JP2008203778A - Toner for positive chargeable electrostatic charge image development, developer for positive chargeable electrostatic charge image development, toner cartridge and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner for positive chargeable electrostatic charge image development, a developer for positive chargeable electrostatic charge image development, a toner cartridge and an image forming apparatus, in which the occurrence of toner splashing is preferably suppressed while keeping an effect of providing a fixed image with preferable scratch resistance. <P>SOLUTION: The toner for positive chargeable electrostatic charge image development contains a binder resin containing a vinyl-based resin to which polyolefin is grafted, wax containing a polyethylene wax, a charge controlling agent, and a colorant, and is characterized in that: the ratio of the polyolefin grafted to the vinyl-based resin ranges from 5 parts by mass to 40 parts by mass with respect to 100 parts by mass of the polyolefin-grafted vinyl-based resin; the ratio (charge controlling agent:vinyl-based resin) of the charge controlling agent to the polyolefin-grafted vinyl-based resin ranges from 20:80 to 80:20; and the ratio (wax:vinyl-based resin) of the wax to the polyolefin-grafted vinyl-based resin ranges from 30:70 to 90:10. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a positively chargeable electrostatic charge developing toner, a positively chargeable electrostatic charge developing developer, a toner cartridge, and an image forming apparatus.

  An image forming apparatus using an electrophotographic apparatus or the like is used as an output device of a computer. In recent years, these image forming apparatuses have been required to increase the speed, and therefore, the image forming toner is also required to have performance suitable for high-speed printing.

  As a toner fixing method, a heat roll method in which toner is directly heated by a roller or the like, an oven fixing method, a light fixing (flash fixing) method in which fixing is performed by light irradiation or far-infrared irradiation, and the like are generally used. Since the optical fixing method is non-contact with the transfer target (recording medium), the paper after fixing is not rolled, no offset occurs, ultra-high-speed printing is possible, and sealing and postcards are fixed. In particular, an optical fixing device is often used in an ultra-high speed machine.

  However, in these ultra-high speed machines, when the post-fixing image is processed by the post-processing device, the processing speed is high, so that the post-processing device and the rubbing image are stained, or the stain due to rubbing between the fixed images is more remarkable. Occurs and causes deterioration of quality.

In the toner used for the above-mentioned photofixing, an attempt has been made to add a wax such as polyethylene in order to improve scratch resistance (see, for example, Patent Document 1). In addition, attempts have been made to add a vinyl resin grafted with polyolefin for the purpose of controlling the dispersion of the wax (see, for example, Patent Documents 2 to 4).
JP-A-4-186250 JP-A-6-295097 JP 2001-249492 A JP 2003-98726 A

  An object of the present invention is to provide a positively-charged electrostatic charge developing toner and a positively-charged electrostatic charge developer developer that can effectively suppress the occurrence of toner scattering while maintaining the effect of obtaining a fixed image having good scratch resistance. Is to provide. It is another object of the present invention to provide a toner cartridge using the toner and an image forming apparatus in which the occurrence of toner scattering is satisfactorily suppressed while maintaining the effect of obtaining a fixed image having good scratch resistance.

The above object is achieved by the present invention described below.
That is, the invention according to claim 1 includes a binder resin containing a vinyl resin grafted with polyolefin, a wax containing polyethylene wax, a charge control agent, and a colorant, and the vinyl resin The ratio of the polyolefin grafted to the resin is 5 to 40 parts by mass with respect to 100 parts by mass of the vinyl resin grafted with the polyolefin, and the ratio of the vinyl resin grafted with the polyolefin and the charge control agent (Charge control agent: vinyl resin) is 20:80 to 80:20, and the ratio of the vinyl resin grafted with the polyolefin and the wax (wax: vinyl resin) is 30:70 to 90. : 10 is a positively chargeable electrostatic charge developing toner.

  In the invention according to claim 2, the ratio of the polyolefin grafted to the vinyl resin according to claim 1 is 8 parts by mass or more and 35 parts by mass or less with respect to 100 parts by mass of the vinyl resin grafted with the polyolefin. This is a positively chargeable electrostatic charge developing toner.

  In the invention according to claim 3, the ratio of the polyolefin grafted to the vinyl resin according to claim 1 is 10 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the vinyl resin grafted with the polyolefin. This is a positively chargeable electrostatic charge developing toner.

  The invention according to claim 4 is characterized in that the ratio (charge control agent: vinyl resin) of the vinyl resin grafted with the polyolefin according to any one of claims 1 to 3 and the charge control agent is 25. : 75-75: 25 positively chargeable electrostatic charge developing toner.

  The invention according to claim 5 is characterized in that the ratio (charge control agent: vinyl resin) between the vinyl resin grafted with the polyolefin according to any one of claims 1 to 3 and the charge control agent is 30. : Positively chargeable electrostatic charge developing toner of 70 to 70:30.

  The invention according to claim 6 is the ratio of the vinyl resin grafted with the polyolefin according to any one of claims 1 to 5 to the wax (wax: vinyl resin) is 35:65 to 85. : 15 is a positively chargeable electrostatic charge developing toner.

