JP2006317711A - Toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner excellent in charging and fixing characteristics. <P>SOLUTION: The toner contains at least a binder resin and a colorant, wherein as the colorant, a colorant is used in which pigment particles having a cationic group on the surface thereof are coated with a polymer having a repeating structural unit derived from an anionic polymerizable surfactant having an anionic group, a hydrophobic group and a polymerizable group. The colorant is obtained by coating the pigment particles having the cationic group on the surface thereof with the polymer by polymerizing the anionic polymerizable surfactant in an aqueous dispersion in which the pigment particles are dispersed. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a toner.

A number of methods are known as electrophotographic methods. In general, a process (exposure process) of forming an electrical latent image on a photoconductor by various means using a photoconductive substance, A developing step of developing the latent image with toner, a transferring step of transferring the toner image onto a transfer material such as paper, and a step of fixing the toner image by heating, pressing, etc. using a fixing roller. is doing.
The toner generally contains a binder resin and a colorant.

As a method for producing such a toner, a pulverization method or a polymerization method is used.
The pulverization method is a method of kneading a raw material containing a binder resin (binder resin) as a main component and a colorant to obtain a kneaded product, and then cooling and pulverizing the kneaded product (for example, non-patent). Reference 1). Such a pulverization method is excellent in that the range of selection of raw materials is wide and toner can be produced relatively easily.

In the polymerization method, toner particles are produced by performing a polymerization reaction in a liquid phase or the like using a monomer that is a constituent component of a binder resin to produce a target binder resin ( For example, see Patent Document 1). Such a polymerization method is excellent in that the shape of the obtained toner particles can be made to have a relatively high sphericity (geometrically close to a perfect sphere).
In general, toner is charged in the developing step by being electrically charged. However, it is difficult to stabilize the charge amount with conventional toners, and problems such as a decrease in image density and fog are likely to occur. Further, since the colorant contained in the conventional toner has a low affinity for the recording medium, there is a problem that the fixing property of the toner to the recording medium is hindered depending on the content.

Supervised by the Society of Electrophotography, “Basics and Applications of Electrophotography” published by Corona, 1988, p482-486 JP-A-6-332257 (page 2, lines 28-35)

  An object of the present invention is to provide a toner excellent in charging characteristics and fixing characteristics.

Such an object is achieved by the present invention described below.
The toner of the present invention is a toner containing at least a binder resin and a colorant,
As the colorant, pigment particles having a cationic group on the surface are coated with a polymer having a repeating structural unit derived from an anionic polymerizable surfactant having an anionic group, a hydrophobic group, and a polymerizable group. It is characterized by using the same.
Thereby, it is possible to provide a toner excellent in charging characteristics and fixing characteristics.

In the toner of the present invention, the colorant polymerizes the pigment particles by polymerizing the anionic polymerizable surfactant in an aqueous dispersion in which the pigment particles having the cationic group on the surface are dispersed. It is preferable that it is coated with.
As a result, the charge on the surface of the pigment particles can be reliably canceled by the anionic group derived from the anionic polymerizable surfactant, and the electrical stability of the entire toner can be obtained.

これにより、着色剤の耐久性が向上し、例えば、トナーを製造する際に、顔料を被覆するポリマーの不本意な剥がれ等を効果的に防止することができる。 In the toner of the present invention, it is preferable that the polymer further has a repeating structural unit derived from a hydrophobic monomer.
As a result, the durability of the colorant is improved and, for example, when the toner is produced, it is possible to effectively prevent unintentional peeling of the polymer covering the pigment.
In the toner of the present invention, the polymer preferably further includes a repeating structural unit derived from a crosslinkable monomer and / or a repeating structural unit derived from a monomer represented by the following general formula (1).

As a result, the durability of the colorant is improved and, for example, when the toner is produced, it is possible to effectively prevent unintentional peeling of the polymer covering the pigment.

In the toner of the present invention, the pigment constituting the pigment particles is preferably carbon black.
Carbon black has a strong tendency to inhibit the charging characteristics and fixing characteristics of the toner. However, by using a microencapsulated carbon black, it is possible to prevent the charging characteristics and fixing characteristics of the toner from being inhibited.

In the toner of the present invention, the cationic group of the pigment particle is selected from the group consisting of a primary amine cation group, a secondary amine cation group, a tertiary amine cation group, and a quaternary ammonium cation group. It is preferable that
Thereby, it is possible to more easily provide a toner having excellent charging characteristics and fixing characteristics.
In the toner of the present invention, the anionic group of the anionic polymerizable surfactant is a sulfonate anion group (—SO ₃ ⁻ ) or a sulfinate anion group (—RSO ₂ ^— : R is a C _{1 to} C ₁₂ alkyl group). Group or a phenyl group and a modified product thereof, and a carboxylate anion group (—COO ⁻ ) are preferable.
Thereby, it is possible to more easily provide a toner having excellent charging characteristics and fixing characteristics.

In the toner of the present invention, the hydrophobic group of the anionic polymerizable surfactant is preferably selected from the group consisting of an alkyl group, an aryl group, and a group in which these are combined.
Thereby, it is possible to more easily provide a toner having excellent charging characteristics and fixing characteristics.
In the toner of the present invention, the polymerizable group of the anionic polymerizable surfactant is an unsaturated hydrocarbon group capable of radical polymerization, and includes a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, a propenyl group, and a vinylidene group. It is preferably selected from the group consisting of a group and a vinylene group.
Thereby, it is possible to more easily provide a toner having excellent charging characteristics and fixing characteristics.

In the toner of the present invention, the colorant is prepared by adding the anionic polymerizable surfactant to an aqueous dispersion of pigment particles having the cationic group on the surface and mixing the mixture, and further adding the anionic polymerizable surfactant. In addition, after emulsification, it is preferably obtained by adding a polymerization initiator and polymerizing in water.
Thereby, the charge on the surface of the pigment particles can be canceled by the anionic group derived from the anionic polymerizable surfactant, and the electrical stability of the entire toner can be obtained.

In the toner of the present invention, the colorant is prepared by adding the anionic polymerizable surfactant to an aqueous dispersion of pigment particles having the cationic group on the surface and mixing the resulting mixture with a hydrophobic monomer and the anionic polymerizable interface. It is preferably obtained by adding and mixing with an activator, emulsifying, adding a polymerization initiator and polymerizing in water.
As a result, the durability of the colorant can be improved more effectively, and the charge on the surface of the pigment particles can be more reliably canceled out by the anionic group derived from the anionic polymerizable surfactant. The electrical stability as can be obtained more effectively.

これにより、着色剤の耐久性をより効果的に向上させることができるとともに、顔料粒子表面の電荷を、アニオン性重合性界面活性剤由来のアニオン性基によってより確実に打ち消すことができ、トナー全体としての電気的安定性をより効果的に得ることができる。 In the toner of the present invention, the colorant may be prepared by adding the anionic polymerizable surfactant to an aqueous dispersion of pigment particles having the cationic group on the surface and mixing, and then mixing a hydrophobic monomer and a crosslinkable monomer and / or It is preferable that the monomer represented by the following general formula (1) and the anionic polymerizable surfactant are added and mixed, and after emulsification, a polymerization initiator is added and polymerized in water.

As a result, the durability of the colorant can be improved more effectively, and the charge on the surface of the pigment particles can be more reliably canceled out by the anionic group derived from the anionic polymerizable surfactant. The electrical stability as can be obtained more effectively.

The toner of the present invention preferably contains a charge control agent.
The contact between the colorant and the charge control agent may interfere with the function of the charge control agent. However, when the microencapsulated pigment is used as the colorant, the toner is finally colored. Since the agent and the charge control agent can be present in a state where they are not in direct contact, the toner obtained has excellent charging characteristics while maintaining excellent color developability.

Hereinafter, preferred embodiments of the toner of the present invention will be described in detail with reference to the accompanying drawings.
FIGS. 1 and 3 are diagrams showing a production process of a colorant applied to the toner of the present invention, and FIGS. 2 and 4 are diagrams showing an example of a microencapsulated pigment applied to the toner of the present invention. .
The toner of the present invention includes at least a binder resin as a main component (hereinafter also simply referred to as “resin”) and a colorant.

<Constituent material of toner particles>
1. Resin (binder resin)
In the present invention, the resin (binder resin) is not particularly limited, and for example, polystyrene, poly-α-methylstyrene, chloropolystyrene, styrene-chlorostyrene copolymer, styrene-propylene copolymer, styrene-butadiene copolymer. Polymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer, styrene-maleic acid copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-acrylic acid ester -Styrene resins such as methacrylic acid ester copolymer, styrene-α-chloroacrylic acid methyl copolymer, styrene-acrylonitrile-acrylic acid ester copolymer, styrene-vinyl methyl ether copolymer, etc. A homopolymer or copolymer, Polyester resin, epoxy resin, urethane modified epoxy resin, silicone modified epoxy resin, vinyl chloride resin, rosin modified maleic acid resin, phenyl resin, polyethylene resin, polypropylene, ionomer resin, polyurethane resin, silicone resin, ketone resin, ethylene-ethyl Examples include acrylate copolymers, xylene resins, polyvinyl butyral resins, terpene resins, phenol resins, aliphatic or alicyclic hydrocarbon resins. One or more of these can be used in combination.

