JP2007298966A - Charge imparting composition and charge imparting member using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a charge imparting composition used as a material of a charge imparting member which imparts negative charges to an electrophotographic toner to develop excellent charging characteristics and charge stability. <P>SOLUTION: The charge imparting composition comprises a positive electrified charge control agent comprising a silicon complex compound represented by chemical formula (I) or the like as an effective component and a solvent and/or a dispersant. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a charge imparting composition that is a raw material of a charge imparting member used for charging a toner for electrophotography with a negative charge, and a charge imparting member using the same.

  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.

  There are two-component toners and one-component toners. The developing method using a two-component toner uses, for example, a developer in which a toner and a carrier that is a magnetic particle that imparts a charge to the toner are used, and the toner is charged by friction between the toner and the carrier. Is conveyed by a carrier and electrostatically adhered to the photosensitive member for development. On the other hand, in the developing method using a one-component toner, for example, the toner is frictionally charged in a gap between a metal blade and a developing sleeve, and then the toner is caused to fly to a photosensitive member by a latent image electric field for development.

  In any case, sufficiently charging the toner is an important factor for increasing the developing speed of electrophotography and forming a clear image.

  A charge control agent is added to the toner together with the toner resin in order to appropriately control and stabilize the charge amount of the toner to increase the charge rising speed. Patent Document 1 discloses a charge control agent in which an organic ligand is coordinated to a semi-metallic silicon which is a central atom, and negatively charges a toner. When the toner to which the charge control agent is added is charged by friction, the charge control agent exposed on the surface falls off due to friction between toner particles, collision with the carrier, friction with the photosensitive member, etc. Or the like, or insufficient chargeability can be exhibited, or the image density is lowered or the image quality is lowered due to fog.

  As an alternative to the method of charging a toner by adding a charge control agent to the toner, Patent Document 2 discloses a charge control agent that is charged in contact with the toner in order to give the toner the necessary charge for development. A charge imparting member such as an exposed carrier is disclosed.

  In order to increase the image quality while increasing the speed of copying and printing, the toner is given sufficient charge to develop better charging characteristics and charging stability than before, and it is safe and long for the environment. A charge imparting member that can be used for a period of time is desired.

JP-A-4-295757 JP 2004-341456 A

  The present invention has been made to solve the above-mentioned problems, and is a charge imparting composition that is a raw material for a charge imparting member that imparts a negative charge to an electrophotographic toner and exhibits excellent charging characteristics and charge stability. The purpose is to provide goods. It is another object of the present invention to provide a charge imparting member which is formed using a charge imparting composition, has sufficient charge imparting properties, friction resistance and durability, and is safe to the environment. It is another object of the present invention to provide a charge control method for toner for electrophotography using this charge imparting member.

  The charge-imparting composition of the present invention made to achieve the above object has the following chemical formula (I)

And / or the following chemical formula (II)

(In the chemical formulas (I) and (II), [D- (SO ₃ ) ₂ ] ^2- is a divalent anion of an organic acid having at least two sulfonic acid groups, p = 0 or 1, and B is p = 0. When p = 1, carbon or nitrogen atom, J is carbon atom or nitrogen atom, A is (B) an organic group forming a ring with _p and J, and two R are the same or different organic groups And a positively chargeable charge control agent comprising a silicon complex compound represented by the following formula as an active ingredient, and a solvent and / or a dispersant.

  The charge imparting composition has the chemical formula (I):

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.) Is represented by,
In the chemical formula (II),

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 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) It is preferable that it is what is represented by this.

  In the charge imparting composition, the silicon complex compound represented by the chemical formula (I) is 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 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 formula (VI), X is a halogen atom, and p, B, J, and R are the same as above.)
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 charge-imparting member of the present invention, any one of a carrier powder, a developing sleeve, and a blade that imparts a charge by contact with the toner for electrophotography is coated or molded with the above-described charge-imparting composition. The silicon complex compound is exposed.

