KR20100079033A - Method of manufacturing organic or organic·inorganic suspension including wax and toner with the suspension manufactured by using the same - Google Patents

Abstract

PURPOSE: A producing method of an organic or organic-inorganic suspension is provided to produce a monomer suspension containing a micro size monomer, and to manufacture a polymer particle including a micro-sized wax. CONSTITUTION: A producing method of an organic or organic-inorganic suspension comprises a step of passing a suspension inserting wax and an organic or organic-inorganic mixed solution into a dispersion agent-containing solution, through a film for a suspension-polymerization. The method is performed at room temperature using the wax with the particle size of 0.7~2 microns.

Description

METHOD OF MANUFACTURING ORGANIC OR ORGANIC INORGANIC SUSPENSION INCLUDING WAX AND TONER WITH THE SUSPENSION MANUFACTURED BY USING THE SAME}

The present invention relates to a method for preparing an organic or organic-inorganic complex suspension containing a wax and a toner prepared by the method. More specifically, the micro-sized wax particles are dispersed in an organic or organic-inorganic complex suspension, and the monomer suspension is In the case of preparing and suspending polymer, it is not necessary to increase the temperature for melting the wax, so that the permeability of the SPG membrane is increased, and thus a method for preparing an organic or organic-inorganic complex suspension containing a wax having an even particle distribution. It is about.

As a suspension used in conventional toners or the like, in an organic or organic-inorganic complex suspension in which wax is added, suspension polymerization is performed by raising the temperature to 45 ° C. or higher in order to melt the wax, in which case the styrene in the suspension is heated by the elevated temperature. And since the initiator initiates the polymerization in advance, the particles are not evenly distributed due to the formation of larger particles, and the viscosity of the organic solution is increased, resulting in poor workability. Therefore, when passing through the SPG membrane, the ratio of passing through the SPG membrane is also lowered, and there is a disadvantage in that it shows a problem of uneven particle distribution. In the end, the polymer is synthesized before passing through the SPG membrane to produce toner particles of a desired size. Can't.

An object of the present invention is to provide a method for preparing an organic or organic-inorganic complex suspension having a uniform particle size distribution using a suspension polymerization method through membrane emulsification.

Another object of the present invention is to provide a toner by suspension prepared using the above production method.

The present invention is to achieve the above object, in the suspension polymerized by passing a suspension, an organic or organic-inorganic mixed solution in an aqueous solution containing a dispersant through a membrane, the wax is 0.7 ~ 2㎛ when preparing the suspension It provides a method for producing an organic or organic-inorganic complex suspension containing a wax, characterized in that the particle size is prepared at room temperature.

In addition, the wax is characterized in that the grinding with a micromixer or homogenizer.

In addition, the suspension is characterized in that the temperature of 5 ~ 30 ℃.

In addition, the membrane is selected from the group consisting of porous alumina, porous zirconia, and porous glass spji, it characterized in that it comprises pores of 0.5 to 5 micro size.

In addition, it is characterized by applying a pressure of 10 to 500 kPa to the dispersed phase when passing through the membrane.

In addition, the dispersing agent is an inorganic dispersing agent selected from the group consisting of calcium phosphate salt, magnesium salt, hydrophilic silica, hydrophobic silica and colloidal silica; At least one selected from the group consisting of polyoxyethylene alkyl ether, polyoxyalkylene alkyl phenol ether, sorbitan fatty acid ester, polyoxyalkylene fatty acid ester, glycerin fatty acid ester, polyvinyl alcohol, alkyl cellulose and polyvinyl pyrrolidone Nonionic polymer dispersants; And polyacrylamide, polyvinyl amine, polyvinyl amine N-oxide, polyvinyl ammonium salt, polydialkyldiallyl ammonium salt, polyacrylic acid, polystyrene sulfonic acid, polyacrylate, polystyrene sulfonate and polyaminoalkyl acrylate At least one ionic polymer dispersant selected from the group; At least one selected from among, characterized in that 0.01 to 10% by weight based on the total weight of the monomer mixture.

