JP5294232B2 - Positively chargeable charge control agent and positively chargeable toner for electrostatic image development containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive electrified charge control agent used for obtaining a positive electrified toner for developing an electrostatic charge image which excels in charge stability, storage stability and environmental resistance and gives excellent developed image quality. <P>SOLUTION: The positive electrified charge control agent comprises a silicon complex compound represented by chemical formula (I) or the like as an effective component. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to a positively chargeable charge control agent used for a positively chargeable toner for developing an electrostatic charge image or a powder coating material, a positively chargeable toner for developing an electrostatic charge image including the charge control agent, and a charge control of the toner. It is about the method.

  Electrophotography used in copiers, printers, facsimiles, etc., develops an electrostatic image on a photoconductor with frictionally charged toner, transfers it onto a recording paper, and fixes it for copying or printing. is there.

  The chargeability of the toner is an important factor for increasing the development speed of electrophotography and forming a clear image. A charge control agent is added to the toner in order to appropriately control and stabilize the charge amount of the toner and increase the charge rising speed. Charge control agents include those for positive charging and those for negative charging. The charge control agent for positive charge is disclosed in, for example, Patent Document 1 and Patent Document 2, and the charge control agent for negative charge is disclosed in, for example, Patent Document 3. All of the charge control agents disclosed in these publications are organic in which an organic ligand is coordinated to a metal atom such as aluminum, tin, lead, cobalt, iron, nickel, zinc, chromium, copper, barium, beryllium as a central atom. It is a metal complex compound. In that respect, the charge control agent disclosed in Patent Document 4 is one in which an organic ligand is coordinated to silicon as a central atom, and is for negative charging. For this reason, the toner using the toner becomes a negatively charged toner and is used for developing a positively charged electrostatic charge image on the photosensitive member.

  In order to realize high image quality while increasing the speed of copying and printing, there is a demand for a toner having better charging characteristics and charging stability than conventional toners. Furthermore, the toner and the charge control agent contained therein are also required to have storage stability and, more recently, safety to the environment.

  On the other hand, a charge control agent with appropriate charging characteristics and charging stability even in powder coatings used for electrostatic powder coating, in which electrostatic charge powder coating is attracted to the surface charge of the structure. Is desired.

JP-A 63-206768 JP-A-62-62369 JP-A-3-276166 JP-A-4-295757

  The present invention has been made in view of such a situation, and includes a charge control agent that develops positive chargeability in a positively chargeable toner for developing an electrostatic image or a powder coating material, and a charge control agent containing the charge control agent. An object of the present invention is to provide a positively chargeable toner for developing an electrostatic charge image, which is excellent in stability, storage stability and environmental resistance, and is excellent in developed image quality. It is another object of the present invention to provide a charge control method using this toner.

  The positively chargeable charge control agent of the present invention made to achieve the above object is represented by the following chemical formula (I)

[In the formula (I), D represents a benzene ring or a naphthalene ring, and [D- (SO ₃ ) ₂ ] ^2- Is a divalent anion obtained from an aromatic organic acid having at least two sulfonic acid groups on the benzene ring or naphthalene ring, the following formula (1)

The group represented by the following formula (III)

(In the formula (III), R ¹ ~ R ⁷ And R ¹⁰ ~ R ¹⁴ Is a hydrogen atom, hydroxy group, hydroxyalkyl group, carboxyl group, alkoxycarbonyl group, halogen atom, alkyl group, alkoxy group, acyl group, alkenyl group, nitro group, cyano group, amino group, alicyclic group, aralkyl group, The same or different groups selected from aryl groups, or groups that form saturated or unsaturated condensed rings with adjacent groups to form a ring having 3 to 7 carbon atoms; R ⁸ And R ¹⁵ Is an oxygen atom, a carbonyl group, an imino group; R ⁹ Is a hydrogen atom, hydroxy group, hydroxyalkyl group, carboxyl group, alkoxycarbonyl group, halogen atom, alkyl group, alkoxy group, acyl group, alkenyl group, nitro group, cyano group, amino group, alicyclic group, aralkyl group, The same or different group chosen from an aryl group is shown. ). ],

  And / or the following chemical formula (II)

[In the formula (II), D represents a benzene ring or a naphthalene ring, and [D- (SO ₃ ) ₂ ] ^2- Is a divalent anion obtained from an aromatic organic acid having at least two sulfonic acid groups on the benzene ring or naphthalene ring, the following formula (2)

The group represented by the following formula (IV)

(In the formula (IV), R ^{16 to} R ¹⁷ and R ^{23 to} R ²⁵ are hydrogen atom, hydroxy group, hydroxyalkyl group, carboxyl group, alkoxycarbonyl group, halogen atom, alkyl group, alkoxy group, acyl group, alkenyl group. , A nitro group, a cyano group, an amino group, an alicyclic group, an aralkyl group, an aryl group, the same or different groups; R ¹⁸ is a methine or nitrogen atom; R ^{19 to} R ²² are hydrogen atoms, hydroxy groups, hydroxyalkyl The same or different groups selected from a group, carboxyl group, alkoxycarbonyl group, halogen atom, alkyl group, alkoxy group, acyl group, alkenyl group, nitro group, cyano group, amino group, alicyclic group, aralkyl group, aryl group Or carbon condensed saturated or unsaturated by adjacent groups 3-7 ring formed by that group; R ²⁶ is a nitrogen atom or a substituent (e.g., methyl group, an ethyl group, a propyl group, an alkyl group having 1 to 8 carbon atoms such as butyl group, a methoxy group, an ethoxy Group, an alkoxy group having 1 to 8 carbon atoms such as a propoxy group and a butoxy group, a halogen such as Cl, Br, I and F, an aryl group such as a phenyl group, a toluyl group and a naphthyl group, and a hydrogen atom) Represents a carbon atom that may be present. The halogen content remaining in the silicon complex compound represented by the chemical formula (I) or (II) is 0.2% at the maximum.

  The positively chargeable charge control agent is a compound represented by the following chemical formula (V):

(In Formula (V), X is a halogen atom, and p, B, J, and A are the same as the group represented by Formula (1) .)
A compound obtained by ion-exchange reaction of the silicon complex salt represented by the above and the organic acid or a salt thereof ,

(In the formula (VI), X is a halogen atom, and p, B, J, and R are the same as the group represented by the formula (2) .)
More preferably, it is a compound obtained by ion-exchange reaction of the silicon complex salt represented by formula (I) and the organic acid or a salt thereof.

In the positively chargeable charge control agent, the aromatic organic acid is preferably a naphthalenedisulfonic acid derivative .

  The positively chargeable charge control agent preferably has a weight reduction rate of 10.0% at the maximum after the heat treatment at 180 ° C. for 2 hours for the silicon complex compound of the chemical formula (I) or (II).

