JP6263059B2 - Charge control agent and toner using the same - Google Patents

Description

The present invention relates to a charge control agent used in an image forming apparatus for developing an electrostatic latent image in fields such as electrophotography and electrostatic recording, and a negatively chargeable toner containing the charge control agent.

In the electrophotographic image forming process, an electrostatic latent image is formed on an inorganic photoreceptor such as selenium, selenium alloy, cadmium sulfide, and amorphous silicon, or an organic photoreceptor using a charge generator and a charge transport agent. Develop with toner, transfer to paper or plastic film, and fix to obtain a visible image.

The photosensitive member has positive and negative charging characteristics depending on the structure. When the printed part is left as an electrostatic latent image by exposure, development is performed with a reverse sign charging toner. On the other hand, the printed part is discharged to perform reverse development. When performing, it develops with the same sign charging toner.

  The toner is composed of a binder resin, a colorant, and other additives. In order to impart desirable charging characteristics (charging speed, charge level, charge stability, etc.), aging stability, environmental stability, etc., a charge control agent is generally added. By adding the charge control agent, the toner characteristics are greatly improved.

Today, as a positive triboelectric charge control agent known in the art, a nigrosine dye, an azine dye, a copper phthalocyanine pigment, a quaternary ammonium salt, or a polymer having a quaternary ammonium salt in the side chain is known. ing. Known negative triboelectric charge control agents include metal complexes of monoazo dyes, metal complexes of salicylic acid, naphthoic acid, dicarboxylic acids, copper phthalocyanine pigments, resins containing acid components, and the like.

In the case of color toners that are expected to expand in the future, a light-colored, preferably colorless, charge control agent that does not affect the hue is indispensable. These light or colorless charge control agents include metal complex salts of hydroxybenzoic acid derivatives (for example, see Patent Documents 1 to 3) and aromatic dicarboxylic acid metal salt compounds (for example, see Patent Document 4) for negatively chargeable toners. ), Metal complex salts of anthranilic acid derivatives (for example, see Patent Documents 5 to 6), organoboron compounds (for example, see Patent Documents 7 to 8), biphenol compounds (for example, see Patent Document 9), calix (n) arene There exist a compound (for example, refer patent documents 10-15), cyclic phenol sulfide (for example, refer patent documents 16-18), etc. Further, there are quaternary ammonium salt compounds (for example, see Patent Documents 19 to 21) for positively chargeable toners.

Japanese Patent Publication No. 55-042752 JP 61-069073 A JP 61-221756 A JP-A-57-111541 JP 61-141453 A JP 62-094856 A US Pat. No. 4,767,688 JP-A-1-3066861 JP 61-003149 A Japanese Patent No. 2568675 Japanese Patent No. 2899038 Japanese Patent No. 3359657 Japanese Patent No. 3313871 Japanese Patent No. 3325730 JP 2003-162100 A JP 2003-295522 A International Publication No. 2007/111346 International Publication No. 2007/119797 Japanese Unexamined Patent Publication No. 57-119364 JP 58-009154 A JP 58-098742 A

However, many of these charge control agents are complexes or salts made of heavy metals such as chromium, and have problems related to waste regulations, and are not necessarily safe. In addition, it cannot be completely colorless, the charge imparting effect is low and the rise of charge is insufficient, so the initial copy image lacks clarity, and the quality of the copy image during continuous copying tends to fluctuate. There are disadvantages such as inability to apply to polymerized toner. Therefore, a charge control agent that has a high charge imparting effect and can be applied to polymerized toners has been desired.

The present invention has been made in order to solve the above-mentioned problems, and provides a safe negatively chargeable charge control agent that increases the rising speed of charge, has a high charge amount, and has no problem with waste regulations. The purpose is to provide. It is another object of the present invention to provide a negatively chargeable toner for developing an electrostatic charge image, particularly a negatively chargeable polymerized toner, having high charging performance using the charge control agent.

The present invention has been obtained as a result of intensive studies to achieve the above object, and has the following gist.

1. A charge control agent comprising one or more aminopiperidine derivatives represented by the general formula (1) as an active ingredient.

[Wherein, X ₁ and X ₂ may be the same or different and each represents an oxygen atom or a sulfur atom, and R ₁ and R ₂ may be the same or different from each other, and represent a hydrogen atom, a deuterium atom, a substituent, A linear or branched alkyl group having 1 to 20 carbon atoms which may have, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, and a substituent; Represents a linear or branched alkenyl group having 2 to 6 carbon atoms, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and R ₃ and R ₄ may be the same or different from each other; Or a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, and substitution. Optionally substituted carbon atom 2-6 linear or branched alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, R ₅ is a deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group , A trifluoromethyl group, an optionally substituted linear or branched alkyl group having 1 to 8 carbon atoms, and an optionally substituted cycloalkyl having 5 to 10 carbon atoms A linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, or a linear or branched group having 1 to 8 carbon atoms which may have a substituent An alkoxy group, an optionally substituted cycloalkoxy group having 5 to 10 carbon atoms, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted aryloxy group Represents ₆ is a hydrogen atom, a deuterium atom, a linear or branched alkyl group which may having 1 to 20 carbon atoms which may have a substituent group, carbon atoms which may have a substituent 5-10 A cycloalkyl group, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group , N represents an integer of 0 to 9, and when n is 2 or more, a plurality of R ₅ may be the same or different from each other. ]

2. 2. The charge control agent according to 1 above, wherein the aminopiperidine derivative represented by the general formula (1) is represented by the following general formula (1 ′).

[Wherein, X ₁ and X ₂ may be the same or different and each represents an oxygen atom or a sulfur atom, and R ₁ and R ₂ may be the same or different from each other, and represent a hydrogen atom, a deuterium atom, a substituent, A linear or branched alkyl group having 1 to 20 carbon atoms which may have, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, and a substituent; Represents a linear or branched alkenyl group having 2 to 6 carbon atoms, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and R ₃ and R ₄ may be the same or different from each other; Or a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, and substitution. Optionally substituted carbon atom 2-6 linear or branched alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, R ₅ is a deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group , A trifluoromethyl group, an optionally substituted linear or branched alkyl group having 1 to 8 carbon atoms, and an optionally substituted cycloalkyl having 5 to 10 carbon atoms A linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, or a linear or branched group having 1 to 8 carbon atoms which may have a substituent An alkoxy group, an optionally substituted cycloalkoxy group having 5 to 10 carbon atoms, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted aryloxy group Represents ₆ is a hydrogen atom, a deuterium atom, a linear or branched alkyl group which may having 1 to 20 carbon atoms which may have a substituent group, carbon atoms which may have a substituent 5-10 A cycloalkyl group, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group , N represents an integer of 0 to 9, and when n is 2 or more, a plurality of R ₅ may be the same or different from each other. ]

3. 2. The charge control agent according to 1 above, wherein the aminopiperidine derivative represented by the general formula (1) is represented by the following general formula (1 ″).

[Wherein, X ₁ and X ₂ may be the same or different and represent an oxygen atom or a sulfur atom, and R ₁ and R ₂ may be the same or different from each other, and each has a hydrogen atom or a substituent. A linear or branched alkyl group having 1 to 16 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms which may have a substituent, a substituted or unsubstituted aryl group, or a substituted or unsubstituted group. Represents a substituted heterocyclic group, and R ₃ and R ₄ may be the same or different from each other, and may have a linear or branched alkyl group having 1 to 16 carbon atoms, a substituent. A cycloalkyl group having 5 to 7 carbon atoms which may have a substituent, a linear or branched alkenyl group having 2 to 4 carbon atoms which may have a substituent, and a substituted or unsubstituted aryl Group or substitution or A substituted heterocyclic group, R ₅ is a halogen atom, a hydroxyl group, a cyano group, a nitro group, a trifluoromethyl group, good C1-4 be substituted linear or branched An alkyl group, an optionally substituted cycloalkyl group having 5 to 7 carbon atoms, an optionally substituted linear or branched alkoxy group having 1 to 4 carbon atoms, substituted Represents a cycloalkoxy group having 5 to 7 carbon atoms which may have a group, a substituted or unsubstituted aryl group, and R ₆ represents a hydrogen atom and optionally having 1 to 16 carbon atoms. A linear or branched alkyl group, an optionally substituted cycloalkyl group having 5 to 7 carbon atoms, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, n represents an integer of 0 to 4, and n is 2 or more A plurality of R ₅ present in the above case may be the same as or different from each other. ]

4). 4. A toner comprising the charge control agent according to any one of 1 to 3 above, a colorant and a binder resin.

  5. 4. A polymerized toner comprising the charge control agent according to any one of 1 to 3, a colorant, and a binder resin.

In the present invention, a charge control agent containing one or more aminopiperidine derivatives represented by the general formula (1) as an active ingredient has a higher charge rising speed than a conventional charge control agent, and has a high charge amount. And has particularly excellent charging characteristics in terms of stability over time and environmental stability. In addition, it does not contain heavy metals such as chromium, which is a concern for environmental problems, and is excellent in dispersibility and compound stability.

The charge control agent according to the present invention is excellent in charge control characteristics, environmental resistance and durability, and has no fog when used for pulverized toner or polymerized toner, and image density, dot reproducibility, fine line reproducibility. Can obtain a good image. The charge control agent is useful for an electrophotographic charge control agent that expresses sufficient triboelectric chargeability in the toner, particularly for a color toner, and further for a polymerized toner.

Hereinafter, embodiments of the present invention will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

The charge control agent according to the present invention contains one or more aminopiperidine derivatives represented by the general formula (1) as an active ingredient. First, the aminopiperidine derivative represented by the general formula (1) will be described.

In the general formula (1), X ₁ and X ₂ may be the same as or different from each other, and represent an oxygen atom or a sulfur atom. X ₁ and X ₂ are preferably oxygen atoms.

“A linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent” represented by R _{1 to} R ₄ and R ₆ in the general formula (1); “The number of carbon atoms” in the “cycloalkyl group having 5 to 10 carbon atoms” which may have or “the linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent” Specific examples of the “linear or branched alkyl group having 1 to 20”, the “cycloalkyl group having 5 to 10 carbon atoms” or the “linear or branched alkenyl group having 2 to 6 carbon atoms” include Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, Isoheptyl group, n-octyl group, isooctyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-hexadecyl group, n-octadecyl group; cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclodecyl group, 1-adamantyl group , 2-adamantyl group; vinyl group, allyl group, isopropenyl group, 2-butenyl group and the like.

“A linear or branched alkyl group having 1 to 20 carbon atoms having a substituent” represented by R _{1 to} R ₄ and R ₆ in the general formula (1), “5 carbon atoms having a substituent” The “substituent” in “-10 cycloalkyl group” or “straight-chain or branched alkenyl group having 2 to 6 carbon atoms” specifically includes deuterium atom; fluorine atom, chlorine atom , Halogen atoms such as bromine atom and iodine atom; trifluoromethyl group; cyano group; nitro group; hydroxyl group; methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group N-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, isoheptyl group, n-octyl group, isooctyl group, etc. A linear or branched alkyl group; a linear or branched alkoxy group having 1 to 8 carbon atoms such as a methyloxy group, an ethyloxy group or a propyloxy group; an alkenyl group such as a vinyl group or an allyl group; a benzyl group Aralkyl groups such as naphthylmethyl group and phenethyl group; aryloxy groups such as phenyloxy group, p-tolyloxy group and naphthyloxy group; arylalkyloxy groups such as benzyloxy group and phenethyloxy group; phenyl group, biphenylyl group, Aryl group such as terphenylyl group, naphthyl group, anthracenyl group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group; pyridyl group, pyranyl group, thienyl group, furyl group, pyrrolyl group Pyrrolidinyl group, Midazolyl, imidazolidinyl, pyrazolyl, pyrazolidinyl, pyridazinyl, pyrazinyl, piperidinyl, piperazinyl, thiolanyl, thianyl, quinolyl, isoquinolyl, benzofuranyl, benzothienyl, indolyl, carbazolyl, benzo Hexacyclic groups such as oxazolyl group, benzothiazolyl group, quinoxalyl group, benzimidazolyl group, dibenzofuranyl group, dibenzothienyl group and carbolinyl group; aryl vinyl groups such as styryl group and naphthyl vinyl group; acetyl group and benzoyl group Acyl group; Dialkylamino group such as dimethylamino group and diethylamino group; Diarylamino group such as diphenylamino group and dinaphthylamino group; Diarylamino group such as dibenzylamino group and diphenethylamino group Aralkylamino group; disubstituted amino group substituted with a heterocyclic group such as dipyridylamino group, dithienylamino group, dipiperidinylamino group; dialkenylamino group such as diallylamino group; alkyl group, alkenyl group, aryl group And a disubstituted amino group substituted with a substituent selected from an aralkyl group or a heterocyclic group. These “substituents” may be one or more, but are preferably unsubstituted. These “substituents” may further have other substituents, and may be bonded to each other via a single bond, an oxygen atom or a sulfur atom to form a ring.

