Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/087—Binders for toner particles
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/0802—Preparation methods
  • G03G9/0812—Pretreatment of components
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/0819—Developers with toner particles characterised by the dimensions of the particles
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/0821—Developers with toner particles characterised by physical parameters
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/087—Binders for toner particles
  • G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • G03G9/08704—Polyalkenes
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/087—Binders for toner particles
  • G03G9/08702—Binders for toner particles comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • G03G9/08706—Polymers of alkenyl-aromatic compounds
  • G03G9/08708—Copolymers of styrene
  • G03G9/08711—Copolymers of styrene with esters of acrylic or methacrylic acid
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/087—Binders for toner particles
  • G03G9/08742—Binders for toner particles comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • G03G9/08755—Polyesters
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/087—Binders for toner particles
  • G03G9/08742—Binders for toner particles comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • G03G9/08759—Polyethers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/087—Binders for toner particles
  • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
  • G03G9/08786—Graft polymers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/087—Binders for toner particles
  • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
  • G03G9/08788—Block polymers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/087—Binders for toner particles
  • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
  • G03G9/08793—Crosslinked polymers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/087—Binders for toner particles
  • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
  • G03G9/08795—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their chemical properties, e.g. acidity, molecular weight, sensitivity to reactants
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/087—Binders for toner particles
  • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
  • G03G9/08797—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their physical properties, e.g. viscosity, solubility, melting temperature, softening temperature, glass transition temperature

Definitions

• the present invention relates to a resin microparticle for a toner raw material which has a uniform particle shape and form, an aqueous dispersed system having a microparticle in a disperse phase, and a toner comprising the microparticle.
• a toner for electrostatic development obtained by that method tends to has a wide particle size distribution and has a lot of coarse powders and fine powders. Therefore, it is pointed out that the deterioration of image quality and a carrier pollution by the toner easily occur. Furthermore, for producing a toner having a small particle diameter and a narrow particle size distribution by the kneading and grinding method, much energy may be required in some cases.
• Patent Document 1 As a method for producing an aqueous dispersed system of a resin microparticle, a method using a twin screw extruder has been disclosed (refer to Patent Document 1). That is a method comprising dissolving a polyester resin in an organic solvent to have a viscosity capable of emulsification and adding water thereto for the phase inversion emulsification. Since that method employs an organic solvent, a process for removing such a solvent is troublesome and there is also a problem of economical efficiency. Further, it is difficult to completely remove an organic solvent from the aqueous dispersed system. Therefore, there are problems of environmental contamination, safety, odor and the like caused by the organic solvent.
• Patent Document 2 a method comprising melting a raw material for a toner comprising a polyester resin, adding water to the melted product for the phase inversion emulsification to form a resin microparticle, and agglomerating and fusing the formed resin microparticle to obtain a toner.
• Patent Document 2 a microparticle having a particle diameter of not less than 2.4 ⁇ m before fusion has only been disclosed.
• a particle diameter of the microparticle before fusion is big, there has been a problem that it is not possible to obtain a resin microparticle having physical properties that the present inventors have targeted.
• Patent Document 1 JP1998-139884A
• Patent Document 2 JP2002-351140A
• An object of the present invention is to provide a resin microparticle for a toner raw material that has a small particle diameter and a narrow particle diameter distribution, having low odor. Furthermore, the invention is to provide a toner comprising the resin microparticle and an aqueous dispersed system of the resin microparticle.
• the present inventors have conducted an extensive study. As a result, they have found that a resin is melted and mixed in the presence of water to form a resin microparticle for a toner and the thus-formed resin microparticle has excellent performance. Thus, the present invention has been completed.
• the present invention relates to:
• a particle diameter of 50% volume (D50) satisfies the relationship 0.05 ⁇ m ⁇ D50 ⁇ 1 ⁇ m;
• the content of an organic solvent is not more than 70 ppm;
• the resin microparticle according to the present invention has a particle diameter of 50% volume (D50) of 0.05 ⁇ m ⁇ D50 ⁇ 1 ⁇ m so that a component such as a dye or a wax is satisfactorily dispersed in the preparation of a toner. Further, the resin microparticle has the relationship of a particle diameter of 10% volume D(10) and a particle diameter of 90% (D90) of D90/D10 ⁇ 7 so that a toner obtained from the resin microparticle does not contaminate a carrier, thus resulting in obtaining excellent image quality. Further, the resin microparticle has the content of an organic solvent of not more than 70 ppm so that a toner obtained from the resin microparticle produces low order. Thus, the toner is preferable from the viewpoint of working environment as well. Therefore, the resin microparticle of the present invention can be suitably used for a toner raw material.
• a particle diameter of 50% volume (D50) of the resin microparticle (A) for a toner raw material is 0.05 ⁇ m ⁇ D50 ⁇ 1 ⁇ m, and preferably 0.1 ⁇ m ⁇ D50 ⁇ 0.7 ⁇ m. Furthermore, the relationship between a particle diameter of 10% volume (D10) and a particle diameter of 90% volume (D90) of the resin microparticle (A) for a toner raw material is D90/D10 ⁇ 7, and preferably D90/D10 ⁇ 4.5.
• the particle diameter of the resin microparticle (A) is within the above range, a toner having a small particle diameter distribution can be obtained in the preparation of a toner using such a microparticle. Furthermore, dispersability of a component such as a colorant, a releasing agent, a charge controlling agent or the like in the toner becomes good so that compositions between toners become homogeneous. Thus, performance or reliability as a toner is stable.
• the content of an organic solvent in the resin microparticle (A) for a toner raw material is not more than 70 ppm and preferably not more than 30 ppm.
• the content of the organic solvent in the resin microparticle (A) is within the above range, a toner without having problems of environmental contamination or odor can be obtained.
• a low molecular weight component in the toner particle or a non-polar component such as a wax having a low melting point is considered to be conveyed to a surface of the toner particle with volatilizing the organic solvent gradually. For this reason, the deterioration in storage stability or development properties of the toner easily takes place.
• the toner according to the present invention does not practically contain an organic solvent so that a toner with excellent storage stability (anti-blocking properties) and development stability can be obtained.
• an organic solvent is not restricted as far as it is volatile.
• aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, tetralin and the like
• aliphatic or alicyclic hydrocarbon type solvent such as n-heptane, n-hexane, cyclohexane and the like
• halogen series solvents such as methylene dichloride, carbon tetrachloride and the like
• ester or ester ether solvents such as ethyl acetate, butyl acetate, methylcellosolve acetate and the like
• ether solvents such as diethyl ether, tetrahydrofuran and the like
• ketone solvents such as acetone, methylethyl ketone and the like
• alcohol solvents such as methanol, ethanol, isopropanol, n-butanol, benzyl alcohol and the like.
• the aqueous dispersed system comprising the resin microparticle (A) for a toner raw material dispersed in water can be preferably produced by melt-mixing a resin in the presence of water.
• a method for melt-mixing is not particularly restricted, but an extruder is preferably used from the viewpoint that the resin can be heated up to not less than the plasticizing temperature of the resin and the resin can be mechanically mixed sufficiently.
• a twin screw extruder capable of carrying out melt-mixing and phase inversion is particularly preferable.
• a twin screw extruder with a water inlet placed at a vent section is preferable from the viewpoint that melt-mixing and phase inversion can be continuously carried out.
• the preferred range of a temperature for carrying out melt-kneading is different depending on the melting temperature of a resin. However, it is preferably from 80° C. to 180° C. from the viewpoint of kneading efficiency. It is more preferably from 80° C. to 170° C. and further preferably from 80° C. to 155° C. When melt-kneading is carried out in the above temperature range, the resin can be fully mixed and decomposition of the resin can be prevented.
• the dispersed system of the present invention is produced by using a twin screw extruder, it is preferable that a single screw extruder is placed at an outlet of the above extruder to pass the dispersed system through the single screw extruder for cooling it down to not more than 100° C.
• the amount of water when water is fed, is preferably from 5 mass % to 50 mass % and more preferably from 10 mass % to 30 mass % in the total amount of a polyester type resin (B) and water.
• the amount of water within the above range is preferable from the viewpoint that a resin microparticle satisfying the relationships of D10 and D90 of D90/D10 ⁇ 7 and D50 of 0.05 ⁇ m ⁇ D50 ⁇ 1 ⁇ m can be easily obtained.
• ion exchange water is suitably used for water, whereas a basic aqueous solution may be used as well.
• the basic aqueous solutions may include the aqueous solution of the substances worked as bases such as alkali metals, alkali earth metals, ammonia, oxides of alkali metals and alkali earth metals, hydroxides and the like. More preferred examples thereof may include aqueous solutions of sodium oxide, sodium peroxide, potassium oxide, potassium peroxide, strontium oxide, barium oxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide and the like.
• a concentration of the basic aqueous solution is preferably not more than 1N and more preferably not more than 0.5N.
• a toner having a slightly dissimilar shape compared to the complete spherical shape, and the like may be produced.
• the toner shape can be controlled flexibly. Therefore, a toner with excellent cleaning properties can be produced.
• polymerization may include the meaning of copolymerization, and the term “polymer” may have the meaning of a copolymer.
• a resin contained in the resin microparticle (A) for a toner raw material used in the present invention is not particularly restricted as far as it is easily dissolved in water or a basic aqueous solution.
• Any of resins which have been conventionally used as a resin for toner can be suitably used. Examples thereof include a polyether polyol based resin, a polyester based resin, a styrene based resin, an acryl based resin and the like.
• a polyester based resin (B) and a polyether polyol based resin (D) are particularly preferable.
• the polyester based resin (B) is excellent in offset resistance, durability, low-temperature fixing properties and the like in the case of using it as a toner.
• the polyester based resin (B) is a resin (polyester resin (a)) obtained by carrying out polycondensation of at least one kind of a polyhydric alcohol and at least one kind of a polycarboxylic acid as main components.
• the polyester based resin (B) in the present invention includes a urethane modified polyester resin (a1) obtained by reacting the polyester resin (a) and a polyisocyanate (b) as well.
• the primary structure of the polyester based resin (B) is not particularly restricted. Any of a linear resin, a branched resin or a crosslinked resin can be used.
• polyhydric alcohols which are used as a raw material of the polyester resin (a) include dihydric alcohols such as aromatic diols, aliphatic diols, alicyclic diols, and tri- or higher polyhydric alcohol.
• aromatic diols include o-xylylene glycol, p-xylylene glycol, m-xylylene glycol, ethylene oxide adducts of bisphenol A, propylene oxide adducts of bisphenol A and the like.
• ethylene oxide adducts of bisphenol A include polyoxyethylene-(2,0)-2,2-bis(4-hydroxyphenyl)propane and the like.
• propylene oxide adducts of bisphenol A include, polyoxypropylene-(2,0)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene-(1,2)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene-(1,1)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene-(2,2)-polyoxyethylene(2,0)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene-(6)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene-(3,3)-2,2-bis(4-hydroxyphenyl)propane and the like.
• Examples of the aliphatic diols include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, triethylene glycol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, dipropylene glycol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol and the like.
• Examples of the alicyclic diols include dihydroxymethyl cyclohexane, hydrogenated bisphenol A and the like.