The positively chargeable charge control agent preferably has a volume resistivity of 1.0 × 10 ^{13 to} 5.0 × 10 ¹⁵ Ω · cm in the silicon complex compound represented by the chemical formula (I) or (II).

  The positively chargeable toner for developing an electrostatic image preferably contains the positively chargeable charge control agent.

  The positively chargeable toner for developing an electrostatic image preferably contains 0.1 to 10 parts by weight of the positively chargeable charge control agent and 100 parts by weight of the toner resin.

  The charge control method is to positively charge the positively chargeable toner for developing the electrostatic image by friction.

  The charge control agent containing the silicon complex compound of the present invention is to develop good positive chargeability in a positively chargeable toner for developing an electrostatic image or a powder coating material. It is particularly excellent in terms of heat resistance, storage stability, and environmental safety. This charge control agent can be used by adding to a wide variety of chromatic toners as well as monochrome toners.

  The positively chargeable toner for developing an electrostatic charge image of the present invention containing this charge control agent has a fast charge rising speed and exhibits excellent charging stability for a long time even when the temperature and humidity change. Further, since the stability to heat is high and the dispersibility of the charge control agent in the resin for toner is good, there is very little variation in charging characteristics among the obtained toner particles.

  This positively chargeable toner for developing electrostatic images is suitable for developing electrostatic images on all types of photoreceptors, whether inorganic or organic. Further, it is suitable for development on transfer recording media such as processed paper and processed film as well as plain paper. Further, the toner image developed with the positively chargeable toner for developing an electrostatic charge image has fixability in a wide temperature range. The fixed image is clear, has no fogging, has no offset, and does not deteriorate for a long time.

BEST MODE FOR CARRYING OUT THE INVENTION

  Examples of the present invention will be described in detail below, but the scope of the present invention is not limited to these examples.

  The positively chargeable charge control agent of the present invention comprises a salt of a silicon complex cation and a divalent anion of an organic acid having at least two sulfonic acid groups, and is represented by the chemical formula (I) or (II). The complex compound is an active ingredient. This silicon complex compound preferably has a group represented by the formula (III) or (IV).

  The silicon complex compound of the chemical formula (I) or (II) is obtained by subjecting the silicon complex salt represented by the chemical formula (V) or (VI) and the organic acid or a salt thereof to an ion exchange reaction. It is.

R ^{1 to} R ²⁶ in the formula (III) or (IV) are groups as described above. More specifically, examples of R ^{1 to} R ⁷ , R ^{9 to} R ¹⁴ , and R ^{16 to} R ²⁵ include the following.

  Examples of the halogen atom include Cl, Br, I, and F.

  The alkyl group may have a substituent such as a nitro group, a halogen atom exemplified by Cl, Br, I, and F, or an alkoxy group having 1 to 18 carbon atoms, and does not have a substituent. For example, an alkyl group having 1 to 18 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group Is mentioned.

  The alkoxy group may have a substituent such as a hydroxy group, a nitro group, a halogen atom exemplified by Cl, Br, I, and F, or an alkyl group having 1 to 18 carbon atoms. For example, an alkoxy group having 1 to 18 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group can be given.

  Examples of the acyl group include formyl group, acetyl group, propionyl group, butyryl group, valeryl group, pivaleroyl group, and benzoyl group.

  Examples of the hydroxyalkyl group include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, and a hydroxyhexyl group.

  Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, and a butenyl group.

  Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group, and a hexyloxycarbonyl group.

  The aryl group has a substituent such as a hydroxy group, a nitro group, a halogen atom exemplified by Cl, Br, I, and F, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms. And may not have a substituent, and examples thereof include a phenyl group, a toluyl group, a butylphenyl group, an octylphenyl group, and a naphthyl group.

  Examples of the alicyclic group include a substituent such as a hydroxy group, a nitro group, a halogen atom exemplified by Cl, Br, I, and F, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms. It may have or may not have a substituent, and examples thereof include a cycloalkyl group having 3 to 7 carbon atoms such as a cyclopropenyl group, a cyclobutyl group, a cyclohexyl group, and a cycloheptyl group.

  The aralkyl group has a substituent such as a hydroxy group, a nitro group, a halogen atom exemplified by Cl, Br, I, and F, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms. And may not have a substituent, and examples thereof include a benzyl group and an α, α′-dimethylbenzyl group.

  Moreover, as group which forms the C3-C7 ring condensed by adjacent or saturated by adjacent groups, it may have a substituent and does not need to have a substituent. Examples thereof include a cyclopropene ring, a cyclopropane ring, a cyclobutadiene ring, a cyclobutane ring, a cyclopentadiene ring, a cyclopentane ring, a cyclohexane ring, a cycloheptatriene ring, and a benzene ring. Of these, a benzene ring is preferred. Examples of the substituent that the condensed ring may have include a hydroxy group, a halogen atom, an alkyl group, an alkoxy group, an acyl group, an aralkyl group, an alicyclic group, and an alkenyl group.

[D- (SO ₃ ) ₂ ] ^2- in the chemical formula (I) or (II) is a polysulfonic acid having at least two sulfonic acid groups (—SO ₃ M M: hydrogen, alkali metal, ammonium). It is a divalent anion obtained from an organic acid. Examples of the organic acid include aromatic or aliphatic organic acids having at least two sulfonic acid groups as substituents. Preferably, it is an aromatic organic acid having at least two sulfonic acid groups on the benzene ring or naphthalene ring.

  The organic acid is preferably a naphthalenedisulfonic acid derivative represented by the following formula (VII).

(In the formula (VII), M is hydrogen, alkali metal, ammonium, R ^{27 to} R ²⁹ are hydrogen atom, hydroxyl group, amino group, alkylamino group [for example, methylamino group, ethylamino group, propylamino group, butyl) Amino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, etc.], acetylamino group, benzoylamino group, nitro group, alkyl group [for example, methyl group, ethyl group, propyl group, And an alkyl group having 1 to 18 carbon atoms such as isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group, heptyl group and octyl group], an alkoxy group [for example, methoxy group, C1-C1 such as ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group 8), an acetyloxy group, a halogen atom (for example, Cl, Br, I, and F), a phenyloxy group, a carboxyl group, an acyl group [for example, a formyl group, an acetyl group, And propionyl group, butyryl group, valeryl group, pivaleroyl group, benzoyl group, etc.].

  More specific examples of the organic acid include naphthalene derivatives represented by the following formula (VIII) having at least two sulfonic acid groups as substituents and shown in Table 1.

  Another specific example of the organic acid is a benzene derivative represented by the following formula (IX) having at least two sulfonic acid groups as a substituent and described in Table 2.

