JP4840923B2 - Charge control agent and toner - Google Patents

Description

  The present invention relates to a charge control agent and a toner.

  The sulfonic acid group is generally used as a drug, and the sulfonic acid derivative group is generally used as a surfactant or a resist material.

  A compound having a sulfonic acid group or a sulfonic acid derivative is expected to be applied to various uses.

In addition, the use as a charge control agent is also being studied. For example, Patent Document 1 discloses use of a metal-containing compound as a charge control agent for a negatively chargeable toner. In this document, a method for producing a charge control agent containing an azo-containing metal complex is disclosed.
JP 2005-121776 A

  As for compounds having a sulfonic acid group or a sulfonic acid derivative, which are expected to be applied to various uses, known materials are not sufficient, and further improvements and provision of new structures have been demanded.

The present invention has an object to provide an electrostatic image developing toner characterized by containing a novel charge control agent and the charge control agent using a compound having a sulfonic San誘 conductor .

  In view of the above background art, as a result of intensive studies aimed at creating various useful compounds that do not contain metals as charge control agents, the following inventions have been achieved.

  The charge control agent according to the present invention is characterized by containing at least one compound represented by the chemical formula (2).

In the formula, R ₁₂ and R ₂₂ satisfy the following conditions 1) to 4).
1) R _{1 2} is, CF ₃ CH ₂ -, n- nonyl group, a phenyl group and a naphthyl group, I der either, when R ₁₂ is a phenyl group, as a substituent, 1 carbon atoms It may have ˜4 alkyl groups, acetyl groups or naphthyl sulfonates.
2 ) R ₂₂ is a —CH ₂ —CH ₂ —SO ₂ R ₃₂ group, a —C (CH ₃ ) ₂ —CH ₂ —SO ₂ R ₃₂ group, a phenyl group having a SO ₂ R ₃₂ group as a substituent, and a substituent. When any of the naphthyl groups having an SO ₂ R ₃₂ group as a group and R ₂₂ is a phenyl group having an SO ₂ R ₃₂ group as a substituent, the group may further have a methoxy group.
3) R ₃₂ is OR ₄₂ .
4) R ₄₂ is a methyl group, an ethyl group and phenyl group state, and are either, when R ₄₂ is a phenyl group, as a substituent, may have a nitro group.

  The electrostatic image developing toner according to the present invention is characterized by containing at least a binder resin, a colorant, and the charge control agent according to the present invention.

  According to the present invention, there is provided a charge control agent and an electrostatic charge image developing toner comprising the above charge control agent.

  Next, a preferred embodiment of the present invention will be described in detail.

Charge control agent according to the present invention are those containing an amide group, a compound obtained by introducing a sulfonic San誘 conductor (sulfonic acid ester le). Specifically, the charge control agent contains at least one compound represented by the chemical formula (2). In the formula, R ₂₂ is phenyl having —CH ₂ —CH ₂ —SO ₂ R ₃₂ group, —C (CH ₃ ) ₂ —CH ₂ —SO ₂ R ₃₂ group, and SO ₂ R ₃₂ group as a substituent. And a naphthyl group having a SO ₂ R ₃₂ group as a substituent , and when R ₂₂ is a phenyl group having a SO ₂ R ₃₂ group as a substituent , it further has a methoxy group. R ₃₂ is OR ₄₂ , R ₄₂ is any one of a methyl group, an ethyl group and a phenyl group, and when R ₄₂ is a phenyl group, it has a nitro group as a substituent. R ₁₂ is any one of CF ₃ CH ₂ —, n-nonyl group, phenyl group and naphthyl group, and when R ₁₂ is a phenyl group, It may have 4 alkyl groups, acetyl groups or naphthyl sulfonates.
In the following, there are also references other than the present invention, which are for reference only .

  [1] The charge control agent according to the first present invention is characterized by containing at least one compound represented by the chemical formula (2).

In the formula, R ₁₂ and R ₂₂ satisfy the following conditions 1) to 4).
1) R ₁₂ and R ₂₂ are any one of a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, and a substituted or unsubstituted heterocyclic structure.
2) At least one of R ₁₂ and R ₂₂ has at least one SO ₂ R ₃₂ group as a substituent.
3) R ₃₂ is OH, a halogen atom, ONa, OK or OR ₄₂ .
4) R ₄₂ is any one of a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, and a substituted or unsubstituted heterocyclic structure.

[2] The charge control agent according to the second aspect of the present invention is characterized in that it contains at least one compound satisfying the following conditions 1) to 4) as the compound represented by the chemical formula (2). To do.
1) R ₁₂ and R ₂₂ are any one of a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, and a substituted or unsubstituted heterocyclic structure.
2) At least one of R ₁₂ and R ₂₂ has at least one SO ₂ R ₃₂ group as a substituent.
3) R ₃₂ is OH, a halogen atom, ONa, OK or OR ₄₂ .
4) R ₄₂ is any one of a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted naphthyl group.

  [3] The charge control agent according to the third aspect of the present invention contains at least one compound satisfying at least one of the following conditions <1> and <2> as the compound represented by the chemical formula (2). It is characterized by.

<1>
In the case where the chemical formula (2) is a structure represented by the chemical formula (21), the following conditions 1) to 4) are satisfied.

1) R ₁₂ is any one of a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted naphthyl group.
2) R ₂₂₁ is any one of a substituted or unsubstituted aliphatic hydrocarbon structure and a substituted or unsubstituted aromatic ring structure.
3) R ₃₂ is OH, a halogen atom, ONa, OK or OR ₄₂ .
4) R ₄₂ is any one of a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted naphthyl group.

<2>
In the case where the chemical formula (2) is a structure represented by the chemical formula (22), the following conditions 1) to 4) are satisfied.

1) R ₁₂₁ is any one of a substituted or unsubstituted aliphatic hydrocarbon structure and a substituted or unsubstituted aromatic ring structure.
2) R ₂₂ is any one of a substituted or unsubstituted alkyl group having 1 to ₁₈ carbon atoms, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted naphthyl group.
3) R ₃₂ is OH, a halogen atom, ONa, OK or OR ₄₂ .
4) R ₄₂ is any one of a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted naphthyl group.

  [4] The charge control agent according to the fourth aspect of the present invention contains at least one compound satisfying at least one of the following conditions <3> and <4> as the compound represented by the chemical formula (2). It is characterized by.

<3>
In the case where the chemical formula (2) is a structure represented by the chemical formula (23), the following conditions 1) to 4) are satisfied.

1) R ₁₂ is any one of a substituted or unsubstituted aliphatic hydrocarbon structure and a substituted or unsubstituted aromatic ring structure.
2) R ₂₂₁ is any one of a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted naphthyl group.
3) R ₃₂ is OH, a halogen atom, ONa, OK or OR ₄₂ .
4) R ₄₂ is any one of a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted naphthyl group.

<4>
In the case where the chemical formula (2) is a structure represented by the chemical formula (24), the following conditions 1) to 4) are satisfied.

1) R ₁₂₁ is any one of a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted naphthyl group.
2) R ₂₂ is any one of a substituted or unsubstituted aliphatic hydrocarbon structure and a substituted or unsubstituted aromatic ring structure.
3) R ₃₂ is OH, a halogen atom, ONa, OK or OR ₄₂ .
4) R ₄₂ is any one of a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted naphthyl group.

[5] The charge control agent according to the fifth aspect of the present invention comprises at least one compound satisfying the following conditions 1) to 4) as the compound represented by the chemical formula (2): To do.
1) R ₁₂ and R ₂₂ are any one of a substituted or unsubstituted alkyl group having 1 to ₁₈ carbon atoms, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted naphthyl group.
2) At least one of R ₁₂ and R ₂₂ has at least one SO ₂ R ₃₂ group as a substituent.
3) R ₃₂ is OH, a halogen atom, ONa, OK or OR ₄₂ .
4) R ₄₂ is any one of a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted naphthyl group.

  [6] The charge control agent according to the sixth aspect of the present invention contains at least one compound satisfying at least one of the following conditions <5> and <6> as the compound represented by the chemical formula (2). It is characterized by.

<5>
In the case where the chemical formula (2) is a structure represented by the chemical formula (25), the following conditions 1) to 4) are satisfied.

1) R ₁₂ is any one of a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a phenyl group, and a naphthyl group. Examples of the substituent include one or more halogen atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups, hydroxyl groups, amino groups, nitro groups, carboxylic acids or carboxylates, acetamide groups, NHPh groups, CF ₃ groups, It has either a C ₂ F ₅ group or a C ₃ F ₇ group. The alkoxy group is a group represented by OR, and R is an alkyl group having 1 to 20 carbon atoms, a phenyl group, or a naphthyl group. The carboxylate is a Na salt or a K salt.
2) R ₂₂₁ is any one of a substituted or unsubstituted aliphatic hydrocarbon structure having 1 to 18 carbon atoms, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted naphthyl group.
3) R ₃₂ is OH, a halogen atom, ONa, OK or OR ₄₂ .
4) R ₄₂ is any one of a substituted or unsubstituted aliphatic hydrocarbon structure having 1 to 18 carbon atoms, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted naphthyl group.

<6>
In the case where the chemical formula (2) is a structure represented by the chemical formula (26), the following conditions 1) to 4) are satisfied.

