KR20040096296A - Method for making a toner for use in electrostatic development through a suspension process with reverse-neutralization - Google Patents

Abstract

PURPOSE: A toner for electrostatic development and its preparation method are provided, to obtain low softening point and low melting viscosity and improve offset resistance even in high rate development and fixation. CONSTITUTION: The method comprises the steps of preparing a linear low molecular weight polyester resin having a carboxyl group at the end; preparing a crosslinked polyester resin having a carboxyl group at the end; neutralizing the polyester resin and adding water to the polyester resin to prepare a polyester resin aqueous solution; preparing a crosslinked ethylenically copolymerized latex; adding a colorant, a charge control agent and a releasing agent to the polyester resin aqueous solution and applying high shear force to mix it to prepare a coloring resin dispersion; adding a colorant, a charge control agent and a releasing agent to the polyester resin aqueous solution, applying high shear force to mix it and mixing the coloring resin dispersion with the latex to prepare a coloring resin dispersion; adding the two coloring resin dispersion in an aqueous solution containing an acidic compound, respectively, applying high shear force to reverse neutralize them to generate toner particles, and heating the toner particles to stabilizer it; filtering and washing the toner particles and vacuum drying it; and adding hydrophobic silica or hydrophobic titanium dioxide to the toner particles and mixing them.

Description

[Method for making a toner for use in electrostatic development through a suspension process with reverse-neutralization}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymerization toner, and more particularly, to a toner for developing electrostatic images excellent in fine development, offset resistance, low melt viscosity, and low temperature fixing property.

The electrophotographic method, the electrostatic lock method, and the like form images by transferring a toner image formed by visualizing a latent image caused by electricity and exposure by a developer to be transferred to a transfer member. Printers or copiers employing the electrostatic image development method are required to save power and speed up in the process of elaborate phenomenon without contamination and compression welding by heat roller. This requirement requires that the toner's electrical characteristics and particle size are fine and have a narrow distribution, and that additives are well dispersed around the toner particles in the developing process, so that an accurate image can be formed. Image quality is determined by the degree of sex. Therefore, research and development of toner performance has been progressed with an emphasis on this point. The toner composition used herein contains a binder resin, a colorant, a charge control agent, a mold release agent, and the like, and is produced by a pulverization method or a neutralization method. The binder resin is a main component in the toner and determines the performance of the toner. Polystyrene, acrylic copolymer resin, epoxy resin, polyester, styrene, acrylate, and latex are used as raw materials for the binder resin for toner, but recently, polyester resins having excellent low temperature fixing characteristics such as low melting point elasticity, adhesiveness, and peeling resistance are used. Was noticed. The pulverization method melts and mixes the binder resin, the colorant, the charge control agent, and the release agent by heating, and classifies the desired particle size to make a toner. This method is inefficient and completely dispersed by mixing raw materials in a flow state by heating. Since the additives do not function properly and the distribution of toner particles is wide, many unnecessary particles are generated, resulting in a low production yield and poor performance of the toner. This manufacturing method is proposed in Korean Patent Registration No. 0135558, Korean Patent Registration No. 0139386, Korean Patent Registration No. 0136598, Japanese Patent Application Laid-Open No. 8-334929, and Japanese Patent Application Laid-open No. 9-106099.

There are two types of neutralization methods: emalonic aggregation and suspension polymerization. Among them, the emalon agglomeration method mainly polymerizes emulsified ethylenic monomer with a surfactant to make a binder, and then mixes a colorant, a charge control agent, and a releasing agent, and heats it for a long time while agitating the emalon particles. To produce the desired toner particles by continuously curing them into secondary particles by repeating the operation. In this process, unstable manufacturing methods with a high risk of producing defective products outside the desired range due to stirring for several hours are disclosed. Japanese Patent Application Laid-Open No. 1998-056791, Korean Patent Publication No. 2001-037273, Japanese Patent Application Laid-Open No. 63-282750, Japanese Patent Application Laid-Open No. 6-250439, US Patent 5278020, and US Patent 5360201.

In the suspension polymerization method, a colorant, a charge agent, and a release agent are mixed with an ethylenic monomer, and a high shear force is applied with a homogenizer to make a monoma droplet having a desired particle size first, followed by suspension polymerization using a stabilizer such as calcium phosphate or silica. As a method of making particles, some additives interfere with the polymerization reaction, and there is a high risk of agglomeration into large particles due to prolonged reactions and high melt viscosity. This manufacturing method is proposed in Korean Patent Laid-Open Publication No. 1999-071156, Korean Patent Laid-Open Publication No. 2000-057424, Japanese Patent Application Laid-Open No. 61-118758, Japanese Patent Application Laid-Open No. 6-282110, US Patent 4794056, and US Patent 5219697. The above polymerization methods are manufacturing methods which are not applicable to polyester toner. In recent years, the need for low-temperature fixing suitable for energy saving power saving and high speed during fixing has increased, and polyester resin toners that are optimal for this demand have attracted attention. Prior arts of polyester resin polymerized toner have been proposed in US Pat. No. 5593807, US Pat. No. 6001524. However, the former is unstable toner particle generation, so the cohesion is severe and there is a high risk of large lump formation. The latter is higher than the melting point temperature of the resin in the poor solvent. The process is inefficient in several steps such as heating to a temperature to melt the resin and slowly cooling to obtain precipitated particles, dyeing them with a dye, coloring them, and separately preparing a resin solution containing a charge agent to coat the toner particles using the same. Since the petroleum solvent must be removed from the produced toner composition, environmental problems are raised.

