JPH09169919A - Monoazo metal compound and its related technique - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound excellent in charge-controlling and increasing characteristics, heat resistance, light resistance, dispersibility in resins, charge characteristic-retaining stability, etc., and useful for toners for electrostatic charge development, etc. SOLUTION: Three molecules of a compound of formula I R<1> to R<10> are H, a halogen, nitro, a 1-10C (halogenated) alkyl, a (substituted) aryl, a (nucleus- substituted) aralkyl, a group of the formula: -SO2 N(R<11> )2 [R<11> is H, a lower alkyl, a (nucleus-substituted) aryl, a (nucleus-substituted) aralkyl], a group of the formula: -N(R<12> )2 (R<12> is R<11> , an acyl), a group of the formula:-CONH(R<13> ) (R<13> is R<11> ); two or more of R<1> to R<10> may be combined with each other to form an aromatic ring or an alicyclic ring} or a compound of formula II (R<21> to R<28> are each a group of R<1> to R<10> ) are coordinated with two metal atoms to form a compound of the formula: D3 (Met)2 (D3 is the compound of formula I or II; Met is a metal atom such as Cr, Fe, Al, Co or Ni).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a monoazo metal compound, a composition comprising a monoazo metal compound, a toner for developing an electrostatic charge image, a charge control agent for controlling or stabilizing the charge amount of the toner, and an electrostatic charge. TECHNICAL FIELD The present invention relates to a powder coating material for painting and a charge enhancer for enhancing the charge of the powder coating material.

[0002]

2. Description of the Related Art In a copying machine, a printer or the like using an electrophotographic method, an electrostatic layer formed on a photoconductor having a photosensitive layer containing an inorganic or organic photoconductive material is used. Various toners including a colorant, a fixing resin, and the like are used to develop a latent image.

The chargeability of such toners is a particularly important factor in this system for developing electrostatic latent images. Therefore, in order to appropriately control or stabilize the charge amount of the toner, a charge control agent having a positive charge or a negative charge is often added to the toner. Among the charge control agents that have been put into practical use, basic dyes such as nigrosine dyes and triarylmethane dyes, and electron donating substances such as quaternary ammonium salts are used to impart a positive charge to the toner. Examples of those that impart a negative charge to the toner include 2: 1 type metal complex salt dyes of monoazo dyes,
And a metal complex of an aromatic oxycarboxylic acid such as alkylsalicylic acid.

However, most of the metal complexes having an azo dye structure used as a charge control agent are generally poor in stability, for example, mechanical friction and shock, changes in temperature and humidity conditions, electric shock, light irradiation, etc. Therefore, the desired charge controllability is likely to be lost due to decomposition or change. In addition, even if it has a charge-imparting property of a practical level, there are problems in charge stability, and it often contains impure chemical substances that do not have a charge control effect due to differences in manufacturing methods, etc. And various problems such as reliability remained.

Also, in electrostatic powder coatings, application of charge control agents conventionally used for controlling or enhancing the charge of toners for developing electrostatic images has been studied in order to improve the coating efficiency. It was

As one of such attempts, an electrostatic powder coating material containing a resin polymer of an azine dye (Japanese Patent Application Laid-Open No. 60-6756).
No. 3), a resin powder composition for electrostatic coating containing a charge enhancer such as a metal-containing complex salt compound (JP-A-63-75077).
No.), a powder coating composition containing a quaternary ammonium salt as a charge control or enhancer (JP-A-2-212563).
No.) and the like.

However, these electrostatic powder coatings are
Further improvement is desired in terms of environmental stability and heat resistance and durability against high heat applied during powder coating.

As a charge control or enhancer capable of solving such a problem, for example, a metal complex salt compound of a monoazo dye having the following structure is known.

[0009]

Embedded image (In each of the above formulas, A represents H, an alkali metal, an amine, etc.) Such a chromium complex salt dye has two molecules of monoazo dye.
It is a so-called 2: 1 type azo-containing metal complex salt dye coordinated to one valent chromium atom, and there was room for improvement in stability and reliability of charging characteristics.

The present invention has been made in view of the above problems existing in the prior art, and an object of the present invention is to provide a novel charge control or enhancement property, and excellent heat resistance and light resistance. Metal compound with a chemical structure; Having the metal compound as an active ingredient, good dispersibility in resin, environment resistance (stability of charge control or enhancement property against changes in temperature and humidity), storage stability (charge control or enhancement) The stability of the characteristics over time) and the durability (stability of charge control or enhancement characteristics when used many times repeatedly) are adversely affected to the fixability and offset characteristics of the toner when used as a toner. No charge control or enhancer; and stable quality,
An object of the present invention is to provide a highly reliable toner for developing an electrostatic image and a powder coating material for electrostatic coating.

[0011]

The monoazo metal compound of the present invention comprises three molecules of a monoazo compound having two metallizable --OH represented by the following formula [II] or [III]:
A metal atom (Met) is coordinated with 2 atoms and is represented by D ₃ (Met) ₂ ... [I]. (In the formula [I], D represents a ligand based on a monoazo compound.)