  The invention according to claim 7 is characterized in that the ratio of the vinyl resin grafted with the polyolefin according to any one of claims 1 to 5 and the wax (wax: vinyl resin) is 40: 60-80. : 20 is a positively chargeable electrostatic charge developing toner.

  The invention according to claim 8 is a positively chargeable electrostatic charge developing developer containing the positively chargeable electrostatic charge developing toner according to any one of claims 1 to 7.

  The invention according to claim 9 is detachable from an image forming apparatus having at least a developing unit for developing an electrostatic charge image to form a toner image, and is used as a toner to be supplied to the developing unit. A toner cartridge containing the positively chargeable electrostatic charge developing toner according to any one of 7 to 7.

  The invention according to claim 10 is an image carrier, image forming means for forming an electrostatic charge image on the surface of the image carrier, and the electrostatic charge developer according to claim 8. Developing means for forming a toner image by developing, a transfer means for transferring the toner image to the surface of the transfer body, a fixing means for fixing the toner image transferred to the surface of the transfer body by an optical fixing method, An image forming apparatus including at least

  According to the first aspect of the present invention, it is possible to satisfactorily suppress the occurrence of toner scattering while maintaining the effect of obtaining a fixed image having good scratch resistance compared to the case without this configuration.

  According to the second aspect of the present invention, it is possible to better suppress the occurrence of toner scattering while maintaining better scratch resistance in a fixed image.

  According to the third aspect of the present invention, it is possible to more effectively suppress the occurrence of toner scattering while maintaining better scratch resistance in a fixed image.

  According to the fourth aspect of the invention, the occurrence of toner scattering can be suppressed more favorably.

  According to the invention of claim 5, the occurrence of toner scattering can be suppressed more favorably.

  According to the sixth aspect of the present invention, it is possible to more effectively suppress the occurrence of toner scattering while maintaining better scratch resistance in a fixed image.

  According to the seventh aspect of the present invention, it is possible to better suppress the occurrence of toner scattering while maintaining better scratch resistance in a fixed image.

  According to the eighth aspect of the invention, it is possible to satisfactorily suppress the occurrence of toner scattering while maintaining the effect of obtaining a fixed image having good scratch resistance.

  According to the ninth aspect of the invention, while maintaining the effect of obtaining a fixed image having good scratch resistance, it is possible to facilitate the supply of toner capable of satisfactorily suppressing the occurrence of toner scattering, and to maintain the above characteristics. Can increase the sex.

  According to the tenth aspect of the present invention, it is possible to satisfactorily suppress the occurrence of toner scattering while maintaining the effect of obtaining a fixed image having good scratch resistance compared to the case without this configuration.

The positively chargeable electrostatic charge developing toner of the present invention comprises a binder resin containing a vinyl resin grafted with polyolefin, a wax containing polyethylene wax, a charge control agent, and a colorant. And it satisfies the following requirements (1) to (3).
(1) The ratio of polyolefin grafted to vinyl resin is 5 parts by weight to 40 parts by weight with respect to 100 parts by weight of vinyl resin grafted with polyolefin. The ratio to the control agent (mass ratio / charge control agent: vinyl resin) is 20:80 to 80:20.
(3) The ratio (mass ratio / wax: vinyl resin) between the vinyl resin grafted with polyolefin and the wax (amount of all wax components including the polyethylene wax) is 30:70 to 90:10.

By adopting the above-described configuration of the positively chargeable electrostatic charge developing toner of the present invention (hereinafter sometimes simply referred to as “toner”), the amount of wax exposed on the toner surface and the amount of charge control agent are in appropriate ranges. In addition to being able to obtain stable chargeability, it is possible to prevent carrier contamination due to wax, and as a result, it is possible to satisfactorily prevent the occurrence of toner scattering from the beginning to the lapse of time without impairing scratch resistance. it can.
Specifically, the amount of polyolefin grafted on a vinyl resin that is highly compatible with the charge control agent (requirement of (1) above), and the ratio of addition of the charge control agent itself (requirement of (2) above) By controlling both of these, the ratio of exposure of the charge control agent to the toner surface can be in a favorable range. Further, the amount of polyolefin in the vinyl-based resin grafted with polyolefin (requirement of (1) above), which is more compatible with a binder resin such as polyester resin than polyethylene wax, and the ratio of addition of wax itself (above By controlling both of the requirements (3), the size of the wax can be controlled, and as a result, the ratio of exposure to the toner surface can be in a good range. As described above, the charge amount is stabilized by controlling the sizes of the wax and the charge control agent within a favorable range. Further, since the exposure of the wax to the toner surface is controlled within a favorable range, the scratch resistance of the fixed image is not impaired.
Further, as the number of printed sheets increases, the wax and the charge control agent are adhered to each other, and the toner and the charge control agent are prevented from being scattered by contaminating the carrier. It is necessary to prevent the wax and the charge control agent from being present in a fused state. Under the condition that the amount of polyolefin grafted on the vinyl resin is in the above range (requirement (1)), the charge control agent addition ratio (requirement (2)) and wax addition ratio (the ( By controlling together with the requirement 3), it is possible to prevent the wax and the charge control agent from existing in an adhering state.
That is, the toner of the present invention satisfies the above requirements (1) to (3), and these relate to each other so that the amount of the wax exposed on the toner surface, the amount of the charge control agent, and the presence form are in an appropriate range. Thus, stable chargeability can be obtained, and carrier contamination by wax can be prevented. As a result, occurrence of toner scattering can be satisfactorily prevented without impairing scratch resistance.