  The electrostatic charging toner charging method described is to charge the toner by bringing the charging member into contact with the electrophotographic toner and rubbing it.

  The charge-imparting composition containing the positively chargeable charge control agent of the present invention imparts a negative charge to the toner for electrophotography, and exhibits good charging characteristics and charging stability. This charge imparting composition is particularly excellent in terms of heat resistance, storage stability, and environmental safety.

  The charge imparting member formed by coating or molding with the charge imparting composition imparts a charge to the toner at a high rising speed. This charge imparting member is used not only for monochrome toner but also for imparting charge to a wide variety of chromatic toners. Since this charge imparting member is excellent in durability, it can be used continuously for a long time without replacement.

  The charge control method of the toner for electrophotography using this charge imparting member is suitable for developing an electrostatic charge image on any type of photoreceptor regardless of 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. The developed toner image has fixability in a wide temperature range. The fixed image is clear, does not cause fogging, has a non-offset property, and does not deteriorate for a long time.

  According to this charge control method for toner for electrophotography, the charge imparting member such as the carrier powder, the developing sleeve, the metal blade or the magnetic blade is not contaminated because the toner does not need to contain a charge control agent.

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 charge imparting composition of the present invention includes a positively chargeable charge control agent containing a silicon complex compound as an active ingredient, and a solvent and / or a dispersant. As the silicon complex compound, the silicon complex compound of the formula (I) or (II) may be used alone, or two or more kinds may be used in combination. It is preferable that the silicon complex compound is contained in an amount of 0.5 to 200 parts by weight with respect to 100 parts by weight of the solvent or / and the dispersant, and it is preferably used in a ratio of 2 to 100 parts by weight. .

  The positively chargeable charge control agent 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 effective for a silicon complex compound represented by the chemical formula (I) or (II). Ingredients. 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.

  Examples of the aralkyl group which may have a substituent and may not have a substituent 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. A positively chargeable charge control agent comprising a silicon complex compound is a charge control agent comprising a silicon complex compound outside the scope of the present invention, wherein the counter ion is various anions other than organic acids having at least two sulfonic acid groups, such as chloro ions. In addition, there is an advantageous effect that charging characteristics, thermal stability, and environmental stability are improved.

  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.

  In the positively chargeable charge control agent, the silicon complex compound represented by the chemical formula (I) or (II) binds to two ions composed of a monovalent silicon complex cation and one ion composed of a divalent organic acid anion. The structure is taken. This silicon complex compound greatly changes the thermal stability and environmental stability in the charge imparting member depending on the type of anion which is a counter ion. When this silicon complex compound has the above-mentioned structure, the characteristics such as thermal stability and environmental stability that are indispensable as a charge imparting member for imparting charge to the toner are silicon having an anion component other than a sulfonic acid group. Greatly improved over complex compounds.

  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. For this reason, a charge imparting member including a charge control agent containing a silicon complex compound as a main component has a very low possibility of generation of a chemical substance derived from a charge control agent 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) is preferably 1.0 × 10 ^{13 to} 5.0 × 10 ¹⁵ Ω · cm, and 1.0 × 10 ^{14 to} 5.0 × 10 ^15. More preferably, it is Ω · cm. The charge imparting member containing the charge control agent has stable charge imparting property of the toner, and the toner charge amount or charge speed can be adjusted to a required appropriate level.

  The solvent or dispersant contained in the charge imparting composition is, for example, a hydrophilic solvent or a hydrophobic organic solvent. Hydrophilic organic solvents include alcohols such as methanol, ethanol, propanol, isopropanol and butanol; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and diethylene glycol dimethyl ether; acetone, methyl ethyl ketone, methyl isobutyl ketone, Ketones such as kilohexanone; aprotic polar solvents such as N, N-dimethylformaldehyde, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and dimethylsulfoxide. Examples of the hydrophobic organic solvent include aromatic solvents such as xylene and toluene; hydrocarbon solvents such as hexane. These solvents may be used alone or in combination.