In addition, Japanese Patent Application Laid-open No. Hei 8-211655 is made of a polymer having an acid value of 2 to 50 mgKOH / g and a weight average amount of 2,000 to 100,000, and dissolved in tatrahydrofuran, a solvent, and neutralized by ammonia water or triethylamine. Create a tetrahydrofuran solution of a polyester having a salt structure, knead pigments and additives, add theoretical exchanged water to form a phase emulsified composition, and distill the contained solvent under reduced pressure to remove tetrahydrofuran to generate toner particles. It takes several hours to several tens of hours. The toner original particles are made and filtered, the wet cake is washed with water, the water is neutralized by adding hydrochloric acid, the neutralized salt structure on the surface of the particle is changed to an acid form, and the finished water is washed. It is a technique of obtaining a toner element by drying. This technology is a method of making toner particles using a solvent, which is difficult to remove the solvent contained in the water and its waste water is extremely difficult and expensive, which is one of the impractical manufacturing methods that can not solve the environmental problems.

U.S. Patent No. 6,203,957 is also a manufacturing method that is not feasible because the above applicants make the toner particles by the same method as the above manufacturing method by using only ethylenic vinyl monomers and different monomers.

The present invention is a method for solving the above problems, the toner particles are fine and the distribution is narrow to obtain a sophisticated phenomenon without contamination and the glass transition temperature (Tg) of the binder as a component is high, but the softening point is low and the melt viscosity Energy saving and high-speed toner capable of high-speed copying with excellent power saving, offset resistance, fixability, adhesion, abrasion resistance, and peeling resistance can be obtained. As a new manufacturing method that satisfies this, the present invention provides a suspension treatment with reverse neutralization. The present invention relates to a toner for developing electrostatic charges and a method of manufacturing the same, and more particularly, by introducing a carboxyl group into the polymer chain terminal to accept and disperse a polymer having a neutral salt structure as an alkali compound, and then suspending it with deneutralization. The present invention relates to a method of making toner particles for producing electrostatic charge.

MEANS TO SOLVE THE PROBLEM As a result of repeating research in order to solve the said subject, the present inventors came to the conclusion that the following structure can solve the problem, and came to this invention.

The present invention

(1) When the polybasic acid and the polyhydric alcohol is reacted, a linear structural accelerator comprising an excessive addition of the polybasic acid to prepare a polymer composition having an acid value of 30 to 110 mgKOH / g is added to form a linear low molecular weight polyester resin composition by a first reaction. In this step, a secondary reaction is carried out by addition reaction so as to have 2 to 3 carboxyl groups at the end of the polymer chain, thereby preparing a polymer composition. In this step, a linear structural accelerator is used to induce a low molecular polymer and a polybasic acid at the end of the polymer chain. Provided is a method for producing a polymer composition having an acid value of 10 to 110 mgKOH / g by addition reaction.

(2) preparing a polymer composition having an acid value of 10 to 110 mgKOH / g by addition reaction to have 2 to 3 carboxyl groups at the end of the crosslinked polyester resin polymer chain, in this step, a diblock crosslinked during the first polymerization reaction The present invention provides a method of preparing an acid value of 10 to 110 mgKOH / g crosslinked polyester resin composition by adding and reacting a polyester resin to make a polyester resin, followed by secondary reaction of a polybasic acid.

(3) preparing a polymer resin solution by reacting the carboxyl group contained in the polymer composition with a basic compound to make a polymer resin salt and making the polymer resin water soluble so that the polymer resin salt has a surfactant function. Provided is a method for producing a water-soluble polyester aqueous solution by diluting by adding 1 to 10 times water.

(4) preparing a polymer resin solution by reacting the carboxyl group contained in the polymer composition with a basic compound to make a polymer resin salt and making it water-soluble so that the polymer resin salt has a surfactant function. Provided is a method of preparing a polyester resin dispersion by diluting by adding a water affinity solvent or a solution of a water affinity solvent and water and adding 1 to 10 times.

(5) Since the polyester resin solution may itself serve as a dispersant, a color resin composition may be prepared by mixing a colorant, a charge control agent, a mold release agent, etc. without adding another dispersant separately, in this step The polymer composition of step (1) and step (2) may be prepared by using the water-soluble resin composition of the polymer composition of (1) and each of the polymer composition of step (2). It is also possible to prepare a colored resin composition by mixing in a ratio, and if necessary, coloring using a water-soluble resin composition obtained by solubilizing the polymer composition of step (1) alone or a mixture of crosslinked ethylenic copolymer latex in an appropriate ratio. It provides a method for producing a resin composition.

(6) The colored resin composition of step (5) was slowly added to the water in which the acidic compound was dissolved, followed by suspension treatment accompanied by a desalination reaction by applying high shear force to instantaneously generate 5-15 탆 particle size toner particles to 30-90 캜. Heating step

(7) manufacturing the colored resin toner particle composition by filtering, washing with water and drying the produced toner particles

(8) adding 1 to 5 parts by weight of an external additive (hydrophobic silica or hydrophobic titanium oxide) to 100 parts by weight of the colored toner particle composition and mixing with a Henschel mixer to prepare an electrostatic image developing toner

The toner thus prepared can produce a toner having a particle size of 5 to 10 탆 and a narrow particle distribution with a high yield of 99% or more. It provides a method of manufacturing.

The present invention will be described in more detail as follows.

