DE102018112373A1 - Charge control agent with macromolecular compounds and toner - Google Patents

Abstract

[Problem] The object of the present invention is to use charge control agents which do not contain metal elements whose safety is excellent to man and environment which are freely dyeable and their charge characteristics such as the charge amount, the charge amount distribution, the increase in charge, etc., and In particular, their environmental stability is excellent, and to provide resin compositions for electrophotography and toners for electrophotography thereof. [Solution] A charge control agent of the present invention having a macromolecular compound as an effective ingredient is characterized by being a copolymerization product of at least one kind is the compound represented by the following general formula (1) and at least one kind of alkenyl group-containing compound. (In the formula: Rbis R independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a nitro group, a cyano group, a substituted carbonyl group, a sulfur substitution group, an alkoxy group, an alkylureido group, a substituted or unsubstituted, a straight-chain or branched-chain alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted cycloalkyl group with 5, for example to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted hetero ring group or a substituted or unsubstituted condensed polycyclic aromatic group. C and C independently represent a carbon atom having a substituted or unsubstituted group Round R, Round R and C and C can form a ring structure. "M1" and "m2" are each an integer between 0 and 4. "x" is an integer between 0 and 2.)

Description

[Indication of the Field of the Invention]

This invention is charge control agents used for charge control of a toner for electronic photography and solid ink for electrostatic printing. Further, there are resin compositions for toners for electronic photography and toners for electronic photography.

[Description of the Related Art]

Photocopiers based on an electrophotographic process are widely used. And along with the development of personal computers, etc., in recent years, the electrophotographic processes have also been applied to laser printers, facsimiles and the like. On the other hand, copying machines that were mainly black and white (monochrome) are becoming more and more a color copier.

In a toner for electrophotography colorants, such as. As dyes, pigments, carbon black [carbon black], etc., as well as charge control agent to a connector resin, such. A styrene-based resin, an acrylic-based resin or a polyester-based resin.

Currently, as a charge control agent, among others. Azo dyes or metal salicylate complexes, etc., but since such charge control agents contain metals such as chromium, zinc, etc., problems of human and environmental safety have been raised in recent years. Further, development of colorless (white) charge control agents for the color devices is also desired because of the problem of discoloration by metal. In addition, since the charge control agents are in most cases low molecular weight crystals, and thus a homogeneous distribution of these in the toner u. a. As a result of aggregation, problems such as a widely distributed charge distribution can occur.

As colorless (white) charge control agents for the color devices, charge control agents which do not contain any metal elements have been developed for this purpose. For example, Patent Document 1 proposes a charge control agent using a thiacalixarene compound and Patent Document 2 proposes a charge control agent using a hydantoin compound. Although charge control agents which do not contain metal elements are already being developed, they are all low molecular weight having a molecular weight of 1,000 or less, and therefore, the risk for the environment due to the solubility or volatility remains.

As a measure for improving the dispersibility and compatibility between the charge control agents and the toner resins, there has been proposed an attempt to achieve the control of the charge by using resins having a charge control effect as the toner raw material. Furthermore, the use of a macromolecular compound, such as resin, can reduce the risks to human and environmental safety. For example, Patent Documents 3 and 4 propose to use a polymer compound which can be obtained by copolymerizing acrylamide sulfonic acid or its salt with styrene, a (meth) acrylic ester, etc. In Patent Document 5, it is proposed to use a polymer of a (meth) acrylate ester having a sulfonylurea structure. In Patent Documents 6 and 7, it is proposed to use a polymer of a unit having a sulfonic acid or a sulfonic acid ester and a unit having a salicylic acid derivative. In Patent Documents 8 and 9, there is proposed a charge control resin which is a copolymer of a styrene derivative having a hydroxybenzoic acid structure and a monomer having a vinyl group. In Patent Document 10, it is proposed to use a polymer of a unit comprising a sulfonic acid or a sulfonic acid ester and a unit having a benzoic acid derivative.

As described above, in recent years, many proposals for charge control using a polymer compound have been proposed for the purpose of improving compatibility with a toner resin and reducing the environmental impact, but there is still room for improvement as compared with existing low molecular compounds, and In many cases these do not reach the level of practical use.

[Documents Related to the Prior Art]

[Patent Documents]

• [Patent Document 1] JP 2013-060444 (A )
• [Patent Document 2] WO2012-102137
• [Patent Document 3] JP 2003-270862 (A )
• [Patent Document 4] JP 2004-191691 (A )
• [Patent Document 5] JP 2001-188386 (A )
• [Patent Document 6] JP 2011-128611 (A )
• [Patent Document 7] JP 2012-256042 (A )
• [Patent Document 8] WO2012-157713
• [Patent Document 9] JP 2014-222356 (A )
• [Patent Document 10] JP 2014-098857 (A )

DESCRIPTION OF THE INVENTION

[Description of the technical problem underlying the invention]

In view of the above-mentioned defects, the object of the present invention is charge control agents which do not contain metal elements excellent in human and environmental safety, which are freely dyeable, and their charge characteristics such as the charge amount, the charge amount distribution, the charge rise etc., and in particular their environmental stability are excellent, and to provide resin compositions for electrophotography and toners for electrophotography thereof.

[Presentation of Problem Solving by the Invention]

As a result of intensive research, the inventors et al. stated that the above objects can be achieved by a charge control agent containing a polymer compound of the present invention as an effective ingredient, and thus have completed this present invention. Thus, these inventions are charge control agents and toners as follows:

[1] A charge control agent having a macromolecular compound as an effective ingredient which is a product of copolymerization of at least one kind of the compound represented by the following general formula (1) and at least one kind of alkenyl group-containing compound.

(In the formula: R ₁ to R ₄ independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a nitro group, a cyano group, a substituted carbonyl group, a sulfur substitution group, an alkoxy group, an alkylureido group, or a substituted one or unsubstituted, straight-chain or branched-chain alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 10 carbon atoms, a substituted or not substituted aromatic hydrocarbon group, a substituted or unsubstituted hetero ring group or a substituted or unsubstituted condensed polycyclic aromatic group. C ₁ and C ₂ independently represent a carbon atom having a substituted or unsubstituted group. Further, R ₁ and R ₂ , R ₃ and R ₄ and C ₁ and C ₂ together form a ring structure. "M1" and "m2" are each an integer between 0 and 4. "x" is an integer between 0 and 2.)

[2] A charge control agent having a macromolecular compound as an effective ingredient, wherein the proportion of the compound represented by the above-mentioned general formula (1) is 0.1 to 80 mol%.

[3] A charge control agent having a macromolecular compound as an effective ingredient, wherein the weight average molecular weight (Mw) of the above-mentioned macromolecular compound is in a range of 1,000 to 100,000.

[4] A charge control agent having a macromolecular compound as an effective ingredient, wherein the above-mentioned alkenyl group-containing compound is at least one compound selected from a group consisting of styrene, styrene derivative, (metha) acrylic acid, (metha) acrylic acid ester, vinyl ether derivative.

[5] A charge control agent comprising a macromolecular compound as an effective ingredient, wherein the above macromolecular compound contains at least 1 unit or more of the unit represented by the following general formula (2).

(In the formula: R ₅ represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a nitro group, a cyano group, a substituted carbonyl group, a sulfur substitution group, an alkoxy group, an alkylureido group, or a substituted or unsubstituted, respectively straight-chain or branched-chain alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted hetero ring group or a substituted or unsubstituted condensed polycyclic aromatic Group. "N" is an integer.)

[6] A toner is characterized by containing one of the above-mentioned charge control agents having a macromolecular compound as an effective ingredient, colorant, and a binder resin.

[Indication of the advantages achieved by the invention]

Since a charge control agent of the present invention has a very high compatibility with the toner resin, and thus can be homogeneously dispersed therein, a toner having excellent charging properties such as charge amount, charge amount distribution, increase in charge, etc. can be obtained therewith. Further, since it is optically almost white, it has no color influence when used for a color toner. In addition, since it contains no metal element and it is a macromolecular compound, the potentials of dissolution and volatilization can be lowered, and thus its possible impact on the environment can be reduced.

Embodiments of this Invention

Hereinafter, embodiments for carrying out this invention will be explained in more detail, but the coverage areas of this invention are not limited to these forms.

The compound of the general formula (1) to be used in this invention can be prepared by a known method. For example, by condensation of maleic anhydride with a corresponding aromatic amine, a compound to be used in this invention can be synthesized.

A macromolecular charge control agent of the present invention is a charge control agent having an effective macromolecular compound which is a product of copolymerization of at least one kind of the compound represented by the following general formula (1) and at least one kind of alkenyl group-containing compound.

