JP5159087B2 - Charge control agent and electrostatic image developing toner - Google Patents

Description

The present invention relates to a charge control agent comprising a specific polymer having a sulfonic acid, a sulfonic acid ester group, or a derivative thereof, and an electrostatic charge image developing toner containing the charge control agent .

  A polymer having a hydrophilic group such as a sulfonic acid group is expected to be applied to various uses. And the synthesis | combining method of this polymer containing a sulfonic acid group is generally restricted to the method of using the specific vinyl monomer containing a sulfonic acid functional group. Specific examples of the monomer include sulfonated styrene or AMPS (2-acrylamido-2-methylpropanesulfonic acid).

For example, Japanese Patent No. 2979222 discloses a charge control agent comprising a copolymer of a styrene sulfonate and another vinyl monomer copolymerizable therewith, and a negatively charged toner for electrophotography using the same. It is disclosed.
Japanese Patent No. 2979222

In order to respond to various applications, sulfonated styrene and AMPS are not sufficient, and it has been desired to provide a new polymer. An object of the present invention is to provide a charge control agent using a specific polymer into which a sulfonic acid group, a sulfonic acid ester group, or a derivative thereof is introduced , and an electrostatic charge image developing toner containing the charge control agent. is there.

Therefore, the present inventors include a charge control agent using a specific polymer into which a hydrophilic group or a polar group is introduced, which is considered useful for improving various functionalities , and the charge control agent. As a result of intensive research aimed at developing an electrostatic image developing toner , the following inventions have been achieved. In addition, the following 1st-3rd polymer and the 1st-3rd monomer for polymer manufacture are described for reference.

  The 1st polymer concerning this invention is a polymer characterized by having a unit shown by Chemical formula (1).

Wherein R _1w , R _1x and R _1y are selected from (i) to (iii). R _1w and R _1x are each independently a halogen atom or a hydrogen atom. R _1y is CH ₃ A group or a hydrogen atom.
In the case of (i) below, R _1a , R _1b , R _1c , R _1d and R _1e are selected from the combinations described in any of the following (i-A) to (i-C). In the case of (ii) below, R _1a , R _1b , R _1c , R _1d and R _1e are selected from the combinations described in any one of (ii-A) to (ii-C) below. In the case of (iii) below, R _1a , R _1b , R _1c , R _1d and R _1e are selected from the combinations described in any of (iii-A) to (iii-C) below.
(I) When R _1w , R _1x and R _1y are each a hydrogen atom (i-A) R _1a is SO ₃ R _1f (R _1f is a linear alkyl group having 1 to 8 carbon atoms, branched carbon R _3b , R _1c , R _1d, and R _1e are hydrogen atoms. Or R _1a is SO ₃ R _1f (R _1f is a linear or branched alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure) R _1b , R _1c , R _1d and R _1e are each independently a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkoxy group having 1 to 8 carbon atoms, or a hydrogen atom (Except for the case where all of R _1b , R _1c , R _1d and R _1e are hydrogen atoms).
(I-B) R _1b is SO ₃ R _1g (R _1g is a linear or branched alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic ring. R _1a , R _1c , R _1d and R _1e are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched carbon number of 1 8 alkoxyl groups.
( _IC ) R _1c is SO ₃ R _1h (R _1h is a branched alkyl group having 5 to 8 carbon atoms, a linear alkyl group having 7 carbon atoms, a substituted or unsubstituted aromatic ring structure, or a substituted group. Or R _1a , R _1b , R _1d and R _1e are hydrogen atoms. Or R _1c is SO ₃ R _1g (R _1g is a linear or branched alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure) R _1a , R _1b , R _1d and R _1e are each independently a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkoxy group having 1 to 8 carbon atoms ( However, R _1a , R _1b , R _1d and R _1e are all hydrogen atoms).
(Ii) When R _1w and R _1x are each a hydrogen atom and R _1y is a CH ₃ group (ii-A) R _1a is SO ₃ R _1g (R _1g is a linear or branched carbon atom of 1 R _1b , R _1c , R _1d and R _1e are each independently a hydrogen atom, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure. It is a chain or branched alkyl group having 1 to 8 carbon atoms, or a straight chain or branched alkyl group having 1 to 8 carbon atoms.
(Ii-B) R _1b is SO ₃ R _1g (R _1g is a linear or branched alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure. R _1a , R _1c , R _1d and R _1e are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched carbon number 1 to 8 An alkoxyl group.
(Ii-C) R _1c represents SO ₃ R _1i (R _1i represents a linear or branched alkyl group having 2 to 8 carbon atoms, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure. R _1a , R _1b , R _1d and R _1e are hydrogen atoms. Or R _1c is SO ₃ R _1g (R _1g is a linear or branched alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure) R _1a , R _1b , R _1d and R _1e are each independently a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkoxy group having 1 to 8 carbon atoms.
(Iii) When at least one of R _1w and R _1x is a halogen atom (iii-A) R _1a is SO ₃ R _1j (R _1j is a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms) R _1b , R _1c , R _1d and R _1e are each independently a hydrogen atom, linear or branched, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure A C1-C8 alkyl group or a linear or branched C1-C8 alkoxyl group.
(Iii-B) R _1b is SO ₃ R _1j (R _1j is a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted group. R _1a , R _1c , R _1d and R _1e are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched carbon number. 1 to 8 alkoxyl groups.
(Iii-C) R _1c is SO ₃ R _1g (R _1g is a linear or branched alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure. R _1a , R _1b , R _1d and R _1e are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched carbon group having 1 to 8 carbon atoms. An alkoxyl group. )
The 2nd polymer concerning this invention is a polymer characterized by having a unit shown by Chemical formula (2).

(In the formula, R _2w and R _2x are each independently a halogen atom or a hydrogen atom. R _2y is a CH ₃ group or a hydrogen atom. R _2e is a hydrogen atom, linear or branched carbon number 1. To R _8h or R _2a , R _2b , R _2c , R _2d , R _2f , and R _2g are each independently SO ₃ R _2h. (R _2h is a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure), hydrogen atom, linear Or a branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkoxy group having 1 to 8 carbon atoms, and at least one of R _2a , R _2b , R _2c , R _2d , R _2f and R _2g. is SO ₃ R _2h. Alternatively, R _2e is SO ₃ R _2i ( _2i is a linear or branched alkyl group having 1 to 8 carbon atoms, an aromatic ring structure substituted or unsubstituted, or a substituted or unsubstituted heterocyclic ring _{structure), R 2a, R 2b,} R 2c , R _2d , R _2f and R _2g are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkoxy group having 1 to 8 carbon atoms. )
The third polymer according to the present invention is a polymer characterized by having a unit represented by the chemical formula (3).

(In the formula, R _3w and R _3x are each independently a halogen atom or a hydrogen atom. R _3y is a CH ₃ group or a hydrogen atom. R _3a , R _3b , R _3c , R _3d , R _3e , R _3f and R _3g are each independently SO ₃ R _3h (R _3h is a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted group. A substituted heterocyclic structure), a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkoxy group having 1 to 8 carbon atoms, R _3a , R (At least one of _3b , R _3c , R _3d , R _3e , R _3f and R _3g is SO ₃ R _3h .)
The 1st monomer for polymer manufacture concerning this invention is a compound shown by Chemical formula (5).

In the formula, R _5x , R _5y and R _5w are selected from the following (i) to (iii). In the formula, R _5w and R _5x each independently represent a halogen atom or a hydrogen atom. R _5y is a CH ₃ group or a hydrogen atom. In the case of (i) below, R _5a , R _5b , R _5c , R _5d and R _5e are selected from the combinations described in any of (iA) to (iC) below, In the case of ii), it is selected from the combinations described in any of the following (ii-A) to (ii-C), and in the case of (iii) below, the following (iii-A) to (iii-C) It is selected from the combinations described in any one of them.
(I) When R _5w , R _5x and R _5y are each a hydrogen atom (i-A) R _5a is SO ₃ R _5f (R _5f is a linear alkyl group having 1 to 8 carbon atoms, branched carbon R _5b , R _5c , R _5d, and R _5e are hydrogen atoms, and are an alkyl group of formulas 3 and 5 to 8, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure. It is. Or R _5a is SO ₃ R _5g (R _5g is a linear or branched alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure) R _5b , R _5c , R _5d and R _5e are each independently a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkoxy group having 1 to 8 carbon atoms, or hydrogen An atom (except when all of R _5b , R _5c , R _5d and R _5e are hydrogen atoms).
(I-B) R _5b is SO ₃ R _5g (R _5g is a linear or branched alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic ring. R _5a , R _5c , R _5d and R _5e are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched carbon. It is an alkoxyl group of formula 1 to 8.
(I-C) R _5c is SO ₃ R _5h (R _5h is a branched alkyl group having 5 to 8 carbon atoms, a linear alkyl group having 7 carbon atoms, a substituted or unsubstituted aromatic ring structure, or a substituted group. Or an unsubstituted heterocyclic structure), and R _5a , R _5b , R _5d and R _5e are hydrogen atoms. R _5c is SO ₃ R _5g (R _5g is a linear or branched alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure. R _5a , R _5b , R _5d and R _5e are each independently a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkoxy group having 1 to 8 carbon atoms. Or a hydrogen atom (except when all of R _5a , R _5b , R _5d and R _5e are hydrogen atoms).
(Ii) When R _5w and R _5x are each a hydrogen atom and R _5y is a CH ₃ group (ii-A) R _5a is SO ₃ R _5f (R _5f is a linear or branched carbon number of 1 R _5b , R _5c , R _5d, and R _5e are each independently a hydrogen atom, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure. It is a chain or branched alkyl group having 1 to 8 carbon atoms, or a straight chain or branched alkyl group having 1 to 8 carbon atoms.
(Ii-B) R _5b represents SO ₃ R _5g (R _5g represents a linear or branched alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure. R _5a , R _5c , R _5d and R _5e are a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkoxy group having 1 to 8 carbon atoms. is there.
(Ii-C) R _5c is SO ₃ R _5i (R _5i is a linear or branched alkyl group having 2 to 8 carbon atoms, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure. R _5a , R _5b , R _5d and R _5e are hydrogen atoms. Alternatively, R _5c is SO ₃ R _5g (R _5g is a linear or branched alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure) R _5a , R _5b , R _5d and R _5e are a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkoxy group having 1 to 8 carbon atoms.
(Iii) When at least one of R _5w and R _5x is a halogen atom (iii-A) R _5a is SO ₃ R _5j (R _5j is a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms) R _5b , R _5c , R _5d and R _5e are each independently a hydrogen atom, linear or branched, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure. A C1-C8 alkyl group or a linear or branched C1-C8 alkoxyl group.
(Iii-B) R _5b is SO ₃ R _5j (R _5j is a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted group. R _5a , R _5c , R _5d and R _5e are each a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched carbon group having 1 to 8 carbon atoms. An alkoxyl group;
(Iii-C) R _5c is SO ₃ R _5g (R _5g is a linear or branched alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure. R _5a , R _5b , R _5d and R _5e are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched carbon group having 1 to 8 carbon atoms. An alkoxyl group.