Substances that promote linear structure and induce low molecular polymers in step (1) include rosin, wood rosin, rosin and rosin derivatives, terpene resins, petroleum resins and derivatives thereof, dicyclopentadiene and derivatives thereof, gum rosin Wood rosin, talose rosin, hydrogenated rosin, marinized rosin, rosin ester, pinene resin, dipentene resin, C5 petroleum resin, C9 petroleum resin, DCPD resin, hydrogenated DCPD resin, marinized styrene resin Preference is given to using alone or in combination. They are preferably added in an amount of 10 to 100% by weight based on the total amount of monomers.

In addition, the polybasic acid which can be used is phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, azeline acid, sebacic acid, tetrahydrophthalic anhydride, maleic anhydride, fumaric acid, itaconic acid, trimellitic anhydride, pyromellitic anhydride, and benzoic acid. Preferably used alone or in combination. These are preferably added in an amount of 10 to 90% by weight in the total amount of monomers.

The polyhydric alcohols that can be used include ethylene glycol, propylphen glycol, 1.3 propanediol, 1.3 butanediol, 1.6 hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, polypropylene glycol, alkylene oxide adducts of bisphenol A, Trimethylolpropane, glycerin, pentaerythritol group is preferably used alone or in combination. It is preferable to add in the quantity of 10-90 weight% in the whole monomer amount.

The catalyst uses an organic acid metal or tin catalyst. The usage-amount is 0.05-0.5 weight% with respect to monomer whole quantity.

Carboxylic acids to be introduced at the polymer chain ends include trimellitic anhydride, trimellitic acid and pyromellitic anhydride. Pyromellitic acid, maleic anhydride, maleic acid, fumaric acid, adipic acid. Among the benzoic acid, sebacic acid, mariinated pine, marylene styrene, and isobutylene maleinate, it is preferred to be used alone or in combination. It is preferable to use it in the quantity of 10 to 70 weight% in a resin composition.

The diblock polyester resin crosslinked in step (2) was selected from commercially available DuPont products and the polybasic acid, polyhydric alcohol and catalyst are preferably selected from the same group as in step (1). Carboxylic acid to be introduced into the polymer chain end second is preferably used alone or in combination in the crowd used for the same purpose of step (1).

The basic compound used in step (3) is used alone or in combination among sodium hydroxide, potassium hydroxide, ammonium hydroxide, lithium hydroxide, triethylamine, diethanolamine, diethylethanolamine, methyl diethanolamine, and dimethylaminoethanol group. This is preferred. It is preferably used in the amount of 5 to 50% by weight in the resin composition.

The water-compatible solvents used in step (4) are alcohols, ethers, acetone, dimethyltoalamide, tetrahydro-fu tube, etaglycol, propylglycol, butylglycol and the like, which may be used alone or in combination. It is preferable to add in the amount of 10-50 weight%.

In the production method of the present invention, when the acid value reaches 10 to 110 mgKOH / g after the reaction using the above-described raw materials in the reactor, the reaction is terminated and cooled to a softening point of 70 to 150 ° C and a weight average molecular weight of 3,000 for the linear low molecular weight polymer. In the case of a high molecular weight polymer having a crosslinking capacity of 50,000 to 50,000, a softening point of 75 to 150 ° C, a Tfb of 100 to 120 ° C and a Tend of 120 to 150 ° C, the weight average molecular weight is 5,000 to 100,000 gel content of 5 to 50% by weight, and an acid value of 10 to 110 mgKOH / g, A polyester resin having a softening point of 100 to 170 ° C, Tfb 90 to 120 ° C, and Tend 130 to 160 ° C is prepared, and a basic compound is added to the resin to dissolve it in water or a hydrophilic solvent and a solution in which water is mixed with the water-soluble poly It is characterized by producing an ester resin composition. The crosslinked ethylenic copolymer latex is prepared in a conventional manner using 20 to 90% by weight of styrene, 5 to 90% by weight of acrylate monomer, 1 to 10% by weight of reactive anionic emulsifier, and 2 to 20% emulsion polymerization catalyst. It is preferably used by emulsion polymerization.

The water-soluble polyester resin composition can obtain the desired softening point, compatibility, adhesiveness and high functional properties according to the composition ratio of the raw materials, and especially the water-soluble polyester resin composition can be used for copying machine, printing machine, electrophotographic apparatus. The toner used in the above is characterized in that a polyester resin toner composition is prepared by a polymerization method.

The polyester resin composition of the present invention is used as a resin binder for toners used for developing electrostatic images on electrophotographic images, electrostatic recordings, etc., to which toners are prepared by adding a colorant, a charge agent, a mold release agent and the like. The colorants are black pigments such as carbon black and magnetite, yellow pigments such as iron oxide, sulfur kanji yellow, and permanent yellow. Blue pigments such as phthalocyanine blue and viloret. Red pigments such as iron oxide, carmine, toluzinet and quinacridone. Green pigments, such as phthalocyanine green and chrome green, are used, and a coloring agent content is 1-40 weight%.

Charge control agents include positive charge charge control agents such as nigrosine dyes and quaternary ammonium salts. Typical product names are BONTRON N-07. BONTRON N-21 Oriental Chemical Co., Ltd. and negative charge control agents are azo metal complex salts, salicylic acid metal complex salts, etc. Typical product names are BONTSON S-34, BONTRON E-84, Orient Chemical Co., Ltd. The amount of use is preferably 0.5 to 5% by weight based on the binder resin.