  The dispersing agent may be a dispersing resin. Examples of such resins include poly (meth) acrylate resins such as polymethyl acrylate resins and polymethyl methacrylate; polystyrene resins; polyacrylonitrile resins; synthetic rubbers having isoprene units and butadiene units; polyester resins; polyurethane resins; Examples include epoxy resins; rosin resins; polycarbonate resins; phenol resins; chlorinated paraffins; polyethylenes; polypropylenes; fluorine resins such as polytetrafluoroethylenes; These resins may be used alone or in combination. A mixture of these resins and the aforementioned solvent may be used.

The charge imparting member of the present invention is any one of a carrier powder, a developing sleeve, and a blade that imparts a charge upon contact with an electrophotographic toner, and is coated or molded with the above-described charge imparting composition. It is a thing. Specifically, the charge control agent is applied in an amount of 0.1 to 10% by weight, more preferably 0.5 to 2% by weight, based on the carrier powder. Also with respect to the developing sleeve and the blade, the amount of 0.01 to 10 mg / cm ^2, more preferably be given the charge control agent in an amount of 0.1 to 2 mg / cm ^2.

  The charge imparting member was dried after the carrier powder base, the developing sleeve, and the blade were immersed in a charge imparting composition in which the charge control agent was dispersed in a solvent or in a dispersant such as a resin. In addition, the charge imparting composition may be sprayed on a carrier powder base material and then dried. Further, the charge imparting composition may be applied to the carrier powder base material by brushing or the like and then dried.

  The charge imparting member may be a developing sleeve or a blade obtained by extrusion laminating or molding the charge imparting composition on a base material.

  The silicon complex compound is exposed from the surface of the charge imparting member thus formed.

  The carrier powder is not particularly limited. For example, metal powder such as iron powder, nickel powder, aluminum powder, and copper powder having a particle size of about 50 to 200 μm; powder made of alloy; metal oxide such as magnetite powder and ferrite powder Glass beads, glass powders; ceramics powders; acrylic acid ester copolymers, styrene-acrylic acid ester copolymers, styrene-methacrylic acid ester copolymers, silicone resins, polyamide resins, or fluorine Powder coated with an ethylene-based resin; resin powder, and magnetic substance-containing resin powder.

  Examples of the material of the developing sleeve include metals such as iron, aluminum, and nickel; alloys such as stainless steel; ceramics and plastics.

  The electrostatic photographic toner may be a two-component toner used in a magnetic brush development method in which toner is conveyed by an iron powder carrier or a cascade development method in which toner is conveyed by a bead carrier. The two-component developer is prepared by mixing the toner and the carrier.

  In addition, the toner for electrophotography may be a one-component toner used in a powder cloud developing method in which the toner is sprayed, a jumping developing method in which the toner is caused to fly by a latent image electric field, or a contact developing method. The one-component developer is obtained by adding and dispersing an appropriate amount of fine powder of a ferromagnetic material such as iron powder, nickel powder, and ferrite powder when the toner is prepared.

  The electrostatic photographic toner may contain a toner resin and, if necessary, a colorant or another charge control agent.

  The method for controlling the charge of the electrophotographic toner of the present invention is to charge the toner by bringing the charge applying member and the electrophotographic toner into contact with each other and rubbing them.

  The charge imparting member containing this positively chargeable charge control agent is excellent in storage stability, environmental resistance and durability. Therefore, it is not necessary to replace the charge imparting member such as the carrier powder, the developing sleeve, and the blade for a long time.

  Since the toner to which the charge is imparted by the charge imparting member is excellent in charging stability, the image developed using the toner has excellent quality.

  The electrophotographic toner contains a toner resin, a colorant, and a magnetic material, a fluidity modifier, and an anti-offset agent that are appropriately used as necessary to improve the quality of the toner.

  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 that purpose, the resin for toner has transparency, is almost colorless so as not to cause a color tone failure in the toner image, has fluidity under appropriate heat or pressure, and can be atomized. It is necessary. 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.