  The 2nd monomer for polymer manufacture concerning this invention is a compound shown by Chemical formula (6).

(In the formula, R _6w and R _6x are each independently a halogen atom or a hydrogen atom. R _6y is a CH ₃ group or a hydrogen atom. R _6e is a hydrogen atom, linear or branched carbon number 1 R _6a , R _6b , R _6c , R _6d , R _6f , and R _6g are each independently SO ₃ R _6h (R _6h is any one of a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure), R _6a , R _6b , R _6c , R _6d , R _6f and R _{6 are} a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkoxy group having 1 to 8 carbon atoms. _At least one of _6g is SO ₃ R _6h or R _{6 e} is SO ₃ R _6i (R _6i is a linear or branched alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure); R _6a , R _6b , R _6c , R _6d , R _6f , and R _6g are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched carbon number of 1 To 8 alkoxyl groups.)
The 3rd monomer for polymer manufacture concerning this invention is a compound shown by Chemical formula (7).

(In the formula, R _7w and R _7x are each independently a halogen atom or a hydrogen atom. R _7y is a CH ₃ group or a hydrogen atom. R _7a , R _7b , R _7c , R _7d , R _7e , R _7f and R _7g are each independently SO ₃ R _7h (R _7h is a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aromatic ring structure, or a substituted group. Or a substituted or unsubstituted heterocyclic structure), a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkoxy group having 1 to 8 carbon atoms, and R _7a Any one of R _7b , R _7c , R _7d , R _7e , R _7f and R _7g is SO ₃ R _7h )
A first charge control agent according to the present invention is a charge control agent that controls a charged state of a granular material and is made of a polymer having a unit represented by the chemical formula (8).

_Wherein R _8w and R _8x are each independently a halogen atom or a hydrogen atom. R _8y is a CH ₃ group or a hydrogen atom. R _8a , R _8b , R _8c , R _8d and R _8e are Each independently SO ₃ R _8f (R _8f is a linear or branched alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure) , A hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkoxy group having 1 to 8 carbon atoms, and R _8a , R _8b , R _8c , R _8d and R _8e At least one is SO ₃ R _8f .)
The second charge control agent according to the present invention is a charge control agent that controls a charged state of a granular material and is made of a polymer having a unit represented by the chemical formula (9).

(In the formula, R _9w and R _9x are each independently a halogen atom or a hydrogen atom. R _9y is a CH ₃ group or a hydrogen atom. R _9a , R _9b , R _9c , R _9d , R _9e , R _9f and R _9g are each independently SO ₃ R _9h (R _9h is a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aromatic ring structure, An unsubstituted heterocyclic structure), a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkoxy group having 1 to 8 carbon atoms, R _9a , R _9b , At least one of R _9c , R _9d , R _9e , R _9f and R _9g is SO ₃ R _9h .)
A third charge control agent according to the present invention is a charge control agent that controls a charged state of a granular material, and is made of a polymer having a unit represented by chemical formula (10).

(Wherein R _10w and R _10x are each independently a halogen atom or a hydrogen atom. R _10y is a CH ₃ group or a hydrogen atom. R _10a , R _10b , R _10c , R _10d , R _10e , R _10f and R _10g are each independently SO ₃ R _10h (where R _10h is a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aromatic ring structure, An unsubstituted heterocyclic structure), a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkoxy group having 1 to 8 carbon atoms, R _10a , R _10b , (At least one of R _10c , R _10d , R _10e , R _10f and R _10g is independently SO ₃ R _10h .)
An electrostatic image developing toner according to the present invention is an electrostatic image developing toner comprising at least a binder resin, a colorant, and any one of the first to third charge control agents. .

The present invention provides a charge control agent using a specific polymer having a sulfonic acid, a sulfonic acid ester group, or a derivative thereof, and an electrostatic charge image developing toner containing the charge control agent .

In the following, explanations other than the charge control agent and the electrostatic image developing toner of the present invention are given, but these are described for reference.
(Polymer and compound according to the present invention)
The first to third polymers according to the present invention each include one or more units having a structure represented by the chemical formulas (1) to (3) described above. In particular, it is preferable to include these specific units as a repeating unit structure.

  In the present invention, when a plurality of units are present in the polymer, each unit is independently represented according to the definition of each formula. For example, even if there are a plurality of the same units represented by the formula (1), different units represented by the formula (1) may be present. This also applies to units represented by other formulas. That is, the present invention includes not only the case where the polymer is composed of the same type of unit but also the case where the polymer is composed of different types of units.

  The fourth polymer according to the present invention includes at least one unit derived from the vinyl monomer represented by the chemical formula (4) in addition to the unit represented by the chemical formula (1). In particular, a copolymer containing a unit represented by the chemical formula (1) and a unit represented by the chemical formula (4) as a repeating unit structure is preferable.

In the formula, R _4w and R _4x each independently represent a halogen atom or a hydrogen atom. R _4y is a CH ₃ group, a halogen atom, or a hydrogen atom. R ₄ is a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure (wherein SO ₃ R _4z (R _4z is a hydrogen atom, straight chain or branched carbon number 1 8 to 8 alkyl groups, substituted or unsubstituted aromatic ring structures, or substituted or unsubstituted heterocyclic structures) (excluding phenyl groups or naphthyl groups), substituted or unsubstituted heterocyclic structures, It is a ring structure containing a halogen atom, —CO—R _4a , —O—R _4b , —COO—R _4c , —OCO—R _4d , —CONR _4e R _4f , —CN, or an N atom. R _4a , R _4b , R _4c , R _4d , R _4e and R _4f are each independently a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or An unsubstituted heterocyclic structure.

  The fifth and sixth polymers according to the present invention include at least one unit derived from a vinyl monomer represented by the chemical formula (4) in addition to the units represented by the chemical formulas (2) and (3), respectively. To do. In particular, a copolymer containing a unit represented by chemical formulas (2) and (3) and a unit represented by chemical formula (4) as a repeating unit structure is preferable.

  The compound as a monomer for introducing the unit of the chemical formula (1) into the polymer has a structure represented by the chemical formula (5).

  The following are mentioned as a compound shown to Chemical formula (5). They are methyl 4-ethenyl-2-methoxybenzenesulfonate, methyl 4-ethenyl-2-methylbenzenesulfonate, and isopentyl 4-ethenylbenzenesulfonate (isopentyl p-styrenesulfonate). Moreover, 4-ethenylbenzenesulfonic acid (2-ethylbutyl), 4-ethenylbenzenesulfonic acid normal heptyl, etc. are mentioned.

  An example of a method for producing the compound represented by the chemical formula (5) is shown below.

  A method for producing n-heptyl 4-ethenylbenzenesulfonate will be described.

  Normal heptyl 4-ethenylbenzenesulfonate can be produced with reference to Journal of Polymer Science, Polymer Chemistry Edition (1981), 19 (8), 1995.

  2- (2-Bromoethyl) -benzenesulfonyl chloride can be obtained by reacting 2-bromoethylbenzene with sulfonyl chloride. Next, when 4- (2-bromoethyl) -benzenesulfonyl chloride is esterified with normal heptyl alcohol and then dehydrobrominated, the desired normal heptyl 4-ethenylbenzenesulfonate can be obtained.

  Therefore, various alkyl ethenylbenzenesulfonates can be obtained by using the same technique. The alkyl ethenylbenzenesulfonate is obtained as follows. That is, 2- (2-bromoethyl) benzenesulfonic acid, 3- (2-bromoethyl) benzenesulfonic acid, and 4- (2-bromoethyl) benzenesulfonic acid obtained by sulfonating (2-bromoethyl) benzene with fuming sulfuric acid are used. Separate and purify. Then, after dehydrobromating each isomer, various alkyl ethenylbenzenesulfonates can be obtained by esterifying the sulfonic acid with an esterifying agent. In addition, esterification of a sulfonic acid can be performed with reference to SYNTHETIC COMMUNICATIONS, 15 (12), 21, 1057-1062 (1985).

  The monomer for introducing the unit represented by the chemical formula (2) into the polymer has a structure represented by the chemical formula (6) described above.

  Examples of the compound represented by the chemical formula (6) include methyl 4-ethenyl-1-naphthalenesulfonate, methyl 4-ethenyl-3-methoxy-1-naphthalenesulfonate, methyl 4-ethenyl-3-methyl-1-naphthalenesulfonate. Etc.

  An example of a method for producing the compound represented by the chemical formula (6) is shown below.

