JP5328097B2 - Polymer having sulfonic acid group or sulfonic acid ester group and amide group, and electrostatic image developing toner having the polymer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new polymer having a sulfonic acid group or a sulfonic ester group and an amide group and to provide a method for producing the polymer. <P>SOLUTION: The polymer has a unit. Furthermore, the unit is represented by chemical formula (1) (wherein, R represents an -A<SB>1</SB>-SO<SB>2</SB>R<SB>1</SB>; R<SB>1w</SB>and R<SB>1x</SB>represent each independently a halogen atom or a hydrogen atom; R<SB>1y</SB>is a CH<SB>3</SB>group, a halogen atom or a hydrogen atom; A<SB>01</SB>is a substituted or an unsubstituted aromatic ring structure; A<SB>1</SB>is a substituted or an unsubstituted aromatic ring structure; R<SB>1</SB>is an OH, a halogen atom, an ONa, an OK or an OR<SB>1a</SB>; and R<SB>1a</SB>is a substituted or an unsubstituted aliphatic hydrocarbon structure). <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  The present invention relates to a novel polymer having a sulfonic acid group or a sulfonic acid ester group and an amide group. Moreover, this invention relates to the novel compound used in order to manufacture the said novel polymer. Furthermore, the present invention relates to an electrostatic image developing toner having the novel polymer.

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, in the following Patent Document 1 (Japanese Patent Laid-Open No. 2002-351147), as an example of sulfonated styrene, a copolymer of acrylamidomethylpropane sulfonate and another vinyl monomer copolymerizable therewith is disclosed. It is disclosed.
JP 2002-351147 A

  However, it cannot be said that sulfonated styrene alone can sufficiently cope with the various uses described above, and further improvements and development of new polymers are required.

  In view of the above-mentioned background art, an object of the present invention is to provide a novel polymer having a sulfonic acid group or a sulfonic acid ester group and an amide group and a method for producing the same. Another object of the present invention is to provide a novel compound for producing the polymer. Still another object of the present invention is to provide an electrostatic image developing toner using the polymer.

  Therefore, as a result of intensive studies aimed at developing a novel polymer into which a hydrophilic group or a polar group is introduced, the present inventors are thought to be useful for improving various functions. The invention as shown in FIG.

The polymer according to the present invention is a polymer characterized by being a copolymer of a unit represented by the chemical formula (1) and a unit represented by the chemical formula (101) .

(In the formula, R represents —A ₁ —SO ₂ R _1. R _1w and R _1X each independently represent a halogen atom or a hydrogen atom. R _1y represents a CH ₃ group, a halogen atom, or hydrogen. Is an atom.
A ₀₁ is a substituted or unsubstituted aromatic ring structure or a substituted or unsubstituted heterocyclic ring structure.
A ₁ is a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure.
R ₁ is OH, a halogen atom, ONa, OK or OR _1a . R _1a is a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure . )

(In the formula, R represents —A ₂₀₁ —SO ₂ R _201. R _201w and R _201X each independently represent a halogen atom or a hydrogen atom. R _201y represents a CH ₃ group, a halogen atom, or a hydrogen atom. Is an atom.
A ₀₂₀₁ is a substituted or unsubstituted aromatic ring structure or a substituted or unsubstituted heterocyclic structure.
A ₂₀₁ is a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure.
R ₂₀₁ is OH, a halogen atom, ONa, OK or OR _201a . R _201a is a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure. )
Moreover, the following manufacturing methods are mentioned as another aspect of the manufacturing method of the polymer concerning this invention. That is, the polymer containing a unit represented by the chemical formula (301) and at least one amine compound represented by the chemical formula (302) are subjected to a condensation reaction to obtain a polymer containing the unit represented by the chemical formula (1). Manufacturing method.

( _Wherein R _301w and R _301x are each independently a halogen atom or a hydrogen atom. R _301y is a CH ₃ group, a halogen atom or a hydrogen atom. R ₃₀₁ is an H atom, a Na atom or K An atom.)

(Wherein R ₃₀₂ is OH, a halogen atom, ONa, OK or OR _302a . A ₃₀₂ and R _302a each independently represents a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic, An aromatic ring structure, or a substituted or unsubstituted heterocyclic structure.)
In another aspect of the method for producing a polymer according to the present invention, the polymer containing the unit represented by the chemical formula (303) is esterified using an esterifying agent to obtain a polymer containing the unit represented by the chemical formula (304). A characteristic production method is mentioned.

(In the formula, R represents —A ₃₀₃ —SO ₂ R _303. R _303w and R _303X each independently represents a halogen atom or a hydrogen atom. R _303y represents a CH ₃ group, a halogen atom, or a hydrogen atom. Is an atom.
A ₀₃₀₃ is a substituted or unsubstituted aromatic ring structure or a substituted or unsubstituted heterocyclic structure.
A ₃₀₃ is a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure. R ₃₀₃ is OH, a halogen atom, ONa or OK. )

(In the formula, R represents —A ₃₀₄ —SO ₃ R _304. R _304w and R _304X each independently represent a halogen atom or a hydrogen atom. R _304y represents a CH ₃ group, a halogen atom, or hydrogen. Is an atom.
A ₀₃₀₄ is a substituted or unsubstituted aromatic ring structure or a substituted or unsubstituted heterocyclic ring structure.
A ₃₀₄ is a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure.
R ₃₀₄ is a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure. )
The charge control agent of the present invention is a charge control agent that controls the charge state of a powder and is characterized by containing at least one of the above polymers.

Electrostatic image developing toner of the present invention, even without low, a binder resin and a colorant, by containing a polymer having a unit represented by the electrostatic image developing toner, wherein in Formula (1) is there. In this case, the polymer should function as a charge control agent in the toner.

  The present invention provides novel polymers and novel compounds for making the polymers. In addition, an electrostatic charge image developing toner using the polymer can be provided.

(Polymer and compound according to the present invention)
The polymer which concerns on 1st this invention is characterized by including 1 unit or more of structures shown by Chemical formula (1) described previously. In particular, it is preferable to include this unit 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.

  As the unit represented by the chemical formula (1) of the polymer according to the present invention, units represented by the following chemical formulas (2) to (11) are preferable.

(In the formula, R represents —A ₂ —SO ₂ R _2. R _2w and R _2X each independently represent a halogen atom or a hydrogen atom. R _2y represents a CH ₃ group, a halogen atom, or hydrogen. Is an atom.
A ₀₂ is a substituted or unsubstituted aromatic ring structure or a substituted or unsubstituted heterocyclic ring structure.
A ₂ is a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure. R ₂ is OH, a halogen atom, ONa, OK or OR _2a .
R _2a is a linear or branched alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted phenyl group. )

(In the formula, R represents —A ₃ —SO ₂ R _3. R _3w and R _3X each independently represent a halogen atom or a hydrogen atom. R _3y represents a CH ₃ group, a halogen atom, or hydrogen. Is an atom.
A ₀₃ is a substituted or unsubstituted phenylene group or a substituted or unsubstituted naphthylene group.
A ₃ is a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure.
R ₃ is OH, a halogen atom, ONa, OK or OR _3a .
R _3a is a linear or branched alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted phenyl group. )

(In the formula, R represents —A ₄ —SO ₂ R _4. R _4w and R _4X each independently represent a halogen atom or a hydrogen atom. R _4y represents a CH ₃ group, a halogen atom, or hydrogen. Is an atom.
A ₀₄ is a substituted or unsubstituted phenylene group. Substituents are halogen atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, OH groups, NH ₂ groups, NO ₂ groups, COOR _4g (R _4g : H atom, Na atom, K atom At least one selected from the group consisting of an acetamide group, an OPh group, an NHPh group, a CF ₃ group, a C ₂ F ₅ group, and a C ₃ F ₇ group.
A ₄ is a linear or branched alkyl group having 1 to 8 carbon atoms.
R ₄ is OH, a halogen atom, ONa, OK or OR _4a .
R _4a is a linear or branched alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted phenyl group. )

(In the formula, R _5w and R _5X each independently represent a halogen atom or a hydrogen atom. R _5y represents a CH ₃ group, a halogen atom, or a hydrogen atom.
A ₀₅ is a substituted or unsubstituted phenylene group. Substituents are halogen atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, OH groups, NH ₂ groups, NO ₂ groups, COOR _05g (R _05g : H atom, Na atom, K atom At least one selected from the group consisting of an acetamide group, an OPh group, an NHPh group, a CF ₃ group, a C ₂ F ₅ group, and a C ₃ F ₇ group. Ph represents a phenyl group (the same applies in each formula).
R _5a , R _5b , R _5c , R _5d and R _5e are each independently SO ₂ R _5f (R _5f is OH, halogen atom, ONa, OK or OR _5h . R _5h is linear or branched. An alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted phenyl group), a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an OH group, NH ₂ group, NO ₂ group, COOR _5g (R _5g : any one of H atom, Na atom and K atom), acetamide group, OPh group, NHPh group, CF ₃ group, C ₂ F ₅ group or C ₃ F ₇ group, and at least one of R _5a , R _5b , R _5c , R _5d and R _5e is SO ₂ R _5f . )

( _Wherein R _6w and R _6X are each independently a halogen atom or a hydrogen atom. R _6y is a CH ₃ group, a halogen atom or a hydrogen atom.
A _06a is a substituted or unsubstituted phenylene group. The substituent is a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, OH group, NH ₂ group, NO ₂ group, COOR _06ag (R _06ag : H atom, Na atom, K atom At least one selected from the group consisting of an acetamide group, an OPh group, an NHPh group, a CF ₃ group, a C ₂ F ₅ group, and a C ₃ F ₇ group. R _6a , R _6b , R _6c , R _6d , R _6e , R _6f and R _6g are each independently SO ₂ R _6o (R _6o is OH, a halogen atom, ONa, OK or OR _6s . R _6s Represents a linear or branched alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted phenyl group.), Hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms Group, OH group, NH ₂ group, NO ₂ group, COOR _6p (R _6p : any one of H atom, Na atom and K atom), acetamide group, OPh group, NHPh group, CF ₃ group, C ₂ F ₅ group or C ₃ F ₇ group, and at least one of R _6a , R _6b , R _6c , R _6d , R _6e , R _6f and R _6g is SO ₂ R _6o . )

