Title of Invention	A METHOD OF PRODUCING A POLYMER FOR USING AS A CHARGE CONTROLLER OF A TONER
Abstract	57) Abstract: The invention relates to a method of producing a polymer for using as a charge controller of a toner. An ethylenically unsaturated first monomer having an aromatic ring substituted with at least one electron-attractive group selected from the class consisting of a halogen atom, nitro group and cyano group with or without another monomer, and/or an ethylenically unsaturated second monomer having an organic acid group or salt thereof is polymerized with another monomer to obtain a polymer having a dielectric loss tangent of 0.008 to 0.3 at 100 KHz and a water absorbancy of at most 10% by weight. PRICE: THIRTY RUPEES.

Title of Invention

A METHOD OF PRODUCING A POLYMER FOR USING AS A CHARGE CONTROLLER OF A TONER

Abstract

57) Abstract: The invention relates to a method of producing a polymer for using as a charge controller of a toner. An ethylenically unsaturated first monomer having an aromatic ring substituted with at least one electron-attractive group selected from the class consisting of a halogen atom, nitro group and cyano group with or without another monomer, and/or an ethylenically unsaturated second monomer having an organic acid group or salt thereof is polymerized with another monomer to obtain a polymer having a dielectric loss tangent of 0.008 to 0.3 at 100 KHz and a water absorbancy of at most 10% by weight. PRICE: THIRTY RUPEES.