  Although the softening temperature of resin (resin material) is not specifically limited, It is preferable that it is 90-170 degreeC, It is more preferable that it is 90-160 degreeC, It is further more preferable that it is 100-155 degreeC. In the present specification, the softening temperature is a measurement condition in a Koka type flow tester (manufactured by Shimadzu Corporation): temperature increase rate: 5 ° C./min, softening start temperature defined by a die hole diameter of 1.0 mm. Point to.

2. Colorant The toner contains a colorant.
The colorant used in the toner of the present invention is a repeating structural unit in which pigment particles having a cationic group are derived from an anionic polymerizable surfactant having an anionic group, a hydrophobic group and a polymerizable group. In other words, it is a pigment coated with a polymer having the following formula, that is, a microencapsulated pigment (hereinafter also simply referred to as a microencapsulated pigment).
As shown in FIG. 2, the microencapsulated pigment 100 includes an anion of a polymer (polymer layer) 60 derived from a cationic group 14 on the surface of the pigment particle 1 and an anionic polymerizable surfactant as described later. The pigment particles 1 are covered with the polymer layer 60 in a state in which the functional group is ionically bonded.

  By the way, in general, toner is used for the development step by being electrically charged. However, it is difficult to stabilize the charge amount with conventional toner, and problems such as a decrease in image density and fogging are likely to occur. It was. This is because many pigments used as colorants have a cationic group on the surface, and such pigments often deteriorate the electrical characteristics (charging characteristics) of the toner. This is probably because it is difficult to sufficiently control the charge amount of the toner even if the resin or the like is selected. Further, it is considered that even when the charge control agent was added, the charge control agent and the colorant were in contact with each other, and it was difficult to control the charge amount.

  In contrast, the pigment particles were coated with the polymer in a state where the cationic groups on the surface of the pigment particles and the cationic groups of the polymer derived from the cationic polymerizable surfactant were ionically bonded. By using the colorant, the charge on the surface of the pigment particles is canceled out by the anionic group derived from the anionic polymerizable surfactant, so that the colorant becomes electrically stable. As a result, the toner can be excellent in charging characteristics (particularly, charging stability).

In addition, the colorant used in the conventional toner has low affinity with the recording medium, and depending on the content, the fixing property of the toner is hindered. By using such a microencapsulated pigment, the pigment is used. Since the affinity of the recording medium itself is improved, the toner fixing characteristics are improved.
Further, by using the encapsulated pigment as described above, the affinity with the above-described resin is improved and the dispersibility in the resin is improved. As a result, the variation in the content of the colorant among the toner particles can be reduced, and the color developability is improved.

Further, since the colorant conventionally used in the toner has a polar group (cationic group) on the surface, the toner containing such a colorant is easily affected by moisture in the air, Although environmental stability is low, environmental stability can also be improved by using the above microencapsulated pigment as a colorant.
Further, since the pigment particles and the polymer are strongly bonded electrically, it is possible to prevent the polymer from peeling off from the pigment particles in, for example, a toner manufacturing process.

  Further, for example, when a charge control agent is contained in the toner, depending on the type of the colorant (particularly in the case of carbon black), the function of the charge control agent may be caused by the contact between the colorant and the charge control agent. However, by using a microencapsulated pigment as the colorant, the colorant and the charge control agent can be present in a state where they are not in direct contact with the toner finally obtained. The finally obtained toner has excellent charging characteristics while maintaining excellent color developability.

In addition, such a microencapsulated pigment is formed by electrically bonding the cationic group on the surface of the pigment particle and the anionic group of the surfactant. It will be relatively small.
The average particle diameter of these microencapsulated pigments is preferably 400 nm or less, more preferably 300 nm or less, and even more preferably 50 to 200 nm. If the average particle size of the microencapsulated pigment is too large, it may be difficult to make the content of the colorant uniform among the toner particles depending on the size of the toner particles. The description of the particle size is described by the measured value of the laser light scattering method.)

  Further, the aspect ratio (long and short) of the microencapsulated pigment is 1.0 to 1.3, and the Zingg index is 1.0 to 1.3 (more preferably 1.0 to 1.2). It is preferable that Thereby, the dispersibility in the resin is improved, and even when the colorant (microencapsulated pigment) is present on the surface of the toner particles, the influence on the shape of the toner can be reduced. As a result, a toner with less variation in shape can be provided.

When the short diameter of the microencapsulated pigment particles is b, the long diameter is l, and the thickness is t (l ≧ b ≧ t> 0), the aspect ratio (long / short) is 1 / b (≧ 1), and the flatness is b / t (≧ 1), Zingg index = long / shortness / flatness = (l · t) / b2. That is, the true sphere has an aspect ratio of 1 and a Zingg index of 1.
When the Zingg index is larger than 1.3, the microencapsulated pigment becomes flatter and becomes less isotropy. Therefore, when the microencapsulated pigment is present on the surface of the toner particle, the shape of the toner particle is changed. May have an impact. The method for setting the aspect ratio and Zingg index within the above ranges is not particularly limited. However, a microencapsulated pigment in which pigment particles having an anionic group on the surface are coated with a polymer by the above-described emulsion polymerization method can easily satisfy these conditions. Can meet.

In addition, in a microencapsulated pigment produced by a method other than an emulsion polymerization method such as an acid precipitation method or a phase inversion emulsification method, which will be described later, the aspect ratio and the Zingg index are unlikely to fall within the above ranges.
When the microencapsulated pigment is in the above aspect ratio and Zingg index range, it becomes a spherical shape. This improves the dispersibility in the resin, and the colorant (microencapsulated pigment) is a toner. Even when it is present on the particle surface, the influence on the toner shape and the like can be reduced. As a result, a toner with less variation in shape can be provided.

Next, the constituent components of the macroencapsulated pigment will be described in detail.
(2-1) Pigment Particles Examples of the pigment constituting the microencapsulated pigment used in the present invention include inorganic pigments and organic pigments.
In general, an amine substituent (primary amine, secondary amine, tertiary amine), quaternary ammonium group (—NR ₃ ⁺ ), quaternary phosphonium group (—PR ₃ ) is formed on the surface of the pigment particle. ⁺ ), And a cationic group such as a sulfonium group (—SR ₂ ⁺ ) or a pyridinium group. However, by encapsulating as described above, the surface of the pigment particles can be made electrically stable (neutral). As a result, the charging characteristics of the finally obtained toner can be improved.

  Examples of such inorganic pigments include carbon blacks such as furnace black, lamb black, acetylene black, and channel black (C.I. pigment black 7), iron oxide pigments, and the like. Organic pigments include azo pigments (including azo lakes, insoluble azo pigments, condensed azo pigments, and chelate azo pigments), polycyclic pigments (eg, phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxanes). Pigments, thioindigo pigments, isoindolinone pigments, or quinofuranone pigments), dye chelates (for example, basic dye-type chelates or acidic dye-type chelates), nitro pigments, nitroso pigments, or aniline black.

  More specifically, as an inorganic pigment used for black, the following carbon black, for example, No. manufactured by Mitsubishi Chemical Corporation is used. 2300, no. 900, MCF88, No. 33, no. 40, no. 45, no. 52, MA7, MA8, MA100, or No2200B, etc .; Columbia-made Raven5750, Raven5250, Raven5000, Raven3500, Raven1255, Raven700, etc .; 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, etc .; or Color Black FW1, Col Black FW2, Col FW2V, Col 200 or Black S150, Color Black S160, Color Black S170, Printex 35, Printex U, Printex V, Printex 140U, Special Black 6, Special Black 5, Special Black 4A, and SpecialBlack 4, and the like.

In particular, since carbon black as described above has a strong tendency to inhibit the charging characteristics and fixing characteristics of toner, the effect of the present invention by microencapsulation appears significantly.
Examples of the organic pigment for black include black organic pigments such as aniline black (C.I. Pigment Black 1).
Examples of organic pigments for yellow toner include C.I. l. Pigment Yellow 1 (Hansa Yellow), 2, 3 (Hansa Yellow 10G), 4, 5 (Hansa Yellow 5G), 6, 7, 10, 11, 12, 13, 14, 16, 17, 24 (Flavantron Yellow) , 34, 35, 37, 53, 55, 65, 73, 74, 75, 81, 83, 93, 94, 95, 97, 98, 99, 108 (anthrapyrimidine yellow), 109, 110, 113, 117 ( (Copper complex pigment), 120, 124, 128, 129, 133 (quinophthalone), 138, 139 (isoindolinone), 147, 151, 153 (nickel complex pigment), 154, 167, 172, 180, and the like.

  Further, organic pigments for magenta toner include C.I. l. Pigment Red 1 (Paral Red), 2, 3 (Toluidine Red), 4, 5 (lTR Red), 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21 , 22, 23, 30, 31, 32, 37, 38 (pyrazolone red), 40, 41, 42, 48 (Ca), 48 (Mn), 57 (Ca), 57: 1, 88 (thioindigo), 112 (Naphthol AS series), 114 (Naphthol AS series), 122 (Dimethylquinacridone), 123, 144, 146, 149, 150, 166, 168 (Antanthrone orange), 170 (Naphthol AS series), 171, 175, 176 , 177, 178, 179 (berylene maroon), 184, 185, 187, 202, 209 (dichloroquinacridone), 219, 224 (berylene), 245 (naphthol AS yarn) ) Or C.I. I. Pigment violet 19 (quinacridone), 23 (dioxazine violet), 32, 33, 36, 38, 43, 50 and the like.