In the general formula (1), R ₁ to R ₄ independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a nitro group, a cyano group, a substituted carbonyl group, a sulfur substitution group, an alkoxy group, an alkylureido group, or a substituted or unsubstituted, straight-chain or branched-chain alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted hetero ring group or a substituted C ₁ and C ₂ independently represent a carbon atom having a substituted or unsubstituted group. Further, R ₁ and R ₂ , R ₃ and R ₄ and C ₁ and C _{2 may} each other form a ring structure. "M1" and "m2" are each an integer between 0 and 4. "x" is an integer between 0 and 2.

As examples of the "substituted carbonyl group, sulfur substitution group" for R ₁ to R ₄ in the general formula (1), there can be mentioned an alkoxycarbonyl group, alkylcarbamoyl group, alkoxysulphonyl group, alkylsulfamoyl group, alkylsulphonyl group, alkylureidosulphonyl group, etc.

As examples of the "straight-chain or branched-chain alkyl group having 1 to 18 carbon atoms" of the "substituted or unsubstituted, straight-chain or branched-chain alkyl group having 1 to 18 carbon atoms" for R ₁ to R ₄ in the general formula (1), a Methyl, ethyl, n-propyl, 2-propyl, n-butyl, sec-butyl, 2-methylpropyl, tert-butyl, n-pentyl, 1-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2 Dimethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1 , 4-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethyl-2-methyl-propyl group, 1,1,2-trimethylpropyl group, etc. are mentioned.

As examples of the "substitution group" of the "substituted or unsubstituted straight-chain or branched-chain alkyl groups having 1 to 18 carbon atoms" for R ₁ to R ₄ in the general formula (1), concrete groups such as a fluorine atom, chlorine atom, cyano group , Hydroxyl group, nitro group, cyclopentyl group, cyclohexyl group, a straight or branched chain alkoxy group having 1 to 8 carbon atoms, an alkylamino group substituted with a straight or branched chain alkyl group having 1 to 8 carbon atoms, a straight or branched chain acyl group having 1 to 8 carbon atoms, a straight chain or branched chain Alkoxycarbonyl group having 1 to 8 carbon atoms, epoxyalkyl groups having 1 to 8 carbon atoms, phenyl, naphthyl, anthryl, fluorenyl, styryl, pyridyl, pyridoindolyl, quinolyl, benzothiazolyl, etc., and these substitution groups may be further substituted.

As examples of the "cycloalkyl group having 5 to 10 carbon atoms" of the "substituted or unsubstituted cycloalkyl group having 5 to 10 carbon atoms" for R ₁ to R ₄ in the general formula (1), a cyclopentyl group, cyclohexyl group, cycloheptylene group, cyclooctylene group, cyclononylene group or cyclodecylene group.

As examples of the "substitution group" of the "substituted or unsubstituted cycloalkyl group having 5 to 10 carbon atoms" for R ₁ to R ₄ in the general formula (1), concrete groups such as fluorine atom, chlorine atom, cyano group, hydroxyl group, nitro group, straight-chain or branched-chain alkyl groups having 1 to 8 carbon atoms, cyclopentyl group, cyclohexyl group, straight-chain or branched-chain alkoxy groups having 1 to 8 carbon atoms, one having a straight-chain or branched-chain Alkyl group having 1 to 8 carbon atoms substituted dialkylamino group, phenyl group, naphthyl group, anthryl group, fluorenyl group, styryl group, pyridyl group, pyridindolyl group, quinolyl group, benzothiazolyl group, etc., and these substitution groups may be further substituted.

As examples of the "aromatic hydrocarbon group" of the "substituted or unsubstituted aromatic hydrocarbon group" for R ₁ to R ₄ in the general formula (1), a group such as a phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthryl group, phenanthryl group, fluorenyl group , Indenyl group, pyrenyl group, etc., may be mentioned.

As examples of the "substitution group" of the "substituted or unsubstituted aromatic hydrocarbon group" for R ₁ to R ₄ in the general formula (1), concrete groups such as a fluorine atom, chlorine atom, cyano group, hydroxyl group, nitro group, straight-chain or branched-chain alkyl group may be used having 1 to 8 carbon atoms, cyclopentyl group, cyclohexyl group, straight-chain or branched alkoxy group having 1 to 8 carbon atoms, a dialkylamino group substituted with a straight-chain or branched-chain alkyl group having 1 to 8 carbon atoms, phenyl group, naphthyl group, anthryl group, fluorenyl group, styryl group, pyridyl group, pyridindolyl group, quinolyl group , Benzothiazolyl group, etc., and these substitution groups may be further substituted.

As examples of the "hetero ring" or "fused polycyclic aromatic group" of the "substituted or unsubstituted hetero ring group or substituted or unsubstituted fused polycyclic aromatic group" for R ₁ to R ₄ in the general formula (1), a group such as a pyridyl, triazyl, pyrimidyl, furanyl, pyranyl, thiophenyl, quinolyl, isoquinolyl, benzofuranyl, benzothiophenyl, indolyl, carbazolyl, benzoxazolyl, benzothiazolyl, quinoxalyl, benzimidazolyl, pyrazolyl, dibenzofuranyl, dibenzothiophenyl, naphthyridinyl, phenanthrolinyl, acridinyl, etc. groups become.

As examples of the "substitution group" of the "substituted or non-substituted hetero ring group or substituted or unsubstituted fused polycyclic aromatic group" for R ₁ to R ₄ in the general formula (1), concrete groups such as a fluorine atom, chlorine atom, cyano group , Hydroxyl group, nitro group, straight-chain or branched-chain alkyl group having 1 to 8 carbon atoms, cyclopentyl group, cyclohexyl group, a straight-chain or branched-chain alkoxy group having 1 to 8 carbon atoms, a dialkylamino group substituted with a straight-chain or branched-chain alkyl group having 1 to 8 carbon atoms, phenyl group, naphthyl group, anthryl group , Fluorenyl group, styryl group, pyridyl group, pyridindolyl group, quinolyl group, benzothiazolyl group, tenoyl group, etc., and these substitution groups may be further substituted.

In the general formula (1), C ₁ and C ₂ independently represent a carbon atom having a substituted or unsubstituted group. As examples of this "substitution group", concrete groups such as a fluorine atom, chlorine atom, cyano group, hydroxyl group, nitro group, straight chain or branched-chain alkyl group having 1 to 8 carbon atoms, cyclopentyl group, cyclohexyl group, straight-chain or branched alkoxy group having 1 to 8 carbon atoms, a dialkylamino group substituted with a straight-chain or branched-chain alkyl group having 1 to 8 carbon atoms, phenyl group, naphthyl group, anthryl group, fluorenyl group, styryl group, pyridyl group , Pyridindolyl group, quinolyl group, benzothiazolyl group, tenoyl group, etc., and these substitution groups may be further substituted.

Further, the above-mentioned R ₁ and R ₂ , R ₃ and R ₄ and C ₁ and C _{2 may} form a ring structure with each other.

As the active ingredient of the copolymerization in which a charge control agent consisting of a macromolecular compound of the present invention can be prepared, a compound represented by the above-mentioned general formula (1) can be used alone, and 2 or more thereof can also be used in combination.

A charge control agent consisting of a macromolecular compound of the present invention is a macromolecular compound in which a compound represented by the above-mentioned general formula (1) is copolymerized with an alkenyl group-containing compound (monomer). The proportion of the compound represented by the above-mentioned general formula (1) in the copolymerized macromolecular compound is 0.1 to 80 mol%. It is preferably 1 to 70 mol%. Here, only the general mode of use, and the proportions of monomers forming the copolymer can be suitably varied to obtain the desired charge effect.

As an alkenyl group-containing monomer used for the copolymerization of the charge control agent consisting of a macromolecular compound of the present invention, any known species can be used. In the following, examples of the styrene-based monomers, acrylate-based monomers and methacrylate-based monomers constituting the macromolecular compound as an alkenyl group-containing monomer which forms the macromolecular compound by copolymerizing with the compound represented by the above-mentioned general formula (1) will be mentioned no restriction.

Styrene species such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-amylstyrene, p-tert-butylstyrene, pn-, may be used as examples of the styrene-based monomers. Hexylstyrene, pn-octylstyrene, pn-nonylstyrene, p-decylstyrene, p-dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene, etc., and their derivatives become.

As examples of the acrylate-based monomers, there may be mentioned acrylic acid such as acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, n-dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, etc. and their ester types become.

As examples of the methacrylate-based monomers, there may be mentioned methacrylic acid such as methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, n-dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, etc. and their ester types become.

