JP2009282238A - Charge control agent, electrostatic charge image developing toner containing charge control agent, and charge control method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a charge control agent which includes negative charge applying performance of a practical level, can be used for a color toner in the colorless or light-colored state, exhibits stable static charge generated by charging of resin powder such as toner irrespective of environmental changes, is excellent in storage stability and endurance, and has high safety, and to provide a charge control method of resin powder and the toner using the charge control agent. <P>SOLUTION: The charge control agent contains a tartaric acid derivative having a predetermined structure as an effective component. The charge control method of resin powder and the toner using the charge control agent are also provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a toner for developing an electrostatic image for developing an electrostatic latent image in electrophotography, electrostatic recording, electrostatic printing, etc., a charge control agent for controlling the charge amount of the toner, and resin powder The present invention relates to a body charge control method.

  In photocopiers, printers, etc., colorants and fixings are used to develop electrostatic latent images formed on photoreceptors with photosensitive layers containing inorganic or organic photoconductive materials. Various toners made of these resins are used.

  Such toner chargeability is a particularly important factor in a system for developing an electrostatic latent image. Therefore, in order to appropriately control or stabilize the charge amount of the toner, a charge control agent imparting positive charge or negative charge is often added to the toner.

  Among charge control agents that have been put into practical use, examples of those that impart a negative charge to the toner include metal complex dyes of monoazo compounds and metal complexes or metal salts of aromatic oxycarboxylic acids such as alkyl salicylic acid. .

  Of these, many of the azo dye structure metal complexes proposed as charge control agents are generally poor in stability, such as mechanical friction and impact, electrical impact and light irradiation, changes in temperature and humidity conditions, etc. Therefore, the charge controllability is likely to be lost due to decomposition or alteration. Further, even those having a practical level of charge imparting properties often have insufficient charge stability or are colored and cannot be used for color toners. On the other hand, metal complexes such as alkyl salicylic acid are generally used in color toners because they are light or colorless, but may be decomposed even under relatively weak acidic or basic conditions.

  Several proposals have been made for a charge control agent having a negative charge imparting property that can solve such problems and contribute to further improvement in performance of a copying machine, a printer, or the like.

  For example, Patent Document 1 discloses the following compounds as charge control agents, for example.

  Patent Document 2 discloses, for example, the following compounds as charge control agents.

In the above formula, X represents an aliphatic residue which may have a substituent, and R ¹ and R ² represent an aromatic residue which may have a substituent. n represents 0 or 1.

  Further, Patent Document 3 discloses the following compounds as charge control agents, for example.

In the above formula, A, R, R ¹ and R ² are each an aromatic residue, and the hydroxyl group and the amide group are located at adjacent substitution positions on the aromatic ring A.

  Patent Document 4 discloses, for example, the following compounds as charge control agents.

In the above formula, R ¹ and R ² are the same or independently substituted alkyl groups or optionally substituted phenyl groups.

  Patent Document 5 discloses the following compounds as charge control agents.

In the above formula, each of A ¹ and A ² has a hydroxyl group and a carboxyl group at adjacent substitution positions on one carbon 6-membered ring at the end, and another substitution position on the carbon 6-membered ring. in represents a naphthyl group or an anthranyl group is bonded to the alkylene group linking the a ¹ and a ^2, which may have a substituent. N represents an integer.

  In recent years, with higher performance such as improved resolution of printers and copiers, there has been a demand for toners that are more excellent in charging characteristics and stability than conventional toners. A charge control agent to be expressed is desired.

  However, when the characteristics of the charge control agents shown in Patent Documents 1, 2, 3, 4, and 5 were examined, they were colorless to light in any case, but did not give sufficient charge amount or environmental stability. I understood.

JP-A-10-239907 Japanese Patent Laid-Open No. 9-179352 Japanese Patent No. 3118921 Japanese Patent Laid-Open No. 7-325431 JP-A-5-11505

The present invention has been made in view of the above-described problems existing in the prior art, and the object is as follows.
(A) having a practical level of negative charge imparting property;
(B) Colorless or light color, which can be used for color toners,
(C) The electrostatic charge due to charging of the resin powder such as the toner used is stable against environmental changes,
(D) Excellent storage stability (stability over time of charge control characteristics),
(E) Excellent durability (stability of charge control characteristics when the used toner is repeatedly used many times),
(F) An object of the present invention is to provide a charge control agent having a characteristic that it does not contain harmful heavy metals and has high safety.

  In addition, the object of the present invention is to realize a charge control method of resin powder using the charge control agent, fixing property and non-offset property in a wide temperature range, and environmental resistance (charging characteristics against changes in temperature and humidity). The present invention provides an electrostatic charge image developing toner that is excellent in stability, storage stability and durability, and that can provide a stable toner image.

  As a result of repeated studies to solve the above problems, the present inventor has found that tartaric acid diesters and monoamides or diamides thereof give good charging characteristics, and have completed the present invention.

  That is, the charge control agent of the invention according to claim 1 of the present invention that achieves the above object is a charge control agent containing a compound represented by the following formulas (I) to (III) as an active ingredient.

式（Ｉ）中、Ｒ^１乃至Ｒ^２は、互いに独立的にアルキル基、シクロアルキル基、アルケニル基、多員環化合物基、アリール基、複素環基、又は多環式炭化水素基を示す。前記アルケニル基、多員環化合物基、アリール基、複素環基、及び多環式炭化水素基は、それぞれ、置換基を有しないか、又は、アルキル基、シクロアルキル基、ハロゲン原子、アルコキシカルボニル基、アリール基、複素環基、多環式炭化水素基、アルコキシ基、アシル基、及びアリールカルボニル基から選ばれる１種又は２種以上の置換基を１又は２以上有する。

In the formula (I), R ^{1 and} R ² each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, a multi-membered compound group, an aryl group, a heterocyclic group, or a polycyclic hydrocarbon group. The alkenyl group, multi-membered compound group, aryl group, heterocyclic group and polycyclic hydrocarbon group each have no substituent, or an alkyl group, a cycloalkyl group, a halogen atom, an alkoxycarbonyl group , An aryl group, a heterocyclic group, a polycyclic hydrocarbon group, an alkoxy group, an acyl group, and one or two or more substituents selected from an arylcarbonyl group.

式（II）中、Ｒ^３乃至Ｒ^４は、互いに独立的にアルキル基、シクロアルキル基、アルケニル基、多員環化合物基、アリール基、複素環基、又は多環式炭化水素基を示す。前記アルケニル基、多員環化合物基、アリール基、複素環基、及び多環式炭化水素基は、それぞれ、置換基を有しないか、又は、アルキル基、シクロアルキル基、ハロゲン原子、アルコキシカルボニル基、アリール基、複素環基、多環式炭化水素基、アルコキシ基、アシル基、及びアリールカルボニル基から選ばれる１種又は２種以上の置換基を１又は２以上有する。

In the formula (II), R ^{3 to} R ⁴ each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, a multi-membered compound group, an aryl group, a heterocyclic group, or a polycyclic hydrocarbon group. The alkenyl group, multi-membered compound group, aryl group, heterocyclic group and polycyclic hydrocarbon group each have no substituent, or an alkyl group, a cycloalkyl group, a halogen atom, an alkoxycarbonyl group , An aryl group, a heterocyclic group, a polycyclic hydrocarbon group, an alkoxy group, an acyl group, and one or two or more substituents selected from an arylcarbonyl group.

R ^{5 to} R ⁶ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, or a polycyclic hydrocarbon group. The aryl group, heterocyclic group and polycyclic hydrocarbon group each have no substituent, or an alkyl group, cycloalkyl group, halogen atom, hydroxyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl Group, sulfonic acid group, sulfonic acid ester group (sulfoester group), aryl group, acylamino group, heterocyclic group, polycyclic hydrocarbon group, aminocarbonyl group, alkoxy group, acyl group, and arylcarbonyl group It has 1 or 2 or more types of substituents.