In addition, the wax is petroleum refined wax selected from the group consisting of paraffin wax, microcrystalline wax and ceresin wax; Natural waxes that are carnuba wax; Synthetic waxes selected from the group consisting of polyethylene and polypropylene; At least one selected from among, characterized in that 0.01 to 30% by weight relative to the total weight of the monomer mixture.

The present invention also provides a toner using a suspension prepared using the above method.

According to the present invention, it is possible to prepare a monomer suspension including a micro-size, when the suspension polymerization may be prepared polymer particles containing a micro-sized wax.

The present invention is a membrane emulsion polymerization by passing a suspension of a wax, organic or organic-inorganic mixed solution in an aqueous solution containing a dispersant through a membrane, the wax is prepared at room temperature using a particle size of 0.7 ~ 2㎛ It relates to a method for producing an organic or organic-inorganic complex suspension containing a wax, characterized in that for producing.

Hereinafter, the manufacturing method of the present invention will be described in detail.

The apparatus used in the film emulsion polymerization method shown in FIG. 1 is provided with a heating device 3, and a dispersed phase is introduced into a dispersed phase tank 1 capable of containing monomers, pigments, etc. Pressurized (9) to disperse into the continuous phase tank (4) containing the continuous phase (5) in which the dispersion stabilizer is dissolved. The stirrer bar 7 is stirred using the stirrer device 8 which can be heated under the continuous tank 4.

Figure 2 conceptually illustrates the mechanism by which particles are produced through the membrane of the module.

The material of the membrane that can be used for the film emulsification includes porous alumina, porous zirconia, porous glass sph, and the like, and preferably, porous glass sph (Shrasu Porous Glass) membrane is used. The processing size of the membrane depends on the size of the particles to be prepared, and preferably, porous glass esppaper having a membrane processing size of 0.5 to 5 microns is used.

The film emulsion polymerization method passes the dispersed phase at a suitable pressure to the module 6 provided with a membrane, in which the pressure is preferably 10 to 500 kPa. If it is 10 kPa or less, the dispersed phase does not pass through the membrane, and if it is 500 kPa or more, the membrane is destroyed. Thus, particles of stable size can be produced by applying a pressure between 10 and 500 kPa to discharge the continuous phase evenly through the membrane.

Hereinafter, the compound used for manufacture of the organic or organic-inorganic complex suspension containing the wax of this invention is demonstrated. The suspension of the present invention uses a binder resin monomer as an organic liquid or an organic-inorganic mixed liquid, and includes a wax and a dispersant.

As the binder resin monomer, one or more selected from the group consisting of aromatic vinyl-based, acrylate-based, methacrylate-based, diene-based, acidic olefin-based and basic olefin-based monomers may be used alone or in combination.

As the aromatic vinyl monomer, at least one selected from the group consisting of styrene, monochlorostyrene, methyl styrene, dimethyl styrene, and the like may be used. The content of the aromatic vinyl monomer is preferably 30 to 90% by weight based on the total weight of the monomer mixture. The reason for limiting the content of the aromatic vinyl monomer to 30 to 90% by weight is to match the glass transition temperature of the toner. When the content is less than 30% by weight, the glass transition temperature of the toner is too low, and the toner is a fusing roller during printing. Offset phenomenon that sticks to the fusing roller may occur, and when the content exceeds 90% by weight, the glass transition temperature of the toner becomes too high and the fixability is deteriorated.

The acrylate monomers include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, and the like. The methacrylate monomers include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, dodecyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, and the like. Examples of the diene monomers include butadiene and isoprene. The acrylate-based, methacrylate-based, and diene-based monomers may be used alone or in combination of one or more thereof, and the content thereof is preferably 5 to 70% by weight based on the total weight of the monomer mixture. The content is thus limited in order to suitably adjust the glass transition temperature of the toner as in the case of the aromatic vinyl monomer.

