KR100811112B1 - Polyester type chemical toner composition containing pigment and manufacturing method thereof - Google Patents

Abstract

The present invention has a number average molecular weight of 2,000 to 10,000, PDI (PolyDispersity Index) of 2 to 15, containing 0.5 to 5.0 parts by weight of sodium sulfonate anion group with respect to 100 parts by weight of resin, and does not have an insoluble fraction The present invention relates to a polyester-based chemical toner composition comprising a pigment containing a polyester resin, and a method for producing the same, having various shapes such as spherical shape, elliptical shape, and potato shape, and having a volume average particle size of 2 to 10 µm and a particle size. 80% span value obtained by dividing the difference between the particle size d ₉₀ corresponding to the cumulative volume by 90% and the particle size d ₁₀ corresponding to the cumulative volume by 50% by the particle size d ₅₀ corresponding to the cumulative volume by 50%. By providing a toner composition having a value of 0.9 or less, it is possible to solve the problem of machine malfunction in the cleaning step by modifying the shape, and by using a pigment pigment master batch, Cost savings are also excellent because the amount of colorant used can be reduced and no additional process is required for separation.

Polyester, Pigment Masterbatch, Sodium Sulfonate, Toner, Printing

Description

Chemical Toner Composition based on Polyester and Pigment, and Method for Preparing the Same

Figure 1 shows the results of observing the shape of the toner prepared according to an embodiment of the present invention with an electron scanning microscope.

2 shows the shape of the toner prepared according to another embodiment of the present invention.

Figure 3 shows the shape of the toner prepared according to another embodiment of the present invention.

4 shows the shape of the toner prepared according to another embodiment of the present invention.

The present invention relates to a toner composition and a method for preparing the same, more particularly, by using a polyester resin having a sodium sulfonate anion group and having a specific range of PDI and using a pigment pigment master batch instead of a conventional pigment. It relates to a polyester-based chemical toner composition having a variety of shapes that can be used as a toner, and comprising a pigment having a suitable particle size and span value and a method for producing the same.

In recent years, the demand for toners suitable for high speed printing is rapidly increasing in the printing market, and various methods for preparing toner compositions using polyester resins are being studied.

US Patent No. 6,416,917 relates to a dry toner comprising a toner binder and a colorant, wherein the toner binder contains a high molecular weight polyester condensation resin (A) and a low molecular weight condensation resin (B) having a urea or urethane bond, The number average molecular weight ratio (MnA / MnB) of A and B is 1.6 or more, and the weight average molecular weight ratio (MwA / MwB) of A and B is 2 or more, and has a sphericity of 0.90 to 1.00 (Wadell's practical sphericity). Toner having is disclosed. The toner thus prepared has a disadvantage that it involves a chemical reaction during the production of particles, and condensation reaction in the aqueous phase does not easily occur.

Further, Japanese Patent Laid-Open No. 2004-198658 relates to a method for producing a toner using a polyester oligomer, a charge control agent, a wax, a solvent, and the like in water, and has an advantage of narrowing the particle distribution. This invention is characterized by producing particles using oligomers rather than using a resin polymer, and producing toner particles with a chemical reaction in a particulate state. However, such a method has a problem in that it is difficult to control when preparing the particle production system due to the chemical reaction.

US Patent No. 6,248,491, on the other hand, relates to a system for producing toner particles of constant shape without chemical reaction by the design of polyester. Specifically, a toner for electrostatic latent image development comprising a binder resin and a colorant, the binder resin is made from a polyester resin, has a weight average molecular weight of 30,000 or more, a PDI (PolyDispersity Index) of 12 or more, and a molecular weight of 600,000 or more It is comprised so that resin may occupy 0.5% or more and resin with less than 10,000 molecular weight occupies 20 to 80%. The toner of the present invention is spherical or generally spherical particles having an average circularity of 0.97 or more. On the other hand, a toner is produced by blending two kinds of polyesters including crosslinked polyesters and linear polyesters with a pigment, dispersing it in water at about 10 ° C, and milling methyl ethyl ketone (MEK). In the case of such a manufacturing method, a methyl volute ketone is not dissolved and a volatilization process for removing the same must be separately added. In order to control the rheological properties of the polyester, crosslinked polyester, low molecular weight linear polyester and high molecular weight linear poly An ester is required, but the use of a high molecular weight polyester makes the particle size distribution wider, and only positively charged toners can be produced, which is undesirable.

On the other hand, recently manufactured chemical toners have become very important to control their shapes from various shapes, such as elliptical and potato, to conventional shapes. This has the advantage that the spherical toner has a uniform charge amount when the printing operation is performed in the machine employing the chemical toner. However, the residual toner is generated on the photoconductor (OPC) drum during the cleaning step, thereby causing problems in the operation of the machine. Because it is known to cause. On the other hand, when the toner of non-spherical shape and uniform shape is used, the surface of the toner is uniform, and when it is used, there is no toner remaining on the photosensitive drum surface when cleaning in the machine. There is an advantage.

Among these shape-controlled chemical toners, toners by emulsion aggregates manufactured by Xerox, Minolta, Konica, etc. are known to form potatoes by a method of agglomerating small emulsified particles with each other, and Sanyo Chemical's toner. It is known that the particles are deformed by the method of blowing strongly through very small nozzles.