  As the colorant for the color toner, 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 olein, perinone red, perylene maroon, rhodamine 6G lake, quinacridone red, rose bengal, copper phthalocyanine blue, copper phthalocyanine green, diketo Organic pigments such as pyrrolopyrrole pigments; carbon black, titanium white, titanium yellow, ultramarine blue, cobalt blue, brown, aluminum powder, bronze, inorganic pigments and metal powders; azo dyes, quinophthalone dyes, anthraquinone dyes Oil-soluble dyes and disperse dyes such as dyes, xanthene dyes, triphenylmethane dyes, phthalocyanine dyes, indophenol dyes, indoaniline dyes; rosin, logistic Modified phenol, triarylmethane dyes modified by a resin as rosin-modified maleic acid; was processed like in higher fatty acids or resin, include 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 toner for electrophotography is manufactured as follows. After thoroughly mixing the resin for the toner, the colorant, and if necessary, the magnetic material, the fluidity modifier, and the offset preventive agent with a mixer such as a ball mill, the mixture is heated to a heating roll, kneader, extruder, etc. Melt and knead using a thermal kneader. 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. The suspension polymerization method includes a monomer for a toner resin, a colorant, and, if necessary, an additive such as a magnetic material, a fluidity modifier, an offset inhibitor, a polymerization initiator, a crosslinking agent, and a release agent. Is uniformly dissolved or dispersed into a monomer composition, and then the monomer composition is dispersed in a continuous layer containing a dispersion stabilizer, for example, in an aqueous phase using an appropriate disperser. The toner particles having a desired particle diameter are obtained by carrying out the polymerization reaction.

  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 a dispersion stabilizer, a surfactant such as sodium dodecylbenzenesulfonate; an organic dispersant such as polyvinyl alcohol, methylcellulose, methylhydroxypropylcellulose; an inorganic dispersant such as calcium phosphate, magnesium phosphate, and aluminum phosphate polyvalent Examples thereof include 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.

  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 which is an active ingredient in the charge control agent used for the charge provision composition 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 CHNS 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, 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 CHNS elemental analysis, C: 71.15% (theoretical value: 71.41%), H: 4.35% (theoretical value: 4.31%), S: 3.85% (theoretical value: 3 .81%), which is almost the same as the theoretical value, and thus was identified as the 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 charge control agent can be obtained by the same synthesis method.

  Preparation of a charge imparting composition comprising the silicon complex compound obtained above as a charge control agent, preparation of a charge imparting member using the charge imparting composition, and a charge control method for an electrophotographic toner using the same Examples are given in the examples below.

Example 1
100 g of polymethyl methacrylate resin was dissolved in 1000 ml of xylene, and 50 g of Compound Example 1 was mixed with it to obtain a charge imparting composition 1.
Using the obtained charge imparting composition 1, 1000 g of a ferrite carrier (F-150: manufactured by Powdertech) was coated with a fluidized bed type coating apparatus to obtain a charge imparting member 1 (carrier).
On the other hand, 100 parts by weight of styrene-acrylic copolymer resin (CPR-600B: trade name made by Mitsui Chemicals) and 3 parts by weight of low molecular weight polypropylene (Biscol 550-P: trade name made by Sanyo Chemical Co., Ltd.) And 5 parts by weight of magenta pigment (CI Pigment Red 57: 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 the charge imparting member 1 (carrier) with 5 parts by weight of the obtained toner. The obtained developer was evaluated by the following evaluation method, and the results are shown in Table 3.

(1) Evaluation of initial charge amount and charge stability The obtained developer was 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 under atmospheric conditions (3 The triboelectric charge amount for each minute value) and the stirring time (minutes) was measured to evaluate the charging stability. The stability of charging was evaluated in two stages, with ○ indicating a stable one and × indicating no.

