JPH08160668A - Electrification control agent and toner for developing electrostatic charge image - Google Patents

Abstract

PURPOSE: To provide an electrification control agent excellent in the electrification control characteristic, environmental resistance, preservation stability, and durability and giving no adverse effect to the fixing property and offset characteristic of the toner to be used by using a specific titanium complex compound as an effective component. CONSTITUTION: A titanium complex compound containing saturated or unsaturated alkyl group-substituted salicylic acid and/or saturated or unsaturated alkyl group-substituted hydroxynaphthoic acid as a ligand is used as the effective component of this electrification control agent. The aromatic oxycarboxylic acid selected from the group of the formulas I, II is used as one ligand for the electrification control agent, the aromatic oxycarboxylic acid selected from the group of the formulas III, IV is used as the other ligand, and the titanium complex compound using titanium as the center atom is preferably used as the effective component. In the formula, R<1> and R<2> independently indicate the alkyl group having a straight chain or a branch chain or the unsaturated alkyl group, and (m) and (n) independently indicate integers of 1-4.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatic charge image developing toner used for developing an electrostatic latent image in an electrophotographic method or an electrostatic printing method, and a toner for controlling the charge amount of the toner. The present invention relates to a charge control agent.

[0002]

2. Description of the Related Art In a copying machine or a printer using electrophotography, an electrostatic latent image formed on a photoconductor having a photosensitive layer containing an inorganic or organic photoconductive substance is used. Various toners having a colorant, a fixing resin, and the like are used for developing an image.

Chargeability is a particularly important factor in systems 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 to practical use,
To give a positive charge to the toner, a basic dye such as a nigrosine dye or a triarylmethane dye,
Alternatively, an electron-donating substance such as a quaternary ammonium salt can be used, and as a substance that imparts a negative charge to the toner, a 2: 1 type metal complex salt dye of an azo dye can be used.

However, many of the charge control agents having a dye structure generally have a complicated structure and are poor in stability, and are decomposed by, for example, mechanical friction and shock, temperature and humidity changes, electric shock, and light irradiation. Alternatively, it is likely to deteriorate and lose charge controllability. Moreover, since the dye is colored, it lacks versatility as a color toner. In comparison, the dispersibility in resin is insufficient.

As a charge control agent capable of solving such a problem, a chelate compound having salicylic acid, alkylsalicylic acid, oxynaphthoic acid, salicylaldehyde, phthalic acid or the like as a ligand (for example, salicylic acid or alkylsalicylic acid, Cr, Zn or Al complex; salicylic acid boron complex; oxynaphthoic acid Cr complex; salicylaldehyde Cr or Co complex; phthalic acid Cr or Fe complex)
And so on.

Many of the complex-structure charge control agents listed here are light-colored and have the advantage that they can be used for color toners. However, regarding the uniform dispersibility in resins and the charge control characteristics, especially the charge characteristics due to the difference in the central metal. There was room for research.

The present invention has been made in view of the above problems existing in the prior art, and its object is to obtain charge control characteristics and environment resistance (charge control characteristics such as temperature and humidity). Stability), storage stability (stability of charge control characteristics over time), and durability (stability of charge control characteristics when the toner is repeatedly used many times). A charge control agent that does not adversely affect fixability and offset characteristics, and a toner for developing an electrostatic charge image that has excellent chargeability, environment resistance, storage stability, and durability, and also has good fixability and offset resistance. To provide.

[0009]

The inventors of the present invention have found that a titanium complex compound having an aromatic oxycarboxylic acid as a ligand is highly safe for the human body, has charge controllability, environmental resistance, storage stability, and The present invention has been completed based on the finding that the toner has excellent durability and does not adversely affect the fixability and offset characteristics of the toner even when used in toners of various compositions.

The charge control agent of the present invention comprises a titanium complex compound having a saturated or unsaturated alkyl group-substituted salicylic acid and / or a saturated or unsaturated alkyl group-substituted oxynaphthoic acid as a ligand, as an active ingredient.