  In the structural formula shown in the chemical formula (I), when J is a carbon atom, the following chemical formula (X)

In the structural formula shown in the chemical formula (II), when J selects a carbon atom, the following chemical formula (XI)

で表記される場合がある。

May be written as

  This positively chargeable charge control agent comprises, as an active ingredient, a silicon complex compound of the above formula (I) or (II) in which a salt of a silicon complex cation and an organic acid anion having at least two sulfonic acid groups is formed. It is prepared by containing.

  The silicon complex compound can be prepared by combining known methods.

  For example, the silicon complex compound of the chemical formula (I) is prepared by the following method. First, in the first step, the following formula (XII) having a hydroxyl group and a carbonyl group in a siliconizing agent such as silicon halide or tetraethoxysilane exemplified by silicon tetrachloride

(In the formula (XII), p, B, J and A are the same as those in the chemical formula (I)). Then, silicon derived from the siliconizing agent becomes a central atom, oxygen derived from a hydroxyl group is covalently bonded, and a carbonyl group is coordinated, and the following formula (XIII)

(In the formula (XIII), p, B, J, and A is the chemical formula (I) in the same [E] ^-.. Is showing an anion) silicon complex intermediate represented by is obtained. Incidentally, the [E] ^- is generally an anion derived from a silicon agent.

In order to obtain a silicon complex intermediate with high yield and high purity, it is preferable to use a silicon halide exemplified by silicon tetrachloride as a siliconizing agent. For example, when a compound represented by the chemical formula (XII) is reacted with silicon tetrachloride, [E] ⁻ in the chemical formula (XIII) is a halogen anion [X ] ⁻ (For example, Cl ⁻ : chloro ion).

In the subsequent second step, the silicon complex intermediate is reacted with an organic acid having at least two sulfonic acid groups or a salt D- (SO ₃ M) ₂ thereof, and the silicon complex intermediate represented by the formula (XIII) is reacted. By ion-converting [E] ⁻ (for example, [X] ⁻ ) in the body and an anion [D- (SO ₃ ) ₂ ] ^{2− of} an organic acid having at least two sulfonic acid groups, A silicon complex compound represented by the chemical formula (I) is obtained.

  Although the example of the silicon complex compound represented by the chemical formula (I) is shown, the same applies to the silicon complex compound represented by the chemical formula (II).

  An important feature of the present invention is that the counter ion in the silicon complex compound is an organic acid having at least two sulfonic acid groups. The positively chargeable charge control agent comprising the silicon complex compound of the present invention comprises a silicon complex compound outside the scope of the present invention in which the counter ion is various anions other than organic acids having at least two sulfonic acid groups, such as chloro ions. Compared to a charge control agent, it has an advantageous effect of improving charging characteristics, thermal stability, and environmental stability.

  In the ion exchange reaction, the residual halogen content derived from the chemical formula (V) or (VI) should be 0.2% or less, more preferably 0.1% or less. This is an important factor for improving the charging characteristics of the chargeable charge control agent. By such a preferred embodiment in which the residual halogen content is low, charging stability, storage stability, and environmental resistance are further improved.

  Specific examples of the silicon complex compound represented by the chemical formula (I) or (II) include the following compounds. Of course, the present invention is not limited to these.

  The positively chargeable charge control agent may include a single compound among these silicon complex compounds, or may include a plurality of compounds having different structures. A silicon complex compound composed of a plurality of different silicon complexes or a higher order compound of different organic acid divalent anions may be included. Furthermore, it may coexist with a conventional charge control agent.

  The positively chargeable toner for developing an electrostatic image of the present invention contains the positively chargeable charge control agent.

  The positively chargeable toner for developing an electrostatic image preferably contains 0.1 to 10 parts by weight of a positively chargeable charge control agent and 100 parts by weight of a toner resin. The charge control agent is more preferably 0.5 to 5 parts by weight. Further, a colorant may be included.

  The positively chargeable toner for developing an electrostatic image may be a toner resin in which a charge control agent and a colorant are kneaded and added internally. Or the child particle | grains containing a charge control agent may adhere to the surface of the mother particle | grains containing resin for toner and a coloring agent. The mother particles may contain a charge control agent, and the child particles may contain a toner resin.

  The charge control method for a positively chargeable toner for developing an electrostatic image according to the present invention is to charge the toner positively by rubbing the toner.

  In the silicon complex compound represented by the chemical formula (I) or (II) in the positively chargeable charge control agent, two ions composed of a monovalent silicon complex cation are converted into one ion composed of a divalent organic acid anion. It has a combined structure. This silicon complex compound greatly changes the thermal stability and environmental stability of the toner when contained in the toner, depending on the type of anion which is a counter ion. When this silicon complex compound has the above structure, characteristics such as thermal stability and environmental stability that are indispensable as a charge control agent are larger than those of a silicon complex compound having an anion component other than a sulfonic acid group. improves.

  Furthermore, the silicon complex compound represented by the chemical formula (I) or (II) is characterized by the fact that it hardly decomposes and hardly loses weight even when exposed to a high temperature for a long time due to the structure. Have. Therefore, the positively chargeable toner for developing an electrostatic charge image containing the charge control agent of the present invention has a very low possibility of generation of a charge control agent-derived chemical substance harmful to the human body in the exhaust gas during printing. The load and safety are excellent.

The volume resistivity of the silicon complex compound represented by the chemical formula (I) or (II) is preferably 1.0 × 10 ^{13 to} 5.0 × 10 ¹⁵ Ω · cm, and 1.0 × 10 ^{14 to} 5. More preferably, it is 0 × 10 ¹⁵ Ω · cm. The positively chargeable toner for developing an electrostatic charge image containing this charge control agent has a stable chargeability, and the charge amount or charge speed of the toner can be adjusted to a required appropriate level.

  The positively chargeable toner for developing an electrostatic charge image containing this positively chargeable charge control agent is excellent in charging stability, storage stability and environmental resistance. An image developed using this charged toner has excellent quality. In addition, this toner contains this positively chargeable charge control agent, so that fluctuations in toner charge amount due to severe environments from high temperature and high humidity to low temperature and low humidity and environmental changes are suppressed. Excellent stability.

  The positively chargeable toner for developing an electrostatic charge image of the present invention includes the charge control agent, the toner resin, the colorant, and a magnetic material and a fluidity modification that are appropriately used as necessary to improve the quality of the toner. It contains a quality agent and an anti-offset agent.

  Resin for toner is a commercially available binder resin such as styrene resin, styrene-acrylic resin, styrene-butadiene resin, styrene-maleic acid resin, styrene-vinyl methyl ether resin, styrene-methacrylic acid ester copolymer, polyester resin. And thermoplastic resins such as polypropylene resins; thermosetting resins such as phenol resins and epoxy resins. These resins may be used alone or may be used by blending a plurality of types.

