JP2014098858A - Toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that suppresses a reduction in fluidity even after storage in a high-temperature and high-humidity environment, and has good charging characteristics.SOLUTION: A toner has toner particles containing a binder resin, a colorant, and a charge control agent; the charge control agent has a polymer A having a structure a indicated by the following formula (1) as a partial structure; and the weight average molecular weight (Mw) of the polymer A is 1000 or more and 100000 or less.

Description

  The present invention relates to a toner for developing an electrostatic charge image in an image forming method such as electrophotography or electrostatic printing, or a toner for forming a toner image in a toner jet type image forming method.

  Many studies have been conducted to improve the charging characteristics of toner. In particular, in recent years, proposals have been made to use a resin having a charge control function (charge control resin) as a raw material for toner because of environmental considerations, more stable chargeability requirements, manufacturing costs, and the like. . For example, there has been proposed a toner containing, as a charge control resin, a resin composed of a neutralized salt of vinyl benzoic acid as a monomer unit (Patent Document 1). According to this method, it is said that a toner having a quick charge rise, a sharp charge amount distribution, and excellent environmental stability and stability over time can be obtained. Further, a toner produced by suspension polymerization using a composition liquid containing a vinyl benzoic acid monomer or a polymer having vinyl benzoic acid has been proposed (Patent Document 2). According to this method, it is said that a toner having a quick rise in charge and good chargeability can be obtained. In addition, a toner using a resin containing a sulfonic acid group as a charge control resin has been proposed (Patent Document 3). According to this method, it is said that a change in charge amount due to environmental change is small and a toner having stable charging characteristics can be obtained.

  However, it has been clarified that such a toner has insufficient charging performance (particularly, initial charge rising property) when the process speed is increased by a contact one-component developing system or the like. For this phenomenon, the toner is required to have a rapid charge that rises to a sufficient charge amount in a short time, and a toner that can achieve this is required. In addition, regarding the charging characteristics, it is also required that the difference in the charge amount of the toner is small before and after being left for a long time, particularly under high temperature and high humidity.

  In recent years, there has been an increasing demand for toners that can be fixed at lower temperatures, and development of toners that melt at lower temperatures is underway. On the other hand, due to the influence of global warming, improvement in storage resistance at higher temperatures and higher humidity is also required. Under such circumstances, the above-described charge control resin is particularly susceptible to moisture absorption and softening under high temperature and high humidity when using toner that melts at low temperature, and the problem is that the fluidity of the toner is reduced. There was room for improvement. Therefore, development of a toner capable of suppressing moisture absorption and softening under high temperature and high humidity while maintaining good charging characteristics is demanded.

JP-A 63-88565 Japanese Patent Laid-Open No. 11-72955 Japanese Patent No. 2807955

  An object of the present invention is to provide a toner capable of raising the charge to a sufficient charge amount in a short time.

  As a result of intensive studies, the present inventors have found that the above problems can be solved by the toner of the present invention, and have reached the present invention.

  That is, the present invention is a toner having toner particles containing a binder resin, a colorant, and a charge control agent, and the charge control agent is a polymer having a structure a represented by the following formula (1) as a partial structure: A toner containing A, wherein the polymer A has a weight average molecular weight (Mw) of 1,000 to 100,000.

式（１）

Formula (1)

(In Formula (1), R ¹ represents an alkyl group having 1 to 18 carbon atoms or an alkoxyl group having 1 to 18 carbon atoms, and R ² represents a hydrogen atom, a hydroxyl group, and 1 to 18 carbon atoms. When the following alkyl group or an alkoxyl group having 1 to 18 carbon atoms is represented, g represents an integer of 1 or more and 3 or less, h represents an integer of 0 or more and 3 or less, and h is 2 or 3 , R ¹ can be selected independently.)

  According to the present invention, it is possible to provide a toner capable of raising the charge to a sufficient charge amount in a short time.

1 is a device for measuring a charge amount according to the present invention. It is an evaluation standard of the charge amount distribution in the present invention.

  Hereinafter, the present invention will be described in detail.

  The present inventors have found that a toner capable of solving the above problems can be obtained by using a polymer A having a structure a represented by the following formula (1) as a partial structure as a charge control agent for toner. I found it.

式（１）

Formula (1)

(In Formula (1), R ¹ represents an alkyl group having 1 to 18 carbon atoms or an alkoxyl group having 1 to 18 carbon atoms, and R ² represents a hydrogen atom, a hydroxyl group, and 1 to 18 carbon atoms. When the following alkyl group or an alkoxyl group having 1 to 18 carbon atoms is represented, g represents an integer of 1 or more and 3 or less, h represents an integer of 0 or more and 3 or less, and h is 2 or 3 , R ¹ can be selected independently.)
Examples of the alkyl group in R ¹ and R ² include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, and a t-butyl group. Examples of the alkoxyl group Includes a methoxy group, an ethoxy group, a propoxy group, and the like.

  The polymer A is a polymer having the structure a. The toner using this polymer A as a charge control agent is a triboelectric charge which raises the charge to a sufficient charge amount in a short time compared to the case where a conventional resin having a benzoic acid structure is used as a charge control resin. Excellent characteristics (hereinafter also referred to as charge rising property). In addition, the difference in charge amount before and after standing for a long time can be reduced. Furthermore, a decrease in toner fluidity can be suppressed even when stored under high temperature and high humidity.

  Structure a is characterized in that a benzyloxy moiety is interposed between the connecting portion with the main chain and the benzoic acid structural moiety, and is structurally flexible. This has the effect of facilitating the arrangement of molecules where charge transfer is more advantageous, and is considered to improve the charge-rise property compared to conventional resins having a benzoic acid structure. Moreover, it is considered that the ease of charge transfer due to the flexibility of the structure a contributes to an increase in the saturation charge amount. As a result, it is possible to reduce the amount of charge control agent added to the toner to obtain a desired saturation charge amount, and thus it is possible to suppress a decrease in toner fluidity when stored under high temperature and high humidity. It becomes.

  Examples of the main chain structure of the polymer A include the following. Examples thereof include vinyl polymers, polyester polymers, polyamide polymers, polyurethane polymers, polyether polymers, and the like. Moreover, the hybrid type polymer which combined these 2 or more types is also mentioned. Among these, considering the affinity of the toner with the binder resin, for example, when the main component of the binder resin is a polyester resin, the main chain structure of the polymer A is preferably a polyester polymer. Moreover, when the main component of binder resin is a vinyl resin, it is preferable to make the main chain structure of the polymer A into a vinyl polymer. Furthermore, in the case of a toner in which the main component of the binder resin is a vinyl resin, the structure a represented by the above formula (1) is preferably included in the polymer A as a unit represented by the following formula (2).

（式２）

(Formula 2)

(In the formula (2), R ³ represents an alkyl group having 1 to 18 carbon atoms or an alkoxyl group having 1 to 18 carbon atoms, and R ⁴ represents a hydrogen atom, a hydroxyl group, 1 to 18 carbon atoms. The following alkyl group or an alkoxyl group having 1 to 18 carbon atoms is represented, R ⁵ represents a hydrogen atom or a methyl group, i represents an integer of 1 to 3, and j represents 0 to 3 Represents an integer, and when j is 2 or 3, each R ³ can be independently selected.)
Examples of the alkyl group in R ³ and R ⁴ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, and a t-butyl group. Examples of the alkoxyl group Examples thereof include a methoxy group, an ethoxy group, and a propoxy group.

  Thus, since the polymer A is a vinyl polymer, it is easily compatible in the toner particles containing the vinyl resin as a main component. Compatibilization makes it possible to take a more optimal molecular arrangement, and the charging ability of the polymer A is more effectively exhibited. When the toner is produced in an aqueous medium, it is easy to exert the effect of the charge control agent by considering the compatibility of the polymer A with the binder resin, and the highly polar polymer A component is applied to the toner particle surface layer. Since the arrangement proceeds smoothly, the charge rising property can be expressed more efficiently.

  As for the molecular weight of the polymer A, the weight average molecular weight calculated by gel permeation chromatography (GPC) is from 1,000 to 100,000, preferably from 10,000 to 90,000. By setting the weight average molecular weight of the polymer A to 1000 or more, exudation of the polymer A from the toner particles to the toner surface when stored under high temperature and high humidity is suppressed, and good fluidity can be secured. . Further, by setting the weight average molecular weight to 100000 or less, the toner has good fixability, and uneven distribution among the toner particles of the polymer A can be suppressed, resulting in a sharp charge amount distribution. In order to make a weight average molecular weight into the said range, it can control by changing conditions, such as the amount of reagents at the time of manufacturing the polymer A, reaction temperature, and solvent concentration. Moreover, the polymer A of desired molecular weight can be obtained by fractionating by GPC.

  Further, the content of the structure a in the polymer A is preferably 10 μmol / g or more and 1500 μmol / g or less. When the content of the structure a in the polymer A is 10 μmol / g or more, good triboelectric chargeability is exhibited. Moreover, by being 1500 micromol / g or less, the influence of the charging property by the hygroscopic property which the structure a has can be suppressed, and especially the fall of the charging property at the time of leaving for a long term can be suppressed more. In addition, a decrease in toner fluidity due to the hygroscopicity of the structure a can be suppressed. The content of the structure “a” in the polymer A can be adjusted by the charging ratio at the time of synthesizing the polymer A and the reaction conditions such as the reaction temperature.

  It does not specifically limit as a manufacturing method of the polymer A, It can manufacture by a well-known method. In the case of a vinyl polymer, for example, a polymerizable monomer (formula (5)) containing structure a having the structure represented by formula (1) and a vinyl monomer are used as a polymerization initiator. It is a method of using and copolymerizing.

式（５）

Formula (5)

(In Formula (5), R ⁹ represents an alkyl group having 1 to 18 carbon atoms or an alkoxyl group having 1 to 18 carbon atoms, and R ¹⁰ represents a hydrogen atom, a hydroxyl group, and 1 to 18 carbon atoms. The following alkyl group or an alkoxyl group having 1 to 18 carbon atoms is represented, R ¹¹ represents a hydrogen atom or a methyl group, m represents an integer of 1 to 3 and n represents 0 to 3 And when n is 2 or 3, each R ⁹ can be independently selected.)
Specific examples of the polymerizable monomer having the structure a are shown in Table 1. In addition, the polymerizable monomer which has the structure a is not limited to these.

  In Table 1, Me is a methyl group and MeO is a methoxy group.

  The vinyl monomer to be copolymerized with the polymerizable polymer A containing the structure a is not particularly limited. Specifically, styrene and its derivatives such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene; ethylene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; Vinyl halides such as vinyl, vinylidene chloride, vinyl bromide, vinyl fluoride; vinyl ester acids such as vinyl acetate, vinyl propionate, vinyl benzoate; acrylic acid-n-butyl, acrylic acid-2-ethylhexyl, etc. Acrylic acid esters; Methacrylic acid esters obtained by changing the acrylic acid of the acrylic acid esters to methacrylic acid; Methacrylic acid amino esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; Vinyl methyl ether, vinyl ethyl ether Vinyl ethers; vinyl ketones such as vinyl methyl ketone; N-vinyl compounds such as N-vinyl pyrrole; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide, acrylic acid, methacrylic acid Can be mentioned. In addition, you may use a vinyl monomer in combination of 2 or more type as needed. Moreover, you may use a well-known crosslinking agent together.

