JP6775975B2 - Toner manufacturing method - Google Patents

Description

The present invention relates to toners used in recording methods such as electrophotographic methods, electrostatic recording methods, magnetic recording methods, and toner jet methods.

In recent years, with the demand for energy saving in society as a whole, power saving is also required in the electrophotographic image forming method. Among them, toner is required to have low-temperature fixability that fixes to a transfer material at a lower temperature. On the other hand, with the expansion of the laser printer and copier market in recent years, it is required that the toner exerts its performance stably even when it is stored or used in a high temperature and high humidity environment as compared with the conventional one. ing.
In order to achieve the above low temperature fixability, the glass transition temperature (hereinafter also referred to as Tg) of the binder resin constituting the toner is designed to be low, and a study is conducted to include a wax having a low melting point as a fixing aid in the toner. (Patent Document 1). Patent Document 1 describes a toner containing a wax having a Tg of 50 ° C. or higher and 65 ° C. or lower and a melting point of 50 ° C. or higher and 90 ° C. or lower as a fixing aid.
However, although the toner having the above configuration is excellent in low-temperature fixability, there is a problem that blooming occurs in which the wax is exposed on the toner surface in a higher temperature and higher humidity environment than in the past. When wax blooming occurs, members such as the developer carrier may be contaminated with the exposed wax, which may cause adverse effects such as a decrease in concentration. Therefore, studies have been conducted to suppress blooming. Patent Document 2). Patent Document 2 describes a toner containing silica fine particles having specific physical properties in order to suppress blooming of a low melting point wax.

Japanese Unexamined Patent Publication No. 2004-117551 Japanese Unexamined Patent Publication No. 2009-276634

The prior art toner has excellent performance. However, further improvement in performance is required from the viewpoint that toner is expected to be stored and used in an environment of higher temperature and humidity and that silica fine particles having a wider range of physical properties are used in the future. .. That is, an object of the present invention is to provide a toner in which blooming of wax is suppressed even during storage and use in a higher high temperature and high humidity environment, which is required in the future, and at the same time, a toner satisfying low temperature fixability is provided.

As a result of diligent studies, the present inventors have obtained low-temperature fixability and wax blooming by containing a binder resin having a low glass transition temperature, a wax having a low melting point, and a fatty acid metal salt in the toner particles. The present invention has been completed by finding that it is possible to achieve both suppression.
That is, the present invention is a method for producing a toner containing toner particles containing a binder resin, a wax and a fatty acid metal salt.
The glass transition temperature measured by the differential scanning calorimeter of the binder resin is 30 ° C. or higher and 55 ° C. or lower.
The melting point measured by the differential scanning calorimeter of the wax is 65 ° C. or higher and 90 ° C. or lower.
When the fatty acid metal salt is a fatty acid metal salt composed of a monovalent or divalent metal and a fatty acid, the number of carbon atoms contained in one molecule of the wax is C1, and the number of carbon atoms contained in one molecule of the fatty acid metal salt is C2. , C1 and C2 satisfy the following relational expression,
10 ≤ C1
10 ≤ C2
0.30 ≤ C2 / C1 ≤ 1.50
In the production method, a polymerizable monomer composition obtained by dissolving or dispersing a colorant, a polar resin, and a wax in a polymerizable monomer is dispersed in an aqueous medium to obtain the polymerizable monomer. step polymerization to generate the binder resin, distillation, the binder resin, the wax and the fatty acid metal salt to obtain the toner particles by a suspension polymerization method including the step of temperature descending in the presence at the same time Have,
The temperature drop is from a temperature equal to or higher than the melting point of the wax to a temperature lower than the glass transition temperature of the binder resin, and the average temperature drop rate between the melting point of the wax and the glass transition temperature of the binder resin is 0. .5 ℃ / minute Ri der below,
When the amount of the wax added to 100 parts by mass of the binder resin is A (parts by mass) and the amount of the fatty acid metal salt added to 100 parts by mass of the binder resin is B (parts by mass), the A and B are Satisfy the following relational expression
1.0 ≤ A ≤ 30.0
0.01 ≤ B / A ≤ 0.10.
The present invention relates to a method for producing a toner.

According to the present invention, it is possible to provide a toner that has excellent low-temperature fixability and does not cause adverse effects such as a decrease in concentration due to blooming of a low-melting point wax even during storage or use in a high-temperature and high-humidity environment.
In response to the request for "storage and use in a higher temperature and humidity environment that will be required in the future", in the examples described later, the temperature and humidity environment is 45 ° C./95% RH for 60 days, and the periodic high temperature is high. The effect of the present invention has been clarified by drawing out and testing a toner exposed to a harsh condition of being left in a high humidity environment for 30 days.

The toner of the present invention is a toner containing toner particles containing a binder resin, wax and a fatty acid metal salt, and the glass transition temperature measured by the differential scanning calorimeter of the binder resin is 30 ° C. or higher and 55 ° C. or lower. The melting point measured by the differential scanning calorimeter of the wax is 65 ° C. or higher and 90 ° C. or lower.

The present inventors presume the reason why the above-mentioned problems are solved in the present invention as follows.

As described above, in order to improve the low temperature fixability of the toner, it is effective to set the Tg of the binder resin low or to use a wax having a low melting point. However, when the Tg of the binder resin is set low and a wax having a low melting point is used in order to achieve further low temperature fixability, blooming of the wax may occur under the high temperature and high humidity environment required in the future. It became clear that there was sex.

In general, since wax has low motility in a temperature range below the melting point, it is predicted that the wax used in the present invention will not originally cause blooming even in a high temperature and high humidity environment that will be required in the future. Nevertheless, it is presumed that the reason why the occurrence of blooming has become a problem is that the toner contains a component that moves molecules in a temperature range lower than the melting point of the wax.

It is known that a crystalline material represented by wax moves in a lower temperature region in an amorphous state than in a crystalline state. From this, if the wax in the amorphous state is present in the toner, the component can cause blooming.

From these, the present inventors presumed that the component that moves in the temperature region lower than the melting point of the wax described above is the wax that exists in the toner in an amorphous state.

In addition, the low Tg of the binder resin is presumed to be one of the causes of blooming. Even when the wax in the amorphous state is present in the toner, if the Tg of the binder resin is high, the binder resin existing around the wax molecules will move molecularly even in the high temperature and high humidity environment required in the future. It is presumed that the occurrence of blooming is suppressed because it inhibits it. However, when the Tg of the binder resin is designed to be low, the movement of the wax molecules is not hindered because the mobility of the binder resin molecular chains is increased in the temperature range above Tg. And, as a result, wax blooming occurs.

That is, the present inventors have speculated that the wax blooming, which is the subject of the present invention, is generated by the molecular motion of the amorphous wax present in the toner in a temperature range of Tg or higher of the binder resin.

In order to solve the above problems, it is effective to set the melting point of the wax and the Tg of the binder resin to higher temperatures. However, it is difficult to achieve low temperature fixability, which is another problem of the present invention, by such means.

