JP7150474B2 - Charge control agent and toner containing polymer compound - Google Patents

Description

The present invention relates to a charge control agent used for charge control of toner for electrophotography and powder coating for electrostatic printing. Further, it relates to a resin composition for electrophotographic toner and an electrophotographic toner.

Copiers using an electrophotographic process are widespread. In recent years, with the development of personal computers and the like, the electrophotographic process has been applied to laser printers, facsimiles and the like. On the other hand, copiers, which have been mainly monochrome until now, are developing to color.

In general, electrophotographic toners are made by adding colorants such as dyes, pigments, carbon black, etc., and charge control agents for controlling chargeability to binder resins such as styrene resins, acrylic resins or polyester resins. there is

At present, azo dyes, salicylic acid metal complexes, etc. are used as charge control agents, but these charge control agents contain metals such as chromium and zinc. issues have been raised from the perspective of In addition, development of a colorless (white) charge control agent corresponding to the coloration is desired from the problem of coloration due to metals. Furthermore, in many cases, the charge control agent is a low-molecular-weight crystal, and it is difficult to uniformly disperse it in the toner due to agglomeration.

Therefore, charge control agents containing no metal element have been developed as colorless (white) charge control agents for colorization. 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. As described above, charge control agents containing no metal elements have been developed, but all of them are low molecular weight substances with a molecular weight of 1000 or less, and the risk of environmental impact due to dissolution or volatilization cannot be completely suppressed.

As an approach to improve the dispersibility and compatibility between the charge control agent and the toner resin, attempts have been made to control the charging property by using a resin having a charge control effect as the raw material of the toner. Furthermore, by using polymer compounds such as resins, it is also possible to reduce the risk of safety to humans and the environment. For example, Patent Documents 3 and 4 propose using a polymer compound obtained by copolymerizing acrylamide sulfonic acid or a salt with styrene, (meth)acrylic acid ester, or the like. Patent Document 5 proposes the use of a (meth)acrylic acid ester polymer having a sulfonylurea structure. Patent Documents 6 and 7 propose using a polymer of a unit having a sulfonic acid or sulfonic acid ester and a unit having a salicylic acid derivative. Patent Documents 8 and 9 propose charge control resins obtained by copolymerizing a styrene derivative having a hydroxybenzoic acid structure and a monomer containing a vinyl group. Patent Document 10 proposes using a polymer of a unit having a sulfonic acid or sulfonic acid ester and a unit having a benzoic acid derivative.

In this way, many proposals have been made in recent years for charge control using polymer compounds for the purpose of improving compatibility with toner resins and reducing environmental impact. Therefore, there are many cases in which it cannot be put to practical use.

JP 2013-060444 A WO2012-102137 Japanese Patent Application Laid-Open No. 2003-270862 Japanese Patent Application Laid-Open No. 2004-191691 Japanese Patent Application Laid-Open No. 2001-188386 JP 2011-128611 A JP 2012-256042 A WO2012-157713 JP 2014-222356 A JP 2014-098857 A

In view of the above, the present invention provides a product that does not contain a metal element, is excellent in safety to humans and the environment, is freely colorable, and has excellent charging characteristics such as charge amount, charge amount distribution, and rise of charge, particularly environmental stability. An object of the present invention is to provide an excellent charge control agent, a resin composition for electrophotographic toner, and an electrophotographic toner using them.

As a result of intensive studies, the present inventors have found that the above problems can be solved by a charge control agent containing the polymer compound of the present invention as an active ingredient, and have completed the present invention. That is, the present invention is a charge control agent and toner as follows.

[1] A charge control agent comprising, as an active ingredient, a polymer compound which is a copolymer reaction product of at least one compound represented by the following general formula (1) and at least one alkenyl group-containing compound.

(wherein R ₁ to R ₄ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a nitro, a cyano group, a substituted carbonyl group, a sulfur substituent, an alkoxy group, an alkylureido group, a substituted or unsubstituted linear or branched alkyl group having 1 to 18 carbon atoms, substituted or unsubstituted cycloalkyl group having 5 to 10 carbon atoms, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted hetero shall represent a cyclic group or a substituted or unsubstituted condensed polycyclic aromatic group, C ₁ to C ₂ each independently represent a carbon atom having a substituted or unsubstituted group, and R ₁ and R ₂ , R ₃ and R ₄ , C ₁ and C ₂ may combine with each other to form a ring structure, m1 and m2 are integers of 0 to 4, x is an integer of 0 to 2; )

[2] A charge control agent containing a polymer compound as an active ingredient, wherein the content of the compound represented by the general formula (1) is 0.1 to 80 mol %.

[3] A charge control agent containing a polymer compound as an active ingredient, wherein the weight average molecular weight (Mw) of the polymer compound is in the range of 1,000 to 100,000.

[4] The active ingredient is a polymer compound, wherein the alkenyl group-containing compound is at least one selected from styrene, styrene derivatives, (meth)acrylic acid, (meth)acrylic acid esters, and vinyl ether derivatives. charge control agent.

[5] A charge control agent containing a polymer compound as an active ingredient, wherein the polymer compound is a polymer compound containing one or more units represented by the following general formula (2).

(In the formula, R ₅ is a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a nitro, a cyano group, a substituted carbonyl group, a sulfur substituent, an alkoxy group, an alkylureido group, a substituted or unsubstituted C 1 to 18 linear or branched alkyl group, substituted or unsubstituted cycloalkyl group having 5 to 10 carbon atoms, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted heterocyclic group or substituted or unsubstituted represents a condensed polycyclic aromatic group of n is an integer.)

[6] A toner containing a charge control agent, a colorant, and a binder resin containing the polymer compound as an active ingredient.

Since the charge control agent of the present invention has high compatibility with the toner resin and can be uniformly dispersed, it is possible to obtain a toner excellent in charging characteristics such as charge amount, charge amount distribution, and charge rise. In addition, it has an almost white appearance and does not affect coloration when used in color toners. Furthermore, since it does not contain metal elements and is a polymer, the possibility of dissolution and volatilization is suppressed, and the impact on the environment is reduced.

Modes for carrying out the present invention will be described in detail below, but the scope of the present invention is not limited to these modes.

The compound represented by general formula (1) used in the present invention can be produced by known methods. For example, compounds for use in the present invention can be synthesized by condensing maleic anhydride with the corresponding aromatic amine.

The charge control agent, which is a polymer compound of the present invention, is a polymer compound which is a copolymer reaction product of at least one compound represented by general formula (1) and at least one alkenyl group-containing compound. It is a charge control agent as an active ingredient.

In general formula (1), R ₁ to R ₄ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a nitro, a cyano group, a substituted carbonyl group, a sulfur substituent, an alkoxy group, an alkylureido group, a substituted or unsubstituted or unsubstituted C1-C18 linear or branched alkyl group, substituted or unsubstituted C5-C10 cycloalkyl group, substituted or unsubstituted aromatic hydrocarbon group, substituted or unsubstituted It represents a substituted heterocyclic group or a substituted or unsubstituted condensed polycyclic aromatic group. Each of C ₁ to C ₂ independently represents a carbon atom having a substituted or unsubstituted group. Furthermore, R ₁ and R ₂ , R ₃ and R ₄ , and C ₁ and C ₂ may combine with each other to form a ring structure. m1 and m2 are integers from 0 to 4; x is an integer from 0 to 2;

In general formula (1), the "substituted carbonyl group, sulfur substituent" for R ₁ to R ₄ includes, for example, an alkoxycarbonyl group, an alkylcarbamoyl group, an alkoxysulfonyl group, an alkylsulfamoyl group, an alkylsulfonyl group, an alkyl A ureidosulfonyl group and the like can be mentioned.