On the other hand, the acidic olefinic monomers include α, β-ethylene compounds having a carboxyl group, and the like. The basic olefinic monomers include methacrylic acid esters and methacrylamides of aliphatic alcohols having amine groups or quaternary ammonium groups. And vinyl amines, diaryl amines, and ammonium salts thereof. The acidic olefinic monomers and basic olefinic monomers may be used alone or in combination of one or more thereof, the content of which is preferably 0.1 to 20% by weight based on the total weight of the monomer mixture. The acidic olefinic monomer and the basic olefinic monomer are added to improve the charging property of the surface. If the amount exceeds 20% by weight, the reaction stability deteriorates during toner polymerization, and the toner particles may aggregate with each other.

As the wax, petroleum refined wax, natural wax, synthetic wax, or the like can be used. Petroleum refined waxes include paraffin wax, microcrystalline wax, ceresin wax and the like, natural waxes include carnauba wax and the like, and synthetic waxes include polyethylene, polypropylene, and the like, but are not particularly limited thereto. The waxes may be used alone or in combination of one or more, the content is preferably 0.01 to 30% by weight based on the total weight of the monomer mixture. If the content is less than 0.01% by weight, it is not preferable because it is not fused to the paper at the time of printing, and if it exceeds 30% by weight is not preferable because it is not compatible with the monomer and the like.

The dispersant may be an inorganic dispersant selected from the group consisting of calcium phosphate salt, magnesium salt, hydrophilic silica, hydrophobic silica and colloidal silica; At least one member of the group consisting of polyoxyethylene alkyl ether, polyoxyalkylene alkyl phenol ether, sorbitan fatty acid ester, polyoxyalkylene fatty acid ester, glycerin fatty acid ester, polyvinyl alcohol, alkyl cellulose and polyvinyl pyrrolidone Selected nonionic polymer dispersants; Or polyacryl amide, polyvinyl amine, polyvinyl amine N-oxide, polyvinyl ammonium salt, polydialkyldiallyl ammonium salt, polyacrylic acid, polystyrene sulfonic acid, polyacrylate, polystyrene sulfonate and polyaminoalkyl acrylate At least one ionic polymer dispersant selected from the group consisting of: It is selected from one or more, and the content thereof is preferably 0.01 to 10 parts by weight based on the total weight of the monomer mixture. If the content of the dispersant is less than 0.01 parts by weight, the reaction stability is broken during polymerization, and if it exceeds 10 parts by weight, the formation of side reactants (emulsion particles) increases.

The composite suspension of the present invention is prepared by the suspension polymerization method by dispersing the wax particles in a monomer and then preparing the suspension, and a method for preparing an organic or organic-inorganic composite suspension containing the wax of the present invention will be described in detail. Is the same as

(Manufacturing method 1)

1. Generation of micro wax droplets

a. Wax in 50 distilled water Melting by determining operating conditions in the temperature range of ~ 200 ° C and in the range of 1 to 30 bar

b. Preparation of suspension using a micromixer or homogenizer in the phase separation of molten wax and secondary distilled water (particle size change depending on rpm of homogenizer or flow rate of fluid in micromixer)

c. After quenching the suspension to room temperature, filtration and low temperature drying

2. Preparation of Suspensions Containing Microwax

a. The prepared wax is stirred with an organic or organic-inorganic mixed solution at a low temperature of 15 ^o C or less.

The mixed solution prepared in ba is added to an aqueous solution layer containing a dispersant, and then stirred at an appropriate rpm for several tens or several hours using a homogenizer at a low temperature of 15 ^o C or less. Alternatively, the suspension is prepared by permeating the mixed solution prepared in 2.A. by direct membrane or permeable membrane at room temperature.

(Production method 2)

1. Preparation of suspension containing micro waxes

a. A wax and an organic or organic-inorganic mixed solution are stirred using a homogenizer at a low temperature of 10 ^° C. or lower at a high speed of 11000 rpm or more for several ten minutes or more to prepare a solution in which the wax is directly ground.