1) R ₁₂₁ is any one of a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted naphthyl group.
2) R ₂₂ is any one of a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a phenyl group, and a naphthyl group. Examples of the substituent include one or more halogen atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups, hydroxyl groups, amino groups, nitro groups, carboxylic acids or carboxylates, acetamide groups, NHPh groups, CF ₃ groups, It has either a C ₂ F ₅ group or a C ₃ F ₇ group. The alkoxy group is a group represented by OR, and R is an alkyl group having 1 to 20 carbon atoms, a phenyl group, or a naphthyl group. The carboxylate is a Na salt or a K salt.
3) R ₃₂ is OH, a halogen atom, ONa, OK or OR ₄₂ .
4) R ₄₂ is any one of a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted naphthyl group.

  [7] The charge control agent according to the seventh aspect of the present invention contains at least one compound satisfying at least one of the following conditions <7> and <8> as the compound represented by the chemical formula (2). It is characterized by.

<7>
In the case where the chemical formula (2) is a structure represented by the chemical formula (27), the following conditions 1) to 4) are satisfied.

1) R ₁₂ is any one of a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted naphthyl group.
2) R ₂₂₁ is a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a phenyl group, and a naphthyl group. Examples of the substituent include one or more halogen atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups, hydroxyl groups, amino groups, nitro groups, carboxylic acids or carboxylates, acetamide groups, NHPh groups, CF ₃ groups, It has either a C ₂ F ₅ group or a C ₃ F ₇ group. The alkoxy group is a group represented by OR, and R is an alkyl group having 1 to 20 carbon atoms, a phenyl group, or a naphthyl group. The carboxylate is a Na salt or a K salt.
3) R ₃₂ is OH, a halogen atom, ONa, OK or OR ₄₂ .
4) R ₄₂ is any one of a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted naphthyl group.

<8>
In the case where the chemical formula (2) is a structure represented by the chemical formula (28), the following conditions 1) to 4) are satisfied.

1) R ₁₂₁ is any one of a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a phenyl group, and a naphthyl group. Examples of the substituent include one or more halogen atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups, hydroxyl groups, amino groups, nitro groups, carboxylic acids or carboxylates, acetamide groups, NHPh groups, CF ₃ groups, It has either a C ₂ F ₅ group or a C ₃ F ₇ group. The alkoxy group is a group represented by OR, and R is an alkyl group having 1 to 20 carbon atoms, a phenyl group, or a naphthyl group. The carboxylate is a Na salt or a K salt.
2) R ₂₂ is any one of a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted naphthyl group.
3) R ₃₂ is OH, a halogen atom, ONa, OK or OR ₄₂ .
4) R ₄₂ is any one of a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted naphthyl group.

[8] The charge control agent according to the eighth aspect of the present invention comprises at least one compound satisfying the following conditions 1) to 4) as the compound represented by the chemical formula (2): To do.
1) R ₁₂ and R ₂₂ are substituted or unsubstituted alkyl groups having 1 to 18 carbon atoms, phenyl groups, and naphthyl groups. Examples of the substituent include one or more halogen atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups, hydroxyl groups, amino groups, nitro groups, carboxylic acids or carboxylates, acetamide groups, NHPh groups, CF ₃ groups, It has either a C ₂ F ₅ group or a C ₃ F ₇ group. The alkoxy group is a group represented by OR, and R is an alkyl group having 1 to 20 carbon atoms, a phenyl group, or a naphthyl group. The carboxylate is a Na salt or a K salt.
2) At least one of R ₁₂ and R ₂₂ has at least one SO ₂ R ₃₂ group as a substituent.
3) R ₃₂ is OH, a halogen atom, ONa, OK or OR ₄₂ .
4) R ₄₂ is any one of a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted naphthyl group.

  [9] The electrostatic image developing toner according to the ninth aspect of the present invention comprises at least a binder resin, a colorant, and the charge control agent according to any one of [1] to [8]. It is characterized by being an electrostatic charge image developing toner.

  [10] The electrostatic charge developing toner according to the tenth aspect of the invention has a binder resin, a colorant, and a compound represented by the following chemical formula (2).

In the formula, R ₁₂ and R ₂₂ satisfy the following conditions 1) to 4).
1) R ₁₂ and R ₂₂ are any one of a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, and a substituted or unsubstituted heterocyclic structure.
2) At least one of R ₁₂ and R ₂₂ has at least one SO ₂ R ₃₂ group as a substituent.
3) R ₃₂ is OH, a halogen atom, ONa, OK or OR ₄₂ .
4) R ₄₂ is any one of a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, and a substituted or unsubstituted heterocyclic structure.

(More specific production method of the compound according to the present invention)
Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. The compound according to the present invention having the above-described configurations has extremely excellent characteristics as a charge control agent. Further, the electrostatic image developing toner containing the charge control agent has a remarkable effect when used in an image forming apparatus having a developing system based on electrophotography. The following method can be illustrated as a manufacturing method of this compound.

  In the present invention, the compound having an amide group and a sulfonic acid group, or a sulfonic acid ester, a sulfonic acid salt, or a sulfonic acid halide can be produced by various synthetic methods.

  For example, amidation can be performed by a condensation reaction between an amino compound and a carboxylic acid or carboxylic acid derivative compound.

  Hereinafter, as a particularly preferable production method, a carboxylic acid compound, an amino compound, an amidation method, and a sulfonic acid synthesis method used for amidation are described.

(Carboxylic acid compound)
The carboxylic acid compound has a structure represented by the following chemical formula (29).

  In the chemical formula (29), R is a complex containing any one or more of a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic hydrocarbon structure, a substituted or unsubstituted N, S, and O. It is a ring structure. Specific examples of the carboxylic acid compound having an aliphatic hydrocarbon skeleton are shown in the examples described later. Specific examples of the carboxylic acid compound having an aromatic ring skeleton are shown in the examples described later.

(Amino compound)
The amino compound has a structure represented by the following chemical formula (30) or chemical formula (31).

In the chemical formulas (30) and (31), R is any one of a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic hydrocarbon structure, a substituted or unsubstituted N, S, and O. Any of the above heterocyclic structures. Two R in the chemical formula (31) may be the same or different.

  For example, specific examples of amino compounds having an aliphatic hydrocarbon skeleton will be shown in the examples described later. For example, specific examples of the amino compound having an aromatic ring skeleton are shown in the examples described later.

(Amidation reaction)
As the condensation reaction of a carboxyl group and an amino group, any of a method using a condensing agent, a method of forming a salt and performing condensation by a dehydration reaction, a method using a dehydrating agent, and the like can be used. A method of converting a carboxyl group into an acid chloride and reacting with an amino group can also be used.

(Amidation reaction using a condensing agent)
As the production method of the present invention, a method using a condensing agent will be described in detail.

  As the condensing agent, a phosphoric acid condensing agent, a carbodiimide condensing agent, and the like can be used. In the reaction of the present invention, a phosphite-based condensing agent is preferably used.

  In the reaction of the present invention, a solvent can be used as necessary. Solvents used include hydrocarbons such as hexane, cyclohexane and heptane; ketones such as acetone and methyl ethyl ketone; ethers such as dimethyl ether, diethyl ether and tetrahydrofuran. In addition, halogenated hydrocarbons such as carbon tetrachloride, dichloromethane, chloroform, dichloroethane, and trichloroethane can be used. Furthermore, aromatic hydrocarbons such as benzene and toluene; aprotic polar solvents such as N, N-dimethylformamide and dimethyl sulfoxide; and pyridine derivatives. Particularly preferably, pyridine is used. The amount of the solvent used can be appropriately determined according to the starting material, the type of base, reaction conditions and the like.

  In this method, the reaction temperature is not particularly limited, but is usually from 0 ° C. to the boiling point of the solvent. However, it is desirable to carry out the reaction at an optimum temperature according to the condensing agent to be used. In the method of the present invention, the reaction time is, for example, in the range of 1 to 48 hours.

  The purification of the product will be described. The reaction solution containing the product can be removed by distillation, which is a conventional method. After removing the contaminants by column chromatography using silica gel or alumina, the product can be purified by recrystallization or reprecipitation in a solvent in which the product is hardly soluble, extraction by separation, etc. .

(Amidation reaction using acid chloride)
As a production method of the present invention, a method for converting a carboxyl group into an acid chloride and reacting an amino group will be described in detail.

  Conversion to acid chloride is possible by using thionyl chloride, which is a conventional method. The amount of thionyl chloride used is in the range of 0.1 to 50.0 times mol, preferably 1.0 to 20.0 times mol, of the carboxylic acid compound. It is also possible to use thionyl chloride itself as a reaction solvent.

  The amino compound is charged in an amount of 0.1 to 50.0 times mol, preferably 1.0 to 20.0 times mol of the acid chloride. In the reaction of the present invention, a solvent can be used as necessary.

  Solvents used include hydrocarbons such as hexane, cyclohexane and heptane; ketones such as acetone and methyl ethyl ketone; ethers such as dimethyl ether, diethyl ether and tetrahydrofuran. In addition, halogenated hydrocarbons such as carbon tetrachloride, dichloromethane, chloroform, dichloroethane, and trichloroethane can be used. Furthermore, aromatic hydrocarbons such as benzene and toluene; aprotic polar solvents such as N, N-dimethylformamide and dimethyl sulfoxide; pyridine derivatives; and water. The solvent is preferably a solvent in which the acid chloride, amino compound, and product of the carboxylic acid compound that is the starting material are dissolved. The amount of the solvent used can be appropriately determined according to the starting materials, reaction conditions and the like.

