KR20120072841A - Method for preparing fragrant polymerized toner - Google Patents

Abstract

PURPOSE: A method for manufacturing toner is provided to protect the material property of the toner from being influenced and to generate fragrance by including aromatic compounds. CONSTITUTION: A method for manufacturing toner includes the following: a polyester resin dispersed solution is prepared by adding a polyester resin and an organic solvent in a polar solvent with a surfactant and a dispersion stabilizer and stirring and heating the products; a coloring agent dispersed solution and a wax dispersed solution are mixed with the polyester resin dispersed solution; a coagulant is added into the mixed solution to be homogenized; the homogenized mixture is coagulated; and the coagulated toner particles are combined.

Description

Method for preparing aromatic polymerized toner {Method for preparing fragrant polymerized toner}

TECHNICAL FIELD This invention relates to the manufacturing method of a polymeric toner. Specifically, It is related with the manufacturing method of the toner which neutralizes an unpleasant odor at the time of use, and smells.

Generally, toner is prepared by adding a colorant, wax, or the like to a thermoplastic resin serving as a binder resin. Further, in order to impart fluidity to the toner or to improve physical properties such as charge control or cleaning property, fine inorganic metal powders such as silica and titanium oxide may be added to the toner as an external additive. As toner production methods, there are physical methods such as grinding method and chemical methods such as suspension polymerization method and emulsion aggregation method.

In the method for preparing toner by emulsion coagulation, the binder resin, the colorant, and the wax, which are present in the latex phase, are coagulated using a coagulant, and then the final toner particles are manufactured by combining. More specifically, mixing a latex dispersion, a colorant dispersion and a wax dispersion, adding and homogenizing a flocculant to the mixture, agglomerating the homogenized mixture to form toner particles, and coalescing the aggregated toner particles. step; And washing and drying the united toner particles.

On the other hand, the toner is produced when the toner is used and the toner container (due to a trace amount of a substance such as a component of the toner itself, impurities generated during the toner manufacturing process, or a substance caused by a part of the toner component decomposed by the storage environment after the toner production). When the cartridge is opened, there is a problem such as an irritating smell and an unpleasant feeling. In particular, when the toner is fixed on a print medium such as paper, a process such as a thermal fixing method heats a print image formed with the toner, thereby releasing a small amount of aromatic substances contained in the toner in the air, which may cause discomfort to the user. have. In order to improve this, a filter or the like for adsorbing ozone, odors or the like may be provided in the main body of the apparatus, but this is disadvantageous in terms of production cost, and also hassle for regular replacement.

U.S. Pat. No. 6,670,9898 and U.S. Pat.No. 6,373,357 disclose aromatic inkjet inks containing fragrances, but it is difficult to apply them to toner as it is.

In addition, U. S. Patent No. 5716751 discloses a method of uniformly applying the aromatic compound to the surface of the pulverized toner by using a fluid energy mill or a jet mill. Go crazy.

SUMMARY OF THE INVENTION The present invention has been made in an effort to provide a method for preparing a toner that does not have an unpleasant odor when using a toner and has a scent.

In the present invention to achieve the above technical problem,

Adding a polyester resin and an organic solvent to a polar solvent containing a surfactant and a dispersion stabilizer while stirring, followed by heating to prepare a polyester resin dispersion;

Mixing a colorant dispersion and a wax dispersion with the polyester resin dispersion;

Homogenizing by adding a flocculant to the mixed solution;

Agglomerating the homogenized mixture; And

In the method of manufacturing a toner comprising the step of coalescing the aggregated toner particles, the wax dispersion is prepared by dispersing a wax and an aromatic compound in a dispersion medium.

According to one embodiment of the invention, the wax dispersion may comprise 0.1 to 10% by weight of aromatic compounds.

According to another embodiment of the present invention, the aromatic compound may be a terpene-based compound.

The toner prepared by the method of the present invention has no unpleasant odor and smells when used.

Hereinafter, the present invention will be described in more detail.

Toner manufacturing method according to the present invention comprises the steps of adding a polyester resin and an organic solvent to the polar solvent containing a surfactant and a dispersion stabilizer while stirring, followed by heating to prepare a polyester resin dispersion;

Mixing a colorant dispersion and a wax dispersion with the polyester resin dispersion;

Homogenizing by adding a flocculant to the mixed solution;

Agglomerating the homogenized mixture; And

In the method of manufacturing a toner comprising the step of coalescing the aggregated toner particles, the wax dispersion is characterized in that it is prepared by dispersing the wax and the aromatic compound in a dispersion medium.