[0012]

Embedded image (In the formula [II], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently hydrogen, halogen, a nitro group, An alkyl group or a haloalkyl group having 1 to 20 carbon atoms, an aryl group which may be nucleus-substituted, an aralkyl group which may be nucleus-substituted, -SO ₂ N (R ¹¹ ) ₂ [two R ¹¹
Are the same or different from each other, hydrogen,
Lower alkyl group, optionally substituted aryl group,
Or, it represents an optionally substituted aralkyl group. ],
-N (R ¹² ) ₂ [Two R ¹² may be the same or different from each other, and are hydrogen, a lower alkyl group, an optionally substituted nucleus group, an optionally substituted nucleus aralkyl. Represents a group or an acyl group. ] Or -CONH (R ¹³ ) [R ¹³
Represents hydrogen, a lower alkyl group, an aryl group which may be nucleus-substituted, or an aralkyl group which may be nucleus-substituted. ]. Two or more of R ^{1 to} R ¹⁰ may be linked to each other to form an aromatic ring or an aliphatic ring. )

[0013]

Embedded image (In the formula [III], R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ ,
R ²⁷ and R ²⁸ are each independently hydrogen, halogen,
A nitro group, an alkyl group or a haloalkyl group having 1 to 20 carbon atoms, an optionally substituted aryl group, an optionally substituted aralkyl group, -SO ₂ N (R ²⁹ ) ₂ [two R ²⁹ are , May be the same as or different from each other,
Hydrogen, a lower alkyl group, an optionally substituted nucleus group, or an optionally substituted nucleus aralkyl group is shown. ], —N (R ³⁰ ) ₂ [Two R ^{30 s} may be the same or different from each other, and are each a hydrogen atom, a lower alkyl group, an optionally substituted nucleus group, or an optionally substituted nucleus group. A good aralkyl group or an acyl group is shown. ] Or -CONH (R
³¹ ) [R ³¹ represents hydrogen, a lower alkyl group, an optionally substituted nucleus group, or an optionally substituted aralkyl group. ]. Two or more of R ^{21 to} R ²⁸ may be linked to each other to form an aromatic ring or an aliphatic ring. ) In another monoazo metal compound of the present invention, 6 molecules of the monoazo compound represented by the above formula [II] or [III] and having two metallizable —OH are coordinated with a metal atom (Met) 4 atom. And is represented by D ₆ (Met) ₄ ... [IV]. (In the formula [IV], D represents a ligand based on a monoazo compound.) The composition of the present invention comprises a monoazo metal compound represented by the following formula [VI] and a monoazo metal represented by the following formula [VII]. The compound and 2 or 3 monoazo metal compounds selected from the group consisting of monoazo metal compounds represented by the following formula [VIII].

[0014]

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[0015]

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[0016]

Embedded image (In the formulas [VI], [VII] and [VIII], R ^{1 to} R ¹⁰ have the same meanings as described above, and R ^{1 to} R ¹⁰ are two or more of them linked to each other to form an aromatic ring or a fat. (A ⁺ represents a cation in the formula [VIII].) Another composition of the present invention is a monoazo metal compound represented by the following formula [IX], a compound represented by the following formula [X: ] A monoazo metal compound represented by the formula [XI] and a monoazo metal compound represented by the following formula [XI].

[0017]

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[0018]

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[0019]

Embedded image (In the formulas [IX], [X] and [XI], R ^{21 to} R ²⁸ have the same meanings as described above, and R ^{21 to} R ²⁸ are two or more of R ^{21 to} R ²⁸ which are linked to each other to form an aromatic ring or a fatty group. It may form a group ring. In formula [XI], A ⁺ represents a cation.) The monoazo metal compound represented by formula [VI] or formula [IX] is represented by formula [I] (D ₃ ( Met) ₂ ) has the same meaning as the monoazo metal compound represented by the formula [VII] or the formula [X], and the monoazo metal compound represented by the formula [IV] (D ₆ (Met) ₄ ) is the monoazo metal compound represented by the formula [IV] (D ₆ (Met) ₄ ). Is synonymous with. Also, the formula [V
III] or the monoazo metal compound represented by the formula [XI] has the same meaning as the monoazo metal compound represented by [D ₂ (Met)] ⁻ · A ⁺ ... · [XII]. (Equation [X
II], D represents a ligand based on a monoazo compound, and A ⁺
Indicates a cation. Specific examples of the metal atom (Met) in each of the above monoazo metal compounds include trivalent metals such as chromium, iron and aluminum, as well as cobalt and nickel. Preferred are trivalent chromium, trivalent iron, and trivalent aluminum.

As each of the substituents R ^{1 to} R ^{10 and} R ^{21 to} R ²⁸ in each of the above monoazo metal compounds, hydrogen [H]; halogen such as Cl, Br, I and F; nitro group; methyl, ethyl, n -Propyl, isopropyl, n-butyl, is
o-butyl, sec-butyl, tert-butyl, n-octyl, te
Rt-octyl, 2-ethylhexyl, n-decyl, dodecyl and the like, alkyl groups or haloalkyl groups having 1 to 20 carbon atoms, preferably alkyl groups having 1 to 12 carbon atoms or haloalkyl groups such as trifluoromethyl group; benzyl, lower Alkyl-substituted benzyl (in the present specification, lower alkyl refers to alkyl having 1 to 4 carbon atoms), aralkyl group such as phenylethyl, phenylpropyl, naphthylmethyl, naphthylethyl (nuclearly substituted by lower alkyl group, etc. Aryl groups such as phenyl, naphthyl, lower alkyl-substituted phenyls, lower alkyl-substituted naphthyls, halogenated phenyls, halogenated naphthyls (including those substituted with lower alkyl groups or halogens);-SO ₂ NH _2, -SO ₂ N (alkyl) _2, -SO ₂ NH (phenyl), - SO ₂ NH (benzyl -SO ₂ N equal (R ¹¹⁾ ₂ and -SO ₂ N
(R ²⁹ ) ₂ [where R ¹¹ and R ²⁹ are hydrogen, a lower alkyl group, an aryl group (including those which are nuclear-substituted by a lower alkyl group or halogen), or an aralkyl group (which is nuclear-substituted by a lower alkyl group, etc. Including things). ]; -NH ₂ ,
-N (alkyl) ₂ , -NH (phenyl), -NH (benzyl), -N
-N (R ¹² ) ₂ and -N (R ³⁰ ) ₂ such as H (acetyl) [R ¹² , R ³⁰
Is hydrogen, a lower alkyl group, an aryl group (including those which are nucleus-substituted with a lower alkyl group or halogen), an aralkyl group (including those which are nucleus-substituted with a lower alkyl group, etc.), or an acyl group. ]; -CONH ₂ , -CONH (alkyl), -CONH (phenyl), -CONH (benzyl) and other -C
ONH (R ¹³ ), and -CONH (R ³¹ ) [wherein R ¹³ and R ³¹ are hydrogen, a lower alkyl group, an aryl group (including a lower alkyl group or a nucleus substituted with a halogen), or an aralkyl group (a lower alkyl group). (Including those that have been nuclear-substituted by groups, etc.). ] Etc. can be illustrated.

