Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/097—Plasticisers; Charge controlling agents
  • G03G9/09783—Organo-metallic compounds

Definitions

• the present invention relates to an electrostatic image developing toner useful for developing an electrostatic latent image in the field of electrophotographic or electrostatic recording materials, More particularly, it relates to an electrostatic image-developing toner to be used in an image forming apparatus whereby a non-transferred toner after the transfer is recovered by a cleaning process and re-used by recycling. Further, it relates to an electrostatic image developing toner having an excellent electrification rising property and electrification stability.
• an electrostatic latent image is formed on a photoreceptor made of an inorganic or organic material, and the latent image is developed by a toner, then transferred to a paper sheet, a plastic film or the like and fixed to obtain a visible image.
• the photoreceptor is positively electrifiable or negative electrifiable depending upon its construction.
• development is carried out by means of an inversely electrifiable toner.
• reversal development is to be carried out by removing electrification of a printed portion, development is carried out by means of a toner electrifiable with the same code of electricity.
• the toner on the photoreceptor will not be all transferred, and a non-transferred toner will remain at a level of from 5 to 20 wt%.
• a non-transferred toner is usually recovered by e.g. a step of scraping by a cleaning blade and collected as a waste toner.
• various properties such as electrification properties or resin properties are substantially changed as compared with a fresh toner, and it used to be usually impossible to reuse such a waste toner.
• JP-A-1-214874 proposes a toner using, as a binder resin, a specific polyester resin containing an aliphatic diol
• JP-A-2-110572 proposes a toner wherein a metal-crosslinked styrene/acrylic copolymer is used as a binder resin, and a large amount of a polyolefin is added thereto.
• JP-A-7-301954 proposes to reuse a waste toner with respect to a toner containing, as a charge control agent, an azo type iron complex compound.
• a toner employing such a charge control agent it is impossible to obtain a recovered toner having a performance equal to the fresh toner, since a decrease in the amount of the charge control agent in the recovered waste toner or broadening of the electrification distribution will occur, and problems have not completely been solved.
• such a charge control agent has a color and thus has had a problem that it can not be used for a color toner which is also increasingly demanded in recent years.
• a toner to be used for such developing methods it has been common to employ a fine powder having a colorant dispersed in a resin.
• a colorant such as carbon black is dispersed in a binder resin such as a styrene/acrylic copolymer resin, followed by pulverization and classification to obtain fine particles of from about 1 to 30 ⁇ m, which are used as a toner.
• a magnetic toner it is common to employ one having e.g. magnetite incorporated as a colorant.
• a dry development method to be used for such electrophotography may generally be classified into a two component development and a mono component development.
• the system employing a mono component development has a merit that the developing apparatus may be made small-sized, but as compared with the two component development, the electrostatic image developing toner is required to gain a predetermined quantity of electrification in a short period of time, whereby it used to have problems that a limited material must be used, and the design allowance of the developing system is very narrow.
• the two component development is excellent in the electrification control, but has had a problem that the apparatus tends to be complex and large-sized.
• JP-A-58-95748 discloses that saturation magnetization is influential over transportability of the magnetic toner particles. Namely, when the saturation magnetization is lower than a certain level, the magnetization transporting force decreases, thereby leading to uneven development. On the other hand, if the saturation magnetization is higher than a certain level, the amount of the magnetic powder necessarily increases, whereby the fixing property or the developing property tends to deteriorate. Whereas, if the coercive force is lower than a certain level, development failure tends to result, and if it is higher than a certain level, coagulation of toner particles increases, thus leading to a decrease in transportability.
• JP-A-6-332240 discloses that stability of an image for a long period of time can be obtained when there is no change in the particle size of the toner, and that in such a case, it is important to maintain the balance of the tribocharge and the magnetic properties by using a certain specific charge control agent.
• JP-A-6-332240 proposes a negatively electrifiable charge control agent of an iron compound taking safety into consideration against the above chromium compounds.
• an iron compound taking safety into consideration against the above chromium compounds.
• the initial rising of electrification and saturated tribocharge are not comparable to the effects obtainable by the above chromium compounds, and it has been difficult to obtain an adequate performance in a mono component development.
• an object of the present invention to provide an electrostatic image developing toner which is capable of obtaining a clear image having an adequate image density free from background fogging or scattering of the toner in the machine, in any environment in an electrophotographic system capable of recycling. Further, it is intended to obtain a similar clear image also in a recycling system of a color toner, for which the demand has been rapidly increasing in recent years.
• Another object of the present invention is to provide an electrostatic image developing toner which is excellent in the rising of electrification and has electrification stability for a long period of time.
• the present invention is to provide an electrostatic image developing toner which is capable of obtaining a clear image having a sufficient imager density from the first print, without background fogging or scattering of the toner in the machine and which is capable of maintaining the clear image for a long period of time, in an electrophotographic system.
• Another object of the present invention is to provide an electrostatic image developing toner which is capable of forming a clear image by maintaining a constant electrification controlling effect even in repeated printing operation for a long period of time and is free from a problem from the viewpoint of environmental safety and which has an excellent electrification rising property and electrification stability.