  The toner resin may be mixed with a subtractive color full color toner or an overhead projector (OHP) toner. For this purpose, the toner resin has transparency, is almost colorless so as not to cause a color tone defect in the toner image, has good compatibility with the charge control agent, and is subjected to appropriate heat or pressure. It is necessary to have fluidity and to be atomized. Such a resin for toner is preferably a styrene resin, an acrylic resin, a styrene-acrylic resin, a styrene- (meth) acrylate copolymer, or a polyester resin.

  Next, the charge of the powder coating material can be controlled or enhanced by adding the charge control agent of the present invention to the resin powder coating material for electrostatic coating. Since the resin powder coating material for electrostatic coating containing the charge control agent of the present invention is excellent in heat resistance and good intensifying properties, it exhibits high coating efficiency without having to collect and reuse the powder coating material. The coating using the powder coating can be performed using a general electrostatic powder coating method such as a corona imprinting method, a friction charging method, or a hybrid method.

  Examples of the resin in the paint include thermoplastic resins such as acrylic resins, polyolefin resins, polyester resins, and polyamide resins; thermosetting resins such as phenol resins and epoxy resins. Can be mentioned. These resins may be used alone or as a blend of a plurality of types.

  As the colorant for the color toner or the colorant for the electrostatic powder coating material, dyes and pigments may be used alone or in combination.

  Examples of colorants for color toners include quinophthalone yellow, hansa yellow, isoindolinone yellow, benzidine yellow, perinone oleidine, perinone red, perylene maroon, rhodamine 6G lake, quinacridone red, rose bengal, copper phthalocyanine blue, copper phthalocyanine green, Organic pigments such as diketopyrrolopyrrole pigments; carbon black, titanium white, titanium yellow, ultramarine, cobalt blue, brown, aluminum powder, bronze, inorganic pigments and metal powders; azo dyes, quinophthalone dyes, Oil-soluble dyes and disperse dyes such as anthraquinone dyes, xanthene dyes, triphenylmethane dyes, phthalocyanine dyes, indophenol dyes, indoaniline dyes; rosin Rosin-modified phenol, triarylmethane dyes modified with a resin as rosin-modified maleic acid; was processed like in higher fatty acid and resins, dyes and pigments. In the color toner, these colorants may be blended singly or in combination. Dyes and pigments having good spectral characteristics can be suitably used for the preparation of full-color three primary color toners.

  In addition, as colorants for chromatic monocolor toners, the same color pigments and dyes, for example, rhodamine pigments and dyes, quinophthalone pigments and dyes, phthalocyanine pigments and dyes are appropriately blended and used. be able to.

  Examples of the magnetic material include fine powder made of a ferromagnetic material exemplified by iron, cobalt, and ferrite. Examples of the fluidity modifier include silica, aluminum oxide, and titanium oxide. Examples of the offset preventive agent include wax and low molecular weight olefin wax.

  The positively chargeable toner for developing an electrostatic image is produced as follows. The charge control agent, toner resin, colorant, and magnetic materials, fluidity modifiers and anti-offset agents, if necessary, are thoroughly mixed using a mixer such as a ball mill, and then the mixture is heated to a heating roll, kneader, extensible Melt and knead using a heat kneader such as a ruder. The kneaded product is cooled and solidified, and then the solidified product is pulverized and classified to obtain a one-component toner having an average particle size of 5 to 20 μm as pulverized toner particles.

  In addition, a method of obtaining toner particles by spray-drying a solution of each component, a suspension polymerization method, an emulsion polymerization method, or the like can also be employed. Suspension polymerization methods include toner resin monomers, charge control agents, colorants, and magnetic materials, fluidity modifiers, offset inhibitors, polymerization initiators, crosslinking agents, and mold release agents as needed. And a suitable dispersing machine in a continuous layer containing a dispersion stabilizer, for example, in an aqueous phase. The toner particles having a desired particle diameter are obtained by carrying out the polymerization reaction while being dispersed using the toner.

  Examples of such polymerizable monomers include styrene derivatives such as styrene and methylstyrene; (meth) acrylic acid esters such as methyl acrylate, ethyl acrylate, ethyl methacrylate, and n-butyl methacrylate. A vinyl monomer such as acrylonitrile, methacrylonitrile, acrylamide;

  As dispersion stabilizers, surfactants such as sodium dodecylbenzenesulfonate; organic dispersants such as polyvinyl alcohol, methylcellulose, methylhydroxypropylcellulose; inorganic dispersants such as phosphorous such as calcium phosphate, magnesium phosphate and aluminum phosphate Examples include acid polyvalent metal salt fine powder, carbonate fine powder such as calcium carbonate and magnesium carbonate, calcium metasilicate, calcium sulfate, barium sulfate, calcium hydroxide, and aluminum hydroxide.

  Examples of the polymerization initiator include azo or diazo polymerization initiators such as 2,2'-azoisobutyronitrile and azobisbutyronitrile; and peroxide polymerization initiators such as benzoyl peroxide.

  Further, the positively chargeable toner for developing an electrostatic image can be produced as follows. The above pulverized toner particles or polymerized toner particles containing a charge control agent are used as mother particles, and on the surface of the mother particles, child particles consisting only of charge control agent particles, or 10 to 10 charge control agent-dispersible resins. A toner is obtained by adhering child particles composed of particles in which 90% by weight of the charge control agent is dispersed.

  Examples of the method of attaching the child particles to the surface of the mother particle include an external addition method and a method of driving the child particle into the mother particle by a hybridization system. Examples of the charge control agent-dispersible resin include styrene resin, styrene-acrylic resin, styrene-butadiene resin, styrene-maleic resin, styrene-vinyl methyl ether resin, styrene-methacrylic acid ester copolymer, phenol resin, and epoxy resin. , Paraffin wax, acrylic resin, and polyester resin. These resins may be used alone or as a blend of a plurality of types.

  Although an example in which pulverized toner particles or polymerized toner particles containing a charge control agent are used as mother particles is shown, pulverized toner particles or polymerized toner particles not containing a charge control agent may be used as mother particles.

  The two-component developer using the positively chargeable toner for developing an electrostatic image is prepared by mixing the toner and a carrier, and is used when developing by a two-component magnetic brush developing method or the like. As this carrier, for example, iron powder, nickel powder, magnetite powder, ferrite powder, glass beads having a particle size of about 50 to 200 μm, and their surfaces are made of acrylate copolymer, styrene-acrylate copolymer, styrene. -Those coated with a methacrylic acid ester copolymer, a silicone resin, a polyamide resin, or a fluorinated ethylene-based resin.

  In the one-component developer using the positively chargeable toner for developing an electrostatic image, an appropriate amount of a fine powder of a ferromagnetic material such as iron powder, nickel powder or ferrite powder is added and dispersed when the toner is prepared. It is used when developing by contact developing method, jumping developing method or the like.

  Examples of the present invention will be specifically described below, but the present invention is not limited to these examples.

  The following synthesis examples 1-6 show the synthesis example of the silicon complex compound used for the charge control agent to which this invention is applied.