Furthermore, as organic pigments for cyan toner, C.I. l. Pigment Blue 1, 2, 3, 15, 15: 1, 15: 2, 15: 3, 15:34, 15: 4, 16 (metal-free phthalocyanine), 18 (alkali blue toner), 22, 25, 60 ( Slen Blue), 65 (Biolantron), 66 (Indigo), C.I. l. Vat blue 4, 60 etc. are mentioned.
Furthermore, as organic pigments used for color toners other than magenta, cyan or yellow toners, C.I. I. Pigment green 7 (phthalocyanine green), 10 (green gold), 36, 37; C.I. I. Pigment brown 3, 5, 25, 26; I. Pigment orange 1, 2, 5, 7, 13, 14, 15, 16, 24, 34, 36, 38, 40, 43, 63, and the like.

In the macroencapsulated pigment used in the toner of the present invention, the above pigments can be used alone or in combination of two or more.
The average particle diameter of the pigment particles having such a cationic group on the surface is preferably 150 nm or less, and preferably 20 nm to 80 nm. Thereby, the average diameter of a microencapsulated pigment can be made suitable.

  Even if the pigment particles are electrically neutral or negatively charged and coated with a conventional resin material, the effect of the present invention cannot be obtained. For example, in the former case, since the average particle diameter of the pigment particles varies due to aggregation of the pigment particles, etc., the content of each toner component among the toner particles may vary. As a result, characteristics such as charging characteristics and fixing characteristics vary. Further, for example, in the latter case, the colorant inhibits the electrical stability of the toner particles, and the charging characteristics of the toner cannot be sufficiently obtained.

  The cationic group may be introduced later. That is, pigment particles having no cationic group or those having a cationic group introduced on the surface of pigment particles having an anionic group may be used. In such a case, a known pigment having no cationic group on the surface or pigment particles having an anionic group can be used as a material for the microencapsulated pigment. Thereby, the variation of the color which can be expressed can be increased.

Examples of the method for introducing a cationic group include the following methods.
The introduction of the cationic group can be performed, for example, by adding an aromatic group to the pigment by diazotization using a diazonium salt and replacing the pigment with a cationic group. Specifically, it can be prepared by reacting a pigment with a diazonium salt in a liquid reaction medium to bond at least one organic ionic group to the pigment surface. The diazonium salt can have an organic ionic group that is bonded to the carbon black.

  A diazonium salt is an organic compound having one or more diazonium groups. Diazonium salts are typically diazotizing agents such as ammonium nitrite, butyl nitrite, dicyclohexylammonium nitrite, ethyl nitrite, isoamyl nitrite, lithium nitrite, sodium nitrite, potassium nitrite, or zinc nitrite. Any metal or organic nitrite, and can include nitrous acid, nitric oxide, nitrogen dioxide, and mixtures thereof) and is generated by reacting the treating agent / reactant at suitable conditions. The cationic treatment agent itself can contain nitrite, in which case the diazonium salt is made by subsequent addition of acid. Thus, the treating agent can include a diazotizing agent (eg, nitrite) that can be made into a diazonium salt by adding an acid.

  For the method of introducing a cationic group on the surface, WO96 / 18688, US Pat. No. 5,554,739, WO96 / 18696, US Pat. Nos. 5,851,280, 5,837, No. 045, No. 5,803,959, No. 5,672,198, No. 5,571,311, No. 5,630,868, No. 5,707,432, No. No. 5,803,959, No. 5,698,016, No. 5,713,988, WO 97/47697, WO 97/47699.

(2-2) Polymer Layer The polymer layer 60 is composed of a polymer derived from an anionic polymerizable surfactant.
Examples of the anionic polymerizable surfactant used in the present invention include anions as described in JP-B-49-46291, JP-B-1-24142, or JP-A-62-104802. Allyl derivatives, anionic propenyl derivatives as described in JP-A-62-221431, JP-A-62-34947 or JP-A-55-11525 Examples thereof include anionic acrylic acid derivatives and anionic itaconic acid derivatives as described in JP-B-46-34898 or JP-A-51-30284.
As a specific example of the anionic polymerizable surfactant used in the present invention, the general formula (31):

Or a compound represented by formula (32):

The compound represented by these is preferable.
The polymerizable surfactant represented by the formula (31) is described in JP-A-5-320276 or JP-A-10-316909. By appropriately adjusting the type of R21 and the value of X in Formula (31), it is possible to correspond to the degree of hydrophilicity or hydrophobicity of the pigment particle surface. As a preferable polymerizable surfactant represented by the formula (31), a compound represented by the following formula (310) can be exemplified. Specifically, in the following formulas (31a) to (31d) Mention may be made of the compounds represented.

A commercial item can also be used as said anionic polymerizable surfactant. For example, Aqualon HS series (Aqualon HS-05, HS-10, HS-20, HS-1025) from Daiichi Kogyo Seiyaku Co., Ltd. or Adeka Soap SE-10N, SE-20N from Asahi Denka Kogyo Co., Ltd. Can be mentioned.
Asahi Denka Kogyo Co., Ltd. Adekaria Soap SE-10N is a compound represented by the formula (310), in which M ¹ is NH ₄ , R 31 is C ₉ H ₁₉ , and m = 10. Adekaria Soap SE-20N manufactured by Asahi Denka Kogyo Co., Ltd. is a compound represented by formula (310) in which M ¹ is NH ₄ , R 31 is C ₉ H ₁₉ , and m = 20.
Examples of the anionic polymerizable surfactant used in the present invention include a general formula (33):

The compound represented by these is preferable. Preferred examples of the anionic polymerizable surfactant represented by the formula (33) include the following compounds.

A commercial item can also be used as said anionic polymerizable surfactant. For example, Aqualon KH series (Aqualon KH-5, Aqualon KH-10) from Daiichi Kogyo Seiyaku Co., Ltd. can be mentioned. Aqualon KH-5 is a mixture of a compound represented by the above formula wherein r is 9 and s is 5 and a compound where r is 11 and s is 5. Aqualon KH-10 is a mixture of a compound represented by the above formula wherein r is 9 and s is 10, and a compound where r is 11 and s is 10.
Moreover, as an anionic polymerizable surfactant, the compound represented by a following formula (A) is also preferable.

The anionic polymerizable surfactants exemplified above can be used alone or as a mixture of two or more.
The polymer layer 60 may have a repeating structural unit derived from an anionic polymerizable surfactant and a hydrophobic monomer, or may have a repeating structural unit derived from a crosslinkable monomer. May be. These will be described in detail later.

(2-3) Production of Microencapsulated Pigment The microencapsulated pigment described above is prepared by adding an anionic polymerizable surfactant to an aqueous dispersion of pigment particles having a cationic group on the surface and mixing them, and then anionic. It can manufacture suitably by adding a polymerization surfactant and emulsifying, and then adding a polymerization initiator and carrying out emulsion polymerization. In addition, since the pigment particles can be encapsulated even if the pigment particles are relatively small by using such a method, the microencapsulated pigment is compared with the size of the toner particles. Can be made sufficiently small. As a result, the colorant content among the toner particles can be made more uniform.

In the following, description will be made with reference to possible dispersion states of pigment particles in a preferred method for producing a microencapsulated pigment. However, the dispersion state of the pigment particles listed below includes estimation.
First, a possible dispersion state of pigment particles will be described with reference to FIG. The pigment particles 1 having a cationic group 14 as a hydrophilic group dispersed in a solvent containing water as a main component (hereinafter also referred to as an aqueous solvent) are mixed with an anionic group 11, a hydrophobic group 12, and a polymerizable group 13. The anionic group 11 of the anionic polymerizable surfactant 2 having the above is arranged so as to face the cationic group 14 of the pigment particle 1 and adsorbs with a strong ionic bond.
In this state, for example, by adding a polymerization initiator, the polymerizable groups 13 of the adjacent anionic polymerizable surfactant 2 are polymerized to form the pigment particles 1 in the polymer layer 60 as shown in FIG. A microencapsulated pigment 100 coated with is produced.

  According to such an emulsion polymerization method, the arrangement form of the anionic polymerizable surfactant existing around the pigment particles before the polymerization reaction is very highly controlled. Then, the anionic polymerizable surfactant is converted into a polymer by the emulsion polymerization reaction while maintaining this highly controlled form. Therefore, the structure of the microencapsulated pigment is controlled with extremely high accuracy. That is, since the cationic group on the surface of the pigment particle and the anionic group of the anionic polymerizable surfactant are ionically bonded in the polymerization system to form a polymer phase by a polymerization reaction, emulsion polymerization is performed. The arrangement form of the monomers existing around the pigment particles in the front affects the polarization state of the surface of the particles after polymerization, and can therefore be controlled with extremely high accuracy. Thereby, the average particle diameter of the obtained microencapsulated pigment can be made relatively small while preventing aggregation and the like of the pigment particles. The microencapsulated pigment obtained in this manner is sufficiently small compared to the toner particles and has high dispersibility in the resin. Therefore, the content of the colorant between the toner particles is reduced. It can be uniform.