Therefore, the present inventors have considered that by increasing the crystallinity of the wax in the toner, it is possible to obtain a toner that suppresses the blooming of the wax and at the same time satisfies the low temperature fixability. As a result of diligent studies, it was found that the crystallinity of the wax can be increased by simultaneously containing the fatty acid metal salt in the toner having the wax having a low melting point and the binder resin having a low Tg, and completed the present invention. It was.

In the present invention, the mechanism by which the crystallinity of the wax can be increased by simultaneously containing the fatty acid metal salt in the toner having the wax having a low melting point and the binder resin having a low Tg has been completely elucidated. Absent. The present inventors presume that the fatty acid metal salt acts as a crystal nucleus in the process of wax crystallization, and the wax around it is crystallized to increase the degree of wax crystallization.

The toner of the present invention will be specifically described below.

(wax)
The wax used in the toner of the present invention has a melting point measured by a differential scanning calorimeter of 65 ° C. or higher and 90 ° C. or lower, more preferably 65 ° C. or higher and 80 ° C. or lower, and further preferably 70 ° C. or higher and 80 ° C. or lower. is there.

When the melting point measured by the differential scanning calorimeter of the wax is 65 ° C. or higher and 90 ° C. or lower, a toner that simultaneously achieves wax blooming suppression and low-temperature fixability can be obtained by a synergistic effect with other requirements of the present invention. .. Further, when the melting point measured by the differential scanning calorimeter of wax is 65 ° C. or higher and 80 ° C. or lower, the above effect is further improved, and the melting point measured by the differential scanning calorimeter of wax is 70 ° C. or higher and 80 ° C. or lower. In the case of, the above effect is further improved.

When the melting point measured by the differential scanning calorimetry of the wax is less than 65 ° C., even when the wax is crystallized in the toner, the movement of the wax molecules is likely to occur, so that blooming is sufficiently suppressed. Not preferable.

As the wax used for the toner of the present invention, a conventionally known wax can be used without any particular limitation as long as the wax has a melting point of 65 ° C. or higher and 90 ° C. or lower as measured by a differential scanning calorimeter. Specifically, the following; monofunctional ester waxes typified by behenyl behate, stearyl behate, etc .; bifunctional ester waxes typified by dibehenyl sebacate, hexanediol dibehenate, etc .; glycerin tribehe Trifunctional ester waxes represented by nate, etc .; Pentaerythritol tetrastearate, tetrafunctional ester waxes represented by pentaerythritol tetrapalmitate, etc .; Dipentaerythritol hexastearate, dipentaerythritol hexapalmitate, etc. Hexofunctional ester waxes; Polyfunctional ester waxes typified by polyglycerin behenate and the like; Natural ester waxes typified by carnauba wax, rice wax and the like; Amido waxes typified by the above; hydrocarbon waxes and derivatives thereof by the Fisher Tropsch method; petroleum waxes such as paraffin wax, microcrystallin wax, petrolatum and derivatives thereof; polyolefin waxes such as polyethylene wax and polypropylene wax and derivatives thereof; Higher aliphatic alcohols; long-chain fatty acids and the like.

Among them, since it is excellent in crystallinity, has a sharp molecular weight distribution, and has a small content of low melting point components, it is possible to suppress blooming of the wax in the present invention by using an ester wax, an amide wax, and a hydrocarbon wax produced by the Fischer-Tropsch method. The effect is improved.

Furthermore, since ester wax and amide wax have high structural similarity with fatty acid metal salts, they have a large interaction with fatty acid metal salts. Therefore, since it is easy to obtain the effect of improving the degree of crystallization when used in combination with the fatty acid metal salt, the effect of suppressing the blooming of the wax in the present invention is further improved by using the ester wax and the amide wax. In order to obtain the above effects, monofunctional saturated fatty acid ester wax and saturated fatty acid amide wax are particularly preferable.

In addition, since ester wax and amide wax have high compatibility with the binder resin in the temperature range above the melting point, the effect of plasticizing the binder resin can be obtained by being compatible with the binder resin at the time of fixing. .. Therefore, by using the ester wax and the amide wax, the low temperature fixability is improved when the process speed is high.

In the present invention, the ester wax is an ester having a ratio of 75% by mass or more in a simple substance of the ester or a mixture of the ester and a free fatty acid, a free alcohol, a hydrocarbon, or the like. That is, carnauba wax (ester ratio 80 to 85% by mass) and rice wax (ester ratio 93 to 97% by mass) are also used as ester wax.

The amount of wax added to the toner of the present invention is preferably 1.0 part by mass or more and 30.0 parts by mass or less, and 5.0 parts by mass or more and 20.0 parts by mass with respect to 100 parts by mass of the binder resin. More preferably, it is less than or equal to a part.

In addition to the wax having a melting point of 65 ° C. or higher and 90 ° C. or lower measured by the differential scanning calorimeter, the toner of the present invention has a melting point of 90 measured by the differential scanning calorimeter from the viewpoint of improving hot offset property. It can further contain waxes above ° C.

(Fatty acid metal salt)
The toner of the present invention contains a fatty acid metal salt.

When a fatty acid metal salt is contained, a toner that simultaneously achieves wax blooming suppression and low temperature fixability can be obtained by a synergistic effect with other requirements of the present invention. In particular, the inclusion of fatty acid metal salts greatly contributes to the suppression of wax blooming.

When the fatty acid metal salt is not contained, it is difficult to simultaneously suppress the blooming of the wax and the low temperature fixability as described above.

As the fatty acid metal salt used in the toner of the present invention, conventionally known fatty acid metal salts can be used without particular limitation. Specifically, the following saturated fatty acids typified by lithium laurate, lithium stearate, etc. and fatty acid metal salts consisting of monovalent metals; saturated fatty acids typified by zinc laurate, zinc stearate, calcium stearate, etc. and 2 Fatty acid metal salt composed of valent metal; fatty acid metal salt composed of saturated fatty acid represented by aluminum stearate and trivalent metal; fatty acid metal composed of unsaturated fatty acid represented by lithium oleate and monovalent metal Salts; fatty acid metal salts composed of unsaturated fatty acids typified by zinc oleate and the like and divalent metals; examples include fatty acid metal salts composed of unsaturated fatty acids typified by aluminum oleate and the like and trivalent metals. Among them, a fatty acid metal salt composed of a monovalent or divalent metal and a saturated fatty acid is preferable because it easily has a linear structure and has a large interaction with wax and has a high crystallinity improving effect on wax.

Further, the amount of the fatty acid metal salt added to the toner of the present invention is preferably 0.10 parts by mass or more and 1.00 parts by mass or less, and 0.15 parts by mass or more and 0. It is more preferably 75 parts by mass or less.