Of the above R ^{1 to} R ⁴ , one or two of them are preferably Cl or nitro group (in the case of two, they may be the same or different from each other).
This is because the charge imparting effect is good. The same applies to R ^{21 to} R ²⁴ .

Regarding R ⁵ and R ²⁵ , hydrogen [H] or an amide group represented by the following formula [V] is preferable.

[0023]

Embedded image (In the formula [V], (R ¹⁴ ) _0-2 represents 0 to 2 substituents, R ¹⁴ represents halogen such as Cl, Br, I and F, a lower alkyl group such as methyl and ethyl, Or an alkoxy group having 1 to 4 carbon atoms such as methoxy or ethoxy.) As for R ^{6 to} R ^{10 and} R ^{26 to} R ²⁸ , hydrogen [H]; halogen such as Cl, Br, I, F; methyl; , Ethyl, propyl, isopropyl, butyl, sec-butyl, te
rt- butyl, amyl, octyl, tert- octyl, alkyl group or a haloalkyl group having a carbon number of 1 to 12 of dodecyl; -NH _2, -N (alkyl) _2, -NH (phenyl), - NH (benzyl), -N such as -NH (acetyl), -NH (benzoyl)
(R ¹² ) ₂ and -N (R ³⁰ ) ₂ are preferred. More preferably, R ^{6 to} R ¹⁰ , or R ^{26 to} R ²⁸ are all hydrogen [H], or one or two of R ^{6 to} R ¹⁰ is halogen,
Alkyl or -N (R ¹² ) ₂ (in the case of two, they may be the same or different from each other), and R ²⁶
To R ²⁸ , one or two of which are halogen, alkyl or
-N (R ³⁰ ) ₂ (in the case of two, they may be the same or different from each other).

Examples of A ⁺ in the formulas [VIII], [XI] and [XII] include cations such as H ⁺ , alkali metal ions, NH ₄ ⁺ and ammonium of organic amine.

The following monoazo compound examples (1) to (19) can be exemplified as the monoazo compound corresponding to the ligand D in each monoazo metal compound.
It is not limited to these.

[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

Embedded image The metallizable monoazo compound represented by the formula [II] or the formula [III] can be obtained by a diazotization coupling reaction.

The monoazo metal compound of the present invention and the composition of the present invention contain the metallizable monoazo compound represented by the formula [II] or [III] in water and / or an organic solvent (preferably in an organic solvent). ), It can be obtained by reacting with a metallizing agent.

In general, the reaction product in an organic solvent can be taken out by dispersing it in an appropriate amount of water, filtering the precipitate, washing with water, and drying.

Examples of the organic solvent used in the metallization reaction include methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, ethylene glycol dimethyl ether (monoglyme), diethylene glycol dimethyl ether (diglyme),
Alcohol-based, ether-based, and glycol-based organic solvents such as ethylene glycol diethyl ether, triethylene glycol dimethyl ether (triglyme), tetraethylene glycol dimethyl ether (tetraglyme), ethylene glycol, and propylene glycol; N, N-dimethylformamide, N Examples thereof include water-soluble organic solvents such as aprotic polar solvents such as N, N-dimethylacetamide, N-methyl-2-pyrrolidone and dimethylsulfoxide. Preferred are ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve) and ethylene glycol.

The amount of the organic solvent used is not particularly limited, but is 2 to 5 times the weight ratio of the monoazo compound (dye) used as the ligand.

Examples of suitable metallizing agents include chromium compounds such as chromium formate, chromium sulfate, chromium chloride, and chromium nitrate; iron compounds such as ferric chloride, ferric sulfate, and ferric nitrate. Aluminum compounds such as aluminum sulfate and basic aluminum acetate.

The metallizing agent is generally used in an amount of 1/3 to 2 atomic equivalents, preferably 1/2 to 2/3 atomic equivalents, relative to 1 mol of the monoazo dye serving as a ligand.

Isolation of the product was difficult although various chromatographic separations were tried. Therefore, the monoazo metal compound of the present invention was confirmed by the FD-MS method, which is known to strongly show only the molecular ion peak.