  Examples of the polymerization initiator that can be used when polymerizing the polymerizable monomer component described above include various substances such as a peroxide polymerization initiator and an azo polymerization initiator. Examples of peroxide polymerization initiators include peroxyesters, peroxydicarbonates, dialkyl peroxides, peroxyketals, ketone peroxides, hydroperoxides, and diacyl peroxides. Examples of the inorganic system include persulfate and hydrogen peroxide. Specifically, t-butyl peroxyacetate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-hexyl peroxyacetate, t-hexyl peroxypivalate, t-hexyl peroxyiso Peroxyesters such as butyrate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate; diacyl peroxides such as benzoyl peroxide; peroxydicarbonates such as diisopropyl peroxydicarbonate; 1 , 1-di-t-hexylperoxycyclohexane and other peroxyketals; di-t-butyl peroxide and other dialkyl peroxides; and other examples include t-butyl peroxyallyl monocarbonate and the like. It is. Examples of the azo polymerization initiator include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1- Carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile, dimethyl-2,2′-azobis (2-methylpropionate) and the like. The

  If necessary, two or more of these polymerization initiators can be used in combination. Under the present circumstances, it is preferable that the usage-amount of the polymerization initiator used is 0.100 mass part or more and 20.0 mass parts or less with respect to 100 mass parts of polymerizable monomers. As the polymerization method, any method such as solution polymerization, suspension polymerization, emulsion polymerization, dispersion polymerization, precipitation polymerization, bulk polymerization and the like can be used, and it is not particularly limited.

On the other hand, when the polymer A containing the structure a of the present invention is a polyester resin, various known production methods can be used. For example,
i) A method of converting to a structure a represented by the formula (1) by an organic reaction using a reaction residue of a carboxyl group or a hydroxyl group contained in a polyester structure;
ii) A method for producing a polyester using a polyhydric alcohol or polyvalent carboxylic acid having the structure a represented by the formula (1) as a substituent;
iii) A method in which a functional group that can be easily introduced as a substituent into the structure a represented by the formula (1) is introduced in advance into a polyhydric alcohol or polycarboxylic acid;
Etc.

In the case of a hybrid resin,
iv) a method of hybridizing a polyester resin containing the structure a represented by the formula (1) as a substituent with a vinyl monomer;
v) A method of polymerizing a vinyl monomer having a carboxyl group such as acrylic acid or methacrylic acid and then converting the carboxyl group into a structure represented by the formula (1) by an organic reaction;
vi) A method of hybridizing a polyester resin using a vinyl monomer having the structure a represented by the formula (1);
Etc.

  As a method for hybridizing the polyester resin with a vinyl monomer, a known method can be used, and it is effective as the method iv). Specific examples include a method of vinyl-modifying polyester with a peroxide-based initiator and a method of preparing a hybrid resin by graft-modifying a polyester resin having an unsaturated group.

  Alternatively, as a specific method of v), when the structure a represented by the formula (1) is introduced, an amide is obtained by using a compound in which an amino group is introduced into the bonding part of the formula (1) for the carboxyl group present in the resin. And the like.

  Further, as a specific method of vi), as the vinyl monomer that can be used, a polymerizable monomer represented by the above formula (5) can be used.

  In the present invention, a known method can be used as a method for adjusting the weight average molecular weight of the polymer. Specifically, in the case of a polyester resin, it can be arbitrarily adjusted by adjusting the charging ratio of the acid component and the alcohol component and the polymerization time. In addition, in the hybrid resin, in addition to the adjustment of the molecular weight of the polyester component, the weight average molecular weight of the polymer can be adjusted by adjusting the molecular weight of the vinyl-modified unit. Specifically, it can be arbitrarily adjusted by adjusting the amount of radical initiator, polymerization temperature and the like in the vinyl modification reaction step. As the vinyl monomer that can be used for hybridization of the polyester resin in the present invention, the above-described vinyl monomers can be used.

  The content of the structure a in the polymer A can be determined by NMR or a method described later. First, the polymer A is titrated by the method described later to determine the acid value of the polymer A, and the amount of carboxyl groups derived from the structure a of the polymer A is calculated. And based on this, content (mmol / g) of the structure a in the polymer A is calculated. In addition, when the polymer A has a carboxyl group at a site other than the structure a, the acid value of the compound (for example, polyester resin) immediately before the addition of the structure a when the polymer A is prepared is measured in advance. Keep it. The addition amount of structure a can be calculated by the difference from the acid value of polymer A after the addition reaction.

  In the toner of the present invention, the content x of the structure a in the toner is preferably 0.10 μmol / g or more and 200.00 μmol / g or less. When the content x of the structure a in the toner is within the above range, a sufficient charge amount can be obtained, and moisture absorption can be suppressed, so that good fluidity can be secured. The content x of the structure a in the toner can be controlled by adjusting the charged amount of the polymer A at the time of toner preparation, the content of the structure a in the polymer A, and the like. The content x of the structure a in the toner described later is calculated from the charged amount of the compound containing the structure a at the time of toner preparation.

  Furthermore, the inventors of the present invention further increase the saturation charge amount by further including, in the toner, a polymer B having the structure b (the following formula (3)) as a partial structure together with the polymer A as a charge control agent. And found that it is effective in improving the charge rising performance.

式（３）

Formula (3)

(In the formula, B ¹ represents an alkylene structure having 1 or 2 carbon atoms which may have a substituent, or an aromatic ring which may have a substituent, and R ⁶ represents a hydrogen atom, or Represents an alkyl group having 1 to 12 carbon atoms, and examples of the substituent in the alkylene structure include a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 or 12 carbon atoms, or 1 or more carbon atoms. And a substituent on the aromatic ring is a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkoxyl group having 1 to 12 carbon atoms.)
The structure b represented by the above formula (3) is preferably included in the polymer B as a unit represented by the following formula (4).

式（４）

Formula (4)

(In the formula (4), B ² represents an alkylene structure having 1 or 2 carbon atoms which may have a substituent, or an aromatic ring which may have a substituent, and R ⁷ represents hydrogen. Represents an atom or an alkyl group having 1 to 12 carbon atoms, R ⁸ represents a hydrogen atom or a methyl group, and examples of the substituent in the alkylene structure include a hydroxyl group and an alkyl group having 1 to 12 carbon atoms. , An aryl group having 6 or 12 carbon atoms, or an alkoxyl group having 1 to 12 carbon atoms, and examples of the substituent in the aromatic ring include a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or carbon It is an alkoxyl group having a number of 1 or more and 12 or less.)
Although the manufacturing method of the polymer B is not specifically limited, It can manufacture with the manufacturing method similar to the polymer A mentioned above. When the polymer B is a vinyl polymer, a vinyl monomer represented by the formula (6) is preferably used.

式（６）

Formula (6)

(In the formula, B ³ represents an alkylene structure having 1 or 2 carbon atoms which may have a substituent, or an aromatic ring which may have a substituent, and R ¹³ represents a hydrogen atom, Alternatively, it represents an alkyl group having 1 to 12 carbon atoms, R ¹⁴ represents a hydrogen atom or a methyl group, and the substituent in the alkylene structure includes a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, carbon An aryl group having 6 or 12 carbon atoms, or an alkoxyl group having 1 to 12 carbon atoms, and examples of the substituent in the aromatic ring include a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or a carbon number of 1 And an alkoxyl group of 12 or less.)
Specific examples of the polymer monomer B containing the structure b include the following. 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamidobenzenesulfonic acid, 2-methacrylamideamidobenzenesulfonic acid, 3-acrylamidobenzenesulfonic acid, 3-methacrylamideamidobenzenesulfonic acid, 4-acrylamidobenzenesulfonic acid, 4- Methacrylamidobenzenesulfonic acid, 2-acrylamido-5-methylbenzenesulfonic acid, 2-methacrylamideamido-5-methylbenzenesulfonic acid, 2-acrylamido-5-methoxybenzenesulfonic acid, 2-methacrylamide-5-methoxybenzenesulfone Acids and their alkyl esters having 1 to 12 carbon atoms. Among these, a sulfonic acid structure, a methyl ester or an ethyl ester is preferable, and a sulfonic acid structure or a methyl ester is more preferable.

  Further, when the polymer B is a polyester resin, the same production method as that for the polymer A can be used. As a method for hybridizing the polyester resin with a vinyl monomer, a known method can be used, and it is effective as the method iv) mentioned as an example of the method for producing the polymer A. Specific examples include a method of vinyl-modifying polyester with a peroxide-based initiator and a method of preparing a hybrid resin by graft-modifying a polyester resin having an unsaturated group.

  In addition, as a specific method of v), when the structure b represented by the formula (3) is introduced, a compound in which an amino group is introduced into the bonding portion of the formula (3) with a carboxyl group present in the resin is used. A method of amidation can be mentioned.

  Further, as a specific method of vi), as the vinyl monomer that can be used, a polymerizable monomer represented by the above formula (6) can be used.

  In the present invention, a known method can be used as a method for adjusting the weight average molecular weight of the polymer. Specifically, in the polyester resin, it can be arbitrarily adjusted depending on the charging ratio of the acid component and the alcohol component and the polymerization time. In addition, in the hybrid resin, in addition to adjusting the molecular weight of the polyester component, it is possible to adjust the molecular weight of the vinyl-modified unit. Specifically, it can be arbitrarily adjusted by the radical initiator amount, the polymerization temperature, etc. in the vinyl modification reaction step. As the vinyl monomer that can be used for hybridization of the polyester resin in the present invention, the above-described vinyl monomers can be used.

  Coexistence of the polymer A and the polymer B in the toner binder improves the charging stability of the toner before and after long-term storage under high temperature and high humidity, and sharpens the charge amount distribution. The reason is not clear, but the present inventors consider as follows. Due to the power generation mechanism by the sulfonic acid group and the charge accumulation function by the amide group in the structure b, the charging speed is increased and the rising of the toner charge is improved.

  On the other hand, the benzoic acid structure and benzyloxyl moiety contained in structure a can dissipate excess charge stored in structure b into the toner binder. As a result, it is considered that excessive charging of the toner is suppressed. Due to this synergistic effect, it is considered that even if there is a variation in the electrification opportunities for each toner particle, the charge amount distribution of the entire toner is likely to be uniform and the charge rise is also good.

  The polymer B is contained in the toner so that the sulfur content is 0.10 μmol / g or more. The content x (μmol / g) of the structure a and the content y (μmol / g) of the structure b are contained in the toner. The molar ratio x / y in g) is preferably from 0.10 to 50.00. When the sulfur content in the toner is 0.10 μmol / g or more, a more sufficient charge amount can be obtained. Further, when x / y is in the above range, the rise of charging is faster and effective due to the synergistic effect of the structure a and the structure b described above. In order to set the sulfur content in the toner to 0.10 μmol / g or more, it can be controlled by the amount of the polymer B added during the production of the toner. Further, in order to make x / y within the above range, the addition amount of the polymer A and the polymer B at the time of toner production is adjusted, the content x of the structure a in the polymer A and the polymer B, and the structure b. It is controllable by adjusting the content y of.

  In the present invention, the sulfur content in the toner and the content y of the structure b are calculated as follows. By elemental analysis of polymer B, the content of sulfur element derived from structure b present in polymer B1g is calculated, and the content of sulfur element is divided by 32.06 (atomic weight of sulfur element), The content (μmol / g) of structure b per 1 g of polymer B is calculated. And the molar ratio a / b of the structure a and the structure b can be calculated | required from content (micromol / g) of the structure a computed from the acid value, and content (micromol / g) of the structure b.

  As addition amount of the polymer A and the polymer B, they are 0.0100 mass part or more and 50.0 mass parts or less with respect to 100.0 mass parts of binder resin. More preferably, it is 0.0100 mass part or more and 30.0 mass part or less.

  The binder resin used in the toner of the present invention is not particularly limited. For example, the following can be exemplified. Styrene resin, acrylic resin, methacrylic resin, styrene-acrylic resin, styrene-methacrylic resin, polyethylene resin, polyethylene-vinyl acetate resin, vinyl acetate resin, polybutadiene resin, phenol resin, polyurethane resin, polybutyral resin, Polyester resins and hybrid resins in which these resins are arbitrarily combined. Among them, the following are preferably used in terms of toner characteristics. Styrenic resin, acrylic resin, methacrylic resin, styrene-acrylic resin, styrene-methacrylic resin, polyester resin, styrene-acrylic resin, or hybrid resin in which styrene-methacrylic resin and polyester resin are combined.