In general formula (1), R ₁ to R ₄ "representing a substituted or unsubstituted linear or branched alkyl group having 1 to 18 carbon atoms" A chain or branched alkyl group" includes, for example, methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, sec-butyl group, 2-methylpropyl group and tert-butyl group. , n-pentyl group, 1-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 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 .

In the general formula (1), the "substituent" in "representing a substituted or unsubstituted C 1 to C 18 linear or branched alkyl group" of R ₁ to R ₄ is specifically a fluorine atom, a chlorine atom, a cyano group, a hydroxyl group, a nitro group, a cyclopentyl group, a cyclohexyl group, a linear or branched alkoxy group having 1 to 8 carbon atoms, a linear or branched chain having 1 to 8 carbon atoms, or dialkylamino group substituted with branched alkyl group, linear or branched acyl group having 1 to 8 carbon atoms, linear or branched alkoxycarbonyl group having 1 to 8 carbon atoms, carbon atom Epoxyalkyl groups, phenyl groups, naphthyl groups, anthryl groups, fluorenyl groups, styryl groups, pyridyl groups, pyridoindolyl groups, quinolyl groups and benzothiazolyl groups of numbers 1 to 8 can be mentioned, and these substituted The group may be further substituted.

In general formula (1), the "cycloalkyl group having 5 to 10 carbon atoms" in the "substituted or unsubstituted cycloalkyl group having 5 to 10 carbon atoms" for R ₁ to R ₄ includes: For example, cyclopentyl, cyclohexyl, cycloheptylene, cyclooctylene, cyclononylene or cyclodecylene.

In general formula (1), the "substituent" in "representing a substituted or unsubstituted cycloalkyl group having 5 to 10 carbon atoms" for R ₁ to R ₄ specifically includes a fluorine atom, chlorine atom, cyano group, hydroxyl group, nitro group, linear or branched alkyl group having 1 to 8 carbon atoms, cyclopentyl group, cyclohexyl group, linear or branched alkoxy group having 1 to 8 carbon atoms, dialkylamino group, phenyl group, naphthyl group, anthryl group, fluorenyl group, styryl group, pyridyl group, pyridoindolyl group, quinolyl group, substituted with a linear or branched alkyl group having 1 to 8 carbon atoms; Groups such as benzothiazolyl groups may be mentioned, and these substituents may be further substituted.

In general formula (1), the "aromatic hydrocarbon group" in "representing a substituted or unsubstituted aromatic hydrocarbon group" for R ₁ to R ₄ includes, for example, a phenyl group, a biphenylyl group, a terphenylyl group and a naphthyl group. , anthryl, phenanthryl, fluorenyl, indenyl and pyrenyl groups.

In general formula (1), specific examples of the "substituent" in "representing a substituted or unsubstituted aromatic hydrocarbon group" for R ₁ to R ₄ include a fluorine atom, a chlorine atom, a cyano group, and a hydroxyl group. , nitro group, linear or branched alkyl group having 1 to 8 carbon atoms, cyclopentyl group, cyclohexyl group, linear or branched alkoxy group having 1 to 8 carbon atoms, 1 to 8 carbon atoms groups such as dialkylamino, phenyl, naphthyl, anthryl, fluorenyl, styryl, pyridyl, pyridoindolyl, quinolyl, and benzothiazolyl groups substituted with linear or branched alkyl groups of and these substituents may be further substituted.

In the general formula (1), the "heterocyclic group" or "condensed polycyclic aromatic group" in "a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted condensed polycyclic aromatic group" for R ₁ to R ₄ group group", for example, pyridyl group, triazyl group, pyrimidyl group, furanyl group, pyranyl group, thiophenyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothiophenyl group, indolyl group, carbazolyl group, benzoxazolyl group , benzothiazolyl, quinoxalyl, benzimidazolyl, pyrazolyl, dibenzofuranyl, dibenzothiophenyl, naphthyridinyl, phenanthrolinyl and acridinyl.

In the general formula (1), the "substituent" for "representing a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted condensed polycyclic aromatic group" for R ₁ to R ₄ is specifically: fluorine atom, chlorine atom, cyano group, hydroxyl group, nitro group, linear or branched alkyl group having 1 to 8 carbon atoms, cyclopentyl group, cyclohexyl group, linear or branched chain having 1 to 8 carbon atoms alkoxy group, dialkylamino group substituted with straight or branched alkyl group having 1 to 8 carbon atoms, phenyl group, naphthyl group, anthryl group, fluorenyl group, styryl group, pyridyl group, pyridoindolyl group , quinolyl group, benzothiazolyl group, and thenoyl group, and these substituents may be further substituted.

In general formula (1), C ₁ to C ₂ each independently represent a carbon atom having a substituted or unsubstituted group. Specific examples of the "substituent" include fluorine atom, chlorine atom, cyano group, hydroxyl group, nitro group, linear or branched alkyl group having 1 to 8 carbon atoms, cyclopentyl group, cyclohexyl group, carbon linear or branched alkoxy group having 1 to 8 atoms, dialkylamino group substituted with linear or branched alkyl group having 1 to 8 carbon atoms, phenyl group, naphthyl group, anthryl group, fluorenyl styryl, pyridyl, pyridoindolyl, quinolyl, benzothiazolyl, thenoyl groups, which substituents may be further substituted.

Furthermore, R ₁ and R ₂ , R ₃ and R ₄ , C ₁ and C ₂ may be bonded to each other to form a ring structure.

As an active ingredient in the copolymerization reaction that produces the charge control agent, which is the polymer compound of the present invention, the compound represented by the general formula (1) may be used alone, or two or more of them may be used in combination. good.

The charge control agent, which is the polymer compound of the present invention, is a polymer compound obtained by copolymerizing the compound represented by the general formula (1) with an alkenyl group-containing compound (monomer). The content of the compound represented by general formula (1) in the copolymer polymer compound is 0.1 to 80 mol %. Preferably, it is 1 to 70 mol %. However, these are intended to illustrate general methods of use, and the amounts of monomers forming the copolymer can be varied appropriately to obtain the desired charging effect.

As the type of alkenyl group-containing monomer used in the copolymerization reaction of the charge control agent, which is the polymer compound of the present invention, any known type can be used. Styrene-based monomers, acrylate-based monomers, and methacrylate-based monomers, which are copolymerized with the compound represented by the general formula (1) to form a polymer compound, are described below. Examples are given but are not limited to these.

Styrenic monomers include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-amylstyrene, p -tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-chloro Styrenes such as styrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene and p-nitrostyrene, and derivatives thereof.

Acrylate-based monomers include acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, n-dodecyl acrylate, and 2-ethyl acrylate. Acrylic acids such as hexyl, stearyl acrylate, 2-chloroethyl acrylate, and phenyl acrylate, and esters thereof can be mentioned.

Methacrylate-based monomers include methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, n-dodecyl methacrylate, and 2-ethyl methacrylate. Methacrylic acids such as hexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate, and esters thereof can be mentioned.