(Synthesis Example 1)
(1-1) Synthesis of Silicon Complex Intermediate 16-0.0 g (0.614 mol) of 1- (4′-t-butylphenyl) -4,4-dimethylpentane-1,3-dione was dissolved in 800 ml of ethyl acetate. . To this, 34.8 g (0.204 mol) of silicon tetrachloride was added dropwise at room temperature. After heating under reflux for 2 hours, the mixture was allowed to cool, and the precipitated white crystals were filtered. After washing with 600 ml of ethyl acetate, washing with 2000 ml of water, and drying at 80 ° C. for 24 hours, 107.4 g (0.128 mol) of a silicon complex intermediate of Compound Example a represented by the following chemical formula was obtained.

  FIG. 1 shows data obtained by performing liquid chromatography mass spectrometry (LC / MS) on the silicon complex intermediate of Compound Example a using an M-8000 LC / 3DQMS system (trade name of Hitachi, Ltd.). As shown in FIG. 1, the actually measured value m / z is 806.13, which is almost the same as the theoretical value 806.2 in which chlorine ions are eliminated from the theoretical value 841.6. Was identified.

(1-2) Anion Exchange 28 g (33.7 mmol) of the silicon complex intermediate of Compound Example a is dispersed in a water-methanol mixed solution, and 5.72 g (17.2 mmol) of 1,5-naphthalenedisulfonic acid disodium salt is dispersed. The mixture was added and dispersed at room temperature for 24 hours. The resulting reaction solution was filtered and washed with water until the conductivity of the filtrate decreased. By drying at 80 ° C., 30.9 g (16.3 mmol) of the silicon complex compound represented by Compound Example 1 was obtained.

(1-3) Identification Data obtained by performing liquid chromatography mass spectrometry (LC / MS) on the silicon complex compound of Compound Example 1 using an M-8000 LC / 3DQMS system (trade name of Hitachi, Ltd.) Is shown in FIG. As shown in FIG. 2, the actually measured value m / z of one of the liquid chromatography peaks was 805.60, and the theoretical value 1612.3 from which 1,5-naphthalenedisulfonic acid was eliminated from the theoretical value 1898.6. 1 of 806.15. In addition, as shown in FIG. 3, the actual measurement value m / z of another peak is 143.20, which is half the theoretical value 286.3 of 1,5-naphthalenedisulfonic acid which is a divalent anion. It is almost coincident with 143.15. In CHS elemental analysis, C: 70.54% (theoretical value: 70.85%), H: 7.91% (theoretical value: 7.64%), S: 3.40% (theoretical value: 3 .38%), which was almost the same as the theoretical value, and thus was identified as the desired Compound Example 1.

(1-4) Chlorine analysis The amount of residual chlorine in the obtained silicon complex compound was measured by a coulometric method using a chlorine-sulfur measuring apparatus TOX-10Σ (manufactured by Mitsubishi Kasei Co., Ltd .; trade name). The amount of residual chlorine in the silicon complex compound was 770 ppm.

(1-5) Thermal Analysis Regarding thermal analysis of the obtained silicon complex compound, differential thermal and thermogravimetric simultaneous measurement device TG / DTA6200 (SII Nanotechnology Inc.) The product was measured by isothermal mass change method using a product name. The weight loss rate was 4.9%.

(1-6) Volume resistivity measurement The volume resistivity of the obtained silicon complex compound was measured under the following conditions.
Test atmosphere: 23 ± 2 ° C, 50 ± 5% RH
Testing machine: Digital ultra-high resistance / micro ammeter R8340A type Applied voltage manufactured by Advantest Co., Ltd., time: 500 V (DC), 1 minute Electrode: main electrode diameter 38 mm
Number of tests: n = 1
The sample was compressed to a load of 2000 kg. The volume specific resistance was 4.37 × 10 ¹⁴ Ω · cm.

(Synthesis Example 2)
(2-1) Synthesis of silicon complex intermediate 50.0 g (0.223 mol) of dibenzoylmethane was dissolved in 250 ml of toluene. To this, 12.6 g (0.074 mol) of silicon tetrachloride was added dropwise at room temperature. After reacting at 50 ° C. for 5 hours, the mixture was allowed to cool, and the precipitated pale yellow crystals were filtered. After washing with 500 ml of toluene, washing with 500 ml of water, and drying at 80 ° C. for 24 hours, 44.8 g (0.061 mol) of a silicon complex intermediate of Compound Example b represented by the following chemical formula was obtained.

  FIG. 4 shows data obtained by performing liquid chromatography mass spectrometry (LC / MS) on the silicon complex intermediate of Compound Example b using an M-8000 LC / 3DQMS system (trade name of Hitachi, Ltd.). As shown in FIG. 4, the actually measured value m / z is 697.47, which is almost the same as the theoretical value 697.78 in which chlorine ions are eliminated from the theoretical value 733.28. Was identified.

(2-2) Anion Exchange 20 g (27.3 mmol) of the silicon complex intermediate of Compound Example b was dispersed in a mixed solution of water and methanol, and 4.62 g (13.9 mmol) of 1,5-naphthalenedisulfonic acid disodium salt was dispersed. The mixture was added and dispersed at room temperature for 24 hours. The resulting reaction solution was filtered and washed with water until the conductivity of the filtrate decreased. By drying at 80 ° C., 21.5 g (12.8 mmol) of Compound Example 27 was obtained.

(2-3) Identification Data obtained by performing liquid chromatography mass spectrometry (LC / MS) on the silicon complex compound of Compound Example 27 using an M-8000 LC / 3DQMS system (trade name of Hitachi, Ltd.) Is shown in FIG. As shown in FIG. 5, the actually measured value m / z is 696.73, which is approximately 697.8, which is a half of the theoretical value 1395.6 from which the 1,5-naphthalenedisulfonic acid is eliminated from the theoretical value 1681.9. Match. Further, as shown in FIG. 6, the actually measured value m / z is 143.33, which is one half of the theoretical value 286.3 of 1,5-naphthalenedisulfonic acid which is a divalent anion. 15 is almost the same. In CHS elemental analysis, C: 71.15% (theoretical value: 71.41%), H: 4.35% (theoretical value: 4.31%), S: 3.85% (theoretical value: 3 .81%), which was almost the same as the theoretical value, and was identified as Desired Compound Example 27.

(2-4) Chlorine analysis, (2-5) Thermal analysis and (2-6) Volume resistivity measurement The obtained silicon complex compound was measured in the same manner as described above, and the residual chlorine content was 336 ppm, 180 ° C. The weight loss rate after heat treatment for 2 hours was 4.4%, and the volume resistivity was 2.8 × 10 ¹⁵ Ω · cm.