  A method for producing methyl 4-ethenyl-1-naphthalenesulfonate will be described.

  4- (2-Bromoethyl) -naphthalenesulfonyl chloride can be obtained by reacting 1- (2-bromoethyl) naphthalene and sulfonyl chloride. Next, 4- (2-bromoethyl) -naphthalenesulfonyl chloride is esterified with methyl alcohol and then dehydrobrominated to obtain the target methyl 4-ethenyl-1-naphthalenesulfonate.

  Therefore, various alkyl ethenylnaphthalene sulfonates can be obtained by using the same technique. The alkyl 4-ethenylnaphthalenesulfonate is obtained as follows. That is, after 4- (2-bromoethyl) naphthalenesulfonic acid obtained by sulfonating 1- (2-bromoethyl) naphthalene with fuming sulfuric acid is dehydrobrominated, the sulfonic acid is esterified with an esterifying agent. Thus, various alkyl 4-ethenylnaphthalenesulfonates can be obtained.

  The compound for introducing the unit represented by the chemical formula (3) into the polymer has a structure represented by the chemical formula (7).

  Examples of the compound represented by the chemical formula (7) include the following. 2-ethenyl-1-naphthalenesulfonic acid, methyl 2-ethenyl-1-naphthalenesulfonate, methyl 2-ethenyl-4-methoxy-1-naphthalenesulfonate, methyl 2-ethenyl-4-methyl-1-naphthalenesulfonate , Etc.

  The compound represented by the chemical formula (7) can be produced by using 2- (2-bromoethyl) naphthalene as a starting material in the same manner as the above-described method for producing the compound represented by the chemical formula (6).

(Production method)
Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. The polymer according to the present invention having the above-described structures has extremely excellent charging characteristics. Examples of the method for producing the polymer according to the present invention include the following methods.

  The first polymer according to the present invention, that is, the polymer containing the unit represented by the chemical formula (1) described above can be produced by polymerizing at least one compound represented by the chemical formula (5).

  The second polymer according to the present invention, that is, the polymer containing the unit represented by the chemical formula (2) described above can be produced by polymerizing at least one compound represented by the chemical formula (6).

  The third polymer according to the present invention, that is, the polymer containing the unit represented by the chemical formula (3) described above can be produced by polymerizing at least one compound represented by the chemical formula (7).

  The fourth polymer according to the present invention, that is, a polymer containing at least one unit derived from the vinyl monomer represented by the chemical formula (4) in addition to the unit represented by the chemical formula (1) is obtained as follows. That is, it can be produced by copolymerizing at least one compound represented by the chemical formula (5) and at least one compound represented by the chemical formula (12).

  The content ratio (mol%) of the unit of chemical formula (1) to the unit of chemical formula (4) is preferably 0.1: 99.9 to 90:10, and more preferably 1.0: 99.0 to 50:50.

In the formula, R _12w and R _12x each independently represent a halogen atom or a hydrogen atom. R _12y is a CH ₃ group, a halogen atom, or a hydrogen atom. R ₁₂ is a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure (wherein SO ₃ R _12z (R _12z is a hydrogen atom, straight chain or branched carbon number 1 8 to 8 alkyl groups, substituted or unsubstituted aromatic ring structures, or substituted or unsubstituted heterocyclic structures) (excluding phenyl groups or naphthyl groups), substituted or unsubstituted heterocyclic structures, halogen atom, a cyclic structure containing _{-CO-R 12a, -O-R} 12b, -COO-R 12c, -OCO-R 12d, -CONR 12e R 12f, -CN , or N atoms. R _12a , R _12b , R _12c , R _12d , R _12e and R _12f are each independently a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or An unsubstituted heterocyclic structure.

  The fifth polymer according to the present invention, that is, a polymer containing at least one unit derived from the vinyl monomer represented by the chemical formula (4) in addition to the unit represented by the chemical formula (2) is obtained as follows. It is done. That is, it can be produced by copolymerizing at least one compound represented by the chemical formula (6) and at least one compound represented by the chemical formula (12).

  The content ratio (mol%) of the unit of chemical formula (2) and the unit of chemical formula (4) is preferably 0.1: 99.9 to 90:10, and more preferably 1.0: 99.0 to 50:50.

  The sixth polymer according to the present invention, that is, a polymer containing at least one unit derived from the vinyl monomer represented by the chemical formula (4) in addition to the unit represented by the chemical formula (3) is obtained as follows. It is done. That is, it can be produced by copolymerizing at least one compound represented by the chemical formula (7) and at least one compound represented by the chemical formula (12).

  The content ratio (mol%) of the unit of the chemical formula (3) to the unit of the chemical formula (4) is preferably 0.1: 99.9 to 90:10, and more preferably 1.0: 99.0 to 50:50.

  Examples of the compound represented by the chemical formula (12) include styrene and its derivatives, unsaturated monoolefins, vinyl halides, vinyl ester acids, α-methylene aliphatic monocarboxylic esters, acrylic esters, vinyl ethers, vinyl ketones. Kind.

  As the polymerization method of the first to sixth polymers according to the present invention, radical polymerization or ionic polymerization can be used.

  In the case of using radical polymerization, examples of the initiator include t-butylperoxy-2-ethylhexanoate. These can be used alone or in combination. The amount used is preferably in the range of 0.0001 to 0.5 moles based on the total amount of the polymerizable monomers, but is appropriately determined according to the type of monomer used, the monomer used in copolymerization, and the initiator used obtain.

  As the solvent used in the polymerization reaction of the present invention, hydrocarbons such as hexane, ketones such as acetone, and ethers such as dimethyl ether and diethyl ether can be applied. In addition, halogenated hydrocarbons such as dichloromethane and chloroform, aromatic hydrocarbons such as benzene and toluene, and aprotic polar solvents such as N, N-dimethylformamide and dimethyl sulfoxide. Particularly preferred are aprotic polar solvents such as N, N-dimethylformamide and dimethyl sulfoxide.

  When copolymerizing styrenesulfonic acid or ethenylnaphthalenesulfonic acid with the compound represented by the chemical formula (12), an esterifying agent such as trimethylsilyldiazomethane, trimethyl orthoformate or triethyl orthoformate can be used for esterification of the sulfonic acid. .

  In this reaction, the above-described solvents and the like can be used as necessary. 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 esterifying agent used is in the range of 0.1 to 50 times mol, preferably 1 to 20 times mol, of the sulfonic acid unit.

  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 not generally defined, but is usually in the range of 1 to 48 hours.

  The polymer according to the present invention preferably has a molecular weight distribution (weight average molecular weight / number average molecular weight = Mw / Mn) of 1 <Mw / Mn <2. Such a polymer can be produced by living polymerization of a compound represented by the chemical formula (5), the chemical formula (6), or the chemical formula (7). Moreover, the copolymer whose molecular weight distribution (weight average molecular weight / number average molecular weight = Mw / Mn) is 1.00 <Mw / Mn <2.00 is obtained as follows. That is, for example, it can be produced by copolymerizing any compound represented by chemical formula (5), chemical formula (6) or chemical formula (7) with the compound represented by chemical formula (12) by living polymerization.

  As living polymerization, living radical polymerization, living anion polymerization, living cation polymerization and the like can be used. As living radical polymerization, for example, atom transfer radical polymerization or nitroxide-mediated polymerization can be used.

  Next, the case where living radical polymerization is nitroxide-mediated polymerization will be described.

  Since 2,2,6,6-tetramethylpiperidine (TEMPO), which is one of the nitroxyl radicals, unpaired electrons are delocalized, it is difficult to bind to a radical that binds and gives low dissociation energy. Using this property, a polymer having a narrow molecular weight distribution or a polymer having a controlled structure such as a block copolymer can be obtained by nitroxide-mediated polymerization using a nitroxyl radical. In addition, benzoyl peroxide (BPO) or azobisisobutyronitrile (AIBN) is used as an initiator.

  A polymerizable monomer, an initiator, and a nitroxyl radical are added to a reaction solvent, and the reaction system is replaced with an inert gas to perform nitroxide-mediated polymerization.

  As the nitroxyl radical, for example, those described below can be used.

  As the reaction solvent, for example, dimethyl sulfoxide, dimethylformamide, benzene, toluene, xylene, ethylbenzene, diphenyl ether and the like can be used. These may be used alone or in combination of two or more. Alternatively, the polymerization may be performed without using a reaction solvent.

(Charge control agent)
The first to third charge control agents according to the present invention control the charged state of the granular material, and include one or more units having the structure represented by the chemical formulas (8) to (10) described above. It is characterized by comprising a polymer.

  The fourth charge control agent according to the present invention controls the charged state of the powder, and in addition to the unit represented by the chemical formula (8), a unit derived from the vinyl monomer represented by the chemical formula (11) is provided. It may consist of a copolymer containing at least one.

In the formula, R _11w and R _11x each independently represent a halogen atom or a hydrogen atom. R _11y is a CH ₃ group, a halogen atom, or a hydrogen atom. R ₁₁ represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure (wherein SO ₃ R _11z (R _11z is a hydrogen atom, a linear or branched carbon number of 1 8 to 8 alkyl groups, substituted or unsubstituted aromatic ring structures, or substituted or unsubstituted heterocyclic structures) (excluding phenyl groups or naphthyl groups), substituted or unsubstituted heterocyclic structures, Any one of a ring structure containing a halogen atom, -CO-R _11a , -O-R _11b , -COO-R _11c , -OCO-R _11d , -CONR _11e R _11f , -CN, or an N atom. R _11a , R _11b , R _11c , R _11d , R _11e and R _11f are each independently a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or An unsubstituted heterocyclic structure.

  The fifth and sixth charge control agents according to the present invention control the charged state of the powder and are represented by the chemical formula (11) in addition to the units represented by the chemical formulas (9) and (10). A copolymer containing at least one unit derived from a vinyl monomer may be used.