Examples of other monomers used in the charge control agent, which is the polymer compound of the present invention, include the following (1) to (18). (1) monoolefins such as ethylene, propylene, butylene and isobutylene; (2) polyenes such as butadiene and isoprene; (3) vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; (4) vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; (5) vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; (6) vinyl methyl ketone, vinyl hexyl ketone, methyl vinyl ketones such as isopropenyl ketone; (7) N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole and N-vinylpyrrolidone; (8) vinylnaphthalenes; (9) acrylonitrile, methacrylic (10) unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenylsuccinic acid, fumaric acid and mesaconic acid; (11) maleic anhydride; , citraconic anhydride, itaconic anhydride, alkenylsuccinic anhydride; (12) maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monobutyl ester, citraconic acid monomethyl ester , citraconic acid monoethyl ester, citraconic acid monobutyl ester, itaconic acid monomethyl ester, alkenylsuccinic acid monomethyl ester, fumaric acid monomethyl ester, mesaconic acid monomethyl ester; (13) dimethyl maleic acid. (14) α,β-unsaturated acids such as crotonic acid and cinnamic acid; (15) α,β-unsaturated acids such as crotonic anhydride and cinnamic anhydride; Saturated acid anhydrides; (16) Carboxyl groups such as anhydrides of said α,β-unsaturated acids and lower fatty acids, alkenylmalonic acids, alkenylglutaric acids, alkenyladipic acids, their acid anhydrides and their monoesters (17) acrylic acid or methacrylic acid hydroxyalkyl esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; (18) 4-(1-hydroxy-1-methylbutyl) having a hydroxy group such as styrene, 4-(1-hydroxy-1-methylhexyl)styrene monomer.

The charge control agent, which is the polymer compound of the present invention, is a charge control agent containing, as an active ingredient, a polymer compound containing one or more units represented by the general formula (2).

R ₅ in general formula (2) is a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a nitro, a cyano group, a substituted carbonyl group, a sulfur substituent, an alkoxy group, an alkylureido group, or a substituted or unsubstituted group having 1 carbon atom. to 18 linear or branched alkyl groups, substituted or unsubstituted cycloalkyl groups having 5 to 10 carbon atoms, substituted or unsubstituted aromatic hydrocarbon groups, substituted or unsubstituted heterocyclic groups or substituted Alternatively, it represents an unsubstituted condensed polycyclic aromatic group. n is an integer.

In general formula (2), the "substituted carbonyl group, sulfur substituent" of R ₅ includes, for example, an alkoxycarbonyl group, an alkylcarbamoyl group, an alkoxysulfonyl group, an alkylsulfamoyl group, an alkylsulfonyl group, and an alkylureidosulfonyl group. etc.

In the general formula (2), "a linear or branched alkyl group having 1 to 18 carbon atoms" in "representing a substituted or unsubstituted linear or branched alkyl group having ₁ to 18 carbon atoms""Branched alkyl group" includes, for example, methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, sec-butyl group, 2-methylpropyl group, tert-butyl group, n- pentyl group, 1-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methyl pentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 1,4-dimethylbutyl group , 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethyl-2-methyl-propyl group, and 1,1,2-trimethylpropyl group.

In general formula (2), the "substituent" in "representing a substituted or unsubstituted linear or branched alkyl group having 1 to 18 carbon atoms" of R ₅ specifically includes fluorine atom, chlorine atom, cyano group, hydroxyl group, nitro group, cyclopentyl group, cyclohexyl group, linear or branched alkoxy group having 1 to 8 carbon atoms, linear or branched chain having 1 to 8 carbon atoms dialkylamino group substituted with an alkyl group, linear or branched acyl group having 1 to 8 carbon atoms, linear or branched alkoxycarbonyl group having 1 to 8 carbon atoms, 1 to 8 carbon atoms groups such as epoxyalkyl, phenyl, naphthyl, anthryl, fluorenyl, styryl, pyridyl, pyridoindolyl, quinolyl, and benzothiazolyl groups of 8, these substituents being further It may be replaced.

In general formula (2), the "cycloalkyl group having 5 to 10 carbon atoms" in "representing a substituted or unsubstituted cycloalkyl group having 5 to 10 carbon atoms" for R ₅ includes, for example, cyclopentyl cyclohexyl group, cycloheptylene group, cyclooctylene group, cyclononylene group or cyclodecylene group.

In general formula (2), the "substituent" in "representing a substituted or unsubstituted cycloalkyl group having 5 to 10 carbon atoms" of R ₅ specifically includes a fluorine atom, a chlorine atom, a cyano hydroxyl group, nitro group, linear or branched alkyl group having 1 to 8 carbon atoms, cyclopentyl group, cyclohexyl group, linear or branched alkoxy group having 1 to 8 carbon atoms, number of carbon atoms dialkylamino group, phenyl group, naphthyl group, anthryl group, fluorenyl group, styryl group, pyridyl group, pyridoindolyl group, quinolyl group, benzothiazolyl group substituted with 1 to 8 linear or branched alkyl groups; and these substituents may be further substituted.

In general formula (2), the "aromatic hydrocarbon group" in "representing a substituted or unsubstituted aromatic hydrocarbon group" for R ₅ includes, for example, a phenyl group, a biphenylyl group, a terphenylyl group, a naphthyl group and an anthryl group. , phenanthryl, fluorenyl, indenyl and pyrenyl groups.

In general formula (2), specific examples of the "substituent" in "representing a substituted or unsubstituted aromatic hydrocarbon group" for R ₅ include a fluorine atom, a chlorine atom, a cyano group, a hydroxyl group, and a nitro group. , a straight or branched alkyl group having 1 to 8 carbon atoms, a cyclopentyl group, a cyclohexyl group, a straight or branched alkoxy group having 1 to 8 carbon atoms, a straight chain having 1 to 8 carbon atoms groups such as dialkylamino groups, phenyl groups, naphthyl groups, anthryl groups, fluorenyl groups, styryl groups, pyridyl groups, pyridoindolyl groups, quinolyl groups, and benzothiazolyl groups substituted with straight or branched alkyl groups; and these substituents may be further substituted.

In the general formula (2), the "heterocyclic group" or "condensed polycyclic aromatic group" in "representing a substituted or unsubstituted heterocyclic group or substituted or unsubstituted condensed polycyclic aromatic group" for R ₅ such as pyridyl group, triazyl group, pyrimidyl group, furanyl group, pyranyl group, thiophenyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothiophenyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzothiazolyl group , quinoxalyl, benzimidazolyl, pyrazolyl, dibenzofuranyl, dibenzothiophenyl, naphthyridinyl, phenanthrolinyl and acridinyl.

In general formula (2), as the "substituent" in "representing a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted condensed polycyclic aromatic group" of R ₅ , specifically, a fluorine atom, chlorine atom, cyano group, hydroxyl group, nitro group, linear or branched alkyl group having 1 to 8 carbon atoms, cyclopentyl group, cyclohexyl group, linear or branched alkoxy group having 1 to 8 carbon atoms , dialkylamino group, phenyl group, naphthyl group, anthryl group, fluorenyl group, styryl group, pyridyl group, pyridoindolyl group, quinolyl group substituted with a linear or branched alkyl group having 1 to 8 carbon atoms , benzothiazolyl group, and thenoyl group, and these substituents may be further substituted.

Among the compounds represented by formula (1) used in the present invention, specific examples of preferred compounds are shown below, but the present invention is not limited to these compounds.