In general, the product obtained by the metallization reaction has, as its main component, a compound of the formula [I] (D ₃ (Met) ₂ ).
And a 3: 2 type monoazo metal compound represented by the formula [IV]
A 6: 4 type monoazo metal compound represented by (D ₆ (Met) ₄ ) is contained, but a small amount of the product is represented by the formula [XII] ([D ₂ (Me
It was confirmed by FD-MS spectrum analysis that the 2: 1 type monoazo metal compound represented by t)] ⁻ · A ⁺ ) was contained.

Since the FD method (Field Desorption) -MS method is a soft ionization method, it is known that fragmentation is unlikely to occur, and therefore a simple spectrum is given and only the molecular ion peak is strongly shown.
[Tsuchiya et al., “New Development of Mass Spectroscopy”, Hyundai Kagaku Special Edition 15 (1
989), Tokyo Kagaku Dojin Shuppan, Mizuno Science and Industry 6
4,578,507 (1990), Mizuno et al. Science and Industry 66,569, (1992)].

The 3: 2 type monoazo metal compound represented by the formula [I] (D ₃ (Met) ₂ ) of the present invention, and the formula [IV] (D
_{The 6} : 4 type monoazo metal compound represented by ₆ (Met) ₄ ) has the following chemical structure (i) or (ii), and
It can be represented by a molecular model such as (iii) or (iv). Although these molecular models are putative structures based on the molecular weight by FD-MS spectrum analysis, they were confirmed to be bondable by chemical bond analysis by the molecular orbital theory.

[0056]

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[0057]

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[0058]

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[0059]

Embedded image Examples of the monoazo metal compound of the present invention represented by the formula [I] (D ₃ (Met) ₂ ) and the formula [IV] (D ₆ (Met) ₄ ) include the following (a) to (h). it can. The range of the molecular weights of these compound examples is based on the isotope of Cl.

[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

Embedded image The charge control agent of the present invention is a charge control agent for controlling or stabilizing the chargeability of a toner for developing an electrostatic image, wherein the monoazo metal compound of the present invention or the composition of the present invention is used as an active ingredient. To do.

The electrostatic image developing toner of the present invention is
It comprises the charge control agent of the present invention, a colorant and a resin. The charge control agent may be composed of, for example, only one kind of the monoazo metal compound of the present invention, or may be one containing a plurality of kinds.

The charge-enhancing agent of the present invention is a charge-enhancing agent for controlling or enhancing the charge amount of the powder coating material for electrostatic coating, which comprises the monoazo metal compound of the present invention or the composition of the present invention. Use as an active ingredient.

The powder coating composition for electrostatic coating of the present invention comprises the charge enhancing agent of the present invention and a resin.

In the toner for developing an electrostatic image and the powder coating material for electrostatic coating according to the present invention, various dyes and pigments can be used as colorants. Specific examples thereof include quinophthalone yellow, isoindolinone yellow, perinone orange, perinone red, perylene maroon, rhodamine 6G lake, quinacridone red, anthanthrone red, rose bengal, copper phthalocyanine blue,
Organic pigments such as copper phthalocyanine green and diketopyrrolopyrrole pigments; inorganic pigments such as carbon black, titanium white, titanium yellow, ultramarine blue, cobalt blue, red iron oxide, aluminum powder, and bronze, and metal powders can be mentioned. .

Examples of the resin used in the toner and powder coating material of the present invention are as follows. That is, as the toner resin, styrene resin,
Styrene-acrylic resin, styrene-butadiene resin,
Styrene-maleic acid resin, styrene-vinyl methyl ether resin, styrene-methacrylic acid ester copolymer, polyester resin, thermoplastic resin such as polypropylene resin; as the coating resin, acrylic resin, polyolefin resin, polyester resin, or It is a thermoplastic resin such as a polyamide resin, or a thermosetting resin such as a phenol resin, an epoxy resin, or a polyester resin.

These resins can be used alone or as a blend of several kinds.

The toner for developing an electrostatic image and the powder coating material for electrostatic coating according to the present invention contain the above-mentioned monoazo metal compound of the present invention or the composition of the present invention as a charge control agent or a charge enhancing agent in an amount of 100% by weight of a resin. It is desirable that 0.1 to 10 parts by weight is blended with respect to parts. A more preferable compounding amount of the charge control or enhancing agent is 0.5 to 5 parts by weight with respect to 100 parts by weight of the resin.

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

That is, the resin, the colorant (preferably carbon black) as described above, the charge control agent of the present invention, and if necessary, the magnetic material, the fluidizing agent, the release agent, etc., are placed in a ball mill or the like. After thoroughly mixing with a mixer, the mixture is melt-kneaded with a heat kneader such as a heating roll, a kneader or an extruder. The melt-kneaded product is cooled and solidified, and then crushed and classified to give, for example, an average particle size of 5
It is possible to obtain a toner having a particle size of 20 μm to 20 μm.

In addition, a method for producing a toner by dispersing another material in a binder resin solution for toner and then spray-drying it, and a method of preparing a predetermined material for a monomer which constitutes the binder resin for toner It is possible to apply a polymerization method, a method for producing a toner, or the like, in which the above is mixed with the emulsified suspension to obtain a toner by polymerization.

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

As the carrier, all known carriers can be used. For example, the particle size is 50 to 200μ
About m of iron powder, nickel powder, ferrite powder, glass beads, and the like, and the surface of these, acrylic acid ester copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, silicone resin, Examples thereof include those coated with a polyamide resin or a fluorinated ethylene resin.

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

Further, the powder coating material for electrostatic coating of the present invention is colored by containing a pigment, and is titanium white, talc, kaolin, silica, alumina, calcium carbonate, aluminum sulfate, barium sulfate, sulfuric acid. It may contain a filler such as calcium, titanium oxide, or calcium phosphate.