As examples of the other monomers used for a charge control agent consisting of a macromolecular compound of the present invention, the following (1) to (18) may be mentioned. (1) monoolefin types such as ethylene, propylene, butylene, isobutylene, etc .; (2) polyene species such as butadiene, isoprene, etc .; (3) halogenated vinyl species such as vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride, etc .; (4) vinyl ester species such as vinyl acetate, vinyl propionate, vinyl benzoate, etc .; (5) vinyl ether types such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, etc .; (6) vinyl ketone species, vinyl methyl ketone, vinyl hexyl ketone, methylisopropenyl ketone, etc .; (7) N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone, etc .; (8) vinyl naphthalene species; (9) acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide, etc .; (10) unsaturated dibasic acid species such as maleic acid, citraconic acid, itaconic acid, alkenylsuccinic acid, fumaric acid, mesaconic acid, etc .; (11) unsaturated dibasic Säureanhydridarten such as maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride, (12) Monomethylester of unsaturated dibasic acid species, such as monomethyl maleate, monoethyl maleate, monobutyl maleate, Citraconsäuremonomethylester, Citraconsäuremonoethylester, Citraconsäuremonobutylester, monomethyl itaconate, Alkenylbernsteinsäuremonomethylester, monomethyl fumarate, Mesaconsäuremonomethylester etc .; (13) unsaturated dibasic acid ester species such as dimethyl maleate, dimethyl fumarate, etc .; (14) α, β-unsaturated acid species such as crotonic acid, cinnamic acid, etc .; (15) α, β-unsaturated anhydride species such as crotonic anhydride, cinnamic anhydride, etc .; (16) monomers with carboxyl group, such as. B. anhydride of one of the above-mentioned α, β-unsaturated acid species and one of the lower fatty acids, alkenylmalonic, alkenylglutaric, Alkenyladipinsäure, and acid anhydrides thereof or monoesters thereof; (17) acrylic acid or methacrylic acid hydroxyalkyl ester species such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, etc .; (18) Monomers having a hydroxy group such as 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1-methylhexyl) styrene, etc.

A charge control agent consisting of a macromolecular compound of the present invention is a charge control agent having an active ingredient macromolecular compound containing 1 unit or more of the unit represented by the following general formula (2).

R _{5 of} the general formula (2) represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a nitro group, a cyano group, a substituted carbonyl group, a sulfur substitution group, an alkoxy group, an alkylureido group, or a substituted or unsubstituted, respectively , straight-chain or branched-chain alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted hetero ring group or a substituted or unsubstituted condensed polycyclic aromatic group. "n" is an integer.

As examples of the "substituted carbonyl group, sulfur substitution group" for R ₅ in the general formula (2), there can be mentioned an alkoxycarbonyl group, an alkylcarbamoyl group, an alkoxysulphonyl group, an alkylsulfamoyl group, an alkylsulphonyl group, an alkylureidosulphonyl group, etc.

As examples of the "straight-chain or branched-chain alkyl group having 1 to 18 carbon atoms" of the "substituted or unsubstituted, straight-chain or branched-chain alkyl group having 1 to 18 carbon atoms" for R ₅ in the general formula (2), a methyl group, ethyl group , n-propyl, 2-propyl, n-butyl, sec-butyl, 2-methylpropyl, tert-butyl, n-pentyl, 1-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, n -Hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1,4-dimethylbutyl , 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethyl-2-methylpropyl group, 1,1,2-trimethylpropyl group, etc. are mentioned.

As examples of the "substitution group" of the "substituted or unsubstituted straight-chain or branched-chain alkyl group having 1 to 18 carbon atoms" for R ₅ in the general formula (2), concrete groups such as fluorine atom, chlorine atom, cyano group, hydroxyl group, Nitro group, cyclopentyl group, cyclohexyl group, a straight or branched chain alkoxy group having 1 to 8 carbon atoms, an alkylamino group substituted with a straight or branched chain alkyl group having 1 to 8 carbon atoms, a straight or branched chain acyl group having 1 to 8 carbon atoms, a straight chain or branched alkoxycarbonyl group having 1 to 8 carbon atoms, epoxyalkyl groups having 1 to 8 carbon atoms, phenyl, naphthyl, anthryl, fluorenyl, styryl, pyridyl, pyridoindolyl, quinolyl, benzothiazolyl, etc., and these substitution groups may be further substituted.

As examples of the "cycloalkyl group having 5 to 10 carbon atoms" of the "substituted or unsubstituted cycloalkyl group having 5 to 10 carbon atoms" for R ₅ in the general formula (2), there may be mentioned a cyclopentyl group, cyclohexyl group, cycloheptylene group, cyclooctylene group, cyclononylene group or cyclodecylene group become.

As examples of the "substitution group" of the "substituted or unsubstituted cycloalkyl group having 5 to 10 carbon atoms" for R ₅ in the general formula (2), concrete groups such as a fluorine atom, chlorine atom, cyano group, hydroxyl group, nitro group, a straight-chain or branched-chain alkyl group having 1 to 8 carbon atoms, cyclopentyl group, cyclohexyl group, a straight-chain or branched-chain alkoxy group having 1 to 8 carbon atoms, a dialkylamino group substituted with a straight-chain or branched-chain alkyl group having 1 to 8 carbon atoms, phenyl group, naphthyl group, anthryl group, fluorenyl group, styryl group, pyridyl group, Pyridindolyl group, quinolyl group, benzothiazolyl group, etc., and these substitution groups may be further substituted.

As examples of the "aromatic hydrocarbon group" of the "substituted or unsubstituted aromatic hydrocarbon group" for R ₅ in the general formula (2), groups such as a phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthryl group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group etc., to be called.

As examples of the "substitution group" of the "substituted or unsubstituted aromatic hydrocarbon group" for R ₅ in the general formula (2), concrete groups such as fluorine atom, chlorine atom, cyano group, hydroxyl group, nitro group, straight-chain or branched-chain alkyl group may be used 1 to 8 carbon atoms, cyclopentyl group, cyclohexyl group, a straight-chain or branched-chain alkoxy group having 1 to 8 carbon atoms, a dialkylamino group substituted with a straight-chain or branched-chain alkyl group having 1 to 8 carbon atoms, phenyl group, naphthyl group, anthryl group, fluorenyl group, styryl group, pyridyl group, pyridindolyl group, quinolyl group , Benzothiazolyl group, etc., and these substitution groups may be further substituted.

As examples of the "hetero ring" or "fused polycyclic aromatic group" of the "substituted or unsubstituted hetero ring group or substituted or unsubstituted fused polycyclic aromatic group" for R ₅ in the general formula (2), groups such as a pyridyl group , Triazyl, pyrimidyl, furanyl, pyranyl, thiophenyl, quinolyl, isoquinolyl, benzofuranyl, benzothiophenyl, indolyl, carbazolyl, benzoxazolyl, benzothiazolyl, quinoxalyl, benzimidazolyl, pyrazolyl, dibenzofuranyl, dibenzothiophenyl, naphthyridinyl, phenanthrolinyl, acridinyl, etc. groups.

As examples of the "substitution group" of the "substituted or non-substituted hetero ring group or substituted or unsubstituted fused polycyclic aromatic group" for R ₅ in the general formula (2), concrete groups such as fluorine atom, chlorine atom, cyano group, hydroxyl group A nitro group, a straight-chain or branched-chain alkyl group having 1 to 8 carbon atoms, cyclopentyl group, cyclohexyl group, a straight-chain or branched-chain alkoxy group having 1 to 8 carbon atoms, a dialkylamino group substituted with a straight-chain or branched-chain alkyl group having 1 to 8 carbon atoms, phenyl group, naphthyl group, anthryl group, Fluorenyl group, styryl group, pyridyl group, pyridindolyl group, quinolyl group, benzothiazolyl group, tenoyl group, etc., and these substitution groups may be further substituted.

In the following, concrete examples of the preferred compounds of the compounds usable in this invention represented by the general formula (1) are shown, but this invention is not limited to these compounds.

The following are concrete examples of the macromolecular compounds obtained by copolymerizing one of the compounds represented by the general formula (1) and one of the alkenyl group-containing compounds, but this invention is not limited to these compounds.

In the following structural formulas, some of the hydrogen atoms are omitted.

A macromolecular compound copolymerized with an alkenyl group-containing compound may also have a crosslinking structure crosslinked with a crosslinking agent having 2 or more alkenyl groups in a charge control agent consisting of a macromolecular compound of the present invention, and crosslinking agents used in such cases For example, an aromatic divinyl compound, for example, divinylbenzene or divinylnaphthalene, may be mentioned. As the diacrylate compounds bonded with an alkyl chain, there may be exemplified ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and compounds in which the acrylates of the above mentioned compounds are each exchanged with a methacrylate, called.

A charge control agent consisting of a macromolecular compound of the present invention is a copolymer, the type of polymerization of which is not particularly limited, i. H. The type of polymerization may be both a random copolymerization and a block copolymerization, or else a graft copolymerization. The method of polymerizing a charge control agent of the present invention is not particularly limited, and exemplified by a bulk polymerization, a solution polymerization, a suspension polymerization, etc.