The ratio of the polyolefin grafted to (1) vinyl resin is more preferably 8 parts by weight or more and 35 parts by weight or less with respect to 100 parts by weight of the vinyl resin grafted with polyolefin. It is particularly preferably 30 parts by mass or less.
The ratio of (2) the vinyl resin grafted with polyolefin and the charge control agent (charge control agent: vinyl resin) is more preferably 25:75 to 75:25, and 30:70. It is particularly preferred that it is ˜70: 30.
Further, the ratio of the above-mentioned (3) vinyl resin grafted with polyolefin and the wax (wax: vinyl resin) is more preferably 35:65 to 85:15, and 40:60 to 80:20. It is particularly preferred that

  Here, (1) the ratio of the polyolefin grafted on the vinyl resin, (2) the ratio of the vinyl resin grafted with the polyolefin and the charge control agent, and (3) the vinyl resin grafted with the polyolefin The ratio to the wax can be calculated from the composition ratio when the toner is produced.

  Hereinafter, the components and manufacturing methods of the toner of the present invention will be described in detail.

<Binder resin>
As the binder resin in the toner of the present invention, it is an essential requirement to contain a vinyl-based resin grafted with polyolefin, and it is preferably used in combination with a polyester resin as a main component of the binder resin.
In addition to the above, as a binder resin, a copolymer of styrene and acrylic acid or methacrylic acid, polyvinyl chloride resin, phenol resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyurethane, polyamide resin, A furan resin, an epoxy resin, a xylene resin, a polyvinyl butyral, a terpene resin, a coumarone indene resin, a petroleum resin, a polyether polyol resin, or the like can be used in combination.

-Vinyl resin grafted with polyolefin-
The vinyl resin grafted with the polyolefin in the present invention is preferably a resin in which a styrene monomer and an alkyl ester of an unsaturated carboxylic acid are used in combination as the vinyl resin of the main skeleton. Further, when a polyester resin is used in combination, an unsaturated nitrile monomer, an α, β-unsaturated carboxylic acid or the like may be used in combination. Moreover, well-known olefins can be used as polyolefin made into a graph, It is preferable that a polypropylene and / or polyethylene contain.
The polyolefin resin grafted with the polyolefin is preferably contained in an amount of 0.5 to 10 parts by mass, more preferably 0.8 to 10 parts by mass with respect to 100 parts by mass of the total solid content of the toner. 8 mass parts or less are more preferable, and 1 mass part or more and 7 mass parts or less are especially preferable. The Tg (glass transition point) of the vinyl resin is preferably in the range of 40 to 80 ° C. Moreover, it is preferable that a weight average molecular weight is 3000-50000.

-Polyester resin-
The polyester resin in the present invention is obtained by condensation polymerization of a carboxylic acid component and an alcohol component, and uses a conventionally known divalent or trivalent or higher carboxylic acid and divalent or trivalent or higher alcohol. be able to.

Specific examples of the divalent carboxylic acids include aliphatic dicarboxylic acids such as maleic acid, fumaric acid, succinic acid, adipic acid, malonic acid, sebacic acid, mesaconic acid, dodecenyl (anhydrous) succinic acid, and anhydrides thereof. Products and lower alkyl esters; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, naphthalenedicarboxylic acid, and their anhydrides and lower alkyl esters; hydrocarbon groups having 4 to 35 carbon atoms in the side chain Or an alkenyl (anhydrous) succinic acid [specifically, dodecenyl (anhydrous) succinic acid, pentadodecenyl (anhydrous) succinic acid, etc.] or an anhydride or a lower alkyl ester thereof.
Specific examples of the trivalent or higher carboxylic acids include trimellitic acid, pyromellitic acid, 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4. -Naphthalenetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,2,7,8-octanetetracarboxylic acid, or their acid anhydrides and lower alkyl esters. These may be used individually by 1 type and may use 2 or more types together.

On the other hand, as the dihydric alcohol, diols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1, C2-C12 alkylene glycol such as 5-pentanediol and 1,6-hexanediol, alkylene ether glycols such as diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene glycol, 1 , 4-cyclohexanedimethanol, hydrogenated bisphenol A and the like alicyclic diols having 6 to 30 carbon atoms, bisphenols such as bisphenol A, bisphenol F and bisphenol S, and bisphenol Alkylene oxide 2-8 moles adducts of the kind can be mentioned.
Further, as trihydric or higher alcohols, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1 , 2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane and other aliphatic polyhydric alcohols having 3 to 20 carbon atoms, Aromatic polyhydric alcohols having 6 to 20 carbon atoms such as 1,3,5-trihydroxylmethylbenzene, and alkylene oxide adducts thereof can be used.