The coating with the powder coating material for electrostatic coating of the present invention can be carried out by using a general electrostatic powder coating method such as a corona loading system, a triboelectric charging system or a hybrid system. Can form thick film without defects
It is possible to improve the performance of the coating film, and it is possible to effectively exhibit the characteristics of the powder coating material, such as no coating loss during coating.

[0083]

The monoazo metal compound and the composition comprising the monoazo metal compound of the present invention have excellent heat resistance and light resistance due to their chemical bonding characteristics.

The charge control agent and charge enhancer containing the monoazo metal compound of the present invention as an active ingredient, and the charge control agent and charge enhancer containing the composition of the present invention as an active ingredient are dispersed in a resin. Good property, excellent controllability or stabilization of chargeability or controllability or enhancement of charge amount, excellent environmental resistance, storage stability, and durability,
It does not adversely affect the fixability and offset characteristics of the toner when used for toner.

The electrostatic charge image developing toner of the present invention is excellent in charging property, environment resistance, storage stability, and durability in that it contains the charge control agent of the present invention, and has good fixing property and offset property. Thus, a high-quality toner image can be formed, and a highly reliable toner having stable product quality can be obtained.

The powder coating composition for electrostatic coating of the present invention is excellent in charging property, environmental resistance, storage stability, durability and coating efficiency in that it contains the charge enhancer of the present invention. It is possible to form a coating film and obtain a highly reliable powder coating material with stable product quality.

[0087]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is of course not limited thereto. In the following description, “parts by weight” is replaced by “parts”.
Abbreviated. Example 1 620 g of ethyl cellosolve and 38 ethylene glycol
A mixture of 0 g and 110 g (0.59 mol) of chromium (III) formate was stirred at 80 ° C. for 1 hour.

415 g of the monoazo compound example (1) was added thereto.
(1.39 mol) was added, the temperature was raised to 125 ° C., and the mixture was stirred for 4 hours.

This reaction solution was added to a 3% aqueous hydrochloric acid solution at a concentration of 4000 m.
It was dispersed in 1 l, stirred at 60 ° C. for 1 hour, filtered, and the filtered material was washed with warm water and dried to obtain 400 g of purple powder.

When the molecular weight of this powder was measured by the FD-MS method, the mass spectrum shown in FIG. 1 was obtained (the horizontal axis is M / Z [mass / charge], the vertical axis is Rela.
tive Abundance [abundance ratio] is shown. The same applies to FIGS. 2 to 5. ).

From the mass spectrum diagram of FIG. 1, the 3: 2 type metal compound (monoazo metal compound example (a)) [M / Z 993 (M ⁺ )] of the present invention, which is the main product, is used together with the 2: 1 type. Metal compound ({[monoazo compound example (1)] ₂ (Cr)} ^-・ H ⁺ )
[M / Z 643 (M ⁺ -2)] and unreacted monoazo compound example (1) [M / Z 298 (M ⁺ )] were confirmed.

The molecular weight was measured by the FD-MS method as follows. The same applies to the examples described later.

A sample was dissolved or dispersed in DMF to prepare a mass spectrometer (trade name: JMS-DX303H manufactured by JEOL).
The mass spectrum diagram showing the molecular weight of the sample was measured. -Analysis condition A: FD-MS method (electrolytic desorption / ionization method) -Use of carbon emitter Resolution: 1500, 35-2200 M / Z Accelerating voltage: 2.5 kV Ion multiplier: 1.5-2.5 kV Emitter current: 0 −40 mA Cathode voltage: 5.0 kV Example 2 82 g (0.6 mol) of salicylic acid was dissolved in 500 g of 16% sodium hydroxide aqueous solution, and the temperature was raised to 60 ° C., and then 13.4% iron (III) chloride aqueous solution was added thereto. 470 g was gradually added and further stirred for 20 minutes to dissolve.

The obtained solution was used as the monoazo compound example (1) 1
50 g (0.5 mol) was added to a solution prepared by dissolving 4% aqueous sodium hydroxide solution, heated to 100 ° C. and stirred for 2 hours, and then 65.9 g of 37% aqueous iron (III) chloride solution was added, Stir for 1.5 hours.

This reaction solution was added with a 1.5% hydrochloric acid aqueous solution 250.
The mixture was dispersed in 0 ml, stirred at 60 ° C. for 10 minutes, filtered, and the filtered material was washed with 2000 ml of hot water and dried to obtain 182 g of a black powder.

When the molecular weight of this powder was measured by the FD-MS method, the mass spectrum diagram shown in FIG. 2 was obtained.

From the mass spectrum of FIG. 2, a small amount of the main product 3: 2 type metal compound of the present invention (monoazo metal compound example (d)) [M / Z 999 (M ⁺ -1)] was obtained. 2: 1 type metal compound ({[monoazo compound example (1)] ₂ (Fe)}
^{- · H +) [M /} Z 647 (M + -2)] has been confirmed.

Example 3 82 g (0.6 mol) of salicylic acid was dissolved in 500 g of a 16% sodium hydroxide aqueous solution and the temperature was raised to 60 ° C., and then 470 g of a 13.4% iron (III) chloride aqueous solution was gradually added thereto. , And was stirred for another 20 minutes to dissolve.

The obtained solution was used as the monoazo compound example (1) 1
50 g (0.5 mol) was added to a solution prepared by dissolving 4% sodium hydroxide aqueous solution, the temperature was raised to 100 ° C., and the mixture was stirred for 4 hours.