In the case of adding a fragrance compound as an external additive in the conventional method for producing a fragrance toner, it adversely affects the external properties of the toner. In addition, when the aromatic compound is added during the production of the latex dispersion in the toner production method by emulsion coagulation, the aromatic compound may not be stably present in the dispersion, and thus the content of the aromatic compound in the finally obtained toner may not be sufficient. In addition, when the aromatic compound is added as an additional component in the mixing process of the latex dispersion, the wax dispersion, and the colorant dispersion, there is a problem such that the presence of the additional component changes the process conditions of the toner, so that aggregation of the toner particles does not occur sufficiently. .

In the present invention, when the aromatic compound is added to prepare a wax dispersion including a hydrophobic wax, the aromatic compound is well mixed with the wax and stably dispersed in the wax dispersion so that the aromatic compound having a desired content exists in the final toner. In addition, by being stably present in the wax dispersion, it does not affect the manufacturing process of the polymerized toner and may not affect the external appearance characteristics of the toner.

In addition, when an image is formed by an electrophotographic imaging apparatus using a toner, the volatile components in the toner give an unpleasant odor due to the heat of the fixing unit. At this time, the aromatic compound present in the wax generates an aroma and causes an unpleasant odor. Neutralize and smell good.

In order to explain the toner manufacturing method according to an aspect of the present invention in more detail, it is roughly divided into (A) dispersion preparation process, (B) aggregation process, (C) aggregation fixing and coalescence process, and (D) washing and drying process. It will be described below.

(1) dispersion production process

Dispersion manufacturing process can be divided into three categories. That is, polyester resin dispersion preparation, colorant dispersion preparation, and wax dispersion preparation are included.

A polyester resin and an organic solvent are added to a polar solvent containing a surfactant and a dispersion stabilizer with stirring to obtain a mixture, and then the mixture is heated to prepare a polyester resin dispersion having a residual organic solvent content of less than 10,000 ppm.

The polyester resin dispersion may be prepared in a single reactor to simplify the process and shorten the time required. In addition, since the neutralization of the dispersion by the dispersion stabilizer is uniform, the particle size in the dispersion may be uniform.

In addition, unlike the conventional polyester resin completely dissolved in an organic solvent and then mixed with the remaining components to prepare a polyester resin dispersion, it is possible to easily remove the organic solvent when preparing the dispersion by sequentially adding the polyester resin in the above order. Can be.

The polar solvent containing the surfactant and the dispersion stabilizer may be prepared by sequentially adding or simultaneously adding the surfactant and the dispersion stabilizer to the polar solvent.

It is preferable to add surfactant, a dispersion stabilizer, a polyester resin, and an organic solvent to the polar solvent sequentially in the above order.

Heating in preparing the polyester resin dispersion may be carried out at a temperature above the boiling point of the organic solvent. The heating can be done for 3 to 15 hours.

The size of the particles in the polyester resin dispersion may be 50 to 300nm .

The polar solvent includes water, methanol, ethanol, butanol, acetonitrile, acetone, ethyl acetate and the like, and water is most preferred. The amount of the polar solvent may be included in an amount of 150 to 500 parts by weight based on 100 parts by weight of the polyester resin.

The weight average molecular weight of the polyester resin used in the present invention is preferably 5,000 to 50,000, and less than 5,000 may adversely affect the storage and fixability of the toner, and may exceed the 50,000 may adversely affect the fixability. have.

In addition, the PDI of the polyester resin is preferably 2 to 10, the peak molecular weight (MP) measured by gel permeation chromatography is preferably 1,000 to 10,000. In the present invention, the peak molecular weight (Mp) in gel permeation chromatography (GPC) is a molecular weight obtained from the peak value of the elution curve obtained by GPC measurement. GPC measurement conditions are as follows.

Device: Ceramics, Inc., HLC8020

Column: Containing three elements of TSKgelGMHXL (column size: 7.8㎜ (ID) × 30.0㎝ (L))

Oven Temperature: 40 ℃

Eluent: THF

From the holding time corresponded to the peak value of the obtained elution curve, the calibration curve was created using standard polystyrene, and the peak molecular weight (Mp) was calculated | required.