• the present invention provides an electrostatic image developing toner to be used for an image forming method wherein in an electrophotographic process of forming an electrostatic latent image on a photoreceptor made of an inorganic or organic material, developing it with a toner, transferring it to a paper sheet, a plastic film or the like, and fixing it to form a visible image, the toner remaining on the photoreceptor after the transfer, is recovered, and the recovered toner is reused in the development process, said electrostatic image developing toner comprising at least a binder resin, a colorant and a charge control agent, wherein the charge control agent is represented by the following formula (1): wherein R 1 is quaternary carbon, methine or methylene and may contain a hetero atom of N, S, O or P, each of R 2 and R 3 which are independent of each other, is an alkyl group, an alkenyl group, an alkoxy group, an aryl, aryloxy,
• the present inventors have measured various physical properties of a fresh toner and a waste toner. As a result, it has been ascertained that with a toner having such problems, the amount of the charge control agent contained in the toner, which should be at the same level as in a fresh toner, is substantially decreased in the waste toner. Further, with respect to both toners, the electrification distributions were measured, and it has been found that as compared with the fresh toner, with the waste toner, the proportion of an inversely electrified toner is increased, and the electrification distribution is broadened.
• the cause for the above-mentioned image deterioration and soiling in the machine is considered to be such that in the transfer process, among developing toner particles on the photoreceptor, only sufficiently electrified toner particles will be selectively transferred, and weakly or inversely electrified toner particles will remain as a non-transferred toner on the photoreceptor and will be recovered in a cleaning process, whereby the electrification distribution of the recovered toner tends to be broadened, and the proportion of inversely electrified toner particles tends to increase.
• the present inventors have conducted an extensive study and as a result, have found it very effective to employ the compound of the above formula (1) as a charge control agent in a toner to be used for a recycling system for a waste toner.
• the compound is also thermally stable and is not susceptible to a thermal change during the electrophotographic process, whereby a stabilized electrification property can be maintained. Further, it can be uniformly dispersed in any binder resin, and thus presents a feature that the electrification distribution of a fresh toner is very uniform. Further, the content of the compound in the non-transferred recovered toner was analyzed and found to be the same content as in the fresh toner, and the saturated tribochange and electrification distribution were also found to be the same.
• the present invention provides an electrostatic image developing toner to be used for an image forming method which comprises forming an electrostatic latent image on a photoreceptor made of an inorganic or organic material, developing it with a toner, transferring it to a paper sheet, a plastic film or the like, and fixing it to form a visible image, said toner comprising at least a binder resin, a colorant and a charge control agent, wherein the charge control agent comprises at least one zirconium compound of the above-mentioned formula (1) and at least one specific azo metal complex.
• the charge control agent comprises a zirconium compound of the above-mentioned formula (1) and a specific azo metal complex.
• the above compound (1) is thermally stable and is not susceptible to a thermal change during the electrophotographic process, whereby a constant electrification property can be maintained. Further, with respect to the electrification property, it shows an extremely quick electrification rising property, and its tribocharge has been found to be higher than an azo metal complex which is presently mostly commonly employed. However, when the above compound (1) is used alone, it has been found that the tribocharge tends to increase gradually during tribe-electrification for a long period of time, whereby it has been found that a problem such as a decrease in the image density is likely to result especially when a long term electrification stability is of importance for e.g. a high speed copying machine.
• the present invention by incorporating the above compound (1) excellent in the electrification rising property and a specific azo metal complex excellent in the long term electrification stability, especially when the zirconium compound is incorporated in an amount of at least 5 wt% of the azo metal complex, it has been made possible to obtain an electrostatic image developing toner having the characteristics of both components.
• the specific azo metal complex may, for example, be an azo type chromium complex, an azo type zinc complex or an azo type iron complex.
• azo metal complexes of the following chemical formula may be mentioned, but the specific azo metal complex is not limited to such specific examples.
• the electrophotographic toner of the present invention i.e. the electrostatic image developing toner suitable for recycling, is composed basically of a binder resin, a colorant (a pigment, a dye or a magnetic material) and a charge control agent comprising a zirconium compound of the above formula (1).
• a method for preparing the electrophotographic toner there may be mentioned, for example, a method wherein such a mixture is kneaded while melting the binder resin by a heat-mixing apparatus and cooled, followed by rough pulverization, fine pulverization and classification, a method wherein such a mixture is dissolved in a solvent, followed by spraying to form fine particles, which are then dried and classified, or a method wherein a colorant and the compound of the formula (1) are dispersed in suspended monomers particles, followed by polymerization.
• the electrophotographic toner of the present invention i.e. the electrostatic image developing toner which is excellent in the electrification rising property and which has a long term electrification stability, is composed basically of a binder resin, a colorant (a pigment, a dye or a magnetic material), and a charge control agent comprising the zirconium compound of the formula (1) and an azo metal complex.
• a method for preparing such an electrophotographic toner there may be mentioned, for example, a method wherein such a mixture is kneaded while melting the binder resin by a heat-mixing apparatus and cooled, followed by rough pulverization, fine pulverization and classification, a method wherein such a mixture is dissolved in a solvent, followed by spraying to form fine particles, which are then dried and classified, or a method wherein a colorant and the charge control agent comprising the compound of the formula (1) and an azo metal complex, are dispersed in suspended monomer particles, followed by polymerization.
• the present invention provides an electrostatic image developing toner to be used for an image forming method which comprises forming an electrostatic latent image on a photoreceptor made of an inorganic or organic material, developing it with a toner, transferring it to a paper sheet, a plastic film or the like, and fixing it to form a visible image, said toner comprising at least a binder resin, a magnetic material and a charge control agent of the above formula (1) and having a saturation magnetization of from 2 to 50 Am 2 /kg and a coercive force of from 40 to 200 oersted.
• a charge control agent in order to impart a sufficient tribocharge in a very short period of time to an electrostatic image developing toner.
• a certain chromium compound is effective for remarkably improving the electrification rising property.
• it has had a problem from the viewpoint of environmental safety, as it is a chromium compound.