The charge control agent of the present invention has the following formulas (a) and (b)
And an aromatic oxycarboxylic acid selected from the group consisting of (c) as one ligand, and an aromatic oxycarboxylic acid selected from the group consisting of the following formulas (d), (e) and (f) It is preferable to use a titanium complex compound having titanium as a central atom as a ligand and a titanium complex compound as an active ingredient.

[0012]

Embedded image [In the formulas (a) to (f), R ¹ and R ² each independently represent a linear or branched alkyl group or an unsaturated alkyl group, and m and n each independently represent 1 to 4
Indicates an integer. In the charge control agent of the present invention, the titanium valence of the titanium complex compound is 3, and hydrogen ion, alkali metal ion, NH ₄ ⁺ or ammonium ion of aliphatic amine is used as a counter ion in the titanium complex compound. It is preferable to have

As the titanium complex compound in which the valence of titanium is 3, there can be mentioned, for example, a compound having a structure represented by the following formula [I] or formula [II]. It may be a mixture of these.

Formula [I]

[0015]

Embedded image [In the formula [I], A ¹ is a residue of an aromatic oxycarboxylic acid selected from the group consisting of the following formulas (a ′), (b ′) and (c ′);
² is a residue of an aromatic oxycarboxylic acid selected from the group consisting of the following formulas (d '), (e') and (f ')

[0016]

[Chemical 4] (In the formulas (a ′) to (f ′), R ¹ and R ² independently of each other represent a linear or branched alkyl group or an unsaturated alkyl group, and m and n are independent of each other. 1 to 4
Indicates an integer. ), M is hydrogen, an alkali metal,
NH ₄ or ammonium of aliphatic amine is shown. ] Formula [II]

[0017]

Embedded image [In the formula [II], A ¹ and A ² have the same meanings as described above. The charge control agent of the present invention may be one in which the valence of titanium in the titanium complex compound is 4.

As the titanium complex compound in which the valence of titanium is 4, for example, a compound having a structure represented by the following formula [III] can be mentioned.

Formula [III]

[0020]

[Chemical 6] [In the formula [III], A ¹ and A ² are as defined above. In the titanium complex compound in the charge control agent of the present invention, both ligands are the same (formula [I], [II], and [III].
], A ¹ = A ² ) is preferable.

Next, the toner for developing an electrostatic charge image of the present invention comprises
At least one of the above charge control agents, a colorant and a binder resin are provided. That is, it may contain one kind of the charge control agent or plural kinds of charge control agents. In the toner of the present invention, the titanium complex compound having the valence of titanium of 3 and the hydrogen ion, the alkali metal ion, NH ₄ ⁺ or the ammonium ion of the aliphatic amine as the counter ion is used as the active ingredient. It is preferable to use a titanium complex compound having the same ligands as the active ingredient.

Formulas (a) to (f) and formulas relating to the ligand of the titanium complex compound which is the active ingredient of the charge control agent of the present invention
Specific examples of the substituents R ¹ and R ² in (a ′) to (f ′) include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert. −
Butyl group, amyl group, isoamyl group, octyl group, te
rt-octyl group, dodecyl group and other linear or branched alkyl groups having about 1 to 12 carbon atoms; and
An unsaturated alkyl group such as an allyl group, a propenyl group and a butenyl group can be mentioned. Particularly preferred as R ¹ and R ² are tert-butyl group and tert-octyl group.

The above formulas (a ') to (f') are

[0024]

[Chemical 7] Is a residue of an aromatic oxycarboxylic acid represented by Specific examples of the aromatic oxycarboxylic acid, that is, the aromatic oxycarboxylic acid represented by the formulas (a) to (f), include:
4-tert-butylsalicylic acid, 5-tert-butylsalicylic acid, 5-propylsalicylic acid, 5-allylsalicylic acid, 3,5-di-tert-butylsalicylic acid, 4-iso
Amyl salicylic acid, 4-tert-octyl salicylic acid,
And alkyl or aryl salicylic acids such as 5-tert-octylsalicylic acid; and 3-hydroxy-7-methyl-
2-naphthalenecarboxylic acid, 3-hydroxy-6-ter
t-Butyl-2-naphthalenecarboxylic acid, 3-hydroxy-7-dodecyl-2-naphthalenecarboxylic acid, 3-hydroxy-7-allyl-2-naphthalenecarboxylic acid, 3-hydroxy-7-tert-butyl-2- Naphthalenecarboxylic acid, 3-hydroxy-7-tert-octyl-2-naphthalenecarboxylic acid, 1-hydroxy-6-ethyl-2-
Naphthalenecarboxylic acid, 2-hydroxy-6-tert-
Examples thereof include butyl-1-naphthalenecarboxylic acid, and alkyl- or allyl-substituted oxynaphthoic acid such as 2-hydroxy-6-tert-octyl-1-naphthalenecarboxylic acid.