  The Tg (glass transition point) of the polyester resin is preferably in the range of 40 to 80 ° C. The weight average molecular weight is preferably 5,000 to 100,000.

<Colorant>
It is an essential requirement that the toner of the present invention contains a colorant.
In the case of the cyan toner, the toner of the present invention is, for example, C.I. I. Pigment Blue 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 13, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 17, 23, 60, 65, 73, 83, 180, C.I. I. Vat cyan 1, 3 and 20, etc., bitumen, cobalt blue, alkali blue lake, phthalocyanine blue, metal-free phthalocyanine blue, partially chlorinated products of phthalocyanine blue, fast sky blue, indanthrene blue BC cyan pigment, C.I. I. Cyan dyes such as solvent cyan 79 and 162 can be used.

  In the case of a magenta toner, the toner of the present invention may be, for example, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90 112, 114, 122, 123, 163, 184, 202, 206, 207, and 209, pigment violet 19 magenta pigments, C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 30, 49, 81, 82, 83, 84, 100, 109, 121, C . I. Disper thread 9, C.I. I. Basic Red 1, 2, 9, 9, 13, 14, 15, 17, 17, 18, 22, 23, 24, 27, 29, 32, 34, the same 35, 36, 37, 38, 39, 40, etc. Magenta dyes, etc., Bengala, Cadmium Red, Lead Tan, Mercury Sulfide, Cadmium, Permanent Red 4R, Resol Red, Pyrazolone Red, Watching Red, Calcium Salt, lake red D, brilliant carmine 6B, eosin lake, rotamin lake B, alizarin lake, brilliant carmine 3B, and the like can be used.

Further, in the case of the yellow toner, the toner of the present invention may be exemplified by C.I. I. Pigment Yellow 2, 3, 15, 15, 17, 74, 97, 180, 185, 139, and the like can be used.
In the toner of the present invention, in the black toner, as the colorant, for example, carbon black, activated carbon, titanium black, iron powder, magnetite, ferrite or other magnetic powder, Mn-containing nonmagnetic powder, or the like may be used. it can. Further, a pigment black toner in which yellow, magenta, cyan, red, green, and blue pigments are mixed may be used.

  The colorant content in the toner of the present invention is preferably 1.5% by mass or more and 20% by mass or less, and more preferably 2% by mass or more and 15% by mass or less.

<Wax>
The toner of the present invention is required to contain a wax containing at least polyethylene wax in an amount defined in the requirement (3).
As the polyethylene wax, those having a weight average molecular weight of 2000 or more are preferably used, and more preferably 3000 or more. Although not particularly limited, the upper limit of the weight average molecular weight of the polyethylene wax is preferably 20000 or less.

  In the toner of the present invention, waxes that can be used in combination with the polyethylene wax include ester wax, polypropylene or a copolymer of polyethylene and polypropylene, polyglycerin wax, microcrystalline wax, paraffin wax, carnauba wax, sazol wax. , Montanic acid ester wax, deacidified carnauba wax, palmitic acid, stearic acid, montanic acid, blandic acid, eleostearic acid, valinalic acid and other unsaturated fatty acids, stearic alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol, Saturated alcohols such as seryl alcohol, melyl alcohol, or long-chain alkyl alcohols having a long-chain alkyl group; such as sorbitol Monohydric alcohols; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; saturated fatty acid bisamides such as methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, hexamethylene bisstearic acid amide , Unsaturated fatty acid amides such as ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sebacic acid amide; Aromatic bisamides such as acid amide and N, N′-distearylisophthalic acid amide; fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate (generally referred to as metal soap) Waxes grafted to aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid; partially esterified products of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; by hydrogenation of vegetable oils and fats, etc. Examples thereof include a methyl ester compound having a hydroxyl group to be obtained.

  As the wax to be contained in the toner of the present invention, a wax material showing an endothermic peak by DSC measurement (differential scanning calorimetry) at 50 to 160 ° C. is preferable. In the DSC measurement, it is preferable to measure with a differential scanning calorimeter of high accuracy internal heat input compensation type from the measurement principle.

The total wax component content in the toner of the present invention is preferably 0.5% by mass or more and 15% by mass or less, and more preferably 1% by mass or more and 10% by mass or less.
The content of the polyethylene wax in the toner is preferably 0.5% by mass or more and 8% by mass or less, and more preferably 1% by mass or more and 6% by mass or less.

<Charge control agent>
The toner of the present invention is required to contain the charge control agent in an amount specified in the requirement (2).
The charge control agent is not particularly limited, and a known one can be used depending on the purpose. For example, as a positively chargeable charge control agent, a nigrosine dye, tributylbenzylammonium-1-hydroxy-4-naphtho is used. Quaternary ammonium salts such as sulfonates, tetrabutylammonium tetrafluoroborate, and onium salts such as phosphonium salts that are analogs thereof and lake pigments thereof; triphenylmethane dyes; metal salts of higher fatty acids; dibutyltin oxide And diorganotin oxides such as dioctyltin oxide and dicyclohexyltin oxide; diorganotin borates such as dibutyltin borate; guanidine compounds, imidazole compounds, and aminoacrylic resins. Of these, nigrosine dyes and quaternary ammonium salts are particularly preferably used. These charge control agents may be used individually by 1 type, and may use 2 or more types together.