Examples of standard polystyrene samples for calibration curve preparation include TSK standard, A-500 (molecular weight 5.0 × 10 ² ), A-2500 (molecular weight 2.74 × 10 ³ ), F-2 (molecular weight 1.96 × 10 ⁴⁾ ), F-20 (molecular weight 1.9 × 10 ⁵ ), F-40 (molecular weight 3.55 × 10 ⁵ ), F-80 (molecular weight 7.06 × 10 ⁵ ), F-128 (molecular weight 1.09 × 10 ⁶ ), F-288 ( Molecular weight 2.89 × 10 ⁶ ), F-700 (molecular weight 6.77 × 10 ⁶ ), and F-2000 (molecular weight 2.0 × 10 ⁷ ) were used.

The peak value of the dissolution curve is a point at which the dissolution curve indicates the maximum, and when the maximum value is two or more points, the dissolution curve gives the maximum value. The eluent is not particularly limited, and in addition to THF, it is also possible to use a solvent in which the polyester resin is dissolved, for example, chloroform.

Moreover, it is preferable that the glass transition temperature of the said polyester resin is 40-80 degreeC, and 50-75 degreeC is more preferable. When the glass transition temperature is lower than 40 ° C., the toner formed by using the polyester resin particles may cause storage stability problems. On the other hand, when the glass transition temperature exceeds 80 ℃, the offset is likely to occur, especially when color printing may be a serious problem.

It is preferable that the said polyester resin does not contain a sulfonic acid group.

The polyester resin may be prepared by polycondensing an acid component and an alcohol component, and a polyester resin is prepared using polyhydric carboxylic acid mainly for an acid component and polyhydric alcohols mainly for an alcohol component.

Specific examples of the polyhydric alcohol component include polyoxyethylene- (2,0) -2,2-bis (4-hydroxyphenyl) propane and polyoxypropylene- (2,0) -2,2-bis (4 -Hydroxyphenyl) propane, polyoxypropylene- (2,2) -polyoxyethylene- (2,0) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene- (2,3) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (6) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (2,3) -2,2 -Bis (4-hydroxyphenyl) propane, polyoxypropylene- (2,4) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (3,3) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene- (6) -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1, 4-butylene glycol, 1,3-butylene glycol, glycerol, polyoxypropylene, and the like. The polyhydric carboxylic acid component specifically includes aromatic polyhydric acids and / or alkyl esters thereof conventionally used for producing polyester resins. Such aromatic polyacids include terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4 Naphthalenetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,2,7,8-octanetetracarboxylic acid or alkyl esters thereof, wherein the alkyl groups are methyl, ethyl, propyl, Butyl group etc. are mentioned. The aromatic polyacids and alkyl esters thereof may be used alone or in combination of two or more thereof.

It is preferable that it is 5-50, and, as for the acid value of the said polyester resin, it is more preferable that it is 10-20.

As the organic solvent used in the polyester resin dispersion, one or more selected from the group consisting of dimethyl ether, diethyl ether, 1,1-dichloroethane, 1,2-dichloroethane, dichloromethane, and chloroform may be used. It is not necessarily limited to these. It is preferable to use the said organic solvent in the quantity of 150-500 weight part with respect to 100 weight part of polyester resins.

The surfactant used in the polyester resin dispersion is preferably an anionic surfactant, and may be used in an amount of 1 to 4 parts by weight based on 100 parts by weight of the polyester resin.

As the dispersion stabilizer used in the polyester resin dispersion, a monovalent cation group-containing base may be used, and potassium hydroxide, sodium hydroxide, sodium carbonate, sodium bicarbonate, lithium hydroxide, potassium carbonate, ammonia, triethylamine, triethanolamine, pyridine , Ammonium hydroxide, diphenylamine and its derivatives, and poly (ethyleneamine) and its derivatives can be used one or more, and sodium hydroxide or potassium hydroxide is preferable.

The amount of the dispersion stabilizer used is related to the acid value of the polyester resin, and the higher the acid value, the higher the content of the dispersion stabilizer is, so that it is possible to prepare a dispersion having a narrow particle size distribution. The dispersion stabilizer is preferably used in an amount of 2 to 3 equivalents based on the acid value of the polyester resin.

