JP5671993B2 - Method for producing toner for developing electrostatic image and toner - Google Patents

Description

  The present invention relates to a toner for developing an electrostatic image and a method for producing the same, and is capable of providing both stable low-temperature fixability and anti-blocking property, excellent gloss, and excellent production stability and stable quality. The present invention relates to a method for producing a toner for developing an electrostatic image and a toner.

  The toner for developing an electrostatic charge image is used for image formation for visualizing an electrostatic charge image in a printer, a copying machine, a facsimile, or the like. For example, when an image is formed by electrophotography, an electrostatic latent image is first formed on a photosensitive drum, then developed with toner, transferred to transfer paper, and fixed by heat or the like. Image formation is performed. As a toner for developing an electrostatic image at that time, usually, a binder resin and a colorant are dry-mixed with a charge control agent, a release agent, a magnetic material, etc., if necessary, and then melt-kneaded with an extruder or the like. Then, for the purpose of imparting various performances such as fluidity to the toner particles obtained by the so-called melt-kneading pulverization method, which is then pulverized and classified, solid fine particles such as silica were adhered to the surface as external additives. The form is used.

  In recent years, high-definition image quality has been required in image formation for copying machines and printers, and in order to meet this demand, the average particle size of toner particles must be about 3 to 8 μm and the particle size distribution must be narrow. In the melt-kneading pulverization method, it is difficult to control the particle size of the toner particles, and when trying to obtain toner particles having an average particle size in the range of 3 to 8 μm, a large amount of fine powder having a desired particle size or less is produced as a by-product, There was a problem that it was difficult to classify this in the classification process.

As a method for improving such problems in the melt-kneading pulverization method, a production method by a polymerization method such as a suspension polymerization method, an emulsion polymerization aggregation method, or a dissolution suspension method has been proposed instead of the melt-kneading pulverization method. .
The suspension polymerization method is a method for producing toner particles by suspending and dispersing a composition containing a polymerizable monomer, a polymerization initiator, a colorant and the like in an aqueous medium and then polymerizing the suspension. In the emulsion polymerization aggregation method, a polymerizable monomer is emulsified in an aqueous medium containing a polymerization initiator and an emulsifier, and the polymerizable monomer is polymerized with stirring to obtain polymer primary particles, which are then colored. In this method, the primary particles of the polymer are aggregated by adding an agent and, if necessary, a charge control agent, and the obtained aggregated particles are aged to produce toner particles. In the dissolution suspension method, a solution phase obtained by dissolving a binder resin in an organic solvent and adding and dispersing a colorant is dispersed in an aqueous phase containing a dispersant by a mechanical shearing force. The toner particles are produced by removing the organic solvent from the droplets.

According to these polymerization methods, it is easy to control the particle size of the toner particles, so that it is possible to obtain toner particles that have a small particle size and a narrow particle size distribution and can form a high-definition image quality.
In the emulsion polymerization aggregation method, the polymerization of the polymerizable monomer and the granulation of the toner particles are performed in the production process. Therefore, the emulsion polymerization aggregation method is more suitable for the toner production than the solution suspension method in which the granulation is performed using a separately produced binder resin. There is an advantage that the required energy is small, and it is easy to adjust the toner having a small particle diameter, and it is easy to control the particle size distribution and the particle diameter.

With the recent spread of copiers and printers, in addition to demands for image quality, toners that are particularly excellent in high-speed printing and low-energy fixability have been desired, and attempts have been made to improve the low-temperature fixability of toner. It has been. Low temperature fixability, blocking resistance, and high temperature offset resistance are usually in a trade-off relationship, and it is desired to achieve both.
In order to achieve the object, wax is used as an anti-offset agent. However, there is a limit to the wax content in the toner, and if it is used excessively, leakage from the toner occurs and the anti-blocking property is deteriorated. For this reason, there is a limit to improving the low-temperature fixability with wax.

As a method for improving low-temperature fixability, techniques for improving low-temperature fixability by including a crystalline polyester resin in an amorphous resin have also been proposed (Patent Documents 1 to 4).
When these crystalline polyester resins are dispersed and contained in an incompatible non-crystalline resin, for example, when the non-crystalline resin is a styrene resin, the dispersion domain of the crystalline polyester component is not dispersed sufficiently small. The resulting toner exhibits brittleness, which is a defect of crystalline resin, adhesion to a member during development, and a problem that the temperature range of fixing becomes very small due to a sudden drop in elasticity during heating. was there.

On the other hand, when these crystalline polyester resins are dispersed and contained in a compatible non-crystalline resin, for example, when the non-crystalline resin is a polyester resin, sufficient dispersion can be obtained by dispersing it by melt-kneading. Only a toner having the same defect as that obtained when dispersed in an amorphous resin having poor compatibility was obtained.
When these crystalline and amorphous polyester resins are finely dispersed in water, mixing the amorphous polyester resin in water requires excessive energy and the assistance of an organic solvent, which is costly. When the alkali is used as the dispersion aid, there is a problem that the performance deteriorates due to hydrolysis. Furthermore, the tin-based catalysts that have been widely used in the past to design the molecular weight so that this amorphous polyester resin obtains good fixability have the disadvantage of contaminating the environment, and support good fixability. At present, no safe resin has been obtained.

  On the other hand, a method using a low melting crystalline resin containing a long chain (meth) acrylic acid ester has been proposed (Patent Document 5). These monomers can be easily emulsified and are very suitable for aqueous toner production. However, when such a long-chain (meth) acrylic acid ester polymer is used as a binder resin, brittleness is developed, the fixed image strength is remarkably deteriorated, and image defects are easily caused by bending or scratching ( Patent Document 5). Moreover, when long chain (meth) acrylic acid ester and a vinyl-type monomer are copolymerized (patent documents 6-7), melting | fusing point will fall and blocking resistance will be deteriorated.

  In addition, a method for producing a latex using a long-chain (meth) acrylic acid ester polymer as a core shell with an amorphous resin and using the long-chain (meth) acrylic acid ester polymer as a release agent has also been proposed (Patent Literature). 8). However, these latexes have a high storage elastic modulus in a state in which the long chain (meth) acrylate polymer is melted, and even if it is made into a toner, the long-chain (meth) acrylate polymer alone has a sufficient releasing effect. However, offset occurs, gloss is low, and the particle size of the latex is large, so that there is a problem that coarse powder is generated when the pigment aggregates.

JP 2002-182428 A JP 2002-284866 A JP 2005-234046 A JP 2006-113473 A Japanese Patent Publication No. 56-13943 JP-A-7-301949 JP-A-8-95294 JP 2005-208653 A

  The present invention relates to a method for producing a toner for developing an electrostatic image, and is capable of providing both stable low-temperature fixability and anti-blocking properties, excellent gloss, and excellent production stability and stable quality. An electrostatic charge image developing toner and a toner manufacturing method are provided.

The present inventor has repeatedly studied to solve the above problems, and has found that the problems can be solved by using a production method using a long-chain (meth) acrylate polymer as a binder resin. The present invention is based on this finding, and the gist of the present invention is as follows.
1. In the method for producing a toner containing at least a binder resin, a colorant, and a wax, the first step in which the binder resin polymerizes a long chain (meth) acrylic acid ester, in the presence of the polymer obtained in the first step. The storage elastic modulus of the polymer produced through the second step of polymerizing the monomer and obtained in the first step at 1 ° Hz at a temperature 20 ° C. higher than the melting point (Tm) of the toner is expressed as G ′ (Tm
+20), a method for producing a toner for developing an electrostatic charge image, which satisfies the condition of the following formula (1).

G ′ (Tm + 20) ≦ 1 × 10 ³ [Pa] (1)
2. 2. The method for producing a toner for developing an electrostatic charge image according to 1 above, wherein an azo initiator is used at least in the polymerization in the first step.
3. 3. The method for producing a toner for developing an electrostatic charge image according to 1 or 2 above, wherein the long-chain (meth) acrylic ester used in the first step is obtained by high-pressure mechanical emulsification.
4). 4. The long-chain (meth) acrylic acid ester polymer obtained in the first step is contained in the binder resin in an amount of 1% by mass to 50% by mass, according to any one of 1 to 3 above. A method for producing a toner for developing an electrostatic image.
5. 5. The production of a toner for developing an electrostatic charge image according to any one of 1 to 4 above, wherein the long-chain (meth) acrylic acid ester used in the first step has an average carbon number of 18 or more in the ester portion. Method.
6). 6. The electrostatic image as described in any one of 1 to 5 above, wherein the long-chain (meth) acrylic acid ester used in the first step contains 50% by number or more of components having 12 or more carbon atoms in the ester moiety. A method for producing a developing toner.
7). 7. An electrostatic charge image developing toner produced by the method according to any one of 1 to 6 above.
8). 8. The electrostatic image developing toner according to 7 above, wherein the toner has a melting point (Tm) of Tm ≦ 100 ° C.
9. 9. The toner for developing an electrostatic charge image according to 7 or 8 above, wherein the melting point (Tm) of the toner is Tm ≧ 40 ° C.