式（ＩＩＩ）中、Ｒ^７乃至Ｒ^８は、互いに独立的にアルキル基、シクロアルキル基、アルケニル基、多員環化合物基、アリール基、複素環基、又は多環式炭化水素基を示す。前記アルケニル基、多員環化合物基、アリール基、複素環基、及び多環式炭化水素基は、それぞれ、置換基を有しないか、又は、アルキル基、シクロアルキル基、ハロゲン原子、アルコキシカルボニル基、アリール基、複素環基、多環式炭化水素基、アルコキシ基、アシル基、及びアリールカルボニル基から選ばれる１種又は２種以上の置換基を１又は２以上有する。

In the formula (III), R ^{7 to} R ⁸ each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, a multi-membered compound group, an aryl group, a heterocyclic group, or a polycyclic hydrocarbon group. The alkenyl group, multi-membered compound group, aryl group, heterocyclic group and polycyclic hydrocarbon group each have no substituent, or an alkyl group, a cycloalkyl group, a halogen atom, an alkoxycarbonyl group , An aryl group, a heterocyclic group, a polycyclic hydrocarbon group, an alkoxy group, an acyl group, and one or two or more substituents selected from an arylcarbonyl group.

R ^{9 to} R ¹² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, or a polycyclic hydrocarbon group. The aryl group, heterocyclic group and polycyclic hydrocarbon group each have no substituent, or an alkyl group, cycloalkyl group, halogen atom, hydroxyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl Group, sulfonic acid group, sulfonic acid ester group (sulfoester group), aryl group, acylamino group, heterocyclic group, polycyclic hydrocarbon group, aminocarbonyl group, alkoxy group, acyl group, and arylcarbonyl group It has 1 or 2 or more types of substituents.

Similarly, the charge control agent of the invention according to claim 2 is the charge control agent of the invention according to claim 1, wherein the substituents R ^{1 to} R ⁴ and R ^{7 to} R ^{8 of the} formulas (I) to (III) are used. Is an aryl group having a substituent or an aryl group having no substituent, and the substituents R ^{5 to} R ⁶ and R ^{9 to} R ¹² are an aryl group having a substituent or an aryl group having no substituent. is there.

  To achieve the above object, an image developing toner according to a third aspect of the present invention comprises a toner resin, a colorant, and the charge control agent according to the first or second aspect.

  Similarly, the charge control method of the invention according to claim 4 of the present invention performs charge control of the resin powder by containing the charge control agent of the invention according to claim 1 or 2 in the resin powder. is there.

  The charge control agent of the present invention is excellent in negative charge imparting property and stability thereof, has good dispersibility in the resin for toner, and is excellent in environmental stability of charge amount and storage stability when used in toner. Excellent in durability and durability, does not contain harmful heavy metals, is highly safe, and is colorless or light-colored.

  According to the charge control method of the present invention, since the negative charge control of the resin powder is stably performed and the colorless or light color charge control agent not containing harmful heavy metals is used, the safety is high and the color tone of the resin powder is high. Hard to cause obstacles.

  The toner for developing an electrostatic charge image of the present invention can realize fixing property and non-offset property in a wide temperature range, and is excellent in environmental resistance, storage stability and durability, and can form a stable copy image. .

  The reason why the charge control agent of the present invention is excellent in negative charge imparting property and its stability is not necessarily clear, but is estimated as follows.

  The tartaric acid derivatives represented by the above general formulas (I) to (III) which are active ingredients have four carbonyl groups at very close positions, and these are close to each other in steric form although they are not conjugated to each other. It is considered that the electron clouds overlap and interact, and as a result, it is considered that an appropriate electron transfer can be performed as a charge control agent. For this reason, the tartaric acid that has not been esterified and the diester form of ethylene glycol and the succinic acid derivative, which have the same number of methylene groups, do not have enough carbonyl groups, so the charging characteristics are not sufficient.

  In addition, when an aromatic ring is substituted on the substituent of the ester part or the amide part, the aromatic rings are also located in a spatially close position, so that the interaction between them or a carbonyl group is conjugated. As a result, it is possible to expect an effect such as enlargement of the electron movement area, so that better charging characteristics are exhibited.

Preferred form for carrying out the invention

  The charge control agent of the present invention comprises a tartaric acid derivative represented by the above formulas (I) to (III) as an active ingredient.

The alkyl group, cycloalkyl group, alkenyl group, multi-membered compound group, aryl group, heterocyclic group, and polycyclic group as R ^{1 to} R ⁴ , R ⁷ , and R ^{8 in the} above formulas (I) to (III) Specific examples of the hydrocarbon group include the following examples, but are not limited thereto.

Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, n-pentyl group, neo-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, And an alkyl group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms, which may be branched, such as a 2-ethylhexyl group.
Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a 4-t-butylcyclohexyl group, and the like.

  Examples of the alkenyl group include a vinyl group, a stynyl group, and a 1,3-pentanedienyl group.

  Examples of the multi-membered ring compound group include a norbornyl group, a norbornenyl group, an adamantyl group, and the like.

  Examples of the aryl group include a phenyl group, a benzyl group, and a naphthyl group.

  Examples of the heterocyclic group include a pyridyl group, a quinolyl group, a furanyl group, and a thiophenyl group.

  Examples of the polycyclic hydrocarbon group include a fluorenyl group and an indanyl group.

  The alkenyl group, polycyclic compound group, aryl group, heterocyclic group, and polycyclic hydrocarbon group may each have no substituent, and may be an alkyl group, a cycloalkyl group, a halogen atom, It has one or two or more substituents selected from an alkoxycarbonyl group, an aryl group, a heterocyclic group, a polycyclic hydrocarbon group, an alkoxy group, an acyl group, and an arylcarbonyl group. Also good. Therefore, it may have one or two or more identical substituents, and may have one or more two or more substituents.

  Specific examples of substituents that can be present in the alkenyl group, polycyclic compound group, aryl group, heterocyclic group, and polycyclic hydrocarbon group include the following, It is not limited to these.

  Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, n-pentyl group, neo-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, Mention may be made of alkyl groups having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms which may be branched, such as 2-ethylhexyl group.

  Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a 4-t-butylcyclohexyl group, and the like.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, t-butoxycarbonyl group, n-pentoxycarbonyl group, neo-pentoxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n- An alkoxycarbonyl group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms, such as an octyloxycarbonyl group.

  Examples of the aryl group include a phenyl group, a benzyl group, and a naphthyl group.

  Examples of the heterocyclic group include a pyridyl group, a quinolyl group, a furanyl group, and a thiophenyl group.

  Examples of the polycyclic hydrocarbon group include a fluorenyl group and an indanyl group.

  Alkoxy groups include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, sec-butoxy, t-butoxy, n-pentoxy, neo-pentoxy , N-hexyloxy group, n-heptyloxy group, n-octyloxy group and the like, which may be an alkoxy group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms, which may be branched. Can do.

  Examples of the aryloxy group include a phenoxy group, a benzyloxy group, and a naphthyloxy group.

  Examples of the acyl group include an acetyl group, an ethylcarbonyl group, and a t-butylcarbonyl group.

  Examples of the arylcarbonyl group include a phenylcarbonyl group, a benzylcarbonyl group, and a naphthylcarbonyl group.

More specific examples of the alkyl group, cycloalkyl group, aryl group, heterocyclic group, or polycyclic hydrocarbon group as R ⁵ and R ⁶ , R ^{9 to} R ^{12 in the} above formulas (II) to (III) Examples include, but are not limited to, the following examples.

  Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, n-pentyl group, neo-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, Mention may be made of alkyl groups having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms which may be branched, such as 2-ethylhexyl group.

  Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a 4-t-butylcyclohexyl group, and the like.

  Examples of the aryl group include a phenyl group, a benzyl group, and a naphthyl group.

Examples of the heterocyclic group include a pyridyl group, a quinolyl group, a furanyl group, and a thiophenyl group.
Examples of the polycyclic hydrocarbon group include a fluorenyl group and an indanyl group.

  The aryl group, heterocyclic group, and polycyclic hydrocarbon group may each have no substituent, and may be an alkyl group, a cycloalkyl group, a halogen atom, a hydroxyl group, a carboxyl group, an alkoxycarbonyl group, One or more substitutions selected from aryloxycarbonyl group, sulfonic acid group, sulfonic acid ester group (sulfoester group), aryl group, acylamino group, aminocarbonyl group, alkoxy group, acyl group, and arylcarbonyl group You may have 1 or 2 or more groups. Therefore, it may have one or two or more identical substituents, and may have one or more two or more substituents.