Full Text	The present invention relates to a method of producing a polymer for using as a charge controller of a toner. Previously an addition of a charge controller for the purpose of controlling electrostatic charge of electrophotographic toner has been employed. As charge controllers chargable negatively among charge controllers previously known there have been known azo dye stuff compounds, salicylic acid-metal complexes and the like. As improved compounds, such polymer Compounds are proposed as follows : (1) Copolymer of styrene and sodium salt of vinyl benzensulfonic acid (Japanese Patent KOKAI No.88564/1985). (2) Combination of a polymer of perfluoroalkylethyl aery late and copolymer of styrene, methyl acrylate and 2-acrylamide-2- methylpropanesu1fonic acid (Japanese Patent KOKAI No. 230609/1994), (3) Block copolymer of methyl methacrylate and methacrylic acid (USP4,925.765). However, by using the polymer compounds disclosed in (l)-(3), as the electrostatic charge of the toner is poor, a lot of charge contoller is required and it is not economical. And it impairs other properties required in toner (low temperature fixing properties, anti-hot offset properties and the like). The charging rate (stirring period using a frictional force when the charge reaches a required charge amount) is also inadequate. Therefore a longer warming-up time of a copying machine is required and a copied image becomes bad in case of continuous copying. The change of charge by humidity is large and environmental stability is inadequate. Furthermore, as the transparency is poor when toner is formulated, bad influences to the color tone is observed in applying color toner. It is an object of the present invention to provide an essentially colorless charge controller containing no metal. Another object of the invention is to provide a charge controller having excellent properties concerning the electrostatic charge amount, the charging rate and the environmental stability of toner. Still another object of the invention is to provide charge controller having no problem concerning the above-mentioned dispersing properties and transparency. Accordingly the present invention provides a method of producing a polymer for using as a charge controller of a toner said method comprising polymerizing an ethylenically unsaturated first monomer having an aromatic ring substituted with at least one electron-attractive group selected from the class consisting of a halogen atom, nitro group and cyano group with or without at least one other monomer, and/or an ethylenically unsaturated second monomer having an organic acid group or salt thereof with at least one other monomer to obtain a polymer having a dielectric loss tangent of 0.008 to 0.3 at 100kHz and a water absorbancy of at most 10% by weight, said other monomer being selected from the class consisting of a perfluoroalkyl group-containing monomer, a silicone group-containing monomer, an olefin, a vinyl ether, an aromatic vinyl hydrocarbon (meth)acrylic acid, a (meth) acrylate, a diene, a vinyl ester and a nonomer having nitrile group. r These and other objects of the present invention will become more readily apparent from the description hereinafter. SUMMARY OF THE INVENTION Briefly the above-mentioned objects of the present invention have been attained broadly by the following [l]-[3] aspects of the invention. [1] k charge controller for a toner which comprises a polymer of an ethylenica 1 1 y unsaturated monomer, said polymer having a dielectric loss tangent [tan d] at 1OOkHz of 0.008 to 0.3 and a water absorbancy of at most 10% by weight, and selecte from the class consisting of : (1) a polymer (Al) of a monomer (1) having an aromatic ring substituted with at least one electron-attractive group (X) selected from the class consisting of a halogen atom, nitro grou and cyano group; and (2) a copolymer (A2) of a monomer (2) having an organic acid group or salt thereof, with another monomer. [2] A toner binder composition, which comprises said charge controller and a toner binder resin. [3] A toner, which comprises a toner binder resin, a colorant and said charge controller. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS According to the present invention, a dielectric loss tangent [tan d ] at 100 kHz is measured as following: A polymer is pulverized into powders of average diamete of not more than 50 ,u with an agate mortar, and a test piece is prepared by compression molding in an electrode for dielectric loss tangent-measurement. The test piece is set to an equipment for the measurement with the electrode, and both conductance and capacitance at 100 kHz are measured, followed by measuring its thickness. The dielectric loss tangent is calculated from the conductance, capacitance and thickness thus measured. A suitable value of dielectric loss tangent is generally in the range of 0.008-0.3, preferably 0.008-0.2, more preferably 0.015-0.1. Polymers having less than 0.008 of dielectric loss tangent may cause insufficiency of charging rate, while polymers having more than 0.3 may result in shortage of the electrostatic charge amount of toner. According to the present invention, a water absorbancy {%) is measured as following: In a same manner as above-mentioned a polynier is pulverized into powders of average diameter not more than 50 u JR with an agate mortar. After drying 2g of the tested powder under reduced pressure at 35°C for 4 hours, followed by control of the moisture of 85 % R.H. at 35°C for 12 hours. Thereafter a weight is measured again and the water absorbancy i%) is calculated from the percentage of an increase of weight (the difference between the weight of after drying and that of before drying) per the weight of before drying. Water absorbancy (%) is generally in the range of at most 10 % by weight, preferably at most 5% by weight, more preferably at most 2 % by weight. Polymers having less than 10 % by weight of water absorbancy nay result in poor environmental stability. Suitable polymers of the invention include polymer (A) of one or more ethylenica 11y unsaturated monomers. Suitable polymers (A) include : (1) polymers (Al) of a monomer (1) having an aromatic ring substituted vith at least onee 1 ectron-attractive group (X) selected from the class consisting of a halogen atom, nitro group and cyano group ; and (2) copolymers (A2) of a monomer (2) having an organic acid group or salt thereof, with one or more other monomers. Suitable electron-attractive groups (X) include, for example, halogen atoms (such as chlorine atom, bromine atom, iodine atom and fluorine atom), nitro group and cyano group. Among these, chlorine and nitro group are preferable Suitable examples of monomer (1) having an aromatic ring substituted with at least one electron-attractive group (X) include : styrenes (such as chlorostyrenen, dichlorostyrene, bromostyrene, f1uorostyrene, nitrostyrene, cyanostyrene) ; aromatic ring-containing maleiraides (such as chloropheny 1-maleimide, dich1oropheny1maleimide, nitrophenyImaleimide, nitroch1orophenyImaleimide); aromatic ring-containing itaconimides (such as ch1oropheny 1 itaconiraide, dich1oropheny1-itaconimide, nitropheny1itaconimide, nitrochlorophenyl-itaconimede); aromatic ring-containing (meth)acry1ates (represent acrylate and methacry1 ate, similar expression are used _hereinafter)(such as chlorophenyl (meth)acrylates, bromophenyl (meth)acry1ates, nitrophenyl (meth)aerylates, chl oropheny loxyethyl (Bieth)acry lates, bromopheny loxyethy ! (iDeth)acry 1 ates, n i tropheny 1 oxyethy 1 (meth) aery 1 ates); aromatic ring-containing (nieth)acry lam ides (such as ch 1 oropheny I-(me th)acry 1 am ides, bromopheny 1 (me th)acry 1 am i des, n i tropiieny 1-(nieth)acry! am i des) ; and aromatic ring-containing vinyl ethers (such as chlorophenyl vinyl ether, nitrophenyl vinyl ether). Among these, preferred are aromatic ring-containing maleimides and aromatic ring-containing itaconimides. Polymers (AD include both horaopolymers or copolymers of at least one said monomer (1), and copolymers of monomer (1) with one or more other copolyraerizable monomers. Suitable examples of copo1yraerizable monomers include monomers (2) having an organic acid group or salt thereof, perf1uoroalkyi group-containing monomers (3-1), silicone group-containing monomers (3-2) and other copolymerizable monomers (4), as well as combinations of two or more of these (ncnomers are pref erab 1 e. Copolymers of said monomer (1) with said monomer (2) are preferable because charging rate of toner is fast. Copolymers of said monomer (1) with said monomer (3-1) or said monomer (3-2) are preferable because they improves charge amount, charging rate and environmental stability of toner. Copolymers (A2) include copolymers of said monomer (2). with one or more other iBonomers. Suitable examples of monomer (2) include sulfonic acid group-containing monoaers (2-1), carboxylic acid group-containing monomers (2-2), sulfaaic acid group-containing monomers (2-3). acid sulfate group-containing nonomers (2-4), acid phosphate group-containing uonoiiiers (2-5) and salt thereof. Suitable examples of monomer (2-1) include aromatic sulfonic acid group-containing monomers (such as styrenesulfonic acid, su1fophenylacry 1 amide, su 1 fophenyImaleimide, sulfophenyl-itaconimide), aliphatic sulfonic acid group-containing monomers (such as VinyIsu1fonic acid, al1yIsulfonic acid, 2-acry1 amide-2-methy1propanesu1fonic acid, methacry1oyloxyethy Isu1fonic acid), and the 1 ike. Suitable examples of monomer (2-2) include (meth)aery 1ic acids, maleic acid, itaconic acid, monobutyl maleate, monoperf1uoroalky1ethy1 maleate, monoperf1uoroalky1ethy1 i taconate and the 11ke. Suitable examples of monomer (2-3) include a 11y1su1famic acid, styry1sulfamc acid, viny 1 su1famic acid and the like. Suitable examples of monomer (2-4) include surfuric monoester of hydroxy group-containing monomer (such as hydroxyethyl (meth)acry1ates, hydroxyethyl vinyl ether, vinyl pheno 1) and the 11ke. Suitable examples of monomer (2-5) include phosphoric raonoesters or diesters of the above-mentioned hydroxy group-containing monomer and the like. Suitable examples of salts of said monomer (2) include those of alkali metal (such as lithium, sodium, potasium), alkaline earth metal (such asmagnesium, calcium, barium), amines (such as tr i ethy lami ne, tr ibuty lami ne, N, N-d imeth.y 1 benO'J anLiiLeX, quarternary ammoniums (such as tributy1benzylammonium, tetraethylammonium, tetrabutylanmonium) and the like. Among these, monoiers having a salt of an organic acid group is preferred to monomers having an organic acid group. And among these, preferred are monomers having a salt of an alkali metal, an alkaline earth metal or amine. As regard to the kind of acid group, preferred are said monomers (2-1),(2-2) and (2-4), in particular, monomer (2-1). Namely, among these, most preferred are an aromatic sulfonic acid group-containing monomers in the form of an alkali metal, alkaline earth metal or amine salt. A salt of heavy metals (such as nickel, copper, zinc, mercury, chromium) is undesirable because of safty. Suitable examples of perf 1 uoroa Iky 1 group-containig fflonoaers (3-1) include perfIuoroa1kyIetyienes, perfluoro-alkylethyl (meth)acry1ates, mono(perf1uoroa 1 ky lethy1) maleates, mono(perf1uoroa1ky!ethyl) itaconates and the like. Suitable examples of silicone group-containig monomers (3-2) include esters of (meth)acry1ic or maleic acids with terminal hydroxyl group-modified silicone oil; amides and imides of (raeth)aery 1ic or maleic acids with terminal amino group-modified silicone oil and the like. Among these monomers (3), perf1uoroaIky I group-containig monomers are prefferred. Those monomers having C8-16 of a perfIuoroalkyI group are more paticularly prefarable. Suitable examples of other copo lymerizable monomers (4), other than said monomer (3) includ.e olefins (such as ethylene, propylene, 1-butene, isobutylene. dodecene); vinyl ethers (such a.s iDPthvl vinyl ether.butyl vinyl ether, stearyl vinyl ether); •aromatic vinyl hydrocarbons (such as styrene. a -methyistyrene, p-cuiny I styrene) ; (nieth)acry 1 i c acids ; a (nieth)acry 1 ates (such as methyl (meth)aery Iates, ethyl (meth)acry1ates, butyl (ineth)acry! ates) ; dienes (such as butadiene, isoprene); a vinyl esters (such as vinyI acetate, vinyl propionate); a monomer having nitrile group (such as (leth)aery Ionitri1es): and the like. Polymer (Al) generally contains the units of said monomer (1) in an amount of at least 5 X by weight, preferably at least 10 % by weight, more preferably 20-89 % by weight, in view of providing sufficient amount of charge of toner. Polymer (Al) generally contains the units of said monomer (2) in an amount of 0-20 % by weight, preferably 0.1-20 % by weight, more preferably 1-10 % by weight. Polymer (Al) generally contains the units of said monomer (3) in an amount of 0-95 % by weight, preferably 10-90 % by weight, more preferably 10-79 % by weight. Polymer (Al) generally contains the units of said monomer (4) in an amount of 0-95 % by weight, preferably 0-50 % by weight, more preferably 0-30 % by weight. Copolymers (A2) include copolymers of said monomers (2) with one or more other copolymerible monomers. Suitable examples of copo1ymerizable monomers with monomer (2) include monomers (3-1), monomers (3-2), and monomers (4) the above-mentioned. Suitable examples and more suitable examples may be the same as mentioned above with respect to polymers (Al). Copolymers of monoBer (2) with monomer (3) are preferred because they improves toner properties such as charge amount, charging rate and environmental stability of toner. Polymer (A2) generally contains the units of said monomer (2) in an amount of at least 0.1 % by weight, preferably 0.1-20 % by veight, more preferably 1-10 % by weight. In case of less than 0.1 % content by weight, a dielectric loss tangent becomes smaller and charging rate of toner may be inadequate. In case of larger amount, a dielectric loss tangent becomes larger , and charge amount and environmental stability of toner may be inadequate. According to the present invention, polymer (A) has a weight-average molecular weight of generally 1,000 to 500,000, preferably 2,000 to 200.000. In case it is jess than 1.000, it becomes compatible with the binder and charge amount is insufficient. Meanwhile, in case it is more than 500,000, it becomes difficult to disperse polymer (A) in the toner. In prefarable embodiments of the invention, besides the above-mentioned polymer (A), is used a copolymer (AB) comprising a polymer moiety (a) of polymer (A) selected from the class consisting of polymer (Al) of at least one containing an aromatic ring substituted with at least one electron-attractive group (X) selected from the class consinting of a halogen atom, nitro group and cyano group ; and copolym.er (A2) of a containing an organic acid group or sa1t thereof ; and a polymer moiety (b) of at least one polymer (B) selected from the class consisting of styren ic po lymer (B1) and polyester (B2) ; the moiety (b) being bound graft-wise or block-wise to the mo 1ety (a). Preferred is (AB) as the particles of the discotinuous domains formed with moiety (a) in the toner can be easily formed i n a sraal 1 s i ze. Suitable styrenic polymers (Bl) include either styrene homopolymers and copolymers of styrene with another copoIymerizab le monomer (6). Suitable examples of the other copolymerizable monomer (6) include aromatic vinyl hydrocarbons other than styrenes, (meth)acry1 ic monomers and other vinyl monomers. Suitable examples of the other aromatic vinyl hydrocarbons include alkyl substututed styrenes (such as a-methy 1styrene, p-methy1styrene, p-cumyIstyrene); halogenated styrenes (such as ch1orostyrene, ch1oromethyIstyrene ); acetoxystyrene, hydroxystyrene and the like. Suitable examples of (meth)aery 1 ic monomers include alkyi substituted (raeth)acryiates (such as methyl (meth)aery 1ates , ethyl (meth)acry lates, butyl (meth)acryI ates. 2-ethy!hexy! (meth)acry1ates, lauryl (meth)acry1ates, stearyl (meth)acrylates) ; hydroxyl group containing (neth)acryIates (such as hydroxyethy 1 (meth)acrylate) ; epoxy group containing _____ (meth)acry1ates (such as glycidyl (meth)acry lates); isocyanate group con tai n i ng iDonoiiiers (such as methacryloyl isocyanate) : and nitrile group containing monomers (such as (nieth)acry 1 on i tr i 1 e) and the I i i Suitable examples of the other vinyl monomers include : vinyl esters (such as vinyl acetate, vinyl propionate);diene monomers (such as butadiene, isoprene); halogenated olefin (such as vinyl chloride, vinyl bromide); a . j3 -ethy 1 en ica 1 ly unsaturated mono or po1ycarboxy 1 ic acids (such as (meth)aery 1ic acids, crotonic acid, sorbinic acid, raaleic acid, itaconic acid, synnamic acid); anhydrides thereof (such as maleic anhydride); half esters thereof (such as monomethyl maleate) and the like. Among thses, preferable styrenic polymer (Bl) are styrene hofflopolyraers, copolymers of styrene vith (meth)acryIic monomers, copolymers of styrene wuth diene monomers, and copolymers of these monomers with a small amount of other copolymerizab I e monomers. Styrenic polymer (B2) generally contains the units of styrene in amount of not less than 40 % by mol. and preferably 60 % by mol.. According to the present invention, suitable examples of the polyester (B2) include po lycondensates of polyol (7) with a polycarboxylie aci d (8). Suitable examples of polyols (7) include diols (7-1) and polyols containing 3 or more hydroxyl groups (7-2), preferably (7-1) and the mixture of (7-1) and a small amount of (7-2). Suitable examples of d-i ols—C7-4-)—L4uU.ude alkylene glycols having 2-12 carbon atoms (such as ethylene glycol. 1,2propyIene glycol, 1,3-propylene glycol. 1,4-butane diol. 1.6-hexane diol); alkylene ether glycols (such as dicthylene glycol, trlethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, po1ytetramethylene glycol); alicyclic diols (such as 1.4-cyc 1 ohexane dimethanol); hydrogenated bisphenols (such as blsphenol A, bisphenol F, bisphenol S); alkylene oxide (such as ethylene oxide, propylene oxide,buty1ene oxide) adducts of the above-mentioned bisphenols and the like. Among these, preferable are alkylene glycols having 2-12 carbon atoms, alkylene oxide adducts of bisphenols and the combination thereof. Suitable examples of polyols containing 3 or more hydroxy! groups (7-2)include aliphatic polyols having 3-20 carbon atoms (such as glycerol, triaethylolethane, trimethylolpropane, pentaerythritol, sorbitol); phenols containing 3 or more hydroxy! groups (such as trisphenol PA, phenol novolac, cresol novolac); oxyalkylene ethers of the above-mentioned phenols. Suitable examples of polycarboxy1ic acids (8) include dicarboxylic acids (8-1) and polycarboxy1ic acids containing 3 or more carboxyl groups (8-2), preferably (8-1) and the mixture of (8-1) with small amount of (8-2). Suitable examples of the dicarboxylic acids (8-1) includ( alkylene dicarboxylic acids having 2-20 carbon atoms (such as succinic acid, adipic acid, sebacic acid); alkenylene dicarboxylic acids (such as maleic acid, fumaric acid); aromatic dicarboxylic acids having 8-20 carbon atoms (such as phthalic acid, isophthalic acid, terephthalic acid, naphthalene —-— — dicarboxylic acid); and the like. Among these, preferable are alkylene dicarboxylic acids having 2-20 carbon atoms and aromatic dicarboxy 1 ic acids having 8-20 carbon atoms. Suitable examples of polycarboxy 1 ic acids containing 3 or more carboxyl groups (8-2) include aromatic po 1 ycarboxy1ic acids having 9-20 carbon atoms (such as trimellitic acid, pyroraellitic acid); and the like. In producing polyester (B2), polyol (7) and dicarboxylic acid (8) are po1ycondensated in a molar ratio of (7):(8) of generally 1:2 to 2:1, preferably 1:1.5 to 1.5:1. The molar ratio of (7-1): (7-2) in (7) is generally 100:0 to 80:20. preferably 100:0 to 90:10. The suitable molar ratio of (8-1): (8-2) in (8) is same as the molar ratio of (7-l):(7-2). The weight ratio of (AB) based on the total weight of charge controller, in case of being graftise or blockwise, is generally 1-100 % by weight, preferably 10-100 %. If the weight ratio of (AB) is less than 1 %, it becomes difficult to make the particle size of a discontinuous domains small. The weight ratio of (A) based on the total weight of charge controller is generally 0-99 % by weight, preferably 0-90 %, and the weight ratio of (B) is generally 0-90 % by weight, preferably 0-50 %. If the weight ratio of (B) is more than 99 %, a lot of charge controller is required in order to get an adequate charge and it is not economical. In the charge controller of the invention, iWa) X_t_he total weight content of (A) and (a) ] is generally 10-99 % by weight, preferably 20-90 X. If (Wa) is less than 10 %. a lot of charge controller is required in order to get an adequate charge and it is not economical. If (Wa) is more than 99 %, the effects due to bonding of graftwise or blockvrise are not apparent Suitable examples of the copolymer (AB), wherein (b) is connected by being grafted or bloci (1) A graft copolymer wherein a superstrate polymer chain of (b) is grafted to a subatrate polymer chain of (a); (2) A graft copolymer wherein a superstrate polymer chain of (a) is grafted to a substrate polymer chain of (b); (3) A block copolymer of (a) and (b). Among these, preferable are the graft copolymers (I) and copolymer (2) above mentioned. Moiety (a) has a weight-average molecular weight of generally 1.000 - 100,000, preferably 2,000 - 50,000. Moiety (b) has a weight-average molecular weight of generally 1,000 - 500,000, preferably 3.000 - 100.000. If the weight-average molecular weight of (a) or (b) is less than 1,000, the flowing properties of the toner is badly influenced, and if weight-average molecular weight of (a) exceeds 100.000 or that of (b) exceeds 500,000, the ch.nrge controNsr can be hardly dispersed in the toner. In order to make the particle size smaller, the total -amoujLL.of polymer (A) is not necessarily copolymer (AB), and (AB) as a portion of (A) is sufficient. That is to say, polymer (A) can be contained together with copolymer (AB). Furthermore ■r polymer (B) without binding to moiety (a) can be contained. In order to obtain this effect, it is more preferable that the structure of (b) resemble to the toner binder . Accordingly, (bl) is preferable as moiety (b) in case the styrenic polymer is used as the toner binder. Meanwhile (b2) is preferable as (b) in case polyester is used as the toner binder. According to the present invention, charge controller may be used together with a salt of a perf1uoroal ky1 group-containing organic acid (a). Siraultanious use of the salt (a) is desirable to better charging rate. Suitable examples of salts of perf1uoroaIky 1 group-containing organic acids (a) include perf 1 uoroa 1 ky 1 group-containing sulfonic acid salts (a-1), perf I uoroal ky 1 group-containing carboxylic acid salts (a-2), per fl uoroal ky i group-containing sulfamic acid salts (a-3), perfIuoroalky 1 group-containing acid sulfate salts (a-4) and perf1uoroalky 1 group-containing acid phosphate salts (a -5) and the like. Suitable salts (a-1) are salts of a perf1uoroalkyl group-containing sulfonic acids and cationic components. Suitable examples of perf1uoroaIky 1 group-containing sulfonic acids include perf1uoroaIkanesulfonic acids (such as perf1uorohexanesu 1 fonic acid, perf1uorooctanesu1fonic acid): perf1uoroalkylethanesuIfonic acids (such as perfluorooctylethane- sulfonic acid, perf 1 uorodecy1ethyanesu1fonic acid); perf1uoroalkeny1oxybenzensulfonic acids (such as - - -——I. i.ii— II t perf1uorononeny1oxybenzensulfonic acid) and the like. Suitable examples of cationic components include alkali metals (such as lithium, sodium, potasiura), alkaline earth metals (such asmagnesiura, calcium, barium), amines (such as triethy1 amine, tributy lamine, N.N-diraethy1benzy1 amine), quaternary ammoniums (such as tributy1benzy1ammoniurn, tetraethylararaoniurn, tetrabutylamraoniurn) and the like. Suitable salts (a -2) are salts of perf1uoroa I ky I group-containing carboxylic acids and the cationic components above-men t i oned. Suitable examples of perf1uoroa1kyI group-containing carboxylic acids include perf luoroaIkanoic acids (such as perf1uorohexanoic acid, perf1uorooctanoic acid); perfIuoroalkenyIoxybenzoic acid (such as perfIuorononeny I oxy-benzoic acid) and the like. Suitable salts (a -3) are salts of perf1uoroalky 1 group-containing sulfamic acids and the cationic components above-men t i oned. Suitable examples of perfluoroa Iky 1 group-containing sulfamic acids include erf luoroalkylethanesu1famic acids (such as perf!uorooctylethanesulfamic acid, perfluorodecylethyanesulfamic acid); and the 1 ike. Suitable salts (a-4) are salts of perf1uoroalky1 group-containing acid sulfates and the cationic components above-ment i oned. Suitable examples of perfluoroalky I group-containing acid sulfates include raonoester sulfates of perf1uoroalky1 group-containing alcohls (such as perfIuoroocty lethano 1, perf1uorodecyI ethyanol, perf1uorohexyI methane 1): and the like. I Suitable salts (a-5) are salts of a perf 1 uoroal ky I group-containing acid phosphates and the cationic components above-mentioned. Suitable examples of perf1uoroa1ky1 group-containing acid phosphates include raonoester or diester phosphates of perf1uoroalky1 group-containing alcohl above-mentioned, and the 1 ike. Among these salts (a ), a perfIuoroa1ky1 group-containing sulfonic acid salt (a-1) is preferred, and alkali metal, alkaline metal or amine salt of a perfluoroalkyl group-containing sulfonicacid is more preferred. Salts of heavy metals (such as nickel, copper, zinc, mercury, chromium) are undesirable because of safty. In the charge controller composition, the weight ratio of salt of a perfluoroalkyl group-contai n ijig organic acid (a) to polymer (A) or copolymer (AB) based on the total weight of charge controller composition, is generally in the range of 0-80 % to 20 -100% by weight, preferably 1-80 % to 20-99 % by weight, more preferably 3-50 to 50-97 % by weight. If the content of (a) is less than 1 % by weight, charging rate is Inadequate. If it is more than 80 % by weight, saturated charge amount and e n V i r 0 n m a n t a 1 stability are i n.? n f f i c i e n t. Suitable examples of polymer(A) include (1) Dich1oropheny1raaleinide homopolymer. (2) N i tropheny 1 mal ei ra i de / the mixture of 1-aIkenes of CI2-CH / maleic anhydride (49/48/3) copolyoer. (3) Dichioropheny1 maleimide / the mixture of 1-alkenes of C12- C14 / maleic anhydride (51/45/4) copolymer. (4) N i tropheny 1 mal ei mi de / perf I uoroa ll(y 1 (the mixture of C8-C12) ethyl nethacrylate (55/45) copolymer. (5) Chi oropheny I ma leiin ide / perf 1 uoroal ky I (the mixture of C8-C12) ethyl methacrylate (55/45) copolymer. (6) DichIoropheny I ma Ieimide / perfIuoroalky I (the mixture of C8-C12) ethyl methacrylate (48/52) copolymer. (7) DichIoropheny 1 itaconinide / perfIuoroalky I (the mixture of C8-C12) ethyl methacrylate (49/51) copolymer. (8) Dich1oropheny 1 itaconifflide / monoperfIuoroa Iky 1 (the mixture of C8-C12) maleate / nethy vinyl ether (34/42/14) copolymer. (9) Perfluoroalkyl (the mixture of C8-C12) ethyl methacrylate / styrenesu1fonic acid sodium salt(91/l) copolymer. (10) Perfluoroalky I (the mixture of C8-C12) ethyl methacrylate / styrenesu1fonic acid barium salt (89/11) copolymer. (11) Perfluoroalkyl (the mixture of C8-C12) ethyl methacrylate / styrenesu1fonic acid tributylamine salt(85/15) copolymer (12) Perfluoroalkyl (the mixture of C8-C12) ethyl acrylate / styrenesuIfonic acid sodium salt(91/l) copolymer. (13) Nitropheny1 ma leimide / perf1uoroalky 1 (the mixture of C8-C12) ethyl methacrylate / 2-acrylamide-2-methy1propane-sulfonic acid (51/41/8) copolymer. (14) ChIorophenyImaleimide / perf1uoroa 1 ky 1 (the mixture of C8-C12) ethyl acrylate / styrenesuIfonic acid sodium salt (50/45/5) copolymer. - — (15) DichlorophenyImaleinide / styrenesu!fonic acid sodium salt (96/4) copolymer. (16) DichlorophenyImaleimide / perf 1 uoroa1ky 1 (the mixture of C8-C12) ethyl methacrylate / styrenesulfonic acid sodium salt (46/50/4) copolymer. (17) Dich1orophenyimaleimide / perf1uoroaiky 1 (the mixture of C8-C12) ethyl raethacrylate / styrenesulfonicacid tributyl amine salt (45/50/5) copolymer. (18) Dich1oropheny1itaconimide / perf 1 uoroa1ky1 (the mixture of C8-C12) ethyl acrylate / styrenesu 1 fonic acid magnesium salt (65/30/5) copolymer. (19) Dichloropheny1itaconimide / perf 1 uoroa1ky1 (the mixture of C8-C12) ethyl acrylate / sulfophenylitaconiaide sodium salt (56/40/6) copolymer. (20) Dich 1 oropheny1itaconimide / perf1uoroalky1 (the mixture of C8-C12) ethyl methacrylate / su1fopheny1itaconimide sodium salt (30/64/6) copolymer. (21) Dichiorophenylmaleinimide / perfluoroalkyl (the mixture of C8-C12) ethyl maleate / su 1 fopheny 1 itaconimide sodium salt / raethl vinyl ether (39/42/5/14) copolymer. Suitable examples of copolymers (AB) of (a) with (b) include graft copolymers of the moiety (a) above-mentioned with the moiety (b) illustrated as follows : (1) A moiety of styrene horaopolymer. (2) A moiety of styrene / butyl acrylate (95/5) copolymer. (3) A moiety of styrene / butyl acrylate (87/13) copolymer. (4) A moiety of styrene / butyl methacrylate (75/25) copolymer. (5) A moiety of styrene / butadiene (90/10) copolymer noiety. (6) A moiety of bisphenoi A propylene oxide 2 moi. adduct / isophthalic acid condensation polymer. (7) A moiety of bisphenoi A propylene oxide.2 niol. adduct / isophthalic acid condensation polymer. (8) A moiety of bisphenoi A propylene oxide 2 mol. adduct / terephthalic acid condensation polymer. (9) A moiety of bisphenoi A ethylene oxide 2 mol. adduct / raaleic acid condensation polymer. (10) A moiety of bisphenoi A propylene oxide 3 mol. adduct / raaleic acid condensation polymer. (11) A moiety of bisphenoi A ethylene oxide 3 mol. adduct / terephthalic acid condensation polymer. Illustrative preparation method of the polymer (A) in the present invention is as follows : The polymer (A) is obtained by polymerizing the monomers required to be the aimed structure from the first stage of the reaction. For example. (A) is obtained by copol ymerizing monomer(l), such as itaconic acid, with monomer (2) under the presence of azobisisobutyronitri1e. followed by reacting a group (X)- substituted aniline. Illustrative preparation methods of the graftwise or hlockwise copolymers (AB) in the invention are as follows : 1) Macromer method of obtaining graft copnlyiner by copoLvnieri?. ing a compound containing a structure introducing pol ymerizable group, such as aryl group, in the end of the styrenic polymer moiety or polyester moiety (b), with the aonojiejs composing (a) by which the copolymer aioiety (a) can be introduced. 