  According to the present invention, a toner for developing an electrostatic charge image having both low-temperature fixability and blocking resistance, excellent gloss, suitable for use in a high-speed printer, and excellent in production stability and stable in quality. A manufacturing method thereof can be provided.

The toner of the present invention contains at least a colorant, a binder resin, and a wax, and may contain a charge control agent, an external additive, and the like as necessary. The toner of the present invention is preferably produced by a wet method.
Examples of the wet method include a suspension polymerization method, an emulsion polymerization aggregation method, and a melt suspension method.
The suspension polymerization method is usually obtained by dissolving a colorant and wax in a binder resin monomer, and then suspending the monomer solution as monomer droplets in an aqueous medium by mechanical shearing force and performing polymerization. .

As the emulsion polymerization aggregation method, the polymer primary monomer is usually obtained by emulsifying the polymerizable monomer of the binder resin in an aqueous medium containing a polymerization initiator and an emulsifier, and polymerizing the polymerizable monomer with stirring. In this method, toner particles are produced by obtaining particles, adding a colorant and, if necessary, a charge control agent to aggregate the polymer primary particles, and aging the resulting aggregated particles.
The melt suspension method is usually obtained by dissolving a binder resin, wax or the like in a solvent to obtain an oil phase, suspending the oil phase as oil droplets in an aqueous medium, and then removing the solvent. It is done.

The binder resin of the present invention is produced through a first step for polymerizing a long-chain (meth) acrylic ester and a second step for polymerizing a monomer in the presence of the polymer obtained in the first step. The
The first step is to prepare a monomer (long chain (meth) acrylic acid ester) solution, disperse the monomer solution in an aqueous medium (for example, an aqueous surfactant solution), A dispersion of resin particles is prepared by polymerizing the resin. Further, if necessary, a monomer solution may be prepared by dissolving a crystalline substance such as wax in the monomer.

In the second step, a resin particle is formed by adding a monomer to the dispersion of resin particles obtained in the first step and polymerizing the monomer in the presence of the resin particle. is there.
The monomers used in the first step and the second step for obtaining the binder resin of the present invention may be used singly or in combination.
In the present invention, the binder resin is obtained through the first step and the second step, and the polymer obtained in the first step has a specific storage elastic modulus, thereby being excellent in low-temperature fixability, blocking resistance, and gloss. In addition, a toner for developing an electrostatic image and a method for producing the same can be provided.

The storage modulus of the polymer obtained in the first step for obtaining the binder resin of the present invention is 20 ° C. higher than the toner melting point Tm after the external addition (Tm + 20) ° C. and 1 Hz, and G ′ (Tm + 20).
In this case, it is essential to satisfy the condition of the following formula (1).
G ′ (Tm + 20) ≦ 1 × 10 ³ [Pa] (1)
Further, it is more preferable that G ′ (Tm + 20) ≦ 1 × 10 ² Pa. Furthermore, it is most preferable that G ′ (Tm + 20) ≦ 5 × 10 ¹ Pa. The lower limit of G ′ (Tm + 20) is not particularly limited because the binder resin melts and becomes the measurement limit value of the measuring machine.

When the expression (1) is satisfied, low-temperature fixing is possible. In addition, the binder resin can be easily deformed below the melting point, and the thermal conductivity is improved during fixing. As a result, the uniformity of the fixed image surface is increased, and a toner having particularly excellent gloss performance can be obtained.
Moreover, although not clear, a polymer having a single melting point can be obtained by first polymerizing a long-chain (meth) acrylic acid ester. Thereafter, since the monomer is polymerized in the second step, it is possible to suppress the generation of a low melting point component that is considered to be generated by copolymerization of the long-chain (meth) acrylic acid ester and the monomer. By suppressing the generation of the low melting point component, it is possible to obtain a toner that is particularly excellent in low-temperature fixability and blocking resistance.

The long chain (meth) acrylic acid ester used in the present invention may be linear or branched, and may be unsaturated.
In the present invention, the long-chain (meth) acrylic acid ester may be used alone or in combination, but the average number of carbon atoms in the ester portion of the long-chain (meth) acrylic acid ester makes the toner melting point a preferable range. Therefore, it is preferably 18 or more, more preferably 19 or more, and particularly preferably 20 or more.

Moreover, it is preferable that the component whose carbon number of the ester part of long-chain (meth) acrylic acid ester is 22 or more is contained at least. In addition, the component having 22 or more carbon atoms in the ester portion of the long chain (meth) acrylate ester tends to have a preferable toner melting point, and therefore, 1% by mass or more of the long chain (meth) acrylate ester is preferable. 5 mass% or more is still more preferable, and it is especially preferable that it is 10 mass% or more. Moreover, 100 mass% may be sufficient.

Furthermore, in the long-chain (meth) acrylic acid ester of the present invention, it is preferable that the component having 12 or more carbon atoms in the ester moiety is 50% by mass or more in optimizing the toner melting point by crystallization. When the number of carbon atoms in the ester portion is too small, the melting point becomes low and the blocking resistance tends to be poor.
The carbon number of the ester portion of the long chain (meth) acrylic acid ester can be measured by DSC, NMR or the like.

Moreover, it is preferable that the long chain (meth) acrylic acid ester of the present invention contains at least a long chain acrylic acid ester. When the long-chain acrylate ester is contained, a graft polymer is easily generated by extracting tertiary hydrogen, and the compatibility with the polymer used in the second step is increased, so that a uniform toner tends to be obtained.
The long-chain (meth) acrylic acid ester used in the present invention is behenyl acrylate, stearyl acrylate, behenyl methacrylate, stearyl methacrylate, cetyl acrylate, cetyl methacrylate, mistyryl acrylate, mistyryl methacrylate, icosyl acrylate, icosyl methacrylate, tetracosyl Monomers having 14 or more, particularly 18 or more, and more preferably 20 or more carbon atoms in the ester moiety such as acrylate and tetracosyl methacrylate are preferred for achieving low-temperature fixing.

In the present invention, the melting point of the long chain (meth) acrylic acid ester polymer is preferably 100 ° C. or lower, more preferably 80 ° C. or lower, and particularly preferably 70 ° C. or lower. The melting point is preferably 40 ° C. or higher, more preferably 50 ° C. or higher. If the melting point is too high, the effect of reducing the fixing temperature will be poor, and if the melting point is too low, problems may occur in the caking property and storage stability.
The amount of the long-chain (meth) acrylic acid ester polymer used in the second step of the present invention is preferably charged so that it is 1 part by mass or more in 100 parts by mass of the binder resin, more preferably 2 parts by mass or more. More preferably, it is 5 parts by mass or more. Moreover, it is preferable to prepare in 50 mass parts or less in 100 mass parts of binder resin, More preferably, it is 45 mass parts or less, More preferably, it is 40 mass parts or less. If the content of the long-chain (meth) acrylic acid ester polymer in the binder resin is too small, the performance such as low-temperature fixability may not be sufficient. If it is too much, the fixed image strength deteriorates, and bending or scratching occurs. May cause image loss.

The polymerization time in the first step of the present invention is not particularly limited, but it is preferable to carry out the polymerization until the monomer remaining after polymerization is less than 1% by mass, usually 5 minutes or more and 3 hours or less, The polymerization is preferably performed at a temperature equal to or higher than the melting point of the monomer used in the first step.
The long-chain (meth) acrylic acid ester used in the first step, which is the production step of the binder resin of the present invention, is preferably subjected to high-pressure mechanical emulsification after being mixed with melt, water, a surfactant and the like, if necessary. . Moreover, you may perform a high pressure mechanical emulsification with a wax. By performing high-pressure mechanical emulsification, the diameter of the long-chain (meth) acrylic acid ester or wax dispersion can be reduced. By reducing the diameter of the dispersion before polymerization, the specific surface area of the dispersion increases, and the graft reaction tends to proceed.