  The carboxyl group and sulfonic acid group may each form a metal salt. Examples of such metals include alkali metals such as lithium, sodium and potassium, and alkaline earth metals such as calcium and magnesium. An ammonium salt such as a quaternary ammonium salt may also be used.

  Specific examples of the substituent that can be present on each aromatic ring of the aryl group, heterocyclic group, and polycyclic hydrocarbon group include the following, but are not limited thereto. It is not something.

  Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, n-pentyl group, neo-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, Mention may be made of alkyl groups having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms which may be branched, such as 2-ethylhexyl group.

  Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a 4-t-butylcyclohexyl group, and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, t-butoxycarbonyl group, n-pentoxycarbonyl group, neo-pentoxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n- An alkoxycarbonyl group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms, such as an octyloxycarbonyl group.

  Examples of the aryloxycarbonyl group include a phenoxycarbonyl group, a benzyloxycarbonyl group, and a naphthoxycarbonyl group.

  Examples of the sulfonic acid ester group (sulfoester group) include a sulfonic acid methyl ester group, a sulfonic acid ethyl ester group, a sulfonic acid t-butyl ester group, a sulfonic acid n-pentyl ester group, a sulfonic acid neo-pentyl ester group, and a sulfonic acid. an alkyl group having 1 to 18, preferably 1 to 8 carbon atoms, such as an n-hexyl ester group, a sulfonic acid n-heptyl ester group, a sulfonic acid n-octyl ester group, and a sulfonic acid 2-ethylhexyl ester group; And sulfonic acid ester groups with aryl groups such as sulfonic acid phenyl ester groups, sulfonic acid benzyl ester groups, and sulfonic acid naphthyl ester groups.

  Examples of the aryl group include a phenyl group, a benzyl group, and a naphthyl group.

  Examples of the acylamino group include an acetylamino group, an ethylcarbonylamino group, a t-butylcarbonylamino group, and a phenylcarbonylamino group.

  Examples of the heterocyclic group include a pyridyl group, a quinolyl group, a furanyl group, and a thiophenyl group.

  Examples of the polycyclic hydrocarbon group include a fluorenyl group and an indanyl group.

  Examples of the aminocarbonyl group include an N-methylaminocarbonyl group, an Nt-butylaminocarbonyl group, and an N-phenylaminocarbonyl group.

  Alkoxy groups include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, sec-butoxy, t-butoxy, n-pentoxy, neo-pentoxy , N-hexyloxy group, n-heptyloxy group, n-octyloxy group and the like, which may be an alkoxy group having 1 to 18 carbon atoms, preferably 1 to 8 carbon atoms, which may be branched. Can do.

  Examples of the aryloxy group include a phenoxy group, a benzyloxy group, and a naphthyloxy group.

  Examples of the acyl group include an acetyl group, an ethylcarbonyl group, and a t-butylcarbonyl group.

  Examples of the arylcarbonyl group include a phenylcarbonyl group, a benzylcarbonyl group, and a naphthylcarbonyl group.

  The tartaric acid derivatives represented by the general formulas (I) to (III) can be obtained from tartaric acid using a known method. For example, it can be obtained by the following method, but is not limited thereto.

  The dicarboxylic acid body is obtained by heating tartaric acid with the corresponding acid chloride and no solvent or by using a solvent such as toluene or xylene, and heating it in a solvent containing water. To obtain a dicarboxylic acid form.

  The monoamide can be obtained by adding an amine in various solvents to the acid anhydride obtained by the above method.

  The diamide can be obtained by reacting a dicarboxylic acid obtained by the above method with a condensing agent such as DCC (dicyclohexylcarbodiimide) or carbonyldiimidazole in THF (tetrahydrofuran) or dichloromethane, and adding an amine thereto. You can get a body.

  Moreover, the said diamide body can be obtained also by mixing and heating a dicarboxylic acid body and amine with aromatic compounds, such as toluene, chlorobenzene, and pyridine, and phosphorus compounds, such as phosphorus trichloride and phosphorous acid.

Preferable specific examples of the tartaric acid derivative represented by the general formula (I) include compound examples 1 to 36 in which R ¹ and R ² in the formula (I) are substituents represented by the following formula. However, the scope of the present invention is not limited to these examples.

Preferred specific examples of the tartaric acid derivative represented by the general formula (II) include the following compound examples 37 to 87. However, preferred examples are not limited to these.
[Compound Examples 37 to 87]

Preferred specific examples of the tartaric acid derivative represented by the general formula (III) include the following compound examples 88 to 142. However, preferred examples are not limited to these.
[Compound Examples 88 to 142]

  The charge control agent of the present invention preferably has an average particle size of 10 μm or less. More preferably, it is 3 micrometers or less, More preferably, it is 1 micrometer or less. There is no particular lower limit of the particle size, but it can be set to 0.01 μm or more, for example. The charge control agent having a target particle size can be obtained by dry or wet pulverization, recrystallization or reprecipitation using various pulverizers such as a ball mill and a bead mill.

  The charge control agent of the present invention preferably has a purity (weight percentage of the tartaric acid derivative represented by the formulas (I) to (III) in the charge control agent) of 90% or more, and is 95% or more. It is more preferable.

  Next, the electrostatic image developing toner of the present invention comprises a toner resin, a colorant, and the charge control agent of the present invention. The compounds represented by the general formulas (I) to (III) constituting the active ingredient of the charge control agent of the present invention in the toner may be a single compound or a mixture of several compounds. Good. The electrostatic image developing toner of the present invention may contain another charge control agent (for example, an azo metal complex or a salicylic acid metal complex).

  In the toner for developing an electrostatic charge image of the present invention, a compound (charge control agent) containing a tartaric acid derivative represented by the above formulas (I) to (III) as an active ingredient is added in an amount of 0. It is desirable that 1 to 10 parts by weight is blended. A more preferable blending amount of the charge control agent is 0.5 to 5 parts by weight with respect to 100 parts by weight of the toner resin.

  Examples of the toner resin that can be used in the toner for developing an electrostatic charge image include the following known toner resins (binder resins). That is, it is a thermoplastic resin such as a styrene resin, a styrene-acrylic resin, a styrene-butadiene resin, a styrene-maleic acid resin, a styrene-vinyl methyl ether resin, a styrene-methacrylic acid ester copolymer, a polyester resin, or a polypropylene resin. . These resins can be used alone or in combination of several kinds. The charge control agent of the present invention can also be used for controlling (enhancing) the charge of resin powder by being contained in an electrostatic powder coating. Examples of the coating resin in this case include thermoplastic resins such as acrylic resins, polyolefin resins, polyester resins, or polyamide resins, and thermosetting resins such as phenol resins or epoxy resins. These can be used alone or in combination with several kinds.

  The acid value of the resin used in the toner for developing an electrostatic charge image of the present invention is preferably 0.1 mgKOH / g to 100 mgKOH / g. More preferably, it is 0.1 mgKOH / g to 70 mgKOH / g, and still more preferably 0.1 mgKOH / g to 50 mgKOH / g.

  The charge control agent of the present invention is prepared by mixing and melting the resin and the charge control agent in advance for the purpose of improving the dispersibility of the charge control agent with respect to the resin, and then pulverizing it after cooling and solidification. You may use as a masterbatch obtained by this.

  In the toner of the present invention, various dyes and pigments can be used alone or in combination of two or more as colorants. Specific examples of colorants that can be used are as follows. That is, quinophthalone yellow, isoindolinone yellow, benzidine yellow, perinone orange, perinone red, perylene maroon, rhodamine 6G lake, quinacridone red, anthanthrone red, rose bengal, copper phthalocyanine blue, copper phthalocyanine green, diketopyrrolopyrrole pigment Organic pigments such as carbon black, titanium white, titanium yellow, ultramarine blue, cobalt blue, brown, aluminum powder, bronze and other inorganic pigments and metal powders; azo dyes, quinophthalone dyes, anthraquinone dyes, phthalocyanine dyes, indophenol In addition to various oil-soluble dyes and disperse dyes such as azo dyes and indoaniline dyes, tria modified with resins such as rosin, rosin-modified phenol and rosin-modified maleic acid It can be exemplified Rumetan dyes and xanthene dyes.