• ethylene oxide adducts of bisphenol A preferable are ethylene oxide adducts of bisphenol A, propylene oxide adducts of bisphenol A, diethylene glycol, triethylene glycol, ethylene glycol and neopentyl glycol. More preferable are propylene oxide adducts of bisphenol A, triethylene glycol, ethylene glycol and neopentyl glycol.
• aromatic dicarboxylic acids examples include phthalic acid, terephthalic acid, isophthalic acid, 1,5-naphthalic acid and the like.
• anhydrides of the above various dicarboxylic acids examples include succinic anhydride, maleic anhydride, phthalic anhydride and the like.
• the lower alkyl esters having 1 to 6 carbon atoms of the above various dicarboxylic acids examples include dimethyl succinate, diethyl maleate, dihexyl phthalate and the like.
• adipic acid, terephthalic acid and isophthalic acid while more preferably used are terephthalic acid and isophthalic acid.
• tri- or higher polyhydric alcohol tri- or higher polycarboxylic acid and anhydrides thereof can also be used as needed.
• the tri- or higher polyhydric alcohols include glycerin, 2-methylpropanetriol, trimethylolpropane, trimethylolethane, sorbitol, sorbitan and the like.
• the tri- or higher polycarboxylic acids include trimellitic acid, pyromellitic acid and the like.
• a monocarboxylic acid and a monohydric alcohol examples include aliphatic monocarboxylic acids having a straight chained structure, a branched structure an unsaturated structure and aromatic monocarboxylic acids.
• examples of the aliphatic monocarboxylic acid include octanoic acid, decanoic acid, dodecanoic acid, myristic acid, palmitic acid, stearic acid and the like.
• the aromatic monocarboxylic acids include benzoic acid, naphthalenecarboxylic acid and the like.
• Aliphatic monohydric alcohols such as octanol, decanol, dodecanol, myristyl alcohol, palmityl alcohol, stearyl alcohol and the like can also be used.
• glycerin trimethylolpropane, stearic acid, trimellitic acid and benzoic acid. More preferable are trimethylolpropane, stearic acid and benzoic acid.
• the molecular weight and glass transition temperature (Tg) of the polyester resin (a) can be controlled, and also a branched structure can be introduced.
• Tg glass transition temperature
• a urethane modified polyester resin (a1) which is crosslinked or polymerized with a polyisocyanate to be described later hereinafter, described as urethane-extending in some cases
• one or more kinds of tri- or higher polyhydric alcohols are preferably used from the viewpoint of effective polymerization.
• the amount of the tri- or higher polyhydric alcohol is preferably in the range of 0.25 mole % to 25 mole % and more preferably in the range of 0.5 mole % to 20 mole % in the total alcohol components, raw materials of the polyester resin (a) (total amount of diol and tri- or higher polyhydric alcohol).
• the amount of the tri- or higher polyhydric alcohol within the above range is preferable in that polycondensation reaction properly takes place during urethane-extending of the polyester resin (a), thus enhancing offset resistance or durability of the toner.
• the temperature of polycondensation reaction is generally from 150° C. to 300° C., preferably from 180° C. to 270° C. and more preferably from 200° C. to 250° C.
• the reaction temperature within the above range is preferable in that the polyester resin (a) with good productivity can be obtained within a short period of time without causing decomposition of the resin.
• the addition of a catalyst is preferable because the reaction proceeds rapidly.
• known catalysts for use in the polycondensation reaction can be used. Examples thereof include catalysts containing elements such as tin, antimony, titanium, germanium, aluminum and the like. Examples of the catalysts containing tin include dibutyltin oxide and the like. Examples of the catalysts containing antimony include antimony trioxide and the like.
• titanium alkoxide, titanium acylate, titanium chelate and the like can be more preferably used, and tetra-n-butyl titanate, tetra(2-ethylhexyl)titanate, tetramethyl titanate and tetraisopropyl titanate are particularly preferably used.
• the catalysts containing germanium include germanium dioxide and the like.
• the amount of the catalyst added is preferably from 0.01 mass part to 1.00 mass part per 100 mass parts of a monomer.
• the above catalyst may be used singly or in combination. Further, the catalyst may be added at the beginning or in the middle of polymerization.
• the hydroxyl value of the polyester resin (a) to be reacted wit the polyisocyanate (b) is preferably from 5 KOHmg/g to 100 KOHmg/g and more preferably from 5 KOHmg/g to 80 KOHmg/g.
• the hydroxyl value within the above range is preferable from the viewpoint of proper reactivity in urethane extending of the polyester resin (a). For that reason, gel portion in the resin becomes proper so that both good offset resistance and fixing properties can be exhibited ; therefore the above range is preferable.
• the hydroxyl value refers to mg of potassium hydroxide necessary to neutralize the acid anhydride necessary to esterify the hydroxyl group present in 1 g of the resin.
• the acid value of the polyester resin (a) to be reacted wit the polyisocyanate (b) is preferably not more than 100 KOHmg/g and more preferably from 1 KOHmg/g to 80 KOHmg/g.
• the acid value within the above range is preferable from the viewpoint that the toner exhibits excellent electrification stability.
• the acid value in the present invention refers to mg of potassium hydroxide necessary to neutralize 1 g of the resin.
• the number-average molecular weight (Mn) of the THF soluble component of the polyester resin (a) is preferably from 1,000 to 50,000, more preferably from 1,000 to 20,000, and further preferably from 1,500 to 8,000.
• the number-average molecular weight within the above range is preferable from the viewpoint that excellent offset resistance, durability and fixing properties of the toner can be obtained.
• the THF soluble component of the polyester resin (a) has at least one peak in the range of 3,000 to 10,000 molecular weight in the molecular weight distribution measured by the gel permeation chromatography (GPC). This is preferable because fixing properties and gloss of the toner becomes excellent.
• a glass transition temperature (Tg) of the polyester resin (a) is preferably from 30° C. to 80° C. and more preferably from 40° C. to 70° C. Tg within the above range is preferable from the viewpoint that a toner exhibiting good storage stability and fixing properties can be obtained.
• the polyester based resin (B) may be used together with two kinds or more polyester resins (a). In that case, even when characteristics of respective acid values or hydroxyl values are out of the above range, those of the whole polyester based resin (B) are preferably within the above range.
• the polyester based resin (B) of the present invention contains the THF insoluble component in an amount of from 0.3 mass % to 20 mass % and more preferably in an amount of from 0.5 mass % to 10 mass %.
• the THF insoluble component within the above range is preferable because sufficient offset resistance and fixing properties can be obtained.
• the THF insoluble component of the polyester based resin (B) in the present invention contains a polyisocyanate-derived structure unit.
• the structure unit is obtained by, for example, reacting a hydroxyl group of the polyester resin (a) with the polyisocyanate (b). Therefore, the polyester resin (a) and polyisocyanate (b) are preferably used in an amount of from 0.1 mole part to 2.5 mole parts and more preferably from 0.2 mole part to 2.0 mole parts of an isocyanate group of the polyisocyanate (b) for 1 mole part of the hydroxyl group of the polyester resin (a).
• the amount of the polyisocyanate (b) is small, the toner does not exhibit sufficient offset resistance in some cases.
• the amount of the polyisocyanate (b) is high, there is a problem of stability in some cases because unreacted polyisocyanate remains in the resin after the reaction.
• Polyisocyanate (b) in the present invention is a compound having two or more isocyanate groups in a molecule.
• the diisocyanate compound containing two isocyanate groups in a molecule there can be exemplified, for example, alicyclic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, aralkyl diisocyanate and the like.
• the aliphatic diisocyanates include hexamethylene diisocyanate (HDI), tetramethylene diisocyanate and the like.
• alicyclic diisocyanates examples include isophorone diisocyanate (IPDI), norbornene diisocyanate (NBDI), hydrogenated diphenylmethane diisocyanate and the like.
• aromatic diisocyanate there can be exemplified, for example, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI) and the like.
• TDI tolylene diisocyanate
• MDI diphenylmethane diisocyanate
• aralkyl diisocyanate examples include xylylene diisocyanate (XDI) and the like.
• polyisocyanates containing three or more isocyanate groups in a molecule such as polyphenylene polymethylene polyisocyanate (polymeric MDI) and the like can also be used.
• modified polyisocyanates obtained by various modifications such as biuret modification, allophanate modification, isocyanurate modification, urethane modification and the like can be used.
• aromatic polyisocyanate is one of polyisocyanates which can be the most suitably used since it is highly reactive and cheap.
• Preferred examples of methods for reacting the polyester resin (a) with the polyisocyanate (b) include the method comprising feeding the polyester resin (a) into a twin screw extruder for kneading, and then feeding the polyisocyanate (b) into the resin mixture during kneading and conveying for further melt-kneading.
• reactors used in the other method than those above include a single screw extruder, a static mixer and a usual reactor with a stirrer.
• the reaction temperature is preferably in the range of 100° C. to 200° C. and more preferably in the range of 140° C. to 190° C.
• the reaction temperature within the above range is preferable since the resin is not pyrolytically decomposed and urethane extending reaction occurs sufficiently, thus resulting in obtaining offset resistance of a toner.
• urethane extending of the polyester resin (a) may be carried out in the presence of a component selected from a colorant, a charge controlling agent, a releasing agent or the like.
• a component selected from a colorant, a charge controlling agent, a releasing agent or the like may be included in the presence of a component selected from a colorant, a charge controlling agent, a releasing agent or the like.
• other resins such as a styrene-acrylic binder resin, a polyol based binder resin or the like can be contained as far as the characteristics are not damaged.
• the amount and structure of the THF insoluble component are determined by using the resin microparticle obtained by drying a dispersed system with a resin microparticle for a toner dispersed therein at 150° C. for 2 hours and then cooled and solidified.
• the structure of the toner binder resin can be analyzed by the combination of known analytical methods such as infrared spectroscopy (IR), ultraviolet spectroscopy, nuclear magnetic resonance spectroscopy (NMR), liquid chromatography (LC), mass spectrometry (MS) resin hydrolysis, distillation and the like. Since the THF insoluble component is hardly dissolved in a solvent, a analytical method is a little restricted. However, the structure can be specified by carrying out thorough hydrolysis of the THF insoluble component and then separating by distillation or LC, and analyzing by the combination of methods such as gas chromatography (GC) as well as IR, NMR, LC and MS.
• IR infrared spectroscopy
• NMR nuclear magnetic resonance spectroscopy
• LC liquid chromatography
• MS mass spectrometry
• the polyester based resin (B) in the present invention is preferably a polyester based resin (B1) having a sulfonic acid group.
• the sulfonic acid includes its metal salt or ammonium salt.
• Examples of the monomers having a sulfonic acid group and/or a sulfonic acid metal salt group which is used as a raw material of the polyester based resin (B) include sulfoisophthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5-(4-sulfophenoxy)isophthalic acid, 5-(sulfopropoxy)isophthalic acid, sulfopropyl malonic acid, sulfosuccinic acid, 2-sulfobenzoic acid, 3-sulfobenzoic acid, 5-sulfosalicylic acid and methyl esters of these carboxylic acids.
• metal salts such as lithium, natrium, kalium, magnesium, calcium, copper, iron or the like of these sulfonic acids, or ammonium salts are included.
• a polyfunctional monomer containing a sulfonic acid group comprising at least one or more hydroxyl groups can also be used.