Another problem that may occur is that the size of the toner becomes smaller and the printed thickness becomes thinner, which requires the use of a large amount of colorant. However, when a large amount of colorant is used in the production of the toner, expensive pigment particles are released from the toner particles during the production, thereby lowering the use rate of the colorant, which in turn affects the economics of the toner. In addition, it is not economical to design additional processes to separate them. Therefore, there is a need for a method that can have a variety of shapes including a spherical shape, and that a toner having a small particle size can be produced even when less colorant is used.

The present inventors have conducted research to solve the problems of the conventional toner and toner manufacturing method, the number average molecular weight is 2,000 to 10,000, PDI (PolyDispersity Index) is 2 to 15, sodium based on 100 parts by weight of resin Using a polyester resin containing 0.5 to 5.0 parts by weight of a sulfonate anionic group, and having no insoluble portion, and using a pigment pigment master batch in which pigments are dispersed in the resin instead of a conventional pigment, volatile processing in the toner manufacturing step Completion of the present invention by discovering that toner compositions having various shapes, particle sizes, and span values suitable for use as toner particles can be prepared by changing the preparation, polar solvent, type of surfactant, and use of thickeners. It became.

An object of the present invention is a volume average particle size of 2 ~ 10㎛, the difference between the particle size d ₉₀ corresponding to the cumulative volume ₉₀ % and the particle size d ₁₀ corresponding to the cumulative volume 10% in the particle size distribution, cumulative volume The present invention provides a chemical toner composition having a 80% span value divided by 50% of a particle size d ₅₀ of 0.9 or less, and a method of manufacturing the same.

 Another object of the present invention is to provide an electrostatic latent image developer prepared by using the chemical toner composition.

Still another object of the present invention is to provide a method of printing an image by applying a chemical toner composition prepared by the chemical toner composition manufacturing method and a printed matter on which the image is printed.

In order to achieve this object, the chemical toner composition according to the present invention is a toner composition comprising a resin, a color pigment, a wax, and a charge control agent. The resin has a number average molecular weight of 2,000 to 10,000, and PDI (PolyDispersity). Index) is 2 to 15, containing 0.5 to 5.0 parts by weight of sodium sulfonate group per 100 parts by weight of resin, and comprises a polyester resin having no insoluble fraction, the composition Particles have a volume average particle size of 2 to 10 µm, and the difference between the particle size d ₉₀ corresponding to 90% of the cumulative volume and the particle size d ₁₀ corresponding to 10% of the cumulative volume is 50% of the cumulative volume. It is characterized in that the 80% span value divided by the corresponding particle size d ₅₀ is 0.9 or less.

In addition, the method for producing a chemical toner composition according to the present invention comprises (1) mixing a resin, a pigment pigment master batch dispersed in the resin, a wax, a volatile processing aid and a charge control agent at 60 to 95 ° C. A first step of preparing a resin mixture; (2) a second step of adding the mixture of the first step into a dispersion medium heated to a temperature of 60 to 95 ° C. consisting of a polar solvent, a surfactant and optionally a thickener and stirring to form a dispersion of the resin mixture; (3) a third step of preparing the resin mixture from which the processing aid is removed by stirring the dispersion of the second step at 60 to 95 ° C and then volatilizing the processing aid; And (4) a fourth step of cooling the mixture of the third step at room temperature, recovering the toner particles, then washing and drying to produce dry toner particles.

On the other hand, the latent electrostatic image developer according to the present invention is applied to the one-component toner used as the toner composition itself produced by the method, or when applied to the two-component system is configured to include a toner and a carrier (carrier), The particle carrier is characterized in that at least one selected from the group consisting of ferrite, steel and iron powder coated with an insulating material.

In the present invention, the volume average particle size is 2 to 10㎛, the difference between the particle size d ₉₀ corresponding to the cumulative volume ₉₀ % and the particle size d ₁₀ corresponding to the cumulative volume 10% in the particle size distribution, cumulative volume 50% A method of printing an image by applying a chemical toner composition having an 80% span value divided by a particle size d ₅₀ corresponding to 0.9 or less, and a coating layer comprising the chemical toner composition and optionally protecting a printed matter. It relates to the image printout.

First, the toner composition of the present invention will be described in detail.

The chemical toner composition according to the present invention is characterized by containing a resin, a coloring pigment, a wax and a charge control agent. Among them, the resin includes a polyester resin, which accounts for the remainder excluding all other components in the composition, and may contain 47 to 97.8% by weight based on the total weight of the toner composition. The polyester resin has a number average molecular weight of 2,000 to 10,000, a PDI of 2 to 15, and contains 0.5 to 5.0 parts by weight of sodium sulfonate group based on 100 parts by weight of the resin, and does not have an insoluble portion. In addition, the resin other than the polyester resin may be contained in 0.1 to 25% by weight based on the total weight of the composition, it is preferable to be dissolved in the solvent of the polyester resin.

On the other hand, the coloring pigments constituting the toner composition are not used as such in the manufacture of the toner composition but as the coloring pigment master batch in which the coloring pigment is dispersed in the resin. Pigment master batch refers to a resin composition in which a high concentration of pigment is evenly dispersed. The amount of the pigment in the master batch is 10 to 60% by weight, and the pigment and resin are kneaded under high temperature and high pressure, or the resin is dissolved in a solvent and the pigment is added. It is then produced by a method of dispersing the pigment by applying a high shear force. In the latter case, all solvents must be removed before use. The master batch is evenly dispersed in pigments compared to simple mixing, and the peculiarity is that the resin used in the master batch is not completely dissolved in the solvent, although the master batch is ground to a very small size during dispersion. That is, no matter how small the particles are, the resin maintains a structure surrounding the surface of the particles when the present step is applied.

