JP2014098857A - Toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that has a saturation charge amount and a start-up property of charging hardly affected by a change in temperature and humidity, and has a stable charge amount even after a long-term storage in high temperature and high humidity.SOLUTION: A toner includes toner particles containing a binder resin, colorant, and a charge control resin. The charge control resin is a polymer including a structure A having a specific benzoic acid derivative structure, and a specific structure B having a sulfonic acid or a sulfonic acid ester as a substituent.

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.

  Studies for improving the triboelectric charging characteristics of toners have been actively conducted. 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 rapid charge rise, a sharp charge 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 charge rise characteristics when the process speed is increased by a contact one-component development system or the like. It was also found that there is room for improvement in the stability of the charge amount before and after long-term storage under high temperature and high humidity.

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

  Accordingly, an object of the present invention is to provide a toner in which the saturation charge amount and the rising property of charge are not easily affected by changes in temperature and humidity, and the charge amount is stable before and after long-term storage under high temperature and high humidity.

  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, according to the present invention, in a toner having toner particles containing a binder resin, a colorant, and a charge control resin, the charge control resin is represented by the structure A and the formula (2) represented by the formula (1) as partial structures. A toner comprising a polymer containing the structure B shown.

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. The following alkyl group or an alkoxyl group having 1 to 18 carbon atoms is represented, m represents an integer of 0 or more and 3 or less, and when m is 2 or 3, R ¹ can be independently selected and n is 1 or more Represents an integer of 3 or less),

式（２）

Formula (2)

(In Formula (2), R ⁶ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and B ¹ is an alkylene structure having 1 or 2 carbon atoms that may have a substituent, Or an aromatic ring which may have a substituent, and 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 carbon And a substituent in 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.)

  According to the present invention, it is possible to provide a toner in which the charge amount before and after long-term storage under high temperature and high humidity is stable because the saturation charge amount and the rising property of charge are not easily affected by changes in temperature and humidity.

It is a figure which shows the structure of the apparatus used for the measurement of the triboelectric charge amount of the developing agent containing a toner.

  In the toner having toner particles containing a binder resin, a colorant, and a charge control resin, the present inventors have the following formula (1) as a partial structure.

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. The following alkyl group or an alkoxyl group having 1 to 18 carbon atoms is represented, m represents an integer of 0 or more and 3 or less, and when m is 2 or 3, R ¹ can be independently selected and n is 1 or more Represents an integer of 3 or less.)
And the structure A shown by the following formula (2)

式（２）

Formula (2)

(In Formula (2), R ⁶ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and B ¹ is an alkylene structure having 1 or 2 carbon atoms that may have a substituent, Or an aromatic ring which may have a substituent, and 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 carbon And a substituent in 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.)
In the polymer containing the structure B represented by the formula, the rising property of the charge with respect to the saturation charge amount and the friction frequency is not easily affected by changes in temperature and humidity, and charging before and after storage under high temperature and high humidity. The inventors have found that the amount is stable and have arrived at the present invention.

Excellent effects are demonstrated with regard to the rapidity of charging that rises to a sufficient amount of charge in a short time, the stability of charging from the initial stage to the time of printing out a large number of sheets, and the stability of charging under high temperature and high humidity. Although the mechanism is not clear, the present inventors have the charge performance of the charge control resin having a charge control function,
(A) Effect of charge generation and charge accumulation (B) It is considered that the charge dissipation rate considered to contribute to charge uniformity is involved.

  By forming a copolymer in which the structure A having a benzoic acid derivative structure represented by the formula (1) and the structure B having a sulfonic acid or a sulfonic acid ester represented by the formula (2) as a substituent coexist. It has been found that, along with the generation and accumulation of charges, the ability to equalize charges is exhibited. Although the mechanism is not clear, the structure A having the benzoic acid derivative represented by the formula (1) contributes to dissipating the excessive charge stored in the structure B and appropriately equalizing the charge in the resin. It is thought that. In the charge control resin of the present invention, since the structure A and the structure B are present in the same polymer, the structure A and the structure B are close to each other at the molecular level. For this reason, it is considered that the rise of charge is improved by instantaneous generation of charge and uniformization of charge.

  Further, the structure A having a benzoic acid derivative structure represented by the formula (1) has an aromatic ring through an alkyl ether advantageous for electron conduction together with the benzoic acid derivative structure. It is believed that this large conjugated system spreading from the benzoic acid derivative improves the charge transfer speed and improves the charge start-up performance. Moreover, it has structural flexibility because it has an aromatic ring via an alkyl ether between the main chain and the benzoic acid derivative structure. This is considered to have produced the effect of facilitating a molecular arrangement that makes it more advantageous to transfer charges with the structure B having the sulfonic acid or sulfonic acid ester represented by the formula (2) as a substituent. In addition, since the structure A having a benzoic acid derivative structure represented by the formula (1) is hardly affected by water molecules, it contributes to stabilizing the chargeability after long-term storage particularly under high temperature and high humidity. I think.

  The main chain structure of the polymer in the charge control resin in the toner of the present invention is not particularly limited. Examples thereof include vinyl polymers, polyester polymers, polyamide polymers, polyurethane polymers, polyether polymers, and the like. In view of ease of production in producing the charge control resin of the present invention, cost merit, and the like, a polyester polymer or a vinyl polymer is preferable.

  As the charge control resin in the toner of the present invention, the structure A represented by the formula (1) is preferably present in the polymer as a unit represented by the formula (3). Moreover, it is preferable that the structure B shown by Formula (2) exists in this polymer as a unit shown by Formula (4).

式（３）

Formula (3)

(In Formula (3), 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, and 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 And R ³ is independently selected when j is 2 or 3.)

式（４）

Formula (4)

(In Formula (4), 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, and B ² has a substituent. Represents an optionally substituted alkylene structure having 1 or 2 carbon atoms, or an aromatic ring optionally having a substituent, and the substituent in the alkylene structure is a hydroxyl group, having 1 to 12 carbon atoms An alkyl group, 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 And an alkoxyl group having 1 to 12 carbon atoms.)
In the case of the structure represented by the formulas (3) and (4), the effects of the present invention are more suitably exhibited in toner particles containing a vinyl resin as a main component.

  This is because the main chain of the structure A represented by the formula (3) and the structure B represented by the formula (4) is a vinyl polymer, so that it is compatible with toner particles mainly composed of a vinyl resin. It becomes easy to be done. It is considered that the structure A and the structure B exist in a state where the distances are kept evenly uniform by compatibilization, and it is possible to take a more optimal molecular arrangement, and the effect of the present invention becomes more remarkable.

  For the same reason, the other structure constituting the charge control resin of the present invention is preferably a unit derived from a vinyl monomer.

  Further, since the glass transition point (Tg) of the charge control resin can be easily controlled by using a vinyl copolymer as the main chain, the effect of the present invention can be expressed while maintaining toner fixing properties. This is a preferred embodiment.