• the polyfunctional monomer is obtained by reacting glycidyl alcohols such as 2,3-epoxy-1-propanol, 3,4-epoxy-1-butanol or the like; difunctional epoxy such as ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether or the like; tri- or higher functional epoxy such as trimethylol propane triglycidyl ether or the like with acidic sulfite at 20° C. to 200° C. in the presence of a catalyst such as amine or imidazole as needed.
• glycidyl alcohols such as 2,3-epoxy-1-propanol, 3,4-epoxy-1-butanol or the like
• difunctional epoxy such as ethylene glycol diglycidyl ether, diethylene glycol digly
• 5-sulfoisophthalic acid sodium 5-sulfoisophthalic acid and sodium dimethyl 5-sulfoisophthalic acid are suitably used.
• the amount of the monomer having a sulfonic acid group is preferably from 0.5 mole part to 8 mole parts and more preferably from 0.5 mole part to 4 mole parts per the total 100 mole parts of the polycarboxylic acid-derived structure unit and polyhydric alcohol-derived structure unit constituting the polyester based resin (B).
• the amount used is the same when the polyester based resin (B) is a polyester based resin (B11) having a vinyl copolymer-derived structure (C).
• the amount of the monomer having a sulfonic acid group and/or a sulfonic acid metal salt group within the above range is preferable because the particle diameter of 50% volume of the resin microparticle in a suspension becomes not more than 1 ⁇ m and toner storage stability becomes good when it is melt-mixed in the presence of water.
• the polyester based resin (B) is also preferably a polyester based resin (B11) having a vinyl copolymer-derived structure (C).
• the vinyl copolymer-derived structure (C) in the present invention is a portion derived from the corresponding vinyl copolymer (c).
• the content of the vinyl based copolymer-derived structure (C) is from 0.5 mass % to 10 mass %, and preferably from 0.5 mass % to 6 mass % in the polyester based resin (B11).
• the content of the vinyl copolymer-derived structure (C) within the above range is preferable in that a resin microparticle for a toner having a small particle diameter and a narrow particle diameter distribution can be easily obtained and also the releasing agent component can be dispersed well when it is used for a toner.
• Examples of methods for producing the polyester based resin (B11) include the method of urethane-extending of the melted mixture of the polyester resin (a) and vinyl based copolymer (c) and the method comprising urethane-extending only the polyester resin (a) and then adding the vinyl copolymer (c) thereto for melt-kneading again.
• the method of grounding each of the urethane-extended polyester resin (a1) and the vinyl copolymer (c) powders and mixing them is also included because the polyester resin (a1) and the vinyl polymer (c) are partly reacted while the mixed resin is kneaded in the presence of water.
• a method of urethane-extending of the melted mixture of the polyester resin (a) and vinyl copolymer (c) is preferable.
• the vinyl copolymer (c) of the present invention is obtained by polymerizing at least one kind of a vinyl monomer.
• the polymerization method known methods such as solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization or the like can be employed. However, a method comprising carrying out solution polymerization in an organic solvent and removing the solvent is preferably used from the viewpoint of its convenience.
• the solvent for the solution polymerization aromatic hydrocarbons such as benzene, toluene, ethylbenzene, o-xylene, m-xylene, p-xylene, cumene and the like are used. These can be used singly or in combination thereof, whereas the molecular weight can also be adjusted by the use of other solvent(s).
• Any polymerization initiators can be usually used as far as they can be used as radical polymerization initiators.
• examples thereof include azo initiators such as 2,2′-azobisisobutyronitrile, 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(2-methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate, 1,1 ′-azobis(1-cyclohexanecarbonitrile), 2-(carbamoylazo)-isobutyronitrile, 2,2′-azobis(2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2′-azobis(2-methylpropane) and the like; ketone peroxides such as methylethylketone peroxide, acetylacetone peroxide, cycl
• the type and amount of polymerization initiator can be suitably selected depending on the reaction temperature, concentration of the monomer and the like.
• the amount thereof is preferably from 0.01 weight part to 10 weight parts per 100 weight parts of the raw material monomer.
• vinyl monomers as a raw material of the vinyl copolymer (c) of the present invention include acrylic esters such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, cyclohexyl acrylate, lauryl acrylate, stearyl acrylate, benzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, ethoxyl acrylate, butoxyl acrylate, dimethylaminomethyl acrylate ester, dimethylaminoethyl acrylate ester and the like; methacrylic esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, octyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, benz
• vinyl monomers are used singly or in combination of two or more kinds.
• particularly preferable examples of the vinyl monomer include styrenes, acrylic acids, methacrylic acids acrylic esters, methacrylic esters and glycidyl group-containing monomers.
• the number-average molecular weight of the vinyl copolymer (c) of the present invention is preferably from 1,000 to 30,000 and more preferably from 3,000 to 25,000.
• the number-average molecular weight of the vinyl copolymer (c) within the above range is preferable from the viewpoints that a toner having good dispersability into the polyester based resin and a toner with good storage stability can be obtained.
• the vinyl copolymer (c) preferably contains the glycidyl group-containing monomer in the range of 0.3 mole part to 13 mole parts per the total 100 mole parts of all vinyl monomers as a raw material.
• the range of 0.6 mole part to 13 mole parts is more preferable from the viewpoint of the dispersability of the vinyl copolymer into the polyester based resin.
• the polyester based resin (B1) in the present invention is preferably a polyester based resin (B12) which does not include the bisphenol A-derived structure unit and contains not more than 5 ppm tin.
• the bisphenol A-derived structure unit is represented by the following formula (1).
• the bisphenol A-derived structure is not included in the polyester based resin (B12) from the viewpoint of reduced environmental burdens.
• polyhydric alcohols in the preparation of the polyester based resin (B12) do not include bisphenol A, bisphenol A-2 propylene oxide adducts, bisphenol A-3 propylene oxide adducts, bisphenol A polypropylene oxide adduct, bisphenol A-2 ethylene oxide adducts, bisphenol A-3 ethylene oxide adducts and bisphenol A polyethylene oxide adduct.
• the meaning of not including the bisphenol A-derived structure is that the bisphenol A-derived structure is preferably contained in an amount of not more than 0.5 mole part, and more preferably in an amount of 0 mole part, based on 100 mole parts of the total of the polycarboxylic acid-derived structure unit and the polyhydric alcohol-derived structure unit.
• a catalyst which is different from a catalyst containing tin or antimony, particularly a catalyst containing titanium is preferably used.
• the catalysts containing titanium include the aforementioned compounds.
• Concrete product names of the aforementioned catalyst containing titanium include, though is not restricted to, Orgatics TA-25 (tetra-n-butyl titanate), TA-30 (tetra(2-ethylhexyl)titanate), TA-70 (tetramethyl titanate) and the like as titanium alkoxide; Orgatics TPHS (polyhydroxy titanium stearate) and the like as titanium acylate; and Orgatics TC-401 (titanium tetra acetylacetonate), TC-200 (titanium octylene glycolate), TC-750 (titanium ethyl acetoacetate), TC-310 (titanium lactate), TC-400 (titanium triethanol aminate) and the like as titanium chelate (all products are a product of Matsumoto Chemical Industry Co., Ltd.).
• the content of tin in the polyester based resin (B12) is not more than 5 pp
• a polyether polyol based resin (D) is preferable.
• the polyether polyol based resin (D) used in the present invention also includes modified resins thereof.
• the polyether polyol based resin (D) can be obtained by reacting at least one kind (E) selected from bisphenols (i), polyhydric alcohols (ii), and reactants (iii) of the polyhydric alcohols and an acid anhydride, an epoxy resin (F), and a compound (G) having at least one active hydrogen in the molecule which can react with an epoxy group.
• E selected from bisphenols (i), polyhydric alcohols (ii), and reactants (iii) of the polyhydric alcohols and an acid anhydride, an epoxy resin (F), and a compound (G) having at least one active hydrogen in the molecule which can react with an epoxy group.
• other components such as a crosslinking agent or the like can be added.
• the primary structure of these resins is not particularly restricted. Any of a linear resin, a branched resin or a crosslinked resin can be used.
• the molecular weight, molecular weight distribution or thermal characteristics can be adjusted.
• Known styrene based resins, styrene-acrylic copolymerized resins, polyester based resins can also be contained as far as the characteristics are not damaged.
• bisphenols (i) include 2,2-bis(4-hydroxyphenyl)propane [commonly called bisphenol A], bis(4-hydroxyphenyl)methane [commonly called bisphenol F], 1,1-bis(4-hydroxyphenyl)ethane [commonly called bisphenol AD], 1-phenyl-1,1-bis(4-hydroxyphenyl)methane, 1-phenyl-1,1-bis(4-hydroxyphenyl)ethane and the like.
• polyhydric alcohols (ii) examples include the polyhydric alcohols used as a raw material of the polyester based resin (B) or the like.
• acid anhydrides examples include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, ethylene glycol bistrimellitate, glycerol tristrimellitate, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylene tetrahydrophthalic anhydride, methylendomethylene tetrahydrophthalic anhydride, methylbutenyl tetrahydrophthalic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, methylcyclohexene dicarboxylic anhydride, alkyl styrene-maleic anhydride copolymer, chlorendic anhydride, polyazelaic anhydride and the like.
• the reaction of polyhydric alcohols and an acid anhydride can be preferably carried out in the presence of a catalyst at 80° C. to 150° C. for 1 hour to 8 hours.
• the reaction of the polyhydric alcohols and an acid anhydride may be carried out during the polyaddition for producing the resins or before the polyaddition.
• an acid anhydride functions as a crosslinking agent and sometimes gelation takes place, the above reaction is more preferably carried out before the polyaddition.
• Examples of the catalyst used in the reaction include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and the like; alkali metal alcoholates such as sodium methylate and the like; tertiary amines such as N,N-dimethylbenzylamine, triethylamine, pyridine and the like; quaternary ammonium salt such as tetramethylammonium chloride, benzyltriethylammonium chloride and the like; organic phosphorus compounds such as triphenylphosphine, triethylphosphine and the like; salts of alkali metals such as lithium chloride, lithium bromide and the like; lewis acids such as boron trifluoride, aluminium chloride, tin (IV) chloride, tin 2-ethylhexanoate, zinc benzoate and the like.
• the amount thereof is preferably from 1 ppm to 1,000 ppm and more preferably from 5 pp
• a solvent is not used from the viewpoint of a remained solvent.
• a solvent can also be used.
• the solvents include aromatic hydrocarbons such as toluene, xylene, ethylbenzene and the like; and ketones such as methylisobutyl ketone, methylethyl ketone and the like.
• epoxy resins (H) include a so-called one-step epoxy resin produced from the above bisphenols and epichlorohydrin and a two-step epoxy resin which is a product of an polyaddition of the one-step epoxy resin and bisphenols (page 30, [New Epoxy Resin] written by Hiroshi Kakiuchi (Shokodo Co., Ltd., 1986)). These epoxy resins may be used singly or in combination of two or more kinds. Also, a mixture in combination of two or more kinds having different number-average molecular weights may be used.
• the ratio (Mw/Mn) of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) becomes greater, as compared to a case where a single kind is used, thus favorably improving offset resistance.
• the number-average molecular weight of a low molecular weight component is preferably from 300 to 3,000, while that of a high molecular weight component is preferably from 3,000 to 10,000.
• epoxy resin epoxy resins obtained by replacing the partial or entire bisphenols by the above aromatic diols can also be used.
