Developer composition

[Detailed Description of the Invention]

Field of the Invention The present invention relates to the development agent constituent which visualizes the electric latent image which opens in electro-photography, electrostatic record, etc., and an electric signal, and relates to the development agent constituent which was excellent in negative triboelectric charging, phenomenon nature, and transfer nature especially. PRIOR ART although various kinds of methods, such as friction, the contact charging method, an ion irradiation method, an electrostatic induction method using conductivity, and an electric charge injection method, are known, being the easiest to use and being used widely rubs and is in the method of giving an electric charge to a development agent (toner), and Do -- it is -- it is by the contact charging method. In this case, in order to give an electric charge to a toner as a development agent to be used, friction electrification of an electrification braid, an electrification roll besides a two-ingredient optical image agent, etc. which mixes with a toner the career particles charged in a toner and reverse 4 Eternal nature, and a toner is used, or the one-ingredient development agent using friction electrification between toners is known. When a toner is charged in such contact electrification and friction electrification, the substance of electron release nature or the substance of electronic suction nature is added, and the necessity of performing electrostatic property control is in the electric charge grant materials side, such as the toner side or a career, and a braid. Although friction electrification development is complicated and a slot is not necessarily clear in the meantime, generally as for an electron release substance, an electronic suction substance is just charged negatively. In order to perform electrification control of a toner conventionally, it is on the inside of a (i) toner, or the toner particle surface, Dye customer, Interface [1 agent, non-Sen: Means which carry out addition mixture of the end of Dress, etc. to use the resin-like substance which has a functional group of A sum Genn, such as -COO A 1, -CN, and -CN, -N O2, and -\1-12 grade as (ii) binding resin were taken. An invention or the problem which it is going to solve However, depending on these means, it does not succeed in control of the temporal stability of toner electrostatic property, and environmental stability, and has not reached the level which is made as for @ leg. Thing with a colorless or light-colored sufficient electrification control agent which can be used for color is not known. Therefore, the thing for which the object of the present invention provides a development agent constituent with an early standup of toner electrification, The development agent constituent in which it is possible and electric charge distribution is sharp is provided [ control of the amount of electrifications of a toner, or ], The development agent constituent which was excellent in the environmental stability of toner electrification and temporal stability is provided, Therefore, it is To shite for providing development nature, transfer nature, or the development agent constituent that is improved and guarantees always good image quality, and providing the development agent constituent which uses the colorless or light-colored electrification control agent which can be used for formation of a color image. Colorant and binding resin of the means for solving a problem and the object of describing the operation present invention above were in the development agent constituent which becomes as the main ingredients 43, and they were achieved by using the polymeric mass which has the sulfonic acid base combined with the aromatic ring. As the polymeric mass which has the sulfonic acid base combined with the aromatic ring used in the present invention, The sulfonic group directly combined with aromatic rings, such as the Ben Seng ring and a naphthalene ring, The polymer which h Carries out the basis which neutralized with the cationic ingredient and took the form of salt is meant, and it is as a cation of a cationic ingredient, Na, K , Zn"+, Ca2+, M 1+ (the metal cation of the --+ value of J" and A134 grade or Many value, ammonium ion, alkylammonium ion, pyridinium ion, quinolinium ion, imidazolium ion, etc. are raised.) Need to does not have at a kind a cation ingredient in the sulfonic acid base combined with the aromatic ring opened in the present invention, and it may be used in two or more sorts of cation ingredients. These polymeric masses are an independent polymer, a random copolymer, a graft copolymer, a block copolymer, and a mutual sedimentary intrusion type copolymer (the thing of which form of IPN> may be used.). This is compounded as follows, for example. 