2) Polymer reaction method of obtaining a copolymer by copolymerizing a compound containing a structure being introduced a group reactive ?ith the copolymer moiety (a), sucli as amino group or hydroxyl group, in the end of the styrenic polymer moiety or polyester moiety (b), with the reactable group in the side chain of the copolymer moiety (a), such as carboxyl group or acid anhydride group. 3) Main chain initiating polymerization method of obtaining graft copolymer by reacting a compound having a structure introducing a polymerization initiating group, such as peroxide group, in the side chain of the styrenic polymer moiety (bl) or polyester moiety (b2). and the monomers composing (a) by which the copolymer raoiety (a) can be introduced ; or by reacting a compound conatining a structure introducing polymerization initiating group in the side chain of (a), with styrene and, if necessary, another copolymerizab le monomer. The preparation method of (a) is fundamentally the same as the above-mentioned production method of polymer (A). For example, the method of introducing a group reactive with the group located at the end of (b). such as carboxyl group or acid anhydride group, is same as the preparation method of the above-mentioned, and in order to introduce acid anhydride group, (a) is obtained by copolymerizing a monomer having an acid anhydride group in the same way as the preparation method of polymer (A) before the-pQly#«ri zat i on of the monomers composing (a). Methods of introducing a polymerization initiating group in the side chain of (a) include, for example, a method of reacting hydroperoxide with (a) having a acid anhydride group. The compound having a structure for introducing the above-mentioned reactive group at the end or side chain of the styrenic polymer moiety (bl) can be prepared by using conventional methods. For example, a compound having a hydroxyl group at the end of (bl) is prepared by a radical copolyracrization of styrene and another copoIyraerizab 1 e monomer under the presence of a hydroxyl group-containing chain transfer agent. A compound having a hydroxyl group at the end of the polyester moiety (b2) can be also prepared by using conventional methods. For example, a compound having a hydroxyl group in the end of (b2) is prepared by using excess amount of polyol (7) in the condensation polymerization process of polyol (7) and pol ycarboxy 1 i c acid (8) which compose (b2). A compound having a raetacryloyl group in the end of (b2) can be obtained by reacting methacryloyl isocyanate with the above-mentioned (b2) having hydroxyl group. Moreover, in preparing (b2), polyol (7) and polycarboxy1ic acid (8) are not necessarily applied for the polycondensation . The aimed polyester moiety (b2) can also be prepared by applying derivatives of (7) (such as lower monocarboxy 1 i c acid ester, alcoholate) and der i vat ives 444-8 (such as lower alcohol ester, acidanhydride, acid halide) for polycondensat ion. The charge controller of the Invention can be preliminarily mixed with a toner binder, before preparing the toner, to be used as a toner binder composition of the invention having a charge controlling properties. Suitable toner binders include styrenic polymers, polyesters, epoxy resins, polyolefins, po1yurethanes and the like polymers previously used as toner binders.. Suitable styrenic polymers include : copolymers of styrene with (raeth)aerylates. copolymers of styrene with diene monomers (such as butadiene and isoprene). and copolmers of styrene with other copolymerizable monomers. Suitable polyesters include po 1 ycondensates of aromatic dicarboxylic acids with oxyalkylene ethers of bisphenols. Suitable epoxy resins include : reaction products of aromatic diols and epich1orohydrines ; and modified compounds thereof. Suitable polyolefins include : polyethylene, polypropylene, copolymers of ethylene, propylene with other copo I ymer i zab le monomer. Suitable polyurethanes include : a poly addition compound of aromatic diisocyanate and an alkylene oxide adduct of an aromatic „d_iol. Illustrative methods of preparing the toner binder composition of the invention include the following : (1) a method of polymerizlag the monomers for preparing the toner binder mentioned above under the presence of the charge control ler. (2) a method of mixing the toner binder and the charge controller in the solvent, such as an aromatic hydrocarbon (toluene, xylene or the like), a halogenated compound (chloroform, ethylene dichloride or the like), ketone (acetone, methylethyl ketone or the like) or amide (dimethy1formamide or the like). (3) Method of thermally melting and mixing the toner binder and the charge controller. The charge contoller of the present is mixed with a toner binder and a colorant, and used as a toner composition of the present invention. Suitable of the example of colorants include such pigments and dyestuffs, used previously, as carbon black, iron black, Sudan black SM, First yellow G. Benzidine yellow. Pigment yellow, India first orange, Irgasine red, Baranito aniline red, Toluidine red. Carmine FB, Pigment o'range R, Raykired 2G, Rodamine FB, Rodamine B rake, Methy1violette B rake, Phtharocyanine blue. Pigment blue, Brilliant green, Phtharocyanine green. Oil yellow GG, Kayaset YG,Orasol brawn B, Oil pink OP and the 1 ike. Polymer is contained, within the toner binder composition and the electrophotographic toner of the invention, in an amount of generally 0.1 -20 %hy weight, preferably 0.3 - 10 X by weight based on toner. If the amount of polymer is less than 0.1 %, the charge in the toner becora small, and if it is more than 20 %, the environmental stability of the toner becomes worse. Toner comorise"?. ha.sed on the weigTit of toner, ;enerally 0.1-20 % by weight of the charge controller. 30-95 % )y weight of the toner binder, and 0-15 % by weight of the ;olorant, and if necessary, less than 60 % by weight of a lagnetic powder. Suitable magnetic powders include powders of >trong magnetic metal (such as iron, cobalt, nickel), magnetite, lematite, ferrite and the like, and these magnetic powders have )roperties as a colorant. In addition, various additives can be contained, for example, a lubricant (such polytetrafluoroethylene, low molecular (feight polyoiefin, fatty acid or metal salt or amide thereof) ind the other charge controllers (such as azo dyestuff containing netal, salicylic acid metal salt). Furthermore, fine particles jf hydrophobic colloidal silica can be used in order to improve flowing properties of the toner. The amount of these additives is generally less than 10 % by weight based on the weight of the toner. Preferable binder compositions include ones comprising: (1) discontinuous domeins composed of at least a portion of the charge controller; and (2) a continuous phase composed of ay least a portion of a toner b inder. The charge controller is easily exposed on the surface and the toner is capable of providing sufficient charge even with addition in a small amout of the charge controller, as compared with a charge controller compatibile with toner binder. _____ Phase or domain of (1) and (2) above-mentioned can be determined by checking the existence of the interface through the observing cut of the toner vrith transmission electro-microscope. For a clear examination of the interface, it is effective to examine the cut of the toner with an electro-microscope after dying the cut with ruthenium tetraoxide, osmium tetraox1de or the 1i ke. Said domains have particle size of generally 0.01-4 / m, preferably 0.05-2 u ti. Particles of more than 4 un cause an insufficient dispersibi1ity and a wider charge distribution, worse transparency in usage of color toner, meanwhile those of less than 0.01 u Jn do not form discontinuous domains and compatibility with the binder. Therefore the content of the charge controller on the surface of the toner becomes smaller and the charge becomes insufficient. The preparation method of the electrophotographic toner of the invention is not paticularly limited. Illustrative methods of the sameare as follows : (1) Kneading and pulverizing method The components of the toner are blended in a dry atmosphere and then kneaded, followed by roughly crushing and finally pulverizing with a jet mill and the like. Furthermore, the product is classified into a fine powder having a particle average size of 5-20 //m, to obtain the toner. (2) Additional blending method In a dry atmosphere, the charge controller of the invention is blended with particles having 5-20 u in diameter, comprising the toner binder and the colorant, with or without, the lubricant and the magnetic powder, followed by mixing the blended product vigorously, under heating with a mixer, optional , to obtain the toner. (3) Polymerization method The charge controller of the invention, the colorant and the other components are dispersed and dissolved in raw material monomers of the toner binder, followed by polymerizing them in water. The product is dried and the toner having 5 - 20 //m d iameter is" obtain The toner of the invention is, if necessary, mixed with a carrier powder, such as iron powder, nicicel powder, glass bead or the like, and may be used as a developer for an electrostatic latent image in an electrophotography. The toner of the invention may be fixed on the substrate, such as a paper, a polyester film and the like, with a copying machine or a printer. Illustrative fixing methods on the substrate include a heat roll fixing method and a flash fixing method. The charge controller of the invention may also be useful for a liquid developer and powder coat and the like. Having generally described the invention, a more complete understanding can be obtained by reference to certain specific examples, which are included for purposes of illustration only and not intended to be limiting unless otherwise specified. Hereinafter, part(s) means weight part(s). (1) Measurement, of the Dielectric Loss Tangent [tan d] A charge controller is pulverized into powders of average diameter of not more than 50 // ra with an agate mortar, and a test piece is prepared by compression molding in an electrode. The equipments used for this measurement: body; TR-1100 (supplied from Ando Denki Co.. Ltd.) electrode; SE-43 (supplied from Ando Denki Co., Ltd.) frequency; 100kHz (2) Measurement of the Water Absorbancy (%) In a same manner as above-mentioned, "after a charge controller is" pulverized into powders of average diameter of not more than 50 u m with an agate mortar, 2g of the tested powder is weighed and dried under reduced pressure at 35°C for 4 hours, followed by control ofthe moisture of 85 % R.H. at 35°C for 12 hours. Thereafter a weight is measured again and the water absorbancy {%) is calculated from the percantage of an increase of weight (the difference between the weight of after drying and that of before drying) per the weight of before drying. (3) Preparation of Developers The developers were prepared by mixing 1 part of the toner and 24 parts of theferrite carrier coated with silicone resin for electrophotography (FL961-150, supplied from Povdertec, Md. ). (4) Measurement of the Electrostatic Charge (Saturated Charge) The moisture of the above-ientioned developers were controlled at 23V under 50 % R. H. for at least than 8 hours, and then each sample was stirred with a terbler shaker mixer using a frictional force at 50 r.p.m. for each period of 1. 3, 7, 20, 60 and 120 minutes, and measured the electrostatic charge in each period. The charge at the period when the growth of the electrostatic charge was not observed was defined as the saturated charge. The equipment used for this measurement: Blow off method charge measuring machine (supplied from Toshiba Chemical Co., Ltd. ) (5) Evaluation Criteria of the Charging Rate In accordance with the above-mentioned results of the amount of the charge measured, the ranking of the charging rate was determined based on the following criteria : A: The stirring period using a frictional force is less than 7 minutes, when the charge reaches upto 80 % of the saturated charge. B: The stirring period using a frictional force is 7-20 minutes C: The stirring period using a frictional force is 20-60 minutes D: The stirring period using a frictional force is more than 60 minutes (6) Measurement of Dependence to the Circumstances After the moisture of the above-mentioned developers is controlled in high temperature and high humidity and in low temperature and low humidity, the electrostatic charge of these samp 1es is measured. Low temperature and low humidity : lOt:, 40% R. H. High temperature and high humidity : 351: , 855IS R. H. Evaluation Criteria : The change of the amount of the electrostatic charge in low temperature and low humidity and in high temperature and high humidity is A: small, B: medium, C: large. (7) Measurement of Charge Distribution The moisture of the above-mentioned developers were controlled at 23°C under 50 % R. H. for not less than 8 hours, and the test samples were mixed with terbler shaker mixer using a frictional force at 50 r.p.m.'for 20 min., and then the charge distributionasmeasured. Equipment: The charge distribution of the particle testing machine (EST-1, supplied from Hosokawa Micron, Co., Ltd.) Eva 1 nation Criteria : A: The charge amount distribution is narrow. B: The charge amount distribution is medium. C: The charge amount distribution is wide. (8) Copying Test A continuous copying test of the above-mentioned developers was done with a copying machin,e for evaluation. Copying machine for evaluation '• An negatively chareed e I pntmnhotbgraph i c copying machine uing selenium sensitized material. The number of papers available for a continuous copying is 20,000. Evaluation Criteria : A: The copied image on the paper is good after the 20,000 sheets of continuous copying. B: The deterioration of the copied image on the paper is slightly observed after the 20,000 sheets of continuous cop y ing. C: The deterioration of the copied image on the paper is apparently observed after the 20,000 sheets of continuous c opy i ng. D: The copied image is poor from the beginning of copying. (9) Evaluation of Transparency The toner binders and the charge controllers were kneaded vithout the addition.,of the colorants and the low molecular weight polypropylene, and then the kneaded samples were molded into cylindrical pellets of about 5 mm with melt indexer and the transparency of the pellets were visually evaluated. Evaluation Criteria A: Transparent B: S1ight1y c loudy C: CI oudy in white color Examp1e Al In xylene at the boiling point, 733 parts of the mixture of 1-alkenes of C12-14 / maleic anhydride copolymer (PA-124, supplied from Mitsubishi Chemical Industries, Ltd.) and 307 parts of m-nitroani1 ine were reacted to form an imide for 4 hours with removal of water, and then xylene was distilled off, to obtain the charge controller (Al) of the invention. Example A2 Example Al was repeated, except using 360 parts of 3,4-di ch 1 oroani1ine in place of m-nitroani1ine, to obtain the charge controller (A2) of the invention. Examp1e A3 In xylene at the boiling point, 647 parts of the mixture of 1-alkenes of C12-14 / maleic anhydride copolymer (PA-124), and 130 parts of perf1uoroalky1ethano1 (Cheminox FA-M[C10up], supplied from Japan Mectron Co., Ltd.) were ha 1f-esterified for 5 hours. Thereafter 256 parts of m-nitroani1ine was added to be reacted to form an imide for 5 hours with removal of water, then xylene was distilled off,to obtain the' charge controller (A3) of the i nven t i on. Examp 1 e A4 Into an autoclave, were charged 800 parts of the mixture of 1-alkenes of C12-14 / maleic anhydride copolymer (PA-124, supplied from Mitsubishi Chemical Industries, Ltd.), and 200 parts of styrene in the presence of 0.4 part of di-tert-butyl peroxide as an ininiator, polyaerized graftwise at 80 "C , to obtain a graftwise-po lymer (1). Example A3 was repeated, except using 809 parts of above-obtained graf tw i se-po 1 ymer (1) in place of tlie mixture of I-al)(enes of C12-H / nialeic anhydride copolymer (PA-I24), to obtain the charge controller (A4) of the invention. Examp1e A5 723 parts of bisphenol A propylene oxide 2 raol.adduct and 348 parts of terephtalic acid were polycondensated at 230 °C using 2 parts of dibutyltin oxide as a catalyst, to obtain a polyester (1) having a weight-average molecular weight of 6,000 and a hydroxyl value of 20 ag KOH/g. In xylene at the boiling point, 647 parts of the mixture of 1-alkenes of C12-I4 / laleic anhydride copolymer (PA-124), 162 parts of the polyester (1),,and 130 parts of perf1uoroalky1ethano 1 (Cheminox FA-M [C lOup]), were ha 1f-esterified for Shours. Thereafter 256 parts od m-aitroani1ine was added to be reacted to form to an imide for 5 hours with removal of .water, then xylene wasdistilled off,to obtain the charge controller (A5) of the invention. Examp1e A6 In N, N-dimethyl formamide (DMF) at the boiling point. 508 parts of m-nitropheny 1 ma leimide, 412 parts of perf1uoroa1ky1ethy 1 methacrylate (Cheminox FAMAC-C8, supplied from Japan Mectron Co.,Ltd.) and 80 parts of 2-acrylamide-2-raethylpropanesulfonic acid were polymerized using di-tert-buty1peroxide as an initiator for 8 hours, 'follofed by distilling off DMF. to obtain the charge controller (A6) of the in ven t i on. Example A7 Example A6 was repeated, except using 457 parts of 3,4-dich1 oropheny1 ma 1 einide, 503 parts of perf1uoroa1ky1ethy 1 methacrylate and 40 parts of styrenesu1fonic acid sodium salt, in place of m-nitropheny 1 ma leimide, 412 parts of perf1uoroaIky 1 ethy 1 methacrylate and 2-acry1 amide-2-methy1propanesu 1 fonic acid, to obtain the charge controller (AT) of the invention. Examp 1 e A8 500 parts of styrene and DMF were further added to 500 parts of the charge controller (AT), and polymerized graftwise using di-tert-buty1 peroxide as an initiator for 4 hours, followed by distilling off DMF, to obtain the charge controller (.A8) of the invention. Examp1e A9 Example A6 was repeated, except using 9 60 parts of 3,4-dich1 oropheny1 ma 1 eimide, 40 parts of styrenesu1fonic acid sodium salt, in place of in-n i tropheny 1 ma 1 e i m i de. perf1uoroa1ky1ethy1 methacrylate and 2-acry1 amide-2-methy 1 propane -sulfonic acid, to obtain the charge controller (A9) of the i nven t i on. Examp1e AlO In methy ethyl ketone (MEK), 511 parts of perf1uoroalkylethy1 acrylate (FLUOfET AC-812, supplied from Hechst Indstries Co.,Ltd.) and 223 parts of itaconic anhydride were polyneTized using 50 parts of azo-bis-isobutyronitrile as an initiator for 4 hours, to obtain a copolymer (1) having i weight-average molecular weight of 18,000. In an autoclave, were charged 800 parts of the copolymer (1) and 1.000 parts of styrene in the presence of di-tert-buty1 peroxide as an ininiator, polymerized graftwise at 180 °C for 4 hours, followed by distilling off MEK under reduced presure. to obtain a graftwise-po 1 ymer (2). 262 parts of 3, 4-dich 1 oroani1ine, 37 parts of p-aminobenzenesulfonic acid sodium salt and DMF were added to 173 4 partsof the graft-copo1ymer (2), and reacted to form an imide for 8 hours in DMF at the boiling point, followed by distilling off DMF, to obtain the charge controller (AlO) of the invention. Examp1e All In DMF, 912 parts of perfIuoroa1ky1ethy 1 methacrylate (Cherainox FAMAC-C8) an.d 88 parts of styrenesulfonic acid sodium salt« were polymerized using azo-bis-isobutyronitrile as an initiator for 4 hours in DMF at the boiling point, followed bydis tilling off DMF, to obtain the charge controller (All) of the invention. Examp1e A12 Example A6 was repeated, except using 476 parts of 3, 4-dich1oropheny1 ma 1eiraide and 524 parts of perf1uoroa1ky 1 ethy 1 methacrylate, in place of m-nitropheny 1 ma 1eimide, 412 parts of perf1uoroa1ky1ethy 1 methacrylate and 2-aery 1 amide-2-methy 1 propane -sulfonic acid, to obtain a copolymer (1). 200 parts of perf1uorooctanesu1fonic acid sodium salt was. added to the rnnnlvmpr (]). anririi.. "by distilling off DMF, to obtain the charge controller (A12) of the invention. Exaup1e Al3 Example A6 was repeated, except using 1,000 parts of 3,4-dich1oropheny 1 ma 1 eimide alone, in place of m-nitropheny1 maleimide, perf1uoroalkylethy 1 methacrylate and 2-aery 1 amide-2-methy1propanesu1fonic acid, to obtain homopolymer (1). 200 parts of barium salt of perf1uorooctanesu1fonic acid was added to the homopolymer (1), and dissolve uniformly, followed by distilling off DMF, to obtain the charge controller {A13) of the invention. Cofflperative Examples CAl Example Al was repeated, except using 243 parts of m-aiB i Bopheno 1 in place of m-n i t roan i 1 i ne, to obtain the charge controller (CAl) for comparison. Comparative Examples CA2 In mixture of toluene and methanol, 920 parts of styrene and 80 parts of 2-acryl am i de-2-methy 1 propanesu 1 f on i c acid were polymerized using azo-bis-isobutyronitrile as an initiator for 8 hours, followed by distilling off solvent under reduced presure, to obtain the charge controller (CA2) for comparison. Comperative Examples CA3 In DMF at the boiling point, 912 parts of styrene and 88 parts of styrenesulfonic acid sodium salt, were polymerized using azo-bis-isobutyronitrile as an initiator for 4 hours, followed by distilling off DMF under reduced presure, to obtain the charge controller (CAS) for coaiparison. Comperative Exanples CA4 In toluene at the boiling point, 1,000 parts of perf1uoroa1kyIethy 1 methacry1 ate was polymerized using azo-bis-isobutyronitri1e as an initiator for 4 hours, followed by distilling off toluene under reduced presure, to obtain the charge controller (CA4) for coiaparison. Comperative Examples CAS Example All was repeated, except using 721 parts of perfluoroalkylethyl methacrylate and 2 78 parts of styrenesulfonic acid sodium salt, in place of 912 parts of perfluoroalkylethyl methacrylate and 88 parts of styrenesulfonic acid sodium salt, to obtain the charge controller (CA5) for comparison. Comperative Examples CA6 Perf1uorooctanesurufonic acid sodium salt was used as the charge controller (CA6) for comparison. Table .. Charge controller Dielectric loss Water No. tangent [ tan (5 ] absorbancy (%) (AD 0. 012 0. 7 (A2) 0.010 0.6 (A3) 0.014 0.6 (A4) 0. 009 0. 5 (A5) 0.013 0.8 (A6) 0.015 1.7 (A7) 0. 039 1. 5 (A8) 0.017 0.9 (A9) 0.016 1.6 (AlO) 0. 015 0. 9 (All) 0. 050 1. 6 (A 12) 0. 0 88 1... 3 (A13) 0. 084 " 0. 9 (CAD 0. 007 3. 1 (CA2) • 0.006 4.3 (CA3) 0. 006 5. 7 (CA4) 0. 007 0. 1 (CA5) 0. 420 8. 4 (CA6) On removing toluene, the toner binder cooposition (Bl) of the "invention was obtained. Exanip I e B2 20 parts of the charge contro1! er (A8) and 1000 parts of a styrenic toner binder (Himer l)NI-3000) were solved and mixed in DMF. On removing DMF, the toner binder composition (B2) of the invention was obtained. After dying the cut of toner binder composition (B2) with ruthenium tetraoxide, about 1 u of dispersed particles were observed with a transmission electro-microscope (TEM). However, in accordance with Himer UNI-3000, none of existence of dispersed particles was observed. Example 83 Condensation polymerization of 417 parts of bisphenol A propylene oxide 2 mol. adduct, 341 parts -of bisphenol A ethylene oxide 2 mol. adduct and" 310 parts of terephthalic acid were done using 2 parts of dibutyitinoxide as a catalyst, to obtain the polyester toner binder (1) having a weight-average molecular weight of 8, 000. 10 parts of the charge controller (A7) and 1,000 parts of the toner binder (1) were mixed in the same manner as Example B2, to obtain the toner binder composition (B3) of the invention. About 2 u tR of dispersed particles were observed by TEM. Examples T1-T4 and Comperative Examples CTl Each toner was prepared using, as components, each charge controller (parts) as shown in Table 2, 1000 parts of styrenic '-3000, supplied from Sanyo Chemical 'I ndusf Ties, ' .), .. of carbon black (MA-100, supplied from Mitsubisr. . Chemical Industries, Ltd.):and 40 parts of low molecular weight polypropylene (Viscol 660P, supplied from Sanyo Chemical Industries, Ltd.) and according to the following p rocess : In the first place, these components were preliminarily mixed with Henschel mixer (FMIOB, supplied from Mitsuimiike Kakouki, Ltd.) and then kneaded with a twin screw extruder(PCM-30, supplied fr'om Ikegai, Ltd.) Each of the resulted products was further pulverized finely with a supersonic jet mill Labo Jet (supplied from Japan Pneumatic Industries, Ltd.) and classified afterwards with a air stream classifier (MDS-I, supplied from Japan Pneumatic Industries. Ltd.) to obtain each powdered product having a particle size of 5-20 /im, namely the toner (T1)-(.T4) of the invention and the toner (CTP for •comparison. The evaluation results are shown in Table 2. Examp 1 e 15 Example Tl was repeated, except using 1040 parts of the toner binder composition (Bl) in placed ofHimer UNI-3000 andexc eptwithout adding any charge controller, to obtain the toner (T5) of the invention. The evaluation results are shown in Table 2. Examples Tfi-Tl' nr' 'moerative Fvamo' r-r") -r,TH Example Tl was repeated, except using 80 "parts of carbon black in placed of 50 parts, to obtain the toner (T6.)-(T13) of the invention and the toner (CT2)-(CT-8) for comparison. The evaluation results are shown in Table 2. Example Tl-I Example T6 was repeated, except using 1020 parts of the toner binder composition (B2) in placed of Himer UNI-3000 and except without adding any charge controller, to obtain the toner (T14) of the invention. The evaluation results are shown in Table 2. 3 ; Dependence to circumstances * -l : Charge distribution *5 : Copying test Examples Tl5-T19 Condensation polymerization was done using 751 parts of bisphenol A propylene oxide 2 mol. adduct and 104 parts of triraellitic anhydride and 2 parts of dibutyltin oxide as a catalyst, to obtain the polyester toner binder (2) having a softening point of 127 °C. Example Tl was repeated, except using polyester toner binder (2) in place of the styrenic toner binder, in accordance with the recipes as shown in Table 3, to obtain the toners (T15) and (T16 of the invention. Example T6 was repeated as well, except using polyester toner binder (2) in place of the styrenic toner binder, in accordance with the recipes as shown in Table 3, to obtain the toners (T17)-(T19) of the invention. The evaluation results are in Table 3. WE CLAIM : 1. A method of producing a polymer for using as a charge controller of a toner said method comprising polymerizing an ethylenically unsaturated first monomer having an aromatic ring substituted with at least one electron-attractive group selected from the class consisting of a halogen atom, nitro group and cyano group with or without at least one other monomer, and/or an ethylenically unsaturated second monomer having an organic acid group or salt thereof with at least one other monomer to obtain a polymer having a dielectric loss tangent of 0.008 to 0.3 at lOOkHz and a water absorbancy of at most 10% by weight, said other monomer being selected from the class consisting of a perfluoroalkyl group- containing monomer, a silicone group-containing monomer, an olefin, a vinyl ether, an aromatic vinyl hydrocarbon (meth)acrylic acid, a (meth) acrylate, a diene, a vinyl ester and a nonomer having nitrile group. 2. The method as claimed in claim 1, wherein said polymer comprises at least 5% by weight of units of said first monomer. 3. The method as claimed in claim 1 or 2, wherein said first monomer is an ethylenically unsaturated monomer selected from the class consisting of a styrene, an aromatic ring-containing maleimide, an aromatic ring-containing itaconimide, an aromatic ring-containing acrylate or methacrylate, an aromatic ring-containing acrylamide o methacrylamide and an aromatic ring-containing vinyl ether, the aromatic ring of said first monomer being substituted with an electron-attractive group such as herein described. 4. The method as claimed in claim 3, wherein said first monomer is a phenylmaleimide or a phenylitaconimide, the aromatic ring of which is substituted with an electron-attractive group such as herein described. 5. The method as claimed in claim 1 or 2, wherein said polymer comprises 0.1-20% by weight of units of said second monomer containing an organic acid group or salt thereof. 6. The method as claimed in claim 2 or 5, wherein said polymer comprises units of a monomer selected from the class consisting of a perfluoroalkyl group-containing monomer and a silicone group-containing monomer. 7. The method as claimed in claim 6, wherein the units of said monomer selected from the class consisting of a perfluoroalkyl group-containing monomer and a silicone group-containing monomer is contained in an amount of 10 to 94.9% by w^eight. V 1 8. The method as claimed in claim 1 or 5, wherein said organic acid group is selected from the class consisting of sulfonic acid group, sulfamic acid group, acid sulfate group, carboxylic acid group and acid phosphate group. 9. The method as claimed in claim 8, wherein said organic acid group is sulfonic acid group. 10. The method as claimed in claim 8, wherein said second monomer is an aromatic sulfonic acid group-containing monomer or salt thereof. 11. The method as claimed in claim 10, wherein said second monomer is a monomer selected from the class consisting of styrenesulfonic acid, sulfophenylacrylamide, sulfophenylmaleimide, sulfophenylitaconimide and salts thereof. 12. The method as claimed in claim 8, wherein said salt is a salt of at least one selected from the class consisting of an alkali metal, an alkaline earth metal, an amine and ammonium. 13. The method as claimed in claim 8, wherein said polymer comprises units of a monomer selected from the class consisting of a perfluoroalkyl group-containing monomer and a silicone group-containing monomer. 14. The method as claimed in claim 1, wherein said polymer has a weight-average molecular weight of 1,000 to 500,000. 15. A method of producing a polymer for using as a charge controller of a toner, substantially as hereinabove described and exemplified.