• Examples of the compounds (G) having at least one active hydrogen reacting with an epoxy group in a molecule include monovalent phenols, secondary amine and monovalent carboxylic acids.
• Examples of the monovalent phenols include phenol, cresol, isopropyl phenol, octyl phenol, nonyl phenol, dodecyl phenol, xylenol, p-cumyl phenol, a-naphthol, ⁇ -naphthol and the like.
• secondary amines examples include aliphatic secondary amines such as diethylamine, dipropylamine, dibutylamine, dipentylamine, didodecylamine, distearylamine, diethanolamine, diallylamine and the like; and aromatic ring-containing secondary amines such as N-methylanilin, N-methyltoluidine, N-methylnitroanilin, diphenylamine, ditolylamine, benzyldimethylamine and the like.
• aromatic secondary amines such as diethylamine, dipropylamine, dibutylamine, dipentylamine, didodecylamine, distearylamine, diethanolamine, diallylamine and the like
• aromatic ring-containing secondary amines such as N-methylanilin, N-methyltoluidine, N-methylnitroanilin, diphenylamine, ditolylamine, benzyldimethylamine and the like.
• Examples of the monovalent carboxylic acids include aliphatic carboxylic acids such as propionic acid, butyric acid, caproic acid, caprylic acid, pelargonic acid, stearic acid and the like; aromatic ring-containing monovalent carboxylic acid such as benzoic acid, toluic acid, ⁇ -naphthoic acid, ⁇ -naphthoic acid, phenyl acetate and the like.
• crosslinking agents examples include polyamines, acid anhydrides, trivalent or higher phenol compounds, trivalent or higher epoxy resins and the like.
• polyamines examples include aromatic polyamine, aliphatic polyamine and the like.
• Preferable examples thereof include diethylene triamine, triethylene triamine, imino bispropylamine, bis(hexamethylene)triamine, trimethylhexamethylene diamine, diethylaminopropylamine, m-xylylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone and the like.
• acid anhydride compounds such as the aforementioned acid anhydrides are preferable.
• Examples of the trivalent or higher phenol compound include phenol novolac resin, ortho-cresol novolak resin, 1,1,1 -tris(4-hydroxyphenyl)methane, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)propane, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1-[ ⁇ -methyl- ⁇ -(4-hydroxyphenyl)ethyl]-3-[ ⁇ , ⁇ -bis(4hydroxyphenyl)ethyl]benzene, and 1-[ ⁇ -methyl- ⁇ -(4-hydroxyphenyl)ethyl]-4-[ ⁇ , ⁇ -bis(4-hydroxyphenyl)ethyl]benzene.
• the trivalent or higher epoxy resin is obtained, for example, by the reaction of a trivalent or higher phenol compound or a trivalent or higher alcohol compound with epihalohydrine.
• the trivalent or higher phenol compounds include phenol novolac resin, ortho-cresol novolak resin, 1,1,1-tris(4-hydroxyphenyl)methane, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)propane, 1, 1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1-[ ⁇ -methyl- ⁇ -(4-hydroxyphenyl)ethyl]-3-[ ⁇ , ⁇ -bis(4hydroxyphenyl)ethyl]benzene, 1-[ ⁇ -methyl- ⁇ -(4-hydroxyphenyl)ethyl]-4-[ ⁇ , ⁇ -bis(4-hydroxyphenyl)ethyl]benzene and the like.
• trivalent or higher alcohol there can be exemplified, for example, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene and the like.
• the polyol based resin is preferably produced by an polyaddition of at least one kind (E) selected from bisphenols (i), polyhydric alcohols (ii), reactants (iii) of the polyhydric alcohols and an acid anhydride, an epoxy resin (F), and a compound (G) having at least one active hydrogen in the molecule which can react with an epoxy group, and optionally a crosslinking agent.
• E bisphenols
• polyhydric alcohols ii
• reactants iii) of the polyhydric alcohols and an acid anhydride
• an epoxy resin F
• G having at least one active hydrogen in the molecule which can react with an epoxy group, and optionally a crosslinking agent.
• the amount of the active hydrogen group capable of reacting with an epoxy group is preferably from 0.5 mole equivalent to 2.0 mole equivalents, and further preferably from 0.7 mole equivalent to 1.5 mole equivalent based on 1 mole equivalent of the epoxy group in the system.
• the amount of less than 0.5 is not preferable because gelation may occur in the system and the reaction may be difficult to control in some cases
• the amount of greater than 2.0 is not preferable because a lot of the monomers remains at the end of the reaction.
• the polyol based resin can be produced, for example, by using bisphenol A in an amount of from 0.01 mole to 3 mole, benzoic acid in an amount of from 0.005 mole to 2 mole, stearic acid in an amount of from 0 mole to 0.2 mole, and a reactant of propylene oxide adducts of bisphenol A and phthalic anhydride in an amount of from 0 mole to 1 mole, as compounds having an active hydrogen in the molecule which can react with an epoxy group, based on 2 mole to 3.5 mole of an epoxy resin.
• the polyaddition may be carried out by using a catalyst.
• the catalysts include the catalysts which can be used for the reaction of the polyhydric alcohol and acid anhydride.
• the amount is usually from 1 ppm to 1,000 ppm and preferably from 5 ppm to 500 ppm based on the amount of a product.
• a solvent is not used from the viewpoint of a remained solvent.
• a solvent can also be used.
• the solvent include aromatic compounds such as toluene, xylene and the like; and ketones such as 2-butanone, methylisobutyl ketone, cyclohexanone and the like; ethers such as ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dioxane, anisole and like; and aprotic polar solvents such as N,N-dimethylformamide, dimethylsulfoxide, 1-methyl-2-pyrrolidone and the like.
• solvents can also be used singly or in combination of two or more kinds.
• the amount thereof is usually in a proportion of from 1 mass % to 100 mass % and preferably from 5 mass % to 50 mass % of the mass of the raw material to be fed.
• the reaction temperature in the polyaddition is different depending on the based or the amount of a catalyst, but it is preferably in the range of 120° C. to 200° C. When the reaction temperature is higher than 200° C., some kinds of catalysts may lose their activities and the resin may be colored remarkably in some cases.
• the reaction can be traced by the epoxy equivalent, softening point, gel permeation chromatography (GPC) or the like.
• the end point of the reaction is preferably determined by the point where the epoxy group disappears substantially, that is, the epoxy equivalent becomes not less than 20,000 g/Eq.
• the epoxy equivalent refers to the mass (g) of an epoxy resin per 1 g equivalent of an epoxy group.
• a number-average molecular weight (Mn) is preferably in the range of 1,000 to 20,000, more preferably in the range of 1,500 to 15,000, and particularly preferably in the range of 2,500 to 5,000.
• Mn is less than 1,000, the resin strength and cohesive force of the resin may be deteriorated so that sufficient durability and offset resistance are not exhibited in some cases.
• Mn exceeds 20,000, sufficient fixing properties or gloss may not be shown in some cases.
• Mw/Mn is preferably from 5 to 50 and particularly preferably from 10 to 35. Mw/Mn of less than 5 is not preferable because sufficient offset resistance may not be exhibited.
• Mw/Mn of more than 50 is not preferable because the high viscosity in the system in the preparation make it difficult to control the reaction.
• the softening point is preferably from 85° C. to 150° C. and particularly preferably from 100° C. to 135° C.
• the softening point mentioned herein is a softening temperature of a sample measured at a heating rate of 1° C./min using a softening point measuring device (FP90, a product of Mettler Toledo K. K.).
• FP90 a softening point measuring device
• the softening point is less than 85° C., it is not preferable from the viewpoint of durability.
• the softening point exceeds 135° C., sufficient fixing properties or gloss may not be exhibited in some cases.
• a glass transition temperature (Tg) is preferably from 50° C. to 90° C. and particularly preferably from 55° C. to 70° C. from the viewpoints of securing fixing properties, offset resistance and anti-blocking properties.
• a hydroxyl value of the polyol based resin used in the present invention is preferably from 100 KOHmg/g to 300 KOHmg/g and more preferably from 150 KOHmg/g to 250 KOHmg/g.
• the hydroxyl value refers to mg of potassium hydroxide necessary to neutralize an acid anhydride necessary to esterify the hydroxyl group present in 1 g of the resin.
• a urethane modified polyol based resin obtained by chain-extending of polyol based resin using a polyisocyanate is preferably used from the viewpoint of the good offset resistance.
• the polyisocyanate is preferably used in an amount of not more than 0.5 mole equivalent and more preferably not more than 0.3 mole equivalent of an isocyanate group per 1 mole equivalent of the hydroxyl group of the polyol based resin.
• it is not less than 0.5 mole equivalent, sufficient fixing properties are not obtained in some cases.
• polyisocyanates examples include compounds such as the aforementioned polyisocyanate (b).
• Preferred examples of methods for reacting the polyol based resin with a polyisocyanate include a method comprising feeding the polyol based resin into a twin screw extruder for kneading, and then feeding the polyisocyanate into the resin mixture during kneading and conveying for further melt-kneading.
• reactors used in the other method than those above include a single screw extruder, a static mixer and a usual reactor with a stirrer.
• the preferred range of the reaction temperature is the same as the temperature range in the aforementioned reaction of the polyester resin (a) and the polyisocyanate (b).
• a emulsifying auxiliary in the preparation of an aqueous dispersed system comprising the resin microparticle (A) for a toner raw material dispersed in water, a emulsifying auxiliary may be used along with the resin.
• the emulsifying auxiliary in the present invention promotes the formation of an aqueous dispersed system. Any known emulsifying auxiliaries can be used without restrictions.
• the emulsifying auxiliaries include a sulfonic acid group-containing polyester based resin, a sulfonic acid group-containing vinyl copolymer and their metal salts and their ammonium salts.
• thermoplastic resins swollen or dissolved in water such as polyvinyl alcohol, partly saponified polyvinyl alcohol, methylcellulose, carboxymethylcellulose or sodium salts thereof are also preferable.
• a sulfonic acid group-containing polyester based resin is suitably used as the emulsifying auxiliary.
• a sulfonic acid group-containing monomer is preferably contained in an amount of from 3 mole % to 35 mole % based on the total acid components of the sulfonic acid group-containing polyester resin.
• Several kinds of the above emulsifying auxiliarys may be used in combination.
• Examples of the sulfonic acid group-containing monomers as a raw material of the sulfonic acid group-containing polyester based resin include the aforementioned ones.
• aromatic dicarboxylic acid metal salts containing a sulfonic acid group is suitably used.
• the amount thereof is not particularly restricted, but it is preferably not more than 35 mole % and more preferably not more than 25 mole % of the total acid components of a raw material of the sulfonic acid group-containing polyester based resin.
• water absorption of a toner can be prevented and a toner with excellent electrification stability can be obtained.
• sulfonic acid group-containing polyester based resin As a raw material of the sulfonic acid group-containing polyester based resin, those described above are preferably used.
• Tg of the sulfonic acid group-containing polyester based resin and a number-average molecular weight (Mn) of the tetrahydrofuran (THF) soluble component are preferably those as described above.
• anionic surfactants may be used.