(Synthesis Example 3: Synthesis of Compound Example 4)
25 g (80.5 mmol) of 4-t-butyl-4′-methoxydibenzoylmethane was dissolved in 250 ml of toluene. To this, 4.56 g (26.8 mmol) of silicon tetrachloride was injected. After reacting at 50 ° C. for 4 hours, the mixture was allowed to cool, and the precipitated yellow crystals were filtered, washed with 200 ml of toluene, further washed with 400 ml of water, and then dried at 80 ° C. for 24 hours to obtain a silicon complex intermediate. Obtained. 10 g (10.1 mmol) of the obtained silicon complex intermediate was dispersed in a mixed solution of water and methanol, and 1.76 g (5.07 mmol) of 4-amino-2,7-naphthalenedisulfonic acid disodium salt was added thereto, and 24 11.0 g (4.97 mmol) of Compound Example 4 was obtained by performing a dispersion treatment at room temperature for an hour.

(Synthesis Example 4: Synthesis of Compound Example 5)
20 g (89.2 mmol) of dibenzoylmethane was dissolved in 80 ml of toluene. A solution prepared by dissolving 5.05 g (29.7 mmol) of silicon tetrachloride in 20 ml of toluene was added dropwise thereto. After reacting at 50 ° C. for 4 hours, the mixture was allowed to cool, and the precipitated pale yellow crystals were filtered, washed with 200 ml of toluene, washed with 100 ml of tetrahydrofuran, further washed with 100 ml of water, and then dried at 80 ° C. for 24 hours. Thus, a silicon complex intermediate was obtained. 10 g (13.6 mmol) of the obtained silicon complex intermediate was dispersed in a mixed solution of water and methanol, and 2.48 g (6.8 mmol) of 4,5-dihydroxy-2,7-naphthalenedisulfonic acid disodium salt was added. Then, dispersion treatment was performed at room temperature for 24 hours to obtain 10.3 g (6.01 mmol) of Compound Example 5.

(Synthesis Example 5: Synthesis of Compound Example 13)
Hinokitiol (5.00 g, 30.5 mmol) was dissolved in hexane (300 ml). A solution prepared by dissolving 1.72 g (10.2 mmol) of silicon tetrachloride in 50 ml of hexane was added dropwise thereto. After heating under reflux for 1 hour, the mixture was allowed to cool, and the precipitated white crystals were filtered, washed with 300 ml of hexane, and dried under reduced pressure at 70 ° C. for 24 hours to obtain a silicon complex intermediate. 5.00 g (9.04 mmol) of the obtained silicon complex intermediate was dispersed in a mixed solution of water and methanol, and 1.50 g (4.52 mmol) of 1,4-naphthalenedisulfonic acid disodium salt was added for 24 hours at room temperature. By subjecting to dispersion treatment, 5.10 g (3.86 mmol) of Compound Example 13 was obtained.

(Synthesis Example 6: Synthesis of Compound Example 17)
4.00 g (18.8 mmol) of N-benzoyl-N-phenylhydroxyamine was dissolved in 20 ml of toluene. A solution prepared by dissolving 1.06 g (6.25 mmol) of silicon tetrachloride in 20 ml of toluene was added dropwise thereto at room temperature. After heating under reflux for 2 hours, the mixture was allowed to cool, and the precipitated white crystals were filtered, washed with 300 ml of toluene, and dried under reduced pressure at 70 ° C. for 24 hours to obtain a silicon complex intermediate. 3.87 g (5.53 mmol) of the obtained silicon complex intermediate was dispersed in a mixed solution of water and methanol, and 1.29 g of 4- (benzoylamino) -5-hydroxy-1,7-naphthalenedisulfonic acid disodium salt ( 2.77 mmol) was added and dispersed at room temperature for 24 hours, thereby obtaining 4.05 g (2.31 mmol) of Compound Example 17.

  In addition, various silicon complex compounds used for the positively chargeable charge control agent to which the present invention is applied can be obtained by the same synthesis method.

  Examples 1 to 13 show examples of the preparation of a positively chargeable toner for developing an electrostatic image containing the silicon complex compound obtained above as a charge control agent, and the formation of an image on a recording paper using this toner. .

Example 1
100 parts by weight of styrene-acrylic copolymer resin (CPR-600B: trade name, manufactured by Mitsui Chemicals), 3 parts by weight of low molecular weight polypropylene (Biscol 550-P: trade name, manufactured by Sanyo Chemical Co., Ltd.), and magenta color 5 parts by weight of the pigment (CI Pigment Red 57: 1) and 1 part by weight of the charge control agent comprising Compound Example 1 were uniformly premixed with a high-speed mixer. Next, the mixture was melt-kneaded with an extruder, and after cooling, coarsely pulverized with a vibration mill. The resulting coarsely pulverized product was finely pulverized using an air jet mill equipped with a classifier to obtain a magenta toner having a particle size of 10 μm.

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

The developer is weighed in a plastic bottle and stirred by a ball mill with a rotation speed of 100 rpm to charge the developer, and the initial charge amount (at 3 minutes) under atmospheric conditions and the frictional charge for each stirring time (minute) The quantity was measured and the stability of charging was evaluated. The stability of charging was evaluated in two stages, with ○ indicating a stable one and × indicating no. In addition, the charge amount (10 minutes value) was measured in the same manner for a developer conditioned for 24 hours or more under the standard conditions of 25 ° C. and 50% relative humidity. 30%) and high-temperature and high-humidity (35 ° C, relative humidity 90%) Developers conditioned for more than 24 hours under the same conditions are measured in the same way to measure the charge amount environmental stability at the same time. did. Regarding environmental stability of charge amount,
{[(Charge amount under standard conditions) − (charge amount under low temperature and low humidity)] / (charge amount under standard conditions)} × 100,
Or
{[(Charge amount under standard conditions) − (Charge amount under high temperature and high humidity)] / (Charge amount under standard conditions)} × 100
The absolute value of the rate of change was 0.0 to 5.0%, the one that was 5.0 to 10.0%, the one that was 10.0% or more It evaluated in three steps made into x.

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

  A toner image was formed with a commercially available copying machine using this developer. The obtained toner image was visually observed for fogging, fine line reproducibility, charging stability and sustainability, and offset phenomenon.

  For fog, ○ indicates that there is no fog, X indicates that there is no fog, and as for thin line reproducibility, ○ indicates that the reproducibility of fine lines is good, and X indicates that the reproducibility is poor. Evaluation was made in two stages, with ○ indicating that the property and durability were good and × indicating bad, and regarding the offset phenomenon, indicating that no offset phenomenon was observed and ○ indicating that the offset phenomenon was observed.

  The results are shown in Table 4.

(Examples 2 to 7)
Examples 2 to 7 were the same as Example 1 except that Compound Example 1 of Example 1 was replaced with Compound Example 2, 6, 7, 8, 13 or 17 as shown in Table 3 below. Thus, a positively chargeable toner for developing an electrostatic image is prepared. Each was evaluated in the same manner as in Example 1.