In the general formula (1), the “optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms” represented by R _{1 to} R ₄ and R ₆ is “substituted. A linear or branched alkyl group having 1 to 16 carbon atoms which may have a group "is preferable, and these are more preferably" unsubstituted ". Moreover, as "the C5-C10 cycloalkyl group which may have a substituent" represented by R < ₁ > -R < ₄ > and R < ₆ > in General formula (1), it has "a substituent. Preferred is an optionally substituted cycloalkyl group having 5 to 7 carbon atoms, more preferably “unsubstituted”. Furthermore, as the “linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent” represented by R _{1 to} R ₄ and R ₆ in the general formula (1), “A linear or branched alkenyl group having 2 to 4 carbon atoms which may have a substituent” is preferable, and these are more preferably “unsubstituted”.

As “aryl group” or “heterocyclic group” in “substituted or unsubstituted aryl group” or “substituted or unsubstituted heterocyclic group” represented by R _{1 to} R ₄ and R ₆ in general formula (1) Specifically, phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthryl group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group; pyridyl group, pyranyl group, thienyl Group, furyl group, pyrrolidinyl group, imidazolyl group, imidazolidinyl group, pyrazolyl group, pyrazolidinyl group, pyridazinyl group, pyrazinyl group, piperidinyl group, piperazinyl group, thiolanyl group, thianyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group , Indolyl group, Examples thereof include aromatic hydrocarbon groups such as rubazolyl group, benzoxazolyl group, benzothiazolyl group, quinoxalyl group, benzimidazolyl group, dibenzofuranyl group, dibenzothienyl group, and carbolinyl group, and condensed polycyclic aromatic groups. In the present invention, the aryl group represents an aromatic hydrocarbon group and a condensed polycyclic aromatic group. Among these, as the “aryl group”, an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 16 carbon atoms is more preferable, and a phenyl group or a naphthyl group is particularly preferable.

As the “substituent” in the “substituted aryl group” or “substituted heterocyclic group” represented by R _{1 to} R ₄ and R ₆ in the general formula (1), R _{1 to} R ₄ in the above general formula (1) And a “linear or branched alkyl group having 1 to 20 carbon atoms having a substituent”, “a cycloalkyl group having 5 to 10 carbon atoms having a substituent” or “substituent” represented by R ₆ Examples thereof are the same as the substituents listed as the “substituents” in the “C2-C6 linear or branched alkenyl group having the above”. Among these “substituents”, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, a linear or branched alkyl group having 1 to 8 carbon atoms, and a linear shape having 1 to 8 carbon atoms Or a branched alkoxy group is preferable, a halogen atom, a trifluoromethyl group, a linear or branched alkyl group having 1 to 4 carbon atoms, or a linear or branched alkoxy group having 1 to 4 carbon atoms. Is more preferable. These “substituents” may be one or more, but the number of “substituents” is preferably 0 to 3, more preferably 0 to 2, and 0 or 1. Is particularly preferred. These “substituents” may further have other substituents, and may be bonded to each other via a single bond, an oxygen atom or a sulfur atom to form a ring.

Specific examples of the “halogen atom” represented by R ₅ in the general formula (1) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

"A linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent" represented by R ₅ in the general formula (1), "may have a substituent "C1-C8 straight chain" in "C5-C10 cycloalkyl group" or "C2-C6 linear or branched alkenyl group optionally having substituents" Specific examples of the “straight or branched alkyl group”, the “cycloalkyl group having 5 to 10 carbon atoms” or the “straight or branched alkenyl group having 2 to 6 carbon atoms” include methyl group, ethyl Group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, n-heptyl group, isoheptyl group, n-octyl group Group, iso Examples include octyl group; cyclopentyl group, cyclohexyl group, 1-adamantyl group, 2-adamantyl group; vinyl group, allyl group, isopropenyl group, and 2-butenyl group.

“A linear or branched alkyl group having 1 to 8 carbon atoms having a substituent” represented by R ₅ in the general formula (1), “a cycloalkyl group having 5 to 10 carbon atoms having a substituent” The “substituent” in the “substituent linear or branched alkenyl group having 2 to 6 carbon atoms” is represented by R _{1 to} R ₄ and R ₆ in the general formula (1). "A linear or branched alkyl group having 1 to 18 carbon atoms having a substituent", "a cycloalkyl group having 5 to 10 carbon atoms having a substituent" or "2 carbon atoms having a substituent" Examples thereof are the same as the substituents exemplified as the “substituent” in the “straight chain or branched alkenyl group of ˜6”. These “substituents” may be one or more, but are preferably unsubstituted. These “substituents” may further have other substituents, and may be bonded to each other via a single bond, an oxygen atom or a sulfur atom to form a ring.

In the general formula (1), represented by R ₅ "optionally substituted linear or branched alkoxy group having 1 to 8 carbon atoms" or "optionally substituted" Specific examples of “a linear or branched alkoxy group having 1 to 8 carbon atoms” or “cycloalkoxy group having 5 to 10 carbon atoms” in “cycloalkoxy group having 5 to 10 carbon atoms” include methyl Oxy group, ethyloxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, tert-butyloxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, isoheptyloxy group, n -Octyloxy group, isooctyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group, Examples thereof include a 1-adamantyloxy group and a 2-adamantyloxy group.

“C1-C8 linear or branched alkoxy group having a substituent” represented by R ₅ in the general formula (1) or “C5-C10 cycloalkoxy group having a substituent” As the “substituent” in the above general formula (1), the “substituent linear or branched alkyl group having 1 to 18 carbon atoms” represented by R _{1 to} R ₄ and R ₆ , "Substituents" mentioned as "Substituents" in "Substituent cycloalkyl groups having 5 to 10 carbon atoms" or "Linear or branched alkenyl groups having 2 to 6 carbon atoms" The same example can be given. These “substituents” may be one or more, but are preferably unsubstituted. These “substituents” may further have other substituents, and may be bonded to each other via a single bond, an oxygen atom or a sulfur atom to form a ring.

In the general formula (1), the “linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent” represented by R ₅ is “having a substituent. Preferred are straight-chain or branched alkyl groups having 1 to 4 carbon atoms, and more preferably “unsubstituted”. Further, in the general formula (1), the “optionally substituted cycloalkyl group having 5 to 10 carbon atoms” represented by R ₅ is “an optionally substituted carbon atom”. A cycloalkyl group having a number of 5 to 7 is preferable, and these are more preferably “unsubstituted”. Furthermore, the “linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent” represented by R ₅ in the general formula (1) includes “having a substituent. Preferred is a linear or branched alkenyl group having 2 to 4 carbon atoms, which is more preferably “unsubstituted”.

In the general formula (1), the “linear or branched alkoxy group having 1 to 8 carbon atoms which may have a substituent” represented by R ₅ is “having a substituent. Further preferred are straight-chain or branched alkoxy groups having 1 to 4 carbon atoms, and these are more preferably “unsubstituted”. Further, in the general formula (1), the “optionally substituted cycloalkoxy group having 5 to 10 carbon atoms” represented by R ₅ is “an optionally substituted carbon atom”. “Cycloalkoxy groups of 5 to 7” are preferable, and these are more preferably “unsubstituted”.

As the “aryl group” or “heterocyclic group” in the “substituted or unsubstituted aryl group” or “substituted or unsubstituted heterocyclic group” represented by R ₅ in the general formula (1), specifically, Phenyl group, biphenylyl group, terphenylyl group, naphthyl group, anthryl group, phenanthryl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group; pyridyl group, pyranyl group, thienyl group, furyl group, Pyrrolidinyl group, imidazolyl group, imidazolidinyl group, pyrazolyl group, pyrazolidinyl group, pyridazinyl group, pyrazinyl group, piperidinyl group, piperazinyl group, thiolanyl group, thianyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, indolyl group, carbazolyl group Group Examples thereof include a benzoxazolyl group, a benzothiazolyl group, a quinoxalyl group, a benzimidazolyl group, a dibenzofuranyl group, a dibenzothienyl group, and a carbolinyl group.

The “substituent” in the “substituted aryl group” or “substituted heterocyclic group” represented by R ₅ in the general formula (1) is represented by R _{1 to} R ₄ and R ₆ in the above general formula (1). "A linear or branched alkyl group having 1 to 18 carbon atoms having a substituent", "a cycloalkyl group having 5 to 10 carbon atoms having a substituent" or "2 carbon atoms having a substituent" Examples thereof are the same as the substituents exemplified as the “substituent” in the “straight chain or branched alkenyl group of ˜6”. These “substituents” may be one or more, but are preferably unsubstituted. These substituents may further have other substituents, and may be bonded to each other via a single bond, an oxygen atom or a sulfur atom to form a ring.

Specific examples of the “aryloxy group” in the “substituted or unsubstituted aryloxy group” represented by R ₅ in the general formula (1) include a phenyloxy group, a tolyloxy group, a biphenylyloxy group, and a terphenylyl group. Examples thereof include an oxy group, a naphthyloxy group, an anthryloxy group, a phenanthryloxy group, a fluorenyloxy group, an indenyloxy group, a pyrenyloxy group, and a perylenyloxy group.

The “substituent” in the “substituted aryloxy group” represented by R ₅ in the general formula (1) is “having a substituent” represented by R _{1 to} R ₄ and R ₆ in the above general formula (1). "C1-C18 linear or branched alkyl group", "Substituent C5-C10 cycloalkyl group" or "Substituent C2-C6 linear Alternatively, the same examples as the substituents listed as the “substituent” in the “branched alkenyl group” can be given. These “substituents” may be one or more, but are preferably unsubstituted. These substituents may further have other substituents, and may be bonded to each other via a single bond, an oxygen atom or a sulfur atom to form a ring.

In General Formula (1), R ₁ and R _{2 each} have a hydrogen atom, a linear or branched alkyl group having 1 to 16 carbon atoms which may have a substituent, or a substituent. An optionally substituted cycloalkyl group having 5 to 7 carbon atoms, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group is preferable, and a hydrogen atom or an optionally substituted carbon atom having 5 carbon atoms. A cycloalkyl group of 7 to 7 and a substituted or unsubstituted aryl group are more preferable, and a hydrogen atom is particularly preferable.

In General Formula (1), R ₃ and R ₄ may have a linear or branched alkyl group having 1 to 16 carbon atoms which may have a substituent, or a substituent. A cycloalkyl group having 5 to 7 carbon atoms, a linear or branched alkenyl group having 2 to 4 carbon atoms which may have a substituent, a substituted or unsubstituted aryl group, or a substituted or unsubstituted group The heterocyclic group is preferably a linear or branched alkyl group having 1 to 16 carbon atoms which may have a substituent, or a cyclo having 5 to 7 carbon atoms which may have a substituent. An alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group is more preferred, and an optionally substituted cycloalkyl group having 5 to 7 carbon atoms, or a substituted or unsubstituted group. Aryl group is particularly preferred Arbitrariness. In view of ease of synthesis, R ₃ and R ₄ are preferably the same group.

In the general formula (1), n represents the number of _{"R 5"} is an integer from 0 to 9. When n is 0, the general formula (1) is a compound represented by the following general formula (2).

In general formula (1), when n is 2 or more, a plurality of R _{5 s} may be the same or different from each other. R ₅ includes a halogen atom, a hydroxyl group, a cyano group, a nitro group, a trifluoromethyl group, a linear or branched alkyl group having 1 to 4 carbon atoms which may have a substituent, and a substituent. An optionally substituted cycloalkyl group having 5 to 7 carbon atoms, an optionally substituted linear or branched alkoxy group having 1 to 4 carbon atoms, and a substituent; A cycloalkoxy group having 5 to 7 carbon atoms or a substituted or unsubstituted aryl group is preferable, and a halogen atom, a trifluoromethyl group, or a linear chain having 1 to 4 carbon atoms which may have a substituent. A linear or branched alkyl group or a substituted or unsubstituted aryl group is more preferable. N is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and particularly preferably 0.

In General Formula (1), R ₆ may have a hydrogen atom, a linear or branched alkyl group having 1 to 16 carbon atoms which may have a substituent, or a substituent. A cycloalkyl group having 5 to 7 carbon atoms, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group is preferable, and a hydrogen atom or an optionally substituted carbon atom having 5 to 7 carbon atoms is preferable. A cycloalkyl group and a substituted or unsubstituted aryl group are more preferable, and a hydrogen atom is particularly preferable.

In the general formula (1), the group containing R ₂ , R ₄ , R ₆ and X ₂ derived from the amino group of aminopiperidine is substituted on any carbon of the piperidine ring. As shown in (1 ′), it is preferably substituted at the 4-position of piperidine.

The aminopiperidine derivative represented by the general formula (1) according to the present invention can be produced by a known method. For example, an aromatic hydrocarbon or alicyclic group having a corresponding aminopiperidine and a corresponding isocyanate group (when X ₁ and X ₂ are oxygen atoms) or isothiocyanate group (when X ₁ and X ₂ are sulfur atoms) By reacting with a hydrocarbon or the like, the aminopiperidine derivative used in the present invention can be synthesized.

Specific examples of preferable compounds among the aminopiperidine derivatives represented by the general formula (1) according to the present invention are shown below, but the present invention is not limited to these compounds. In the following structural formula, some hydrogen atoms are omitted. Further, even when stereoisomers exist, the planar structural formula is described.