(Relationship between wax and fatty acid metal salt)
Since the interaction between the wax and the fatty acid metal salt is important in the present invention, it is preferable to use a suitable fatty acid metal salt depending on the wax type. Specifically, when the number of carbon atoms contained in one molecule of wax is C1 and the number of carbon atoms contained in one molecule of fatty acid metal salt is C2,
10 ≤ C1
10 ≤ C2
0.30 ≤ C2 / C1 ≤ 1.50
Is preferable. When the carbon number of the wax and the fatty acid metal salt satisfies the above relationship, the interaction between the wax and the fatty acid metal salt is enhanced, and the effect of the present invention is further improved. Also, more preferably
15 ≤ C1
15 ≤ C2
0.40 ≤ C2 / C1 ≤ 0.90
Is. When the carbon numbers of the wax and the fatty acid metal salt satisfy the above relationship, the crystal nucleation rate of the fatty acid metal salt is optimized, and the effect of the present invention is further improved.

When the carbon numbers of the wax and the fatty acid metal salt have a distribution, the carbon number of the component having the largest number in the above distribution is defined as the carbon number of the wax and the fatty acid metal salt.

Further, it is possible to use a monofunctional saturated fatty acid ester wax or a saturated fatty acid amide wax as the wax and a fatty acid metal salt composed of a monovalent or divalent metal and a saturated fatty acid as the fatty acid metal salt between the wax and the fatty acid metal salt. It is more preferable from the viewpoint of enhancing the interaction.

Further, when the amount of the wax added to 100 parts by mass of the binder resin is A (parts by mass) and the amount of the fatty acid metal salt added to 100 parts by mass of the binder resin is B (parts by mass).
1.0 ≤ A ≤ 30.0
0.01 ≤ B / A ≤ 0.10.
Is preferable. When the amount of the wax and the fatty acid metal salt added satisfies the above relationship, the amount of the fatty acid metal salt added is optimal with respect to the amount of wax, so that a higher crystallinity improving effect can be obtained. Also, more preferably
5.0 ≤ A ≤ 20.0
0.02 ≤ B / A ≤ 0.08
Is. When the addition amount of the wax and the fatty acid metal salt satisfies the above relationship, the above effect is further improved.

(Bundling resin)
The glass transition temperature measured by the differential scanning calorimeter of the binder resin used for the toner of the present invention is 30 ° C. or higher and 55 ° C. or lower, more preferably 35 ° C. or higher and 50 ° C. or lower.

When the glass transition temperature measured by the differential scanning calorimeter of the binder resin is 30 ° C. or higher and 55 ° C. or lower, the blooming suppression of the wax and the low temperature fixability are simultaneously achieved by the synergistic effect with the other requirements of the present invention. Toner is obtained. Further, when the glass transition temperature measured by the differential scanning calorimeter of the binder resin is 35 ° C. or higher and 50 ° C. or lower, the above effect is further improved.

As the binder resin used for the toner of the present invention, a conventionally known resin can be used without any particular limitation as long as the glass transition temperature measured by the differential scanning calorimeter is 30 ° C. or higher and 55 ° C. or lower. .. Specific examples thereof include the following; vinyl resin; polyester resin; polyamide resin; furan resin; epoxy resin; xylene resin; silicone resin and the like. These resins can be used alone or in admixture. The vinyl-based resin is a styrene-based monomer represented by styrene, α-methylstyrene, divinylbenzene, etc .; methyl acrylate, butyl acrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, t-methacrylate. Unsaturated carboxylic acid ester represented by butyl, 2-ethylhexyl methacrylate; unsaturated carboxylic acid represented by acrylic acid, methacrylic acid, etc .; unsaturated dicarboxylic acid represented by maleic acid, etc .; maleic acid anhydride, etc. Unsaturated dicarboxylic acid anhydride typified by; nitrile-based vinyl monomer typified by acrylonitrile; halogen-containing vinyl monomer typified by vinyl chloride and the like; nitro-based vinyl polymer typified by nitrostyrene and the like Monopolymers or copolymers of monomers such as meth; can be used. Above all, considering the compatibility with wax, it is preferable to use a vinyl resin.

(Polar resin)
The toner of the present invention may further contain a polar resin. Specific examples thereof include the following carboxy group-containing vinyl resins; carboxy group-containing polyester resins; carboxy group-containing polyurethane resins; and carboxy group-containing polyamide resins. The carboxy group-containing vinyl-based resin includes the following: unsaturated carboxylic acid; unsaturated dicarboxylic acid; and the like, and the above-mentioned carboxy group-containing monomer; styrene-based single amount. A copolymer of a body; an unsaturated carboxylic acid ester; an unsaturated dicarboxylic acid anhydride; a nitrile-based vinyl monomer; a halogen-containing vinyl monomer; a nitro-based vinyl monomer; or the like can be used. In the present invention, the polar resin refers to a resin containing a carboxy group in its structure. Above all, from the viewpoint of effectively suppressing the blooming of the wax, it is preferable to contain a carboxy group-containing vinyl resin or a carboxy group-containing polyester resin, and the carboxy group-containing vinyl resin and the carboxy group-containing polyester resin are contained. Is more preferable.

The content of the polar resin in the toner of the present invention is preferably 3.0 parts by mass or more and 30.0 parts by mass or less with respect to 100 parts by mass of the binder resin.

(Colorant)
The toner of the present invention may further contain a colorant. As the colorant used in the toner of the present invention, known black / yellow / magenta / cyan colors and other color pigments, dyes, magnetic substances and the like can be used without particular limitation.

As the black colorant, specifically, a black pigment typified by carbon black or the like is used.

Specific examples of the yellow colorant include the following monoazo compounds; disazo compounds; condensed azo compounds; isoindolin compounds; isoindolinone compounds; benzimidazolone compounds; anthracinone compounds; azo metal complexes; methine compounds; allylamide compounds. Examples thereof include yellow pigments and yellow dyes typified by the above.

Specific examples of the magenta colorant include the following monoazo compounds; condensed azo compounds; diketopyrrolopyrrole compounds; anthraquinone compounds; quinacridone compounds; base dye lake compounds; naphthol compounds: benzimidazolone compounds; thioindigo compounds; perylene compounds. Examples thereof include magenta pigments and magenta dyes typified by the above.

Specific examples of the cyan colorant include the following copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds; cyan pigments and cyan dyes typified by basic dye lake compounds and the like.

Further, the toner of the present invention can be made into a magnetic toner by containing a magnetic material as a colorant. In this case, the magnetic material can also serve as a colorant. Examples of magnetic materials include the following iron oxides typified by magnetite, hematite, ferrite, etc .; metals typified by iron, cobalt, nickel, etc. or these metals and aluminum, cobalt, copper, lead, magnesium, tin, zinc. , Antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium and other alloys with metals and mixtures thereof.

The content of the colorant in the toner of the present invention is preferably 3.0 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the binder resin.