M ⁺ is an inorganic or organic cation having the necessary number of charges to neutralize the charge defined by the matrix (anion component) of the compound.

Examples of such cations are hydrogen ions; alkali metal ions such as Na ⁺ and K ⁺ ; NH ₄ ⁺ ; ammonium ions of aliphatic primary amines and aliphatic secondary amines (primary amine and Secondary amines include n-butylamine, tert-butylamine, amylamine, dibutylamine, isoamylamine, pentylamine, hexylamine, octylamine, 2-ethylhexylamine, dodecylamine, cyclohexylamine, dicyclohexylamine, interrupted with oxygen. Examples thereof include butoxypropylamine and octoxypropylamine, and ammonium ions of tertiary amines (the tertiary amines include N, N-dimethylbenzylamine, triethylamine, etc.). You can.), 4th Ammoni Ion (The quaternary ammonium, tetramethylammonium, can be exemplified trimethylbenzylammonium, or the like.) And the like. Among these cations, hydrogen ion and ammonium ion of aliphatic amine having about 4 to 14 carbon atoms are preferable.

The complex compound of trivalent titanium in the present invention is
For example, according to a known method, after the above alkylsalicylic acid or alkyloxynaphthoic acid is chelated with a titanium-providing agent (for example, titanium trichloride), the product is treated with a desired mineral acid, an alkaline agent, or an aliphatic compound. It can be obtained by treating with an amine, and filtering and washing in the form of a protic acid, an alkali metal salt, or an amine salt.

Particularly preferred as a complex compound of trivalent titanium in the present invention is a form of a complex of a protonic acid whose counter ion (M ⁺ ) is hydrogen ion. The pulverizability in this form is extremely good, and the bulk (cc / g) at that time is 6.0 cc.
/ g or more, excellent in uniform dispersibility in the resin. In addition, this compound is externally added to styrene-acrylic resin,
When the charge amount was measured by the blow-off method, the charge amount was −40.0 to −55.0 μC / g, which confirmed that the charge control agent was excellent.

The complex compound of tetravalent titanium in the present invention is
According to a known method, the above alkylsalicylic acid or alkyloxynaphthoic acid is chelated with a titanium-providing agent (for example, titanium isopropoxide) in an alcohol medium to give a hydrate or a hydroxyTi complex compound. It can be obtained by filtering in the form and washing.

Next, specific examples of the titanium complex compound, which is the active ingredient of the charge control agent of the present invention, are represented by the formulas [I] and [III].
] As a representative structure, another structure having a common ligand with titanium as a central atom (for example, formula [II]
The structure) of the titanium complex compound is also included. However, the present invention is not limited to these. All of these can be suitably used as the charge control agent.

[0031]

Embedded image

[0032]

[Chemical 9]

[0033]

[Chemical 10]

[0034]

[Chemical 11]

[0035]

[Chemical 12]

[0036]

[Chemical 13]

[0037]

Embedded image

[0038]

[Chemical 15]

[0039]

Embedded image

[0040]

[Chemical 17]

[0041]

Embedded image

[0042]

[Chemical 19]

[0043]

Embedded image

[0044]

[Chemical 21]

[0045]

[Chemical formula 22]

[0046]

[Chemical formula 23] In the electrostatic charge developing toner of the present invention, the titanium complex compound, which is the active ingredient of the charge control agent of the present invention, is added to the binder resin 10.
It is desirable to mix 0.1 to 10 parts by weight with respect to 0 parts by weight. A more preferable blending amount is 0.5 to 5 parts by weight with respect to 100 parts by weight of the binder resin.