In general, when a large amount of polar groups present in the pigment appears on the surface of the toner particles, the charge accumulated in the toner is rather discharged, resulting in lowering the charge amount as well as the charge rate of the toner. However, in the case of the toner using the master batch as in the present invention, direct exposure of the pigment on the toner surface can be prevented because a high concentration of pigment utilizes a master batch, which is a colorant evenly dispersed in a polyester resin. In other words, it is advantageous to use a master batch for dispersing the colorant because the pigment particles have an encapsulated effect and are very advantageous in controlling the charge of the toner. In the production of the polymerized toner, the pigment particles may be evenly dispersed in the monomer mixture. As the monomer polymerizes during the polymerization process, it is known that the dispersion degree is changed by the change of the surface tension. However, when the master batch is used, the dispersion of the pigment is unlikely to change since the dispersed master batch is again dispersed.

To this end, the pigment content in the pigment pigment master batch used in the present invention is preferably 10 to 60% by weight, more preferably about 20 to 40% by weight. Therefore, when the master batch is used, the above-mentioned problems do not occur when the toner is dispersed, and it is particularly advantageous when the toner of the small particle is manufactured.

The pigments used here include cyan pigments, magenta pigments, yellow pigments, black pigments and white pigments, or mixtures thereof, which are commonly used pigments. It may be selected appropriately in consideration of the like. Examples of such pigments include P.Y 155, P.Y 180, and magenta. 57: 1, P.R. 184, P.R 122, P.B 15: 3, etc. are frequently used as the pure color of the cyan color. In addition to manufacturing other toners for industrial use, P.Y 17, P.Y. 97, P.Y. 174, P.Y 139, P.O. Yellow color and P.R. 146, P.V. Magenta tone pigments such as 19, and P.V. 23, P.V. 19, P.G.7 and other pigments and P.B. 15: 4 or the like. In addition, black, such as SB4, SB7, SB9, can be used as a black color, and it can manufacture using a titanium oxide as a white pigment. These selection criteria are selected appropriately, taking into account color coordinates and color depth. When the pigment is contained in excess, the elasticity of the resin composition becomes strong, so that it is difficult to form fine particles or the particle size can be widened. When the pigment is contained in a small amount, the coloring of the toner may be low, resulting in insufficient color expression during printing. . Therefore, the coloring pigment should be appropriately selected by the interaction between the physicochemical structure of the pigment crystal structure, crystal size, chemical composition, etc. and the physicochemical structure of the resin mixed therewith, and 2 to 15 to the total weight of the toner composition Weight% is preferable and 4-12 weight% is more preferable.

As the wax, all common waxes can be used. For example, ester wax, carnauba wax, polyethylene wax, polypropylene wax, bead wax, paraffin wax, or a mixture of two or more thereof is preferably used. The addition of the wax is preferable because the toner particles can be fused to printed matter such as paper or plastic even without using oil. However, when the added amount exceeds 30% by weight, the toner may be aggregated during storage, so it is preferably contained in an amount of 0.1 to 30% by weight based on the total weight of the composition.

On the other hand, as the charge control agent, one or more of a positive charge control agent, a negative charge control agent or a mixture thereof commonly used may be used without limitation, and may be appropriately selected according to the charge to be applied to the final toner. Positive charge control agents are classified into azine type and quaternary ammonium salt series due to their chemical structure.The positive charge control agents of azine type are mainly black, so they can be used only in the manufacture of black toner. Since the ammonium salt is in the form of a white powder, there is no restriction on the toner color. Negative charge control agents are commonly used in the tert- butyl salicylic acid metal salt-based white charge regulators and azo black charge regulators. Chromium, aluminum, zinc, calcium, boron, acetyl boron and the like are used as the center metal in the tert-butyl salicylic acid metal salt, and in the case of the azo system, chromium and iron are mainly used. The metal salt used for this can adjust the charging speed, the charging amount, etc. when included in the toner. In the present invention, when the amount of the charge control agent is small, there may be a problem in that the charging speed of the toner is low and the amount of charging is not large, and when it is contained in an excessive amount, the charge may be excessively increased, resulting in distortion in the image. It is preferable to contain 0.1-8 weight% with respect to a weight, and 0.3-5 weight% is more preferable.

In addition, very small organic-inorganic particles may be coated on the surface of the toner particles to further add an external additive such as a fluidizing agent. The external additive serves to improve the fluidity of the particles to be used as the toner or to control the charging characteristics such as the charge amount and the charging speed, and is a silica coated with conductive materials such as finely classified hydrophobic silica, hydrophilic silica, strontium, and calcium. , Titanium oxide coated with conductive materials such as silica, titanium oxide, strontium, calcium, etc. coated on the surface of semiconductors such as indium tin oxide, antimony tin oxide, semiconductor indium tin oxide, antimony tin oxide, etc. Titanium oxide, zinc stearate, magnesium stearate, alumina, polymethyl methacrylate particles, polystyrene particles, silicon particles and the like can be used.