  In this method, the reaction temperature is not particularly limited, but is usually from −30 ° C. to the boiling point of the solvent. However, it is desirable to carry out the reaction at an optimum temperature according to the acid chloride, amino compound, and reaction solvent of the carboxylic acid compound that is the starting material. In the process of the present invention, the reaction time ranges from 1 to 48 hours.

  The purification of the product will be described. The reaction liquid containing the product can be removed by distillation which is a conventional method. After removing the contaminants by column chromatography using silica gel or alumina, the product can be purified by recrystallization or reprecipitation in a solvent in which the product is hardly soluble, extraction by separation, etc. .

(Synthesis reaction of sulfonate ester)
In the synthesis of a compound having a sulfonic acid ester, a sulfonic acid, a sulfonate, or a sulfonic acid halide is used as a starting material. This is achieved by using trimethylsilyldiazomethane, trimethyl orthoformate, triethyl orthoformate, or the like as the esterifying agent.

  In this reaction, a solvent can be used if necessary. Examples of the solvent to be used include hydrocarbons such as hexane, cyclohexane, and heptane; alcohols such as methanol and ethanol; ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, and dioxane. Further, halogenated hydrocarbons such as carbon tetrachloride, dichloromethane, chloroform, dichloroethane, and trichloroethane; aromatic hydrocarbons such as benzene and toluene can be used. Furthermore, aprotic polar solvents such as N, N-dimethylformamide and dimethyl sulfoxide; pyridine derivatives are exemplified. Particularly preferably, chloroform and methanol are used. The amount of the solvent used can be appropriately determined according to the starting materials, reaction conditions and the like.

  The amount of the esterifying agent used is in the range of 0.1 to 50 times mol, preferably 1 to 20 times mol, of the sulfonic acid, sulfonate, or sulfonic acid halide.

  In this method, the reaction temperature is not particularly limited, but is usually a temperature in the range of −20 ° C. to 30 ° C. The reaction time is usually in the range of 1 to 48 hours.

  The purification of the product will be described. The reaction liquid containing the product can be removed by distillation which is a conventional method. After removing the contaminants by column chromatography using silica gel or alumina, the product can be purified by recrystallization or reprecipitation in a solvent in which the product is hardly soluble, extraction by separation, etc. .

(Application to toner)
Applications of the charge control agent according to the present invention include an electrostatic charge image developing toner and application to an image forming process using the same. Specifically, it can be used as a charge control agent that is internally or externally added to the toner. That is, the present invention is a charge control agent containing the above-mentioned compound, and further an electrostatic charge image developing toner containing the charge control agent.

  The toner for developing an electrostatic image is used in an image forming method or an image forming apparatus described below.

  Here, a technique relating to toner will be described.

  A number of methods are known as electrophotographic methods using toner. In general, electrophotography uses a photoconductive substance, and an electric latent image is formed on an image carrier (photoreceptor) by various means, and then the latent image is developed with toner. A step of making a visual image. After the visible image is transferred to a transfer material such as paper as necessary, the toner image is fixed on the transfer material by heat and / or pressure to obtain a copy.

  As a method for visualizing an electric latent image, a cascade development method, a magnetic brush development method, a pressure development method, and the like are known. Further, there is also used a method in which a magnetic toner and a rotating developing sleeve having a magnetic pole at the center are used, and the magnetic toner is ejected from the developing sleeve onto the photoreceptor by a magnetic field. Development methods used when developing an electrostatic latent image include a two-component development method using a two-component developer composed of a toner and a carrier, and a one-component developer composed only of a toner not using a carrier. There is a one-component development system to be used. Here, the colored fine particles generally referred to as toner are composed of a binder resin and a coloring material as essential components, and other components such as a charge control agent and magnetic powder as required. The compound according to the present invention can be used for such a toner.

  As a charge control agent used in the toner composition for developing an electrostatic image, for example, by using a compound represented by the chemical formula (2), the charging property is excellent and the dispersibility and spent property of the compound in the toner resin are improved. Good products can be provided. In addition, when the charge control agent according to the present invention is used, it is possible to provide a toner for developing an electrostatic image with reduced image fogging and excellent transferability even when output by an image forming apparatus. Become. Furthermore, since the charge control agent using the compound according to the present invention can be colorless or weak in coloration degree, it is not affected by the charge control agent and can be arbitrarily selected according to the hue required for the color toner. It is possible to select a colorant. A colorless or weakly colored charge control agent is preferable because it hardly inhibits the original hue of the dye or pigment.

  Since the toner containing the charge control agent of the present invention has a high specific charge amount and good stability over time, a stable and clear image can be formed in electrostatic recording image formation even if the toner is stored for a long time. give. Further, since colorless or colored is extremely thin and has a favorable negative charging performance, both black negatively charged toner and color toner can be produced.

  Here, the charge control agent will be described. As a method for imparting charge to the toner, the charging characteristics of the binder resin itself can be used without using a charge control agent. In that case, however, the charging stability with time and moisture resistance are poor, and good image quality can be obtained. May not be possible.

  Therefore, usually, a charge control agent is added for the purpose of charge retention and charge control of the toner. Known charge control agents known in the art today include, for example, azo dye metal complexes, aromatic dicarboxylic acid metal complexes, and salicylic acid derivative metal complexes as negative triboelectric charging properties. Also known as positive charge control agents are nigrosine dyes, triphenylmethane dyes, organotin compounds such as various quaternary ammonium salt dibutyltin oxides, and the like.

  When using the compound which concerns on this invention for a charge control agent, it can also be used with the said well-known charge control agent.

(Addition of the compound according to the present invention to the toner)
In the present invention, as a method of incorporating the charge control agent comprising the above-described compound into the toner, there are a method of internally adding to the toner and a method of externally adding to the toner. In the case of internal addition, the amount of the charge control agent is usually 0.1 to 50% by mass, preferably 0.2 to 20% by mass, based on the total mass of the toner binder and the charge control agent. If the amount is less than 0.1% by mass, the degree of improvement in the chargeability of the toner may not be noticeable. On the other hand, when it exceeds 50 mass%, it may be unpreferable from an economical viewpoint. In the case of external addition, the mass ratio of the toner binder and the charge control agent is preferably 0.01 to 5% by mass of the charge control agent with respect to the total mass of the toner binder and the charge control agent. It is preferable to fix it to the toner surface in a mechanochemical manner.

  The composition of the electrostatic image developing toner of the present invention is usually 0.1 to 50% by mass of the charge control agent, 20 to 95% by mass of the toner binder, and 0 to 15% by mass of the colorant based on the toner mass.

  If necessary, magnetic powder (ferromagnetic metal powder such as iron, cobalt, nickel or a compound such as magnetite, hematite, ferrite) may be contained in an amount of 60% by mass or less in order to function as a colorant. In addition, various additives (such as lubricants (polytetrafluoroethylene, low molecular weight polyolefins, fatty acids, or metal salts or amides thereof) and other charge control agents (metal-containing azo dyes, salicylic acid metal salts, etc.) are included. Can do. Also, hydrophobic colloidal silica fine powder or the like can be used to improve toner fluidity. The amount of these additives is usually 10% by mass or less based on the toner mass.

  In the toner of the present invention, in one toner particle, at least a part of the toner binder forms a continuous phase that does not contain a charge control agent, and at least a part of the charge control agent does not contain a toner binder. It is preferable to form a simple domain. Compared with the case where the charge control agent is completely compatible in the toner binder without forming discontinuous domains, the added charge control agent is more easily exposed on the toner surface, and the effect is exhibited with a small amount of addition. The dispersed particle size of the domain is preferably 0.01 to 4 μm, more preferably 0.05 to 2 μm. If it exceeds 4 μm, the dispersibility is insufficient, the charge amount distribution becomes wide, and the transparency of the toner may deteriorate. In addition, when the dispersed particle size is less than 0.01 μm, it is the same as in the case of complete compatibility in the toner binder without forming discontinuous domains, and does not include a toner binder that requires the addition of a large amount of charge control agent. . The fact that at least a part of the charge control agent forms a discontinuous domain and the dispersed particle size thereof can be confirmed by observing a section of the toner with a transmission electron microscope or the like. In order to clearly observe the interface, it is also effective to observe the electron microscope after dyeing the toner slice with ruthenium tetroxide, osmium tetroxide or the like.

<Other components>
Hereinafter, other constituent materials constituting the toner for developing an electrostatic charge image of the present invention will be described. The toner for developing an electrostatic charge image according to the present invention may include a binder resin, a colorant, and other additives added as necessary, in addition to the charge control agent.

(Binder resin)
First, as the binder resin, a thermoplastic resin generally used for toner can be used as the binder resin. For example, polystyrene, polyacrylate ester, styrene-acrylate ester copolymer, polyvinyl chloride, polyvinyl acetate, polyvinylidene chloride, phenol resin, epoxy resin, polyester resin, and the like can be given. Any binder resin can be used as long as it is usually used in the production of toner, and is not particularly limited.