  The electrostatic image developing toner of the present invention is produced, for example, as follows.

  Resin for toner as described above, colorant, charge control agent of the present invention, and magnetic material (for example, fine powder made of ferromagnetic material such as iron, cobalt, ferrite, etc.), fluidity modifier as required (For example, silica, aluminum oxide, titanium oxide), anti-offset agent (for example, wax, low molecular weight olefin wax), etc., are thoroughly mixed by a ball mill or other mixer, and then the mixture is heated by a roll, kneader, extruder, etc. A toner having an average particle size of 5 to 20 μm can be obtained by melt-kneading using a thermal kneader, cooling and solidifying the kneaded product, and then pulverizing and classifying the solidified product.

  In addition, a method obtained by dispersing the material in the binder resin solution and then spray-drying, or polymerization after a predetermined material is mixed with the monomer to constitute the binder resin to form an emulsion suspension For example, a toner production method by a polymerization method for obtaining a toner (so-called polymerized toner) can be applied.

  For example, in the suspension polymerization method, a polymerization monomer, a colorant and a charge control agent, and, if necessary, a polymerization initiator, a crosslinking agent, a release agent, and other additives are uniformly dissolved or dispersed to form a simple substance. After preparing the monomer composition, the monomer composition is dispersed in a continuous layer containing a dispersion stabilizer (for example, an aqueous phase) using an appropriate disperser and a polymerization reaction is performed. It is possible to obtain toner particles having a particle size of.

  Examples of the polymerizable monomer for forming the resin for the polymerized toner include styrene, such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, and p-ethylstyrene. Monomer: methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, acrylic acid Acrylic acid esters such as 2-chloroethyl and phenyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, methacrylic acid 2-ethylhexyl, methacrylate Stearyl, phenyl methacrylate, dimethylaminoethyl methacrylate, methacrylic acid esters such as diethylaminoethyl methacrylate; acrylonitrile, methacrylonitrile, vinyl monomers of acrylamide.

  As the dispersion stabilizer, various surfactants, organic or inorganic dispersants, and the like can be used. Examples of the surfactant include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, sodium stearate, potassium stearate and the like. Examples of the organic dispersant include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose and the like. Examples of inorganic dispersants include fine powders of polyvalent metal phosphates such as calcium phosphate, magnesium phosphate, aluminum phosphate, and zinc phosphate; carbonate fine powders such as calcium carbonate and magnesium carbonate; calcium metasilicate, Examples include inorganic salts such as calcium sulfate and barium sulfate, inorganic hydroxides such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide; inorganic oxides such as silica, bentonite, alumina, magnetic substances, and ferrite. it can.

  Examples of the polymerization initiator include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile). Azo or diazo polymerization initiators such as 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate Peroxide-based polymerization initiators such as cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, t-butylperoxy 2-ethylhexanoate, t-butylperoxypivalate, etc. It can be illustrated.

  As the cross-linking agent, compounds having two or more polymerizable double bonds are mainly used. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; for example, ethylene glycol diacrylate and ethylene glycol dimethacrylate Carboxylic acid esters having two double bonds such as 1,3-butanediol dimethacrylate; divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfone; and compounds having three or more vinyl groups Can be mentioned.

  Examples of the release agent include petroleum waxes such as paraffin wax, microcrystalline wax, petrolactam and derivatives thereof, montan wax and derivatives thereof, hydrocarbon waxes and derivatives thereof according to the Fischer-Push method, and polyolefin waxes typified by polyethylene. And derivatives thereof, natural waxes such as carnauba wax and candelilla wax and derivatives thereof, and the like include oxides, block copolymers with vinyl monomers, and graft modified products. Furthermore, fatty acids such as higher aliphatic alcohols, stearic acid and palmitic acid or compounds thereof, acid amide waxes, ester waxes, ketones, hydrogenated castor oil and derivatives thereof, plant waxes, animal waxes and the like can be mentioned.

  In emulsion polymerization, for example, a release agent, a charge control agent, a polymerization initiator, etc. are added to the polymerizable monomer as necessary, and after these are dissolved or dispersed, a homomixer or a homogenizer is used. Disperse in oil droplets of a desired size as resin fine particles in an aqueous medium, and then carry out a polymerization reaction by heating in a reaction apparatus equipped with a stirring blade. In addition, toner can be obtained by heat-sealing at a temperature equal to or higher than the glass transition temperature of the polymer formed at the same time as salting out to obtain the desired particle size.

  As the polymerizable monomer, in addition to the above, olefins such as ethylene, propylene, and isobutylene; halogen-based vinyls such as vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride, and vinylidene fluoride; vinyl propionate Vinyl esters such as vinyl acetate and vinyl benzoate; vinyl ethers such as vinyl methyl ether and vinyl ethyl ether; vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl hexyl ketone; N vinyl carbazole, N-vinyl indole, N-vinyl compounds such as N-vinylpyrrolidone; vinyl compounds such as vinylnaphthalene and vinylpyridine; and acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide.

  Examples of the polymerization initiator may include persulfates such as potassium persulfate and ammonium persulfate, azobisaminodipropane acetate, azobiscyanovaleric acid and salts thereof, hydrogen peroxide and the like in addition to the above.

  Examples of the aggregating agent include monovalent metal salts such as alkali metal salts such as sodium, potassium and lithium, divalent metal salts such as alkaline earth metal salts such as calcium and magnesium, manganese, and the like. , Salts of divalent metals such as copper, salts of trivalent metals such as iron and aluminum, etc., and specific salts include sodium chloride, potassium chloride, lithium chloride, calcium chloride, zinc chloride, sulfuric acid Examples include copper, magnesium sulfate, and manganese sulfate.

  Furthermore, the following are mentioned when comprising a polyester-type polymer.

  The polyvalent carboxylic acid that can be used as the polycondensation monomer is a compound containing two or more carboxyl groups in one molecule. Among these, dicarboxylic acid is a compound containing two carboxyl groups in one molecule. For example, oxalic acid, glutaric acid, succinic acid, maleic acid, adipic acid, methyl adipic acid, azelaic acid, sebacic acid, nonanedicarboxylic Acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, citraconic acid, diglycolic acid, cyclohexane-3,5-diene-1,2-carboxylic acid, malic acid, citric acid, hexahydroterephthalic acid, Malonic acid, pimelic acid, tartaric acid, mucous acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-phenylenediglycolic acid, p-phenylene diglycolic acid, o-phenylene jig Cholic acid, diphenylacetic acid, diphenyl-p, p'-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracene dicarboxylic acid, cyclohexanedicarboxylic acid Etc. Examples of the polyvalent carboxylic acid other than dicarboxylic acid include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, and pyrenetetracarboxylic acid. Moreover, you may use what derived the carboxyl group of these carboxylic acid to the acid anhydride, mixed acid anhydride, acid chloride or ester.

  A polyol that can be used as a polycondensation monomer is a compound containing two or more hydroxyl groups in one molecule. Among these, diol is a compound containing two hydroxyl groups in one molecule. For example, ethylene glycol, propylene glycol, butanediol, diethylene glycol, hexanediol, cyclohexanediol, octanediol, decanediol, dodecanediol, etc. Can be mentioned. Examples of polyols other than diols include glycerin, pentaerythritol, hexamethylol melamine, hexaethylol melamine, tetramethylol benzoguanamine, and tetraethylol benzoguanamine.

  Furthermore, examples of the hydroxycarboxylic acid that can be used as the polycondensation monomer include hydroxyheptanoic acid, hydroxyoctanoic acid, hydroxydecanoic acid, and hydroxyundecanoic acid.

  When the toner of the present invention is used as a two-component developer, the toner of the present invention can be used by mixing with carrier powder and can be developed by a magnetic brush developing method or the like.

  The carrier is not particularly limited, and any known carrier can be used. Illustratively, iron powder, nickel powder, ferrite powder, glass beads and the like having a particle size of about 50 to 200 μm, and the surfaces thereof are acrylic acid ester copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid. Examples include those coated with an ester copolymer, a silicone resin, a polyamide resin, an ethylene fluoride resin, and the like.