(Charge control agent)
The toner of the present invention may further contain a charge control agent. As the charge control agent used for the toner of the present invention, a conventionally known charge control agent can be used without any particular limitation. Specifically, the following metal complexes of aromatic carboxylic acids typified by salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid, dicarboxylic acid and the like as negative charge control agents; sulfonic acid groups, sulfonic acid bases or sulfonic acids. Polymers or copolymers having an ester group; metal salts or metal complexes of azo dyes or azo pigments; boron compounds, silicon compounds, calix arenes and the like. In addition, examples of the positive charge control agent include the following polymer compounds having a quaternary ammonium salt and a quaternary ammonium salt in the side chain; a guanidine compound; a niglosin compound; an imidazole compound and the like. Examples of the polymer or copolymer having a sulfonic acid base or a sulfonic acid ester group include styrene sulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, 2-methacrylamide-2-methylpropanesulfonic acid, and vinylsulfone. Use a homopolymer of a sulfonic acid group-containing vinyl-based monomer represented by an acid, methacrylsulfonic acid, etc., or a copolymer of the vinyl-based monomer shown in the section of binder resin and the above-mentioned sulfonic acid group-containing vinyl-based monomer. Can be done.

The content of the charge control agent in the toner of the present invention is preferably 0.01 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the binder resin.

(External additive)
The toner of the present invention may contain an external additive for the purpose of improving fluidity and stabilizing charge. As the external additive used in the toner of the present invention, a conventionally known external additive can be used without any particular limitation. Specifically, the following; raw silica fine particles typified by wet manufacturing silica, dry manufacturing silica, etc., or the surface of these raw silica fine particles with a silane coupling agent, a titanium coupling agent, a treatment agent typified by silicone oil, etc. Treated silica fine particles; metal oxide fine particles typified by titanium oxide fine particles, aluminum oxide fine particles, zinc oxide fine particles, etc. or metal oxide fine particles obtained by hydrophobizing the above metal oxides; zinc stearate, calcium stearate, stear Fatty acid metal salts such as zinc acid acid; metal complexes of aromatic carboxylic acids such as salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid, and dicarboxylic acid; clay minerals such as hydrotalcite; fluorine Examples thereof include fluorine-based resin fine particles typified by vinylidene fine particles and polytetrafluoroethylene fine particles. Above all, from the viewpoint of simultaneously achieving fluidity, charge stability and suppression of blooming of wax, it is preferable to use silica fine particles obtained by treating the original silica fine particles with silicone oil and then further treating with silane or silazane.

The content of the external additive in the toner of the present invention is preferably 0.5 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the toner particles.

Subsequently, the method for producing the toner used in the present invention will be specifically described below.

As the method for producing the toner of the present invention, a conventionally known method can be used without any particular limitation. Specific examples thereof include a suspension polymerization method; a dissolution suspension method; an emulsification / aggregation method; a spray dry method; a pulverization method and the like. Above all, it is preferable to use the suspension polymerization method or the dissolution suspension method because the blooming of the wax can be effectively suppressed by including the wax.

When the toner of the present invention is obtained by the suspension polymerization method, a colorant and, if necessary, a polar resin, a wax, a charge control agent and other materials are uniformly dissolved or dispersed in the polymerizable monomer to make the toner polymerizable. It is a monomer composition. Then, this polymerizable monomer composition is dispersed in an aqueous medium containing a dispersion stabilizer, if necessary, using an appropriate stirrer. Then, by polymerizing the polymerizable monomer, toner particles having a desired particle size are obtained. After the polymerization is completed, the toner particles are filtered, washed, dried and classified by a known method, and if necessary, a fluidity improver is mixed and adhered to the surface to obtain the toner of the present invention.

Examples of the polymerizable monomer when the toner of the present invention is obtained by the suspension polymerization method include the vinyl-based monomer shown in the section of the binder resin.

When the toner of the present invention is obtained by the suspension polymerization method, a polymerization initiator may be further used. As the polymerization initiator used in the production of the toner of the present invention, a known polymerization initiator can be used without particular limitation. Specifically, the following; 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile) ), 2,2'-Azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile, and other azo or diazo polymerization initiators; benzoyl peroxide, t-butylperoxy 2-Ethylhexanoate, t-butylperoxypivalate, t-butylperoxyisobutyrate, t-butylperoxyneodecanoate, methylethylketone peroxide, diisopropylperoxycarbonate, cumenehydroper Examples thereof include peroxide-based polymerization initiators typified by oxides, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide and the like.

When the toner of the present invention is obtained by the suspension polymerization method, a known chain transfer agent, polymerization inhibitor and the like can be used.

When the toner of the present invention is obtained by the suspension polymerization method, an inorganic or organic dispersion stabilizer may be further contained in the aqueous medium. As the dispersion stabilizer, a known dispersion stabilizer can be used without any particular limitation. Specifically, as an inorganic dispersion stabilizer, the following phosphates typified by hydroxyapatite, calcium triphosphate, calcium dibasic phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, etc .; calcium carbonate, magnesium carbonate, etc. Carbonates represented by; metal hydroxides represented by calcium hydroxide, magnesium hydroxide, aluminum hydroxide, etc .; sulfates represented by calcium sulfate, barium sulfate, etc., calcium metasilicate, bentonite, silica, alumina And so on. Examples of the organic dispersion stabilizer include the following polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, polyacrylic acid and its salt, starch and the like.

When the toner of the present invention is obtained by the suspension polymerization method, a surfactant may be further contained in the aqueous medium. As the surfactant, a known surfactant can be used without any particular limitation. Specific examples thereof include anionic surfactants typified by sodium dodecylbenzene sulfate, sodium oleate and the like; cationic surfactants; amphoteric surfactants; nonionic surfactants; and the like.

When an inorganic compound is used as the dispersion stabilizer, a commercially available one may be used as it is, or the above-mentioned inorganic compound may be generated and used in an aqueous medium in order to obtain finer particles. For example, in the case of calcium phosphates such as hydroxyapatite and tricalcium phosphate, it is preferable to mix the phosphate aqueous solution and the calcium salt aqueous solution under high stirring.

Further, in the method for producing a toner of the present invention, there is a step of lowering the temperature from a temperature equal to or higher than the melting point of the wax to a temperature lower than the glass transition temperature of the binding resin in a state where the binder resin, wax and fatty acid metal salt are present at the same time. In this case, the average temperature lowering rate between the melting point of the wax and the glass transition temperature of the binder resin is preferably 1.0 ° C./min or less. When the average temperature lowering rate between the melting point of the wax and the glass transition temperature of the binder resin is 1.0 ° C./min or less, the crystallization of the wax can be further promoted.

Subsequently, the measuring method of the present invention will be specifically described below.

(Method of measuring the melting point of wax with a differential scanning calorimeter)
The peak temperature of the maximum endothermic peak of wax is measured according to ASTM D3418-82 using a differential scanning calorimetry device "Q1000" (manufactured by TA Instruments).

The melting points of indium and zinc are used for temperature correction of the device detector, and the heat of fusion of indium is used for the correction of calorific value. Specifically, about 3 mg of wax is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference, and the temperature rise rate is 10 in the measurement temperature range of 30 to 200 ° C. Measure at ° C / min. In the measurement, the temperature is raised to 200 ° C., then lowered to 30 ° C., and then raised again. The maximum endothermic peak of the DSC curve in the temperature range of 30 to 200 ° C. in the second temperature raising process is defined as the melting point of the wax of the present invention by the differential scanning calorimeter.