• a certain iron compound exhibits a negative electrification control effect, but as compared with a chromium compound, this compound is inadequate in the electrification rising property in a mono component development.
• the charge control agent is a zirconium compound of the above formula (1).
• the compound (1) is thermally stable and is not susceptible to a thermal change during the electrophotographic process, whereby a constant electrification property can be maintained. Further, with respect to the electrification property, it exhibits a very quick electrification rising property, and its tribocharge has been found to be higher than the above-mentioned azo chromium complex or the azo iron complex which are presently most commonly employed.
• the present inventors have made a magnetic toner for a mono component development by using the above compound (1) excellent in the electrification rising property. Further, in order to obtain a clear initial image by using this toner, a study has been made by applying various magnetic properties of the magnetic toner, and as a result, it has been found that when the magnetic properties are within a certain range, the image quality of an initial image will be excellent.
• Such an electrophotographic toner of the present invention is composed basically of a binder resin, a magnetic material as a colorant and a charge control agent comprising the zirconium compound of the above formula (1).
• a method for producing such an electrophotographic toner there may be mentioned, for example, a method wherein such a mixture is kneaded while melting the binder resin by a heat-mixing apparatus and cooled, followed by rough pulverization, fine pulverization and classification, a method wherein such a mixture is dissolved in a solvent, followed by spraying to obtain fine particles, which are then dried and classified, or a method wherein a colorant and a compound of the formula (1) are dispersed in suspended monomer particles, followed by polymerization.
• the binder resin to be used in the present invention preferably has a glass transition point of from 40 to 90°C, a number average molecular weight (Mn) of from 1,500 to 50,000, a weight average molecular weight (Mw) of from 10,000 to 3,000,000, an acid value of at most 50 and an acid value of at least 50.
• the binder resin is, for example, a polymer or a copolymer of a monomer selected from the group consisting of styrene type monomers, acrylic monomers and methacrylic monomers, and specifically it may be made of a monomer component selected from the group consisting of styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-ethylstyrene, acrylic acid, ⁇ -ethylacrylic acid, crotonic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phen
• the alcohol component may, for example, be a diol such as ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol or a bisphenol A derivative such as hydrogenated bisphenol A, or a known polyhydric alcohol such as glycerol, sorbitol, sorbitan or pentaerythritol.
• a diol such as ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexaned
• the acid component may, for example, be a benzenedicarboxylic acid or its anhydride, such as phthalic acid, terephthalic acid, isophthalic acid or phthalic anhydride; an alkyldicarboxylic acid such as succinic acid, adipic acid, sebacic acid or azelaic acid, or its anhydride; succinic acid having a C 6-18 alkyl or alkenyl group as a substituent, or its anhydride: a known unsaturated dicarboxylic acid such as fumaric acid, maleic acid, citraconic acid or itaconic acid, or its anhydride, or a tri- or higher hydric carboxylic acid such as trimellitic acid, pyromellitic acid or benzophenonetetracarboxylic acid, or its anhydride. Further, it may be a polyester composed solely of an aromatic compound or an aliphatic compound. These binder resins may be used alone or in combination as a mixture of two
• colorant for a black colored toner, carbon black is usually employed for a two component development.
• a certain magnetic material is used for a mono component development, and the following colorants may be employed for a color toner.
• a yellow colorant an azo type organic pigment such as CI pigment yellow-l, CI pigment yellow 5, CI pigment yellow 12 or CI pigment yellow 17, or an inorganic pigment such as Chinese yellow, or an oil-soluble dye such as CI solvent yellow 2, CI solvent yellow 6, CI solvent yellow 14 or CI solvent yellow 19, may, for example, be mentioned.
• an azo pigment such as CI pigment 57 or CI pigment red 57;1, a xanthene pigment such as CI pigment violet 1 or CI pigment 81, a thioindigo pigment such as CI pigment red 87, CI vat red 1 or CI pigment violet 38, or an oil-soluble dye such as CI solvent red 19, CI solvent red 49 or CI solvent red 52, may, for example, be mentioned.
• a triphenylmethane pigment such as CI pigment blue 1, a phthalocyanine pigment such as CI pigment blue 15 or CI pigment blue 17, or an oil-soluble dye such as CI solvent blue 25, CI solvent blue 40 or CI solvent blue 70, may, for example, be used.
• the zirconium compound to be used in the present invention may usually be obtained by reacting a metal-imparting agent with a salicylic acid derivative in water and/or an organic solvent, obtaining the product by filtration, followed by washing.
• the metal-imparting agent to be used for the preparation of this compound may, for example, be a halogenated zirconium compound such as ZrCl 4 , ZrF 4 , ZrBr 4 or ZrI 4 , an organic acid zirconium compound such as Zr(OR) 4 wherein R is hydrogen, an alkyl group or an alkenyl group, or an inorganic acid zirconium compound such as Zr(SO 4 ) 2 , in the case of a tetravalent cationic compound.
• a bivalent cationic compound of an oxo complex it may, for example, be an inorganic zirconium compound such as ZrOCl 2 , ZrO(NO 3 ) 2 , ZrO(ClO 4 ) 2 , H 2 ZrO(SO 4 ) 2 , ZrO(SO 4 )Na 2 SO 4 or ZrO(HPO 4 ) 2 , or an organic zirconium compound such as ZrO(CO 3 ), (NH 4 ) 2 ZrO(CO 3 ) 2 , ZrO(C 2 H 3 O 2 ) 2 , (NH 4 ) 2 ZrO(C 2 H 3 O 2 ) 3 or ZrO(C 18 H 35 O 2 ) 2 .