<Infrared absorber>
When the toner of the present invention is used in an image forming apparatus using a light fixing system, an infrared absorber may be contained.
As the infrared absorber used in the present invention, a known infrared absorber can be used. For example, cyanine compounds, merocyanine compounds, benzenethiol metal complexes, mercaptophenol metal complexes, aromatic diamine metal complexes, diimonium A compound, an aminium compound, a nickel complex compound, a phthalocyanine compound, an anthraquinone compound, a naphthalocyanine compound, or the like can be used.

  Specific infrared absorbers include nickel metal complex infrared absorbers (Mitsui Chemical Co., Ltd .: SIR-130, SIR-132), bis (dithiobenzyl) nickel (Midori Chemical Co., Ltd .: MIR-101), bis [ 1,2-bis (p-methoxyphenyl) -1,2-ethylenedithiolate] nickel (manufactured by Midori Chemical Co., Ltd .: MIR-102), tetra-n-butylammonium bis (cis-1,2-diphenyl-1, 2-Ethylenedithiolate) nickel (Midori Chemical Co., Ltd .: MIR-1011), tetra-n-butylammonium bis [1,2-bis (p-methoxyphenyl) -1,2-ethylenedithiolate] nickel (Midori Chemical) Manufactured by MIR-1021), bis (4-tert-1,2-butyl-1,2-dithiophenolate) nickel-tetra-n Butylammonium (manufactured by Sumitomo Seika Co., Ltd .: BBDT-NI), cyanine infrared absorber (Fuji Film Co., Ltd .: IRF-106, IRF-107), cyanine infrared absorber (manufactured by Yamamoto Kasei Co., Ltd., YKR2900), aminium, Diimonium-based infrared absorber (manufactured by Nagase Chemtech: NIR-AM1, IM1), imonium compound (manufactured by Nippon Carlit: CIR-1080, CIR-1081), aminium compound (manufactured by Nippon Carlit: CIR-960, CIR-961) ), Anthraquinone compounds (Nippon Kayaku Co., Ltd .: IR-750), aminium compounds (Nippon Kayaku Co., Ltd .: IRG-002, IRG-003, IRG-003K), polymethine compounds (Nippon Kayaku Co., Ltd .: IR-820B), a diimonium compound (Nippon Kayaku Co., Ltd .: IRG-022, I G-023), dianine compound (Nippon Kayaku Co., Ltd .: CY-2, CY-4, CY-9), soluble phthalocyanine (Nippon Shokubai Co., Ltd .: TX-305A), naphthalocyanine (Yamamoto Kasei Co., Ltd .: YKR5010), Sanyo Dye Co., Ltd .: Sample 1), inorganic material system (Shin-Etsu Chemical Co., Ltd .: Ytterbium UU-HP, Sumitomo Metals Co., Ltd .: Injumetin Oxide) and the like. Of these, diimonium, aminium, naphthalocyanine, and cyanine are preferable for photofixing.

<Toner production method>
Next, a method for producing the toner of the present invention will be described. The toner of the present invention can be produced by a known toner production method such as a pulverization method.
When the pulverization method is used, for example, the toner of the present invention can be prepared as follows. First, components such as the above-described binder resin, wax, charge control agent, and colorant are mixed, and then the above materials are melt-kneaded using a kneader, an extruder, or the like. Thereafter, the obtained melt-kneaded product is roughly pulverized and then finely pulverized with a jet mill or the like, and toner particles having a target particle diameter are obtained with an air classifier. Further, an external additive such as silica can be added to the toner particles as necessary to obtain the toner of the present invention.

The volume average particle diameter of the toner particles is preferably 4 μm or more and 12 μm or less.
As a measuring method of the volume average particle diameter of the toner particles, for example, a Coulter Multisizer-II type can be used. Specifically, 0.5 to 50 mg of a measurement sample is added to a surfactant as a dispersant, and this is added to 100 to 150 ml of an electrolytic solution. The electrolytic solution in which the measurement sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for 1 minute, and the particle size is 2.0 to 60 μm using the Coulter counter TA-II type with an aperture having an aperture diameter of 100 μm. The particle size distribution of the particles in the range is measured. The number of particles to be measured is 50,000. For the particle size range (channel) obtained by dividing the obtained particle size distribution, the volume cumulative distribution is subtracted from the small particle size side, and the particle size that becomes 50% cumulative is defined as the volume average particle size D50.

The toner of the present invention may further be added with an external additive such as inorganic particles. The ratio of the external additive externally added to the toner particles before external addition is preferably in the range of 0.01 to 5 parts by mass, more preferably in the range of 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the toner particles. preferable. As an external additive, inorganic particles include, for example, silica powder, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, Examples include diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride, but at least of silica, titanium oxide, and alumina. It is particularly preferable that one kind is included. Furthermore, higher fatty acid metal salts typified by zinc stearate, organic particles such as vinyl polymers such as styrene polymers, (meth) acrylic polymers, ethylene polymers, ester-based, melamine-based In addition, various polymers such as amides and allyl phthalates, fluorine polymers such as vinylidene fluoride, and organic particles made of higher alcohols may be added.
The above external additives can be further externally added by mixing them with a desired additive as required, using a mixer such as a Henschel mixer.