(Measurement method of glass transition temperature of binder resin by differential scanning calorimeter)
The glass transition temperature of the binder resin is measured according to ASTM D3418-82 using a differential scanning calorimeter "Q1000" (manufactured by TA Instruments).

The melting points of indium and zinc are used for temperature correction of the device detector, and the heat of fusion of indium is used for the correction of calorific value.

Specifically, about 3 mg of the binder resin is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference, and the temperature rise rate is 10 ° C. in the measurement range of 30 to 200 ° C. Measure at / min. In this temperature raising process, a change in specific heat is obtained in the temperature range of 40 ° C. to 100 ° C. The intersection of the line at the midpoint of the baseline before and after the specific heat change at this time and the differential thermal curve is defined as the glass transition temperature of the binder resin.

(Measuring method of weight average particle size (D4) and number average particle size (D1) of toner)
The weight average particle size (D4) and the number average particle size (D1) of the toner are calculated as follows. As the measuring device, a precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter) equipped with a 100 μm aperture tube by the pore electrical resistance method is used. For the setting of measurement conditions and the analysis of measurement data, the attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter) is used. The measurement is performed with 25,000 effective measurement channels.

As the electrolytic aqueous solution used for the measurement, a special grade sodium chloride dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter) can be used.

Before performing the measurement and analysis, the dedicated software was set as follows.

On the "Change standard measurement method (SOMME)" screen of the dedicated software, set the total count number in the control mode to 50,000 particles, measure once, and set the Kd value to "standard particles 10.0 μm" (Beckman Coulter). Set the value obtained using (manufactured by the company). By pressing the "threshold / noise level measurement button", the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, and the electrolyte to ISOTON II, and check “Flash of aperture tube after measurement”.

On the "Pulse to particle size conversion setting" screen of the dedicated software, the bin spacing is set to logarithmic particle size, the particle size bin is set to 256 particle size bins, and the particle size range is set from 2 μm to 60 μm.

The specific measurement method is as follows.
(1) Approximately 200 ml of the electrolytic aqueous solution is placed in a glass 250 ml round bottom beaker dedicated to Multisizer 3 and set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and air bubbles in the aperture tube are removed by the "aperture flash" function of the dedicated software.
(2) Put about 30 ml of the electrolytic aqueous solution in a 100 ml flat bottom beaker made of glass. Among them, as a dispersant, "Contaminone N" (a 10% by mass aqueous solution of a neutral detergent for cleaning a precision measuring instrument with a pH of 7 consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd. ) Is diluted about 3 times by mass with ion-exchanged water, and about 0.3 ml of the diluted solution is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are built in with their phases shifted by 180 degrees, and an ultrasonic disperser "Ultrasonic Dispersion System Tera150" (manufactured by Nikkaki Bios Co., Ltd.) having an electrical output of 120 W is prepared. Approximately 3.3 liters of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 ml of contaminantinon N is added into the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker is maximized.
(5) With the electrolytic aqueous solution in the beaker of (4) being irradiated with ultrasonic waves, about 10 mg of toner is added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion processing is continued for another 60 seconds. In ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10 ° C. or higher and 40 ° C. or lower.
(6) Using a pipette, the aqueous electrolyte solution of (5) in which toner is dispersed is dropped onto the round-bottom beaker of (1) installed in the sample stand, and the measured concentration is adjusted to about 5%. .. Then, the measurement is performed until the number of measurement particles reaches 50,000.
(7) The measurement data is analyzed by the dedicated software attached to the device, and the weight average particle size (D4) and the number average particle size (D1) are calculated. The "average diameter" of the "analysis / volume statistical value (arithmetic mean)" screen when the graph / volume% is set with the dedicated software is the weight average particle size (D4), and the graph / volume is set with the dedicated software. The "average diameter" of the "analysis / number statistical value (arithmetic mean)" screen when the number% is set is the number average particle size (D1).

The toner of the present invention can be used in a conventionally known image forming method without any particular limitation. Specific examples thereof include a non-magnetic one-component contact development method, a magnetic one-component jumping development method, and a two-component development method.

The present invention will be specifically described with reference to the following examples. However, this does not limit the present invention in any way. Examples 5 , 6, 13 , 22, 27 , 36 to 38 are reference examples.

<Wax production example>
(Production example of wax 1)
300 parts by mass of toluene was placed in a 1 liter round bottom three-necked flask equipped with a stirrer, a thermometer and a reflux tube, and the mixture was refluxed at 120 ° C.

-Behenic acid 100.00 parts by mass-Behenyl alcohol 96.00 parts by mass-p-toluenesulfonic acid 0.50 parts by mass The above materials were added under reflux, and the esterification reaction was allowed to proceed at 120 ° C. for 6 hours. During this period, the water produced was removed from the system by azeotropic toluene / water. After completion of the reaction, p-toluenesulfonic acid was neutralized with sodium hydrogen carbonate. Toluene was removed by evaporation of the resulting solution. The product was heated to 90 ° C. and then filtered through Celite to remove sodium p-toluenesulfonate to obtain wax 1. The melting point and carbon number of wax 1 are shown in Table 1.

(Production example of wax 2)
In the production example of wax 1, wax 2 was obtained in the same manner as in the production example of wax 1 except that behenyl alcohol: 96.00 parts by mass was changed to stearyl alcohol: 79.40 parts by mass. The melting point and carbon number of wax 2 are shown in Table 1.

(Production example of wax 3)
In the production example of wax 1, wax 3 was obtained in the same manner as in the production example of wax 1 except that behenic acid was changed to stearic acid and behenic alcohol was changed to stearyl alcohol. The melting point and carbon number of wax 3 are shown in Table 1.

(Wax 4 to Wax 12)
As the wax 4 to 12, the commercially available waxes shown in Table 1 were used. Table 1 shows the melting points and the number of carbon atoms of the waxes 4 to 12.

<Production example of silica fine particles>
(Production example of silica fine particles 1)
25.0 parts by mass of dimethyl silicone oil (viscosity = 100 mm ² / s) was sprayed on 100 parts by mass of fumed silica (trade name AEROSIL200, average number of primary particles 12 nm, manufactured by Nippon Aerosil Co., Ltd.) for 30 minutes. Stirring was continued. Then, the temperature was raised to 300 ° C. with stirring, and the mixture was further stirred for 2 hours to bake dimethyl silicone oil on the surface of fumed silica, and the reaction was terminated to obtain silica fine particles 1.

(Production example of silica fine particles 2)
As the first treatment step, 8.0 parts by mass of dimethyl silicone oil (viscosity = 100 mm ² / s) with respect to 100 parts by mass of fumed silica (trade name: AEROSIL200, average number of primary particles: 12 nm, manufactured by Nippon Aerosil Co., Ltd.). Was sprayed and stirring was continued for 30 minutes. Then, the temperature was raised to 300 ° C. with stirring, and the mixture was further stirred for 2 hours to bake dimethyl silicone oil on the surface of fumed silica, and the reaction was completed.