Examples of polymer compounds obtained by copolymerizing the compound represented by the general formula (1) and the alkenyl group-containing compound of the present invention are shown below, but the present invention is limited to these compounds. not a thing

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

In the charge control agent, which is the polymer compound of the present invention, the polymer compound copolymerized with the alkenyl group-containing compound may have a crosslinked structure crosslinked with a crosslinker having two or more alkenyl groups. Examples of cross-linking agents used in this case include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene. Examples of alkyl chain-linked diacrylate compounds include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 - hexanediol diacrylate, neopentyl glycol diacrylate, or the above compounds in which acrylate is replaced by methacrylate.

The charge control agent, which is a polymer compound of the present invention, is a copolymer, and its polymerization form is not particularly limited, and random, block, graft, or other polymerization forms can be employed. Moreover, the method for polymerizing the charge control agent of the present invention is not particularly limited, and examples thereof include bulk polymerization, solution polymerization, suspension polymerization, and the like.

A polymerization initiator is used for the polymerization reaction of the charge control agent of the present invention. The polymerization initiator used in the polymerization of the present invention is not particularly limited as long as it is used in ordinary radical polymerization. Examples include benzoyl peroxide, lauroyl peroxide, orthochlorobenzoyl peroxide, orthomethoxy benzoyl peroxide, Organic peroxides such as 3,5,5-trimethylhexanoyl peroxide, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxide; azobisisobutyronitrile, azobiscyclohexanecarbohydrate azo compounds such as nitriles and azobis(2,4-dimethylvaleronitrile); and persulfide initiators such as potassium persulfate. These may be used alone, or two or more of them may be used in combination.

Polymerization initiators for cationic or anionic polymerization can be used depending on the type of monomer selected for copolymerization. For example, for cationic polymerization, sulfuric acid, hydrochloric acid, nitric acid, p-toluenesulfonic acid, trifluoroacetic acid and the like can be used. For anionic polymerization, lithium, sodium, potassium, lithium hydroxide, sodium hydroxide, sodium methoxide, t-butoxypotassium, lithium aluminum tetrahydroxide, pyridine, triethylamine and the like can be used. These may be used alone, or two or more of them may be used in combination.

The polymerization initiator is used at a concentration of 0.05 to 30 parts by weight, preferably 0.1 to 15 parts by weight, per 100 parts by weight of the monomer. The reaction temperature is not particularly limited and can be set according to the solvent, initiator and monomers used, but the polymerization reaction is preferably carried out at 40°C to 150°C.

The weight-average molecular weight (Mw) of the polymer compound used as the active ingredient of the charge control agent of the present invention may be from 1,000 to 100,000, preferably from 5,000 to 80,000. If the weight average molecular weight (Mw) is lower than 1000, good affinity with the toner resin cannot be expected, and improvement in dispersibility cannot be obtained. On the other hand, when it has a weight average molecular weight (Mw) of more than 100,000, the viscosity becomes too high, and the fixability deteriorates when used as a toner.

The charge control agent of the present invention is preferably used after adjusting the volume average particle size (laser diffraction/scattering particle size measurement method) within the range of 0.1 to 20 μm, more preferably within the range of 0.1 to 10 μm. It is particularly preferred to use If the volume average particle diameter is less than 0.1 μm, the amount of the charge control agent appearing on the toner surface is extremely small, and the desired charge control effect cannot be obtained. It is not preferable because it will increase and cause adverse effects such as in-flight pollution. On the other hand, when the average particle size is within the above range, the above defects are eliminated, and uneven distribution among toner particles is reduced, resulting in good dispersion in the toner, which is advantageous in terms of reducing variations in performance and reliability.

When the charge control agent, which is the polymer compound of the present invention, is used as a triboelectrically charged toner, it contains a binder resin, a colorant, a wax, and other various additives as necessary, in addition to the charge control agent.

As a method for incorporating the charge control agent used in the present invention into the toner, a method of adding it to a binder resin together with a coloring agent and the like, kneading and pulverizing (pulverized toner), or a method of adding a polymerizable monomer to a general monomer. A method of adding a compound represented by the formula (1) and polymerizing it to obtain a toner, or a copolymer ( A polymer compound) is dispersed and polymerized to obtain a toner (polymerized toner). Further, as a method of adding the charge control agent, there are a method of adding the charge control agent inside the toner particles in advance (internal addition) and a method of preparing the toner particles in advance and adding it to the surface of the toner particles (external addition).

When the charge control agent, which is the polymer compound of the present invention, is internally added to the toner particles, the preferred addition amount is preferably 0.1 to 20 parts by mass, more preferably 1 part by mass, with respect to 100 parts by mass of the binder resin. ~10 parts by mass is used.

When the charge control agent, which is the polymer compound of the present invention, is externally added to the toner particles, it is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the binder resin. Department. It is also preferable to mechanochemically adhere to the surface of the toner particles.

In the present invention, the charge control agent containing, as an active ingredient, a polymer compound which is a copolymer reaction product of the compound represented by the general formula (1) and an alkenyl group-containing compound may be any other known negatively charged charge control agent. It can be used in combination with a charge control agent. Preferred charge control agents used in combination include azo iron complexes or complex salts, azo chromium complexes or complex salts, azo manganese complexes or complex salts, azo cobalt complexes or complex salts, azo zirconium complexes or complex salts, and chromium complexes of carboxylic acid derivatives. Alternatively, a complex salt, a zinc complex or complex salt of a carboxylic acid derivative, an aluminum complex or complex salt of a carboxylic acid derivative, or a zirconium complex or complex salt of a carboxylic acid derivative may be mentioned. The carboxylic acid derivative is preferably an aromatic hydroxycarboxylic acid, more preferably 3,5-di-tert-butylsalicylic acid. Further examples include boron complexes or complex salts, negative chargeable resin-type charge control agents, and the like.

When the charge control agent that is the polymer compound of the present invention is used in combination with another charge control agent, the charge control agent other than the charge control agent that is the polymer compound is added in an amount of 0 per 100 parts by mass of the binder resin. .1 to 10 parts by mass is preferred.

As for the types of the binder resin used in the toner of the present invention, any known binder resin can be used. Vinyl polymers such as styrene-based monomers, acrylate-based monomers, and methacrylate-based monomers, or copolymers composed of two or more of these monomers, polyester-based polymers, polyol resins, phenolic resins, Examples include silicone resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, terpene resins, coumarone-indene resins, polycarbonate resins, and petroleum-based resins.

Examples of other monomers forming the vinyl polymer or copolymer include the following (1) to (18). (1) monoolefins such as ethylene, propylene, butylene and isobutylene; (2) polyenes such as butadiene and isoprene; (3) vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; (4) vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; (5) vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; (6) vinyl methyl ketone, vinyl hexyl ketone, methyl vinyl ketones such as isopropenyl ketone; (7) N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole and N-vinylpyrrolidone; (8) vinylnaphthalenes; (9) acrylonitrile, methacrylic (10) unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenylsuccinic acid, fumaric acid and mesaconic acid; (11) maleic anhydride; , citraconic anhydride, itaconic anhydride, alkenylsuccinic anhydride; (12) maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monobutyl ester, citraconic acid monomethyl ester , citraconic acid monoethyl ester, citraconic acid monobutyl ester, itaconic acid monomethyl ester, alkenylsuccinic acid monomethyl ester, fumaric acid monomethyl ester, mesaconic acid monomethyl ester; (13) dimethyl maleic acid. (14) α,β-unsaturated acids such as crotonic acid and cinnamic acid; (15) α,β-unsaturated acids such as crotonic anhydride and cinnamic anhydride; Saturated acid anhydrides; (16) Carboxyl groups such as anhydrides of said α,β-unsaturated acids and lower fatty acids, alkenylmalonic acids, alkenylglutaric acids, alkenyladipic acids, their acid anhydrides and their monoesters (17) acrylic acid or methacrylic acid hydroxyalkyl esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; (18) 4-(1-hydroxy-1-methylbutyl) having a hydroxy group such as styrene, 4-(1-hydroxy-1-methylhexyl)styrene monomer.