• anionic surfactants include anionic surfactants obtained by reacting with basic substances, such as primary higher fatty acid salts, secondary higher fatty acid salt, primary higher alcohol sulfate ester salts, secondary higher alcohol sulfate ester salts, higher alkyl disulfonic acid salts, sulfonated higher fatty acid salts, higher fatty acid sulfate ester salts, higher fatty acid ester sulfonic acid salts, sulfate ester salts of higher alcohol ether, sulfonic acid salts of higher alcohol ether, alkyroled sulfate ester salts of higher fatty acid amide, alkylbenzene sulfonic acid salts, alkylphenol sulfonic acid salts, alkylnaphthalene sulfonic acid salts, alkylbenzoimidazole sulfonic acid salts and the like.
• a method comprising forming an aggregate of the resin microparticle (A) for a toner raw material and thermally fusing the aggregate is suitably used.
• an aggregate is formed by adding water-soluble salts of an alkali metal, an alkali earth metal or aluminium, such as magnesium sulfate, aluminium sulfate, barium chloride, magnesium chloride, calcium chloride, sodium chloride and the like dissolved in water as a coagulant.
• an aggregate is formed by adding an ionic surfactant as a coagulant. Examples of the above surfactants include alkylbenzene dimethyl ammonium chloride, alkyl trimethyl ammonium chloride, distearyl ammonium chloride and the like.
• a dispersed system with the resin microparticle for a toner of the present invention dispersed therein in addition to a dispersed system with the resin microparticle for a toner of the present invention dispersed therein, a dispersed system with a releasing agent dispersed therein, a dispersed system with a colorant dispersed therein, a dispersed system with a magnetic powder dispersed therein or the like may be used. In that case, the aforementioned method for forming an aggregate can also be applied.
• an aggregate is also formed by charging at least one kind of a dispersed system of a dispersed system with resin microparticle for a toner dispersed therein, a dispersed system with a releasing agent dispersed therein, a dispersed system with a colorant dispersed therein and a dispersed system with a magnetic powder dispersed therein reversely with respect to the other, and then mixing them. Further, these aggregation processes can be used together.
• the aggregate in the case of forming the above aggregate, may be formed by multistage process for the purpose of controlling the toner surface structure.
• a dispersed system with the resin microparticle for a toner of the present invention dispersed therein or a dispersed system comprising other known binder resins or a binder resin and a emulsifying auxiliary is added subsequently for attaching to the aggregate surface in order to prevent a releasing agent or a colorant from being exposed to the toner surface.
• a dispersed system with a known binder resin such as a styrene-acrylic binder resin, a polyol based binder resin or the like can also be post-added for attaching to the aggregate surface for controlling the surface.
• the above aggregate is preferably subjected to thermal fusion for enhancing stability as a particle.
• the thermal fusion is preferably carried out at not less than a glass transition temperature or a melting point of the resin constituting the aggregate, and not more than a thermal decomposition temperature of the resin, for 30 minutes to 10 hours according to the target toner shape.
• the temperature is preferably from 40° C. to 180° C. and more preferably from 50° C. to 1 40° C.
• the thermal fusion can be carried out using a known heating device or apparatus.
• a known releasing agent having a melting point of from 70° C. to 155° C. can be preferably used.
• a known releasing agent having a melting point of from 70° C. to 155° C. can be preferably used.
• Concrete examples thereof include polyolefins having a low molecular weight such as polyethylene, polypropylene, polybutene and the like; silicones having a softening point by heating; aliphatic amides such as oleamide, erucamide, ricinoleamide, stearylamide and the like; or natural waxes such as ceramic wax, rice wax, sugar wax, urushi wax, beeswax, carnauba wax, candelilla wax, montan wax and the like; a Fisher-Tropsch wax, modified materials thereof and the like.
• releasing agents are dispersed in water with an ionic surfactant or a polymer electrolyte such as polymer acid, polymer base and the like, heated to not less than the melting point, and treated using a homogenizer or a pressure discharge type dispersing machine which is capable of applying a strong shearing force, whereby a dispersed system with a releasing agent having a diameter of not more than 1 ⁇ m dispersed therein can be obtained.
• an ionic surfactant or a polymer electrolyte such as polymer acid, polymer base and the like
• known dyes and pigments can be used for colorants.
• known dyes and pigments can be used for colorants.
• Concrete examples thereof include carbon black, magnetite, Phthalocyanine Blue, Peacock blue, Permanent red, lake red, Rhodamine lake, Hansa Yellow, Permanent yellow, benzidine yellow, oil black, azo oil black or the like. More concrete examples thereof include nigrosine dyes (C. I. No. 50415), aniline blue (C. I. No. 50405), charcoal blue (C. I. No. azoec Blue 3), chrome yellow (C. I. No. 14090), ultra marine blue (C. I. No.77103), Dupont oil red (C. I. No.26105), Orient oil red # 330 (C. I. No.
• a surface-treated colorant obtained by polymerizing a polymerizable monomer in the presence of a colorant can also be used.
• An aqueous dispersed system of a colorant is obtained, for example, by mixing a colorant and a surfactant, and dispersing the mixture in water according to a known method.
• any known charge controlling agents can be used as a charge controlling agent.
• known charge controlling agents such as nigrosine-based dyes, triphenyl methane-based dyes, quaternary ammonium salt, amine compounds or imine compounds, metal salicylate compounds, metal alkylsalicylate compounds or metal-containing azo dyes can be suitably selected and used accordingly. However, they are preferably hardly dissolved in water from the viewpoint of ionic strength or contamination by waste water.
• examples of the magnetic powders include metals such as ferrite, magnetite, reduced iron, cobalt, nickel, manganese and the like, alloys, or compounds comprising these metals.
• the compound ratio of a component for toner in the formation of a toner aggregate of the present invention is described below when the total mass of the resin microparticle (A) for a toner raw material of the present invention, a colorant, a charge controlling agent and a releasing agent is 100 mass %.
• the content of the resin microparticle (A) for a toner raw material of the present invention is from 50 mass % to 99 mass % and more preferably from 60 mass % to 95 mass %.
• the content of the colorant is preferably from 1 mass % to 25 mass % and more preferably from 1 mass % to 15 mass % from the viewpoint of transparency.
• the content of the charge controlling agent is usually preferably from 0 mass % to 10 mass %.
• the content of the releasing agent is preferably from 0 mass % to 20 mass % and more preferably from 0 mass % to 15 mass %.
• the amount of the releasing agent is within the above range, the toner has good storage stability.
• other components than the colorant, charge controlling agent, releasing agent, for example, magnetic powder or the like can be compounded as far as the effect of the present invention is not damaged.
• a colorant, a releasing agent or a charge controlling agent may be added in the preparation of the resin microparticle (A) for a toner raw material of the present invention.
• the amount thereof is the same as the compound ratio of the component for a toner in the formation of an aggregate.
• a particle obtained via the formation of the resin microparticle (A) for a toner raw material, the formation of an aggregate, a thermal fusion process and proper processes such as washing, drying or the like can be suitably used as a toner.
• the surface-treating agent exists between the toners and carriers or between the toners.
• the powder fluidity and the life of developing agent can be improved.
• Specific examples of the surface-treating agent include fine powders such as colloidal silica, alumina, titanium oxide, polytetrafluoroethylene, polyvinylidene chloride, polymethyl methacrylate, polystyrene ultrafine particles and silicone.
• Examples of commercial products include AEROSIL 130, 200, 200V, 200CF, 200FAD, 300, 300CF, 380, R972, R972V, R972CF, R974, R976, RX200, R200, R202, R805, R812, R812S, TT600, MOX80, MOX170, COK84, titanium oxide T805 and titanium oxide P25 (these are products of Nippon Aerosil Co., Ltd.
• the specific surface area of the surface-treating agent is preferably not less than 30 m 2 /g, and particularly in the range of 50 m 2 /g to 400 m 2 /g as measured by nitrogen adsorption by the BET method.
• the amount of the surface-treating agent added is preferably from 0.1 mass part to 20 mass parts per 100 mass parts of the toner.
• the toner obtained by the present invention can be applied to various fixing methods such as a so-called oil-free fixing method, an oil-coated heat roll fixing method, a flash fixing method, an oven fixing method, and a pressure fixing method.
• the toner according to the present invention can be applied to various cleaning methods, for example, a so-called fur brush method, a blade method or the like. It can also be applied to the image formation method omitting a cleaning process.
• a glass transition temperature in the present invention was measured in accordance with JIS K-7121.
• the hydroxyl value was measured by the back titration with the acid anhydride.
• 500 ml of pyridine, 70 g of phthalate and 10 g of imidazole were mixed to prepare a phthalized reagent.
• 5 ml of the phthalized reagent was added to 2g of a resin and dissolved therein. Then, the resulting solution was allowed to stand at 100° C. for 1 hour.
• 1 ml of water, 70 ml of tetrahydrofuran and several droplets of a phenolphthalane-ethanol solution were added to the resin solution and then the resulting mixture was titrated with a 0.4 normal NaOH aqueous solution.
• the hydroxyl value (KOHmg/g) was calculated from the titration amount and sample mass at the end point where the color of the sample solution was painted from colorlessness to purple.
• the content of the bisphenol A-derived structure unit in the resin was determined by NMR measurement of the hydrolyzed sample.
• the amount of the THF insoluble component was determined according to the following method.
• a solution of about 5 mass % was prepared by using a resin of about 2.5 g and THF of about 47.5 g.
• the concentration of the solution is referred to as “RC.”
• RC was obtained from an precise weighing value of the resin mass and THF mass.
• the above solution was stirred at 25 ⁇ 3° C. for 12 hours to dissolve the soluble component of the resin completely.
• the obtained solution was allowed to stand for 16 hours.
• 5 g of the supernatant liquid was collected and weighed precisely.
• the solution was dried at 150° C. for an hour and the mass of remaining resin was measured. From these values, the concentration of the supernatant liquid “SC” was calculated.
• the amount of the THF insoluble component was determined by the following formula from the values of RC and SC.
• the sample obtained by drying an aqueous dispersed system of the resin microparticle at 150° C. for 2 hours and then cooling and solidifying was measured.
• the molecular weight was determined using the gel permeation chromatography (GPC). The measurement was conducted under the following conditions, based on the commercially available monodispersed standard polystyrene.
• An average particle diameter of 50% volume (D50), a particle diameter of 10% volume (D10) and a particle diameter of 90% volume (D90) were measured using Microtrac HRA (a product of Microtrac Inc.).
• a particle diameter of 50% volume of the toner was measured using a coulter counter.
• a 5-liter, 4-necked flask was provided with a reflux condenser, a water-separating unit, a nitrogen gas inlet tube, a thermometer and a stirrer. Thereinto were fed 24.0 mole of ACTCOL KB300 (bisphenol A derivative, a product of Mitsui Takeda Chemicals, Inc.), 56.0 mole of ethylene glycol (EG), 10.0 mole of trimethylolpropane (TMP), 4.0 mole of triethylene glycol (TEG), 83.5 mole % of terephthalic acid (TPA) and 18.3 mole of benzoic acid (Benz A). Dehydration and polycondensation were conducted at 180° C. to 240° C. with nitrogen being introduced into the flask to obtain a resin (A-1-1). The physical properties of the resin were shown in Table 1.
• Resins (A-1-2) to (A-1-4) were produced in the same manner as in the preparation of the resin (A-1-1), except that the raw material compositions were changed to the contents in Table 1. The physical properties thereof were shown in Table 1.