As the second treatment step, 40.0 parts by mass of hexamethyldisilazane was sprayed inside the silica fine particles produced in the first treatment step, and the silica compound was treated in a fluidized state of silica. After continuing this reaction for 60 minutes, the reaction was terminated to obtain silica fine particles 2.

(Production example of silica fine particles 3)
As the first treatment step, 40.0 parts by mass of hexamethyldisilazane is sprayed inside 100 parts by mass of fumed silica (trade name AEROSIL200, average number of primary particles 12 nm, manufactured by Nippon Aerosil Co., Ltd.) to obtain silica. The silica compound treatment was performed in the fluidized state. After continuing this reaction for 60 minutes, the reaction was terminated.

As the second treatment step, 8.0 parts by mass of dimethyl silicone oil (viscosity = 100 mm ² / s) was sprayed on the silica fine particles produced in the first treatment step, and stirring was continued for 30 minutes. Then, the temperature was raised to 300 ° C. with stirring, and the mixture was further stirred for 2 hours to bake dimethyl silicone oil on the surface of fumed silica, and the reaction was completed to obtain silica fine particles 3.

<Manufacturing example of toner 1>
Suspension polymerization toner was produced by the following method.

The following materials were mixed and stirred for 2 hours to dissolve the polar resin to obtain a polar resin-containing monomer composition.
-Styrene 37.00 parts by mass-n-butyl acrylate 27.00 parts by mass-Polar resin 1 Vinyl-based polar resin [styrene / methyl methacrylate / methacrylic acid / -2-hydroxyethyl methacrylate copolymer: Mw = 14000 , Mn = 6000, Mp = 14000, Tg = 92 ° C., Av (acid value) = 20 mgKOH / g, OHv (hydroxyl value) = 10 mgKOH / g] 10.00 parts by mass · Charge control agent Bontron E-88 (Orient Chemistry) 1.00 parts by mass

Further, the following materials were mixed and stirred with zirconia beads (3/16 inch) at 200 rpm for 3 hours with an attritor (manufactured by Mitsui Mining Co., Ltd.) to separate the beads to obtain a colorant dispersion.
-Styrene 36.00 parts by mass-Colorant C. I. Pigment Blue 15: 3 (manufactured by Dainichiseika Co., Ltd.)
6.00 parts by mass, fatty acid metal salt Zinc stearate (zinc stearate: manufactured by Nichiyu Co., Ltd.) 0.25 parts by mass

Then
-Polar resin-containing monomer composition 75.00 parts by mass-Colorant dispersion liquid 42.25 parts by mass The above materials were mixed. The mixture was subsequently heated to 60 ° C. and 10.00 parts by mass of wax 1 was added. Next, 5.0 parts by mass of the polymerization initiator Perbutyl O (manufactured by NOF CORPORATION) was added, and the mixture was stirred for 5 minutes to obtain a polymerizable monomer composition.

On the other hand, the addition of 0.1mol / L-Na ₃ PO ₄ aqueous solution 850 parts by mass and 10% hydrochloric acid 8.0 parts by weight in a container equipped with a high speed stirrer CLEARMIX (manufactured by M Technique Co., Ltd.), the rotational speed It was adjusted to 15000 rpm and heated to 60 ° C. 68 parts by mass of a 1.0 mol / L-CaCl ₂ aqueous solution was added thereto to prepare an aqueous medium containing a minute water-insoluble dispersant Ca ₃ (PO ₄ ) ₂ .

Five minutes after the addition of the polymerization initiator, the polymerizable monomer composition at 60 ° C. was charged into an aqueous medium heated to a temperature of 60 ° C., and Clairemix was granulated for 15 minutes while rotating at 15000 rpm. Then, the stirrer was changed from a high-speed stirrer to a propeller stirring blade, and the mixture was reacted at 70 ° C. for 5 hours while refluxing, and then the liquid temperature was adjusted to 80 ° C. and further reacted for 5 hours to complete the polymerization reaction. After completion of the polymerization, distillation was carried out at a liquid temperature of 95 ° C. for 4 hours while blowing heated steam. After completion of the distillation, the liquid temperature was lowered to 20 ° C. at a rate of 0.5 ° C. for 1 minute. Dilute hydrochloric acid was added to set the pH of the aqueous medium to 2.0 or less, and the poorly water-soluble dispersant was dissolved. Further, filtration, washing, drying and classification were performed to obtain toner particles 1.

Then
-Toner particles 1 100.00 parts by mass-Silica fine particles 1 1.00 parts by mass The above materials were mixed at 4000 rpm for 5 minutes using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) to obtain toner 1. Table 4 shows the physical properties of the toner 1. Regarding the glass transition temperature of the binder resin, the resin obtained by similarly producing the material excluding wax, fatty acid metal salt, colorant and vinyl polar resin in the above-mentioned production example of toner 1. The glass transition temperature was measured and used as the glass transition temperature of the binder resin.

<Manufacturing example of toner 2 to toner 24>
Toners 2 to 24 were obtained in the same manner as in the production example of toner 1 except that the wax and the fatty acid metal salt used in the production example of toner 1 were changed to those shown in Table 4. As the fatty acid metal salt, those shown in Table 2 were used. Table 4 shows the physical properties of the toners 2 to 24.

<Manufacturing example of toner 25 to toner 30>
In the production example of the toner 1, the toner 25 to the toner is the same as in the production example of the toner 1 except that the addition amount of the monomer contained in the polar resin-containing monomer composition is changed to the one shown in Table 3. I got 30. Table 4 shows the physical properties of the toner 25 to the toner 30.

<Manufacturing example of toner 31>
In the production example of toner 1, the toner 31 was obtained in the same manner as in the production example of toner 1 except that the temperature lowering rate after the completion of distillation was changed from 0.5 ° C./min to 5.0 ° C./min. Table 4 shows the physical properties of the toner 31.

<Manufacturing example of toner 32>
In the production example of the toner 21, the toner 32 was obtained in the same manner as in the production example of the toner 21 except that the temperature lowering rate after the completion of distillation was changed from 0.5 ° C./min to 5.0 ° C./min. Table 4 shows the physical properties of the toner 32.

<Manufacturing example of toner 33 to toner 45>
Toner 33 to toner 45 were obtained in the same manner as in the production example of toner 8 except that the polar resin and silica fine particles used in the production example of toner 8 were changed to those shown in Table 4. The polar resin 2 includes the following polyester-based polar resins [produced from terephthalic acid and PO-modified bisphenyl A: Mp = 9000, Tg = 72 ° C., acid value = 12.0 mgKOH / g].
Was used.

Table 4 shows the physical properties of the toners 33 to 45.

<Manufacturing example of toner 46>
A dissolved suspended toner was produced by the following method.

(Production example of wax dispersion)
・ Wax 2 100.00 parts by mass ・ Fatty acid metal salt 1 2.50 parts by mass ・ Ethyl acetate 97.50 parts by mass Attritor (manufactured by Mitsui Mining Co., Ltd.) containing zirconia beads (3/16 inch) mixed with the above materials. ) And dispersed at 150 rpm for 2 hours. Zirconia beads were separated to obtain a wax dispersion.