(Example 8)
100 parts by weight of styrene-acrylic copolymer resin (CPR-600B: trade name manufactured by Mitsui Chemicals), 5 parts by weight of yellow pigment (CI Pigment Yellow 180), and low molecular weight polypropylene (Biscol 550- P: 3 parts by weight of Sanyo Chemical Co., Ltd. (trade name) and 1 part by weight of the charge control agent comprising Compound Example 4 were processed in the same manner as in Example 1 to produce a yellow toner and a developer having an average particle diameter of 10 μm. Was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 4.

Example 9
100 parts by weight of a polyester resin (HP313: trade name manufactured by Nippon Synthetic Chemical Co., Ltd.), 3 parts by weight of low-polymerized polypropylene (Biscol 550-P: trade name of Sanyo Kasei Co., Ltd.), and carbon black (# 44: Mitsubishi) A black toner and an average particle size of 10 μm were prepared by treating 6 parts by weight of a trade name of Chemical Co., Ltd.) and 1 part by weight of the charge control agent comprising Compound Example 16 in the same manner as in Example 1. Evaluation was conducted in the same manner as in Example 1. The results are shown in Table 4.

(Example 10)
80 parts by weight of styrene monomer, 20 parts by weight of n-butyl acrylate monomer, 5 parts by weight of yellow pigment (CI Pigment Yellow 180), and 1.2 of 2,2′-azoisobutyronitrile. 8 parts by weight and 1 part by weight of the charge control agent comprising Compound Example 1 were uniformly premixed with a high-speed mixer to obtain a polymerizable monomer composition.

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

  After adding this dispersion to the polymerizable monomer composition, the temperature was raised to 65 ° C. while stirring at a high speed with a TK homomixer (manufactured by Tokki Kako), and after stirring for 30 minutes, The temperature was raised to 80 ° C., and the system was switched to stirring at a rotation speed of 100 rpm using a normal stirrer, and polymerization was carried out for 6 hours while maintaining the temperature at 80 ° C.

  After completion of the polymerization, the reaction mixture is cooled and solids are filtered off. The filtered product is immersed in a 5% by weight hydrochloric acid aqueous solution to decompose calcium phosphate used as a dispersant, and then the solids are washed. The toner was washed with water until it became neutral, dehydrated and dried to obtain a yellow toner having an average particle size of 10 μm.

  A developer was prepared by mixing 95 parts by weight of a ferrite carrier (F-150: trade name, manufactured by Powder Tech Co., Ltd.) with 5 parts by weight of the obtained toner, and evaluated in the same manner as in Example 1. The results are shown in Table 4.

(Example 11)
80 parts by weight of styrene monomer, 20 parts by weight of n-butyl acrylate monomer, 5 parts by weight of carbon black (MA-100: trade name manufactured by Mitsubishi Chemical Corporation), and 2,2′-azoisobutyronitrile A black polymerized toner having a mean particle size of 13 μm and a developer were prepared by treating 1.8 parts by weight of the above and 1 part by weight of the charge control agent comprising Compound Example 20 in the same manner as in Example 10. Evaluation was performed in the same manner. The results are shown in Table 4.

(Example 12)
100 parts by weight of styrene-acrylic copolymer resin (CPR-600B: trade name, manufactured by Mitsui Chemicals), 3 parts by weight of low molecular weight polypropylene (Biscol 550-P: trade name, manufactured by Sanyo Chemical Co., Ltd.), and magenta color 5 parts by weight of a pigment (CI Pigment Red 57: 1) was uniformly premixed with a high-speed mixer. Next, the mixture was melt-kneaded with an extruder, and after cooling, coarsely pulverized with a vibration mill. The obtained coarsely pulverized product was finely pulverized using an air jet mill equipped with a classifier to obtain magenta toner mother particles having a particle size of 10 μm.

  To 108 parts by weight of the obtained mother particles, 1 part by weight of child particles made of Compound Example 10 as a charge control agent was externally added to obtain a positively chargeable toner for developing an electrostatic image.

  A developer was prepared by mixing 95 parts by weight of a ferrite carrier (F-150: a trade name manufactured by Powder Tech Co., Ltd.) with 5 parts by weight of the toner, and evaluated in the same manner as in Example 1. The results are shown in Table 4.

(Example 13)
100 parts by weight of styrene-acrylic copolymer resin (CPR-600B: trade name made by Mitsui Chemicals), 3 parts by weight of low molecular weight polypropylene (Biscol 550-P: trade name made by Sanyo Chemical Co., Ltd.), oil-soluble 5 parts by weight of magenta dye (oil pink # 312: trade name manufactured by Orient Chemical Co., Ltd.), 0.5 parts by weight of charge control agent (BONTRON P-51: trade name manufactured by Orient Chemical Industries, Ltd.), A magenta toner and a developer having an average particle size of 10 μm were prepared by treating 0.5 parts by weight of the charge control agent (Compound Example 1) in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The results are shown in Table 4.

(Comparative Example 1)
In Comparative Example 1, instead of 1,5-naphthalenedisulfonic acid disodium salt used for anion exchange in Synthesis Example 2, 2-naphthalenesulfonic acid sodium salt was used, and equimolar reaction of silicon complex intermediate and anion component was charged. Compound Example c was synthesized by adjusting the amount. The obtained compound example c was C: 72.94% (theoretical value: 72.99%), H: 4.58% (theoretical value: 4.45%), S: 3.32 in CHS elemental analysis. % (Theoretical value: 3.10%), which was almost the same as the theoretical value, and thus was identified as the desired compound example c. The weight reduction rate was 41.0%.

  Further, a toner was prepared in the same manner as in Example 1 except that the silicon complex compound of Compound Example 1 used in Example 1 was replaced with the following Compound Example c, and evaluated in the same manner as in Example 1. The results are shown in Table 4.

(Comparative Example 2)
A toner was prepared in the same manner as in Example 1 except that the silicon complex compound of Compound Example 1 used in Example 1 was replaced with Compound Example d below, and evaluated in the same manner as in Example. The results are shown in Table 4.

(Comparative Example 3)
A positively chargeable toner for developing an electrostatic charge image was prepared in the same manner as in Example 1 except that the silicon complex compound of Compound Example 1 of Example 1 was replaced with the silicon complex intermediate of Compound Example a. Evaluation was performed in the same manner.

(Comparative Example 4)
A compound with an incomplete anion exchange reaction was prepared in the same manner as in (2) of Example 1 except that the conditions for the anion exchange reaction in the synthesis of Compound Example 1 were changed as follows.

