KR100846766B1 - Method of preparing polyester toner by suspension process with reverse-neutralization - Google Patents

Abstract

The present invention has a low softening point and a low melting viscosity, and thus, a toner for developing a polyester resin-type electrostatic charge developer having excellent adhesion resistance and peeling resistance to a fixing image that can simultaneously secure offset and fixing performance even in high-speed development and fixing It is about a method. The method for producing a polyester resin toner of the present invention comprises (1) a linear polyester resin having 2 to 3 carboxyl groups at the chain end, a crosslinked polyester resin having 2 to 3 carboxyl groups at the chain end, or both Preparing a polyester resin composition; (2) water, a water affinity solvent, or the water in the polyester resin composition comprising a linear polyester resin, a crosslinked polyester resin, or a water-soluble polyester resin in the form of a polymer resin salt obtained by reacting all of these with a basic compound Preparing a polyester resin aqueous solution by adding and diluting a mixed solvent of water and affinity solvent to 1 to 10 times by weight with respect to the weight of the composition; (3) mixing and dispersing a colorant, a charge control agent, and a release agent in the aqueous polyester resin solution to prepare a colored resin composition; And (4) preparing the colored toner particles by adding the colored resin composition in the water in which the acidic compound is dissolved, followed by suspension treatment with desalination.

Description

Method for preparing polyester toner produced by underwater suspension with desalination {Method of preparing polyester toner by 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 require power saving and high speed in the process of elaborate phenomenon without contamination and pressing melt fixing process by heating 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 releasing 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. As the binder resin for toner, polystyrene, acrylic copolymer resin, epoxy resin, polyester, styrene, acrylate, latex, etc. are used, but recently, polyester resin having excellent low-temperature fixing properties such as low melting point elasticity, adhesiveness, peeling resistance, etc. Was noticed. In the pulverization method, a binder resin, a colorant, a charge control agent, a mold releasing agent, and the like are melt mixed and pulverized by heating to classify a desired particle size to make a toner. This method is inefficient due to mixing raw materials in the flow state by heating, incomplete dispersion and improper function of additives, and because of wide distribution of toner particles, many unnecessary particles are produced, resulting in low production yield and poor performance. Is how it is made. 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.

Neutralization methods include emulsion flocculation and suspension polymerization. Among them, the emulsion coagulation method mainly emulsifies the ethylenic monomer with a surfactant, polymerizes it to make a binder, and then mixes a colorant, a charge control agent, and a release agent, and heats the emulsion particles continuously by stirring for a long time while heating the primary particles. And continue to cure it to secondary particles by repeated operation to make the desired toner particles. In this process, unstable manufacturing process with a high risk of producing defective products out of a desired range due to stirring for several hours is produced. -056791, Korean Patent Application Laid-Open No. 2001-037273, Japanese Patent Laid-Open No. 63-282750, Japanese Patent 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 monoma, and a high shear force is applied with a homogenizer to make a monoma droplet having a desired particle size first, and then it is suspended and polymerized using a stabilizer such as calcium phosphate or silica. As a method of making particles, some additives interfere with the polymerization reaction, have a high risk of agglomeration into large particles due to prolonged reactions, and have a high melt viscosity, and thus are not suitable for color toner. 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 resin in 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.

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 Toner for high-speed copying with excellent power saving, offset resistance, fixability, adhesion, abrasion resistance, and peeling resistance can be obtained, and a new manufacturing method that satisfies this purpose is to provide an electrostatic charge image toner. It is done.