  As the polyester resin, a polyester resin that is usually produced using a polyhydric alcohol and a carboxylic acid, a carboxylic acid anhydride, or a carboxylic acid ester as raw material monomers can be used. Specifically, the same polyhydric alcohol component and polyvalent carboxylic acid component as the above-described polyester resin can be used. Among these, polyester resins obtained by condensation polymerization of the following components are particularly preferable. The diol component is a bisphenol derivative. As the acid component, a carboxylic acid composed of a divalent or higher carboxylic acid or an acid anhydride thereof; a lower alkyl ester such as fumaric acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid component.

The toner of the present invention can also be used as a magnetic toner. In this case, the following magnetic materials are used. Iron oxide including magnetite, maghemite, ferrite, or other metal oxides; metals such as Fe, Co, Ni, or these metals and Al, Co, Cu, Pb, Mg, Ni, Sn, Alloys with metals such as Zn, Sb, Ca, Mn, Se, Ti, and mixtures thereof. Iron trioxide (Fe ₃ O ₄ ), iron trioxide (γ-Fe ₂ O ₃ ), iron oxide zinc (ZnFe ₂ O ₄ ), copper iron oxide (CuFe ₂ O ₄ ), iron oxide neodymium (NdFe ₂ O) ₃ ), iron barium oxide (BaFe ₁₂ O ₁₉ ), iron magnesium oxide (MgFe ₂ O ₄ ), iron manganese oxide (MnFe ₂ O ₄ ). The magnetic materials described above are used alone or in combination of two or more. A particularly suitable magnetic material is a fine powder of triiron tetroxide or γ-iron sesquioxide.

These magnetic materials preferably have an average particle size of 0.1 μm to 2 μm, and more preferably 0.1 μm to 0.3 μm. The magnetic characteristics when 795.8 kA / m (10 k Oersted) is applied are such that the coercive force (Hc) is 1.6 kA / m to 12 kA / m (20 Oersted to 150 Oersted), and the saturation magnetization (σs) is 5 Am ² / kg to 200 Am ² / kg. Preferably they are 50 Am < ² > / kg or more and 100 Am < ² > / kg or less. Residual magnetization (.sigma.r) is, ^2Am 2 / kg or more 20 Am ² / kg or less being preferred.

  The magnetic material is used in an amount of 10.0 parts by mass or more and 200 parts by mass or less, preferably 20.0 parts by mass or more and 150 parts by mass or less based on 100 parts by mass of the binder resin.

  On the other hand, as a colorant for use as a non-magnetic toner, a known colorant such as various conventionally known dyes and pigments can be used. As the yellow colorant, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complex methine compounds, and allylamide compounds are used. Specifically, C.I. I. Pigment Yellow 3, 7, 10, 12, 13, 14, 15, 17, 23, 24, 60, 62, 74, 75, 83, 93, 94, 95, 99, 100, 101, 104, 108, 109, 110, 111, 117, 123, 128, 129, 138, 139, 147, 148, 150, 155, 166, 168, 169, 177, 179, 180, 181, 183, 185, 191: 1, 191, 192, 193, 199; C.I. I. solvent Yellow 33, 56, 79, 82, 93, 112, 162, 163; C.I. I. Disperse Yellow 42, 64, 201, 211 are listed.

  As the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 31, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 147, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. And CI Pigment Bio Red 19.

  As the cyan colorant, phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds are used. Specifically, C.I. I. Pigment blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66.

  As the black colorant, carbon black, aniline black, acetylene black, titanium black, and those which are toned in black using the yellow / magenta / cyan colorant shown above can be used.

  The colorants can be used alone or mixed and further used in the form of a solid solution. In the present invention, the colorant is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHT transparency, and dispersibility in the toner. The amount of the colorant added is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin.

  The toner of the present invention may contain a release agent. The release agent includes aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax and paraffin wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax; aliphatic hydrocarbon waxes Block copolymers of these: waxes based on fatty acid esters such as carnauba wax, sazol wax, and montanic acid ester wax; Examples thereof include partially esterified products of fatty acids such as monoglycerides and polyhydric alcohols; methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and fats.

  As for the molecular weight distribution of the release agent, the main peak is preferably in a region having a molecular weight of 400 or more and 2400 or less, and more preferably in a region of 430 or more and 2000 or less. Thereby, preferable thermal characteristics can be imparted to the toner. The addition amount of the release agent is preferably 2.50 parts by mass or more and 40.0 parts by mass or less, and 3.00 parts by mass or more and 15.0 parts by mass or less with respect to 100 parts by mass of the binder resin. More preferably.

  Examples of the method for producing toner particles include a kneading pulverization method, a suspension polymerization method, a dissolution suspension method, and an emulsion aggregation method. Among them, a production method for obtaining toner particles by granulating a composition containing a colorant, a release agent and a charge control agent in an aqueous medium, specifically, suspension polymerization, dissolution The suspension method and the emulsion aggregation method are preferable, and the suspension polymerization method is more preferable. The reason is that in the step of granulating in an aqueous medium (granulation step), the polymer A and / or the polymer B can be effectively localized on the surface of the toner particles, and the uniform chargeability can be obtained. This is because good charge rising property and charge amount distribution are more effectively exhibited.

  In the method for producing toner particles by suspension polymerization, first, a colorant is uniformly dissolved and mixed or dispersed in a polymerizable monomer constituting a binder resin by a stirrer or the like. In particular, when the colorant is a pigment, it is preferably treated with a disperser to obtain a pigment dispersion paste. As a polymerizable monomer, a polymerization initiator, and a charge control agent, the polymer A and / or polymer B, together with wax and other additives as required, are uniformly dissolved and mixed by a stirrer or the like. Alternatively, it is dispersed to prepare a polymerizable monomer composition. In addition, you may mix the polymer A and / or the polymer B at the time of preparation of a pigment paste. The polymerizable monomer composition thus obtained is added to a dispersion medium (preferably an aqueous medium) containing a dispersion stabilizer, and a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser is used as a stirrer. Used to finely disperse to the toner particle size (granulation step). The polymerizable monomer composition finely dispersed in the granulation step is polymerized by light or heat (polymerization step) to obtain toner particles.

  As a method for dispersing the pigment in the organic medium, a known method can be used. For example, if necessary, a resin and a pigment dispersant are dissolved in an organic medium, and the pigment powder is gradually added while being stirred, so that the solvent is sufficiently blended. Further, by applying mechanical shearing force with a dispersing machine such as a ball mill, paint shaker, dissolver, attritor, sand mill, or high speed mill, the pigment can be stably finely dispersed, that is, dispersed into uniform fine particles.

  As the polymerizable monomer that can be suitably used in the suspension polymerization method, the aforementioned vinyl monomers can be used in the same manner.

  In the method for producing toner particles by the suspension polymerization method, a dispersion medium that can be used is determined based on solubility in a dispersion medium such as a binder resin, an organic medium, a polymerizable monomer, a polymer A, and a polymer B. However, an aqueous dispersion medium is preferable. Examples of water-based dispersion media that can be used include water; alcohols such as methyl alcohol, ethyl alcohol, modified ethyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, sec-butyl alcohol; Ether alcohols such as cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve, diethylene glycol monobutyl ether, and other water-soluble ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc .; esters such as ethyl acetate; ethyl Selected from ethers such as ether and ethylene glycol; acetals such as methylal and diethyl acetal; acids such as formic acid, acetic acid and propionic acid. Particularly preferably it is an alcohol. Two or more of these solvents can be mixed and used. The concentration of the liquid mixture or the polysynthetic monomer composition with respect to the dispersion medium is preferably 1% by mass or more and 80% by mass or less, more preferably 10% by mass or more and 65% by mass or less with respect to the dispersion medium.

  As a dispersion stabilizer that can be used when an aqueous dispersion medium is used, known ones can be used. Specific examples include inorganic compounds such as calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate. , Bentonite, silica, alumina and the like. As the organic compound, polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, polyacrylic acid and its salt, starch and the like can be dispersed in an aqueous phase. The concentration of the dispersion stabilizer is preferably 0.2 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the liquid mixture or the polymerizable monomer composition.

  As the polymerization initiator used for the production of toner particles by the suspension polymerization method, the polymerization initiators exemplified when polymerizing the polymerizable monomer of the polymer A can be used.

  In the production of toner particles by suspension polymerization, a known crosslinking agent may be added. A preferable addition amount is 0 to 15.0 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

  In the dissolution suspension method, polymer A or / and polymer B are dissolved or dispersed in an organic solvent together with other necessary components, suspended and granulated in an aqueous medium, and then the organic solvent contained in the droplets is removed. By removing the toner particles, toner particles can be produced.

  In the emulsion aggregation method, polymer A or / and polymer B are finely dispersed in an aqueous medium by a method such as phase inversion emulsification, mixed with fine particles of other necessary components, and control of their zeta potential in the aqueous medium. The toner particles can be aggregated to form toner particles.

  The toner of the present invention preferably has an inorganic fine powder on the surface of toner particles. The inorganic fine powder is added to and mixed with toner particles to improve the fluidity of the toner and make the charge uniform, and the added inorganic fine powder exists in a state of being uniformly attached to the surface of the toner particles.

  The inorganic fine powder in the present invention preferably has a number average particle diameter (D1) of primary particles of 4 nm or more and 500 nm or less.

  As the inorganic fine powder used in the present invention, an inorganic fine powder selected from silica, alumina and titania or a composite oxide thereof can be used. Examples of the composite oxide include silica alumina fine powder and strontium titanate fine powder. These inorganic fine powders are preferably used after hydrophobizing the surface.

  Further, the toner used in the present invention may further contain other additives, for example, a lubricant powder such as Teflon (registered trademark) powder, zinc stearate powder, polyvinylidene fluoride powder, or the like within a range that does not substantially adversely affect the toner. Development of abrasives such as cerium oxide powder, silicon carbide powder, strontium titanate powder, fluidity-imparting agents such as titanium oxide powder and aluminum oxide powder, anti-caking agent, and organic and / or inorganic fine particles of opposite polarity A small amount can be used as a property improver. These additives can also be used after hydrophobizing the surface.

  The amount of the inorganic fine powder or additive added to 100 parts by mass of the toner particles is preferably 0.010 parts by mass or more and 8.0 parts by mass or less, more preferably 0.10 parts by mass with respect to 100 parts by mass of the toner particles. Part to 4.0 parts by weight.

  The toner preferably has a weight average particle diameter (D4) of 3.0 μm or more and 15.0 μm or less in order to faithfully develop finer latent image dots, and is 4.0 μm or more and 12.0 μm or less. Is more preferable. Further, the ratio (D4 / D1) of the weight average particle diameter (D4) to the number average particle diameter (D1) is preferably less than 1.40.

  The toner of the present invention can be mixed with a magnetic carrier and used as a two-component developer. As the magnetic carrier, known magnetic carriers such as magnetic particles themselves, coated carriers in which magnetic particles are coated with a resin, and magnetic material-dispersed resin carriers in which magnetic particles are dispersed in resin particles can be used. Examples of magnetic particles include surface oxidized or unoxidized iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, rare earth metal particles, alloy particles thereof, oxide particles, ferrite, etc. Can be used.

  The average particle size of the magnetic carrier is 50% (D50) on a volume basis, preferably 10.0 μm or more and 100.0 μm or less, and more preferably 20.0 μm or more and 70.0 μm or less. When preparing a two-component developer, the mixing ratio is preferably 2.0% by mass or more and 15.0% by mass or less, more preferably 4.0% by mass or more and 13% as the toner concentration in the developer. 0.0 mass% or less.

  Below, the measuring method of each physical property is shown.