• inorganic zirconium compound such as ZrOCl 2 , ZrO(NO 3 ) 2 , ZrO(ClO 4 ) 2 , H 2 ZrO(SO 4 ) 2 , ZrO(SO 4 )Na
• Zirconium compounds represented by the formula (1) to be used in the present invention thus obtainable, will be shown below.
• the electrophotographic toner of the present invention may contain other additives including, for example, hydrophobic silica, a metal soap, a fluorine type surfactant, dioctyl phthalate, wax, a conductivity-imparting agent such as tin oxide, zinc oxide, carbon black or antimony oxide, or an inorganic fine powder such as titanium oxide, aluminum oxide or alumina, as the case requires.
• additives including, for example, hydrophobic silica, a metal soap, a fluorine type surfactant, dioctyl phthalate, wax, a conductivity-imparting agent such as tin oxide, zinc oxide, carbon black or antimony oxide, or an inorganic fine powder such as titanium oxide, aluminum oxide or alumina, as the case requires.
• the inorganic fine powder to be used in the present invention may preferably be treated with a treating agent or a combination of various treating agents, such as silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, a silane coupling agent, a silane coupling agent having a functional group and other organic silicone compounds, for the purpose of imparting hydrophobicity or controlling the tribocharge.
• a lubricant such as Teflon, zinc stearate or polyvinylidene fluoride, an abrasive such as cesium oxide, silicon carbide or strontium titanate and a caking-preventive agent may be incorporated.
• white fine particles and black fine particles having a polarity opposite to toner particles may also be used in a small amount as a developability-improving agent.
• the toner at the present invention is employed in a two-component developer, it is possible to use, as the carrier, a binder type carrier of resin particles having fine glass beads, iron powder, ferrite powder, nickel powder or magnetic particles dispersed therein, or a resin-coated carrier having the surface coated with e.g. a polyester resin, a fluorine resin, a vinyl resin, an acrylic resin or a silicone resin. Further, a toner containing the compound of the formula (1) according to the present invention exhibits excellent performance also when used as a single component toner. Furthermore, it can be used for a capsule toner and a polymerized toner.
• a binder type carrier of resin particles having fine glass beads, iron powder, ferrite powder, nickel powder or magnetic particles dispersed therein or a resin-coated carrier having the surface coated with e.g. a polyester resin, a fluorine resin, a vinyl resin, an acrylic resin or a silicone resin.
• the magnetic material may, for example, be a metal fine powder of e.g. iron, nickel or cobalt, an alloy of a metal such as iron, lead, magnesium, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, cobalt, copper, aluminum, nickel or zinc, a metal oxide such as aluminum oxide, iron oxide or titanium oxide, a ferrite of e.g. iron, manganese, nickel, cobalt or zinc, a nitride such as vanadium nitride or chromium nitride, a carbide such as tungsten carbide or silicon carbide, or a mixture thereof.
• an iron oxide such as magnetite, hematite or ferrite is preferred.
• the charge control agent of the present invention presents excellent electrification performance irrespective of the type of the magnetic material.
• Styrene-acrylic copolymer resin (CPR-100, tradename, manufactured by Mitsui Chemical Co., Ltd.) 91 parts Zirconium compound (Compound No. 1) 1 part Carbon black (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 5 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized by a jet mill and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus, and the electrification distribution was measured by an E-SPART analyzer. Further, an image test by a modified commercial copying machine was also carried out.
• Styrene-acrylic copolymer resin (CPR-100, tradename, manufactured by Mitsui Chemical Co., Ltd.) 91 parts Zirconium compound (Compound No. 2) 1 part Carbon black (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 5 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized by a jet mill and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus, and the electrification distribution was measured by an E-SPART analyzer. Further, an image test by a modified commercial copying machine was also carried out.
• Styrene-acrylic copolymer resin (CPR-100, tradename, manufactured by Mitsui Chemical Co., Ltd.) 91 parts Zirconium compound (Compound No. 10) 1 part Carbon black (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 5 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized by a jet mill and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus, and the electrification distribution was measured by an E-SPART analyzer. Further, an image test by a modified commercial copying machine was also carried out.
• Polyester resin HP-301, tradename, manufactured by Nippon Gosei Kagaku K.K.
• Zirconium compound Compound No. 1
• Carbon black MA-100, tradename, manufactured by Mitsubishi Chemical Corporation
• Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 160°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized by a jet mill and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus, and the electrification distribution was measured by an E-SPART analyzer. Further, an image test by a modified commercial copying machine was also carried out.
• Polyester resin HP-301, tradename, manufactured by Nippon Gosei Kagaku K.K.
• Zirconium compound Compound No. 2
• Carbon black MA-100, tradename, manufactured by Mitsubishi Chemical Corporation
• Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 160°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized by a jet mill and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus, and the electrification distribution was measured by an E-SPART analyzer. Further, an image test by a modified commercial copying machine was also carried out.
• Polyester resin HP-301, tradename, manufactured by Nippon Gosei Kagaku K.K.
• Zirconium compound Compound No. 10
• Carbon black MA-100, tradename, manufactured by Mitsubishi Chemical Corporation
• Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 160°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized by a jet mill and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus, and the electrification distribution was measured by an E-SPART analyzer. Further, an image test by a modified commercial copying machine was also carried out.
• Styrene-acrylic copolymer resin (FB-1258, tradename, manufactured by Mitsubishi Rayon Co., Ltd.) 91 parts Zirconium compound (Compound No. 1) 1 part Carbon black (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 5 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized by a jet mill and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus, and the electrification distribution was measured by an E-SPART analyzer. Further, an image test by a modified commercial copying machine was also carried out.