In the toner of the present invention, the vinyl polymer or copolymer of the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more alkenyl groups. Examples of the agent include divinylbenzene and divinylnaphthalene as aromatic divinyl compounds. Examples of alkyl chain-linked diacrylate compounds include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 - hexanediol diacrylate, neopentyl glycol diacrylate, or the above compounds in which acrylate is replaced by methacrylate.

These cross-linking agents are preferably used in an amount of 0.01 to 10 parts by mass, particularly preferably 0.03 to 5 parts by mass, per 100 parts by mass of other monomer components. Among these crosslinkable monomers, aromatic divinyl compounds (especially divinylbenzene are preferred), aromatic groups and ether Diacrylate compounds linked by a linking chain containing Among these, a combination of monomers that form a styrene copolymer or a styrene-acrylate copolymer is preferred.

When the binder resin is a styrene-acrylate resin, the molecular weight distribution of the resin component tetrahydrofuran (hereinafter abbreviated as THF) by gel permeation chromatography (hereinafter abbreviated as GPC) showed a molecular weight of 3,000. A resin that has at least one peak in the region of ~50,000 (in terms of number average molecular weight) and has at least one peak in the region of molecular weight of 100,000 or more is preferable in terms of fixability, offset property, and storage stability. As the THF-soluble component, a binder resin containing 50 to 90% of components having a molecular weight distribution of 100,000 or less is also preferable. More preferably, it has a main peak in the molecular weight range of 5,000 to 30,000, most preferably in the molecular weight range of 5,000 to 20,000.

The acid value of the vinyl polymer such as a styrene-acrylate resin as the binder resin is preferably 0.1 mgKOH/g to 100 mgKOH/g, more preferably 0.1 mgKOH/g to 70 mgKOH/g, and still more preferably. 0.1 mgKOH/g to 50 mgKOH/g is preferable.

Monomers constituting the polyester polymer include the following.
Dihydric alcohol components include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1, Examples include 6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, and diols obtained by polymerizing bisphenol A with cyclic ethers such as ethylene oxide and propylene oxide.

In order to crosslink the polyester resin, it is preferable to use a trihydric or higher alcohol together. Trihydric or higher polyhydric alcohols include 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 and the like. be done.

Acid components forming the polyester polymer include benzene dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid, or their anhydrides, alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid, or Unsaturated dibasic acids such as anhydride, maleic acid, citraconic acid, itaconic acid, alkenylsuccinic acid, fumaric acid, mesaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, alkenylsuccinic anhydride, etc. and unsaturated dibasic acid anhydrides. Further, trivalent or higher polyvalent carboxylic acid components include trimellitic acid, pyromellitic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, tetra(methylenecarboxy)methane, 1,2,7,8-octanetetracarboxylic acid, enpol trimer Examples include monoacids, anhydrides thereof, and partial lower alkyl esters thereof.

When the binder resin is a polyester-based resin, the molecular weight distribution of the THF-soluble component of the resin component shows at least one peak in the molecular weight range of 3,000 to 50,000. It is also preferable to use a binder resin in which 60 to 100% of the THF-soluble component has a molecular weight of 100,000 or less. More preferably, at least one peak exists in the molecular weight region of 5,000 to 20,000. In the present invention, the molecular weight distribution of the binder resin is measured by GPC using THF as a solvent.

In the present invention, the acid value of the binder resin component of the toner composition is obtained by the following method, and the basic operation conforms to JIS K-0070.
(1) The sample is used after removing additives other than the binder resin (polymer component) in advance, or the acid value and content of the binder resin and crosslinked components other than the binder resin are obtained in advance. . Accurately weigh 0.5 to 2.0 g of the pulverized sample, and let the weight of the polymer component be Wg. For example, when measuring the acid value of the binder resin from the toner, the acid value and content of the coloring agent or magnetic substance are separately measured, and the acid value of the binder resin is obtained by calculation.
(2) A sample is placed in a 300 (ml) beaker, and 150 (ml) of a mixture of toluene/ethanol (volume ratio 4/1) is added and dissolved.
(3) Titrate with a 0.1 mol/L KOH ethanol solution using a potentiometric titrator.
(4) The amount of KOH solution used at this time is defined as S (ml), a blank is measured at the same time, and the amount of KOH solution used at this time is defined as B (ml), which is calculated by the following formula (1). where f is the KOH concentration factor.
Acid value (mgKOH/g) = [(SB) x f x 5.61]/W (1)

The binder resin of the toner and the composition containing the binder resin preferably have a glass transition temperature (T _g ) of 35 to 80° C., particularly preferably 40 to 75° C., from the viewpoint of toner storage stability. If the _Tg is lower than 35° C., the toner tends to deteriorate in a high-temperature atmosphere, and offset tends to occur during fixing. On the other hand, when the _Tg exceeds 80°C, the fixability tends to be lowered. A binder resin having a softening point in the range of 80 to 140° C. is preferably used in the polymerized toner of the present invention. If the softening point of the binder resin is less than 80° C., the toner and the image stability of the toner after fixing and during storage may deteriorate. On the other hand, if the softening point exceeds 140° C., the low-temperature fixability may deteriorate.

Colorants that can be used in the present invention include black or blue dye or pigment particles in the case of black toner. Black or blue pigments include carbon black, aniline black, acetylene black, phthalocyanine blue, and indanthrene blue. Examples of black or blue dyes include azo dyes, anthraquinone dyes, xanthene dyes and methine dyes.

When used as a color toner, any known colorant can be used without any particular limitation. As magenta colorants, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dyes, lake dyes, naphthol dyes, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. Although the pigment may be used alone, it is more preferable to use the pigment in combination with the dye to improve the definition from the viewpoint of the image quality of the full-color image.

As cyan colorants, copper phthalocyanine compounds and their derivatives, anthraquinones, and basic dye lake compounds can be used.

Condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds are used as yellow colorants.

The toner of the present invention may further contain wax. Waxes that can be used in the present invention are not particularly limited, but include the following. Aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax, paraffin wax and Sasol wax. Oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene waxes. or block copolymers thereof. Vegetable waxes such as candelilla wax, carnauba wax, Japan wax, and jojoba wax. Animal waxes such as beeswax, lanolin and spermaceti. Mineral waxes such as ozokerite, ceresin and petrolatum, and waxes mainly composed of fatty acid esters such as montan acid ester wax and castor wax. A partly or wholly deoxidized fatty acid ester such as deoxidized carnauba wax can be mentioned.

The wax used in the present invention preferably has a melting point of 50 to 140°C, more preferably 70 to 120°C, in order to balance fixability and offset resistance. If the temperature is less than 50°C, the anti-blocking property tends to decrease, and if it exceeds 140°C, the anti-offset effect becomes difficult to develop.

Also, by using two or more different kinds of waxes together, the plasticizing action and the releasing action, which are the action of the wax, can be exhibited at the same time.
Examples of use include a combination of two or more different waxes with a melting point difference of 10° C. to 100° C., and a combination of polyolefin and graft-modified polyolefin.