  Further, the charge control agent of the present invention can be mixed with a binder resin in advance before producing the toner and used as a toner-forming composition having charge control ability. For example, examples of the binder resin include styrene-based polymers, polyester-based polymers, epoxy-based polymers, polyolefin-based polymers, and polyurethane-based polymers, which can be used alone or in combination.

  Styrene polymers include copolymers of styrene and (meth) acrylic acid esters and copolymers of other monomers copolymerizable with these, styrene and diene monomers (butadiene, isoprene, etc.) It is a copolymer. Moreover, the copolymer of the other monomer copolymerizable with these etc. are mentioned. Examples of polyester polymers include polycondensates of aromatic dicarboxylic acids and alkylene oxide adducts of aromatic diols. Examples of the epoxy polymer include a reaction product of an aromatic diol and epichlorohydrin and a modified product thereof. Examples of polyolefin-based polymers include polyethylene, polypropylene, and copolymer chains of these and other copolymerizable monomers. Examples of the polyurethane polymer include a polyaddition product of an aromatic diisocyanate and an alkylene oxide adduct of an aromatic diol.

  Specific examples of the binder resin used in combination with the charge control agent of the present invention include polymers of the following polymerizable monomers, a mixture thereof, or a copolymerized product. Specific examples of such a polymer include styrene polymers such as styrene-acrylic acid copolymers and styrene-methacrylic acid copolymers. Furthermore, polyester polymers, epoxy polymers, polyolefin polymers, polyurethane polymers and the like can be mentioned and can be preferably used.

(Crosslinking agent)
When forming the binder resin used in combination with the charge control agent of the present invention, a crosslinking agent can also be used. For example, divinylbenzene is mentioned as a bifunctional crosslinking agent.

(Polymerization initiator)
When forming a binder resin to be used in combination with the charge control agent of the present invention, a polymerization initiator such as 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) is used as necessary. Can be used. The amount used is 0.05 parts by mass or more (preferably 0.1 to 15 parts by mass) with respect to 100 parts by mass of the monomer.

<Charge control agent: other than the compound of the present invention>
In addition to the charge control agent of the present invention, a conventionally used charge control agent can be used together with the charge control agent of the present invention. Specific examples include nigrosine dyes, quaternary ammonium salts, monoazo metal complex salt dyes, and the like.

  The addition amount of the charge control agent can be determined in consideration of conditions such as the chargeability of the binder resin, the production method including the addition amount / dispersing method of the colorant, and the chargeability of other additives. For example, it can be used at a ratio of 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the binder resin. In addition, inorganic particles such as metal oxides or inorganic materials surface-treated with the organic materials may be used. These charge control agents may be mixed and added to the binder resin, or may be used in a form adhered to the toner particle surface.

<Colorant>
As the colorant constituting the toner for developing an electrostatic charge image of the present invention, any colorant can be used as long as it is usually used in the production of toner, and is not particularly limited. For example, any other pigment and / or dye such as carbon black, titanium white, monoazo red pigment, disazo yellow pigment, quinacridone magenta pigment, anthraquinone dye, and the like can be used.

  When the electrostatic image developing toner of the present invention is used as a two-component full color toner, the following can be used as a colorant. For example, carbon black, C.I. pigment blue 15, Hansa yellow G, C.I. pigment red 114, etc. can be used.

  In the present invention, the above-mentioned pigments may be used alone, but it is more preferable from the viewpoint of the image quality of a full-color image to improve the sharpness by using a dye and a pigment together. The dyes and pigments may be used alone or else may be used in any mixture in order to obtain a desired toner color tone.

  The content of the colorant in the toner as described above can be widely changed according to a desired coloring effect.

  Usually, in order to obtain the best toner characteristics, that is, when considering the coloring power of printing, toner shape stability, toner scattering, etc., these colorants are usually used in the following proportions. That is, it is used at a ratio of 0.1 to 60 parts by mass, preferably about 0.5 to 20 parts by mass with respect to 100 parts by mass of the binder resin.

<Other components of toner>
In the toner for developing an electrostatic image of the present invention, in addition to the binder resin and the colorant component described above, the following compounds may be contained as long as the effects of the present invention are not adversely affected. For example, waxes such as silicone resin, polyester, polyurethane, and polyamide.

  Specific examples of the waxes preferably used include low molecular weight polypropylene and its by-products, low molecular weight polyesters and ester waxes, and aliphatic derivatives. Of these waxes, waxes obtained by fractionating waxes by molecular weight by various methods are also preferably used in the present invention. Further, oxidation, block copolymerization, and graft modification may be performed after fractionation.

  The toner for developing an electrostatic charge image of the present invention contains the wax component, and when the tomographic observation of the toner is performed using a transmission electron microscope (TEM), the wax component is substantially contained in the binder resin. It is preferable to disperse into spherical and / or spindle-shaped islands.

<Toner production method>
As a specific method for producing the electrostatic image developing toner of the present invention having the above-described configuration, any conventionally known method can be used. The electrostatic image developing toner of the present invention can be produced by, for example, a so-called pulverization method in which a toner is obtained by the following steps. Specifically, the resins such as a binder resin, the charge control agent according to the present invention, other charge control agents added as necessary, and wax are sufficiently mixed with a mixer such as a Henschel mixer or a ball mill. .

  While the obtained mixture was melt-kneaded using a heat kneader such as a heating roll, kneader, extruder, etc., and the resins were mutually compatible, a pigment, dye, or magnetic substance as a colorant, if necessary Additives such as metal compounds added accordingly are dispersed or dissolved.

  After cooling and solidification, the solidified product is pulverized by a pulverizer such as a jet mill and a ball mill, and then classified to obtain the electrostatic image developing toner of the present invention having a desired particle size. In the classification step, it is preferable to use a multi-division classifier in terms of production efficiency.

  Further, a binder resin, a charge control agent, and the like are mixed in a solution using a solvent, stirred, and then re-precipitated in water. After filtration and drying, the solidified product is pulverized by a pulverizer such as a jet mill or a ball mill. Thereafter, classification can be performed to obtain the electrostatic image developing toner of the present invention having a desired particle size. In the classification step, it is preferable to use a multi-division classifier in terms of production efficiency. Here, the solvent includes aromatic hydrocarbons such as toluene and xylene, halides such as chloroform and ethylene dichloride, ketones such as acetone and methyl ethyl ketone, and amides such as dimethylformamide.

  The electrostatic image developing toner of the present invention can also be produced by the so-called polymerization method as described below. That is, in this case, a polymerizable monomer of the binder resin, a charge control agent, a pigment, a dye, or a magnetic material as a colorant, and if necessary, a crosslinking agent, a polymerization initiator, a wax, and other binders Materials such as resin and other additives are mixed and dispersed. Using the obtained mixture, polymerizable colored resin particles are synthesized by suspension polymerization in an aqueous dispersion medium in the presence of a surfactant or the like. The obtained particles are subjected to solid-liquid separation, then dried, and classified as necessary to obtain the electrostatic image developing toner of the present invention. Further, coloring fine particles not containing a charge control agent are prepared by the above method, and then the charge control agent is added to the particle surface by a mechanochemical method or the like alone or together with an external additive such as colloidal silica. You can also.

(Silica external additive)
In the present invention, it is preferable to externally add fine silica powder to the toner produced by the above method in order to improve charging stability, developability, fluidity and durability. As the silica fine powder used at this time, a fine powder having a specific surface area of 20 m ² / g or more (particularly 30 to 400 m ² / g) by nitrogen adsorption measured by the BET method gives good results. The amount of silica fine powder in this case is preferably about 0.01 to 8 parts by mass, preferably about 0.1 to 5 parts by mass with respect to 100 parts by mass of toner particles.

  As silica fine powder, what was processed with the following processing agents as needed can be used. Treatment agents are silicone varnishes, various modified silicone varnishes, silicone oils, various modified silicone oils, silane coupling agents, silane coupling agents having functional groups, and other organosilicon compounds for the purpose of hydrophobicity and chargeability control. It is such a material. These treatment agents may be used as a mixture.

(Inorganic powder)
In order to improve the developability and durability of the toner, it is also preferable to add the following inorganic powder.

For example,
Oxides of metals such as magnesium, zinc, aluminum, cerium, cobalt, iron, zirconium, chromium, manganese, strontium, tin, antimony;
Complex metal oxides such as calcium titanate, magnesium titanate, strontium titanate; metal salts such as calcium carbonate, magnesium carbonate, aluminum carbonate;
Clay minerals such as kaolin;
Phosphate compounds such as apatite;
Silicon compounds such as silicon carbide and silicon nitride;
Examples thereof include carbon powder such as carbon black and graphite. Among these, it is preferable to use fine powders of zinc oxide, aluminum oxide, cobalt oxide, manganese dioxide, strontium titanate, and magnesium titanate.

(Lubricant)
Further, a lubricant powder as described below may be added to the toner. Examples thereof include fluorine resins such as Teflon and polyvinylidene fluoride; fluorine compounds such as carbon fluoride; fatty acid metal salts such as zinc stearate; fatty acid derivatives such as fatty acids and fatty acid esters; molybdenum sulfide and the like.