(Production example of colorant dispersion)
-Colorant C. I. Pigment Blue 15: 3 (manufactured by Dainichiseika Co., Ltd.)
18.00 parts by mass and 72.00 parts by mass of ethyl acetate were added, and the mixture was rotated at a rotation speed of 300 rpm for 8 hours. Zirconia beads were separated to obtain a colorant dispersion.

(Toner manufacturing example)
Bending resin n-butyl copolymer styrene-acrylate 100.00 parts by mass (n-butyl copolymer styrene-acrylate = 73.00: 27.00, Tg = 40 ° C)
-Polar resin 1 10.00 parts by mass-Wax dispersion 20.00 parts-Colorant dispersion 30.00 parts-Charge control agent Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) 1.00 parts by mass uniformly It was mixed to form a toner composition.

On the other hand, the addition of 0.1mol / L-Na ₃ PO ₄ aqueous solution 850 parts by mass and 10% hydrochloric acid 8.0 parts by weight in a container equipped with a high speed stirrer CLEARMIX (manufactured by M Technique Co., Ltd.), the rotational speed It was adjusted to 15000 rpm and heated to 60 ° C. 68 parts by mass of a 1.0 mol / L-CaCl ₂ aqueous solution was added thereto to prepare an aqueous medium containing a minute water-insoluble dispersant Ca ₃ (PO ₄ ) ₂ .

The toner composition was put into the aqueous medium and granulated for 2 minutes while maintaining the aqueous medium at 60 ° C. and the rotation speed of 15000 rpm. Then, 500 parts by mass of ion-exchanged water was added. Then, the device was changed to a normal propeller agitator, and distillation was performed at a liquid temperature of 95 ° C. for 4 hours while blowing heated steam. After completion of the distillation, the liquid temperature was lowered to 20 ° C. at a rate of 0.5 ° C. for 1 minute. Dilute hydrochloric acid was added to set the pH of the aqueous medium to 2.0 or less, and the poorly water-soluble dispersant was dissolved. Further, filtration, washing, drying and classification were performed to obtain toner particles 46.

Then
Toner particles 46 100.00 parts by mass and silica fine particles 11.00 parts by mass The above materials were mixed at 4000 rpm for 5 minutes using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) to obtain toner 46. Table 4 shows the physical properties of the toner 46.

<Manufacturing example of toner 47>
An emulsified aggregated toner was produced by the following method.

(Preparation of resin fine particle dispersion)
The following materials were mixed in a flask to prepare an aqueous medium.
-Ion-exchanged water 500.00 parts by mass-Nonionic surfactant Nonipol 400 (manufactured by Kao) 6.00 parts by mass-Anionic surfactant Neogen SC (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 10.00 parts by mass In addition, the following The materials of the above were mixed to obtain a mixed solution.
73.00 parts by mass of styrene ・ 27.00 parts by mass of n-butyl acrylate ・ 1.00 parts by mass of charge control agent Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) Disperse and emulsify the above mixed solution in the above aqueous medium. Then, while slowly stirring and mixing for 10 minutes, 50 parts by mass of an ion exchange aqueous solution in which 4 parts by mass of ammonium persulfate was dissolved was added as a polymerization initiator. Then, after sufficiently replacing the inside of the system with nitrogen, the flask was heated in an oil bath with stirring until the temperature inside the system reached 70 ° C., and emulsion polymerization was continued as it was for 5 hours. As a result, an anionic resin fine particle dispersion was obtained. The glass transition temperature of the obtained anionic resin fine particles was defined as the glass transition temperature of the binder resin.

(Preparation of colorant particle dispersion)
-Ion-exchanged water 100.00 parts by mass-Colorant C. I. Pigment Blue 15: 3 (manufactured by Dainichiseika Co., Ltd.) 6.00 parts by mass, nonionic surfactant Nonipol 400 (manufactured by Kao) 1.00 parts by mass The above components are mixed and dissolved, and Ultratarax T50 (manufactured by IKA) For 10 minutes, a colorant particle dispersion was obtained.

(Preparation of wax particle dispersion)
・ Ion-exchanged water 100.00 parts by mass ・ Wax 2 10.00 parts by mass ・ Fatty acid metal salt 1 0.25 parts by mass ・ Cationic surfactant Sanizol B50 (manufactured by Kao) 5.00 parts by mass The temperature of the above components is 95 ° C. After sufficiently dispersing with Ultratalax T50, the mixture was dispersed with a pressure discharge homogenizer to obtain a wax particle dispersion.

(Preparation of polar resin fine particle dispersion)
-Ion-exchanged water 100.00 parts by mass-Ethyl acetate 50.00 parts by mass-Polar resin 1 10.00 parts by mass The above components were mixed and stirred. While emulsifying the solution with Ultratarax T50, the solvent was removed by heating at a temperature of 80 ° C. and holding for 6 hours to obtain a polar resin fine particle dispersion.

(Preparation of toner particles)
The resin fine particle dispersion, the colorant particle dispersion, the wax particle dispersion, and 1.2 parts by mass of polyaluminum chloride are mixed and sufficiently mixed using Ultratarax T50 in a round stainless steel flask. After the particles were dispersed, the flask was heated to a temperature of 51 ° C. while stirring in a heating oil bath. After holding at a temperature of 51 ° C. for 60 minutes, the polar resin fine particle dispersion was added thereto. Then, after adjusting the pH in the system to 6.5 using an aqueous sodium hydroxide solution having a concentration of 0.5 mol / L, the stainless flask was sealed, the stirring shaft was magnetically sealed, and stirring was continued. It was heated to a temperature of 95 ° C. and held for 6 hours.

After completion of the reaction, the mixture was cooled to 20 ° C. at a rate of 0.5 ° C./min and filtered, washed, dried and classified to obtain toner particles 47.

Then
Toner particles 47 100.00 parts by mass and silica fine particles 11.00 parts by mass The above materials were mixed at 4000 rpm for 5 minutes using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) to obtain toner 47. Table 4 shows the physical properties of the toner 47.

<Manufacturing example of toner 48>
A pulverized toner was produced by the following method.
Bending resin n-butyl copolymer styrene-acrylate 100.00 parts by mass (n-butyl copolymer styrene-acrylate = 73.00: 27.00, Tg = 40 ° C)
-Colorant C. I. Pigment Blue15: 3 6.00 parts by mass, charge control agent Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) 1.00 parts by mass, wax 2 10.00 parts by mass, fatty acid metal salt 1 0.25 parts by mass Melt the above material After kneading, the mixture was cooled at a rate of 0.5 ° C./min. After that, pulverization is performed, and 10.0 parts by mass of resin fine particles (number average particle diameter: 300 nm) of polar resin 1 are further added and treated with a hybridization system (manufactured by Nara Machinery Co., Ltd.) to obtain toner particles 48. It was.