  The polymer constituting the charge control agent according to the present invention is for controlling the charged state of the granular material, and the number average molecular weight is preferably 1,000 to 1,000,000.

  The polymer constituting the charge control agent according to the present invention controls the charged state of the powder, and its molecular weight distribution (weight average molecular weight / number average molecular weight = Mw / Mn) is 1.00 <Mw / Mn. <2.00.

  The polymer constituting the charge control agent according to the present invention can be a block copolymer.

  The powder is preferably an electrostatic image developing toner.

(Preparation of the charge control agent according to the present invention)
The first charge control agent according to the present invention, that is, the charge control agent composed of the polymer containing the unit represented by the chemical formula (8) described above is obtained by polymerizing at least one compound represented by the chemical formula (13). Can be manufactured.

In the formula, R _13w and R _13x each independently represent a halogen atom or a hydrogen atom. R _13y is a CH ₃ group or a hydrogen atom. R _13a , R _13b , R _13c , R _13d and R _13e are each independently SO ₃ R _13f (R _13f is a linear or branched alkyl group having 1 to 8 carbon atoms, or substituted or unsubstituted A phenyl group), a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkoxy group having 1 to 8 carbon atoms, R _13a , R _13b , R _13c , At least one of R _13d and R _13e is SO ₃ R _13f .

  Examples of the compound represented by the chemical formula (13) include the following compounds in addition to the compounds specifically mentioned as the compound of the chemical formula (5). Examples include methyl 4-ethenylbenzenesulfonate (methyl p-styrenesulfonate) and ethyl 4-ethenylbenzenesulfonate.

  The second charge control agent according to the present invention, that is, the charge control agent composed of the polymer containing the unit represented by the chemical formula (9) described above is obtained by polymerizing at least one compound represented by the chemical formula (14). Can be manufactured.

In the formula, R _14w and R _14x each independently represent a halogen atom or a hydrogen atom. R _14y is a CH ₃ group or a hydrogen atom. R _14a , R _14b , R _14c , R _14d , R _14e , R _14f and R _14g are each independently SO ₃ R _14h (R _14h is a linear or branched alkyl group having 1 to 8 carbon atoms, or A substituted or unsubstituted phenyl group), a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkoxy group having 1 to 8 carbon atoms, R _14a , R _14b, at least one of _{R 14c, R 14d, R 14e} , R 14f and R _{14 g} is SO ₃ R _14h.

  Examples of the compound represented by the chemical formula (14) include 4-ethenyl-1-naphthalenesulfonic acid and the like in addition to the specific compound described in the chemical formula (6).

  The third charge control agent according to the present invention, that is, the charge control agent composed of the polymer containing the unit represented by the chemical formula (10) described above is obtained by polymerizing at least one compound represented by the chemical formula (15). Can be manufactured.

In the formula, R _15w and R _15x each independently represent a halogen atom or a hydrogen atom. R _15y is a CH ₃ group or a hydrogen atom. R _15a , R _15b , R _15c , R _15d , R _15e , R _15f and R _15g are each independently SO ₃ R _15h (R _15h is a linear or branched alkyl group having 1 to 8 carbon atoms, or A substituted or unsubstituted phenyl group), a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkoxy group having 1 to 8 carbon atoms, R _15a , R _{15b, R 15c, R 15d,} R 15e, at least one of R _15f and R _{15 g} is SO ₃ R _15h.

  Examples of the compound represented by the chemical formula (15) include the specific compounds exemplified in the chemical formula (7).

  The fourth charge control agent according to the present invention, that is, the charge control agent comprising a polymer containing at least one unit derived from the vinyl monomer represented by the chemical formula (11) in addition to the unit represented by the chemical formula (8) is: It is obtained as follows. That is, it can be produced by copolymerizing at least one compound represented by the chemical formula (13) and at least one compound represented by the chemical formula (12).

  The content ratio (mol%) of the unit of the chemical formula (8) and the unit of the chemical formula (11) is preferably 0.1: 99.9 to 90:10, and more preferably 1.0: 99.0 to 49:51.

  Further, a fifth charge control agent according to the present invention, that is, a charge control agent comprising a polymer containing at least one unit derived from a vinyl monomer represented by the chemical formula (11) in addition to the unit represented by the chemical formula (9), Is obtained as follows. That is, it can be produced by copolymerizing at least one compound represented by the chemical formula (14) and at least one compound represented by the chemical formula (12).

  The content ratio (mol%) of the unit of chemical formula (9) and the unit of chemical formula (11) is preferably 0.1: 99.9 to 90:10, and more preferably 1.0: 99.0 to 49:51.

  Further, a sixth charge control agent according to the present invention, that is, a charge control agent comprising a polymer containing at least one unit derived from a vinyl monomer represented by the chemical formula (11) in addition to the unit represented by the chemical formula (10), Is obtained as follows. That is, it can be produced by copolymerizing at least one compound represented by the chemical formula (15) and at least one compound represented by the chemical formula (12).

  The content ratio (mol%) of the unit of the chemical formula (10) and the unit of the chemical formula (11) is preferably 0.1: 99.9 to 90:10, and more preferably 1.0: 99.0 to 49:51.

  As a method for polymerizing the charge control agent according to the present invention, it is possible to use the radical polymerization or ionic polymerization described above.

  When using radical polymerization, the same initiator and solvent as described above can be used.

  The polymer constituting the charge control agent according to the present invention preferably has a molecular weight distribution (weight average molecular weight / number average molecular weight = Mw / Mn) of 1.00 <Mw / Mn <2.00. The polymer constituting such a charge control agent can be produced by living polymerization of a compound represented by the chemical formula (13), the chemical formula (14), or the chemical formula (15). Moreover, the copolymer whose molecular weight distribution (weight average molecular weight / number average molecular weight = Mw / Mn) is 1.00 <Mw / Mn <2.00 is obtained as follows. That is, for example, any compound represented by chemical formula (13), chemical formula (14) or chemical formula (15) and the compound represented by chemical formula (12) can be produced by copolymerization by living polymerization.

  The polymer constituting the charge control agent according to the present invention is preferably a block copolymer. The polymer constituting such a charge control agent can be obtained, for example, as follows. That is, a homopolymer is produced by living polymerization of any compound represented by chemical formula (13), chemical formula (14), or chemical formula (15). Then, it can manufacture by block-copolymerizing the compound shown by Chemical formula (12) at the terminal of the homopolymer by living polymerization. The order in which the block copolymers are formed may be reversed.

<Use as charge control agent>
The charge control agent according to the present invention has a structure containing a sulfonic acid ester group or a derivative thereof in the side chain as in the units represented by the chemical formulas (8) to (10). The presence of these anionic or electron-withdrawing functional groups has excellent negative chargeability. The charge control agent according to the present invention has good compatibility with the binder resin of the toner, and in particular, has very good compatibility with the polyester binder resin.

  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. In addition, the charge control agent of the present invention is colorless or can be very lightly colored even when colored, and has a good negative charging performance. Therefore, it can be suitably used for both black negatively charged toner and color toner. Furthermore, wide compatibility control is possible by appropriately selecting the type / composition ratio of the monomer units constituting the polymer of the present invention.

  Here, when the resin composition is selected so that the charge control agent has a microphase separation structure in the toner binder, the electric continuity of the toner does not occur, so that the charge can be stably held.

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

(Application to toner)
Examples of the charge control agent according to the present invention include toner for developing an electrostatic charge image 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 polymer, and further an electrostatic charge image developing toner containing the charge control agent.

  In addition, as a charge control agent used in the toner composition for developing an electrostatic charge image, for example, by using a copolymer of a unit having a structure represented by the chemical formula (8) and a unit having a structure represented by the chemical formula (11), Such effects can be obtained. That is, the charging property is excellent, and the dispersibility and spent property of the compound in the toner resin are improved. 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 according to the present invention can be made colorless or weak in coloration degree, any colorant can be used in accordance with the hue required for the color toner without being affected by the charge control agent. It is possible to select. A colorless or weakly colored charge control agent is preferable because it hardly inhibits the original hue of the dye or pigment.

(Addition of charge control agent according to the present invention to toner)
In the present invention, as a method of incorporating the above-described charge control agent comprising a polymer 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 number average molecular weight of the polymer constituting the charge control agent of the present invention is usually 1,000 to 1,000,000, preferably 1,000 to 300,000. If it is less than 1,000, it becomes difficult to form discontinuous domains due to complete compatibility with the toner binder, so that the charge amount becomes insufficient and the fluidity of the toner may be affected. If it exceeds 1,000,000, it may be difficult to disperse in the toner.

  The molecular weight of the polymer constituting the charge control agent of the present invention was measured by GPC (gel permeation chromatography). As a specific GPC measurement method, a sample obtained by previously dissolving the above polymer in 0.1% by mass LiBr-containing dimethylformamide (DMF), chloroform or the like is measured with the same mobile phase, and the molecular weight distribution is obtained from a standard polystyrene resin calibration curve. Asked.

  The molecular weight distribution (weight average molecular weight / number average molecular weight = Mw / Mn) of the polymer constituting the charge control agent of the present invention is preferably 1.00 <Mw / Mn <2.00, and 1 <Mw / Mn ≦ 1.50 is more preferable, and 1 <Mw / Mn ≦ 1.30 is more preferable.

  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 (compounds such as iron and ferrite) may be contained in an amount of 60% by mass or less in order to function as a colorant.