In addition, in order to improve the quality of the toner, additives such as conductive particles, a fluidity improver, a release agent and an image peeling preventive agent may be added internally or externally.

As the resin used in the toner of the present invention, the following known binder resins for toner can be exemplified. That is, styrene resin, styrene-acrylic resin, styrene-butadiene resin, styrene-maleic acid resin, styrene-vinyl methyl ether resin, styrene-methacrylic acid ester copolymer, phenol resin, epoxy resin, polyester resin, polypropylene resin, paraffin For example, wax. These resins are
They can be used alone or as a blend of several kinds.

As the colorant in the toner of the present invention,
Various known dyes and pigments may be used alone or in combination of two or more.

Specific examples of the pigment include quinophthalone yellow, Hansa yellow, isoindolinone yellow, perinone orange, perylene maroon, rhodamine 6G lake, quinacridone red, anthanthrone red,
Organic pigments such as rose bengal, copper phthalocyanine blue, copper phthalocyanine green, and diketopyrrolopyrrole pigments; inorganic pigments such as carbon black, titanium white, titanium yellow, ultramarine blue, cobalt blue, and red iron oxide.

Examples of suitable colorants for color toners include various oil-soluble dyes such as azo dyes, quinophthalone dyes, atraquinone dyes, phthalocyanine dyes, indophenol dyes, indoaniline dyes, and the like. In addition to disperse dyes, xanthene dyes and triarylmethane dyes modified with resins such as rosin, rosin-modified phenol, and rosin-modified maleic acid can be used.

In the toner for developing an electrostatic image of the present invention, the above colorants may be used alone or in combination of two or more. For chromatic monocolor toners, the same color pigments and dyes (for example, quinophthalone pigments and dyes, xanthene or rhodamine pigments and dyes, phthalocyanine pigments and dyes) are appropriately mixed as colorants. Can be used.

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

That is, the binder resin, the colorant, the charge control agent of the present invention, and if necessary, the magnetic material, the fluidizing agent and the like are thoroughly mixed by a ball mill or other mixer, and then heated rolls, A dry toner having an average particle size of 5 to 20 μm can be obtained by melt-kneading with a heat kneader such as a kneader or extruder, cooling and solidifying, and then pulverizing and classifying the mixture.

A method in which a material such as a colorant and a charge control agent according to the present invention is dispersed in a binder resin solution and then spray-dried, or a unit amount of the binder resin to be constituted It is also possible to apply a toner production method or the like, which is a polymerization method in which a predetermined material is mixed with the body to obtain an emulsified suspension, which is then polymerized to obtain a toner.

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

As the carrier, all known carriers can be used. For example, the particle size is 50 to 200 μm
Iron powder, nickel powder, ferrite powder, glass beads, etc., and their surface are acrylic acid ester copolymers,
Examples thereof include those coated with a styrene-acrylic acid ester copolymer, a styrene-methacrylic acid ester copolymer, a silicone resin, a polyamide resin, a fluorinated ethylene resin or the like.

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.

[0059]

INDUSTRIAL APPLICABILITY The charge control agent of the present invention has good dispersibility in a binder resin and is excellent in charge control characteristics, environment resistance, storage stability and durability, and also various binders used in toner. It does not adversely affect the fixability and offset characteristics exhibited by the resin.

In addition, the toner for developing an electrostatic charge image of the present invention is highly safe to the human body in that it contains the charge control agent, and is excellent in charging characteristics, environment resistance, storage stability and durability. Moreover, the toner of the present invention does not impair the fixability and offset characteristics exhibited by the various binder resins used. Therefore, a good quality image can be obtained.

[0061]

EXAMPLES Next, the present invention will be specifically described with reference to examples, but of course the present invention is not limited thereto. In the following description, "part by weight" is abbreviated as "part". -Synthesis of titanium complex compound which is an active ingredient of the charge control agent of the present invention- Example 1 ( synthesis of trivalent titanium complex compound example 1) 12 parts of 3,5-di-tert-butylsalicylic acid and 3 parts of water Sodium oxide was dissolved in 2000 parts of water and the aqueous solution was heated to 60 to 70 ° C.
A mixed solution of 4 parts of titanium trichloride and 20 parts of water was added, followed by stirring at 60 to 70 ° C. for 1 hour to cause a reaction.