This reaction solution was added with a 1.5% hydrochloric acid aqueous solution 250.
After dispersing in 0 ml and stirring at 60 ° C. for 10 minutes, the product was filtered, washed with 2000 ml of hot water, and dried to obtain 147 g of a black powder.

When the molecular weight of this powder was measured by the FD-MS method, the mass spectrum diagram shown in FIG. 3 was obtained.

From the mass spectrum of FIG. 3, the 3: 2 type metal compound of the present invention (monoazo metal compound example (d)) [M
^{/ Z 999 (M + -1)} ] and 2: 1 type metal compound ({[monoazo compound Example _{(1)] 2 (Fe)} } - · Na +) [M / Z
670 (M ⁺ -1)] was contained in almost the same amount.

Example 4 82 g (0.6 mol) of salicylic acid was dissolved in 500 g of a 16% sodium hydroxide aqueous solution and the temperature was raised to 60 ° C., and then 470 g of a 13.4% iron (III) chloride aqueous solution was gradually added thereto. , And was stirred for another 20 minutes to dissolve.

The obtained solution was used as the monoazo compound example (11) 2
09 g (0.5 mol) was added to a solution prepared by dissolving 4% sodium hydroxide aqueous solution, the temperature was raised to 100 ° C., and the mixture was stirred for 2 hours.

This reaction solution was added with a 1.5% hydrochloric acid aqueous solution 250.
After dispersing in 0 ml and stirring at 60 ° C. for 10 minutes, the product was filtered, washed with 2000 ml of hot water and dried to obtain 176 g of a black powder.

When the molecular weight of this powder was measured by the FD-MS method, the mass spectrum diagram shown in FIG. 4 was obtained.

From the mass spectrum of FIG. 4, the main product, 3: 2 type metal compound of the present invention (monoazo metal compound example (e)) [M / Z 1359 (M ⁺ )] was confirmed.

Example 5 Monoazo Compound Example (1) 228 g (0.76 mol), ethyl cellosolve 340 g and ethylene glycol 220
g, Chromium (III) formate 76.0 g (0.41 mo
1) and a mixture of 24 g of urea were added at 130 ° C.
For 3 hours.

The reaction solution was filtered while hot, and the filtrate was washed with 3
The dispersion was dispersed in an aqueous solution containing 30 g of 5% hydrochloric acid and 2000 ml of water, stirred at 50 to 60 ° C. for about 30 minutes, filtered, washed with water, and dried to obtain 220 g of a black-purple powder.

81 g of the obtained powder was washed with a Soxhlet extractor using methanol, and then dried to obtain 71 g of a blackish brown powder.

When the molecular weight of this powder was measured by the FD-MS method, the mass spectrum diagram shown in FIG. 5 was obtained.

From the mass spectrum of FIG. 5, a very small amount of the main product along with the 6: 4 type metal compound of the present invention (monoazo metal compound example (g)) [M / Z 1987 (M ⁺ )] was obtained. Inventive 3: 2 type metal compound (monoazo metal compound example (a)) [M / Z 993 (M ⁺ )] and 2: 1 type metal compound ({[monoazo compound example (1)] ₂ (Cr)} ⁻・ H ⁺ ) [M /
Z 644 (M ⁺ -1)] was confirmed. —Electrostatic Image Developing Toner— Next, with respect to the electrostatic image developing toner in which the main component of the contained charge control agent is the monoazo metal compound of the present invention (and the composition of the present invention), Examples A to An explanation will be given with reference to C.

Example A Styrene-acrylic copolymer resin [manufactured by Sanyo Chemical Co., Ltd., trade name: Hymer SMB600] ... 100 parts Low-polymerization polypropylene [manufactured by Sanyo Chemical Co., Ltd. trade name: Viscole 550P] ... 3 parts carbon Black [trade name: MA-100 manufactured by Mitsubishi Kasei Co., Ltd.] ... 6 parts Charge control agent [composition obtained in Example 1] 1 part After uniformly premixing the above composition with a high-speed mixer, It was melted and kneaded with a heating roll, cooled, and coarsely pulverized with a vibration mill.

The obtained coarsely pulverized product was finely pulverized using an air jet mill equipped with a classifier to give a particle size of 10 to 2
A 0 μm negative charge toner was obtained.

An iron powder carrier (trade name: TEFV 200/3, manufactured by Powder Tech Co., Ltd.) was added to 5 parts of the obtained toner.
00) 95 parts were mixed to prepare a developer.

The obtained developer was thoroughly stirred and a blow-off charge amount measuring device (trade name: TB-20, manufactured by Toshiba Chemical Co., Ltd.) was used.
0) was used to measure the charge amount by the blow-off method, the initial blow-off charge amount of the developer was −29.7 μC.
/ G. The initial blow-off charge amounts of the developer at low temperature and low humidity and at high temperature and high humidity are −29.0, respectively.
It was extremely stable at μC / g and −28.8 μC / g and had good storage stability.

Further, when repeatedly reproduced using a commercially available copying machine using this developer, the charging stability and sustainability were good, no offset phenomenon was observed, and a high-quality image without image density reduction or fog was observed. was gotten.

Example B The toner and developer of the present invention were prepared and evaluated in the same manner as in Example A, except that the charge control agent used in Example A was replaced with the composition obtained in Example 2. As a result, the initial blow-off charge amount of this developer was -21.3 μC / g. Further, the initial blow-off charge amounts of this developer at low temperature and low humidity and high temperature and high humidity are -21.5 μC / g and -20.0 μC / g, respectively, which are very stable, and storage stability is also good. It was Further, when repeatedly photographed in the same manner as in Example A, as in Example A, the charging stability and sustainability were good, no offset phenomenon was observed, and a high-quality image without image density reduction or fog was observed. was gotten.