In a polymerization reaction of a charge control agent of the present invention, a polymerization initiator (s) is / are used. A polymerization initiator used in a polymerization according to the present invention is not particularly limited as long as it is usable for a normal radical polymerization, and as examples thereof, organic peroxides such as e.g. Benzoyl peroxide, lauroyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, t-butyl peroxy-2-ethylhexanoate, di-t-butyl peroxide, etc .; Azo connections, such as Azobisisobutyronitrile, azobiscyclohexanecarbonitrile, azobis (2,4-dimethylvaleronitrile), etc .; Persulfide-based initiator, such as. As potassium persulfate, etc. may be mentioned. These may be used singly, and 2 or more of them may be used in combination.

Depending on the type of the monomer selected for the copolymerization, a polymerization initiator for cationic polymerization and anionic polymerization, respectively, may be used. For example, if this is a cationic polymerization, sulfuric acid, hydrochloric acid, nitric acid, p-toluenesulfonic acid, trifluoroacetic acid, etc. may be used. For example, if this is anionic polymerization, lithium, sodium, potassium, lithium hydroxide, sodium hydroxide, sodium methoxide, t-butoxy-potassium, lithium aluminum tetrahydroxide, pyridine, triethylamine, etc. may be used. These may be used singly, and 2 or more of them may be used in combination.

A polymerization initiator is used based on 100 parts by weight of the monomer in a concentration of 0.05 to 30 parts by weight, preferably 0.1 to 15 parts by weight. The reaction temperature is not particularly limited, and is adjusted depending on the kinds of the solvents, the initiator and the monomers, and preferably the polymerization reaction is carried out at a temperature of 40 ° C to 150 ° C.

The weight-average molecular weight (Mw) of a macromolecular compound serving as an effective ingredient in a charge control agent of the present invention is acceptable as long as it is in a range of 1,000 to 100,000, and it should preferably be in a range of 5,000 to 80,000. If its weight-average molecular weight (Mw) is less than 1,000, sufficient affinity with the toner resin can not be expected more, and thus the dispersibility can not be improved. However, if it has a weight-average molecular weight (Mw) of more than 100,000, its viscosity becomes so high that the fixability of the toner using it deteriorates.

The volume-average particle diameter (laser diffraction / scattering particle size measurement method) of the charge control agent according to the invention should preferably be adjusted in the application in a range between 0.1 and 20 .mu.m, in particular in a range between 0.1 and 10 .mu.m. If the volume-average particle diameter is 0.1 μm or smaller, the charge control agents appearing on the toner surface become so small that the target can not be attained, i. H. no charge control effect is obtained, but on the other hand, if it is 20 μm or larger, more and more charge control agents will fall out of the toner, and thus adverse effects such as contamination of the inside of a device may occur, and this is undesirable. However, if the above-mentioned average particle diameter is within the above-mentioned range, not only the above-mentioned defects do not occur, but also decreases an inhomogeneous distribution among the toners, that is. H. The distribution in the toner is improved, and the variations in performance and reliability are thus advantageously smaller.

If a charge control agent consisting of a macromolecular compound according to the invention is used in a triboelectrification toner, this toner additionally contains u in addition to the charge amount. a. a binder resin, a colorant, a wax, and other various additives as needed.

As a method of adding the charge control agent to the toner to be used in the present invention, a method of mixing, mixing and pulverizing (powdered toner) together with the colorant, etc., to the compound resin, or a method of polymerizing single-use Monomer, a compound represented by the general formula (1) is added, and a toner is obtained by this polymerization, and a method in which the polymerizable single monomer is a copolymer of the compound represented by the general formula (1) and the Alkenylgruppenhaltigen monomer (macromolecular compound) is dispersed, and a toner is obtained by polymerization (polymerization toner). As other methods of adding the charge control agent, a method of preliminarily adding (toning) the toner to the toner in advance to prepare toner particles or a method of applying to the surface of these toner particles (external charging) may be employed. Addition) will be called.

The suitable amount of a charge control agent consisting of a macromolecular compound of the present invention, when added internally to the toner particles, is preferably 0.1 to 20 parts by weight, more preferably 1 to 10 parts by weight, to the 100 parts by weight of the binder resin.

The suitable amount of a charge control agent consisting of a macromolecular compound of the present invention, when externally added to the toner particles, is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, to the 100 parts by weight of the binder resin. shares. In this case, it is preferably mechanochemically fixed on the toner particle surface.

In this invention, a charge control agent whose active ingredient is a macromolecular compound consisting of a copolymerization product between a compound represented by the following general formula (1) and an alkenyl group-containing compound can be used together with other previously known negatively chargeable charge control agents. As suitable charge control agents which can be used together, azo-iron complexes or complex salts thereof, azo-chromium complexes or complex salts thereof, azo-manganese complexes or complex salts thereof, azo-cobalt complexes or complex salts thereof, azo-zirconium complexes or complex salts thereof , Chromium complexes of carboxylic acid derivatives or complex salts thereof, zinc complexes of carboxylic acid derivatives or complex salts thereof, aluminum complexes of carboxylic acid derivatives or complex salts thereof and zirconium complexes of carboxylic acid derivatives or complex salts thereof. As the above-mentioned carboxylic acid derivative, an aromatic hydroxycarboxylic acid is further preferable preferably 3,5-di-tert-butylsalicylic acid. Further examples which may be mentioned are boron complexes or complex salts thereof and a negatively chargeable resin charge control agent.

The suitable amount of charge control agents other than the charge control agent consisting of a macromolecular compound of the present invention in a common use of the charge control agent consisting of a macromolecular compound of the present invention with further charge control agents is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the binder resin ,

As a connector resin to be used for a toner of the present invention, any of the already known connector resins can be used. For this, polyester-based polymers such as vinyl polymers of styrene-based monomer, acrylate-based monomer, methacrylate-based monomer, etc., or copolymers of 2 or more kinds of the above-mentioned monomers, as well as polyol resins, phenolic resins, silicone resins, polyurethane resins, polyamide resins, furan resins , Epoxy resins, xylene resins, terpene resins, coumarone-indene resins, polycarbonate resins and petroleum-based resins, etc.

As examples of the monomers or the other monomers which form the abovementioned vinyl polymers or the copolymers, the following (1) to (18) may be mentioned. (1) monoolefin types such as ethylene, propylene, butylene, isobutylene, etc .; (2) polyene species such as butadiene, isoprene, etc .; (3) halogenated vinyl species such as vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride, etc .; (4) vinyl ester species such as vinyl acetate, vinyl propionate, vinyl benzoate, etc .; (5) vinyl ether types such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, etc .; (6) vinyl ketone species, vinyl methyl ketone, vinyl hexyl ketone, methylisopropenyl ketone, etc .; (7) N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone, etc .; (8) vinyl naphthalene species; (9) acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide, etc .; (10) unsaturated dibasic acid species such as maleic acid, citraconic acid, itaconic acid, alkenylsuccinic acid, fumaric acid, mesaconic acid, etc .; (11) unsaturated dibasic Säureanhydridarten such as maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride, (12) Monomethylester of unsaturated dibasic acid species, such as monomethyl maleate, monoethyl maleate, monobutyl maleate, Citraconsäuremonomethylester, Citraconsäuremonoethylester, Citraconsäuremonobutylester, monomethyl itaconate, Alkenylbernsteinsäuremonomethylester, monomethyl fumarate, Mesaconsäuremonomethylester etc .; (13) unsaturated dibasic acid ester species such as dimethyl maleate, dimethyl fumarate, etc .; (14) α, β-unsaturated acid species such as crotonic acid, cinnamic acid, etc .; (15) α, β-unsaturated anhydride species such as crotonic anhydride, cinnamic anhydride, etc .; (16) monomers with carboxyl group, such as. B. anhydride of one of the above-mentioned α, β-unsaturated acid species and one of the lower fatty acids, alkenylmalonic, alkenylglutaric, Alkenyladipinsäure, and acid anhydrides thereof or monoesters thereof; (17) acrylic acid or methacrylic acid hydroxyalkyl ester species such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, etc .; (18) Monomers having a hydroxy group such as 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1-methylhexyl) styrene, etc.

A vinyl polymer or copolymer for a binder resin in a toner of the present invention may also have a crosslinking structure crosslinked with a crosslinking agent having 2 or more alkenyl groups, and as a crosslinking agent which can be used in such cases, a divinylbenzene, for example, divinylbenzene or Divinylnaphthalene, called. As the diacrylate compounds bonded with an alkyl chain, there may be exemplified ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and compounds in which the acrylates of the above mentioned compounds are each exchanged with a methacrylate, called.