The colorant dispersion can be prepared by dispersing the colorant in water using a dispersant such as a surfactant. In the case of dispersion in water, anionic surfactants and nonionic surfactants are preferable, and anionic surfactants are more preferable. By using a dispersing agent, it becomes easy to disperse a pigment in water, the dispersion particle diameter of the pigment in toner can be made small, and the toner which has a more excellent characteristic can be manufactured. Unnecessary dispersant may be removed by a subsequent washing process.

The colorant may be appropriately selected from black pigments, cyan pigments, magenta pigments, yellow pigments, and mixtures thereof, which are commonly used pigments.

The content of the colorant may be sufficient to color the toner to form a visible image by development, for example, 3 to 15 parts by weight based on 100 parts by weight of the polyester resin. If the content is less than 3 parts by weight, the coloring effect may be insufficient. If the content is more than 15 parts by weight, the electric resistance of the toner is lowered, so that a sufficient amount of triboelectric charge may not be obtained, resulting in contamination.

The wax dispersion can be prepared by adding and dispersing a wax and an aromatic compound in the dispersion medium.

The dispersion medium may include at least one of water and a water-soluble organic solvent. As water, purified water is preferably used. The dielectric constant of such a water-soluble organic solvent becomes like this. Preferably it is five or more, More preferably, it is ten or more. If the relative dielectric constant is less than 5, the relative dielectric constant of the wax dispersion is also reduced, so that the electrostatic repulsive force between the wax particles is weakened, and the dispersion stability may be lowered. As the water-soluble organic solvent that satisfies the relative dielectric constant range, ethers, alcohols, ether alcohols, esters, ketones, acids, amines, acid amines Organic solvents; More specifically, the water-soluble organic solvent is diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monobutyl ether, ethylene glycol ( ethylene glycol, diethylene glycol, propylene glycol, dimethyl sulfoxide, ethylene carbonate, propylene carbonate, and the like.

The wax contained in the wax dispersion may include at least one of a paraffin wax and a polyester wax. The paraffin wax mainly consists of linear saturated hydrocarbons having 20 to 36 carbon atoms, and has a weight average molecular weight of about 30 to 500 and a melting point of about 40 to 80 ° C. When the paraffin wax is added to the toner, it exhibits excellent releasability, but may cause a problem of contaminating the surface of the fixing roller due to its high penetration. Here, the penetration degree is a measure of the consistency of the substance, the hardness, and the like. In order to overcome this problem, polyester wax, which is a kind of synthetic wax, may be added to the toner.

Mixed waxes of paraffinic waxes and polyester waxes such as HNP-9 and HNP-11 waxes can be used.

The amount of the wax used is preferably in the range of 10 to 40% by weight of the wax dispersion, more preferably in the range of 25 to 35% by weight. When the amount of use is within the above range, it is excellent in dispersion stability and can sufficiently serve as a release agent.

The wax dispersion may further include a surfactant. As the surfactant, at least one selected from nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants may be used.

Nonionic surfactants include polyvinyl alcohol, polyacrylic acid, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene octylphenyl ether, polyoxyethylene stearyl ether, polyoxyethylene noylphenyl ether, ethoxylate , Phosphate norylphenol-based, tritone, dialkylphenoxypoly (ethyleneoxy) ethanol, and the like. Anionic surfactants include sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium dodecyl naphthalene sulfate, and dialkyl benzenealkyl. Sulfate, sulfonate, and the like, and cationic surfactants include alkyl benzenedimethyl ammonium chloride, alkyl trimethyl ammonium chloride, distearyl ammonium chloride, and the like, and amino acid type amphoteric surfactants and betaines. Amphoteric surfactants, lecithin, taurine and the like. The aforementioned surfactants may be used alone or in combination of two or more thereof.

The wax dispersion may comprise 0.1 to 10% by weight of aromatic compound. When the aromatic compound falls within the above range, it is possible to prepare a toner having an aromatic property while having suitable physical properties as an electrostatic charge image developing toner.

The aromatic compound may be a terpene-based compound, and the terpene-based compound particularly has a hydrophobic functional group so that the wax and the aromatic compound may be well mixed.