Meanwhile, the term 'volume average particle size (L)' used in the present invention is defined in pages 3 to 13 of the Power Technology Handbook (author K. Gotoh et al., 2nd edition, Marcell Dekker Publications, 1997). In the present invention, it is measured using a commercial Coulter LS particle size analyzer (Coulter Electronics Co., Ltd., St. Pittsburgh, FL). This provides toner particles containing a uniform amount of charge in each toner particle, and uniformly colored resin particles having a narrow particle size distribution, and also provide a high quality radiant image, and facilitate charge control at a developing site. Because it makes you.

In addition, the 'particle size distribution span value' used in the present invention is an index defining the size distribution of particles, and the particle size corresponding to 10% based on the volume in the size distribution corresponds to d ₁₀ , 90%. By defining the particle diameter to be d ₉₀ , and the particle diameter of the 50% distribution corresponding to the average value as d ₅₀ , the 80% span value can be obtained by applying the three values to Equation 1 below.

80% Span Value = (d ₉₀ -d ₁₀ ) / d ₅₀

As can be seen from the above formula, the smaller the span value, the narrower the particle distribution, and the larger the value, the exponent indicating the wider particle distribution. To use as a toner, a 80% span is obtained by dividing the difference between a particle size d90 corresponding to a cumulative volume of 90% and a particle size d10 corresponding to a cumulative volume of 10% by a particle size distribution by a particle size d50 corresponding to a cumulative volume of 50% It is preferable that the value is 0.9 or less. If it is higher than this, the non-uniformity of the toner particle size causes charging characteristics or contamination in the device, and thus it is difficult to use, and in order to use it, a classification process is required. It is more preferable to have an 80% span value of 0.7 or less.

Hereinafter, the method for preparing the chemical toner composition of the present invention will be described in more detail.

The chemical toner composition according to the present invention comprises the steps of: (1) preparing a resin mixture by mixing a resin, a coloring pigment master batch dispersed in a resin, a wax, a volatile processing aid, and a charge control agent at 60 to 95 ° C; (2) a second step of adding the mixture of the first step into a dispersion medium heated to a temperature of 60 to 95 ° C. containing a polar solvent, a surfactant and optionally a thickener and stirring to form a dispersion of the resin mixture; (3) a third step of preparing the resin mixture from which the processing aid is removed by stirring the dispersion of the second step at 60 to 95 ° C and then volatilizing the processing aid; And (4) cooling the mixture of the third step at room temperature, and then recovering the toner particles, followed by washing and drying to prepare dry toner particles.

The resin, the pigment pigment master batch, the wax and the charge control agent used in the manufacturing method are the same materials as those of the toner composition.

The processing aids are volatile and have a lower boiling point than the polar solvent and are not mixed with the polar solvent which is subsequently added, for example, methyl acetate, ethyl acetate, isopropyl acetate, methyl ethyl ketone, dimethyl ether, diethyl ether, It can select and use 1 or more types from the group which consists of 1, 1- dichloroethane, 1, 2- dichloroethane, dichloromethane, and chloroform.

The thickener may be optionally used, which is dissolved in at least 1% by weight in a polar solvent including water, preferably about 0.01 to 5 parts by weight based on the polar solvent, 0.1 to 100 parts by weight of the total resin used More preferably, it is added in an amount of 10 to 10 parts by weight. For example, polyvinylpyrrolidone, anionic copolymer of polyvinylpyrrolidone, cationic copolymer of polyvinylpyrrolidone, polyvinyl alcohol, copolymer of polyvinyl alcohol, polyacrylic acid, copolymer of polyacrylic acid, At least one selected from the group consisting of gelatin, chitosan, sodium alginate, alginic acid and agar can be used.

 On the other hand, as the polar solvent, one or more selected from the group consisting of water, glycerol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol and sorbitol can be used, and water is most preferred.

The surfactant may be used without limitation as long as the HLB value is 10 or more, for example, sodium steroyl lactylate, polyethylene glycol cocamine, polyethylene glycol sorbitan hexanolate, polyethylene glycol dilaurate, Steamine Acetate, Taloamine Acetate, Glyceryl Stearate, Polyethylene Glycol Lanoleate, Polyethylene Glycol Palmitate, Polypropylene Glycol Hydroxyethyl Cocamine, Polyethylene Glycol Glyceryl Laurate, Polyethylene Glycol Stearate, Triethylamine Olate, One or more selected from the group consisting of polyethylene glycol taloamine, squarose laurate, sodium dodecyl sulfate, potassium dodecyl sulfate, alkylammonium chloride and alkylammonium bromide can be used.

In the present invention, toners having a variety of non-spherical shapes can be produced by changing the types of these volatile processing aids, polar solvents and surfactants, changing the use of thickeners, and applying physically the same shear stress.

Hereinafter, an example of preparing a toner composition using the resin and the master batch prepared in the preparation example will be described first, followed by a preparation example for preparing the polyester resin and the pigment pigment master batch used in the preparation of the chemical toner composition. Explain.