The colorants are dispersed in a water-soluble polyester resin composition to form a colored resin composition, and then a release agent is added thereto to disperse the colored resin composition.

The release agent may be 0.5 to 10% by weight of the binder resin alone or in combination with polyethylene wax, polypropylene wax, higher fatty acid ester, higher aliphatic alcohol, canava wax, and montan wax. These additives must be well dispersed in the binder resin to form satisfactory images.

Since the polyester resin composition of the present invention is well dispersed and dissolved in water or a water affinity solvent and a solvent and a mixed solvent of water, a toner having excellent performance can be prepared by dispersing the additives therein after preparing the liquid resin composition.

The colored resin composition thus obtained is gradually added to another reactor in an aqueous solution in which an acidic compound is dissolved, followed by suspension treatment with desalination to prepare a colored resin toner.

The acidic compound may be hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, phosphoric acid, bromic acid, acetic acid, nitrate, oxalic acid, P-toluenesulfic acid, etc., and the amount of the acidic compound is preferably 5 to 30% by weight based on the colored resin composition.

The toner thus obtained can obtain a toner having an outflow start (Tfb) of 80 to 95 DEG C and a discharge end temperature (Tend) of 120 to 135 DEG C by a rheometer, so that the image formation speed is fast, low temperature fixing is possible, and the off-section resistance is good. It is possible to obtain a clear image and a high quality image.

Although an Example demonstrates in detail, this invention is not limited by this Example.

Synthesis Example 1 Preparation of Water-Soluble Polyester Resin (1)

Into a reactor equipped with a stirrer, a reflux cooler, a thermometer, and a nitrogen inlet, 300 g of terephthalic acid, 40 g of adipic acid, 25 g of isophthalic acid, 100 g of neopentyl glycol, 100 g of bisphenol A ethylene oxide adduct, and 1.5 g of monobutyltin were added at 250 ° C under a nitrogen atmosphere. After the reaction was carried out by heating under reduced pressure, the reaction water was condensation-polymerized while removing the reaction water and reacted for 10 hours. When the softening point reaches 95, it is cooled to 150 ° C, 65 g of trimellitic anhydride is added, the temperature is raised to 240 ° C, and the reaction is continued. When the acid value reaches 57 mgKOH / g, the reaction is terminated. A polyester resin composition having a weight average molecular weight of 11,000, TS 95 ℃, Tfb 120 ℃, Tend 135 ℃, Tg 57 ℃ through the above process. 50 g of sodium hydroxide and 1,500 g of distilled water were added to the composition, the mixture was stirred at 90 ° C. for 30 minutes, and finished to prepare a water-soluble polyester resin (referred to as Resin Solution A).

Synthesis Example 2 Preparation of Water-Soluble Polyester Resin (2)

Trimeric anhydride as a carboxylic acid for secondary polycondensation and introduction of a carboxyl group at the polymer end using 300 g of terephthalic acid, 30 g of isophthalic acid, 100 g of gum rosin, 50 g of ethylene glycol, 150 g of bisphenol Aethylene oxide adduct, and 1.5 g of monobutyltin as reactants. A water-soluble polyester resin having an acid value of 59 mg KOH / g was prepared after the same process as in <Synthesis Example 1>, except that 60 g of maleic anhydride was used instead of the acid. The resin has a weight average molecular weight of 9,500, TS of 91 ° C, Tfb of 105 ° C, Tend of 127 ° C, and Tg of 61 ° C (referred to as resin solution B).

Synthesis Example 3 Preparation of Water-Soluble Polyester Resin (3)

Water-soluble polyester resin having an acid value of 53 mgKOH / g in the same manner as in <Synthesis Example 1> using 250 g of terephthalic acid, 100 g of crosslinked polyester block polymer, 30 g of neopentyl glycol, 150 g of bisphenol A ethylene oxide adduct, and 1.5 g of monobutyltin. Was prepared (called Resin Solution C). The gel content of the resin is 35%, the weight average molecular weight is 100,000, TS is 93 ℃, Tfb is 135 ℃, Tend is 150 ℃, Tg is 59 ℃.

Synthesis Example 4 Preparation of Water-Soluble Polyester Resin (4)

Acid value of 58 mg KOH / g prepared in the same manner as in <Synthesis Example 2> using 300 g of terephthalic acid, 35 g of adipic acid, 100 g of marinated gumazine, 50 g of ethylene glycol, 170 g of bisphenol A ethylene oxide adduct, and 1.5 g of monobutyltin. A water-soluble polyester resin was prepared (referred to as resin solution D). The resin has a weight average molecular weight of 11,500, TS of 85 ° C, Tfb of 101 ° C, Tend of 121 ° C, and Tg of 63 ° C.

Synthesis Example 5 Preparation of Water-Soluble Polyester Resin (5)

An acid value 52 mg KOH / g water-soluble polyester resin was prepared in the same manner as in <Synthesis Example 1> using 250 g of terephthalic acid, 100 g of DCPP resin, 30 g of propylene resin, 150 g of bisphenol Aethylene oxide adduct, and 1.5 g of monobutyltin as reactants. Solution E). The weight average molecular weight of the said resin is 9,700, TS is 87 degreeC, Tfb is 105 degreeC, Tend is 125 degreeC, Tg is 61 degreeC.