(2) Evaluation of environmental stability In addition, the charge amount (10 minute value) was measured in the same manner for a developer conditioned for 24 hours or more under standard conditions of 25 ° C. and 50% relative humidity. By measuring the charge amount in the same manner for a developer conditioned for 24 hours or more under conditions of low temperature and low humidity (5 ° C., relative humidity 30%) and high temperature and high humidity (35 ° C., relative humidity 90%), The charge amount environmental stability was also evaluated at the same time.

  The environmental stability of the charge amount is evaluated by the change rate of the charge amount value under the low temperature and low humidity condition and the high temperature and high humidity condition with respect to the charge amount value under the standard condition, and the absolute value of the change rate is 0. Evaluations were made in three stages, with 0 to 5.0% being ◯, 5.0 to 10.0% being Δ, and 10.0% or more being x.

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

(3) Characteristics of toner image 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.

(Example 2)
100 g of styrene-methyl methacrylate copolymer resin was dissolved in 1000 ml of toluene, and 50 g of Compound Example 13 was mixed therewith to obtain a charge imparting composition 2.
Using the obtained charge imparting composition 2, 1000 g of a ferrite carrier (F-150: manufactured by Powdertech) was coated with a fluidized bed coating apparatus to obtain a charge imparting member 2 (carrier).

  A developer was prepared by mixing 95 parts by weight of the charge applying member 2 (carrier) with 5 parts of the toner obtained in the same manner as in Example 1. The obtained developer was evaluated in the same manner as in Example 1, and the results are shown in Table 3.

(Example 3)
100 g of a silicone resin was dissolved in a mixed solvent of 500 ml of toluene and 500 ml of acetone, and 50 g of Compound Example 4 was mixed therewith to obtain a charge imparting composition 3.
Using the obtained charge imparting composition 3, 1000 g of a ferrite carrier (F-150: manufactured by Powdertech) was coated with a fluidized bed coating apparatus to obtain a charge imparting member 3 (carrier).

On the other hand, 100 parts by weight of 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 (MA100: 6 parts by weight of Mitsubishi Chemical Corporation product name) was treated in the same manner as in Example 1 to obtain a black toner having an average particle size of 10 μm.
A developer was prepared by mixing 95 parts by weight of the charging member 3 (carrier) with 5 parts of the toner.
The obtained developer was evaluated in the same manner as in Example 1, and the results are shown in Table 3.

(Comparative Example 1)
A comparative charge imparting member 1 was prepared in the same manner as in Example 1 except that Compound Example 1 was not mixed in the solvent in which the resin of Example 1 was dissolved.
A developer was prepared by mixing 95 parts by weight of the comparative charging member 1 (carrier) with 5 parts of the toner obtained in the same manner as in Example 1.
The results evaluated in the same manner as in Example 1 are shown in Table 3.

  As is apparent from Table 3, the developers of Examples 1 to 3 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 Comparative Example 1 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.

Example 4
100 g of phenol resin was dissolved in 1000 ml of methyl ethyl ketone, and 50 g of Compound Example 1 was mixed therewith to obtain a charge imparting composition 4.
A coating layer was formed by applying the charge imparting composition 4 to the surface of the developing sleeve (made of stainless steel) by a dipping coating method to obtain a charging member 4 (developing sleeve).

On the other hand, 100 parts by weight of polyester resin (ER-561: trade name manufactured by Mitsubishi Rayon Co., Ltd.) and 5 parts by weight of magenta pigment (CI Pigment Red 57: 1) were treated in the same manner as in Example 1. As a result, a magenta toner having an average particle size of 10 μm was obtained. Toner 100 was obtained by externally adding 0.2 part of hydrophobic colloidal silica to 100 parts of this toner.
Using a commercially available printer equipped with the charge imparting member 4 (developing sleeve), using the toner 1, images were formed under various conditions, and the results are shown in Table 4.

(1) Evaluation of charging stability and environmental stability Under standard conditions of 25 ° C and 50% relative humidity, low temperature and low humidity (5 ° C, 30% relative humidity), and high temperature and high humidity (35 ° C, relative humidity 90%) Images were formed under the following conditions.