Synthesis of Polyester Resin

Preparation Example 1 Synthesis of Polyester Resin

A reactor was installed in the oil chain oil tank, and the reactor was provided with a thermometer, a stirrer, a cooler, and a nitrogen inlet at a normal position. 0.5 mole of dimethyl terephthalate, 0.47 mole of dimethyl isophthalate, 0.03 mole of dimethyl 5-sulfoisophthalate sodium salt, 2.3 mole of 1,2-propylene glycol and 0.02 mole of trimellitic acid were quantitatively added to the reactor thus installed, and the polymerization reaction was carried out. Tetrabutyl titanate as a catalyst was added in an amount of 500 ppm relative to the total weight of the monomers. The temperature was heated to 150 ° C. while stirring at a reactor stirring speed of 100 rpm. The reaction proceeded for approximately 5 hours. During the course of the reaction, the reactants form methanol as a byproduct, starting the ester reaction. Once the side reactions were no longer formed in the cooler, the reactor was depressurized to 0.1torr to warm to 220 ° C. and facilitate the removal of the side reactions, and proceeded for 15 hours under the same pressure conditions to complete the reaction. After completion of the reaction, the glass transition temperature (Tg) of the polyester was measured using a differential scanning calorimeter (DSC), and the result was 65 ° C. As a result of dissolving this in tetrahydrofuran (THF), it could be confirmed that all of them were dissolved without the insoluble gel component, and the acid value thereof was about 5. In addition, the number average molecular weight measured using a gel permeation chromography (GPC) verified using a polystyrene reference sample was 4,500, PDI was 3.5, and sodium sulfonate anion group content was 3 with respect to 100 parts by weight of the polyester resin formed It could be confirmed that the weight part.

Comparative Production Example 1 Synthesis of Polyester Resin Containing Gel

In the same reactor as in Preparation Example 1, only 0.5 mol of dimethyl terephthalate, 0.47 mol of dimethyl isophthalate, 0.03 mol of dimethyl 5-sulfoisophthalate, 2.3 mol of 1,2-propylene glycol, and 0.1 mol of trimellitic acid were used. Polyester resins were prepared. It was 67 degreeC when the glass transition temperature of the polyester manufactured using DSC was measured. As a result of dissolving it in tetrahydrofuran (THF), 5% of insoluble gel component was observed, and the number average molecular weight measured using GPC verified using polystyrene reference sample using the dissolved component was 5,700, and PDI Was 8.5, and the content of sodium sulfonate anion group was 3 parts by weight based on 100 parts by weight of the polyester resin formed.

Comparative Production Example 2 Synthesis of Polyester Resin Without Sodium Sulfonate Anion Group

In the same reactor as in Preparation Example 1, only the content of the composition was changed to 0.5 mol of terephthalate, 0.47 mol of isophthalate, 2.3 mol of 1,2-propylene glycol, and 0.03 mol of trimellitic acid to prepare a polyester resin. The glass transition temperature of the polyester prepared using DSC was 62 ° C., the number average molecular weight was 4,300, and the PDI was 3.5 using GPC verified using a polystyrene reference sample. The acid value measured by the titration was 15, and when it was dissolved in THF, an organic solvent, it was found that it was dissolved without insoluble components. It was confirmed that the formed polyester resin did not have an anionic group.

Preparation of Pigment Masterbatch

Preparation Example 2 Cyan Pigment Master Batch Preparation

Ethyl acetate after mixing the polyester synthesized in Preparation Example 1 with a blue pigment (CI Pigment Blue 15: 3, Color Index (CI) No. 74160, Japan Ink Company (DIC)) at 6: 4 by weight. 50% of the polymer was added and heated to about 60 ° C., followed by dispersion with stirring with a kneader. Thereafter, the mixture was mixed at a speed of 50 rpm using a twin extruder connected with a vacuum apparatus, and ethyl acetate, a solvent, was removed using a vacuum apparatus, thereby preparing a cyan pigment master batch.

Preparation Example 3 Preparation of Magenta Pigment Master Batch

Magenta pigment master batch by repeating the same procedure as in Preparation Example 2, except that the same polyester obtained in Preparation Example 1 was used, and the pigment was replaced with Magenta pigment (manufactured by Japan Ink, Inc., Red122). Was prepared.

Preparation Example 4 Preparation of Yellow Pigment Masterbatch

The same procedure as in Preparation Example 2 was repeated except that the same polyester obtained in Preparation Example 1 was used and the pigment was replaced with a yellow pigment (manufactured by Clariant, Germany) to prepare a yellow pigment master batch.

Preparation Example 5 Preparation of Black Pigment Masterbatch

A black pigment master batch was prepared by repeating the same procedure as in Preparation Example 2, except that the same polyester obtained in Preparation Example 1 was used, and the pigment was replaced with a carbon black pigment (CB4, manufactured by Degussa, Germany). It was.

Comparative Production Examples 3 to 6: Pigment Master Batch Preparation

Except for using the polyester obtained in Comparative Preparation Example 1 instead of the polyester obtained in Preparation Example 1, the same procedure as in Preparation Examples 2, 3, 4, and 5 was repeated, and Comparative Preparation Examples 3, 4, 5, and 6 were used. Cyan, magenta, yellow and black pigment master batches were prepared respectively.

Comparative Production Examples 7 to 10: Preparation of Pigment Master Batch

Except for using the polyester obtained in Comparative Preparation Example 2 instead of the polyester obtained in Preparation Example 1, the same procedure as in Preparation Examples 2, 3, 4, and 5 was repeated, and Comparative Preparation Examples 7, 8, and 9 were used. And cyan, magenta, yellow and black pigment master batches at 10, respectively.

Manufacture of toner

Example 1: Preparation of substantially spherical basic toner

85 g of polyester resin prepared in Preparation Example 1, 15 g of cyan pigment master batch prepared in Preparation Example 2, charge control agent (HB Dinglong, N-23, Hubei, China) in a 1 liter round bottom flask equipped with an impeller-type stirrer and a cooler. ) 2g, 5g of carnauba wax (SX-70; Max Chemical, Daejeon, Korea) as a fusing agent, and 150g of ethyl acetate (Aldrich Chemical Company, Milwaukee, Wis.) As a volatile processing aid. The contents were stirred to form a mixture, which was then heated to reflux at 72 ° C. and mixed for 10 hours. After confirming that the resin mixture had sufficient fluidity, the resin mixture was finely dispersed by stirring at 500 rpm for 2 hours at the same temperature.