Synthesis Example 6 Preparation of Water-Soluble Polyester Resin (6)

150 g of terephthalic acid, 150 g of adipic acid, 100 g of maleic anhydride, 100 g of neopentyl glycol, 150 g of bisphenol A ethylene oxide adduct, 50 g of ethylene glycol, and 1.5 g of monobutyl tin were placed in a reactor and heated to 180 ° C. in a nitrogen atmosphere for 2 hours. React for a while. Subsequently, the mixture was reduced in pressure while reacting for 3 hours at 190 ° C. and 5 hours at 230 ° C., followed by condensation polymerization while removing the reaction water for 5 hours. The polymer is cooled to 150 ° C. when the softening point reaches 95 and the reaction is terminated when the acid value reaches 55 mgKOH / g. The weight average molecular weight of the manufactured polyester resin composition is 7,000, TS is 81 degreeC, Tfb is 101 degreeC, Tend is 125 degreeC, and Tg is 53 degreeC. 45 g of sodium hydroxide and 2,000 g of distilled water were added to the product, followed by stirring at 90 ° C. for 30 minutes to complete a water-soluble polyester resin (referred to as resin solution F).

Synthesis Example 7 Preparation of Crosslinked Water-Soluble Polyester Resin (1)

Terephthalic acid 300g, trimellitic anhydride 70g, glycerin 100g, bisphenol Aethylene oxide adduct, 100g, monobutyltin 1.5g is used as a reactant for polycondensation polymerization and introducing a carboxyl group at the end of the polymer instead of trimellitic anhydride. A water-soluble polyester resin having an acid value of 90 mg KOH / g was prepared after the same procedure as in <Synthesis Example 1>, except that 60 g of maleic anhydride was used. The weight average molecular weight of the resin is 35,000, gel content 50w%, TS is 95 ° C, Tfb is 110 ° C, Tend is 135 ° C, and Tg is 62 ° C (referred to as resin solution G).

Synthesis Example 8 Preparation of Crosslinked Water-Soluble Polyester Resin (2)

250 g of terephthalic acid, 8 g of pyromellitic anhydride, 100 g of cross-linked polyester block polymer, 30 g of glycerin, 30 g of pentaerythritol, 150 g of bisphenol A ethylene oxide adduct, and 1.5 g of monobutyltin, instead of trimellitic anhydride A water-soluble polyester resin having an acid value of 105 mgKOH / g was prepared in the same manner as in <Synthesis Example 1>, except that 90 g was used (referred to as resin solution H). The gel content of the resin is 65w%, the weight average molecular weight is 110,000, TS is 101 ℃, Tfb is 137 ℃, Tend is 160 ℃, Tg is 63 ℃.

Synthesis Example 9 Preparation of Crosslinked Water-Soluble Polyester Resin (3)

250 g of terephthalic acid, 80 g of maleic anhydride, 100 g of crosslinked polyester block polymer, 30 g of trimethylolpropane, 30 g of pentaerythritol, 150 g of bisphenol A ethylene oxide adduct, and 1.5 g of monobutyltin were used to use 90 g of trimellitic anhydride. A water-soluble polyester resin having an acid value of 110 mg KOH / g was prepared in the same manner as in <Synthesis Example 1>, except that Resin Solution 1 was used. The gel content of the resin is 61w%, the weight average molecular weight is 105,000, TS is 99 ℃, Tfb is 135 ℃, Tend is 155 ℃, Tg is 61 ℃.

Synthesis Example 10 Preparation of Emulsion Latex

100 g of styrene, 100 g of methyl methacrylate, 100 g of ethyl acrylate, 6 g of acrylic acid, and 10 g of divinylbenzene were mixed in a reactor equipped with a stirrer, a reflux cooler, a thermometer, and a nitrogen inlet. Was added dropwise to a solution of pre-emulsion, and then a solution of 4 g of reactive anionic emulsifier, 8 g of reactive nonionic emulsifier, 1.5 g of peroxide and 200 g of distilled water was added dropwise for 3 hours. While the polymerization was carried out, the reaction mixture was continuously added for 5 hours while adding 1.5 g of sodium hypochlorous acid and 30 g of distilled water at a temperature of 90 ° C. to prepare a crosslinked high molecular weight emulsion latex. Glass transition point 65 ℃, weight average molecular weight 300,000 gel content 45%

Example 1 Preparation of Toner for Electrostatic Development (1)

5 g of carbon black (Degussa FW200), 0.5 g of charge control agent (BONTRON S-34), and 50 g of distilled water were mixed and placed in 200 g of the resin solution A of <Synthesis Example 1> and dispersed in a high-speed disperser to prepare a colored resin dispersion. The release agent is mixed with the dispersion to further disperse to form a colored resin dispersion. 5 g of hydrochloric acid and 150 g of distilled water were added to another container to form a mixed aqueous solution. The colored resin dispersion was added slowly to form toner particles through a suspension treatment with reverse neutralization while stirring at high temperature at 50 ° C. Potato-shaped toner particles having a particle diameter of 7 μm were obtained in a yield of 99% or more, washed with water, filtered and dried. Toner for electrostatic charge development was prepared by mixing 1 part by weight of hydrophobic silica (Degus Co. R972) with a Henschel mixer with respect to 100 parts by weight of the dried toner particle composition. The toner was put in a cartridge made by remodeling a commercially available Samsung laser printer (ML6060), and images were formed to obtain clear, high-quality images.