  The charge control resin in the toner of the present invention may be a polymer having a polyester structure. In this case, a polyester structure formed by polycondensation of a polyhydric alcohol component and a polyvalent carboxylic acid component is used as the main chain, and a structure A represented by the formula (1) and a structure B represented by the formula (2) May be contained. It is also possible to use a hybrid resin modified with a vinyl monomer as a resin having a polyester structure.

  When a hybrid resin is used, a known method can be used to adjust the vinyl modification ratio in the hybrid resin. Specifically, an arbitrary modification ratio can be adjusted by changing the charged amount ratio of the polyester resin component to be used and the vinyl monomer component. When the hybrid resin is used, the structure A having a benzoic acid derivative structure represented by the formula (1) and the structure B having a sulfonic acid and a sulfonic acid ester represented by the formula (2) as substituents are a vinyl resin unit and a polyester. It may exist in either of the resin units. Moreover, you may exist in a side chain or the terminal.

  The following are mentioned as a polyhydric alcohol component which comprises resin containing the said polyester structure. Specifically, for example, as the dihydric alcohol component, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis ( 4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2 -Alkylene oxide adducts of bisphenol A such as bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, Opentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A And hydrogenated bisphenol A.

  Examples of the trivalent or higher alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, etc. Can be mentioned.

Examples of the polyvalent carboxylic acid component include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof; And succinic acid substituted with an alkyl group having 6 to 12 carbon atoms or an anhydride thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or the anhydride thereof; and the like.
Among them, in particular, a carboxylic acid component (for example, fumaric acid, maleic acid, maleic anhydride, phthalate, which includes a bisphenol derivative as a diol component and a divalent or higher carboxylic acid or an acid anhydride thereof, or a lower alkyl ester thereof) A polyester resin obtained by polycondensation of these compounds using acid, terephthalic acid, trimellitic acid, pyromellitic acid, or the like as an acid component can be preferably used.
It does not specifically limit as a manufacturing method of charge control resin, It can manufacture by a well-known method. In the case of a vinyl resin, for example, as an example, a polymerizable monomer containing the structure A represented by the formula (1) (formula (5)) and the structure B having the structure represented by the formula (2) are used. What is necessary is just to copolymerize the polymerizable monomer (Formula (6)) to contain using a polymerization initiator.

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. When 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 0 to 3 and m is 2 or 3 , R ⁹ can be independently selected, and n represents an integer of 1 to 3.

式（６）

Formula (6)

(In Formula (6), R ¹² represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R ¹³ represents a hydrogen atom or a methyl group, and B ³ has a substituent. Represents an optionally substituted alkylene structure having 1 or 2 carbon atoms, or an aromatic ring optionally having a substituent, and the substituent in the alkylene structure is a hydroxyl group, an alkyl having 1 to 12 carbon atoms Group, an aryl group having 6 or 12 carbon atoms, or an alkoxyl group having 1 to 12 carbon atoms, and the substituent in the aromatic ring is 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.)
Specific examples of the polymerizable monomer having the structure A (formula (5)) include the following. The examples shown here are merely examples, and the present invention is not limited to these examples.

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

  Specific examples of the polymerizable monomer having the structure B (formula (6)) 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 Examples thereof include acids and alkyl esters having 1 to 12 carbon atoms. A sulfonic acid structure, methyl ester or ethyl ester is preferable, and a sulfonic acid structure or sulfonic acid methyl ester structure is more preferable.

  In addition, when the main chain of the charge control resin is a vinyl copolymer resin, other vinyl monomers that can be used are not particularly limited, but specific examples include the following compounds. Can do. Styrene and derivatives thereof such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene; ethylene unsaturated monoolefins such as ethylene, propylene, butylene, isobutylene; vinyl chloride, vinylidene chloride, Vinyl halides such as vinyl bromide and vinyl fluoride; vinyl ester acids such as vinyl acetate, vinyl propionate and vinyl benzoate; acrylic acid esters such as acrylic acid-n-butyl and acrylic acid-2-ethylhexyl; Methacrylic acid esters in which the acrylic acid of the acrylic acid esters is changed to methacrylic acid; methacrylic acid amino esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; vinyl ethers such as vinyl methyl ether and vinyl ethyl ether; Ethers; such vinyl ketones of vinyl methyl ketone; N- vinyl pyrrole, such as N- vinyl compounds, vinyl naphthalenes; acrylonitrile, methacrylonitrile, acrylamide, acrylic acid and methacrylic acid.

  As a polymerization initiator that can be used when copolymerizing the polymerizable monomer component described above, various substances such as a peroxide polymerization initiator and an azo polymerization initiator can be used. Examples of the peroxide polymerization initiator that can be used 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 that can be used 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), etc. Illustrated.

  If necessary, two or more of these polymerization initiators can be used simultaneously. It is preferable that the usage-amount of the polymerization initiator used in this case is 0.1 to 20.0 parts by mass with respect to 100 parts by mass of the polymerizable monomer. 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 charge control resin in the toner of the present invention is a polyester resin, various known production methods can be used. For example,
(A) The structure represented by the structure A and the structure represented by the formula (2) having the structure represented by the formula (1) as a substituent by an organic reaction using a reaction residue of a carboxyl group or a hydroxyl group contained in the polyester structure. A method of converting to structure B having:
(B) A method for producing a polyester using a polyhydric alcohol or a polycarboxylic acid having a structure A having a structure represented by formula (1) as a substituent and a structure B having a structure represented by formula (2);
(C) A functional group that easily introduces the structure A having the structure represented by the formula (1) and the structure B having the structure represented by the formula (2) into the polyhydric alcohol or polyvalent carboxylic acid in advance. How to keep;
Etc.

In the case of a hybrid resin,
(D) A method of hybridizing a polyester resin containing a structure A having a structure represented by formula (1) as a substituent and a structure B having a structure represented by formula (2) with a vinyl monomer;
(E) After polymerization using a vinyl monomer having a carboxyl group such as acrylic acid or methacrylic acid, the carboxyl group is subjected to an organic reaction to form structure A represented by formula (1) or formula (2) A method of converting to the structure B represented by
(F) a method of hybridizing a polyester resin using a vinyl monomer having a structure A represented by the formula (1) and a structure B represented by the formula (2);
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 (D). 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 (E), when the structure represented by the formula (1) is introduced by an organic reaction, a carboxyl group present in the resin is replaced with a compound having a benzoic acid structure such as the following formula (7). Examples thereof include a method of amidation using the compound.

式（７）

Formula (7)

(In Formula (7), R ¹⁴ is an alkyl group having 1 to 18 carbon atoms or an alkoxyl group having 1 to 18 carbon atoms.)
In addition, when the structure represented by the formula (2) is introduced, the carboxyl group present in the resin is converted to a sulfonic acid group such as aminomethanesulfonic acid, aminoethanesulfonic acid (taurine), 2-aminobenzenesulfonic acid and amino group. Examples thereof include amidation using a group-containing compound and further esterification of sulfonic acid with a known esterifying agent.