In the present invention, the volume average particle size of the long chain (meth) acrylic acid ester and wax dispersion is preferably 0.03 μm or more, more preferably 0.05 μm or more, and particularly preferably 0.1 μm or more. Further, it is preferably 2 μm or less, more preferably 1 μm or less, and particularly preferably 0.5 μm or less.
The apparatus used for the high-pressure mechanical emulsification used in the present invention is not particularly limited, but it is preferable to use an apparatus having a pump pressure of 5 MPa or more, more preferably 10 MPa or more.

The high-pressure mechanical emulsification is preferably carried out at a temperature equal to or higher than the melting point of the long-chain (meth) acrylic acid ester and the wax. If the emulsification temperature is too low, the particle size of the dispersion tends to be difficult to decrease.
As the monomer used in the second step, which is the production step of the binder resin of the present invention, a monomer conventionally used in the binder resin of toner can be used as appropriate.

  When the monomer is polymerized in the second step, radicals derived from the monomer or initiator draw a tertiary hydrogen in the acrylic acid portion of a part of the long-chain (meth) acrylate polymer, thereby grafting. A polymer is formed. This graft polymer serves as a compatibilizing agent, stabilizes the interface between the long-chain (meth) acrylic acid ester polymer that is a crystalline resin and the polymer in the second step, and the long-chain in the copolymer obtained in the second step. By obtaining a toner in which a (meth) acrylic acid ester polymer is dispersed, it is considered that a toner having excellent low-temperature fixability, blocking resistance and gloss can be produced.

Examples of the monomer of the present invention include a polymerizable monomer having an acidic group (hereinafter sometimes simply referred to as “acidic monomer”), and a polymerizable monomer having a basic group (hereinafter simply referred to as “ A polymerizable monomer having no acidic group or basic group (hereinafter, also referred to as “other monomer”). Meters can also be used.
Examples of the monomer include polymerizable monomers having a carboxyl group such as acrylic acid, methacrylic acid, maleic acid, fumaric acid and cinnamic acid, polymerizable monomers having a sulfonic acid group such as sulfonated styrene, Examples thereof include polymerizable monomers having a sulfonamide group such as vinylbenzenesulfonamide. Examples of the basic monomer include aromatic vinyl compounds having an amino group such as aminostyrene, nitrogen-containing heterocyclic-containing polymerizable monomers such as vinylpyridine and vinylpyrrolidone, dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, etc. And (meth) acrylic acid ester having an amino group. These acidic monomers and basic monomers may be used singly or as a mixture of a plurality of types, and may exist as a salt with a counter ion. Among these, it is preferable to use an acidic monomer, more preferably acrylic acid and / or methacrylic acid.

  Also, styrenes such as styrene, methyl styrene, chlorostyrene, dichlorostyrene, p-tert-butyl styrene, pn-butyl styrene, pn-nonyl styrene, methyl acrylate, ethyl acrylate, propyl acrylate, Acrylic esters such as n-butyl acrylate, isobutyl acrylate, hydroxyethyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacrylic acid Methacrylic acid esters such as hydroxyethyl acid, 2-ethylhexyl methacrylate, acrylamide, N-propylacrylamide, N, N-dimethylacrylamide, N, N-dipropylacrylamide, N, N-dibutyla Riruamido and the like, the polymerizable monomer may be used singly, or may be used in combination.

  Further, when the binder resin is a cross-linked resin, a polyfunctional monomer having radical polymerizability is used together with the above-mentioned monomers, for example, divinylbenzene, hexanediol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diester. Examples include methacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, and diallyl phthalate. It is also possible to use a polymerizable monomer having a reactive group in a pendant group, such as glycidyl methacrylate, methylol acrylamide, acrolein and the like. Among these, radically polymerizable bifunctional polymerizable monomers are preferable, and divinylbenzene and hexanediol diacrylate are particularly preferable. These polyfunctional polymerizable monomers may be used alone or as a mixture of plural kinds.

The polymerization time in the second step of the present invention can be appropriately adjusted by the addition method of the monomer and emulsifier used in the second step, and is not particularly limited, but the monomer remaining after polymerization is 1% by mass. It is preferable to carry out the polymerization until it becomes less than the value. Moreover, it is preferable to perform superposition | polymerization at the temperature more than melting | fusing point of the polymer obtained at the 1st process.
In the present invention, the polymerization initiator used in the step of producing the binder resin is not particularly limited in the first step and the second step, but a known polymerization initiator can be used as necessary. One or a combination of two or more can be used.

The polymerization initiator includes a radical polymerization initiator and an ionic polymerization initiator, and a radical polymerization initiator is preferred for use in water.
The radical polymerization initiator includes an organic polymerization initiator and an inorganic polymerization initiator, and hydrogen peroxide and an organic polymerization initiator are preferably used. Inorganic polymerization initiators such as potassium persulfate, sodium persulfate, and ammonium persulfate may need to be used in a large amount, and since a hydrophilic group is generated at the polymerization terminal, there is a tendency to adversely affect charging characteristics.

In the first step, in particular, the hydrogen peroxide and the organic polymerization initiator are most preferably organic azo initiators which are unlikely to cause a crosslinking reaction due to hydrogen abstraction.
In the first step, the radical derived from the initiator is cross-linked by extracting tertiary hydrogen in the acrylic acid portion of a part of the long-chain (meth) acrylic acid ester polymer, and the elastic modulus increases. Reduced. Thereby, an improvement in gloss is obtained at the time of fixing.

In the second step of obtaining the binder resin, in particular, the hydrogen peroxide and the organic polymerization initiator are preferably a ketone peroxide that easily undergoes a graft reaction due to hydrogen abstraction, and a hydroperoxide containing hydrogen peroxide. Furthermore, hydroperoxide containing hydrogen peroxide is most preferable.
These polymerization initiators may be added to the polymerization system before, simultaneously with the addition of the monomer, or after the addition, and these addition methods may be combined as necessary.

  In the present invention, a known chain transfer agent can be used as necessary. Specific examples of the chain transfer agent include t-dodecyl mercaptan, 2-mercaptoethanol, diisopropylxanthogen, carbon tetrachloride, trichlorobromomethane and the like. The chain transfer agent may be used alone or in combination of two or more, and is usually used in an amount of 0 to 5% by mass with respect to the polymerizable monomer.

  In the present invention, a known suspension stabilizer can be used as necessary. Specific examples of the suspension stabilizer include calcium phosphate, magnesium phosphate, calcium hydroxide, magnesium hydroxide and the like. These may be used alone or in combination of two or more, and may be used in an amount of 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer.

Both the polymerization initiator and the suspension stabilizer may be added to the polymerization system at any time before, simultaneously with, or after the addition of the polymerizable monomer. You may combine.
In addition, a pH adjuster, a polymerization degree adjuster, an antifoaming agent, and the like can be appropriately added to the reaction system.

In the present invention, when the binder resin is polymerized by emulsion polymerization, known emulsifiers can be used, but one kind selected from a cationic surfactant, an anionic surfactant and a nonionic surfactant Alternatively, two or more emulsifiers can be used in combination.
Examples of the cationic surfactant include dodecyl ammonium chloride, dodecyl ammonium bromide, dodecyl trimethyl ammonium bromide, dodecyl pyridinium chloride, dodecyl pyridinium bromide, hexadecyl trimethyl ammonium bromide, and examples of the anionic surfactant include And fatty acid soap such as sodium stearate and sodium dodecanoate, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, sodium lauryl sulfate and the like.

Nonionic surfactants include, for example, polyoxyethylene dodecyl ether, polyoxyethylene hexadecyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene sorbitan monooleate ether, monodecanoyl sucrose, etc. Is mentioned.
In this invention, it is preferable that the usage-amount of an emulsifier is used by 0.1 to 10 mass parts with respect to 100 mass parts of polymerizable monomers. In addition, these emulsifiers can be used as protective colloids, for example, one or more of partially or completely saponified polyvinyl alcohols such as polyvinyl alcohol and cellulose derivatives such as hydroxyethyl cellulose.

In the present invention, the volume average particle diameter of the polymer primary particles after multistage polymerization obtained by emulsion polymerization is usually 0.03 μm or more, preferably 0.05 μm or more, more preferably 0.1 μm or more, and usually 3 μm or less. The thickness is preferably 2 μm or less, more preferably 1 μm or less.
If the particle size is too small, it may be difficult to control the aggregation rate in the aggregation process. If the particle size is too large, the particle size of the toner particles obtained by aggregation tends to be large. It may be difficult to obtain toner.