• TABLE 1 Resin A-1-1 A-1-2 A-1-3 A-1-4 Raw KB-300 24 28.5 24 0 material TMP 10 5 12 0 (mole EG 56 66.5 56 66 part) DEG 0 0 0 24 TEG 4 0 8 10 TPA 83.5 96.5 85 60 Benz A 18.3 25.5 0 0 IPA 0 0 0 20 5-sulfoisophthalic 0 0 0 10 acid Physical Tg (° C.) 45 51 36.6 49.4 properties Hydroxyl value 22 3 87.8 6.5 (KOHmg/g) Acid value 2.1 24.7 12.8 2.5 (KOHmg/g) Mn 2,800 2,400 1,830 2,400 Mw 15,600 6,000 6,330 55,000 KB-300: Bisphenol A derivative TMP:
• a mixture of 70 mass parts of the resin (A-1-1) and 30 mass parts of the resin (A-1-4) was fed into a twin screw extruder at a flow rate of 10 kg/hr for kneading at 175° C. and 3.0 mass parts of tolylene diisocyanate (TDI) was further fed into the resin mixture during kneading and conveying the resin mixture for further kneading to obtain a resin (A-2-1).
• Tg of the obtained resin was shown in Table 2.
• Resins (A-2-2) and (A-2-3) were produced in the same manner as in the preparation of the resin (A-2-1), except that the raw material compositions were changed to the contents in Table 2. Tg thereof were also shown in Table 2. TABLE 2 Resin A-2-1 A-2-2 A-2-3 Raw material resin A-1-1 70 A-1-2 55 A-1-2 70 (mass part) A-1-4 30 A-1-3 15 A-1-3 30 A-1-4 30 TDI (mass part) 3 2.4 2.1 Tg (° C.) 62 52 54
• a 5-liter, 4-necked flask was provided with a reflux condenser, a water-separating unit, a nitrogen gas inlet tube, a thermometer and a stirrer. Thereinto were fed at a ratio of 12.8 mole parts of ACTCOL KB300, 30.0 mole parts of EG, 2.3 mole parts of TMP, 43.5 mole parts of TPA and 11.5 mole parts of Benz A.
• Dibutyltin oxide was added in an amount of 0.3 mass % based on the total mass of monomers. Dehydration and polycondensation were conducted at 180° C. to 240° C. with nitrogen being introduced into the flask to obtain a resin (b1-1).
• Resins (b1-2) and (b1-3) were produced in the same manner as in the preparation of the resin (b1-1), except that the raw material compositions were changed to the contents in Table 3. The physical properties thereof were also shown in Table 3.
• a 5-liter, 4-necked flask was provided with a reflux condenser, a 5 water-separating unit, a nitrogen gas inlet tube, a thermometer and a stirrer. Thereinto were fed 4.2 mole parts of sodium dimethyl 5-sulfoisophthalic acid and 30.5 mole parts of EG. 0.2 mass part of titanium lactate (Orgatics TC-310, a product of Matsumoto Chemical Industry Co., Ltd.) was added thereto for carrying out demethanolation at 180° C. to 220° C. and then 13.7 mole parts of DEG, 6.3 mole parts of TEG, 31.6 mole parts of TPA and 13.7 mole parts of IPA were fed thereinto.
• a resin (b2-2) was produced in the same manner as in the preparation of the resin (b2-1), except that the raw material compositions were changed to the contents in Table 4. The physical properties thereof were also shown in Table 4. TABLE 4 Resin b2-1 b2-2 Raw material Styrene 78 75 (mass part) n-butyl acrylate 20 17 Glycidyl methacrylate 2 8 Glycidyl methacrylate (mole part) 2.6 10.2 Physical Tg (° C.) 57 61 properties Mn 8,500 6,000
• Glycidyl methacrylate (mole part): moles of glycidyl methacrylate based on 100 moles of all vinyl monomers.
• a 5-liter, 4-necked flask was provided with a reflux condenser, a water-separating unit, a nitrogen gas inlet tube, a thermometer and a stirrer. Thereinto were fed 14.5 mole parts of NPG, 33.7 mole parts of EG, 33.7 mole parts of TPA, 15.2 mole parts of IPA and 2.9 mole parts of Benz A. 0.2 mass % of titanium lactate (Orgatics TC-310, a product of Matsumoto Chemical Industry Co., Ltd.) based on the total mass of monomers was added thereto. Dehydration and polycondensation were conducted at 180° C. to 240° C. with nitrogen being introduced into the flask to obtain a resin (b3-1). The physical properties of the resin were shown in Table 5.
• Resins (b3-2) and (b3-3) were produced in the same manner as in the preparation of the resin (b3-1), except that the raw material compositions were changed to the contents in Table 5. The physical properties thereof were also shown in Table 5.
• a 5-liter, 4-necked flask was provided with a reflux condenser, a water-separating unit, a nitrogen gas inlet tube, a thermometer and a stirrer. Thereinto were fed 1.4 mole part of sodium dimethyl 5-sulfoisophthalic acid and 14.5 mole parts of NPG. 0.2 mass % of titanium lactate (Orgatics TC-310, a product of Matsumoto Chemical Industry Co., Ltd.) based on the total mass of monomers was added thereto for carrying out demethanolation at 180° C. to 220° C. Then, 33.7 mole parts of EG, 33.7 mole parts of TPA, 13.7 mole parts of IPA and 2.9 mole parts of Benz A were fed thereinto. Dehydration and polycondensation were conducted at 180° C. to 240° C. with nitrogen being introduced into the flask to obtain a resin (b3-4). The physical properties of the resin (b3-4) were shown in Table 5.
• a resin (b3-5) was produced in the same manner as in the preparation of the resin (b3-4), except that the raw material compositions were changed to the contents in Table 5. The physical properties thereof were also shown in Table 5.
• TABLE 5 Resin b3-1 b3-2 b3-3 b3-4 b3-5
• Raw material Sodium dimethyl 0 0 0 1.4 4.8 (mass part) 5-sulfoisophthalic acid NPG 14.5 13.3 13.6 14.5 14.5 EG 33.7 31 31.7 33.7 33.7 TEG 0 0 4.5 0 0 TMP 0 2.3 3.6 0 0 TPA 33.7 46.5 46.6 33.7 33.7 IPA 15.2 0 0 13.7 10.4 Benz A 2.9 7 2.9 2.9 Physical Tg (° C.) 57 54 45 56 63 properties Hydroxyl value 2.4 5 60.2 2.5 1.5 (KOHmg/g) Acid value 25.4 26 8.2 30 32 (KOHmg/g) Mn 2,600 2,600 3,900 2,300 2,100 Mw
• Resins (B1-2) to (B1-5) were produced in the same manner as in the preparation of the resin (B1-1), except that the raw material compositions were changed to the contents in Table 6. The physical properties thereof were also shown in Table 6. TABLE 6 Resin B1-1 B1-2 B1-3 B1-4 B1-5 Raw material resin b1-1 53 b1-2 53 b1-1 60 b1-1 45 b1-1 70 (mass part) b1-3 17 b1-3 17 b1-3 20 b1-3 15 b1-3 30 b1-4 30 b1-4 30 b1-4 20 b1-4 40 TDI (mass part) 4.1 4.3 3.9 2.5 2.5 Sulfonic acid group 1.4 1.4 1 1.9 0 (mole %) Polyisocyanate-derived Yes Yes Yes Yes structure Physical Tg (° C.) 55.1 58.5 57.6 53.6 54.4 properties THF 6.8 9 4.3 3.5 3 insoluble component (mass %) Peak 5,500 7,100 5,400 5,600 5,300 molecular weight
• Sulfonic acid group (mole %): The ratio of a structure unit having a sulfonic acid group in the total of a polycarboxylic acid-derived structure unit and a polyhydric alcohol-derived structure unit constituting a polyester based resin.
• Polyisocyanate-derived structure Existence of a polyisocyanate-derived structure in the THF insoluble component.
• Peak molecular weight Peak molecular weight of the THF soluble component.
• the mixture contains 1.5 mole % of a structure unit having a sulfonic acid group and/or a sulfonic acid metal salt group in the total of the polycarboxylic acid-derived structure unit and the polyhydric alcohol-derived structure unit constituting polyester. Thereto was mixed 3 mass parts of the resin (b2-1).
• the resulting mixture was fed into a twin screw extruder at a flow rate of 10 kg/hr for kneading at 175° C., and 4.3 mass parts of TDI was fed into the resin mixture during kneading and conveying the resin mixture for further kneading to obtain a resin (B2-1).
• the resin (B2-1) contains 3 mass % of a vinyl copolymer.
• Tg of the obtained resin was 56.0° C. and the THF insoluble component was 7.1 mass %.
• THF insoluble component was 7.1 mass %.
• Resins (B2-2) to (B2-4) were produced in the same manner as in the preparation of the resin (B2-1), except that the raw material compositions were changed to the contents in Table 7. The physical properties thereof were also shown in Table 7. TABLE 7 Resin B2-1 B2-2 B2-3 B2-4 Raw material resin (mass part) b1-1 53 b1-1 51 b1-1 53 b3-1 53 b1-3 14 b1-3 14 b3-3 14 b1-4 30 b1-4 29 b1-4 30 b3-5 30 b2-1 3 b2-1 6 b2-2 3 b2-1 3 TD (mass part) 4.3 4.3 4.3 2.1 Content of sulfonic acid group 1.5 1.5 1.5 1.5 (mole %) Content of vinyl copolymer 3 6 3 3 (mass %) Polyisocyanate-derived structure Yes Yes Yes Yes Yes Physical Tg (° C.) 56 56.3 55.8 61 properties THF insoluble 7.1 7.4 7.9 7.1 component (mass %) Peak molecular 5,400 5,500 5,500 6,200 weight
• Content of vinyl copolymer (mass %): Content of a vinyl copolymer-derived structure in a polyester based resin.
• Resins (B3-2) to (B3-4) were produced in the same manner as in the preparation of the resin (B3-1), except that the raw material compositions were changed to the contents in Table 8. The physical properties thereof were shown in Table 8. TABLE 8 Resin B3-1 B3-2 B3-3 B3-4 Raw material resin (mass part) b3-1 53 b3-1 53 b3-2 53 b3-4 75 b3-3 17 b3-3 17 b3-3 17 b3-3 25 b1-4 30 b3-5 30 b3-5 30 TDI (mass part) 2.1 2.1 2.1 2.1 Content of sulfonic acid group 1.2 1.4 1.4 1.1 (mole %) Polyisocyanate-derived structure Yes Yes Yes Yes Bisphenol A-derived structure unit No No No No Content of tin (ppm) 0 0 0 0 0 Physical Tg (° C.) 61 60.5 60.5 55.5 properties THF insoluble 7 7.4 7.4 10 component (mass %) Peak molecular 6,700 6,100 6,100
• Performance as a toner was evaluated according to the following method and criteria.
• An unfixed image was formed using a copier produced by remodeling of a commercial electrophotographic copier.
• the unfixed image was fixed using a heat roller fixing apparatus produced by remodeling of the fixing section of a commercial copier.
• the fixing of a toner was conducted at a fixing speed of the heat roll of 210 mm/sec with the temperature of the heat roller being changed at intervals of 5° C.
• the fixed image obtained was rubbed 10 times by applying a load of 0.5 kgf using a sand eraser (a product of Tombow Pencil Co., Ltd.), and the image densities before and after the rubbing test were measured using a Macbeth reflection densitometer.