<Method for Measuring Weight Average Molecular Weight (Mw) of Polymer A and Polymer B>
The molecular weights of the polymer A and the polymer B are calculated in terms of polystyrene by gel permeation chromatography (GPC). In the polymer B having a sulfonic acid group, the column elution rate also depends on the amount of the sulfonic acid group, and thus the accurate molecular weight and molecular weight distribution are not measured. Therefore, it is necessary to prepare a sample in which sulfonic acid groups are capped in advance. Methyl esterification is preferable for capping, and a commercially available methyl esterifying agent can be used. Specifically, a method of treating with trimethylsilyldiazomethane can be mentioned.

The molecular weight is measured by GPC as follows. The above resin was added to THF (tetrahydrofuran), and the solution which was allowed to stand at room temperature for 24 hours was filtered through a solvent-resistant membrane filter having a pore size of 0.2 μm “Mysholy Disc” (manufactured by Tosoh Corporation) to obtain a sample solution. Measure under the following conditions. In addition, sample preparation adjusts the quantity of THF so that the density | concentration of resin may be 0.8 mass%. If the resin is difficult to dissolve in THF, a basic solvent such as DMF can be used.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow velocity: 1.0ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml

  In calculating the molecular weight of the sample, a molecular weight calibration curve prepared using a standard polystyrene resin column listed below is used. Specifically, trade names “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F manufactured by Tosoh Corporation -4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ".

<Composition analysis of polymer A and polymer B>
The following measuring devices can be used to determine the structures of the polymer A and the polymer B.
[FT-IR spectrum]
NICOLET AVATAR360FT-IR
[ ¹ H-NMR, ¹³ C-NMR]
FT-NMR JNM-EX400 manufactured by JEOL (solvent: heavy chloroform)

<Method for measuring acid value of resin>
The acid value is the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample. The acid value in the present invention is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.

  Titration is performed using a 0.1 mol / l potassium hydroxide ethyl alcohol solution (manufactured by Kishida Chemical Co., Ltd.). The factor of the potassium hydroxide ethyl alcohol solution can be determined using a potentiometric titrator (potential difference titrator AT-510 manufactured by Kyoto Electronics Industry Co., Ltd.). 100 ml of 0.100 mol / l hydrochloric acid is placed in a 250 ml tall beaker, titrated with the potassium hydroxide ethyl alcohol solution, and determined from the amount of the potassium hydroxide ethyl alcohol solution required for neutralization. As the 0.100 mol / l hydrochloric acid, one prepared according to JIS K 8001-1998 is used.

The measurement conditions for the acid value measurement are shown below.
Titration device: potentiometric titration device AT-510 (manufactured by Kyoto Electronics Industry Co., Ltd.)
Electrode: Composite glass electrode double junction type (manufactured by Kyoto Electronics Industry Co., Ltd.)
Titrator control software: AT-WIN
Titration analysis software: Tview
The titration parameters and control parameters at the time of titration are as follows.
Titration parameters Titration mode: Blank titration Titration style: Total titration Maximum titration: 20 ml
Waiting time before titration: 30 seconds Titration direction: Automatic control parameter end point judgment potential: 30 dE
End point determination potential value: 50 dE / dmL
End point detection judgment: Not set Control speed mode: Standard gain: 1
Data collection potential: 4 mV
Data collection titration: 0.1 ml
main exam;
0.100 g of the measurement sample is precisely weighed in a 250 ml tall beaker, 150 ml of a mixed solution of toluene / ethanol (3: 1) is added and dissolved over 1 hour. Titrate with the potassium hydroxide ethyl alcohol solution using the potentiometric titrator.
Blank test;
Titration is performed in the same manner as described above, except that no sample is used (that is, only a mixed solution of toluene / ethanol (3: 1) is used).

The acid value is calculated by substituting the obtained result into the following formula.
A = [(C−B) × f × 5.611] / S
(In the formula, A: acid value (mgKOH / g), B: addition amount of potassium hydroxide ethyl alcohol solution in blank test (ml), C: addition amount (ml) of potassium hydroxide ethyl alcohol solution in this test, f: Factor of potassium hydroxide solution, S: Sample (g))

<Method for Measuring Content of Structure b in Polymer B>
The number of moles of structure b in polymer B corresponds to the number of moles of elemental sulfur in the resin. Therefore, the structure b is quantified by measuring the content of sulfur element in the resin as described below.

(Measurement method of sulfur element content in resin and toner)
A method for measuring the content of sulfur element in the resin or toner will be described below. Specifically, resin is introduced into an automatic sample combustion device (device name: pretreatment device for ion chromatograph AQF-100, manufactured by Dia Instruments Co., Ltd.), the resin is combusted and gas is absorbed into the absorbent. Let Next, the content (ppm) of elemental sulfur in the resin or toner is measured by ion chromatography (device name: ion chromatograph ICS2000, column: IONPAC AS17, manufactured by Nippon Dionex Co., Ltd.). The content of elemental sulfur (μmol / g) is calculated by dividing the obtained value by the atomic weight of elemental sulfur (32.06).

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

  As the electrolytic aqueous solution used for the measurement, a solution obtained by dissolving special grade sodium chloride in ion-exchanged water to a concentration of 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  Prior to measurement and analysis, the dedicated software is set as follows. On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked. In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

  The specific measurement method is as follows.

  (1) In a glass 250 ml round bottom beaker for exclusive use of Multisizer 3, 200 ml of the electrolytic aqueous solution is placed and set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.

  (2) Put 30 ml of the aqueous electrolytic solution into a glass 100 ml flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. 0.3 ml of a diluted solution obtained by diluting 3) with ion-exchanged water.

  (3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikkaki Bios Co., Ltd.) having an electrical output of 120 W is prepared. Into the water tank of the ultrasonic disperser, 3.3 l of ion-exchanged water is added, and 2 ml of Contaminone N is added to the water tank.

  (4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.

  (5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.

  (6) To the round bottom beaker (1) installed in the sample stand, the electrolyte aqueous solution (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to 5%. Measurement is performed until the number of measured particles reaches 50,000.

  (7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) are calculated. The “average diameter” on the “analysis / volume statistic (arithmetic average)” screen when the graph / volume% is set in the dedicated software is the weight average particle size (D4). When the number% is set, the “average diameter” on the “analysis / number statistics (arithmetic average)” screen is the number average particle diameter (D1).

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. “Part” means “part by mass”.

  A synthesis example of a polymerizable monomer of a compound having a vinyl group represented by the formula (3) among the structures represented by the formula (1) is shown below.

<Synthesis example of vinyl monomer 1a>
100.0 g of p-hydroxybenzoic acid was dissolved in 710 mL of methanol. To this solution, 147.8 g of potassium carbonate was added and heated to 67 ° C. 4- (Chloromethyl) styrene (113.8 g) was dropped into a solution containing p-hydroxybenzoic acid and reacted at 67 ° C. for 12 hours. The obtained reaction solution was cooled and then filtered, and methanol in the filtrate was distilled off under reduced pressure to obtain a precipitate. The precipitate was dispersed in water at pH = 2 and extracted by adding ethyl acetate. Then, after washing with water, it was dried with magnesium sulfate, and ethyl acetate was distilled off under reduced pressure to obtain a precipitate. This precipitate was dissolved in methanol, dropped into water, reprecipitated, and collected by filtration to obtain a precipitate. This reprecipitation operation was performed twice, and the obtained precipitate was dried at 80 ° C. for 48 hours to obtain 63.5 g of a vinyl monomer 1a having the following structure.
(Vinyl monomer 1a)

<Synthesis example of vinyl monomer 1b>
281.9 g of 3-hydroxybenzoic acid was dissolved in 2 L of methanol, 414.4 g of potassium carbonate was added, and the mixture was heated to 60 ° C. To this solution, 353.4 g of 4- (chloromethyl) styrene was added and reacted under reflux for 3 hours. The obtained reaction solution was cooled, and methanol was distilled off under reduced pressure to obtain a residue. The obtained residue was dispersed in water with pH = 3, and extracted with ethyl acetate. Thereafter, the organic layer was washed with saturated brine, and then ethyl acetate was distilled off under reduced pressure, followed by recrystallization in ethyl acetate. The obtained precipitate was dried at 60 ° C. for 24 hours to obtain 261.1 g of vinyl monomer 1b having the following structure.
(Vinyl monomer 1b)

<Synthesis example of vinyl monomer 1c>
168.2 g of 3-hydroxy-3-methoxybenzoic acid was dissolved in 1000 mL of methanol. To this solution, 207.3 g of potassium carbonate was added and heated to 60 ° C. 176.7 g of 4- (chloromethyl) styrene was added dropwise to the solution containing 3-hydroxy-3-methoxybenzoic acid and reacted for 4 hours under reflux. The obtained reaction solution was cooled, and methanol was distilled off under reduced pressure to obtain a residue. The obtained residue was dispersed in water with pH = 3, and extracted with ethyl acetate. Thereafter, the organic layer was washed with saturated brine, and then ethyl acetate was distilled off under reduced pressure, followed by recrystallization in ethyl acetate. The obtained precipitate was dried at 60 ° C. for 24 hours to obtain 115.0 g of a vinyl monomer 1c having the following structure.
(Vinyl monomer 1c)

<Synthesis example of vinyl monomer 1d>
Except for changing 3-hydroxy-3-methoxybenzoic acid to 152.1 g of 3-hydroxy-3-methylbenzoic acid, the vinyl monomer 1d having the following structure was obtained in the same manner as the vinyl monomer 1c. It was.
(Vinyl monomer 1d)

<Synthesis example of vinyl monomer 1e>
4- (chloromethyl) styrene is a mixture of 3- (chloromethyl) methylstyrene and 4- (chloromethyl) styrene (manufactured by AGC Seikagaku Co., Ltd., trade name “CMS-P”) A vinyl monomer 1e having the following structure was obtained by the same synthesis method as the synthesis example of the body 1a.
(Vinyl monomer 1e)

及び

as well as

の混合物

Mixture of

<Synthesis Example of Polymer A-1>
7.19 g of vinyl monomer 1a and 60.1 g of styrene were dissolved in 42.0 ml of toluene, stirred for 1 hour, and then heated to 110 ° C. To this reaction solution, a mixed solution of 4.62 g of tert-butyl peroxyisopropyl monocarbonate (trade name: Perbutyl I, manufactured by NOF Corporation) and 42 ml of toluene was added dropwise. Furthermore, it reacted at 110 degreeC for 4 hours. Then, it cooled and it was dripped at methanol 1L, and the deposit was obtained. The obtained precipitate was dissolved in 120 ml of THF and then added dropwise to 1.80 L of methanol to precipitate a white precipitate, which was filtered and dried at 90 ° C. under reduced pressure to obtain 55.4 g of polymer A-1. It was. The acid value of the obtained polymer A-1 was measured, and the content of components derived from the vinyl monomer 1a was confirmed.

<Synthesis Example of Polymer A-2>
In the synthesis example of the polymer A-1, a polymer was synthesized by the same method except that the amount of toluene was changed to 91.2 ml and tert-butylperoxyisopropyl monocarbonate was changed to 7.09 g. The obtained polymer was fractionated into 10 fractions by GPC, and the second and third fractions were collected from the low molecular weight side and concentrated and dried to obtain polymer A-2. The acid value of the polymer A-2 was measured, and the content of components derived from the vinyl monomer 1a was confirmed.

<Synthesis Example of Polymer A-3>
In the synthesis example of the polymer A-1, a polymer was synthesized by the same method except that the amount of toluene was changed to 100.0 ml and tert-butylperoxyisopropyl monocarbonate was changed to 7.40 g. The obtained polymer was fractionated into 10 fractions by GPC, and the second and third fractions were collected from the low molecular weight side and concentrated and dried to obtain polymer A-3. The acid value of the polymer A-3 was measured, and the content of components derived from the vinyl monomer 1a was confirmed.

<Synthesis Example of Polymer A-4>
In the synthesis example of polymer A-1, synthesis was performed in the same manner as polymer A-1, except that the amount of toluene was changed to 30.2 ml and tert-butylperoxyisopropyl monocarbonate was changed to 3.02 g. Compound A-4 was synthesized. The acid value of the polymer A-4 was measured, and the content of components derived from the vinyl monomer 1a was confirmed.