  As the wax used in the toner of the present invention, known waxes can be arbitrarily used. Specifically, olefin waxes such as low molecular weight polyethylene, low molecular weight polypropylene, copolymer polyethylene, paraffin wax, and behenyl behenate. , Ester waxes having a long chain aliphatic group such as montanic acid ester and stearyl stearate, plant waxes such as hydrogenated castor oil and carnauba wax, ketones having a long chain alkyl group such as distearyl ketone, having an alkyl group Examples include higher fatty acids such as silicone and stearic acid, long-chain fatty acid polyhydric alcohols such as long-chain fatty acid alcohols and pentaerythritol, and partial ester forms thereof, higher fatty acid amides such as oleic acid amide and stearic acid amide, etc. Paraffin wax Other hydrocarbons such as Fischer-Tropsch wax, ester wax, and silicone waxes.

  In the present invention, hydrocarbon waxes are preferred because of their low compatibility with resins generally used as binder resins for toners obtained by polymerization. If a wax that is too compatible with the binder resin is used, the wax dissolves in the resin and changes the resin characteristics, making it difficult to achieve both fixing and blocking resistance, and exposing the wax to the toner surface. It may adversely affect the toner performance, for example, it may cause image quality degradation due to release from the toner.

  In the present invention, the wax may be used alone or in combination. Among these waxes, in order to improve fixability, the melting point of the wax is preferably 110 ° C. or lower, more preferably 90 ° C. or lower, and particularly preferably 80 ° C. or lower. As a minimum of melting | fusing point, 40 degreeC or more is preferable, More preferably, it is 50 degreeC or more. If the melting point is too high, the effect of reducing the fixing temperature is poor, and if the melting point is too low, problems may occur in the caking property and storage stability.

In the present invention, the amount of the wax is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and further preferably 5 parts by mass or more based on 100 parts by mass of the toner. Moreover, it is preferable that it is 40 mass parts or less, More preferably, it is 35 mass parts or less, More preferably, it is 30 mass parts or less. If the wax content in the toner is too low, performance such as high temperature offset property may not be sufficient, and if the content is too high, the blocking resistance may not be sufficient, or the wax may leak from the toner. It may become contaminated.

  A known colorant can be arbitrarily used as the colorant of the present invention. Specific examples of colorants include carbon black, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa yellow, rhodamine dyes, chrome yellow, quinacridone, benzidine yellow, rose bengal, triallylmethane dye, monoazo, Any known dyes and pigments such as disazo dyes and condensed azo dyes can be used alone or in combination. In the case of a full color toner, it is preferable to use benzidine yellow for yellow, monoazo and condensed azo dyes, magenta for quinacridone and monoazo dyes, and cyan for phthalocyanine blue. The colorant is preferably used so as to be 3 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polymer primary particles.

  The blending of the colorant in the emulsion polymerization aggregation method is usually performed in an aggregation step. A dispersion of polymer primary particles and a dispersion of colorant particles are mixed to form a mixed dispersion, which is then aggregated to form a particle aggregate. The colorant is preferably used in the state of being dispersed in water in the presence of an emulsifier, and the volume average particle diameter of the colorant particles is 0.01 μm or more, more preferably 0.05 μm or more, and more preferably 3 μm or less. 1 μm.

  In the present invention, when a charge control agent is used, any known one can be used alone or in combination. For example, a quaternary ammonium salt, a basic or electron donating metal as a positive charge control agent. Substances such as metal chelates, metal salts of organic acids, metal-containing dyes, nigrosine dyes, amide group-containing compounds, phenolic compounds, naphthol compounds and their metal salts, urethane bond-containing compounds, Examples include acidic or electron-withdrawing organic substances.

  In addition, when the toner for developing an electrostatic image obtained by the production method of the present invention is used as a toner other than a black toner in a color toner or a full color toner, a charge control agent that is colorless or light in color and does not impair the color tone of the toner is used. It is preferable to use, for example, a quaternary ammonium salt compound as a positively chargeable charge control agent, a metal salt of salicylic acid or an alkylsalicylic acid with chromium, zinc, aluminum, a metal complex as a negatively chargeable charge control agent, Hydroxys such as metal salts of benzylic acid, metal complexes, amide compounds, phenolic compounds, naphthol compounds, phenolamide compounds, 4,4′-methylenebis [2- [N- (4-chlorophenyl) amide] -3-hydroxynaphthalene] Naphthalene compounds are preferred.

  In the present invention, when a charge control agent is contained in the toner by the emulsion polymerization aggregation method, the charge control agent is added together with a polymerizable monomer or the like at the time of emulsion polymerization, or the aggregation step is performed together with the polymer primary particles and the colorant. Or by adding the polymer primary particles and the colorant after agglomeration of the polymer primary particles and the colorant to a target particle size. Among these, it is preferable to disperse the charge control agent in water using a surfactant and add it to the aggregation step as a dispersion having a volume average particle size of 0.01 μm or more and 3 μm or less.

The toner of the present invention may be produced by any polymerization method such as a suspension polymerization method, an emulsion polymerization aggregation method, or a dissolution suspension method, and is not particularly limited.
In the present invention, as a method for producing a suspension polymerization toner, a coloring agent, a polymerization initiator, and, if necessary, a wax, a polar resin, a charge control agent, a crosslinking agent, etc. in the above-mentioned binder resin monomer. An additive is added to prepare a monomer composition that is uniformly dissolved or dispersed. This monomer composition is dispersed in an aqueous medium containing a dispersion stabilizer and the like. Preferably, granulation is performed by adjusting the stirring speed and time so that the droplets of the monomer composition have a desired toner particle size. Thereafter, polymerization is performed by stirring to such an extent that the particle state is maintained and the sedimentation of the particles is prevented by the action of the dispersion stabilizer. These are collected by washing and filtration, and dried to obtain toner mother particles. Further, if necessary, toner can be obtained by external addition or the like.

  As a production method of the emulsion polymerization aggregation method, polymer primary particles of a binder resin monomer obtained by emulsion polymerization, a colorant dispersion, a wax dispersion, etc. are prepared, and these are dispersed in an aqueous medium. By carrying out heating or the like, it undergoes an agglomeration step and an aging step. These are collected by washing and filtration, and dried to obtain toner mother particles. Further, if necessary, toner can be obtained by external addition or the like.

  In the emulsion polymerization aggregation method, the aggregation is usually carried out in a tank equipped with a stirrer, but there are a heating method, a method of adding an electrolyte, and a method of combining them. When polymer primary particles are agglomerated with stirring to obtain particle aggregates of the desired size, the particle size of the particle aggregates is controlled based on the balance between the agglomeration force between the particles and the shearing force due to agitation. However, the cohesive force can be increased by heating or adding an electrolyte.

In the present invention, the electrolyte in the case of performing aggregation by adding an electrolyte may be either an organic salt or an inorganic salt. Specifically, NaCl, KCl, LiCl, Na ₂ SO ₄ , K ₂ SO ₄ , Li ₂ SO ₄ , MgCl ₂ , CaCl ₂ , MgSO ₄ , CaSO ₄ , ZnSO ₄ , Al ₂ (SO ₄ ) ₃ , Fe ₂ (SO ₄ ) ₃ , CH ₃ COONa, C ₆ H ₅ SO ₃ Na, etc. It is done. Of these, inorganic salts having a divalent or higher polyvalent metal cation are preferred.

  In the present invention, the amount of electrolyte added varies depending on the type of electrolyte, target particle size, etc., but is preferably 0.05 parts by mass or more, and 0.1 parts by mass with respect to 100 parts by mass of the solid component of the mixed dispersion. Part or more is more preferable. Further, it is preferably 25 parts by mass or less, more preferably 15 parts by mass or less, and particularly preferably 10 parts by mass or less. If the amount added is too small, the progress of the agglutination reaction will be slow, and there will be problems such as fine powder of 1 μm or less remaining after the agglomeration reaction, or the average particle size of the obtained particle aggregate will not reach the target particle size. If the amount is too large, rapid aggregation tends to occur, making it difficult to control the particle diameter, and the resulting aggregated particles may include problems such as coarse powders and irregular shapes.

When the aggregation is performed by adding an electrolyte, the aggregation temperature is 20 ° C. or higher, more preferably 30 ° C. or higher, and 70 ° C. or lower, more preferably 60 ° C. or lower.
The aggregation temperature in the case of performing aggregation only by heating without using an electrolyte is preferably (Tg-20) ° C. or higher, and more preferably (Tg-10) ° C. or higher, where Tg is the glass transition temperature of the polymer primary particles. . Moreover, Tg or less is preferable and (Tg-5) degree C or less is preferable.