(In the formula, R _6v and R _6u are each independently a halogen atom or a hydrogen atom. R _6z is a CH ₃ group, a halogen atom, or a hydrogen atom.
A _06b is a substituted or unsubstituted phenylene group. Substituents are halogen atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, OH groups, NH ₂ groups, NO ₂ groups, COOR _06br (R _06br : H atom, Na atom, K atom) At least one selected from the group consisting of an acetamide group, an OPh group, an NHPh group, a CF ₃ group, a C ₂ F ₅ group, and a C ₃ F ₇ group.
R _6h , R _6i , R _6j , R _6k , R _6l , R _6m and R _6n are each independently SO ₂ R _6q (R _6q is OH, a halogen atom, ONa, OK or OR _6t . R _6t Represents a linear or branched alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted phenyl group.), Hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms Group, OH group, NH ₂ group, NO ₂ group, COOR _6r (R _6r : any one of H atom, Na atom and K atom), acetamide group, OPh group, NHPh group, CF ₃ group, C ₂ F ₅ group or C ₃ F ₇ group, and at least one of R _6h , R _6i , R _6j , R _6k , R _6l , R _6m and R _6n is SO ₂ R _6q . )

(Wherein R _7w and R _7X each independently represent a halogen atom or a hydrogen atom. R _7y represents a CH ₃ group, a halogen atom or a hydrogen atom. R _7a represents OH, a halogen atom, ONa, OK or OR _7b .
R _7b is a linear or branched alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted phenyl group. )

( _Wherein R _8w and R _8X are each independently a halogen atom or a hydrogen atom. R _8y is a CH ₃ group, a halogen atom or a hydrogen atom. R _8a is OH, a halogen atom, ONa, OK or OR _8b .
R _8b is a linear or branched alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted phenyl group. )

(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, a halogen atom, or a hydrogen atom.
R _9a is OH, a halogen atom, ONa, OK or OR _9b .
R _9b is a linear or branched alkyl group having 1 to 8 carbon atoms, or a substituted or unsubstituted phenyl group. )

(Wherein R _10w and R _10X each independently represent a halogen atom or a hydrogen atom. R _10y represents a CH ₃ group, a halogen atom or a hydrogen atom. R _10a represents OH, a halogen atom, ONa, OK or OR _10b .
R _10b is a linear or branched alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted phenyl group. )

(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 _11a represents OH, a halogen atom, ONa, OK or OR _11b .
R _11b is a linear or branched alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted phenyl group. )
Polymer according to the present invention, for example, in addition to the unit represented by the chemical formula (2) to (11) formula, such as (1) a copolymer comprising at least one unit derived from a vinyl monomer represented by the chemical formula (101) is there.

(In the formula, R _101w and R _101x are each independently a halogen atom or a hydrogen atom. R _101y is a CH ₃ group, a halogen atom, or a hydrogen atom. R ₁₀₁ is a hydrogen atom, substituted or unsubstituted. Aliphatic hydrocarbon structure, substituted or unsubstituted aromatic ring structure, substituted or unsubstituted heterocyclic structure, halogen atom, —CO—R _101a , —O—R _101b , —COO—R _101c , —OCO— R _101d , —CONR _101e R _101f , —CN, or any ring structure containing an N atom R _101a , R _101b , R _101c , R _101d , R _101e and R _101f are each independently a hydrogen atom , A substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure, provided that the unit represented by the chemical formula (101) includes the above chemical formula ( Units that can be indicated in 1) include I can't go wrong.)
In the present invention, the proportion of the copolymer unit having the unit represented by the chemical formula (1) and the unit derived from the vinyl monomer represented by the chemical formula (101) is 0.1 for the unit represented by the chemical formula (1). It is -100 mol%, More preferably, it is 1.0-50 mol%.

The molecular weight distribution (weight average molecular weight / number average molecular weight = Mw / Mn) of the polymer according to the present invention can be 1 <Mw / Mn <10, and preferably 1 <Mw / Mn <2.

The copolymer comprising the unit represented by the chemical formula (1) and the unit derived from the vinyl monomer represented by the chemical formula (101), which is the polymer of the present invention, can be a block copolymer. The number average molecular weight of the polymer according to the present invention is preferably 1,000 to 1,000,000.

  Examples of the compound that can be used as a monomer for producing a polymer according to the present invention include a compound having a structure represented by the chemical formula (201).

(In the formula, R represents —A ₂₀₁ —SO ₂ R _201. R _201w and R _201X each independently represent a halogen atom or a hydrogen atom. R _201y represents a CH ₃ group, a halogen atom, or a hydrogen atom. Is an atom.
A ₀₂₀₁ is a substituted or unsubstituted aromatic ring structure or a substituted or unsubstituted heterocyclic structure.
A ₂₀₁ is a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure.
R ₂₀₁ is OH, a halogen atom, ONa, OK or OR _201a . R _201a is a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure. )
Examples of the compound that can be used as a monomer for producing a polymer according to the present invention include a compound having a structure represented by the chemical formula (202).

(In the formula, R represents —A ₂₀₂ —SO ₂ R _202. R _202w and R _202X each independently represent a halogen atom or a hydrogen atom. R _202y represents a CH ₃ group, a halogen atom, or a hydrogen atom. Is an atom.
A ₀₂₀₂ is a substituted or unsubstituted aromatic ring structure or a substituted or unsubstituted heterocyclic structure.
A ₂₀₂ is a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure. R ₂₀₂ is OH, a halogen atom, ONa, OK or OR _202a . R _202a is a methyl group, an ethyl group, or a phenyl group. )
(Production method)
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 (201).

  In addition, the polymer including the unit represented by the chemical formula (1) according to the present invention is obtained by condensation reaction of a polymer including the unit represented by the chemical formula (301) and at least one amine compound represented by the chemical formula (302). be able to.

  In the method for producing a polymer containing a unit represented by the chemical formula (1), it is preferable to form an amide bond in the same reaction field using a condensing agent. As the condensing agent in this case, a phosphoric acid condensing agent can be used. Further, the condensation reaction can be further performed in the presence of pyridine.

  In addition, the polymer containing the unit represented by the chemical formula (304) according to the present invention can be obtained by esterifying the polymer containing the unit represented by the chemical formula (303) using an esterifying agent.

  Examples of the esterifying agent employed in the method for producing a polymer including a unit represented by the chemical formula (304) include trimethylsilyldiazomethane, trimethyl orthoformate, triethyl orthoformate, tributyl orthoformate, and tripropyl orthoformate.

(Charge control agent)
The charge control agent which concerns on this invention controls the charge state of a granular material, and contains the polymer which has a unit of the structure shown to Chemical formula (1), It is characterized by the above-mentioned. Examples of this polymer include a copolymer of a unit having a structure represented by the chemical formula (1) and a unit represented by the chemical formula (101) .

  The powder is preferably an electrostatic charge image developing toner.

  Furthermore, as the unit represented by the chemical formula (1) of the polymer constituting the charge control agent, units represented by the chemical formulas (2) to (11) can be used.

(More specific production method of the polymer according to the present invention)
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 configurations has extremely excellent characteristics as a charge control agent. Furthermore, an electrostatic charge image developing toner containing a charge control agent using this polymer has a remarkable effect when used in an image forming apparatus having a developing system by electrophotography. The following method can be illustrated as a manufacturing method of this polymer.

  For example, a polymer having a unit represented by the chemical formula (1) is produced by a reaction between a polymer having a unit represented by the chemical formula (301) used as a starting material and at least one compound represented by the chemical formula (302).

  In this method, a polymer having a unit represented by the chemical formula (301) having a molecular weight distribution of 1 <Mw / Mn <2 is used as a starting material, so that the molecular weight distribution is within the above range (1) It is possible to synthesize a polymer having a unit represented by

  Further, a block copolymer composed of a unit represented by the chemical formula (301) and a unit derived from the vinyl monomer represented by the chemical formula (101) can be used as a starting material. In such a case, it is possible to synthesize a block copolymer composed of a unit represented by the chemical formula (1) and a unit derived from the vinyl monomer represented by the chemical formula (101).

(Method for producing polymer containing unit represented by chemical formula (301))
The polymer having a carboxyl group represented by the chemical formula (301) has a vinyl monomer unit represented by the chemical formula (101) in addition to the unit of the chemical formula (301) by using a known polymerization method and polymer reaction. It can also be produced as a copolymer.

  In addition, examples of the vinyl monomer for introducing the unit represented by the chemical formula (101) include the following compounds. Styrene and its derivatives, ethylenically unsaturated monoolefins, vinyl halides, vinyl ester acids, α-methylene aliphatic monocarboxylic esters, vinyl ethers, acrylic acid or methacrylic acid derivatives.

  A polymer having a vinyl benzoic acid unit can be obtained as follows. As a polymer having a carboxyl group represented by the chemical formula (301), a monomer in which a protecting group is introduced into the carboxylic acid of vinyl benzoic acid is synthesized and polymerized, and then the polymer is reacted to remove the protecting group, thereby producing vinyl. A polymer having benzoic acid units is obtained.

  Further, by using the living polymerization method, it is possible to synthesize a polymer having a unit represented by the chemical formula (301) having a molecular weight distribution of 1.00 <Mw / Mn <2.00.

  Below, the case where atom transfer radical polymerization and nitroxide mediated polymerization are used as living radical polymerization is demonstrated, for example.

  First, the case where living radical polymerization is atom transfer radical polymerization will be described.

  In atom transfer radical polymerization, for example, when a copper halide-bipyridyl complex is used, a polymer having a narrow molecular weight distribution can be obtained by a rapid transfer reaction of the polymer chain end. As the reaction solvent, for example, dimethyl sulfoxide, dimethylformamide and the like 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. Utilizing this property, a polymer having a narrow molecular weight distribution can be obtained by nitroxide-mediated polymerization using nitroxyl radical using benzoyl peroxide (BPO) or azobisisobutyronitrile (AIBN) 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 and the like can be used.

