimeter is 4 ° C.) as the wax 11.0 parts by mass).
Next, the liquid mixture of the vinyl monomer resin and the polymerization initiator was dropped from the dropping funnel over 1 hour while stirring at a temperature of 160 ° C. in a mantle heater in a nitrogen atmosphere. Next, the addition polymerization reaction was aged for 2 hours while maintaining the temperature at 160 ° C., and then the temperature was raised to 230 ° C. to perform the 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 synthesize binder resin A. About the obtained binder resin A, the softening point measured as follows was 130 degreeC.

<Synthesis of Binder Resin B>
In a 5-liter four-necked flask equipped with a thermometer, a stainless steel stirrer, a flow-down condenser, and a nitrogen inlet tube, 2210 g of polyoxypropylene-2,2-bis (4-hydroxyphenyl) propane as a polyol and 850 g of terephthalic acid , 120 g of 1,2,4-benzenetricarboxylic anhydride, and 0.5 g of dibutyltin oxide as an esterification catalyst were charged. Subsequently, the temperature was raised to 230 ° C. under a nitrogen atmosphere in a mantle heater to perform a condensation polymerization reaction. The degree of polymerization was tracked by the softening point measured using a constant-load extrusion type capillary rheometer, and when the desired softening point was reached, the reaction was terminated and a binder resin B was synthesized. The obtained binder resin B had a softening point of 115 ° C. measured as follows.

<Measurement of softening point (Tm)>
Using a flow tester (CFT-500, manufactured by Shimadzu Corporation), 1.5 g of a measurement sample is weighed, using a die having a height of 1.0 mm and a diameter of 1.0 mm, a heating rate of 3.0 ° C./min, preheating Measurement was performed under the conditions of a time of 180 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 defined as the softening point (Tm).

<Production of toner particles>
With respect to 94 parts by mass (including the mass of the internally added wax) of the binding resin A and the binding resin B having a mixing mass ratio (H1: L1 = 5: 5), the pigment C.I. I. Pigment Blue 15: 3 containing 4 parts by mass of a masterbatch, and E-84: salicylic acid-based Zn complex (manufactured by Orient Chemical Co., Ltd.) as a charge control agent, and Compound 1 as a compound of chemical formula (1) 1 part by weight was added to make a total amount of 3 kg. Next, after mixing for 5 minutes at a peripheral speed of 20 m / s with a 20 liter Henschel mixer, melt kneading was performed using a biaxial extrusion kneader (PCM-30, manufactured by Ikekai Tekko Co., Ltd.) with the discharge part removed. did. The obtained kneaded material was rolled to a thickness of 2 mm with a cooling press roller, cooled with a cooling belt, and then roughly pulverized with a feather mill. Then, it grind | pulverized until it became an average particle diameter of 10-12 micrometers with the mechanical grinder (KTM, Kawasaki Heavy Industries, Ltd. make). Next, after pulverizing with coarse powder classification with a jet pulverizer (IDS, manufactured by Nippon Pneumatic Industry Co., Ltd.), fine powder classification is performed using a rotor type classifier (teaplex type classifier type, 100 ATP, manufactured by Hosokawa Micron Corporation). Classification was performed to obtain colored resin particles. The mass average particle diameter of the colored resin particles obtained was 7.9 μm as measured as follows. To 100 parts by mass of the colored resin particles obtained, 1 part by mass of silica (RX200, manufactured by Nippon Aerosil Co., Ltd.) is added, and the mixture is processed with a Henschel mixer at a peripheral speed of 40 m / sec for 60 seconds. [Developer 8] of the present invention was produced.

[Examples 2 to 7]
[Developers 2 to 7] of the present invention were obtained in the same manner as in Example 1 except that the amount of the compound represented by chemical formula (1) in Example 1 was adjusted to the addition amount shown in Table 4.

[Comparative Example 1]
[Developer 16] was obtained in the same manner as in Example 1 except that the compound of the chemical formula (1) in Example 1 was not added.