Full Text

The present invention relates to a method of producing a polymer for using as a charge controller of a toner.
Previously an addition of a charge controller for the purpose of controlling electrostatic charge of electrophotographic toner has been employed. As charge controllers chargable negatively among charge controllers previously known there have been known azo dye stuff compounds, salicylic acid-metal complexes and the like.
As improved compounds, such polymer Compounds are
proposed as follows :
(1) Copolymer of styrene and sodium salt of vinyl benzensulfonic acid (Japanese Patent KOKAI No.88564/1985).
(2) Combination of a polymer of perfluoroalkylethyl aery late and copolymer of styrene, methyl acrylate and 2-acrylamide-2-

methylpropanesu1fonic acid (Japanese Patent KOKAI No. 230609/1994), (3) Block copolymer of methyl methacrylate and methacrylic acid (USP4,925.765).
However, by using the polymer compounds disclosed in (l)-(3), as the electrostatic charge of the toner is poor, a lot of charge contoller is required and it is not economical. And it impairs other properties required in toner (low temperature fixing properties, anti-hot offset properties and the like). The charging rate (stirring period using a frictional force when the charge reaches a required charge amount) is also inadequate. Therefore a longer warming-up time of a copying machine is required and a copied image becomes bad in case of continuous copying. The change of charge by humidity is large and environmental stability is inadequate.
Furthermore, as the transparency is poor when toner is formulated, bad influences to the color tone is observed in applying color toner.
It is an object of the present invention to provide an essentially colorless charge controller containing no metal.
Another object of the invention is to provide a charge controller having excellent properties concerning the electrostatic charge amount, the charging rate and the environmental stability of toner.
Still another object of the invention is to provide charge controller having no problem concerning the above-mentioned dispersing properties and transparency.