In another 1 liter round bottom flask, 400 g of distilled water, 10 g of polyvinyl alcohol (P-24; manufactured by DC Chemical Co., Seoul, Korea), 7 g of neutral surfactant (tween 20, manufactured by Aldrich), and sodium dodecyl sulfate (Junsei Chemical Co., Tokyo, Japan) containing 4.2g, the contents were stirred to form a mixture, and then heated to reflux, 72 ℃ temperature and stirred at 500 rpm for 1 hour. The resin mixture prepared above was poured into this dispersion medium. The mixture was stirred at 1000 rpm for 1 hour at the same temperature to disperse the resin mixture to form a resin mixture dispersion.

Subsequently, the stirring speed was reduced to 300 rpm, the mixture was stirred at the same temperature, and then heated to 90 ° C. under partial pressure, thereby obtaining ethyl acetate as a processing aid.

After 4 hours, the amount of ethyl acetate obtained was confirmed to confirm that all of the added ethyl acetate was removed in the reactor, and the dispersion was cooled. The toner particles were then separated from the organic medium using a conventional filtration device. The filter cake was redispersed and refiltered four times in distilled water to remove the surfactants and thickeners in the filter cake. The refiltered particles were dried in a convection oven at 40 ° C. for one day to obtain dried toner particles.

Component analysis of the obtained toner particles revealed that it contained 87.9% by weight of polyester resin, 5.6% by weight of pigment, 4.6% by weight of paraffin wax, and 1.9% by weight of charge control agent. In addition, when the particle size was measured using a Coulter LS particle size analyzer (Coulter Electronics Co., Ltd., St. Pittsburgh, Florida), the volume average particle size was 7.0㎛, 80% span value was 0.62. In addition, as a result of inspecting the toner particles using a conventional scanning electron microscope (SEM), the toner particles had a serrated surface structure and substantially spherical shape as shown in FIG.

After mixing the prepared toner and silica (810G, manufactured by cabot), the blow-off charge amount, which is a charge amount measurement method of a two-component toner commonly used in the art, was measured. As a result, the initial charging speed was about −15 μC / g · min, and the charge amount when reaching equilibrium was −20 μC / g.

Example 2: Preparation of Spherical Toner

Toner particles were prepared in the same manner as in Example 1, except that polyvinyl alcohol, which was a thickener, was not used.

Component analysis of the obtained toner particles revealed that it contained 87.9% by weight of polyester resin, 5.6% by weight of pigment, 4.6% by weight of paraffin wax, and 1.9% by weight of charge control agent. When the particle size was determined, the volume average particle size measured was 7.6 μm and the 80% span value was 0.54. In addition, as a result of inspecting the toner particles using a conventional electron scanning microscope, it was confirmed that the toner particles were deformed into a perfect spherical shape having a smooth surface as shown in FIG. On the other hand, the initial charging speed was about −5 μC / g · min, and the charge amount when reaching equilibrium was −19 μC / g.

Example 3 Preparation of Long-Lined Toner

Toner particles were prepared in the same manner as in Example 1, except that methyl ethyl ketone was used instead of ethyl acetate as a processing aid.

Component analysis of the obtained toner particles revealed that it contained 87.9% by weight of polyester resin, 5.6% by weight of pigment, 4.6% by weight of paraffin wax, and 1.9% by weight of charge control agent. When the particle size was determined, the volume average particle size measured was 7.2 μm and the 80% span value was 0.51. In addition, as a result of inspecting the toner particles using a conventional electron scanning microscope, it was confirmed that the toner particles had a deformed grain shape elongated as shown in FIG. 3. On the other hand, the initial charging speed was about −16 μC / g · min, and the charge amount when reaching equilibrium was −22 μC / g.

Example 4 Preparation of Potato Shape Toner

Toner particles were prepared in the same manner as in Example 1, except that methyl ethyl ketone was used instead of ethyl acetate as a processing aid without using polyvinyl alcohol as a thickener.

The measured volume average particle size was 7.6 mu m and the 80% span value was 0.54. In addition, as a result of inspecting the toner particles using a conventional electron scanning microscope, it was confirmed that the toner particles were deformed into a potato shape as shown in FIG. On the other hand, the initial charging rate was about −14 μC / g · min, and the charge amount when reaching equilibrium was −19 μC / g.

Examples 5-7

The same procedure as in Example 1 was repeated except that the pigment master batches prepared in Preparation Examples 3, 4, and 5 were used instead of the cyan pigment master batch prepared in Preparation Example 2. Toner particles were prepared. As a result, each of the toner particles showed a similar volume average particle size as in Example 1, and the charging behavior expressed by their initial charging speed and the equilibrium charging amount was also very similar.

Example 8

The toner of Example 8 was repeated in the same manner as in Example 1 except that the content of the neutral surfactant tween 21 was reduced from 7.0 g to 6 g, and the content of sodium dodecyl sulfate was changed from 4.2 g to 3.5 g. Particles were prepared. The volume average particle size of the obtained toner particles was about 5.5 μm, the 80% span value was 0.56, and the overall shape of the toner particles was the same as in Example 1. The charging speed was improved to about -20 μC / g · min, and the amount of charge that reached equilibrium was observed to be -22 μC / g. This result confirmed that the adjustment of the particle size can be easily changed by adjusting the amount of the surfactant.