  In the specific method of (F), as the vinyl monomer having the benzoic acid derivative structure A represented by the formula (1), a polymerizable monomer represented by the above formula (5) can be used. As the vinyl monomer having the structure B having the sulfonic acid or sulfonic acid ester represented by the formula (2) as a substituent, the polymerizable monomer represented by the above-described formula (6) can be used. .

  Further, when the content of the structure A of the formula (1) in the toner is a (μmol / g) and the content of the structure B of the formula (2) in the toner is b (μmol / g), the molar ratio a / B is preferably 0.10 ≦ a / b ≦ 10.00, and the content b of the structure B in the toner is preferably 0.10 μmol / g or more.

  If the content b in the toner is 0.10 μmol / g or more, there will be a sufficient charge generation and charge accumulation portion in the toner. As a result, a desired charge amount can be given to the toner. Within the above range, uniform charge will occur more rapidly.

  The molar ratio a / b between the content A of structure A and the content b of structure B in the toner particles is set to 0.10 to 10.00 and the content b in the toner is controlled to 0.10 μmol / g or more. As a method, for example, it can be controlled by the following method.

  In the case of a vinyl resin, a polymerizable monomer containing the structure A represented by the formula (1) so that the content a of the structure A and the content b of the structure B are in the above ranges when the charge control resin is produced ( Polymerization is carried out by the method described above after controlling the amount of the polymerizable monomer (formula (6)) containing the structure B having the structure represented by formula (5)) and formula (2). After confirming that the content a of structure A and the content b of structure B in the obtained charge control resin had a molar ratio a / b of 0.10 or more and 10.00 or less, further in the toner The charge control resin can be added to the toner so that the content b in the toner is 0.100 μmol / g or more.

  Also in the case of a polyester-based resin, the charge control resin is manufactured so that the content A of the structure A and the content b of the structure B are within the above ranges, and the amount of the charge control resin added to the toner is further increased. This can be achieved by adding so that the content b in the toner is 0.100 μmol / g or more.

  In the present invention, the content (μmol / g) of structure B in the polymer is calculated as follows. By elemental analysis of polymer B, the amount of sulfur element derived from structure B present in 1 g of polymer B is calculated, and the amount of sulfur element is divided by 32.06 (the atomic weight of the sulfur element). The content (μmol / g) of structure B per 1 g of B is calculated.

  In the present invention, the content (μmol / g) of the structure A in the polymer can be calculated by the following two methods. When the main chain is a vinyl resin, the acid value of the polymer is quantified by titrating the polymer by the method described later, and the amount of acid groups derived from Structure A and Structure B of the polymer is calculated. By subtracting the acid value calculated from the content of the structure B described above, the amount of acid groups derived from the structure A of the polymer is calculated, and based on this, the content of the structure A in the polymer (μmol) / G).

  When the main chain is a polyester resin, the content of the structure A in the polymer (μmol / g) is calculated by NMR measurement of the polymer by the method described later.

  The molar ratio a / b between the structure A and the structure B in the toner is a molar ratio a between the content of the structure A (μmol / g) and the content of the structure B (μmol / g) calculated by the above-described method. / B.

  Further, the content (μmol / g) of the structure B in the toner is calculated by calculating the amount of sulfur element derived from the structure B present in 1 g of toner by elemental analysis of the toner. The content (μmol / g) of structure B per gram of toner is calculated by dividing by the atomic weight of sulfur element.

  As a method for adjusting the weight average molecular weight of the charge control resin in the toner of the present invention, a known method can be used.

  In the vinyl resin, it can be arbitrarily adjusted by the charging ratio of the vinyl monomer and the radical initiator amount, the polymerization temperature, and the like.

  Moreover, in a polyester-type resin, it can adjust arbitrarily with the preparation ratio and polymerization time of an acid component and an alcohol component. 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.

  As for the molecular weight of the charge control resin, the weight average molecular weight calculated by gel permeation chromatography (GPC) is preferably 1,000 or more and 200,000 or less. As a more preferable range, the weight average molecular weight is 2,000 or more and 100,000 or less. When the molecular weight of the charge control resin in the toner of the present invention is within the above range, contamination of members such as a sleeve and a carrier is satisfactorily suppressed.

  In addition, from the viewpoint of charging characteristics and fixability, the charge control resin preferably has a narrow molecular weight distribution. The ratio (Mw / Mn) between the weight average molecular weight Mw and the number average molecular weight Mn calculated by gel permeation chromatography is preferably 1.0 or more and 6.0 or less. More preferably, it is 1.0 or more and 4.0 or less.

  In the toner of the present invention, the charge control resin is preferably added separately from a resin used as a binder resin. The content of the charge control resin is not particularly limited, but is preferably 0.05 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the binder resin. When the content is in the above range, the dispersibility in the toner particles is good, and the effect of addition is sufficiently obtained.

  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, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 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 addition amount of the colorant 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.

A method for producing the toner is not particularly limited, and a known production method is used. In particular,
(A) A method of directly producing toner particles using the suspension polymerization method described in JP-B-36-10231, JP-A-59-53856, and JP-A-59-61842; B) A method for producing toner particles by an interfacial polymerization method such as a microcapsule production method;
(C) a method for producing a toner by a coacervation method;
(D) Toner particles by an associative polymerization method in which at least one kind of fine particles are aggregated to obtain a desired particle size as disclosed in JP-A-62-106473 and JP-A-63-186253. How to obtain;
(E) a method of producing toner particles by a dispersion polymerization method characterized by monodispersion;
(F) a polymer dissolution (melting) suspension method in which necessary resins are dissolved in a water-insoluble organic solvent and then converted into a toner in water;
(G) a method of obtaining toner particles by an emulsion dispersion method;
(H) A toner component is kneaded and uniformly dispersed using a pressure kneader, an extruder, a media disperser, etc., and then cooled, and the kneaded product is allowed to collide with a target under a mechanical or jet stream to obtain a desired value. A pulverization method in which toner particles are produced by finely pulverizing the toner to a particle size and further sharpening the particle size distribution through a classification step;
(I) A method in which the toner obtained by the pulverization method is spheroidized by heating or the like in a solvent to obtain toner particles.

  Among them, the effect of the present invention is particularly remarkable when toner particles are produced by a suspension polymerization method. Specifically, a polymerizable monomer composition containing a polymerizable monomer and a charge control resin is added to an aqueous medium, and the polymerizable monomer composition is granulated in the aqueous medium to perform the polymerization. In this method, toner particles are obtained by forming particles of a polymerizable monomer composition and polymerizing the polymerizable monomer contained in the particles. The reason is that in the step of granulating the polymerizable monomer composition in the aqueous medium (granulation step), the charge control resin can be effectively localized in the vicinity of the toner particle surface. It is.