More specifically, the microencapsulated pigment is preferably produced by the following procedure.
(1) First, an anionic polymerizable surfactant is added to a dispersion in which a pigment having a cationic group on its surface is dispersed in water. A part of the added anionic polymerizable surfactant is adsorbed on the cationic group of the “pigment having a cationic group on the surface” and is ionically bound to be immobilized.

  Addition of the anionic polymerizable surfactant to the pigment having the cationic group on the surface when the anionic polymerizable surfactant is added to the aqueous dispersion of pigment particles having the cationic group on the surface The amount is 0 based on the total number of moles of the cationic group relative to the amount of the pigment having a cationic group on the surface (= weight of the pigment used (g) × anionic group on the pigment surface (mol / g)). The range of 0.5 to 2 times mol is preferable, and the range of 0.8 to 1.2 times mol is more preferable. By setting the addition amount to 0.5 times mole or more, the pigment particles having a cationic group are strongly ionically bound and can be easily encapsulated. By setting the addition amount to 2 times or less, the generation of an anionic polymerizable surfactant not adsorbed on the pigment particles can be reduced.

(2) Next, a polymerization initiator is added and polymerized in water. Specifically, emulsion polymerization is performed.
As such a polymerization initiator, a water-soluble polymerization initiator is preferable, and potassium persulfate, ammonium persulfate, sodium persulfate, 2,2-azobis- (2-methylpropionamidine) dihydrochloride, or 4,4 -Azobis- (4-cyanovaleric acid) and the like.
The addition of the polymerization initiator can be suitably carried out by dropping an aqueous solution in which a water-soluble polymerization initiator is dissolved in pure water.

The polymerization initiator is preferably added in an activated state.
The activation of the polymerization initiator can be preferably carried out by raising the temperature of the aqueous dispersion to a predetermined polymerization temperature.
The polymerization reaction preferably uses a reaction vessel equipped with an ultrasonic generator, a stirrer, a reflux condenser, a dropping funnel and a temperature controller.

  After completion of the polymerization, it is preferable to adjust the pH within the range of 7.0 to 9.0 and perform filtration. Here, as described above, the aqueous solvent is a solvent containing water as a main component. In addition to water, the aqueous solvent includes, as an optional component, for example, a water-soluble solvent such as glycerin or glycol. May be. The polymerization temperature is preferably in the range of 60 ° C to 90 ° C. In addition, when the pigment particles having a cationic group as a hydrophilic group on the surface are not in the state of an aqueous dispersion, as a pretreatment, a dispersion treatment is performed using a general disperser such as a ball mill, a roll mill, an Eiger mill, or a jet mill. It is preferable to carry out.

In the microencapsulated pigment obtained as described above, pigment particles having a small average particle diameter are completely covered with a polymer layer (no defect portion).
By the above procedure, a microencapsulated pigment coated with a polymer having a repeating structural unit derived from an anionic polymerizable surfactant can be suitably produced.
Other comonomer may be added for the purpose of improving the fixing property of the toner particles and improving the storage stability of the microencapsulated pigment.

  In addition, an anionic polymerizable surfactant and a hydrophobic monomer may be present in the aqueous dispersion as necessary during the polymerization. In this case, the polymer layer has an anionic polymerizable surfactant. It becomes a copolymer layer copolymerized from the agent and the hydrophobic monomer. That is, the microencapsulated pigment has a repeating structure in which pigment particles having a cationic group are derived from an anionic polymerizable surfactant having an anionic group, a hydrophobic group, and a polymerizable group and a hydrophobic monomer. It is coated with a polymer (copolymer) having structural units.

  In such a microencapsulated pigment, the anionic polymerizable surfactant is added to an aqueous dispersion of pigment particles having a cationic group on the surface and mixed, and then a hydrophobic monomer and an anionic polymerizable surfactant are added. In addition, after emulsification, it can be suitably produced by adding a polymerization initiator and emulsion polymerization. Thereby, a more durable colorant can be manufactured. As a result, unintentional peeling of the polymer covering the pigment can be effectively prevented when the toner is manufactured. Moreover, the affinity with the resin is improved, and the dispersibility in the resin can be further increased.

The hydrophobic monomer has at least a hydrophobic group and a polymerizable group in its structure, and the hydrophobic group is selected from the group consisting of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. Can be illustrated. Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, and a propyl group. Examples of the alicyclic hydrocarbon group include a cyclohexyl group, a dicyclopentenyl group, a dicyclopentanyl group, and an isobornyl group, and an aromatic hydrocarbon group. Examples thereof include a benzyl group, a phenyl group, and a naphthyl group.
The polymerizable group is an unsaturated hydrocarbon group capable of radical polymerization, and is preferably selected from the group consisting of a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, a propenyl group, a vinylidene group, and a vinylene group. .

  Specific examples of the hydrophobic monomer include styrene and methylstyrene, dimethylstyrene, chlorostyrene, dichlorostyrene, bromostyrene, p-chloromethylstyrene, divinylbenzene, and other styrene derivatives; methyl acrylate, ethyl acrylate, acrylic acid n-butyl, butoxyethyl acrylate, benzyl acrylate, phenyl acrylate, phenoxyethyl acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, tetrahydrofurfuryl acrylate, isobol Monofunctional acrylic esters such as nyl acrylate; methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate Butoxymethyl methacrylate, benzyl methacrylate, phenyl methacrylate, phenoxyethyl methacrylate, cyclohexyl methacrylate, dicyclopentanyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, tetrahydrofurfuryl methacrylate, isobornyl methacrylate, etc. Monofunctional methacrylate esters of allyl compounds such as allylbenzene, allyl-3-cyclohexanepropionate, 1-allyl-3,4-dimethoxybenzene, allylphenoxyacetate, allylphenylacetate, allylcyclohexane, allyl polycarboxylic acid allyl, etc. ; Ester cheeks of fumaric acid, maleic acid, itaconic acid; radically polymerizable groups such as N-substituted maleimides and cyclic olefins Monomer, and the like that. As the hydrophobic monomer, those satisfying the above-mentioned required characteristics are appropriately selected, and the addition amount thereof is arbitrarily determined.

The amount of the hydrophobic monomer added is preferably in the range of about 5 to 900 parts by weight, more preferably in the range of 10 to 500 parts by weight, and particularly preferably 15 to 200 parts by weight with respect to 100 parts by weight of the pigment. It is a range. The amount of the anionic polymerizable surfactant that forms the outermost shell of the capsule is preferably in the range of about 0.5 to 5 times the mole of the anionic polymerizable surfactant added first, more preferably 1-2. The range is about a double mole. By setting it in the range of 1 mol or more, the dispersibility and dispersion stability of the encapsulated particles are excellent. Since the addition amount of 2 mol or less can suppress the generation of an anionic polymerizable surfactant that does not contribute to encapsulation, the generation of polymer particles in addition to the encapsulated particles can be prevented.
The polymer that coats the pigment particles also preferably has a repeating structural unit derived from a crosslinkable monomer.
By having a repeating structural unit derived from a crosslinkable monomer, a crosslinked structure is formed in the polymer, and the durability of the polymer can be improved.

Examples of the crosslinkable monomer include compounds having two or more unsaturated hydrocarbon groups selected from vinyl group, allyl group, acryloyl group, methacryloyl group, propenyl group, vinylidene group, and vinylene group. , Ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, allyl acrylate, bis (acryloxyethyl) hydroxyethyl isocyanurate, bis (acryloxy neopentyl glycol) adipate 1,3-butylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, propylene glycol diacrylate Rate, polypropylene glycol diacrylate, 2-hydroxy-1,3-diaacryloxypropane, 2,2-bis [4- (acryloxy) phenyl] propane, 2,2-bis [4- (acryloxyethoxy) phenyl] propane 2,2-bis [4- (acryloxyethoxy diethoxy) phenyl] propane, 2,2-bis [4- (acryloxyethoxy polyethoxy) phenyl] propane, hydroxypentylglycol diacrylate, 1 , 4-butanediol diacrylate, dicyclopentanyl diacrylate, dipentaerythritol hexaacrylate, dipentaerythritol monohydroxypentaacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate , Tetrabromopisphenol A diacrylate, triglycerol diacrylate, trimethylolpropane triacrylate, tris (acryloxyethyl) isocyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate Methacrylate, polyethylene glycol dimethacrylate, propylene glycol dimethacrylate, polypropylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate 2-hydroxy-1,3-dimethacryloxypropane, 2,2 -Bis [41- (methacryloxy) phenyl] propane, 2,2-bis [4- (methacryloxyethoxy) phenyl] propane, 2,2-bis [4- (methacryloxyethoxydiethoxy) phenyl] propane, 2, 2-bis [4- (methacryloxyethoxypolyethoxy) phenyl] propane, tetrabromobisphenol A dimethacrylate, dicyclopentanyl dimethacrylate, dipentaerythritol hexamethacrylate, glycerol dimethacrylate, hydroxypentylglycol dipentaglycol dimethacrylate Dipentaerythritol monohydroxypentamethacrylate, ditrimethylolpropane tetramethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, Rig Lise over roll dimethacrylate, trimethylolpropane trimethacrylate, tris (methacryloxyethyl) isocyanurate, allyl methacrylate, divinylbenzene, diallyl phthalate, diallyl terephthalate, diallyl isophthalate, diethylene glycol bis allyl carbonate.
Moreover, it is preferable that the polymer which coat | covers a pigment particle further has the repeating structural unit induced | guided | derived from the monomer represented by following General formula (1).