<Developer>
Next, a positively charged developer for developing an electrostatic charge (hereinafter sometimes simply referred to as “developer”) containing the toner of the present invention will be described. The developer of the present invention may be either a one-component developer composed of the toner of the present invention or a two-component developer composed of a carrier and the toner of the present invention. Hereinafter, the case where the developer is a two-component developer will be described in detail.
The carrier that can be used in the two-component developer is not particularly limited, and a known carrier can be used. For example, a resin-coated carrier having a resin coating layer on the surface of the core material can be exemplified. Further, a resin-dispersed carrier in which a conductive material or the like is dispersed in a matrix resin may be used.

The carrier used in the present invention will be described.
Ferrite, magnetite, iron powder, etc. can be used as the material of the magnetic particles that will be the main body (core material) of the carrier.

  A preferred carrier for use in the present invention has, for example, an average particle size of preferably 20 to 100 μm, more preferably 30 to 80 μm. The carrier can be obtained by coating the core material with a resin by a known method such as a spray drying method using a fluidized bed, a rotary drying method, an immersion drying method using a universal stirrer, or the like.

  In the carrier used in the present invention, various resins can be used as the resin used for coating the surface of the core material. For example, fluorinated resin, acrylic resin, epoxy resin, polyester resin, fluorine acrylic resin, acrylic / styrene resin, silicone resin, modified silicone resin modified with acrylic resin / polyester resin / epoxy resin / alkyd resin / urethane resin, etc. And a fluorine-modified silicone resin. Moreover, you may add a charge control agent, a resistance control agent, etc. as needed.

  The above two-component developer is manufactured by mixing the toner and the carrier described above. The mixing ratio (mass ratio) of the toner and carrier in the developer is preferably in the range of toner: carrier = 1: 99 to 20:80, and preferably in the range of 3:97 to 12:88. More preferred.

<Image forming apparatus>
The image forming apparatus using the developer of the present invention is not particularly limited as long as it forms a toner image on a transfer target (recording medium) using the developer containing the toner of the present invention. The developer of the present invention can be suitably used particularly for the following image forming apparatus of the present invention.
The image forming apparatus of the present invention includes an image carrier, an image forming unit for forming an electrostatic image on the surface of the image carrier, and developing the electrostatic image with a positively charged developer for developing electrostatic images. A developing means for forming the toner image, a transfer means for transferring the toner image to the surface of the transfer target, and a fixing means for fixing the toner image transferred to the surface of the transfer target by an optical fixing method. The developer of the present invention described above is used as a developer for developing electrostatic charge.

  Examples of the light source (fixing means) used for the light fixing in the present invention include a normal halogen lamp, mercury lamp, flash lamp, infrared laser, and the like. Because it is optimal.

Hereinafter, an example of the image forming apparatus of the present invention will be described with reference to the drawings. FIG. 1 is a schematic configuration diagram showing an example of an image forming apparatus of the present invention.
The image forming apparatus 10 shown in FIG. 1 feeds a recording medium P wound in a roll shape by a paper feed roller 28, and the feeding direction of the recording medium P on one side of the recording medium P fed in this way. Four image forming units 12 (black (K), yellow (Y), magenta (M), cyan (C)) are provided in parallel from the upstream side to the downstream side, and the image forming unit 12 is further provided. A light fixing type fixing device 26 is provided on the downstream side.

The black image forming unit 12K is a known electrophotographic image forming unit. Specifically, a charger 16K, an exposure unit 18K, a developing unit 20K, and a cleaner 22K are provided around the photoconductor 14K, and a transfer unit 24K is provided via the recording medium P. The same applies to the other yellow, magenta, and cyan image forming units 12Y, 12M, and 12C.
When used for black and white printing, only black (K) may be provided as the image forming unit 12.

  Here, as the photosensitive member 14 (K, Y, M, C), generally, an inorganic photosensitive member such as amorphous silicon or selenium, or an organic photosensitive member such as polysilane or phthalocyanine can be used. A photoreceptor is preferred.

  As the fixing device 26, a flash lamp such as a xenon lamp, a neon lamp, an argon lamp, or a krypton lamp can be used.

  In the image forming apparatus 10 shown in FIG. 1, toner images are sequentially transferred by a known electrophotographic method by the image forming units 12 </ b> K, Y, M, and C onto the recording medium P drawn from the roll state. The toner image is light-fixed by the fixing device 26 to form an image.

  The light source as the light fixing means has the strongest light emission peak depending on the type, and the optimum light absorption characteristics in the near-infrared region required corresponding to this are also different. However, the adjustment of the light absorption characteristics in the near infrared region can be easily performed by controlling the molecular structure.