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) preparing a polyester resin composition comprising a linear polyester resin having 2 to 3 carboxyl groups at the chain end, a crosslinked polyester resin having 2 to 3 carboxyl groups at the chain end, or both;
(2) water, a water affinity solvent, or the water in the polyester resin composition comprising a linear polyester resin, a crosslinked polyester resin, or a water-soluble polyester resin in the form of a polymer resin salt obtained by reacting all of these with a basic compound Preparing a polyester resin aqueous solution by adding and diluting a mixed solvent of water and affinity solvent to 1 to 10 times by weight with respect to the weight of the composition;
(3) mixing and dispersing a colorant, a charge control agent, and a release agent in the aqueous polyester resin solution to prepare a colored resin composition; And
(4) A method of producing a polyester resin toner, comprising the steps of preparing the colored toner particles by adding the colored resin composition in water dissolved in an acidic compound and suspending it with desalination.
The linear polyester resin is rosin, wood rosin, rosin, rosin derivatives, terpene resins, petroleum resins, petroleum resin derivatives, dicyclopentadiene, dicyclopentadiene derivatives, gum rosin, wood rosin, delogin, hydrogenated Selected from the group consisting of rosin, marinized rosin, rosin ester, pinene resin, dipentene resin, C5 petroleum resin, C9 petroleum resin, dicyclopentadiene (DCPD) resin, hydrogenated DCPD resin, and marenized styrene resin Produced by polymerization of a polybasic acid and a polyalcohol in the presence of at least one low-molecular linear accelerator, wherein the low-molecular linear accelerator is added in an amount of 10 to 100% by weight, based on the total amount of the polybasic acid and the polyalcohol. . Carboxylic acids which can be used to introduce 2-3 carboxyl groups at the chain end in a secondary reaction after the polymerization of the linear polyesters are maleic anhydride, maleic acid, trimellitic anhydride, trimellitic acid and pyromellitic anhydride. , And at least one selected from the group consisting of pyromellitic acid, wherein the carboxylic acid is added in an amount of 10 to 70% by weight based on the total amount of the linear polyester, thereby forming a carboxyl group at the end of the chain having an acid value of 10 to 110 mgKOH / g. The linear polyester resin which has -3 pieces is manufactured.

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The crosslinked polyester resin may be phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, azaline acid, sebacic acid, tetrahydrophthalic anhydride, maleic anhydride, maleic acid, fumaric acid, itaconic acid, trimellitic anhydride, trimellitic acid, At least one polybasic acid selected from the group consisting of pyromellitic anhydride, and pyromellitic acid; Ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, alkylene oxide adducts of bisphenol A, At least one polyhydric alcohol selected from the group consisting of trimethylolpropane, glycerin, and pentaerythritol; And polybasic acid is added in an amount of 10 to 90% by weight based on the total amount of monomers, and polyhydric alcohol is in an amount of 10 to 90% by weight based on the total amount of monomers. It is added, and the gel content of the said crosslinked polyester resin is 20 to 70 weight%. The crosslinked polyester resin is added and reacted to have 2 to 3 carboxyl groups at the polymer chain terminal to prepare a crosslinked polyester resin having 2 to 3 carboxyl groups at the chain terminal having an acid value of 10 to 110 mgKOH / g.

Since the aqueous polyester resin solution may itself serve as a dispersant, a color resin composition is prepared by mixing a colorant, a charge control agent, a mold release agent, and the like without adding another dispersant separately. In this step, the water-soluble resin composition in which the linear polyester resin is solvated and the water-soluble resin composition in which the crosslinked polyester resin is solubilized can be used to prepare a colored resin composition, or they can be mixed in an appropriate ratio to form the colored resin composition. The present invention also provides a method for producing a colored resin composition using a mixture of a water-soluble resin composition containing a linear polyester resin and a crosslinked ethylenic copolymer latex in an appropriate ratio, if necessary.

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The colored resin composition is slowly added to the water in which the acidic compound is dissolved, and a high shear force is applied to cause a suspension treatment accompanied with a desalination reaction to instantaneously generate toner particles having a particle diameter of 5 to 15 µm and heated to 30 to 90 ° C.

The produced toner particles are filtered, washed with water and dried to prepare a colored resin toner particle composition.

Toner for electrostatic image development is prepared by 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.

The toner thus prepared can produce a toner having a particle size of 5 to 15 탆 and a narrow particle distribution with a high yield of 99% or higher, and a polyester resin toner as a source of a new method for producing a polymerized toner that has excellent development and fixability. 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, Talrose rosin, Hydrogenated rosin, Marinized rosin, Rosin ester, Pinene resin, Dipentene resin, C5 petroleum resin, C9 petroleum resin, Dicyclopentadiene (DCPD) resin, Hydrogenated DCPD resin, It is preferable to use individually or in mixture among the styrene resin group. They are preferably added in an amount of 10 to 100% by weight based on the total amount of monomers.