The terpene-based compound may be used without limitation, but geraniol, nerol, citral, citronellal, citronellol, linanol, nerolidol, limonene, camphor, terpineol, alpha-ronone, tuzon, eugenol , Cinnamic aldehyde, ethyl maltol, vanillin, anisole, anetol, estradiol, thymol, furaneol, farnesol, methol, 1-hexanol, fuructone, hexyl acetate, ethyl methylphenyl glycidate, gamma-decaractone, It may be at least one selected from the group consisting of gamma-nonalactone, delta-octalactone, jasmine lactone, masoa lactone, wine lactone, sotolone, nerolin, isoamyl acetate and pentyl pentanolate.

The dispersion may be performed in a state in which the reactant is heated above the melting point of the wax.

At this time, a dispersing machine for dispersing includes a high speed mill, a high speed mill with a classifier built-in, a ball mill, a medium stirring mill, a compaction shear mill, a colloid mill, a roll mill, and the like. In this case, as the grinding medium, steel beads such as stainless steel and steel, or ceramic beads such as alumina, ensterite, zirconium oxide, zircon, silica, silicon carbide, and silicon nitride may be used as the grinding media. It is also possible to obtain a wax dispersion of nano-sized particles using an Ultimaizer system (Amstec., Model HJP-25030).

(B) flocculation process

Each of the dispersions prepared in the dispersion preparation process is mixed, homogenized by adding a flocculant and an acid while stirring, and then toner particles are aggregated.

Although the coagulation process is preferably performed at room temperature, it may be heated up to the glass transition temperature (Tg) of the polyester resin, and the particle diameter and shape are uniform by stirring the mixed liquid of each dispersion liquid by using a stirrer and mechanical shear force. Agglomerates can be formed in one particle state.

As said flocculant, a well-known thing can be used, For example, the organic substance etc. which contain ions of opposite polarity to an electrolyte or a pigment can be used. In addition, sodium chloride (NaCl) which is easy to wash with pure water and has high solubility in water is more preferable. The amount of the flocculant used is 0.3 to 6% by weight, preferably 1.0 to 5% by weight based on the total solids. When the amount of the flocculant is less than 0.3% by weight, aggregation may not occur well, and when the amount of the flocculant is greater than 6% by weight, the aggregated particles may be too large.

Although the amount of flocculant is 0.3 ~ 6% by weight based on the solid content of the raw materials used during flocculation, the dispersion stabilizer used in the preparation of the polyester resin dispersion serves as a coagulation aid during the flocculation process. .

The pH may be adjusted by addition of acid in the flocculation process, and the preferred pH may be 4.5 to 6.5.

The coagulation step may be performed by stirring the reaction solution at 1.0 to 7.0 m / sec at a temperature of 40 to 60 ℃.

 (C) flocculation fixation and coalescence process

In order to freeze aggregation, the temperature of the reaction solution is maintained and the pH is raised to 10.

At this time, an inorganic base such as NaOH, KOH or LiOH is added to raise the pH.

Then, the mixed liquid containing the toner particles is heated to uniform the particle size and shape of the aggregated toner particles. It is preferable to adjust to a particle diameter of 1 to 20 µm by heating to a temperature higher than or equal to the glass transition temperature (Tg) of the polyester resin, whereby toner particles having almost uniform particle sizes and shapes can be obtained.

The surface properties of the particles can be improved by heating to a temperature above the glass transition temperature (Tg) of the polyester resin, and the polyester resin dispersion or polystyrene butylacryl before heating to a temperature above the glass transition temperature (Tg) of the polyester resin. The latex is added to cover the toner particles generated in the flocculation process once, thereby preventing the pigment or wax contained therein from coming out and making the toner firm. At this time, the polyester resin dispersion or polystyrene butyl acrylate latex added may use a resin dispersion having the same physical properties (Tg, molecular weight) as the polyester resin dispersion used in the previous step. You may use it. When using Tg and a higher molecular weight, Tg is 60-85 degreeC, and it is preferable that molecular weight is 10,000-300,000. The additionally added resin dispersion may increase the particle size while wrapping the toner particles generated in the flocculation step. To prevent this, a surfactant is added or the pH is adjusted, and the temperature is raised to a temperature higher than the glass transition temperature of the polyester resin. The coalescing process can proceed.