The time required for agglomeration is optimized depending on the shape of the apparatus and the processing scale, but in order for the toner particle size to reach the target particle size, it is usually held at the predetermined temperature for at least 30 minutes. desirable. The temperature rise until reaching the predetermined temperature may be raised at a constant rate, or may be raised stepwise.
On the surface of the particle aggregate after the above-described aggregation treatment, particles with resin fine particles attached or fixed can be formed as necessary. By attaching or fixing resin fine particles whose properties are controlled to the surface of the particle aggregate, the chargeability and heat resistance of the obtained toner may be improved, and the effects of the present invention can be further enhanced. .

When resin fine particles having a glass transition temperature higher than the glass transition temperature of the polymer primary particles are used as the resin fine particles, it is preferable because blocking resistance can be further improved without impairing fixability. The volume average particle size of the resin fine particles is preferably 0.02 μm or more, and more preferably 0.05 μm or more. Moreover, 3 micrometers or less, Furthermore, 1.5 micrometers or less are preferable. As the resin fine particles, those obtained by emulsion polymerization of monomers similar to the polymerizable monomers used for the above-described polymer primary particles can be used.

The resin fine particles are usually used as a dispersion dispersed in water or a liquid mainly composed of water using a surfactant. However, when a charge control agent is added after the aggregation treatment, charge control is performed on the dispersion containing particle aggregates. It is preferable to add resin fine particles after adding the agent.
In order to increase the stability of the particle aggregate obtained in the aggregation step, it is preferable to perform fusion in the aggregated particles in the aging step after the aggregation step. The temperature of the ripening step is preferably not less than Tg of the polymer primary particles, more preferably not less than 5 ° C higher than Tg, and preferably not more than 80 ° C higher than Tg, more preferably not less than 50 ° C higher than Tg. It is as follows. The time required for the aging step varies depending on the shape of the target toner, but after reaching the glass transition temperature or higher of the polymer primary particles, it is usually held for 0.1 to 10 hours, preferably 1 to 6 hours. Is desirable.

  In addition, it is preferable to add a surfactant or raise the pH value after the aggregation process, preferably before the aging process or during the aging process. As the surfactant used here, one or more emulsifiers can be selected from the emulsifiers that can be used when producing the polymer primary particles. In particular, the emulsifiers used when producing the polymer primary particles. It is preferable to use the same. Although the addition amount in the case of adding surfactant is not limited, Preferably it is 0.1 mass part or more with respect to 100 mass parts of solid components of a mixed dispersion liquid, More preferably, it is 1 mass part or more, More preferably, it is 3 masses. It is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less. After the aggregation process, before the completion of the ripening process, by adding a surfactant or raising the pH value, it is possible to suppress aggregation of the particle aggregates aggregated in the aggregation process, In some cases, the generation of coarse particles can be suppressed.

  By heat treatment in the aging step, the polymer primary particles in the aggregate are fused and integrated, and the toner particle shape as the aggregate becomes close to a spherical shape. The particle aggregate before the aging step is considered to be an aggregate due to electrostatic or physical aggregation of the polymer primary particles, but after the aging step, the polymer primary particles constituting the particle aggregate are fused to each other. In addition, the shape of the toner particles can be made nearly spherical. According to such an aging process, by controlling the temperature and time of the aging process, the shape of the polymer primary particles is agglomerated, a potato type with advanced fusion, a spherical form with further fusion For example, various shapes of toner can be manufactured according to the purpose.

The toner produced by the polymerization method is separated from the aqueous solvent, washed, dried, subjected to external addition treatment as necessary, and used as an electrostatic image developing toner.
Although water is used as the liquid used for washing, it can be washed with an acid or alkali aqueous solution, and it is preferable to use an inorganic acid such as nitric acid, hydrochloric acid or sulfuric acid, or an organic acid such as citric acid. Moreover, it can also wash | clean with warm water or hot water, and these methods can also be used together. Through such a washing step, the suspension stabilizer, the emulsifier, the unreacted residual monomer and the like can be reduced and removed, which is preferable. In the washing step, the liquid to be washed is subjected to, for example, filtration, decantation, etc., so that the colored particles are made into a thick slurry or wet cake, and the operation for dispersing the toner by adding the liquid for washing to this is repeated. preferable. The colored particles after washing are preferably collected in the form of a wet cake in terms of handling in the subsequent drying step.

In the drying process, a fluidized drying method such as a vibration type fluidized drying method or a circulation type fluidized drying method, an air flow drying method, a vacuum drying method, a freeze drying method, a spray drying method, a flash jet method, or the like is used. Operating conditions such as temperature, air volume, and degree of reduced pressure in the drying step are appropriately optimized based on the Tg of the colored particles, the shape, mechanism, size, etc. of the apparatus used.
The volume median diameter of the toner base particles of the present invention is preferably 3 μm or more, and more preferably 4 μm or more. Moreover, 10 micrometers or less are preferable, Furthermore, 9 micrometers or less are more preferable, and 7 micrometers or less are still more preferable.

  Further, the shape has an average circularity measured by using a flow type particle image analyzer FPIA-3000, preferably 0.90 or more, more preferably 0.92 or more, further preferably 0.94 or more, preferably Is 0.99 or less, more preferably 0.98 or less. If the average circularity is too small, the image density may be lowered due to deterioration of charging due to poor adhesion of the external additive to the colored particles, and if it is too large, the cleaning may be poor due to the shape of the colored particles.

To the toner of the present invention, externally added fine particles can be added as necessary to improve toner fluidity and charge control properties. Examples of such externally added fine particles include various inorganic or organic fine particles. It can be appropriately selected and used.
Examples of inorganic fine particles include silicon carbide, boron carbide, titanium carbide, zirconium carbide, hafnium carbide, vanadium carbide, tantalum carbide, niobium carbide, tungsten carbide, chromium carbide, molybdenum carbide, calcium carbide, and other carbides, boron nitride, titanium nitride. , Various nitrides such as zirconium nitride, various borides such as zirconium boride, various oxides such as titanium oxide, calcium oxide, magnesium oxide, zinc oxide, copper oxide, aluminum oxide, cerium oxide, silica, colloidal silica, titanium Various titanate compounds such as calcium oxide, magnesium titanate and strontium titanate, phosphate compounds such as calcium phosphate, sulfides such as molybdenum disulfide, fluorides such as magnesium fluoride and fluorocarbon, aluminum stearate, stearin Calcium, zinc stearate, can be used various metal soaps such as magnesium stearate, talc, bentonite, various carbon black or conductive carbon black, magnetite, ferrite or the like. As the organic fine particles, fine particles such as styrene resin, acrylic resin, epoxy resin, and melamine resin can be used.

  Among these externally added fine particles, silica, titanium oxide, alumina, zinc oxide, various carbon blacks, conductive carbon blacks, and the like are preferably used. Further, the externally added fine particles are obtained by applying the surface of the inorganic or organic fine particles to a silane coupling agent, a titanate coupling agent, a silicone oil, a modified silicone oil, a silicone varnish, a fluorine silane coupling agent, a fluorine silicone oil, What has been subjected to surface treatment such as hydrophobization with a treating agent such as a coupling agent having an amino group or a quaternary ammonium base can also be used. Two or more kinds of the treatment agents can be used in combination.

The externally added fine particles of the present invention preferably have an average particle size of 0.001 μm or more, more preferably 0.005 μm or more. Moreover, 3 micrometers or less are preferable, More preferably, it is 1 micrometer. Also, a plurality of types having different particle sizes can be blended. The average particle diameter of the externally added fine particles can be determined by observation with an electron microscope.
In addition, the externally added fine particles can be used in combination of two or more different types, can be used in combination with those that have been surface-treated and those that have not been surface-treated, or can be used in combination with those that have been surface-treated differently, A positively chargeable one and a negatively chargeable one can be used in appropriate combination.

The content of the externally added fine particles of the present invention is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, preferably 5 parts by mass or less, more preferably 100 parts by mass of the toner particles. Is 3 parts by mass or less.
Examples of the method for adding the externally added fine particles include a method using a high-speed stirrer such as a Henschel mixer, a method using an apparatus capable of applying a compressive shear stress, and the like.

Further, inorganic fine powders such as magnetite, ferrite, cerium oxide, strontium titanate, and conductive titania can be added. The amount of these additives used may be appropriately selected depending on the desired performance, and is preferably 0.05 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the toner.
The melting point (Tm) of the toner after the external addition of the present invention is preferably 100 ° C. or less, and more preferably 70 ° C. or less. Moreover, it is preferable that it is 40 degreeC or more, and it is still more preferable that it is 50 degreeC or more. If the melting point is within this range, low-temperature fixing and blocking resistance tend to be compatible.