The R ² group, which is a “bulky” group derived from the monomer represented by the general formula (1) in the polymer, reduces the flexibility of the polymer molecule, that is, restricts the mobility of the molecule. The mechanical strength and heat resistance of the polymer are improved.
In the general formula (1), examples of the alicyclic hydrocarbon group represented by R ² include a cycloalkyl group, a cycloalkenyl group, a benzyl group, a phenyl group, an isobornyl group, a dicyclopentanyl group, a dicyclopentenyl group, and an adamantane. Group, tetrahydrofuran group, naphthyl group, t-butyl group, and the like.

As described above, a polymer having a repeating structural unit derived from a crosslinkable monomer and a polymer having a repeating structural unit derived from the monomer represented by the general formula (1) have high Tg, mechanical strength, and heat resistance. There is an advantage that it is excellent in durability such as resistance and solvent resistance.
Moreover, the following are mentioned as a specific example of the monomer represented by the said General formula (1).

  Moreover, the following hydrophilic monomers can be used with an anionic polymerizable surfactant. As such a hydrophilic monomer, for example, a hydrophilic monomer having an anionic group as a hydrophilic group can be used. In this case, the polymer layer can be a copolymer layer copolymerized from an anionic polymerizable surfactant and / or a hydrophilic monomer having an anionic group and a comonomer.

Preferable specific examples of the hydrophilic monomer having an anionic group include, for example, methacrylic acid, acrylic acid, phosphoric acid group-containing (meth) acrylate, sodium vinyl sulfonate, 2-sulfoethyl methacrylate, 2-acrylamido-2-methyl. And propanesulfonic acid.
Moreover, you may use hydrophilic monomers other than the hydrophilic monomer which has an anionic group. Examples of the hydrophilic monomer other than the hydrophilic monomer having an anionic group include those having a hydroxyl group, an ethylene oxide group, an amide group, or an amino group as the hydrophilic group.

  Specific examples of the hydrophilic monomer include 2-hydroxyethyl methacrylate having an OH group, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, and the like, ethyldiethylene glycol acrylate having an ethylene oxide group, polyethylene glycol monomethacrylate, Methoxypolyethylene glycol methacrylate, amide group-containing acrylamide, N, N-dimethylacrylamide, etc., amino group-containing N-methylaminoethyl methacrylate, N-methylaminoethyl acrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl Alkylamines of acrylic acid or methacrylic acid such as methacrylate and diethylaminoethyl methacrylate Esters: N- (2-dimethylaminoethyl) acrylamide, N- (2-dimethylaminoethyl) methacrylamide, N, N-dimethylaminopropylacrylamide, and other unsaturated amides having an alkylamino group, and vinyl Examples thereof include monovinyl pyridines such as pyridine, vinyl ethers having an alkylamino group such as dimethylaminoethyl vinyl ether; vinyl imidazole, N-vinyl-2-pyrrolidone and the like.

  The microencapsulated pigment is produced by adding the anionic polymerizable surfactant to an aqueous dispersion of pigment particles having a cationic group as a hydrophilic group on the surface, and water or water and aqueous as necessary. After adding a solvent and mixing and irradiating ultrasonic waves for a predetermined time, the anionic polymerizable surfactant and / or the hydrophilic monomer (in addition to the above-mentioned hydrophobic monomer, crosslinkable monomer, general formula (1 The monomer represented by) can also be added.) If necessary, water is added and dispersed again by irradiating with ultrasonic waves for a predetermined time, and at a predetermined temperature (polymerization initiator) while performing ultrasonic irradiation and stirring. The temperature can be suitably increased by adding the polymerization initiator to activate the polymerization initiator and emulsion polymerization.

  When the hydrophobic monomer is used, more specifically, an anionic polymerizable property having an anionic group, a hydrophobic group, and a polymerizable group in an aqueous dispersion of pigment particles having the cationic group on the surface. An anionic polymerizable surfactant having an anionic group, a hydrophobic group, and a polymerizable group, a step of adding and mixing a surfactant and irradiating with ultrasonic waves, a step of adding and mixing a hydrophobic monomer, and an anionic group, a hydrophobic group and a polymerizable group It comprises a step of adding and mixing an agent and / or a hydrophilic monomer and irradiating with ultrasonic waves, and a step of emulsion polymerization by adding a polymerization initiator, and it is more preferably produced by carrying out in the order of the steps described above. Can do.

  In the case of using the crosslinkable monomer and / or the monomer represented by the general formula (1), more specifically, an anionic group is added to the aqueous dispersion of pigment particles having the cationic group on the surface. And a step of adding an anionic polymerizable surfactant having a hydrophobic group and a polymerizable group, mixing and irradiating with ultrasonic waves, a crosslinkable monomer and / or the general formula (1) A step of adding and mixing the monomer, a step of adding and mixing the anionic polymerizable surfactant and / or the hydrophilic monomer and irradiating with ultrasonic waves, and a step of emulsion polymerization by adding a polymerization initiator It can comprise more suitably by implementing in order of the said process.

  Further, when the crosslinkable monomer and / or the monomer represented by the general formula (1) is used, more specifically, an anionic group is added to the aqueous dispersion of pigment particles having the cationic group on the surface. And a step of adding an anionic polymerizable surfactant having a hydrophobic group and a polymerizable group, mixing and irradiating with ultrasonic waves, a crosslinkable monomer and / or the general formula (1) A step of adding and mixing a monomer and a monomer having a long-chain alkyl group, a step of adding and mixing an anionic polymerizable surfactant and / or the hydrophilic monomer and irradiating with ultrasonic waves, and a polymerization initiator It can be more suitably manufactured by carrying out the emulsion polymerization step and adding the step.

As described above, first, an anionic polymerizable surfactant is adsorbed to the cationic group on the surface of the pigment particle having a cationic group on the surface, and then a hydrophobic monomer is added, and then the anionic polymerizable surfactant and / or Alternatively, by adding a hydrophilic monomer and irradiating with ultrasonic waves, the arrangement of the polymerizable surfactant and monomer present around the pigment particles is extremely highly controlled. Then, by emulsion polymerization, the monomer is converted into a polymer in this highly controlled form, and the microencapsulated pigment according to this embodiment is obtained. Thereby, the production | generation of the water-soluble oligomer and polymer which are a by-product can be reduced.
In the microencapsulated pigment obtained as described above, pigment particles having a small average particle diameter are completely covered with a polymer layer (no defect portion).

Next, another dispersion state in which pigment particles can occur in the preferred method for producing a microencapsulated pigment described above will be described with reference to FIG. The anionic group 11 of the anionic polymerizable surfactant 2 having an anionic group 11, a hydrophobic group 12 and a polymerizable group 13 is added to the pigment particle 1 having a cationic group 14 on the surface as a hydrophilic group. It arrange | positions so that it may face 1 cationic group 14, and it adsorb | sucks by a strong ionic bond. Further, the surface of the pigment particle 1 has a cationic group 14 chemically bonded at a specific density, and has a hydrophobic region between the cationic groups 14, and an anionic polymerizable surfactant in the hydrophobic region. The anionic group of another anionic polymerizable surfactant 2 is arranged on the anionic group 11 of the anionic polymerizable surfactant 2. .
In this state, for example, a polymerization initiator is added to polymerize the polymerizable groups 13 of the adjacent anionic polymerizable surfactants 2, whereby the pigment particles 1 become polymer layers 60 as shown in FIG. A microencapsulated pigment 101 coated with 'is produced.

  Further, the toner may contain wax. The wax is usually used for the purpose of improving releasability. Examples of such wax include plant waxes such as candelilla wax, carnauba wax, rice wax, cotton wax, and wood wax, animal waxes such as beeswax and lanolin, montan wax, ozokerite, and ceresin. Mineral waxes such as mineral waxes, paraffin waxes, microwaxes, microcrystalline waxes, petroleum waxes such as petrolatum waxes, Fischer-Tropsch waxes, polyethylene waxes (polyethylene resins), polypropylene waxes (polypropylene resins) ), Synthetic hydrocarbon waxes such as oxidized polyethylene wax and oxidized polypropylene wax, 12-hydroxy stearamide, stearamide, phthalic anhydride, chlorinated hydrocarbon Fatty acid amides, esters, ketones, synthetic wax wax such as ether and the like, can be used singly or in combination of two or more of them. Further, as the wax, a crystalline polymer resin having a lower molecular weight may be used. For example, a homopolymer or copolymer of polyacrylate such as poly n-stearyl methacrylate and poly n-lauryl methacrylate (for example, It is also possible to use a crystalline polymer having a long alkyl group in the side chain, such as an n-stearyl acrylate-ethyl methacrylate copolymer).

The content of the wax in the toner is not particularly limited, but is preferably 1.0 wt% or less, and more preferably 0.5 wt% or less. If the content of the wax is too large, the wax is liberated and coarsened in the finally obtained toner particles, and the toner seeps into the toner particle surface and the transfer efficiency of the toner tends to decrease. Indicates.
The softening point of the wax is not particularly limited, but is preferably 50 to 180 ° C, and more preferably 60 to 160 ° C.