<Synthesis Example of Polymer A-5>
In the synthesis example of polymer A-1, synthesis was performed in the same manner as polymer A-1, except that the amount of toluene was changed to 30.0 ml and tert-butyl peroxyisopropyl monocarbonate was changed to 2.30 g. Combined A-5 was synthesized. The acid value of the polymer A-5 was measured, and the content of components derived from the vinyl monomer 1a was confirmed.

<Synthesis Example of Polymer A-6>
In the synthesis example of polymer A-1, except that vinyl monomer 1a was changed to vinyl monomer 1b, synthesis was performed in the same manner as polymer A-1, and polymer A-6 was synthesized. The acid value of the polymer A-6 was measured, and the content of components derived from the vinyl monomer 1b was confirmed.

<Synthesis Example of Polymer A-7>
In the synthesis example of the polymer A-1, except that 7.19 g of the vinyl monomer 1a is changed to 5.83 g of the vinyl monomer 1c, the polymer A-1 is synthesized by the same method as the polymer A-1. Synthesized. The acid value of the polymer A-7 was measured, and the content of components derived from the vinyl monomer 1c was confirmed.

<Synthesis Example of Polymer A-8>
In the synthesis example of the polymer A-1, except that 7.19 g of the vinyl monomer 1a is changed to 5.51 g of the vinyl monomer 1d, the polymer A-1 is synthesized by the same method as the polymer A-1. Synthesized. The acid value of the polymer A-8 was measured, and the content of components derived from the vinyl monomer 1d was confirmed.

<Synthesis Example of Polymer A-9>
In the synthesis example of polymer A-1, except that vinyl monomer 1a was changed to vinyl monomer 1e, synthesis was performed in the same manner as polymer A-1, and polymer A-9 was synthesized. The acid value of the polymer A-9 was measured, and the content of components derived from the vinyl monomer 1e was confirmed.

<Synthesis Example of Polymer A-10>
In the synthesis example of polymer A-1, polymer A-10 was synthesized in the same manner as polymer A-1, except that vinyl monomer 1a was changed to 30.77 g and styrene was changed to 31.6 g. . The acid value of the polymer A-10 was measured, and the content of components derived from the vinyl monomer 1a was confirmed.

<Synthesis Example of Polymer A-11>
In the synthesis example of polymer A-1, polymer A-11 was synthesized in the same manner as polymer A-1, except that vinyl monomer 1a was changed to 0.167 g and styrene was changed to 73.8 g. . The acid value of the polymer A-11 was measured, and the content of components derived from the vinyl monomer 1a was confirmed.

<Synthesis Example of Polymer A-12>
In the synthesis example of polymer A-1, polymer A-12 was synthesized in the same manner as polymer A-1, except that vinyl monomer 1a was changed to 0.254 g and styrene was changed to 73.7 g. . The acid value of the polymer A-12 was measured, and the content of the component derived from the vinyl monomer 1a was confirmed.

<Synthesis Example of Polymer A-13>
In the synthesis example of polymer A-1, polymer A-13 was synthesized in the same manner as polymer A-1, except that vinyl monomer 1a was changed to 25.76 g and styrene was changed to 38.5 g. . The acid value of the polymer A-13 was measured, and the content of components derived from the vinyl monomer 1a was confirmed.

<Synthesis Example of Polymer A-14>
In the synthesis example of polymer A-1, the composition of the reaction solution was changed to polymer A-1 except that the vinyl monomer 1a was changed to 8.70 g, styrene 57.0 g, and butyl acrylate 8.30 g. Polymer A-14 was synthesized in the same manner as in Example 1. The acid value of polymer A-14 was measured, and the content of components derived from vinyl monomer 1a was confirmed.

<Synthesis Example of Polymer A-15>
A compound represented by the following formula (7) was obtained by the same method as the synthesis of the vinyl monomer 1a except that 4- (chloromethyl) styrene was changed to 105.6 g of p-aminobenzyl chloride.

next,
-67.8 parts of bisphenol A, propylene oxide 2.2 mol adduct, 22.2 parts of terephthalic acid, 10.0 parts of trimellitic anhydride, 0.005 part of dibutyltin oxide are put into a four-necked flask and a thermometer. Then, a stirring bar, a condenser, and a nitrogen introduction tube were attached, and the mixture was reacted at 220 ° C. for 5 hours in a nitrogen atmosphere to obtain polyester resin P-1.

  In a reaction vessel, 85.0 parts of the obtained polyester resin P-1 and 14.1 parts of a compound represented by the following formula (7) were put, and a condenser, a stirrer, and a thermometer were immersed therein. After adding 270 parts of pyridine and stirring, 96.0 parts of triphenyl phosphite is added and stirred at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 360 parts of ethanol. The obtained polymer was washed twice with 140 parts of 1N hydrochloric acid, then washed twice with 140 parts of water, and dried under reduced pressure to obtain a polymer A-15. The structure was identified and confirmed using NMR. The content of structure 1a in the polymer was calculated from NMR and molecular weight.

式（７）

Formula (7)

<Synthesis Example of Polymer A-16>
In the synthesis example of the polymer A-1, in the same manner as the polymer A-1, except that butyl acrylate is changed to 66.6 g and the vinyl monomer 1a is changed to 7.40 g instead of styrene, A-16 was synthesized. The acid value of the polymer A-16 was measured, and the content of components derived from the vinyl monomer 1a was confirmed.

<Synthesis Example of Polymer A-17>
In the synthesis example of the polymer A-1, the vinyl monomer 1a was polymerized in the same manner as the polymer A-1 except that the compound represented by the following formula (8) was changed to 6.86 g and styrene 66.6 g. Compound A-17 was synthesized. The acid value of polymer A-17 was measured, and the content of the component derived from formula (8) was confirmed.

式（８）

Formula (8)

<Synthesis Example of Polymer B-1>
In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 200 parts of xylene was charged and refluxed under a nitrogen stream.
-6.0 parts of 2-acrylamido-2-methylpropanesulfonic acid-78.0 parts of styrene-16.0 parts of 2-ethylhexyl acrylate-dimethyl-2,2'-azobis (2-methylpropionate) 5.00 Part The above materials were mixed and added dropwise to the reaction vessel with stirring for 10 hours. Thereafter, distillation was performed to distill off the solvent, followed by drying at 40 ° C. under reduced pressure to obtain a polymer B-1. Obtained polymer B-1 quantified the sulfur atom by elemental analysis, and confirmed the content of the unit derived from the sulfonic acid.

<Synthesis example of polymer B-2>
A polymer B-2 was synthesized in the same manner as the polymer B-1, except that the following materials were used, to obtain a polymer B-2.
・ Methyl 2-acrylamido-5-methoxybenzenesulfonate 16.0 parts ・ Styrene 74.0 parts ・ N-butyl acrylate 10.0 parts ・ Dimethyl-2,2′-azobis (2-methylpropionate) 00 parts The obtained polymer B-2 quantified sulfur atoms by elemental analysis and confirmed the content of units derived from sulfonic acid.

<Synthesis Example of Polymer B-3>
A polymer B-3 was synthesized in the same manner as the polymer B-1, except that the following materials were used, to obtain a polymer B-3.
・ Methyl 2-acrylamido-2-methylpropanesulfonate 12.0 parts ・ Styrene 72.0 parts ・ 2-ethylhexyl acrylate 16.0 parts ・ Dimethyl-2,2′-azobis (2-methylpropionate) 5. 00 parts The obtained polymer B-3 quantified sulfur atoms by elemental analysis, and confirmed the content of units derived from sulfonic acid.

<Synthesis Example of Polymer B-4>
A polymer B-4 was synthesized in the same manner as the polymer B-1, except that the following materials were used, to obtain a polymer B-4.
-2-acrylamido-5-methoxybenzenesulfonic acid 8.00 parts-Styrene 76.0 parts-2-ethylhexyl acrylate 16.0 parts-Dimethyl-2,2'-azobis (2-methylpropionate) 5.00 Part The obtained polymer B-4 quantified sulfur atoms by elemental analysis, and confirmed the content of units derived from sulfonic acid.

<Synthesis Example of Polymer B-5>
A polymer B-5 was synthesized in the same manner as the polymer B-1, except that the following materials were used, to obtain a polymer B-5.
-6.0 parts of 2-acrylamido-2-methylpropanesulfonic acid-78.0 parts of styrene-16.0 parts of 2-ethylhexyl acrylate-dimethyl-2,2'-azobis (2-methylpropionate) 5.00 Part The obtained polymer B-5 quantified sulfur atoms by elemental analysis, and confirmed the content of units derived from sulfonic acid.

<Synthesis Example of Polymer B-6>
Preparation of polyester resin P-2:
・ Bisphenol A ・ Propylene oxide 2.2 mol adduct 69.0 parts ・ Terephthalic acid 28.0 parts ・ Fumaric acid 3.00 parts ・ Dibutyltin oxide 0.005 parts are put into a four-necked flask, thermometer, stirring A polyester resin P-2 was obtained by attaching a rod, a condenser, and a nitrogen introducing tube and reacting at 220 ° C. for 5 hours in a nitrogen atmosphere.

In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 200 parts of xylene was charged and refluxed under a nitrogen stream. Thereto, 70 parts of the previously produced resin P-2 was added and dissolved.
・ Methyl 2-acrylamido-5-methoxybenzenesulfonate 15.0 parts ・ Styrene 15.0 parts ・ Dimethyl-2,2′-azobis (2-methylpropionate) 1.50 parts

Next, the above materials were mixed, dropped into the reaction vessel with stirring, and held for 10 hours. Thereafter, distillation was performed to distill off the solvent, followed by drying at 40 ° C. under reduced pressure to obtain a polymer B-6.
Obtained polymer B-6 determined the sulfur atom by the elemental analysis, and confirmed content of the unit derived from the sulfonic acid.

  Table 2 shows the physical properties of the polymer prepared above.

<Example 1>
(1) Preparation of pigment dispersion paste:
-Styrene 58.5 parts-C.I. I. Pigment Blue 15: 3 (Cu phthalocyanine pigment) 9.75 parts, Polymer A-1 1.13 parts, Polymer B-1 1.59 parts After the above material was well premixed in a container, it was treated at 20 ° C. While maintaining the following, the mixture was dispersed for 10 hours by a bead mill to prepare a pigment dispersion paste.

(2) Preparation of toner particles:
350 parts of a 0.1 mol / l-Na ₃ PO ₄ aqueous solution was added to 1200 parts of ion-exchanged water, heated to 60 ° C., and then stirred at 11,000 rpm using CLEARMIX (manufactured by M Technique). did. To this, 52.0 parts of a 1.00 mol / l-CaCl ₂ aqueous solution was added to obtain a dispersion medium containing Ca ₃ (PO ₄ ) ₂ .
- the pigment dispersed paste 47.2 parts Styrene 31.0 parts n-Butyl acrylate 30.0 parts Ester wax 10.0 parts (main component _{C 19 H 39 COOC 20 H 41} , the maximum endothermic peak temperature 68.6 ℃)
・ Saturated polyester resin 5.00 parts (terephthalic acid-propylene oxide modified bisphenol A copolymer, acid value 10.0 mgKOH / g, Mw 16000)
The above material was heated to 60 ° C., and stirred for 1 hour while maintaining the temperature at 60 ° C. in order to sufficiently dissolve and disperse the mixture. Further, while maintaining the temperature at 60 ° C., 10.0 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was added and dissolved as a polymerization initiator to prepare a monomer composition.