  The silicon complex intermediate 28g (33.7 mmol) of the compound example a was disperse | distributed to water, 1, 5- naphthalene disulfonic acid disodium salt 5.72g (17.2 mmol) was added, and the dispersion process was carried out at room temperature for 24 hours. The resulting reaction solution was filtered and washed with water until the conductivity of the filtrate decreased. By drying at 80 ° C., 29.0 g of a charge control agent mainly containing the silicon complex compound of Compound Example 1 and incomplete anion exchange reaction was obtained. This charge control agent had a residual chlorine content of 0.36%.

  A toner was prepared in the same manner as in Example 1 except that Compound Example 1 in Example 1 was replaced with a charge control agent having an incomplete anion exchange reaction, and evaluated in the same manner as in Example 1. The results are shown in Table 4.

  As is clear from Table 4, the developers of the examples were excellent in charging stability and sustainability, and further excellent in environmental stability. Further, the toner image formed using the toner image was free from fogging, excellent in reline reproducibility, charging stability and sustainability, and no offset phenomenon was observed. On the other hand, the developer of the comparative example was poor in environmental stability and was not suitable for use under high-temperature and high-humidity conditions such as in summer or when the temperature and humidity fluctuated.

  The positively chargeable charge control agent of the present invention contains a positively chargeable toner for developing an electrostatic image and a powder paint, and is used for copying and printing by electrophotography such as copying machines, printers and facsimiles, and electrostatic powder coating. Can be used for

  The positively chargeable toner for developing an electrostatic charge image containing the positively chargeable charge control agent is used to fix a clear and fog-free image on a transfer recording medium such as paper or film.

It is a figure which shows the result of the liquid chromatography mass spectrometry of the intermediate body of the silicon complex compound of the compound example 1 contained in the positively chargeable charge control agent to which this invention is applied.

It is a figure which shows one result of the peak by the liquid chromatography mass spectrometry of the silicon complex compound of the compound example 1 contained in the positively chargeable charge control agent to which this invention is applied.

It is a figure which shows the result of another peak by the liquid chromatography mass spectrometry of the silicon complex compound of the compound example 1 contained in the positive charge control agent to which this invention is applied.

It is a figure which shows the result of the liquid chromatography mass spectrometry of the intermediate body of the silicon complex compound of the compound example 27 contained in the positive charge control agent to which this invention is applied.

It is a figure which shows one result of the peak by the liquid chromatography mass spectrometry of the silicon complex compound of the compound example 27 contained in the positive charge control agent to which this invention is applied.

It is a figure which shows the result of another peak by the liquid chromatography mass spectrometry of the silicon complex compound of the compound example 27 contained in the positive charge control agent to which this invention is applied.

Claims (8)

The following chemical formula (I)

[In the formula (I), D represents a benzene ring or a naphthalene ring, and [D- (SO ₃ ) ₂ ] ^2- represents an aromatic organic acid having at least two sulfonic acid groups on the benzene ring or the naphthalene ring. 2 monovalent anion derived from,

The group has the following formula (III)

(In the formula (III), R ^{1 to} R ⁷ and R ^{10 to} R ¹⁴ are hydrogen atom, hydroxy group, hydroxyalkyl group, carboxyl group, alkoxycarbonyl group, halogen atom, alkyl group, alkoxy group, acyl group, alkenyl group. , A nitro group, a cyano group, an amino group, an alicyclic group, an aralkyl group, an aryl group, the same or different group, or a saturated or unsaturated condensed ring formed by adjacent groups. R ⁸ and R ¹⁵ are oxygen atom, carbonyl group, imino group; R ⁹ is hydrogen atom, hydroxy group, hydroxyalkyl group, carboxyl group, alkoxycarbonyl group, halogen atom, alkyl group, alkoxy group, acyl group Alkenyl, nitro, cyano, amino, alicyclic, aralkyl, ali The same or different groups selected from Le group.) Represented by. ],
And / or the following chemical formula (II)

[In the formula (II), D represents a benzene ring or a naphthalene ring, and [D- (SO ₃ ) ₂ ] ²⁻ is an aromatic organic acid having at least two sulfonic acid groups on the benzene ring or naphthalene ring. A divalent anion obtained from

The group is represented by the following formula (IV)

(In the formula (IV), R ^{16 to} R ¹⁷ and R ^{23 to} R ²⁵ are hydrogen atom, hydroxy group, hydroxyalkyl group, carboxyl group, alkoxycarbonyl group, halogen atom, alkyl group, alkoxy group, acyl group, alkenyl group. , A nitro group, a cyano group, an amino group, an alicyclic group, an aralkyl group, an aryl group, the same or different groups; R ¹⁸ is a methine or nitrogen atom; R ^{19 to} R ²² are hydrogen atoms, hydroxy groups, hydroxyalkyl The same or different groups selected from a group, carboxyl group, alkoxycarbonyl group, halogen atom, alkyl group, alkoxy group, acyl group, alkenyl group, nitro group, cyano group, amino group, alicyclic group, aralkyl group, aryl group Or carbon condensed saturated or unsaturated by adjacent groups Groups form a ring of 3 to 7; R ²⁶ is represented by a nitrogen atom or an optionally carbon atoms which may have a substituent,).. ]
A positively charged charge, characterized in that the halogen content remaining in the silicon complex compound of formula (I) or (II) is 0.2% at maximum Control agent. The silicon complex compound of the chemical formula (I) is represented by the following chemical formula (V)

(In the formula (V), X is a halogen atom,

The group is the same as described above. )
A compound obtained by ion-exchange reaction of the silicon complex salt represented by the above and the organic acid or a salt thereof,
The silicon complex compound of the chemical formula (II) is represented by the following chemical formula (VI)

(In the formula (VI), X is a halogen atom,

The group is the same as described above. )
The positively chargeable charge control agent according to claim 1, which is a compound obtained by subjecting a silicon complex salt represented by formula (I) and the organic acid or a salt thereof to an ion exchange reaction. The positively chargeable charge control agent according to claim 1, wherein the aromatic organic acid is a naphthalenedisulfonic acid derivative .   2. The positively charged charge according to claim 1, wherein the silicon complex compound represented by the chemical formula (I) or (II) has a maximum weight loss rate of 10.0% after heat treatment at 180 ° C. for 2 hours. Control agent. 2. The positive charge according to claim 1, wherein the silicon complex compound of the chemical formula (I) or (II) has a volume resistivity of 1.0 × 10 ^{13 to} 5.0 × 10 ¹⁵ Ω · cm. Charge control agent. Positively chargeable charge control agent, contained positively chargeable toner for developing electrostatic images, wherein a is as defined in any one of claims 1-5. 7. The positive chargeability for electrostatic image development according to claim 6 , wherein 0.1 to 10 parts by weight of the positively chargeable charge control agent and 100 parts by weight of a toner resin are contained. toner. A charge control method for a positively chargeable toner for developing an electrostatic charge image, wherein the positively chargeable toner for developing an electrostatic charge image according to claim 6 is positively charged by friction.

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