  In addition, for the purpose of reducing the particle size of the discontinuous domains formed by the charge control agent of the present invention, a heavy material having compatibility with the charge control agent of the present invention and compatibility with the toner binder. A coalescence can also be contained as a compatibilizing agent. As the compatibilizing agent, a polymer chain containing 50 mol% or more of a monomer having substantially the same structure as the constituent monomer of the charge control agent of the present invention, and a constituent monomer of the toner binder are substantially included. And a polymer in which a polymer chain containing 50 mol% or more of the monomer having the same structure is bonded. In addition, it is preferable that these two polymer chains are a polymer in which a graft shape or a block shape is bonded. The amount of the compatibilizing agent used is usually 30% by mass or less, preferably 1 to 10% by mass with respect to the charge control agent of the present invention.

<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. Examples thereof include polystyrene and polyacrylic acid ester.

  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 styrenic polymers and polyester polymers, which can be used alone or in combination.

  Examples of the styrenic polymer include a copolymer of styrene and (meth) acrylic acid ester and a copolymer of other monomers copolymerizable with these.

  Specific examples of the binder resin used in combination with the charge control agent of the present invention include styrene polymers such as styrene-acrylic acid copolymers or styrene-methacrylic acid copolymers. Specific examples of the polymerizable monomer include styrene and its derivatives, ethylenically unsaturated monoolefins, methacrylic acid esters, acrylic acid esters, vinyl ethers, vinyl ketones and the like.

  When forming the binder resin to be used in combination with the charge control agent of the present invention, the following crosslinking agents may be used as necessary.

  Moreover, when forming binder resin used in combination with the charge control agent of this invention, a polymerization initiator as listed below can be used as needed. For example, t-butylperoxy-2-ethylhexanoate and the like can be mentioned. These can be used alone or in combination. 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.

  The mass ratio for internally adding the charge control agent of the present invention to the binder resin is usually 0.1 to 50 mass%, preferably 0.2 to 20 mass%. Here, when the mass ratio of the charge control agent added internally is less than 0.1 mass%, the charge amount is low, and when it exceeds 50 mass%, the charging stability of the toner is deteriorated.

  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.

  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.

  In addition, when the electrostatic charge image developing toner of the present invention is used as a two-component full-color toner, CI pigment red 1, 2 or the like is used as a colorant.

  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 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 0.1 to 60 masses per 100 mass parts of binder resin. Parts, preferably about 0.5 to 20 parts by weight.

  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.

<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.

(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.

(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, a metal oxide such as magnesium can be used. It is preferable to use fine powders of zinc oxide, aluminum oxide, cobalt oxide, manganese dioxide, strontium titanate, and magnesium titanate.

  Further, a lubricant powder as described below may be added to the toner. An example is Teflon.

<About Career>
The toner of the present invention, for example, can be used as a non-magnetic one-component developer alone. Further, it can be used as a non-magnetic toner that constitutes 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.

<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 the present invention, the average particle size and particle size distribution of the toner are measured using a device such as Coulter Counter TA-II type or Coulter Multisizer (manufactured by Beckman Coulter). Then, an interface (manufactured by Nikkei Bios) that outputs the number distribution and volume distribution and a personal computer are connected to the apparatus and measured. 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. The measurement is performed as follows. The electrolytic solution in which the measurement sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes. Thereafter, the volume and number of toners of 2 μm or more were measured using the Coulter counter TA-II with a 100 μm aperture as the aperture, and 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 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. 1 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 (trade name, 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 at 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. In other words, if the GPC peak in the low molecular weight region exceeds 15,000, it may be difficult to obtain a product with sufficiently improved 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). For 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. For the column configuration, A-801, 802, 803, 804, 805, 806, and 807 manufactured by Showa Denko were connected 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.

  The present invention does not exclude the case where the polymer or copolymer according to the present invention described above contains sulfonated styrene or AMPS described in the background art.

First, Examples A to X describe polymers that can be used in the charge control agent of the present invention. Thereafter, Examples 1 to 34 show the usefulness of the present invention while using comparative examples. Examples A to X are production examples, and Examples Y-1 to Y-2 and Examples Z-1 to Z-2 are reference examples.

  In addition, the novel charge control agent according to the present invention and the production method thereof are not limited to the following examples.

In the following experiment, the structure of the obtained charge control agent is determined as follows. That is, analysis by ¹ H-NMR (FT-NMR: Bruker Avance 500; resonance frequency: 500 MHz; measurement nuclide: ¹ H; solvent used: heavy DMF, heavy DMSO, heavy chloroform, heavy THF, heavy acetone; measurement temperature: room temperature) I do.

  The average molecular weight of the obtained polymer was determined by gel permeation chromatography (GPC; Tosoh, column; Polymer Laboratories PLgel 5μ MIXED-C, solvent; DMF / LiBr 0.1% (w / v), polystyrene conversion). evaluated.

(Example A)
Styrene (108 g), methyl p-styrene sulfonate (10.8 g), 2,2′-azobisisobutyronitrile (1.2 g) are dissolved in DMF (120 g), and the nitrogen atmosphere is at 70 ° C. Polymerized for 5 hours. As a result, the following formula (A):

A unit represented, content ratio _{(mol%) (M 0) :( F} 0) = 95: obtain copolymer containing 5 to (90 g). The content ratio of each unit of the polymer was confirmed by ¹ H-NMR measurement. The number average molecular weight Mn was 17000, and the molecular weight distribution (Mw / Mn) was 2.54. ^{The 1} H-NMR data is shown below.
¹ H-NMR (500 MHz, heavy DMF)
δ / ppm: 7.45 to 7.75 (peak of benzene ring)
6.40 to 7.40 (peak of benzene ring)
3.65 to 3.80 (CH ₃ peak of methyl sulfonate)
1.20 to 2.50 (main chain peak)
(Example B)
Copolymerization was carried out in the same manner as in Example A, except that methyl p-styrenesulfonate in Example A was replaced with ethyl p-styrenesulfonate. As a result, the following formula (B):

A unit represented, content ratio _{(mol%) (M 1) :( F} 1) = 95: obtain copolymer containing 5 to (100 g). The number average molecular weight Mn = 22000 and the molecular weight distribution (Mw / Mn) = 2.62. ^{The 1} H-NMR data is shown below.
¹ H-NMR (500 MHz, heavy DMF)
δ / ppm: 7.45 to 7.80 (peak of benzene ring)
6.40 to 7.40 (peak of benzene ring)
3.95 to 4.20 (CH ₂ peak of ethyl sulfonate)
1.30 to 2.50 (main chain peak)
1.15 to 1.30 (CH ₃ peak of ethyl sulfonate)
(Example C)
Methyl methacrylate (100 g), methyl m-styrenesulfonate (34.9 g) and 2,2′-azobisisobutyronitrile (1.4 g) were dissolved in DMF (135 g), Polymerization was carried out at 5 ° C. for 5 hours. As a result, the following formula (C):

A unit represented, content ratio _{(mol%) (M 2) :( F} 2) = 85: to give a copolymer containing 15 to (113 g). The content ratio of each unit of the polymer was confirmed by ¹ H-NMR measurement. Number average molecular weight Mn = 16000 and molecular weight distribution (Mw / Mn) = 2.66.

(Example D)
Copolymerization was carried out in the same manner as in Example C, except that methyl m-styrenesulfonate in Example C was replaced with ethyl m-styrenesulfonate. As a result, the following formula (D):

The copolymer (113g) which contains the unit shown in content ratio (mol%) (M3) :( F3) = 85: 15 was obtained. The content ratio of each unit of the polymer was confirmed by ¹ H-NMR measurement. Number average molecular weight Mn = 19000 and molecular weight distribution (Mw / Mn) = 2.61.

(Example E)
Styrene (108 g), methyl o-styrenesulfonate (10.8 g), 2,2′-azobisisobutyronitrile (1.2 g) are dissolved in DMF (120 g), and the mixture is heated at 70 ° C. in a nitrogen atmosphere. Polymerized for 5 hours. As a result, the following formula (E):

The copolymer (93g) which contains the unit shown in content ratio (mol%) (M4) :( F4) = 90: 10 was obtained. The content ratio of each unit of the polymer was confirmed by ¹ H-NMR measurement. The number average molecular weight Mn was 12000, and the molecular weight distribution (Mw / Mn) was 2.59.

(Example F)
Copolymerization was carried out in the same manner as in Example E, except that methyl o-styrenesulfonate in Example E was replaced with ethyl o-styrenesulfonate. As a result, the following formula (F):

The copolymer (100g) which contains the unit shown in content ratio (mol%) (M5) :( F5) = 90: 10 was obtained. The content ratio of each unit of the polymer was confirmed by ¹ H-NMR measurement. The number average molecular weight Mn = 13000 and the molecular weight distribution (Mw / Mn) = 2.53.

(Example G)
Styrene (110 g), methyl 4-ethenyl-1-naphthalenesulfonate (20 g), 2,2′-azobisisobutyronitrile (1.3 g) was dissolved in DMF (130 g), and the solution was added under a nitrogen atmosphere. Polymerization was carried out at 5 ° C. for 5 hours. As a result, the following formula (G):

The copolymer (92g) which contains the unit shown in content ratio (mol%) (M6) :( F6) = 93: 7 was obtained. Number average molecular weight Mn = 19000 and molecular weight distribution (Mw / Mn) = 2.61.

(Example H)
Ethyl methacrylate (115 g), ethyl 4-ethenyl-1-naphthalene sulfonate (30 g), 2,2′-azobisisobutyronitrile (1.4 g) were dissolved in DMF (145 g), and nitrogen atmosphere was used. And polymerized at 70 ° C. for 5 hours. As a result, the following formula (H):

The copolymer (101g) which contains the unit shown in content ratio (mol%) (M7) :( F7) = 90: 10 was obtained. The number average molecular weight Mn = 25000 and the molecular weight distribution (Mw / Mn) = 2.64.