The monomer composition was charged into the dispersion medium. The mixture was stirred at 10000 rpm for 30 minutes using a CLEARMIX at 60 ° C. in a nitrogen atmosphere to granulate the monomer composition. Thereafter, the mixture was reacted at 75 ° C. for 5 hours while stirring with a paddle stirring blade to complete the polymerization of the polymerizable monomer. After cooling to room temperature, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ on the particle surface, filtered, washed with water, dried, and further classified to obtain toner particles 1. The particle size distribution of the obtained toner particles was evaluated by calculating D4 / D1.

(3) Preparation of toner:
0.8 parts by mass of hydrophobic silica fine powder surface-treated with dimethyl silicone oil (number average primary particle diameter: 7 nm, BET specific surface area 125 m ² / g), i 100 parts of the toner particles 1 obtained, i -0.2 part by mass of anatase-type titanium oxide fine powder (number average primary particle size: 15 nm, BET specific surface area 30 m ² / g) surface-treated with butyltrimethoxysilane and dimethylsilicone oil was added to a Henschel mixer (Mitsui Miike Chemical Industries, Ltd.) Toner 1 was obtained by mixing and external addition.

  Table 3 shows the physical properties of the obtained toner. The obtained toner was evaluated as follows. The evaluation results are shown in Tables 4-1 and 4-2.

(Measurement of cohesion)
The aggregation degree of the toner 1 that was not severely left and the aggregation degree of the toner 1 that was severely left was measured.

As the measuring device, a device in which a digital display vibrometer “Digivibro MODEL 1332A” (manufactured by Showa Keiki Co., Ltd.) was connected to the side surface portion of the “powder tester” (manufactured by Hosokawa Micron Corporation) was used. Then, a sieve with a mesh size of 20 μm (635 mesh), a sieve with a mesh size of 38 μm (390 mesh), and a sieve with a mesh size of 75 μm (200 mesh) were stacked in this order on the vibrating table of the powder tester. The measurement was performed as follows in an environment of 23 ° C. and 60% Rh.
(1) The vibration width of the shaking table was adjusted in advance so that the displacement value of the digital display vibrometer was 0.50 mm (peak-to-peak).
(2) 5 g of the toner was gently put on a sieve having a top opening of 75 μm.
(3) After vibrating the screen for 15 seconds, the mass of the toner remaining on each screen was measured, and the degree of aggregation was calculated based on the following equation.
Aggregation degree (%) = {(Sample mass (g) / 5 (g)} on a sieve having an opening of 75 μm} × 100
+ {(Sample mass on a sieve having an opening of 38 μm (g) / 5 (g)} × 100 × 0.6
+ {(Sample mass (g) / 5 (g)} × 100 × 0.2 on a sieve having an opening of 20 μm)

(Preparation of sample for aggregation degree measurement)
i) Aggregation degree of toner 1 not subjected to severe storage 5.00 g of toner 1 obtained in Example 1 was weighed into a 100 ml polycup, placed in a thermostat set at 23 ° C. and 60% Rh, and left for 2 days. .
ii) Agglomeration degree of toner 1 subjected to severe storage 5.00 g of toner 1 obtained in Example 1 was weighed into a 100 ml polycup, placed in a thermostatic bath set at 40 ° C. and 95% Rh, and allowed to stand for 30 days. . Then, it was left to stand at 23 ° C. and 60% Rh for 3 days.

(Evaluation of liquidity)
The difference between the degree of aggregation of the toner 1 that was severely left and the degree of aggregation of the toner 1 that was not severely left was evaluated and evaluated. Ranking was based on the following criteria.
Rank A: Difference in cohesion is 0% or more and less than 8.0% Rank B: Difference in cohesion is 8.0% or more and less than 13.0% Rank C: Difference in cohesion is 13.0% or more and 18.0% %Less than

[Evaluation of toner saturation charge]
A two-component developer was prepared as follows.

(Creation of carrier)
The lipophilic treatment of magnetite powder having a number average particle diameter of 0.25 μm and hematite powder having a number average particle diameter of 0.60 μm is performed as follows. Specifically, 4.0% by mass of a silane coupling agent (3- (2-aminoethylaminopropyl) trimethoxysilane) was mixed, and high-speed mixing and stirring were performed at 100 ° C. or higher in a container.
・ Phenol 10.0 parts ・ Formaldehyde solution 6.0 parts (formaldehyde 40%, methanol 10%, water 50%) ・ Lipophilic treatment of magnetite 63.0 parts ・ Lipophilic treatment of hematite 21.0 parts

  The above material, 5 parts of 28% aqueous ammonia and 10 parts of water were placed in a flask, heated and maintained at 85 ° C. over 30 minutes while stirring and mixing, and cured by polymerization reaction for 3 hours. Then, it cools to 30 degreeC, Furthermore, water is added, A supernatant liquid is removed, After washing a deposit with water, it air-drys. Subsequently, this was dried under reduced pressure (5 mmHg or less) at 60 ° C. to obtain spherical magnetic resin particles in which a magnetic material was dispersed.

As the coating resin, a copolymer of methyl methacrylate and methyl methacrylate having a perfluoroalkyl group (m = 7) (copolymerization ratio 8: 1 weight average molecular weight 45,000) was used. To 100 parts of the coating resin, 6 parts of melamine particles having a particle size of 290 nm, 2 parts of carbon particles having a specific resistance of 1 × 10 ⁻² Ω · cm and a particle size of 30 nm were added and dispersed for 30 minutes by an ultrasonic disperser. Further, a mixed solvent coating solution of methyl ethyl ketone and toluene was prepared so that the coating resin content was 2.5 parts with respect to the carrier core (solution concentration 10% by mass).

The coating solution was applied to the surface of the magnetic resin particles by volatilizing the solvent at 70 ° C. while continuously applying shear stress. The resin-coated magnetic carrier particles were heat-treated with stirring at 100 ° C. for 2 hours, cooled and crushed. Thereafter, the particles were classified with a 200-mesh sieve to obtain a carrier having a number average particle diameter of 33 μm, a true specific gravity of 3.53 g / cm ³ , an apparent specific gravity of 1.84 g / cm ³ , and a magnetization strength of 42 Am ² / kg.

  Toner 1 and the obtained carrier were mixed to a toner concentration of 7.0% by mass to obtain a two-component developer. 50.0 g of the obtained two-component developer was weighed and allowed to stand in an environment of 23 ° C. and 60% Rh for 2 days. Then, it is put into a 50 ml plastic container, shaken for 2 minutes at a speed of 4 reciprocations per second with a shaker (YS-LD: manufactured by Yayoi Co., Ltd.), and the amount of charge is measured using the apparatus of FIG. It was measured. This was defined as a saturated charge amount.

[Evaluation of charge rise characteristics]
50.0 g of the two-component developer which was allowed to stand for 2 days in an environment of 23 ° C. and 60% Rh was measured and placed in a 50 ml plastic container. This was shaken with a shaker (YS-LD: manufactured by Yayoi Co., Ltd.) for 90 seconds at a speed of 2 reciprocations per second, and the charge amount was measured using the apparatus of FIG. The ratio (%) of the charge amount with respect to the saturated charge amount when the charge amount at the time of 180 times of shaking was defined as the saturated charge amount was calculated by the following equation as the charge rising characteristic (%).
Charging rise characteristics (%) =
{Charge amount when shaking for 90 seconds (mC / kg) / Saturation charge amount (mC / kg)} × 100

[Evaluation of toner charge distribution]
The spread of the charge amount distribution was evaluated from the obtained q / d distribution using a charge amount distribution measuring apparatus (manufactured by Hosokawa Micron Corp .; model espart analyzer EST-3).

275 g of the two-component developer prepared under the conditions of “Evaluation of Charging Rise Characteristics” was left for 2 days in a normal temperature and humidity environment (23 ° C./60% Rh). The amount of charge of the two-component developer when this is loaded into a developing device of a color laser copying machine imageRUNNER ADVANCE C7065 (manufactured by Canon Inc.) and rotated for 5 minutes with an idle rotating machine equipped with an external motor (initial) Distribution was measured. The following criteria were used as evaluation criteria.
Rank A: As shown in FIG. 2A, the toner charged on the (+) side is small and the distribution width is narrow.
Rank B: The distribution width is wide as shown in FIG.
Rank C: The distribution range is wide as shown in FIG. 2C, and the amount of toner charged on the (+) side is large.

[Image output test]
Image evaluation was performed in each environment using a Canon printer LBP7200C. The LBP 7200C is a system that does not have a cleaning member in the intermediate transfer unit portion, and collects primary and secondary transfer residual toner with the cleaning member in the photoreceptor unit portion. An image output test was carried out by attaching 70 g of toner 1 to the cyan station of the printer and attaching a dummy cartridge to the others.

  The image evaluation was performed under each environment of 15 ° C./10% Rh (low temperature and low humidity environment, hereinafter also referred to as LL environment) and 32.5 ° C./90% Rh (high temperature and high humidity environment, hereinafter also referred to as HH environment). The operation of outputting an image with a printing rate of 1% was repeated under each environment, and left for one week under each environment every time the number of output sheets reached 200. Thereafter, the process of outputting 200 sheets as described above was repeated. Finally, 4600 sheets of images were output, and evaluation was performed by the following method.

(1) Fog evaluation In the above image output test, after leaving for one week, an image having a white background portion was output one by one. Thereafter, with respect to the image having all the white background portions, the fogging is determined from the difference between the whiteness (reflectance Ds (%)) of the white background portion of the image having the white background portion and the whiteness (average reflectance Dr (%)) of the transfer paper. The concentration (%) (= Dr (%) − Ds (%)) was calculated. In addition, the whiteness was measured by “REFLECTMETER MODEL TC-6DS” (manufactured by Tokyo Denshoku Co., Ltd.). An amberlite filter was used as the filter. As for the fogging, the following rankings were given for the worst ones in each evaluation.
A: The fog density is less than 0.3%.
B: The fog density is 0.3% or more and less than 0.8%.
C: The fog density is 0.8% or more and less than 1.3%.
D: The fog density is 1.3% or more.

(2) Image Density Stability Image density was measured with a color reflection densitometer (X-RITE 404 Amanufactured by X-Rite Co.). In the above image output test, a solid image was output one by one before and after being left for one week, and the density of each image was measured. Of the obtained image densities, the difference between the maximum density and the minimum density was determined and shown based on the following evaluation criteria.
A: The image density difference is 0.1 or less.
B: The image density difference is larger than 0.1 and not larger than 0.3.
C: The image density difference is greater than 0.3 and less than or equal to 0.5.
D: Image density difference is larger than 0.5.

(3) Fine line reproducibility (image quality)
The fine line reproducibility was evaluated from the viewpoint of image quality. In the above image output, after outputting 4600 images, an image (print area ratio 4%) in which a grid pattern with a line width of 3 pixels was printed on the entire surface of A4 paper was printed, and the fine line reproducibility was evaluated. The line width of 3 pixels is theoretically 127 μm. The line width of the image is measured with a microscope VK-8500 (manufactured by Keyence). The line width is measured by selecting 5 points at random, and the following L is defined as the fine line reproducibility index when the average value of 3 points excluding the minimum value and the maximum value is d (μm).
L (μm) = | 127−d |

  L defines the difference between the theoretical line width of 127 μm and the line width d on the output image. Since d may be larger than 127 or smaller than 127, it is defined as the absolute value of the difference. Smaller L indicates better fine line reproducibility.

(Evaluation criteria)
A: L is 0 μm or more and less than 5 μm.
B: L is 5 μm or more and less than 15 μm.
C: L is 15 μm or more and less than 30 μm.
D: L is 30 μm or more.

<Examples 2 and 3>
Toners 2 and 3 were obtained in the same manner as in Example 1 except that the polymer A-1 in Example 1 was changed to the polymers A-2 and A-3, respectively. Table 3 shows the physical properties of the obtained toner. The obtained toner was evaluated in the same manner as in Example 1, and the results are shown in Tables 4-1 and 4-2.