After that, the precipitate was collected by filtration, washed with water,
By drying, 13 parts of an orange titanium complex compound (Compound Example 1) was obtained. When this was crushed by a table crusher, a powder having a bulk of 8.1 cc / g was obtained. This powder was externally added to styrene-acrylic resin to prepare a pseudo toner, and the pseudo toner was measured by a blow-off method with a blow-off powder charge amount measuring device [MODEL TB-200 manufactured by Toshiba Chemical Co., Ltd.] to find that it was -41.2 μC / g.
Met.

Example 2 (combining Example 2 of trivalent titanium complex compound)
Adult) 12 parts of 5-tert sodium hydroxide octyl salicylic acid and 3 parts was dissolved in 2000 parts of water, while heating the aqueous solution to 60 to 70 ° C., whereas titanium trichloride 4 parts of water 20 Part of the mixed solution, and then 60
The reaction was allowed to stir at ˜70 ° C. for 1 hour.

Thereafter, the precipitate is filtered off, washed with water,
By drying, 12 parts of an orange titanium complex compound (Compound Example 2) was obtained. When this was crushed by a table crusher, a powder having a bulk of 6.1 cc / g was obtained. The charge amount of this powder was measured in the same manner as in Example 1 and found to be −53.9 μC / g.

Example 3 (combining Example 3 of trivalent titanium complex compound)
20 parts of 3-hydroxy-6-tert-butyl-2-naphthalenecarboxylic acid and 3 parts of sodium hydroxide are added.
It is dissolved in 00 parts of water and the aqueous solution is heated to 60 to 70 ° C., while 4 parts of titanium trichloride and 20 parts of water are added.
Part of the mixed solution was added, and the mixture was continuously stirred at 60 to 70 ° C. for 1 hour for reaction.

Then, the precipitate is filtered off, washed with water,
By drying, 12 parts of an orange titanium complex compound (Compound Example 3) was obtained. When this was crushed with a table crusher, a powder having a bulk of 7.3 cc / g was obtained. When the charge amount of this powder was measured in the same manner as in Example 1, it was -45.7 μC / g.

Example 4 (combining Example 4 of tetravalent titanium complex compound)
Composition) 12 parts of 3,5-di-tert-butylsalicylic acid were dissolved in 100 parts of methyl alcohol. 9 parts of titanium isopropoxide was added to the solution and refluxed for 1 hour.

The resulting precipitate was collected by filtration, washed with methyl alcohol and water, and dried to obtain 7 parts of orange powder (Compound Example 4). When this was crushed with a table crusher, a powder having a bulk of 9.0 cc / g was obtained. The charge amount of this powder was measured in the same manner as in Example 1 and found to be −50.8 μC / g.

Example 5 (combining Example 5 of tetravalent titanium complex compound)
Composition) 12 parts of 3-hydroxy-6-tert-butyl-2-naphthalenecarboxylic acid was dissolved in 100 parts of methyl alcohol. 9 parts of titanium isopropoxide was added to the solution and refluxed for 1 hour.

The resulting precipitate was collected by filtration, washed with methyl alcohol and water, and dried to obtain 10 parts of orange powder (Compound Example 5). When this was crushed with a table crusher, a powder having a bulk of 7.0 cc / g was obtained. When the charge amount of this powder was measured in the same manner as in Example 1, it was -48.4 μC / g.

Example 6 (combining Example 6 of tetravalent titanium complex compound)
Composition) 12 parts of 5-tert-butylsalicylic acid was dissolved in 50 parts of methyl alcohol. 9 parts of titanium isopropoxide was added to the solution and refluxed for 1 hour.