  Moreover, the block copolymer which consists of the unit represented by Chemical formula (301) and the unit derived from the vinyl-type monomer shown by Chemical formula (101) uses the living polymerization method in a well-known polymerization method, It is possible to synthesize. In particular, living radical polymerization is relatively easy among living polymerization methods.

  Specifically, after a homopolymer having a structure represented by the chemical formula (301) is formed by living radical polymerization, a polymer having a structure represented by the chemical formula (101) is copolymerized by living radical polymerization at one end of the homopolymer. By carrying out like this, the precursor of the target block copolymer can be obtained. Note that the order of forming the block copolymers may be reversed.

  This living radical polymerization, preferably atom transfer radical polymerization and nitroxide-mediated polymerization can be carried out in the same manner as in the case of the polymer having the unit of the chemical formula (301).

(Compound shown in chemical formula (302))
As the compound represented by the chemical formula (302) used in the present invention, A ₃₀₂ may be the following compound. That is, A ₃₀₂ is any one of a linear or branched alkylene group having 1 to 8 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted N, S, or O. The compound may represent a heterocyclic structure containing two or more. When A ₃₀₂ is a ring structure, the unsubstituted ring may be further condensed. Specific examples when A ₃₀₂ is a straight-chain or branched alkylene group compound having 1 to 8 carbon atoms include the following. That is, 2-aminoethanesulfonic acid (taurine), 3-aminopropanesulfonic acid, 4-aminobutanesulfonic acid, 2-amino-2-methylpropanesulfonic acid, and alkali metal salts thereof.

When A ₃₀₂ is a substituted or unsubstituted phenyl group, it is represented by the chemical formula (26).

(Wherein R _26a , R _26b , R _26c , R _26d and R _26e are each independently SO ₂ R _26f (R _26f is OH, a halogen atom, ONa, OK or OR _26h . R _26h is Represents a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure.), A hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, OH groups, NH ₂ groups, NO ₂ groups, COOR _26g (R _26g:. of H atom, Na atom, or a K atom), an acetamide group, OPh group, NHPh group CF ₃ group, C ₂ F ₅ group or C ₃ F ₇ group, wherein at least one of R _26a , R _26b , R _26c , R _26d and R _26e is SO ₂ R _26f .)
Examples of the compound represented by the chemical formula (26) include various aminobenzenesulfonic acid derivatives such as p-aminobenzenesulfonic acid (sulfanilic acid) and salts thereof. Furthermore, esterified products such as methyl esterified products and phenyl esterified products of various aminobenzenesulfonic acid derivatives such as 2-aminobenzenesulfonic acid methyl ester are also included.

When A ₃₀₂ is a substituted or unsubstituted naphthyl group, it is represented by chemical formula (27a) or (27b).

_{(Wherein, R 27a, R 27b, R} 27c, R 27d, R 27e, R 27f and R _{27 g} are each independently, SO ₂ R _27o (R _27o represents OH, halogen atom, ONa, OK, or by OR _27s R _27s represents a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure.), Hydrogen atom, halogen atom, carbon number 1 ˜20 alkyl group, C 1-20 alkoxy group, OH group, NH ₂ group, NO ₂ group, COOR _27p (R _27p : represents any of H atom, Na child, K atom), acetamide group. , OPh group, NHPh group, CF ₃ group, C ₂ F ₅ group, or C ₃ F ₇ group, R _27a , R _27b , R _27c , R _27d , R _27e , R _27f , R _27g At least one is independently SO ₂ R _27o .)

(Wherein, R _27h, the _{R 27i, R 27j, R 27k} , R 27l, R 27m and R _27n are each independently _{SO 2 R 27q (R 27q OH} , is halogen atom, ONa, OK, or OR _{27 t} R _27t represents a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure.), Hydrogen atom, halogen atom, carbon number 1 to 20 alkyl groups, alkoxy groups having 1 to 20 carbon atoms, OH group, NH ₂ group, NO ₂ group, COOR _27r (R _27r represents any one of H atom, Na atom and K atom), acetamide group, OPh group, NHPh group, CF ₃ group, a C ₂ F ₅ group or a C ₃ F _{7 group, R 27h, R 27i, R} 27j, R 27k, R 27l, at least one SO of R _27m and R _{27n 2} R _27q .)
Examples of the compound represented by the chemical formula (27a) or (27b) include various naphthylamine sulfonic acid derivatives such as 1-naphthylamine-4-sulfonic acid and salts thereof. Furthermore, esterified products such as methyl esterified products and phenyl esterified products of various naphthylamine sulfonic acid derivatives such as 1-naphthylamine-8-sulfonic acid methyl ester are also included.

When A ₃₀₂ is a heterocyclic structure containing one or more of substituted or unsubstituted N, S, and O, a pyridine ring, a piperazine ring, a furan ring, a thiol ring, and the like can be given.

(Production method of polymer having at least one unit represented by chemical formula (1) in the molecule)
The condensation reaction of the polymer containing the unit represented by the chemical formula (301) and the aminosulfonic acid compound represented by the chemical formula (302) in the present invention will be described in detail.

  As the condensation reaction of a carboxyl group and an amino group, any of a method using a condensing agent, a method of forming a salt and performing condensation by a dehydration reaction, a method using a dehydrating agent, and the like can be used.

  As the production method of the present invention, a method using a condensing agent will be described in detail. As the condensing agent, a phosphoric acid condensing agent or the like can be used. In the reaction of the present invention, a phosphite-based condensing agent is preferably used. As the phosphites used at this time, triphenyl phosphite is preferably used. The amount of the condensing agent to be used is in the range of 0.1-fold mol or more, preferably 1-fold mol or more, relative to the compound represented by Chemical Formula (302). Further, the condensing agent itself can be used as a reaction solvent.

  The amount of the compound represented by the chemical formula (302) used in this method is 0.1 to 50.0 moles, preferably 1.0 to 20 moles relative to the unit represented by the chemical formula (301) used as the starting material. The range is 0.0 mole. In the reaction of the present invention, a solvent can be used as necessary. As the solvent to be used, pyridine is preferably used.

  In the method of the present invention, the reaction time is, for example, in the range of 1 to 48 hours. The reaction solution containing a polymer having one or more units represented by the chemical formula (1) in the molecule can be removed by distillation, which is a conventional method.

  A solvent such as ethers is mixed with a solvent that is uniform in the reaction solution and insoluble in a polymer having at least one unit represented by chemical formula (1) in the molecule. And it can collect | recover by reprecipitation of the polymer which has 1 unit or more in a molecule | numerator which has the unit shown to the target Chemical formula (1).

  If necessary, the polymer having one or more units represented by the chemical formula (1) in the molecule can be isolated and purified. This isolation and purification method is not particularly limited, and a method of reprecipitation using a solvent insoluble in a polymer having at least one unit represented by chemical formula (1) in the molecule, or a method using column chromatography may be used. it can.

  In this method, even when a polymer having a unit represented by the chemical formula (301) having a molecular weight distribution of 1.00 <Mw / Mn <2.00 is used as a starting material, the condensation reaction is performed in the same manner. It is possible.

  Also, when a block copolymer comprising a unit represented by the chemical formula (301) and a unit derived from the vinyl monomer represented by the chemical formula (101) is used as a starting material, the condensation reaction is performed in the same manner. Is possible.

  Moreover, it is also possible to synthesize | combine by copolymerizing using the compound shown by Chemical formula (201), another polymerizable monomer, and a polymerization initiator.

(Method for producing compound represented by chemical formula (201))
The compound represented by the chemical formula (201) can be produced by the following method.

  A method for synthesizing the compound represented by the chemical formula (201) in the present invention will be described in detail. Synthesis by a condensation reaction between a polymerizable monomer having a carboxyl group such as vinyl benzoic acid, an acid chloride polymerizable monomer in which the carboxyl group is an acid chloride, and various compounds having an amino group represented by chemical formula (401) described later Is done.

  Examples of the condensation reaction of a carboxyl group and an amino group include a method using a condensing agent, a method of forming a salt and performing condensation by a dehydration reaction, a method using a dehydrating agent, a method of converting a carboxyl group into an acid chloride and reacting an amino group, etc. Either can be used.

  As a production method according to the present invention, a method for converting a carboxyl group into an acid chloride and reacting an amino group will be described in detail.

  Conversion of the polymerizable monomer represented by the chemical formula (203) to an acid chloride can be performed by using thionyl chloride which is a conventional method.

(In the formula, R _203w and R _203X are each independently a halogen atom or a hydrogen atom. R _203y is a CH ₃ group, a halogen atom, or a hydrogen atom.
A ₀₂₀₃ is either a substituted or unsubstituted aromatic ring structure or a substituted or unsubstituted heterocyclic ring structure. R ₂₀₃ is an H atom, a Na atom or a K atom. )
The usage-amount of thionyl chloride is 0.1-50.0 times mole with respect to the compound shown in Chemical formula (203), Preferably, it is the range of 1.0-20.0 times mole. It is also possible to use thionyl chloride itself as a reaction solvent.

  The amount of the compound represented by the following chemical formula (401) used in this method is 0.1 to 50.0 times mol, preferably 1.0, with respect to the unit represented by the chemical formula (203) used as a starting material. It is the range of -20.0 times mole. In the reaction of the present invention, a solvent can be used as necessary. Examples of the solvent to be used include dichloromethane, chloroform, carbon tetrachloride, dichloroethane, trichloroethane and the like. In this method, the reaction temperature is not particularly limited, but is usually a temperature in the range of −30 ° C. to the boiling point of the solvent. However, it is desirable to perform the reaction at an optimum temperature in accordance with the compound represented by the chemical formula (401) to be used later and the reaction solvent. In the method of the present invention, the reaction time cannot be generally specified, but is usually in the range of 1 to 48 hours. The reaction solution containing the compound represented by the chemical formula (201) generated in this way can be removed by distillation which is a conventional method.