Example I
A copolymer represented by the following formula (I) was synthesized using atom transfer radical polymerization. Styrene (104 g), methyl p-styrenesulfonate (17 g), 1-bromoethylbenzene (0.9 g) as the starting species, and copper bromide (1.3 g) as the catalyst were dissolved in DMF. Furthermore, 1,1,4,7,10,10-hexamethyltriethylenetetramine (2.1 g) as a ligand is also dissolved in the DMF (115 g) and polymerized at 70 ° C. for 7 hours in a nitrogen atmosphere. It was. As a result, the following formula (I):

The copolymer (91g) which contains the unit shown in content ratio (mol%) (M8) :( F8) = 92: 8 was obtained. The number average molecular weight Mn was 20,000 and the molecular weight distribution (Mw / Mn) was 1.24.

(Example J)
A copolymer represented by the following formula (J) was synthesized using atom transfer radical polymerization. Copolymerization was carried out in the same manner as in Example I except that methyl p-styrenesulfonate in Example I was replaced with methyl m-styrenesulfonate. As a result, the following formula (J):

The copolymer (92g) which contains the unit shown by content ratio (mol%) (M9) :( F9) = 92: 8 was obtained. Number average molecular weight Mn = 19000 and molecular weight distribution (Mw / Mn) = 1.22.

(Example K)
A copolymer represented by the following formula (K) was synthesized using atom transfer radical polymerization. Copolymerization was carried out in the same manner as in Example I, except that methyl p-styrenesulfonate in Example I was replaced with methyl o-styrenesulfonate. As a result, the following formula (K):

The copolymer (93g) which contains the unit shown in content ratio (mol%) (M10) :( F10) = 92: 8 was obtained. Number average molecular weight Mn = 21,000 and molecular weight distribution (Mw / Mn) = 1.21.

(Example L)
A copolymer represented by the following formula ( L ) was synthesized using nitroxide-mediated polymerization. The following materials were dissolved in DMF (130 g) and polymerized at 120 ° C. for 5 hours under a nitrogen atmosphere.
Styrene (108g)
p-Styrene sulfonate ethyl (24.5 g)
2,2′-Azobisisobutyronitrile (0.9 g)
TEMPO (0.8g)
Ziclel peroxide (0.3g)
As a result, the following formula (L):

The copolymer (93g) which contains the unit shown in content ratio (mol%) (M11) :( F11) = 90: 10 was obtained. The number average molecular weight Mn = 22000 and the molecular weight distribution (Mw / Mn) = 1.30.

(Example M)
A copolymer represented by the following formula (M) was synthesized using nitroxide-mediated polymerization. Copolymerization was carried out in the same manner as in Example L, except that ethyl p-styrenesulfonate in Example L was replaced with ethyl m-styrenesulfonate. As a result, the following formula (M):

The copolymer (90g) which contains the unit shown in content ratio (mol%) (M12) :( F12) = 90: 10 was obtained. The number average molecular weight Mn = 21,000 and the molecular weight distribution (Mw / Mn) = 1.28.

Example N
A copolymer represented by the following formula (N) was synthesized using nitroxide-mediated polymerization. Copolymerization was carried out in the same manner as in Example L, except that ethyl p-styrenesulfonate in Example L was replaced with ethyl o-styrenesulfonate. As a result, the following formula (N):

The copolymer (91g) which consists of a copolymer which contains the unit shown in content ratio (mol%) (M13) :( F13) = 90: 10 was obtained. The number average molecular weight Mn = 23,000 and the molecular weight distribution (Mw / Mn) = 1.29.

(Example O)
A copolymer represented by the following formula (O) was synthesized using atom transfer radical polymerization. The discretion shown below was dissolved in DMF (128 g) and polymerized at 70 ° C. for 7 hours in a nitrogen atmosphere.
Methyl methacrylate (100g)
4-Ethenyl-1-naphthalenesulfonic acid methyl ester (28 g)
Starting species ethyl 2-bromoisobutyrate (0.95 g)
Catalyst copper bromide (4.2 g)
Sparteine (3.4 g) as a ligand
As a result, the following formula (O):

The copolymer (96g) which contains the unit shown in content ratio (mol%) (M14) :( F14) = 90: 10 was obtained. The number average molecular weight Mn = 21,000 and the molecular weight distribution (Mw / Mn) = 1.20.

(Example P)
A copolymer represented by the following formula (P) was synthesized using atom transfer radical polymerization. Copolymerization was carried out in the same manner as in Example O, except that methyl 4-ethenyl-1-naphthalenesulfonate in Example O was replaced with ethyl 4-ethenyl-1-naphthalenesulfonate. As a result, the following formula (P):

The copolymer (99g) which contains the unit shown in content ratio (mol%) (M15) :( F15) = 90: 10 was obtained. The number average molecular weight Mn = 23,000 and the molecular weight distribution (Mw / Mn) = 1.21.

(Example Q)
A copolymer represented by the following formula (Q) was synthesized using nitroxide-mediated polymerization. The following materials were dissolved in DMF (130 g) and polymerized at 120 ° C. for 5 hours under a nitrogen atmosphere.
Styrene (108g)
4-Ethenyl-1-naphthalenesulfonic acid ethyl ester (17.4 g)
2,2′-Azobisisobutyronitrile (0.9 g)
TEMPO (0.8g)
Ziclel peroxide (0.3g)
As a result, the following formula (Q):

The copolymer (94g) which contains the unit shown in content ratio (mol%) (M16) :( F16) = 93: 7 was obtained. The number average molecular weight Mn was 20,000 and the molecular weight distribution (Mw / Mn) was 1.21.

(Example R)
A copolymer represented by the following formula (R) was synthesized using atom transfer radical polymerization. Copolymerization was carried out in the same manner as in Example Q, except that ethyl 4-ethenyl-1-naphthalenesulfonate in Example Q was replaced with methyl 4-ethenyl-1-naphthalenesulfonate. As a result, the following formula (R):

The copolymer (92g) which contains the unit shown in content ratio (mol%) (M17) :( F17) = 93: 7 was obtained. The number average molecular weight Mn = 19000 and the molecular weight distribution (Mw / Mn) = 1.18.

(Example S)
A block copolymer represented by the following formula (S) was synthesized using atom transfer radical polymerization. First, the following materials were dissolved in DMF (22 g) and polymerized at 70 ° C. for 1 hour in a nitrogen atmosphere.
p-Methyl styrenesulfonate (22 g)
1-bromoethylbenzene (0.9 g) as the starting species
Copper bromide (0.7g) as catalyst
Ligand 1,1,4,7,10,10-hexamethyltriethylenetetramine (1.1 g)
As a result, a poly (methyl p-styrenesulfonate) macroinitiator (18 g, number average molecular weight Mn = 3500, molecular weight distribution (Mw / Mn) = 1.15) was obtained.

Subsequently, the following materials were dissolved in DMF (125 g) and copolymerized at 70 ° C. for 5 hours under a nitrogen atmosphere.
Poly (p-styrene sulfonate methyl) (18 g) as a macroinitiator (starting species),
Styrene (104 g),
Catalyst copper bromide (2.1 g),
Ligand 1,1,4,7,10,10-hexamethyltriethylenetetramine (3.5 g)
As a result, the following formula (S):

The block copolymer (90g) which contains the unit shown in content ratio (mol%) (M18) :( F18) = 90: 10 was obtained. The number average molecular weight Mn was 20,000 and the molecular weight distribution (Mw / Mn) was 1.21.

(Example T)
A block copolymer represented by the following formula (T) was synthesized using atom transfer radical polymerization. Copolymerization was carried out in the same manner as in Example S except that methyl p-styrenesulfonate in Example S was replaced with methyl m-styrenesulfonate. As a result, the following formula (T):

The block copolymer (91g) which contains the unit shown in content ratio (mol%) (M19) :( F19) = 90: 10 was obtained. The number average molecular weight Mn was 20,000 and the molecular weight distribution (Mw / Mn) was 1.20.

(Example U)
A block copolymer represented by the following formula (U) was synthesized using atom transfer radical polymerization. Copolymerization was carried out in the same manner as in Example S, except that methyl p-styrenesulfonate in Example S was replaced with methyl o-styrenesulfonate. As a result, the following formula (U):

The charge control agent (90g) which consists of a block copolymer which contains the unit shown by content ratio (mol%) (M20) :( F20) = 90: 10 was obtained. In addition, the obtained charge control agent had a number average molecular weight Mn = 22000 and a molecular weight distribution (Mw / Mn) = 1.19.

(Example V)
A block copolymer represented by the following formula (V) was synthesized using nitroxide-mediated polymerization. First, ethyl p-styrenesulfonate (25 g), 2,2′-azobisisobutyronitrile (1.0 g), TEMPO (1.0 g), and dicurmyl peroxide (0.4 g) were added to DMF ( 25 g) and polymerized in a nitrogen atmosphere at 120 ° C. for 1 hour. As a result, a macroinitiator (20 g, number average molecular weight Mn = 3000, molecular weight distribution (Mw / Mn) = 1.20) of poly (p-styrene sulfonate) was obtained.

Subsequently, the following materials were dissolved in DMF (145 g) and polymerized at 120 ° C. for 5 hours in a nitrogen atmosphere.
A macroinitiator (starting species), poly (p-ethyl styrenesulfonate) (20 g),
Styrene (124 g),
2,2′-azobisisobutyronitrile (1.0 g),
TEMPO (1.0 g), diclemyl peroxide (0.4 g)
As a result, the following formula (V):

The block copolymer (100g) which contains the unit shown in content ratio (mol%) (M21) :( F21) = 91: 9 was obtained. Number average molecular weight Mn = 18000, molecular weight distribution (Mw / Mn) = 1.24.