Example C Polyester Resin [Nippon Gosei Kagaku Co., Ltd., trade name: HP-301] ... 100 parts Low-polymerization polypropylene [Sanyo Kasei Co., Ltd. trade name: Viscole 550P] ... 2 parts Carbon black [ Product name: MA-100 manufactured by Mitsubishi Kasei Co., Ltd .... 6 parts Charge control agent [composition obtained in Example 5] 1 part The above composition was treated in the same manner as in Example A to give a negatively chargeable toner. Was prepared to obtain a developer.

Further, when repeatedly reproduced using this developer, a high-quality image having good charge stability and sustainability and no image density reduction or fog was obtained. No offset phenomenon was observed at all.

Comparative Example 1 The charge control agent used in Example A was a chromium complex compound having the following structure (a monoazo compound described in JP-A-59-29254).
Example A in place of the Cr complex compound of t-butylsalicylic acid)
When a toner and a developer were prepared in the same manner as in Example 1 and evaluated in the same manner as in Example A, there were problems in the charge amount and the stability of charge. Further, when the image was repeatedly reproduced using this developer, image scattering, disorder, fog, and the like were observed.

[0122]

Embedded image Comparative Example 2 A toner and a developer were prepared in the same manner as in Example A, except that the charge control agent used in Example A was replaced with a Mg complex compound of t-butylsalicylic acid having the following structure (described in JP-A-62-163061). Was prepared and evaluated, and there were problems in the charge amount and charge stability. Further, when repeatedly reproduced using this developer, image scattering, turbulence, fog, etc. were observed, and it was not satisfactory as a charge control agent.

[0123]

Embedded image —Powder Coating for Electrostatic Coating— Next, the powder coating for electrostatic coating in which the main component of the contained charge enhancer is the monoazo metal compound of the present invention (and the composition of the present invention) is described in Examples. This will be described with reference to D to G.

The powder coating material for electrostatic coating of the present invention can be powder coated by a general electrostatic coating method such as a corona charging method, a friction charging method, and a hybrid method. The explanation will be centered on electrostatic coating by the method.

As shown in Table 1, resin 9 for powder coating
7 to 98 parts, 2 to 3 parts of the composition as a charge enhancer obtained in Examples 1, 3, 4 and 5 and 0 to 5 parts of a colorant are uniformly premixed in a ball mill to form a premix. After the preparation, the mixture was melt-kneaded using a hot roll, cooled, and then coarsely pulverized and finely pulverized to obtain a powder coating material for electrostatic coating having a particle size range of 20 to 250 μm.

Using the obtained powder coating material for electrostatic coating, a friction charging type electrostatic powder coating machine (trade name: manufactured by Nordson Co.)
Tribomatic), a steel plate was subjected to a coating test by a tribocharge system. As a result, it was possible to obtain a coated product with a coating efficiency of 96% or more and no coating defects and a good coating appearance.

[0127]

[Table 1]

[Brief description of the drawings]

1 is an FD-MS spectrum diagram of the composition obtained in Example 1. FIG.

2 is an FD-MS spectrum diagram of the composition obtained in Example 2. FIG.

FIG. 3 is an FD-MS spectrum diagram of the composition obtained in Example 3.

FIG. 4 is an FD-MS spectrum diagram of the composition obtained in Example 4.

5 is an FD-MS spectrum diagram of the composition obtained in Example 5. FIG.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Toru Tsuruhara 8-1 Sanrahigashi-cho, Neyagawa-shi Orient Chemical Research Institute Co., Ltd. (72) Inventor Masashi Yasumatsu 8-1 Sanrahigashi-cho, Neyagawa-shi Orient chemical science Industry Research Institute

Claims (11)