<About Career>
The electrostatic image developing toner of the present invention can be applied to various conventionally known toners. For example, the electrostatic image developing toner can be used alone as a non-magnetic one-component developer. The electrostatic image developing toner of the present invention can be used as a non-magnetic toner that forms a magnetic two-component developer together with a magnetic carrier, a magnetic toner that is used alone as a magnetic one-component toner, or the like. Here, as the carrier for use in the two-component development method, any conventionally known carrier can be used. Specifically, particles having an average particle size of 20 to 300 μm formed of surface oxidized or unoxidized metal such as iron, nickel, cobalt, manganese, chromium, rare earth and their alloys or oxides are used as carrier particles. it can. In addition, the carrier used in the present invention is such that the surface of the carrier particles described above is attached or coated with a substance such as a styrene resin, an acrylic resin, a silicone resin, a fluorine resin, or a polyester resin. preferable.

<Magnetic toner>
The toner for developing an electrostatic charge image of the present invention may be a magnetic toner containing a magnetic material in toner particles. In this case, the magnetic material can also serve as a colorant.

As a magnetic material used at this time,
Iron oxides such as magnetite, hematite and ferrite; or metals such as iron, cobalt and nickel; or these metals and aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, Examples include alloys with metals such as manganese, selenium, titanium, tungsten, vanadium and mixtures thereof. These magnetic materials that can be used in the present invention preferably have an average particle diameter of 2 μm or less, preferably about 0.1 to 0.5 μm. The amount contained in the toner is preferably 20 to 200 parts by mass, particularly preferably 40 to 150 parts by mass with respect to 100 parts by mass of the binder resin.

  Furthermore, in order to achieve high image quality, it is necessary to be able to faithfully develop finer latent image dots. For this purpose, for example, the weight of toner particles for electrostatic image development according to the present invention is required. It is preferable to adjust so that the average diameter is in the range of 4 μm to 9 μm. That is, toner particles having a weight average diameter of less than 4 μm are not preferable because the transfer efficiency is lowered, and a large amount of residual toner tends to remain on the photoconductor, which easily causes uneven image unevenness due to fog and transfer failure. . Further, when the weight average diameter of the toner particles exceeds 9 μm, characters and line images are likely to be scattered.

  In the present invention, for the average particle size and particle size distribution of the toner, a device such as Coulter Counter TA-II type or Coulter Multisizer (trade name, manufactured by Beckman Coulter, Inc.) is used.

  Then, an interface (manufactured by Nikka Ki Bios) that outputs the number distribution and volume distribution and a personal computer were connected to the apparatus for measurement. As the electrolytic solution used at that time, a 1% NaCl aqueous solution is prepared using primary sodium chloride. As the electrolytic solution, for example, commercially available ISOTON R-II (trade name, manufactured by Coulter Scientific Japan Co., Ltd.) can also be used. As a specific measurement method, 0.1 to 5 ml of a surfactant (preferably using an alkylbenzene sulfonate) is added as a dispersing agent to 100 to 150 ml of the above electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. To make a measurement sample. At the time of measurement, the electrolytic solution in which the measurement sample is suspended is subjected to a dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser.

  Thereafter, the volume and the number of toners of 2 μm or more are measured using the Coulter counter TA-II type, using a 100 μm aperture as an aperture. Then, the volume distribution and the number distribution were calculated. Then, the volume-based weight average particle diameter (D4) obtained from the volume distribution according to the present invention and the number-based length average particle diameter (D1) obtained from the number distribution were obtained.

<Charge amount>
The toner for developing an electrostatic image of the present invention has a charge amount per unit mass (two-component method) of −10 to −80 μC / g, more preferably −15 to −70 μC / g. This is preferable in improving transfer efficiency in a transfer method using an applied transfer member.

  The method for measuring the charge amount by the two-component method used in the present invention is shown below. For the measurement, the charge amount measuring apparatus shown in FIG. 5 was used. First, a mixture is prepared by adding 0.5 g of toner to be measured to 9.5 g of EFV 200/300 (manufactured by Powdertech) as a carrier. Place this mixture in a polyethylene bottle with a volume of 50 to 100 ml, place it on a shaker with constant amplitude, set the shaking conditions to 100 mm amplitude, and 100 rounds per minute for a shaking speed. Shake time. Next, 1.0 to 1.2 g of the mixture is put in a metal measuring container 42 having a 500 mesh screen 43 in the bottom of the charge amount measuring device 41 shown in FIG. The total mass of the measurement container 42 at this time is weighed and is defined as W1 (g). Next, suction is performed from the suction port 47 with a suction machine (not shown) (at least the part in contact with the measurement container 42), and the air volume control valve 46 is adjusted so that the pressure of the vacuum gauge 45 becomes 2450 Pa (250 mmAq). To do. In this state, suction is performed for 1 minute to remove the toner by suction. The potential of the electrometer 49 at this time is set to V (volt). Here, 48 is a capacitor, and the capacity is C (μF). Moreover, the mass of the whole measuring machine after suction is weighed and is defined as W2 (g). The triboelectric charge amount (μC / g) of the toner is calculated from these measured values according to the following equation.

Calculation formula: triboelectric charge amount (μC / g) = C × V / (W1-W2)
These operations are performed under a certain environment (for example, under a certain temperature and humidity condition).

<Method for measuring molecular weight and molecular weight distribution of binder resin>
In addition, the binder resin used for the constituent material of the toner for developing an electrostatic charge image of the present invention has a peak in the low molecular weight region in the range of 3,000 to 15,000 in the molecular weight distribution by GPC, particularly when produced by a pulverization method. It is preferable to have it. That is, if the GPC peak in the low molecular weight region exceeds 15,000, it may be difficult to obtain a product with sufficient improvement in transfer efficiency. In addition, it is not preferable to use a binder resin having a GPC peak of less than 3000 in the low molecular weight region because fusion tends to occur during the surface treatment.

  In the present invention, the molecular weight of the binder resin was measured by GPC (gel permeation chromatography). As a specific GPC measurement method, a sample obtained by previously extracting toner with a THF (tetrahydrofuran) solvent using a Soxhlet extractor for 20 hours is used for measurement. The column configuration was A-801, 802, 803, 804, 805, 806, 807 (trade name) manufactured by Showa Denko, and the molecular weight distribution was measured using a standard polystyrene resin calibration curve. In the present invention, a binder resin having a ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured as described above in the range of 2 to 100 is used. It is preferable.

<Glass transition point of toner>
Furthermore, the toner of the present invention has a glass transition point Tg of 40 ° C. to 75 ° C., more preferably 52 ° C. to 70 ° C., from the viewpoint of fixability and storage stability by using an appropriate material. It is preferable to be prepared. In this case, the glass transition point Tg can be measured by using a differential scanning calorimeter of high accuracy internal heat input compensation type such as DSC-7 (trade name) manufactured by PerkinElmer. Good. The measurement is performed according to ASTM D 3418-82. In the present invention, when measuring the glass transition point Tg, the measurement sample is heated once and the entire history is taken, then rapidly cooled, and again at a temperature rate of 10 ° C / min and a temperature range of 0 to 200 ° C. A DSC curve measured when the temperature is raised may be used.

  The present inventors have found that the above-described charge control agent has extremely excellent characteristics. This will be shown in the examples described later.

First, Examples A-1 to O-1, A-2 to L-2, B-3, B-4, and H-3 will explain the compound obtained by the present invention and the production method thereof. Thereafter, Examples 1 to 40 show the usefulness of the charge control agent according to the present invention while using Comparative Examples.
Examples A-1 to L-1 in which R ₃₂ in the chemical formula (2) is OH, and Examples B-3, B-4, and H-3 in which R ₃₂ is ONa or OK are reference examples. It is.
Furthermore, Examples 1, 4, 5, 7, 8, 11, 13, 17, using the compounds shown in these examples (A-1 to L-1, B-3, B-4, H-3) 19-21, 23, 26, 28, 30, 31, 33, 35-37, 39 and 40 are reference examples.

  The charge control agent according to the present invention and the electrostatic image developing toner using the same are not limited to the following examples.

In the following experiment, the structure of the obtained compound was determined by analysis using a nuclear magnetic resonance ( ¹ H-NMR) spectrum and a Fourier transform-infrared absorption (FT-IR) spectrum. The equipment used is as follows. ¹ H-NMR (FT-NMR: Bruker DPX400 (trade name); resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: heavy DMSO or heavy chloroform; measurement temperature: room temperature)
FT-IR (Nicolet AVATAR360FT-IR (trade name))
(Example A-1)
Under a nitrogen atmosphere, 1.0 g (8.2 mmol) of benzoic acid and 2.1 g (12.3 mmol) of 2-aminobenzenesulfonic acid were placed in a 100 ml three-necked flask, and 30 ml of pyridine was added and stirred. Thereafter, 3.2 ml (12.3 mmol) of triphenyl phosphite was added and heated at 115 ° C. for 6 hours. After completion of the reaction, the solvent was distilled off, and 30 ml of chloroform was added to dissolve the product. Separating and washing was performed 5 times with 30 ml of 4N hydrochloric acid, and then chloroform was distilled off. The obtained product was dissolved in 5 ml of chloroform and purified by column chromatography packed with silica gel. The collected product was dried under reduced pressure to obtain 1.0 g (3.6 mmol, yield 44%) of the product. ^From the result of ¹ H-NMR, a signal derived from the amide group was newly observed, and the signal derived from the benzene ring proton of benzoic acid was shifted, so that the obtained product was represented by the following formula (A-1 ) Was confirmed.