(Example W)
A block copolymer represented by the following formula (W) was synthesized using atom transfer radical polymerization. First, the following materials were dissolved in DMF (30 g) and polymerized at 70 ° C. for 1 hour in a nitrogen atmosphere.
Methyl 4-ethenyl-1-naphthalenesulfonate (28 g),
1-bromoethylbenzene (0.7 g) as the starting species,
Catalyst copper bromide (0.5 g),
Ligand 1,1,4,7,10,10-hexamethyltriethylenetetramine (0.8 g)

As a result, a macroinitiator (22 g, number average molecular weight Mn = 6200, molecular weight distribution (Mw / Mn) = 1.13) of poly (4-ethylene-1-naphthalenesulfonate) was obtained.

Subsequently, the following materials were dissolved in DMF (110 g) and copolymerized at 70 ° C. for 5 hours in a nitrogen atmosphere.
Poly (4-ethylene-1-naphthalenesulfonate methyl) as a macroinitiator (starting species) (22 g)
Styrene (83 g),
Catalyst copper bromide (1.5 g),
Ligand 1,1,4,7,10,10-hexamethyltriethylenetetramine (2.4 g)
As a result, the following formula (W):

The block copolymer (84g) which contains the unit shown in content ratio (mol%) (M22) :( F22) = 88: 12 was obtained. The number average molecular weight Mn = 25000 and the molecular weight distribution (Mw / Mn) = 1.20.

(Example X)
A block copolymer represented by the following formula (X) was synthesized using nitroxide-mediated polymerization. First, the following materials were dissolved in DMF (31 g) and polymerized at 120 ° C. for 1.5 hours in a nitrogen atmosphere.
Ethyl 4-ethenyl-1-naphthalenesulfonate (31 g),
2,2′-azobisisobutyronitrile (0.5 g),
TEMPO (0.5 g),
Ziclel peroxide (0.2g)
As a result, a macroinitiator (25 g, number average molecular weight Mn = 8000, molecular weight distribution (Mw / Mn) = 1.20) of poly (4-ethylene-1-naphthalenesulfonate) was obtained.

Subsequently, the following materials were dissolved in DMF (110 g) and polymerized at 120 ° C. for 6 hours in a nitrogen atmosphere.
Macroinitiator (starting species) poly (4-ethylene-1-naphthalene sulfonate ethyl) (25 g),
Styrene (86 g),
2,2′-azobisisobutyronitrile (0.5 g),
TEMPO (0.5 g),
Ziclel peroxide (0.2g)
As a result, the following formula (X):

The block copolymer (88g) which contains the unit shown in content ratio (mol%) (M23) :( F23) = 87: 13 was obtained. The number average molecular weight Mn was 30000, and the molecular weight distribution (Mw / Mn) was 1.25.

(Example Y-1)
In an ice bath, the mixture is stirred while slowly dropping fuming sulfuric acid (40 g) into (2-bromoethyl) benzene (100 g). After dropping, the mixture is stirred at 0 ° C. for 20 hours. A mixture of 2- (2-bromoethyl) benzenesulfonic acid, 3- (2-bromoethyl) benzenesulfonic acid and 4- (2-bromoethyl) benzenesulfonic acid can be obtained, and these mixtures are separated by a silica gel column. Purify. Next, 2- (2-bromoethyl) benzenesulfonic acid (10 g) is slowly added dropwise to a 1 mol / L aqueous sodium hydroxide solution (100 mL) and stirred at room temperature for 1 hour. Thereafter, the mixture is refluxed for 4 hours, and sodium o-styrenesulfonate can be obtained by dehydrobromination reaction. Next, sodium o-styrenesulfonate is desalted using an ion exchange resin. At that time, methyl o-styrenesulfonate can be synthesized with reference to SYNTHETIC COMMUNICATIONS, 15 (12), 21, 1057-1062 (1985). Under a nitrogen stream, desalted sodium o-styrenesulfonate (5 g), trimethyl orthoformate (50 mL) and p-benzoquinone as a polymerization inhibitor are placed in a flask and heated at 70 ° C. for 5 hours. The reaction mixture is cooled and concentrated under reduced pressure. Wash twice with 3 L of water, wash twice with 3 L of hexane, redissolve in chloroform, then dry over anhydrous magnesium sulfate, and remove the solvent.

The structure of the resulting compound is determined by ¹ H-NMR, and a peak derived from methyl sulfonate is observed at 3 to 4 ppm, so that it can be confirmed that the sulfonic acid is methyl sulfonate. Furthermore, it can be confirmed that the sulfonic acid is methyl sulfonate because the equivalent point derived from the sulfonic acid is not observed by acid value titration using a potentiometric titrator.

(Example Y-2)
The 3- (2-bromoethyl) benzenesulfonic acid obtained in Example Y-1 can be dehydrobrominated in the same manner as in Example Y-1 to obtain sodium m-styrenesulfonate. .

  Next, in the same manner as in Example Y-1, methyl m-styrene sulfonate can be obtained by methyl esterifying a desalted form of sodium m-styrene sulfonate with trimethyl orthoformate.

(Example Z-1)
In an ice bath, 1- (2-bromoethyl) naphthalene (120 g) is stirred while slowly dropping fuming sulfuric acid (50 g). After the dropwise addition, the mixture is stirred at 0 ° C. for 24 hours to obtain 4- (2-bromoethyl) naphthalenesulfonic acid.

  Next, 4- (2-bromoethyl) naphthalenesulfonic acid (10 g) is slowly added dropwise to a 1 mol / L sodium hydroxide aqueous solution (100 mL), and the mixture is stirred for 1 hour at room temperature. Thereafter, the mixture is refluxed for 6 hours, and sodium 4-ethenylnaphthalenesulfonate can be obtained by dehydrobromination reaction.

  Next, sodium 4-ethenylnaphthalenesulfonate is desalted using an ion exchange resin, and methyl esterification is performed in the same manner as in Example Y-1 to synthesize methyl 4-ethenylnaphthalenesulfonate. it can.

(Example Z-2)
In an ice bath, stirring is performed while slowly adding dropwise fuming sulfuric acid (50 g) to 2- (2-bromoethyl) naphthalene (120 g). After dropping, the mixture is stirred at 0 ° C. for 30 hours to obtain 2- (2-bromoethyl) naphthalenesulfonic acid and a plurality of isomers, which are separated and purified.

  Next, 2- (2-bromoethyl) naphthalenesulfonic acid (5 g) is slowly added dropwise to a 1 mol / L sodium hydroxide aqueous solution (50 mL), and the mixture is stirred for 1 hour at room temperature. Thereafter, the mixture is refluxed for 6 hours, and sodium 2-ethenylnaphthalenesulfonate can be obtained by a dehydrobromination reaction.

  Next, sodium 2-ethenylnaphthalenesulfonate is desalted using an ion exchange resin and methyl esterified in the same manner as in Example Z-1 to synthesize methyl 2-ethenylnaphthalenesulfonate. it can.

  Next, various toners were produced using the produced charge control agent made of a polymer, and evaluated (Examples 1 to 34). In addition, the polymer manufactured by Example AX is described as exemplary compound AX, respectively.

Example 1
First, an aqueous Na ₃ PO ₄ solution was added to a 2-liter four-necked flask equipped with a high-speed stirrer TK-homomixer, the rotation speed was adjusted to 10,000 rpm, and the mixture was heated to 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 using a ball mill, 10 parts by weight of a release agent (carnauba wax, melting point 83 ° C.) and 2,2′-azobis (2,4-dimethylvalero) which is a polymerization initiator. (Nitrile) 10 parts by mass 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: 2 parts by mass Next, the polymerizable monomer composition obtained above was charged into the aqueous dispersion medium prepared above and rotated. Granulation was performed while maintaining a number 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 Inc.) is a weight average particle size of 7.0 μm and the amount of fine powder (abundance of particles of 3.17 μm or less in the number distribution) Was 5.1% by number.

100 parts by weight of the blue polymer particles prepared above (1) 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 And add it. 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)
Blue toners (2) to (5) of Examples 2 to 5 were obtained in the same manner as in Example 1 except that Exemplified Compound A was changed to Exemplified Compounds F, K, P, and U, respectively. 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 the exemplified compound 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.

<Evaluation>
With respect to the two-component blue developers (1) to (5) obtained in Examples 1 to 5 and the two-component blue developer (6) obtained in Comparative Example 1, the toner charge amount was measured. Specifically, in the respective environments of normal temperature and normal humidity (25 ° C., 60% RH) and high temperature and high humidity (30 ° C., 80% RH), 10 The charge amount of the toner after stirring for 300 seconds and 300 seconds 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 (-20 μC / g or less)
○: Good (-19.9 to -10.0μC / g)
Δ: Practical use possible (-9.9 to -5.0μC / g)
×: Not practical (-4.9μC / g or more)
(Examples 6 to 10)
Example Compound B, G, M, Q, and V were used in the same manner as in Example 1 except that 2.0 parts by mass of each of Exemplified Compounds B, G, M, Q, and V were used, and a yellow colorant (Hansa Yellow G) was used instead of the cyan colorant. 6 to 10 yellow (yellow) toners (1) to (5) 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)
A yellow (yellow) toner (6) of Comparative Example 2 was obtained in the same manner as in Example 1 except that the exemplified compound was not used and a yellow colorant (Hansa Yellow G) was used instead of the cyan colorant. It was. 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.

<Evaluation>
The two-component yellow (yellow) developers (1) to (5) obtained in Examples 6 to 10 and the two-component yellow (yellow) developer (6) obtained in Comparative Example 2 were used. In the same manner as in Example 1, the charge amount of the toner was measured and evaluated. The results are summarized in Table 1.

(Examples 11 to 15)
Except for using 2.0 parts by mass of each of Exemplified Compounds C, H, L, R, and W, and using carbon black (DBP oil absorption 110 mL / 100 g) instead of the cyan colorant, the same method as in Example 1, 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)
A black toner (6) of Comparative Example 3 was obtained in the same manner as in Example 1 except that the exemplified compound was not used and carbon black (DBP oil absorption 110 mL / 100 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. In addition, using this, the two-component black developer (6) of Comparative Example 3 was obtained in the same manner as in Example 1.