  The method for producing toner particles by the suspension polymerization method will be described in detail below. First, the colorant is uniformly dissolved and mixed or dispersed in the polymerizable monomer constituting the 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. This is uniformly dissolved or dispersed with a stirrer etc. together with a polymerizable monomer, the charge control resin and the polymerization initiator, and further, other additives as necessary, to prepare a polymerizable monomer composition. To do. 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. Is finely dispersed to the toner particle size (granulation step). Then, the polymerizable monomer contained in the polymerizable monomer composition finely dispersed in the granulation step is polymerized by light or heat (polymerization step) to obtain toner particles. The polymerization initiator may be added after the granulation step.

  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, a vinyl monomer that can be used in the charge control resin can be used in the same manner.

  The dispersion medium that can be used in the production method is determined based on the solubility in a dispersion medium such as a binder resin, an organic medium, a polymerizable monomer, and the charge control resin, but is an aqueous dispersion medium. Is preferred. 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 polymerizable monomer composition with respect to the dispersion medium is preferably 1% by mass or more and 80% by mass or less, and 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 in the toner of the present invention using the suspension polymerization method, a polymerization initiator that can be used in the production of the charge control resin can be used in the same manner.

  Further, when a toner is produced by a suspension polymerization method, 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.

  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 aluminum 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.

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

<Measurement Method of Weight Average Molecular Weight (Mw) and Molecular Weight Distribution of Resin>
The weight average molecular weight (Mw) and molecular weight distribution of the resin used in the present invention are calculated in terms of polystyrene by gel permeation chromatography (GPC). When measuring the molecular weight of a resin having an acid group, the column elution rate also depends on the amount of the acid group. Therefore, it is necessary to prepare a sample in which the acid group is 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 solution 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 rate: 1.0 mL / 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 ".

<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 differential value: 50 dE / dmL
End point detection range setting: 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 a measurement sample is precisely weighed in a 250 mL tall beaker, and 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 of potassium hydroxide ethyl alcohol solution in this test (mL), f: Factor of potassium hydroxide solution, S: Sample (g))

<Measurement method of hydroxyl value of resin>
The hydroxyl value is the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when 1 g of a sample is acetylated. The hydroxyl value in the present invention is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.

  Add 25.0 g of special grade acetic anhydride to a 100 mL volumetric flask, add pyridine to bring the total volume to 100 mL, and shake well to obtain an acetylating reagent. The obtained acetylating reagent is stored in a brown bottle so as not to come into contact with moisture, carbon dioxide gas and the like.

  Titration is performed using a 1.0 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 (potentiometric titrator AT-510 manufactured by Kyoto Electronics Co., Ltd.). 100 mL of 1.00 mol / L hydrochloric acid is placed in a 250 mL tall beaker, titrated with the potassium hydroxide solution, and determined from the amount of the potassium hydroxide ethyl alcohol solution required for neutralization. As the 1.00 mol / L hydrochloric acid, one prepared according to JIS K 8001-1998 is used.

The measurement conditions for the hydroxyl 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: 80 mL
Waiting time before titration: 30 seconds Titration direction: Automatic control parameter end point judgment potential: 30 dE
End point determination differential value: 50 dE / dmL
End point detection range setting: Not set Control speed mode: Standard gain: 1
Data collection potential: 4 mV
Data collection titration: 0.5 mL

main exam;
2.00 g of the pulverized measurement sample is precisely weighed into a 200 mL round bottom flask, and 5.00 mL of the acetylating reagent is accurately added to this using a whole pipette. At this time, if the sample is difficult to dissolve in the acetylating reagent, a small amount of special grade toluene is added and dissolved.

  Place a small funnel in the mouth of the flask and immerse 1 cm of the bottom of the flask in a 97 ° C. glycerin bath and heat. At this time, in order to prevent the temperature of the neck of the flask from rising due to the heat of the bath, it is preferable to cover the base of the neck of the flask with a cardboard having a round hole.

  After 1 hour, the flask is removed from the glycerin bath and allowed to cool. After standing to cool, 1.00 mL of water is added from the funnel and shaken to hydrolyze acetic anhydride. The flask is again heated in the glycerin bath for 10 minutes for further complete hydrolysis. After cooling, wash the funnel and flask walls with 5.00 mL of ethyl alcohol.

The obtained sample is transferred to a 250 mL tall beaker, and 100 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 similar to the above operation is performed except that no sample is used.
The obtained results are substituted into the following formula to calculate the hydroxyl value.
A = [{(BC) × 28.05 × f} / S] + D
Here, A: hydroxyl value (mgKOH / g), B: addition amount (mL) of potassium hydroxide ethyl alcohol solution in blank test, C: addition amount (mL) of potassium hydroxide ethyl alcohol solution in final test, f : Factor of potassium hydroxide solution, S: Sample (g), D: Acid value of resin (mgKOH / g).

<Measurement method of content of structure B in polymer>
The calculation of the content (μmol / g) of the structure B represented by the formula (2) in the polymer can be performed by measuring the sulfur element amount (ppm) contained in the polymer and calculating from the sulfur element amount. it can. Specifically, an automatic sample combustion device (device name: pretreatment device for ion chromatography AQF-100 type (device specification: autoboat controller ABC type, AQF-100, GA-100 integrated type) The polymer is combusted and gasified, and the gas is absorbed in an absorbing solution (H ₂ O ₂ , 30 ppm aqueous solution), and then ion chromatography (device name: ion chromatograph ICS2000, column: The amount of sulfur element (ppm) contained in the polymer is calculated by measuring the amount of SO ₄ contained in the absorption liquid by IONPAC AS17 (manufactured by Nippon Dionex Co., Ltd.). From the amount (ppm), the content (μmol) of the structure B represented by the formula (2) in the polymer is calculated. Structure identified, it can be performed by analysis using NMR to be described later.

<Method for Measuring Content of Structure B in Toner>
The content (μmol / g) per gram of toner of structure B can be calculated from the amount of sulfur element contained in the toner by measuring the amount of sulfur element (ppm) contained in the toner. The measurement can be performed in the same manner as described above in <Method for measuring content of structure B in polymer>, except that the object to be measured is changed from polymer to toner.

<Structural analysis of polymer and polymerizable monomer>
The structures of the polymer and the polymerizable monomer having the structure A and the structure B are determined using a nuclear magnetic resonance apparatus ( ¹ H-NMR, ¹³ C-NMR) and an FT-IR spectrum, and the formula in the polymer The content (μmol / g) of the structure A represented by (1) can be calculated. The apparatus used in the present invention is described below.
(I) ¹ H-NMR, ¹³ C-NMR
FT-NMR JNM-EX400 manufactured by JEOL (solvent: heavy chloroform)
(Ii) FT-IR spectrum AVATAR360FT-IR manufactured by Nicolet

<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) Put 200 mL of the aqueous electrolytic solution into a 250 mL round bottom beaker made exclusively for Multisizer 3, set it on a sample stand, and stir the stirrer rod 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 electrolytic aqueous 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. Put 3.3 L of ion exchange water in the water tank of the ultrasonic disperser, and add 2 mL of Contaminone N into this 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”.
Production examples of the polymerizable monomer represented by the formula (5) are shown below.