(D) washing and drying process

The toner particles obtained in the coalescence process are washed with water and dried. In this process, the mixed liquid containing toner is cooled to room temperature, the mixed liquid is filtered, the filtrate is removed, and the toner is washed with water. It is preferable to use pure water having a conductivity of 10 µS / cm or less for washing, and it is preferable to wash the toner until the filtrate having washed the toner has a conductivity of 50 µS / cm or less. The washing of the toner using pure water may be performed batchwise or continuously. The cleaning of the toner using pure water is performed to remove unnecessary components other than toner components such as impurities that may affect the chargeability of the toner and unnecessary coagulants that do not participate in aggregation.

When inorganic salts of monovalent metals are used as flocculants, the toner particles are not likely to be reaggregated by reactivation of the inorganic salts due to pH change in the washing process. The solubility in toner is so great that it is easy to remove during washing, and the amount of inorganic salt remaining in the toner is also significantly lowered, so that the melt viscosity of the toner particles does not increase and is preferable for fixing characteristics.

The toner obtained after the washing step is dried using a fluidized bed dryer, a flash jet dryer, or the like. In addition, a desired external additive may be added to the toner obtained by drying.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1

Preparation Example 1 Synthesis of Polyester Resin

A 3L reactor equipped with a stirrer, a nitrogen gas inlet, a thermometer, and a cooler was installed in the oil chain oil tank. 45 g of terephthalic acid, 39 g of isophthalic acid, 75 g of 1,2-propylene glycol, and 3 g of trimellitic acid were added to the reactor thus installed, and 500 ppm of dibutyltin oxide was added to the total weight of the monomer as a catalyst. The temperature was raised to 150 ° C. while the reactor was stirred at 150 rpm. The reaction was carried out for 6 hours, the temperature was raised to 220 ℃, the reactor was reduced to 0.1torr to remove the side reactions, the reaction was carried out for 15 hours under the same pressure conditions to obtain a polyester resin.

Glass transition temperature (Tg, ℃) measurement

Using a differential scanning calorimeter (manufactured by Netzsch), the sample was heated to 20 ° C. to 200 ° C. at a heating rate of 10 ° C./min, quenched to 10 ° C. at a cooling rate of 20 ° C./min, and then 10 ° C. again. It measured by heating up at the heating rate of / min.

Acid value measurement

The acid value (mgKOH / g) was measured by dissolving the resin in dichloromethane, cooling it, and titrating with 0.1 N KOH methyl alcohol solution.

Weight average molecular weight and Mp measurement

The weight average molecular weight of the binder resin was measured by gel permeation chromatography (GPC) using a calibration curve using a polystyrene reference sample.

Peak molecular weight (Mp) was calculated | required by standard polystyrene conversion from the holding time corresponded to the peak value of the elution curve obtained by GPC method. In addition, the peak value of an elution curve is a point where an elution curve shows a maximum value, and when a maximum value is two or more points, it is a point which gives the maximum value of an elution curve. In addition, signal intensity I (Mp) of the GPC curve in the position of a peak molecular weight, and signal intensity I (M100000) of the GPC curve in the position of molecular weight 100,000 are respectively signal intensity and a base in the position of a peak molecular weight. It is the difference of the signal intensity of a line, the difference of the signal intensity in the position of molecular weight 100,000, and the signal intensity of a baseline, and is shown by electric potential.

Device: Ceramics, Inc., HLC8020

Column: Containing three elements of TSKgelGMHXL (column size: 7.8㎜ (ID) × 30.0㎝ (L))

Oven Temperature: 40 ℃

Eluent: THF

Sample concentration: 4 mg / 10 ml

Filtration conditions: filter the sample solution with 0.45㎛ Teflon® membrane filter

Flow rate: 1 ml / min

Injection volume: 0.1ml

Detector: RI

Standard polystyrene sample for calibration curve preparation: TSK standard, A-500 (molecular weight 5.0 × 10 ² ), A-2500 (molecular weight 2.74 × 10 ³ ), F-2 (molecular weight 1.96 × 10 ⁴ ) F-20 (molecular weight 1.9 × 10 ⁵ ), F-40 (molecular weight 3.55 × 10 ⁵ ), F-80 (molecular weight 7.06 × 10 ⁵ ), F-128 (molecular weight 1.09 × 10 ⁶ ), F-288 (molecular weight 2.89 × 10 ⁶ ), F-700 (molecular weight 6.77 × 10 ⁶ ), F-2000 (molecular weight 2.0 × 10 ⁷ ).