When the storage elastic modulus at a temperature 50 ° C. higher than the melting point (Tm) of the toner after the external addition of the present invention is G ′ (Tm + 50 ° C.), G ′ (Tm + 50 ° C.) is 1 × 10 ⁶ dyn / cm. ² or less is preferable, and 10 dyn / cm ² or more is preferable.
The storage elastic modulus at a temperature 100 ° C. higher than the melting point (Tm) of the toner after the external addition of the present invention is expressed as G ′.
If (Tm + 100 ℃) to, preferably G'(Tm + 100 ℃) is 1 × 10 ⁵ dyn / cm ² or less and preferably 1 dyn / cm ² or more.

In the present invention, if the storage elastic modulus of the toner after external addition at 50 ° C. is G ′ (50 ° C.), G ′ (50 ° C.) is 1 × 10 ⁹ dyn / cm ^{2 to} prevent toner blocking. The above is preferable.
The electrostatic image developing toner obtained by the production method of the present invention may be used in the form of a two-component developer using the toner together with a carrier, or a magnetic or non-magnetic one-component developer using no carrier. Good. When used as a two-component developer, the carrier may be a magnetic substance such as iron powder, magnetite powder, ferrite powder or the like, or a known material such as a resin-coated surface or a magnetic carrier. As the coating resin of the resin coating carrier, generally known styrene resin, acrylic resin, styrene acrylic copolymer resin, silicone resin, modified silicone resin, fluororesin, or a mixture thereof can be used.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In the following examples, “part” means “part by mass”. In addition, the live-action test was conducted by the following method.
Each particle diameter, circularity, electrical conductivity, thermal characteristics, etc. were measured as follows.
<Volume average diameter measurement (MV)>
The volume average diameter (MV) of particles with a volume average diameter (MV) of less than 1 micron is from Nikkiso Co., Ltd. Model Microtrac Nanotrac150 (hereinafter abbreviated as Nanotrack) and analysis software Microtrac Particle Analyzer Ver10.1.2-019EE The method described in the instruction manual using the ion-exchanged water having an electric conductivity of 0.5 μS / cm as the solvent, the solvent refractive index: 1.333, the measuring time: 600 seconds, and the number of times of measurement: once. Measured with Other setting conditions were particle refractive index: 1.59, transparency: transmission, shape: true sphere, density: 1.04.

<Volume median diameter measurement (Dv50)>
The volume median diameter (Dv50) of the particles with a volume median diameter (Dv50) of 1 micron or more is measured by using the Beckman Coulter Multisizer III (aperture diameter 100 μm: hereinafter abbreviated as Multisizer). Using II as a dispersion medium, the dispersion was dispersed so that the dispersoid concentration was 0.03%.

<Average circularity>
The “average circularity” in the present invention is measured as follows and is defined as follows. That is, the toner base particles are dispersed in a dispersion medium (Isoton II, manufactured by Beckman Coulter, Inc.) so as to be in the range of 5720 to 7140 particles / μL, and a flow particle image analyzer (manufactured by Sysmex Corporation, FPIA 3000) is used. Measured under the following apparatus conditions, the value is defined as “average circularity”. In the present invention, the same measurement is performed three times, and an arithmetic average value of three “average circularity” is adopted as the “average circularity”.
・ Mode: HPF
-HPF analysis amount: 0.35 μL
-Number of HPF detected: 8,000-10,000 The following are measured by the above device and automatically calculated and displayed in the above device, but "roundness" is defined by the following formula The

[Circularity] = [Perimeter of a circle with the same area as the projected particle area] / [Perimeter of projected particle image]
Then, the number of HPF detected is 8,000 to 10,000, and the arithmetic average (arithmetic mean) of the circularity of each particle is displayed on the apparatus as “average circularity”.
<Thermal characteristics>
Main peak of the endothermic curve when the temperature is increased from 30 ° C to 120 ° C at a rate of 10 ° C / min using the Seiko Electronics Co., Ltd. thermal analyzer DSC220CU. Measure the melting point, heat of fusion, half-width of melting peak, and then measure the crystallization temperature and half-width of crystallization peak from the exothermic curve when the temperature was lowered from 120 ° C to 30 ° C at a rate of 10 ° C / min. did.

<Weight average molecular weight (Mw)>
The THF-soluble component of the polymer primary particle dispersion was measured by gel permeation chromatography (GPC) under the following conditions.
Apparatus: GPC apparatus HLC-8020 manufactured by Tosoh Corporation, column: PL-gel Mixed-B 10μ manufactured by Polymer Laboratory, solvent: THF, sample concentration: 0.1% by mass, calibration curve: standard polystyrene

<Loss elastic modulus and storage elastic modulus of toner>
The loss elastic modulus and storage elastic modulus of the toner were measured under the following conditions.
Equipment: ARES manufactured by TA Instruments Japan, Temperature condition: Temperature rising from 30 ° C to 200 ° C at a rate of 4 ° C / min Plate: Parallel plate (diameter 8mm), Frequency: 1Hz, Initial value of measured strain: 0.1%
Measurement sample: About 0.25g of toner using a heat press (50 ℃, 10kg, 5min)
Molded into a cylindrical sample

<Loss modulus, storage modulus, viscosity (complex viscosity) of long chain (meth) acrylate polymer>
The loss elastic modulus, storage elastic modulus, and viscosity (complex viscosity) of the long chain (meth) acrylate polymer were measured under the following conditions.
Equipment: VAR-50 manufactured by REOLOGICA, Temperature conditions: Toner melting point Tm + 20 ° C after external addition
Plate: Parallel plate (diameter 20mm), Frequency: 1Hz, Initial value of measurement strain: 2.0%
Measurement sample: About 0.25 g of the freeze-dried latex obtained in the first step is molded into a cylindrical sample with a diameter of about 20 mm and a height of about 1 mm using a hot press machine (50 ° C, 10 kg, 5 min).

<Viscosity of long chain (meth) acrylate polymer>
The viscosity of the long chain (meth) acrylate polymer having a storage elastic modulus of 10 Pa or less at the toner melting point Tm + 20 ° C. after the external addition was measured under the following conditions.
Equipment: E type rotational viscometer VISCONIC EHD made by Tokyo Keiki
Temperature conditions: toner melting point Tm + 20 ° C. after external addition, rotation speed: 20 to 100 rpm

[Example 1]
<Preparation of emulsion A1>
100 parts behenyl acrylate, 25 parts paraffin wax (Nippon Seiwa Co., Ltd., HNP-9, melting point 82 ° C.), 20% sodium dodecylbenzenesulfonate aqueous solution (Daiichi Kogyo Seiyaku Co., Ltd., Neogen S20D, 20% below) Abbreviated as DBS aqueous solution) 5.5 parts, 9 parts of 359 parts of demineralized water
The mixture was heated to 0 ° C. and stirred for 10 minutes using a homomixer (Mark IIf model manufactured by Tokushu Kika Kogyo Co., Ltd.). Next, under heating at 90 ° C., circulation emulsification was started under a pressure of 20 MPa using a high-pressure emulsifier (manufactured by Gorin Co., Ltd., LAB 60-10TBS type). ) Was dispersed to 500 nm or less to prepare an emulsion A1. The final particle size (MV) was 246 nm.

<Preparation of polymer primary particle dispersion C1>
<First step>
A reactor equipped with a stirrer (three blades), a heating / cooling device, a concentrating device, and a raw material / auxiliary charging device, 194.8 parts of emulsion A1 and 197 parts of demineralized water (monomer added in the second step) And the temperature was raised to 90 ° C. under a nitrogen stream while stirring.

Thereafter, 12.5 parts of trichlorobromomethane and 22.5 parts of an aqueous solution of 0.5% V-50 (2,2′-azobis (2-amidinopropane) dihydrochloride manufactured by Wako Pure Chemical Industries) were added while stirring was continued. . G ′ (Tm + 20) of the freeze-dried latex obtained in the first step was 8.7 × 10 ⁻¹ Pa. The viscosity at 90 ° C. was 1200 Pa · s.
<Second step>
The following monomer / emulsifier mixture was added to the liquid of the first step over 5 hours. Simultaneously with the start of dropping of the mixture of monomers and emulsifier solution, dropping of the following aqueous initiator solution 1 was also started. Thereafter, the aqueous initiator solution 2 was further added over 2 hours. Thereafter, the inner temperature was maintained at 9 ° C. for 1 hour under stirring.
[Monomers]
Styrene 76.3 parts Butyl acrylate 23.7 parts Acrylic acid 1.5 parts Hexanediol diacrylate 0.5 parts Trichlorobromomethane 1.0 part [Emulsifier aqueous solution]
20% DBS aqueous solution 1.0 part demineralized water 67.3 parts [initiator aqueous solution 1]
8% aqueous hydrogen peroxide solution 17.2 parts 8% L-(+) ascorbic acid aqueous solution 17.2 parts [initiator aqueous solution 2]
8% L-(+) Ascorbic acid aqueous solution 14.2 parts After the completion of the polymerization reaction, the mixture was cooled to obtain a milky white primary polymer particle dispersion C1. The volume average particle diameter (MV) measured by using a nano track was 263 nm. The weight average molecular weight (Mw) was 40,000.