Example 2 Preparation of Toner for Developing Electrostatic Charges (2)

5 g of carbon black (Degussa FW200), 0.5 g of charge control agent (BONTRON S-34), and 50 g of distilled water were mixed, and 100 g of resin solution B of <Synthesis Example 2> and 100 g of resin solution C of <Synthesis Example 3> were mixed. It is added to the mixed resin solution thus prepared and dispersed with a high-speed disperser to form a colored resin dispersion, and then a release agent is mixed and dispersed again to prepare a colored resin dispersion. 5 g of hydrochloric acid and 150 g of distilled water were added to another container to make an aqueous solution. The colored resin dispersion was added slowly to form a toner particle through a suspension treatment with reverse neutralization while stirring at 50 ° C. under high speed. Toner particles having a particle size of 8 µm were obtained in a yield of 99% or more, washed with water, filtered and dried. Toner for developing electrostatic charge was prepared by mixing 1 part by weight of hydrophobic silica (Degussa R972) with a Henschel mixer with respect to 100 parts by weight of the dried toner particle composition. The toner was placed in a cartridge made by remodeling a commercially available Samsung laser printer (ML6060), and images were formed to obtain clear, high-quality images.

Example 3 Preparation of Electrostatic Toner (3)

5 g of carbon black (PRINTEX 150T), 0.5 g of charge control agent (BONTRON S-34), and 50 g of distilled water were mixed and mixed with 100 g of resin solution C of <Synthesis Example 3> and 100 g of resin solution D of <Synthesis Example 4>. It is added to a resin solution and dispersed with a high-speed disperser to form a colored resin dispersion, and a mold release agent is mixed therein and dispersed again to form a colored resin dispersion. 5 g of hydrochloric acid and 150 g of distilled water were added to another container to make an aqueous solution. The colored resin dispersion was added slowly to form a toner particle through a suspension treatment with reverse neutralization while stirring at 50 ° C. under high speed. Potato-shaped toner particles having a particle diameter of 9 µm were obtained in a yield of 99% or more, washed with water, filtered and dried. Toner for developing electrostatic charge was prepared by mixing 1 part by weight of hydrophobic silica (Degussa R972) with a Henschel mixer with respect to 100 parts by weight of the dried toner particle composition. The toner was placed in a cartridge made by remodeling a commercially available Samsung laser printer (ML6060), and images were formed to obtain clear, high-quality images.

Example 4 Preparation of Toner for Developing Electrostatic Charges (4)

5 g of carbon black (PRINTEX 150T), 0.5 g of charge control agent (BONTRON S-34), and 50 g of middle flow water are mixed and dispersed in 200 g of the resin solution E of <Synthesis Example 5> to disperse with a high-speed disperser to form a colored resin dispersion. The release agent is mixed and dispersed again to form a colored resin dispersion. 5 g of hydrochloric acid and 150 g of distilled water were added to another container to form an aqueous solution. The colored resin dispersion was added slowly to form a toner particle through a suspension treatment accompanied with reverse neutralization while stirring at 50 ° C. at high speed. Potato-shaped toner particles having a particle diameter of 8 μm were obtained in a yield of 99% or more, washed with water, filtered and dried. Toner for developing electrostatic charge was prepared by mixing 1 part by weight of hydrophobic silica (Degussa R972) with a Henschel mixer with respect to 100 parts by weight of the dried toner particle composition. The toner was placed in a cartridge made by remodeling a commercially available laser printer (ML6060) of Samsung Electronics, and images were formed to obtain clear, high-quality images.

Example 5 Preparation of Toner for Electrostatic Development (5)

5 g of carbon black (PRINTEX 150T), 0.5 g of charge control agent (BONTRON S-34), and 50 g of distilled water were mixed to a mixed resin solution of 100 g of resin solution B of <Synthesis Example 2> and 100 g of emulsion latex of <Synthesis Example 10>. After dispersing with a high-speed disperser to form a colored resin dispersion, the release agent is mixed and dispersed again to form a colored resin dispersion. 5 g of hydrochloric acid and 150 g of distilled water were added to another container to make an aqueous solution. The colored resin dispersion was added slowly to form a toner particle through a suspension treatment with reverse neutralization while stirring at 50 ° C. under high speed. Potato-shaped toner particles having a particle diameter of 6 µm were obtained in a yield of 99% or more, washed with water, filtered and dried. Toner for developing electrostatic charge was prepared by mixing 1 part by weight of hydrophobic silica (Degussa R972) with a Henschel mixer with respect to 100 parts by weight of the dried toner particle composition. The toner was placed in a cartridge made by remodeling a commercially available Samsung laser printer (ML6060), and images were formed to obtain clear, high-quality images.

Example 6 Preparation of Toner for Electrostatic Development (6)

5 g of carbon black (PRINTEX 150T), 0.5 g of charge control agent (BONTRON S-34), and 50 g of distilled water were mixed and mixed into a mixed resin solution of 100 g of resin solution F of <Synthesis Example 6> and 100 g of emulsion latex of <Synthesis Example 10>. After dispersing with a high-speed disperser to form a colored resin dispersion, the release agent is mixed and dispersed again to form a colored resin dispersion. 5 g of hydrochloric acid and 150 g of distilled water were added to another container to form an aqueous solution. The colored resin dispersion was added slowly to form a toner particle through a suspension treatment accompanied with reverse neutralization while stirring at 50 ° C. at high speed. Potato-shaped toner particles having a particle diameter of 10 μm were obtained in a yield of 99% or more, washed with water, filtered and dried. Toner for developing electrostatic charge was prepared by mixing 1 part by weight of hydrophobic silica (Degussa R972) with a Henschel mixer with respect to 100 parts by weight of the dried toner particle composition. The toner was placed in a cartridge made by remodeling a commercially available Samsung laser printer (ML6060), and images were formed to obtain clear, high-quality images.