The mixed solution prepared in ba is added to an aqueous solution layer containing a dispersant and then stirred at an appropriate rpm for several tens or several hours using a homogenizer at a low temperature of 15 ^° C. or less. Alternatively, the suspension is prepared by permeating the mixed solution prepared in a. By direct membrane method or permeable membrane method at room temperature.

The suspension prepared through the above process has a uniform particle size distribution after polymerization compared to the suspension made by the conventional manufacturing method.

Hereinafter, the toner manufacturing method of the present invention through the preferred embodiment of the present invention. The above examples are intended to illustrate the present invention, and the scope of the present invention includes changes and substitutions within the scope and equivalent ranges determined by the following claims, and are not determined by the present examples.

Example 1

(Manufacture of wax droplets)

36.0 g of nonionic paraffin wax was melted at 60 ° C. and 1 bar in 1000.0 mL of secondary distilled water, and then waxed at 11000 rpm using a homogenizer (IKA T25 digital ULTRA-TURRAX) in a state in which the melted wax and the secondary distilled water were in phase separation. Suspension was prepared. The prepared suspension was quenched at room temperature, filtered and dried at low temperature. The average particle size of the prepared paraffin wax droplets is 0.7 μm.

(Organic or organic-inorganic mixed liquid)

Put 211.4 g of styrene, 52.9 g of butyl acrylate, 3.0 g of allyl methacrylate, 2.2 g of styrene butadiene styrene block copolymer, 16.2 g of carbon black, 9.0 g of charge control agent, and 7.3 g of initiator AIBN at a speed of 1100 rpm. The mixture was stirred for hours to prepare a monomer mixture.

(Preparation of organic or organic-inorganic complex suspension containing wax)

The prepared wax is added to the organic or organic-inorganic complex suspension and stirred at 25 ° C. at a speed of 1100 rpm. The stirred mixed solution was added to an aqueous solution layer containing a dispersant, stirred at 25 ° C. for 15 minutes using a homogenizer, and then permeated in a permeable membrane through an SPG membrane having pores having a diameter of 10 μm at room temperature. To prepare.

(Suspension polymerization)

The suspension thus prepared was polymerized by suspension polymerization at 70 ° C. for 10 hours, and then the average particle size was measured, and the results are shown in Table 1 below.

[Example 2]

Instead of using the permeable membrane method in Example 1, except that the mixed solution was added to the aqueous solution layer containing the dispersant by permeating the SPG membrane having a pore of 2 ㎛ diameter at room temperature using a direct membrane method The suspension was prepared in the same manner as in Example 1, suspension polymerization was performed, and the results are shown in Table 1.

Comparative Example 1

Instead of using the method of preparing a micro droplet of paraffin wax in Example 1 to prepare a suspension at room temperature, the same as in Example 1 except that the paraffin wax was melted at 45 ^o C or more and stirred with a monomer mixture solution. The suspension was prepared by the suspension suspension polymerization, and the results are shown in Table 1.

Comparative Example 2

Instead of using the method of preparing a micro droplet of paraffin wax in Example 2 to prepare a suspension at room temperature, the same as in Example 2 except that the paraffin wax was melted at 45 ^o C or more and stirred with a monomer mixture solution. The suspension was prepared by the suspension suspension polymerization, and the results are shown in Table 1.

[Experimental Example]

The particle sizes after the suspension and suspension polymerization prepared in Examples and Comparative Examples were measured by using a scanning electron microscope (SEM), and the particle size distribution was calculated using the following equation.