<Synthesis Example of Compound 5A>
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 Compound 5A having the following structure.

（化合物５Ａ）

(Compound 5A)

<Synthesis Example of Compound 5B>
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 Compound 5B having the following structure.

（化合物５Ｂ）

(Compound 5B)

<Synthesis Example of Compound 5C>
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 Compound 5C having the following structure.

（化合物５Ｃ）

(Compound 5C)

<Synthesis Example of Compound 5D>
Compound 5D having the following structure was obtained in the same manner as Compound A-3, except that 3-hydroxy-3-methoxybenzoic acid was changed to 152.1 g of 3-hydroxy-3-methylbenzoic acid.

（化合物５Ｄ）

(Compound 5D)

<Synthesis Example of Compound 5E>
4- (chloromethyl) styrene is a mixture of 3- (chloromethyl) methylstyrene and 4- (chloromethyl) styrene (manufactured by AGC Seikagaku Co., Ltd., trade name “CMS-P”, except for compound 5A). Compound 5E having the following structure was obtained by the same method as the synthesis.

（化合物５Ｅ）
及び

(Compound 5E)
as well as

の混合物

Mixture of

<Compound 5F>
As the polymerizable monomer used in the comparative example, 4-vinylbenzoic acid (Compound 5F) having the following structure was used.

（化合物５Ｆ）

(Compound 5F)

<Compound 5G>
As a polymerizable monomer used in the comparative example, sodium 4-vinylbenzoate (Compound 5G) having the following structure was used.

（化合物５Ｇ）

(Compound 5G)

  Next, production examples of the polymerizable monomer represented by the formula (6) are shown below.

<Compound 6A>
As the polymerizable monomer having the structure B, 2-acrylamido-2-methylpropanesulfonic acid (Compound 6A) having the following structure was used.

（化合物６Ａ）

(Compound 6A)

<Synthesis Example of Compound 6B>
Into a reaction vessel equipped with a stirrer, condenser, thermometer, and nitrogen introduction tube, was charged 1500 g of 2-acrylamido-2-methylpropanesulfonic acid, 2060 g of trimethylorthoformate, and 1.50 g of p-benzoquinone, and at 80 ° C. for 5 hours. Reacted. The reaction mixture was cooled and concentrated under reduced pressure. The precipitated crystals were filtered, added to 5 L of water, dispersed and washed, filtered, and washed twice with 2.5 L of water. The obtained crystals were air-dried at 30 ° C., then dispersed and washed with 4 L of hexane, and filtered. The obtained crystal was dried at 30 ° C. under reduced pressure to obtain 1063 g of methyl 2-acrylamido-2-methylpropanesulfonate (Compound 6B) represented by the following structure.

（化合物６Ｂ）

(Compound 6B)

<Synthesis Example of Compound 6C>
Into a reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 788 g of 2-amino-5-methoxybenzenesulfonic acid, 642 g of triethylamine and 4 L of tetrahydrofuran are charged, and 352 g of methacrylic acid chloride is dropped at 15 ° C. over 15 minutes. did. The mixture was stirred for 6 hours while maintaining at 5 ° C. or lower. While maintaining the temperature at 5 ° C. or lower, 800 mL of concentrated hydrochloric acid and 12.8 L of water were added to the reaction mixture for liquid separation, and the organic layer was washed with 6.4 L of 2% hydrochloric acid, and then washed with 6.4 L of water three times. did. The obtained solution was concentrated under reduced pressure to obtain crystals. The obtained crystals were charged into a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, and 1680 g of trimethyl orthoformate and 1.50 g of p-benzoquinone were charged and reacted at 80 ° C. for 10 hours. The reaction mixture was cooled and concentrated under reduced pressure. The precipitated crystals were filtered, added to 5 L of water, dispersed and washed, filtered, and washed twice with 2.5 L of water. The obtained crystals were air-dried at 30 ° C. and then purified by column chromatography (silica gel 5 kg, mobile phase hexane / ethyl acetate = 1/1) to give 2-acrylamido-5-methoxy represented by the following structure 6C. 383 g of methyl benzenesulfonate (Compound 6C) was obtained.

（化合物６Ｃ）

(Compound 6C)

<Production example of polymer 1>
To a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 60.00 parts of toluene was charged and refluxed under a nitrogen stream.

  Next, the following polymerizable monomer and solvent were mixed to prepare a polymerizable monomer mixture.

<Monomer composition, mixing ratio>
・ Compound 5A 6.0 parts ・ Compound 6A 6.0 parts ・ Styrene 88.0 parts ・ Toluene 60.0 parts To this polymerizable monomer mixed solution, 60.0 parts of toluene and tert-butyl persulfate as a polymerization initiator were added. A mixed solution of 6.6 parts of oxyisopropyl monocarbonate (trade name: Perbutyl I, manufactured by NOF Corporation) was added dropwise. The mixture was stirred at 110 ° C. for 5 hours and cooled to room temperature. The obtained polymer-containing composition was dropped into a mixed solution of 1400 parts of methanol and 10 parts of acetone over 10 minutes with stirring to precipitate and crystallize the resin composition. The obtained resin composition was filtered and washed twice with 200 parts of methanol. The obtained resin powder was dried at 90 ° C. under reduced pressure to obtain a polymer 1. About the obtained polymer 1, content (micromol / g) and molecular weight of the structure A and the structure B in the polymer in a polymer were confirmed by performing NMR measurement, acid value measurement, sulfur content measurement, and GPC measurement. . The composition ratio and molecular weight of the polymer 1 are shown in Table 3.

<Production example of polymers 2 to 11>
In the same manner as in the production example of polymer 1, except that the monomer composition, the mixing ratio, and the number of parts of t-butylperoxyisopropyl monocarbonate as a polymerization initiator are changed as shown in Table 2, polymers 2 to 11 and obtained. Table 3 shows the composition ratios and molecular weights of the polymers 2 to 11.

<Production example of polymer 12>
In a reaction vessel equipped with a condenser, a stirrer, a thermometer and a nitrogen inlet tube, 95.0 parts of propylene glycol, 103.8 parts of terephthalic acid, 5 parts of trimellitic acid, 14.0 parts of adipic acid, maleic anhydride 24.0 parts and 2.0 parts of tetrastearyl titanate as a condensation catalyst were added and reacted at 230 ° C. for 6 hours while distilling off water produced under a nitrogen stream. Subsequently, it was made to react under reduced pressure of 5-20 mmHg for 8 hours, and the unsaturated polyester resin 1 was obtained. The physical properties of the unsaturated polyester resin 1 were an acid value of 34.0 mgKOH / g, a hydroxyl value of 8.5 mgKOH / g, Mn of 2700, and Mw of 5100.