Further, the toner of the present invention may contain a component other than these as a constituent material. Examples of such components include a charge control agent, magnetic powder, and an external additive.
Examples of the charge control agent include benzoic acid metal salt, salicylic acid metal salt, alkyl salicylic acid metal salt, catechol metal salt, metal-containing bisazo dye, nigrosine dye, tetraphenylborate derivative, quaternary ammonium salt, alkyl Examples include pyridinium salts, chlorinated polyesters, and nitrofunic acid.

Examples of the magnetic powder include magnetite, maghemite, various ferrites, cupric oxide, nickel oxide, zinc oxide, zirconium oxide, titanium oxide, magnesium oxide, and other metal oxides, and magnetic materials such as Fe, Co, and Ni. The thing etc. which were comprised with the magnetic material containing a metal are mentioned.
The external additive will be described in detail later.
In addition to the above materials, the toner may contain, for example, zinc stearate, zinc oxide, cerium oxide, silica, titanium oxide, iron oxide, fatty acid, fatty acid metal salt, and the like.

<Toner production method>
Next, a preferred embodiment of the toner production method of the present invention will be described.
FIG. 5 is a longitudinal sectional view schematically showing an example of the configuration of a kneader and a cooler for producing a kneaded product.
In the following description, a case where toner is manufactured using a kneaded material K7 containing a colorant and a resin material will be described.

Since the colorant (microencapsulated pigment) used in the present invention has a high affinity with the resin material and a high dispersibility in the resin, it can be easily and uniformly dispersed in the kneaded product. Therefore, a toner having a small variation in characteristics among the toner particles can be easily produced by the following method (kneading and pulverizing method).
The kneaded material K7 can be manufactured using, for example, an apparatus as shown in FIG.

(Kneading process)
The raw material K5 used for kneading contains the components as described above. In particular, in a composition containing a colorant, since the colorant easily embeds air, air tends to remain in the composition. However, by kneading in this step, In particular, air entrained by the colorant can be efficiently removed, and bubbles can be effectively prevented from being mixed (remaining) inside the toner particles.

The raw material K5 used for kneading is preferably a mixture of these components.
This embodiment demonstrates the structure which uses a biaxial kneading extruder as a kneading machine.
The kneading machine K1 includes a process part K2 for kneading while conveying the raw material K5, a head part K3 for extruding the kneaded raw material (kneaded material K7) into a predetermined cross-sectional shape, and a raw material K5 in the process part K2. And a feeder K4 to be supplied.

The process part K2 includes a barrel K21, a screw K22 and a screw K23 inserted into the barrel K21, and a fixing member K24 for fixing the head part K3 to the tip of the barrel K21.
In the process part K2, when the screw K22 and the screw K23 rotate, a shearing force is applied to the raw material K5 supplied from the feeder K4, and a uniform kneaded material K7 is obtained.

  The total length of the process part K2 is preferably 50 to 300 cm, and more preferably 100 to 250 cm. If the total length of the process part K2 is less than the lower limit, it may be difficult to mix the components in the raw material K5 sufficiently uniformly. On the other hand, when the total length of the process part K2 exceeds the upper limit, depending on the temperature in the process part K2, the number of rotations of the screw K22, the screw K23, and the like, the material K5 is easily denatured by heat, and finally obtained. It may be difficult to sufficiently control the physical properties of the toner.

  Moreover, although the raw material temperature at the time of kneading | mixes changes with compositions etc. of the raw material K5, it is preferable that it is 80-260 degreeC, and it is more preferable that it is 90-230 degreeC. Note that the raw material temperature in the process part K2 may be uniform or may vary depending on the part. For example, the process unit K2 includes a first region having a relatively low set temperature and a second region that is provided on the base end side from the first region and whose set temperature is higher than the first region. You may have.

  In addition, the residence time (time required for passage) of the raw material K5 in the process part K2 is preferably 0.5 to 12 minutes, and more preferably 1 to 7 minutes. If the residence time in the process part K2 is less than the lower limit, it may be difficult to mix the components in the raw material K5 sufficiently uniformly. On the other hand, when the residence time in the process part K2 exceeds the upper limit, the production efficiency is lowered. Depending on the temperature in the process part K2, the rotational speed of the screw K22, the screw K23, and the like, Modification tends to occur, and it may be difficult to sufficiently control the physical properties of the finally obtained toner.

  The number of rotations of the screw K22 and the screw K23 varies depending on the composition of the binder resin and the like, but is preferably 50 to 600 rpm. If the rotational speeds of the screws K22 and K23 are less than the lower limit, it may be difficult to mix the components in the raw material K5 sufficiently uniformly. On the other hand, when the rotation speed of the screw K22 and the screw K23 exceeds the upper limit value, the molecular chain of the resin may be cut by shearing, and the resin characteristics may be deteriorated.

  Further, in the kneader K1 used in the present embodiment, the inside of the process unit K2 is connected to the pump P via the deaeration port K25. Thereby, the inside of the process part K2 can be degassed, and an increase in the pressure in the process part K2 due to heating or heat generation of the raw material K5 (kneaded material K7) can be prevented. As a result, the kneading process can be performed safely and efficiently. Further, since the inside of the process part K2 is connected to the pump P via the deaeration port K25, it is possible to effectively prevent bubbles (particularly relatively large bubbles) from being contained in the obtained kneaded material K7. And the properties of the finally obtained toner can be made more excellent.

(Extrusion process)
The kneaded material K7 kneaded in the process part K2 is pushed out of the kneader K1 through the head part K3 by the rotation of the screw K22 and the screw K23.
The head part K3 has an internal space K31 into which the kneaded material K7 is fed from the process part K2, and an extrusion port K32 from which the kneaded material K7 is extruded.

  The temperature of the kneaded material K7 in the internal space K31 (at least in the vicinity of the extrusion port K32) is not particularly limited, but is preferably a temperature equal to or higher than the softening temperature of the resin material contained in the raw material K5. As a result, the toner particles can be obtained as a mixture of the constituent components more uniformly, and variations in characteristics (charging characteristics, fixing properties, etc.) among the toner particles can be particularly reduced.

The specific temperature of the kneaded material K7 in the internal space K31 (at least the temperature near the extrusion port K32) is not particularly limited, but is preferably 80 to 150 ° C, more preferably 90 to 140 ° C. preferable. When the temperature of the kneaded material K7 in the internal space K31 is a value within the above range, the kneaded material K7 does not solidify in the internal space K31 and is easily extruded from the extrusion port K32.
In the illustrated configuration, the internal space K31 has a cross-sectional area gradually decreasing portion K33 in which the cross-sectional area gradually decreases in the direction of the extrusion port K32. By having such a cross-sectional area gradually decreasing portion K33, the extrusion amount of the kneaded material K7 extruded from the extrusion port K32 is stabilized, and the cooling rate of the kneaded material K7 in the cooling step described later is stabilized. As a result, the toner produced using the toner has a small variation in characteristics among the toner particles, and has excellent overall characteristics.

(Cooling process)
The softened kneaded material K7 extruded from the extrusion port K32 of the head portion K3 is cooled and solidified by the cooler K6.
The cooler K6 includes rolls K61, K62, K63, and K64, and belts K65 and K66.
The belt K65 is wound around a roll K61 and a roll K62. Similarly, the belt K66 is wound around the roll K63 and the roll K64.

  The rolls K61, K62, K63, and K64 rotate around the rotation axes K611, K621, K631, and K641 in the directions indicated by e, f, g, and h in the drawing. Thereby, the kneaded material K7 extruded from the extrusion port K32 of the kneading machine K1 is introduced between the belt K65 and the belt K66. The kneaded material K7 introduced between the belt K65 and the belt K66 is cooled while being formed into a plate shape having a substantially uniform thickness. The cooled kneaded material K7 is discharged from the discharge portion K67. The belts K65 and K66 are cooled by a method such as water cooling or air cooling. When such a belt type is used as the cooler, the contact time between the kneaded product extruded from the kneader and the cooling body (belt) can be increased, and the cooling efficiency of the kneaded product is particularly excellent. Can be.

  By the way, in the kneading process, since shearing force is applied to the raw material K5, phase separation (particularly macrophase separation) is sufficiently prevented, but the kneaded product K7 that has finished the kneading process is not subjected to shearing force. Therefore, depending on the constituent materials of the kneaded product, phase separation (macrophase separation) or the like may occur again if left for a long period of time. Therefore, it is preferable to cool the kneaded material K7 obtained as described above as soon as possible. Specifically, the cooling rate of the kneaded material K7 (for example, the cooling rate when the kneaded material K7 is cooled to about 60 ° C.) is preferably 3 ° C./second or more, and is preferably 5-100 ° C./second. Is more preferable. Further, the time required from the end of the kneading step (when the shearing force is no longer applied) to the completion of the cooling step (for example, the time required for cooling the temperature of the kneaded product K7 to 60 ° C. or lower) is 20 seconds. Or less, more preferably 3 to 12 seconds.