In addition, polybasic acids which can be used are phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, azeline acid, sebacic acid, tetrahydrophthalic anhydride, maleic anhydride, fumaric acid, itaconic anhydride, 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, and bisphenol A. The alkylene oxide adducts, trimethylolpropane, glycerin and pentaerythritol are 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. Preference is given to using alone or in combination in the benzoic acid, sebacic acid, maleic acid feeder, styrene maleinate, isobutylene maleate. It is preferred to be used in the resin composition in an amount of 10 to 70% by weight.

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). The carboxylic acid to be introduced at the end of the polymer chain secondly is preferably used alone or in a mixture in a crowd used for the same use of step (1). The basic compounds used in step (3) include sodium hydroxide, potassium hydroxide, ammonium hydroxide, Lithium hydroxide, triethylamine, diethanolamine, diethylethanolamine, methyl diethanolamine and dimethylaminoethanol are preferably used alone or in combination. It is preferable to use it in the quantity of 5-50 weight% in a resin composition.

The water-compatible solvents used in step (3) are alcohols, ethers, acetone, dimethylformamide, tetrahydrofuran, ethylene glycol, propylene glycol, butylene glycol 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. Polyester resin with a weight average molecular weight of -50,000, softening point 75-150 ° C, Tfb 100-120 ° C, and Tend 120-150 ° C, with a weight average molecular weight of 100-170 ° C, Tfb 90-120 ° C and Tend 130-160 ° C. And preparing a water-soluble polyester resin composition by adding a basic compound to the resin and dissolving it in water or a hydrophilic solvent and a solution in which water is mixed with the solvent. The crosslinked ethylenic copolymer latex is emulsified 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% emulsification polymerization catalyst. It is preferred to be used by 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 produced by a polymerization method.

The polyester resin aqueous solution of the present invention is used as a resin binder for a toner used to develop electrostatic images on electrophotographic images, electrostatic recordings, and the like, and a colorant, a charge agent, a mold release agent, and the like are added thereto to prepare a toner by a polymerization method. Colorants are black pigments such as carbon black and magnetite. Yellow pigments such as iron oxide, Chinese character 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 the negative charge control agent are azo metal complex salts, silicic acid metal complex salts, etc. The typical trade names are BONTRON S-34, BONTRON E-84, Orient Chemical Co., Ltd. The amount used yesterday is preferably 0.5 to 5% by weight based on the binder resin.

Dispersing the colorant in an aqueous solution of a water-soluble polyester resin to form a colored resin composition, and then put a release agent therein 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 aqueous polyester resin solution of the present invention is well dispersed and dissolved in water or a water-friendly solvent and a mixed solvent of a solvent and water, it is possible to prepare a toner having excellent performance by dispersing the additives therein.

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-toluenesulfonic acid, and the like. 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.

<Production example 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 neopentineglycone, 100 g of bisphenol Aethylene oxide adduct, and 1.5 g of monobutyltin were placed at 250 ° C in a nitrogen stream. The reaction was carried out by heating to reduce the pressure, axial polymerization while removing the reaction water, and the reaction was carried out 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. Weight average molecular weight 11,000, TS: 95 ° C, Tfb; 120, Tend: 135, Tg: 57 ℃ polyester resin composition was prepared. 50 g of sodium hydroxide and 1500 g of distilled water were added to the product, followed by stirring at 90 ° C. for 30 minutes, to thereby prepare a water-soluble polyester resin. (Referred to as resin solution A.)                     

<Production example 2>

Carboxylic acid that primary polycondensation of terephthalic acid 300g, isophthalic acid 30g, gum rosin 100g, ethylene glycol 50g, bisphenol Aethylene oxide adduct 150g, monobutyltin 1.5g and introduced into the polymer terminal is substituted for trimellitic anhydride Except that 60 g of maleic anhydride was used in the same manner as in Production Example 1, an acid value of 59 mg KOH / g water-soluble polyester resin was prepared (referred to as resin solution B). Weight average molecular weight 9,500 TS: 91 ° C, Tfb: 105 ° C, Tend: 127 ° C, Tg 61 ° C

<Production example 3>

Acid value 53 mgKOH / g water-soluble polyester resin in 250g of teretanic acid, 100g of crosslinked polyester block polymer, 30g of neopentylglycol, 150g of ethylene oxide adduct of bisphenol A, and 1.5g of monobutyltin in the same manner as in <Preparation Example 1> Was prepared. (Referred to as resin solution C.) Gel content 35% s, Weight average molecular weight 100,000, TS: 93 ° C, Tfb: 135 ° C, Tend: 150 ° C, Tg 59 ° C.