Accordingly the present invention provides a method of producing a polymer for using as a charge controller of a toner said method comprising polymerizing an ethylenically unsaturated first monomer having an aromatic ring substituted with at least one electron-attractive group selected from the class consisting of a halogen atom, nitro group and cyano group with or without at least one other monomer, and/or an ethylenically unsaturated second monomer having an organic acid group or salt thereof with at least one other monomer to obtain a polymer having a dielectric loss tangent of 0.008 to 0.3 at 100kHz and a water absorbancy of at most 10% by weight, said other monomer being selected from the class consisting of a perfluoroalkyl group-containing monomer, a silicone group-containing monomer, an olefin, a vinyl ether, an aromatic vinyl hydrocarbon (meth)acrylic acid, a (meth) acrylate, a diene, a vinyl ester and a nonomer having nitrile group.
r

These and other objects of the present invention will become more readily apparent from the description hereinafter.
SUMMARY OF THE INVENTION Briefly the above-mentioned objects of the present invention have been attained broadly by the following [l]-[3] aspects of the invention.
[1] k charge controller for a toner which comprises a polymer of an ethylenica 1 1 y unsaturated monomer, said polymer having a dielectric loss tangent [tan d] at 1OOkHz of 0.008 to 0.3 and a water absorbancy of at most 10% by weight, and selecte from the class consisting of :
(1) a polymer (Al) of a monomer (1) having an aromatic ring substituted with at least one electron-attractive group (X) selected from the class consisting of a halogen atom, nitro grou and cyano group; and
(2) a copolymer (A2) of a monomer (2) having an organic acid group or salt thereof, with another monomer.
[2] A toner binder composition, which comprises said charge controller and a toner binder resin.
[3] A toner, which comprises a toner binder resin, a colorant and said charge controller.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
According to the present invention, a dielectric loss tangent [tan d ] at 100 kHz is measured as following:
A polymer is pulverized into powders of average diamete of not more than 50 ,u with an agate mortar, and a test piece

is prepared by compression molding in an electrode for dielectric loss tangent-measurement. The test piece is set to an equipment for the measurement with the electrode, and both conductance and capacitance at 100 kHz are measured, followed by measuring its thickness. The dielectric loss tangent is calculated from the conductance, capacitance and thickness thus measured.
A suitable value of dielectric loss tangent is generally in the range of 0.008-0.3, preferably 0.008-0.2, more preferably 0.015-0.1. Polymers having less than 0.008 of dielectric loss tangent may cause insufficiency of charging rate, while polymers having more than 0.3 may result in shortage of the electrostatic charge amount of toner.
According to the present invention, a water absorbancy {%) is measured as following:
In a same manner as above-mentioned a polynier is pulverized into powders of average diameter not more than 50 u JR with an agate mortar. After drying 2g of the tested powder under reduced pressure at 35°C for 4 hours, followed by control of the moisture of 85 % R.H. at 35°C for 12 hours. Thereafter a weight is measured again and the water absorbancy i%) is calculated from the percentage of an increase of weight (the difference between the weight of after drying and that of before drying) per the weight of before drying.
Water absorbancy (%) is generally in the range of at most 10 % by weight, preferably at most 5% by weight, more preferably at most 2 % by weight. Polymers having less than 10 % by weight of water absorbancy nay result in poor environmental stability.

Suitable polymers of the invention include polymer (A) of one or more ethylenica 11y unsaturated monomers. Suitable polymers (A) include :
(1) polymers (Al) of a monomer (1) having an aromatic ring substituted vith at least onee 1 ectron-attractive group (X) selected from the class consisting of a halogen atom, nitro group and cyano group ; and
(2) copolymers (A2) of a monomer (2) having an organic acid group or salt thereof, with one or more other monomers.
Suitable electron-attractive groups (X) include, for example, halogen atoms (such as chlorine atom, bromine atom, iodine atom and fluorine atom), nitro group and cyano group. Among these, chlorine and nitro group are preferable
Suitable examples of monomer (1) having an aromatic ring substituted with at least one electron-attractive group (X) include : styrenes (such as chlorostyrenen, dichlorostyrene, bromostyrene, f1uorostyrene, nitrostyrene, cyanostyrene) ; aromatic ring-containing maleiraides (such as chloropheny 1-maleimide, dich1oropheny1maleimide, nitrophenyImaleimide, nitroch1orophenyImaleimide); aromatic ring-containing itaconimides (such as ch1oropheny 1 itaconiraide, dich1oropheny1-itaconimide, nitropheny1itaconimide, nitrochlorophenyl-itaconimede); aromatic ring-containing (meth)acry1ates (represent acrylate and methacry1 ate, similar expression are used _hereinafter)(such as chlorophenyl (meth)acrylates, bromophenyl (meth)acry1ates, nitrophenyl (meth)aerylates, chl oropheny loxyethyl (Bieth)acry lates, bromopheny loxyethy !

(iDeth)acry 1 ates, n i tropheny 1 oxyethy 1 (meth) aery 1 ates); aromatic ring-containing (nieth)acry lam ides (such as ch 1 oropheny I-(me th)acry 1 am ides, bromopheny 1 (me th)acry 1 am i des, n i tropiieny 1-(nieth)acry! am i des) ; and aromatic ring-containing vinyl ethers (such as chlorophenyl vinyl ether, nitrophenyl vinyl ether). Among these, preferred are aromatic ring-containing maleimides and aromatic ring-containing itaconimides.
Polymers (AD include both horaopolymers or copolymers of at least one said monomer (1), and copolymers of monomer (1) with one or more other copolyraerizable monomers.
Suitable examples of copo1yraerizable monomers include monomers (2) having an organic acid group or salt thereof, perf1uoroalkyi group-containing monomers (3-1), silicone group-containing monomers (3-2) and other copolymerizable monomers (4), as well as combinations of two or more of these (ncnomers are pref erab 1 e.
Copolymers of said monomer (1) with said monomer (2) are preferable because charging rate of toner is fast.
Copolymers of said monomer (1) with said monomer (3-1) or said monomer (3-2) are preferable because they improves charge amount, charging rate and environmental stability of toner.
Copolymers (A2) include copolymers of said monomer (2). with one or more other iBonomers.
Suitable examples of monomer (2) include sulfonic acid group-containing monoaers (2-1), carboxylic acid group-containing monomers (2-2), sulfaaic acid group-containing monomers (2-3). acid sulfate group-containing nonomers (2-4), acid phosphate

group-containing uonoiiiers (2-5) and salt thereof.
Suitable examples of monomer (2-1) include aromatic sulfonic acid group-containing monomers (such as styrenesulfonic acid, su1fophenylacry 1 amide, su 1 fophenyImaleimide, sulfophenyl-itaconimide), aliphatic sulfonic acid group-containing monomers (such as VinyIsu1fonic acid, al1yIsulfonic acid, 2-acry1 amide-2-methy1propanesu1fonic acid, methacry1oyloxyethy Isu1fonic acid), and the 1 ike.
Suitable examples of monomer (2-2) include (meth)aery 1ic acids, maleic acid, itaconic acid, monobutyl maleate, monoperf1uoroalky1ethy1 maleate, monoperf1uoroalky1ethy1 i taconate and the 11ke.
Suitable examples of monomer (2-3) include a 11y1su1famic acid, styry1sulfamc acid, viny 1 su1famic acid and the like.
Suitable examples of monomer (2-4) include surfuric monoester of hydroxy group-containing monomer (such as hydroxyethyl (meth)acry1ates, hydroxyethyl vinyl ether, vinyl pheno 1) and the 11ke.
Suitable examples of monomer (2-5) include phosphoric raonoesters or diesters of the above-mentioned hydroxy group-containing monomer and the like.
Suitable examples of salts of said monomer (2) include those of alkali metal (such as lithium, sodium, potasium), alkaline earth metal (such asmagnesium, calcium, barium), amines (such as tr i ethy lami ne, tr ibuty lami ne, N, N-d imeth.y 1 benO'J anLiiLeX, quarternary ammoniums (such as tributy1benzylammonium, tetraethylammonium, tetrabutylanmonium) and the like.

Among these, monoiers having a salt of an organic acid group is preferred to monomers having an organic acid group. And among these, preferred are monomers having a salt of an alkali metal, an alkaline earth metal or amine. As regard to the kind of acid group, preferred are said monomers (2-1),(2-2) and (2-4), in particular, monomer (2-1). Namely, among these, most preferred are an aromatic sulfonic acid group-containing monomers in the form of an alkali metal, alkaline earth metal or amine salt.
A salt of heavy metals (such as nickel, copper, zinc, mercury, chromium) is undesirable because of safty.
Suitable examples of perf 1 uoroa Iky 1 group-containig fflonoaers (3-1) include perfIuoroa1kyIetyienes, perfluoro-alkylethyl (meth)acry1ates, mono(perf1uoroa 1 ky lethy1) maleates, mono(perf1uoroa1ky!ethyl) itaconates and the like.
Suitable examples of silicone group-containig monomers (3-2) include esters of (meth)acry1ic or maleic acids with terminal hydroxyl group-modified silicone oil; amides and imides of (raeth)aery 1ic or maleic acids with terminal amino group-modified silicone oil and the like.
Among these monomers (3), perf1uoroaIky I group-containig monomers are prefferred. Those monomers having C8-16 of a perfIuoroalkyI group are more paticularly prefarable.
Suitable examples of other copo lymerizable monomers (4), other than said monomer (3) includ.e olefins (such as ethylene, propylene, 1-butene, isobutylene. dodecene); vinyl ethers (such a.s iDPthvl vinyl ether.butyl vinyl ether, stearyl vinyl ether);

•aromatic vinyl hydrocarbons (such as styrene. a -methyistyrene, p-cuiny I styrene) ; (nieth)acry 1 i c acids ; a (nieth)acry 1 ates (such as methyl (meth)aery Iates, ethyl (meth)acry1ates, butyl (ineth)acry! ates) ; dienes (such as butadiene, isoprene); a vinyl esters (such as vinyI acetate, vinyl propionate); a monomer having nitrile group (such as (leth)aery Ionitri1es): and the like.
Polymer (Al) generally contains the units of said monomer
(1) in an amount of at least 5 X by weight, preferably at least
10 % by weight, more preferably 20-89 % by weight, in view of
providing sufficient amount of charge of toner.
Polymer (Al) generally contains the units of said monomer
(2) in an amount of 0-20 % by weight, preferably 0.1-20 % by
weight, more preferably 1-10 % by weight.
Polymer (Al) generally contains the units of said monomer
(3) in an amount of 0-95 % by weight, preferably 10-90 % by
weight, more preferably 10-79 % by weight.
Polymer (Al) generally contains the units of said monomer
(4) in an amount of 0-95 % by weight, preferably 0-50 % by
weight, more preferably 0-30 % by weight.
Copolymers (A2) include copolymers of said monomers (2) with one or more other copolymerible monomers.
Suitable examples of copo1ymerizable monomers with monomer (2) include monomers (3-1), monomers (3-2), and monomers (4) the above-mentioned.
Suitable examples and more suitable examples may be the same as mentioned above with respect to polymers (Al).
Copolymers of monoBer (2) with monomer (3) are preferred

because they improves toner properties such as charge amount, charging rate and environmental stability of toner.
Polymer (A2) generally contains the units of said monomer (2) in an amount of at least 0.1 % by weight, preferably 0.1-20 % by veight, more preferably 1-10 % by weight.
In case of less than 0.1 % content by weight, a dielectric loss tangent becomes smaller and charging rate of toner may be inadequate. In case of larger amount, a dielectric loss tangent becomes larger , and charge amount and environmental stability of toner may be inadequate.
According to the present invention, polymer (A) has a weight-average molecular weight of generally 1,000 to 500,000, preferably 2,000 to 200.000. In case it is jess than 1.000, it becomes compatible with the binder and charge amount is insufficient. Meanwhile, in case it is more than 500,000, it becomes difficult to disperse polymer (A) in the toner.
In prefarable embodiments of the invention, besides the above-mentioned polymer (A), is used a copolymer (AB) comprising
a polymer moiety (a) of polymer (A) selected from the class consisting of polymer (Al) of at least one containing an aromatic ring substituted with at least one electron-attractive group (X) selected from the class consinting of a halogen atom, nitro group and cyano group ; and copolym.er (A2) of a containing an organic acid group or sa1t thereof ; and a polymer moiety (b) of at least one polymer (B)

selected from the class consisting of styren ic po lymer (B1) and polyester (B2) ; the moiety (b) being bound graft-wise or block-wise to the mo 1ety (a). Preferred is (AB) as the particles of the discotinuous domains formed with moiety (a) in the toner can be easily formed i n a sraal 1 s i ze.
Suitable styrenic polymers (Bl) include either styrene homopolymers and copolymers of styrene with another copoIymerizab le monomer (6).
Suitable examples of the other copolymerizable monomer (6) include aromatic vinyl hydrocarbons other than styrenes, (meth)acry1 ic monomers and other vinyl monomers.
Suitable examples of the other aromatic vinyl hydrocarbons include alkyl substututed styrenes (such as a-methy 1styrene, p-methy1styrene, p-cumyIstyrene); halogenated styrenes (such as ch1orostyrene, ch1oromethyIstyrene ); acetoxystyrene, hydroxystyrene and the like.
Suitable examples of (meth)aery 1 ic monomers include alkyi substituted (raeth)acryiates (such as methyl (meth)aery 1ates , ethyl (meth)acry lates, butyl (meth)acryI ates. 2-ethy!hexy! (meth)acry1ates, lauryl (meth)acry1ates, stearyl (meth)acrylates) ; hydroxyl group containing (neth)acryIates (such as
hydroxyethy 1 (meth)acrylate) ; epoxy group containing _____
(meth)acry1ates (such as glycidyl (meth)acry lates); isocyanate group con tai n i ng iDonoiiiers (such as methacryloyl isocyanate) : and