In the present embodiment, the configuration using a continuous biaxial kneading extruder as the kneading machine has been described, but the kneading machine used for kneading the raw materials is not limited to this. For kneading the raw materials, for example, various kneaders such as a kneader, a batch type triaxial roll, a continuous biaxial roll, a wheel mixer, and a blade type mixer can be used.
In the illustrated configuration, a kneader having two screws has been described. However, the number of screws may be one or three or more. Further, the kneading apparatus may have a disc (kneading disc) portion.

Further, in the present embodiment, the configuration using one kneader has been described, but kneading may be performed using two kneaders. In this case, the heating temperature of the raw material, the rotational speed of the screw, and the like may be different between one kneader and the other kneader.
In the present embodiment, a configuration using a belt type as the cooler has been described. However, for example, a roll type (cooling roll type) cooler may be used. Further, the cooling of the kneaded product extruded from the extrusion port K32 of the kneader is not limited to the one using the above-described cooler, and may be performed by, for example, air cooling.

(Crushing process)
First, the kneaded material K7 that has undergone the cooling process as described above is pulverized.
The pulverization method is not particularly limited, and can be performed using various pulverizers and crushers such as a ball mill, a vibration mill, a jet mill, and a pin mill.
The pulverization process may be performed in multiple steps (for example, two stages of a coarse pulverization process and a fine pulverization process).

In addition, after such a pulverization step, a classification process, an external addition process, a thermal spheronization process, or the like may be performed as necessary.
For the classification treatment, for example, a sieve, an airflow classifier or the like can be used.
Examples of the external additive used for the external addition treatment include metal oxides such as silica, aluminum oxide, titanium oxide, strontium titanate, cerium oxide, magnesium oxide, chromium oxide, titania, zinc oxide, alumina, and magnetite. Fine particles composed of inorganic materials such as nitrides such as silicon nitride, carbides such as silicon carbide, calcium sulfate, calcium carbonate, aliphatic metal salts, acrylic resins, fluororesins, polystyrene resins, polyester resins, aliphatic metal salts Fine particles composed of organic materials such as these, and fine particles composed of a composite of these.

As the external additive, the surface of the fine particles as described above is subjected to a surface treatment with HMDS, a silane coupling agent, a titanate coupling agent, a fluorine-containing silane coupling agent, silicone oil or the like. It may be used.
The toner of the present invention produced as described above has a uniform shape and a sharp particle size distribution (small width).

  The volume-based average particle diameter of the toner obtained as described above is preferably 2 to 20 μm, and more preferably 4 to 15. When the average particle size of the toner is less than the lower limit, it becomes difficult to uniformly charge, and the adhesion force to the surface of the electrostatic latent image carrier (for example, a photoreceptor) increases. As a result, There may be an increase in the residual toner. On the other hand, when the average particle size of the toner exceeds the upper limit, the reproducibility of the contour portion of an image formed using the toner, particularly a character image or a light pattern, is deteriorated.

Further, the toner preferably has a standard deviation of the particle size between particles of 1.5 μm or less, more preferably 1.3 μm or less, and even more preferably 1.0 μm or less. When the standard deviation of the particle diameter between the particles is 1.5 μm or less, variations in charging characteristics, fixing characteristics and the like are particularly small, and the reliability of the toner as a whole is further improved.
As mentioned above, although this invention was demonstrated based on suitable embodiment, this invention is not limited to this.
For example, in the above-described embodiment, the toner is obtained by pulverizing the kneaded product. However, the present invention is not limited to this, and the toner may be manufactured using, for example, an emulsion polymerization method.

[1] Production of toner (Example 1)
<Manufacture of colorant (microencapsulated pigment)>
First, a magenta pigment (CI Pigment Red 122) composed of pigment particles having a cationic group on the surface was prepared.

4 g of Aqualon KH-10 as an anionic polymerizable surfactant was added to and mixed with an aqueous dispersion obtained by dispersing 15 g of this magenta pigment particle in 75 g of ion-exchanged water, and then irradiated with ultrasonic waves for 15 minutes. Next, 6 g of benzyl methacrylate, 4 g of dodecyl methacrylate, 2 g of anionic polymerizable surfactant Aqualon KH-10, 0.5 g of 2-acrylamido-2-methylpropanesulfonic acid and 50 g of ion-exchanged water as hydrophilic monomers were added. Then, the mixture was again irradiated with ultrasonic waves for 30 minutes. This was put into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature controller, a nitrogen introduction tube and an ultrasonic generator. After the internal temperature of the reaction vessel was raised to 80 ° C., an aqueous potassium persulfate solution in which 0.4 g of potassium persulfate was dissolved as a polymerization initiator was added dropwise to 20 g of ion-exchanged water. Polymerized for hours. After the polymerization is completed, the pH is adjusted to 8, and unreacted substances are removed by ultrafiltration. Then, coarse particles are removed by a membrane filter having a pore size of 1 μm to obtain a dispersion of the target microencapsulated pigment “AMP magenta pigment”. Obtained.
The volume average particle diameter of the obtained dispersion was measured using a laser Doppler type particle size distribution analyzer Microtrac UPA150 manufactured by Leeds & Northrop Co. As a result, it was 130 nm.
Thereafter, the dispersion was heat-dried under reduced pressure to obtain an AMP magenta pigment.

<Manufacture of toner>
First, styrene-acrylic copolymer (manufactured by Sekisui Chemical Co., Ltd .: trade name “ESREC P, Grade SE-0040”): 60 parts by weight and AMP magenta pigment: 40 parts by weight are mixed by a flushing method, and the mixture is mixed. It was created. This mixture was coarsely pulverized to a diameter of about 2 mm to obtain a pigment master batch.

  Next, styrene-acrylic copolymer (manufactured by Sekisui Chemical Co., Ltd .: trade name “ESREC P, Grade SE-0040”): 100 parts by weight, pigment masterbatch: 10 parts by weight, and fourth as a charge control agent. Styrene-acrylic copolymer having a quaternary ammonium base (manufactured by Fujikura Kasei Co., Ltd .: trade name “acrylic base FCA-201-PS”): 2 parts by weight, and carnauba wax (molecular weight 850) as a wax: 3 parts by weight Prepared.

These components were mixed using a 20 L type Henschel mixer to obtain a raw material for toner production.
Next, this raw material (mixture) was kneaded using a twin-screw kneading extruder (Toshiba Machine Co., Ltd., TEM-41 type) as shown in FIG.
The total length of the process part of the biaxial kneading extruder was 160 cm.

In addition, the temperature of the raw material in the process section was set to 120 ° C.
The screw rotation speed was 120 rpm, and the raw material charging speed was 20 kg / hour.
The time required for the raw material to pass through the process part, determined from such conditions, is about 4 minutes.

The kneading as described above was performed while degassing the inside of the process unit by operating a vacuum pump connected to the process unit via a degassing port.
The raw material (kneaded material) kneaded in the process part was extruded outside the biaxial kneading extruder through the head part. The temperature of the kneaded material in the head part was adjusted to 100 ° C.
Thus, the kneaded material extruded from the extrusion port of the biaxial kneading extruder was cooled using a cooling machine as shown in FIG. The temperature of the kneaded material immediately after the cooling step was about 45 ° C.

The cooling rate of the kneaded product was 6 ° C./second. In addition, the time required from the end of the kneading process to the end of the cooling process was 10 seconds.
The kneaded product cooled as described above was coarsely pulverized (average particle size: 1 to 2 mm), and then finely pulverized. A hammer mill was used for coarse pulverization of the kneaded product, and a jet mill (200 AFG, manufactured by Hosokawa Micron Corporation) was used for fine pulverization. The fine pulverization was performed at a pulverization air pressure: 500 [kPa] and a rotor rotational speed: 7000 [rpm].
The pulverized material thus obtained was classified with an airflow diverter (manufactured by Hosokawa Micron Corporation, 100 ATP).

Thereafter, an external additive was applied to the classified powder for toner production to obtain a toner. Application of the external additive was performed by mixing 100 parts by weight of the powder for toner production and 2.5 parts by weight of the external additive using a 20 L type Henschel mixer. As external additives, positively charged silica (manufactured by Nippon Aerosil Co., Ltd .: trade name “positively chargeable silica RA200HS”): 1 part by weight, positively chargeable silica (manufactured by Wacker: trade name “positively chargeable silica HVK-”) 2150 "): 0.5 parts by weight.
The finally obtained toner had a weight-based average particle size of 7.5 μm. The particle size standard deviation based on weight was 0.8 μm.