<Production example 4>

300 g of terephthalic acid, 35 g of adipic acid, 100 g of marinated gumin, 50 g of ethylene glycol, 170 g of bisphenol Aethyleloxide addition product, and 1.5 g of monobutyltin were prepared in the same manner as in Production Example 2, and the acid value was 58 mg KOH / g water-soluble polyester. Resin was prepared. (Referred to as resin solution D.) Weight average molecular weight 11,500, TS: 85 ° C, Tfb: 101 ° C, Tend: 121 ° C, Tg 63 ° C

<Production example 5>                     

An acid value of 52 mg KOH / g water-soluble polyester resin was prepared in the same manner as in <Preparation Example 1> of 250 g of terephthalic acid, 100 g of DCPD resin, 30 g of propylene resin, 150 g of ethylene oxide adduct of bisphenol A, and 1.5 g of monobutyltin. (Referred to as resin solution E.) Weight average molecular weight 9,700, TS: 87 ° C, Tfb: 105 ° C, Tend: 125 ° C, Tg 61 ° C

<Production example 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 Aethyleloxide adduct, 50 g of ethylene glycol, and 1.5 g of monobutyltin were added and reacted for 2 hours by heating at 180 ° C. in a nitrogen stream. The reaction was carried out under reduced pressure while reacting at 230 ° C. for 5 hours at 230 ° C. for 5 hours by condensation polymerization while removing the reaction water. The reaction is terminated when the acid value reaches 55 mgKOH / g by cooling to 150 ° C. when the softening point reaches 95. A polyester resin composition having a weight average molecular weight of 7,000, TS: 81 ° C, Tfb: 101, Tend: 150 ° C, and Tg: 53 ° C was prepared. 45 g of sodium hydroxide and 2000 g of distilled water were added to the product, the mixture was stirred at 90 ° C. for 30 minutes, and finished to prepare a water-soluble polyester resin. (Referred to as resin solution F.)

〈Emulsion Latex Manufacturing Example〉

In a reactor equipped with a stirrer, a reflux cooler, a thermometer, and a nitrogen inlet, 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, 9 g of reactive anionic emulsifier, 16 g of reactive nonionic emulsifier, and distilled water 190 Pre-emulsion was added dropwise to the mixed solution of ℃, 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 reaction was performed at a temperature of 90 ° C., 1.5 g of sodium bicarbonate and 30 g of distilled water were added dropwise to continuously react for 5 hours to prepare a crosslinked emulsion latex. Glass transition point 65 degreeC, the weight average molecular weight 300,000 gel content 45 weight%.

<Example 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, prepared in <Production Example 1> of 200 g of Resin Solution A, and dispersed in a high-speed disperser to form a colored resin dispersion. The mixture is dispersed again to prepare a colored resin dispersion. 5g of hydrochloric acid and 150g of distilled water were mixed in another container to make an aqueous solution. The colored resin dispersion was added slowly, and the toner particles were formed by suspending with desalination reaction at high temperature at 50 ° C. to form toner particles. Obtained toner particles having a yield of 99% or more, washed with toner particles, filtered and dried to mix 1 part by weight of hydrophobic silica (Degussa R972) with a Henschel mixer based on 100 parts by weight of the dried toner particle composition. Toner was prepared. 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 2>