Example 7 Preparation of Toner for Electrostatic Development (7)

5 g of carbon black (Degus Co. FW200), 0.5 g of charge control agent (BONTRON S-34), and 50 g of distilled water were mixed and placed in 200 g of the resin solution G of <Synthesis Example 7> and dispersed with a high-speed disperser to form a colored resin dispersion. The release agent is mixed with the dispersion to further disperse to form a colored resin dispersion. 5 g of hydrochloric acid and 150 g of distilled water were added to another container to form an aqueous solution, and the colored resin dispersion was added slowly to form a toner particle through suspension treatment with reverse neutralization while stirring at high temperature at 50 ° C. Potato-shaped toner particles having a particle diameter of 7.5 μm were obtained in a yield of 99% or more, washed with water, filtered and dried. Toner for developing electrostatic charge was prepared by mixing 2 parts by weight of hydrophobic silica (Degussa R972) with a Henschel mixer with respect to 100 parts by weight of the dried toner particle composition. The toner was put in a cartridge made by remodeling a commercially available Samsung laser printer (ML6060), and images were formed to obtain clear, high-quality images.

Therefore, the toner for developing electrostatic charge by the suspension treatment with the reverse neutralization of the present invention and its manufacturing method can easily form toner particles instantaneously through the suspension treatment with the reverse neutralization in water, the diameter of the toner particles A toner capable of producing a high-quality image having fine fixation and good offset resistance that does not have a fog phenomenon and does not deteriorate even after long use because it is fine with a particle size of about 10 microns or less and as small as about 1.30 GSD can be produced. In addition, when the toner of the present invention is redissolved in the basic solution and subjected to the reverse neutralization suspension again, the toner particles can be obtained again, so that the waste toner can be collected and recycled.

Claims (19)