• Styrene-acrylic copolymer resin (FB-1258, tradename, manufactured by Mitsubishi Rayon Co., Ltd.) 91 parts Zirconium compound (Compound No. 2) 1 part Carbon black (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 5 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized by a jet mill and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus, and the electrification distribution was measured by an E-SPART analyzer. Further, an image test by a modified commercial copying machine was also carried out.
• Styrene-acrylic copolymer resin (FB-1258, tradename, manufactured by Mitsubishi Rayon Co., Ltd.) 91 parts Zirconium compound (Compound No. 10) 1 part Carbon black (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 5 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized by a jet mill and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus, and the electrification distribution was measured by an E-SPART analyzer. Further, an image test by a modified commercial copying machine was also carried out.
• Styrene-acrylic copolymer resin (CPR-100, tradename, manufactured by Mitsui Chemical Co., Ltd.) 91 parts Charge control agent (T-77, tradename manufactured by Hodogaya Chemical Co., Ltd.) 1 part Carbon black (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 5 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized by a jet mill and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus, and the electrification distribution was measured by an E-SPART analyzer. Further, an image test by a modified commercial copying machine was also carried out.
• Styrene-acrylic copolymer resin (CPR-100, tradename, manufactured by Mitsui Chemical Co., Ltd.) 91 parts Charge control agent (Spilonblack TRH, tradename manufactured by Hodogaya Chemical Co., Ltd.) 1 part Carbon black (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 5 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized by a jet mill and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus, and the electrification distribution was measured by an E-SPART analyzer. Further, an image test by a modified commercial copying machine was also carried out.
• Styrene-acrylic copolymer resin (CPR-100, tradename, manufactured by Mitsui Chemical Co., Ltd.) 91 parts Charge control agent (Borotoron E-84, Tradename, manufactured by Orient Chemical Co., Ltd.) 1 part Carbon black (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 5 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized by a jet mill and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus, and the electrification distribution was measured by an E-SPART analyzer. Further, an image test by a modified commercial copying machine was also carried out.
• Polyester resin HP-301, tradename, manufactured by Nippon Gosei Kagaku K.K.
• Charge control agent T-77, tradename, manufactured by Hodogaya Chemical Co., Ltd.
• Carbon black MA-100, tradename, manufactured by Mitsubishi Chemical Corporation
• Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 160°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized by a jet mill and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus, and the electrification distribution was measured by an E-SPART analyzer. Further, an image test by a modified commercial copying machine was also carried out.
• Polyester resin HP-301, tradename, manufactured by Nippon Gosei Kagaku K.K.
• Charge control agent Spilonblack TRH, Tradename, manufactured by Hodogaya Chemical Co., Ltd.
• Carbon black MA-100, tradename, manufactured by Mitsubishi Chemical Corporation
• Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 160°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized by a jet mill and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus, and the electrification distribution was measured by an E-SPART analyzer. Further, an image test by a modified commercial copying machine was also carried out.
• Polyester resin HP-301, tradename, manufactured by Nippon Gosei Kagaku K.K.
• Charge control agent (Borotoron E-84, tradename, manufactured by Orient Chemical Co., Ltd. 1 part Carbon black (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 5 parts
• Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 160°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized by a jet mill and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus, and the electrification distribution was measured by an E-SPART analyzer. Further, an image test by a modified commercial copying machine was also carried out.
• symbol ⁇ represents "sufficient image density”
• symbol ⁇ represents “fair image density”
• symbol X represents "insufficient image density”.
• symbol ⁇ represents “no fogging”
• symbol ⁇ represents “slight fogging”
• symbol X represents "substantial fogging”.
• symbol ⁇ represents “no scattering”
• symbol ⁇ represents “slight scattering”
• symbol X represents "substantial scattering”.
• Styrene-acrylic copolymer resin (acid value: 0.1) (CPR-100, tradename, manufactured by Mitsui Chemical Co., Ltd.) 91 parts Charge control agent 1 part Zirconium compound (Compound No, 1) (0.05 part) T-77 (tradename, manufactured by Hodogaya Chemical Co., Ltd.) (0.95 part) Carbon black (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 5 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized by a jet mill and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus. Further, the electrification rising property was compared by the time constant. Further, an image test by a modified commercial copying machine was also carried out. The results are shown in Table 3. The electrification rising property was excellent, and a sufficient image density was obtained under all conditions. A high quality image with sufficient reproducibility of a fine line was obtained over a long period of time without fogging.
• Styrene-acrylic copolymer resin (acid value: 0.1) (CPR-100, tradename, manufactured by Mitsui Chemical Co., Ltd.) 91 parts Charge control agent 1 part Zirconium compound (Compound No. 1) (0.10 part) T-77 (tradename, manufactured by Hodogaya Chemical Co., Ltd.) (0.90 part) Carbon black (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 5 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized by a jet mill and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus. Further, the electrification rising property was compared by the time constant. Further, an image test by a modified commercial copying machine was also carried out. The results are shown in Table 3. The electrification rising property was excellent, and a sufficient image density was obtained under all conditions. A high quality image with sufficient reproducibility of a fine line was obtained over a long period of time without fogging.
• Styrene-acrylic copolymer resin (acid value: 0.1) (CPR-100, tradename, manufactured by Mitsui Chemical Co., Ltd.) 91 parts Charge control agent 1 part Zirconium compound (Compound No. 1) (0.50 part) T-77 (tradename, manufactured by Hodogaya Chemical Co., Ltd.) (0.50 part) Carbon black (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 5 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized by a jet mill and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus. Further, the electrification rising property was compared by the time constant. Further, an image test by a modified commercial copying machine was also carried out. The results are shown in Table 3. The electrification rising property was excellent, and a sufficient image density was obtained under all conditions. A high quality image with sufficient reproducibility of a fine line was obtained over a long period of time without fogging.