1) Or [ polymerizing vinyl aromatic-sulphonic-acid salt, such as Na salt of vinyl benzenesulfonic acid, Zn salt, and ammonium salt, ], Or it is an ionic exchange reaction further about the polymeric mass compounded by other single 8 bodies, for example, styrene, methacrylate, acrylate, Diene, the method of Co-mating(ing), and the method of 2 above-mentioned], How to combine directly the compound which has the sulfonic acid base combined with the aromatic ring with the method and three polymeric masses which are replaced by other cations by a chemical reaction. The above-mentioned polymeric mass in the present invention is glass-transition-temperature TQ>=50'C, although the thing of arbitrary molecular weights is used according to the object, and the thing of number average Molecule Mn<=10.000 is used advantageously. moreover -- Common of the sulfonic acid base combined with the aromatic ring is the molar concentration based on the monomeric unit which has the sulfonic acid base combined with ''7'J Aromatic ring to the toner binding resin whole quantity -- about 0.01-mol % -- ~ about 10-mol %, preferably about 0.1 -- it is preferred that it is mol %~5 mol %. the above-mentioned polymeric mass in the present invention -- t -- it Fat calculus *1 and may use independently in itself, and it may mix with other polymer and may use. the case where it mixes -- 1 -- various methods, such as fusion mixture, solution mixture, a coexistence polymerization, and emulsion mixture, are applicable. As other binding resin, arbitrary things, such as a Styrene system, acrylic, an olefin system, polyester, epoxy, polycarbonate, polyamide, polyurethane, a silicone series, a fluorine system, and oil system fat, can be used. In the development agent constituent of the present invention, a publicly known thing can be used as an ingredient of 5-color Removal. for example, as colorant, use dye and paints, such as carbon black, cyanogen, magenta, and a yellow color, and include inorganic substances, such as magnetic bodies, such as the Slack ferrite, an electric conduction 1 student adjustment agent, and a metal oxide, a reinforcement bulking agent, an antioxidant, etc. -- things are made. A publicly known electrification control agent may be used together. An external additive may be used for the development agent constituent of the present invention. As an external additive, conventionally publicly known things, such as silica, carbon, alumina, titanium oxide, a zinc oxide, resin fine powder, and tin oxide, are used. In the phenomenon agent constituent of the present invention, a toner can be manufactured by publicly known arbitrary methods, such as the kneading Shredding method, the spray-drying method, and a direct polymerization method. The particle diameter of a toner is in the range of 5 micrometers ~ 15 micrometers preferably and more preferably about whether it is in the range whose average particle size d50 measured by the Coulter counter method is 1~20 micrometers. EXAMPLE Next, the present invention is not limited by this etc. although an example explains the present invention. Example 1 Styrene, /n-butyl meta-Clear It is a copolymer to amount part of 60 hands-1. (Dish low 65 degreeC1Hn=30000. Hw = 70000 > styrene / amount part Bon acid Na copolymer of vinyl Benzenesulf 30 hands) (About 3m01% of vinyl benzene Sulfone MNa.) Tq=75degreeC, Hn=7000, and hv=10000 carbon black The ingredient of the amount part above of 10 hands was mixed and ground, the particle diameter d 50=13micrometer toner was adjusted, and the amount of electrifications was measured. It is to Sy and a Dress career under low-humidity/temperature (10'C, RH20%) and high temperature quantity 9ToothC and RH80% of all the environment, When abbreviation-30microc/g and a high electrification gutter were shown and the standup of electrification moreover measured electric charge distribution by the early and charge Spectrograph method extremely, electric charge distribution was sharp and the reverse polarity toner was not seen at all. Although the amount of electrifications was similarly measured to the career covered with the A mesh methacrylate system copolymer, abbreviation-35microC/SJ and high Charging were indicated to be also all the environment, and electric charge distribution was also very sharp. the acrylic resin fine powder compounded to this toner by about 0.7% of the weight of hydrophobic silica fine powder, and soap free emulsification polymerization -- about 0.8 -- pile skewer % -- carrying out addition mixture When it was considered as the phenomenon agent in combination with the career and the run test was done by copying machine FX-2300 (made by Fuji Xerox, Inc.), also by the continuation copy test of 30000 sheets, image quality change was not seen, but also to environment, it was stable and the very good copy was obtained. Example 2 Attach hO mixture of 1.0% of the weight of the hydrophobic silica fine powder was carried out, and the - ingredient phase [a development agent was adjusted to Dub- of Example 1. the place which mounted this phenomenon agent in one-ingredient Developing equipment 100 of the following composition, and did the run test with the copying machine FX-2300 