  If necessary, the compound represented by the chemical formula (201) obtained here can be isolated and purified. The isolation and purification method is not particularly limited, and a method of recrystallization using a solvent in which the compound represented by the chemical formula (201) is hardly soluble, or a method by column chromatography can be used.

Moreover, the compound which does not have a sulfonic-acid ester unit among the compounds shown by Chemical formula (201) is compoundable by the said method. For example, when a compound in which R ₂₀₁ is OH, a halogen atom, ONa, or OK is synthesized, by using an esterifying agent, R ₂₀₁ has a sulfonic acid ester unit represented by OR _201a (201) Can be synthesized. Examples of esterifying agents include trimethylsilyldiazomethane, trimethyl orthoformate, and triethyl orthoformate.

  In this reaction, the above-described solvents and the like can be used as necessary.

The amount of the esterifying agent used is 0.1 to 50 times mol, preferably 1 to 20 times mol, based on the unit represented by chemical formula (201) wherein R ₂₀₁ is OH, halogen atom, ONa, or OK. It is.

  In this method, the reaction temperature is not particularly limited, but is usually in the range of −20 ° C. to 200 ° C. The reaction time cannot be generally specified, but is usually in the range of 1 to 48 hours.

The reaction solution containing a compound having a sulfonic acid ester unit in which R ₂₀₁ is represented by OR _201a among the chemical formula (201) thus produced can be removed by distillation which is a conventional method.

Of the chemical formula (201) obtained here, the compound having a sulfonic acid ester unit in which R ₂₀₁ is represented by OR _201a can be isolated and purified if necessary. The isolation and purification method is not particularly limited, and in the chemical formula (201), R ₂₀₁ is a compound having a sulfonate ester unit represented by OR _201a , which is recrystallized using a poorly soluble solvent, column chromatography. Graphical methods can be used.

  (Compound shown in chemical formula (401))

(Wherein R ₄₀₁ is OH, a halogen atom, ONa, OK or OR _401a . R _401a is independently a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure. Or a substituted or unsubstituted heterocyclic structure.)
As the compound represented by the chemical formula (401) used in the present invention, the following are preferable. That is, A ₄₀₁ is a linear or branched alkylene group having 1 to 8 carbon atoms, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, or a substituted or unsubstituted N, S, or O. It is a compound showing a heterocyclic structure containing two or more. When A ₄₀₁ has a ring structure, the unsubstituted ring may be further condensed.

When A ₄₀₁ is a straight-chain or branched alkylene group compound having 1 to 8 carbon atoms, examples thereof include the following. That is, 2-aminoethanesulfonic acid (taurine), 3-aminopropanesulfonic acid, 4-aminobutanesulfonic acid, 2-amino-2-methylpropanesulfonic acid, and alkali metal salts thereof. When A ₄₀₁ is a substituted or unsubstituted phenyl group, it is represented by the chemical formula (26) described above. When A ₄₀₁ is a substituted or unsubstituted naphthyl group, it is represented by the chemical formulas (27a) and (27b) described above. When A ₄₀₁ is a heterocyclic structure containing any one or more of substituted, unsubstituted N, S, and O, a pyridine ring, a piperazine ring, a furan ring, a thiol ring, and the like can be given.

(Method of polymerizing compound represented by chemical formula (201))
As a polymerization method of the compound represented by the chemical formula (201), various known polymerization reactions can be used. Further, it can be copolymerized with various known monomers. Examples of the copolymerizable monomer include styrene and o-methylstyrene.

In the case of polymerizing a compound having no sulfonic acid ester unit in the chemical formula (201) (for example, a compound in which R ₂₀₁ is OH, a halogen atom, ONa, or OK), radical polymerization in which the polymerization conditions are relatively easy to control. Can be used. Moreover, when it has a sulfonic acid ester unit, utilization of ionic polymerization is also possible.

  When radical polymerization is used, examples of the initiator include 2,2′-azobisisobutyronitrile. Also, a water-soluble initiator such as potassium persulfate or ammonium persulfate can be used. 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 the copolymerization, and the initiator used. obtain.

  In the polymerization reaction of the present invention, the above-described solvent, toluene, or N, N-dimethylformamide can be used as necessary.

  Among known polymerization methods, a polymer having a unit represented by the chemical formula (1) having a molecular weight distribution of 1.00 <Mw / Mn <2.00 is obtained by using a living polymerization method. It is possible to synthesize. Among living polymerization methods, living radical polymerization is relatively easy. This living radical polymerization, preferably atom transfer radical polymerization and nitroxide-mediated polymerization can be carried out in the same manner as in the case of the polymer having the unit of the chemical formula (301).

  Moreover, the block copolymer which consists of the unit represented by Chemical formula (1), and the unit derived from the vinyl-type monomer shown by Chemical formula (101) also uses a living polymerization method in a well-known polymerization method, It is possible to synthesize. In particular, living radical polymerization is relatively easy among living polymerization methods.

  Specifically, after a homopolymer having a structure represented by the chemical formula (301) is formed by living radical polymerization, a polymer having a structure represented by the chemical formula (101) is copolymerized by living radical polymerization at one end of the homopolymer. In this way, the target block copolymer precursor can be obtained. Note that the order of forming the block copolymers may be reversed. This living radical polymerization can also be performed in the same manner as in the case of the polymer having the unit of the chemical formula (301).

  The solvent in the reaction solution containing the polymer according to the present invention produced as described above can be removed by distillation which is a conventional method. Alternatively, a solvent in which the polymer according to the present invention is insoluble, such as water, alcohols such as methanol and ethanol, and ethers, is uniformly mixed in the reaction solution to precipitate the target polymer according to the present invention. And the said deposit can be collect | recovered. Examples of ethers include dimethyl ether, diethyl ether, and tetrahydrofuran.

  If necessary, the polymer according to the present invention obtained here can be isolated and purified. This isolation and purification method is not particularly limited. A method of precipitation using a solvent insoluble in the polymer according to the present invention and a method by column chromatography can be used.

(Production method of polymer having at least one unit represented by chemical formula (304) in the molecule)
When R ₃₀₃ in Chemical Formula (303) is OH, a halogen atom, ONa or OK, a polymer represented by Chemical Formula (304) where R is —A ₃₀₄ —SO ₃ R ₃₀₄ is synthesized using an esterifying agent. Is possible. Examples of the esterifying agent include trimethylsilyldiazomethane, trimethyl orthoformate, and triethyl orthoformate.

  The reaction is described in detail below.

  In this reaction, the above-described or later-described solvents 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 usage-amount of an esterifying agent is 0.1-50 times mole with respect to the unit shown to Chemical formula (303), Preferably, it is the range of 1-20 times mole.

  In this method, the reaction temperature is not particularly limited, but is usually in the range of −20 ° C. to 200 ° C. The reaction time cannot be generally specified, but is usually in the range of 1 to 48 hours.

  The solvent in the reaction solution containing the polymer according to the present invention produced as described above can be removed by distillation which is a conventional method.

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

  As a charge control agent used in the toner composition for developing an electrostatic image, for example, by using a polymer compound represented by the chemical formula (1), the charging property is excellent and the dispersibility and spent property of the compound in the toner resin are improved. Can provide a good one.

  Further, by using the polymer according to the present invention, 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.

  Furthermore, since the charge control agent using the polymer according to the present invention can be made colorless or weak in coloration degree, it is not affected by the charge control agent and can be arbitrarily selected according to the hue required for the color toner. It is possible to select a colorant. A colorless or weakly colored charge control agent is preferable because it hardly inhibits the original hue of the dye or pigment.

<Use as charge control agent>
When the polymer according to the present invention is used as a charge control agent, it preferably has a structure containing a sulfonic acid group or a derivative thereof in the side chain as in the monomer unit represented by the chemical formula (1). The presence of these anionic or electron-withdrawing functional groups has excellent negative chargeability.

  The polymer according to the present invention has a good compatibility with the binder resin of the toner, and particularly has a very good compatibility with the polyester binder resin.

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

(Addition of polymer 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 charge control agent is usually used in an amount of 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 with respect to the total mass of the toner binder and the charge control agent. It is preferable to chemically fix the toner surface.

The molecular weight of the polymer of the present invention was measured by GPC (gel permeation chromatography). When used as a charge control agent, in the present invention, the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured as described above is in the range of 1 to 10. It is preferable to use the polymer described above.

  In addition, for the purpose of reducing the particle size of the discontinuous domains formed by the polymer of the present invention, a polymer having compatibility with the polymer of the present invention and compatibility with the toner binder is made compatible. It can also be contained as an agent. Examples of the compatibilizer include the following. For example, a polymer chain containing 50 mol% or more of a monomer having substantially the same structure as the constituent monomer of the polymer of the present invention, and a single unit having substantially the same structure as the constituent monomer of the toner binder. It is a polymer in which polymer chains containing 50 mol% or more of monomers are bonded. As a form of bonding, it can be bonded in a graft shape or a block shape. The amount of the compatibilizer used is usually 30% by mass or less, preferably 1 to 10% by mass, based on the polymer of the present invention.

  In the toner according to the present invention, a general thermoplastic resin can be used as a binder resin. For example, polystyrene etc. can be mentioned.

  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. For example, divinylbenzene and the like can be mentioned as a bifunctional crosslinking agent.

  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.

  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. Furthermore, it is more preferable from the viewpoint of the image quality of a full-color image that the combination of a dye and a pigment improves the sharpness. Usually, in order to obtain the best toner characteristics, that is, when considering the coloring power of printing, toner shape stability, toner scattering, etc., the colorant is usually 0.1 to 100 parts by weight of the binder resin. 60 parts by mass, preferably 0.5 to 20 parts by mass is used.

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

  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.

  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.

  In order to improve the developability and durability of the toner, it is also preferable to add the following inorganic powder. For example, 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 such as Teflon may be added to the toner.