  Further, by scaling up this system, 50 g of a compound represented by the following formula (A-1) was obtained. This compound was designated as the exemplified compound A-1 in Examples 1 to 40.

(Examples B-1 to O-1)
The experiment was performed in the same manner as in Example A-1 using a carboxylic acid compound, an amino compound, triphenyl phosphite, and 30 ml of pyridine. Reagent charge ratio (unit: g or ml, mmol) The structures of the obtained compounds are summarized in Tables A-1 to A-3.

  The amino compound used for the synthesis of N-1 was synthesized using the method described in Journal of Organic Chemistry, 1985, 50, 3336-3341 and subjected to experiments. The amino compound used for the synthesis of O-1 was subjected to an experiment using ethanol instead of 2-pentanol according to the method described in Journal of the American Chemical Society, 1962, 84, 3289-3295.

The product was confirmed by confirming the signal derived from the amide group by ¹ H-NMR measurement. FIG. 1 shows the result of ¹ H-NMR measurement of B-1 and FIG. 2 of E-1.

  Moreover, 50 g of each target compound was obtained by scaling up this system. These compounds were designated as Exemplified Compounds B-1 to O-1 in Examples 1 to 40. Hereinafter, compound 1 will be described using a table. The indications A-1, B-1... O-1 described at the lower right of the chemical structural formula in the table are respectively implemented. It shows that it is a compound obtained by Example A-1, B-1 ... O-1.

(Example A-2)
0.30 g (1.1 mmol) of the product (Exemplary Compound A-1) obtained in Example A-1 was added to a 50 ml eggplant flask, dissolved by adding 15 ml of chloroform and 5 ml of methanol, and cooled to 0 ° C. To this was added 5.4 ml (10.8 mmol) of a 2 mol / L trimethylsilyldiazomethane-hexane solution (Aldrich) and stirred for 3 hours. After completion of the reaction, the solvent was distilled off by an evaporator, and then the product was recovered. Further, 15 ml of chloroform and 5 ml of methanol were added to redissolve the product, and the solvent was distilled off by an evaporator. This operation was repeated three times. The product collected here was dried under reduced pressure to obtain 0.30 g (1.0 mmol, yield 95%) of the product. ^{From the 1} H-NMR measurement, a peak derived from methyl sulfonate was observed at 3-4 ppm. Thus, the obtained product was confirmed to be a compound represented by the following formula (A-2).

  Further, by scaling up this system, 50 g of a compound represented by the following formula (A-2) was obtained. This compound was designated as the exemplified compound A-2 in Examples 1 to 40.

(Examples B-2 to L-2)
The products obtained in Examples B-1 to L-1 (Exemplary compounds B-1 to L-1) and a trimethylsilyldiazomethane-hexane solution (in Tables B-1 and B-2) instead of Exemplified Compound A-1 , Abbreviated as TMS diazomethane), and an experiment was conducted in the same manner as in Example A-2. The reagent charge ratio (unit: g or ml, mmol) and the structure of the resulting compound are summarized in Tables B-1 and B-2. The product can be confirmed by confirming a peak derived from methyl sulfonate by ¹ H-NMR measurement. As an example, FIG. 3 shows the results of ¹ H-NMR measurement of B-2 and FIG. 4 of E-2.

  Moreover, 50 g of each target compound was obtained by scaling up this system. These compounds were designated as Exemplified Compounds B-2 to L-2 in Examples 1 to 40.

(Example B-3)
An aqueous solution in which 50 mg (1.25 mmol) of sodium hydroxide was dissolved in 10 ml of water was prepared, and 0.4 g (1.25 mmol) of the product (Exemplary Compound B-1) obtained in Example B-1 was added at room temperature for 30 minutes. Stir. After the reaction, water was distilled off with an evaporator and then dried under reduced pressure to obtain 0.35 g (1.03 mmol, yield 82%) of the product. Since the peak around 3200 cm ⁻¹ derived from the sulfonic acid OH bond disappeared from FT-IR, it was confirmed that the obtained product was a compound represented by the following formula (B-3).

  Further, this system was scaled up to obtain 50 g of a compound represented by the following formula (B-3). This compound was designated as the exemplified compound B-3 in Examples 1 to 40.

(Example B-4)
An aqueous solution in which 70 mg (1.25 mmol) of potassium hydroxide was dissolved in 10 ml of water was prepared, and 0.4 g (1.25 mmol) of the product (Exemplary Compound B-1) obtained in Example B-1 was added at room temperature for 30 minutes. Stir. After the reaction, water was distilled off with an evaporator and then dried under reduced pressure to obtain 0.40 g (1.12 mmol, yield 89%) of the product. From the FT-IR spectrum, the peak around 3200 cm ⁻¹ derived from the sulfonic acid OH bond disappeared, and thus the obtained product was confirmed to be a compound represented by the following formula (B-4).

  Further, this system was scaled up to obtain 50 g of a compound represented by the following formula (B-4). This compound was designated as the exemplified compound B-4 in Examples 1 to 40.

(Example H-3)
An aqueous solution in which 52 mg (1.31 mmol) of sodium hydroxide was dissolved in 10 ml of water was prepared, and 0.3 g (1.31 mmol) of the product (Exemplary Compound H-1) obtained in Example H-1 was added at room temperature for 30 minutes. Stir. After the reaction, water was distilled off with an evaporator and then dried under reduced pressure to obtain 0.30 g (1.31 mmol, yield 91%) of the product. Since the peak around 3200 cm ⁻¹ derived from the sulfonic acid OH bond disappeared from FT-IR, it was confirmed that the obtained product was a compound represented by the following formula (H-3).

  Further, this system was scaled up to obtain 50 g of a compound represented by the following formula (H-3). This compound was designated as the exemplified compound H-3 in Examples 1 to 40.

  Next, various toners were produced and evaluated using the charge control agent of the present invention comprising the above exemplary compounds.

(Example 1)
First, an aqueous Na ₃ PO ₄ solution was added to a 2 liter four-necked flask equipped with a high-speed stirring device TK-homomixer, and the rotational speed was 10,000 rpm and the temperature was 60 ° C. An aqueous CaCl ₂ solution was gradually added thereto to prepare an aqueous dispersion medium containing a minute hardly water-soluble dispersant Ca ₃ (PO ₄ ) ₂ . On the other hand, after the following composition was dispersed for 3 hours by a ball mill, 10 parts by weight of a release agent (carnauba wax) and 10 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator Was added to prepare a polymerizable monomer composition.
-Styrene monomer: 82 parts by mass-Ethylhexyl acrylate monomer: 18 parts by mass-Divinylbenzene monomer: 0.1 part by mass-Cyan colorant (C.I. Pigment Blue 15): 6 parts by mass-Polyethylene oxide resin (Molecular weight 3200, acid value 8): 5 parts by mass / Exemplary compound A-1: 2 parts by mass Next, the polymerizable monomer composition obtained above was charged into the aqueous dispersion medium prepared above. The granulation was carried out while maintaining the rotational speed of 10,000 rpm. Thereafter, while stirring with a paddle stirring blade, the mixture was reacted at 65 ° C. for 3 hours and then polymerized at 80 ° C. for 6 hours to complete the polymerization reaction. After completion of the reaction, the suspension was cooled and acid was added to dissolve the poorly water-soluble dispersant Ca ₃ (PO ₄ ) ₂ , followed by filtration, washing with water and drying to obtain blue polymer particles (1). The particle size of the resulting blue polymer particles (1) measured using a Coulter Counter Multisizer (manufactured by Coulter Co., Ltd.) is a weight average particle size of 7.5 μm, and the amount of fine powder (abundance of particles of 3.17 μm or less in the number distribution) Was 5.5% by number.

To 100 parts by weight of the blue polymer particles (1) prepared above, 1.3 parts by weight of hydrophobic silica fine powder (BET: 270 m ^{2 /} g) treated with hexamethyldisilazane as a flow improver is dry-mixed with a Henschel mixer. Thus, the blue toner (1) of this example was obtained. Further, 7 parts by weight of the blue toner (1) and 93 parts by weight of a resin-coated magnetic ferrite carrier (average particle size: 45 μm) were mixed to prepare a two-component blue developer (1) for magnetic brush development. .

(Examples 2 to 5)
From the blue toners (2) of Examples 2 to 5 in the same manner as in Example 1 except that Exemplified Compound A-1 was changed to Exemplified Compounds D-2, N-1, F-1, and H-3, respectively ( 5) was obtained. The characteristics of this toner were measured in the same manner as in Example 1. The results are shown in Table 1. Using this, in the same manner as in Example 1, the two-component blue developers (2) to (5) of Examples 2 to 5 were obtained.

(Comparative Example 1)
A blue toner (6) of Comparative Example 1 was obtained in the same manner as in Example 1 except that Example Compound A-1 was not used. The characteristics of this toner were measured in the same manner as in Example 1. The results are shown in Table 1. In addition, using this, the two-component blue developer (6) of Comparative Example 1 was obtained in the same manner as Example 1.