• the lowest fixing temperature at which the change ratio of image density became not less than 60% was taken as the lowest fixing temperature of the toner.
• the heat roller fixing apparatus used had no silicon oil feeder.
• the offset resistance was evaluated according to the above measurement of the lowest fixing temperature. After an unfixed image was formed using the above copier; the toner image was transferred and fixed using the above heat roller fixing apparatus. Then, a white transfer paper was fed into the heat roller fixing apparatus under the same conditions; and the appearance of toner staining on the transfer paper was examined visually. This operation was repeated by gradually increasing the set temperature of the heat roller of the heat roller fixing apparatus. The lowest set temperature at which toner staining appeared on the transfer paper was taken as the temperature of offset appearance.
• the atmosphere of the above copier was a temperature of 22° C. and a relative humidity of 55%.
• the toner was allowed to stand under the environmental conditions of a temperature of 45° C. and a relative humidity of 60% for 24 hours, and 5 g thereof was fed into a sieve of 150 mesh. Then, the scale of a rheostat of a powder tester (HOSOKAWA POWDER TECHNOLOGY RESEARCH INSTITUTE) was set to 3 for vibrating it for 1 minute. After vibration, the mass remained on the sieve of 150 mesh was measured to obtain the residual mass ratio.
• HOSOKAWA POWDER TECHNOLOGY RESEARCH INSTITUTE HOSOKAWA POWDER TECHNOLOGY RESEARCH INSTITUTE
• the resulting material was fed into a twin screw extruder PCM30-41.5 (a product of Ikegai Corporation) at 3.6 kg/hr and melt-kneaded at 140° C., and distilled water was continuously fed from a feeding port placed at a vent section of the extruder at 960 g/hr to obtain an aqueous dispersed system comprising a microparticle dispersed in water.
• An average particle diameter of 50% volume (D50) of the obtained microparticle was 0.29 ⁇ m.
• the solid content ratio of the aqueous dispersed system was adjusted to be 20 mass %.
• 300 g of the aqueous dispersed system and 400 g of 2 weight % sodium chloride aqueous solution were fed into a stainless flask, and stirred and mixed at 30° C. for 30 minutes using CLEARMIX (a product of Emtec Co., Ltd.) to aggregate at a prescribed particle diameter.
• 800 g of distilled water was added thereto.
• the resulting material was kept at 90° C. for 6 hours for the thermal fusion, and cooled down to a room temperature, followed by filtering, washing and drying.
• a toner was obtained in the same manner as in Example 1, except that the resin (A-2-2) was used as a raw material and the concentration of the sodium chloride aqueous solution was changed to 1.5 mass %.
• the evaluation results are shown in Table 9.
• a toner was obtained in the same manner as in Example 1, except that 64 mass parts of the resin (A-2-3) was used as a raw material and 27 mass parts of WR-901 (a product of Nippon Synthetic Chemical Industry Co., Ltd.) was used as a emulsifying auxiliary.
• the evaluation results are shown in Table 9.
• a toner was obtained in the same manner as in Example 1, except that 64 mass parts of the resin (A-2-3) was used as a raw material, 27 mass parts of WR-960 (a product of Nippon Synthetic Chemical Industry Co., Ltd.) was used as a emulsifying auxiliary, 0.1 normal sodium hydroxide aqueous solution was continuously fed from a feeding port placed at a vent section of the extruder at 960 g/hr. The evaluation results are shown in Table 9.
• a toner was obtained in the same manner as in Example 1, except that 81 mass parts of the resin (A-2-3) was used as a raw material and 10 mass parts of sodium dodecylbenzene sulfonate was used as a emulsifying auxiliary.
• the evaluation results are shown in Table 9.
• 270 g of the microparticle aqueous dispersed system, 20 g of the colorant dispersed system, 10 g of the releasing agent dispersed system and 400 g of 2 weight % sodium chloride aqueous solution were fed into a stainless flask and stirred and mixed at 30° C. for 30 minutes using CLEARMIX (a product of Emtec Co., Ltd.) to form an aggregate at a prescribed particle diameter. Then, 800 g of distilled water was added thereto. The resulting material was kept at 90° C. for 6 hours for the thermal fusion, and cooled down to a room temperature, followed by filtering, washing and drying.
• CLEARMIX a product of Emtec Co., Ltd.
• Example 2 Example 3
• Example 4 Example 5
• Example 6 Example 1 Raw material resin A-2-1 A-2-2 A-2-3 A-2-3 A-2-3 A-2-2 A-2-1 Resin D50 ( ⁇ m) 0.29 0.3 0.29 0.35 0.31 0.23 — microparticle D90/D10 2.1 2.1 2.1 2.1 2.1 — Content of less than less than less than less than less than — organic 10 10 10 10 10 10 10 solvent (ppm) Toner D50 ( ⁇ m) 7.5 6.2 6.5 7.5 6.2 6.5 11.3 D90/D10 1.5 1.5 1.5 1.5 1.5 1.5 2.1 Content of less than less than less than less than less than less than 840 organic 10 10 10 10 10 10 10 10 10 10 solvent (ppm) Fixing 1 1 1 1 1 1 properties Offset 1 1 1 1 1 1 2 resistance Cleaning 1 1 1 1 1 1 3 properties Storage 1 1 1 1 1 1 3 stability
• a particle diameter of 50% volume (D50) of the obtained resin microparticle for a toner was 0.32 ⁇ m, D90/D10 was 2.1, 5.0 mass parts of the THF insoluble component was included, a polyisocyanate-derived structure in the THF insoluble component was confirmed, and the peak molecular weight of the THF soluble component was 5,500.
• the ratio of the resin microparticle for a toner in the dispersed system was adjusted to be 30 mass %.
• 310 mass parts of the dispersed system comprising a resin microparticle for a toner, 20 g of the colorant dispersed system, 20 mass parts of the releasing agent dispersed system and 500 g of 0.75 weight % sodium hydroxide aqueous solution were fed into a stainless flask and stirred and mixed at 30° C. at 5,000 rpm for 30 minutes using CLEARMIX (a product of Emtec Co., Ltd.). Then, the resulting material was aggregated at 65° C. at 8,000 rpm until a prescribed particle diameter was obtained. Then, 800 mass parts of distilled water was added thereto. The resulting material was kept at 85° C.
• Example 10 Example/Comparative Example Nos. Com- Example Example Comparative Comparative parative Example 7
• Example 8 Example 9 10 19
• Example 2 Example 3
• Example 4 Raw material resin B1-1 B1-2 B1-3 B1-4 B1-1 — B1-5 B1-1 Resin D50 ( ⁇ m) 0.32 0.25 0.49 0.24 0.25 — — — microparticle D90/D10 2.1 2.8 3 2.1 2.3 — — — Content of organic less than less than less than less than less than — — — solvent 10 10 10 10 10 Content of THF 5 7 2.8 2 5.2 — — — insoluble component Polyisocyanate-derived Yes Yes Yes Yes — — — structure Peak molecular weight 5,500 7,000 5,400 5,500 7,000 — — — Toner D50 ( ⁇ m) 4.7 5 6.3 4.9 6 6.1
• a dispersed system comprising a resin microparticle for a toner and water was obtained in the same manner as in Example 7, except that the resin (B2-1) was used instead of the resin (B1-1).
• a particle diameter of 50% volume (D50) of the obtained resin microparticle for a toner was 0.30 ⁇ m, D90/D10was 1.5, 5.2 mass parts of the THF insoluble component was included, a polyisocyanate-derived structure in the THF insoluble component was confirmed, a vinyl copolymer in the resin was confirmed, and the peak molecular weight of the THF soluble component was 5,500.
• D50 of the obtained toner was 4.7 ⁇ m.
• Example 11 Example/Comparative Example Nos.
• Example 11 Example 12
• Example 13 Example 14
• Raw material resin B2-1 B2-2 B2-3 B2-4 Resin D50 ( ⁇ m) 0.3 0.35 0.31 0.32 microparticle D90/D10 1.5 1.6 1.5 1.5 Content of organic less than 10 less than 10 less than 10 less than 10 solvent Content of THF 5.2 5.8 6 5.3 insoluble component
• Polyisocyanate-derived Yes Yes Yes Yes structure Vinyl Yes Yes Yes Yes Yes copolymer-derived structure Peak molecular weight 5,500 5,500 5,500 6,100
• Content of organic less than 10 less than 10 less than 10 less than 10 less than 10 solvent Fixing properties 1 1 1 1
• Offset resistance 1
• 1 1 Cleaning properties
• 1 Storage stability
• 1 Charging performance
• An aqueous dispersed system obtained by dispersing a resin microparticle for a toner was obtained in the same manner as in Example 7, except that the resin (B3-1) was used instead of the resin (B1-1). In that resin microparticle, a bisphenol A-derived structure and tin were not included.
• a particle diameter of 50% volume (D50) of the obtained resin microparticle for a toner was 0.31 ⁇ m, D90/D10 was 2.0, 5.3 mass parts of the THF insoluble component was included, a polyisocyanate-derived structure in the THF insoluble component was confirmed, and the peak molecular weight of the THF soluble component was 6,700.
• D50 of the obtained toner was 4.9 ⁇ m. The evaluation results are shown in Table 12.
• Example 15 Example 16
• Example 18 Raw material resin B3-1 B3-2 B3-3 B3-4 Resin D50 ( ⁇ m) 0.31 0.29 0.29 0.4 microparticle D90/D10 2 2 2 2.5 Content of organic less than 10 less than 10 less than 10 less than 10 solvent (ppm) Content of THF 5.3 5.9 5.8 7.9 insoluble component Polyisocyanate-derived Yes Yes Yes Yes structure Peak molecular weight 6,700 6,100 6,000 6,000 Bisphenol A-derived No No No No No No No No No structure Content of tin (ppm) 0 0 0 0 Toner D50 ( ⁇ m) 4.9 4.7 4.8 5.1 D90/D10 1.5 1.5 1.5 1.5 Content of organic less than 10 less than 10 less than 10 less than 10 solvent (ppm) Fixing properties 1 1 1 1 Offset resistance 1 1 1 1 Cleaning properties 1
• a dispersed system comprising a resin microparticle for a toner and water was obtained in the same manner as in Example 7 using the resin (B1-1).
• a particle diameter of 50% volume (D50) of the obtained resin microparticle for a toner was 0.32 ⁇ m, D90/D10 was 2.1, 7.0 mass parts of the THF insoluble component was included, a polyisocyanate-derived structure in the THF insoluble component was confirmed, and the peak molecular weight of the THF soluble component was 7,000.
• a toner was obtained in the same manner as in Example 7, except that 0.78% sodium chloride aqueous solution was used.
• An average particle diameter of 50% volume of the obtained toner was 6.0 ⁇ m. The evaluation results are shown in Table 10.
• a 5-liter, 4-necked flask was provided with a reflux condenser, a nitrogen gas inlet tube, a thermometer and a stirrer. Thereinto were fed 47.6 mass parts of ion exchange water, 37.0 mass parts of styrene, 3.0 mass parts of n-butyl acrylate, 0.6 mass part of acrylic acid, 2.4 mass parts of dodecanethiol, 0.4 mass part of carbon tetrabromide and 4.0 mass parts of Neoperex F-25 (a product of Kao Corporation).
• styrene resin dispersion 1 having an average particle diameter of 50% volume of 0.16 nm, Tg of 59° C. and the weight-average molecular weight of 12,000 was obtained.