After allowing the solution to cool, 50 parts of water was added thereto and the resulting precipitate was collected by filtration and washed with water,
Orange powder by drying (Compound Example 6)
10 parts were obtained. When this was crushed with a table crusher, a powder having a bulk of 8.2 cc / g was obtained. The charge amount of this powder was measured in the same manner as in Example 1 and found to be −5.
It was 9.7 μC / g. -Toner for developing electrostatic image- Example 7 Styrene-acrylic copolymer resin: 100 parts [Sanyo Chemical Co., Ltd. product name: Hymer SMB600] Low-polymerization polypropylene: 5 parts [Sanyo Chemical Co., Ltd. product name: Viscol 550P] Carbon black ... 5 parts [trade name: MA-100 manufactured by Mitsubishi Kasei Co., Ltd.] Charge control agent (Compound Example 1) ... 1 part The above mixture was uniformly premixed with a high-speed mixer. Next, the mixture was melt-kneaded with an extruder, cooled, and coarsely pulverized with a vibration mill. The obtained coarsely pulverized product is finely pulverized by using an air jet mill equipped with a classifier to obtain a particle size of 10 to 20 μm.
To obtain a negatively chargeable toner.

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

The initial blow-off charge amount of this developer is -3.
It was 0.6 μC / g. Low temperature and low humidity (temperature 5 ° C, relative humidity 30%), high temperature and high humidity (temperature 35 ° C,
The initial blow-off charge amounts at a relative humidity of 90%) were very stable at -30.1 μC / g and −29.6 μC / g, respectively, and the storage stability was also good.

Further, when the image was repeatedly reproduced using a commercially available copying machine using this developer, the charging stability (the variation in the charging value was small) and the sustainability of the charging were good, and the offset phenomenon was not recognized. A high-quality image with no density decrease or fog was obtained.

Example 8 A toner and a developer were prepared in the same manner as in Example 7 except that the charge control agent used in Example 7 was replaced with Compound Example 6.

The initial blow-off charge amount of this developer is -3.
It was 1.2 μC / g. Low temperature and low humidity (temperature 5 ° C, relative humidity 30%), high temperature and high humidity (temperature 35 ° C,
The initial blow-off charge amounts at a relative humidity of 90%) were very stable at -31.4 μC / g and -30.9 μC / g, respectively, and the storage stability was also good.

Further, when the image was repeatedly reproduced using a commercially available copying machine using this developer, the charging stability and the sustainability of the charging were good, the offset phenomenon was not recognized, and the image quality was not deteriorated or fogged. An image was obtained.

Example 9 A toner and a developer were prepared in the same manner as in Example 7, except that the charge control agent used in Example 7 was changed to Compound Example 3.

The initial blow-off charge amount of this developer is -3.
It was 4.3 μC / g. Low temperature and low humidity (temperature 5 ° C, relative humidity 30%), high temperature and high humidity (temperature 35 ° C,
The initial blow-off charge amounts at a relative humidity of 90%) were very stable at −34.1 μC / g and −35.3 μC / g, respectively, and the storage stability was also good.

Further, when the image was repeatedly reproduced using a commercially available copying machine using this developer, the charging stability and the sustainability of the charging were good, the offset phenomenon was not recognized, and the image quality was good without deterioration of image density or fogging. An image was obtained.

Example 10 Polyester resin: 100 parts [Nippon Gosei Kagaku Co., Ltd. trade name: HP-301] Low polymerization polypropylene: 5 parts [Sanyo Chemical Co., Ltd. trade name: Viscol 550P] Rhodamine dye ...・ Part 3 [Product name of Oil Chemical Co., Ltd .: Oil Pink # 3
12] Quinacridone red ... 3 parts Charge control agent (Compound Example 2) ... 2 parts The above formulation was treated in the same manner as in Example 7 to prepare a negatively chargeable magenta toner to obtain a developer.

When repeatedly reproduced using this developer, a high-quality magenta color image having good charge stability and long-lasting charge and no image density reduction or fog was obtained.
No offset phenomenon was observed at all.

Example 11 Polyester resin: 100 parts [Nippon Gosei Kagaku Co., Ltd. trade name: HP-301] Low-polymerization polypropylene: 5 parts [Sanyo Chemical Co., Ltd. trade name: Viscole 550P] Quinophthalone dye [CIDisperse] Yellow 64] ...
2 parts Charge control agent (Compound Example 4) 1 part The above formulation was treated in the same manner as in Example 7 to prepare a negatively chargeable yellow toner to obtain a developer.