<Toner cartridge>
The toner cartridge of the present invention will be described. The toner cartridge of the present invention is detachably attached to the image forming apparatus, and at least the toner cartridge for storing toner to be supplied to the developing means provided in the image forming apparatus, the toner described above. Toner.

  The developing devices 12Y, 12M, 12C, and 12K shown in FIG. 1 are connected to toner cartridges corresponding to the respective developing devices (colors) by a developer supply pipe (not shown). Further, when the amount of toner stored in the toner cartridge is low, the toner cartridge can be replaced.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by the following examples. In the following examples, “part” is based on mass.

(Preparation of vinyl resin 1)
80 parts of styrene-acrylonitrile-butyl acrylate copolymer (Tg = 59 ° C., weight average molecular weight: 9000), 10 parts of polyethylene wax (manufactured by Clariant: trade name PE520) and polypropylene wax (trade name: NP105, manufactured by Mitsui Chemicals) ) A vinyl resin 1 grafted with 10 parts was prepared.
The ratio of the polyolefin in the obtained vinyl resin 1 is 20 parts with respect to 100 parts of the vinyl resin grafted with polyolefin.

(Preparation of vinyl resin 2)
55 parts of styrene-acrylonitrile-butyl acrylate copolymer (Tg = 59 ° C., weight average molecular weight: 9000), 30 parts of polyethylene wax (Clariant: trade name PE520) and polypropylene wax (Mitsui Chemicals: trade name: NP105) ) A vinyl resin 2 grafted with 15 parts was prepared.
The ratio of polyolefin in the obtained vinyl resin 1 is 45 parts with respect to 100 parts of the vinyl resin grafted with polyolefin.

(Preparation of vinyl resin 3)
A vinyl-based resin 3 was produced by grafting 3 parts of polyethylene wax (manufactured by Clariant: trade name PE520) on 97 parts of a styrene-acrylonitrile-butyl acrylate copolymer (Tg = 59 ° C., weight average molecular weight: 9000).
The ratio of polyolefin in the obtained vinyl resin 1 is 3 parts with respect to 100 parts of the vinyl resin grafted with polyolefin.

(Preparation of vinyl resin 4)
94 parts of styrene-acrylonitrile-butyl acrylate copolymer (Tg = 59 ° C., weight average molecular weight: 9000), 3 parts of polyethylene wax (manufactured by Clariant: trade name PE520), polypropylene wax (trade name: NP105, manufactured by Mitsui Chemicals) ) A vinyl resin 4 grafted with 3 parts was prepared.
The ratio of polyolefin in the obtained vinyl resin 4 is 6 parts with respect to 100 parts of the vinyl resin grafted with polyolefin.

(Preparation of vinyl resin 5)
62 parts of styrene-acrylonitrile-butyl acrylate copolymer (Tg = 59 ° C., weight average molecular weight: 9000), 30 parts of polyethylene wax (manufactured by Clariant: trade name PE520), polypropylene wax (trade name: NP105, manufactured by Mitsui Chemicals) ) 8 parts grafted vinyl resin 5 was produced.
The ratio of polyolefin in the obtained vinyl resin 5 is 38 parts with respect to 100 parts of vinyl resin grafted with polyolefin.

(Preparation of vinyl resin 6)
91 parts of styrene-acrylonitrile-butyl acrylate copolymer (Tg = 59 ° C., weight average molecular weight: 9000), 5 parts of polyethylene wax (manufactured by Clariant: trade name PE520), polypropylene wax (trade name: NP105, manufactured by Mitsui Chemicals) ) 4 parts grafted vinyl resin 6 was produced.
The ratio of polyolefin in the obtained vinyl resin 6 is 9 parts with respect to 100 parts of the vinyl resin grafted with polyolefin.

(Preparation of vinyl resin 7)
68 parts of styrene-acrylonitrile-butyl acrylate copolymer (Tg = 59 ° C., weight average molecular weight: 9000), 22 parts of polyethylene wax (manufactured by Clariant: trade name PE520), polypropylene wax (trade name: NP105, manufactured by Mitsui Chemicals) ) A vinyl resin 7 grafted with 10 parts was prepared.
The ratio of polyolefin in the obtained vinyl resin 7 is 32 parts with respect to 100 parts of the vinyl resin grafted with polyolefin.

[Example 1]
(Preparation of developer 1)
84 parts of polyester resin (Bisphenol A propylene oxide adduct / Bisphenol A ethylene
Mainly oxide adduct / terephthalic acid / trimellitic acid
(Polyester resin: Tg = 62 ° C., weight average molecular weight: 38000)
Vinyl resin 1 3 parts Carbon black (Mitsubishi Chemical Corporation: trade name # 25) 8 parts Polyethylene wax 3 parts (Mitsui Chemicals trade name: 400P, weight average molecular weight 4000)
Positive charge control agent 2 parts (Nigrosine dye: manufactured by Orient Chemical Co., Ltd .: trade name Bontron N-04)
The above composition is powder-mixed with a Henschel mixer, heat-kneaded with an extruder with a set temperature of 105 ° C., cooled, coarsely pulverized, finely pulverized and classified, and toner base particles having a volume average particle diameter D50 of 8.8 μm Got.
100 parts of the toner base particles and 1.0 part of hydrophobic silica particles (manufactured by Nippon Aerosil Co., Ltd .: trade name RA200H) were mixed with a Henschel mixer to obtain a positively chargeable toner 1.
Further, 5 parts of the toner 1 and 95 parts of a silicone resin coated carrier were mixed to obtain a positively chargeable developer 1.