  When the toner of the present invention is used as a one-component developer, an appropriate amount of fine powder made of a ferromagnetic material such as iron powder, nickel powder or ferrite powder is added and dispersed when the toner is manufactured as described above. Can be used. Examples of the developing method in this case include a contact developing method and a jumping developing method.

  In the development of an electrostatic charge image using the toner of the present invention, the charge control of the toner that is a resin powder is performed by the charge control agent of the present invention in the toner.

  Next, the toner of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the following description, “parts by weight” is abbreviated as “parts”.

Synthesis Example 1 (Synthesis of Compound Example 1)
L (+)-tartaric acid (3.12 g, 20.7 mmol) was added to 16.7 g (84.9 mmol) of p-t-butylbenzoic acid chloride, and the mixture was stirred at 130 ° C. for 3 hours. The temperature was raised to 140 ° C. and the mixture was stirred for 2 hours and then allowed to cool. To this was added n-hexane and refluxed for 0.5 hours. After allowing to cool, the precipitated crystals were collected by suction filtration and dried at room temperature under reduced pressure to obtain 5.98 g (yield 36.0%) of an acid anhydride.

  2.50 g (3.16 mmol) of the obtained acid anhydride substance was dissolved in 10 mL of acetone, and 0.2 mL of water was added thereto and refluxed for 3 hours. After allowing to cool, the solvent was distilled off under reduced pressure, and the obtained crystals were recrystallized from toluene-n-hexane to obtain 0.244 g (yield 16.4%) of the desired product (Compound Example 1). .

Synthesis Example 2 (Synthesis of Compound Example 9)
To 25.0 g (0.131 mol) of 1-naphthoyl chloride, 4.80 g (32.0 mmol) of L (+)-tartaric acid was added and stirred at 130 ° C. for 3 hours. The temperature was raised to 140 ° C., stirred for 2 hours and then allowed to cool to 110 ° C., and 50 mL of toluene was added thereto and stirred. The insoluble material was filtered off and allowed to stand, and the precipitated crystals were collected by suction filtration and dried at room temperature under reduced pressure to obtain 11.6 g (yield 82.6%) of an acid anhydride.

  3.00 g (6.81 mmol) of the obtained acid anhydride substance was dissolved in 20 mL of acetone, and 0.4 mL of water was added thereto and refluxed for 3 hours. After allowing to cool, the solvent was distilled off under reduced pressure, and the residue was recrystallized from ethyl acetate-n-hexane to obtain 1.75 g (yield 55.9%) of the desired product (Compound Example 9).

Synthesis Example 3 (Synthesis of Compound Example 10)
To 5 mL of xylene, 10.0 g (52.5 mmol) of 2-naphthoyl chloride and 1.92 g (12.8 mmol) of L (+)-tartaric acid were added and stirred at 130 ° C. for 3 hours. The temperature was raised to 140 ° C., and the mixture was stirred for 1 hour and allowed to cool. Toluene (20 mL) was added thereto, and the crystals were heated and dissolved. The crystals were dried to obtain 3.69 g (yield 65.4%) of acid anhydride.

  2.00 g (4.58 mmol) of the obtained acid anhydride substance was dispersed in 120 mL of acetone, and 1 mL of water was added thereto and refluxed for 21 hours. After allowing to cool, the solvent was distilled off under reduced pressure, and the residue was recrystallized from ethyl acetate-n-hexane to obtain 1.22 g (yield 58.9%) of the desired compound example 10).

Synthesis Example 4 (Synthesis of Compound Example 12)
To 25.0 g (0.162 mol) of o-toluic acid chloride was added 5.93 g (39.5 mmol) of L (+)-tartaric acid, and the mixture was stirred at 130 ° C. for 3 hours. The temperature was raised to 140 ° C. and stirred for 1 hour, and then allowed to cool to 100 ° C. Toluene was added to 20 mL, and the mixture was allowed to cool to 70 ° C. Then, 20 mL of n-hexane was added and allowed to cool to room temperature. The precipitated crystals were collected by suction filtration and dried at room temperature under reduced pressure to obtain 9.98 g (yield 64.9%) of an acid anhydride.

  3.00 g (8.14 mmol) of the obtained acid anhydride substance was dissolved in 10 mL of acetone, and 0.5 mL of water was added thereto and refluxed for 4 hours. After allowing to cool, the solvent was distilled off under reduced pressure, and the residue was recrystallized from ethyl acetate-n-hexane to obtain 1.84 g (yield 58.6%) of the desired product (Compound Example 12).

Synthesis Example 5 (Synthesis of Compound Example 13)
To 25.0 g (0.162 mol) of m-toluic acid chloride was added 5.93 g (39.5 mmol) of L (+)-tartaric acid, and the mixture was stirred at 130 ° C. for 3 hours. The temperature was raised to 140 ° C., and the mixture was stirred for 1 hour and then allowed to cool. 25 mL of n-hexane was added to the filtrate and allowed to stand, and the precipitated crystals were collected by suction filtration and dried at room temperature under reduced pressure to obtain 7.32 g (yield 50.2%) of an acid anhydride.

  3.00 g (8.14 mmol) of the obtained acid anhydride substance was dissolved in 10 mL of acetone, and 0.5 mL of water was added thereto and refluxed for 4 hours. After allowing to cool, the solvent was distilled off under reduced pressure, toluene was added to the residue and dissolved by heating. A small amount of n-hexane was added, and the separated oil was separated by decantation. N-Hexane was added to the supernatant, and after standing, the crystallized precipitate was collected by suction filtration and dried at room temperature under reduced pressure to obtain 0.274 g (yield 8.7%) of the desired product (Compound Example 13). Obtained.

Synthesis Example 6 (Synthesis of Compound Example 14)
1.37 g (9.14 mmol) of L (+)-tartaric acid was added to 10.0 g (37.4 mmol) of 2,4,6-triisopropylbenzoic chloride and stirred at 130 ° C. for 3 hours. The temperature was raised to 140 ° C. and stirred for 1 hour. After allowing to cool, 15 mL of n-hexane was added for recrystallization, and the solvent of the filtrate was distilled off under reduced pressure. Acetone 20 mL and 0.7 mL of water were added to the residue, and the mixture was refluxed for 3 hours. After distilling off the solvent under reduced pressure, the residue was recrystallized from toluene-n-hexane to obtain 1.89 g (yield 34.0%) of the desired product (Compound Example 14).

Synthesis Example 7 (Synthesis of Compound Example 16)
7.27 g (48.2 mmol) of L (+)-tartaric acid was added to 34.6 g (0.198 mol) of o-chlorobenzoic acid chloride and stirred at 130 ° C. for 3 hours. The temperature was raised to 140 ° C. and the mixture was stirred for 1 hour and allowed to cool. Toluene 40 mL was added and dissolved by heating. After cooling, the precipitated crystals were dried at room temperature under reduced pressure to yield 19.2 g (yield 97.9). %) Acid anhydride body.

  3.00 g (7.40 mmol) of the obtained acid anhydride substance was dissolved in 20 mL of acetone, 0.4 mL of water was added thereto, and the mixture was refluxed for 4 hours. After allowing to cool, the solvent was distilled off under reduced pressure, the residue was dissolved in ethyl acetate, the insoluble material was filtered off, and the solvent of the filtrate was distilled off under reduced pressure. The residue was recrystallized from chloroform-n-hexane to obtain 1.08 g (yield 34.3%) of the desired product (Compound Example 16).

Synthesis Example 8 (Synthesis of Compound Example 18)
To 25.0 g (0.147 mol) of 4-methoxybenzoic acid chloride, 7.00 g (46.7 mmol) of L (+)-tartaric acid was added and stirred at 130 ° C. for 2 hours. The temperature was raised to 140 ° C. and the mixture was stirred for 1 hour and allowed to cool. 35 mL of toluene was added thereto, dissolved by heating and allowed to cool, and the precipitated crystals were dried at room temperature under reduced pressure to yield 19.8 g (yield 61.7). %) Acid anhydride body.