On the other hand, 200 parts of toluene and 100 parts of the unsaturated polyester resin 1 were charged into a reaction vessel equipped with a cooling pipe, a stirrer, a thermometer, and a nitrogen introduction pipe, and stirred at 50 ° C. in a nitrogen stream.
-Compound 5A 8.0 parts-Compound 6A 8.0 parts-Styrene 40.0 parts-Toluene 50.0 parts To the mixed solution of the above monomers, t-butylperoxyisopropyl monocarbonate ( 4.0 parts of 75% hydrocarbon solvent diluted product) was mixed and added dropwise to the reaction vessel over 30 minutes. Stir at 110 ° C. for 5 hours and cool to room temperature. The resulting polymer-containing composition is dropped into a mixed solution of 2800 parts of methanol and 20 parts of acetone over 10 minutes with stirring to precipitate and crystallize the resin composition. The resulting resin composition is filtered and washed twice with 300 parts of methanol. The obtained resin powder was dried at 60 ° C. under reduced pressure for 10 hours to obtain a polymer 12.

  About the obtained polymer 12, content (micromol / g) and molecular weight of the structure A and the structure B in the polymer in a polymer were confirmed by performing NMR measurement, acid value measurement, sulfur content measurement, and GPC measurement. . The composition ratio and molecular weight of the polymer 12 are shown in Table 3.

<Production example of polymer 13>
In a reaction vessel equipped with a condenser, stirrer, thermometer and nitrogen inlet tube, 100.0 parts propylene glycol, 103.8 parts terephthalic acid, 5.0 parts trimellitic anhydride, 8.0 parts adipic acid and As a condensation catalyst, 2.0 parts of tetrastearyl titanate was added and reacted at 230 ° C. for 5 hours while distilling off the water generated in a nitrogen stream. Subsequently, it was made to react under reduced pressure of 5-20 mmHg for 8 hours, and the polyester resin 2 was obtained. The physical properties of this polyester resin 2 were an acid value of 34.5 mgKOH / g, a hydroxyl value of 7.8 mgKOH / g, Mn of 2400, and Mw of 4300.

  Next, 100 parts of polyester resin 3 and 7 parts of 2-amino-5-methoxybenzenesulfonic acid were put into a reaction vessel equipped with a cooling pipe, a stirrer, a thermometer and a nitrogen introduction pipe, and 380 parts of pyridine were added. After stirring, 135 parts of triphenyl phosphite is added and heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 500 parts of ethanol. Next, it was washed twice with 200 parts of 1 mol / L hydrochloric acid, further washed twice with 200 parts of water, and dried under reduced pressure to obtain polyester resin 3. Next, 100 parts of polyester resin 3 and 10 parts of the compound represented by the following formula (8) are put in a reaction vessel equipped with a cooling pipe, a stirrer, a thermometer and a nitrogen introduction pipe, and 380 parts of pyridine is added and stirred. Then, 135 parts of triphenyl phosphite is added and heated at 120 ° C. for 6 hours. After completion of the reaction, it is recovered by reprecipitation in 500 parts of ethanol. Next, it was washed twice with 200 parts of 1 mol / L hydrochloric acid, further washed twice with 200 parts of water, and dried under reduced pressure to obtain polymer 13. About the obtained polymer 13, content (micromol / g) and molecular weight of the structure A and the structure B in the polymer in a polymer were confirmed by performing NMR measurement, acid value measurement, sulfur content measurement, and GPC measurement. . The composition ratio and molecular weight of the polymer 13 are shown in Table 3.

式（８）

Formula (8)

<Production Example of Polymer 14 for Comparative Example>
To a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 60.00 parts of toluene was charged and refluxed under a nitrogen stream.

Next, the following polymerizable monomer and solvent were mixed to prepare a polymerizable monomer mixture.
<Monomer composition, mixing ratio>
Compound 5F 6.0 parts Styrene 94.0 parts Toluene 60.0 parts To this polymerizable monomer mixture, 60.0 parts of toluene and tert-butylperoxyisopropyl monocarbonate as a polymerization initiator (Japan) A mixed solution of 6.6 parts of oil and fat, trade name Perbutyl I) was added dropwise. The mixture was stirred at 110 ° C. for 5 hours and cooled to room temperature. The obtained polymer-containing composition was dropped into a mixed solution of 1400 parts of methanol and 10 parts of acetone over 10 minutes with stirring to precipitate and crystallize the resin composition. The obtained resin composition was filtered and washed twice with 200 parts of methanol. The obtained resin powder was dried at 90 ° C. under reduced pressure to obtain a comparative polymer 14. About the obtained polymer 14 for a comparison, content (micromol / g) and molecular weight of the structure A in a polymer were confirmed by carrying out NMR measurement, acid value measurement, and GPC measurement. The composition ratio and molecular weight of the polymer 14 for comparative example are shown in Table 3.

<Production Example of Polymer 15 for Comparative Example>
Except for changing the monomer composition, the mixing ratio, and the number of parts of the polymerization initiator t-butylperoxyisopropyl monocarbonate as shown in Table 2, the same method as in the production example of the polymer 14 was used. Combined 15 was obtained. Table 3 shows the composition ratio and molecular weight of the polymer 15 for comparative example.

<Production Example of Comparative Example Polymer 16>
To a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 60.00 parts of toluene was charged and refluxed under a nitrogen stream.

Next, the following polymerizable monomer and solvent were mixed to prepare a polymerizable monomer mixture.
<Monomer composition, mixing ratio>
Compound 6A 6.0 parts Styrene 94.0 parts Toluene 60.0 parts To this polymerizable monomer mixture, 60.0 parts of toluene and tert-butylperoxyisopropyl monocarbonate as a polymerization initiator (Japan) A mixed solution of 6.6 parts of oil and fat, trade name Perbutyl I) was added dropwise. The mixture was stirred at 60 ° C. for 8 hours and cooled to room temperature. The obtained polymer-containing composition was dropped into a mixed solution of 1400 parts of methanol and 10 parts of acetone over 10 minutes with stirring to precipitate and crystallize the resin composition. The obtained resin composition is filtered and washed twice with 200 parts of methanol. The obtained resin powder was dried at 90 ° C. under reduced pressure to obtain a polymer 16 for comparative example.

  About the obtained polymer 16 for comparative examples, the content (micromol / g) and molecular weight of the structure B in a polymer were confirmed by carrying out NMR measurement, acid value measurement, sulfur content measurement, and GPC measurement. The composition ratio and molecular weight of the polymer 16 for comparative example are shown in Table 3.