The glass transition temperature (Tg) of the obtained polyester resin was 66 degreeC, the acid value was 11 mgKOH / g, the weight average molecular weight was 18,000, Mp was 5100, T _1/2 was 125 degreeC.

Preparation Example 2 Preparation of Polyester Resin Dispersion

Into a 3L reactor equipped with a thermometer and an impeller-type stirrer, 46 g (2.5 equivalents of polyester resin acid value) of a 4 wt% sodium hydroxide solution as a dispersion stabilizer was added, and a surfactant (dowfax, Dow Corning, 1 weight percent of polyester resin) ) 6.67 g, and 958 g of water. 300 g of a polyester resin was added thereto, 500 g of methyl ethyl ketone was added thereto, and the mixture was refluxed at 70 ° C. for 1 hour, followed by nitrogen purging at 80 ° C. for 4 hours or more to remove the organic solvent. Finally, a polyester resin dispersion was obtained.

Preparation Example 3 Preparation of Pigment Dispersion

3 kg of cyan pigment (ECB-303, manufactured by Daeil Jeong Co.) was put into a 20L reactor, and 11.5 kg of purified water and 0.6 kg of hydroxypropylmethyl cellulose acetate phthalate (AnyCoat-P, manufactured by Samsung Fine Chemicals Co., Ltd.) were additionally added to the reactor. And stirred at a rate of 50 rpm. The reactor contents were then transferred to a ball mill type reactor for predispersion. As a result of the predispersion, the dispersed cyan pigment particles having a volume average particle diameter (D50 (v)) of 3.4 µm (measured using a Coulter multisizer manufactured by Beckman Coulter) were obtained. The reactor contents were then subjected to high dispersion at a pressure of 1,500 bar using an Ultimaizer system (Amstec Ltd., Model HJP25030). As a result of the high dispersion, cyan pigment particles dispersed at a nano size having a volume average particle diameter (D50 (v)) of 150 nm (measured using Microtrac 252 from Microtrac Inc) were obtained.

Preparation Example 4 Preparation of Wax Dispersion

Into a 5L reactor, 65 g of anionic surfactant alkyldiphenyloxide disulfonate (45% Dowfax 2A1), 1.935 kg of distilled water, 580 g of wax (CHUKYO YUSHI, Japan) and 58 mg of Farnesol as an aromatic compound were added. After the addition, the temperature was elevated to high temperature (80 ° C. or higher), followed by stirring for 2 hours. When the wax melted, it was dispersed for 2 hours at 600 bar pressure using a HOMO (Niro-Soavi) instrument. The temperature at the time of dispersal proceeded to the melting point of wax + 15 ℃. The particle size of the wax dispersion after dispersion was 220 nm (microtrac measurement).

Example 1

89.6 wt% of the polyester resin dispersion prepared in Preparation Example 2, 5.20 wt% of the pigment dispersion prepared in Preparation Example 3, and 5.20 wt% of the wax dispersion prepared in Preparation Example 4 were mixed to obtain a mixed solution. The content is based on solids content. At this time, it adjusted with pure water so that total solid concentration might be 13 weight%. The temperature of the reactor was raised to 25 ° C and stirred and mixed at 120 rpm. 5.18% by weight of a 4.5 wt% NaCl aqueous solution (weight of NaCl solids based on the total solids content) was added as a flocculant, followed by homogenization with a homogenizer (T-50, IKA) while stirring at 140 rpm. Then, the temperature of the reactor was increased to 50 ° C., and the agglomeration was continued until D50 (v) became 6.45˜6.50 μm, and then 3.63 wt% of 1N aqueous sodium hydroxide solution (weight of NaCl solids based on the total solid content) was added to the reactor. The growth was stopped, the stirring speed was lowered to 80 rpm, and the temperature of the reactor was raised to 80 ° C. to allow toner particles to coalesce. The union continued until the circularity reached 0.970. The temperature of the reactor was lowered to 40 ° C., the toner was separated using a filtration device (device name: filter press), and the separated toner was washed with 1N aqueous nitric acid solution and washed again with distilled water to remove all surfactants. Thereafter, the washed toner particles were dried in a fluid bed dryer at a temperature of 40 ° C. for 5 hours to obtain dried toner particles.