[Claims] 1. D _{3 in} which three molecules of a monoazo compound having two metallizable —OH represented by the following formula [II] or [III] are coordinated with a metal atom (Met) 2 atom: (Met) ₂ ... A monoazo metal compound represented by [I]. (In the formula [I], D
Represents a ligand based on a monoazo compound. ) (In the formula [II], R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently hydrogen, halogen, a nitro group, An alkyl group or a haloalkyl group having 1 to 20 carbon atoms, an aryl group which may be nucleus-substituted, an aralkyl group which may be nucleus-substituted, -SO ₂ N (R ¹¹ ) ₂ [two R ¹¹
Are the same or different from each other, hydrogen,
Lower alkyl group, optionally substituted aryl group,
Or, it represents an optionally substituted aralkyl group. ],
-N (R ¹² ) ₂ [Two R ¹² may be the same or different from each other, and are hydrogen, a lower alkyl group, an optionally substituted nucleus group, an optionally substituted nucleus aralkyl. Represents a group or an acyl group. ] Or -CONH (R ¹³ ) [R ¹³
Represents hydrogen, a lower alkyl group, an aryl group which may be nucleus-substituted, or an aralkyl group which may be nucleus-substituted. ]. Two or more of R ^{1 to} R ¹⁰ may be linked to each other to form an aromatic ring or an aliphatic ring. ) (In the formula [III], R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ ,
R ²⁷ and R ²⁸ are each independently hydrogen, halogen,
A nitro group, an alkyl group or a haloalkyl group having 1 to 20 carbon atoms, an optionally substituted aryl group, an optionally substituted aralkyl group, -SO ₂ N (R ²⁹ ) ₂ [two R ²⁹ are , May be the same as or different from each other,
Hydrogen, a lower alkyl group, an optionally substituted nucleus group, or an optionally substituted nucleus aralkyl group is shown. ], —N (R ³⁰ ) ₂ [Two R ^{30 s} may be the same or different from each other, and are each a hydrogen atom, a lower alkyl group, an optionally substituted nucleus group, or an optionally substituted nucleus group. A good aralkyl group or an acyl group is shown. ] Or -CONH (R
³¹ ) [R ³¹ represents hydrogen, a lower alkyl group, an optionally substituted nucleus group, or an optionally substituted aralkyl group. ]. Two or more of R ^{21 to} R ²⁸ may be linked to each other to form an aromatic ring or an aliphatic ring. ) 2. The monoazo metal compound according to claim 1, which is capable of being metallized by the formula [II] or [III].
6 molecules of monoazo compound having two -OH are metal atoms
(Met) A monoazo metal compound represented by D ₆ (Met) ₄ ... [IV] coordinated to 4 atoms. (D in formula [IV]
Represents a ligand based on a monoazo compound. ) 3. The monoazo metal compound according to claim 1, wherein R ⁵ is hydrogen or an amide group represented by the following formula [V]. Embedded image (In the formula [V], (R ¹⁴ ) _0-2 represents 0 to 2 substituents, and R ¹⁴ represents a halogen, a lower alkyl group, or a lower alkoxy group.) 4. The monoazo metal compound according to claim 1, 2 or 3, wherein the metal atom (Met) is trivalent chromium or trivalent iron. 5. A monoazo metal compound represented by the following formula [VI], a monoazo metal compound represented by the following formula [VII],
And a composition comprising 2 or 3 monoazo metal compounds selected from the group consisting of monoazo metal compounds represented by the following formula [VIII]. Embedded image Embedded image [Chemical 6] (In the formulas [VI], [VII] and [VIII], R ¹ , R ² , R ³ , R ⁴ ,
R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently hydrogen, halogen, a nitro group, an alkyl group having 1 to 20 carbon atoms or a haloalkyl group, and may be nucleus-substituted. Aryl group, optionally substituted aralkyl group, -SO ₂
N (R ¹¹ ) ₂ [Two R ^{11 s} may be the same or different from each other, and are hydrogen, a lower alkyl group, an optionally substituted nucleus group, or an optionally substituted aralkyl group. Indicates a group. ], —N (R ¹² ) ₂ [Two R ¹² may be the same or different from each other, and may be hydrogen, a lower alkyl group, an optionally substituted aryl group, or an optionally substituted nucleus. A good aralkyl group or an acyl group is shown. ],
Alternatively, -CONH (R ¹³ ) [R ¹³ represents hydrogen, a lower alkyl group, an optionally substituted aryl group, or an optionally substituted aralkyl group. ]. R ^{1 to} R ¹⁰ are
Two or more of them may be linked to each other to form an aromatic ring or an aliphatic ring. In formula [VIII], A ⁺ represents a cation. ) 6. The composition according to claim ⁵ , wherein R ⁵ is hydrogen or an amide group represented by the following formula [V]. Embedded image (In the formula [V], (R ¹⁴ ) _0-2 represents 0 to 2 substituents, and R ¹⁴ represents a halogen, a lower alkyl group, or a lower alkoxy group.) 7. A monoazo metal compound represented by the following formula [IX], a monoazo metal compound represented by the following formula [X],
And a composition comprising 2 or 3 monoazo metal compounds selected from the group consisting of monoazo metal compounds represented by the following formula [XI]. Embedded image Embedded image Embedded image (In the formulas [IX], [X] and [XI], R ²¹ , R ²² , R ²³ ,
R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are each independently hydrogen, halogen, a nitro group, an alkyl group or a haloalkyl group having 1 to 20 carbon atoms, an optionally substituted aryl group, aralkyl group which may be substituted on the ^{_{nucleus, -SO 2 N (R 29)}} 2 [2 both R ²⁹ may be the being the same or different, hydrogen, a lower alkyl group, be nucleus-substituted A good aryl group or an optionally substituted aralkyl group is shown. ], -N (R ³⁰ ) ₂ [Two R ³⁰
Are the same or different from each other, hydrogen,
Lower alkyl group, optionally substituted aryl group,
It represents an aralkyl group or an acyl group which may be nuclear-substituted. ], Or —CONH (R ³¹ ) [R ³¹ represents hydrogen, a lower alkyl group, an optionally substituted nucleus group, or an optionally substituted nucleus aralkyl group. ]. R ²¹
Two to more of R ²⁸ to R ²⁸ may combine with each other to form an aromatic ring or an aliphatic ring. In formula [XI],
A ⁺ represents a cation. ) 8. A charge control agent for controlling or stabilizing the chargeability of a toner for developing an electrostatic charge image, which comprises:
A charge control agent comprising the monoazo metal compound according to 2, 3 or 4 or the composition according to claim 5, 6 or 7 as an active ingredient. 9. A charge enhancer for controlling or enhancing the charge amount of a powder coating material for electrostatic coating, which is the monoazo metal compound according to claim 1, 2, 3 or 4, or 5. A charge enhancer comprising the composition according to 7 as an active ingredient. 10. A toner for developing an electrostatic charge image, comprising the charge control agent according to claim 8, a colorant and a resin. 11. A powder coating material for electrostatic coating, comprising the charge enhancer according to claim 9 and a resin.