nitrile group containing monomers (such as (nieth)acry 1 on i tr i 1 e) and the I i i Suitable examples of the other vinyl monomers include : vinyl esters (such as vinyl acetate, vinyl propionate);diene monomers (such as butadiene, isoprene); halogenated olefin (such as vinyl chloride, vinyl bromide); a . j3 -ethy 1 en ica 1 ly unsaturated mono or po1ycarboxy 1 ic acids (such as (meth)aery 1ic acids, crotonic acid, sorbinic acid, raaleic acid, itaconic acid, synnamic acid); anhydrides thereof (such as maleic anhydride); half esters thereof (such as monomethyl maleate) and the like.
Among thses, preferable styrenic polymer (Bl) are styrene hofflopolyraers, copolymers of styrene vith (meth)acryIic monomers, copolymers of styrene wuth diene monomers, and copolymers of these monomers with a small amount of other copolymerizab I e monomers.
Styrenic polymer (B2) generally contains the units of styrene in amount of not less than 40 % by mol. and preferably 60 % by mol..
According to the present invention, suitable examples of the polyester (B2) include po lycondensates of polyol (7) with a polycarboxylie aci d (8).
Suitable examples of polyols (7) include diols (7-1) and polyols containing 3 or more hydroxyl groups (7-2), preferably (7-1) and the mixture of (7-1) and a small amount of (7-2).
Suitable examples of d-i ols—C7-4-)—L4uU.ude alkylene glycols having 2-12 carbon atoms (such as ethylene glycol. 1,2propyIene glycol, 1,3-propylene glycol. 1,4-butane diol. 1.6-hexane diol);

alkylene ether glycols (such as dicthylene glycol, trlethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, po1ytetramethylene glycol); alicyclic diols (such as 1.4-cyc 1 ohexane dimethanol); hydrogenated bisphenols (such as blsphenol A, bisphenol F, bisphenol S); alkylene oxide (such as ethylene oxide, propylene oxide,buty1ene oxide) adducts of the above-mentioned bisphenols and the like. Among these, preferable are alkylene glycols having 2-12 carbon atoms, alkylene oxide adducts of bisphenols and the combination thereof.
Suitable examples of polyols containing 3 or more hydroxy! groups (7-2)include aliphatic polyols having 3-20 carbon atoms (such as glycerol, triaethylolethane, trimethylolpropane, pentaerythritol, sorbitol); phenols containing 3 or more hydroxy! groups (such as trisphenol PA, phenol novolac, cresol novolac); oxyalkylene ethers of the above-mentioned phenols.
Suitable examples of polycarboxy1ic acids (8) include dicarboxylic acids (8-1) and polycarboxy1ic acids containing 3 or more carboxyl groups (8-2), preferably (8-1) and the mixture of (8-1) with small amount of (8-2).
Suitable examples of the dicarboxylic acids (8-1) includ( alkylene dicarboxylic acids having 2-20 carbon atoms (such as succinic acid, adipic acid, sebacic acid); alkenylene dicarboxylic acids (such as maleic acid, fumaric acid); aromatic dicarboxylic acids having 8-20 carbon atoms (such as phthalic acid, isophthalic acid, terephthalic acid, naphthalene
—-— —
dicarboxylic acid); and the like.
Among these, preferable are alkylene dicarboxylic acids having

2-20 carbon atoms and aromatic dicarboxy 1 ic acids having 8-20 carbon atoms.
Suitable examples of polycarboxy 1 ic acids containing 3 or more carboxyl groups (8-2) include aromatic po 1 ycarboxy1ic acids having 9-20 carbon atoms (such as trimellitic acid, pyroraellitic acid); and the like.
In producing polyester (B2), polyol (7) and dicarboxylic acid (8) are po1ycondensated in a molar ratio of (7):(8) of generally 1:2 to 2:1, preferably 1:1.5 to 1.5:1.
The molar ratio of (7-1): (7-2) in (7) is generally 100:0 to 80:20. preferably 100:0 to 90:10.
The suitable molar ratio of (8-1): (8-2) in (8) is same as the molar ratio of (7-l):(7-2).
The weight ratio of (AB) based on the total weight of charge controller, in case of being graft*ise or blockwise, is generally 1-100 % by weight, preferably 10-100 %. If the weight ratio of (AB) is less than 1 %, it becomes difficult to make the particle size of a discontinuous domains small.
The weight ratio of (A) based on the total weight of charge controller is generally 0-99 % by weight, preferably 0-90 %, and the weight ratio of (B) is generally 0-90 % by weight, preferably 0-50 %. If the weight ratio of (B) is more than 99 %, a lot of charge controller is required in order to get an adequate charge and it is not economical.
In the charge controller of the invention, iWa) X_t_he
total weight content of (A) and (a) ] is generally 10-99 % by weight, preferably 20-90 X. If (Wa) is less than 10 %. a lot of

charge controller is required in order to get an adequate charge and it is not economical. If (Wa) is more than 99 %, the effects due to bonding of graftwise or blockvrise are not apparent
Suitable examples of the copolymer (AB), wherein (b) is connected by being grafted or bloci (1) A graft copolymer wherein a superstrate polymer chain of (b) is grafted to a subatrate polymer chain of (a);
(2) A graft copolymer wherein a superstrate polymer chain of (a) is grafted to a substrate polymer chain of (b);
(3) A block copolymer of (a) and (b).
Among these, preferable are the graft copolymers (I) and copolymer (2) above mentioned.
Moiety (a) has a weight-average molecular weight of generally 1.000 - 100,000, preferably 2,000 - 50,000.
Moiety (b) has a weight-average molecular weight of generally 1,000 - 500,000, preferably 3.000 - 100.000.
If the weight-average molecular weight of (a) or (b) is less than 1,000, the flowing properties of the toner is badly influenced, and if weight-average molecular weight of (a) exceeds 100.000 or that of (b) exceeds 500,000, the ch.nrge controNsr can be hardly dispersed in the toner.
In order to make the particle size smaller, the total
-amoujLL.of polymer (A) is not necessarily copolymer (AB), and (AB)
as a portion of (A) is sufficient. That is to say, polymer (A) can be contained together with copolymer (AB). Furthermore

■r
polymer (B) without binding to moiety (a) can be contained.
In order to obtain this effect, it is more preferable that the structure of (b) resemble to the toner binder . Accordingly, (bl) is preferable as moiety (b) in case the styrenic polymer is used as the toner binder. Meanwhile (b2) is preferable as (b) in case polyester is used as the toner binder.
According to the present invention, charge controller may be used together with a salt of a perf1uoroal ky1 group-containing organic acid (a). Siraultanious use of the salt (a) is desirable to better charging rate.
Suitable examples of salts of perf1uoroaIky 1 group-containing organic acids (a) include perf 1 uoroa 1 ky 1 group-containing sulfonic acid salts (a-1), perf I uoroal ky 1 group-containing carboxylic acid salts (a-2), per fl uoroal ky i group-containing sulfamic acid salts (a-3), perfIuoroalky 1 group-containing acid sulfate salts (a-4) and perf1uoroalky 1 group-containing acid phosphate salts (a -5) and the like.
Suitable salts (a-1) are salts of a perf1uoroalkyl group-containing sulfonic acids and cationic components.
Suitable examples of perf1uoroaIky 1 group-containing
sulfonic acids include perf1uoroaIkanesulfonic acids (such as
perf1uorohexanesu 1 fonic acid, perf1uorooctanesu1fonic acid):
perf1uoroalkylethanesuIfonic acids (such as perfluorooctylethane-
sulfonic acid, perf 1 uorodecy1ethyanesu1fonic acid);
perf1uoroalkeny1oxybenzensulfonic acids (such as -
- -——I. i.ii— II t
perf1uorononeny1oxybenzensulfonic acid) and the like.
Suitable examples of cationic components include alkali

metals (such as lithium, sodium, potasiura), alkaline earth metals (such asmagnesiura, calcium, barium), amines (such as triethy1 amine, tributy lamine, N.N-diraethy1benzy1 amine), quaternary ammoniums (such as tributy1benzy1ammoniurn, tetraethylararaoniurn, tetrabutylamraoniurn) and the like.
Suitable salts (a -2) are salts of perf1uoroa I ky I group-containing carboxylic acids and the cationic components above-men t i oned.
Suitable examples of perf1uoroa1kyI group-containing carboxylic acids include perf luoroaIkanoic acids (such as perf1uorohexanoic acid, perf1uorooctanoic acid); perfIuoroalkenyIoxybenzoic acid (such as perfIuorononeny I oxy-benzoic acid) and the like.
Suitable salts (a -3) are salts of perf1uoroalky 1 group-containing sulfamic acids and the cationic components above-men t i oned.
Suitable examples of perfluoroa Iky 1 group-containing sulfamic acids include erf luoroalkylethanesu1famic acids (such as perf!uorooctylethanesulfamic acid, perfluorodecylethyanesulfamic acid); and the 1 ike.
Suitable salts (a-4) are salts of perf1uoroalky1 group-containing acid sulfates and the cationic components above-ment i oned.
Suitable examples of perfluoroalky I group-containing acid sulfates include raonoester sulfates of perf1uoroalky1 group-containing alcohls (such as perfIuoroocty lethano 1, perf1uorodecyI ethyanol, perf1uorohexyI methane 1): and the like.

I
Suitable salts (a-5) are salts of a perf 1 uoroal ky I group-containing acid phosphates and the cationic components above-mentioned.
Suitable examples of perf1uoroa1ky1 group-containing acid phosphates include raonoester or diester phosphates of perf1uoroalky1 group-containing alcohl above-mentioned, and the 1 ike.
Among these salts (a ), a perfIuoroa1ky1 group-containing sulfonic acid salt (a-1) is preferred, and alkali metal, alkaline metal or amine salt of a perfluoroalkyl group-containing sulfonicacid is more preferred. Salts of heavy metals (such as nickel, copper, zinc, mercury, chromium) are undesirable because of safty.
In the charge controller composition, the weight ratio of salt of a perfluoroalkyl group-contai n ijig organic acid (a) to polymer (A) or copolymer (AB) based on the total weight of charge controller composition, is generally in the range of 0-80 % to 20 -100% by weight, preferably 1-80 % to 20-99 % by weight, more preferably 3-50 to 50-97 % by weight. If the content of (a) is less than 1 % by weight, charging rate is Inadequate. If it is more than 80 % by weight, saturated charge amount and e n V i r 0 n m a n t a 1 stability are i n.? n f f i c i e n t.
Suitable examples of polymer(A) include
(1) Dich1oropheny1raaleinide homopolymer.
(2) N i tropheny 1 mal ei ra i de / the mixture of 1-aIkenes of CI2-CH / maleic anhydride (49/48/3) copolyoer.
(3) Dichioropheny1 maleimide / the mixture of 1-alkenes of C12-

C14 / maleic anhydride (51/45/4) copolymer.
(4) N i tropheny 1 mal ei mi de / perf I uoroa ll(y 1 (the mixture of C8-C12) ethyl nethacrylate (55/45) copolymer.
(5) Chi oropheny I ma leiin ide / perf 1 uoroal ky I (the mixture of C8-C12) ethyl methacrylate (55/45) copolymer.
(6) DichIoropheny I ma Ieimide / perfIuoroalky I (the mixture of C8-C12) ethyl methacrylate (48/52) copolymer.
(7) DichIoropheny 1 itaconinide / perfIuoroalky I (the mixture of C8-C12) ethyl methacrylate (49/51) copolymer.
(8) Dich1oropheny 1 itaconifflide / monoperfIuoroa Iky 1 (the mixture of C8-C12) maleate / nethy vinyl ether (34/42/14) copolymer.
(9) Perfluoroalkyl (the mixture of C8-C12) ethyl methacrylate / styrenesu1fonic acid sodium salt(91/l) copolymer.

(10) Perfluoroalky I (the mixture of C8-C12) ethyl methacrylate / styrenesu1fonic acid barium salt (89/11) copolymer.
(11) Perfluoroalkyl (the mixture of C8-C12) ethyl methacrylate / styrenesu1fonic acid tributylamine salt(85/15) copolymer
(12) Perfluoroalkyl (the mixture of C8-C12) ethyl acrylate / styrenesuIfonic acid sodium salt(91/l) copolymer.
(13) Nitropheny1 ma leimide / perf1uoroalky 1 (the mixture of C8-C12) ethyl methacrylate / 2-acrylamide-2-methy1propane-sulfonic acid (51/41/8) copolymer.
(14) ChIorophenyImaleimide / perf1uoroa 1 ky 1 (the mixture of C8-C12) ethyl acrylate / styrenesuIfonic acid sodium salt (50/45/5) copolymer. - —
(15) DichlorophenyImaleinide / styrenesu!fonic acid sodium salt (96/4) copolymer.

(16) DichlorophenyImaleimide / perf 1 uoroa1ky 1 (the mixture of C8-C12) ethyl methacrylate / styrenesulfonic acid sodium salt (46/50/4) copolymer.
(17) Dich1orophenyimaleimide / perf1uoroaiky 1 (the mixture of C8-C12) ethyl raethacrylate / styrenesulfonicacid tributyl amine salt (45/50/5) copolymer.
(18) Dich1oropheny1itaconimide / perf 1 uoroa1ky1 (the mixture of C8-C12) ethyl acrylate / styrenesu 1 fonic acid magnesium salt (65/30/5) copolymer.
(19) Dichloropheny1itaconimide / perf 1 uoroa1ky1 (the mixture of C8-C12) ethyl acrylate / sulfophenylitaconiaide sodium salt (56/40/6) copolymer.
(20) Dich 1 oropheny1itaconimide / perf1uoroalky1 (the mixture of C8-C12) ethyl methacrylate / su1fopheny1itaconimide sodium salt (30/64/6) copolymer.
(21) Dichiorophenylmaleinimide / perfluoroalkyl (the mixture of C8-C12) ethyl maleate / su 1 fopheny 1 itaconimide sodium salt / raethl vinyl ether (39/42/5/14) copolymer.
Suitable examples of copolymers (AB) of (a) with (b) include graft copolymers of the moiety (a) above-mentioned with the moiety (b) illustrated as follows :
(1) A moiety of styrene horaopolymer.
(2) A moiety of styrene / butyl acrylate (95/5) copolymer.
(3) A moiety of styrene / butyl acrylate (87/13) copolymer.
(4) A moiety of styrene / butyl methacrylate (75/25) copolymer.
(5) A moiety of styrene / butadiene (90/10) copolymer noiety.
(6) A moiety of bisphenoi A propylene oxide 2 moi. adduct /

isophthalic acid condensation polymer.
(7) A moiety of bisphenoi A propylene oxide.2 niol. adduct / isophthalic acid condensation polymer.
(8) A moiety of bisphenoi A propylene oxide 2 mol. adduct / terephthalic acid condensation polymer.
(9) A moiety of bisphenoi A ethylene oxide 2 mol. adduct / raaleic acid condensation polymer.