  3.00 g (4.37 mmol) of the obtained acid anhydride substance was dissolved in 20 mL of acetone, and 0.3 mL of water was added to this and refluxed for 3 hours. After allowing to cool, the solvent was distilled off under reduced pressure, the residue was dissolved in ethyl acetate with heating, the insoluble material was filtered off, and the solvent of the filtrate was distilled off under reduced pressure. The residue was recrystallized from ethyl acetate-n-hexane to obtain 1.17 g (yield 63.2%) of the desired product (Compound Example 18).

  Compound examples 2 to 8, 11, 15, 17, 19 to 36 were synthesized in the same manner.

Synthesis Example 9 (Synthesis of Compound Example 51)
3.00 g (8.14 mmol) of the acid anhydride substance obtained in Synthesis Example 4 was dissolved in 20 mL of THF, 0.758 g (8.14 mmol) of aniline was added thereto, and the mixture was refluxed at room temperature for 3 hours. The solvent was distilled off under reduced pressure, and the residue was recrystallized from ethyl acetate-n-hexane to give 1.56 g (yield 41.5%) of the desired product (Compound Example 51).

  Compound examples 37 to 50 and 52 to 87 were synthesized in the same manner.

Synthesis Example 10 (Synthesis of Compound Example 89)
Dipt-Butylbenzoic acid-D-tartaric acid (Compound Example 1) 0.712 g (1.51 mmol) was added to 12 mL of dichloromethane, and while cooling with ice water, 0.623 g (3.06 mmol) of DCC was added little by little. Stir for 15 minutes. While cooling with ice water, 0.282 g (3.01 mmol) of aniline was added, and the mixture was stirred at room temperature for 3 hours. A small amount of water was added, the insoluble material was filtered off, and the solvent was distilled off under reduced pressure. The residue was recrystallized from toluene to obtain 0.390 g (yield 41.6%) of the desired product (Compound Example 89).

Synthesis Example 11 (Synthesis of Compound Example 90)
25.0 g (64.7 mmol) of di-p-toluoyl-D-tartaric acid (Compound Example 2) was added to 500 mL of dichloromethane, and 26.6 g (0.129 mol) of DCC was added little by little while cooling with ice water, followed by stirring for 15 minutes. . While cooling with ice water, 12.1 g (0.129 mol) of aniline was added, and the mixture was stirred at room temperature for 3 hours. A small amount of water was added, the crystals were collected by suction filtration, dried at 80 ° C. overnight, and purified from ethyl acetate to obtain 21.6 g (yield 60.9%) of the desired product (Compound Example 90).

Synthesis Example 12 (Synthesis of Compound Example 91)
Dissolve 2.01 g (5.18 mmol) of di-p-toluoyl-D-tartaric acid (Compound Example 2) in 40 mL of dichloromethane, add 2.15 g (10.4 mmol) of DCC little by little while cooling with ice water, and stir for 15 minutes. did. While cooling with ice water, 1.55 g (10.1 mmol) of pt-butylaniline was added, and the mixture was stirred at room temperature for 3 hours. A small amount of water was added, insolubles were filtered off, and the solvent was distilled off under reduced pressure. The residue was recrystallized from ethyl acetate to obtain 0.982 g (yield 29.2%) of the desired product (Compound Example 91).

Synthesis Example 13 (Synthesis of Compound Example 98)
1.86 g (5.18 mmol) of dibenzoic acid-D-tartaric acid (Compound Example 8) was added to 40 mL of dichloromethane, and 2.15 g (10.4 mmol) of DCC was added little by little while cooling with ice water, followed by stirring for 15 minutes. While cooling with ice water, 0.969 g (10.4 mmol) of aniline was added, and the mixture was stirred at room temperature for 3 hours. A small amount of water was added and insoluble matter was filtered off, and this was recrystallized from DMF. The precipitated crystals were separated by filtration, and the filtrate was added to water to precipitate crystals. This was collected by suction filtration, dried, and recrystallized from ethyl acetate to obtain 0.446 g (yield 16.9%) of the desired product (Compound Example 98).

Synthesis Example 14 (Synthesis of Compound Example 102)
1.50 g (3.88 mmol) of di-o-toluoyl-D-tartaric acid (Compound Example 12) was added to 30 mL of dichloromethane, and 1.60 g (7.77 mmol) of DCC was added little by little while cooling with ice water, followed by stirring for 15 minutes. did. While cooling with ice water, 0.727 g (7.81 mmol) of aniline was added, and the mixture was stirred at room temperature for 3 hours. A small amount of water was added, and the crystals obtained after filtering off insolubles were recrystallized from DMF. The precipitated crystals were separated by filtration, and the filtrate was added to water to precipitate crystals. This was collected by suction filtration, dried and recrystallized from ethyl acetate to obtain 1.38 g (yield 66.7%) of the desired product (Compound Example 102).

  Compound examples 88, 92 to 97, 99 to 101, and 103 to 142 were synthesized in the same manner.

Example 1
Styrene-acrylic copolymer resin (manufactured by Sanyo Chemical Co., Ltd., trade name: CPR-600B) ... 100 parts low-polymerized polypropylene (trade name: Viscol 550P, produced by Sanyo Chemical Co., Ltd.) ... 3 parts carbon black (manufactured by Mitsubishi Chemical Corporation) Name: MA-100) ... 6 parts Charge control agent (Compound Example 1) ... 1 part

  A premix was prepared by uniformly premixing the above blend with a high speed mill. The premix was melt-kneaded with a heating roll, the kneaded product was cooled, and then coarsely pulverized with an ultracentrifugal pulverizer. The resulting coarsely pulverized product was finely pulverized using an air jet mill equipped with a classifier to obtain a black toner having an average particle size of 10 μm.

  A developer was prepared by mixing 95 parts of a ferrite carrier (trade name: F-150, manufactured by Powdertech Co., Ltd.) with 5 parts of the obtained toner.

  The developer was weighed into a plastic bottle, stirred by a ball mill with a rotation speed of 100 rpm, and the developer was charged, and the amount of electrification with time was measured under standard conditions (20 ° C., relative humidity 60%). Table 9 shows the measurement results of the triboelectric charge amount (minus) for each stirring time (min). Also, the initial blow-off charge amount (minus) was measured in the same manner under each condition of low temperature and low humidity (5 ° C., relative humidity 30%) and high temperature and high humidity (35 ° C., relative humidity 90%) (stirring time: 10 minutes). Table 9 shows the results of the measurement of the environmental stability of the charge amount, together with the measurement results of the standard conditions (20 ° C., relative humidity 60%).

  The charge amount was measured with a blow-off charge amount measuring machine (trade name: TB-200) manufactured by Toshiba Chemical Corporation.

  Using this developer, a toner image was formed on a commercially available copying machine (model using an organic photoreceptor OPC drum). The resulting toner image was visually observed for fogging and offset phenomenon and evaluated in three or two stages, respectively. Table 9 shows the evaluation results of the toner images.

  As for fog, ◎ indicates that there is no fog, ◯ indicates that fog is observed in several places but is hardly discernable, and X indicates that fog is clearly recognized. Regarding the offset phenomenon, the case where the offset phenomenon was not observed was marked with ◯, and the case where the offset phenomenon was observed was marked with ×.

Example 2
Styrene-acrylic copolymer resin (trade name: CPR-600B manufactured by Sanyo Chemical Co., Ltd.) ... 100 parts Low-polymerized polypropylene (trade name: Viscol 550P manufactured by Sanyo Chemical Co., Ltd.) ... 3 parts C.I. I. Pigment Red 122 ... 5 parts Charge Control Agent (Compound Example 38) ... 1 part

  The blend was processed in the same manner as in Example 1 to prepare a magenta toner and a developer, and the measurement results of the amount of time-dependent charge (minus) and charge amount environment stability measured in the same manner as in Example 1 are shown in Table 9. Show.

  Table 9 shows the evaluation results of toner images formed using this developer in the same manner as in Example 1.