[Suspension Polymerized Toner Example (Examples 8 to 9, Comparative Example 2)]
Next, a toner base particle is obtained from a particle forming step by suspension polymerization in water of an oil droplet in which a pigment or wax is dispersed in a polymerizable monomer, followed by a washing and drying step. Each example using toner is shown.

[Example 8]
(Production example)
In a four-necked vessel, 340 parts by weight of ion-exchanged water and 380 parts by weight of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution were added, and the mixture was stirred at 15,000 rpm using a high-speed stirrer homomixer at 60 ° C. Held on. 30 parts by weight of a 1.0 mol / liter-CaCl ₂ aqueous solution was gradually added thereto to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .
On the other hand, as dispersoid,
Styrene 79 parts by weight n-butyl acrylate 10 parts by weight Copper phthalocyanine pigment 5 parts by weight Compound 1 (toner content 2 wt%) 2 parts by weight Salicylic acid zinc salt (E-304 manufactured by Orient Chemical Industries) 0.8 parts by weight Paraffin wax (melting point) 73 ° C.) A mixture consisting of 4 parts by weight was dispersed for 3 hours using an attritor (manufactured by Mitsui Kinzoku Co., Ltd.), and then 3 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added and polymerized. A functional monomer composition was prepared.
Next, the polymerizable monomer composition is charged into the aqueous dispersion medium, and stirred for 4 minutes while maintaining the rotation speed of the high-speed stirrer at 15000 rpm in an N ₂ atmosphere at an internal temperature of 60 ° C., The polymerizable monomer composition was granulated. Thereafter, the stirring apparatus was replaced with a paddle stirring blade, and the polymerization was carried out for 5 hours while maintaining the same temperature while stirring at 200 rpm.
After completion of the polymerization, the internal temperature was raised to 80 ° C., and further polymerization was performed. Then, after cooling, dilute hydrochloric acid was added to adjust the pH of the aqueous dispersion medium to 1.2 to dissolve the hardly water-soluble dispersant. Further, after solid-liquid separation by pressure filtration, washing was performed with 18000 parts by weight of water. Thereafter, the toner is sufficiently dried using a vacuum dryer, and the toner base particles having an average circularity of 0.976, a volume average particle diameter (Dv) of 6.8 μm, and a number average particle diameter (Dp) of 6.2 μm. 8 was obtained.
Next, 0.5 part of hydrophobic silica and 0.5 part of hydrophobized titanium oxide were mixed with 100 parts by weight of the toner base by a Henschel mixer to obtain [Developer 8] of the present invention.

[Example 9]
A toner base having a volume average particle size (Dv) of 6.7 μm and an average circularity of 0.975 was carried out in the same manner as in Example 8 except that the content of Compound 1 in the toner in Example 8 was adjusted to 4 wt%. Particles 9 were obtained. Next, toner base particle 8: 0.5 part of hydrophobic silica and 0.5 part of hydrophobic titanium oxide were mixed with 100 parts by weight of a toner using a Henschel mixer to obtain [Developer 9] of the present invention.

[Comparative Example 2]
In Example 8, the same procedure as in Example 8 was performed except that Compound 1 was not used, and toner base particles 17 having a volume average particle diameter (Dv) of 6.8 μm and an average circularity of 0.978 were obtained. Next, toner base particles 8: 100 parts by weight of hydrophobic silica 0.5 part and hydrophobic titanium oxide 0.5 part were mixed with a Henschel mixer to obtain [Developer 17].

[Production of emulsion aggregation toner (Examples 10 to 11, Comparative Example 3)]
This toner manufacturing method includes at least a binder resin, a wax, and a coloring material, and a particle forming step for aggregating each constituent material such as a pigment dispersion, a binder resin latex, and a wax dispersion in an aqueous phase, followed by washing and drying. The toner base particles are obtained through the process.