When two kinds of waxes are selected, in the case of waxes having the same structure, the wax with a relatively low melting point exerts a plasticizing effect, and the wax with a relatively high melting point exerts a releasing effect. At this time, when the melting point difference is 10 to 100° C., functional separation is effectively exhibited. When the temperature is less than 10°C, the function separation effect is difficult to appear, and when it exceeds 100°C, it is difficult to emphasize the functions by interaction. In this case, the melting point of at least one of the waxes is preferably 70 to 120°C, more preferably 70 to 100°C, and tends to facilitate the function separation effect.

In the toner of the present invention, the total content of these waxes is preferably 0.2 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the binder resin. It is effective to be

A fluidity improver may be added to the toner of the present invention. The fluidity improver is added to the surface of the toner to improve the fluidity of the toner (make it easier to flow). Any known fluidity improver can be used without any particular limitation. Fine powder silica, fine powder unoxidized titanium, and fine powder unoxidized alumina are preferred, and treated silica obtained by surface-treating these with a silane coupling agent or silicone oil is more preferred. The particle size of the fluidity improver is preferably 0.001 to 2 μm, particularly preferably 0.002 to 0.2 μm, as an average primary particle size.

In the toner of the present invention, other additives may be added for the purpose of protecting photoreceptors and carriers, improving cleanability, adjusting thermal properties, electrical properties, and physical properties, adjusting resistance, adjusting softening points, and improving fixing rates. , various metal soaps, fluorine-based surfactants, dioctyl phthalate, tin oxide, zinc oxide, carbon black, antimony oxide, etc. as conductivity imparting agents, and inorganic fine powders such as titanium oxide, aluminum oxide, alumina, etc. are required. can be added according to In addition, these inorganic fine powders may be hydrophobized as necessary. In addition, lubricants such as polytetrafluoroethylene, zinc stearate, and polyvinylidene fluoride, abrasives such as cesium oxide, silicon carbide, and strontium titanate, anti-caking agents, and white and black fine particles having a polarity opposite to that of the toner particles are also added. It can also be used in small amounts as a developability improver.

These additives include silicone varnishes, various modified silicone varnishes, silicone oils, various modified silicone oils, silane coupling agents, silane coupling agents with functional groups, and other organosilicon compounds for the purpose of controlling the amount of charge. Treatment with a treating agent, or different treating agents, is also preferred.

In the present invention, the charge control agent is sufficiently mixed and stirred together with the above-described additives and toner by a mixer such as a Henschel mixer, ball mill, Nauta mixer, V-type mixer, W-type mixer, super mixer, etc. to obtain a toner. The desired toner for electrostatic charge development can also be obtained by uniformly subjecting the surface of the particles to an external addition treatment.

The toner of the present invention is also thermally stable and is not subject to thermal changes during electrophotographic processes, and can maintain stable charging characteristics. In addition, since it is uniformly dispersed in any binder resin, the charge distribution of the fresh toner is very uniform. Therefore, in the toner of the present invention, even in untransferred toner and collected toner (waste toner), there is almost no change in saturated triboelectric charge amount and charge distribution compared to fresh toner.

As a method for producing the toner of the present invention, it can be produced by a known production method. As an example of the manufacturing method, the above-described toner constituent materials such as the binder resin, the charge control agent, and the colorant are thoroughly mixed using a mixer such as a ball mill. A preferred method is a method (pulverization method) in which the mixture is well kneaded by a heating kneader such as a hot roll kneader, solidified by cooling, pulverized, and then classified.

It can also be produced by dissolving the above mixture in a solvent, atomizing by spraying, drying and classifying. Furthermore, a toner manufacturing method by a polymerization method in which a toner is obtained by mixing a predetermined material with a monomer constituting a binder resin to form an emulsification or suspension, followed by polymerization to obtain a toner, a so-called toner manufacturing method comprising a core material and a shell material The microcapsule toner can also be produced by a method in which the core material, the shell material, or both of them contain a predetermined material. Further, the toner of the present invention can be produced by sufficiently mixing desired additives and toner particles, if necessary, using a mixer such as a Henschel mixer.

Furthermore, the charge control agent used in the present invention is also suitable as a charge control agent (charge enhancer) in a paint for electrostatic powder coating. That is, the electrostatic paint using this charge enhancer is excellent in environmental resistance, storage stability, especially thermal stability and durability, and has a coating efficiency of 100% and a thick film without coating film defects. can be formed.

EXAMPLES The present invention will be described below with reference to Examples, but these are not intended to limit the present invention in any way. In the examples, "parts" all represent "mass parts".

Synthesis Example 1 (Synthesis of Exemplified Compound 1)
23.06 g (0.235 mol) of maleic anhydride was weighed into a 500 ml Kolben, added with 100 ml of acetone, and stirred at room temperature under a nitrogen atmosphere to dissolve. 25.00 g (0.196 mol) of 4-chloroaniline dissolved in 50 ml of acetone was slowly dropped from the dropping funnel. After reacting at room temperature for 2.5 hours, the reaction solution was poured into 1 L of ice water, and after confirming a yellow precipitate, the mixture was stirred until the ice melted. Suction filtration was performed, and the filtrate was dried under reduced pressure at 60° C. overnight to obtain 43.69 g of the intermediate with a yield of 98.8%.

A 300 ml Kolben was charged with 43.69 g (0.194 mol) of the intermediate, 10.00 g of sodium acetate and 100 ml of acetic anhydride were added, and the mixture was heated to 50° C. and reacted for 2 hours. After completion of the reaction, the reaction solution was transferred to a 1,000 ml separating funnel, and extracted three times using 300 ml of toluene and 300 ml of water. The toluene layer was concentrated, and city water was added to the concentrate to obtain a yellow precipitate. The precipitated yellow solid was filtered by suction, and the filtrate was dried under reduced pressure at 60°C overnight. The crude crystals were purified by silica gel column chromatography using chloroform as a developing solvent, and concentrated to dryness using an evaporator to obtain 33.82 g of the desired product as a yellow solid at a yield of 83.1%.

The structure of the obtained yellow solid was identified using NMR, and exemplary compound 1 was obtained. The measurement results of 1H-NMR (DMSO-d ₆ ) were as follows. 7.57 ppm (d, 2H), 7.39 ppm (d, 2H), 7.21 ppm (s, 2H). Moreover, the melting point was 98.3°C.

Synthesis Example 2 (Synthesis of Exemplified Compound 2)
11.34 g (0.116 mol) of maleic anhydride was weighed into a 500 ml Kolben, added with 200 ml of acetone, and stirred at room temperature under a nitrogen atmosphere to dissolve. 10.30 g (0.0962 mol) of o-toluidine (orthotoluidine) was slowly added dropwise from the dropping funnel. After reacting at room temperature for 4 hours, the reaction solution was poured into 500 mL of ice water, and after confirming a pale yellow precipitate, the mixture was stirred until the ice melted. Suction filtration was performed, and the filtrate was dried under reduced pressure at 70° C. overnight to obtain 14.51 g of the intermediate with a yield of 73.5%.