From the above examples, it is possible to manufacture toners of various shapes, not limited to spherical shapes, by changing the types of volatile processing aids, polar solvents, or surfactants added when manufacturing the toner of the present invention, or by using thickeners. You can check it.

On the other hand, after the toner fine particles are manufactured in the above embodiments, the fumed silica particles may be added as an external additive to improve the fluidity of the particles or to control the charging properties, and may be coated with suitable organic-inorganic fine particles. The fluidity improving agent helps to improve the fluidity of the particles to be used as the color toner or to control the charging properties such as the charging speed and the charging amount. Suitable fluidity improvers include finely classified hydrophobic silica, titanium oxide, zinc stearate, magnesium stearate and the like. These fluidity improvers are coated on the particles by dry mixing, solvent mixing or the like. In general, fumed silica (commercially available under the trade name 'Cab-O-Sil' from Cabot, Tuscany, Ill.) In a tumble mixer for 10 to 60 minutes Mixed with particles coated with CCA.

Comparative Example 1

A toner was prepared in the same manner as in Example 1, except that the polyester resin prepared in Comparative Preparation Example 1 and the cyan pigment master batch prepared in Comparative Preparation Example 3 were used. When the toner product was filtered through 200 mesh, it was found that very large particles which were not pulverized by chemical grinding were mixed. The volume average particle size of the toner passed through the mesh was about 10 μm and the 80% span value was A large value of about 2.3 was shown, indicating that application as a toner was difficult. That is, it was found that the chemical grinding method is not appropriate in the resin composition containing the gel.

Comparative Examples 2-4

Toner was prepared in the same manner as in Comparative Example 1, except that the pigment master batches prepared in Comparative Preparation Examples 4, 5, and 6 were used instead of the cyan pigment master batch prepared in Comparative Preparation Example 3. In this case, too much residue remained when the filtrate was filtered at 200 mesh, and the filtered toner composition showed a large particle distribution of about 2.0 to 3.0 similarly to Comparative Example 1.

Comparative Example 5

A toner was prepared in the same manner as in Example 1, except that the polyester resin prepared in Comparative Preparation Example 2 and the cyan pigment master batch prepared in Comparative Preparation Example 7 were used. When the toner composition liquid was filtered using 200 mesh after the production was completed, all the composition liquids passed. The measured volume average particle size was about 15 mu m, and the 80% span value showed a large value of about 3.5, indicating that the toner was not suitable. This result shows that the most suitable functional group for the chemical grinding method is SO _3- . On the other hand, as a result of component analysis of the obtained toner particles, it was found to contain 87.9 wt% of polyester resin, 5.6 wt% of pigment, 4.6 wt% of paraffin wax, and 1.9 wt% of charge control agent. When the particle size was determined, the volume average particle size measured was 20.0 mu m and the 80% span value was 4.8, which was determined to have an unsuitable value for use as a toner. In addition, inspection of the toner particles using a conventional electron scanning microscope confirmed that the particles had a rough surface texture and were substantially spherical.

The composition for electrostatic latent image development may also be prepared by treating a toner composition prepared by the above methods with a particle carrier such as ferrite, steel, iron powder or the like coated with an insulating material according to a conventional method. In addition, the toner composition may be applied to print an image according to a conventional method, and various printed materials including the toner composition and optionally having a protective coating layer for protecting the printed matter may be formed.

Although a preferred embodiment of the present invention has been described so far, those skilled in the art will be able to implement the present invention in a modified form without departing from the essential characteristics of the present invention. Accordingly, the embodiments of the present invention should be considered in descriptive sense only and not for purposes of limitation, and the scope of the present invention should be construed as including all inventions within the scope equivalent to the claims.

Through the present invention, it is possible to prepare a toner composition suitable for high speed printing having various shapes without being limited to a sphere, having a volume average particle size of 2 to 10 μm, and an 80% span value of 0.9 or less. In addition, it is possible to solve the problem of machine malfunction in the cleaning step according to the shape deformation, and to prevent the out of the toner generated when the colorant is added by using the color pigment master batch, and additional process for separation Cost savings are also excellent because they are not required.

Claims (21)