In the measurement of the toner charge amount, the toner carried on the developing sleeve was sucked and measured with a suction method specific charge measuring device.
The charging stability was evaluated by measuring the toner charge amount before and after the durability test up to 5,000 sheets. The stability of charging was evaluated in two stages, with ○ indicating a stable one and × indicating no.
In addition, regarding the environmental stability of the charge amount, up to 5,000 sheets under low temperature and low humidity conditions and high temperature and high humidity conditions with respect to the toner charge amount values after the durability test up to 5,000 sheets under standard conditions. Evaluation was made based on the change rate of the toner charge amount value after the endurance test, and the absolute value of the change rate was 0.0 to 5.0%, and that which was 5.0 to 10.0% Were evaluated in three stages, with Δ and 10.0% or more being x.

(2) Characteristics of toner image 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.

(Example 5)
100 g of phenol resin was dissolved in 1000 ml of methyl ethyl ketone, and 50 g of Compound Example 6 was mixed therewith to obtain a charge imparting composition 5.
The charge imparting composition 5 was applied to the surface of the developing sleeve (made of stainless steel) by a dipping coating method to form a coating layer, whereby a charge imparting member 5 (developing sleeve) was obtained.

  Using a commercially available printer equipped with the charge imparting member 5 (developing sleeve), using the toner 1 prepared in Example 4, an image was formed and evaluated in the same manner as in Example 4, and the results were displayed. 4 shows.

(Example 6)
100 g of a silicone resin was dissolved in a mixed solvent of 500 ml of toluene and 500 ml of acetone, and 50 g of Compound Example 27 was mixed therewith to obtain a charge imparting composition 6.
The charge imparting composition 6 was applied to the surface of the developing sleeve (made of stainless steel) by a dipping coating method to form a coating layer, whereby a charge imparting member 6 (developing sleeve) was obtained.

On the other hand, 100 parts by weight of styrene-acrylic copolymer resin (CPR-600B: trade name manufactured by Mitsui Chemicals) and 3 parts by weight of low molecular weight polypropylene (Biscol 550-P: trade name manufactured by Sanyo Chemical Co., Ltd.) 90 parts by weight of magnetic iron oxide was treated in the same manner as in Example 1 to obtain a black toner having an average particle size of 10 μm. Toner 100 was obtained by externally adding 0.2 part of hydrophobic colloidal silica to 100 parts of this toner.
Using a commercially available printer equipped with the charge imparting member 6 (developing sleeve), using the prepared toner 2, an image was formed and evaluated in the same manner as in Example 4, and the results are shown in Table 4.

(Example 7)
100 g of styrene-acrylic resin was dissolved in 1000 ml of toluene, and 50 g of Compound Example 1 was mixed therewith to obtain a charge imparting composition 7.
The charge imparting composition 7 was applied to the surface of an elastic blade (made of stainless steel) by a spray method to form a coating layer, whereby a charge imparting member 7 (elastic blade) was obtained.

On the other hand, 100 parts by weight of polyester resin (ER-561: trade name manufactured by Mitsubishi Rayon Co., Ltd.), 3 parts by weight of low-polymerized polypropylene (Biscol 550-P: trade name manufactured by Sanyo Chemical Co., Ltd.) and carbon black (MA100: Mitsubishi) A black toner having an average particle size of 10 μm was obtained by treating 6 parts by weight of a trade name of Chemical Co., Ltd. in the same manner as in Example 1. To 100 parts of this toner, 0.2 part of hydrophobic colloidal silica was externally added to obtain toner 3.
Using a commercially available printer equipped with the charge imparting member 7 (elastic blade), an image was formed and evaluated in the same manner as in Example 4 using the prepared toner 3, and the results are shown in Table 4.