14.51 g (0.0707 mol) of the intermediate was placed in a 500 ml Kolben, 0.5 g of p-toluenesulfonic acid, 250 ml of toluene and 25 ml of dimethylacetamide (DMA) were added, heated to 110° C. and reacted for 6 hours. After completion of the reaction, the reaction solution was transferred to an eggplant flask and concentrated with an evaporator under the conditions of an oil bath of 80° C. and reduced pressure until the solvent (toluene) was no longer distilled off. The concentrate was purified by silica gel column chromatography using toluene as a developing solvent. The fractions were collected in a 1000 ml round-bottomed flask and concentrated with an evaporator under the conditions of an oil bath of 80° C. and reduced pressure until the solvent (toluene) was no longer distilled off. Vacuum drying was carried out at 60° C. overnight to obtain 12.1 g of a yellow solid with a yield of 91.0%.

The structure of the obtained yellow solid was identified using NMR, and exemplary compound 2 was obtained. The measurement results of 1H-NMR (DMSO-d ₆ ) were as follows. 7.37 ppm (m, 2H), 7.30 ppm (m, 1H), 7.22 ppm (m, 3H), 2.07 ppm (m, 3H).

Synthesis Example 3 (Synthesis of Exemplified Compound 3)
The procedure was repeated except that o-toluidine in Synthesis Example 2 was changed to o-methyl-p-chloroaniline to obtain 11.85 g of a pale yellow solid in a yield of 85.4%.

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

Synthesis Example 4 (Synthesis of Exemplified Compound 4)
200 ml of toluene was placed in a 500 ml Kolben, and degassing and nitrogen replacement were performed for 2 hours. 32.35 g (0.156 mol) of exemplary compound 1 obtained in Synthesis Example 1, 16.23 g (0.156 mol) of styrene, and 0.42 g (1.93 mmol) of azobisisobutyronitrile (AIBN) were added. The mixture was stirred, heated to 80° C. under nitrogen, and reacted for 4 hours. After completion of the reaction, the reaction solution was gradually added to 3 L of methanol to precipitate a white solid. Suction filtration was performed, and the filtrate was dried overnight at 60° C. under reduced pressure to obtain 46.11 g of a white solid with a yield of 94.6%.

Regarding the structure identification of the obtained white solid, 1H-NMR (DMSO-d ₆ ) was measured, and the disappearance of protons derived from the double bond site of maleic anhydride and the broadening of the peak due to polymerization caused Exemplified Compound 4, which is a copolymer of Exemplified Compound 1 and styrene, was confirmed. The observed peaks were 7.50 ppm and 7.18 ppm.

When the molecular weight of the resulting Exemplified Compound 4 was measured using GPC, the weight average molecular weight (Mw) was 51,353.

Synthesis Example 5 (Synthesis of Exemplified Compound 5)
100 ml of toluene was placed in a 300 ml Kolben, and degassing and nitrogen replacement were performed for 2 hours. 12.00 g (0.0641 mol) of exemplary compound 2 obtained in Synthesis Example 2, 6.68 g (0.0641 mol) of styrene, and 0.11 g (0.641 mmol) of azobisisobutyronitrile (AIBN) were added. The mixture was stirred, heated to 80° C. under nitrogen, and reacted for 4 hours. After completion of the reaction, the reaction solution was gradually added to 2 L of methanol to precipitate a white solid. Suction filtration was performed, and the filtrate was dried under reduced pressure at 70° C. overnight to obtain 15.92 g of a white solid with a yield of 85.2%.

Regarding the structure identification of the obtained white solid, 1H-NMR (DMSO-d ₆ ) was measured, and the disappearance of protons derived from the double bond site of maleic anhydride and the broadening of the peak due to polymerization caused Exemplified Compound 5, which is a copolymer of Exemplified Compound 2 and styrene, was confirmed. The observed peaks were 7.29 ppm and 2.03 ppm.

The weight average molecular weight (Mw) of Exemplified Compound 5 obtained was 66,148 when the molecular weight was measured using GPC.

Synthesis Example 6 (Synthesis of Exemplified Compound 6)
80 ml of toluene was placed in a 300 ml Kolben, and degassing and nitrogen replacement were performed for 2 hours. 11.85 g (0.0535 mol) of exemplary compound 3 obtained in Synthesis Example 3, 6.68 g (0.0535 mol) of styrene, and 0.16 g (0.932) mmol of azobisisobutyronitrile (AIBN) was added, stirred, heated to 80° C. under nitrogen, and reacted for 4 hours. After completion of the reaction, the reaction solution was gradually added to 1 L of methanol to precipitate a white solid. Suction filtration was performed, and the filtrate was dried under reduced pressure at 60° C. overnight to obtain 14.47 g of a white solid with a yield of 82.6%.

Regarding the structure identification of the obtained white solid, 1H-NMR (DMSO-d ₆ ) was measured, and the disappearance of protons derived from the double bond site of maleic anhydride and the broadening of the peak due to polymerization caused Exemplified Compound 6, which is a copolymer of Exemplified Compound 3 and styrene, was confirmed. The observed peak was 7.34 ppm.

The weight average molecular weight (Mw) was 78,043 when the molecular weight of the resulting Exemplified Compound 6 was measured using GPC.

[Method for measuring charge amount]
Using a blow-off charge meter (TB-200, manufactured by Toshiba Chemical Co., Ltd.), the charge control agent or toner, which is the polymer compound synthesized above, is charged, and then the initial charge and saturated charge in each environment ( A charging time of 30 minutes) was measured. The blow-off charge amount measurement conditions are as follows.
amount of developer: 0.2000g±0.005g,
blow time: 60 seconds,
N ₂ blow pressure: 0.2 kgf/cm ² (silicon coat F96-150),
T/C=4%,
Ball mill rotation speed: 110 rpm.

[Example 1]
[Measurement of Charge Amount of Single Compound as Charge Control Agent]
The polymer compound (exemplified compound No. 4) obtained in Synthesis Example 4 was mixed at a rate of 0.5 part with respect to 100 parts of a silicone-coated ferrite carrier (F96-150, manufactured by Powdertech Co., Ltd.). Then, the compound obtained in Synthesis Example 4 is charged. After electrification, the saturation charge was measured in an atmosphere of 25° C. and 50% humidity (NN environment) using a blow-off charge meter (Toshiba Chemical Co., Ltd., model TB-200). A non-coated carrier (F-150 manufactured by Powdertech Co., Ltd.) was also measured in the same manner.

[Pseudo toner charge amount measurement]
Polyester resin (manufactured by Mitsubishi Rayon Co., Ltd., trade name FC-316, acid value 9 mgKOH / g) 91 parts, polymer compound synthesized in Synthesis Example 4 (exemplary compound No. 4) 1 part, carbon black (Mitsubishi Chemical Corporation 5 parts of MA-100 (trade name, manufactured by Sanyo Chemical Co., Ltd.) and 3 parts of low-molecular-weight polypropylene (Viscol 550P, trade name, manufactured by Sanyo Kasei Co., Ltd.) were melt-blended with a heating mixer (twin-screw extruder kneader) at 130°C. The cooled mixture was coarsely pulverized with a hammer mill, finely pulverized with a jet mill, and classified to obtain a non-magnetic toner having a volume average particle size of 9±0.5 μm.

The obtained non-magnetic toner was mixed with a silicon-coated ferrite carrier (F96-150 manufactured by Powdertech Co., Ltd.) in a ratio of 4 parts to 100 parts by mass (toner:carrier) and shaken to negatively charge the toner. Using a blow-off powder charge meter (TB-200, manufactured by Toshiba Chemical Co., Ltd.), the saturated charge was measured in an atmosphere of 25° C. and 50% humidity (NN environment). Table 1 shows the results. A non-coated carrier (F-150 manufactured by Powdertech Co., Ltd.) was also measured in the same manner.