<Manufacture of toner mother particles E1>
A mixer equipped with a stirrer (double helical blade), heating / cooling device, concentrating device, and each raw material / auxiliary charging device was charged with 80 parts (solid content) of polymer primary particle dispersion C1 and the internal temperature was set to 26 ° C. Then, 0.05 parts (solid content) of 20% DBS aqueous solution was added and mixed uniformly. Furthermore, a 5 mass% aqueous solution of ferrous sulfate (0.53 parts as FeSO ₄ .7H ₂ O) was added over 5 minutes, and stirring was continued for 5 minutes to mix uniformly. Subsequently, 4.4 parts (solid content) of cyan pigment dispersion (EP700 manufactured by Dainichi Seika Co., Ltd.) was added over 5 minutes and mixed uniformly, and then 100 parts of demineralized water was added dropwise. During this time, the internal temperature was kept at 26 ° C. Thereafter, the temperature was raised to 51 ° C. over 43 minutes, and further raised to 54 ° C. over 46 minutes. Here, the volume-median particle size (Dv50) was measured using a multisizer and found to be 5.2 μm. Thereafter, 20 parts (solid content) of the polymer primary particle dispersion C1 was added over 5 minutes and held for 30 minutes, and then 6 parts of 20% DBS aqueous solution (solid content) was added over 10 minutes. The temperature was raised to 95 ° C. over 60 minutes and held for 30 minutes.

  Thereafter, the slurry obtained by cooling to 30 ° C. over 20 minutes was extracted, and suction filtered with an aspirator using 5 types C (No. 5C, manufactured by Toyo Roshi Kaisha, Ltd.). The cake remaining on the filter paper is transferred to a stainless steel container with an internal volume of 10 L equipped with a stirrer (propeller blade), added with 8 kg of ion-exchanged water having an electric conductivity of 1 μS / cm, and uniformly dispersed by stirring at 50 rpm. Thereafter, stirring was continued for 30 minutes.

  After that, using 5 C filter paper again, suction filtration with an aspirator, the solid matter remaining on the filter paper was again equipped with a stirrer (propeller blade), containing 8 kg of ion-exchanged water with electrical conductivity of 1 μS / cm The product was transferred to a stainless steel container having a volume of 10 L and uniformly dispersed by stirring at 50 rpm, and stirring was continued for 30 minutes. When this process was repeated 5 times, the electrical conductivity of the filtrate was 2 μS / cm.

The obtained cake was spread on a stainless steel bat so as to have a height of 20 mm, and dried in a blow dryer set at 40 ° C. for 48 hours to obtain toner mother particles E1.
The volume median particle size (Dv50) of the toner base particles E1 measured using Multisizer III is 5.
The average circularity measured by a flow type particle analyzer was 0.976.

<Manufacture of development toner F1>
Into Kyoritsu Riko Co., Ltd. sample mill KR-3, 100 parts of toner base particles E1 were introduced.
Subsequently, 2.04 parts of colloidal silica having a volume average primary particle diameter of 80 nm and 0.36 parts of large particle diameter silica having a volume average primary particle diameter of 30 nm were added and stirred and mixed for a total of 5 minutes. Thereafter, 0.30 part of titania particles having a volume average primary particle size of 250 nm treated with alumina and 0.76 part of small particle size silica having a volume average primary particle size of 10 nm are added, stirred and mixed for a total of 6 minutes, and sieved. Thus, developing toner F1 was obtained. The melting point (Tm) of the developing toner F1 was 65.3 ° C.

[Comparative Example 1]
<Preparation of polymer primary particle dispersion C2>
<First step>
A reactor equipped with a stirrer (three blades), a heating / cooling device, a concentrating device, and a raw material / auxiliary charging device, 194.8 parts of emulsion A1 and 197 parts of demineralized water (monomer added in the second step) And the temperature was raised to 90 ° C. under a nitrogen stream while stirring.

Then, 4.16 parts of 8 mass% hydrogen peroxide aqueous solution and 8 mass% L-(+) ascorbic acid aqueous solution were added with continuing stirring. G ′ (Tm + 20) of the freeze-dried latex obtained in the first step was 3.5 × 10 ³ Pa.
<Second step>
A polymer primary particle dispersion C2 was obtained in the same manner except that the amount of hexanediol diacrylate was changed to 1 part. The volume average particle diameter (MV) measured using a nanotrack was 245 nm. The weight average molecular weight (Mw) was 75,000.

<Manufacture of toner mother particles E2>
Toner base particle E2 is produced in the same manner as E1, except that C2 is used instead of polymer primary particle dispersion C1 and the temperature is raised to 51 ° C. over 40 minutes and further raised to 53 ° C. over 30 minutes. Got. The volume median particle size (Dv50) was 5.5 μm, and the average circularity measured by a flow particle analyzer was 0.971.

<Manufacture of development toner F2>
A developing toner F2 was obtained in the same manner as F1, except that E2 was used instead of the toner base particles E1. The melting point (Tm) of the developing toner F2 was 66.2 ° C.
[Example 2]
<Preparation of emulsion A2>
Emulsion A2 in the same manner as A1, except that the composition was 100 parts behenyl acrylate, 100 parts stearyl acrylate, 2.2 parts 20% by weight DBS aqueous solution, and 798 parts demineralized water.
Was made. The final particle size (MV) was 360 nm.

<Preparation of emulsion A3>
The composition is 100 parts paraffin wax (Nippon Seiwa Co., Ltd., HNP-9, melting point 82 ° C.), 6.91 parts stearyl acrylate, 3.3 parts decaglycerin decabehenate (acid value 3.2, hydroxyl value 27). An emulsion A3 was prepared in the same manner as A1, except that 1.415 parts of 20% by weight DBS aqueous solution and 255.9 parts of demineralized water were used. The final particle size (MV) was 225 nm.

<Preparation of polymer primary particle dispersion C3>
Instead of emulsifying liquid A1, emulsifying liquid A2 is 71.9 parts, emulsifying liquid A3 is 40.6 parts, the amount of water is 246 parts, trichlorobromomethane in the first step is 0 part, and V-50 aqueous solution concentration The polymer primary particle dispersion C3 was obtained in the same manner as in C1, except that the amount of hexanediol diacrylate in the second step was 0.7 parts by mass. The volume average particle size (MV) was 219 nm and the weight average molecular weight (Mw) was 70,000.

G ′ (Tm + 20) of the freeze-dried latex obtained in the first step was 7.4 × 10 ² Pa.
<Manufacture of toner mother particles E3>
Toner mother particles E3 were obtained in the same manner as E1, except that C3 was used instead of the polymer primary particle dispersion C1 and the internal temperature was raised to 54 ° C. over 60 minutes. The volume median particle size (Dv50) was 5.6 μm, and the average circularity measured by a flow particle analyzer was 0.969.

<Manufacture of developing toner F3>
A developing toner F3 was obtained in the same manner as F1, except that E3 was used instead of the toner base particles E1.
[Example 3]
<Preparation of polymer primary particle dispersion C4>
Instead of the emulsified liquid A1, the emulsified liquid A2 is 132.8 parts, the emulsified liquid A3 is 35.9 parts, the amount of water is 331 parts, and the hexanediol diacrylate in the second step is 1.0 part. Produced a polymer primary particle dispersion C4 in the same manner as in C1. Volume average particle size (MV) is 2
It was 45 nm and the weight average molecular weight (Mw) was 51,000.

G ′ (Tm + 20) of the freeze-dried latex obtained in the first step was 4.3 × 10 ⁻¹ Pa. The viscosity at 90 ° C. was 1420 Pa · s.
<Manufacture of toner mother particle E4>
Toner base particles E4 were obtained in the same manner as E1, except that C4 was used instead of the polymer primary particle dispersion C1 and the internal temperature was raised to 54 ° C. over 30 minutes. The volume median particle size (Dv50) was 5.8 μm, and the average circularity measured by a flow particle analyzer was 0.981.