<About Career>
The electrostatic image developing toner of the present invention can be applied to various conventionally known toners. For example, the electrostatic image developing toner can be used alone as a non-magnetic one-component developer. The electrostatic image developing toner of the present invention can be used as a non-magnetic toner that forms a magnetic two-component developer together with a magnetic carrier, a magnetic toner that is used alone as a magnetic one-component toner, or the like.

<Magnetic toner>
The toner for developing an electrostatic charge image of the present invention may be a magnetic toner containing a magnetic material in toner particles. In this case, the magnetic material can also serve as a colorant. These magnetic materials that can be used in the present invention preferably have an average particle size of 2 μm or less, preferably about 0.1 to 0.5 μm. The amount to be contained in the toner is preferably 20 to 200 parts by mass, particularly preferably 40 to 150 parts by mass with respect to 100 parts by mass of the binder resin.

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

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

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

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

<Method for measuring molecular weight and molecular weight distribution of binder resin>
In addition, the binder resin used for the constituent material of the toner for developing an electrostatic charge image of the present invention has a peak in the low molecular weight region in the range of 3,000 to 15,000 in the molecular weight distribution by GPC, particularly when produced by a pulverization method. It is preferable to have it. 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). As a specific GPC measurement method, a sample obtained by previously extracting toner with a THF (tetrahydrofuran) solvent using a Soxhlet extractor for 20 hours is used for measurement. 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.

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

  First, Examples A-1 to R-2 describe a novel polymer obtained by the present invention, a production method thereof, and a novel compound. Then, the usefulness of the polymer etc. which concern on this invention is shown by Examples 1-40, using a comparative example.

  In addition, the novel polymer and compound which concern on this invention, and these manufacturing methods are not limited only to the Example shown below.

In the following experiment, the structure of the obtained compound is determined as follows. For NMR, ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; measurement temperature: room temperature) is used.
Further, the structure is determined by performing analysis by Fourier transform-infrared absorption (FT-IR) spectrum (Nicolet AVATAR 360FT-IR).

Further, ¹ H-NMR measurement was performed using heavy acetone unless otherwise specified.

  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. For acid value titration, potentiometric titrator AT510 (manufactured by Kyoto Electronics) was used.

<Example A-0>
With reference to Macromolecules, 24, 4310-4321 (1991) and Macromolecules, 26, 2791-2795 (1993), styrene and 4-vinylbenzoic acid were copolymerized. As a result, the following formula (A-0):

The polymer copolymer which contains the unit shown by content ratio (mol%) (M) :( F) = 93: 7 was obtained. The average molecular weight of the obtained polymer was a number average molecular weight Mn = 22000 and a weight average molecular weight Mw = 52000.

<Example A-1>
Under a nitrogen atmosphere, 1.5233 g of the polymer obtained in Example A-0 and 0.8492 g of 2-aminobenzenesulfonic acid are placed in a 200 ml three-necked flask, and 56.5 ml of pyridine are added and stirred. Thereafter, 2.57 ml of triphenyl phosphite was added and heated at 120 ° C. for 6 hours. After completion of the reaction, pyridine was distilled off, and 150 ml of chloroform was added to dissolve the polymer. After separation and washing with 600 ml of 2N hydrochloric acid, the solvent was distilled off to recover 1.2535 g of polymer. The polymer was dissolved in THF, and purified using a dialysis membrane using distilled water and isopropanol.

^From the result of ¹ H-NMR, the peak derived from the phenyl group of 2-aminobenzenesulfonic acid was shifted. As a result, the obtained polymer has the following formula (A-1):

It was confirmed that it was a polymer copolymer containing 6 mol% of the unit shown in FIG. The obtained polymer had Mn = 20000 and Mw = 48000. By scaling up, 50 g of the above copolymer was obtained, and this compound was used as exemplary compound A-1 for toner preparation and evaluation.

<Example A-2>
0.9777 g of the polymer obtained in Example A-1 was placed in a 300 mL eggplant flask, dissolved by adding 68.44 ml of chloroform and 17.11 ml of methanol, and cooled to 0 ° C. To this was added 3.00 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution (Aldrich) as an esterifying agent, and the mixture was stirred for 4 hours. After completion of the reaction, the solvent was removed by an evaporator, and then the polymer was recovered. Further, 68.44 ml of chloroform and 17.11 ml of methanol were added to redissolve the polymer, and the solvent was distilled off by an evaporator. This re-dissolution and solvent distillation operation was repeated three times. The polymer collected here was dried under reduced pressure to obtain 0.9552 g of polymer.

^From the result of ¹ H-NMR, a peak derived from methyl sulfonate was observed at 3 to 4 ppm. From this, the obtained polymer has the following formula (A-2):

It was confirmed that it was a polymer copolymer containing 6 mol% of the unit shown in FIG. Moreover, it was clarified from the fact that the equivalent point derived from sulfonic acid was not found by acid value titration, and that sulfonic acid was methyl sulfonate. The obtained polymer had Mn = 19000 and Mw = 45000. By scaling up, 50 g of the above copolymer was obtained, and this compound was used as exemplary compound A-2 for toner preparation and evaluation.

<Example B-1>, <Example C-1>, <Example D-1>, <Example E-1>, <Example F-1>, <Example G-1>
Similarly to Example A-1, the polymer obtained in Example A-0 was used as a raw material.
As shown in Table 1-1,
-Aminosulfonic acid to be used-Polymer usage amount-Aminosulfonic acid usage amount-Condensing agent usage amount-Solvent usage amount were the same as in Example A-1, and Examples B-1, C-1, Polymers of D-1, E-1, F-1, and G-1 were synthesized.
The synthesis results and analysis results are shown in Table 1-2.

  By scale-up, 50 g of each copolymer was obtained, and the compounds were used for the preparation and evaluation of toners as exemplified compounds B-1, C-1, D-1, E-1, F-1, and G-1.

<Example B-2>, <Example D-2>, <Example E-2>, <Example F-2>, <Example G-2>
As shown in Table 1-3,
-The point which uses other polymers instead of the polymer obtained in A-1 as a raw material-The amount of polymer used-The amount of esterifying agent used-The same operation as Example A-2 is performed except the amount of solvent used The polymers of Examples B-2, D-2, E-2, F-2, and G-2 were synthesized.
The synthesis results and analysis results are shown in Table 1-4.

  By scaling up, 50 g of each copolymer was obtained, and the respective compounds were used for preparation and evaluation of toners as exemplified compounds B-2, D-2, E-2, F-2, and G-2.

<Example H-1>
Styrene and 4-vinylbenzoic acid were copolymerized according to the same literature as Example A-1.
As a result, the following formula (H-0):

The polymer copolymer which contains the unit shown by content ratio (mol%) (M) :( F) = 89: 11 was obtained. This was used in the following experiment. The obtained polymer had Mn = 25000 and Mw = 60000.

As shown in Table 2-1.
-The polymer was synthesized by the same operation as in Example A-1, except for the amount of polymer used, the amount of aminosulfonic acid used, and the amount of condensing agent used.
The synthesis results and analysis results are shown in Table 2-2.

50 g was obtained by scale-up, and used for preparation and evaluation of toner as Exemplified Compound H-1.

<Example H-2>
As shown in Table 2-3,
-The point which uses the polymer obtained by H-1 instead of the polymer obtained by A-1 as a raw material-The amount of polymer used-The amount of esterifying agent used-Except for the amount of solvent used, Example A-2 The same operation was performed to synthesize a polymer.
The synthesis results and analysis results are shown in Table 2-4.

  By scale-up, 50 g of the above copolymer was obtained and used as exemplary compound H-2.

<Example I-0>
With reference to Macromolecules, 32, 1453-1462 (1999), the following formula (I-0C):

The polymer copolymer which contains the unit shown by content ratio (F) = 15 (mol%) was synthesize | combined, and it used for the following experiment. The other units are styrene units. The average molecular weight of the obtained polymer was a number average molecular weight Mn = 15000 and a weight average molecular weight Mw = 17000.

<Example I-1>
In a nitrogen atmosphere, 1.4956 g of the polymer obtained in Example I-0 and 0.8844 g of 2-aminobenzenesulfonic acid were placed in a 200 ml three-necked flask, and 113.0 ml of pyridine was added and stirred. 2.68 ml of phenyl was added. And it heated at 120 degreeC for 6 hours. After completion of the reaction, pyridine was distilled off, and 150 ml of chloroform and 50 ml of methanol were added to dissolve the polymer. Separating and washing with 150 ml of 2N hydrochloric acid, the solvent of the organic layer was distilled off, washed with 100 ml of isopropanol twice, washed with 100 ml of hexane and filtered to recover 1.2323 g of polymer. did. The polymer was dissolved in THF, and purified using a dialysis membrane using distilled water and isopropanol.

^From the result of ¹ H-NMR, the peak derived from the phenyl group of 2-aminobenzenesulfonic acid was shifted. From this, the obtained polymer was, as a result, the following formula (I-1):

It was confirmed that it was a polymer copolymer containing 12 mol% of the unit shown in FIG. The obtained polymer had Mn = 13000 and Mw = 15000. By repeating the preparation method, 50 g was obtained, and this compound was used as exemplary compound I-1 for toner preparation and evaluation.

<Example I-2>
As shown in Table 3-3
-The point which uses the polymer obtained by I-1 instead of the polymer obtained by A-1 as a raw material-The amount of polymer used-The amount of esterifying agent used-Except for the amount of solvent used, Example A-2 and The same operation was performed to synthesize a polymer.
The results are shown in Table 3-4.

By repeating the preparation method, 50 g of the above-mentioned copolymer was obtained, and it was subjected to toner preparation and evaluation as exemplified compound I-2.

<Example J-0>
Styrene and 4-vinylbenzoic acid block copolymer were synthesized with reference to Macromol. Chem. Phys, 195, 3173-3187 (1994) and J. Am. Chem. Soc., 125, 715-728 (2003). . As a result, the following formula (J-0):

A block copolymer represented by m = 210 n = 21 was obtained. This was used in the following experiment. The obtained polymer had Mn = 25000 and Mw = 30000.