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 to prepare a mixed resin solution of <Production Example 2> resin solution B 100g and <Production Example 3> resin solution C 100g. 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. 5g of hydrochloric acid and 15Og of distilled water were mixed in another container to make an aqueous solution. The colored resin dispersion was added slowly, and the toner particles were suspended by high-speed stirring at 50 ° C with desalination to form toner particles. Obtained toner particles having a diameter in a yield of 99% or more were washed with water, filtered and dried to mix 1 part by weight of hydrophobic silica (Degussa R972) with a Henschel mixer based on 100 parts by weight of the dried toner particle composition. A static charge developing toner was prepared. 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 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 placed in a mixed resin solution of <Production Example 3> Resin solution C 100g and <Production Example 4> Resin solution D 100g. Dispersion is carried out with a high speed disperser to form a colored resin dispersion, and a mold release agent is mixed therein to disperse again to form a colored resin dispersion. 5g of hydrochloric acid and 150g of distilled water were added to another container to make an aqueous solution. The above dispersion of colored resin was slowly added thereto, and the toner particles were formed by suspension treatment with desalination reaction at 50 ° C. with high speed stirring to form toner particles. Obtained toner particles having a yield of 99% or more, washed with toner particles, filtered and dried to mix 1 part by weight of hydrophobic silica (Degussa R972) with a Henschel mixer based on 100 parts by weight of the dried toner particle composition. Toner was prepared. 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 4>

5 g of carbon black (PRINTEX 150T), 0.5 g of charge control agent (BONTRON S-34), and 50 g of distilled water are mixed and prepared in <Production Example 5> of resin solution E 200 g, dispersed with a high-speed disperser to form a colored resin dispersion. The mixture is dispersed again to form a colored resin dispersion. 5g of hydrochloric acid and 150g of distilled water were added to another container to make an aqueous solution. The above dispersion of colored resin was added slowly, and the toner particles were formed by suspending with desalination reaction at high temperature at 50 ° C. to form toner particles. Obtained toner particles having a yield of 99% or more, washed with toner particles, filtered and dried to mix 1 part by weight of hydrophobic silica (Degussa R972) with a Henschel mixer based on 100 parts by weight of the dried toner particle composition. Toner was prepared. 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>

5 g of carbon black (PRINTEX 150T), 0.5 g of charge control agent (BONTRON S-34), and 50 g of distilled water are mixed and placed in a mixed resin solution of <100 g of Resin Solution B> and <100 g of Emulsion Latex>. Disperse into a colored resin dispersion to form a colored resin dispersion, and then add a release agent and disperse again to form a colored resin dispersion. 5g of hydrochloric acid and 150g of distilled water were mixed in another container to make an aqueous solution, and the colored resin dispersion was slowly added thereto, followed by suspension treatment with desalination reaction at 50 ° C. with high speed stirring to form toner particles. Obtained toner particles having a yield of 99% or more, washed with toner particles, filtered and dried to mix 1 part by weight of hydrophobic silica (Degussa R972) with a Henschel mixer based on 100 parts by weight of the dried toner particle composition. Toner was prepared. 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 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 placed in a mixed resin solution of <100 g of Resin Solution F> and <100 g of Emulsion Latex>. Disperse into a colored resin dispersion to form a colored resin dispersion, and then add a release agent and disperse 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 above dispersion of colored resin was added slowly, and the toner particles were formed by suspension treatment with desalination reaction at 50 ° C. under high speed stirring to form toner particles. Obtained toner particles having a yield of 99% or more, washed with toner particles, filtered and dried to mix 1 part by weight of hydrophobic silica (Degussa R972) with a Henschel mixer based on 100 parts by weight of the dried toner particle composition. Toner was prepared. 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.

 The electrostatically charged toner according to the present invention is a polymerized polyester toner capable of obtaining a high quality image having excellent image formation, low softening point, low melt viscosity, and fixing characteristics. In particular, it is a method for stably producing a recyclable, eco-friendly toner that is not only suitable for digital devices because it is excellent in pollution-free phenomenon, offset resistance, adhesion, peeling resistance, and fixing property.