Repeated actual copying using this developer gave good charge stability and charge continuity, a good yellow image free from image density reduction and fog was obtained, and no offset phenomenon was observed. It was

Example 12 Styrene-acrylic copolymer resin: 100 parts [Sanyo Chemical Co., Ltd. trade name: Hymer SMB600] Low polymerization polypropylene: 10 parts [Sanyo Chemical Co., Ltd. trade name: Viscole 550P] Iron: 50 parts [Product name: EPT-500 manufactured by Toda Kogyo Co., Ltd.] Carbon black: 6 parts [MA-100 manufactured by Mitsubishi Kasei] Charge control agent (Compound Example 5): 2 parts The above formulation The materials were uniformly premixed with a ball mill to prepare a premix. Then, using a twin-screw extruder,
After melt-kneading at 0 ° C., cooling this, coarse pulverization, fine pulverization, and classification were performed to prepare a one-component toner having a particle size range of 5 to 15 μm.

When a toner image was formed using a commercially available copying machine using the toner of the present invention, a high-quality image free of fog and good in fine line reproducibility was obtained.

Comparative Example 1 The charge control agent (Compound Example 1) used in Example 7 was used as a Cr complex compound of oxynaphthoic acid having the following structure [color: pale yellow, charge amount: −25.0 μC / g, bulk: 3.0 cc / G], a toner was prepared in the same manner as in Example 7 and evaluated in the same manner as in Example 7. As a result, the dispersibility in the resin was poor and there were problems in uniform charging property and charging stability. . Also,
Repeated shootings showed image scatter, distortion, and fog.

[0089]

[Chemical formula 24] Comparative Example 2 The charge control agent (Compound Example 1) used in Example 7 was replaced with a 1: 2 type titanium complex compound having the following structure [color: gray brown, charge amount: -2].
7.0 μC / g Bulk: 4.0 cc / g] A toner was prepared and evaluated in the same manner as in Example 7, except that the charging stability and durability were poor.

[0090]

[Chemical 25] Comparative Example 3 The charge control agent (Compound Example 4) used in Example 11 was replaced with a Mg complex compound of tert-butyl) salicylic acid having the following structure [color: white, charge amount: −22.6 μC / g bulk: 4.4 cc /
g], a toner was prepared in the same manner as in Example 11 and evaluated in the same manner as in Example 11. The hue of the copied image was clear yellow, but the initial blow-off charge amount was inferior, and repeated. When the image was actually taken, the image was scattered, disturbed, and fogged, which was not satisfactory.

[0091]

[Chemical formula 26]

Claims (6)

[Claims] 1. A charge control agent comprising a titanium complex compound having a saturated or unsaturated alkyl group-substituted salicylic acid and / or a saturated or unsaturated alkyl group-substituted oxynaphthoic acid as a ligand, as an active ingredient. 2. An aromatic oxycarboxylic acid selected from the group consisting of the following formulas (a), (b) and (c) as one ligand,
An aromatic oxycarboxylic acid selected from the group consisting of the following formulas (d), (e) and (f) as the other ligand, and a titanium complex compound having titanium as a central atom as an active ingredient. Charge control agent. Embedded image [In the formulas (a) to (f), R ¹ and R ² each independently represent a linear or branched alkyl group or an unsaturated alkyl group, and m and n each independently represent 1 to 4
Indicates an integer. ] 3. The titanium valence of the titanium complex compound is 3, and the counter ion of the titanium complex compound is hydrogen ion, alkali metal ion, NH ₄ ⁺ or ammonium ion of aliphatic amine. Charge control agent. 4. The charge control agent according to claim 2, wherein the valence of titanium in the titanium complex compound is 4. 5. At least one of the charge control agents according to claim 1.
A toner for developing an electrostatic charge image, which comprises a seed, a colorant and a binder resin. 6. At least one of the charge control agents according to claim 2.
A toner for developing an electrostatic charge image, which comprises a seed, a colorant and a binder resin.