(Examples 6 to 10)
Instead of the exemplified compound A-1, 2.0 parts by mass of each of the exemplified compounds M-1, D-1, I-1, B-2, and H-2 were used, and a yellow colorant (hansa yellow G) was used instead of the cyan colorant. The same operation as in Example 1 was performed except that Then, yellow (yellow) toners (1) to (5) of Examples 6 to 10 were obtained. The characteristics of these toners were measured in the same manner as in Example 1, and the results are shown in Table 1. Using this, in the same manner as in Example 1, two-component yellow (yellow) developers (1) to (5) were obtained.

(Comparative Example 2)
The yellow (yellow) toner (6) of Comparative Example 2 was prepared in the same manner as in Example 1 except that Example Compound A-1 was not used and a yellow colorant (Hansa Yellow G) was used instead of the cyan colorant. ) The characteristics of this toner were measured in the same manner as in Example 1. The results are shown in Table 1. Further, using this, the two-component yellow (yellow) developer (6) of Comparative Example 2 was obtained in the same manner as in Example 1.

(Examples 11 to 15)
Instead of Exemplified Compound A-1, Exemplified Compounds H-1, K-2, B-1, O-1, G-2 are used in an amount of 2.0 parts by mass, respectively, and carbon black (DBP oil absorption 110 mL) is used instead of the cyan colorant. The same operation as in Example 1 was carried out except that / 100 g) was used. Then, black toners (1) to (5) of Examples 11 to 15 were obtained. The characteristics of these toners were measured in the same manner as in Example 1, and the results are shown in Table 1. In addition, using this, in the same manner as in Example 1, two-component black developers (1) to (5) were obtained.

(Comparative Example 3)
The black toner (6) of Comparative Example 3 was prepared in the same manner as in Example 1 except that Example Compound A-1 was not used and carbon black (DBP oil absorption 110 mL / 100 g) was used instead of the cyan colorant. Got. The characteristics of this toner were measured in the same manner as in Example 1. The results are shown in Table 1. In addition, using this, the two-component black developer (6) of Comparative Example 3 was obtained in the same manner as in Example 1.

(Example 16)
Styrene-butyl acrylate copolymer resin (glass transition temperature 70 ° C): 100 parts by mass Wax (low molecular polyethylene, melting point 94 ° C): 7 parts by mass Magenta pigment (C.I. Pigment Red 114): 5 parts by mass Exemplified compound J-2: 2 parts by mass The above composition was mixed and melt kneaded with a biaxial extruder (L / D = 30). The kneaded product was cooled, coarsely pulverized with a hammer mill, finely pulverized with a jet mill, and then classified to obtain magenta colored particles (1) by a pulverization method. The magenta colored particles (1) had a weight average particle size of 7.3 μm and a fine powder amount of 5.0 number%.

To 100 parts by mass of the magenta colored particles (1), 1.5 parts by mass of a hydrophobic silica fine powder (BET: 250 m ^{2 /} g) treated with hexamethyldisilazane as a flow improver is dry-mixed with a Henschel mixer. A magenta (red) toner (1) of this example was obtained. Further, 7 parts by mass of the obtained magenta (red) toner (1) and 93 parts by mass of a resin-coated magnetic ferrite carrier (average particle size: 45 μm) are mixed to form a two-component magenta (red) for magnetic brush development. Developer (1) was prepared.

(Example 17-20)
The magenta (red) toners (2) of Examples 17 to 20 were prepared in the same manner as in Example 16 except that Exemplified Compound J-2 was changed to Exemplified Compounds E-1, A-2, L-1, and B-3, respectively. ) To obtain (5). The characteristics of this toner were measured in the same manner as in Example 1. The results are shown in Table 1. Using this, in the same manner as in Example 16, the two-component magenta (red) developers (2) to (5) of Examples 17 to 20 were obtained.

(Comparative Example 4)
A magenta (red) toner (6) of Comparative Example 4 was obtained in the same manner as in Example 16 except that Example Compound J-2 was not used. The characteristics of this toner were measured in the same manner as in Example 1. The results are shown in Table 1. In addition, using this, the two-component magenta (red) developer (6) of Comparative Example 4 was obtained in the same manner as in Example 16.

(Example 21-25)
Instead of Exemplified Compound J-2, 2.0 parts by mass of Exemplified Compounds C-1, I-2, J-1, L-2, and E-2 were used, respectively, and carbon black (DBP oil absorption 110 mL / The same operation as in Example 16 was performed except that 100 g) was used. Then, black toners (7) to (11) of Examples 21 to 25 were obtained. The characteristics of these toners were measured in the same manner as in Example 1, and the results are shown in Table 1. Using this, in the same manner as in Example 16, two-component black developers (7) to (11) were obtained.

(Comparative Example 5)
The black toner (12) of Comparative Example 5 was prepared in the same manner as in Example 16, except that Example Compound J-2 was not used and carbon black (DBP oil absorption 110 mL / 100 g) was used instead of the magenta pigment. Obtained. The characteristics of this toner were measured in the same manner as in Example 1. The results are shown in Table 1. Further, using this, the two-component black developer (12) of Comparative Example 5 was obtained in the same manner as in Example 16.

(Example 26)
Polyester resin: 100 parts by massCarbon black (DBP oil absorption 110 mL / 100 g): 5 parts by massExemplary compound G-1: 2 parts by mass The polyester resin was synthesized as follows. Bisphenol A propylene oxide 2-mole adduct 751 parts, terephthalic acid 104 parts and trimellitic anhydride 167 parts were polycondensed using 2 parts of dibutyltin oxide as a catalyst to obtain a polyester resin having a softening point of 125 ° C.

  The above compositions were mixed and melt kneaded with a biaxial extruder (L / D = 30). The kneaded product was cooled, coarsely pulverized with a hammer mill, finely pulverized with a jet mill, and classified to obtain black colored particles (13) by a pulverization method. The black colored particles (13) had a weight average particle size of 7.7 μm and a fine powder amount of 5.2% by number.

To 100 parts by mass of these black colored particles (13), 1.5 parts by mass of a hydrophobic silica fine powder (BET: 250 m ^{2 /} g) treated with hexamethyldisilazane as a flow improver was dry-mixed with a Henschel mixer. A black toner (13) of this example was obtained. Further, 7 parts by mass of the obtained black toner (13) and 93 parts by mass of a resin-coated magnetic ferrite carrier (average particle size: 45 μm) were mixed to prepare a two-component black developer (13) for magnetic brush development. Prepared.

(Examples 27 to 30)
From black toners (14) of Examples 27 to 30 in the same manner as in Example 26 except that Exemplified Compound G-1 was changed to Exemplified Compounds C-2, K-1, F-2, and B-4, respectively ( 17) was obtained. The characteristics of this toner were measured in the same manner as in Example 1. The results are shown in Table 1. Using this, in the same manner as in Example 26, the two-component black developers (14) to (17) of Examples 27 to 30 were obtained.

(Comparative Example 6)
A black toner (18) of Comparative Example 6 was obtained in the same manner as in Example 26 except that Example Compound G-1 was not used. The characteristics of this toner were measured in the same manner as in Example 1. The results are shown in Table 1. In addition, using this, the two-component black developer (18) of Comparative Example 6 was obtained in the same manner as in Example 26.

<Evaluation>
The two-component developers obtained in Examples 1 to 30 and the two-component developers obtained in Comparative Examples 1 to 6 were evaluated. Specifically, the charge amount measuring device shown in FIG. 5 was used for the evaluation.

  First, EFV 200/300 (manufactured by Powdertech) was used as a carrier in a fixed environment, and a mixture obtained by adding 0.5 g of the toner to be measured to 9.5 g of the carrier was a polyethylene bottle having a capacity of 50 to 100 ml. Put in. It is installed in a shaker with a constant amplitude, and the shaking condition is set to 100 mm amplitude and a shake speed of 100 reciprocations for 1 minute, and shaken for a fixed time. Next, 1.0 to 1.2 g of the mixture is put in a metal measuring container 42 having a 500 mesh screen 43 in the bottom of the charge amount measuring device 41 shown in FIG. The total mass of the measurement container 42 at this time is weighed and is defined as W1 (g). Next, suction is performed from the suction port 47 with a suction machine (not shown) (at least the part in contact with the measurement container 42), and the air volume control valve 46 is adjusted so that the pressure of the vacuum gauge 45 becomes 2450 Pa (250 mmAq). To do. In this state, suction is performed for 1 minute to remove the toner by suction. The potential of the electrometer 49 at this time is set to V (volt). Here, 48 is a capacitor, and the capacity is C (μF). Moreover, the mass of the whole measuring machine after suction is weighed and is defined as W2 (g). The triboelectric charge amount (μC / g) of the toner is calculated from these measured values according to the following equation.

Calculation formula: triboelectric charge amount (μC / g) = C × V / (W1-W2)
10 seconds and 300 seconds using the above-mentioned method for measuring the amount of charge in each environment of normal temperature and humidity (25 ° C., 60% RH) and high temperature and high humidity (30 ° C., 80% RH). The charge amount of the toner after stirring was measured. And the second decimal place was rounded off from the measured value of the two-component blow-off charge amount, and the following criteria were used for evaluation. The results are summarized in Table 1.