<Evaluation>
The two-component black developers (1) to (5) obtained in Examples 11 to 15 and the two-component black developer (6) obtained in Comparative Example 3 are the same as in Example 1. The amount of charge was measured and evaluated. The results are summarized in Table 1.

(Example 16)
・ Styrene-butyl acrylate copolymer resin (glass transition temperature 70 ° C .: 100 parts by mass) • Magenta pigment (C.I. Pigment Red 114): 5 parts by mass • Wax (low molecular polyethylene melting point 94 ° C.): 7 parts by mass Compound D: 2 parts by mass The above composition was mixed and melt-kneaded with a biaxial extruder (L / D = 30) After cooling, this kneaded product was coarsely pulverized with a hammer mill and finely pulverized with a jet mill. Thus, magenta colored particles (1) were obtained by a pulverization method, and the magenta colored particles (1) had a weight average particle size of 7.1 μm and a fine powder amount of 5.1% by 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.

(Examples 17 to 20)
Magenta (red) toners (2) to (5) of Examples 17 to 20 were obtained in the same manner as in Example 16 except that Exemplified Compound D was changed to Exemplified Compounds I, N, S, and X, respectively. 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 the exemplified compound 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.

<Evaluation>
The two-component magenta (red) developers (1) to (5) obtained in Examples 16 to 20 and the two-component magenta (red) developer (6) obtained in Comparative Example 4 were used. In the same manner as in Example 1, the charge amount of the toner was measured and evaluated. The results are summarized in Table 1.

(Example 21)
Polyester resin: 100 parts by mass Carbon black (DBP oil absorption 110 mL / 100 g): 5 parts by mass Wax (low molecular polyethylene melting point 94 ° C): 7 parts by mass Compound E: 2 parts by mass The polyester resin is as follows And synthesized. 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 (7) by a pulverization method. The black colored particles (7) had a weight average particle size of 7.3 μm and a fine powder amount of 5.1% by number.

To 100 parts by mass of these black colored particles (7), 1.5 parts by mass of 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 (7) of this example was obtained. Further, 7 parts by mass of the obtained black toner (7) 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 (7) for magnetic brush development. Prepared.

(Examples 22 to 24)
Black toners (8) to (10) of Examples 22 to 24 were obtained in the same manner as in Example 21 except that Exemplified Compound E was changed to Exemplified Compounds J, O, and T, respectively. 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 21, the two-component black developers (8) to (10) of Examples 22 to 24 were obtained.

(Comparative Example 5)
A black toner (11) of Comparative Example 5 was obtained in the same manner as in Example 21 except that the exemplified compound 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 (11) of Comparative Example 5 was obtained in the same manner as in Example 21.

<Evaluation>
The two-component black developers (7) to (10) obtained in Examples 21 to 24 and the two-component black developer (11) obtained in Comparative Example 5 are the same as in Example 1. The amount of charge was measured and evaluated. The results are summarized in Table 1.

(For convenience, yellow is called yellow and magenta is called red)
Examples 25 to 30 and Comparative Examples 6 to 10
First, LBP5500 (trade name, manufactured by Canon Inc.) was used as an image forming apparatus used in the image forming methods of Examples 25 to 30 and Comparative Examples 6 to 10.

  At that time, a toner image was formed with the yellow toner, magenta toner, cyan toner or black toner obtained in Examples 1, 6, 11, 16, 21, 24 and Comparative Examples 1 to 5 as a developer.

<Evaluation>
While performing replenishment, a printout test was performed in a single-color intermittent mode (i.e., a mode in which the developer is paused for 10 seconds each time a single printout is made, and toner deterioration is promoted by a preliminary operation upon restart). . The LBP5500 was remodeled so that the printout speed was 8 sheets (A4 size) / min under normal temperature and humidity (25 ° C, 60% RH) and high temperature and high humidity (30 ° C, 80% RH). did. The toners of Examples 1, 6, 11, 16, 21, and 24 and the toners of Comparative Examples 1 to 5 were used, respectively. The obtained printout images were evaluated for the following items. 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 the 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. Evaluation was made 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 of 0% to less than 1.5%)
○: Good (fogging amount 1.5% or more and less than 3.0%)
△: Practical use (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 25 to Example 30 and Comparative Example 6 to Comparative Example 10, 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 the image forming apparatus) were visually evaluated. In the systems using the toners of Examples 25 to 30, no scratches on the surface of the photosensitive drum and the intermediate transfer member and no adhesion of residual toner were confirmed, and the matching with the LBP 5500 was very good.

  On the other hand, in all of the systems using the toners of Comparative Examples 6 to 10, the toner adhered to the photosensitive drum surface. Further, in the system using the toners of Comparative Examples 6 to 10, it is possible to confirm toner fixation and surface scratches on the surface of the intermediate transfer member, and to cause vertical streak-like image defects on the image. There was a problem in matching.

(Example 31 to Example 33, Comparative Example 11 to Comparative Example 13)
In carrying out the image forming methods of Examples 31 to 33 and Comparative Examples 11 to 13, the toners obtained in Examples 1, 6, 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 collected toner) to the LBP 5500 is used.

  Under normal temperature and humidity (25 ° C, 60% RH) environment, with continuous printout of toner at a printout speed of 8 sheets (A4 size) / min. Print out up to 30,000 sheets in the mode to promote. 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 appearance of each device constituting the LBP 5500 after the endurance test was observed, and the matching between each device and each toner was also evaluated. The above results are summarized in Table 3.

[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) 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 the 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 (trade name: REFLECTOMETER MODEL TC-6DS manufactured by TOKYO DENSHOKU CO., LTD).

[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)
Δ: Practical use possible (although there is sticking, there is little effect on the image)
×: Not practical (much sticking and causes 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 stuck or scratched, but has little effect on the image)
×: Impossible to practical use (there is a lot of sticking and causes 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 ×: Impractical use
(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 ×: Impractical use

(Example 34)
The same procedure as in Example 31 was performed, except that the toner reuse mechanism of LBP5500 was removed and the printout speed was changed to 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 obtained printout image and matching with the used LBP5500 were evaluated for the same items as in Example 31 to Example 33 and Comparative Example 11 to Comparative Example 13. As a result, good results were obtained for all items.

  The present invention can be used for a charge control agent contained in a toner used in electrophotographic technology.

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 (7)

The charge control agent which controls the charge state of a granular material consists of a polymer which has a unit shown by Chemical formula (8), The charge control agent characterized by the above-mentioned.

( _Wherein R _8w and R _8x are each independently a halogen atom or a hydrogen atom. R _8y is a CH ₃ group or a hydrogen atom. R _8a , R _8b , R _8c , R _8d and R _8e are Each independently SO ₃ R _8f (R _8f is a linear or branched alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure) , A hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkoxy group having 1 to 8 carbon atoms, and R _8a , R _8b , R _8c , R _8d and R _8e At least one is SO ₃ R _8f .) The charge control agent which controls the charge state of a granular material consists of a polymer which has a unit shown by Chemical formula (9), The charge control agent characterized by the above-mentioned.

(In the formula, R _9w and R _9x are each independently a halogen atom or a hydrogen atom. R _9y is a CH ₃ group or a hydrogen atom. R _9a , R _9b , R _9c , R _9d , R _9e , R _9f and R _9g are each independently SO ₃ R _9h (R _9h is a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aromatic ring structure, An unsubstituted heterocyclic structure), a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkoxy group having 1 to 8 carbon atoms, R _9a , R _9b , At least one of R _9c , R _9d , R _9e , R _9f and R _9g is SO ₃ R _9h .) The charge control agent which controls the charge state of a granular material consists of a polymer which has a unit shown by Chemical formula (10), The charge control agent characterized by the above-mentioned.

(Wherein R _10w and R _10x are each independently a halogen atom or a hydrogen atom. R _10y is a CH ₃ group or a hydrogen atom. R _10a , R _10b , R _10c , R _10d , R _10e , R _10f and R _10g are each independently SO ₃ R _10h (where R _10h is a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a substituted or unsubstituted aromatic ring structure, An unsubstituted heterocyclic structure), a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkoxy group having 1 to 8 carbon atoms, R _10a , R _10b , (At least one of R _10c , R _10d , R _10e , R _10f and R _10g is independently SO ₃ R _10h .) The charge control agent according to any one of claims 1 to 3 , wherein the charge control agent comprises a copolymer having a unit represented by the chemical formula (11).

(Wherein R _11w and R _11x each independently represent a halogen atom or a hydrogen atom. R _11y represents a CH ₃ group, a halogen atom or a hydrogen atom. R ₁₁ represents a hydrogen atom, a substituted or an Substituted aliphatic hydrocarbon structure, substituted or unsubstituted aromatic ring structure (wherein SO ₃ R _11z (R _11z is a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, substituted or unsubstituted) Or a substituted or unsubstituted heterocyclic structure), a substituted or unsubstituted heterocyclic structure, a halogen atom, —CO—R _11a , — It is a ring structure containing O—R _11b , —COO—R _11c , —OCO—R _11d , —CONR _11e R _11f , —CN, or N. R _11a , R _11b , R _11c , R _11d , R _11e and R _11f are each, independently, water Atom, aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure or a substituted or unsubstituted, or a substituted or unsubstituted heterocyclic ring structure.) Charge control agent according to any one of claims 1 to 3 molecular weight distribution (weight average molecular weight / number average molecular weight = Mw / Mn) is 1 <Mw / Mn <2 of the polymer. Charge control agent according to any one of claims 1 to 5 wherein the polymer is a block copolymer. An electrostatic charge image developing toner comprising at least a binder resin, a colorant, and the charge control agent according to any one of claims 1 to 6 .

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