[Examples 2 to 13, Comparative Examples 1 to 9]
In the preparation of the developer 1, except that the kind of vinyl resin to be added, the addition amount of the vinyl resin, the addition amount of the polyethylene wax, and the addition amount of the positive charge control agent were changed as shown in Table 1 below, A developer was prepared by the method described in Example 1.

(Evaluation methods)
The positively chargeable toner and the positively chargeable developer obtained in the above-mentioned examples and comparative examples are placed in a Docu Print 1100CF remodeling machine manufactured by Fuji Xerox Co., Ltd. (modified so that the process speed and the like can be adjusted). Scatter resistance and scratch resistance of the fixed image were evaluated.

-Toner scattering-
Using a chart with an image printing rate of 3%, printing equivalent to 600,000 sheets in terms of A4 and printing equivalent to 1.2 million sheets was performed, and then the contamination inside the machine was visually observed and evaluated according to the following criteria. The process speed was 1000 mm / s.
◎: The level at which the inside of the machine cannot be visually confirmed ○: The level at which the inside of the machine is slightly noticeable but hardly noticeable △; ×: The dirt inside the machine is noticeable and unacceptable level by visual observation. XX: The dirt inside the machine is very noticeable and visually unacceptable level.

-Scratch resistance-
The obtained fixed image and the unused paper are overlapped, and after 10 reciprocations with a load of 50 g / cm ² , the unused copy paper is visually observed for dirt, and the scratch resistance is evaluated according to the following criteria. did.
◎: Level at which stains cannot be visually confirmed ○: Slightly visible stain can be confirmed, but level is almost inconspicuous △: Stains on the paper are observed but acceptable levels ×: Table 2 below shows the results where dirt is conspicuous and an unacceptable level of dirt is generated.

1 is a schematic configuration diagram illustrating an example of an image forming apparatus of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Image forming apparatus 12 Image forming unit 14 Photoconductor 16 Charging device 18 Exposure means 20 Developing device 22 Cleaner 24 Transfer device 26 Fixing device 28 Paper feed roller P Recording medium

Claims (10)

A binder resin containing a vinyl resin grafted with polyolefin, a wax containing polyethylene wax, a charge control agent, and a colorant,
The ratio of the polyolefin grafted to the vinyl resin is 5 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the vinyl resin grafted with the polyolefin,
A ratio of the vinyl resin grafted with the polyolefin and the charge control agent (charge control agent: vinyl resin) is 20:80 to 80:20,
A positively chargeable electrostatic charge developing toner, wherein a ratio of the vinyl resin grafted with the polyolefin and the wax (wax: vinyl resin) is 30:70 to 90:10.   2. The positive chargeability according to claim 1, wherein the ratio of the polyolefin grafted to the vinyl resin is 8 parts by mass or more and 35 parts by mass or less with respect to 100 parts by mass of the vinyl resin grafted with the polyolefin. Toner for electrostatic charge development.   2. The positive chargeability according to claim 1, wherein the ratio of the polyolefin grafted to the vinyl resin is 10 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the vinyl resin grafted with the polyolefin. Toner for electrostatic charge development.   The ratio between the vinyl resin grafted with the polyolefin and the charge control agent (charge control agent: vinyl resin) is 25:75 to 75:25. The positively chargeable electrostatic charge developing toner according to item 1.   The ratio between the vinyl resin grafted with the polyolefin and the charge control agent (charge control agent: vinyl resin) is 30:70 to 70:30. The positively chargeable electrostatic charge developing toner according to item 1.   6. The ratio according to claim 1, wherein a ratio of the vinyl resin grafted with the polyolefin and the wax (wax: vinyl resin) is 35:65 to 85:15. Toner for positively chargeable electrostatic charge development.   The ratio of the vinyl resin grafted with the polyolefin and the wax (wax: vinyl resin) is 40:60 to 80:20, according to any one of claims 1 to 5. Toner for positively chargeable electrostatic charge development.   A positively chargeable electrostatic charge developing developer, comprising the positively chargeable electrostatic charge developing toner according to claim 1.   8. The toner according to claim 1, wherein the toner is detachable from an image forming apparatus including at least a developing unit that develops an electrostatic charge image to form a toner image, and is supplied to the developing unit. A toner cartridge containing the positively chargeable electrostatic charge developing toner described above.   An image carrier, image forming means for forming an electrostatic image on the surface of the image carrier, and developing the electrostatic image with the positively charged electrostatic charge developing developer according to claim 8 to form a toner image. Development means for transferring, transfer means for transferring the toner image to the surface of the transfer target, and fixing means for fixing the toner image transferred to the surface of the transfer target by an optical fixing method. Image forming apparatus.

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