<Example L-0>
With reference to Macromolecules, 24, 4310-4321 (1991) and Macromolecules, 26, 2791-2795 (1993), styrene and 4-vinylbenzoic acid were copolymerized to obtain a raw material polymer. The recovered polymer was purified using a dialysis membrane with a molecular weight cut off of 2000. Next, the polymer recovered after dialysis purification was purified using a dialysis membrane with a molecular weight cut off of 3500. In the same manner, purification was performed using a dialysis membrane having a molecular weight cut off of 8,000 and 10,000. As a result, the following formula (L-0):

The polymer copolymer which contains the unit shown by content ratio (mol%) (M) :( F) = 93: 7 was obtained. This was used in the following experiment. The obtained polymer had Mn = 23000 and Mw = 32000.

<Example M-0>
With reference to Macromolecules, 24, 4310-4321 (1991) and Macromolecules, 26, 2791-2795 (1993), styrene and 4-vinylbenzoic acid were copolymerized to obtain a raw material polymer. The recovered polymer was purified using a dialysis membrane with a molecular weight cut off of 2000. Next, the polymer recovered after dialysis purification was purified using a dialysis membrane with a molecular weight cut off of 3500. In the same manner, purification was performed using a dialysis membrane having a molecular weight cut off of 8,000 and 10,000. As a result, the following formula (M-0):

The polymer copolymer which contains the unit shown by content ratio (mol%) (M) :( F) = 88: 12 was obtained. This was used in the following experiment. The obtained polymer had Mn = 26000 and Mw = 36000.

<Example J-1><ExampleK-1><ExampleL-1><ExampleM-1>
As shown in Table 4-1,
The raw material polymer used, the aminosulfonic acid used, the amount of polymer used, the amount of aminosulfonic acid used, the amount of condensing agent used, and the amount of solvent used were the same as in Example A-1 to synthesize a polymer.
The synthesis results and analysis results are shown in Table 4-2.

By repeating the preparation method, 50 g of each copolymer was obtained, and the respective compounds were used as exemplary compounds J-1, K-1, L-1, and M-1 for toner preparation and evaluation.

<Example J-2><ExampleK-2><ExampleL-2><ExampleM-2>
As shown in Table 4-3,
-As a raw material, instead of the polymer obtained in A-1, the point of using other polymer-The amount of polymer used-The amount of esterifying agent used-The same operation as in Example A-2 except for the amount of solvent used And polymer was synthesized.
The synthesis results and analysis results are shown in Table 4-4.

  By scaling up, 50 g of each copolymer was obtained, and each compound was used as exemplary compounds J-2, K-2, L-2, and M-2 for toner preparation and evaluation.

<Example N-0>
With reference to JP 2002-138111, Macromolecules, 30, 2016-2020 (1997), the following formula (N-0):

A monomer represented by is synthesized.

  As a raw material, 50.0 g of 4-aminobenzenesulfonic acid was dissolved in 120 ml of ion-exchanged water. Further, 12.0 g of sodium hydroxide was added and heated to 40 ° C. to dissolve. After stirring, 100 ml of ion exchange water was added, and then water was distilled off. Furthermore, the operation of redissolving in 100 ml of ion exchange water and distilling off the solvent was repeated three times. To this powder, 25.0 ml of distilled water, 24.5 g of sodium hydrogen carbonate and 15.0 ml of methanol were added and stirred for 4 hours. A solution prepared by dissolving 33.3 g of p-vinylbenzoyl chloride in 150 ml of THF was slowly added dropwise thereto. After completion of the dropwise addition, the solution was stirred for 30 minutes, cooled to 0 ° C., and filtered to recover crystals. Furthermore, washing was performed using methanol, and 10.5 g of a monomer could be obtained.

The structure of the obtained compound was determined by ¹ H-NMR measurement. The monomer obtained here was used for the next polymerization.

<Example N-1>
The monomer obtained in Example N-0 (0.467 g) and 2.7 ml of styrene were added to a 30-mL rubbing test tube, dissolved in 20 ml of DMSO, and degassed by nitrogen bubbling for 12 hours. As an initiator, 41.2 mg of 2,2′-Azobis (isobutyronitrile) was dissolved in 5.0 ml of DMSO, added to a test tube, and then heated and stirred at 70 ° C. After 9 hours, the obtained polymer was purified using a dialysis membrane and washed with water and hydrochloric acid to remove the homopolymer of the unreacted monomer and the monomer of the chemical formula (N-0). 0.9681 g of polymer was recovered.

^From the result of ¹ H-NMR, the peak derived from the phenyl structure of the monomer was shifted. From this, the obtained polymer is, as a result, the following formula (N-1):

It was confirmed that the polymer was a polymer copolymer containing the units shown in (5) in a content ratio (mol%) (NM) :( NF) = 95: 5. The obtained polymer had Mn = 21000 and Mw = 36000. By scaling up, 50 g was obtained, and this compound was used as an exemplary compound N-1 for toner preparation and evaluation.

<Example N-2>
As shown in Table 5-1,
-The point which uses the polymer obtained by N-1 instead of the polymer obtained by A-1 as a raw material-The amount of polymer used-The amount of esterifying agent used-Except for the amount of solvent used, Example A-2 The same operation was performed to synthesize a polymer.
The synthesis results and analysis results are shown in Table 5-2.

  By scale-up, 50 g of the above copolymer was obtained, and this compound was designated as exemplified compound N-2.

<Example OO>
The monomer obtained in Example N-0 was desalted using an ion exchange resin, and with reference to SYNTHETIC COMMUNICATIONS, 15 (12), 21, 1057-1062 (1985), the following formula (O-0):

Was synthesized.

  Under a nitrogen stream, 3.5032 g of a desalted compound of the compound represented by the chemical formula (N—O), 20 ml of trimethyl orthoformate and p-benzoquinone as a polymerization inhibitor were placed in a flask and heated at 70 ° C. for 5 hours. The reaction mixture was cooled and concentrated under reduced pressure. The extract was washed twice with 3 L of water and twice with 3 L of hexane, redissolved in chloroform, dried over anhydrous magnesium sulfate, and the solvent was distilled off.

The structure of the obtained compound was determined by ¹ H-NMR (FT-NMR: Bruker DPX400; resonance frequency: 400 MHz; measurement nuclide: ¹ H; solvent used: CDCl ₃ ; measurement temperature: room temperature). ^From the result of ¹ H-NMR, since a peak derived from methyl sulfonate was observed at 3 to 4 ppm, it became clear that the sulfonic acid was methyl sulfonate. In addition, elemental analysis also suggested that methylsterylation was progressing because the presence of Na was below the detection limit. Furthermore, the acid value titration using the potentiometric titrator AT510 (manufactured by Kyoto Electronics Co., Ltd.) revealed that the equivalent point derived from sulfonic acid was not found, and that sulfonic acid was methyl sulfonate. It was. This monomer was used for the next polymerization.

<Example O-2>
The monomer obtained in Example O-0 (0.3930 g) and styrene (2.7 ml) were added to a 30-mL rubbing test tube, DMSO (20 ml) was added and dissolved, and nitrogen gas was bubbled for 12 hours for deaeration. As an initiator, 41.2 mg of 2,2′-Azobis (isobutyronitrile) was dissolved in 5.0 ml of DMSO, added to a test tube, and then heated and stirred at 70 ° C. After 9 hours, the obtained polymer was purified using a dialysis membrane and washed with water and hydrochloric acid to remove the homopolymer of the unreacted monomer and the monomer of the chemical formula (O-0). 0.9658 g of polymer was recovered.

^From the result of ¹ H-NMR, the peak derived from the phenyl structure of the monomer was shifted. From this, the obtained polymer is, as a result, the following formula (O-2):

It was confirmed that the polymer was a polymer copolymer containing the unit shown in (5) in a content ratio (mol%) (OM) :( OF) = 95: 5. The obtained polymer had Mn = 20000 and Mw = 35000. 50g was obtained by scale-up and this compound was used as exemplary compound O-1.

<Example P-2>
0.9993 g of the polymer obtained in Example A-1 was placed in a flask, 7.30 g of trimethyl orthoformate was added, and the mixture was stirred at 80 ° C. for 8 hours. After completion of the reaction, it was dropped into 100 ml of hexane and the polymer was recovered by filtration. Furthermore, it melt | dissolved in THF10ml, it reprecipitated in hexane 100ml, and 0.8700g of polymers were collect | recovered.

^From the result of ¹ H-NMR, a peak derived from methyl sulfonate was observed at 3 to 4 ppm. From this, the obtained polymer has the following formula (P-2):

It was confirmed that it was a polymer copolymer containing 6 mol% of the unit shown in FIG. Moreover, it was clarified from the fact that the equivalent point derived from sulfonic acid was not found by acid value titration, and that sulfonic acid was methyl sulfonate. The obtained polymer had Mn = 17000 and Mw = 43000.

<Example Q-2>
1.0032 g of the polymer obtained in Example A-1 was put in a flask, 10.20 g of triethyl orthoformate was added, and the mixture was stirred at 100 ° C. for 8 hours. After completion of the reaction, it was dropped into 100 ml of hexane and the polymer was recovered by filtration. Furthermore, it melt | dissolved in THF10ml, it reprecipitated in hexane 100ml, and 0.850g of polymers were collect | recovered.

^From the result of ¹ H-NMR, the obtained polymer has the following formula (Q-2):

It was confirmed that it was a polymer copolymer containing 6 mol% of the unit shown in FIG. Moreover, it was clarified from the fact that the equivalent point derived from sulfonic acid was not found by acid value titration, and that sulfonic acid was methyl sulfonate. The obtained polymer had Mn = 18000 and Mw = 46000.

<Example R-0>
With reference to JP 2002-138111, Macromolecules, 30, 2016-2020 (1997), the following formula (R-0):

A monomer represented by is synthesized.

As raw materials, 6.5 g of 2-aminobenzenesulfonic acid and 8.9 g of triethylamine were dissolved in 70 ml of THF, cooled in an ice bath, and stirred. The p-vinyl benzoyl chloride was dripped little by little, and it stirred for 5 hours after completion | finish of dripping. After completion of the reaction, 70 ml of ion exchange water was added and the solvent was distilled off. After separating and washing with 70 ml of ethyl acetate and 4N hydrochloric acid, the solvent was distilled off and purification using a silica gel column was performed to obtain 8.0 g of a monomer. The structure of the obtained compound was determined by ¹ H-NMR measurement.