Coefficient of Variation (CV) =

SD (Standard Deviation) / Number average particle size (d _n : Number average particle size) X 100

 division Particle size after suspension polymerization Coefficient of variation SPG penetration Example 1 7.7 μm 1.95 30 psi Example 2 8.2 μm 1.84 32 psi Comparative Example 1 7.5 2.25 500 psi Comparative Example 2 6.3 2.12 500 psi

As shown in the table, in Examples 1 and 2 produced by the present invention, the particle size distribution was improved compared to Comparative Examples 1 and 2 prepared in the conventional manner, and in particular, in Examples 1 and 2, Compared with the example, the SPG transmission pressure is small, which is advantageous for toner mass production. When mixing wax and monomer at a high temperature, polymerization proceeds over time. When a suspension is prepared using an SPG membrane or a homogenizer, the suspension must be prepared by polymerization in a short time. It is difficult to produce continuously and it is a difficult method to produce a large amount of polymerized toner. According to the experimental results, since the suspension can be made by uniformly stirring the wax and the monomer liquid at room temperature and permeating the SPG membrane, the suspension can be continuously produced and the polymerization toner with a uniform particle size distribution can be produced through the subsequent polymerization process. Can be.

1 is a cross-sectional view of an apparatus used in the film emulsion polymerization method of the present invention.

Figure 2 is a schematic diagram showing the production of particles in the film emulsion polymerization method of the present invention.

Explanation of symbols on the main parts of the drawing

1: Disperse phase tank 2: Disperse phase (monomer mixture) 3: Warmer

4: continuous phase tank 5: continuous phase (aqueous dispersion) 6: module with membrane installed

7: Stirrer 8: Stirrer device

10: dispersed phase

20: continuous phase

30: membrane

Claims (8)

In the suspension polymerization of a wax, organic or organic-inorganic mixed solution in an aqueous solution containing a dispersant, through a membrane, the wax is prepared at room temperature using a particle size of 0.7 ~ 2㎛ when preparing the suspension. A method for producing an organic or organic-inorganic complex suspension containing a wax. The method of claim 1, The wax is a method of producing an organic or organic-inorganic complex suspension comprising a wax, characterized in that the grinding with a micromixer or homogenizer. The method of claim 1, Method for producing an organic or organic-inorganic complex suspension containing a wax, characterized in that the temperature at the time of preparation of the suspension is 5 ~ 30 ℃. The method of claim 1, The membrane is selected from the group consisting of porous alumina, porous zirconia and porous glass spji, and a method for producing an organic or organic-inorganic complex suspension comprising a wax, characterized in that it comprises pores of 0.5 to 5 micro size. The method of claim 1, Method for producing an organic or organic-inorganic complex suspension comprising a wax, characterized in that the pressure of 10 to 500 kPa against the dispersed phase when passing through the membrane. The method of claim 1, The dispersant may be an inorganic dispersant selected from the group consisting of calcium phosphate salt, magnesium salt, hydrophilic silica, hydrophobic silica and colloidal silica; At least one selected from the group consisting of polyoxyethylene alkyl ether, polyoxyalkylene alkyl phenol ether, sorbitan fatty acid ester, polyoxyalkylene fatty acid ester, glycerin fatty acid ester, polyvinyl alcohol, alkyl cellulose and polyvinyl pyrrolidone Nonionic polymer dispersants; And Group consisting of polyacrylamide, polyvinyl amine, polyvinyl amine N-oxide, polyvinyl ammonium salt, polydialkyldiallyl ammonium salt, polyacrylic acid, polystyrene sulfonic acid, polyacrylate, polystyrene sulfonate and polyaminoalkyl acrylate At least one ionic polymer dispersant selected from; At least one selected from among, Method for producing an organic or organic-inorganic complex suspension comprising a wax, characterized in that 0.01 to 10% by weight based on the total weight of the monomer mixture. The method of claim 1, The wax is a petroleum refined wax selected from one or more selected from the group consisting of paraffin wax, microcrystalline wax and ceresin wax; Natural waxes that are carnuba wax; Synthetic waxes selected from the group consisting of polyethylene and polypropylene; As one or more kinds are chosen from, A method for producing an organic or organic-inorganic complex suspension comprising a wax, characterized in that 0.01 to 30% by weight based on the total weight of the monomer mixture. A toner using a suspension prepared using the method of any one of claims 1 to 7.

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