[Examples 2-3]
In the same manner as in Example 1, the polymer compound obtained in Synthesis Example 5 or Synthesis Example 6 (Exemplary Compound No. 5 or Exemplary Compound No. 6) alone was subjected to saturation charge measurement. shown in

A pseudo toner was prepared using the polymer compound obtained in Synthesis Example 5 or Synthesis Example 6 in the same manner as in Example 1, and the saturation charge amount of the obtained non-magnetic toner was measured. Table 1 shows the results. shown in

[Comparative Example 1]
For comparison, comparative compound 1, which is a polymer compound having the following structural formula, was synthesized.

Synthesis of an intermediate compound, which is a raw material for copolymerizing Comparative Compound 1, was carried out as follows. 10.0 g (0.073 mol) of 4-aminobenzoic acid was weighed into a 300 ml Kolben, 10 ml of dimethylformamide (DMF) was added, and the mixture was stirred at room temperature under a nitrogen atmosphere and dissolved. 7.85 g (0.080 mol) of maleic anhydride dissolved in 30 ml of DMF was slowly dropped from the dropping funnel. After reacting at room temperature for 4 hours, the reaction solution was poured into 1 L of ice water, and after confirming a yellow precipitate, the mixture was stirred until the ice melted. Suction filtration was performed, and the filtrate was dried under reduced pressure at 70° C. overnight to obtain 17.1 g of the intermediate with a yield of 99.5%.

10.0 g (0.043 mol) of the intermediate was charged in a 1000 ml Kolben, 2 g of p-toluenesulfonic acid, 500 ml of toluene, 100 ml of N-methylpyrrolidone and 50 ml of dimethylacetamide were added, heated to 110° C. and reacted for 7 hours. let me After completion of the reaction, the reaction solution was transferred to an eggplant flask and concentrated by an evaporator under the conditions of an oil bath of 100° C. and reduced pressure until the solvent was no longer distilled off. The concentrate was poured into 500 ml of ice water. The precipitated yellow solid was filtered with suction, and the filtrate was dried under reduced pressure at 70° C. overnight to obtain 8.8 g of a pale yellow solid with a yield of 95.3%.

The structure of the resulting pale-yellow solid was identified by NMR, and an intermediate compound, which is a raw material for copolymerizing Comparative Compound 1, was obtained. The measurement results of 1H-NMR (DMSO-d6) were as follows. 8.05 ppm (d, 2H), 7.50 ppm (d, 2H), 7.22 ppm (s, 2H). Moreover, the melting point was 233°C.

50 ml of dimethylformamide (DMF) was placed in a 100 ml Kolben, and degassing and nitrogen replacement were performed for 2 hours. 5.0 g (0.023 mol) of the obtained intermediate compound of comparative compound 1, 2.4 g (0.023 mol) of styrene, and 0.1 g (0.460 mmol) of azobisisobutyronitrile (AIBN) were added. The mixture was stirred, heated to 80° C. under nitrogen, and reacted for 4 hours. After completion of the reaction, the reaction solution was gradually added to 1 L of methanol to precipitate a white solid. Suction filtration was performed, and the filtrate was dried overnight at 70° C. under reduced pressure to obtain 5.17 g of a white solid in a yield of 69.9%.

Regarding the structure identification of the obtained white solid, 1H-NMR (DMSO-d ₆ ) was measured, and the disappearance of protons derived from the double bond site of maleic anhydride and the broadening of the peak due to polymerization caused Comparative compound 1, which is a maleimide-styrene copolymer, was confirmed. The observed peaks were 7.99 ppm and 7.15 ppm. From the proton ratio, the intermediate compound:styrene composition of Comparative Compound 1 was 55:45.

When the molecular weight of Comparative Compound 1 obtained was measured using GPC, the weight average molecular weight (Mw) was 66,300.

In the same manner as in Example 1, the saturation chargeability of Comparative Compound 1 alone as a charge control agent and the saturation chargeability of a pseudo toner prepared using Comparative Compound 1 were measured. Those results are shown in Table 1.

[Comparative Example 2]
For comparison, a commercially available charge control agent (T-77: colored azo complex, manufactured by Hodogaya Chemical Industry Co., Ltd.) was used as a comparison compound, and saturation with the charge control agent compound alone was performed in the same manner as in Example 1. The chargeability and saturation chargeability of the pseudo-toner were measured. Those results are shown in Table 1.

[Comparative Example 3]
For comparison, a commercially available charge control agent (TN-105: white salicylic acid complex, manufactured by Hodogaya Chemical Industry Co., Ltd.) was used as a comparison compound, and saturation with the charge control agent compound alone was performed in the same manner as in Example 1. The chargeability and saturation chargeability of the pseudo-toner were measured. Those results are shown in Table 1.

From the triboelectrification evaluation results shown in Table 1, the synthesized copolymer of the compound represented by the general formula (1) and the alkenyl group-containing compound exhibited negative chargeability. The value of the saturated charge amount was superior to the charge control agent on the market. The copolymer of the compound represented by the general formula (1) and the alkenyl group-containing compound used in the present invention is a metal-free compound and is excellent in safety to humans and the environment. Moreover, since it is almost white, it can be freely colored and used. Furthermore, since it is composed of a polymer having a molecular weight of more than 1,000, it is possible to improve the dispersibility and compatibility with the toner resin in electrophotography. Therefore, the copolymer of the compound represented by the general formula (1) and the alkenyl group-containing compound used in the present invention is certainly useful as a polymeric charge control agent.

From the pseudo-toner charging results shown in Table 1, the toner produced using the charge control agent, which is a polymer compound of the present invention, has charging performance comparable to that of commercially available colored toners or white toners. It was shown that the charge control agent, which is the polymer compound of the present invention, has an excellent charge imparting effect.

A polymer compound, which is a copolymer of the compound represented by the general formula (1) according to the present invention and an alkenyl group-containing compound, has excellent charging performance. In addition, it does not contain heavy metals such as chromium compounds, which are of concern for environmental problems, and is excellent in safety for humans and the environment. Furthermore, it is suitable as a charge control agent for color toners, and can provide toners that are extremely useful for both pulverized toners and polymerized toners.

Claims (5)

A charge control agent comprising, as an active ingredient, a polymer compound which is a copolymer reaction product of at least one compound represented by the following general formula (1) and at least one alkenyl group-containing compound.

(wherein R ₁ and R ₂ represent a hydrogen atom, R ₃ represents a halogen atom, and R ₄ represents a substituted or unsubstituted C 1-18 linear or branched alkyl group and m1 and m2 are 1. x is 0.) 2. The charge control agent comprising a polymer compound as an active ingredient according to claim 1, wherein the content of the compound represented by the general formula (1) is 0.1 to 80 mol %. 3. The charge control agent according to claim 1, wherein the weight average molecular weight (Mw) of said polymer compound is in the range of 1,000 to 100,000. The alkenyl group-containing compound is at least one selected from styrene, styrene derivatives, (meth)acrylic acid, (meth)acrylic acid esters, and vinyl ether derivatives, according to any one of claims 1 to 3. A charge control agent containing a polymer compound as an active ingredient. A toner comprising a charge control agent, a colorant, and a binder resin containing the polymer compound according to any one of claims 1 to 4 as an active ingredient.