<Examples 4 and 5>
Toners 4 and 5 were obtained in the same manner as in Example 1 except that the polymer A-1 in Example 1 was changed to the polymers A-4 and A-5, respectively. Table 3 shows the physical properties of the obtained toner. The obtained toner was evaluated in the same manner as in Example 1, and the results are shown in Tables 4-1 and 4-2.

<Examples 6 to 9>
A toner was prepared in the same manner as in Example 1 except that the polymer A-1 in Example 1 was changed to each of polymers A-6, A-7, A-8, and A-9. Obtained. Table 3 shows the physical properties of the obtained toner. The obtained toner was evaluated in the same manner as in Example 1, and the results are shown in Tables 4-1 and 4-2.

<Example 10>
Toner 10 was obtained in the same manner as in Example 1 except that the material used for preparing the pigment dispersion paste of Example 1 was changed as follows. Table 3 shows the physical properties of the obtained toner. The obtained toner was evaluated in the same manner as in Example 1, and the results are shown in Tables 4-1 and 4-2.
-Styrene 58.5 parts-C.I. I. Pigment Blue 15: 3 9.75 parts, Polymer A-1 0.0375 parts, Polymer B-1 0.37 parts

<Example 11>
The material used for the preparation of the pigment dispersion paste of Example 1 was changed to the following, and the toner was changed in the same manner as in Example 1 except that the pigment dispersion paste used for the preparation of the monomer mixture was changed to 45.6 parts. The toner 11 was produced. Table 3 shows the physical properties of the obtained toner. The obtained toner was evaluated in the same manner as in Example 1, and the results are shown in Tables 4-1 and 4-2.
-Styrene 58.5 parts-C.I. I. Pigment Blue 15: 3 9.75 parts, Polymer A-1 0.048 parts, Polymer B-1 0.37 parts

<Example 12>
The material used for preparation of the pigment dispersion paste of Example 1 was changed to the following, and the toner was changed in the same manner as in Example 1 except that the pigment dispersion paste used for preparation of the monomer mixture was changed to 47.2 parts. The toner 12 was produced. Table 3 shows the physical properties of the obtained toner. The obtained toner was evaluated in the same manner as in Example 1, and the results are shown in Tables 4-1 and 4-2.
-Styrene 58.5 parts-C.I. I. Pigment Blue 15: 3 9.75 parts, Polymer A-10 1.13 parts, Polymer B-1 1.59 parts

<Example 13>
The material used for preparation of the pigment dispersion paste of Example 1 was changed to the following, and the toner was changed in the same manner as in Example 1 except that the pigment dispersion paste used for preparation of the monomer mixture was changed to 45.2 parts. Thus, a toner 13 was obtained. Table 3 shows the physical properties of the obtained toner. The obtained toner was evaluated in the same manner as in Example 1, and the results are shown in Tables 4-1 and 4-2.
-Styrene 58.5 parts-C.I. I. Pigment Blue 15: 3 9.75 parts, Polymer A-11 1.88 parts

<Example 14>
The material used in the preparation of the pigment dispersion paste of Example 1 was changed to the following, and the toner was changed in the same manner as in Example 1 except that the pigment dispersion paste used for the preparation of the monomer mixture was changed to 49.0 parts. The toner 14 was produced. Table 3 shows the physical properties of the obtained toner. The obtained toner was evaluated in the same manner as in Example 1, and the results are shown in Tables 4-1 and 4-2.
-Styrene 58.5 parts-C.I. I. Pigment Blue 15: 3 9.75 parts, Polymer A-11 5.00 parts, Polymer B-1 0.50 parts

<Example 15>
The material used for preparation of the pigment dispersion paste of Example 1 was changed to the following, and the toner was changed in the same manner as in Example 1 except that the pigment dispersion paste used for preparation of the monomer mixture was changed to 47.2 parts. Thus, toner 15 was obtained. Table 3 shows the physical properties of the obtained toner. The obtained toner was evaluated in the same manner as in Example 1, and the results are shown in Tables 4-1 and 4-2.
-Styrene 58.5 parts-C.I. I. Pigment Blue 15: 3 9.75 parts. Polymer A-12 2.25 parts. Polymer B-1 0.50 parts.

<Example 16>
The material used for preparation of the pigment dispersion paste of Example 1 was changed to the following, and the toner was changed in the same manner as in Example 1 except that the pigment dispersion paste used for preparation of the monomer mixture was changed to 47.2 parts. The toner 16 was produced. Table 3 shows the physical properties of the obtained toner. The obtained toner was evaluated in the same manner as in Example 1, and the results are shown in Tables 4-1 and 4-2.
-Styrene 58.5 parts-C.I. I. Pigment Blue 15: 3 9.75 parts, Polymer A-13 1.13 parts, Polymer B-1 1.59 parts

<Example 17>
Preparation of polyester resin P-3:
-Bisphenol A-Propylene oxide 2.2 mol adduct 1200 parts-Bisphenol A-Ethylene oxide 2.2 mol adduct 475 parts-Terephthalic acid 249 parts-Trimellitic anhydride 192 parts-Fumaric acid 290 parts-Dibutyltin oxide 0 .100 parts

The above material was placed in a 4-liter 4-neck flask made of glass, and a thermometer, a stir bar, a condenser, and a nitrogen inlet tube were attached and placed in a mantle heater. Under a nitrogen atmosphere, reaction was carried out at 220 ° C. for 5 hours to obtain a polyester resin P-3.
Polyester resin P-3 100 parts Polymer A-1 0.600 parts Polymer B-1 0.600 parts C.I. I. Pigment Blue 15: 3 5.00 parts, paraffin wax (HNP-7: manufactured by Nippon Seiki Co., Ltd.) 3.00 parts

  Next, the toner material is sufficiently premixed with a Henschel mixer (Mitsui Miike Chemical Co., Ltd.), melt-kneaded with a twin-screw extruder, cooled, and then cooled to about 1 to 2 mm using a hammer mill. Next, the resultant was finely pulverized by an air jet type fine pulverizer, and the obtained finely pulverized product was classified by a multi-division classifier to obtain toner particles.

0.8 parts by mass of hydrophobic silica fine powder surface-treated with dimethyl silicone oil (number average primary particle diameter: 7 nm, BET specific surface area 125 m ² / g), i 100 parts of the toner particles 1 obtained, i -0.2 part by mass of anatase-type titanium oxide fine powder (number average primary particle size: 15 nm, BET specific surface area 30 m ² / g) surface-treated with butyltrimethoxysilane and dimethylsilicone oil was added to a Henschel mixer (Mitsui Miike Chemical Industries, Ltd.) Toner 17 was obtained by mixing and external addition. Table 3 shows the physical properties of the obtained toner. The obtained toner was evaluated in the same manner as in Example 1, and the results are shown in Tables 4-1 and 4-2.

<Example 18>
A toner is prepared in the same manner as in Example 11 except that the polymer A-1 in Example 11 is changed to the polymer A-13 (20.0 parts) and the polymer B-1 is changed to 5 parts. It was. Table 3 shows the physical properties of the obtained toner. The obtained toner was evaluated in the same manner as in Example 1, and the results are shown in Tables 4-1 and 4-2.

<Example 19>
A toner is prepared in the same manner as in Example 11 except that the polymer A-1 in Example 11 is changed to the polymer A-13 (18.0 parts) and the polymer B-1 is changed to 5 parts. It was. Table 3 shows the physical properties of the obtained toner. The obtained toner was evaluated in the same manner as in Example 1, and the results are shown in Tables 4-1 and 4-2.

<Example 20>
Preparation of toner composition mixture:
Copolymerized polyester resin of bisphenol A propylene oxide adduct / bisphenol A ethylene oxide adduct / terephthalic acid derivative (Tg 62 ° C., softening point 102 ° C., Mw 21000) 100 parts I. Pigment Blue 15: 3 5.00 parts, paraffin wax (melting point: 72.3 ° C.) 8.00 parts, Polymer A-1 0.64 parts, Polymer B-1 0.60 parts, Ethyl acetate 100 parts Was thoroughly premixed in a container, and then dispersed in a bead mill for 6 hours while being kept at 20 ° C. or lower to prepare a toner composition mixed solution.

Preparation of toner particles:
70.0 parts of 0.100 mol / liter-Na ₃ PO ₄ aqueous solution was put into 240 parts of ion-exchanged water, heated to 60 ° C., and then used at 14,000 rpm using Creamix (manufactured by M Technique). Stir. To this, 12 parts of a 1.00 mol / liter-CaCl ₂ aqueous solution was added to obtain a dispersion medium containing Ca ₃ (PO ₄ ) ₂ . Furthermore, 1.00 part of carboxymethyl cellulose (trade name: Serogen BS-H, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added and stirred for 10 minutes.

While the dispersion medium prepared in the homomixer container was adjusted to 30 ° C. and stirred, 180 parts of the toner composition mixed solution adjusted to 30 ° C. was added, stirred for 1 minute, and then stopped. A toner composition dispersion suspension was obtained. The obtained toner composition dispersion suspension is stirred at a constant temperature of 40 ° C., and the gas phase on the surface of the suspension is forcibly renewed by an exhaust device, and is kept for 17 hours to remove the solvent. After cooling to room temperature, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ and filtered, washed with water, dried and classified to obtain toner particles. Toner 20 was obtained by externally adding hydrophobic silica fine powder to the obtained toner particles in the same manner as in Toner Production Example 1.

  Table 3 shows the physical properties of the toner thus obtained. The obtained toner was evaluated in the same manner as in Example 1, and the results are shown in Tables 4-1 and 4-2.

<Example 21>
Toner 21 was obtained in the same manner as in Example 1 except that the polymer A-1 in Example 1 was changed to A-14. Table 3 shows the physical properties of the obtained toner. The obtained toner was evaluated in the same manner as in Example 1, and the results are shown in Tables 4-1 and 4-2.

<Example 22>
Preparation of polyester P-4:
-Bisphenol A-Propylene oxide 2.2 mol adduct 1200 parts-Bisphenol A-Ethylene oxide 2.2 mol adduct 475 parts-Terephthalic acid 250 parts-Trimellitic anhydride 190 parts-Fumaric acid 300 parts-Dibutyltin oxide 0 100 parts were placed in a glass 4-liter four-necked flask, and a thermometer, a stir bar, a condenser, and a nitrogen inlet tube were attached and placed in a mantle heater. Under a nitrogen atmosphere, the mixture was reacted at 220 ° C. for 5 hours to obtain a polyester resin P-4.

next,
-Polyester resin P-4 100 parts-Polymer A-15 2.00 parts-Polymer B-1 1.00 parts-C.I. I. Pigment Blue 15: 3 5.00 parts, paraffin wax (HNP-7: manufactured by Nippon Seiki Co., Ltd.) 3.00 parts After sufficiently premixing the toner material with a Henschel mixer (Mitsui Miike Chemical Co., Ltd.), After melt-kneading with a twin-screw extruder, after cooling, coarsely pulverized to a particle size of about 1 to 2 mm using a hammer mill, and then finely pulverized with an air jet type fine pulverizer. Was classified with a multi-division classifier to obtain toner particles 22.

0.8 parts by mass of hydrophobic silica fine powder surface-treated with dimethyl silicone oil (number average primary particle size: 7 nm, BET specific surface area 125 m ² / g), i 100 parts of the toner particles 22 obtained, i -0.2 part by mass of anatase-type titanium oxide fine powder (number average primary particle size: 15 nm, BET specific surface area 30 m ² / g) surface-treated with butyltrimethoxysilane and dimethylsilicone oil was added to a Henschel mixer (Mitsui Miike Chemical Industries, Ltd.) Toner 22 was obtained by mixing and external addition. Table 3 shows the physical properties of the obtained toner. The obtained toner was evaluated in the same manner as in Example 1, and the results are shown in Tables 4-1 and 4-2.

<Example 23>
A toner was prepared in the same manner as in Example 1 except that the polymer A-1 in Example 1 was changed to the polymer A-16, and a toner 23 was obtained. Table 3 shows the physical properties of the obtained toner. The obtained toner was evaluated in the same manner as in Example 1, and the results are shown in Tables 4-1 and 4-2.