<Manufacture of development toner F4>
A developing toner F4 was obtained in the same manner as F1 except that E4 was used instead of the toner base particles E1.
[Example 4]
<Preparation of polymer primary particle dispersion C5>
Emulsion A2 is 71.8 parts, Emulsion A3 is 40.5 parts, the amount of water is 249 parts, hexanediol diacrylate in the second step is 0.7 parts, and trichlorobromomethane is 0.9 parts. Polymer primary particle dispersion C5 was obtained in the same manner as C4 except that the parts were changed to parts. The volume average particle diameter (MV) is 216 nm, and the weight average molecular weight (Mw) is 58,800. G ′ (Tm + 20) of the freeze-dried latex obtained in the first step was 6.5 × 10 ⁻¹ Pa. The viscosity at 90 ° C. was 1290 Pa · s.

<Manufacture of toner mother particles E5>
Toner mother particles E5 were obtained in the same manner as E1, except that C5 was used instead of the polymer primary particle dispersion C1 and the internal temperature was raised to 54 ° C. over 40 minutes. The volume median particle size (Dv50) was 5.6 μm, and the average circularity measured by a flow particle analyzer was 0.973.
<Manufacture of development toner F5>
A developing toner F5 was obtained by the same method as F1 except that E5 was used instead of the toner base particles E1.

[Comparative Example 2]
<Preparation of polymer primary particle dispersion C6>
Emulsion A1 was 0 part, Emulsion A3 was 34.4 parts, the amount of water was 256 parts, V-50 aqueous solution was 0 parts, and the second step hexanediol diacrylate was 0.7 parts. Except for the above, a polymer primary particle dispersion C6 was obtained in the same manner as in C1. The volume average particle size (MV) was 250 nm, and the weight average molecular weight (Mw) was 64,000.

<Production of toner base particles E6>
Toner mother particles E6 were obtained in the same manner as E1, except that C6 was used instead of the polymer primary particle dispersion C1 and the internal temperature was raised to 55 ° C. over 50 minutes. The volume median particle size (Dv50) was 5.7 μm, and the average circularity measured by a flow particle analyzer was 0.970.
<Manufacture of developing toner F6>
A developing toner F6 was obtained in the same manner as F1, except that E6 was used instead of the toner base particles E1.

Using the developing toners F1 to F6, the image quality was evaluated as follows.
<Image quality evaluation>
The resulting toner is an organic photosensitive member charged with a developing rubber roller, a metal blade, a charging roller (PCR) at a printing speed of 210 mm / s, a non-magnetic single component, a guaranteed number of 10,000 sheets (at 5% printing), a belt transfer, Using a full color printer equipped with a belt fixing machine using a thermal fixing system, 6000 sheets were continuously printed at a printing rate of 5%.

<Measurement method of fog>
Using an image forming apparatus, the color difference of the white background of each standard paper (OKI Excellent White) before and after printing was measured with X-Rite 938 (manufactured by X-Rite), and the magnitude of ΔE Based on the following criteria.
◎ (Good): △ E <0.8
○ (Slightly generated): 0.8 ≦ ΔE <1.2
X (Generation): 1.2 ≦ ΔE
<Fixing test>
Prepare recording paper (OKI Excellent White) carrying an unfixed toner image, change the surface temperature of the heating roller from 100 ° C to 195 ° C in increments of 5 ° C, transport it to the fixing nip, and speed of 243 mm / sec The state of fixation when discharged with the was observed. A temperature range in which toner on the heating roller or paper wrapping does not occur at the time of fixing and the toner on the recording paper after fixing is sufficiently adhered to the recording paper is determined as the fixing temperature range. As the fixing machine, a belt fixing machine using a thermal fixing system was used, and evaluation was performed without application of silicone oil.

<Evaluation of fixing strength> Tape peeling method Using a fixing paper with 100% (non-fixed toner adhesion amount of 0.3 to 0.4 mg / cm2) of unfixed toner on recording paper (OKI Excellent White) Evaluate peel strength. In the evaluation method, a mending tape was affixed to the central portion of the toner fixing range on the recording paper after fixing, a weight (2 kg, contact surface disk diameter 9 cm) was slowly reciprocated once, and then the tape was peeled off. The image density before and after tape peeling is measured with X-Rite 938 (manufactured by X-Rite), and the change in density (density after tape peeling / density before tape peeling × 100%) is recorded. The recording temperature was changed in increments of 5 ° C. to obtain a temperature range in which the density change exceeded 98%.
Concentration change = 98% Peel strength insufficient ×
Concentration change> 98% Peel strength ○

<Glossy evaluation>
Gloss is evaluated using a fixing paper having a non-fixed toner adhesion amount of 100% (attachment amount of 0.3 to 0.4 mg / cm ² ) on recording paper (OKI Excellent White). The evaluation method is measured by GlossMeter VG2000 manufactured by NIPPON DENSHOKU. The measurement angle at the time of measurement was set to 75 °. The larger the gloss number, the higher the glossiness. The number showing the highest glossiness is recorded as the maximum gloss value in the fixing temperature region.
◎ (good): 30 or more ○ (practical): 25 or more and less than 30 △ (insufficient): 20 or more and less than 25 x (unusable): 20

<Blocking resistance>
10 g of developing toner is put into a cylindrical container having an inner diameter of 3 cm and a height of 6 cm, a load of 20 g is put on it, left in an environment of 50 ° C. and 40% RH for 24 hours, and then the toner is taken out of the container and loaded from above. The degree of aggregation was confirmed based on the following criteria.
A (good): It collapses with a load of less than 50 g.
○ (Practical use possible): Although aggregated, it collapses under a load of less than 500 g.
Δ (insufficient): Agglomerated and collapses under a load of 500 g or more and less than 1500 g.
X (Unusable): Aggregates and does not collapse unless a load of 1500 g or more is applied.

The measurement results are summarized in Table 1. The viscosity of the polymer in Examples 2 and 4 was not measured because the storage elastic modulus at the toner melting point Tm + 20 ° C. after the external addition exceeded 10 Pa.
As is apparent from Table 1, all of Examples 1 and 3 were good in low-temperature fixability, blocking resistance, fixing strength, and gloss. Examples 2 and 4 have the same fixing strength and blocking resistance as Comparative Example 1, but other gloss and fixing were better than Comparative Example 1. On the other hand, Comparative Example 1 having a storage elastic modulus higher than the range of the present invention has no problem with low-temperature fixability, blocking resistance, and fixing strength, but has insufficient gloss. In Comparative Example 2 in which the polymerization in the first step was not performed, the gloss and blocking resistance were good, but the fixing and fixing strength were very poor.

Claims (8)

In the method for producing a toner containing at least a binder resin, a colorant, and a wax, the first step in which the binder resin polymerizes a long chain (meth) acrylic acid ester, in the presence of the polymer obtained in the first step. The storage modulus of the polymer produced through the second step of polymerizing the monomer and obtained in the first step at a temperature 20 ° C. higher than the melting point (Tm) of the toner and 1 Hz is expressed as G ′ (Tm +
If a 20), meets the conditions of the following formula (1),
The long-chain (meth) acrylic acid ester used for the first step is formed by high-pressure mechanical emulsification,
A method for producing a toner for developing an electrostatic charge image, wherein the first step and the second step are carried out by an emulsion polymerization method.
G ′ (Tm + 20) ≦ 1 × 10 ³ [Pa] (1)   2. The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein an azo initiator is used at least in the polymerization in the first step. 3. The electrostatic charge according to claim 1, wherein the long-chain (meth) acrylic acid ester polymer obtained in the first step is contained in the binder resin in an amount of 1% by mass to 50% by mass. A method for producing a toner for image development. 4. The electrostatic charge image developing according to claim 1, wherein the long-chain (meth) acrylic acid ester used in the first step has an average carbon number of 18 or more in the ester portion. 5. Toner manufacturing method. Long chain (meth) acrylic acid ester to be subjected to the first step, the number of carbon atoms in the ester moiety according to any one of claims 1 to 4, characterized in that more than 12 components is 50% by number or more A method for producing a toner for developing an electrostatic image. An electrostatic image developing toner produced by the method according to claim 1 . The toner for developing an electrostatic charge image according to claim 6 , wherein the toner has a melting point (Tm) of Tm ≦ 100 ° C. The toner for developing an electrostatic image according to claim 6 , wherein the toner has a melting point (Tm) of Tm ≧ 40 ° C.