• Styrene-acrylic copolymer resin (acid value: 0.1) (CPR-100, tradename, manufactured by Mitsui Chemical Co., Ltd.) 91 parts Charge control agent 1 part Zirconium compound (Compound No. 1) (0.80 part) T-77 (tradename, manufactured by Hodogaya Chemical Co., Ltd.) (0.20 part) Carbon black (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 5 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized by a jet mill and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus. Further, the electrification rising property was compared by the time constant. Further, an image test by a modified commercial copying machine was also carried out. The results are shown in Table 3. The electrification rising property was excellent, and a sufficient image density was obtained under all conditions. A high quality image with sufficient reproducibility of a fine line was obtained over a long period of time without fogging.
• Styrene-acrylic copolymer resin (acid value: 0.1) (CPR-100, tradename, manufactured by Mitsui Chemical Co., Ltd.) 91 parts Charge control agent 1 part Zirconium compound (Compound No. 1) (0.05 part) Spilonblack TRH (tradename, manufactured by Hodogaya Chemical Co., Ltd.) (0.95 part) Carbon black (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 5 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized by a jet mill and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus. Further, the electrification rising property was compared by the time constant. Further, an image test by a modified commercial copying machine was also carried out. The results are shown in Table 3. The electrification rising property was excellent, and a sufficient image density was obtained under all conditions. A high quality image with sufficient reproducibility of a fine line was obtained over a long period of time without fogging.
• Styrene-acrylic copolymer resin (acid value: 0.1) (CPR-100, tradename, manufactured by Mitsui Chemical Co., Ltd.) 91 parts Charge control agent 1 part Zirconium compound (Compound No. 1) (0.10 part) Spilonblack TRH (tradename, manufactured by Hodogaya Chemical Co., Ltd.) (0.90 part) Carbon black (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 5 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized by a jet mill and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus. Further, the electrification rising property was compared by the time constant. Further, an image test by a modified commercial copying machine was also carried out. The results are shown in Table 3. The electrification rising property was excellent, and a sufficient image density was obtained under all conditions. A high quality image with sufficient reproducibility of a fine line was obtained over a long period of time without fogging.
• Styrene-acrylic copolymer resin (acid value: 0.1) (CPR-100, tradename, manufactured by Mitsui Chemical Co., Ltd.) 91 parts Charge control agent 1 part Zirconium compound (Compound No. 1) (0.50 part) Spilonblack TRH (tradename, manufactured by Hodogaya Chemical Co., Ltd.) (0.50 part) Carbon black (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 5 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized by a jet mill and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus. Further, the electrification rising property was compared by the time constant. Further, an image test by a modified commercial copying machine was also carried out. The results are shown in Table 3. The electrification rising property was excellent, and a sufficient image density was obtained under all conditions. A high quality image with sufficient reproducibility of a fine line was obtained over a long period of time without fogging.
• Styrene-acrylic copolymer resin (acid value: 0.1) (CPR-100, tradename, manufactured by Mitsui Chemical Co., Ltd.) 91 parts Charge control agent 1 part Zirconium compound (Compound No. 1) (0.80 part) Spilonblack TRH (tradename, manufactured by Hodogaya Chemical Co., Ltd.) (0.20 part) Carbon black (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 5 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized by a jet mill and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus. Further, the electrification rising property was compared by the time constant. Further, an image test by a modified commercial copying machine was also carried out. The results are shown in Table 3. The electrification rising property was excellent, and a sufficient image density was obtained under all conditions. A high quality image with sufficient reproducibility of a fine line was obtained over a long period of time without fogging.
• Styrene-acrylic copolymer resin (acid value: 0.1) (CPR-100, tradename, manufactured by Mitsui Chemical Co., Ltd.) 91 parts Charge control agent 1 part Zirconium compound (Compound No. 1) (0.05 part) T-95 (tradename, manufactured by Hodogaya Chemical Co., Ltd.) (0.95 part) Carbon black (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 5 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized by a jet mill and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus. Further, the electrification rising property was compared by the time constant. Further, an image test by a modified commercial copying machine was also carried out. The results are shown in Table 3. The electrification rising property was excellent, and a sufficient image density was obtained under all conditions. A high quality image with sufficient reproducibility of a fine line was obtained over a long period of time without fogging.
• Styrene-acrylic copolymer resin (acid value: 0.1) (CPR-100, tradename, manufactured by Mitsui Chemical Co., Ltd.) 91 parts Charge control agent 1 part Zirconium compound (Compound No. 1) (0.10 part) T-95 (tradename, manufactured by Hodogaya Chemical Co., Ltd.) (0.90 part) Carbon black (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 5 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized by a jet mill and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus. Further, the electrification rising property was compared by the time constant. Further, an image test by a modified commercial copying machine was also carried out. The results are shown in Table 3. The electrification rising property was excellent, and a sufficient image density was obtained under all conditions. A high quality image with sufficient reproducibility of a fine line was obtained over a long period of time without fogging.