<Example 24>
The material used for preparation of the pigment dispersion paste of Example 1 was changed to the following, and the toner was changed in the same manner as in Example 1 except that the pigment dispersion paste used for preparation of the monomer mixture was changed to 46.1 parts. The toner 24 was produced. Table 3 shows the physical properties of the obtained toner. The obtained toner was evaluated in the same manner as in Example 1, and the results are shown in Tables 4-1 and 4-2.
-Styrene 58.5 parts-C.I. I. Pigment Blue 15: 3 9.75 parts, Polymer A-1 1.13 parts

<Example 25>
The material used for the preparation of the pigment dispersion paste of Example 1 was changed to the following, and the toner was changed in the same manner as in Example 1 except that the pigment dispersion paste used for the preparation of the monomer mixture was changed to 46.2 parts. Thus, a toner 25 was obtained. Table 3 shows the physical properties of the obtained toner. The obtained toner was evaluated in the same manner as in Example 1, and the results are shown in Tables 4-1 and 4-2.
-Styrene 58.5 parts-C.I. I. Pigment Blue 15: 3 9.75 parts, Polymer A-1 1.13 parts, Polymer B-1 0.045 parts

<Example 26>
The material used in the preparation of the pigment dispersion paste of Example 1 was changed to the following, and the toner was changed in the same manner as in Example 1 except that the pigment dispersion paste used for the preparation of the monomer mixture was changed to 46.5 parts. Thus, toner 26 was obtained. Table 3 shows the physical properties of the obtained toner. The obtained toner was evaluated in the same manner as in Example 1, and the results are shown in Tables 4-1 and 4-2.
-Styrene 58.5 parts-C.I. I. Pigment Blue 15: 3 9.75 parts Polymer A-1 1.50 parts Polymer B-1 0.12 parts

<Example 27>
The material used for preparation of the pigment dispersion paste of Example 1 was changed to the following, and the toner was changed in the same manner as in Example 1 except that the pigment dispersion paste used for preparation of the monomer mixture was changed to 47.1 parts. Thus, a toner 27 was obtained. Table 3 shows the physical properties of the obtained toner. The obtained toner was evaluated in the same manner as in Example 1, and the results are shown in Tables 4-1 and 4-2.
-Styrene 58.5 parts-C.I. I. Pigment Blue 15: 3 9.75 parts, Polymer A-1 1.13 parts, Polymer B-2 1.50 parts

<Example 28>
The material used for preparation of the pigment dispersion paste of Example 1 was changed to the following, and the toner was changed in the same manner as in Example 1 except that the pigment dispersion paste used for preparation of the monomer mixture was changed to 47.1 parts. The toner 28 was obtained. Table 3 shows the physical properties of the obtained toner. The obtained toner was evaluated in the same manner as in Example 1, and the results are shown in Tables 4-1 and 4-2.
-Styrene 58.5 parts-C.I. I. Pigment Blue 15: 3 9.75 parts, Polymer A-1 1.13 parts, Polymer B-3 1.50 parts

<Example 29>
Toner 29 was obtained in the same manner as in Example 24 except that the polymer B-3 in Example 24 was changed to the polymer B-4. Table 3 shows the physical properties of the obtained toner. The obtained toner was evaluated in the same manner as in Example 1, and the results are shown in Tables 4-1 and 4-2.

<Example 30>
Toner 30 was obtained in the same manner as in Example 24 except that the polymer B-3 in Example 24 was changed to the polymer B-5. Table 3 shows the physical properties of the obtained toner. The obtained toner was evaluated in the same manner as in Example 1, and the results are shown in Tables 4-1 and 4-2.

<Example 31>
Toner 31 was obtained in the same manner as in Example 24 except that the polymer B-3 in Example 24 was changed to the polymer B-6. Table 3 shows the physical properties of the obtained toner. The obtained toner was evaluated in the same manner as in Example 1, and the results are shown in Tables 4-1 and 4-2.

<Example 32>
The material used for the preparation of the pigment dispersion paste of Example 1 was changed to the following, and the toner was changed in the same manner as in Example 1 except that the pigment dispersion paste used for the preparation of the monomer mixture was changed to 46.2 parts. The toner 32 was produced. Table 3 shows the physical properties of the obtained toner. The obtained toner was evaluated in the same manner as in Example 1, and the results are shown in Tables 4-1 and 4-2.
-Styrene 58.5 parts-C.I. I. Pigment Blue 15: 3 9.75 parts, Polymer A-1 0.20 part, Polymer B-2 1.00 part

<Example 33>
The material used for the preparation of the pigment dispersion paste of Example 1 was changed to the following, and the toner was changed in the same manner as in Example 1 except that the pigment dispersion paste used for the preparation of the monomer mixture was changed to 47.7 parts. The toner 33 was produced. Table 3 shows the physical properties of the obtained toner. The obtained toner was evaluated in the same manner as in Example 1, and the results are shown in Tables 4-1 and 4-2.
-Styrene 58.5 parts-C.I. I. Pigment Blue 15: 3 9.75 parts, Polymer A-1 0.15 parts, Polymer B-2 1.50 parts

<Example 34>
The material used in the preparation of the pigment dispersion paste of Example 1 was changed to the following, and the toner was changed in the same manner as in Example 1 except that the pigment dispersion paste used for the preparation of the monomer mixture was changed to 47.4 parts. Thus, a toner 34 was obtained. Table 3 shows the physical properties of the obtained toner. The obtained toner was evaluated in the same manner as in Example 1, and the results are shown in Tables 4-1 and 4-2.
-Styrene 58.5 parts-C.I. I. Pigment Blue 15: 3 9.75 parts Polymer A-1 3.00 parts Polymer B-1 0.10 parts

<Example 35>
The material used in the preparation of the pigment dispersion paste of Example 1 was changed to the following, and the toner was changed in the same manner as in Example 1 except that the pigment dispersion paste used for the preparation of the monomer mixture was changed to 47.8 parts. The toner 35 was produced. Table 3 shows the physical properties of the obtained toner. The obtained toner was evaluated in the same manner as in Example 1, and the results are shown in Tables 4-1 and 4-2.
Pigment dispersion paste:
-Styrene 58.5 parts-C.I. I. Pigment Blue 15: 3 9.75 parts, Polymer A-1 3.50 parts, Polymer B-1 0.10 parts

<Example 36>
The material used in the preparation of the pigment dispersion paste of Example 1 was changed to the following, and the toner was changed in the same manner as in Example 1 except that the pigment dispersion paste used for the preparation of the monomer mixture was changed to 47.0 parts. Thus, a toner 36 was obtained. Table 3 shows the physical properties of the obtained toner. The obtained toner was evaluated in the same manner as in Example 1, and the results are shown in Tables 4-1 and 4-2.
Styrene 67.5 parts Carbon black 11.3 parts Polymer A-1 1.13 parts Polymer B-1 1.59 parts

<Example 37>
The material used for preparation of the pigment dispersion paste of Example 1 was changed to the following, and the toner was changed in the same manner as in Example 1 except that the pigment dispersion paste used for preparation of the monomer mixture was changed to 47.2 parts. Thus, toner 37 was obtained. Table 3 shows the physical properties of the obtained toner. The obtained toner was evaluated in the same manner as in Example 1, and the results are shown in Tables 4-1 and 4-2.
-Styrene 58.5 parts-C.I. I. Pigment Red 122 9.75 parts Polymer A-1 1.13 parts Polymer B-1 1.59 parts

<Comparative Example 1>
The material used for preparation of the pigment dispersion paste of Example 1 was changed to the following, and the toner was changed in the same manner as in Example 1 except that the pigment dispersion paste used for preparation of the monomer mixture was changed to 45.2 parts. The toner 38 was produced. Table 3 shows the physical properties of the obtained toner. The obtained toner was evaluated in the same manner as in Example 1, and the results are shown in Tables 4-1 and 4-2.
-Styrene 58.5 parts-C.I. I. Pigment Blue 15: 3 9.75 parts, Polymer B-2 1.50 parts

<Comparative example 2>
The material used in the preparation of the pigment dispersion paste of Example 1 was changed to the following, and the toner was changed in the same manner as in Example 1 except that the pigment dispersion paste used for the preparation of the monomer mixture was changed to 44.6 parts. The toner 39 was produced. Table 3 shows the physical properties of the obtained toner. The obtained toner was evaluated in the same manner as in Example 1, and the results are shown in Tables 4-1 and 4-2.
-Styrene 58.5 parts-C.I. I. Pigment Blue 15: 3 9.75 parts, Polymer A-17 4.50 parts

DESCRIPTION OF SYMBOLS 1 Suction machine 2 Measuring container 3 Screen 4 Lid 5 Vacuum gauge 6 Air volume control valve 7 Suction port 8 Condenser 9 Electrometer

Claims (8)

A toner having toner particles containing a binder resin, a colorant and a charge control agent;
The charge control agent includes a polymer A having a structure a represented by the following formula (1) as a partial structure, and the polymer A has a weight average molecular weight (Mw) of 1,000 to 100,000. Toner.

Formula (1)
(In formula (1), R ¹ represents an alkyl group having 1 to 18 carbon atoms or an alkoxyl group having 1 to 18 carbon atoms,
R ² represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, or an alkoxyl group having 1 to 18 carbon atoms,
g represents an integer of 1 to 3, h represents an integer of 0 to 3, and when h is 2 or 3, each R ¹ can be independently selected. ) The toner according to claim 1, wherein the structure a is a unit represented by the following formula (2) and is contained in the polymer A.

Formula (2)
(In the formula (2), R ³ represents an alkyl group having 1 to 18 carbon atoms or an alkoxyl group having 1 to 18 carbon atoms,
R ⁴ represents a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 18 carbon atoms, or an alkoxyl group having 1 to 18 carbon atoms,
R ⁵ represents a hydrogen atom or a methyl group,
i represents an integer of 1 to 3, j represents an integer of 0 to 3, and when j is 2 or 3, R ³ can be independently selected. )   The toner according to claim 1, wherein the content of the structure a in the polymer A is 10 μmol / g or more and 1500 μmol / g or less.   4. The toner according to claim 1, wherein the content x of the structure a in the toner is 0.10 μmol / g or more and 200.00 μmol / g or less. 5. The toner according to claim 1, wherein the charge control agent further includes a polymer B having a structure b represented by the following formula (3) as a partial structure.

Formula (3)
(In the formula, B ¹ represents an alkylene structure having 1 or 2 carbon atoms which may have a substituent, or an aromatic ring which may have a substituent,
R ⁶ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms,
The substituent in the alkylene structure is a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 or 12 carbon atoms, or an alkoxyl group having 1 to 12 carbon atoms, and in the aromatic ring The substituent is a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkoxyl group having 1 to 12 carbon atoms. ) The toner according to claim 5, wherein the structure b is a unit represented by the following formula (4) and is contained in the polymer B.

Formula (4)
(In the formula (4), B ² represents an alkylene structure having 1 or 2 carbon atoms which may have a substituent, or an aromatic ring which may have a substituent,
R ⁷ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms,
R ⁸ represents a hydrogen atom or a methyl group,
The substituent in the alkylene structure is a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 or 12 carbon atoms, or an alkoxyl group having 1 to 12 carbon atoms, and in the aromatic ring The substituent is a hydroxyl group, an alkyl group having 1 to 12 carbon atoms, or an alkoxyl group having 1 to 12 carbon atoms. )   The sulfur content in the toner is 0.10 μmol / g or more, and the molar ratio x / y of the content x (μmol / g) of structure a and the content y (μmol / g) of structure b in the toner is The toner according to claim 5, wherein the toner is 0.10 or more and 50.00 or less. 8. The toner particles according to claim 1, wherein the toner particles are obtained by granulating a composition containing the colorant, the release agent, and the charge control agent in an aqueous medium. The toner described.

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