  In the present invention, the charge control agent comprising the aminopiperidine derivative represented by the general formula (1) as an active ingredient is preferably prepared by using a volume average particle diameter of 0.1 to 20 μm, preferably 0.1 to 10 μm. It is particularly preferable to prepare and use. If the volume average particle size is smaller than 0.1 μm, the amount of the charge control agent appearing on the toner surface tends to be extremely small, and the desired charge control effect tends to be difficult to be obtained. It is not preferable because the charge control agent to be increased tends to cause adverse effects such as in-machine contamination.

Further, when a charge control agent having an aminopiperidine derivative represented by the general formula (1) as an active ingredient is used for the polymerized toner, it is preferable to adjust the volume average particle size to 1.0 μm or less. It is particularly preferable to use it prepared to 01 to 1.0 μm. When the volume average particle size exceeds 1.0 μm, the particle size distribution of the finally obtained electrophotographic toner is broadened, or free particles are generated, leading to deterioration in performance and reliability. There is. On the other hand, when the volume average particle size is within the above range, there are no disadvantages, and it is advantageous in that uneven distribution among toners is reduced, dispersion in the toner is improved, and variations in performance and reliability are reduced. .

As a method of incorporating the aminopiperidine derivative represented by the general formula (1), which is an active ingredient of the charge control agent used in the present invention, into the toner together with a colorant and the like, kneading and pulverizing. As in the method (pulverized toner) or the method in which the aminopiperidine derivative represented by the general formula (1) is added to the polymerizable monomer monomer and polymerized to obtain the toner (polymerized toner), There are a method of adding to the inside (internal addition) and a method of producing toner particles in advance and adding (external addition) to the surface of the toner particles. The addition amount of the aminopiperidine derivative when internally added to the toner particles is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the binder resin. In addition, when externally added to the toner particles, 0.01 to 5 parts by mass is preferable and 0.01 to 2 parts by mass is more preferable with respect to 100 parts by mass of the binder resin. Further, it is preferable that the toner particles are fixed mechanochemically.

In the present invention, the charge control agent containing the aminopiperidine derivative represented by the general formula (1) as an active ingredient can be used in combination with other known negatively chargeable charge control agents. Other preferred charge control agents used in combination include azo-based iron complexes or complex salts, azo-based chromium complexes or complex salts, azo-based manganese complexes or complex salts, azo-based cobalt complexes or complex salts, azo-based zirconium complexes or complex salts, and carboxylic acid derivatives. Examples include chromium complexes or complex salts, zinc complexes or complex salts of carboxylic acid derivatives, aluminum complexes or complex salts of carboxylic acid derivatives, and zirconium complexes or complex salts of carboxylic acid derivatives. As the carboxylic acid derivative, an aromatic hydroxycarboxylic acid is preferable, and 3,5-di-tert-butylsalicylic acid is more preferable. Further, boron complexes or complex salts, negatively chargeable resin type charge control agents and the like can be mentioned.

In the present invention, when the aminopiperidine derivative represented by the general formula (1) is used in combination with another known charge control agent, the amount of the other charge control agent added is 100 parts by mass of the binder resin. It is preferable that it is 0.1-10 mass parts.

Any binder resin may be used as the binder resin used in the toner of the present invention. Polyester polymers, polyol resins, such as vinyl polymers obtained by polymerizing styrene monomers, acrylate monomers, methacrylate monomers, or copolymers of two or more of these monomers, Examples thereof include phenol resin, silicone resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, terpene resin, coumarone indene resin, polycarbonate resin, and petroleum resin.

Examples of the styrene monomer, acrylate monomer, and methacrylate monomer that form the vinyl polymer or copolymer are illustrated below, but are not limited thereto.

Styrene monomers include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-amylstyrene, p -Tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-chloro Examples thereof include styrene such as styrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, and p-nitrostyrene, or derivatives thereof.

Examples of the acrylate monomer include acrylic acid or methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, n-dodecyl acrylate, 2-acrylic acid 2- Examples thereof include acrylic esters such as ethylhexyl, stearyl acrylate, 2-chloroethyl acrylate, and phenyl acrylate.

Examples of methacrylate monomers include methacrylic acid or methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, n-dodecyl methacrylate, 2-methacrylic acid 2- And methacrylic acid esters such as ethylhexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, and diethylaminoethyl methacrylate.

Examples of other monomers forming the vinyl polymer or copolymer include monoolefins such as ethylene, propylene, butylene and isobutylene; polyenes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, vinyl bromide, Vinyl halides such as vinyl fluoride; 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; vinyl methyl ketone and vinyl Vinyl ketones such as hexyl ketone and methyl isopropenyl ketone; N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; Vinyl naphthalenes; Acrylonitrile, methacrylonitrile, Acrylic acid or methacrylic acid derivatives such as rilamide; unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride , Unsaturated dibasic acid anhydrides such as alkenyl succinic anhydride; maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monobutyl ester, citraconic acid monomethyl ester, citraconic acid monoethyl ester, citraconic acid monobutyl ester Monoesters of unsaturated dibasic acids such as itaconic acid monomethyl ester, alkenyl succinic acid monomethyl ester, fumaric acid monomethyl ester and mesaconic acid monomethyl ester; unsaturated dibasic acid esters such as dimethylmaleic acid and dimethylfumaric acid An α, β-unsaturated acid such as crotonic acid and cinnamic acid; an α, β-unsaturated acid anhydride such as crotonic acid anhydride and cinnamic anhydride; and the α, β-unsaturated acid and a lower fatty acid Monomers having a carboxyl group such as mixed acid anhydrides, alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, these acid anhydrides and monoesters thereof; 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxy Acrylic acid or methacrylic acid hydroxyalkyl esters such as propyl methacrylate; monomers having a hydroxy group such as 4- (1-hydroxy-1-methylbutyl) styrene and 4- (1-hydroxy-1-methylhexyl) styrene; can give.

In the toner of the present invention, the vinyl polymer or copolymer of the binder resin may have a crosslinked structure crosslinked by a crosslinking agent having two or more vinyl groups. Examples of such crosslinking agents include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol di Diacrylate compounds of alkylene diols such as acrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate or the corresponding dimethacrylate compounds; diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, etc. Diacrylate compounds or the corresponding methacrylate compound in Le and the like.

Other examples include diacrylate compounds or dimethacrylate compounds linked by a chain containing an aromatic group and an ether bond. Examples of polyester diacrylates include trade name MANDA (manufactured by Nippon Kayaku Co., Ltd.).

As polyfunctional cross-linking agents, diacrylate compounds of oxyalkylene diols such as pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, or corresponding methacrylate compounds, And those obtained by replacing acrylates of the above compounds with methacrylate, triallyl cyanurate, and triallyl trimellitate.

These crosslinking agents are preferably used in an amount of 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, with respect to 100 parts by mass of other monomer components. Among these cross-linking agents, one that is suitably used for a toner resin from the viewpoint of fixability and offset resistance is one aromatic divinyl compound (especially divinylbenzene is preferable), one aromatic group, and one ether bond. Examples thereof include diacrylate compounds linked by a linking chain. Among these, a combination of monomers that becomes a styrene copolymer or a styrene-acrylate copolymer is preferable.

In the present invention, examples of the polymerization initiator used for producing the vinyl polymer or copolymer include 2,2′-azobisisobutyronitrile and 2,2′-azobis (4-methoxy-2,4). -Dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), dimethyl-2,2'-azobisisobutyrate, 1,1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo-2 ', 4'-dimethyl-4'-methoxyvaleronitrile, 2,2'-azobis (2-methylpropane), methyl ethyl ketone peroxide, acetylacetone peroxide, cyclo Ketone peroxides such as xanone peroxide, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroper Oxide, di-tert-butyl peroxide, tert-butyl cumyl peroxide, dicumyl peroxide, α- (tert-butylperoxy) isopropylbenzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl Peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-tolyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexylperoxydi -Bonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, diethoxyisopropyl peroxydicarbonate, bis (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl Peroxide, tert-butylperoxyacetate, tert-butylperoxyisobutyrate, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxylaurate, tert-butyloxybenzoate, tert- Butyl peroxyisopropyl carbonate, di-tert-butyl peroxyisophthalate, tert-butyl peroxyallyl carbonate, isoamyl peroxy-2-ethylhexanoate, di-t rt- butylperoxy to hexa hydro terephthalate, etc. tert- butylperoxy azelate and the like.

When the binder resin is a styrene-acrylate resin, the molecular weight distribution by gel permeation chromatography (hereinafter abbreviated as GPC) of the soluble component of tetrahydrofuran (hereinafter abbreviated as THF) as the resin component has a molecular weight of 3,000 to A resin having at least one peak in a region of 50,000 (in terms of number average molecular weight) and having at least one peak in a region having a molecular weight of 100,000 or more is preferable in terms of fixing property, offset property, and storage property. The THF-soluble component is preferably a binder resin in which a component having a molecular weight distribution of 100,000 or less is 50 to 90%, more preferably in a region having a molecular weight of 5,000 to 30,000, most preferably 5,000 to 2. It is good to have a main peak in the region of 10,000.

When the binder resin is a vinyl polymer such as a styrene-acrylate resin, the acid value is preferably 0.1 mgKOH / g to 100 mgKOH / g, and preferably 0.1 mgKOH / g to 70 mgKOH / g. More preferably, it is 0.1 mgKOH / g-50 mgKOH / g. In addition, an acid value means the mass of potassium hydroxide required in order to neutralize the free fatty acid in 1 g of binder resin, and is measured based on JIS K-0070.

As a monomer constituting the polyester polymer, the divalent alcohol component includes ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol. , 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, or cyclic ethers such as ethylene oxide and propylene oxide are polymerized on bisphenol A The diol obtained by doing this.

In order to crosslink the polyester resin, it is preferable to use a trivalent or higher alcohol together. Examples of the trihydric or higher polyhydric alcohol 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 It is done.

Examples of the acid component forming the polyester polymer include benzene dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or the like. Anhydrous anhydride; unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid, or anhydrides thereof. Examples of the trivalent or higher polyvalent carboxylic acid component 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, trimer acid ( (Trade name: Empol trimer acid), anhydrides thereof, and partial lower alkyl esters.

In the case where the binder resin is a polyester-based resin, at least one peak is present in the molecular weight region of 3,000 to 50,000 in the molecular weight distribution of the THF soluble component of the resin component, and the toner fixing property and offset resistance property are reduced. The THF-soluble component is preferably a binder resin in which a component having a molecular weight of 100,000 or less is 60 to 100%, and at least one peak exists in a region having a molecular weight of 5,000 to 20,000. Is more preferable.
In the present invention, the molecular weight distribution of the binder resin is measured by GPC using THF as a solvent.

When the binder resin is a polyester resin, the acid value 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. ~ 50 mg KOH / g is good. Moreover, it is preferable that a hydroxyl value is 30 mgKOH / g or less, and 10 mgKOH / g-25 mgKOH / g are still more preferable. The hydroxyl value means the mass of potassium hydroxide required to neutralize acetic acid produced when acetylating the hydroxyl group in 1 g of the binder resin with acetic anhydride, and conforms to JIS K-0070. Measured.

In the present invention, a mixture of two or more of an amorphous polyester resin and a crystalline polyester resin may be used. In this case, it is preferable to select a material in consideration of the compatibility of each, and the amorphous polyester resin includes a polyvalent carboxylic acid component, preferably an aromatic polyvalent carboxylic acid and a polyhydric alcohol component. Those synthesized are preferably used, and as the crystalline polyester resin, those synthesized from a divalent carboxylic acid component, preferably an aliphatic dicarboxylic acid and a dihydric alcohol component, are suitably used.

As the binder resin that can be used in the toner of the present invention, a resin containing a monomer component capable of reacting with both of these resin components in the vinyl polymer component and / or polyester resin can also be used. Examples of monomers that can react with the vinyl polymer among the monomers constituting the polyester resin component include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. Examples of the monomer constituting the vinyl polymer component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

When the polyester polymer, vinyl polymer and other binder resin are used in combination, it is preferable that the total binder resin has a resin having an acid value of 0.1 to 50 mgKOH / g in an amount of 60% by mass or more.

In the present invention, the acid value of the binder resin component of the toner composition is determined 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 components other than the binder resin and the crosslinked binder resin are calculated in advance. Keep it. The sample pulverized product 0.5 to 2.0 g is precisely weighed, and the weight of the polymer component is defined as W (g). For example, when the acid value of the binder resin is measured from the toner, the acid value and content of the colorant or magnetic material are separately measured, and the acid value of the binder resin is obtained by calculation.
(2) A sample is put into a 300 (mL) beaker, and a mixed solution 150 (mL) of toluene / ethanol (volume ratio 4/1) is added and dissolved.
(3) Titrate with a potentiometric titrator using an ethanol solution of 0.1 mol / L potassium hydroxide (KOH).
(4) The amount of potassium hydroxide solution used at this time is set to S (mL), a blank is measured at the same time, and the amount of potassium hydroxide solution used at this time is set to B (mL). Here, f is a factor of potassium hydroxide concentration.
Acid value (mgKOH / g) = [(SB) × f × 5.61] / W

The toner binder resin and the composition containing the binder resin preferably have a glass transition temperature (Tg) of 35 to 80 ° C., particularly preferably 40 to 75 ° C., from the viewpoint of toner storage stability. When Tg is lower than 35 ° C., the toner is likely to deteriorate in a high temperature atmosphere, and offset is likely to occur during fixing. On the other hand, when Tg is higher than 80 ° C., the toner fixing property tends to be lowered.

In the polymerized toner of the present invention, a binder resin having a softening point in the range of 80 to 140 ° C. is preferably used. When the softening point of the binder resin is less than 80 ° C., the toner and the image stability of the toner may be deteriorated after fixing and during storage. On the other hand, when the softening point exceeds 140 ° C., the low-temperature fixability may deteriorate.

Magnetic materials that can be used in the present invention include magnetic iron oxides such as magnetite, maghemite, and ferrite, and iron oxides containing other metal oxides; metals such as iron, cobalt, and nickel, or these metals and aluminum, cobalt And alloys with metals such as copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, and vanadium. These can be used alone or in combination of two or more.

Specific examples of the magnetic material include Fe ₃ O ₄ , γ-Fe ₂ O ₃ , ZnFe ₂ O ₄ , Y ₃ Fe ₅ O ₁₂ , CdFe ₂ O ₄ , Gd ₃ Fe ₅ O ₁₂ , CuFe ₂ O ₄ , and PbFe. Examples thereof include ₁₂ O, NiFe ₂ O ₄ , NdFe ₂ O, BaFe ₁₂ O ₁₉ , MgFe ₂ O ₄ , MnFe ₂ O ₄ , LaFeO ₃ , iron powder, cobalt powder, and nickel powder. A particularly suitable magnetic material is a fine powder of Fe ₃ O ₄ or γ-Fe ₂ O ₃ .

In addition, magnetic iron oxides such as magnetite, maghemite, and ferrite containing different elements as a magnetic material, or a mixture thereof can be used. Specific examples of the different elements include lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, germanium, zirconium, tin, sulfur, calcium, scandium, titanium, vanadium, chromium, manganese, cobalt, nickel, copper, zinc, Examples include gallium. Preferred heterogeneous elements are selected from magnesium, aluminum, silicon, phosphorus, or zirconium. The foreign element may be incorporated into the iron oxide crystal lattice, may be incorporated into the iron oxide as an oxide, or may exist as an oxide or hydroxide on the surface of the iron oxide. However, it is preferably incorporated in iron oxide as an oxide.

The different elements can be incorporated into the particles by adjusting the pH by mixing salts of the different elements at the time of producing the magnetic substance. Moreover, it can be made to deposit on the particle | grain surface by adjusting pH after magnetic body particle | grain production | generation, or adding salt of each element and adjusting pH.

The usage-amount of the said magnetic body is 10-200 mass parts of magnetic bodies with respect to 100 mass parts of binder resin, and it is preferable that it is 20-150 mass parts. The number average particle diameter of these magnetic materials is preferably 0.1 to 2 μm, and more preferably 0.1 to 0.5 μm. The number average particle diameter can be determined by measuring a photograph taken with a transmission electron microscope with a digitizer or the like.

Further, it is preferable that the magnetic material has a magnetic property at a coercive force of 20 to 150 oersted, a saturation magnetization of 50 to 200 emu / g, and a residual magnetization of 2 to 20 emu / g when applied with 10K oersted.

The magnetic material can also be used as a colorant. As the colorant that can be used in the present invention, in the case of a black toner, a black or blue dye such as an azo dye, an anthraquinone dye, a xanthene dye, or a methine dye, or carbon black, aniline black, acetylene black, phthalocyanine Examples include black or blue pigments such as blue and indanthrene blue.

In the case of a color toner, the following can be used as a colorant. As the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dyes, lake dyes, naphthol dyes, benzimidazolone compounds, thioindigo compounds, and perylene compounds can be used. Specifically, examples of pigment-based magenta colorants include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 202, 206, 207, 209, C.I. I. Pigment violet 19, C.I. I. Vat red 1, 2, 10, 13, 15, 23, 29, 35 and the like. These pigments may be used alone, but it is more preferable from the viewpoint of the image quality of a full-color image to improve the sharpness by using a dye and a pigment together.

Examples of the dye-based magenta colorant include C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121, C.I. I, disperse thread 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I. I. Oil-soluble dyes such as Desperperiolet 1, C.I. I. Basic red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40, C.I. I. Examples include basic dyes such as basic violet 1,3,7,10,14,15,21,25,26,27,28.

As the cyan colorant, copper phthalocyanine compounds and derivatives thereof, anthraquinones, basic dye lake compounds can be used. Specific examples of the pigment-based cyan colorant include C.I. I. Pigment blue 2, 3, 15, 16, 17, C.I. I. Bat Blue 6, C.I. I. Acid Blue 45 or a copper phthalocyanine pigment having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton.

As the yellow colorant, condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds can be used. Specifically, examples of pigment-based yellow colorants include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 65, 73, 83, C.I. I. Bat yellow 1, 3, 20 and the like.

Examples of the orange pigment include red chrome yellow, molybdenum orange, permanent orange GTR, pyrazolone orange, Vulcan orange, benzidine orange G, indanthrene brilliant orange RK, and indanthrene brilliant orange GK. Examples of purple pigments include manganese purple, fast violet B, and methyl violet lake. Examples of the green pigment include chromium oxide, chrome green, pigment green, malachite green lake, final yellow green G, and the like. Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide. As for the usage-amount of the said coloring agent, 0.1-20 mass parts is preferable with respect to 100 mass parts of binder resin.

The toner of the present invention may be mixed with a carrier and used as a two-component developer. As the carrier, ordinary carriers such as ferrite and magnetite, and resin-coated carriers can also be used.

The resin-coated carrier comprises carrier core particles and a coating material that is a resin that coats (coats) the surface of the carrier core particles. Examples of the resin used for the coating material include styrene-acrylate copolymer, styrene-methacrylic resin. Styrene-acrylate resins such as acid ester copolymers; acrylate resins such as acrylic ester copolymers and methacrylic acid ester copolymers; polytetrafluoroethylene, monochlorotrifluoroethylene polymers, polyvinylidene fluoride, etc. Fluorine resin; silicone resin; polyester resin; polyamide resin; polyvinyl butyral; In addition, resins that can be used as carrier coating materials such as ionomer resins and polyphenylene sulfide resins can be used. In these resins alone or may be used in combination.

Also, a binder type carrier core in which magnetic powder is dispersed in a resin can be used. In the resin-coated carrier, as a method for coating the surface of the carrier core with at least a resin coating material, a method in which the resin is dissolved or suspended in a solvent and attached to the applied carrier core, or a method in which the resin core is simply mixed in a powder state Is applicable. The ratio of the resin coating material to the resin-coated carrier may be appropriately determined, but is preferably 0.01 to 5% by mass and more preferably 0.1 to 1% by mass with respect to the resin-coated carrier.

Examples of use in which a magnetic material is coated with a coating agent comprising two or more mixtures are as follows: (1) Dimethyldichlorosilane and dimethylsilicone oil (mass ratio 1: 5) with respect to 100 parts by mass of fine titanium oxide powder And (2) those treated with 20 parts by mass of a mixture of dimethyldichlorosilane and dimethylsilicone oil (mass ratio 1: 5) with respect to 100 parts by mass of silica fine powder.

Among the above resins, a styrene-methyl methacrylate copolymer, a mixture of a fluorine-containing resin and a styrene copolymer, or a silicone resin is preferably used, and a silicone resin is particularly preferable.

Examples of the mixture of the fluorine-containing resin and the styrene copolymer include, for example, a mixture of polyvinylidene fluoride and a styrene-methyl methacrylate copolymer, a mixture of polytetrafluoroethylene and a styrene-methyl methacrylate copolymer, Vinylidene fluoride-tetrafluoroethylene copolymer (copolymer mass ratio 10:90 to 90:10) and styrene-acrylic acid 2-ethylhexyl copolymer (copolymer mass ratio 10:90 to 90:10) And a mixture with a styrene-acrylic acid-2-ethylhexyl-methyl methacrylate copolymer (copolymer mass ratio 20: 60: 5 to 30:10:50).

Examples of the silicone resin include a nitrogen-containing silicone resin and a modified silicone resin produced by a reaction between a nitrogen-containing silane coupling agent and a silicone resin.

As the magnetic material for the carrier core, oxides such as ferrite, iron-rich ferrite, magnetite, and γ-iron oxide, metals such as iron, cobalt, and nickel, or alloys thereof can be used. Examples of elements contained in these magnetic materials include iron, cobalt, nickel, aluminum, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, calcium, manganese, selenium, titanium, tungsten, and vanadium. . Among these, copper-zinc-iron-based ferrites mainly composed of copper, zinc and iron components, and manganese-magnesium-iron-based ferrites mainly composed of manganese, magnesium and iron components are preferable.

The resistance value of the carrier is preferably 10 ⁶ to 10 ¹⁰ Ω · cm by adjusting the degree of unevenness on the surface of the carrier and the amount of resin to be coated. The particle size of the carrier is preferably 4 to 200 μm, preferably 10 to 150 μm, more preferably 20 to 100 μm. In particular, the resin-coated carrier preferably has a 50% particle size of 20 to 70 μm.

In the two-component developer, it is preferable to use 1 to 200 parts by weight, more preferably 2 to 50 parts by weight of the toner of the present invention with respect to 100 parts by weight of the carrier.

The toner of the present invention may further contain a wax. Specific examples of the wax used in the present invention include aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax, paraffin wax and sazol wax; aliphatic carbonization such as oxidized polyethylene wax. Oxide of hydrogen wax, or block copolymer thereof; plant wax such as candelilla wax, carnauba wax, wood wax, jojoba wax; animal wax such as beeswax, lanolin, whale wax; ozokerite, ceresin, petrolatum Mineral waxes such as; waxes mainly composed of fatty acid esters such as montanic acid ester wax and castor wax; and fatty acid esters such as deoxidized carnauba wax that have been partially or fully deoxidized .

Examples of waxes further include saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, or linear alkyl carboxylic acids having a linear alkyl group; brassic acid, eleostearic acid, parinaric acid, etc. Unsaturated fatty acids; Stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnauvir alcohol, seryl alcohol, melyl alcohol, or saturated alcohol such as long chain alkyl alcohol; polyhydric alcohols such as sorbitol; linoleic acid amide, oleic acid amide, Fatty acid amides such as lauric acid amide; saturated fatty acid bisamides such as methylene biscapric acid amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide; ethylene bis oleic acid amide, hexame Unsaturated fatty acid amides such as lenbisoleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sebacic acid amide; m-xylene bisstearic acid amide, N, N′-distearyl Aromatic bisamides such as isophthalamide; fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate; grafted onto aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylate Waxes; partial ester compounds of fatty acids such as behenic acid monoglyceride and polyhydric alcohols; and methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and fats.

Preferred waxes include polyolefins obtained by radical polymerization of olefins under high pressure; polyolefins obtained by purifying low molecular weight by-products obtained during polymerization of high molecular weight polyolefins; polymerized using catalysts such as Ziegler catalysts and metallocene catalysts under low pressures Polyolefins; polyolefins polymerized using radiation, electromagnetic waves or light; low molecular weight polyolefins obtained by thermal decomposition of high molecular weight polyolefins; paraffin wax, microcrystalline wax, Fischer-Tropsch wax; Jintole method, hydrocol method, age method, etc. Synthetic hydrocarbon wax synthesized by: synthetic wax using a compound having 1 carbon atom as a monomer, hydrocarbon wax having a functional group such as a hydroxyl group or a carboxyl group; hydrocarbon wax Mixture of hydrocarbon wax having a functional group and; styrene these waxes as a matrix, maleic acid esters, acrylates, methacrylates, graft modified wax with vinyl monomers such as maleic anhydride.

In addition, these waxes have a sharp molecular weight distribution using a press sweating method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method or a liquid crystal deposition method, and low molecular weight solid fatty acids, low A molecular weight solid alcohol, a low molecular weight solid compound, and other impurities are also preferable.

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 the fixability and offset resistance. If it is less than 50 degreeC, there exists a tendency for blocking resistance to fall, and if it exceeds 140 degreeC, it will become difficult to express an offset-proof effect. In the present invention, the melting point of the wax is the temperature at the peak top of the maximum endothermic peak of the wax measured by differential thermal analysis (hereinafter abbreviated as DSC).

Further, by using two or more kinds of waxes in combination, the plasticizing action and the releasing action which are the actions of the wax can be expressed at the same time. Examples of the wax having a plasticizing action include a wax having a low melting point, a wax having a branched structure or a wax having a polar group in the molecular structure, and a wax having a releasing action includes a wax having a high melting point, or Examples of the molecular structure include linear wax and nonpolar wax having no functional group. Examples of use include a combination of two or more different waxes having a difference in melting point of 10 ° C. to 100 ° C., a combination of polyolefin and graft-modified polyolefin, and the like.

In the case of selecting two types of waxes and having a similar structure, a wax having a relatively low melting point exhibits a plasticizing action, and a wax having a high melting point exhibits a releasing action. At this time, when the difference in melting point is 10 to 100 ° C., functional separation is effectively expressed. If it is less than 10 ° C., the function separation effect is difficult to appear, and if it exceeds 100 ° C., the function is not easily emphasized by interaction. In this case, the melting point of at least one of the waxes is preferably 70 to 120 ° C, and more preferably 70 to 100 ° C. When the melting point is in this range, the function separation effect tends to be easily exhibited.

In addition, relatively waxes having a branched structure, those having a polar group, or those modified with a component different from the main component exhibit a plastic action, and have a more linear structure and a functional group. Nonpolar or non-denatured straight ones exhibit mold release action. Preferred combinations of waxes include polyethylene homopolymers or copolymers based on ethylene and polyolefin homopolymers or copolymers based on olefins other than ethylene; polyolefins and graft modified polyolefins; alcohol waxes, fatty acid waxes or Combination of ester wax and hydrocarbon wax; combination of Fischer-Tropsch wax or polyolefin wax and paraffin wax or microcrystal wax; combination of Fischer-Tropsch wax and polyolefin wax; combination of paraffin wax and microcrystal wax; carnauba wax, candelilla Wax, rice wax or montan wax The combination of hydrocarbon waxes with.

In any case, the peak top temperature of the maximum peak is in the region of 70 to 120 ° C. in the endothermic peak observed by DSC measurement of the toner from the viewpoint of easy balance between toner storage stability and fixing property. Is preferable, and it is more preferable that it exists in the range of 70-110 degreeC.

In the toner of the present invention, the total content of these waxes is preferably 0.2 to 20 parts by mass, and 0.5 to 10 parts by mass with respect to 100 parts by mass of the binder resin. More preferred.

In the present invention, the DSC measurement of the wax or toner is preferably performed using a highly accurate internal heating type input compensation type differential scanning calorimeter. The measurement method is performed according to ASTM D3418-82. In the present invention, a DSC curve measured when the temperature is raised at a temperature rate of 10 ° C./min after the previous history is obtained by raising and lowering the temperature once is used.

A fluidity improver may be added to the toner of the present invention. The fluidity improver improves the fluidity of the toner by adding it to the toner surface (the toner becomes easier to flow). Specifically, carbon black, vinylidene fluoride fine powder, fluorine-based resin powder such as polytetrafluoroethylene fine powder, wet process silica, fine powder silica such as dry process silica, fine powder titanium oxide, fine powder alumina, and Examples thereof include treated silica, treated titanium oxide, and treated alumina obtained by surface treatment with a silane coupling agent, a titanium coupling agent, or silicone oil. Among these, fine powder silica, fine powder titanium oxide, and fine powder alumina are preferable, and treated silica obtained by performing surface treatment with a silane coupling agent or silicone oil is more preferable.

A preferable fine powder silica is a fine powder produced by vapor phase oxidation of a silicon halogen compound, which is called so-called dry silica or fumed silica. Examples of commercially available silica fine powders produced by vapor phase oxidation of silicon halogen compounds include those having the following trade names. AEROSIL (manufactured by Nippon Aerosil Co., Ltd., hereinafter the same) -130, -300, -380, -TT600, -MOX170, -MOX80, -COK84; Ca-O-SiL (manufactured by CABOT Corp., hereinafter the same) -M-5 , -MS-7, -MS-75, -HS-5, -EH-5, Wacker HDK (manufactured by WACKER-CHEMIEGMBH Co., Ltd., the same shall apply hereinafter) -N20 V15, -N20E, -T30, -T40; D-CFineSi1ica (Manufactured by Dow Corning): Francol (manufactured by Francil).

Furthermore, a treated silica fine powder obtained by hydrophobizing a silica fine powder produced by vapor phase oxidation of a silicon halogen compound is more preferable, and the hydrophobized degree measured by a methanol titration test is 30 to 80% in the treated silica fine powder. What processed the silica fine powder so that this value may be shown is especially preferable. Hydrophobization can be performed by a chemical or physical treatment with an organosilicon compound that reacts or physically adsorbs with silica fine powder. Among these, a method of treating silica fine powder obtained by vapor phase oxidation of a silicon halogen compound with an organosilicon compound is preferable.

Examples of the organosilicon compound include hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane, vinylmethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, dimethylvinylchlorosilane, Divinylchlorosilane, γ-methacryloxypropyltrimethoxysilane, hexamethyldisilane, trimethylsilane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α -Chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane , Triorganosilyl mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane , Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane and 2-12 siloxane units per molecule, each of which is located at the end Examples thereof include silicone oils such as dimethylpolysiloxane and dimethylsilicone oil containing 0 to 1 hydroxyl groups bonded to. These may be used alone or in admixture of two or more.

The particle size of the fluidity improver is preferably 0.001 to 2 [mu] m, more preferably 0.002 to 0.2 [mu] m, as an average primary particle size. The number average particle size of the fluidity improver is preferably 5 to 100 nm, and more preferably 5 to 50 nm. In addition, the specific surface area by nitrogen adsorption of preferably not less than 30 m ² / g as measured by BET method, is more preferable in 60~400m ² / g. The surface-treated fine powder, preferably at least ^{20m 2 / g, 40~300m 2 /} g is more preferable. These fine powders are preferably used in an amount of 0.03 to 8 parts by mass with respect to 100 parts by mass of toner particles.

The toner of the present invention can be used for the purpose of protecting the photoreceptor / carrier, improving the cleaning property, adjusting the thermal characteristics / electrical characteristics / physical characteristics, adjusting the resistance, adjusting the softening point, improving the fixing rate, etc. These additives may be added. Other additives include various metal soaps; fluorinated surfactants; dioctyl phthalate; conductivity imparting agents such as tin oxide and zinc oxide; inorganic fine powders such as carbon black, antimony oxide, titanium oxide, aluminum oxide, and alumina The body is raised. These inorganic fine powders may be hydrophobized as necessary. Also develops lubricants such as polytetrafluoroethylene, zinc stearate, polyvinylidene fluoride, abrasives such as cesium oxide, silicon carbide, strontium titanate, anti-caking agent, white particles and black particles with polarity opposite to toner particles Can be used in small quantities as an improver

These additives include silicone varnishes, various modified silicone varnishes, silicone oils, various modified silicone oils, silane coupling agents, silane coupling agents having functional groups, and other organosilicon compounds for the purpose of charge control. It is also preferable to treat with a treating agent or various treating agents.

In the present invention, the charge control agent is sufficiently mixed and stirred together with the additive and the toner by a mixer such as a Henschel mixer, a ball mill, a nauter mixer, a V-type mixer, a W-type mixer, and a super mixer. The desired electrostatic charge developing toner can also be obtained by performing an external addition process uniformly.

The toner of the present invention is thermally stable, is not subjected to thermal changes during the electrophotographic process, and can maintain stable charging characteristics. Further, since it is uniformly dispersed in any binder resin, the charge distribution of the fresh toner is very uniform. Therefore, even if the toner is untransferred and collected (waste toner), the saturated triboelectric charge amount and the charge distribution are hardly changed compared to the fresh toner, but the waste toner from the toner of the present invention is reused. By selecting a polyester resin containing an aliphatic diol as a binder resin, or using a metal-crosslinked styrene-acrylate copolymer as a binder resin, and adding a large amount of polyolefin to the toner to produce a toner. Further, the difference between the fresh toner and the waste toner can be further reduced.

The toner of the present invention can be produced by a known method. For example, the above-described toner constituent materials such as a binder resin, a charge control agent, and a colorant are sufficiently mixed by a mixer such as a ball mill, and the resulting mixture is kneaded by a heating and kneading apparatus such as a hot roll kneader and cooled and solidified. A method obtained by classification after pulverization (pulverization method) is preferred.

It can also be produced by a method in which the mixture is dissolved in a solvent and atomized, dried and classified by spraying. Furthermore, a so-called toner production method comprising a core material and a shell material, a core material and a shell material, which are obtained by mixing a predetermined material with a monomer that constitutes the binder resin to form an emulsified or suspended emulsion, and then polymerizing the binder. The microcapsule toner can also be manufactured by a method in which a predetermined material is contained in the core material, the shell material, or both. Furthermore, if necessary, the toner of the present invention can be produced by sufficiently mixing the desired additive and toner particles with a mixer such as a Henschel mixer.

The method for producing the toner of the present invention by the pulverization method will be described in more detail. First, a binder resin, a colorant, a charge control agent, and other necessary additives are mixed uniformly. For mixing, a known stirrer such as a Henschel mixer, a super mixer, or a ball mill can be used. The obtained mixture is hot-melt kneaded using a closed kneader or a single-screw or twin-screw extruder. After cooling, the kneaded product is coarsely pulverized by a crusher or a hammer mill, and finely pulverized by a pulverizer such as a jet mill or a high-speed rotor rotary mill. Subsequently, using an air classifier, for example, an inertia class elbow jet utilizing the Coanda effect, a cyclone (centrifugal) classification microplex, a DS separator, and the like, classification is performed to a predetermined particle size. Further, when the external additive is treated on the toner surface, the toner and the external additive are agitated and mixed by a high-speed agitator such as a Henschel mixer or a super mixer.

The toner of the present invention can also be produced by suspension polymerization or emulsion polymerization. In the suspension polymerization method, a polymerizable monomer, a colorant, a polymerization initiator, a charge control agent, and if necessary, a crosslinking agent, a dispersion stabilizer and other additives are uniformly dissolved or dispersed, After preparing the body composition, a suitable stirrer or disperser such as a homomixer, homogenizer, atomizer, microfluidizer, one liquid in a continuous phase containing the monomer composition and the dispersion stabilizer, such as an aqueous phase. Disperse using a fluid nozzle, gas-liquid fluid nozzle, electric emulsifier and the like. Preferably, granulation is performed by adjusting the stirring speed, temperature, and time so that the droplets of the polymerizable monomer composition have a desired toner particle size. At the same time, the polymerization reaction is carried out at 40 to 90 ° C. to obtain toner particles having a desired particle size. The obtained toner particles are washed, filtered, and dried. For the external addition treatment after the production of the toner particles, the method described above can be used.

When produced by the emulsion polymerization method, the average particle diameter is 0.1 to 1.0 μm, which is excellent in uniformity compared with the particles obtained by the above suspension polymerization method. As described above, it can be produced by a method of so-called seed polymerization in which a polymerizable monomer is added after the growth to grow particles, or a method in which emulsified particles are united and fused to an appropriate average particle size.

Since the production by these polymerization methods does not go through the pulverization step, it is not necessary to impart brittleness to the toner particles, and it is possible to use a large amount of low softening point materials that were difficult to use by conventional pulverization methods. The selection range of can be expanded. Further, the release agent and the colorant, which are hydrophobic materials, are hardly exposed on the surface of the toner particles, and contamination of the toner carrying member, the photoconductor, the transfer roller, and the fixing device can be reduced.

By producing the toner of the present invention by a polymerization method, it is possible to further improve characteristics such as image reproducibility, transferability, and color reproducibility. A toner having a sharp particle size distribution can be easily obtained.

As the polymerizable monomer used when the toner of the present invention is produced by the polymerization method, a vinyl polymerizable monomer capable of radical polymerization is used. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used.

Monofunctional polymerizable monomers include styrene, α-methyl styrene, β-methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, 2,4-dimethyl styrene, pn-butyl. Styrenic polymerizable monomers such as styrene, p-tert-butylstyrene, pn-hexylstyrene, p-phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl Acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, benzyl acrylate, dimethyl phosphate methyl acrylate, dibutyl phosphate ethyl acetate Acrylate polymerizable monomers such as acrylate and 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, Methacrylate-based polymerizable monomers such as n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, diethyl phosphate methacrylate, dibutyl phosphate ethyl methacrylate; unsaturated aliphatic monocarboxylic acid esters; vinyl acetate, propionic acid Vinyl esters such as vinyl and vinyl benzoate; vinyl such as vinyl methyl ether and vinyl isobutyl ether Ether like; vinyl methyl ketone, vinyl hexyl ketone, vinyl ketones such as vinyl isopropyl ketone.

As the polymerization initiator used when the toner of the present invention is produced by the polymerization method, known ones such as organic peroxides can be used. Water-soluble initiators include ammonium persulfate, potassium persulfate, 2,2′-azobis (N, N′-dimethyleneisobutyroamidine) hydrochloride, 2,2′-azobis (2-aminodipropane) hydrochloric acid Salts, sodium azobis (isobutylamidine) hydrochloride, sodium 2,2′-azobisisobutyronitrile sulfonate, ferrous sulfate or hydrogen peroxide. These may be used alone or in combination of two or more. be able to. As for the addition amount of a polymerization initiator, 0.5-20 mass parts is preferable with respect to 100 mass parts of polymerizable monomers.

Examples of the dispersant used when producing the polymerized toner include tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, aluminum hydroxide, calcium metasilicate, calcium sulfate, and sulfuric acid. Inorganic oxides such as barium, bentonite, silica, and alumina; organic compounds such as polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, and starch. Commercially available dispersants may be used as they are, but in order to obtain dispersed particles having a fine uniform particle size, the inorganic compound can be produced in a dispersion medium under high-speed stirring. Moreover, it is preferable that these dispersing agents use 0.2-2.0 mass parts with respect to 100 mass parts of polymerizable monomers.

The toner obtained by the polymerization method has a tendency that the degree of unevenness of the toner particles is smaller than that of the toner by the pulverization method without any special treatment, and is indefinite, so that the contact between the electrostatic latent image carrier and the toner Since the area increases, the toner adhesion becomes high, and as a result, there is less in-machine contamination, and it is easy to obtain a higher image density and higher quality image.

In addition, in the toner by the pulverization method, the toner particles are dispersed in water and heated by a hot water bath method, a heat treatment method in which the toner particles pass through a hot air current, or a mechanical impact method in which mechanical energy is applied and processed. A method for reducing the degree of unevenness on the toner surface is mentioned. Effective devices for reducing the degree of unevenness include a mechano-fusion system (manufactured by Hosokawa Micron Co., Ltd.) applying dry mechanochemical method, an I-type jet mill, and a hybridizer that is a mixing device having a rotor and a liner (Nara Machinery) Manufactured by Seisakusho Co., Ltd.) and a Henschel mixer which is a mixer having high-speed stirring blades.

One of the values indicating the degree of unevenness of the toner particles is an average circularity. The average circularity (C) is a value obtained by dividing the total circularity of all measured particles by the total number of measured particles (m), and the circularity (Ci) obtained by the following formula (3). From this, it can be calculated using the following formula (4).

The circularity (Ci) is measured using a flow type particle image analyzer (for example, FPIA-1000 manufactured by Toa Medical Electronics Co., Ltd.). As a measuring method, a dispersion liquid in which about 5 mg of toner is dispersed in 10 ml of water in which about 0.1 mg of nonionic surfactant is dissolved is prepared, and ultrasonic waves (20 kHz, 50 W) are irradiated to the dispersion liquid for 5 minutes. The concentration of the dispersion is set to 5000 to 20000 particles / μL, and the circularity distribution of particles having a circle-equivalent diameter of 0.60 μm or more and less than 159.21 μm is measured using the flow particle image analyzer.

The average circularity value is preferably 0.955 to 0.995, more preferably 0.960 to 0.985. When the toner particles are prepared so that the average circularity falls within this range, it is difficult to increase the amount of residual toner, and retransfer tends not to occur.

In the case of the toner of the present invention, in the case of measurement using a laser type particle size distribution measuring device such as a micron sizer (for example, manufactured by Seishin Enterprise Co., Ltd.) Is preferably 2 to 15 μm, and more preferably 3 to 12 μm in terms of volume average particle size. If the volume average particle size is larger than 15 μm, the resolution and sharpness tend to be dull. If the volume average particle size is smaller than 2 μm, the resolution is improved, but the problem of high cost due to the deterioration of the yield during toner production There is a tendency for health problems such as toner scattering and skin penetration in the machine to easily occur.

On the other hand, in the case of a polymerized toner, the volume average particle size is preferably 3 to 9 μm, more preferably 4 to 8.5 μm, and particularly preferably 5 to 8 μm. When the volume average particle size is smaller than 4 μm, the toner fluidity is lowered, the chargeability of each particle is likely to be lowered, and the charge distribution is widened, so that fogging to the background and toner spilling from the developing device are likely to occur. Become. On the other hand, if it is smaller than 4 μm, the cleaning property may be extremely difficult. When the volume average particle size is larger than 9 μm, the resolution is lowered, and sufficient image quality cannot be obtained, and it may be difficult to satisfy recent high image quality requirements.

In addition, the polymerized toner of the present invention draws a cumulative distribution from the smaller diameter side to the particle size range (channel) obtained by dividing the particle size distribution measured by the following method from the smaller diameter side, and the cumulative particle size is 16%. The volume calculated from (D84% / D16%) 1/2 when the diameter is defined as volume D16%, the particle size at 50% cumulative is defined as volume D50%, and the particle size at 84% cumulative is defined as volume D84%. The average particle size distribution index (GSDv) is preferably 1.15 to 1.30, and more preferably 1.15 to 1.25.

Regarding the particle size distribution of the toner, for example, the particle content of 2 μm or less is preferably 10 to 90% based on the number of particles by particle size measurement using a Coulter counter (TA-II manufactured by Coulter Co., Ltd.). The content of is preferably 0 to 30% by volume. Further, those having high particle size uniformity (volume average particle size / number average particle size of 1.00 to 1.30) are preferred.

In the present invention, the specific surface area of the toner is preferably 1.2 to 5.0 m ² / g, more preferably 1.5 to 3.0 m ² / g, in the BET specific surface area measurement using nitrogen as the desorption gas. The specific surface area is measured using, for example, a BET specific surface area measuring apparatus (for example, FlowSorb II2300, manufactured by Shimadzu Corporation), desorbing the adsorbed gas on the toner surface at 50 ° C. for 30 minutes, and then rapidly cooling with liquid nitrogen. It is defined as a value obtained by re-adsorbing the gas, raising the temperature again to 50 ° C., and degassing at this time.

In the case of the toner of the present invention, the apparent specific gravity (bulk density) was measured using, for example, a powder tester (for example, manufactured by Hosokawa Micron Corporation). The apparent specific gravity is preferably from 0.2 to 0.6 g / cm ³ in the case of non-magnetic toner, although the case of the magnetic toner depends on the type and content of magnetic powder is 0.2 to 2.0 g / cm ³ preferable.

In the present invention, the true specific gravity in the case of a non-magnetic toner is preferably 0.9 to 1.2 g / cm ³ , and in the case of a magnetic toner, it depends on the kind and content of the magnetic powder, but 0.9 to 4.0 g / cm cm ³ is preferred. The true specific gravity of the toner is calculated as follows. 1.000 g of toner is precisely weighed, put into a 10 mmφ tablet molding machine, and compression molded while applying a pressure of 200 kgf / cm ² under vacuum. The height of this cylindrical molded product is measured with a micrometer, and the true specific gravity is calculated from this.

The fluidity of the toner is defined by, for example, a flow repose angle and a static repose angle by a repose angle measuring device (for example, manufactured by Tsutsui Rika Co., Ltd.). In the case of the electrostatic charge developing toner using the charge control agent of the present invention, the flow angle of repose is preferably 5 to 45 degrees, and the static angle of repose is preferably 10 to 50 degrees. In the toner of the present invention, the average value of the shape factor (SF-1) in the case of the pulverized toner is preferably 100 to 400, and the average value of the shape factor (SF-2) is 100 to 350. It is preferable.

In the present invention, SF-1 and SF-2 indicating the shape factor of the toner are, for example, a group of toner particles magnified 1000 times using an optical microscope (for example, BH-2 manufactured by Olympus Corporation) equipped with a CCD camera. Are sampled so that there are about 30 in one field of view, and the obtained image is transferred to an image analyzer (for example, Luzex FS manufactured by Nireco Corporation), and the same operation is repeated until the number of toner particles reaches about 1000. This is a value obtained by calculating the shape factor. The shape factor (SF-1) and the shape factor (SF-2) are calculated by the following equations.
SF-1 = ((ML ² × π) / 4A) × 100
(In the formula, ML represents the maximum particle length, and A represents the projected area of one particle.)
SF-2 = (PM ² / 4Aπ) × 100
(In the formula, PM represents the perimeter of the particle, and A represents the projected area of one particle.)

SF-1 represents the distortion of the particle. The closer the particle is to a sphere, the closer to 100, and the longer the particle, the larger the numerical value. SF-2 represents the unevenness of the particle. The closer the particle is to a sphere, the closer to 100, and the more complicated the particle shape, the larger the value.

In the present invention, the volume resistivity of the toner is preferably 1 × 10 ¹² to 1 × 10 ¹⁶ Ω · cm in the case of a non-magnetic toner, and also depends on the type and content of the magnetic powder in the case of a magnetic toner. Is preferably 1 × 10 ⁸ to 1 × 10 ¹⁶ Ω · cm. In this case, the volume resistivity of the toner is obtained by compression-molding toner particles to produce a disk-shaped test piece having a diameter of 50 mm and a thickness of 2 mm, and applying this to a solid electrode (for example, SE-70 manufactured by Ando Electric Co., Ltd.). It is defined as a value after elapse of 1 hour when a DC voltage of 100 V is continuously applied using a high insulation resistance meter (for example, 4339A manufactured by Hewlett-Packard Co., Ltd.).

In the toner of the present invention, the dielectric loss tangent of the toner is preferably 1.0 × 10 ^{−3 to} 15.0 × 10 ⁻³ in the case of a non-magnetic toner, and in the case of a magnetic toner, the kind and content of magnetic powder are included. Depending on the amount, it is preferably 2 × 10 ⁻³ to 30 × 10 ⁻³ . In this case, the dielectric loss tangent of the toner is obtained by compression-molding toner particles to produce a disk-shaped test piece having a diameter of 50 mm and a thickness of 2 mm, and setting this on an electrode for solid, and an LCR meter (for example, Hewlett-Packard) It is defined as a dielectric loss tangent value (Tanδ) obtained when measured at a measurement frequency of 1 KHz and a peak-to-peak voltage of 0.1 KV using 4284A).

The toner of the present invention preferably has an Izod impact value of 0.1 to 30 kg · cm / cm. The Izod impact value of the toner in this case is measured in accordance with JIS standard K-7110 (hard plastic impact test method) by thermally melting toner particles to produce a plate-like test piece.

The toner of the present invention preferably has a melt index value (MI value) of 10 to 150 g / 10 min. The MI value of the toner in this case is measured according to JIS standard K-7210 (A method). In this case, the measurement temperature is 125 ° C. and the load is 10 kg.

In the toner of the present invention, the melting start temperature of the toner is preferably 80 to 180 ° C., and the 4 mm drop temperature is preferably 90 to 220 ° C. In this case, the toner melting start temperature is obtained by compressing and molding toner particles to produce a cylindrical test piece having a diameter of 10 mm and a thickness of 20 mm, which is then used as a thermal melting characteristic measuring device such as a flow tester (for example, CFT manufactured by Shimadzu Corporation). -500C) and is defined as a value at which melting starts and the piston starts to descend when measured at a load of 20 kgf / cm ² . Further, the temperature when the piston drops by 4 mm by the same measurement is defined as a 4 mm drop temperature.

The toner of the present invention preferably has a glass transition temperature (Tg) of 35 to 80 ° C, more preferably 40 to 75 ° C. The glass transition temperature of the toner in this case is measured using a DSC device, and is defined as a value obtained from the peak value of the phase change that appears when the temperature is raised at a constant temperature, then rapidly cooled, and reheated. When the Tg of the toner is lower than 35 ° C., the offset resistance and the storage stability tend to be lowered, and when it is higher than 80 ° C., the fixing strength of the image tends to be lowered.

The toner of the present invention preferably has a melt viscosity of 1000 to 50000 poise, more preferably 1500 to 38000 poise. In this case, the toner melt viscosity is obtained by compressing and molding toner particles to prepare a cylindrical test piece having a diameter of 10 mm and a thickness of 20 mm, and using this, a thermal melt property measuring apparatus, for example, a flow tester (CFT-500C manufactured by Shimadzu Corporation). Is defined as a value when measured at a load of 20 kgf / cm ² .

The solvent-dissolved residue of the toner of the present invention is preferably 0 to 30% by mass as a THF-insoluble content, 0 to 40% by mass as an ethyl acetate-insoluble content, and 0 to 30% by mass as a chloroform-insoluble content. The solvent-dissolved residue is obtained by uniformly dissolving / dispersing 1 g of toner in 100 ml of each solvent of THF, ethyl acetate and chloroform, pressure-filtering the solution / dispersion, drying the filtrate, and quantifying. From this value, the ratio of insoluble matter in the organic solvent in the toner is calculated.

The toner of the present invention can be used in a one-component development method which is one of image forming methods. The one-component developing method is a method for developing a latent image by supplying a thinned toner to a latent image carrier. The toner thinning usually includes a toner conveying member, a toner layer thickness regulating member and a toner replenishing auxiliary member, and the replenishing auxiliary member and the toner conveying member, and the toner layer thickness regulating member and the toner conveying member are in contact with each other. It is performed using the device.

The toner of the present invention can also be used in a two-component development system. The two-component development system is a system that uses toner and a carrier (having a role as a charge imparting material and a toner transport material), and the above-described magnetic material and glass beads are used for the carrier. The developer (toner and carrier) is agitated by the agitating member to generate a predetermined amount of charge, and is conveyed to the development site by a magnet roller or the like. On the magnet roller, a developer is held on the roller surface by a magnetic force, and a magnetic brush whose layer is regulated to an appropriate height by a developer regulating plate or the like is formed. The developer moves on the roller as the developing roller rotates, and is brought into contact with the electrostatic charge latent image holding member or opposed in a non-contact state at a constant interval to develop and visualize the latent image. In the case of development in a non-contact state, it is possible to obtain a driving force for the toner to fly through a space at a constant interval by generating a direct current electric field between the developer and the latent image holding member. It can also be applied to a method of superimposing alternating current in order to develop an image.

The charge control agent used in the present invention is also suitable as a charge control agent (charge enhancer) in a coating for electrostatic powder coating. That is, the coating material for electrostatic coating using this charge enhancer is excellent in environmental resistance, storage stability, in particular thermal stability and durability, has a coating efficiency of 100%, and is a thick film free from coating film defects. Can be formed.

EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, these do not limit this invention at all. In the following examples, all “parts” represent “parts by mass”.

The aminopiperidine derivative represented by the general formula (1) was purified by column chromatography, adsorption purification using silica gel, activated carbon or activated clay, recrystallization using a solvent or crystallization. The compound was identified by NMR analysis.

[Synthesis Example 1] (Synthesis of Compound 1)
To a reaction vessel purged with nitrogen, 7.33 g (61.5 mmol) of phenyl isocyanate and 250 ml of dioxane were added, and 100 ml of a dioxane solution of 3.00 g (30.0 mmol) of aminopiperidine was added dropwise with stirring. The mixture was stirred at 6 ° C for 6 hours. After standing overnight, the reaction solution was added to 1000 ml of water with stirring. Hydrochloric acid was added to bring the pH of the solution to 3, and the mixture was further stirred for 1 hour. The precipitated crude product was collected by filtration, washed with water, and then dried under reduced pressure at 60 ° C. to obtain 9.64 g (yield 95.0%) of white crystals.

The structure of the white crystals obtained was identified using NMR.
^The following 22 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ). δ (ppm) = 1.30-1.35 (2H), 1.84-1.85 (2H), 2.97-3.01 (2H), 3.69 (1H), 3.99-4 .01 (2H), 6.20-6.21 (1H), 6.87-6.93 (2H), 7.20-7.47 (8H), 8.34 (1H), 8.52 ( 1H).

[Synthesis Example 2] (Synthesis of Compound 2)
To a reaction vessel purged with nitrogen, 8.19 g (61.5 mmol) of 2-methylphenyl isocyanate and 250 ml of dioxane were added, and 100 ml of a dioxane solution of 3.00 g (30.0 mmol) of aminopiperidine was added dropwise with stirring. Thereafter, the mixture was heated and stirred at 60 ° C. for 6.5 hours. After standing overnight, the reaction solution was added to 1000 ml of water with stirring. Hydrochloric acid was added to bring the pH of the solution to 3, and the mixture was further stirred for 1 hour. The precipitated crude product was collected by filtration, washed with water, and then dried under reduced pressure at 60 ° C. to obtain 10.68 g (yield 97.2%) of white crystals.

The structure of the white crystals obtained was identified using NMR.
^The following 26 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ). δ (ppm) = 1.32 (2H), 1.87 (2H), 2.17 (6H), 3.01 (2H), 3.57 (1H), 3.95 (2H), 6.65 (1H), 6.86 (1H), 7.04-7.18 (6H), 7.54 (1H), 7.87 (1H), 8.08 (1H).

[Synthesis Example 3] (Synthesis of Compound 3)
To a reaction vessel purged with nitrogen, 8.19 g (61.5 mmol) of 3-methylphenyl isocyanate and 250 ml of dioxane were added, and 100 ml of a dioxane solution of 3.00 g (30.0 mmol) of aminopiperidine was added dropwise with stirring. Thereafter, the mixture was heated and stirred at 60 ° C. for 6.5 hours. After standing overnight, the reaction solution was added to 1000 ml of water with stirring. Hydrochloric acid was added to bring the pH of the solution to 3, and the mixture was further stirred for 1 hour. The precipitated crude product was separated by filtration, washed with water, and then dried under reduced pressure at 60 ° C. to obtain 10.32 g (yield 94.2%) of white crystals.

The structure of the white crystals obtained was identified using NMR.
^The following 26 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ). δ (ppm) = 1.31 (2H), 1.84 (2H), 2.24 (6H), 2.98 (2H), 3.68 (1H), 3.99 (2H), 6.18 (1H), 6.73 (2H), 7.08-7.30 (6H), 8.25 (1H), 8.44 (1H).

[Synthesis Example 4] (Synthesis of Compound 4)
To a reaction vessel purged with nitrogen, 8.19 g (61.5 mmol) of 4-methylphenyl isocyanate and 250 ml of dioxane were added, and 100 ml of a dioxane solution of 3.00 g (30.0 mmol) of aminopiperidine was added dropwise with stirring. Thereafter, the mixture was heated and stirred at 60 ° C. for 6.5 hours. After standing overnight, the reaction solution was added to 1000 ml of water with stirring. Hydrochloric acid was added to bring the pH of the solution to 3, and the mixture was further stirred for 1 hour. The precipitated crude product was collected by filtration, washed with water, and then dried under reduced pressure at 60 ° C. to obtain 10.74 g (yield 97.7%) of white crystals.

The structure of the white crystals obtained was identified using NMR.
^The following 26 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ). δ (ppm) = 1.31 (2H), 1.83 (2H), 2.19 (3H), 2.23 (3H), 2.96 (2H), 3.68 (1H), 3.98 (2H), 6.14 (1H), 7.02 (4H), 7.26 (2H), 7.34 (2H), 8.22 (1H), 8.42 (1H).

[Synthesis Example 5] (Synthesis of Compound 5)
To a nitrogen-substituted reaction vessel, 9.17 g (61.5 mmol) of 2-methoxyphenyl isocyanate and 250 ml of dioxane were added, and 100 ml of a dioxane solution of 3.00 g (30.0 mmol) of aminopiperidine was added dropwise with stirring. Then, it heated and stirred at 60 degreeC for 6 hours. After standing overnight, the reaction solution was added to 1000 ml of water with stirring. Hydrochloric acid was added to bring the pH of the solution to 3, and the mixture was further stirred for 1 hour. The precipitated crude product was collected by filtration, washed with water, and then dried under reduced pressure at 60 ° C. to obtain 7.21 g of white crystals (yield 60.3%).

The structure of the white crystals obtained was identified using NMR.
^The following 26 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ). δ (ppm) = 1.31 (2H), 1.85 (2H), 3.05 (2H), 3.70 (1H), 3.82 (6H), 3.89 (2H), 6.83 -7.00 (7H), 7.65 (2H), 7.85 (1H), 8.10 (1H).

[Synthesis Example 6] (Synthesis of Compound 6)
To a reaction vessel purged with nitrogen, 9.17 g (61.5 mmol) of 3-methoxyphenyl isocyanate and 250 ml of dioxane were added, and 100 ml of a dioxane solution of 3.00 g (30.0 mmol) of aminopiperidine was added dropwise with stirring. Thereafter, the mixture was heated and stirred at 60 ° C. for 6.5 hours. After standing overnight, the reaction solution was added to 1000 ml of water with stirring. Hydrochloric acid was added to bring the pH of the solution to 3, and the mixture was further stirred for 1 hour. The precipitated crude product was collected by filtration, washed with water, and then dried under reduced pressure at 60 ° C. to obtain 10.58 g (yield 88.5%) of white crystals.

The structure of the white crystals obtained was identified using NMR.
^The following 26 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ). δ (ppm) = 1.32 (2H), 1.84 (2H), 2.98 (2H), 3.70 (7H), 3.99 (2H), 6.19 (1H), 6.47 -7.16 (8H), 8.34 (1H), 8.49 (1H).

[Synthesis Example 7] (Synthesis of Compound 7)
To a reaction vessel purged with nitrogen, 9.17 g (61.5 mmol) of 4-methoxyphenyl isocyanate and 250 ml of dioxane were added, and 100 ml of a dioxane solution of 3.00 g (30.0 mmol) of aminopiperidine was added dropwise with stirring. Thereafter, the mixture was heated and stirred at 60 ° C. for 7.5 hours. After standing overnight, the reaction solution was added to 1000 ml of water with stirring. Hydrochloric acid was added to bring the pH of the solution to 3, and the mixture was further stirred for 1 hour. The precipitated crude product was filtered off, washed with water, and then dried under reduced pressure at 60 ° C. to obtain 11.39 g of white crystals (yield 95.3%).

The structure of the white crystals obtained was identified using NMR.
^The following 26 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ). δ (ppm) = 1.31 (2H), 1.83 (2H), 2.96 (2H), 3.69 (7H), 3.97 (2H), 6.08 (1H), 6.81 (4H), 7.27-7.35 (4H), 8.13 (1H), 8.35 (1H).

[Synthesis Example 8] (Synthesis of Compound 8)
To a reaction vessel purged with nitrogen, 9.44 g (61.5 mmol) of 2-chlorophenyl isocyanate and 250 ml of dioxane were added, and 100 ml of a dioxane solution of 3.00 g (30.0 mmol) of aminopiperidine was added dropwise with stirring. The mixture was heated and stirred at 60 ° C. for 6.5 hours. After standing overnight, the reaction solution was added to 1000 ml of water with stirring. Hydrochloric acid was added to bring the pH of the solution to 3, and the mixture was further stirred for 1 hour. The precipitated crude product was collected by filtration, washed with water, and then dried under reduced pressure at 60 ° C. to obtain 11.89 g (yield 97.3%) of white crystals.

The structure of the white crystals obtained was identified using NMR.
^The following 20 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ). δ (ppm) = 1.34 (2H), 1.84 (2H), 3.07 (2H), 3.75 (1H), 3.94 (2H), 6.94-7.48 (8H) 7.95 (1H), 8.18 (1H), 8.23 (1H).

[Synthesis Example 9] (Synthesis of Compound 9)
To a reaction vessel purged with nitrogen, 9.44 g (61.5 mmol) of 3-chlorophenyl isocyanate and 250 ml of dioxane were added, and 100 ml of a dioxane solution of 3.00 g (30.0 mmol) of aminopiperidine was added dropwise with stirring. The mixture was heated and stirred at 60 ° C. for 7 hours. After standing overnight, the reaction solution was added to 1000 ml of water with stirring. Hydrochloric acid was added to bring the pH of the solution to 3, and the mixture was further stirred for 1 hour. The deposited crude product was separated by filtration, washed with water, and then dried under reduced pressure at 60 ° C. to obtain 11.42 g (yield 93.5%) of white crystals.

The structure of the white crystals obtained was identified using NMR.
^The following 20 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ). δ (ppm) = 1.35 (2H), 1.85 (2H), 3.00 (2H), 3.70 (1H), 4.00 (2H), 6.31 (1H), 6.92 -7.67 (8H), 8.58 (1H), 8.71 (1H).

[Synthesis Example 10] (Synthesis of Compound 10)
To a reaction vessel purged with nitrogen, 9.44 g (61.5 mmol) of 4-chlorophenyl isocyanate and 250 ml of dioxane were added, and 100 ml of a dioxane solution of 3.00 g (30.0 mmol) of aminopiperidine was added dropwise with stirring. The mixture was heated and stirred at 60 ° C. for 6.5 hours. After standing overnight, the reaction solution was added to 1000 ml of water with stirring. Hydrochloric acid was added to bring the pH of the solution to 3, and the mixture was further stirred for 1 hour. The precipitated crude product was separated by filtration, washed with water, and then dried under reduced pressure at 60 ° C. to obtain 12.07 g (yield 98.8%) of white crystals.

The structure of the white crystals obtained was identified using NMR.
^The following 20 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ). δ (ppm) = 1.33 (2H), 1.84 (2H), 2.99 (2H), 3.70 (1H), 3.99 (2H), 6.25 (1H), 7.25 -7.51 (8H), 8.50 (1H), 8.65 (1H).

[Synthesis Example 11] (Synthesis of Compound 11)
To a reaction vessel purged with nitrogen, 8.56 g (77.0 mmol) of cyclopentyl isocyanate and 250 ml of dioxane were added, and 100 ml of a dioxane solution of 3.00 g (30.0 mmol) of aminopiperidine was added dropwise with stirring. The mixture was stirred at 6 ° C for 6 hours. After standing overnight, the reaction solution was added to 1000 ml of water with stirring. Hydrochloric acid was added to bring the pH of the solution to 3, and the mixture was further stirred for 1 hour. The precipitated crude product was filtered off, washed with water, and then dried under reduced pressure at 60 ° C. to obtain 7.53 g of white crystals (yield 77.9%).

The structure of the white crystals obtained was identified using NMR.
^The following 30 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ). δ (ppm) = 1.11-1.78 (20H), 2.75 (2H), 3.50 (1H), 3.77-3.90 (4H), 5.63-5.66 (2H) ), 6.14 (1H).

[Synthesis Example 12] (Synthesis of Compound 12)
To a reaction vessel purged with nitrogen, 7.70 g (61.5 mmol) of cyclohexyl isocyanate and 250 ml of dioxane were added, and 100 ml of a dioxane solution of 3.00 g (30.0 mmol) of aminopiperidine was added dropwise with stirring. The mixture was heated and stirred at ° C for 6.5 hours. After standing overnight, the reaction solution was added to 1000 ml of water with stirring. Hydrochloric acid was added to bring the pH of the solution to 3, and the mixture was further stirred for 1 hour. The precipitated crude product was filtered off, washed with water, and then dried under reduced pressure at 60 ° C. to obtain 8.85 g of white crystals (yield 84.1%).

The structure of the white crystals obtained was identified using NMR.
^The following 34 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ). δ (ppm) = 1.02-1.28 (12H), 1.50-1.73 (12H), 2.50 (1H), 2.72-2.77 (2H), 3.37-3 .77 (4H), 5.59 (1H), 5.68 (1H), 6.09 (1H).

[Synthesis Example 13] (Synthesis of Compound 13)
To a reaction vessel purged with nitrogen, 8.55 g (61.5 mmol) of cycloheptyl isocyanate and 250 ml of dioxane were added, and 100 ml of a dioxane solution of 3.00 g (30.0 mmol) of aminopiperidine was added dropwise with stirring. The mixture was heated and stirred at 60 ° C. for 7 hours. After standing overnight, the reaction solution was added to 1000 ml of water with stirring. Hydrochloric acid was added to bring the pH of the solution to 3, and the mixture was further stirred for 1 hour. The precipitated crude product was separated by filtration, washed with water, and then dried under reduced pressure at 60 ° C. to obtain 10.13 g of white crystals (yield 92.3%).

The structure of the white crystals obtained was identified using NMR.
^The following 38 hydrogen signals were detected by ¹ H-NMR (DMSO-d ₆ ). δ (ppm) = 1.14 (2H), 1.38-1.75 (26H), 2.78 (2H), 3.50-3.75 (5H), 5.48-5.57 (2H) ), 5.89 (1H).

[Example 14] (Production and evaluation of non-magnetic toner 1)
(Manufacture of non-magnetic toner 1)
Styrene-acrylate copolymer resin (manufactured by Mitsui Chemicals, trade name CPR-100, acid value 0.1 mg KOH / g) 91 parts, aminopiperidine derivative synthesized in Example 4 (compound 4) 1 part, carbon black (Mitsubishi Chemical Co., Ltd., trade name MA-100) 5 parts and low molecular weight polypropylene (Sanyo Kasei Co., Ltd., trade name Biscol 550P) 3 parts are melt-mixed by a 130 ° C heating mixing device (biaxial extrusion kneader). did. The cooled mixture was coarsely pulverized with a hammer mill, then finely pulverized with a jet mill, and classified to obtain a nonmagnetic toner 1 having a volume average particle size of 9 ± 0.5 μm.

(Evaluation of non-magnetic toner 1)
The obtained nonmagnetic toner 1 was mixed and shaken at a ratio of 4 parts by mass with respect to 100 parts by mass of a non-coated ferrite carrier (F-150, manufactured by Powdertech Co., Ltd.) to negatively charge the toner. The charge amount was measured with a blow-off powder charge amount measuring device. The results are summarized in Table 1.

Similarly, the charge amount was also evaluated when mixed with a silicon-coated ferrite carrier (F96-150, manufactured by Powdertech). The results are summarized in Table 1.

Example 15 (Production and Evaluation of Nonmagnetic Toner 2)
In Example 14, the volume average particle diameter was the same as in Example 14 except that the aminopiperidine derivative synthesized in Example 4 (Compound 4) was replaced with the aminopiperidine derivative synthesized in Example 2 (Compound 2). A nonmagnetic toner 2 of 9 ± 0.5 μm was prepared, and the charge amount was evaluated under the same conditions as in Example 14. The results are summarized in Table 1.

Example 16 (Production and Evaluation of Nonmagnetic Toner 3)
In Example 14, the volume average particle diameter was the same as in Example 14 except that the aminopiperidine derivative synthesized in Example 4 (Compound 4) was replaced with the aminopiperidine derivative synthesized in Example 5 (Compound 5). A nonmagnetic toner 3 of 9 ± 0.5 μm was prepared, and the charge amount was evaluated under the same conditions as in Example 14. The results are summarized in Table 1.

[Comparative Example 1] (Production and Evaluation of Comparative Nonmagnetic Toner)
For comparison, in Example 14, except that the aminopiperidine derivative synthesized in Example 4 (Compound 4) was replaced with a salt of 3,5-tert-butylsalicylic acid and zinc (Comparative Compound 1). A comparative nonmagnetic toner was prepared under the same conditions, and the charge amount was evaluated under the same conditions as in Example 14. The results are summarized in Table 1.

As is apparent from Table 1, it was found that the toner using the charge control agent containing the aminopiperidine derivative represented by the general formula (1) of the present invention as an active ingredient has a high charge amount.

[Example 17] (Production and evaluation of polymerized toner)
(Preparation of resin dispersion)
80 parts of a polyester resin (Mitsubishi Rayon Co., Ltd., DIACRON ER-561), 320 parts of ethyl acetate, and 32 parts of isopropyl alcohol are mixed, and a homogenizer (Made Co., Ltd., foamless mixer NGM-0.5TB) is used. While stirring at a rotational speed of 5000 to 10000 rpm, an appropriate amount of 0.1% by mass of ammonia water was added dropwise for phase inversion emulsification, and the solvent was removed while reducing the pressure with an evaporator to obtain a resin dispersion. The volume average particle size of the resin particles in this dispersion was 0.2 μm (the resin particle concentration was adjusted to 20% by mass with ion-exchanged water).

(Preparation of charge control agent dispersion)
0.2 parts of sodium dodecylbenzenesulfonate, 0.2 part of sorbon T-20 (manufactured by Toho Chemical Co., Ltd.) and 17.6 parts of ion-exchanged water were mixed and dissolved, and the aminopiperidine derivative synthesized in Example 4 ( Compound 4) 2.0 parts, zirconia beads (bead particle size 0.65 mmφ, equivalent to 15 ml) were added, and paint conditioner (UNION NJ (USA), Red Devil No. 5400-5L) was used. Dispersed for 3 hours. The zirconia beads were removed using a sieve and the dispersion was prepared with ion-exchanged water to obtain a 10% by mass charge control agent dispersion.

(Preparation of polymerization toner)
125 parts of the resin dispersion, 1.0 part of a 20% by weight sodium dodecylbenzenesulfonate aqueous solution and 125 parts of ion-exchanged water are added to a reaction vessel equipped with a thermometer, pH meter, and stirrer, and the liquid temperature is controlled at 30 ° C. The mixture was stirred at 150 rpm for 30 minutes. A 1% by mass aqueous nitric acid solution was added to adjust the pH to 3.0, and the mixture was further stirred for 5 minutes. While dispersing with a homogenizer (IKA Japan, Ultra Tarrax T-25), 0.125 part of polyaluminum chloride was added, the temperature was raised to 50 ° C., and the mixture was further dispersed for 30 minutes. After adding 62.5 parts of the resin dispersion and 4.0 parts of the charge control agent dispersion, a 1% by mass aqueous nitric acid solution was added to adjust the pH to 3.0, and the mixture was further dispersed for 30 minutes. While stirring at 400 to 700 rpm using a stirrer, 8.0 parts of a 5% by mass aqueous sodium hydroxide solution was added, and stirring was continued until the volume average particle diameter of the toner reached 9.5 μm. After the liquid temperature was raised to 75 ° C., the mixture was further stirred for 2 hours, and after confirming that the volume average particle size was 6.0 μm and the particle shape was spheroidized, it was rapidly cooled using ice water. The toner particles were collected by filtration and then dispersed and washed with ion exchange water. Dispersion washing was repeated until the electrical conductivity of the filtrate after dispersion (measuring device: HORIBA ES-51, manufactured by Horiba, Ltd.) was 20 μS / cm or less. Thereafter, the toner particles were obtained by drying with a dryer at 40 ° C. The obtained toner particles were sieved with a 166 mesh (aperture 90 μm) sieve to obtain a polymerized toner for evaluation.

(Evaluation of polymerized toner)
The obtained polymerization toner for evaluation was mixed and shaken at a ratio of 2 parts to 100 parts of a silicon-coated ferrite carrier (F96-150, manufactured by Powdertech), and the toner was negatively charged. Using a blow-off powder charge amount measuring device, the saturation charge amount was measured in an atmosphere at a temperature of 25 ° C. and a humidity of 50%. As a result, the saturated charge amount was −45.2 μc / g.

[Comparative Example 2]
For comparison, a polymerized toner was prepared under the same conditions as in Example 17 except that the operation of adding the charge control agent dispersion in Example 17 was omitted, and the saturated charge amount was measured. As a result, the saturation charge amount was −21.1 μC / g.

As is clear from the above results, it was found that the polymerized toner containing the aminopiperidine derivative represented by the general formula (1) of the present invention as an active ingredient exhibits excellent charging performance. That is, high charge performance can be imparted to the polymerized toner by using a charge control agent containing the aminopiperidine derivative represented by the general formula (1) of the present invention as an active ingredient.

The aminopiperidine derivative represented by the general formula (1) of the present invention has excellent charging performance, and the charge control agent containing the compound as an active ingredient is clearly higher in charging performance than conventional charge control agents. have. Further, it is optimal for color toners, particularly for polymerized toners. Furthermore, it does not contain heavy metals such as chromium compounds that are concerned about environmental problems, and can provide a very useful toner.

Claims (5)

A charge control agent comprising one or more aminopiperidine derivatives represented by the following general formula (1) as an active ingredient.

[Wherein, X ₁ and X ₂ may be the same or different and each represents an oxygen atom or a sulfur atom, and R ₁ and R ₂ may be the same or different from each other, and represent a hydrogen atom, a deuterium atom, a substituent, A linear or branched alkyl group having 1 to 20 carbon atoms which may have, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, and a substituent; Represents a linear or branched alkenyl group having 2 to 6 carbon atoms, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and R ₃ and R ₄ may be the same or different from each other; Or a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, and substitution. Optionally substituted carbon atom 2-6 linear or branched alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, R ₅ is a deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group , A trifluoromethyl group, an optionally substituted linear or branched alkyl group having 1 to 8 carbon atoms, and an optionally substituted cycloalkyl having 5 to 10 carbon atoms A linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, or a linear or branched group having 1 to 8 carbon atoms which may have a substituent An alkoxy group, an optionally substituted cycloalkoxy group having 5 to 10 carbon atoms, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted aryloxy group Represents ₆ is a hydrogen atom, a deuterium atom, a linear or branched alkyl group which may having 1 to 20 carbon atoms which may have a substituent group, carbon atoms which may have a substituent 5-10 A cycloalkyl group, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group , N represents an integer of 0 to 9, and when n is 2 or more, a plurality of R ₅ may be the same or different from each other. ] The charge control agent according to claim 1, wherein the aminopiperidine derivative represented by the general formula (1) is represented by the following general formula (1 ').

[Wherein, X ₁ and X ₂ may be the same or different and each represents an oxygen atom or a sulfur atom, and R ₁ and R ₂ may be the same or different from each other, and represent a hydrogen atom, a deuterium atom, a substituent, A linear or branched alkyl group having 1 to 20 carbon atoms which may have, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, and a substituent; Represents a linear or branched alkenyl group having 2 to 6 carbon atoms, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and R ₃ and R ₄ may be the same or different from each other; Or a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, a cycloalkyl group having 5 to 10 carbon atoms which may have a substituent, and substitution. Optionally substituted carbon atom 2-6 linear or branched alkenyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, R ₅ is a deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group , A trifluoromethyl group, an optionally substituted linear or branched alkyl group having 1 to 8 carbon atoms, and an optionally substituted cycloalkyl having 5 to 10 carbon atoms A linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, or a linear or branched group having 1 to 8 carbon atoms which may have a substituent An alkoxy group, an optionally substituted cycloalkoxy group having 5 to 10 carbon atoms, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted or unsubstituted aryloxy group Represents ₆ is a hydrogen atom, a deuterium atom, a linear or branched alkyl group which may having 1 to 20 carbon atoms which may have a substituent group, carbon atoms which may have a substituent 5-10 A cycloalkyl group, a linear or branched alkenyl group having 2 to 6 carbon atoms which may have a substituent, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group , N represents an integer of 0 to 9, and when n is 2 or more, a plurality of R ₅ may be the same or different from each other. ] The charge control agent according to claim 1, wherein the aminopiperidine derivative represented by the general formula (1) is represented by the following general formula (1 ″).

[Wherein, X ₁ and X ₂ may be the same or different and represent an oxygen atom or a sulfur atom, and R ₁ and R ₂ may be the same or different from each other, and each has a hydrogen atom or a substituent. A linear or branched alkyl group having 1 to 16 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms which may have a substituent, a substituted or unsubstituted aryl group, or a substituted or unsubstituted group. Represents a substituted heterocyclic group, and R ₃ and R ₄ may be the same or different from each other, and may have a linear or branched alkyl group having 1 to 16 carbon atoms, a substituent. A cycloalkyl group having 5 to 7 carbon atoms which may have a substituent, a linear or branched alkenyl group having 2 to 4 carbon atoms which may have a substituent, and a substituted or unsubstituted aryl Group or substitution or A substituted heterocyclic group, R ₅ is a halogen atom, a hydroxyl group, a cyano group, a nitro group, a trifluoromethyl group, good C1-4 be substituted linear or branched An alkyl group, an optionally substituted cycloalkyl group having 5 to 7 carbon atoms, an optionally substituted linear or branched alkoxy group having 1 to 4 carbon atoms, substituted Represents a cycloalkoxy group having 5 to 7 carbon atoms which may have a group, a substituted or unsubstituted aryl group, and R ₆ represents a hydrogen atom and optionally having 1 to 16 carbon atoms. A linear or branched alkyl group, an optionally substituted cycloalkyl group having 5 to 7 carbon atoms, a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, n represents an integer of 0 to 4, and n is 2 or more A plurality of R ₅ present in the above case may be the same as or different from each other. ] A toner comprising the charge control agent according to any one of claims 1 to 3, a colorant, and a binder resin. A polymerized toner comprising the charge control agent according to any one of claims 1 to 3, a colorant, and a binder resin.