[Example 10]
<Manufacture of pigment dispersion>
The following composition was mixed and dissolved, and dispersed with a homogenizer (IKA Ultra Tarrax) and ultrasonic irradiation to obtain a blue pigment dispersion P (pigment concentration 25 wt%) having a central particle size of 150 nm.
Cyan pigment CIPigment Blue 15: 3 (Copper phthalocyanine Dainippon Ink)
50g
Anionic surfactant Neogen SC 5g
145 g of ion exchange water

<Example of production of wax dispersion>
The following composition was mixed, heated to 97 ° C., and then dispersed with IKA Ultra Turrax T50. Thereafter, the dispersion was dispersed with a gorin homogenizer (manufactured by Reiwa Shoji) and treated 20 times at 105 ° C. and 550 kg / cm ² to obtain a wax dispersion W (wax concentration 25 wt%) having a center diameter of 190 nm.
100 g of paraffin wax (HNP-09 manufactured by NOF Corporation)
Anionic surfactant Neogen SC 5g
295 g of ion exchange water

<Production Example of Compound 1 Dispersion>
The following composition was mixed and dissolved and dispersed by homogenizer (IKA Ultra Tarrax) and ultrasonic irradiation to obtain Compound 1 Dispersion T (compound 1 concentration 25 wt%) having a central particle size of 100 nm.
Compound 1 50g
Anionic surfactant Neogen SC 5g
145 g of ion exchange water
<Example of binder resin latex production>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 1.6 parts of sodium dodecyl sulfate and 492 parts of ion exchange water are heated to 80 ° C., and then 2.5 parts of potassium persulfate is ion exchanged. A solution dissolved in 100 parts of water is added, and after 15 minutes, 70 parts of styrene, 30 parts of methacrylic acid, 60 parts of p-styryltrimethoxysilane, 40 parts of 3-methacryloyloxypropylmethyldimethoxysilane, n-octyl mercaptan3. 5 parts of the mixture was added dropwise over 90 minutes and kept at 80 ° C. for a further 60 minutes. Thereafter, the mixture was cooled to obtain a binder resin latex BL (resin latex concentration (25 wt%) having an average particle diameter of 50 nm. The dispersion was taken in a small petri dish and the solid obtained by evaporating the dispersion medium was measured. The number average molecular weight was 10,000, the weight average molecular weight was 16000, and Tg was 58 ° C.

<Preparation of developer 10>
Blue pigment dispersion P: 5 parts by weight, wax dispersion W: 5 parts by weight, compound 1 dispersion T: 2 parts by weight, binder resin latex BL: 88 parts by weight in a round stainless steel flask, The mixture was sufficiently mixed and dispersed with a modifier (IKA, Ultra Turrax T50), and then the flask was heated to 48 ° C. with stirring in an oil bath for heating to aggregate the particles. When it was confirmed that the particle size was 5.7 μm, the pH in the system was adjusted to 6.0 with a 0.5 mol / l sodium hydroxide aqueous solution, and the mixture was heated to 94 ° C. while stirring was continued. During the temperature increase to 94 ° C., the pH in the system decreased to about 5.0 but was maintained as it was. When the circularity reached 0.970, it was cooled, filtered, thoroughly washed with ion exchange water, and then solid-liquid separated by Nutsche suction filtration. And it re-dispersed in 3 liters of ion-exchanged water at 40 ° C. and stirred and washed for 15 minutes. This washing operation was repeated 5 times, followed by solid-liquid separation by Nutsche suction filtration, followed by vacuum drying for 12 hours to obtain toner particles having a volume average particle diameter (Dv) of 5.7 μm and an average circularity of 0.970. Subsequently, 100 parts of this base toner was mixed with 0.5 part of hydrophobic silica and 0.5 part of hydrophobic titanium oxide using a Henschel mixer to obtain “Developer 10” of the present invention.

[Example 11]
Toner particles were produced in the same manner as in Example 10 except that the content of Compound 1 of Example 10 in the toner particles was adjusted to 4 wt%, and the volume average particle diameter (Dv) was 5.8 μm and the average circular shape was. Toner particles having a degree of 0.971 were obtained. Subsequently, 0.5 parts of hydrophobic silica and 0.5 parts of hydrophobic titanium oxide were mixed with 100 parts of the base toner using a Henschel mixer to obtain “Developer 11” of the present invention.

[Comparative Example 3]
A “developer 18” was obtained in the same manner as in Example 10 except that Compound 1 was not contained in Example 10.