<Example 1>
Example of toner production:
(Preparation of pigment dispersion paste 1)
-Styrene 80.0 parts-C.I. I. Pigment Blue 15: 3 14.0 parts The above materials were well premixed in a container, and then dispersed in a bead mill for 5 hours while being kept at 20 ° C. or lower to prepare Pigment Dispersion Paste 1.

(Production of toner particles)
390 parts of 0.1 mol / liter-Na ₃ PO ₄ aqueous solution was added to 1150 parts of ion-exchanged water, heated to 60 ° C., and then stirred at 11000 rpm using CLEARMIX (M Technique). did. To this, 58 parts of 1.0 mol / liter-CaCl ₂ aqueous solution was added to obtain dispersion medium 1 containing Ca ₃ (PO ₄ ) ₂ .
-Pigment dispersion paste 1 38.0 parts-Styrene 34.0 parts-N-butyl acrylate 15.0 parts-Paraffin wax (HNP-7: manufactured by Nippon Seiwa) 8.00 parts-Saturated polyester resin 4 5.00 parts (Terephthalic acid-propylene oxide modified bisphenol A copolymer, acid value 11 mgKOH / g, Mw: 15500)
Polymer 1 1.00 parts These were heated to 60 ° C, melted and dispersed to obtain a monomer mixture. Further, while maintaining the temperature at 60 ° C., 5.00 parts of 2,2-azobis (2,4-dimethylvaleronitrile) was added as a polymerization initiator and dissolved to prepare polymerizable monomer composition 1.

The polymerizable monomer composition 1 was charged into the dispersion medium 2. The mixture was stirred at 10000 rpm for 20 minutes using a CLEARMIX at 60 ° C. in a nitrogen atmosphere to granulate the monomer composition. Thereafter, the mixture was reacted at 60 ° C. for 5 hours while stirring with a paddle stirring blade, and then stirred at 80 ° C. for 5 hours to complete the polymerization. After cooling to room temperature, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ and filtered, washed with water, and dried to obtain toner particles. Further, toner particles 1 were prepared by classifying the obtained toner particles so as to select particles of 2 μm or more and less than 10 μm.

Toner 1 was obtained by externally adding 1.00 part of hydrophobic silica fine powder having a BET of 200 m ² / g to 100 parts of the toner particles 1 using a Henschel mixer. Table 4 shows the physical properties of the toner thus obtained. The toner was evaluated as follows. The toner evaluation results are shown in Tables 5 and 6.

<Evaluation of saturated charge amount of toner>
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%)
63.0 parts-lipophilic hematite 21.0 parts Put the above material, 5 parts 28% ammonia water and 10 parts water in a flask and heat up to 85 ° C in 30 minutes with stirring and mixing. The mixture was polymerized for 3 hours to be cured. 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 6.0% 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 4 minutes at a speed of 2 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 rising property of charging>
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 charge rise (%) with respect to the saturated charge amount when shaken 180 times was calculated by the following formula.
Charging start-up property (%) =
{Charge amount when shaking for 90 seconds (mC / kg) / Saturation charge amount (mC / kg)} × 100
Evaluation is based on the following criteria.
A rank: 90% or more B rank: 80% or more and less than 90% C rank: 70% or more and less than 80% D rank: less than 70%

<Evaluation of neglect characteristics under high temperature and high humidity>
50.0 g of each of the two-component developers that were allowed to stand for 2 days in an environment of 23 ° C. and 60% Rh was measured and left for 1 day and 30 days in an environment of 40 ° C./90% Rh. Thereafter, each was left for 2 days in an environment of 23 ° C. and 60% Rh. Then, it put into 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 triboelectric charge after standing for 30 days was divided by the triboelectric charge after standing for 1 day, and evaluated according to the following criteria.
Leaving characteristics under high temperature and high humidity (%) =
[{Amount of triboelectric charge after standing for 30 days (mC / kg) −Amount of triboelectric charge after standing for 1 day (mC / kg)} / Amount of triboelectricity after standing for 1 day (mC / kg)}] × 100
A rank: Less than 5% B rank: 5% or more and less than 10% C rank: 10% or more and less than 15% D rank: 15% or more

<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. As image output paper, A4 size high white paper GF-C081 (manufactured by Canon Marketing Japan Inc.) was used.

  Image evaluation is 15 ° C./10% Rh (low temperature and low humidity environment, hereinafter abbreviated as LL environment) and 32.5 ° C./90% Rh (high temperature and high humidity environment, hereinafter abbreviated as HH environment). Performed in the 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 those that were worst 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.

<Example 2>
A toner 2 was obtained in the same manner as in Example 1 except that the number of parts of the polymer 1 used in Example 1 was 0.500 part.

<Example 3>
A toner 3 was obtained in the same manner as in Example 1 except that the number of parts of the polymer 1 used in Example 1 was 4.00 parts.

<Example 4>
A toner 4 was obtained in the same manner as in Example 1 except that the number of parts of the polymer 1 used in Example 1 was 0.100 part.

<Example 5>
A toner 5 was obtained in the same manner as in Example 1 except that the polymer 1 used in Example 1 was changed to the polymer 2 of Production Example 2 and the number of parts was 1.00 parts.

<Example 6>
The toner 1 was produced in the same manner as in Example 1 except that the polymer 1 used in Example 1 was changed to the polymer 3 in Production Example 3 and the number of parts was 1.00 parts.

<Example 7>
A toner 7 was obtained in the same manner as in Example 1 except that the polymer 1 used in Example 1 was changed to the polymer 4 of Production Example 4 and the number of parts was 1.00 parts.

<Example 8>
The toner 1 was obtained in the same manner as in Example 1 except that the polymer 1 used in Example 1 was changed to the polymer 5 of Production Example 5 and the number of parts was 1.00 parts.

<Example 9>
A toner 9 was obtained in the same manner as in Example 1 except that the polymer 1 used in Example 1 was changed to the polymer 6 of Production Example 6 and the number of parts was 1.00 parts.

<Example 10>
(Preparation of pigment dispersion paste 2)
Styrene 80.0 parts Carbon black 14.0 parts The above materials were well premixed in a container and then dispersed in a bead mill for 4 hours while maintaining the temperature at 20 ° C or lower to prepare a pigment dispersion paste 2.

(Production of toner particles)
350 parts of 0.1 mol / liter-Na ₃ PO ₄ aqueous solution is added to 1200 parts of ion-exchanged water, heated to 60 ° C., and then at 11,000 rpm using CLEARMIX (manufactured by M Technique). Stir. To this, 52 parts of 1.0 mol / liter-CaCl ₂ aqueous solution was added to obtain dispersion medium 2 containing Ca ₃ (PO ₄ ) ₂ .
Pigment dispersed paste 2 38.0 parts Styrene 30.0 parts n-Butyl acrylate 17.0 parts Ester wax 10.0 parts (main component _{C 19 H 39 COOC 20 H 41} , mp 68.6 ° C.)
Saturated polyester resin 5 5.00 parts (terephthalic acid-propylene oxide modified bisphenol A copolymer, acid value 11 mg KOH / g, Mw 14800)
-Polymer 7 1.00 part These are heated at 60 degreeC, and melt | dissolved and disperse | distributed to make a monomer mixture. Further, while maintaining the temperature at 60 ° C., 5.00 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was added as a polymerization initiator and dissolved to prepare polymerizable monomer composition 2.