Claims (10)

(1) preparing a polyester resin composition comprising a linear polyester resin having 2 to 3 carboxyl groups at the chain end, a crosslinked polyester resin having 2 to 3 carboxyl groups at the chain end, or both; (2) water, a water affinity solvent, or the water in the polyester resin composition comprising a linear polyester resin, a crosslinked polyester resin, or a water-soluble polyester resin in the form of a polymer resin salt obtained by reacting all of these with a basic compound Preparing a polyester resin aqueous solution by adding and diluting a mixed solvent of water and affinity solvent to 1 to 10 times by weight with respect to the weight of the composition; (3) mixing and dispersing a colorant, a charge control agent, and a release agent in the aqueous polyester resin solution to prepare a colored resin composition; And (4) A method for producing a polyester resin toner, comprising the steps of adding the colored resin composition in water dissolved in an acidic compound and suspending with desalting to produce colored toner particles. The method of claim 1, wherein the linear polyester resin is rosin, wood rosin, rosin, rosin derivative, terpene-based resin, petroleum resin, petroleum resin derivative, dicyclopentadiene, dicyclopentadiene derivative, gum rosin, woodlo Gin, Talrose, Hydrogenated Rosin, Marinized Rosin, Rosin Ester, Pinene Resin, Dipentene Resin, C5 Petroleum Resin, C9 Petroleum Resin, Dicyclopentadiene (DCPD) Resin, Hydrogenated DCPD Resin, and Marinated Styrene It is produced by the polymerization of polybasic acid and polyhydric alcohol in the presence of at least one low molecular weight linear accelerator selected from the group consisting of a resin, wherein the low molecular weight linear accelerator is 10 to 100% by weight based on the total amount of the polybasic acid and polyhydric alcohol Toner manufacturing method, characterized in that added in the amount of. The carboxylic acid which can be used when introducing 2 to 3 carboxyl groups at the chain end in a secondary reaction after polymerization of the linear polyester is maleic anhydride, maleic acid, trimellitic anhydride, trimellitic acid. At least one selected from the group consisting of an acid, pyromellitic anhydride, and pyromellitic acid, wherein the carboxylic acid is added in an amount of 10 to 70% by weight based on the total amount of the linear polyester, and has an acid value of 10 to 110 mgKOH / g. A process for producing a toner, characterized in that a linear polyester resin having 2-3 carboxyl groups at the chain end is produced. The method of claim 1, wherein the crosslinked polyester resin is phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, azeline acid, sebacic acid, tetrahydrophthalic anhydride, maleic anhydride, maleic acid, fumaric acid, itaconic acid, trimellitic anhydride. At least one polybasic acid selected from the group consisting of acid, trimellitic acid, pyromellitic anhydride, and pyromellitic acid; Ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, alkylene oxide adducts of bisphenol A, At least one polyhydric alcohol selected from the group consisting of trimethylolpropane, glycerin, and pentaerythritol; And polybasic acid is added in an amount of 10 to 90% by weight based on the total amount of monomers, and polyhydric alcohol is in an amount of 10 to 90% by weight based on the total amount of monomers. And the gel content of the crosslinked polyester resin is 20 to 70% by weight. The method of claim 1, wherein the basic compound is at least selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonium hydroxide, lithium hydroxide, triethylamine, diethanolamine, diethylethanolamine, methyl diethanolamine, and dimethylaminoethanol Any one of them is added in an amount of 5 to 50% by weight based on the polyester resin composition. The method of claim 1, wherein the crosslinked ethylenic copolymer emulsion latex is mixed with the aqueous polyester resin solution at a weight ratio of 10: 1 to 1:10. The method of claim 6, wherein a color resin composition is prepared by mixing a colorant, a charge control agent, and a release agent with the aqueous polyester resin solution. The toner manufacturing method according to claim 7, wherein the colored resin composition is introduced into water in which the acidic compound is dissolved and suspended by a desalination reaction with a high speed disperser to produce toner particles having a particle diameter of 5 to 15 탆. The acidic compound of claim 8, wherein the acidic compound is at least one selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, phosphoric acid, bromic acid, acetic acid, medicinal acid, hydroxyl acid, and p-toluenesulfonic acid, and the amount of the acidic compound is used in the colored resin composition. A method of producing a toner, characterized in that from 5 to 30% by weight. 9. The colored toner particle composition is prepared by filtration, washing with water and drying the resulting toner particles, and adding 1 to 5 parts by weight of hydrophobic silica or hydrophobic titanium oxide to 100 parts by weight of the particle composition. A toner manufacturing method comprising mixing to produce a toner for electrostatic image development.