A first step (a) of preparing a linear low molecular weight polyester resin having a carboxyl group (-COOH group) at the polymer chain terminal; A first step (b) of preparing a crosslinked polyester resin having a carboxyl group at the polymer chain terminal; A second step (a) of preparing a polyester resin solution having a dispersant function by adding water to the neutralized composition by adding a basic compound to the polyester resin prepared in the first step; A method of preparing a polyester resin dispersion having a dispersant function by adding a basic compound to the polyester resin prepared in the first step and neutralizing and adding a solution of a water affinity solvent or a water affinity solvent and water to the neutralized product ( b) step; A third step of preparing a crosslinked ethylenic copolymer latex; A second step of preparing a colored resin dispersion by adding and dispersing a coloring agent, a charge control agent and a releasing agent to a polyester resin aqueous solution in a second step (a) and applying a high shearing force; A second step of preparing a colored resin dispersion by adding a coloring agent, a charge control agent, and a releasing agent to the polyester resin dispersion, mixing and dispersing by applying a high shearing force, and then mixing and dispersing the crosslinked ethylenic copolymer latex; The colored resin dispersions of the fourth step and the fifth step were added to an aqueous solution containing an acidic compound, respectively, and subjected to high shear force to reverse neutralization to immediately generate toner particles, and then to stabilize them by heating to prepare toner particles in a short time. Sixth step; A seventh step of preparing the colored toner particle composition by repeating the process of filtering and washing the toner particles two to three times, followed by vacuum drying; Eighth step of preparing toner by adding any one of hydrophobic silica or hydrophobic titanium oxide to the dried colored toner particle composition and mixing with a powder mixer Method for producing a toner for electrostatic charge development by suspension treatment with a reverse neutralization characterized in that it comprises a. The method of claim 1, The polybasic acid having a crosslinked structure of the crosslinked polyester resin of step (b) may be at least one selected from trimellitic anhydride, trimellitic acid, pyromellitic anhydride, pyromellitic acid, maleic anhydride, maleic acid, and a group. A method for producing a toner for electrostatic charge development by suspension treatment with reverse neutralization, characterized in that the gel content is 1 to 70 w% by selecting from 1 to 90 w% of the total monomers alone or in combination. The method of claim 1 The polyhydric alcohol having the crosslinked structure of the crosslinked polyester resin of step (b) may be selected from one or more selected from the group consisting of glycerin, pentaerystilol, trimethylolpropane, or a mixture of 1 to 90 based on the total amount of monomers. Method for producing a toner for electrostatic charge development by suspension treatment with reverse neutralization characterized in that the gel content is 1 to 70w% by axial polymerization reaction using The method of claim 1, The aqueous solution of the polyester resin of the second step is composed of the linear low molecular weight polyester resin of the first step (a), the crosslinked polyester resin of the first step (b), or the polyester resin crosslinked with the linear low molecular weight polyester resin. A process for producing a toner for electrostatic charge development by suspension treatment with reverse neutralization characterized in that a water-soluble polyester resin solution is prepared by adding a basic compound and water to the mixture. The method of claim 1 The aqueous polyester resin solution prepared in step 2 (a) is neutralized by adding a basic compound to the polyester resin prepared in step 1 to add water to the resulting composition to prepare an aqueous polyester resin solution having a dispersant function. Manufacturing method of toner for electrostatic charge development by suspension treatment with reverse neutralization The method of claim 1 The polyester resin dispersion of step 2 (b) is prepared as a polyester resin dispersion by adding a solution containing a water affinity solvent, a water affinity solvent, and water to form a static charge phenomenon by suspension treatment with reverse neutralization. Manufacturing Method of Toner The method of claim 1, In the suspension with deneutralization further comprising the step of adding a crosslinked ethylenic co-condensation latex in addition to the fourth step of the colored resin dispersion, and further mixing and dispersing to prepare a new colored resin dispersion. Method for producing toner for developing electrostatic charges. The method of claim 7, wherein The crosslinked ethylenic copolymer latex is 20 to 90 w% of styrene, 5 to 90 w% of acrylate monomer, 1 to 10 w% of reactive anionic emulsifier, 2 to 20 w% of reactive nonionic emulsifier, and 5 to 70 w of gel using emulsion polymerization catalyst. A method for producing a toner for electrostatic development by suspension treatment with reverse neutralization, characterized in that the weight average molecular weight of 100,000 to 1,000,000, and prepared by the emulsion polymerization method. The method of claim 7, wherein The crosslinked ethylenic copolymer latex is mixed so as to have a ratio of 10: 1 to 1:10 with respect to each of the linear low molecular weight polyester resin of step 1 (a) and the crosslinked polyester resin of step 1 (b). A method for producing a toner for electrostatic charge development by suspension treatment with reverse neutralization. The method of claim 1, The linear low molecular weight polyester resin of step (a) Adding a polybasic acid, a polyhydric alcohol and a promoter for promoting the formation of the linear structure and inducing the production of the low molecular polymer to produce a low molecular weight polymer of the linear structure; Carrying out the addition reaction with the polybasic acid to have a carboxyl group at the end of the polymer chain. Method for producing a toner for electrostatic charge development by suspension treatment with a reverse neutralization characterized in that it is prepared. The method of claim 10, The promoters for promoting the formation of the linear structure and inducing the production of low molecular weight polymers are rosin and rosin derivatives, terpene resins, petroleum resins and derivatives thereof, dicyclopentadiene and derivatives thereof, gumrozin, wood rosin, thalrosene, hydrogenated furnace Gin, Marinized Rosin, Rosin Ester, Pinene Resin, Dipentene Resin, C5 Petroleum Resin, C9 Petroleum Resin, Dammar Resin, Copal Resin, DCPD Resin, Hydrogenated DCPD Resin, Marinated Styrene A method for producing a toner for electrostatic charge development by suspension treatment, characterized in that at least one or more of the resin groups is selected alone or mixed to use 1 to 70 w% of the total monoma amount. The method of claim 1, The crosslinked polyester resin of step (b) is prepared by adding a crosslinked diblock polyester resin, polybasic acid and polyhydric alcohol, and then axially polymerizing the same using a catalyst. Process for producing toner for developing. The method according to claim 1, 10 and 12, The compounds added to introduce the carboxyl group into the linear low molecular weight polyester resin and the crosslinked low molecular weight polyester resin include trimellitic anhydride, trimellitic acid, pyromellitic anhydride, pyromellitic acid, maleic anhydride, maleic acid and fumaric acid. Obtained by using at least one or more selected from adipic acid, benzoic acid, sebacic acid, maleinized pine, marinated styrene, and isobutylene maleinate in an amount of 1 to 70 w% based on the total amount of the polymer, alone or in a mixture. A process for producing a toner for electrostatic charge development by suspension treatment with reverse neutralization, characterized in that the polymer has an acid value of 10 to 100 mgKOH / g and a weight average molecular weight of 5,000 to 7,000. The method of claim 1, The basic compound of the second step is selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonium hydroxide, lithium hydroxide, triethylamine, diethanolamine, diethylethanolamine, methyl diethanolamine, dimethylaminoethanol alone or mixed A process for producing a toner for electrostatic charge development by suspension treatment with reverse neutralization, characterized in that it is used in an amount of 1 to 50 w% with respect to a resin. The method of claim 1, The second affinity solvent is characterized in that one or more selected from alcohols, ethers, acetone, dimethylformamide, tetrahydrofuran, ethyl selsolve, propyl selsolve and butyl selsolve are used alone or in combination. A process for producing a toner for electrostatic charge development by suspension treatment accompanied with reverse neutralization. The method of claim 1, The colored resin dispersions of the 4th and 5th steps were added dropwise to each reactor in the presence of dissolved acidic compound, and then suspended in a high speed disperser with de-neutralization to immediately generate toner particles and stabilized by heating to 30 ~ 90 ℃. A method of manufacturing a toner for electrostatic charge development by suspension treatment with reverse neutralization characterized in that The acid neutralizing compound according to claim 1, wherein the acidic compound is hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, phosphoric acid, bromic acid, acetic acid, medicinal acid, oxalic acid, P toluene sulphonic acid, etc. Method for preparing static charge developing toner by suspension treatment with The method of claim 1, The toner particles of the sixth stage are easily suspended in the water in an extremely short time and are environmentally safe and have no risk of disaster through the suspension treatment with reverse neutralization generated in water and the stabilization by heating. A method for producing a toner for electrostatic charge development by suspension treatment with reverse neutralization, characterized in that fine particles of -10 탆 and GSD 1.1 to 1.7 are produced. In the electrostatic charge toner, Toner particles prepared according to the method according to claim 1 to 18 added to the external additives (hydrophobic silica or hydrophobic titanium oxide) by adding 1 to 5% by weight, characterized by mixing with a powder mixer Toner for developing electrostatic charge by treatment.