Then
-Toner particles 48 100.00 parts by mass-Silica fine particles 11.00 parts by mass The above materials were mixed at 4000 rpm for 5 minutes using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) to obtain toner 48. Table 4 shows the physical properties of the toner 48.

[Examples 1 to 38, and Comparative Examples 1 to 10]
The evaluation described below was performed using the toners 1 to 48. The results are shown in Tables 5 and 6.

As the image forming apparatus, a commercially available laser printer LBP-7700C (manufactured by Canon) and a process cartridge toner cartridge 323 (cyan) (manufactured by Canon) were used. The product toner was removed from the inside of the cartridge, cleaned by air blowing, and then filled with 100 g of the toner of the present invention.

<1. Evaluation of low temperature fixability>
<1-1 Fixing temperature>
The toner-filled process cartridge was left in a room temperature and humidity environment (23 ° C./50% RH: hereinafter also referred to as N / N environment) for 48 hours. After that, an unfixed image of an image pattern in which 9 points of 10 mm × 10 mm square images were evenly arranged on the entire transfer paper was output. The toner loading amount on the transfer paper was 0.50 mg / cm ² , and the fixing start temperature was evaluated. As the transfer material, Fox River Bond (90 g / m ² ) was used. As the fuser, an external fuser made by removing the fuser of LBP-7700C (manufactured by Canon) to the outside and operating outside the laser beam printer was used. The external fuser made it possible to arbitrarily set the fixing temperature, and the process speed was measured under the fixing condition of 160 mm / sec.

In addition, the determination of the start of fixing is made by applying a load of 50 g / cm ² (4.9 kPa) to the fixed image (including the image offset at low temperature) and applying a load of Sylbon paper [Lens Cleaning Paper “dasper (R)” (Ozu Paper Co. Ltd.). )], And the temperature at which the rate of decrease in concentration before and after rubbing is less than 20% is defined as the fixing start point. The judgment criteria are shown below.
A: Fixing start point is 130 ° C or lower B: Fixing start point is higher than 130 ° C and 140 ° C or lower C: Fixing start point is higher than 140 ° C and 150 ° C or lower D: Fixing start point is higher than 150 ° C high

<1-2 Dependence of fixing temperature on process speed>
The same unfixed image was output under the same conditions as 1-1. As the fuser, an external fuser made by removing the fuser of LBP-7700C (manufactured by Canon) to the outside and operating outside the laser beam printer was used. The process speed of the external fuser could be set arbitrarily, and the measurement was performed under fixing conditions of a fixing temperature of 150 ° C. As in 1-1, the fixing start is determined by applying a load of 50 g / cm ² to the fixed image (including the image offset at low temperature) and using Sylbon paper [Lens Cleaning Paper “dasper (R)” (Ozu Paper Co. Ltd)). ], And the temperature at which the rate of decrease in concentration before and after rubbing is less than 20% is defined as the fixing start point. The judgment criteria are shown below.
A: Fixing start point is 240 mm / sec or more B: Fixing start point is 200 mm / sec or more and less than 240 mm / sec C: Fixing start point is 160 mm / sec or more and less than 200 mm / sec D: Fixing start point is Less than 160 mm / sec

<2. Decrease in concentration due to wax blooming>
High temperature and high humidity environment (45 ° C / 95% RH) and periodic high temperature and high humidity environment (heat up from 25 ° C to 50 ° C in 11 hours, hold at 55 ° C for 1 hour, cool down to 25 ° C in 11 hours, 1 at 25 ° C The process cartridge filled with toner was left for 60 days in a high temperature and high humidity environment and for 30 days in a periodic high temperature and high humidity environment.) The humidity was adjusted to 95% RH repeatedly.

After that, the process cartridge was moved to a normal temperature and humidity environment (23 ° C./50% RH; N / N) and a low temperature and low humidity environment (15 ° C./10% RH; L / L), and LBP-7700C (manufactured by Canon) was used. Then, as a sample image for density evaluation, a sample image in which a solid black image of 20 mm square was printed at the four corners and the center of the paper surface was output to Canon color laser copy paper (A4: 81.4 g / m ² ). After outputting the sample image, 200 images with a printing rate of 1% were output. After that, a sample image for density evaluation was output in the same manner. The density of the obtained sample image for density evaluation was measured, and the density change before and after the output of 200 sheets was evaluated.

The density of the image was determined as the average value of the densities of the five solid black portions of the sample image. To measure the image density, use the "Macbeth Reflection Densitometer RD918" (manufactured by Macbeth) and measure the relative density of the white background with an image density of 0.00 according to the attached instruction manual. The relative density obtained was taken as the value of the image density.

It is known that when wax blooming occurs, the concentration decreases in the above evaluation.

The judgment criteria are shown below.
A: Concentration decrease is 0.05 or less B: Concentration decrease is more than 0.05 and less than 0.10 C: Concentration decrease is more than 0.10 and less than 0.15 D: Concentration decrease is more than 0.15

Claims (3)

A method for producing a toner containing toner particles containing a binder resin, a wax, and a metal salt of a fatty acid.
The glass transition temperature measured by the differential scanning calorimeter of the binder resin is 30 ° C. or higher and 55 ° C. or lower.
The melting point measured by the differential scanning calorimeter of the wax is 65 ° C. or higher and 90 ° C. or lower.
When the fatty acid metal salt is a fatty acid metal salt composed of a monovalent or divalent metal and a fatty acid, the number of carbon atoms contained in one molecule of the wax is C1, and the number of carbon atoms contained in one molecule of the fatty acid metal salt is C2. , C1 and C2 satisfy the following relational expression,
10 ≤ C1
10 ≤ C2
0.30 ≤ C2 / C1 ≤ 1.50
In the production method, a polymerizable monomer composition obtained by dissolving or dispersing a colorant, a polar resin, and a wax in a polymerizable monomer is dispersed in an aqueous medium to obtain the polymerizable monomer. step polymerization to generate the binder resin, distillation, the binder resin, the wax and the fatty acid metal salt to obtain the toner particles by a suspension polymerization method including the step of temperature descending in the presence at the same time Have,
The temperature drop is from a temperature equal to or higher than the melting point of the wax to a temperature lower than the glass transition temperature of the binder resin, and the average temperature drop rate between the melting point of the wax and the glass transition temperature of the binder resin is 0. .5 ℃ / minute Ri der below,
When the amount of the wax added to 100 parts by mass of the binder resin is A (parts by mass) and the amount of the fatty acid metal salt added to 100 parts by mass of the binder resin is B (parts by mass), the A and B are Satisfy the following relational expression
1.0 ≤ A ≤ 30.0
0.01 ≤ B / A ≤ 0.10.
A method for producing toner, which is characterized by the fact that. The method for producing a toner according to claim 1, wherein the wax is an ester wax or an amide wax. The fatty acid metal salt is a fatty acid metal salt composed of a monovalent or divalent metal and a saturated fatty acid.
The method for producing a toner according to claim 1 or 2, wherein the wax is a monofunctional saturated fatty acid ester wax or a saturated fatty acid amide wax.