(Example 2)
A toner was manufactured in the same manner as in Example 1 except that the colorant manufactured as follows was used. The finally obtained toner had a weight-based average particle size of 7.5 μm. The particle size standard deviation based on weight was 0.7 μm.
<Manufacture of colorant (microencapsulated pigment)>
First, a yellow pigment composed of pigment particles having a cationic group on the surface (CI Pigment Yellow 180) was prepared.
4 g of Aqualon KH-10 as an anionic polymerizable surfactant was added to and mixed with an aqueous dispersion obtained by dispersing 15 g of this yellow pigment particle in 75 g of ion-exchanged water, and then irradiated with ultrasonic waves for 15 minutes. Next, 6 g of benzyl methacrylate, 4 g of dodecyl methacrylate, 2 g of anionic polymerizable surfactant Aqualon KH-10, 0.5 g of 2-acrylamido-2-methylpropanesulfonic acid and 50 g of ion-exchanged water as hydrophilic monomers were added. Then, the mixture was again irradiated with ultrasonic waves for 30 minutes. This was put into a reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a temperature controller, a nitrogen introduction tube and an ultrasonic generator. After the internal temperature of the reaction vessel was raised to 80 ° C., an aqueous potassium persulfate solution in which 0.4 g of potassium persulfate was dissolved as a polymerization initiator was added dropwise to 20 g of ion-exchanged water. Polymerized for hours. After the polymerization is completed, the pH is adjusted to 8, and unreacted substances are removed by ultrafiltration. Then, coarse particles are removed by a membrane filter having a pore size of 1 μm to obtain a dispersion of the target microencapsulated pigment “AMP yellow pigment”. Obtained.
The volume average particle diameter of the obtained dispersion was measured using a laser Doppler type particle size distribution analyzer Microtrac UPA150 manufactured by Leeds & Northrop Co. As a result, it was 130 nm.
Thereafter, the dispersion was heated and dried under reduced pressure to obtain an AMP yellow pigment.

(Comparative Example 1)
A toner was produced in the same manner as in Example 1 except that the pigment particles were not encapsulated.
(Comparative Example 2)
A toner was produced in the same manner as in Example 2 except that the pigment particles were not encapsulated.

[2] Evaluation Each toner obtained as described above was evaluated for charging uniformity, fogging, and fixing strength.
[2.1] Charge Uniformity The toners obtained in each Example and each Comparative Example were respectively charged into a developing device of a color laser printer (manufactured by Seiko Epson Corporation, LP-9300C). The toner regulating blade of the developing device of the same machine was adjusted so that a predetermined amount of toner (0.65 mg / cm 2) was supplied from the developing roller to the photoconductor, and the LP9300 was operated.

The charge amount of the toner regulated by the toner regulating blade and conveyed to the photosensitive member was evaluated by analyzing the toner on the developing roller. The charge amount was measured by an E-SPART analyzer manufactured by Hosokawa Micron Corporation. The measurement conditions were a suction flow rate of 0.2 liters / minute, a dust collection air flow rate of 0.6 liters / minute, a blowing nitrogen gas pressure of 0.02 MPa, and the charge amount (Q / m) for each toner was measured. The charge amount distribution was obtained with a toner count of 3000.
The uniformity of the toner charge amount is obtained by dividing the maximum charge amount (Q ₁ / m ₁ ) and the total toner charge amount measured by the measurement count (number) in the number distribution of the charge amount per toner. The smaller the absolute value of the difference from the value (Q ₂ / m ₂ ), the more uniform the charge amount distribution, and the larger the absolute value, the more nonuniform.

[2.2] Cover evaluation A mending tape manufactured by Sumitomo 3M Co., Ltd. is affixed to plain paper manufactured by Fuji Xerox Office Supply Co., Ltd. (product name J). The color of this tape is measured with a color difference meter CR-221 manufactured by Minolta Co., Ltd. (this is the reference value).
A color laser printer (manufactured by Seiko Epson Corporation, LP-3000C) modified to a positive charge reversal development system was used.

  The toner to be evaluated was put in a developing machine, and white (solid white) was printed on the entire surface. The operation of the printer was stopped during printing, and the photosensitive member was taken out. Attach the mending tape to the area where the photoconductor and transfer belt are in contact (transfer nip) and the area where the developing roller and photoconductor are close (development nip). The color difference between this tape and the reference value was measured. A smaller color difference means less fogging.

[2.3] Fixing Strength Using a color laser printer (manufactured by Seiko Epson Corporation, LP-2000C), images of a predetermined pattern with the toners obtained in the respective Examples and Comparative Examples were recorded on a recording paper manufactured by Seiko Epson Corporation. , High quality paper LPCPPA4). Thereafter, the image formed on the recording paper was thermally fixed by an oven. This heat fixing was performed under the condition of 120 ° C. × 30 minutes.

Thereafter, after confirming the non-offset area, the fixed image on the recording paper is erased twice (rubber eraser “LION 261-11” manufactured by Lion Business Machine Co., Ltd.) with a pressing load kgf, and the residual ratio of the image density is X -Measured by "X-Rite model 404" manufactured by Rite Inc, and evaluated according to the following three-stage criteria.
○: Image density residual ratio is 90% or more.
Δ: Image density remaining ratio is 70% or more and less than 90%.
X: Image density residual ratio is less than 70%.
These results are shown in Table 1.

As is clear from Table 1, the toners of the present invention (Examples 1 and 2) were all excellent in charging uniformity and fixing strength and had little fog. On the other hand, all of the toners of the comparative examples were inferior in charging uniformity and fixing strength, and had a lot of fog.
In each example and each comparative example, C.I. I. Pigment Blue 15: 3, copper phthalocyanine pigment, Pigment Red 57: 1, C.I. I. Toner was produced in the same manner except that Pigment Yellow 93 and carbon black microencapsulated were used, and each of these toners was evaluated in the same manner as described above. As a result, the same results as those of the respective Examples and Comparative Examples were obtained.

It is a figure which shows the manufacturing process of the coloring agent applied to the toner of this invention. It is a figure which shows an example of the microencapsulation pigment applied to the toner of this invention. It is a figure which shows the manufacturing process of the coloring agent applied to the toner of this invention. It is a figure which shows an example of the microencapsulation pigment applied to the toner of this invention. FIG. 3 is a longitudinal sectional view schematically showing an example of the configuration of a kneader and a cooler used in the toner production method of the present invention.

Explanation of symbols

  K1 ... kneading machine K2 ... process part K21 ... barrel K22, K23 ... screw K24 ... fixing member K25 ... deaeration port K3 ... head part K31 ... internal space K32 ... extrusion port K33 ... cross-sectional area gradually decreasing part K4 ... feeder K5 ... raw material K6 ... Cooling machines K61, K62, K63, K64 ... Rolls K611, K621, K631, K641 ... Rotating shaft K65, K66 ... Belt K67 ... Discharge part K7 ... Kneaded material 1 ... Pigment particles 11 ... Anionic group 12 ... Hydrophobic group 13 ... Polymerizable group 14 ... Cationic group 2 ... Cationic polymerizable surfactant 60 ... Polymer layer 100, 101 ... Microencapsulated pigment

Claims (13)

A toner containing at least a binder resin and a colorant,
As the colorant, pigment particles having a cationic group on the surface are coated with a polymer having a repeating structural unit derived from an anionic polymerizable surfactant having an anionic group, a hydrophobic group, and a polymerizable group. A toner characterized by using a toner.   The colorant is obtained by coating the pigment particles with a polymer by polymerizing the anionic polymerizable surfactant in an aqueous dispersion in which the pigment particles having a cationic group on the surface are dispersed. The toner according to claim 1, wherein   The toner according to claim 1, wherein the polymer further has a repeating structural unit derived from a hydrophobic monomer. The toner according to claim 1, wherein the polymer further has a repeating structural unit derived from a crosslinkable monomer and / or a repeating structural unit derived from a monomer represented by the following general formula (1). .

  The toner according to claim 1, wherein the pigment constituting the pigment particles is carbon black.   The cationic group of the pigment particle is selected from the group consisting of a primary amine cation group, a secondary amine cation group, a tertiary amine cation group, and a quaternary ammonium cation group. The toner according to any one of 5. The anionic group of the anionic polymerizable surfactant is a sulfonate anion group (—SO ₃ ^— ), a sulfinate anion group (—RSO ₂ ^— : R is a C _{1 to} C ₁₂ alkyl group or a phenyl group, and The toner according to claim 1, wherein the toner is selected from the group consisting of a modified product) and a carboxylate anion group (—COO ⁻ ).   The toner according to claim 1, wherein the hydrophobic group of the anionic polymerizable surfactant is selected from the group consisting of an alkyl group, an aryl group, and a group in which these are combined.   The polymerizable group of the anionic polymerizable surfactant is an unsaturated hydrocarbon group capable of radical polymerization, and includes a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, a propenyl group, a vinylidene group, and a vinylene group. The toner according to claim 1, wherein the toner is selected from the group.   The colorant is prepared by adding the anionic polymerizable surfactant to the aqueous dispersion of pigment particles having the cationic group on the surface and mixing, and then adding the anionic polymerizable surfactant and emulsifying, followed by polymerization. The toner according to claim 1, which is obtained by adding an agent and polymerizing in water.   The colorant is prepared by adding the anionic polymerizable surfactant to an aqueous dispersion of pigment particles having the cationic group on the surface and mixing, and then adding a hydrophobic monomer and the anionic polymerizable surfactant. The toner according to claim 1, which is obtained by mixing, emulsifying, adding a polymerization initiator and polymerizing in water. The colorant is prepared by adding the anionic polymerizable surfactant to an aqueous dispersion of pigment particles having a cationic group on the surface and mixing the resulting mixture with a hydrophobic monomer and a crosslinkable monomer and / or the following general formula (1). The monomer represented by formula (I) and the anionic polymerizable surfactant are added and mixed, and after emulsification, a polymerization initiator is added and polymerization is performed in water. toner.

  The toner according to claim 1, comprising a charge control agent.

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