• a 5-liter, 4-necked flask was provided with a reflux condenser, a nitrogen gas inlet tube, a thermometer and a stirrer. Thereinto were fed 50.2 mass parts of ion exchange water, 28.0 mass parts of styrene, 12.0 mass parts of n-butyl acrylate, 0.8 mass part of acrylic acid and 4.0 mass parts of Neoperex F-25 (a product of Kao Corporation). While the resulting material was dispersed and emulsified in the flask and slowly mixed for 10 minutes, 5.0 mass parts of ion exchange water in which 0.3 mass part of ammonium persulfate was dissolved was fed thereinto and the flask was purged with nitrogen.
• the flask was stirred for carrying out the emulsion polymerization at 70° C. for 5 hours.
• a styrene resin dispersion 2 having an average particle diameter of 50% volume of 105 nm, Tg of 53° C. and the weight-average molecular weight of 55,000 was obtained.
• styrene resin dispersion 1 180 g of the styrene resin dispersion 1, 80 g of the styrene resin dispersion 2, 30 g of the colorant dispersion, 30 g of the releasing agent dispersion and 1.5 g of sanisol B-50 (a product of Kao Corporation) were mixed and dispersed in a circular flask using a homo mixer, and then the flask was stirred in an oil bath and heated up to 50° C. The resulting material was kept at 50° C. for an hour. Thereafter, 9.0 g of Neoperex F-25 was added thereto. Then, the flask was sealed and heated up to 105° C. while stirring, and kept for 3 hours.
• sanisol B-50 a product of Kao Corporation
• the mixture was cooled down to a room temperature, followed by filtering, washing and drying.
• 0.1 mass part of a hydrophobic silica (Aerosil R972, a product of Nippon Aerosil Co., Ltd.) was added and mixed to obtain a toner.
• An average particle diameter of 50% volume of the obtained toner was 6.1 ⁇ m. Fixing properties and offset resistance of this toner were determined and the degree of contamination of the heat roller was examined. Further, cleaning properties, storage stability and chargeability were determined. The evaluation results of this toner are shown in Table 10.
• REGAL33OR a product of Cabot Specialty Chemicals, Inc.
• ⁇ -(2-aminoethyl)aminopropyltrimethoxysilane a product of Dow Coming Toray Silicone Co., Ltd.
• the coarsely ground resin was finely ground using a jet grinder (IDS2, a product of Nippon Pneumatic Co., Ltd.), followed by air classification, to obtain a toner particle.
• a jet grinder IDS2, a product of Nippon Pneumatic Co., Ltd.
• To 100 mass parts of the obtained toner particle 0.1 mass part of a hydrophobic silica (Aerosil R972, a product of Nippon Aerosil Co., Ltd.) was added and mixed to obtain a toner.
• An average particle diameter of 50% volume of the obtained toner was 6.0 ⁇ m.
• the evaluation results are shown in Table 10.
• a polyether polyol based resin was used as a resin.
• a separable flask was provided with a stirrer, a thermometer, a nitrogen inlet and a reflux tube. Thereinto were fed 91 mass parts of polyoxypropylene-(1,1)-2,2-bis(4-hydroxyphenyl)propane (KB-280, a product of Mitsui Takeda Chemicals, Inc.) and 70 mass parts of phthalic anhydride. The resulting material was stirred at an internal temperature of 100° C. until the system became homogeneous. Subsequently, 0.08 mass part of benzyldimethylamine (BDMA) was added as a catalyst, and then heated to 130° C. and reacted for 6 hours.
• BDMA benzyldimethylamine
• a separable flask was provided with a stirrer, a thermometer, a nitrogen inlet and a reflux tube. Thereinto were fed 91 mass parts of polyoxypropylene-(1,1)-2,2-bis(4-hydroxyphenyl)propane (KB-280, a product of Mitsui Takeda Chemicals, Inc.) and 70 mass parts of phthalic anhydride. The resulting material was stirred at an internal temperature of 100° C. until the system became homogeneous. Subsequently, 0.08 mass part of benzyldimethylamine (BDMA) was added as a catalyst, and then heated to 130° C. and reacted for 6 hours.
• BDMA benzyldimethylamine
• the resulting mixture was reacted at 160° C. for an hour, and then 0.03 mass part of 50% tetramethylammonium chloride aqueous solution was further added thereto.
• the reflux tube was replaced by a vacuum distillation unit and the degree of decompression was increased little by little for removing the water. After an hour, the degree of decompression reached 1,333 Pa (10 mmHg).
• the pressure in the reaction system was returned to a normal pressure and stirring was continued for 7 hours.
• the generated polyol resin was sampled for measuring the epoxy equivalent.
• the epoxy equivalent was confirmed to be not less than 20,000, and then the generated polyol resin was taken out of the flask to obtain a resin (C-2).
• the softening point of the obtained resin was 113° C., Tg was 60° C., Mn was 2,900, Mw was 21,000, Mw/Mn was 7.2, and the hydroxyl value was 141 KOHmg/g.
• a 5-liter, 4-necked flask was provided with a reflux condenser, a water-separating unit, a nitrogen gas inlet tube, a thermometer and a stirrer. Thereinto were fed 66.0 mole of ethylene glycol (EG), 10.0 mole of triethylene glycol (TEG), 24.0 mole of diethylene glycol (DEG), 60.0 mole of terephthalic acid (TPA), 20 mole of isophthalic acid (IPA) and 20.0 mole of sodium 5-sulfoisophthalic acid. Dehydration and polycondensation were conducted at 180° C. to 240° C. with nitrogen being introduced into the flask to obtain a emulsifying auxiliary (D-1). Tg of (D-1) was 47° C., Mn was 2,300 and Mw was 50,000.
• An unfixed image was formed using a copier produced by remodeling of a commercial electrophotographic copier.
• the unfixed image was fixed using a heat roller fixing apparatus produced by remodeling of the fixing section of a commercial copier.
• the fixing of a toner was conducted at a fixing speed of the heat roll of 190 mm/sec with the temperature of the heat roller being changed at intervals of 5° C.
• the fixed image obtained was rubbed 6 times by applying a load of 1.0 kgf using a sand eraser (a product of Tombow Pencil Co., Ltd.), and the image densities before and after the rubbing test were measured using a Macbeth reflection densitometer.
• the offset resistance was evaluated according to the above measurement of the lowest fixing temperature. After an unfixed image was formed using the above copier; the toner image was transferred and fixed using the above heat roller fixing apparatus. Then, a white transfer paper was fed into the heat roller fixing apparatus under the same conditions; and the appearance of toner staining on the transfer paper was examined visually. This operation was repeated by gradually increasing the set temperature of the heat roller of the heat roller fixing apparatus. The lowest set temperature at which toner staining appeared on the transfer paper was taken as the temperature of offset appearance.
• the atmosphere of the above copier was a temperature of 22° C. and a relative humidity of 55%.
• the toner was allowed to stand for 24 hours under the environmental conditions of a temperature of 40° C. and a relative humidity of 60%, and 5 g thereof was fed into a sieve of 150 mesh. Then, the scale of a rheostat of a powder tester (HOSOKAWA POWDER TECHNOLOGY RESEARCH INSTITUTE) was set to 3 for vibrating it for 1 minute. After vibration, the mass remained on the sieve of 150 mesh was measured to obtain the residual mass ratio.
• HOSOKAWA POWDER TECHNOLOGY RESEARCH INSTITUTE HOSOKAWA POWDER TECHNOLOGY RESEARCH INSTITUTE
• Toners were obtained in the same manner as in Example 20, except that the raw materials illustrated in Table 13 were used.
• a toner was obtained in the same manner as in Example 20, except that a nichigo polyester WR-901 (a product of The Nippon Synthetic Chemical Industry Co., Ltd.), i.e., a polyester containing a sulfonic acid group was used instead of the emulsifying auxiliary (D-1).
• the evaluation results are shown in Table 13.
• a toner was obtained in the same manner as in Example 20, except that a nichigo polyester W-0223 (a product of The Nippon Synthetic Chemical Industry Co., Ltd.), i.e., a polyester containing a sulfonic acid group was used instead of the emulsifying auxiliary (D-1).
• the evaluation results are shown in Table 13.
• the solid content of the microparticle aqueous dispersion was adjusted to be 20 mass %. Furthermore, 20.0 mass parts of refined carnauba wax 1 powder (a product of Nippon Wax Co., Ltd.), 2.0 mass parts of Neoperex F-25 (a product of Kao Corporation) and 78.0 mass parts of ion exchange water were heated at 140° C. and emulsified at a discharge pressure of 560 ⁇ 10 5 N/m 2 using a gaulin homogenizer, and then chilled to obtain a releasing agent dispersion. An average particle diameter of 50% volume of this releasing agent dispersion was 0.12 ⁇ m. Further, 20.0 mass parts of a cyanine dye FG7351 (a product of Toyo Ink Mfg.
• Neoperex F-25 (a product of Kao Corporation)
• 75.0 mass parts of ion exchange water were mixed and dispersed at an oscillating frequency of 28 kHz for 10 minutes using an ultrasonic wave cleaning machine W-113 (a product of Honda Electronics Co., Ltd.) to obtain a colorant dispersion.
• An average particle diameter of 50% volume of this colorant dispersion was 0.15 ⁇ m.
• 270 g of the microparticle aqueous dispersion, 20 g of the colorant dispersion, 10 g of the releasing agent dispersion and 400 g of 2 mass % sodium hydroxide aqueous solution were fed into a stainless flask, and stirred and mixed at 30° C.
• a toner was obtained in the same manner as in Example 20, except that a magenta dye TONER MAGENTA E02 (a product of Clariant Ltd.) was used instead of the cyanine dye FG7351 (a product of Toyo Ink Mfg. Co., Ltd.).
• the evaluation results are shown in Table 13.
• a toner was obtained in the same manner as in Example 20, except that a yellow dye TONER YELLOW HG VP2155 (a product of Clariant Ltd.) was used instead of the cyanine dye FG7351 (a product of Toyo Ink Mfg. Co., Ltd.).
• the evaluation results are shown in Table 13.
• a toner was produced and evaluated in the same manner as in Comparative Example 1. The evaluation results are shown in Table 13.
• Example Example Comparative Comparative 25 26 27 Example 5
• Example 6 Raw material resin C-1 C-1 C-1 — C-1 Emulsifying auxiliary W-0223 W-0223 W-0223 — — Resin D50 ( ⁇ m) 0.5 0.5 0.6 — — microparticle D90/D10 2.8 2.8 2.8 — — Content of less than less than less than — — organic solvent 10 10 10 (ppm) Toner D50 ( ⁇ m) 6.5 7.3 7.3 6.1 11.3 D90/D10 1.5 1.5 1.5 1.5 2.1 Content of less than less than less than 520 840 organic solvent 10 10 10 (ppm) Fixing 1 1 1 2 1 properties Offset 1 1 1 1 1 1 1 1 resistance Cleaning 1 1 1 1 2 properties Storage stability 1 1 1 1 2 Gloss 1 1 1 2 1
• a microparticle aqueous dispersion and a toner obtained by the aggregation and fusion of the microparticle aqueous dispersion according to the present invention are confirmed to have excellent fixing properties, offset resistance, gloss, cleaning properties and storage stability.

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