Example 3
Styrene-acrylic copolymer resin (trade name: CPR-600B manufactured by Sanyo Chemical Co., Ltd.) ... 100 parts Low-polymerized polypropylene (trade name: Viscol 550P manufactured by Sanyo Chemical Co., Ltd.) ... 3 parts C.I. I. Pigment Yellow 180 ... 5 parts Charge Control Agent (Compound Example 97) ... 1 part

  The above blend was treated in the same manner as in Example 1 to prepare a yellow toner and a developer. The results of measurement of the amount of time-dependent charge (minus) and charge amount environment stability measured in the same manner as in Example 1 are shown in Table 9. Show. Table 9 shows the evaluation results of toner images formed using this developer in the same manner as in Example 1.

Example 4
Styrene ... 80 parts n-butyl methacrylate ... 20 parts C.I. I. Pigment Yellow 180 ... 5 parts 2,2'-azoisobutyronitrile ... 1.8 parts Charge Control Agent (Compound Example 47) ... 1 part

  The above blend was uniformly premixed with a high-speed mixer to obtain a polymerizable monomer composition.

  On the other hand, 100 mL of 0.1 mol / L tribasic sodium phosphate aqueous solution was diluted with 600 mL of distilled water, and 18.7 mL of 1.0 mol / L calcium chloride aqueous solution was added to this solution while stirring this solution. Gradually added. Further, while stirring this mixed solution, 0.15 g of a sodium dodecylbenzenesulfonate aqueous solution having a concentration of 20% by weight was added to this mixed solution to prepare a dispersion.

  The dispersion was added to the polymerizable monomer composition, and the mixture was heated to 65 ° C. while stirring at high speed with a TK homomixer (manufactured by Tokki Kako Co., Ltd.). The temperature was raised to 0 ° C., and the mixture was stirred at a rotational speed of 100 rpm with a normal stirrer, and polymerized for 6 hours while maintaining the temperature at 80 ° C.

  After completion of the polymerization, the reaction mixture was cooled to separate solids, and the filtered product was immersed in an aqueous hydrochloric acid solution having a concentration of 5% by weight to decompose calcium phosphate used as a dispersant. The obtained solid was washed with water until the washing solution became neutral, dehydrated and dried to obtain a yellow toner having an average particle size of 13 μm.

  A developer was prepared by mixing 5 parts of the polymerized toner with 95 parts of a ferrite carrier (trade name: F-150, manufactured by Powdertech Co., Ltd.). Table 9 shows the measurement results of the minus) and charge amount environment stability. Table 9 shows the evaluation results of toner images formed using this developer in the same manner as in Example 1.

Example 5
Styrene ... 80 parts n-butyl methacrylate ... 20 parts carbon black [trade name: MA-100 manufactured by Mitsubishi Chemical Corporation] ... 5 parts 2,2'-azoisobutyronitrile ... 1.8 Part charge control agent (Compound Example 16) 1 part

  The above blend was treated in the same manner as in Example 4 to prepare a black polymerized toner and a developer. The measurement results of the time-dependent charge amount (minus) and charge amount environment stability measured in the same manner as in Example 1 are shown in Table 9. Shown in Table 9 shows the evaluation results of toner images formed using this developer in the same manner as in Example 1.

Example 6
Styrene-acrylic copolymer resin [trade name: CPR-600B manufactured by Sanyo Chemical Co., Ltd.] ... 100 parts Low-polymerized polypropylene [trade name: Viscol 550P manufactured by Sanyo Chemical Co., Ltd.] 3 parts C.I. I. Pigment Red 122 ... 5 parts

  A premix was prepared by uniformly premixing the above blend with a high speed mill. The premix was melt-kneaded with a heating roll, the kneaded product was cooled, and then coarsely pulverized with an ultracentrifugal pulverizer. The obtained coarsely pulverized product was finely pulverized using an air jet mill equipped with a classifier to obtain magenta toner mother particles having an average particle size of 10 μm.

  A toner was obtained by externally adding 1 part of child particles comprising Compound Example 99 (charge control agent) to 108 parts of the obtained mother particles.

  The developer was prepared by mixing 5 parts of this toner with 95 parts of a ferrite carrier (F-150: trade name, manufactured by Powder Tech Co., Ltd.). Table 9 shows the measurement results of the environmental stability of the charge amount. Table 9 shows the evaluation results of toner images formed using this developer in the same manner as in Example 1.

Example 7
Polyester resin (trade name: Diacron ER-561, manufactured by Mitsubishi Rayon Co., Ltd.) ... 100 parts carbon black (trade name: MA-100, manufactured by Mitsubishi Chemical Corporation) ... 5 parts Charge control agent compound example (106) ... 1 copy

  A black toner and a developer were prepared by treating the above-mentioned formulation in the same manner as in Example 1. Table 9 shows the measurement results of the time-dependent charge amount (minus) and charge amount environment stability measured in the same manner as in Example 1. Show. Table 9 shows the evaluation results of toner images formed using this developer in the same manner as in Example 1.

Example 8
A black toner and developer were obtained in the same manner as in Example 1 except that the charge control agent was changed to Compound Example 2. Table 9 shows the measurement results of the time-dependent charge amount (minus) and charge amount environment stability measured in the same manner as in Example 1. Table 9 shows the evaluation results of toner images formed using this developer in the same manner as in Example 1.

Example 9
A black toner and developer were obtained in the same manner as in Example 1 except that the charge control agent was changed to Compound Example 9. Table 9 shows the measurement results of the time-dependent charge amount (minus) and charge amount environment stability measured in the same manner as in Example 1. Table 9 shows the evaluation results of toner images formed using this developer in the same manner as in Example 1.

Example 10
A black toner and developer were obtained in the same manner as in Example 1 except that the charge control agent was changed to Compound Example 10. Table 9 shows the measurement results of the time-dependent charge amount (minus) and charge amount environment stability measured in the same manner as in Example 1. Table 9 shows the evaluation results of toner images formed using this developer in the same manner as in Example 1.

Example 11
A black toner and developer were obtained in the same manner as in Example 1 except that the charge control agent was changed to Compound Example 12. Table 9 shows the measurement results of the time-dependent charge amount (minus) and charge amount environment stability measured in the same manner as in Example 1. Table 9 shows the evaluation results of toner images formed using this developer in the same manner as in Example 1.

Example 12
A black toner and a developer were obtained in the same manner as in Example 1 except that the charge control agent was changed to Compound Example 14. Table 9 shows the measurement results of the time-dependent charge amount (minus) and charge amount environment stability measured in the same manner as in Example 1. Table 9 shows the evaluation results of toner images formed using this developer in the same manner as in Example 1.

Example 13
A black toner and developer were obtained in the same manner as in Example 1 except that the charge control agent was changed to Compound Example 39. Table 9 shows the measurement results of the time-dependent charge amount (minus) and charge amount environment stability measured in the same manner as in Example 1. Table 9 shows the evaluation results of toner images formed using this developer in the same manner as in Example 1.

Example 14
A black toner and developer were obtained in the same manner as in Example 1 except that the charge control agent was changed to Compound Example 51. Table 9 shows the measurement results of the time-dependent charge amount (minus) and charge amount environment stability measured in the same manner as in Example 1. Table 9 shows the evaluation results of toner images formed using this developer in the same manner as in Example 1.

Example 15
A black toner and a developer were obtained in the same manner as in Example 1 except that the charge control agent was changed to Compound Example 78. Table 9 shows the measurement results of the time-dependent charge amount (minus) and charge amount environment stability measured in the same manner as in Example 1. Table 9 shows the evaluation results of toner images formed using this developer in the same manner as in Example 1.

Example 16
A black toner and developer were obtained in the same manner as in Example 1 except that the charge control agent was changed to Compound Example 89. Table 9 shows the measurement results of the time-dependent charge amount (minus) and charge amount environment stability measured in the same manner as in Example 1. Table 9 shows the evaluation results of toner images formed using this developer in the same manner as in Example 1.

Example 17
A black toner and developer were obtained in the same manner as in Example 1 except that the charge control agent was changed to Compound Example 90. Table 9 shows the measurement results of the time-dependent charge amount (minus) and charge amount environment stability measured in the same manner as in Example 1. Table 9 shows the evaluation results of toner images formed using this developer in the same manner as in Example 1.