Example 2

Toner particles were prepared in the same manner as in Example 1, except that 58 g (10 wt%) of Jasmine lactone was used instead of Farnesol as the aromatic compound when preparing the wax dispersion.

Example 3

Toner particles were prepared in the same manner as in Example 1, except that 290 mg (0.05 wt%) of Geraniol was used instead of Farnesol as the aromatic compound in preparing the wax dispersion.

Example 4

Toner particles were prepared in the same manner as in Example 1, except that 5.8 g (1% by weight) of Geraniol was used as the aromatic compound in preparing the wax dispersion.

Comparative Example 1

Toner particles were prepared in the same manner as in Example 1, except that the aromatic compound was not added when preparing the wax dispersion.

Comparative Example 2

Toner particles were prepared in the same manner as in Example 1, except that Farnesol was not added to the wax dispersion preparation process as the aromatic compound and 0.5 wt% was used based on the mass of the reaction solution solid in the flocculation process.

The odor test of the toners prepared in Examples and Comparative Examples was carried out.

Twenty randomly selected test participants were printed with the toners prepared in Examples 1 to 5 and Comparative Example 1 in a closed space. First, each of the toners prepared above was filled in a Samsung CLP-510 printer cartridge, and after printing 1000 sheets of A4 paper with an image having a printing letter ratio of 5%, statistics on the subjective smell of the printing place and the printing paper were obtained.

The panel test results were scored as follows.

1: very unpleasant

2: unpleasant

3: not unpleasant or fragrant

4: some scent

5: strong scent

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Aromatic substances in the wax dispersion Farnesol Jasmine Lactone Geraniol Geraniol - Farnesol
(Aggregation process) Aromatic substance content in the wax dispersion
(weight%) 0.01 10 0.05 1.00 0 0.5 Panel test result 3 5 3 4 One One

It can be seen from Table 1 that the toner according to the present invention does not have an unpleasant smell when used, but remains scented.

The physical properties of the toner prepared in Examples and Comparative Examples are as follows.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 D50 (m) 6.2 6.4 6.1 6.4 6.3 5.0 GSDv 1.25 1.28 1.27 1.27 1.28 1.82 GSDp 1.23 1.24 1.24 1.22 1.21 1.66

It was confirmed from Table 2 that the toner according to the present invention was not different from the physical properties of the toner prepared in the conventional process conditions (Comparative Example 1). However, polyester resin dispersions. When the aromatic compound is added as an additional component in the mixing process of the wax dispersion and the colorant dispersion (Comparative Example 2), the presence of the additional component causes a change in the processing conditions of the toner so that aggregation of the toner particles does not occur sufficiently and the distribution of the toner particles It can be seen that there is a problem such as the wrong.

Claims (5)

Adding a polyester resin and an organic solvent to a polar solvent containing a surfactant and a dispersion stabilizer while stirring, followed by heating to prepare a polyester resin dispersion;
Mixing a colorant dispersion and a wax dispersion with the polyester resin dispersion;
Homogenizing by adding a flocculant to the mixed solution;
Agglomerating the homogenized mixture; And
In the manufacturing method of the toner comprising the step of coalescing the aggregated toner particles,
The wax dispersion is prepared by dispersing the wax and the aromatic compound in a dispersion medium. The method of claim 1,
The aromatic compound is added in an amount of 0.01 to 10% by weight of the wax dispersion. The method of claim 1,
The wax is added in an amount of 10 to 45% by weight of the wax dispersion. The method of claim 1,
The aromatic compound is a production method, characterized in that the terpene-based compound. The method of claim 4, wherein
The terpene compounds include geraniol, nerol, citral, citronellal, citronellol, linanol, nerolidol, limonene, camphor, terpineol, alpha-ronone, tozone, eugenol, cinnaaldehyde, ethyl maltol , Vanillin, anisole, anetol, estradiol, thymol, furaneol, farnesol, methol, 1-hexanol, fuructone, hexyl acetate, ethyl methylphenyl glycidate, gamma-dekaralactone, gamma-nonaralactone, At least one member selected from the group consisting of delta-octalactone, jasmine lactone, masoia lactone, wine lactone, sotolone, nerolin, isoamyl acetate and pentyl pentanolate.