[Charging]
A: Very good (-20μC / g or less)
○: Good (-19.9 to -10.0μC / g)
△: Practical (-9.9 to -5.0μC / g)
×: Not practical (-4.9μC / g or more)

Examples 31 to 36 and Comparative Examples 7 to 12
In Examples 31 to 36 and Comparative Examples 7 to 12, LBP5500 (manufactured by Canon Inc.) was modified and used for evaluation.

  At that time, toner images were formed with cyan toner, yellow toner, magenta toner or black toner obtained in Examples 1, 6, 11, 16, 21, 26 and Comparative Examples 1 to 6 as developers.

<Evaluation>
Under the above conditions, set the LBP5500 to a printout speed of 8 sheets (A4 size) / min under normal temperature and humidity (25 ° C, 60% RH) and high temperature and high humidity (30 ° C, 80% RH) environment. Remodeled and printed.

  The toners of Examples 1, 6, 11, 16, 21, and 26 and the toners of Comparative Examples 1 to 6 were respectively used, and a printout test was performed in a monochromatic intermittent mode while being sequentially replenished. The obtained printout images were evaluated for the following items.

  The intermittent mode is a mode in which the developing device is paused for 10 seconds every time one sheet is printed out, and toner deterioration is promoted by a preliminary operation at the time of restart.

  The evaluation results are summarized in Table 2.

[Printout image evaluation]
1. Image density A predetermined number of printouts were made on ordinary copying machine plain paper (75 g / m ² ), and the evaluation was based on the degree of image density maintenance at the end of printing of the initial image. For the image density, a Macbeth reflection densitometer (manufactured by Macbeth) was used, and the relative density with respect to the printout image of the white background portion where the original density was 0.00 was measured and used for evaluation.

◎: Excellent (Image density at the end is 1.40 or more)
○: Good (image density at the end is 1.35 or more and less than 1.40)
△: Yes (Image density at end is 1.00 or more and less than 1.35)
×: Impossible (Image density at end is less than 1.00)
2. Image fog A predetermined number of printouts were made on ordinary copying machine plain paper (75 g / m ² ), and evaluation was performed using a solid white image at the end of printing. Specifically, the evaluation was performed by the following method. The measurement was performed using a reflection densitometer (trade name: REFLECTOMETER MODEL TC-6DS, manufactured by TOKYO DENSHOKU CO., LTD). In other words, the minimum value of the white background reflection density after printing is Ds, the average reflection density value of the paper before printing is Dr, and (Ds-Dr) is obtained from these values, and this is used as the fog amount. evaluated.

A: Very good (fogging amount is 0% or more and less than 1.5%)
○: Good (fogging amount is 1.5% or more and less than 3.0%)
Δ: Practical use possible (fogging amount is 3.0% or more and less than 5.0%)
×: Not practical (fogging amount is 5.0% or more)
3. Transferability Print out a predetermined number of solid black images on regular copier plain paper (75g / m ² ), visually observe the amount of missing images at the end of printing, and evaluate according to the following criteria. did.

A: Very good (almost no occurrence)
○: Good (slight)
Δ: practical use ×: impractical use Further, in Example 31 to Example 36 and Comparative Example 7 to Comparative Example 12, scratches on the surface of the photosensitive drum and the intermediate transfer member and residual toner fixation when 5000 sheets of images were output The appearance of the image and the effect on the printout image (matching with LBP5500) were evaluated visually.

  As a result, in the system using the toner of Examples 31 to 36, scratches on the surface of the photosensitive drum and the intermediate transfer member and adhesion of residual toner could not be confirmed at all, and the matching with LBP5500 was very good. On the other hand, in all of the systems using the toners of Comparative Examples 7 to 12, toner adhesion was observed on the surface of the photosensitive drum. Further, in the systems using the toners of Comparative Examples 7 to 12, toner adhesion and surface damage were confirmed on the surface of the intermediate transfer member, and vertical streak-like image defects were also generated on the image.

Examples 37 to 39, Comparative Examples 13 to 15
In the implementation of Examples 37 to 39 and Comparative Examples 13 to 15, the toners obtained in Examples 1, 6, and 11 and Comparative Examples 1 to 3 were used as developers. Further, as a means for forming an image, an image forming apparatus which is remodeled by attaching a reuse mechanism (a system using a collected toner) to the LBP 5500 is used.

  As described above, in a normal mode and humidity (25 ° C, 60% RH) environment, print out up to 30,000 sheets in continuous mode at a printout speed of 8 sheets (A4 size) / min. To do. The image density of the obtained printout image was measured, and its durability was evaluated according to the following criteria. The 10,000th image was observed and image fogging was evaluated according to the following criteria. At the same time, the state of each device constituting the LBP 5500 after the durability test was observed, and the matching between each device and each toner was also evaluated. The above results are summarized in Table 3. The continuous mode is a mode that promotes toner consumption without pausing the developing device.

[Image density transition during durability]
A predetermined number of printouts were made on ordinary copying machine plain paper (75 g / m ² ), and evaluation was performed based on the degree of image density maintenance at the end of printing of the initial image. For the image density, a Macbeth reflection densitometer (manufactured by Macbeth Co., Ltd.) was used, and a relative density with respect to a printout image of a white background portion having an original density of 0.00 was measured and used for evaluation.

◎: Excellent (Image density at the end is 1.40 or more)
○: Good (image density at the end is 1.35 or more and less than 1.40)
△: Yes (Image density at end is 1.00 or more and less than 1.35)
×: Impossible (Image density at end is less than 1.00)
[Image fog]
A predetermined number of printouts were made on ordinary copying machine plain paper (75 g / m ² ), and evaluation was performed using a solid white image at the end of printing. The evaluation was performed by the method using the reflection densitometer described above (manufactured by TOKYO DENSHOKU CO., LTD, trade name: REFLECTOMETER MODEL TC-6DS).

[Image forming device matching evaluation]
1. Matching with developing sleeve After completion of the printout test, the appearance of the residual toner on the surface of the developing sleeve and the effect on the printout image were visually evaluated.

◎: Very good (not generated)
○: Good (almost no occurrence)
△: Practical (possibly fixed, but less affected on the image)
×: Impractical use (much sticking and image unevenness)
2. Matching with the photosensitive drum The appearance of scratches on the surface of the photosensitive drum and sticking of residual toner and the effect on the printed image were visually evaluated.

◎: Very good (not generated)
○: Good (slight scratches are seen, but there is no effect on the image)
△: Practical (possibly fixed or scratched, but less affected on the image)
×: Impractical (Fixed, causing vertical streak-like image defects)
3. Matching with the fixing device The appearance of the surface of the fixing film was observed, and the results of the surface property and the fixing state of the residual toner were averaged, and the durability was evaluated.

(1) Surface property The appearance of scratches or abrasions on the surface of the fixing film after completion of the printout test was visually observed and evaluated.

◎: Very good (not generated)
○: Good (almost no occurrence)
△: Practical use ×: Practical use impossible
(2) Residual Toner Fixing Status The residual toner fixing status on the surface of the fixing film after the printout test was visually observed and evaluated.

◎: Very good (not generated)
○: Good (almost no occurrence)
△: Practical use ×: Practical use impossible

Example 40
The same procedure as in Example 37 was performed except that the toner reuse mechanism of LBP5500 used in Examples 37 to 39 and Comparative Examples 13 to 15 was removed and the printout speed was 16 sheets (A4 size) / min.

  Then, a printout test was performed in a continuous mode (that is, a mode that promotes toner consumption without pausing the developing device) while sequentially supplying the blue toner (1) of Example 1. Evaluation of the printout image obtained and matching with the used LBP5500 were evaluated for the same items as in Examples 37 to 39 and Comparative Examples 13 to 15. As a result, good results were obtained for all items.

2 is a ¹ H-NMR measurement result of Example Compound B-1. 1 is a ¹ H-NMR measurement result of Example Compound E-1. 2 is a ¹ H-NMR measurement result of Example Compound B-2. 2 is a ¹ H-NMR measurement result of Example Compound E-2. It is a schematic diagram showing a blow-off charge amount measuring device for measuring the charge amount of toner.

Explanation of symbols

41 Charge amount measuring device 42 Measuring container 43 Screen 44 Lid 45 Vacuum gauge 46 Air volume control valve 47 Suction port 48 Condenser 49 Electrometer

Claims (2)

A charge control agent comprising at least one compound represented by the chemical formula (2).

(In the formula , R ₂₂ represents a —CH ₂ —CH ₂ —SO ₂ R ₃₂ group, —C (CH ₃ ) ₂ —CH ₂ —SO ₂ R ₃₂ group, and a phenyl group having a SO ₂ R ₃₂ group as a substituent. And a naphthyl group having a SO ₂ R ₃₂ group as a substituent , and when R ₂₂ is a phenyl group having a SO ₂ R ₃₂ group as a substituent , it may further have a methoxy group well,
R ₃₂ is O R _42,
R ₄₂ is any one of a methyl group, an ethyl group, and a phenyl group . When R ₄₂ is a phenyl group, it may have a nitro group as a substituent.
R ₁₂ is any of CF ₃ CH ₂ —, n-nonyl group, phenyl group and naphthyl group, and when R ₁₂ is a phenyl group, the substituent is an alkyl group having 1 to 4 carbon atoms. , May have an acetyl group or naphthyl sulfonate. ) An electrostatic charge image developing toner comprising a binder resin, a colorant, and the charge control agent according to claim 1 .

Images