modified machine -- between the continuation copy tests (cheer up -- the good copy which carried out The stable was obtained.) of 10000 sheets, The amount of electrifications of a toner sampled from the present @ machine is abbreviation-15microC/g. And electric charge distribution was also very sharp. One-ingredient development device (it consists of 1> bridge construction phenol resin, a reinforcement agent, and carbon black), The development roll of diameter 20 willow which has a surface coat of electric resistivity about 10 omega-cm, (2) The toner fountain roll which consists of conductive rubber which supplies a toner on a development roll, And it comprises a braid which has a surface coat which consists of the silicone rubber, reinforcement agent, and electrification control agent which regulate the layer thickness of the toner supplied on the phenomenon roll by (3) toner fountain roll, and give an electric charge to a toner. In this - ingredient development device, with the braid which was mainly mechanically supplied to the development roll by the toner fountain roll, and was welded by pressure to the development roll after that, a toner is charged, and forms the toner layer of Kofu mostly on a development roll, and is conveyed and developed by the electrostatic latent image part by mirror-power. Example 3 Adjusting the styrene / vinyl benzene Sulfone MZrl copolymer which is by the toner component of Example 1 and which replaced Na+ of Styrene / ' vinyl benzenesulfonic acid \a copolymer by 1/2Zn"+, others obtained the particle diameter d50=13micrometer toner by the same prescription as Example 1. When the amount of electrifications of this toner was measured like Example 1, abbreviation-20microC/g and the good amount of electrifications were presented in all the environments to the iron powder system career. Although absolute Field of the amount of electrifications was slightly low compared with the toner of Example 1, the sharpness of an environmental stability i student and electric charge distribution was further excellent in the direction of this toner. the place which added 0.5% of the weight of fatty acid metal salt to this toner, and was mixed with 8% of 0.7-fold hydrophobic silica fine powder to it, and also was mixed with the career, and did the continuation copy test of 30000 sheets by copying machine FX-2300 -- Example 2 -- the same (cheer up -- the picture with good The was obtained.) Example 4 10@1 copy of car phone black of the toner of Example 1 -- (C, 1, Piament Blue 15:3) cyanogen paints magenta paints (C, 1, Pigment Red 57:1) yellow paints (C, 1, Pigmerit Yellow 12) each, It replaced at 5 weight sections and made three sorts of particle diameter d50=13micrometer color toner as an experiment. the place which was alike and measured electrification ♀ to the iron powder system career like Example 1 -- cyanogen, magenta, and 3 colors of yellow toner To -- about [ The ] -- the amount of high electrifications which was very well equal to -50~-60tiC/7 was shown, and the standup of electrification, the sharpness of electric charge distribution, and environmental stability were also still better. It is a very surprising thing for the above-mentioned three-primary-colors paints to cover the bad influence to the electrostatic property of paints in this way, although cyanogen is usually known as paints of positive-triboelectric-charging, magenta, and yellow 1 Good negative chargeability, and for electrification control to be attained. And a copolymer containing vinyl benzenesulfonic acid Na of the present invention is water-white resin. A bad influence does not give at all a color tone of color toner, and the optical characteristic. Addition mixture of 0.7 % of the weight of hydrophobic silica fine powder fatty acid Gold bending salt 0.8 Accusation % was carried out at the above and three sorts of toners, respectively, and also it mixed with the ferrite career by 6% of toner density, and adjusted the 3-color color 1 agent. When the run test was done by copying machine F X-2300, in a 3-color toner, color-enhancing good color copies are jW Was done stably very much by the continuation copy test of 10000 sheets each. Example 5 Nam and the ammonium salt mixture copolymer of the styrene / vinyl benzene Shimonoseki which replaced a part of Na of the styrene / vinyl benzene Sulfone fli N a copolymer which is the toner Evening material of Example 1 by NH4+ are adjusted, Others are the same prescription as Example 1, and obtained the toner of particle diameter d 50= 13micrometer. When the amount of electrifications of this toner was measured like Example 1, abbreviation-25microC/9, and good electrostatic property were shown in all the environments to the iron powder system career. The standup speed of electrification and the sharpness of electric charge distribution are also very good, and rash. Addition mixture was carried out, and also 0.7ffifit% of hydrophobic silica fine powder and 0.5@ffN% of fat In carat Flexion salt were carried out to a career, and