Such crosslinking agents may preferably be used in an amount of 0.01 to 10 parts by weight, in particular 0.03 to 5 parts by weight, based on the 100 parts by weight of the other monomer components. Of the above-mentioned crosslinking monomers, with respect to the fixing property on the toner resin and the anti-offset properties, aromatic divinyl compounds (particularly, the divinylbenzene) and diacrylate compounds having a linking chain, which is an aromatic group, are preferable. n and an ether bond. Of these, particularly suitable are those combinations of monomers with which a styrene-based copolymer or a copolymer based on styrene-acrylate can be obtained.

When a styrene-acrylate-based resin is to be used as the binder resin, this resin should preferably be a resin having at least one peak of molecular weight, referred to as molecular weight distribution, due to its fixing property, offset property and storability Measuring the soluble component of the resin component in tetrahydrofuran (hereinafter abbreviated to THF) by gel permeation chromatography (hereinafter abbreviated to GPC) in the molecular weight range of 3k to 50k (converted into the number average molecular weight) and at least one peak in the molecular weight range of ≥ 100k. Also, a binder resin is suitable for this, in which the proportion of 50 to 90% of the molecular weight distribution of the THF-soluble portion is ≦ 100k. More preferred is a resin having a major peak in the molecular weight range between 5k and 30k, optimally in the molecular weight range between 5k and 20k.

When the binder resin is a vinyl polymer, such as. G., A styrene-acrylate-based resin, its acid value is preferably 0.1 mg KOH / g to 100 mg KOH / g, more preferably 0.1 mg KOH / g to 70 mg KOH / g, still more preferably 0.1 mg KOH / g to 50mg KOH / g.

As the monomer which forms a polyester-based polymer, the following may be mentioned.
Examples of the dihydric alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 6-hexanediol, neopentyl glycol, 2-ethyl-1 , 3-hexanediol, hydrogenated bisphenol A and diol, which is obtained by polymerization of cyclic ethers, such as. For example, ethylene oxide, propylene oxide, etc. may be mentioned.

Preferably, a trihydric or higher alcohol is used to crosslink the polyester resin. As examples of the trihydric or higher alcohols, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentatriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene, etc. may be mentioned.

As examples of the acid component constituting the above-mentioned polyester-based polymer, there may be mentioned benzenedicarboxylic acids such as benzoic acid. As phthalic acid, isophthalic acid, terephthalic acid, etc., or anhydrides thereof, alkyl dicarboxylic acids, such as. As succinic acid, adipic acid, sebacic acid, azelaic acid, etc., or anhydrides thereof, unsaturated dibasic acids, such as. For example, maleic acid, citraconic, itaconic, alkenyl, fumaric, mesaconic, etc., and unsaturated dibasic acid anhydrides, such. For example, maleic anhydride, citraconic anhydride, itaconic anhydride, alkenylsuccinic anhydride, etc. may be mentioned. Further, as examples of the trihydric or higher polycarboxylic acid components, trimellitic acid, pyromellitic acid, 2,5,7-naphthalene tricarboxylic acid, 1,2,4-naphthalene tricarboxylic acid, 1,2,4-butane tricarboxylic acid, 1,2,5-hexane tricarboxylic acid, 1,3-dicarboxy 2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxy) methane, 1,2,7,8-octantetracarboxylic acid, Empol-trimer acid, etc., or anhydrides or partially lower alkyl esters thereof.

When a polyester-based resin is to be used as the binder resin, this resin should preferably be a resin having at least one peak of molecular weight as the molecular weight distribution of the THF-soluble portion in terms of the fixing property of the toner and the anti-offset property Resin component specified, in a molecular weight range between 3k to 50k is present, and also suitable is a connector resin for this, in which the proportion of 60 to 100% of the molecular weight distribution of the THF-soluble portion is ≤ 100k. It is further preferred if at least one peak in the molecular weight range between 5k and 20k is present. The molecular weight distributions of the binder resins in this invention are measured by GPC using THF as a solvent.

1. (1) Die Proben werden vor der Nutzung so präpariert, dass alle Zusatzstoffe außer dem Verbinderharz (Polymerkomponente) beseitigt werden, oder dass die Säurewerte sowie der Anteil an allen Komponenten außer dem Verbinderharz und vernetztem Verbinderharz vorab ermittelt werden. 0,5 bis 2,0g der zerkleinerten Proben werden präzise abgemessen, und das Gewicht der Polymerkomponenten wird mit Wg bezeichnet. Beispielsweise, wenn der Säurewert des Verbinderharzes des Toners ermittelt werden soll, werden vorab der Säurewert und der Anteil des Färbemittels oder des magnetischen Körpers separat gemessen, und der Säurewert des Verbinderharzes rechnerisch ermittelt.
2. (2) In ein 300 (ml) Becherglas wird die Probe gegeben, und um diese zu lösen, wird dazu 150 (ml) Mischlösung aus Toluen/Ethanol (Volumenverhältnis = 4/1) gegeben.
3. (3) Eine Titration mittels eines potentiometrischen Titrators unter Verwendung von 0,1mol/L Ethanollösung von KOH wird durchgeführt.
4. (4) Die verwendete Menge an KOH-Lösung wird mit S (ml) und die gleichzeitig bei der Nullprobe verwendete Menge an KOH-Lösung wird mit B (ml) bezeichnet, und dies wird in die folgende Formel (1) eingesetzt. Hierbei ist f der Faktor der KOH-Konzentration. $$\text{Säurewert }\left(\text{mgKOH/g}\right)=\left[\left(\text{S}-\text{B}\right)\times \text{f}\times 5.61\right]\text{/W}$$
   

In this invention, the acid value of the binder resin components of the toner composition is determined by the following method, with the basic operations being carried out according to JIS K-0070.

1. (1) The samples are prepared before use so as to eliminate any additives other than the binder resin (polymer component), or the acid values as well as the content of all components other than the binder resin and crosslinked resin binder are preliminarily determined. 0.5 to 2.0 g of the crushed samples are precisely measured, and the weight of the polymer components is designated Wg. For example, when the acid value of the binder resin of the toner is to be detected, the acid value and the content of the colorant or the magnetic body are previously measured separately, and the acid value of the binder resin is calculated.
2. (2) In a 300 (ml) beaker, the sample is added, and to solve this, 150 (ml) mixed solution of toluene / ethanol (volume ratio = 4/1) is added.
3. (3) Titration by means of a potentiometric titrator using 0.1 mol / L ethanol solution of KOH is performed.
4. (4) The amount of KOH solution used is designated by S (ml), and the amount of KOH solution simultaneously used in the blank sample is designated by B (ml), and this is substituted into the following formula (1). Here f is the factor of the KOH concentration. $$\text{acid value}\left(\text{mg KOH / g}\right)=\left[\left(\text{S}-\text{B}\right)\times \text{f}\times 5.61\right]\text{/ W}$$
   

The binder resin of the toner and the compound having the binder resin should have a glass transition temperature (Tg) with respect to the storability of the toner, which is preferably a temperature between 35 and 80 ° C, especially 40 to 75 ° C. If the Tg is lower than a temperature of 35 ° C, the toner tends to deteriorate in a high-temperature atmosphere, causing more frequent offsets when fixing. However, if the Tg is higher than a temperature of 80 ° C, the fixation property tends to deteriorate. For the polymer toner of the present invention, it is preferable to use a binder resin whose softening point is in a range between 80 and 140 ° C. If the softening point of the bonding resin is at a temperature of 80 ° C or lower, image stability after fixing or stability in storage of the toner may deteriorate. On the other hand, if the softening point is at a temperature of 140 ° C or higher, fixability at a low temperature may possibly deteriorate.

For a black toner, black or blue dyes or pigments may be used as the colorants in this invention. As the black and blue pigments, for example, carbon black, aniline black, acetylene black, phthalocyanine blue, indanthrene blue, etc. can be used. Further, as the black and blue dyes, azo dyes, anthraquinone dyes, xanthene dyes, methine dyes, etc. can be used.

If this is to be used for color toners, all known colorants may be used as colorants without particular limitation. As the colorant for magenta, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dyes, lake dyes, naphthol dyes, benzimidazolone compounds, thioindigo compounds, perylene compounds, etc. can be used. While each of the above-mentioned pigments can be used one by one, it is better for the image quality of a full-color image to be improved by the conjoint application with one of the colorants.

As the colorant for cyan, copper phthalocyanine compounds and derivatives thereof, anthraquinone, brine compounds for basic colorants, etc. can be used.

As the colorant for yellow, condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, allylamide compounds, etc. can be used.