[Resin Component Elongation Method in Liquid Medium (Examples 12 to 15 and 16, Comparative Example 4)]
In this toner production method, a binder resin having at least an aromatic group-containing polyester skeleton, a colorant, and a release agent are dissolved or dispersed in an organic solvent, and then the dissolved or dispersed material is dispersed in an aqueous medium. In this example, toner base particles are obtained through a washing and drying process following the granulating process. “Parts” means all parts by mass.

[Example 12]

<Synthesis of polyester>
(Polyester 1) 553 parts of bisphenol A ethylene oxide 2-mole adduct, 196 parts of bisphenol A propylene oxide 2-mole adduct, 220 parts of terephthalic acid, adipic acid in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe 45 parts and 2 parts of dibutyltin oxide were added, reacted for 8 hours at 230 ° C. under normal pressure, and further reacted for 5 hours under reduced pressure of 10 to 15 mmHg. Then, 46 parts of trimellitic anhydride was added to the reaction vessel, and 180 ° C. Reaction was performed at normal pressure for 2 hours to obtain [Polyester 1]. [Polyester 1] had a number average molecular weight of 2200, a weight average molecular weight of 5600, a Tg of 43 ° C., and an acid value of 13.

<Synthesis of prepolymer>
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, 22 parts of trimellitic anhydride Then, 2 parts of dibutyltin oxide was added, reacted at 230 ° C. under normal pressure for 8 hours, and further reacted at reduced pressure of 10-15 mmHg for 5 hours to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, Tg of 55 ° C., an acid value of 0.5, and a hydroxyl value of 49.
Next, 411 parts of [Intermediate polyester 1], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained. [Prepolymer 1] had a free isocyanate weight% of 1.53%.

<Synthesis of master batch>
Carbon black (Regal 400R manufactured by Cabot Corporation): 40 parts, Binder resin: Polyester resin (Sanyo Kasei RS-801 Acid value 10, Mw 20000, Tg 64 ° C.): 60 parts, Water: 30 parts are mixed in a Henschel mixer, A mixture in which water was soaked into the pigment aggregate was obtained. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 130 ° C. and pulverized to a size of 1 mmφ with a pulverizer to obtain [Masterbatch 1].

<Preparation of pigment / WAX dispersion (oil phase)>
378 parts of [Polyester 1], 120 parts of paraffin wax (HNP9) and 1200 parts of ethyl acetate were charged in a container equipped with a stirring bar and a thermometer, heated to 80 ° C. with stirring, and maintained at 80 ° C. for 5 hours. Thereafter, it was cooled to 30 ° C. in 1 hour. Next, 500 parts of [Masterbatch 1] and 400 parts of ethyl acetate were charged into a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw material solution 1] 1500 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feed speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. Carbon black and WAX were dispersed under conditions of filling and 3 passes. Next, 425.75 parts of [Polyester 1] was added, and one pass was performed with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1]. 78 g of ethyl acetate was added to adjust the solid content concentration of [Pigment / WAX Dispersion 1] (130 ° C., 30 minutes) to 50%.

<Preparation of aqueous phase>
953 parts of ion-exchanged water, 88 parts of a 25 wt% aqueous dispersion of organic resin fine particles (styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt copolymer) for dispersion stabilization, dodecyl diphenyl ether 90 parts of a 48.5% aqueous solution of sodium disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 113 parts of ethyl acetate were mixed and stirred to obtain a milky white liquid. This is designated as [Aqueous Phase 1].

<Emulsification process>
[Pigment / WAX Dispersion 1] 967 parts, E-84 as a charge control agent: 14 parts by mass of a salicylic acid-based Zn complex (manufactured by Orient Chemical Co., Ltd.) and 11.7 parts of the compound 1 shown in Table 1 (toner content) 2 parts by weight) and 6 parts of isophoronediamine as amines and TK homomixer (made by Tokushu Kika) for 1 minute at 5,000 rpm, and then add 137 parts of [Prepolymer 1] and add TK homomixer (special After mixing for 1 minute at 5,000 rpm, the mixture is added to 1200 parts of [Aqueous phase 1] and mixed for 20 minutes with a TK homomixer while adjusting the rotational speed at 8,000 to 13,000 rpm [emulsification Slurry 1] was obtained.