• Styrene-acrylic copolymer resin (acid value: 0.1) (CPR-100, tradename, manufactured by Mitsui Chemical Co., Ltd.) 91 parts Charge control agent 1 part Zirconium compound (Compound No. 1) (0.50 part) T-95 (tradename, manufactured by Hodogaya Chemical Co., Ltd.) (0.50 part) Carbon black (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 5 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized by a jet mill and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus. Further, the electrification rising property was compared by the time constant. Further, an image test by a modified commercial copying machine was also carried out. The results are shown in Table 3. The electrification rising property was excellent, and a sufficient image density was obtained under all conditions. A high quality image with sufficient reproducibility of a fine line was obtained over a long period of time without fogging.
• Styrene-acrylic copolymer resin (acid value: 0.1) (CPR-100, tradename, manufactured by Mitsui Chemical Co., Ltd.) 91 parts Charge control agent 1 part Zirconium compound (Compound No. 1) (0.80 part) T-95 (tradename, manufactured by Hodogaya Chemical Co., Ltd.) (0.20 part) Carbon black (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 5 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized by a jet mill and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus. Further, the electrification rising property was compared by the time constant. Further, an image test by a modified commercial copying machine was also carried out. The results are shown in Table 3. The electrification rising property was excellent, and a sufficient image density was obtained under all conditions. A high quality image with sufficient reproducibility of a fine line was obtained over a long period of time without fogging.
• Styrene-acrylic copolymer resin (acid value: 0.1) (CPR-100, tradename, manufactured by Mitsui Chemical Co., Ltd.) 91 parts Zirconium compound (Compound No. 1) 1.0 part Carbon black (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 5 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized by a jet mill and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus. Further, the electrification rising property was compared by the time constant. Further, an image test by a modified commercial copying machine was also carried out. The results are shown in Table 3. The electrification rising property was good, but no adequate image density was obtained when 50,000 sheets were copied.
• Styrene-acrylic copolymer resin (acid value: 0.1) (CPR-100, tradename, manufactured by Mitsui Chemical Co., Ltd.) 91 parts Charge control agent (T-77, tradename, manufactured by Hodogaya Chemical Co., Ltd.) 1.0 part Carbon black (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 5 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture containing only T-77 as the charge control agent was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized by a jet mill and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus. Further, the electrification rising property was compared by the time constant. Further, an image test by a modified commercial copying machine was also carried out. The results are shown in Table 3. The electrification rising property was poor, and no adequate image density was obtained at the initial stage of printing.
• Styrene-acrylic copolymer resin (acid value: 0.1) (CPR-100, tradename, manufactured by Mitsui Chemical Co., Ltd.) 91 parts Charge control agent (Spilonblack TRH, tradename, manufactured by Hodogaya Chemical Co., Ltd.) 1.0 part Carbon black (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 5 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture containing only Spilonblack TRH as the charge control agent was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized by a jet mill and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus. Further, the electrification rising property was compared by the time constant. Further, an image test by a modified commercial copying machine was also carried out. The results are shown in Table 3. The electrification rising property was poor, and no adequate image density was obtained at the initial stage of printing.
• Styrene-acrylic copolymer resin (acid value: 0.1) (CPR-100, tradename, manufactured by Mitsui Chemical Co., Ltd.) 91 parts Charge control agent (T-95, tradename, manufactured by Hodogaya Chemical Co., Ltd.) 1.0 part Carbon black (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 5 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture containing only T-95 as the charge control agent was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized by a jet mill and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus. Further, the electrification rising property was compared by the time constant. Further, an image test by a modified commercial copying machine was also carried out. The results are shown in Table 3. The electrification rising property was poor, and no adequate image density was obtained at the initial stage of printing.
• Styrene-acrylic copolymer resin (acid value: 0.1) (CPR-100, tradename, manufactured by Mitsui Chemical Co., Ltd.) 91 parts Charge control agent 1 part Zirconium compound (Compound No. 1) (0.03 part) T-77 (tradename, manufactured by Hodogaya Chemical Co., Ltd.) (0.97 part) Carbon black (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 5 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized by a jet mill and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus. Further, the electrification rising property was compared by the time constant. Further, an image test by a modified commercial copying machine was also carried out. The results are shown in Table 3. The electrification rising property was poor, and no adequate image density was obtained at the initial stage of printing.
• Styrene-acrylic copolymer resin (acid value: 0.1) (CPR-100, tradename, manufactured by Mitsui Chemical Co., Ltd.) 91 parts Charge control agent 1 part Zirconium compound (Compound No. 1) (0.85 part) T-77 (tradename, manufactured by Hodogaya Chemical Co., Ltd.) (0.15 part) Carbon black (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 5 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized by a jet mill and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus. Further, the electrification rising property was compared by the time constant. Further, an image test by a modified commercial copying machine was also carried out. The results are shown in Table 3. The electrification rising property was poor, and no adequate image density was obtained at the initial stage of printing.
• symbol ⁇ represents "sufficient image quality”, and symbol ⁇ represents “fair image quality”.
• symbol ⁇ represents "safe”.
• symbol ⁇ represents "slight fogging or slight scattering of toner”.
• Styrene-acrylic copolymer resin (acid value: 0.1) (CPR-100, tradename, manufactured by Mitsui Chemical Co., Ltd.) 100 parts Zirconium compound (Compound No. 1) 2 parts Magnetic powder (average particle size: 0.2 ⁇ m, coercive force: 60 oersted) (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 80 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• the saturation magnetization of this toner was 28 Am 2 /kg, and the coercive force was 60 oersted.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus.
• Styrene-acrylic copolymer resin (acid value: 0.1) (CPR-100, tradename, manufactured by Mitsui Chemical Co., Ltd.) 100 parts Zirconium compound (Compound No. 1) 2 parts Magnetic powder (average particle size: 0.2 ⁇ m, coercive force: 90 oersted) (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 80 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• the saturation magnetization of this toner was 28 Am 2 /kg, and the coercive force was 90 oersted.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus.