A toner according to the invention may contain wax. There is no limitation to the wax usable in this invention, and the following may be used. Examples are aliphatic hydrocarbon wax, such as. Low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax, paraffin wax, sazole wax, etc. Oxides of aliphatic hydrocarbon wax, such as. Oxidized polyethylene wax etc., as well as block copolymers thereof. Vegetable waxes, such as. As candelilla wax, carnauba wax, wood wax, jojoba wax, etc. Animal waxes such. As beeswax, lanolin, whale wax, etc. Mineral waxes, such as. Ozokerite, ceresin, petrolatum etc.
Wax varieties with fatty acid esters as the main ingredient, such as. As montan ester wax, castor wax, etc., and fatty acid esters, which is partially or completely deoxidized, such as. B. deoxidized carnauba wax etc.

The wax useful in this invention preferably has a melting point of 50 to 140 ° C, more preferably 70 to 120 ° C, to set a trade-off between the fixing property and the anti-offset property. If the melting point is lower than 50 ° C, the blocking resistance tends to deteriorate, but if it is higher than 140 ° C, it becomes more difficult for the anti-offset effect to be effective.

In addition, use of 2 or more different types of wax makes it possible for the softening effect and the demolding effect, which are the respective effects of the wax, to be effective at the same time.
As examples of use may include a combination of 2 or more waxes, in which the difference between the melting points 10 ° C to 100 ° C, and a combination between polyolefin and graft-modified polyolefin may be mentioned.

If 2 types of waxes are to be selected and they have a similar structure, the wax with a relatively lower melting point contributes to the softening effect, and the wax with a relatively higher melting point contributes to the demolding effect. If the difference in melting points is 10 to 100 ° C, the functions can be efficiently separated. If the difference is less than 10 ° C, the effect of separating the functions hardly occurs, but if the difference is higher than 100 ° C, the gain due to mutual influences (i.e., their interaction) hardly occurs. For this, at least one of the waxes should have its melting point in a range between 70 and 120 ° C, more preferably between 70 and 100 ° C, so that the effects of separating the functions tend to be better evoked.

In the case of a toner according to the invention, with regard to the efficiency, the total amount of waxes is preferably 0.2 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of binder resin.

To a toner of the present invention may further be incorporated a fluidity improver. A flowability improver can improve the flowability of the toner (toner flows better) by adding it to the surface of the toner. As the flowability improver, any known ones can be used without any particular limitation. Powdered silica, finely powdered titanium oxide, finely pulverized alumina, and even more suitable are treated silica which has been surface-treated with a silane coupling agent or silicone oil. The grain size of the flowability improver is, given as the average primary grain size, preferably in a range between 0.001 and 2 .mu.m, in particular between 0.002 and 0.2 .mu.m.

To a toner according to the invention may be used as further additives to achieve the objectives, e.g. the protection of the photoreceptor and the support, the improvement of the cleaning properties, the adjustment of the thermal properties, the electrical properties as well as the physical properties, the adjustment of the resistance, the setting of the softening point, the improvement of the fixing ratio, various metal soaps, fluorochemical surfactants , Dioctyl phthalate, etc., as a conductivity mediator, such as. As tin oxide, zinc oxide, carbon black, antimony oxide, etc., as well as inorganic fine powder such. For example, titanium oxide, alumina, alumina powder, etc. may be added as needed. Here, these inorganic fine powders can be rendered hydrophobic as needed. In addition, lubricants such. As polytetrafluoroethylene, zinc stearate, polyvinylidene fluoride, etc., abrasives such. Cesium oxide, silicon carbide and strontium titanate, etc., anti-caking agents and white particles and black fine particles having opposite polarities to the toner particles are used as a developer improver.

These additives can, for example, to control the amount of charge with (a) treatment / n, such. As silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane coupling agents, silane coupling agent with functional groups, other organosilicon compounds, etc., as well as treated with various treatment agents.

In this invention, the electrostatic developing toner as a target product can be obtained by adding a charge control agent together with the above additive (s) and the toner to a mixing apparatus such as a toner. As a HENSCHEL mixer, a ball mill, a Nauta mixer, a V-type mixer, a W-type mixer, a super-mixer, etc., sufficiently mixed, and so homogeneously applied to the toner particle surface.

The toner of the present invention is thermally stable, thus it does not thermally change during the electrophotographic process, and can stably maintain the charging property. In addition, since it is homogeneously dispersible in the binder resin, the charge distribution of the fresh toner is very uniform. Therefore, even in a toner not yet transferred and recovered (waste toner) of this toner of the present invention, almost no difference to a fresh toner in the saturation triboelectric charge amount and the charge distribution is observed.

As a method for producing a toner of the present invention, a known production method can be used. In a production process, the above-mentioned toner components such as binder resin, charge control agent, colorant, etc., in a mixing apparatus such as a ball mill, mixed enough. In this case, a method is preferred in which the mixture in a heatable kneading apparatus, such as. B. a thermo-roll kneading machine, further kneaded, fixed by cooling, pulverized and classified (pulverization method).

It is also possible to prepare this by a method in which the above mixture is dissolved in a solvent, finely pulverized by spraying, dried and classified. Further, the toner may be incorporated according to a polymerization toner manufacturing method in which certain ingredients are mixed, emulsified and polymerized into the monomers constituting the binder resin and polymerized into toner, and a method for producing a so-called microcapsule toner which is made of a core material and a shell material, and wherein certain ingredients are added to the core material or shell material or both. Furthermore, a toner according to the invention can also be prepared by adding additives as needed and toner particles by means of a mixing apparatus, such. B. a HENSCHEL mixer, are mixed well.

The charge control agent to be used in this invention is also useful as a charge control agent (electric charge amplifier) for electrostatic powder coating paint. At this time, the electrostatic coating material having this electric charge amplifier has excellent environmental resistance, storage stability, and especially thermal stability and durability, and 100% coating efficiency, and with this, a thick film can be formed without defects.

[Embodiments]

In the following, this invention will be explained with reference to the embodiments, but in no way limits this invention. In the exemplary embodiments, the statements "shares" always represent the "parts by weight".

Synthesis Example 1 (Synthesis of Exemplified Compound 1)

In a 500 ml flask, 23.06 g (0.235 mol) of maleic anhydride was weighed, added to 100 ml of acetone, then stirred at room temperature and under a nitrogen atmosphere and dissolved. 25.00 g (0.196 mol) of 4-chloroaniline dissolved in 50 ml of acetone were slowly added dropwise from a dropping funnel. After reacting for 2.5 hours at room temperature, the reaction solution was poured into 1L of ice water, and after ensuring the yellow precipitates, stirred until the ice melted. A suction filtration was carried out and the filter residue was dried overnight at a temperature of 60 ° C under reduced pressure, and 43.69 g of intermediate product was recovered with a yield of 98.8%.

43.69 g (0.194 mol) of the intermediate was placed in a 300 ml flask and, after addition of 10.00 g of sodium acetic acid and 100 ml of acetic anhydride, heated to a temperature of 50 ° C and reacted over a period of 2 hours. After the reaction, 1000 ml of the reaction solution was transferred to a separatory funnel and subjected to extraction with 300 ml of toluene and 300 ml of water 3 times. The toluene layer was concentrated and a yellow precipitate was obtained by adding tap water to the concentrated solution. The precipitated yellow solid was suction filtered and the filter cake was dried overnight at a temperature of 60 ° C under reduced pressure. The crude crystals were purified by silica gel column chromatography with chloroform as eluent, concentrated by evaporation, and 33.82 g of yellow solid as the target product were obtained in a yield of 83.1%.

For the obtained yellow solid, the structure was determined by NMR, and Example Compound 1 was recovered. The measurement results of ₁ H-NMR (DMSO-d ₆ ) were as follows. 7.57ppm (d, 2H), 7.39ppm (d, 2H), 7.21ppm (s, 2H). The melting point was a temperature of 98.3 ° C.

Synthesis Example 2 (Synthesis of Exemplified Compound 2)

In a 500 ml flask, 11.34 g (0.116 mol) of maleic anhydride was weighed, to which was added 200 ml of acetone, then stirred and dissolved at room temperature under a nitrogen atmosphere. 10.30 g (0.0962 mol) of o-toluidine (ortho toluidine) was dropped slowly from a dropping funnel. After reacting for 4 hours at room temperature, the reaction solution was poured into 500mL of ice-water and, after ensuring the yellow precipitates, stirred until the ice melted. A suction filtration was carried out and the filter residue was dried overnight at a temperature of 70 ° C under reduced pressure, and 14.51 g of intermediate product was recovered in a yield of 73.5%.