<Desolvent>
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 8 hours to obtain [Dispersion slurry 1].

<Washing->Drying>
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(2): 900 parts of ion-exchanged water was added to the filter cake of (1), ultrasonic vibration was applied, and the mixture was mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure. This operation was repeated so that the electric conductivity of the reslurry liquid was 10 μC / cm or less.
(3): 10% hydrochloric acid was added so that the reslurry solution of (2) had a pH of 4, and the mixture was directly filtered with a three-one motor for 30 minutes.
(4): 100 parts of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (10 minutes at 12,000 rpm) and then filtered. This operation was repeated so that the reslurry liquid had an electric conductivity of 10 μC / cm or less to obtain [Filter Cake 1]. [Filtration cake 1] was dried at 45 ° C. for 48 hours in a circulating drier and sieved with a mesh having a mesh size of 75 μm to obtain [Toner Base 1]. The volume average particle diameter (Dv) was 5.8 μm, the number average particle diameter (Dp) was 5.2 μm, Dv / Dp was 1.12 and the average circularity was 0.973. Subsequently, 100 parts of this base toner was mixed with 0.5 part of hydrophobic silica and 0.5 part of hydrophobic titanium oxide using a Henschel mixer to obtain “Developer 12” of the present invention.

[Examples 13 to 15]
“Developer 13-15” was obtained in the same manner as in Example 12 except that Compound 1 and the addition amount thereof were changed as shown in Table 4 in <Emulsification step> of Example 12 above.

[Example 16]
In Example <Emulsification step> in Example 12 above, Compound 6 (CAS No.493-77-6 Sigma-Aldrich) was used instead of Compound 1, and the amount added was changed as shown in Table 4. The developer 20 was obtained in the same manner as in Example 12.

[Comparative Example 4]
“Developer 19” was obtained in the same manner as in Example 12 except that Compound 1 was not added in <Emulsification step> of Example 12 above.

  Next, using the obtained toners, various characteristics were evaluated as follows. The results are shown in Table 4.

[Measurement and evaluation methods]
<Measurement of toner weight average particle diameter>
The average particle size and particle size distribution of the toner are determined by the Carcoulter counter method. Examples of the measurement device for the particle size distribution of toner particles include Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). In the present invention, a Coulter counter TA-II type was used, and measurement was performed by connecting an interface (Nichiken Giken Co., Ltd.) that outputs number distribution and volume distribution and a PC 9801 personal computer (manufactured by NEC).
That is, first, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the aqueous electrolytic solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample is further added. 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. Volume distribution and number distribution are calculated.
As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Uses 13 channels less than 40 μm; 25.40 to less than 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. The volume-based volume average particle diameter (Dv) obtained from the volume distribution according to the present invention and the number average particle diameter (Dn) obtained from the number distribution and the ratio Dv / Dn were obtained.

<Average circularity>
The average circularity can be measured by an optical detection band method in which a suspension containing toner is passed through an imaging unit detection band on a flat plate, a particle image is optically detected by a CCD camera, and analyzed. It can be measured using a flow type particle image analyzer FPIA-2100 (manufactured by Sysmex Corporation).

<Evaluation of actual machine>
Using each toner, using an image forming apparatus (IPSiO CX2500, manufactured by Ricoh Co., Ltd.), a predetermined print pattern with a printing rate of 6% is printed in an N / N environment (temperature 23 ° C., 45% RH). The background stain after continuous copying of 2,000 sheets and 2,000 sheets was evaluated as follows.
After continuously copying 5 sheets and 2,000 sheets, the toner on the photoreceptor when the blank paper was passed was peeled off by tape, observed visually, and evaluated according to the following criteria. The evaluation results are shown in “Table 2”.
〔Evaluation criteria〕
○: Good △: Slight coloring is confirmed but no problem ×: Unusable level

1 is a schematic diagram illustrating a configuration in an embodiment of an image forming apparatus according to the present invention. 1 is a schematic diagram illustrating a configuration of a fixing device that is a part of an embodiment of an image forming apparatus according to the present invention. It is the schematic which shows the other example of the image forming apparatus which concerns on this invention. It is the schematic which shows the further another example of the image forming apparatus which concerns on this invention. It is the schematic which shows an example of the process cartridge which concerns on this invention.