(10) A moiety of bisphenoi A propylene oxide 3 mol. adduct / raaleic acid condensation polymer.
(11) A moiety of bisphenoi A ethylene oxide 3 mol. adduct / terephthalic acid condensation polymer.
Illustrative preparation method of the polymer (A) in the present invention is as follows :
The polymer (A) is obtained by polymerizing the monomers required to be the aimed structure from the first stage of the reaction. For example. (A) is obtained by copol ymerizing monomer(l), such as itaconic acid, with monomer (2) under the presence of azobisisobutyronitri1e. followed by reacting a group (X)- substituted aniline.
Illustrative preparation methods of the graftwise or hlockwise copolymers (AB) in the invention are as follows :
1) Macromer method of obtaining graft copnlyiner by copoLvnieri?. ing a compound containing a structure introducing pol ymerizable group, such as aryl group, in the end of the styrenic polymer moiety or polyester moiety (b), with the aonojiejs composing (a) by which the copolymer aioiety (a) can be introduced.
2) Polymer reaction method of obtaining a copolymer by

copolymerizing a compound containing a structure being introduced a group reactive ?ith the copolymer moiety (a), sucli as amino group or hydroxyl group, in the end of the styrenic polymer moiety or polyester moiety (b), with the reactable group in the side chain of the copolymer moiety (a), such as carboxyl group or acid anhydride group. 3) Main chain initiating polymerization method of obtaining graft copolymer by reacting a compound having a structure introducing a polymerization initiating group, such as peroxide group, in the side chain of the styrenic polymer moiety (bl) or polyester moiety (b2). and the monomers composing (a) by which the copolymer raoiety (a) can be introduced ; or by reacting a compound conatining a structure introducing polymerization initiating group in the side chain of (a), with styrene and, if necessary, another copolymerizab le monomer.
The preparation method of (a) is fundamentally the same as the above-mentioned production method of polymer (A). For example, the method of introducing a group reactive with the group located at the end of (b). such as carboxyl group or acid anhydride group, is same as the preparation method of the above-mentioned, and in order to introduce acid anhydride group, (a) is obtained by copolymerizing a monomer having an acid anhydride group in the same way as the preparation method of polymer (A) before the-pQly#«ri zat i on of the monomers composing (a).
Methods of introducing a polymerization initiating group

in the side chain of (a) include, for example, a method of reacting hydroperoxide with (a) having a acid anhydride group.
The compound having a structure for introducing the above-mentioned reactive group at the end or side chain of the styrenic polymer moiety (bl) can be prepared by using conventional methods.
For example, a compound having a hydroxyl group at the end of (bl) is prepared by a radical copolyracrization of styrene and another copoIyraerizab 1 e monomer under the presence of a hydroxyl group-containing chain transfer agent.
A compound having a hydroxyl group at the end of the polyester moiety (b2) can be also prepared by using conventional methods.
For example, a compound having a hydroxyl group in the end of (b2) is prepared by using excess amount of polyol (7) in the condensation polymerization process of polyol (7) and pol ycarboxy 1 i c acid (8) which compose (b2). A compound having a raetacryloyl group in the end of (b2) can be obtained by reacting methacryloyl isocyanate with the above-mentioned (b2) having hydroxyl group.
Moreover, in preparing (b2), polyol (7) and polycarboxy1ic acid (8) are not necessarily applied for the polycondensation . The aimed polyester moiety (b2) can also be prepared by applying derivatives of (7) (such as lower
monocarboxy 1 i c acid ester, alcoholate) and der i vat ives 444-8
(such as lower alcohol ester, acidanhydride, acid halide) for polycondensat ion.

The charge controller of the Invention can be preliminarily mixed with a toner binder, before preparing the toner, to be used as a toner binder composition of the invention having a charge controlling properties.
Suitable toner binders include styrenic polymers, polyesters, epoxy resins, polyolefins, po1yurethanes and the like polymers previously used as toner binders..
Suitable styrenic polymers include : copolymers of styrene with (raeth)aerylates. copolymers of styrene with diene monomers (such as butadiene and isoprene). and copolmers of styrene with other copolymerizable monomers.
Suitable polyesters include po 1 ycondensates of aromatic dicarboxylic acids with oxyalkylene ethers of bisphenols.
Suitable epoxy resins include : reaction products of aromatic diols and epich1orohydrines ; and modified compounds thereof.
Suitable polyolefins include : polyethylene, polypropylene, copolymers of ethylene, propylene with other copo I ymer i zab le monomer.
Suitable polyurethanes include : a poly addition compound of aromatic diisocyanate and an alkylene oxide adduct of an aromatic „d_iol.
Illustrative methods of preparing the toner binder composition of the invention include the following : (1) a method of polymerizlag the monomers for preparing the toner binder mentioned above under the presence of the charge control ler.

(2) a method of mixing the toner binder and the charge controller
in the solvent, such as an aromatic hydrocarbon (toluene, xylene
or the like), a halogenated compound (chloroform, ethylene
dichloride or the like), ketone (acetone, methylethyl ketone
or the like) or amide (dimethy1formamide or the like).
(3) Method of thermally melting and mixing the toner binder and
the charge controller.
The charge contoller of the present is mixed with a toner binder and a colorant, and used as a toner composition of the present invention.
Suitable of the example of colorants include such pigments and dyestuffs, used previously, as carbon black, iron black, Sudan black SM, First yellow G. Benzidine yellow. Pigment yellow, India first orange, Irgasine red, Baranito aniline red, Toluidine red. Carmine FB, Pigment o'range R, Raykired 2G, Rodamine FB, Rodamine B rake, Methy1violette B rake, Phtharocyanine blue. Pigment blue, Brilliant green, Phtharocyanine green. Oil yellow GG, Kayaset YG,Orasol brawn B, Oil pink OP and the 1 ike.
Polymer is contained, within the toner binder composition and the electrophotographic toner of the invention, in an amount of generally 0.1 -20 %hy weight, preferably 0.3 - 10 X by weight based on toner.
If the amount of polymer is less than 0.1 %, the charge in the toner becora small, and if it is more than 20 %, the environmental stability of the toner becomes worse.
Toner comorise"?. ha.sed on the weigTit of toner,

;enerally 0.1-20 % by weight of the charge controller. 30-95 % )y weight of the toner binder, and 0-15 % by weight of the ;olorant, and if necessary, less than 60 % by weight of a lagnetic powder. Suitable magnetic powders include powders of >trong magnetic metal (such as iron, cobalt, nickel), magnetite, lematite, ferrite and the like, and these magnetic powders have )roperties as a colorant.
In addition, various additives can be contained, for example, a lubricant (such polytetrafluoroethylene, low molecular (feight polyoiefin, fatty acid or metal salt or amide thereof) ind the other charge controllers (such as azo dyestuff containing netal, salicylic acid metal salt). Furthermore, fine particles jf hydrophobic colloidal silica can be used in order to improve flowing properties of the toner. The amount of these additives is generally less than 10 % by weight based on the weight of the toner.
Preferable binder compositions include ones comprising:
(1) discontinuous domeins composed of at least a portion of the charge controller; and
(2) a continuous phase composed of ay least a portion of a toner b inder.
The charge controller is easily exposed on the surface and the toner is capable of providing sufficient charge even with addition in a small amout of the charge controller, as compared with a charge controller compatibile with toner binder. _____
Phase or domain of (1) and (2) above-mentioned can be determined by checking the existence of the interface through

the observing cut of the toner vrith transmission electro-microscope. For a clear examination of the interface, it is effective to examine the cut of the toner with an electro-microscope after dying the cut with ruthenium tetraoxide, osmium tetraox1de or the 1i ke.
Said domains have particle size of generally 0.01-4 / m, preferably 0.05-2 u ti. Particles of more than 4 un cause an insufficient dispersibi1ity and a wider charge distribution, worse transparency in usage of color toner, meanwhile those of less than 0.01 u Jn do not form discontinuous domains and compatibility with the binder. Therefore the content of the charge controller on the surface of the toner becomes smaller and the charge becomes insufficient.
The preparation method of the electrophotographic toner of the invention is not paticularly limited. Illustrative methods of the sameare as follows :
(1) Kneading and pulverizing method
The components of the toner are blended in a dry atmosphere and then kneaded, followed by roughly crushing and finally pulverizing with a jet mill and the like. Furthermore, the product is classified into a fine powder having a particle average size of 5-20 //m, to obtain the toner.
(2) Additional blending method
In a dry atmosphere, the charge controller of the invention is blended with particles having 5-20 u in diameter, comprising the toner binder and the colorant, with or without, the lubricant and the magnetic powder, followed by mixing the

blended product vigorously, under heating with a mixer, optional , to obtain the toner. (3) Polymerization method
The charge controller of the invention, the colorant and the other components are dispersed and dissolved in raw material monomers of the toner binder, followed by polymerizing them in water. The product is dried and the toner having 5 - 20 //m d iameter is" obtain
The toner of the invention is, if necessary, mixed with a carrier powder, such as iron powder, nicicel powder, glass bead or the like, and may be used as a developer for an electrostatic latent image in an electrophotography.
The toner of the invention may be fixed on the substrate, such as a paper, a polyester film and the like, with a copying machine or a printer. Illustrative fixing methods on the substrate include a heat roll fixing method and a flash fixing method.
The charge controller of the invention may also be useful for a liquid developer and powder coat and the like.

Having generally described the invention, a more complete understanding can be obtained by reference to certain specific examples, which are included for purposes of illustration only and not intended to be limiting unless otherwise specified. Hereinafter, part(s) means weight part(s).
(1) Measurement, of the Dielectric Loss Tangent [tan d]
A charge controller is pulverized into powders of average diameter of not more than 50 // ra with an agate mortar, and a test piece is prepared by compression molding in an electrode. The equipments used for this measurement:
body; TR-1100 (supplied from Ando Denki Co.. Ltd.) electrode; SE-43 (supplied from Ando Denki Co., Ltd.) frequency; 100kHz
(2) Measurement of the Water Absorbancy (%)
In a same manner as above-mentioned, "after a charge controller is" pulverized into powders of average diameter of not more than 50 u m with an agate mortar, 2g of the tested powder is weighed and dried under reduced pressure at 35°C for 4 hours, followed by control ofthe moisture of 85 % R.H. at 35°C for 12 hours. Thereafter a weight is measured again and the water absorbancy {%) is calculated from the percantage of an increase of weight (the difference between the weight of after drying and that of before drying) per the weight of before drying.
(3) Preparation of Developers
The developers were prepared by mixing 1 part of the toner and 24 parts of theferrite carrier coated with silicone

resin for electrophotography (FL961-150, supplied from Povdertec, Md. ).
(4) Measurement of the Electrostatic Charge (Saturated
Charge)
The moisture of the above-ientioned developers were controlled at 23V under 50 % R. H. for at least than 8 hours, and then each sample was stirred with a terbler shaker mixer using a frictional force at 50 r.p.m. for each period of 1. 3, 7, 20, 60 and 120 minutes, and measured the electrostatic charge in each period. The charge at the period when the growth of the electrostatic charge was not observed was defined as the saturated charge.
The equipment used for this measurement: Blow off method charge measuring machine (supplied from Toshiba Chemical Co., Ltd. )
(5) Evaluation Criteria of the Charging Rate
In accordance with the above-mentioned results of the amount of the charge measured, the ranking of the charging rate was determined based on the following criteria : A: The stirring period using a frictional force is less than 7
minutes, when the charge reaches upto 80 % of the saturated
charge. B: The stirring period using a frictional force is 7-20 minutes C: The stirring period using a frictional force is 20-60 minutes D: The stirring period using a frictional force is more than 60
minutes
(6) Measurement of Dependence to the Circumstances

After the moisture of the above-mentioned developers is controlled in high temperature and high humidity and in low temperature and low humidity, the electrostatic charge of these samp 1es is measured.
Low temperature and low humidity : lOt:, 40% R. H.
High temperature and high humidity : 351: , 855IS R. H.
Evaluation Criteria :
The change of the amount of the electrostatic charge in
low temperature and low humidity and in high temperature and
high humidity is A: small, B: medium, C: large.
(7) Measurement of Charge Distribution
The moisture of the above-mentioned developers were controlled at 23°C under 50 % R. H. for not less than 8 hours, and the test samples were mixed with terbler shaker mixer using a frictional force at 50 r.p.m.'for 20 min., and then the charge distributionasmeasured.
Equipment: The charge distribution of the particle testing machine (EST-1, supplied from Hosokawa Micron, Co., Ltd.) Eva 1 nation Criteria :
A: The charge amount distribution is narrow. B: The charge amount distribution is medium. C: The charge amount distribution is wide.
(8) Copying Test
A continuous copying test of the above-mentioned developers was done with a copying machin,e for evaluation. Copying machine for evaluation '• An negatively chareed e I pntmnhotbgraph i c copying machine

uing selenium sensitized material. The number of papers available for a continuous copying is 20,000. Evaluation Criteria : A: The copied image on the paper is good after the 20,000
sheets of continuous copying. B: The deterioration of the copied image on the paper is
slightly observed after the 20,000 sheets of continuous cop y ing.
C: The deterioration of the copied image on the paper is
apparently observed after the 20,000 sheets of continuous c opy i ng.
D: The copied image is poor from the beginning of copying. (9) Evaluation of Transparency
The toner binders and the charge controllers were kneaded vithout the addition.,of the colorants and the low molecular weight polypropylene, and then the kneaded samples were molded into cylindrical pellets of about 5 mm with melt indexer and the transparency of the pellets were visually evaluated. Evaluation Criteria A: Transparent
B: S1ight1y c loudy
C: CI oudy in white color

Examp1e Al
In xylene at the boiling point, 733 parts of the mixture of 1-alkenes of C12-14 / maleic anhydride copolymer (PA-124, supplied from Mitsubishi Chemical Industries, Ltd.) and 307 parts of m-nitroani1 ine were reacted to form an imide for 4 hours with removal of water, and then xylene was distilled off, to obtain the charge controller (Al) of the invention. Example A2
Example Al was repeated, except using 360 parts of 3,4-di ch 1 oroani1ine in place of m-nitroani1ine, to obtain the charge controller (A2) of the invention. Examp1e A3
In xylene at the boiling point, 647 parts of the mixture of 1-alkenes of C12-14 / maleic anhydride copolymer (PA-124), and 130 parts of perf1uoroalky1ethano1 (Cheminox FA-M[C10up], supplied from Japan Mectron Co., Ltd.) were ha 1f-esterified for 5 hours.
Thereafter 256 parts of m-nitroani1ine was added to be reacted to form an imide for 5 hours with removal of water, then xylene was distilled off,to obtain the' charge controller (A3) of the i nven t i on. Examp 1 e A4
Into an autoclave, were charged 800 parts of the mixture of 1-alkenes of C12-14 / maleic anhydride copolymer (PA-124, supplied from Mitsubishi Chemical Industries, Ltd.), and 200 parts of styrene in the presence of 0.4 part of di-tert-butyl peroxide as an ininiator, polyaerized graftwise at 80 "C , to

obtain a graftwise-po lymer (1).
Example A3 was repeated, except using 809 parts of above-obtained graf tw i se-po 1 ymer (1) in place of tlie mixture of I-al)(enes of C12-H / nialeic anhydride copolymer (PA-I24), to obtain the charge controller (A4) of the invention. Examp1e A5
723 parts of bisphenol A propylene oxide 2 raol.adduct and 348 parts of terephtalic acid were polycondensated at 230 °C using 2 parts of dibutyltin oxide as a catalyst, to obtain a polyester (1) having a weight-average molecular weight of 6,000 and a hydroxyl value of 20 ag KOH/g.
In xylene at the boiling point, 647 parts of the mixture of 1-alkenes of C12-I4 / laleic anhydride copolymer (PA-124), 162 parts of the polyester (1),,and 130 parts of perf1uoroalky1ethano 1 (Cheminox FA-M [C lOup]), were ha 1f-esterified for Shours.
Thereafter 256 parts od m-aitroani1ine was added to be reacted to form to an imide for 5 hours with removal of .water, then xylene wasdistilled off,to obtain the charge controller (A5) of the invention. Examp1e A6
In N, N-dimethyl formamide (DMF) at the boiling point. 508 parts of m-nitropheny 1 ma leimide, 412 parts of perf1uoroa1ky1ethy 1 methacrylate (Cheminox FAMAC-C8, supplied from Japan Mectron Co.,Ltd.) and 80 parts of 2-acrylamide-2-raethylpropanesulfonic acid were polymerized using di-tert-buty1peroxide as an initiator for 8 hours,