A toner composition comprising a resin, a color pigment, a wax, and a charge control agent, The resin has a number average molecular weight of 2,000 to 10,000, a PDI (PolyDispersity Index) of 2 to 15, containing 0.5 to 5.0 parts by weight of a sodium sulfonate group based on 100 parts by weight of the resin, and an insoluble portion ( polyester resins with no insoluble fraction) The composition particles have a volume average particle size of 2 to 10㎛, the difference between the particle size d ₉₀ corresponding to 90% cumulative volume and the particle size d ₁₀ corresponding to 10% cumulative volume in the particle size distribution, cumulative volume 50 A polyester-based chemical toner composition comprising a pigment, wherein the 80% span value divided by the particle size d ₅₀ corresponding to% is 0.9 or less. The chemical composition according to claim 1, comprising 2 to 15% by weight of the colored pigment, 0.1 to 30% by weight of the wax, 0.1 to 8% by weight of the charge control agent, and the resin based on the total weight of the composition. Toner composition. The pigment according to claim 1 or 2, wherein the coloring pigment is a coloring pigment dispersed in a resin using a master batch, and is selected from the group consisting of cyan pigment, magenta pigment, yellow pigment, black pigment and white pigment. A chemical toner composition, characterized in that at least one species selected. The chemical toner composition of claim 1 or 2, wherein the wax is selected from the group consisting of ester waxes, carnauba waxes, polyethylene waxes, polypropylene waxes, bead waxes, and paraffin waxes. The chemical toner composition of claim 1 or 2, wherein the charge control agent is selected from at least one of a positive charge control agent, a negative charge control agent or a mixture thereof. (a) a first step of preparing a resin mixture by mixing a resin, a pigment pigment master batch dispersed in the resin, a wax, a volatile processing aid and a charge control agent at 60 to 95 ℃; (b) a second step of adding the mixture of the first step into a dispersion medium heated to 60-95 ° C. comprising a polar solvent, a surfactant and optionally a thickener and stirring to form a dispersion of the resin mixture; (c) a third step of preparing the resin mixture from which the processing aid is removed by stirring the dispersion of the second step at 60 to 95 ° C and then volatilizing the processing aid; And (d) cooling the mixture of the third step at room temperature, and then recovering the toner particles, and then washing and drying the fourth to prepare dry toner particles. The resin has a number average molecular weight of 2,000 to 10,000, a PDI of 2 to 15, containing 0.5 to 5.0 parts by weight of a sodium sulfonate group with respect to 100 parts by weight of resin, and comprising a polyester resin having no insoluble portion. A method of producing a polyester-based chemical toner composition comprising a pigment. The method of claim 6, wherein the pigment pigment constituting the master batch of the pigment pigment is at least one selected from the group consisting of cyan pigment, magenta pigment, yellow pigment, black pigment and white pigment production of a chemical toner composition Way. 7. The method of claim 6, wherein the wax is selected from the group consisting of ester waxes, carnauba waxes, polyethylene waxes, polypropylene waxes, bead waxes and paraffin waxes. The method of claim 6, wherein the charge control agent is selected from at least one of a positive charge control agent, a negative charge control agent or a mixture thereof. The method of claim 6, wherein the processing aid is not mixed with the polar solvent and has a lower boiling point than the polar solvent. The process aid according to claim 10, wherein the processing aid is methyl acetate, ethyl acetate, isopropyl acetate, methyl ethyl ketone, dimethyl ether, diethyl ether, 1,1-dichloroethane, 1,2-dichloroethane, dichloromethane and chloroform. At least one selected from the group consisting of a method for producing a chemical toner composition. The method of claim 6, wherein the thickener is polyvinylpyrrolidone, anionic copolymer of polyvinylpyrrolidone, cationic copolymer of polyvinylpyrrolidone, polyvinyl alcohol, copolymer of polyvinyl alcohol, polyacrylic acid, poly A method for producing a chemical toner composition, characterized in that at least one selected from the group consisting of copolymers of acrylic acid, gelatin, chitosan, sodium alginate, alginic acid and agar. The method of claim 6, wherein the thickener is dissolved in water at least 1% by weight. The method of claim 6, wherein the thickener is added in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the resin. The method of claim 6, wherein the surfactant is sodium steroyl lactylate, polyethylene glycol cocamine, polyethylene glycol sorbitan hexanolate, polyethylene glycol dilaurate, steamine acetate, tallowamine acetate, glyceryl stearate, polyethylene Glycol Lanoleate, Polyethylene Glycol Palmitate, Polypropylene Glycol Hydroxyl Ethyl Cocamine, Polyethylene Glycol Glyceryl Laurate, Polyethylene Glycol Stearate, Triethylamine Olate, Polyethylene Glycol Taloamine, Squarose Laurate, Sodium Dodecyl Sulfate , Potassium dodecyl sulfate, alkylammonium chloride and alkylammonium bromide, at least one selected from the group consisting of.       The method of claim 6, wherein the polar solvent is selected from the group consisting of water, glycerol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, and sorbitol. The method of claim 16, wherein the polar solvent is water. The volume average particle size is 2 to 10㎛, and the difference between the particle size d ₉₀ corresponding to the cumulative volume of 90% and the particle size d ₁₀ corresponding to the cumulative volume of 10% in the particle size distribution diagram corresponds to the cumulative volume of 50%. An electrostatic latent image developer comprising the chemical toner composition according to claim 1 and a particle carrier having an 80% span value divided by a particle size d ₅₀ of 0.9 or less.       19. The latent electrostatic image developer according to claim 18, wherein the particle carrier is selected from the group consisting of ferrite, steel and iron powder coated with an insulating material. The volume average particle size is 2 to 10㎛, and the difference between the particle size d ₉₀ corresponding to the cumulative volume of 90% and the particle size d ₁₀ corresponding to the cumulative volume of 10% in the particle size distribution diagram corresponds to the cumulative volume of 50%. A method of printing an image by applying the chemical toner composition according to claim 1, wherein the 80% span value divided by the particle size d ₅₀ is 0.9 or less. The volume average particle size is 2 to 10㎛, and the difference between the particle size d ₉₀ corresponding to the cumulative volume of 90% and the particle size d ₁₀ corresponding to the cumulative volume of 10% in the particle size distribution diagram corresponds to the cumulative volume of 50%. An image print printed with the chemical toner composition according to claim 1 having an 80% span value of 0.9 or less divided by the particle size d ₅₀ .

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