The polymerizable monomer composition 2 was added to the dispersion medium 2. At 60 ° C., a nitrogen atmosphere was used, and the mixture was stirred for 20 minutes at 10,000 rpm using CLEARMIX to granulate the polymerizable monomer composition 2. Then, the mixture is reacted at 60 ° C. for 5 hours while stirring with a paddle stirring blade, and then stirred at 80 ° C. for 5 hours to complete the polymerization. After cooling to room temperature, hydrochloric acid is added to dissolve Ca ₃ (PO ₄ ) ₂ , filtered, washed with water, dried, and classified in the same manner as in toner production example 1 to obtain toner particles 10. Toner 10 was obtained by externally adding hydrophobic silica fine powder to toner particles 10.

<Example 11>
C. of the colorant used in Example 1 I. Pigment Blue 15: 3 was changed to quinacridone (CI Pigment Violet 19), the number of parts was 14.0 parts, the polymer 1 was changed to the polymer 8 obtained in Production Example 8, and the number of parts was 1.000 parts. A toner 11 was obtained in the same manner as in Example 1 except for the above.

<Example 12>
A toner 12 was obtained in the same manner as in Example 1 except that the polymer 1 used in Example 1 was changed to the polymer 9 of Production Example 9 and the number of parts was 1.00 parts.

<Example 13>
The toner 1 was obtained in the same manner as in Example 1 except that the polymer 1 used in Example 1 was changed to the polymer 10 of Production Example 10 and the number of parts was 1.00 parts.

<Example 14>
A toner 14 was obtained in the same manner as in Example 1 except that the polymer 1 used in Example 1 was changed to the polymer 11 of Production Example 11 and the number of parts was changed to 1.00 parts.

<Example 15>
A toner 15 was obtained in the same manner as in Example 1 except that the polymer 1 used in Example 1 was changed to the polymer 12 of Production Example 12 and the number of parts was 1.00 parts.

<Example 16>
A toner 16 was obtained in the same manner as in Example 1 except that the polymer 1 used in Example 1 was changed to the polymer 13 of Production Example 13 and the number of parts was 1.00 parts.

<Example 17>
Preparation of saturated polyester resin 6:
-Bisphenol A-Propylene oxide 2.2 mol adduct 1200.0 parts-Bisphenol A-Ethylene oxide 2.2 mol adduct 475.0 parts-Terephthalic acid 250.0 parts-Trimellitic anhydride 190.0 parts-Fumar 290.0 parts of acid and 0.1 part of dibutyltin oxide are placed in a 4-liter 4-neck flask made of glass, and a thermometer, a stir bar, a condenser, and a nitrogen inlet tube are attached and placed in a mantle heater. Under a nitrogen atmosphere, reaction was carried out at 220 ° C. for 5 hours to obtain polyester resin 5.
-Saturated polyester resin 6 89.5 parts-C.I. I. Pigment Blue 15: 3 5.50 parts, paraffin wax (HNP-7: manufactured by Nippon Seiwa) 5.00 parts, Polymer 1 1.00 parts After sufficiently premixing the above toner materials with a Henschel mixer, two The mixture was melt-kneaded with a shaft extruder, cooled, and coarsely pulverized to a particle size of about 1 to 2 mm using a hammer mill. Subsequently, it was finely pulverized by an air jet type fine pulverizer. Further, the obtained finely pulverized product was classified by a multi-division classifying apparatus, whereby toner particles 17 were obtained. Further, in the same manner as in toner production example 1, toner 17 was obtained by externally adding hydrophobic silica fine powder to toner particles 17.

<Example 18>
The toner 1 was obtained in the same manner as in Example 17 except that the polymer 1 used in Example 17 was changed to the polymer 5 of Production Example 5 and the number of parts was changed to 1.00 parts.

<Comparative Example 1>
Toner for Comparative Example was produced in the same manner as in Example 1 except that Polymer 1 used in Example 1 was changed to Polymer 14 for Comparative Example of Production Example 14 and the number of parts was 1.00 parts. 19 was obtained.

<Comparative example 2>
Toner for Comparative Example was produced in the same manner as in Example 1 except that Polymer 1 used in Example 1 was changed to Polymer 15 for Comparative Example of Production Example 15 and the number of parts was 1.00 parts. 20 was obtained.

<Comparative Example 3>
Toner for Comparative Example was produced in the same manner as in Example 1 except that Polymer 1 used in Example 1 was changed to Polymer 16 for Comparative Example of Production Example 16 and the number of parts was 1.00 parts. 21 was obtained.

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

Claims (4)

A toner having toner particles containing a binder resin, a colorant, and a charge control resin, wherein the charge control resin has a structure represented by the following formula (1) and a structure represented by the following formula (2): A toner comprising a polymer having B.

Formula (1)
(In Formula (1),
R ¹ represents a hydroxyl group, a carboxyl group, 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,
n represents an integer of 1 to 3, m represents an integer of 0 to 3, and when m is 2 or 3, each R ¹ is independently selected. ),

Formula (2)
(In Formula (2),
R ⁶ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms,
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 the substituent in the alkylene structure is a hydroxyl group, It is 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 the substituent in the aromatic ring is a hydroxyl group, 1 to 12 carbon atoms. It is the following alkyl group or an alkoxyl group having 1 to 12 carbon atoms. ) The structure A is contained in the polymer as a unit represented by the following formula (3), and the structure B is contained in the polymer as a unit represented by the following formula (4). Item 2. The toner according to Item 1.

Formula (3)
(In Formula (3),
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 is independently selected. ),

Formula (4)
(In Formula (4),
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,
B ² is an alkylene structure having 1 or 2 carbon atoms which may have a substituent, or an aromatic ring which may have a substituent, and the substituent in the alkylene structure is a hydroxyl group, It is 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. It is the following alkyl group or an alkoxyl group having 1 to 12 carbon atoms. )   When the content of the structure A of the formula (1) in the toner is a (μmol / g) and the content of the structure B of the formula (2) in the toner is b (μmol / g), the molar ratio a The toner according to claim 1, wherein / b is 0.10 ≦ a / b ≦ 10.00, and the content b is 0.10 μmol / g or more.   The toner particles are prepared by adding a polymerizable monomer composition containing a polymerizable monomer and the charge control resin to an aqueous medium, and granulating the polymerizable monomer composition in the aqueous medium. The toner particles obtained by forming particles of a polymerizable monomer composition and polymerizing the polymerizable monomer contained in the particles. The toner described.

Images