Example 18
A black toner and developer were obtained in the same manner as in Example 1 except that the charge control agent was changed to Compound Example 91. Table 9 shows the measurement results of the time-dependent charge amount (minus) and charge amount environment stability measured in the same manner as in Example 1. Table 9 shows the evaluation results of toner images formed using this developer in the same manner as in Example 1.

Example 19
A black toner and developer were obtained in the same manner as in Example 1 except that the charge control agent was changed to Compound Example 98. Table 9 shows the measurement results of the time-dependent charge amount (minus) and charge amount environment stability measured in the same manner as in Example 1. Table 9 shows the evaluation results of toner images formed using this developer in the same manner as in Example 1.

Example 20
A black toner and developer were obtained in the same manner as in Example 1 except that the charge control agent was changed to Compound Example 102. Table 9 shows the measurement results of the time-dependent charge amount (minus) and charge amount environment stability measured in the same manner as in Example 1. Table 9 shows the evaluation results of toner images formed using this developer in the same manner as in Example 1.

Comparative Example 1
Charge control agent

に変えた以外は実施例１と同様にして黒色トナー及び現像剤を得た。なお、荷電制御剤は特開平１０−２３９９０７号公報に記載の実施例１の化合物である。上記実施例１と同様に測定した経時帯電量（マイナス）及び帯電量環境安定性の測定結果をそれぞれ表９に示す。また、この現像剤を用いて実施例１と同様に形成したトナー画像の評価結果を表９に示す。

A black toner and a developer were obtained in the same manner as in Example 1 except that. The charge control agent is the compound of Example 1 described in JP-A-10-239907. Table 9 shows the measurement results of the time-dependent charge amount (minus) and charge amount environment stability measured in the same manner as in Example 1. Table 9 shows the evaluation results of toner images formed using this developer in the same manner as in Example 1.

Comparative Example 2
A black toner and a developer were obtained in the same manner as in Example 1 except that the charge control agent was changed to the compound of Example 34 (described below) described in JP-A-10-239907. Table 9 shows the measurement results of the time-dependent charge amount (minus) and charge amount environment stability measured in the same manner as in Example 1. Table 9 shows the evaluation results of toner images formed using this developer in the same manner as in Example 1.

Comparative Example 3
The charge control agent is compound No. 9 described in JP-A-9-173952. A black toner and a developer were obtained in the same manner as in Example 1 except that the number of compounds was changed to 12 (below). Table 9 shows the measurement results of the time-dependent charge amount (minus) and charge amount environment stability measured in the same manner as in Example 1. Table 9 shows the evaluation results of toner images formed using this developer in the same manner as in Example 1.

Comparative Example 4
A black toner and a developer were obtained in the same manner as in Example 1 except that the charge control agent was changed to the compound shown in Example 40 described in JP-A-7-3254341 (described below). Table 9 shows the measurement results of the time-dependent charge amount (minus) and charge amount environment stability measured in the same manner as in Example 1. Table 9 shows the evaluation results of toner images formed using this developer in the same manner as in Example 1.

Comparative Example 5
A black toner and a developer were obtained in the same manner as in Example 1 except that the charge control agent was changed to the compound shown in Compound Example 11 (described below) described in JP-A No. 5-11505. Table 9 shows the measurement results of the time-dependent charge amount (minus) and charge amount environment stability measured in the same manner as in Example 1. Table 9 shows the evaluation results of toner images formed using this developer in the same manner as in Example 1.

Comparative Example 6
A black toner and a developer were obtained in the same manner as in Example 1 except that the charge control agent was changed to a diamide form of tartaric acid and aniline (below). Table 9 shows the measurement results of the time-dependent charge amount (minus) and charge amount environment stability measured in the same manner as in Example 1. Table 9 shows the evaluation results of toner images formed using this developer in the same manner as in Example 1.

Comparative Example 7
A black toner and a developer were obtained in the same manner as in Example 1 except that the charge control agent was changed to ethylene glycol di (4-isopropylbenzoic acid) ester (described below). Table 9 shows the measurement results of the time-dependent charge amount (minus) and charge amount environment stability measured in the same manner as in Example 1. Table 9 shows the evaluation results of toner images formed using this developer in the same manner as in Example 1.

The tartaric acid derivative of the present invention has a higher charge amount than the compound of the comparative example and is excellent in environmental stability. Furthermore, both fog and offset characteristics are good.
For example, the charge amount after stirring for 3 minutes in Example 1 is -50.4 μC / g, which is clearly higher than the −20.7 μC / g of Comparative Example 2, and the environmental stability is also low in the examples. While the difference between low humidity and high temperature and high humidity is only about 1 μC / g, the comparative example has a difference of 7 μC / g, indicating that the environmental stability is excellent.

  The present invention provides a charge control agent having excellent heat resistance, charging characteristics, and environmental stability. Moreover, since the charge control agent of the present invention does not contain harmful heavy metals, the load on the environment is small. Furthermore, since the charge control agent of the present invention is colorless or pale, it can be used for color toners.

Claims (4)

A charge control agent comprising a compound represented by the following formulas (I) to (III) as an active ingredient.

[In the formula (I), R ^{1 and} R ² each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, a multi-membered compound group, an aryl group, a heterocyclic group, or a polycyclic hydrocarbon group. . The alkenyl group, multi-membered compound group, aryl group, heterocyclic group and polycyclic hydrocarbon group each have no substituent, or an alkyl group, a cycloalkyl group, a halogen atom, an alkoxycarbonyl group , An aryl group, a heterocyclic group, a polycyclic hydrocarbon group, an alkoxy group, an acyl group, and one or two or more substituents selected from an arylcarbonyl group. ]

[In the formula (II), R ^{3 to} R ⁴ each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, a multi-membered compound group, an aryl group, a heterocyclic group, or a polycyclic hydrocarbon group. . The alkenyl group, multi-membered compound group, aryl group, heterocyclic group and polycyclic hydrocarbon group each have no substituent, or an alkyl group, a cycloalkyl group, a halogen atom, an alkoxycarbonyl group , An aryl group, a heterocyclic group, a polycyclic hydrocarbon group, an alkoxy group, an acyl group, and one or two or more substituents selected from an arylcarbonyl group.
R ^{5 to} R ⁶ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, or a polycyclic hydrocarbon group. The aryl group, heterocyclic group and polycyclic hydrocarbon group each have no substituent, or an alkyl group, cycloalkyl group, halogen atom, hydroxyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl 1 or 2 types selected from a group, sulfonic acid group, sulfonic acid ester group, aryl group, acylamino group, heterocyclic group, polycyclic hydrocarbon group, aminocarbonyl group, alkoxy group, acyl group, and arylcarbonyl group It has 1 or 2 or more of the above substituents. ]

[In the formula (III), R ^{7 to} R ⁸ each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, a multi-membered compound group, an aryl group, a heterocyclic group, or a polycyclic hydrocarbon group. . The alkenyl group, multi-membered compound group, aryl group, heterocyclic group, and polycyclic hydrocarbon group each have no substituent, or an alkyl group, a cycloalkyl group, a halogen atom, an alkoxycarbonyl group , An aryl group, a heterocyclic group, a polycyclic hydrocarbon group, an alkoxy group, an acyl group, and one or two or more substituents selected from an arylcarbonyl group.
R ^{9 to} R ¹² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, or a polycyclic hydrocarbon group. The aryl group, heterocyclic group and polycyclic hydrocarbon group each have no substituent, or an alkyl group, cycloalkyl group, halogen atom, hydroxyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl 1 or 2 types selected from a group, a sulfonic acid group, a sulfonic acid ester group, an aryl group, an acylamino group, a heterocyclic group, a polycyclic hydrocarbon group, an aminocarbonyl group, an alkoxy group, an acyl group, and an arylcarbonyl group It has 1 or 2 or more of the above substituents. ] The substituents R ^{1 to} R ⁴ and R ^{7 to} R ^{8 in the} formulas (I) to (III) are an aryl group having a substituent or an aryl group having no substituent, and the substituents R ^{5 to} R ^6. , R ^{9 to} R ¹² are an aryl group having a substituent or an aryl group not having a substituent.   An electrostatic image developing toner comprising a toner resin, a colorant, and the charge control agent according to claim 1.   A charge control method for controlling charge of a resin powder by containing the charge control agent according to claim 1 in the resin powder.