The measurement result of ¹ H-NMR is shown in FIG. The monomer obtained here was used for the next polymerization.

<Example R-1>
303.3 mg of the monomer obtained in Example R-0 and 1.8 ml of styrene were placed in a three-necked flask, dissolved by adding 45.6 ml of THF, and deaerated by bubbling with nitrogen. After adding 32.8 mg of 2,2′-Azobis (isobutyronitrile) as an initiator, the mixture was heated and stirred at 70 ° C. After 9 hours, the obtained polymer was dialyzed with water and isopropanol, and further, the resulting polymer was washed with water and hydrochloric acid to recover 1.5876 g of the polymer. ^From the result of ¹ H-NMR, the peak of the double bond of the monomer disappeared, and the peak derived from the phenyl structure of the monomer was shifted. From this, the obtained polymer was, as a result, the following formula (R-1):

It was confirmed that the polymer was a polymer copolymer containing the unit shown in (4) at a content ratio (mol%) (RM) :( RF) = 93: 7. The obtained polymer had Mn = 15000 and Mw = 28000.

<Example R-2>
As shown in Table 6-1,
-The point which uses the polymer obtained by R-1 instead of the polymer obtained by A-1 as a raw material-The amount of polymer used-The amount of esterifying agent used-Except for the amount of solvent used, Example A-2 The same operation was performed to synthesize a polymer.
The synthesis results and analysis results are shown in Table 6-2.

<Example S-O>
Using the monomer obtained in Example R-0, the following formula (S-0):

Was synthesized.

  Under a nitrogen stream, 6.0 g of the monomer represented by the chemical formula (R—O) was dissolved by adding 150 ml of chloroform and 50 ml of methanol, and cooled to 0 ° C. in an ice bath. 60 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution (manufactured by Aldrich) was added dropwise little by little, and the mixture was stirred for 3 hours after completion of the addition. After the completion of the reaction, the solvent was distilled off, and the operation of adding 300 ml of chloroform and 100 ml of methanol to dissolve and dissolving the solvent was repeated three times, followed by purification using a silica gel column to obtain 4.0 g of monomer. I was able to get it.

The measurement result of ¹ H-NMR is shown in FIG. ^From the result of ¹ H-NMR, since a peak derived from methyl sulfonate was observed at 3 to 4 ppm, it became clear that the sulfonic acid was methyl sulfonate.

<Example S-2>
317.4 mg of the monomer obtained in Example S-0 and 1.8 ml of styrene were placed in a three-necked flask, dissolved by adding 45.9 ml of THF, and deaerated by bubbling with nitrogen. After adding 32.8 mg of 2,2′-Azobis (isobutyronitrile) as an initiator, the mixture was heated and stirred at 70 ° C. Nine hours later, the obtained polymer was dialyzed with water and isopropanol to recover 1.7600 g of the polymer.

^From the result of ¹ H-NMR, the peak of the double bond of the monomer disappeared, and the peak derived from the phenyl structure of the monomer was shifted. From this, the obtained polymer is, as a result, the following formula (R-2):

It was confirmed that the polymer was a polymer copolymer containing the unit shown in (4) at a content ratio (mol%) (SM) :( SF) = 92: 8. The obtained polymer had Mn = 21000 and Mw = 34000.

<Example T-1>
The following formula (T-0):

A polymer having a content ratio (mol%) (M) :( F) = 91: 9, a number average molecular weight Mn = 63000, and a weight average molecular weight Mw = 84000 was used as a raw material.

  In a nitrogen atmosphere, 0.5 g of the polymer and 0.3597 g of 2-aminobenzenesulfonic acid were placed in a three-necked flask, and 4.0 ml of pyridine was added and stirred. Then, 1.10 ml of triphenyl phosphite was added, Heated for hours. After completion of the reaction, pyridine was distilled off, and 50 ml of chloroform was added to dissolve the polymer. After separating and washing with 50 ml of 2N hydrochloric acid and 50 ml of water, the solvent was distilled off to recover the polymer. 0.27 g of the polymer was separated, dissolved in 1.0 ml of chloroform, and reprecipitated in 200 ml of isopropanol. The recovered polymer was purified using a dialysis membrane.

The measurement result of ¹ H-NMR is shown in FIG. ^From the result of ¹ H-NMR, the peak derived from the phenyl group of 2-aminobenzenesulfonic acid was shifted. As a result, the obtained polymer was, as a result, the following formula (T-1):

It was confirmed that it was a polymer copolymer containing 6 mol% of the units shown in FIG.

<Example T-2>
0.079969 g of the polymer obtained in Example T-1 was put in an eggplant flask, dissolved by adding 2.0 ml of chloroform and 0.5 ml of methanol, and cooled to 0 ° C. To this, 0.3 ml of a 2 mol / L trimethylsilyldiazomethane-hexane solution (manufactured by Aldrich) was added and stirred for 4 hours. After completion of the reaction, the solvent was removed by an evaporator, and then the polymer was recovered. Further, 8.0 ml of chloroform and 2.0 ml of methanol were added to redissolve the polymer, and the solvent was distilled off by an evaporator. This re-dissolution and solvent distillation operation was repeated three times. The polymer collected here was dried under reduced pressure to obtain 0.08339 g of polymer.

The measurement result of ¹ H-NMR is shown in FIG. ^From the result of ¹ H-NMR, a peak derived from methyl sulfonate was observed at 3 to 4 ppm. From this, the obtained polymer has the following formula (T-2):

It was confirmed that it was a polymer copolymer containing 6 mol% of the unit shown in FIG. Moreover, it was clarified from the fact that the equivalent point derived from sulfonic acid was not found by acid value titration, and that sulfonic acid was methyl sulfonate. The obtained polymer had Mn = 43000 and Mw = 70000.

Example 1
First, an aqueous Na ₃ PO ₄ solution was added to a two-liter four-necked flask equipped with a high-speed stirring device 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 H-2: 2 parts by mass Next, the polymerizable monomer composition obtained above was charged into the aqueous dispersion medium prepared above. The granulation was carried out while maintaining the rotational speed of 10,000 rpm. Thereafter, while stirring with a paddle stirring blade, the mixture was reacted at 65 ° C. for 3 hours and then polymerized at 80 ° C. for 6 hours to complete the polymerization reaction. After completion of the reaction, the suspension was cooled and acid was added to dissolve the poorly water-soluble dispersant Ca ₃ (PO ₄ ) ₂ , followed by filtration, washing with water and drying to obtain blue polymer particles (1). The particle size of the resulting blue polymer particles (1) measured using a Coulter Counter Multisizer (manufactured by Coulter Co., Ltd.) is a weight average particle size of 7.4 μm, and the amount of fine powder (the presence ratio of particles of 3.17 μm or less in the number distribution) Was 4.9% 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. This was used as the blue toner (1) of this example. 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)
The blue toners (2) to (2) of Examples 2 to 5 were prepared in the same manner as in Example 1 except that Exemplified Compound H-2 was changed to Exemplified Compounds B-1, F-1, M-1, and G-2. 5) was obtained. The characteristics of this toner were measured in the same manner as in Example 1. The results are shown in Table 7. In addition, using this, the two-component blue developers (2) to (5) of Examples 2 to 4 were obtained in the same manner as Example 1.

(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 7. In addition, using this, the two-component blue developer (6) of Comparative Example 1 was obtained in the same manner as Example 1.

<Evaluation>
The two-component blue developers (1) to (5) obtained in Example 1 and the two-component blue developer (6) obtained in Comparative Example 1 are evaluated as follows. 10 seconds and 300 seconds using the above-mentioned method for measuring the charge amount under the environment of normal temperature and humidity (25 ° C, 60% RH) and high temperature and high humidity (30 ° C, 80% RH). The charge amount of the toner after stirring is 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 7.

[Charging]
A: Very good (-20.0μC / g or less)
○: Good (over -20.0 to -10.0μC / g or less)
△: Practical use possible (over -10.0 and below -5.0μC / g)
×: Not practical (greater than -5.0μC / g)
(Examples 6 to 10)
Except using 2.0 parts by mass of Exemplified Compounds B-2, L-1, H-1, J-2, and A-2 respectively, and using a yellow colorant (Hansa Yellow G) instead of a cyan colorant In the same manner as in Example 1, yellow (yellow) toners (1) to (5) of Examples 6 to 10 were obtained. The characteristics of these toners were measured in the same manner as in Example 1. The results are shown in Table 7. Also, 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 7. 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 7.

(Examples 11 to 15)
Exemplified compounds K-2, C-1, G-1, I-2, and N-1 are each used in an amount of 2.0 parts by mass, and carbon black (DBP oil absorption 110 mL / 100 g) is used in place of the cyan colorant. Except for this, black toners (1) to (5) of Examples 11 to 15 were obtained in the same manner as in Example 1. The characteristics of these toners were measured in the same manner as in Example 1. The results are shown in Table 7. 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 7. 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>
As in Example 1, 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 were used. The toner charge amount was measured and evaluated. The results are summarized in Table 7.

(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 Illustrative compound N-2: 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. After classification, magenta colored particles (1) were obtained by a pulverization method, and the magenta colored particles (1) had a weight average particle size of 7.2 μm and a fine powder amount of 5.7% 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 of Examples 17 to 20 (2) were prepared in the same manner as in Example 16 except that Exemplified Compound N-2 was changed to Exemplified Compounds F-2, I-1, K-1, and M-2, respectively. ) To (5) were obtained. The characteristics of this toner were measured in the same manner as in Example 1. The results are shown in Table 7. Using this, in the same manner as in Example 16, 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 7. 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 17 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 7.