14.51 g (0.0707 mol) of the intermediate was placed in a 500 ml flask and, after addition of 0.5 g of p-toluenesulphonic acid, 250 ml of toluene and 25 ml of dimethylacetamide (DMA) was heated to a temperature of 110 ° C and over a period of 6 hours implemented. After the reaction, the reaction solution was transferred to an eggplant flask, concentrated by means of evaporator in an oil bath at a temperature of 80 ° C under reduced pressure until the solvent (toluene) no longer evaporated. The concentrated solution was purified by silica gel column chromatography with toluene as the eluent. This fraction was collected in a 1000 ml eggplant flask, concentrated by evaporation in an oil bath at a temperature of 80 ° C under reduced pressure until the solvent (toluene) no longer evaporated. This was dried overnight at a temperature of 60 ° C under reduced pressure, and 12.1g yellow solid obtained in a yield of 91.0%.

For the obtained yellow solid, the structure was determined by NMR, and Example Compound 2 was recovered. The measurement results of ₁ H-NMR (DMSO-d ₆ ) were as follows. 7.37ppm (m, 2H), 7.30ppm (m, 1H), 7.22ppm (m, 3H), 2.07ppm (m, 3H).

Synthesis Example 3 (Synthesis of Exemplified Compound 3)

Except that o -toluidine was used instead of o-methyl-p-chloroaniline, the procedures were carried out as in the Synthesis example, and 11.85 g of a pale yellow solid were obtained in a yield of 85.4%.

For the obtained pale yellow solid, the structure was determined by NMR and the example compound 3 was recovered. The measurement results of ₁ H-NMR (DMSO-d ₆ ) were as follows. 7.49ppm (d, 1H), 7.39ppm (dd, 1H), 7.28ppm (d, 1H), 7.22ppm (s, 2H), 2.08ppm (s, 3H).

Synthesis Example 4 (Synthesis of Exemplified Compound 4)

After 200 ml of toluene was added to a 500 ml flask, degassing and nitrogen exchange were carried out over a period of 2 hours. Example 1, 16.23 g (0.156 mol) of styrene and 0.42 g (1.93 mmol) of azobisisobutyronitrile (AIBN) obtained in Synthesis Example 1, 32.35 g (0.156 mol) were measured, stirred, under a nitrogen atmosphere to a temperature of 80 ° C heated and reacted over a period of 4 hours. After the reaction, the reaction solution was slowly added to 3L methanol to precipitate a white solid. A suction filtration was carried out and the filter residue was dried overnight at a temperature of 60 ° C under reduced pressure, and 46.11 g of white solid was recovered with a yield of 94.6%.

In order to determine the structure of the white solid, ₁ H-NMR (DMSO-d ₆ ) was measured, and the disappearance of the double-bond-originated proton and the broadening of the peaks by polymerization, and thus Example Compound 4, which was a copolymer of Example compound 1 and styrene is found. The observed peaks were 7.50ppm and 7.18ppm.

The thus-obtained Exemplified Compound 4 was measured by GPC to determine its molecular weight, and the weight-average molecular weight (Mw) was 51353.

Synthesis Example 5 (Synthesis of Exemplified Compound 5)

After adding 100 ml of toluene to a 300 ml flask, degassing and nitrogen exchange were carried out over a period of 2 hours. 12.00 g (0.0641 mol) of Exemplified Compound 2, 6.68 g (0.0641 mol) of styrene and 0.11 g (0.641 mmol) of azobisisobutyronitrile (AIBN) obtained in Synthesis Example 2 were measured, stirred, under a nitrogen atmosphere to a temperature of 80 ° C heated and reacted over a period of 4 hours. After the reaction, the reaction solution was slowly added to 2L methanol to precipitate a white solid. A suction filtration was performed, and the filter residue was dried under vacuum at a temperature of 70 ° C overnight, and 15.92 g of white solid was recovered in 85.2% yield.

To determine the structure of the white solid, ₁ H-NMR (DMSO-d ₆ ) was measured, and the disappearance of the double-bond-originated proton and the broadening of the peaks by polymerization, and thus an example compound 5 constituting a copolymer of Example compound 2 and styrene is found. The observed peaks were 7.29ppm and 2.03ppm.

The thus-obtained Exemplified Compound 5 was measured by GPC to determine its molecular weight, and the weight-average molecular weight (Mw) was 66,148.

Synthesis Example 6 (Synthesis of Exemplified Compound 6)

After adding 80 ml of toluene to a 300 ml flask, degassing and nitrogen exchange were carried out over a period of 2 hours. Example 8 3.65 g (0.0535 mol) of Exemplified Compound 3, 6.68 g (0.0535 mol) of styrene and 0.16 g (0.932 mmol) of azobisisobutyronitrile (AIBN) were measured, stirred, under a nitrogen atmosphere to a temperature of 80 ° C and reacted over a period of 4 hours. After the reaction, the reaction solution was slowly added to 1L methanol to precipitate white solid. A suction filtration was carried out and the filter residue was dried overnight at a temperature of 60 ° C under reduced pressure, and 14.47 g of white solid was recovered in a yield of 82.6%.

In order to determine the structure of the white solid, ₁ H-NMR (DMSO-d ₆ ) was measured, and the disappearance of the double-bond-originated proton and the broadening of the peaks by polymerization, and thus an example compound 6 constituting a copolymer of Example compound 3 and styrene is found. The observed peak was 7.34ppm.

The thus-obtained Exemplified Compound 6 was measured to determine its molecular weight by GPC, and the weight-average molecular weight (Mw) was 7,803.

[Measuring Method of Charge Quantity]

After the charge control agents, that is, the above-mentioned synthesized macromolecular compounds, and toner were charged by means of a blow-off charge quantity measuring apparatus (type TB-200, TOSHIBA Chemical), the initial charge amount and the saturated charge amount (charge over a Duration of 30 minutes) under the respective ambient conditions. The conditions in the blow-off charge amount measurement were as follows.
Amount of developing agent: 0.2000 g ± 0.005 g
Blow duration: 60 seconds
N ₂ blow pressure: 0.2 kgf / cm ² (silicone coating F96-150),
T / C = 4%,
Speed of the ball mill: 110rpm.

[Embodiment 1]

[Measurement of the amount of charge only from the compound which is the charge control agent]

0.5 parts of the macromolecular compound obtained in Synthesis Example 4 (Example Compound No. 4) were mixed, shaken, and so on as in Synthesis Example 4, per 100 parts of ferrite carrier with silicone coating (Powder Tech KABUSHIKI GAISHA, F96-150) obtained compound electrically charged. After charging, the saturated charge amount was measured by means of a blow-off charge amount measuring apparatus (Type TB-200, TOSHIBA Chemical Co.) at a temperature of 25 ° C and under an atmosphere of 50% humidity (NN atmosphere). The same measurement was also carried out with the uncoated carrier (Powder Tech KABUSHIKI GAISHA, F150). The measurement results of the charge amount are shown in Table 1.

[Measurement of the charge amount of the dummy toner]

91 parts of polyester-based resin (MITSUBUISHI RAYON KABUSHIKI GAISHA, trade name FC-316, acid value 9 mgKOH / g), 1 part of the macromolecular compound synthesized in Synthetic Example 4 (Example Compound No. 4), 5 parts of carbon black (MITSUBUISHI KYGAKU KABUSHIKI GAISHA , Trade name MA-100) and 3 parts of low molecular weight polypropylene (SANYŌ KASEI KABUSHIKI GAISHA, trade name VISCOL 550P) was mixed by means of a heatable mixing apparatus (2-axis extruder kneader) at a temperature of 130 ° C in the molten state. The cooled mixture was coarsely crushed by means of a hammer mill, finely crushed by a jet mill, classified, thereby obtaining non-magnetic toner having a volume-average particle diameter of 9 ± 0.5 μm.

The thus obtained non-magnetic toner and ferrite carrier (Powder Tech KABUSHIKI GAISHA, F96-150) was mixed in a ratio of 4 to 100 parts by weight (toner: carrier) and shaken to mix, thus negatively charged, and the saturated charge amount was measured by means of a blow-off charge quantity measuring apparatus (type TB-200, TOSHIBA Chemical) at a temperature of 25 ° C and under an atmosphere of 50% humidity (NN atmosphere). The results are shown in Table 1. The same measurement was also carried out with the uncoated carrier (Powder Tech KABUSHIKI GAISHA, F150). The measurement results of the charge amount are shown in Table 1.

[Embodiments 2 - 3]

The saturated charge amount of the respective macromolecular compound (Example Compound No. 5 and Example Compound No. 6) obtained in Synthesis Example 5 and Synthesis Example 6, respectively, was measured by the same method as Embodiment 1, and the results are shown in FIG Table 1 shown.

From the respective macromolecular compound obtained in Synthesis Example 5 and Synthesis Example 6, respectively, a dummy toner was prepared by the same method as Embodiment 1, then the saturated charge amount of the non-magnetic toner thus obtained was measured, and the results are shown in Table 1.

Comparative Example 1

In order to carry out comparisons, comparative compound 1, ie a macromolecular compound having the following structural formula, was synthesized.