'follofed by distilling off DMF. to obtain the charge controller (A6) of the in ven t i on. Example A7
Example A6 was repeated, except using 457 parts of 3,4-dich1 oropheny1 ma 1 einide, 503 parts of perf1uoroa1ky1ethy 1 methacrylate and 40 parts of styrenesu1fonic acid sodium salt, in place of m-nitropheny 1 ma leimide, 412 parts of perf1uoroaIky 1 ethy 1 methacrylate and 2-acry1 amide-2-methy1propanesu 1 fonic acid, to obtain the charge controller (AT) of the invention. Examp 1 e A8
500 parts of styrene and DMF were further added to 500 parts of the charge controller (AT), and polymerized graftwise using di-tert-buty1 peroxide as an initiator for 4 hours, followed by distilling off DMF, to obtain the charge controller (.A8) of the invention. Examp1e A9
Example A6 was repeated, except using 9 60 parts of 3,4-dich1 oropheny1 ma 1 eimide, 40 parts of styrenesu1fonic acid sodium salt, in place of in-n i tropheny 1 ma 1 e i m i de.
perf1uoroa1ky1ethy1 methacrylate and 2-acry1 amide-2-methy 1 propane -sulfonic acid, to obtain the charge controller (A9) of the i nven t i on. Examp1e AlO
In methy ethyl ketone (MEK), 511 parts of perf1uoroalkylethy1 acrylate (FLUOfET AC-812, supplied from Hechst Indstries Co.,Ltd.) and 223 parts of itaconic anhydride were polyneTized using 50 parts of azo-bis-isobutyronitrile as

an initiator for 4 hours, to obtain a copolymer (1) having i weight-average molecular weight of 18,000.
In an autoclave, were charged 800 parts of the copolymer (1) and 1.000 parts of styrene in the presence of di-tert-buty1 peroxide as an ininiator, polymerized graftwise at 180 °C for 4 hours, followed by distilling off MEK under reduced presure. to obtain a graftwise-po 1 ymer (2).
262 parts of 3, 4-dich 1 oroani1ine, 37 parts of p-aminobenzenesulfonic acid sodium salt and DMF were added to 173 4 partsof the graft-copo1ymer (2), and reacted to form an imide for 8 hours in DMF at the boiling point, followed by distilling off DMF, to obtain the charge controller (AlO) of the invention. Examp1e All
In DMF, 912 parts of perfIuoroa1ky1ethy 1 methacrylate (Cherainox FAMAC-C8) an.d 88 parts of styrenesulfonic acid sodium salt« were polymerized using azo-bis-isobutyronitrile as an initiator for 4 hours in DMF at the boiling point, followed bydis tilling off DMF, to obtain the charge controller (All) of the invention. Examp1e A12
Example A6 was repeated, except using 476 parts of 3, 4-dich1oropheny1 ma 1eiraide and 524 parts of perf1uoroa1ky 1 ethy 1 methacrylate, in place of m-nitropheny 1 ma 1eimide, 412 parts of perf1uoroa1ky1ethy 1 methacrylate and 2-aery 1 amide-2-methy 1 propane -sulfonic acid, to obtain a copolymer (1).
200 parts of perf1uorooctanesu1fonic acid sodium salt was. added to the rnnnlvmpr (]). anririi..
"by distilling off DMF, to obtain the charge controller (A12) of the invention. Exaup1e Al3
Example A6 was repeated, except using 1,000 parts of 3,4-dich1oropheny 1 ma 1 eimide alone, in place of m-nitropheny1 maleimide, perf1uoroalkylethy 1 methacrylate and 2-aery 1 amide-2-methy1propanesu1fonic acid, to obtain homopolymer (1).
200 parts of barium salt of perf1uorooctanesu1fonic acid was added to the homopolymer (1), and dissolve uniformly, followed by distilling off DMF, to obtain the charge controller {A13) of the invention. Cofflperative Examples CAl
Example Al was repeated, except using 243 parts of m-aiB i Bopheno 1 in place of m-n i t roan i 1 i ne, to obtain the charge controller (CAl) for comparison. Comparative Examples CA2
In mixture of toluene and methanol, 920 parts of styrene and 80 parts of 2-acryl am i de-2-methy 1 propanesu 1 f on i c acid were polymerized using azo-bis-isobutyronitrile as an initiator for 8 hours, followed by distilling off solvent under reduced presure, to obtain the charge controller (CA2) for comparison. Comperative Examples CA3
In DMF at the boiling point, 912 parts of styrene and 88 parts of styrenesulfonic acid sodium salt, were polymerized using azo-bis-isobutyronitrile as an initiator for 4 hours, followed by distilling off DMF under reduced presure, to obtain the charge controller (CAS) for coaiparison.

Comperative Exanples CA4
In toluene at the boiling point, 1,000 parts of perf1uoroa1kyIethy 1 methacry1 ate was polymerized using azo-bis-isobutyronitri1e as an initiator for 4 hours, followed by distilling off toluene under reduced presure, to obtain the charge controller (CA4) for coiaparison. Comperative Examples CAS
Example All was repeated, except using 721 parts of perfluoroalkylethyl methacrylate and 2 78 parts of styrenesulfonic acid sodium salt, in place of 912 parts of perfluoroalkylethyl methacrylate and 88 parts of styrenesulfonic acid sodium salt, to obtain the charge controller (CA5) for comparison. Comperative Examples CA6
Perf1uorooctanesurufonic acid sodium salt was used as the charge controller (CA6) for comparison.

Table ..
Charge controller Dielectric loss Water
No. tangent [ tan (5 ] absorbancy (%)
(AD 0. 012 0. 7
(A2) 0.010 0.6
(A3) 0.014 0.6
(A4) 0. 009 0. 5
(A5) 0.013 0.8
(A6) 0.015 1.7
(A7) 0. 039 1. 5
(A8) 0.017 0.9
(A9) 0.016 1.6
(AlO) 0. 015 0. 9
(All) 0. 050 1. 6
(A 12) 0. 0 88 1... 3
(A13) 0. 084 " 0. 9
(CAD 0. 007 3. 1
(CA2) • 0.006 4.3
(CA3) 0. 006 5. 7
(CA4) 0. 007 0. 1
(CA5) 0. 420 8. 4
(CA6)

On removing toluene, the toner binder cooposition (Bl) of the "invention was obtained. Exanip I e B2
20 parts of the charge contro1! er (A8) and 1000 parts of a styrenic toner binder (Himer l)NI-3000) were solved and mixed in DMF. On removing DMF, the toner binder composition (B2) of the invention was obtained.
After dying the cut of toner binder composition (B2) with ruthenium tetraoxide, about 1 u of dispersed particles were observed with a transmission electro-microscope (TEM). However, in accordance with Himer UNI-3000, none of existence of dispersed particles was observed. Example 83
Condensation polymerization of 417 parts of bisphenol A propylene oxide 2 mol. adduct, 341 parts -of bisphenol A ethylene oxide 2 mol. adduct and" 310 parts of terephthalic acid were done using 2 parts of dibutyitinoxide as a catalyst, to obtain the polyester toner binder (1) having a weight-average molecular weight of 8, 000.
10 parts of the charge contr*oller (A7) and 1,000 parts of the toner binder (1) were mixed in the same manner as Example B2, to obtain the toner binder composition (B3) of the invention.
About 2 u tR of dispersed particles were observed by TEM.
Examples T1-T4 and Comperative Examples CTl
Each toner was prepared using, as components, each charge controller (parts) as shown in Table 2, 1000 parts of styrenic

'-3000, supplied from Sanyo Chemical *'I ndusf Ties, ' .), .. of carbon black (MA-100, supplied from Mitsubisr. . Chemical Industries, Ltd.):and 40 parts of low molecular weight polypropylene (Viscol 660P, supplied from Sanyo Chemical Industries, Ltd.) and according to the following p rocess :
In the first place, these components were preliminarily mixed with Henschel mixer (FMIOB, supplied from Mitsuimiike Kakouki, Ltd.) and then kneaded with a twin screw extruder(PCM-30, supplied fr'om Ikegai, Ltd.) Each of the resulted products was further pulverized finely with a supersonic jet mill Labo Jet (supplied from Japan Pneumatic Industries, Ltd.) and classified afterwards with a air stream classifier (MDS-I, supplied from Japan Pneumatic Industries. Ltd.) to obtain each powdered product having a particle size of 5-20 /im, namely the toner (T1)-(.T4) of the invention and the toner (CTP for •comparison.
The evaluation results are shown in Table 2. Examp 1 e 15
Example Tl was repeated, except using 1040 parts of the toner binder composition (Bl) in placed ofHimer UNI-3000 andexc eptwithout adding any charge controller, to obtain the toner (T5) of the invention.
The evaluation results are shown in Table 2. Examples Tfi-Tl' nr' 'moerative Fvamo' r-r") -r,TH
Example Tl was repeated, except using 80 "parts of carbon black in placed of 50 parts, to obtain the toner (T6.)-(T13) of the invention and the toner (CT2)-(CT-8) for comparison.

The evaluation results are shown in Table 2. Example Tl-I
Example T6 was repeated, except using 1020 parts of the toner binder composition (B2) in placed of Himer UNI-3000 and except without adding any charge controller, to obtain the toner (T14) of the invention.
The evaluation results are shown in Table 2.

*3 ; Dependence to circumstances * -l : Charge distribution *5 : Copying test
Examples Tl5-T19

Condensation polymerization was done using 751 parts of bisphenol A propylene oxide 2 mol. adduct and 104 parts of triraellitic anhydride and 2 parts of dibutyltin oxide as a catalyst, to obtain the polyester toner binder (2) having a softening point of 127 °C.

Example Tl was repeated, except using polyester toner binder (2) in place of the styrenic toner binder, in accordance with the recipes as shown in Table 3, to obtain the toners (T15) and (T16 of the invention.
Example T6 was repeated as well, except using polyester toner binder (2) in place of the styrenic toner binder, in accordance with the recipes as shown in Table 3, to obtain the toners (T17)-(T19) of the invention.
The evaluation results are in Table 3.

WE CLAIM :
1. A method of producing a polymer for using as a charge
controller of a toner said method comprising polymerizing an
ethylenically unsaturated first monomer having an aromatic ring
substituted with at least one electron-attractive group selected from
the class consisting of a halogen atom, nitro group and cyano group
with or without at least one other monomer, and/or an ethylenically
unsaturated second monomer having an organic acid group or salt
thereof with at least one other monomer to obtain a polymer having
a dielectric loss tangent of 0.008 to 0.3 at lOOkHz and a water
absorbancy of at most 10% by weight, said other monomer being
selected from the class consisting of a perfluoroalkyl group-
containing monomer, a silicone group-containing monomer, an
olefin, a vinyl ether, an aromatic vinyl hydrocarbon (meth)acrylic
acid, a (meth) acrylate, a diene, a vinyl ester and a nonomer having
nitrile group.
2. The method as claimed in claim 1, wherein said polymer comprises at least 5% by weight of units of said first monomer.
3. The method as claimed in claim 1 or 2, wherein said first monomer is an ethylenically unsaturated monomer selected from the class consisting of a styrene, an aromatic ring-containing maleimide, an aromatic ring-containing itaconimide, an aromatic ring-containing acrylate or

methacrylate, an aromatic ring-containing acrylamide o methacrylamide and an aromatic ring-containing vinyl ether, the aromatic ring of said first monomer being substituted with an electron-attractive group such as herein described.
4. The method as claimed in claim 3, wherein said first monomer is a phenylmaleimide or a phenylitaconimide, the aromatic ring of which is substituted with an electron-attractive group such as herein described.
5. The method as claimed in claim 1 or 2, wherein said polymer comprises 0.1-20% by weight of units of said second monomer containing an organic acid group or salt thereof.
6. The method as claimed in claim 2 or 5, wherein said polymer comprises units of a monomer selected from the class consisting of a perfluoroalkyl group-containing monomer and a silicone group-containing monomer.
7. The method as claimed in claim 6, wherein the units of said monomer selected from the class consisting of a perfluoroalkyl group-containing monomer and a silicone group-containing monomer is contained in an amount of 10 to 94.9% by w^eight.

V 1
8. The method as claimed in claim 1 or 5, wherein said organic
acid group is selected from the class consisting of sulfonic acid
group, sulfamic acid group, acid sulfate group, carboxylic acid
group and acid phosphate group.
9. The method as claimed in claim 8, wherein said organic acid group is sulfonic acid group.
10. The method as claimed in claim 8, wherein said second monomer is an aromatic sulfonic acid group-containing monomer or salt thereof.
11. The method as claimed in claim 10, wherein said second monomer is a monomer selected from the class consisting of styrenesulfonic acid, sulfophenylacrylamide, sulfophenylmaleimide, sulfophenylitaconimide and salts thereof.
12. The method as claimed in claim 8, wherein said salt is a salt of at least one selected from the class consisting of an alkali metal, an alkaline earth metal, an amine and ammonium.
13. The method as claimed in claim 8, wherein said polymer comprises units of a monomer selected from the class

consisting of a perfluoroalkyl group-containing monomer and a silicone group-containing monomer.
14. The method as claimed in claim 1, wherein said polymer
has a weight-average molecular weight of 1,000 to 500,000.
15. A method of producing a polymer for using as a charge
controller of a toner, substantially as hereinabove described and
exemplified.

Documents:

449-mas-96 abstract.pdf

449-mas-96 claims.pdf

449-mas-96 correspondence others.pdf

449-mas-96 correspondence po.pdf

449-mas-96 description (complete).pdf

449-mas-96 form-1.pdf

449-mas-96 form-26.pdf

449-mas-96 form-4.pdf

449-mas-96 form-9.pdf

449-mas-96 petition.pdf

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Patent Number

193013

Indian Patent Application Number

449/MAS/1996

PG Journal Number

30/2009

Publication Date

24-Jul-2009

Grant Date

Date of Filing

21-Mar-1996

Name of Patentee

SANYO CHEMICAL INDUSTRIES, LTD

Applicant Address

11-1, ICHINOHASHI-NOMOTO-CHO, HIGASHIYAMA-KU, KYOTO

Inventors:

#	Inventor's Name	Inventor's Address
1	HIDEO NAKANISHI	C/O SANYO CHEMICAL INDUSTRIES, LTD., 11-1, ICHINOHASHI-NOMOTO-CHO, HIGASHIYAMA-KU, KYOTO
2	TOHRU OHAMA	C/O SANYO CHEMICAL INDUSTRIES, LTD., 11-1, ICHINOHASHI-NOMOTO-CHO, HIGASHIYAMA-KU, KYOTO
3	NAOKI TAKASE	C/O SANYO CHEMICAL INDUSTRIES, LTD., 11-1, ICHINOHASHI-NOMOTO-CHO, HIGASHIYAMA-KU, KYOTO
4	AKIRA KODANI	C/O SANYO CHEMICAL INDUSTRIES, LTD., 11-1, ICHINOHASHI-NOMOTO-CHO, HIGASHIYAMA-KU, KYOTO
5	MUNEKAZU SATAKE	C/O SANYO CHEMICAL INDUSTRIES, LTD., 11-1, ICHINOHASHI-NOMOTO-CHO, HIGASHIYAMA-KU, KYOTO

PCT International Classification Number

N/A

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA