JP2013072915A - Toner containing compound with azo dye skeleton - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner with good dispersibility of an azo pigment in a binder resin and good tone.SOLUTION: The toner contains a binder resin, a compound in which a specific azo dye skeleton unit is bonded to a specific polymer resin unit, and toner base particles at least containing an azo pigment as a colorant.

Description

  The present invention relates to a toner containing, as a pigment dispersant, a novel compound in which an azo dye skeleton unit and a polymer resin unit are combined, which is used for electrophotography, electrostatic recording, electrostatic printing, or toner jet recording.

  A method of using an azo pigment as a toner colorant is disclosed in, for example, Patent Document 1, but when such an azo pigment is used as a toner colorant, spectral characteristics such as coloring power and transparency are improved. In order to improve, it is necessary to finely disperse the pigment in the binder resin or polymerizable monomer of the toner. However, in general, when the azo pigment is made finer, crystal growth or transition is likely to occur due to thermal history or contact with a solvent in the dispersion process or the subsequent manufacturing process, which causes problems such as a reduction in coloring power or transparency. End up. Further, in a toner manufacturing process using an azo pigment, particularly a toner manufacturing process using a polymerization method, the viscosity of the pigment dispersion increases due to re-aggregation of the fine azo pigment.

In order to improve these problems, various pigment dispersants have been proposed. For example, a polymer dispersant is disclosed in which a site having an affinity for an azo pigment as a colorant and an oligomer or polymer site having an affinity for a solvent and a binder resin are bonded by a covalent bond (Patent Document). 2). Further, an example using an acid known as Solsperse (registered trademark) or a comb polymer dispersant having a basic site is disclosed (see Patent Document 3).
On the other hand, in recent years, there has been a demand for higher image quality of output images, and there are problems such as image fogging in which toner is developed in the margins of the image and image defects such as uneven image density due to low toner transfer efficiency. It has become.

Japanese Patent No. 03917764 Japanese Patent No. 0398840 International Publication No. 99-42532 Pamphlet

  However, since the pigment dispersants described in Patent Document 2 and Patent Document 3 have insufficient affinity for azo pigments, the dispersibility of the pigment is not sufficient, and the toner color tone and image fog required for high-definition images are insufficient. It has not yet been achieved to satisfy suppression, improvement in transfer efficiency, and the like. Further, when a toner is produced by a polymerization method using the pigment dispersant and an azo pigment, there is a problem that in the pigment dispersion step, the viscosity of the pigment dispersion increases as the pigment becomes finer.

  Accordingly, an object of the present invention is to provide a toner having improved color tone by improving dispersibility of an azo pigment in a binder resin. It is another object of the present invention to provide a toner that suppresses image fogging and has high transfer efficiency. Another object of the present invention is to provide a toner obtained by a production method in which the dispersion stability of a pigment dispersion is improved and an increase in viscosity of the pigment dispersion is suppressed in a toner production process using the azo pigment.

  The above object is solved by the present invention described below. That is, the present invention provides a polymer having a binder resin, a partial structural formula represented by the following general formula (2) and / or a partial structural formula represented by the following general formula (3) with the following general formula (1 And a toner containing an azo pigment as a colorant.

［式（１）中、Ｒ₁は炭素数１乃至６のアルキル基、フェニル基を表し、Ｒ₂乃至Ｒ₆は水素原子、ＣＯＯＲ₁₁基、ＣＯＮＲ₁₂Ｒ₁₃基を表す。Ｒ₇乃至Ｒ₁₀は水素原子、ハロゲン原子を表す。Ｒ₁₁乃至Ｒ₁₃は水素原子、炭素原子数１乃至３のアルキル基を表す。Ｌ₁乃至Ｌ₂は二価の連結基を表す。］

[In Formula (1), R ₁ represents an alkyl group having 1 to 6 carbon atoms and a phenyl group, and R _{2 to} R ₆ represent a hydrogen atom, a COOR ₁₁ group, and a CONR ₁₂ R ₁₃ group. R _{7 to} R ₁₀ represent a hydrogen atom or a halogen atom. R _{11 to} R _{13 each} represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. L _{1 to} L ₂ represent a divalent linking group. ]

［式（２）中、Ｒ₁₄は水素原子、アルキル基を表す。］

[In the formula (2), R ₁₄ represents a hydrogen atom or an alkyl group. ]

［式（３）中、Ｒ₁₅は水素原子、アルキル基を表し、Ｒ₁₆は水素原子、アルキル基、アラルキル基を表す。］

[In the formula (3), R ₁₅ represents a hydrogen atom or an alkyl group, and R ₁₆ represents a hydrogen atom, an alkyl group or an aralkyl group. ]

  According to the present invention, a toner containing a compound having the above-described structure as a pigment dispersant is provided. This compound according to the present invention has a high affinity for water-insoluble solvents, polymerizable monomers, binder resins for toners, and azo pigments, particularly acetoacetanilide pigments. By using as a pigment dispersant for toner, C.I. I. An azo pigment represented by Pigment Yellow 155 is well dispersed in the binder resin, and a toner having a good color tone is provided. Further, by adding the compound having the azo dye skeleton unit to the toner, image fog is suppressed and a toner having high transfer efficiency is provided.

  Furthermore, since the compound can improve the dispersion stability of the azo pigment in the water-insoluble solvent and suppress the increase in the viscosity of the pigment dispersion, it has good pigment dispersibility even in the toner production process by the polymerization method. A retained toner is provided.

In CDCl ₃ the compound having an azo dye skeleton unit according to the present invention (19) is a diagram showing the ¹ H NMR spectrum at room temperature, at 400 MHz. In CDCl ₃ the compound having an azo dye skeleton unit according to the present invention (20) is a diagram showing the ¹ H NMR spectrum at room temperature, at 400 MHz.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments.

  The toner of the present invention will be described.

  The toner of the present invention is a polymer having a partial structural formula represented by the following general formula (2) and / or a partial structural formula represented by the following general formula (3) (also referred to as “polymer resin unit”). And a toner base particle containing an azo pigment as a colorant, and a compound to which a unit represented by the following general formula (1) (also referred to as an “azo dye skeleton unit”) is bonded.

［式（１）中、Ｒ₁は炭素数１乃至６のアルキル基、フェニル基を表し、Ｒ₂乃至Ｒ₆は水素原子、ＣＯＯＲ₁₁基、ＣＯＮＲ₁₂Ｒ₁₃基を表す。Ｒ₇乃至Ｒ₁₀は水素原子、ハロゲン原子を表す。Ｒ₁₁乃至Ｒ₁₃は水素原子、炭素原子数１乃至３のアルキル基を表す。Ｌ₁乃至Ｌ₂は二価の連結基を表す。］

[In Formula (1), R ₁ represents an alkyl group having 1 to 6 carbon atoms and a phenyl group, and R _{2 to} R ₆ represent a hydrogen atom, a COOR ₁₁ group, and a CONR ₁₂ R ₁₃ group. R _{7 to} R ₁₀ represent a hydrogen atom or a halogen atom. R _{11 to} R _{13 each} represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. L _{1 to} L ₂ represent a divalent linking group. ]

［式（２）中、Ｒ₁₄は水素原子、アルキル基を表す。］

[In the formula (2), R ₁₄ represents a hydrogen atom or an alkyl group. ]

［式（３）中、Ｒ₁₅は水素原子、アルキル基を表し、Ｒ₁₆は水素原子、アルキル基、アラルキル基を表す。］

[In the formula (3), R ₁₅ represents a hydrogen atom or an alkyl group, and R ₁₆ represents a hydrogen atom, an alkyl group or an aralkyl group. ]

  First, the structure of the compound having an azo dye skeleton unit of the present invention will be described. The compound having an azo dye skeleton unit of the present invention comprises at least an azo dye skeleton unit represented by the above formula (1) having a high affinity for an azo pigment and a polymer resin unit having a high affinity for a water-insoluble solvent. Composed.

  First, the azo dye skeleton unit represented by the above formula (1) provided in the present invention will be described in detail.

The alkyl group for R ₁ in the above formula (1) is not particularly limited as long as it has 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, and n-butyl. And linear, branched or cyclic alkyl groups such as a group, n-pentyl group, n-hexyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group and cyclohexyl group.

The substituent of R _{1 in} the above formula (1) may be further substituted with a substituent as long as the affinity for the pigment is not significantly inhibited. In this case, examples of the substituent that may be substituted include a halogen atom, a nitro group, an amino group, a hydroxyl group, a cyano group, and a trifluoromethyl group.

R ₁ in the above formula (1) can be arbitrarily selected from the substituents listed above, but is preferably a methyl group from the viewpoint of affinity for the pigment.

R _{2 to} R ₆ in the formula (1) can be selected from a hydrogen atom, a COOR ₁₁ group, and a CONR ₁₂ R ₁₃ group so that at least one is a COOR ₁₁ group or a CONR ₁₂ R ₁₃ group. From the viewpoint of the affinity, it is preferable that R ₂ and R ₅ are COOR ₁₁ groups, and R ₃ , R ₄ and R ₆ are hydrogen atoms.

Examples of the alkyl group in R _{11 to} R ₁₃ in the above formula (1) include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

R _{11 to} R ₁₃ in the above formula (1) can be arbitrarily selected from the substituents listed above and a hydrogen atom, but from the viewpoint of affinity for the pigment, R ₁₁ and R ₁₂ are methyl groups, The case where R ₁₃ is a methyl group or a hydrogen atom is preferred.

Examples of the halogen atom in R _{7 to} R ₁₀ in the above formula (1) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

R _{7 to} R ₁₀ in the above formula (1) can be arbitrarily selected from the substituents listed above and a hydrogen atom, but are preferably hydrogen atoms from the viewpoint of affinity for the pigment.

The formula (1) substitution position of R ₇ to R _10, acyl acetamide group and L ₁ in the acyl acetamide group and position o- position of L _1, m-position, exemplified when substituted with p- position It is done. Regarding the affinity for the pigment due to the difference in these substitution positions, the case where the acylacetamide group and L ₁ are substituted at the p-position is most preferred, which is preferable.

Specific examples of L _{1 in} the above formula (1) include —O—, —O—CO—, —O—CO—NR ₁₇ —, —O—R ₁₈ —, —O—R ₁₈ —O—CO. —, —O—R ₁₈ —O—CO—NR ₁₇ —, —CO—, —CO—O—, —CO—NR ₁₇ —, —CO—O—R ₁₈ —, —CO—O—R ₁₈ —. O—, —NR ₁₇ —CO—, —NR ₁₇ —CO—NR ₁₇ —, —R ₁₈ —O—CO—, —R ₁₈ —O—CO—NR ₁₇ — (R ₁₇ represents a hydrogen atom, an alkyl group, And R ₁₈ represents an alkylene group).

In the specific example of L _{1 in} the above formula (1), examples of the alkyl group represented by R ₁₇ include a methyl group, an ethyl group, and a propyl group.

In the specific example of L _{1 in} the above formula (1), examples of the alkylene group represented by R ₁₈ include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group.

L ₁ in the above formula (1) can be arbitrarily selected from the specific examples listed above, but —NH—CO—, —O—CO—, —O—C ₂ H ₄ —O from the viewpoint of ease of production. The case of -CO- is preferred.

L ₂ in the above formula (1) represents a divalent linking group, and binds the azo dye skeleton unit and the polymer resin unit via L ₂ .

L ₂ in the above formula (1) is not particularly limited as long as it is a divalent linking group, but is preferably a carboxylic acid ester group or a carboxylic acid amide group from the viewpoint of ease of production.

In the above formula (1), the substitution positions of L ₁ and L ₂ are in terms of affinity for the pigment, and the position of L ₁ is 2,5-position, 3,5-position relative to L ₂ Is preferred.

  A preferred combination of substituents in the azo dye skeleton unit represented by the above formula (1) is a combination of the units represented by the above formula (1) represented by units of the following formulas (4) and (5). The case is preferable in terms of affinity for the pigment.

［式（４）中、Ｌ₁乃至Ｌ₂は二価の連結基を表す。］

[In Formula (4), L < ₁ > thru | or L < ₂ > represent a bivalent coupling group. ]

［式（５）中、Ｌ₁乃至Ｌ₂は二価の連結基を表す。］

[In Formula (5), L < ₁ > thru | or L < ₂ > represent a bivalent coupling group. ]

  Next, the polymer resin unit having either or both of the monomer units represented by the above formula (2) or (3) of the present invention will be described.

Examples of the alkyl group for R ₁₄ in the general formula (2) include a methyl group and an ethyl group. R ₁₄ can be arbitrarily selected from the above alkyl group and a hydrogen atom, but is preferably a hydrogen atom or a methyl group from the viewpoint of ease of production.

Examples of the alkyl group represented by R ₁₅ in the general formula (3) include a methyl group and an ethyl group. R ₁₅ can be arbitrarily selected from the above alkyl group and a hydrogen atom, but is preferably a hydrogen atom or a methyl group from the viewpoint of ease of production.

Examples of the alkyl group represented by R ₁₆ in the general formula (3) include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, n -Octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-behenyl group, isopropyl group, isobutyl group, Examples thereof include linear, branched or cyclic alkyl groups such as isodecyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, cyclopentyl group and cyclohexyl group.

Examples of the aralkyl group for R ₁₆ in the general formula (3) include a benzyl group and a phenethyl group.

R ₁₆ in the general formula (3) can be arbitrarily selected from the substituents listed above, but in a non-aqueous solvent, the case where R ₁₆ has 4 or more carbon atoms has an affinity for the dispersion medium. This is preferable.

  The polymer resin unit of the present invention can control the affinity with the dispersion medium by changing the ratio of the monomer unit represented by the above formula (2) or (3).

  When the dispersion medium is a nonpolar solvent such as styrene, it is preferable to increase the proportion of the monomer unit represented by the above formula (2) from the viewpoint of affinity with the dispersion medium. In the case of a solvent having a certain degree of polarity such as an acid ester, it is preferable from the viewpoint of affinity with the dispersion medium to increase the proportion of the monomer unit represented by the above formula (3).

  The molecular weight of the polymer resin unit of the present invention is preferably such that the number average molecular weight is 500 or more in terms of improving the dispersibility of the pigment. A higher molecular weight is more effective in improving the dispersibility of the pigment, but an excessively high molecular weight is not preferable because the affinity for a water-insoluble solvent deteriorates. Accordingly, the number average molecular weight of the polymer resin unit is preferably up to 200000. In addition, considering the ease of production, the number average molecular weight of the polymer resin unit is more preferably in the range of 2,000 to 50,000.

  In addition, as disclosed in JP-A-2003-53001, a polyoxyalkylenecarbonyl-based dispersant is known in which a dispersibility is improved by introducing an aliphatic chain branched to the terminal. In the polymer resin unit of the present invention, if a telechelic polymer resin unit is synthesized by a method such as ATRP (Atom Transfer Radial Polymerization) described later, an aliphatic chain branched at the end can be introduced. Dispersibility may be improved.

  The position of the azo skeleton unit in the compound having the azo skeleton unit of the present invention may be randomly scattered, but it is more dispersible if it is unevenly distributed by forming one or more blocks at one end. The effect to improve is high.

  The greater the number of azo skeleton units in the compound having an azo skeleton unit of the present invention, the higher the affinity for the pigment. However, if the number is too large, the affinity for the water-insoluble solvent deteriorates. Accordingly, the number of azo skeleton units is preferably in the range of 1 to 10 and more preferably in the range of 1 to 5 with respect to the number of monomers 100 forming the polymer resin unit.

  The bisazo skeleton unit represented by the above formula (1) has tautomers represented by the following formulas (7) and (8) as shown in the following figure. The body is also within the scope of the present invention.

［式（７）及び（８）中のＲ₁乃至Ｒ₁₀、Ｌ₁、Ｌ₂は式（１）におけるＲ₁乃至Ｒ₁₀、Ｌ₁、Ｌ₂と各々同義である。］

[R ₁ to R _10, L _1, L ₂ in Formula (7) and (8) are each synonymous with R ₁ through R _10, L _1, L ₂ in Formula (1). ]

  The azo skeleton unit represented by the above formula (1) according to the present invention can be synthesized according to a known method. An example of a synthesis scheme up to the azo compound intermediate (13) is shown below.

［式（９）乃至（１３）中のＲ₁乃至Ｒ₁₀は、上記式（１）と同意義を表す。式（１０）中のＸ₁は脱離基を表す。式（９）及び（１３）中のＸ₂は、反応して上記式（１）における連結基Ｌ₁を形成する置換基を表す。］

[R _{1 to} R _{10 in} Formulas (9) to (13) have the same meaning as in Formula (1) above. X ₁ in the formula (10) represents a leaving group. X ₂ in the formulas (9) and (13) represents a substituent that reacts to form the linking group L ₁ in the above formula (1). ]

  In the scheme exemplified above, Step 1 of amidating an aniline derivative represented by Formula (9) and an acetoacetate analog represented by Formula (10) to synthesize an intermediate (11) that is an acetoacetanilide analog 1 The intermediate (11) and the aniline derivative (12) are diazo-coupled to synthesize the azo compound (13), thereby synthesizing the azo compound intermediate (13).

First, step 1 will be described. In Step 1, a known method can be used [eg, Datta E. Ponde, et al., “The Journal of Organic Chemistry” (USA), American Chemical Society, 1998, Vol. 63, No. 4, pages 1058-1063]. In addition, when R ₁ in formula (11) is a methyl group, it can be synthesized by a method using diketene instead of the raw material (10) [for example, Kiran Kumar Solinguram Sai, two others, “The Journal of Organic Chemistry "(USA), American Chemical Society, 2007, Vol. 72, No. 25, pages 9761-9964].

  The aniline derivative (9) and the acetoacetic acid analog (10) are each commercially available and can be easily obtained. Further, it can be easily synthesized by a known method.

  Although this step can be performed without a solvent, it is preferably performed in the presence of a solvent in order to prevent rapid progress of the reaction. The solvent is not particularly limited as long as it does not inhibit the reaction. For example, alcohols such as methanol, ethanol and propanol, esters such as methyl acetate, ethyl acetate and propyl acetate, diethyl ether and tetrahydrofuran , Ethers such as dioxane, hydrocarbons such as benzene, toluene, xylene, hexane and heptane, halogen-containing hydrocarbons such as dichloromethane, dichloroethane and chloroform, N, N-dimethylformamide, N, N-dimethylimidazolidinone Amides such as acetonitrile, nitriles such as acetonitrile and propionitrile, acids such as formic acid, acetic acid and propionic acid, water and the like. In addition, two or more of the above solvents can be used as a mixture, and the mixing ratio at the time of mixing and use can be arbitrarily determined according to the solubility of the substrate. Although the usage-amount of the said solvent can be defined arbitrarily, the range of 1.0 thru | or 20 mass times is preferable with respect to the compound represented by the said Formula (9) at the point of reaction rate.

  This step is usually performed in a temperature range of 0 ° C. to 250 ° C. and is usually completed within 24 hours.

  Next, step 2 will be described. In step 2, a known method can be used. Specifically, the method shown below is mentioned, for example. First, the corresponding diazonium salt is synthesized by reacting the aniline derivative (12) with a diazotizing agent such as sodium nitrite or nitrosylsulfuric acid in a methanol solvent in the presence of an inorganic acid such as hydrochloric acid or sulfuric acid. Further, this diazonium salt is coupled with intermediate (11) to synthesize azo compound (13).

  The said aniline derivative (12) is marketed variously and can be obtained easily. Further, it can be easily synthesized by a known method.

  Although this step can be performed without a solvent, it is preferably performed in the presence of a solvent in order to prevent rapid progress of the reaction. The solvent is not particularly limited as long as it does not inhibit the reaction. For example, alcohols such as methanol, ethanol and propanol, esters such as methyl acetate, ethyl acetate and propyl acetate, diethyl ether and tetrahydrofuran , Ethers such as dioxane, hydrocarbons such as benzene, toluene, xylene, hexane and heptane, halogen-containing hydrocarbons such as dichloromethane, dichloroethane and chloroform, N, N-dimethylformamide, N, N-dimethylimidazolidinone Amides such as acetonitrile, nitriles such as acetonitrile and propionitrile, acids such as formic acid, acetic acid and propionic acid, water and the like. In addition, two or more of the above solvents can be used as a mixture, and the mixing ratio at the time of mixing and use can be arbitrarily determined according to the solubility of the substrate. Although the usage-amount of the said solvent can be defined arbitrarily, the range of 1.0 thru | or 20 mass times is preferable with respect to the compound represented by the said Formula (12) at the point of reaction rate.

  This step is usually performed in a temperature range of −50 ° C. to 100 ° C. and is usually completed within 24 hours.

  Examples of the method for synthesizing the compound having the azo skeleton unit represented by the above formula (1) from the obtained bisazo compound intermediate (13) include the methods shown in the following (i) to (ii). .

  First, the method (i) will be described in detail with a scheme shown below.

［式（１３）乃至（１５）中のＲ₁乃至Ｒ₁₀は、上記式（１）と同意義を表す。式（１３）及び（１４）中のＸ_2、Ｘ₃は、反応して上記式（１）における連結基Ｌ₁を形成する置換基を表す。式（１４）及び（１５）中のＸ₄は反応して上記式（１）における連結基Ｌ₂を形成する置換基を表す。Ｐ₁は、少なくとも上記式（２）もしくは（３）で表される単量体単位のいずれか、もしくは両方を有する高分子樹脂ユニットを表す。］

[R _{1 to} R _{10 in} Formulas (13) to (15) are as defined above in Formula (1). X _{2 and} X ₃ in the formulas (13) and (14) represent a substituent that reacts to form the linking group L ₁ in the formula (1). X ₄ in the formulas (14) and (15) represents a substituent which reacts to form the linking group L ₂ in the above formula (1). P ₁ represents a polymer resin unit having at least _one of the monomer units represented by the above formula (2) or (3) or both. ]

First, step 3 will be described. In step 3, a known method can be used. Specifically, for example, by using an azo compound (13) in which X ₂ is a substituent having an amino group and a raw material in which X ₃ in formula (14) is a substituent having a carboxyl group, the linking group L An azo skeleton unit represented by the above formula (1) in which ₁ has a —NH—CO— bond can be synthesized. Further, by using the azo compound (13) in which X ₂ is a substituent having a hydroxyl group and a raw material in which X ₃ in the formula (14) is a substituent having a carboxyl group, the linking group L ₁ is —O—. An azo skeleton unit represented by the above formula (1) having a CO-bond can be synthesized. Further, by using the azo compound (13) in which X ₂ is a substituent having a carboxyl group and a raw material in which X ₃ in the formula (14) is a substituent having a hydroxyl group, the linking group L ₁ is —CO—. An azo skeleton unit represented by the above formula (1) having an O-bond can be synthesized. Further, by using the azo compound (13) in which X ₂ is a substituent having a carboxyl group and a raw material in which X ₃ in the formula (14) is a substituent having an amino group, the linking group L ₁ is —CO—. An azo skeleton unit represented by the above formula (1) having an NH-bond can be synthesized. Further, the azo compound (13) in which X ₂ is a substituent having —O—C ₂ H ₄ —OH and a raw material in which X ₃ in the formula (14) is a substituent having a carboxyl group are linked. The azo skeleton unit represented by the above formula (1) in which the group L ₁ has a —O—C ₂ H ₄ —O—CO— bond can be synthesized. Specifically, a method using a dehydrating condensing agent such as 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (for example, Melvin S. Newman, et al., “The Journal of Organic Chemistry”). ", (USA), American Chemical Society, 1961, Vol. 26, No. 7, p. 2525-2528), the Schotten-Baumann method (e.g. Norman O. V. Sontag," Chemical Reviews ", (USA)). , American Chemical Society, 1953, Vol. 52, No. 2, p. 237-416).

Further, the linking group L ₁ is —NH— by using an azo compound (13) in which X ₂ is a substituent having an amino group and a raw material in which X ₃ in the formula (14) is a substituent having an isocyanate group. An azo skeleton unit represented by the above formula (1) having a CO—NH— bond can be synthesized. Further, the linking group L ₁ is —O— by using an azo compound (13) in which X ₂ is a substituent having a hydroxyl group and a raw material in which X ₃ in the formula (14) is a substituent having an isocyanate group. An azo skeleton unit represented by the above formula (1) having a CO—NH— bond can be synthesized. Specific examples of the method using these isocyanate groups include a method using an amine catalyst such as triethylamine.

  Although this step can be performed without a solvent, it is preferably performed in the presence of a solvent in order to prevent rapid progress of the reaction. The solvent is not particularly limited as long as it does not inhibit the reaction. For example, ethers such as diethyl ether, tetrahydrofuran and dioxane, hydrocarbons such as benzene, toluene, xylene, hexane and heptane, dichloromethane Halogen-containing hydrocarbons such as dichloroethane and chloroform, amides such as N, N-dimethylformamide and N, N-dimethylimidazolidinone, and nitriles such as acetonitrile and propionitrile. Moreover, the said solvent can be used in mixture of 2 or more types according to the solubility of a board | substrate, The mixing ratio in the case of mixing use can be defined arbitrarily. Although the usage-amount of the said solvent can be defined arbitrarily, the range of 1.0 thru | or 20 mass times is preferable with respect to the compound represented with the said General formula (13) at the point of reaction rate.

  This step is usually performed in a temperature range of 0 ° C. to 250 ° C. and is usually completed within 24 hours.

Next, a method for synthesizing the polymer resin unit P ₁ used in step 4 will be described. In the synthesis of the polymer resin unit P ₁ , a known polymerization method can be used [for example, Krzysztof Matyjazewski, et al., “Chemical Reviews” (USA), American Chemical Society, 2001, 101, 2921-90. ].

  Specific examples include radical polymerization, cationic polymerization, and anionic polymerization. From the viewpoint of ease of production, radical polymerization is preferably used.

  The radical polymerization can be performed by using a radical polymerization initiator, irradiation with radiation, laser light, or the like, combined use of a photopolymerization initiator and light, heating, or the like.

  The radical polymerization initiator is not particularly limited as long as it can generate radicals and initiate a polymerization reaction, and is selected from compounds that generate radicals by the action of heat, light, radiation, redox reaction, and the like. For example, an azo compound, an organic peroxide, an inorganic peroxide, an organometallic compound, a photopolymerization initiator, and the like can be given. More specifically, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethyl) Valeronitrile), azo polymerization initiators such as 2,2′-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, di-tert-butyl peroxide, tert-butyl peroxyisopropyl carbonate, tert-to Organic peroxide polymerization initiators such as xylperoxybenzoate and tert-butylperoxybenzoate, inorganic peroxide polymerization initiators such as potassium persulfate and ammonium persulfate, hydrogen peroxide-ferrous iron, peroxide Examples thereof include redox initiators such as benzoyl-dimethylaniline and cerium (IV) salt-alcohol. Examples of the photopolymerization initiator include benzophenone series, benzoin series, acetophenone series, and thioxanthone series. These radical polymerization initiators may be used in combination of two or more.

  The amount of the polymerization initiator used here is in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass of the monomer, and the amount is adjusted so that a copolymer having a target molecular weight distribution can be obtained. It is preferable to do this.

The polymer resin unit represented by P ₁ can be produced by any method such as solution polymerization, suspension polymerization, emulsion polymerization, dispersion polymerization, precipitation polymerization, bulk polymerization, etc., and is particularly limited. However, solution polymerization in a solvent capable of dissolving each component used in production is preferred. Specifically, for example, alcohols such as methanol, ethanol and 2-propanol, ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran and diethyl ether, ethylene glycol monoalkyl ethers, or acetates thereof, propylene glycol Polar organic solvents such as monoalkyl ethers or their acetates and diethylene glycol monoalkyl ethers, and nonpolar solvents such as toluene and xylene may be used alone or in admixture. Among these, it is more preferable to use a solvent having a boiling point of 100 to 180 ° C. alone or in combination.

  The preferred range of the polymerization temperature varies depending on the type of radical polymerization reaction. Specifically, polymerization is generally performed in a temperature range of −30 to 200 ° C., and a more preferable temperature range is 40 to 180 ° C.

The polymer resin unit represented by P ₁ can control the molecular weight distribution and the molecular structure using a known method. Specifically, for example, a method using an addition-cleavage type chain transfer agent (see Japanese Patent No. 4254292 and Japanese Patent No. 0372617), an NMP method using amine oxide radical dissociation and bonding [for example, Craig J . Hawker, et al., “Chemical Reviews” (USA), American Chemical Society, 2001, Vol. 101, pages 3661-3688], an ATRP method in which a halogen compound is used as a polymerization initiator and polymerization is performed using a heavy metal and a ligand. [For example, Masami Kamigaito, two others, “Chemical Reviews” (USA), American Chemical Society, 2001, Vol. 101, pages 3687-3746], dithiocarboxylic acid ester, xanthate compound, etc. are used as polymerization initiators. RAFT method (for example, Japanese translations of PCT publication No. 2000-515181), MADIX method (for example, WO99 / 05099 pamphlet), DT method [for example, Atsushi G oto, et al., “Journal of The American. Chemical. Society” (USA), American Chemical Society, 2003, Vol. 125, pages 8720-8721], etc. are used to control molecular weight distribution and molecular structure. The polymer resin unit can be manufactured.

Next, step 4 will be described. In step 4, a known method can be used. Specifically, for example, by using a polymer resin unit P ₁ having a carboxyl group and a raw material in which X ₄ in the formula (14) is a substituent having an amino group, the linking group L ₂ is bonded to a carboxylic acid amide bond. It is possible to synthesize a compound having an azo dye skeleton unit represented by the above formula (1). Further, by using a polymer resin unit P ₁ having a carboxyl group and a raw material in which X ₄ in the formula (14) is a substituent having a hydroxyl group, the linking group L ₂ has the above-described formula ( A compound having an azo dye skeleton unit represented by 1) can be synthesized. Specifically, a compound having an azo dye skeleton unit can be synthesized using the same method as in Step 3 above.

  Next, the method (ii) will be described in detail with the scheme shown below.

［式（１３）中のＲ₁乃至Ｒ₁₀は、上記式（１）と同意義を表す。式（１３）乃至（１８）中のＸ_2、Ｘ₃は、反応して上記式（１）における連結基Ｌ₁を形成する置換基を表す。式（１４）及び（１６）中のＸ₄、Ｘ₅は反応して上記式（１）における連結基Ｌ₂を形成する置換基を表す。式（１６）及び式（１７）中のＡは、Ａは、塩素原子、臭素原子、ヨウ素原子を有する置換基、もしくは重合性基を有する置換基を表す。Ｐ₁は、少なくとも上記式（２）もしくは（３）で表される単量体単位のいずれか、もしくは両方を有する高分子樹脂ユニットを表す。］

[R _{1 to} R _{10 in} Formula (13) represent the same meaning as in Formula (1) above. X _{2 and} X ₃ in the formulas (13) to (18) represent a substituent that reacts to form the linking group L ₁ in the formula (1). X ₄ and X _{5 in the} formulas (14) and (16) represent a substituent that reacts to form the linking group L ₂ in the formula (1). A in Formula (16) and Formula (17) represents a substituent having a chlorine atom, a bromine atom or an iodine atom, or a substituent having a polymerizable group. P ₁ represents a polymer resin unit having at least _one of the monomer units represented by the above formula (2) or (3) or both. ]

In the scheme exemplified above, Step 6 in which the raw material (14) and the raw material (16) are esterified or amidated to synthesize the intermediate (17), A in the intermediate (17) is used as an initiator, or Step 7 for polymerizing intermediate polymer resin unit (18) having either or both of the monomer units represented by formula (2) or (3) as a monomer, X _{2 in} formula (13) And X3 in the formula (18) react to form a linking group L ₂ to synthesize a compound having an azo dye skeleton unit.

  First, step 6 will be described. In step 6, intermediate (17) can be synthesized using the same method as in step 4 of method (i) above.

Specifically, for example, by using a compound (14) in which X ₄ is a substituent having an amino group and X ₅ is a carboxylic acid derivative (16), an intermediate in which the linking group L ₂ has a carboxylic acid amide bond. (17) can be synthesized. Further, by using the compound (14) in which X ₄ is a substituent having a hydroxyl group and X ₅ is a carboxylic acid derivative (16), an intermediate (17) in which the linking group L ₂ has a carboxylic acid ester bond is obtained. Can be synthesized. Further, by using the compound (14) in which X ₄ is a substituent having a carboxyl group or an acid derivative group thereof and X ₅ is an alcohol derivative (16), an intermediate in which the linking group L ₂ has a carboxylic acid ester bond. (17) can be synthesized.

  Examples of the carboxylic acid derivative (16) include chloroacetic acid, α-chloropropionic acid, α-chlorobutyric acid, α-chloroisobutyric acid, α-chlorovaleric acid, α-chloroisovaleric acid, α-chlorocaproic acid, α- Chlorophenylacetic acid, α-chlorodiphenylacetic acid, α-chloro-α-phenylpropionic acid, α-chloro-β-phenylpropionic acid, bromoacetic acid, α-bromopropionic acid, α-bromobutyric acid, α-bromoisobutyric acid, α- Bromovaleric acid, α-bromoisovaleric acid, α-bromocaproic acid, α-bromophenylacetic acid, α-bromodiphenylacetic acid, α-bromo-α-phenylpropionic acid, α-bromo-β-phenylpropionic acid, iodoacetic acid , Α-iodopropionic acid, α-iodobutyric acid, α-iodoisobutyric acid, α-iodovaleric acid, α-iodoisovaleric acid, α-iodo Proic acid, α-iodophenylacetic acid, α-iododiphenylacetic acid, α-iodo-α-phenylpropionic acid, α-iodo-β-phenylpropionic acid, β-chlorobutyric acid, β-bromoisobutyric acid, iododimethylmethylbenzoic acid And halogen atom-containing compounds such as 1-chloroethylbenzoic acid, and polymerizable group-containing compounds such as acrylic acid, methacrylic acid, vinylbenzoic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, and cinnamic acid. In the present invention, acid halides and acid anhydrides of these carboxylic acid derivatives can be used in the same manner.

  Examples of the alcohol derivative (16) include 1-chloroethanol, 1-bromoethanol, 1-iodoethanol, 1-chloropropanol, 2-bromopropanol, 2-chloro-2-propanol, 2-bromo-2- Examples include halogen atom-containing compounds such as methylpropanol, 2-phenyl-1-bromoethanol and 2-phenyl-2-iodoethanol, and polymerizable group-containing compounds such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate. .

Next, step 7 will be described. In step 7, the polymer resin unit represented by the formula (18) can be synthesized using the same method as the synthesis of the polymer resin unit P _{1 in} the method (i).

  Next, step 8 will be described. In step 8, a known method can be used. Specifically, a compound having an azo dye skeleton unit can be synthesized using the same method as in step 3 of the above method (i).

  The compounds represented by the above formulas (1), (11), (13), (15), (17), and (18) obtained in each step use ordinary organic compound isolation and purification methods. be able to. Examples of isolation and purification methods include recrystallization methods and reprecipitation methods using organic solvents, column chromatography using silica gel, and the like. By purifying these methods alone or in combination of two or more, it can be obtained with high purity.

  The compounds represented by the above formulas (11), (13), (15), and (17) obtained in the above steps are analyzed by nuclear magnetic resonance spectroscopy [ECA-400, manufactured by JEOL Ltd.], ESI. -Identification and quantification were performed by TOF MS (LC / MSD TOF, manufactured by Agilent Technologies) and HPLC analysis [LC-20A, manufactured by Shimadzu Corporation].

  The compounds represented by the above formulas (1) and (18) obtained in the above steps are high-speed GPC [HLC8220GPC, manufactured by Tosoh Corporation], nuclear magnetic resonance spectroscopy [ECA-400, JEOL Ltd. The product was identified and quantified by acid value measurement [automatic titration measuring device COM-2500, manufactured by Hiranuma Sangyo Co., Ltd.] based on JIS K-0070.

  Next, the toner binder resin of the present invention will be described.

  Examples of the binder resin of the toner of the present invention include commonly used styrene-methacrylic acid copolymers, styrene-acrylic acid copolymers, polyester resins, epoxy resins, and styrene-butadiene copolymers. In a method for directly obtaining toner particles by a polymerization method, a monomer for forming them is used. Specific examples include styrene-based monomers such as styrene, α-methylstyrene, α-ethylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, and p-ethylstyrene. Mer, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, octyl methacrylate, dodecyl methacrylate, stearyl methacrylate, behenyl methacrylate, 2-ethylhexyl methacrylate, dimethylaminoethyl methacrylate, diethylamino methacrylate Methacrylate monomers such as ethyl, methacrylonitrile, methacrylamide, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, octyl acrylate, dodecyl acrylate, stear acrylate Preferred are acrylate monomers such as ril, behenyl acrylate, 2-ethylhexyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate, acrylonitrile, acrylamide, and olefin monomers such as butadiene, isoprene, and cyclohexene. Used. These may be used alone or by appropriately mixing monomers so that the theoretical glass transition temperature (Tg) is in the range of 40 to 75 ° C. [J. Brandrup, E.I. H. Immergut, “Polymer Handbook”, (USA), 3rd edition, John Wiley & Sons, 1989, 209-277]. When the theoretical glass transition temperature is less than 40 ° C., problems are likely to occur from the viewpoint of storage stability and durability stability of the toner. On the other hand, when it exceeds 75 ° C., the transparency decreases in the case of full-color image formation of the toner.

  The binder resin in the toner of the present invention uses a non-polar resin such as polystyrene in combination with a polar resin such as a polyester resin or polycarbonate resin, so that the distribution of additives such as colorants, charge control agents, and waxes in the toner is distributed. Can be controlled. For example, when the toner particles are directly produced by suspension polymerization or the like, the polar resin is added during the polymerization reaction from the dispersion step to the polymerization step. The polar resin is added according to the balance of the polarities of the polymerizable monomer composition that becomes toner particles and the aqueous medium. As a result, the resin concentration can be controlled to continuously change from the toner particle surface toward the center, for example, the polar resin forms a thin layer on the surface of the toner particle. At this time, by using a polar resin that interacts with the polyester having the bisazo dye skeleton unit, the colorant, and the charge control agent, the state of the colorant in the toner particles can be brought into a desired form. It is.

  Examples of the azo pigment that can be used in the toner of the present invention include a monoazo pigment, a bisazo pigment, and a polyazo pigment. Among them, C.I. I. Pigment Yellow 74, C.I. I. Pigment Yellow 93, C.I. I. Pigment Yellow 128, C.I. I. Pigment Yellow 155, C.I. I. Pigment Yellow 175, C.I. I. An acetoacetanilide pigment typified by Pigment Yellow 180 has a stronger affinity with the compound having the bisazo dye skeleton unit. In particular, C.I represented by the following formula (6): I. Pigment Yellow 155 is more preferable because the dispersion effect of the compound having the bisazo dye skeleton unit is high. The above pigments may be used alone or in combination of two or more.

  In addition, as a pigment that can be used in the present invention, a pigment other than the pigment as described above can be suitably used as long as it is compatible with the compound having the azo dye skeleton unit, and is not limited. .

  For example, C.I. I. Pigment Orange 1, C.I. I. Pigment Orange 5, C.I. I. Pigment Orange 13, C.I. I. Pigment Orange 15, C.I. I. Pigment Orange 16, C.I. I. Pigment Orange 34, C.I. I. Pigment Orange 36, C.I. I. Pigment Orange 38, C.I. I. Pigment Orange 62, C.I. I. Pigment Orange 64, C.I. I. Pigment Orange 67, C.I. I. Pigment Orange 72, C.I. I. Pigment Orange 74, C.I. I. Pigment Red 2, C.I. I. Pigment Red 3, C.I. I. Pigment Red 4, C.I. I. Pigment Red 5, C.I. I. Pigment Red 12, C.I. I. Pigment Red 16, C.I. I. Pigment Red 17, C.I. I. Pigment Red 23, C.I. I. Pigment Red 31, C.I. I. Pigment Red 32, C.I. I. Pigment Red 41, C.I. I. Pigment Red 17, C.I. I. Pigment Red 48, C.I. I. Pigment Red 48: 1, C.I. I. Pigment Red 48: 2, C.I. I. Pigment Red 53: 1, C.I. I. Pigment Red 57: 1, C.I. I. Pigment Red 112, C.I. I. Pigment Red 144, C.I. I. Pigment Red 146, C.I. I. Pigment Red 166, C.I. I. Pigment Red 170, C.I. I. Pigment Red 176, C.I. I. Pigment Red 185, C.I. I. Pigment Red 187, C.I. I. Pigment Red 208, C.I. I. Pigment Red 210, C.I. I. Pigment Red 220, C.I. I. Pigment Red 221, C.I. I. Pigment Red 238, C.I. I. Pigment Red 242, C.I. I. Pigment Red 245, C.I. I. Pigment Red 253, C.I. I. Pigment Red 258, C.I. I. Pigment Red 266, C.I. I. Pigment Red 269, C.I. I. Pigment Violet 13, C.I. I. Pigment Violet 25, C.I. I. Pigment Violet 32, C.I. I. Pigment Violet 50, C.I. I. Pigment Blue 25, C.I. I. Pigment Blue 26, C.I. I. Pigment Brown 23, C.I. I. Pigment Brown 25, C.I. I. And azo pigments such as Pigment Brown 41.

  These may be crude pigments, or may be prepared pigment compositions as long as they do not significantly inhibit the effect of the compound having an azo dye skeleton unit.

  The mass composition ratio of the pigment and the compound having an azo dye skeleton unit in the toner of the present invention is preferably in the range of 100: 1 to 100: 100. More preferably, it is a range of 100: 3 to 100: 50 in terms of pigment dispersibility.

  As the colorant of the toner used in the present invention, the above azo pigment is always used, but the above pigment and another colorant can be used in combination as long as the dispersibility of the azo pigment is not impaired.

  Examples of the colorant that can be used in combination include various compounds such as condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and compounds represented by allylamide compounds. Specifically, C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 15, C.I. I. Pigment Yellow 17, C.I. I. Pigment Yellow 62, C.I. I. Pigment Yellow 83, C.I. I. Pigment Yellow 94, C.I. I. Pigment Yellow 95, C.I. I. Pigment Yellow 97, C.I. I. Pigment Yellow 109, C.I. I. Pigment Yellow 110, C.I. I. Pigment Yellow 111, C.I. I. Pigment Yellow 120, C.I. I. Pigment Yellow 127, C.I. I. Pigment Yellow 129, C.I. I. Pigment Yellow 147, C.I. I. Pigment Yellow 151, C.I. I. Pigment Yellow 154, C.I. I. Pigment Yellow 168, C.I. I. Pigment Yellow 174, C.I. I. Pigment Yellow 176, C.I. I. Pigment Yellow 181, C.I. I. Pigment Yellow 185, C.I. I. Pigment Yellow 191, C.I. I. Pigment Yellow 194, C.I. I. Pigment Yellow 213, C.I. I. Pigment Yellow 214, C.I. I. Bat Yellow 1, 3, 20, Mineral Fast Yellow, Navel Yellow, Naphthol Yellow S, Hansa Yellow G, Permanent Yellow NCG, C.I. I. Solvent Yellow 9, C.I. I. Solvent Yellow 17, C.I. I. Solvent Yellow 24, C.I. I. Solvent Yellow 31, C.I. I. Solvent Yellow 35, C.I. I. Solvent Yellow 58, C.I. I. Solvent Yellow 93, C.I. I. Solvent Yellow 100, C.I. I. Solvent Yellow 102, C.I. I. Solvent Yellow 103, C.I. I. Solvent Yellow 105, C.I. I. Solvent Yellow 112, C.I. I. Solvent Yellow 162, C.I. I. Solvent Yellow 163 or the like can be used.

  Furthermore, in the present invention, a crosslinking agent can be used during the synthesis of the binder resin in order to increase the mechanical strength of the toner particles and to control the molecular weight of the particle constituent molecules.

  As the crosslinking agent used in the toner particles of the present invention, divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1 , 4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 diacrylate, dipropylene glycol diacrylate, polypropylene glycol diacrylate, polyester type diacrylate, and These diacrylate include those instead dimethacrylate.

  Polyfunctional crosslinkers include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate and its methacrylate, 2,2-bis (4-methacryloxyphenyl) Examples include propane, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate and triallyl trimellitate.

  These crosslinking agents are preferably in the range of 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the monomer, in terms of toner fixability and offset resistance. It is good to use in the range of the part.

  Furthermore, in the present invention, a wax component can be used during the synthesis of the binder resin in order to prevent adhesion to the fixing member.

  Specific examples of the wax component that can be used in the present invention include petroleum waxes such as paraffin wax, microcrystalline wax, petrolactam and derivatives thereof, montan wax and derivatives thereof, hydrocarbon waxes by Fischer-Tropsch method, and the derivatives thereof. Derivatives, polyolefin waxes typified by polyethylene and derivatives thereof, natural waxes such as carnauba wax and candelilla wax, and derivatives thereof include oxides, block copolymers with vinyl monomers, grafts, etc. Modified products are also included. Also included are alcohols such as higher aliphatic alcohols, fatty acids such as stearic acid and palmitic acid, fatty acid amides, fatty acid esters, hydrogenated castor oil and derivatives thereof, vegetable waxes and animal waxes. These can be used alone or in combination.

  The amount of the wax component added is preferably 2.5 to 15.0 parts by mass with respect to 100 parts by mass of the binder resin, more preferably 3.0 to 10.0 parts by mass. A range is more preferable. If the added amount of the wax component is less than 2.5 parts by mass, oilless fixing becomes difficult. If the added amount exceeds 15.0 parts by mass, the amount of the wax component in the toner particles is too large. It is not preferable because it is present on the surface in a large amount and may inhibit desired charging characteristics.

  In the toner of the present invention, a charge control agent can be mixed and used as necessary. This makes it possible to control the optimum triboelectric charge amount according to the development system.

  As the charge control agent, a known one can be used, and a charge control agent that has a high charging speed and can stably maintain a constant charge amount is particularly preferable. Furthermore, when the toner particles are produced by a direct polymerization method, a charge control agent having a low polymerization inhibitory property and substantially free from a solubilized product in an aqueous dispersion medium is particularly preferable.

  The charge control agent is, for example, a polymer or copolymer having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group, a salicylic acid derivative and a metal complex thereof, a monoazo metal compound, acetylacetone. Metal compounds, aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids, their metal salts, anhydrides, esters, phenol derivatives such as bisphenol, urea derivatives, metal-containing naphthoic acid compounds, boron compounds, quaternary Ammonium salts, calixarene, resin charge control agents and the like can be mentioned. Examples of toners that can be positively charged include nigrosine-modified products with nigrosine and fatty acid metal salts, guanidine compounds, imidazole compounds, tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoro. Quaternary ammonium salts such as borates, and onium salts such as phosphonium salts and analogs thereof, and lake lakes, triphenylmethane dyes and lake lakes (the rake agents include phosphotungstic acid and phosphomolybdic acid) Phosphotungstomolybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.), metal salts of higher fatty acids, dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide, etc. Ganoderma tin oxide, dibutyl tin borate, dioctyl tin borate, diorgano tin borate such as dicyclohexyl tin borate, resin charge control agent and the like. These can be used alone or in combination of two or more.

  In the toner of the present invention, an inorganic fine powder may be added to the toner particles as a fluidizing agent. As the inorganic fine powder, fine powder such as silica, titanium oxide, alumina, or a double oxide thereof, or a surface-treated product thereof can be used.

  Examples of the method for producing the toner particles constituting the toner of the present invention include conventionally used pulverization method, suspension polymerization method, suspension granulation method, emulsion polymerization method and the like. From the viewpoint of environmental load during production and controllability of the particle size, among these production methods, it is particularly preferable to obtain by a production method of granulating in an aqueous medium such as a suspension polymerization method or a suspension granulation method.

  In the method for producing the toner of the present invention, the dispersibility of the pigment is improved by preparing a pigment composition by previously mixing a compound having an azo dye skeleton unit represented by the above formula (1) with an azo pigment. Can be made.

  The pigment composition can be produced by a wet method or a dry method. Considering that the compound having an azo dye skeleton unit represented by the above formula (1) has high affinity with a water-insoluble solvent, production by a wet method capable of easily producing a uniform pigment composition is preferable. . Specifically, for example, it is obtained as follows. A compound having an azo dye skeleton unit in a dispersion medium, and a resin as necessary are dissolved, and the pigment powder is gradually added while stirring to fully adjust the dispersion medium. Furthermore, the pigment can be stably finely dispersed into uniform fine particles by applying mechanical shearing force with a disperser such as a kneader, roll mill, ball mill, paint shaker, dissolver, attritor, sand mill, or high speed mill.

  The dispersion medium that can be used in the pigment composition is not particularly limited, but in order to obtain a high pigment dispersion effect of the compound having an azo dye skeleton unit represented by the above formula (1), the dispersion medium is water-insoluble. A case of a solvent is preferred. Specific examples of the water-insoluble solvent include esters such as methyl acetate, ethyl acetate, and propyl acetate, hydrocarbons such as hexane, octane, petroleum ether, cyclohexane, benzene, toluene, and xylene, carbon tetrachloride, and trichloroethylene. And halogen-containing hydrocarbons such as tetrabromoethane.

  The dispersion medium that can be used in the pigment composition may be a polymerizable monomer. Specifically, styrene, α-methylstyrene, α-ethylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4- Dichlorostyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, ethylene, propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinyl bromide, vinyl iodide, vinyl acetate, vinyl propionate, vinyl benzoate, methyl methacrylate , Ethyl methacrylate, propyl methacrylate, butyl methacrylate, Methacrylic acid-n-octyl, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, behenyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, methyl acrylate, ethyl acrylate, acrylic Acid-n-butyl, isobutyl acrylate, propyl acrylate, acrylate-n-octyl, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, behenyl acrylate, 2-chloroethyl acrylate, phenyl acrylate , Vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone, vinyl naphthalene, acrylonitrile Methacrylonitrile, it can be mentioned acrylamide.

  As the resin that can be used in the pigment composition, a resin that can be used as the binder resin of the toner of the present invention can be used. Specific examples include styrene-methacrylic acid copolymers, styrene-acrylic acid copolymers, polyester resins, epoxy resins, and styrene-butadiene copolymers. Two or more of these dispersion media can be mixed and used. Further, the pigment composition can be isolated by a known method such as filtration, decantation or centrifugation. The solvent can also be removed by washing.

  An auxiliary agent may be further added to the pigment composition during production. Specifically, for example, surface active agents, pigments and non-pigment dispersants, fillers, standardizers, resins, waxes, antifoaming agents, antistatic agents, dustproofing agents, extenders, dark colorants ( shading colorants), preservatives, drying inhibitors, rheology control additives, wetting agents, antioxidants, UV absorbers, light stabilizers, or combinations thereof. The compound having the azo dye skeleton unit may be added in advance during the production of the crude pigment.

  The toner particles produced by the suspension polymerization method of the present invention are produced, for example, as follows. The above-mentioned pigment composition, polymerizable monomer, wax component, polymerization initiator and the like are mixed to prepare a polymerizable monomer composition. Next, the polymerizable monomer composition is dispersed in an aqueous medium to granulate particles of the polymerizable monomer composition. Then, the polymerizable monomer in the particles of the polymerizable monomer composition is polymerized in an aqueous medium to obtain toner particles.

  The polymerizable monomer composition in the above process is prepared by mixing a dispersion obtained by dispersing the pigment composition in the first polymerizable monomer with the second polymerizable monomer. Preferably there is. That is, after the pigment composition is sufficiently dispersed with the first polymerizable monomer, the pigment composition is mixed with the second polymerizable monomer together with the other toner materials, so that the pigment is in a better dispersion state. Can be present in the toner particles.

  Examples of the polymerization initiator used in the suspension polymerization method include known polymerization initiators such as azo compounds, organic peroxides, inorganic peroxides, organometallic compounds, and photopolymerization initiators. Can be mentioned. More specifically, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethyl) Valeronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), azo polymerization initiators such as dimethyl 2,2′-azobis (isobutyrate), benzoyl peroxide, ditert-butyl peroxide, tert -Organic peroxide polymerization initiators such as butyl peroxyisopropyl monocarbonate, tert-hexyl peroxybenzoate, tert-butyl peroxybenzoate, inorganic peroxide polymerization initiators such as potassium persulfate, ammonium persulfate, Hydrogen peroxide-ferrous, BPO-dimethylaniline, cerium (IV) salt-alcohol It includes redox initiators such is. Examples of the photopolymerization initiator include acetophenone series, benzoin ether series, and ketal series. These methods can be used alone or in combination of two or more.

  The concentration of the polymerization initiator is preferably in the range of 0.1 to 20 parts by mass, more preferably in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymerizable monomer. is there. The kind of the polymerizable initiator is slightly different depending on the polymerization method, but is used alone or in combination with reference to the 10-hour half-life temperature.

  The aqueous medium used in the suspension polymerization method preferably contains a dispersion stabilizer. As the dispersion stabilizer, known inorganic and organic dispersion stabilizers can be used. Examples of inorganic dispersion stabilizers include calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, and calcium sulfate. , Barium sulfate, bentonite, silica, alumina and the like. Examples of the organic dispersion stabilizer include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, starch and the like. Nonionic, anionic and cationic surfactants can also be used. For example, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate and the like can be mentioned.

  Among the above dispersion stabilizers, in the present invention, it is preferable to use a poorly water-soluble inorganic dispersion stabilizer that is soluble in an acid. In the present invention, when preparing an aqueous dispersion medium using a hardly water-soluble inorganic dispersion stabilizer, these dispersion stabilizers are added in an amount of 0.2 to 2 with respect to 100 parts by mass of the polymerizable monomer. From the viewpoint of droplet stability in the aqueous medium of the polymerizable monomer composition, it is preferable to use the monomer in a ratio of 0.0 part by mass. In the present invention, it is preferable to prepare an aqueous medium using water in the range of 300 to 3000 parts by mass with respect to 100 parts by mass of the polymerizable monomer composition.

  In the present invention, when preparing an aqueous medium in which the poorly water-soluble inorganic dispersion stabilizer is dispersed, a commercially available dispersion stabilizer may be used as it is, but a dispersion having a fine uniform particle size may be used. In order to obtain stabilizer particles, it is preferable to prepare by preparing the poorly water-soluble inorganic dispersion stabilizer under high-speed stirring in water. For example, when calcium phosphate is used as a dispersion stabilizer, a preferable dispersion stabilizer can be obtained by mixing a sodium phosphate aqueous solution and a calcium chloride aqueous solution under high speed stirring to form calcium phosphate fine particles.

  Even when the toner particles of the present invention are produced by suspension granulation, suitable toner particles can be obtained. Since the suspension granulation method does not have a heating step, it suppresses the compatibilization of the resin and the wax component that occurs when using a low-melting wax, and reduces the glass transition temperature of the toner due to the compatibilization. Can be prevented. In addition, the suspension granulation method has a wide range of options for the toner material used as the binder resin, and it is easy to use a polyester resin, which is generally advantageous for fixability, as a main component. Therefore, this is an advantageous production method for producing a toner having a resin composition to which the suspension polymerization method cannot be applied.

  The toner particles produced by the suspension granulation method are produced, for example, as follows. First, the pigment composition, the binder resin, the wax component and the like are mixed in a solvent to prepare a solvent composition. Next, the solvent composition is dispersed in an aqueous medium and particles of the solvent composition are granulated to obtain a toner particle suspension. Then, the toner particles can be obtained by heating the obtained suspension or removing the solvent by reducing the pressure.

  The solvent composition in the above step is preferably prepared by mixing a dispersion obtained by dispersing the pigment composition in the first solvent with the second solvent. That is, after the pigment composition is sufficiently dispersed in the first solvent, the pigment can be present in the toner particles in a better dispersion state by mixing with the second solvent together with other toner materials.

  Examples of the solvent that can be used in the suspension granulation method include hydrocarbons such as toluene, xylene, and hexane, halogen-containing hydrocarbons such as methylene chloride, chloroform, dichloroethane, trichloroethane, and carbon tetrachloride, methanol, Alcohols such as ethanol, butanol and isopropyl alcohol, polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol and triethylene glycol, cellosolves such as methyl cellosolve and ethyl cellosolve, and ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone , Ethers such as benzyl alcohol ethyl ether, benzyl alcohol isopropyl ether and tetrahydrofuran, and esters such as methyl acetate, ethyl acetate and butyl acetate. . These can be used alone or in admixture of two or more. Among these, in order to easily remove the solvent in the toner particle suspension, it is preferable to use a solvent having a low boiling point and capable of sufficiently dissolving the binder resin.

  The amount of the solvent used is preferably 50 to 5000 parts by mass, more preferably 120 to 1000 parts by mass with respect to 100 parts by mass of the binder resin.

  The aqueous medium used in the suspension granulation method preferably contains a dispersion stabilizer. As the dispersion stabilizer, known inorganic and organic dispersion stabilizers can be used. Examples of the inorganic dispersion stabilizer include calcium phosphate, calcium carbonate, aluminum hydroxide, calcium sulfate, and barium carbonate. Examples of organic dispersion stabilizers include polyvinyl alcohol, methylcellulose, hydroxyethylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, water-soluble polymers such as sodium polyacrylate and sodium polymethacrylate, sodium dodecylbenzenesulfonate, Anionic surfactants such as sodium octadecyl sulfate, sodium oleate, sodium laurate, potassium stearate, cationic surfactants such as laurylamine acetate, stearylamine acetate, lauryltrimethylammonium chloride, amphoteric such as lauryldimethylamine oxide Ionic surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene Surfactants such as nonionic surfactants down alkylamines, and the like.

  The amount of the dispersant used is in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the binder resin, from the viewpoint of droplet stability in the aqueous medium of the solvent composition. preferable.

  In the present invention, the preferred toner has a weight average particle diameter (hereinafter referred to as D4) in the range of 3.00 to 15.0 μm, and more preferably in the range of 4.00 to 12.0 μm. When D4 is less than 3.00 μm, it becomes difficult to achieve charging stabilization when applied to an electrophotographic development system, and fog and toner scattering are likely to occur in the continuous development operation (endurance operation) of a large number of sheets. . When D4 exceeds 15.0 μm, the reproducibility of the halftone portion is greatly lowered, and the obtained image becomes an image having irregularities on the surface, which is not preferable.

  Further, the ratio (hereinafter referred to as D4 / D1) of the toner D4 and the number average particle diameter (hereinafter referred to as D1) is 1.35 or less, preferably 1.30 or less. When D4 / D1 exceeds 1.35, fogging and transferability decrease, and high resolution is difficult to obtain.

  The toner D4 and D1 of the present invention have different adjustment methods depending on the toner particle manufacturing method. For example, in the case of the suspension polymerization method, it can be adjusted by controlling the concentration of the dispersing agent used at the time of preparing the aqueous dispersion medium, the reaction stirring speed, or the reaction stirring time.

  The toner of the present invention may be either magnetic toner or non-magnetic toner. When used as a magnetic toner, the toner particles constituting the toner of the present invention may be used by mixing magnetic materials. Examples of such magnetic materials include iron oxides such as magnetite, maghemite and ferrite, iron oxides including other metal oxides, metals such as Fe, Co and Ni, or these metals and Al, Co, Examples thereof include alloys with metals such as Cu, Pb, Mg, Ni, Sn, Zn, Sb, Be, Bi, Cd, Ca, Mn, Se, Ti, W, and V, and mixtures thereof.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example and a comparative example, this invention is not limited to the following Example, unless the summary is exceeded. In the following description, “parts” and “%” are based on mass unless otherwise specified.

  The measurement method used in this example is shown below.

(1) Molecular weight measurement The molecular weight of the compound having the polymer resin unit and the azo dye skeleton unit used in the present invention is calculated in terms of polystyrene by size exclusion chromatography (SEC). Measurement of molecular weight by SEC was performed as follows.

The sample was added to the eluent below so that the sample concentration was 1.0% by mass, and the solution that was allowed to stand at room temperature for 24 hours was filtered through a solvent-resistant membrane filter with a pore diameter of 0.2 μm as the sample solution. The measurement was performed under the following conditions.
Device: High-speed GPC device "HLC-8220GPC" [manufactured by Tosoh Corporation]
Column: Double eluent of LF-804: THF
Flow rate: 1.0 ml / min
Oven temperature: 40 ° C
Sample injection volume: 0.25 ml

  In calculating the molecular weight of the sample, standard polystyrene resin [TSO Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, manufactured by Tosoh Corporation] F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500] were used.

(2) Acid value measurement The acid value of the compound having the upper polymer resin unit and the azo dye skeleton unit is determined by the following method.

Basic operation is based on JIS K-0070.
1) Weigh accurately 0.5 to 2.0 g of sample. The mass at this time is defined as W (g).
2) Put the sample in a 50 ml beaker, and add 25 ml of a tetrahydrofuran / ethanol (2/1) mixture to dissolve.
3) Titration is performed using a 0.1 mol / l ethanol solution of KOH and a potentiometric titration measuring device [for example, an automatic titration measuring device “COM-2500” manufactured by Hiranuma Sangyo Co., Ltd. can be used. ].
4) The amount of KOH solution used at this time is S (ml). At the same time, a blank is measured, and the amount of KOH used at this time is defined as B (ml).
5) Calculate the acid value according to the following formula. f is a factor of the KOH solution.

(3) Composition analysis The structure of the polymer resin unit and the compound having an azo dye skeleton unit in the present invention was determined using the following apparatus.
¹ H NMR
ECA-400 manufactured by JEOL Ltd. (solvent heavy chloroform)

[Example 1]
The polymer resin unit represented by P ₁ was obtained by the following method.

<Synthesis example of polymer resin unit (1)>
A polymer resin unit (1) having an isophthalic acid moiety at the terminal and containing a monomer unit in which R ₁₄ in the above formula (2) is a hydrogen atom was produced according to the following method.

  In a four-necked flask, 10.0 parts of dimethyl 5-aminoisophthalate (69) and 5.00 parts of triethylamine were dissolved in 100.0 parts of chloroform and cooled to 10 ° C. or lower with ice. To this solution, 10.9 parts of 2-bromoisobutyric acid bromide (70) was added and stirred at room temperature for 12 hours. After completion of the reaction, the organic phase was washed with water, the solution was concentrated, methanol was added, and purification by recrystallization gave 9,58 parts of compound (71) (yield 57.1%).

  In a four-neck flask, 0.60 part of compound (71), 58.2 parts of styrene (72), N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine 0.60 part, copper bromide ( I) 0.24 parts and 5.00 parts of N, N-dimethylformamide were added and dissolved by stirring, and nitrogen bubbling was performed for 1 hour. Then, it heated up at 110 degreeC and stirred for 1 hour. After completion of the reaction, the reaction mixture was diluted with chloroform and the organic phase was washed with water. Then, the solution was concentrated, reprecipitated with methanol, and the deposited precipitate was separated by filtration to obtain Compound (73). 160.0 parts of dioxane was added to 20.0 parts of the obtained compound (73), dissolved by stirring, 6.00 parts of concentrated hydrochloric acid was added, and the mixture was refluxed at 120 ° C. for 7 hours. After completion of the reaction, the solution was concentrated, reprecipitated with methanol, and the precipitated precipitate was filtered to obtain a polymer resin unit (1). The obtained polymer resin unit (1) was subjected to physical property confirmation using the above apparatus. The analysis results are shown below.

[Result of analysis of polymer resin unit (1)]
[1] Results of molecular weight measurement (GPC):
Weight average molecular weight (Mw) = 10508, Number average molecular weight (Mn) = 9610
[2] Results of acid value measurement:
5.05mg KOH / g
[3] Results of ¹ H NMR (400 MHz, CDCl ₃ , room temperature):
δ [ppm] = 8.52 (s, 1H), 8.14 (d, 2H), 8.07 (t, 1H), 7.37-6.27 (m, 462H), 2.45-0 .77 (m, 277H)

<Synthesis example of polymer resin unit (2)>
A polymer resin unit (2) having a carboxylic acid moiety at the end and containing a monomer unit in which R ₁₄ in the above formula (2) is a hydrogen atom was produced according to the following method.

  In a four-necked flask, 0.30 part of ethyl 2-bromoisobutyrate (74), 60.0 parts of styrene (72), 5.00 parts of N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, bromide 0.24 parts of copper (I) and 5.0 parts of N, N-dimethylformamide were added and dissolved by stirring, and nitrogen bubbling was performed for 1 hour. Then, it heated up at 110 degreeC and stirred for 2 hours. After completion of the reaction, the reaction mixture was diluted with chloroform and the organic phase was washed with water. Then, the solution was concentrated, reprecipitated with methanol, and the deposited precipitate was separated by filtration to obtain a compound (75). To 20.0 parts of the obtained compound (75), 160.0 parts of dioxane was added and dissolved by stirring, 6.00 parts of concentrated hydrochloric acid was added, and the mixture was refluxed at 120 ° C. for 7 hours. After completion of the reaction, the solution was concentrated, reprecipitated with methanol, and the precipitated precipitate was filtered to obtain a polymer resin unit (2). The obtained polymer resin unit (2) was subjected to physical property confirmation by the above apparatus. The analysis results are shown below.

[Result of analysis of polymer resin unit (2)]
[1] Results of molecular weight measurement (GPC):
Weight average molecular weight (Mw) = 37367, number average molecular weight (Mn) = 29626
[2] Results of acid value measurement:
3.05mgKOH / g
[3] Results of ¹ H NMR (400 MHz, CDCl ₃ , room temperature):
[delta] [ppm] = 7.37-6.27 (m, 1430H), 2.45-0.77 (m, 858H)

<Synthesis example of polymer resin unit (3)>
A monomer unit having a carboxylic acid moiety at the end, wherein R ₁₄ in the above formula (2) is represented by a hydrogen atom, and R ₁₅ in the above formula (3) is represented by a hydrogen atom and R ₁₆ is represented by a hydrogen atom. A polymer resin unit (3) containing monomer units was produced according to the following method.

  In a four-necked flask, 1.85 parts of methyl 2-bromopropionate (76), 35.2 parts of t-butyl acrylate (77), N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine 80 parts, 1.54 parts of copper (I) bromide and 250 parts of N, N-dimethylformamide were added and dissolved by stirring, and nitrogen bubbling was performed for 1 hour. Then, it heated up at 70 degreeC and stirred for 20 minutes. After completion of the reaction, the reaction mixture was diluted with chloroform and the organic phase was washed with water. The solution was then concentrated and dried with a vacuum pump to obtain a tert-butyl acrylate polymer.

  In a four-necked flask, 4.00 parts of tert-butyl acrylate polymer, 42.0 parts of styrene (72), 0.63 parts of N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, copper bromide ( I) 0.26 part and 10.0 part of N, N-dimethylformamide were added and dissolved by stirring, and nitrogen bubbling was performed for 1 hour. Then, it heated up at 110 degreeC and stirred for 1 hour. After completion of the reaction, the reaction mixture was diluted with chloroform and the organic phase was washed with water. Then, the solution was concentrated, reprecipitated with methanol, and the deposited precipitate was separated by filtration to obtain Compound (78). To 20.0 parts of the obtained compound (78), 160.0 parts of dioxane was added and dissolved by stirring, 6.00 parts of concentrated hydrochloric acid was added, and the mixture was refluxed at 120 ° C. for 7 hours. After completion of the reaction, the solution was concentrated, reprecipitated with methanol, and the deposited precipitate was filtered off to obtain a polymer resin unit (3). The obtained polymer resin unit (3) was subjected to physical property confirmation by the above apparatus. The analysis results are shown below.

[Analysis results of polymer resin unit (3)]
[1] Results of molecular weight measurement (GPC):
Weight average molecular weight (Mw) = 16802, number average molecular weight (Mn) = 10230
[2] Results of acid value measurement:
40.2mgKOH / g
[3] Results of ¹ H NMR (400 MHz, CDCl ₃ , room temperature):
δ [ppm] = 7.37-6.27 (m, 713H), 2.45-0.77 (m, 428H)

<Synthesis example of polymer resin unit (4)>
A polymer resin unit (4) having a carboxylic acid moiety at the terminal and containing a monomer unit in which R ₁₄ in the above formula (2) is a hydrogen atom was produced according to the following method.

  100 parts of propylene glycol monomethyl ether was heated while being purged with nitrogen, and refluxed at a liquid temperature of 120 ° C. or higher. To this solution, 100 parts of styrene (72), 1.2 parts of β-mercaptopropionic acid (79) and tert-butyl peroxybenzoate [Organic peroxide polymerization initiator Perbutyl Z (registered trademark) (manufactured by NOF Corporation) A mixture of 1.0 part was added dropwise over 3 hours, and after completion of the addition, the solution was stirred for 3 hours. Distilling at atmospheric pressure while raising the liquid temperature to 170 ° C, and after the liquid temperature reached 170 ° C, the solvent was distilled off at 1 hPa under reduced pressure for 1 hour to obtain a polymer solid. The solid was dissolved in tetrahydrofuran, reprecipitated with n-hexane, and the precipitated solid was separated by filtration to obtain a polymer resin unit (4). The obtained polymer resin unit (4) was subjected to physical property confirmation using the above apparatus. The analysis results are shown below.

[Result of analysis of polymer resin unit (4)]
[1] Results of molecular weight measurement (GPC):
Weight average molecular weight (Mw) = 25303, number average molecular weight (Mn) = 10450
[2] Results of acid value measurement:
5.0mgKOH / g
[3] Results of ¹ H NMR (400 MHz, CDCl ₃ , room temperature):
[delta] [ppm] = 7.37-6.27 (m, 500H), 2.45-0.77 (m, 300H)

<Synthesis example of polymer resin unit (5)>
A monomer unit in which R ₁₄ in the above formula (2) is a hydrogen atom and a monomer unit in which R ₁₅ in the above formula (3) is a hydrogen atom, R ₁₆ is a hydrogen atom and an n-butyl group A polymer resin unit (5) containing units was produced according to the following method.

  100 parts of propylene glycol monomethyl ether was heated while being purged with nitrogen, and refluxed at a liquid temperature of 120 ° C. or higher. To this solution, 152 parts of styrene (72), 38 parts of n-butyl acrylate (80), 10 parts of acrylic acid (81), and tert-butyl peroxybenzoate [organic peroxide polymerization initiator perbutyl Z (trademark registration) ) (Manufactured by NOF Corporation)] A mixture of 1.0 part was added dropwise over 3 hours, and after completion of the addition, the solution was stirred for 3 hours. Distilling at atmospheric pressure while raising the liquid temperature to 170 ° C, and after the liquid temperature reached 170 ° C, the solvent was distilled off at 1 hPa under reduced pressure for 1 hour to obtain a polymer solid. The solid was dissolved in tetrahydrofuran, reprecipitated with n-hexane, and the precipitated solid was separated by filtration to obtain a polymer resin unit (5). The obtained polymer resin unit (5) was subjected to physical property confirmation by the above apparatus. The analysis results are shown below.

[Result of analysis of polymer resin unit (5)]
[1] Results of molecular weight measurement (GPC):
Weight average molecular weight (Mw) = 36820, Number average molecular weight (Mn) = 19530
[2] Results of acid value measurement:
36.0 mgKOH / g
[3] Results of ¹ H NMR (400 MHz, CDCl ₃ , room temperature):
[delta] [ppm] = 7.37-6.27 (m, 695H), 3.98 (br, 35H) 2.45-0.77 (m, 417H)

  Resins (6) to (26) listed in Table 1 below were obtained by a method according to the above resins (1) to (5). The results are shown below.

［表１中、Ｘ、は下記式（２）を表し、Ｙは下記式（３）を表し、Ｚは上記式（３）のＲ₁₆が水素原子である場合を表す。Ｂｎは無置換のベンジル基を表す。重合形態が「ランダム」とは下記（Ｘ）、（Ｙ）、（Ｚ）で表さられる単量体単位の配列が無秩序な共重合体であることを表し、「ブロック」とは下記（Ｘ）、（Ｙ）、（Ｚ）で表さられる単量体単位の配列がブロックを形成しているブロック共重合体であることを表す。「＊＊＊」は高分子樹脂ユニットとの連結部位を表す。］

[In Table 1, X represents the following formula (2), Y represents the following formula (3), and Z represents the case where R _{16 in the} above formula (3) is a hydrogen atom. Bn represents an unsubstituted benzyl group. The polymerization form “random” means that the arrangement of the monomer units represented by the following (X), (Y), (Z) is a disordered copolymer, and “block” means the following (X ), (Y), and (Z) represent that the arrangement of the monomer units is a block copolymer forming a block. “***” represents a connecting portion with the polymer resin unit. ]

［式（２）中、Ｒ₁₄は水素原子、アルキル基を表す。］

[In the formula (2), R ₁₄ represents a hydrogen atom or an alkyl group. ]

［式（３）中、Ｒ₁₅は水素原子、アルキル基を表し、Ｒ₁₆は水素原子、アルキル基、アラルキル基を表す。］

[In the formula (3), R ₁₅ represents a hydrogen atom or an alkyl group, and R ₁₆ represents a hydrogen atom, an alkyl group or an aralkyl group. ]

［式（Ｚ）中、Ｒ₁₉は水素原子、アルキル基を表す。］

[In the formula (Z), R ₁₉ represents a hydrogen atom or an alkyl group. ]

[Example 2]
A compound having an azo dye skeleton unit represented by the above formula (1) was obtained by the following method.

<Synthesis Example 1 of Azo Dye Intermediate (84)>
An azo dye intermediate (84) represented by the following structure was produced according to the following scheme.

  To 30 parts of chloroform, 3.11 parts of p-nitroaniline (82) was added, and the mixture was ice-cooled to 10 ° C. or less, and 1.89 parts of diketene (83) was added. Then, it stirred at 65 degreeC for 2 hours. After completion of the reaction, the mixture was extracted with chloroform and concentrated to obtain 4.80 parts of compound (84) (yield 96.0%).

  40.0 parts of methanol and 5.29 parts of concentrated hydrochloric acid were added to 4.25 parts of dimethyl 2-aminoterephthalate (85), and the mixture was ice-cooled to 10 ° C or lower. To this solution, 2.10 parts of sodium nitrite dissolved in 6.00 parts of water was added and reacted at the same temperature for 1 hour. Next, 0.990 parts of sulfamic acid was added and the mixture was further stirred for 20 minutes (diazonium salt solution). 4.51 parts of the compound (84) was added to 70.0 parts of methanol, and the mixture was cooled to 10 ° C. or less with ice, and the diazonium salt solution was added. Thereafter, a solution obtained by dissolving 5.83 parts of sodium acetate in 7.00 parts of water was added and reacted at 10 ° C. or lower for 2 hours. After completion of the reaction, 300 parts of water was added and stirred for 30 minutes, and then the solid was filtered off and purified by recrystallization from N, N-dimethylformamide to obtain 8.65 parts of compound (86) ( Yield 96.1%).

  To 58 parts of N, N-dimethylformamide, 8.58 parts of the compound (86) and 0.40 part of palladium-activated carbon (palladium 5%) were added, and the reaction was carried out in a hydrogen gas atmosphere (reaction pressure 0.1 to 0.4 MPa). ) And stirred at 40 ° C. for 3 hours. After completion of the reaction, the solution was filtered and concentrated to obtain 7.00 parts of compound (87) (yield 87.5%).

<Synthesis Example of Compound (19) Having Azo Dye Skeleton Unit>
A compound (19) having an azo dye skeleton unit was produced from the azo dye intermediate (87) according to the following scheme.

  10.0 parts of the polymer resin unit (1) synthesized in Example 1 was dissolved in 100 parts of chloroform and cooled to 10 ° C. or lower with ice. To this solution, 0.78 part of oxalyl chloride and 0.10 part of N, N-dimethylformamide were added and stirred at room temperature for 12 hours. To the resulting reaction mixture, a mixture of 3.30 parts of the azo dye intermediate (87) and 1.0 g of triethylamine was added dropwise over 1 hour at 0 ° C. or lower. After completion of dropping, the solution was heated to 60 ° C. and stirred for 3 hours. After completion of the reaction, the reaction mixture was neutralized with acetic acid, poured into 250 mL of water, extracted with chloroform, and the organic phase was washed twice with 250 mL of water. After drying the organic phase with anhydrous sodium sulfate, the precipitate was filtered off, the filtrate was concentrated, and purified by reprecipitation with methanol to obtain 9.5 parts of compound (19) having an azo dye skeleton unit (yield) 95.0%).

  It was confirmed using the above-described devices that the obtained product had a structure represented by the above formula. The analysis results are shown below.

[Analytical result of compound (19) having azo dye skeleton unit]
[1] Results of molecular weight measurement (GPC):
Weight average molecular weight (Mw) = 17240, number average molecular weight (Mn) = 10680
[2] Results of acid value measurement:
0.34mgKOH / g
[3] Results of ¹ H NMR (400 MHz, CDCl ₃ , room temperature) (see FIG. 1):
δ [ppm] = 15.67 (s, 2H), 11.44 (s, 2H), 8.64 (s, 2H), 8.38 (s, 1H), 8.16 (d, 2H), 8.04 (t, 1H) 7.80 (d, 2H), 7, 77 (s, 2H), 7, 71 (br, 2H), 7.37-6.27 (m, 497H), 4. 08 (s, 6H), 3.98 (s, 6H), 2.95 (s, 2H), 2.88 (s, 2H), 2.70 (s, 6H), 2.61 (s, 2H) ) 2.45-0.77 (m, 298H)

<Synthesis Example of Compound (20) Having Azo Dye Skeleton Unit>
A compound (20) having an azo dye skeleton unit was produced from the azo dye intermediate (87) according to the following scheme.

  1.00 parts of 5-nitroisophthalic acid (88) was dissolved in a mixture of 10.0 parts of chloroform and 0.10 parts of N, N-dimethylformamide, and ice-cooled to 10 ° C or lower. To this solution, 3.60 parts of oxalyl chloride was added and stirred at room temperature for 12 hours. A mixture of 4.00 parts of the azo dye intermediate (87), 1.00 parts of triethylamine, and 40.0 parts of N-methylpyrrolidone was added dropwise to the obtained reaction mixture over 1 hour. After completion of dropping, the solution was heated to 60 ° C. and stirred for 3 hours. After completion of the reaction, the reaction mixture was neutralized with acetic acid, filtered, and dispersed and washed twice in water to obtain 4.32 parts of an azo dye intermediate (89) (yield 93.1%).

  Next, 4.00 parts of the azo dye intermediate (89) and 0.30 parts of palladium-activated carbon (palladium 5%) were added to 150.0 parts of N, N-dimethylformamide, and the reaction was performed under a hydrogen gas atmosphere (reaction). The mixture was stirred at 70 ° C. for 12 hours under a pressure of 0.1 to 0.4 MPa. After completion of the reaction, the solution was filtered and concentrated to obtain 3.35 parts of Compound (90) (yield 86.3%).

  Next, 1.00 parts of the azo dye intermediate (90) was added to 200.0 parts of dehydrated tetrahydrofuran and dissolved. After dissolution, 10.0 parts of the polymer resin unit (2) obtained in Example 1 dissolved in dehydrated tetrahydrofuran 40.0 parts at 50 ° C. was added, and 1-ethyl-3- (3-dimethylaminopropyl) was added. 1.15 parts of carbodiimide hydrochloride (EDC.HCl) was added and stirred at 50 ° C. for 5 hours. After completion of the reaction, the mixture was poured into 250 mL of water and extracted with chloroform, and then the organic layer was washed twice with 250 mL of water. After drying the organic layer with anhydrous sodium sulfate, the precipitate is filtered off, the solvent of the filtrate is distilled off, purified by column chromatography, and then purified by reprecipitation with methanol (20) 9.5 parts were obtained (yield 95.0%).

  It was confirmed using the above-described devices that the obtained product had a structure represented by the above formula. The analysis results are shown below.

[Analytical result of compound (20) having azo dye skeleton unit]
[1] Results of molecular weight measurement (GPC):
Weight average molecular weight (Mw) = 26395, Number average molecular weight (Mn) = 2420
[2] Results of acid value measurement:
0.82mgKOH / g
[3] Results of ¹ H NMR (400 MHz, CDCl ₃ , room temperature) (see FIG. 2):
δ [ppm] = 15.67 (s, 2H), 11.44 (s, 2H), 8.64 (s, 2H), 8.38 (s, 1H), 8.16 (d, 2H), 8.04 (t, 1H) 7.80 (d, 2H), 7, 77 (s, 2H), 7, 71 (br, 2H), 7.37-6.27 (m, 1140H), 4. 08 (s, 6H), 3.98 (s, 6H), 2.95 (s, 2H), 2.88 (s, 2H), 2.70 (s, 6H), 2.61 (s, 2H) ) 2.45-0.77 (m, 684H)

  The same operations as in the production examples of the compounds (19) and (20) having the azo skeleton unit were performed to produce compounds (21) to (68) having an azo skeleton unit represented by the above formula (1). Table 2 below shows compounds having an azo skeleton unit of the present invention.

［表２中、Ｘ、は下記式（２）を表し、Ｙは下記式（３）を表し、Ｚは上記式（３）のＲ₁₆が水素原子である場合を表す。Ｗは下記（Ｗ−１）、（Ｗ−２）及び（Ｗ−３）を表し、Ｖは下記（Ｖ−１）、（Ｖ−２）を表す。「Ｐｈ」は無置換のフェニル基を表し、「Ｂｎ」は無置換のベンジル基を表し、（ｎ）、（ｉ）はそれぞれアルキル基が直鎖状、分岐状であることを表し、「＊」はＷとの連結部位を表し、「＊＊」はＶとの連結部位を表し、「＊＊＊」は高分子樹脂ユニットとの連結部位を表す。］

[In Table 2, X represents the following formula (2), Y represents the following formula (3), and Z represents the case where R _{16 in the} above formula (3) is a hydrogen atom. W represents the following (W-1), (W-2) and (W-3), and V represents the following (V-1) and (V-2). “Ph” represents an unsubstituted phenyl group, “Bn” represents an unsubstituted benzyl group, (n) and (i) represent that the alkyl group is linear or branched, and “*” "Represents a connecting site to W," ** "represents a connecting site to V, and" *** "represents a connecting site to the polymer resin unit. ]

［式（２）中、Ｒ₁₄は水素原子、アルキル基を表す。］

[In the formula (2), R ₁₄ represents a hydrogen atom or an alkyl group. ]

［式（３）中、Ｒ₁₅は水素原子、アルキル基を表し、Ｒ₁₆は水素原子、アルキル基、アラルキル基を表す。］

[In the formula (3), R ₁₅ represents a hydrogen atom or an alkyl group, and R ₁₆ represents a hydrogen atom, an alkyl group or an aralkyl group. ]

［式（Ｚ）中、Ｒ₁₉は水素原子、アルキル基を表す。］

[In the formula (Z), R ₁₉ represents a hydrogen atom or an alkyl group. ]

［式（Ｗ−１）中、Ｒ₁乃至Ｒ₁₀は、式（１）におけるＲ₁乃至Ｒ₁₀と各々同義である。］

[In Formula (W-1), R _{1 to} R ₁₀ are respectively synonymous with R _{1 to} R ₁₀ in Formula (1). ]

［式（Ｗ−２）中、Ｒ₁乃至Ｒ₁₀は、式（１）におけるＲ₁乃至Ｒ₁₀と各々同義である。］

Wherein (W-2), R ₁ to R ₁₀ are each synonymous with R ₁ through R ₁₀ in the formula (1). ]

［式（Ｗ−３）中、Ｒ₁乃至Ｒ₁₀は、式（１）におけるＲ₁乃至Ｒ₁₀と各々同義である。］

[In Formula (W-3), R _{1 to} R ₁₀ are respectively synonymous with R _{1 to} R ₁₀ in Formula (1). ]

［式（Ｖ−１）中、Ｗは上記（Ｗ−１）、（Ｗ−２）及び（Ｗ−３）を表し、Ｌ₂は式（１）におけるＬ₂と同義である。］

Wherein (V-1), W is the (W-1), represents a (W-2) and (W-3), L ₂ has the same meaning as L ₂ in Formula (1). ]

［式（Ｖ−２）中、Ｗは上記（Ｗ−１）、（Ｗ−２）及び（Ｗ−３）を表し、Ｌ₂は式（１）におけるＬ₂と同義である。］

Wherein (V-2), W is the (W-1), represents a (W-2) and (W-3), L ₂ has the same meaning as L ₂ in Formula (1). ]

[Comparative Example 1]
As a comparative example of the azo dye skeleton unit represented by the above formula (1), a comparative azo dye skeleton unit represented by the following formulas (91) and (92) was produced according to the above production method, The compounds for comparison (91) and (92) were obtained by amidating the group and the carboxyl group of the resin (4).

[Example 3]
First, a pigment dispersion containing a pigment and a compound having an azo dye skeleton unit in a toner production process by a suspension polymerization method was prepared by the following method.

<Preparation Example 1 of Pigment Dispersion>
18.0 parts of the pigment represented by the above formula (6) as the azo pigment, 5.4 parts of the compound (19) having the azo dye skeleton unit, 180 parts of styrene as the water-insoluble solvent, 130 parts of glass beads (φ1 mm) Were mixed with an attritor (manufactured by Nihon Coke Kogyo Co., Ltd.) for 3 hours and filtered through a mesh to obtain a pigment dispersion (DIS1).

<Preparation Example 2 of Pigment Dispersion>
The same procedure was carried out except that the compound (19) having an azo dye skeleton unit was changed to compounds (20) to (68) having an azo dye skeleton unit in Preparation Example 1 of the pigment dispersion, respectively. Liquids (DIS2) to (DIS50) were obtained.

<Preparation Example 3 of Pigment Dispersion>
In Preparation Example 1 of the pigment dispersion, the same operation was performed except that the pigment represented by the above formula (6) was changed to the pigment represented by the following formulas (93) and (94). Liquids (DIS51) and (DIS52) were obtained.

[Comparative Example 2]
A pigment dispersion serving as a reference value for evaluation and a pigment dispersion for comparison were prepared by the following method.

<Preparation Example 1 for Reference Pigment Dispersion>
A pigment dispersion for reference (DIS53) was obtained in the same manner as in Preparation Example 1 for pigment dispersion of Example 3 except that the compound (19) having an azo dye skeleton unit was not added.

<Preparation Example 2 of Reference Pigment Dispersion>
In Preparation Example 3 of the pigment dispersion of Example 3 above, the same operation was performed except that the compound (19) having an azo dye skeleton unit was not added, and the reference pigment dispersions (DIS54) and (DIS55) Got.

<Preparation Example 1 for Comparative Pigment Dispersion>
The compound (19) having an azo dye skeleton unit in Preparation Example 1 of the pigment dispersion liquid of Example 3 was used as a polymer dispersant Solsperse 24000SC (registered trademark) [manufactured by Lubrizol Co., Ltd.] described in Patent Document 3, and the above comparative compound Except for changing to (91) and (92), the same operation was performed to obtain comparative pigment dispersions (DIS56) to (DIS58), respectively.

[Example 4]
The pigment dispersion was evaluated by the following method.

<Viscosity evaluation of pigment dispersion>
For the pigment dispersions (DIS1) to (DIS50), the pigment dispersions (DIS1) to (DIS58) were measured using a viscoelasticity measuring device Physica MCR300 [manufactured by Anton Paar, cone plate type measuring jig: 75 mm diameter, 1 °]. ) measured at a shear rate of 10s ^-1 of the following criteria were subjected to viscosity evaluation of the pigment dispersion.
A: Less than 500 mPa · s B: 500 mPa · s or more and less than 1000 mPa · s C: 1000 mPa · s or more and less than 2000 mPa · s D: 2000 mPa · s or more

  Here, if the viscosity was less than 1000 mPa · s, it was judged that the pigment dispersion of the pigment dispersion was good and the viscosity was sufficiently lowered. Table 3 shows the viscosity evaluation results of the pigment dispersion.

[Example 5]
Next, the toner of the present invention was produced by the suspension polymerization method in the following manner.

<Toner Production Example 1>
High-speed stirrer K. 710 parts of ion-exchanged water and 450 parts of a 0.1 mol / l-Na ₃ PO ₄ aqueous solution were added to a 2-liter four-necked flask equipped with a homomixer [manufactured by Primix Co., Ltd.], and the rotational speed was adjusted to 12000 rpm. Warmed to 60 ° C. To this, 68 parts of 1.0 mol / l-CaCl ₂ aqueous solution was gradually added to prepare an aqueous medium containing a minute hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ . Next, the following composition was heated to 60 ° C. K. Using a homomixer [manufactured by Primix Co., Ltd.], the mixture was uniformly dissolved and dispersed at 5000 rpm.
-132 parts of the above pigment dispersion (DIS1)-46 parts of styrene monomer-34 parts of n-butyl acrylate monomer-Polar resin [saturated polyester resin (terephthalic acid-propylene oxide modified bisphenol A, acid value 15, peak molecular weight 6000)] 10 parts ester wax (maximum endothermic peak in DSC measurement = 70 ° C., Mn = 704) 25 parts aluminum salicylate compound [Orient Chemical Industries, trade name: Bontron E-88] 2 parts divinyl Benzene monomer 0.1 part

  To this was added 10 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator, and the mixture was put into the aqueous medium and granulated for 15 minutes while maintaining the rotation speed of 12000 rpm. Thereafter, the stirrer was changed from a high-speed stirrer to a propeller stirring blade, and the polymerization was continued for 5 hours at a liquid temperature of 60 ° C. Then, the liquid temperature was raised to 80 ° C. and the polymerization was continued for 8 hours. After completion of the polymerization reaction, the residual monomer was distilled off at 80 ° C. under reduced pressure, and then the mixture was cooled to 30 ° C. to obtain a polymer fine particle dispersion.

Transfer the resulting polymer fine particle dispersion to a washing container, add dilute hydrochloric acid while stirring, and stir at pH 1.5 for 2 hours to dissolve the phosphoric acid and calcium compound containing Ca ₃ (PO ₄ ) ₂ Then, solid-liquid separation was performed with a filter to obtain polymer fine particles. This was poured into water and stirred to obtain a dispersion again, followed by solid-liquid separation with a filter. The redispersion of polymer fine particles in water and solid-liquid separation were repeated until the compound of phosphoric acid and calcium containing Ca ₃ (PO ₄ ) ₂ was sufficiently removed. Thereafter, the polymer particles finally solid-liquid separated were sufficiently dried with a dryer to obtain toner particles.

  To 100 parts of the obtained toner particles, 1.0 part of hydrophobic silica fine powder surface-treated with hexamethyldisilazane (number average primary particle diameter 7 nm), 0.15 part of rutile titanium oxide fine powder (number average) Primary particle diameter 45 nm) and 0.5 part of rutile titanium oxide fine powder (number average primary particle diameter 200 nm) are dry mixed for 5 minutes with a Henschel mixer [manufactured by Nippon Coke Industries, Ltd.] to obtain toner (T1). It was.

<Toner Production Example 2>
The toner (T2) of the present invention is the same as the toner production example 1 except that the pigment dispersion liquid (DIS1) in the toner production example 1 is changed to pigment dispersion liquids (DIS2) to (DIS50), respectively. To (T50) were obtained.

<Toner Production Example 3>
The toner (T51) of the present invention is the same as the toner production example 1 except that the pigment dispersion liquid (DIS1) in the toner production example 1 is changed to the pigment dispersion liquids (DIS51) and (DIS52), respectively. , (T52) was obtained.

[Comparative Example 3]
For the toner of the present invention produced in Example 5 above, a toner as a reference value for evaluation and a comparative toner were produced by the following methods.

<Manufacture example 1 of reference toner>
A reference toner (T53) was obtained in the same manner as in Toner Production Example 1 except that the compound (19) having the azo dye skeleton unit was not added.

<Manufacture example 2 of reference toner>
Reference toners (T54) and (T55) were obtained in the same manner as in Toner Production Example 3 except that the compound (19) having the azo dye skeleton unit was not added.

<Comparative Toner Production Example 1>
Except that the compound (19) having the azo dye skeleton unit is changed to Solsperse 24000SC (registered trademark) [manufactured by Lubrizol] and compounds (91) and (92), respectively, in the same manner as in Production Example 1 of the toner. Comparative toners (T56) to (T58) were obtained.

[Example 6]
Next, the toner of the present invention was produced by the suspension granulation method in the following manner.

<Toner Production Example 4>
180 parts of ethyl acetate, 12 parts of the pigment of the above formula (6), 2.4 parts of the compound (19) having the azo dye skeleton unit, and 130 parts of glass beads (φ1 mm) were mixed together. The pigment dispersion (DIS59) was prepared by dispersing for 3 hours and then filtering through a mesh.

The following composition was dispersed with a ball mill for 24 hours to obtain 200 parts of a toner composition mixed solution.
-96.0 parts of the above pigment dispersion (DIS59)-Polar resin [saturated polyester resin (polycondensate of propylene oxide modified bisphenol A and phthalic acid, Tg = 75.9 ° C, Mw = 11000, Mn = 4200, acid value 11)] 85.0 parts · Hydrocarbon wax (Fischer Tropsch wax, maximum endothermic peak in DSC measurement = 80 ° C, Mw = 750) 9.0 parts · Aluminum salicylate compound [Bontron E-88, Orient Chemical Co., Ltd. 2) ethyl acetate (solvent) 10.0 parts The following composition was dispersed for 24 hours with a ball mill to dissolve carboxymethyl cellulose to obtain an aqueous medium.
・ Calcium carbonate (coated with acrylic acid copolymer) 20.0 parts ・ Carboxymethylcellulose [Serogen BS-H, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.] 0.5 part ・ Ion-exchanged water 99.5 parts

  The aqueous medium (1200 parts) was mixed with a high-speed stirring device T.I. K. Place in a homomixer [manufactured by Primix Co., Ltd.], add 1000 parts of the toner composition mixture while stirring the rotating blade at a peripheral speed of 20 m / sec, and stir for 1 minute while maintaining a constant 25 ° C. A liquid was obtained.

  While stirring 2200 parts of the suspension with a full-zone blade (manufactured by Shinko Environmental Solution Co., Ltd.) at a peripheral speed of 45 m / min, the liquid temperature was kept constant at 40 ° C., and a blower was used to The gas phase was forcibly aspirated and solvent removal was started. At that time, 15 minutes after the start of solvent removal, 75 parts of ammonia water diluted to 1% as an ionic substance was added, and then 25 parts of ammonia water was added 1 hour after the start of solvent removal, followed by solvent removal. Two hours after the start, 25 parts of the ammonia water was added. Finally, 25 parts of the ammonia water was added three hours after the start of solvent removal, so that the total addition amount was 150 parts. Further, while maintaining the liquid temperature at 40 ° C., the toner dispersion was maintained for 17 hours from the start of the solvent removal to remove the solvent (ethyl acetate) from the suspended particles.

  To 300 parts of the toner dispersion obtained in the solvent removal step, 80 parts of 10 mol / l hydrochloric acid are added, neutralized with a 0.1 mol / l sodium hydroxide aqueous solution, and then washed with ion-exchanged water by suction filtration four times. Thus, a toner cake was obtained. The obtained toner cake was dried with a vacuum dryer and sieved with a sieve having an opening of 45 μm to obtain toner particles. Subsequent operations were carried out in the same manner as in Toner Production Example 1 to obtain a toner (T59).

<Toner Production Example 5>
The toners (T60) to (T108) of the present invention are obtained in the same manner except that the compound (19) having an azo dye skeleton unit in the toner production example 4 is changed to (20) to (68), respectively. Obtained.

<Toner Production Example 6>
Toners (T109) and (T110) of the present invention were obtained in the same manner as in Toner Production Example 4 except that the pigment of formula (6) was changed to formulas (93) to (94), respectively. .

[Comparative Example 4]
For the toner of the present invention produced in Example 6, a toner serving as a reference value for evaluation and a comparative toner were produced by the following method.

<Manufacture example 3 of reference toner>
A reference toner (T111) was obtained in the same manner as in Toner Production Example 4 except that the compound (19) having the azo dye skeleton unit was not added.

<Manufacture example 4 of reference toner>
Reference toners (T112) and (T113) were obtained in the same manner as in Toner Production Example 6 except that the compound (19) having the azo dye skeleton unit was not added.

<Production Example 2 for Comparative Toner>
Except for changing the compound (19) having the azo dye skeleton unit to Solsperse 24000SC (registered trademark) [manufactured by Lubrizol], (91), and (92), respectively, in the same manner as in Toner Production Example 4, Comparative toners (T114) to (T116) were obtained.

[Example 7]
The toner obtained in the present invention, the reference toner, and the comparative toner were evaluated by the following methods.

<Toner color tone evaluation>
Using toners (T1) to (T52) and (T59) to (T110), image samples were output and image characteristics described later were compared and evaluated. In comparison of image characteristics, paper passing durability was performed using a modified machine of LBP-5300 (manufactured by Canon Inc.) as an image forming apparatus (hereinafter abbreviated as LBP). As a modification, the developing blade in the process cartridge (hereinafter referred to as CRG) was replaced with a SUS blade having a thickness of 8 [μm]. Then, a blade bias of −200 [V] can be applied to the developing bias applied to the developing roller as a toner carrier.

<Toner color tone evaluation>
A solid image having a toner loading of 0.5 mg / cm ² was prepared on a transfer paper (75 g / m ² paper) in a normal temperature and normal humidity (N / N (23.5 ° C., 60% RH)) environment. . The image in CIE L in (International Commission on Illumination) by a defined L ^* a ^* b ^* color system ^*, manufactured by C ^* a reflection densitometer Spectrolino [GretagMacbeth), a light source: D50, field of view: the 2 ° Measured under conditions. The color tone of the toner was evaluated based on the improvement rate of C ^* at L ^* = 95.5.

The toner (T1) to C ^* rate of improvement of the image (T52) was a reference value C ^* of the image of the reference toner (T53) to (T55).

The toner (T59) to C ^* rate of improvement of the image (T110) was set to reference value C ^* of the image of the reference toner (T111) to (T113).

The evaluation criteria for the improvement rate of C ^* are shown below.
A: C ^* improvement rate is 5% or more of B: C ^* less than 5 improvement rate is 1% or more of the% C: C ^* of improvement rate of less than 1% D: C ^* decrease

If the improvement rate of C ^* was 1% or more, it was judged that the color tone was good.

  Table 3 shows the toner color tone evaluation results obtained by the suspension polymerization method of the present invention, and Table 4 shows the toner color tone evaluation results obtained by the suspension granulation method.

<Toner image fog evaluation>
Transfer paper (75 g / m ² ) under normal temperature and normal humidity (N / N (23.5 ° C., 60% RH)) environment and high temperature and high humidity (H / H (30 ° C., 80% RH)) environment In an image formation test that prints up to 10,000 images with a printing ratio of 2% using paper), an image having a white background is output at the end of the durability evaluation, and “REFECTRECTER MODEL TC-6DS” (TEPCO) From the difference between the whiteness (reflectance Ds (%)) of the white portion of the printout image measured by the color company and the whiteness of the transfer paper (average reflectance Dr (%)), the fog density (%) (= Dr (%) − Ds (%)) was calculated, and the image fogging at the end of the durability evaluation was evaluated. A blue light filter was used as the filter.
A: Less than 1.0% B: 1.0% or more and less than 3.0% C: 3.0% or more and less than 5.0% D: 5.0% or more

  If the fog density was less than 5%, it was judged that the level was not problematic for practical use.

  Table 3 shows the evaluation results of the image fog of the toner by the suspension polymerization method of the present invention, and Table 4 shows the evaluation results of the image fog of the toner by the suspension granulation method.

<Toner transferability evaluation>
An image that prints up to 10,000 images with a printing ratio of 2% using transfer paper (75 g / m ² paper) in a high-temperature and high-humidity (H / H (30 ° C., 80% RH)) environment. In the dispensing test, the transfer efficiency was confirmed at the end of the durability evaluation. A solid image with a toner loading of 0.65 mg / cm 2 was developed on a drum and then transferred to transfer paper (75 g / m ² paper) to obtain an unfixed image. The transfer efficiency was determined from the change in weight between the toner amount on the drum and the toner amount on the transfer paper (the transfer efficiency is 100% when the entire toner amount on the drum is transferred onto the transfer paper).
A: Transfer efficiency is 90% or more B: Transfer efficiency is 80% or more and less than 90% C: Transfer efficiency is 70% or more and less than 80% D: Transfer efficiency is less than 70%

  If the transfer efficiency was 70% or more, it was judged that the transfer was good.

  Table 3 shows the evaluation results of the transferability of the toner by the suspension polymerization method of the present invention, and Table 4 shows the evaluation results of the transferability of the toner by the suspension granulation method.

[Comparative Example 5]
For the comparative toners (T56) to (T58) and (T114) to (T116), the color tone, the image fog, and the transferability were evaluated in the same manner as in Example 7. C ^* rate of improvement of the image of the comparative toner (T53) to (T58) was a reference value C ^* of the image of the reference toner (T53).

C ^* rate of improvement of the image of the comparative toner (T114) to (T116) was set to reference value C ^* of the image of the reference toner (T111).

  Table 3 shows the evaluation results of the comparative toner by the suspension polymerization method, and Table 4 shows the evaluation results of the comparative toner by the suspension granulation method.

［粘度評価の括弧内の数値は粘度値（単位：ｍＰａ・ｓ）である。］

[Numerical values in parentheses for viscosity evaluation are viscosity values (unit: mPa · s). ]

  As can be seen from Table 3, by using a compound having an azo skeleton unit, the azo pigment is well dispersed in the binder resin, has a good color tone, suppresses image fogging, has a good transferability, and is long-lasting. It was confirmed that a toner capable of obtaining a stable image was provided. Furthermore, since it is possible to suppress an increase in the viscosity of the pigment dispersion, it has been confirmed that a toner having good pigment dispersibility can be provided even in a toner manufacturing process using a polymerization method. Further, as apparent from Table 4, the azo pigment is well dispersed in the binder resin even in the granulation method, has a good color tone, suppresses image fogging, has a good transferability, and is stable for a long time. It was confirmed that a toner capable of obtaining a toner was provided.

  Since the toner of the present invention has a good color tone, it can be used not only for electrophotography but also for toner display used in electronic paper and as a circuit pattern forming toner for digital fabrication.

Claims (14)

A unit represented by the following general formula (1) is a binder resin, a partial structural formula represented by the following general formula (2) and / or a polymer having a partial structural formula represented by the following general formula (3). A toner containing an azo pigment as a colorant and a compound to which is bonded.

[In Formula (1), R ₁ represents an alkyl group having 1 to 6 carbon atoms and a phenyl group, and R _{2 to} R ₆ represent a hydrogen atom, a COOR ₁₁ group, and a CONR ₁₂ R ₁₃ group. R _{7 to} R ₁₀ represent a hydrogen atom or a halogen atom. R _{11 to} R _{13 each} represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. L _{1 to} L ₂ represent a divalent linking group. ]

[In the formula (2), R ₁₄ represents a hydrogen atom or an alkyl group. ]

[In the formula (3), R ₁₅ represents a hydrogen atom or an alkyl group, and R ₁₆ represents a hydrogen atom, an alkyl group or an aralkyl group. ] The toner according to claim ₁ , wherein R ₁ in formula (1) is a methyl group. R ₂ and R ₅ in the formula (1) are COOR ₁₁ (R ₁₁ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms), and R ₃ , R ₄ and R ₆ are hydrogen atoms. The toner according to claim 1. 4. The toner according to claim 1, wherein R ₁₁ and R ₁₂ in the formula (1) are methyl groups, and R ₁₃ is a hydrogen atom and a methyl group. L ₁ in Formula (1) is —O—, —CO—, —NR ₁₇ — (R ₁₇ represents a hydrogen atom or an alkyl group), —R ₁₈ — (R ₁₈ represents an alkylene group.) The toner according to claim 1, wherein the toner is a divalent linking group selected from the group consisting of a combination thereof. L ₁ in Formula (1) is —NH—CO—, —O—CO—, —O—R ₁₈ —O—CO— (R ₁₈ represents an alkylene group), Item 6. The toner according to any one of Items 1 to 5. The L ₂ in the formula (1) and the carboxyl group in the polymer according to claim 1 are bonded via a carboxylic acid amide bond or a carboxylic acid ester bond. 7. The toner according to any one of items 1 to 6. The toner according to claim 1, wherein R _{7 to} R ₁₀ in the formula (1) are hydrogen atoms. The toner according to any one of claims 1 to 8, wherein the unit represented by the formula (1) is represented by the following general formula (4) to general formula (5).

[In Formula (4), L < ₁ > thru | or L < ₂ > represent a bivalent coupling group. ]

[In Formula (5), L < ₁ > thru | or L < ₂ > represent a bivalent coupling group. ]   The toner according to claim 1, wherein the azo pigment is an acetoacetanilide pigment. The toner according to claim 10, wherein the azo pigment is an azo pigment represented by the formula (6).

  The toner according to claim 1, wherein the toner particles are produced in an aqueous medium.   The toner according to claim 12, comprising a step of producing the toner particles using a suspension polymerization method.   The toner according to claim 12, comprising a step of producing the toner particles using a suspension granulation method.

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