(Example 8)
100 g of styrene-acrylic resin was dissolved in 1000 ml of toluene, and 50 g of Compound Example 2 was mixed therewith to obtain a charge imparting composition 8.
The charge imparting composition 8 was applied to the surface of an elastic blade (made of stainless steel) by a spray method to form a coating layer, whereby a charge imparting member 8 (elastic blade) was obtained.

  Using a commercially available printer equipped with the charge imparting member 8 (elastic blade), an image was formed and evaluated in the same manner as in Example 4 using the prepared toner 3, and the results are shown in Table 4.

(Comparative Example 2)
A developing sleeve was prepared in the same manner as in Example 4 except that Compound Example 1 was not mixed in the solvent in which the resin of Example 4 was dissolved to obtain a comparative charge imparting member 2 (developing sleeve).
An image was formed and evaluated in the same manner as in Example 4 using a commercially available printer equipped with the comparative charge imparting member 2, and the results are shown in Table 4.

(Comparative Example 3)
An elastic blade was prepared in the same manner as in Example 7 except that Compound Example 1 was not mixed in the solvent in which the resin of Example 7 was dissolved, to obtain a comparative charge imparting member 3 (elastic blade).
An image was formed and evaluated in the same manner as in Example 4 using a commercially available printer equipped with the comparative charge imparting member 3, and the results are shown in Table 4.

  As is apparent from Table 4, the toner charged by the printer equipped with the charge imparting member (developing sleeve or elastic blade) of the example was excellent in charging stability and sustainability, and further 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, toner charged by a printer equipped with a comparative charge imparting member (development sleeve or elastic blade) of a comparative example has poor environmental stability, and under high-temperature and high-humidity conditions such as in summer or when the temperature and humidity fluctuate. It was not suitable for use.

  The charge-imparting composition of the present invention is used as a raw material for a carrier-providing member such as a carrier powder, a developing sleeve, a blade, or the like used for copying or printing by electrophotography such as a copying machine, a printer, or a facsimile machine. The charge control method of the toner for electrophotography using the charge imparting member formed of this charge imparting composition imparts a negative charge to the toner for electrophotography and exhibits excellent charging characteristics and charge stability. Thus, the toner is fixed on a transfer recording medium such as paper or film to obtain a clear and fog-free image.

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 of the positive charge control agent contained in the charge provision composition 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 of the positive charge control agent contained in the charge provision composition 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 positively chargeable charge control agent contained in the charge imparting composition to which the present 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 of the positive charge control agent contained in the charge provision composition 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 of the positive charge control agent contained in the charge provision composition 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 positively chargeable charge control agent contained in the charge imparting composition to which the present invention is applied.

Claims (5)

The following chemical formula (I)

And / or the following chemical formula (II)

(In the chemical formulas (I) and (II), [D- (SO ₃ ) ₂ ] ^2- is a divalent anion of an organic acid having at least two sulfonic acid groups, p = 0 or 1, and B is p = 0. When p = 1, carbon or nitrogen atom, J is carbon atom or nitrogen atom, A is (B) an organic group forming a ring with _p and J, and two R are the same or different organic groups A group that may form a heterocyclic ring)
A charge imparting composition comprising a positively chargeable charge control agent comprising a silicon complex compound represented by formula (1) as an active ingredient, and a solvent and / or a dispersant. In the chemical formula (I),

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.) Is represented by,
In the chemical formula (II),

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 3-7 ring; R ²⁶ represents a nitrogen atom or a carbon atoms which may have a substituent,).
The charge-imparting composition according to claim 1, wherein The silicon complex compound of the chemical formula (I) is 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 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 formula (VI), X is a halogen atom, and p, B, J, and R are the same as above.)
3. The charge-imparting composition 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.   Any one of a carrier powder, a developing sleeve, and a blade that apply charge by contact with an electrophotographic toner is coated or molded with the charge-imparting composition according to claim 1. And a charge imparting member, wherein the silicon complex compound is exposed.   A charge control method for an electrophotographic toner, wherein the toner is charged by bringing the charge applying member according to claim 4 and the electrophotographic toner into contact with each other and causing friction.

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