mixture and present 9^11, and the continuation copy test of 30000 sheets was done on this toner by copy 1Fx-2300, or good image quality was obtained by eye Longing. Example 6 Styrene/butyl acrylate 50-weight section copolymer (TIj=65degreeC and Mn=170000) Iw=420000 styrene / butyl acrylate / 35-fold i section vinyl benzene Sulfone MZn Copolymer (Ti;]=60degreeC) fn=7000 Hw=15000> (vinyl benzenesulfonic acid Z verbal promise 2mo1%) low-molecular-weight-polypropylene wax Five rice water part carbon black The ingredient of the 10 hand i section above was mixed and ground, and the particle diameter d 50=12micrometer toner was adjusted. When electrification ♀ was measured like Example 1, abbreviation-20microC/g and stable electrostatic property were shown in both all the environments to both a Iron cast system career and methyl methacrylate system copolymer covering Kitoria. Of course, the standup speed of electrification of early and electric charge distribution was also sharp, and reverse ~ and [student toner was not seen at all. It is although the amount of electrifications was similarly measured to the ferrite career (particle diameter 70 micrometers) which covered silicone series resin, and the ferrite career which covered the copolymer of a par 70 Loakli rate and methyl methacrylate, In toner density and about 5%, electrification ♀ of abbreviation-15microC/9~-20 uc/g was shown, and very good and stable electrostatic property was carried out Sure delta2. Further, to this toner, the amount % of acrylic resin fine powder 0.5 shells was added, and it mixed with 0.7 % of the weight of hydrophobic silica fine powder to it, combined with the previous silicone series resin coating career, and did the run test by the product made from copying machine FX-2830< Fuji Xerox Even number @. Stability and a very good copy are always 19 Was done between the copy tests of 50000 continuation. Comparative example 1 Styrene / n-butyl Methacrylic 90-fold ff1i section rate copolymer (Tg = 65"C, Hn=30000) IW=70000 > carbon black It kneaded and ground, the part class of the 10-weight section above-mentioned ingredient was carried out, and the particle diameter d50=13micrometer toner was adjusted. the place which measured addition mixture () and the amount of electrifications for 3 weight sections of the above-mentioned toners on 100 weight sections of iron powder careers of d= 100 micrometers of particle diameter -- the ratio of A ladle-7microC/g -- it was obtained in the electrification question. It is fi about environmental dependence of the amount of electrifications! When the private seal was carried out, the fall of the amount of electrifications was conspicuous under high humidity. When electric charge part A I was measured by the charge Spectrograph method, electric charge distribution was large and there were many reverse polarity toners. All the environment of the standup of the amount of electrifications was late. Comparative example 2 Styrene / n-butyl Methacrylic 88-weight section rate copolymer (T (]=65degreeC and Hn=30000. Hw=70000> dodecylbenzenesulfonic acid Na 2-weight section car phone black)) The 10-weight section above-mentioned ingredient is mixed and ground, and it is 19 about the toner of 50 = 13 micrometers at particle diameter. When the amount measurement of electrifications was carried out at comparative example] and ri1 Ja, electrostatic property almost equivalent to comparative example 1 was usually indicated to be abbreviation-7microG /"i in the environment. However, the electrostatic property under highly humid was still larger than comparative example 1, and when it measured electric charge distribution, it was a Is teratogenic toner. The standup of electrification was almost comparable as comparative example 1 seemingly. EFFECT OF THE INVENTION Since the development agent constituent of the present invention contains the polymeric mass which has the sulfonic acid base combined with the aromatic ring as a Fostering resinous principle, it is excellent in negative triboelectric charging, development nature, and transfer nature. That is, the standup of toner electrification is possible for control of the amount of electrifications of early and a toner, and the development agent constituent of the present invention has sharp electric charge distribution, and the environmental stability of toner electrification is excellent, and temporal stability is also excellent. Therefore, it is improved in the development nature in the conventional development agent constituent, and transfer nature, and the copy of always good image quality is obtained. Common, since the above-mentioned polymers are colorlessness thru/or light color, the development agent constituent of the present invention which will be effective in formation of a color image as for the development agent constituent of the present invention is applicable to both the two-ingredient developing-negatives method for using a career, and one-ingredient Image formation method which does not use a career.