(Examples 21 to 25)
Exemplified compounds P-2, D-1, E-2, J-1, and L-2 are each used in an amount of 2.0 parts by mass, and carbon black (DBP oil absorption 110 mL / 100 g) is used in place of the magenta pigment. Otherwise, the black toners (7) to (11) of Examples 21 to 25 were obtained in the same manner as in Example 16. The characteristics of these toners were measured in the same manner as in Example 1. The results are shown in Table 7. In addition, using this, in the same manner as in Example 16, two-component black developers (7) to (11) were obtained.

(Comparative Example 5)
A black toner (12) of Comparative Example 5 was obtained in the same manner as in Example 16, except that the exemplified compound was not used and carbon black (DBP oil absorption 110 mL / 100 g) was used instead of the magenta pigment. The characteristics of this toner were measured in the same manner as in Example 1. The results are shown in Table 7. Further, using this, the two-component black developer (12) of Comparative Example 5 was obtained in the same manner as in Example 16.

<Evaluation>
As in Example 1, the two-component black developers (7) to (11) obtained in Examples 21 to 25 and the two-component black developer (12) obtained in Comparative Example 5 were used. The toner charge amount was measured and evaluated. The results are summarized in Table 7.

(Example 26)
・ 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 ・ Example compound E-1: 2 parts by mass It was synthesized as follows. Bisphenol A propylene oxide 2-mole adduct 751 parts, terephthalic acid 104 parts and trimellitic anhydride 167 parts were polycondensed using 2 parts of dibutyltin oxide as a catalyst to obtain a polyester resin having a softening point of 125 ° C. The above compositions were mixed and melt kneaded with a biaxial extruder (L / D = 30). The kneaded product was cooled, coarsely pulverized with a hammer mill, finely pulverized with a jet mill, and classified to obtain black colored particles (13) by a pulverization method. The black colored particles (13) had a weight average particle size of 7.6 μm and a fine powder amount of 4.8% by number.

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

(Examples 27 to 30)
Except that Exemplified Compound E-1 was Exemplified Compound A-1, D-2, Q-2, O-2, respectively, by the same method as in Example 26, the black toners (14)-( 17) was obtained. The characteristics of this toner were measured in the same manner as in Example 1. The results are shown in Table 7. Further, using this, in the same manner as in Example 26, two-component black developers (14) to (17) of Examples 27 to 30 were obtained.

(Comparative Example 6)
A black toner (18) of Comparative Example 6 was obtained in the same manner as in Example 26 except that 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 7. In addition, using this, the two-component black developer (18) of Comparative Example 6 was obtained in the same manner as in Example 26.

<Evaluation>
In the same manner as in Example 1, the two-component black developers (13) to (17) obtained in Examples 26 to 30 and the two-component black developer (18) obtained in Comparative Example 6 were used. The amount of charge was measured and evaluated. The results are summarized in Table 7.

(Examples 31 to 36 and Comparative Examples 7 to 12)
In Examples 31 to 36 and Comparative Examples 7 to 12, LBP5500 (trade name, manufactured by Canon Inc.) was modified and used for evaluation. At that time, toner images were formed with cyan toner, yellow toner, magenta toner or black toner obtained in Examples 1, 6, 11, 16, 21, 26 and Comparative Examples 1 to 6 as the developer.

<Evaluation>
Under the above conditions, set the LBP5500 to a printout speed of 8 sheets (A4 size) / min under normal temperature and humidity (25 ° C, 60% RH) and high temperature and high humidity (30 ° C, 80% RH) environment. Remodeled and printed. Using the toners of Examples 1, 6, 11, 16, 21, and 26 and the toners of Comparative Examples 1 to 6, respectively, a printout test was performed in a monochromatic intermittent mode while being replenished sequentially. The obtained printout images were evaluated for the following items. The evaluation results are summarized in Table 8. The intermittent mode is a mode in which the developing device is paused for 10 seconds every time one sheet is printed, and toner deterioration is promoted by a preliminary operation at the time of restart.

[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. Specifically, the evaluation was performed by the following method. 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 31 to Example 36 and Comparative Example 7 to Comparative Example 12, scratches on the surface of the photosensitive drum and the intermediate transfer member and residual toner fixation when 5000 sheets of images were output The appearance of the image and the effect on the printout image (matching with LBP5500) were evaluated visually.

  In the systems using the toners of Examples 31 to 36, scratches on the surfaces of the photosensitive drum and the intermediate transfer member and adhesion of residual toner could not be confirmed at all, and the matching with LBP5500 was very good. On the other hand, in the systems using the toners of Comparative Examples 7 to 12, the toner was fixed on the surface of the photosensitive drum. Further, in the system using the toners of Comparative Examples 7 to 12, in the matching with the LBP5500, the fixing of the toner and the surface flaw can be confirmed on the surface of the intermediate transfer member, and the vertical streak-like image defect is generated on the image. Caused a problem.

(Example 37 to Example 39, Comparative Example 13 to Comparative Example 15)
In the implementation of Examples 37 to 39 and Comparative Examples 13 to 15, the toners obtained in Examples 1, 6, and 11 and Comparative Examples 1 to 3 were used as developers. Further, as a means for forming an image, an image forming apparatus which is remodeled by attaching a reuse mechanism (system using a collected toner) to the LBP5500 is used.

  As described above, in a normal mode and humidity (25 ° C, 60% RH) environment, print out up to 30,000 sheets in continuous mode at a printout speed of 8 sheets (A4 size) / min. To do. The continuous mode is a mode that promotes toner consumption without pausing the developing device.

  The image density of the obtained printout image was measured, and its durability was evaluated according to the following criteria. The 10,000th image was observed and image fogging was evaluated according to the following criteria. At the same time, the state of each device constituting the LBP 5500 after the durability test was observed, and the matching between each device and each toner was also evaluated. The above results are summarized in Table 9.

[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 to evaluate the durability.

(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 40)
The toner reuse mechanism of LBP5500 used in Examples 37 to 39 and Comparative Examples 13 to 15 was removed, and the printout speed was 16 sheets (A4 size) / min. Other than that was carried out similarly to Example 37, and performed the printout test in the continuous mode while supplying blue toner (1) of Example 1 sequentially. Note that the continuous mode is a mode that promotes toner consumption without pausing the developing device.

  Evaluation of the obtained printout image and matching with the used LBP5500 were evaluated for the same items as in Examples 37 to 39 and Comparative Examples 13 to 15. As a result, good results were obtained for all items.

  The polymer according to the present invention can be applied to, for example, a charge control agent contained in a toner used in electrophotographic technology.

Measurement result of ¹ H-NMR in Example R-0 Measurement result of ¹ H-NMR in Example S-0 Measurement result of ¹ H-NMR in Example T-1 Measurement result of ¹ H-NMR in Example T-2 It is a schematic diagram showing a blow-off charge amount measuring device for measuring the charge amount of toner.

Explanation of symbols

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

Claims (5)

A polymer characterized by being a copolymer of a unit represented by the chemical formula (1) and a unit represented by the chemical formula (101) .

(In the formula, R represents —A ₁ —SO ₂ R _1. R _1w and R _1X each independently represent a halogen atom or a hydrogen atom. R _1y represents a CH ₃ group, a halogen atom, or hydrogen. Is an atom.
A ₀₁ is a substituted or unsubstituted aromatic ring structure or a substituted or unsubstituted heterocyclic ring structure.
A ₁ is a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure.
R ₁ is OH, a halogen atom, ONa, OK or OR _1a . R _1a is a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure. )

(In the formula, R _101w and R _101x are each independently a halogen atom or a hydrogen atom. R _101y is a CH ₃ group, a halogen atom, or a hydrogen atom. R ₁₀₁ is a hydrogen atom, substituted or unsubstituted. Aliphatic hydrocarbon structure, substituted or unsubstituted aromatic ring structure, substituted or unsubstituted heterocyclic structure, halogen atom, —CO—R _101a , —O—R _101b , —COO—R _101c , —OCO— R _101d , —CONR _101e R _101f , —CN, or any ring structure containing an N atom R _101a , R _101b , R _101c , R _101d , R _101e and R _101f are each independently a hydrogen atom , A substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure, provided that the unit represented by the chemical formula (101) includes the above chemical formula ( Units that can be indicated in 1) include I can't go wrong.) In the chemical formula (1), A ₁ Is a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted phenylene structure, a substituted or unsubstituted naphthylene structure, or a substituted or unsubstituted heterocyclic structure. Polymer. An electrostatic charge image developing toner comprising at least a binder resin, a colorant, and a polymer having a unit represented by the chemical formula (1) .

(In the formula, R represents —A ₁ —SO ₂ R _1. R _1w and R _1X each independently represent a halogen atom or a hydrogen atom. R _1y represents a CH ₃ group, a halogen atom, or hydrogen. Is an atom.
A ₀₁ is a substituted or unsubstituted aromatic ring structure or a substituted or unsubstituted heterocyclic ring structure.
A ₁ is a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure.
R ₁ is OH, a halogen atom, ONa, OK or OR _1a . R _1a is a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure. ) The electrostatic image developing toner according to claim 3, wherein the polymer is a copolymer of a unit represented by the chemical formula (1) and a unit represented by the chemical formula (101).

(Where R _101w And R _101x Are each independently a halogen atom or a hydrogen atom. R _101y Is CH _Three A group, a halogen atom, or a hydrogen atom. R ₁₀₁ Is a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, a substituted or unsubstituted heterocyclic structure, a halogen atom, -CO-R _101a , -O-R _101b , -COO-R _101c , -OCO-R _101d , -CONR _101e R _101f , -CN, or a ring structure containing an N atom. R _101a , R _101b , R _101c , R _101d , R _101e And R _101f Are each independently a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted aromatic ring structure, or a substituted or unsubstituted heterocyclic structure. However, the unit represented by the chemical formula (101) does not include the unit that can be represented by the chemical formula (1). ) In the chemical formula (1), A ₁ Is a substituted or unsubstituted aliphatic hydrocarbon structure, a substituted or unsubstituted phenylene structure, a substituted or unsubstituted naphthylene structure, or a substituted or unsubstituted heterocyclic structure. The electrostatic image developing toner according to 1.

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