Explanation of symbols

(Figure 1)
DESCRIPTION OF SYMBOLS 1 Image carrier 2 Charging apparatus 3 Exposure apparatus 4 Developing apparatus 7 Cleaning member 8 Intermediate transfer body 9 Recording medium 10 Support roller 11 Transfer roller 40 Developing roller 41 Supply roller 43 Regulating blade 44 Developer (FIG. 2)
DESCRIPTION OF SYMBOLS 12 Pressure roller 13 Aluminum core metal 14 Elastic body layer 15 PFA surface layer 16 Heater 17 Aluminum core metal 18 Elastic body layer 19 PFA surface layer 20 Unfixed image 21 Paper 22 Heating roller (FIGS. 3, 4, and 5)
2 Photoconductor (electrostatic latent image carrier)
DESCRIPTION OF SYMBOLS 3 Charging part 4 Writing part 5 Developing part 6 Intermediate transfer part 7 Transfer part 8 Electric discharge part 10 Fixing part 13 Cleaning part 15 Control device 16 Voltage application part 201 Photoconductor 202 Charging means 203 Exposure means 204 Developing means 205 Recording medium 207 Cleaning Means 208 Transfer means P Recording paper

Claims (15)

An electrostatic latent image developing toner comprising a triaryltriazine compound represented by the following general formula (1) in an electrostatic latent image developing toner containing at least a binder resin and a coloring material.

In the formula, Ar = a substituted or unsubstituted arylene group having 6 to 10 carbon atoms
R = halogen atom, branched or straight chain alkyl group or alkoxyl group having 1 to 12 carbon atoms, —COCH ₃ , —NO ₂ , —CN, —O—CH ₂ Ph or —X—Ph, where n ≧ 2. Each R may be the same or different.
x = —O—, —S—, —CH ₂ —, —CO—, —SO ₂ —, —C (CH ₃ ) ₂ —, —NH—, —CONH—, —NHCO— or —CONHCO—,
n = 1, 2, 3   2. The electrostatic latent image developing toner according to claim 1, wherein the triaryltriazine compound has a structure represented by Ar = 6 carbon atoms, n = 1 or 2 in the general formula (1).   The electrostatic latent image developing toner according to claim 1, further comprising a charge control agent.   The content of the triaryltriazine compound of the general formula (1) is 0.12 to 20 parts by mass with respect to 100 parts by mass of the binder resin. The toner for developing an electrostatic latent image.   5. The electrostatic latent image developing toner according to claim 1, which is used in a one-component developing system.   An image forming method comprising forming an image using the toner for developing an electrostatic latent image according to claim 1.   An image forming apparatus, comprising: an electrostatic latent image developing toner according to claim 1;   The image forming apparatus according to claim 7, wherein the image is a multicolor image.   The image forming apparatus according to claim 7, further comprising an endless intermediate transfer unit.   9. The image according to claim 8, further comprising a photosensitive member and a cleaning unit that cleans toner remaining on the photosensitive member and / or the intermediate transfer unit, and the cleaning unit does not include a cleaning blade. Forming equipment.   9. The image forming apparatus according to claim 8, further comprising: a photosensitive member; and a cleaning unit that cleans toner remaining on the photosensitive member and / or the intermediate transfer unit, and the cleaning unit includes a cleaning blade. .   12. The image forming apparatus according to claim 7, further comprising a fixing unit that fixes an image using a roller having a heating device.   12. The image forming apparatus according to claim 7, further comprising a fixing unit that fixes an image using a belt having a heating device.   The image forming apparatus according to claim 12, wherein the fixing unit is a fixing unit that does not require oil application to the fixing member.   A photosensitive member and a developing unit that develops the electrostatic latent image formed on the photosensitive member using the electrostatic charge latent image developing toner according to any one of claims 1 to 5 are supported at least integrally. A process cartridge which is detachable from a forming apparatus main body.

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