• Styrene-acrylic copolymer resin (acid value: 0.1) (CPR-100, tradename, manufactured by Mitsui Chemical Co., Ltd.) 100 parts Zirconium compound (Compound No. 1) 2 parts Magnetic powder (average particle size: 0.2 ⁇ m, coercive force: 140 oersted) (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 80 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• the saturation magnetization of this toner was 28 Am 2 /kg, and the coercive force was 140 oersted.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus.
• Styrene-acrylic copolymer resin (acid value: 0.1) (CPR-100, tradename, manufactured by Mitsui Chemical Co., Ltd.) 100 parts Zirconium compound (Compound No. 1) 1 parts Magnetic powder (average particle size: 0.2 ⁇ m, coercive force; 180 oersted) (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 80 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• the saturation magnetization of this toner was 28 Am 2 /kg, and the coercive force was 180 oersted.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus.
• Styrene-acrylic copolymer resin (acid value: 0.1) (CPR-100, tradename, manufactured by Mitsui Chemical Co., Ltd.) 100 parts Zirconium compound (Compound No. 1) 2 parts Magnetic powder (average particle size: 0.2 ⁇ m, coercive force: 140 oersted) (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 100 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• the saturation magnetization of this toner was 32 Am 2 /kg, and the coercive force was 140 oersted.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus.
• Styrene-acrylic copolymer resin (acid value: 0.1) (CPR-100, tradename, manufactured by Mitsui Chemical Co., Ltd.) 100 parts Zirconium compound (Compound No. 1) 2 parts Magnetic powder (average particle size: 0.2 ⁇ m, coercive force: 140 oersted) (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 120 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• the saturation magnetization of this toner was 36 Am 2 /kg, and the coercive force was 140 oersted.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus.
• Styrene-acrylic copolymer resin (acid value: 0.1) (CPR-100, tradename, manufactured by Mitsui Chemical Co., Ltd.) 100 parts Zirconium compound (Compound No. 1) 2 parts Magnetic powder (average particle size: 0.2 ⁇ m, coercive force: 90 oersted) (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 100 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• the saturation magnetization of this toner was 32 Am 2 /kg, and the coercive force was 90 oersted.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus.
• Styrene-acrylic copolymer resin (acid value: 0.1) (CPR-100, tradename, manufactured by Mitsui Chemical Co., Ltd.) 100 parts Zirconium compound (Compound No. 1) 2 parts Magnetic powder (average particle size: 0.2 ⁇ m, coercive force; 90 oersted) (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 120 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• the saturation magnetization of this toner was 36 Am 2 /kg, and the coercive force was 90 oersted.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus.
• Styrene-acrylic copolymer resin (acid value: 0.1) (CPR-100, tradename, manufactured by Mitsui Chemical Co., Ltd.) 100 parts Zirconium compound (Compound No. 1) 2 parts Magnetic powder (average particle size: 0.2 ⁇ m, coercive force: 300 oersted) (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 80 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• the saturation magnetization of this toner was 28 Am 2 /kg, and the coercive force was 300 oersted.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus.
• Styrene-acrylic copolymer resin (acid value: 0.1) (CPR-100, tradename, manufactured by Mitsui Chemical Co., Ltd.) 100 parts Zirconium compound (Compound No. 1) 2 parts Magnetic powder (average particle size: 0.2 ⁇ m, coercive force: 90 oersted) (MA-100, tradename, manufactured by Mitsubishi Chemical Corporation) 150 parts Low molecular weight polypropylene (Biscoal 550P, tradename, manufactured by Sanyo Kasei K.K.) 3 parts
• the above mixture was melted and kneaded by a heat-mixing apparatus at 140°C, and the mixture was cooled and roughly pulverized by a hammer mill. It was further finely pulverized and then classified to obtain a black toner having a particle size of from 10 to 12 ⁇ m.
• the saturation magnetization of this toner was 52 Am 2 /kg, and the coercive force was 90 oersted.
• This toner was mixed with a silicon coated ferrite carrier (F96-100, tradename, manufactured by Powder Tech Co.) in a weight ratio of 4:100, and the mixture was shaked to negatively electrify the toner. Then, the charge was measured by a blow off charge measuring apparatus.
• symbol ⁇ represents "sufficient image quality”
• symbol X represents "insufficient image quality”.
• symbol ⁇ represents "good fixing property”
• symbol X represents “poor fixing property”.
• symbol ⁇ represents "no fogging or scattering of toner”
• symbol ⁇ represents “slight fogging or slight scattering of toner”
• symbol X represents "substantial fogging or substantial scattering of toner”.
• the zirconium compound of the formula (1) to be used in the present invention is a colorless or slightly colored thermally stable compound which can be uniformly dispersed in a binder resin, and thus it always presents an image of high quality even when it is used in a recycling system.
• the zirconium compound of the formula (1) to be used in the present invention is a colorless or slightly colored highly stable compound, and by using it in combination with a specific azo metal complex, it is possible to present an electrostatic image developing toner having an extremely quick electrification rising property, whereby it is possible to always present an image of high quality from the initial stage of printing.
• the magnetic toner employing the zirconium compound of the formula (1) to be used in the present invention it has been made possible to present an electrostatic image developing toner which is excellent in the electrification rising property and which is capable of presenting an image of a sufficient image quality under all conditions.

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• 2000
  • 2000-03-02 EP EP00104385A patent/EP1035448A1/de not_active Withdrawn

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