The synthesis of the intermediate compound which is the starting material for the polymerization of Comparative Compound 1 was carried out as follows. In a 300 ml flask, 10.0 g (0.073 mol) of 4-aminobenzoic acid was weighed, to which was added 10 ml of dimethylformamide (DMF), then stirred and dissolved at room temperature under a nitrogen atmosphere. 7.85 g (0.080 mol) of maleic anhydride dissolved in 30 ml of DMF was slowly added dropwise from a dropping funnel. After reacting for 4 hours at room temperature, the reaction solution was added to 1 L of ice-water and, after ensuring the yellow precipitates, stirred until the ice had melted. A suction filtration was carried out and the filter residue was dried overnight at a temperature of 70 ° C under reduced pressure, and 17.1 g of intermediate product was recovered with a yield of 99.5%.

10.0 g (0.043 mol) of the intermediate was placed in a 1000 ml flask and, after addition of 2 g of p-toluenesulphonic acid, 500 ml of toluene, 100 ml of N-methylpyrrolidone and 50 ml of dimethylacetamide, heated to a temperature of 110 ° C over a period of 7 hours implemented. After the reaction, the reaction solution was transferred to an eggplant flask, and by means of an evaporator in an oil bath at a Temperature of 100 ° C under reduced pressure while concentrated until the solvent is no longer evaporated. The concentrated solution was added to 500 ml of ice water. The precipitated yellow solid was suction filtered and the filter cake was dried overnight at 70 ° C under reduced pressure to yield 8.8 g of light yellow solid with a yield of 95.3%.

For the light yellow solid obtained, the structure was determined by means of NMR, and the intermediate compound, which is the starting material for the copolymerization of comparative compound 1, was obtained. The measurement results of ₁ H-NMR (DMSO-d ₆ ) were as follows. 8.05ppm (d, 2H), 7.50ppm (d, 2H), 7.22ppm (s, 2H). The melting point was a temperature of 233 ° C.

After 50 ml of dimethylformamide (DMF) was placed in a 100 ml flask, degassing and nitrogen exchange were carried out over a period of 2 hours. 5.0 g (0.023 mol) of the thus obtained intermediate compound for Comparative Compound 1, 2.4 g (0.023 mol) of styrene and 0.1 g (0.460 mmol) of azobisisobutyronitrile (AIBN) were measured, stirred, under a nitrogen atmosphere to a temperature of 80 ° C heated and reacted over a period of 4 hours. After the reaction, the reaction solution was slowly added to 1L methanol to precipitate white solid. A suction filtration was performed and the filter residue was dried under vacuum at a temperature of 70 ° C overnight, and 5.17 g of white solid was recovered with a yield of 69.9%.

In order to determine the structure of the white solid, ₁ H-NMR (DMSO-d ₆ ) was measured, and the disappearance of the double-bond-derived proton and the broadening of the peaks by polymerization, and thus a comparative compound 1 containing a maleimide Styrene copolymer is to be determined. The observed peaks were 7.99ppm and 7.15ppm. The composition of the intermediate compound and comparative compound 1: styrene, determined from the proton ratio, was 55:45.

The comparative compound 1 thus obtained was measured by GPC to determine its molecular weight, and the weight-average molecular weight (Mw) was 66,300.

As in the embodiment 1, the saturated amount of charge was measured only by the comparative compound 1 used as the charge control agent and the saturated amount of charge of the dummy toner prepared by using the comparative compound 1. The results are shown in Table 1.

Comparative Example 2

For comparison, commercially available charge control agent (T-77: colored azo complex, HODOGAYA KAGAKU KŌGYŌ KABUSHIKI GAISHA) was used as a comparative compound, and just as in Embodiment 1, the saturated charge amount was used only by this compound used as the charge control agent and the saturated one Charge amount of the dummy toner measured. The results are shown in Table 1.

Comparative Example 3

For comparison, commercially available charge control agent (TN-105: white salicylic acid complex, HODOGAYA KAGAKU KŌGYŌ KABUSHIKI GAISHA Co.) was used as the comparative compound, and just as in the embodiment 1, the saturated charge amount was used only by this compound used as a charge control agent, and measured the saturated charge amount of the dummy toner. The results are shown in Table 1.
[Table 1] connection Charge amount of individual CCAs Charge amount of the dummy toner N / N N / N N / N N / H ratio N / N F-150 F96-150 F-150 F96-150 Embodiment 1 Example compound 4 -143.38 -104.22 -28.92 1.90 -10.11 Embodiment 2 Example compound 5 -228.37 -163.66 -34.73 1.97 -11.43 Embodiment 3 Example compound 6 -179.79 -160.35 -36.43 1.9 -11.60 Comparative Example 1 Comparative Compound 1 -5.36 -103.80 -28.03 2.65 -10.58 Comparative Example 2 T-77 -119.30 -52.25 -35.49 1.15 -13.65 Comparative Example 3 TN-105 -133.48 -16.32 -30.15 -1.60 -12.93

The results of triboelectric charging evaluation shown in Table 1 show that a copolymer of a synthesized compound represented by the general formula (1) and an alkenyl group-containing compound has a negative chargeability. The value of the saturated charge amount and thus the charging property were much better than the value and the property of a commercial charge control agent. Since a copolymer of the synthesized compound represented by the general formula (1) of the present invention and the alkenyl group-containing compound is a metal-free compound, it is much safer to the human and the environment. Since it is also almost white, it can be used in any color. Further, since it is a macromolecule having a molecular weight of 1,000 or more, in a toner resin for electrophotography, its dispersibility and compatibility can be improved. Thus, a copolymer of the synthesized compound of the present invention represented by the general formula (1) and the alkenyl group-containing compound is a compound which is undoubtedly useful as a charge control agent of macromolecular compounds.

The results on the charging properties of the dummy toners shown in Table 1 show that a toner having a charge control agent consisting of a macromolecular compound of the present invention does not have a poorer charging property than a commercial colored toner or white toner, and hence a charge control agent consisting of a charge control agent The macromolecular compound of the present invention has an excellent effect of imparting a charging property.

[Industrial Applications]

The macromolecular compound which is a copolymer of a synthesized compound of the present invention represented by the general formula (1) and an alkenyl group-containing compound has excellent charging properties. In addition, since it does not contain heavy metal such as a chromium compound which is harmful to the environment, it is excellent in terms of human and environmental safety. It is also useful as a color toner charge control agent and can be used to provide useful toner, both comminuted and polymerized toner.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

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Claims (6)

A charge control agent having a macromolecular compound as an effective ingredient, characterized in that it is a product of a copolymerization of at least one kind of the compound represented by the following general formula (1) and at least one kind of an alkenyl group-containing compound.

(In the formula: R ₁ to R ₄ independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a nitro group, a cyano group, a substituted carbonyl group, a sulfur substitution group, an alkoxy group, an alkylureido group, or a substituted one or unsubstituted, a straight-chain or branched-chain alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted hetero ring group or a substituted or . non-substituted condensed polycyclic aromatic group. C ₁ and C ₂ each independently represent a carbon atom with a substituted or unsubstituted group. Further, R ₁ and R _2, R ₃ and R ₄ and C ₁ and C ₂ together form a Form ring structure "m1" and "m2" are each an integer between 0 and 4. "x" is an integer between 0 and 2.) Charge control agent with a macromolecular compound as an effective ingredient after Claim 1 , characterized in that the proportion of the compound represented by the above-mentioned general formula (1) is 0.1 to 80 mol%. Charge control agent with a macromolecular compound as an effective ingredient after Claim 1 respectively. Claim 2 characterized in that the weight average molecular weight (Mw) of the above-mentioned macromolecular compound is in a range between 1000 and 100,000. Charge control agent with a macromolecular compound as an active ingredient according to any one of Claims 1 to 3 characterized in that the above-mentioned alkenyl group-containing compound is at least one compound selected from a group consisting of styrene, styrene derivative, (metha) acrylic acid, (metha) acrylic acid ester, vinyl ether derivative. Charge control agent with a macromolecular compound as an active ingredient according to any one of Claims 1 to 4 characterized in that the above-mentioned macromolecular compound contains at least 1 unit or more of the unit represented by the following general formula (2).

(In the formula: R ₅ represents a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a nitro group, a cyano group, a substituted carbonyl group, a sulfur substitution group, an alkoxy group, an alkylureido group, or a substituted or unsubstituted, respectively straight-chain or branched-chain alkyl group having 1 to 18 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted hetero ring group or a substituted or unsubstituted condensed polycyclic aromatic Group. "N" is an integer.) Toner, characterized in that this (a) charge control agent after Claim 1 to 5 containing a macromolecular compound as an effective ingredient, colorant and binder resin.