JPH04140756A - Color toner - Google Patents

Abstract

PURPOSE:To provide the toner having triboelectrostatic chargeability which is hardly affected by environment, such as temp. and humidity, and is always stable by adding specific external additives to the toner. CONSTITUTION:The external additives of the color toner contg. at least nonmagnetic coloring agent-contg. resin particles and the external additives consist of the org. resin particles which have 20 to 800mum grain size and 10<6> to 10<16>OMEGA.cm specific electric resistivity and are charged to the polarity reverse from the polarity of the coloring agent-contg. resin particles when triboelectrostatically charged with iron powder. The components thereof are the org. resin particles having iota30wt.% structure of formula I and one or more of the structures expressed by formula II, formula III. In the formula I, R1 denote a hydrogen or 1 to 5C straight chain or branched alkyl group; R2 denotes a hydrogen atom or 1 to 12C straight chain or branched alkyl group. In the formulas II, III, A denotes 1 to 6C straight chain or branched alkyl group, phenylene group or substd. phenylene group.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a color toner for dry electrophotography for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, and the like.

BACKGROUND OF THE INVENTION It is well known in the art to form and develop images on the surface of photoconductive materials by electrostatic means.

That is, U.S. Patent No. 2,297,691, Japanese Patent Publication No. 4
A number of methods are known, such as those disclosed in Japanese Patent Publication No. 2-23910 and Japanese Patent Publication No. 43-24748, but generally a photoconductive substance is used to form an electrical latent image on a photoreceptor by various means. Next, a toner image corresponding to an electrostatic latent image is formed by depositing an extremely finely pulverized electrostatic material called toner on the latent image.

Then, if necessary, the toner is transferred onto the surface of an image support such as paper, and then fixed by heating, pressure, solvent vapor, etc. to obtain a copy. Furthermore, when a step of transferring a toner image is included, a step for removing residual toner is usually provided.

Development methods for visualizing electrical latent images using toner include, for example, the powder cloud method described in U.S. Patent No. 2,221,776, and the powder cloud method described in U.S. Pat. Cascade development method, No. 2,874.0
The magnetic brush method described in Japanese Patent No. 3,909,258, and the method using conductive magnetic toner described in Japanese Patent No. 3,909,258 are known.

The toner R3 used in these development methods is a mixture of thermoplastic 81 resin mixed with a colorant and dispersed therein, which is then pulverized. As the thermoplastic resin, polystyrene resin is most commonly used, but polyester resin, epoxy resin, acrylic resin, urethane resin, etc. are also used. As a coloring agent, carbon black is most widely used, and in the case of magnetic toner, iron oxide-based black magnetic powder is often used. In the case of a system using a so-called two-component development side, the toner is usually mixed with carrier particles such as glass beads and iron powder.

The toner image on the final copy imaging member, such as paper, is permanently affixed to the support, such as by heat or pressure. Traditionally,
This fixing process often uses heat.

Also, if there is a step of transferring a toner image, usually
A step is provided to remove residual toner on the photoreceptor.

In recent years, there has been a rapid shift from monochrome copying to full-color copying in copying machines, and two-color copying machines and full-color copying machines are being extensively studied and put into practical use. For example, “Journal of Electrophotography Society J Vol 22.N
o, 1 (1983) and “Electronic Photography Society Journal” Vol.
25. There are also reports on color reproducibility and gradation reproducibility, such as No. IP52 (1986).

However, unlike television, photographs, and color printed matter, they cannot be immediately compared with the real thing, and for people who are used to seeing color images that are more beautifully processed than the real thing, the full-color electrophotographic images that are currently in practical use are not necessarily It has not been a satisfying experience.

Color image formation by full-color electrophotography generally requires 3
All colors are reproduced using toner of three primary colors: yellow, magenta, and cyan.

In this method, light from the original is first passed through a color-separating light transmitting filter that has a complementary color to the toner color to form an electrostatic latent image on the photoconductive layer, and then the toner is transferred to the support through a development and transfer process. hold it. Repeat this process several times in sequence,
After overlapping the toners on the same support while adjusting the registration, a final full-color image is obtained by -times of fixing.

In general, in the case of a so-called two-component development system in which the developer is composed of toner and carrier, the developer charges the toner to the required charge amount and charge polarity by friction with the carrier, and uses electrostatic attraction to create a static image. The toner is used to develop an electric image, and therefore, in order to obtain a good visible image, it is necessary that the toner have good triboelectric charging properties, which is determined mainly by the relationship with the carrier.

Today, in response to the above-mentioned problems, we are searching for carrier core agents and carrier coating agents, optimizing coat i, examining charge control agents and fluidity imparting agents to be added to toner, and improving the base binder. Many studies have been conducted to achieve excellent triboelectric charging properties in all materials constituting the developer.

For example, charged particles such as 1! ! :As a technique for adding an electrically auxiliary agent to toner, Japanese Patent Publication No. 52-32256 and Japanese Patent Application Laid-open No. 56-64352 disclose fine resin powder that is continuous with the toner, and Japanese Patent Publication No. 61-160760 The publication states that fluorine-containing compounds are added to each developer to achieve stable friction 1! : Techniques for obtaining chargeability have been proposed, and even today many charging aids are being developed.

Furthermore, various methods have been devised to add the above-mentioned "4EN auxiliary agent. For example, toner particles:!i!:
A common method is to make the toner particles adhere to the surface of the toner particles by electrostatic force with an electrolytic auxiliary agent or van der Waals force, and a stirring machine, a mixer, etc. are used. However, in this method, it is not easy to uniformly disperse the additive on the surface of the toner particles, and the presence of additives that are not attached to the toner particles and become aggregates with each other and become so-called free. It is difficult to avoid. This trend shows that V g
The larger the specific electrical resistance of the auxiliary agent, the larger the particle size, the more noticeable it becomes. In such a case, the performance of the developer will be affected. For example, toner friction! The amount of electricity becomes unstable, resulting in inconsistent image density and images with a lot of fog.

Alternatively, when continuous copying or the like is performed, the content of the charging auxiliary agent changes, making it impossible to maintain the initial image quality.

Another method of addition is to add a charging aid in advance together with a binder resin and a colorant during toner production. However, it is not easy to make the charge control agent uniform, and it is the substances near the surface of the toner particles that substantially contribute to the chargeability, and the charge aids and charge control agents present inside the particles have a chargeability. Therefore, it is not easy to control the amount of charging aid added or the amount of dispersion on the surface. Furthermore, even in the toner obtained by such a method, the amount of triboelectric charge of the toner is unstable, and as mentioned above, it is not easy to obtain one that satisfies the developer characteristics. The reality is that products of sufficiently satisfactory quality are not available.

Furthermore, in recent years, there has been an increasing demand in the market for high definition and high image quality in copying machines, and attempts have been made in the technical field to achieve high quality color images by reducing the particle size of toner. As the particle size becomes finer, the surface area per unit weight increases, and the amount of charge on the toner tends to increase, leading to concerns about low image density and deterioration of durability. In addition, since the amount of charge on the toner is large, the adhesion between the toners is strong, resulting in a decrease in fluidity, which causes problems in the stability of toner replenishment and in applying triboelectricity to the replenishing toner.

In addition, in the case of color toner, since it does not contain a magnetic substance or a conductive substance such as carbon black, there is no part that leaks fit, and the isoelectricity generally tends to be large. This tendency is particularly noticeable when a polyester binder with high charging performance is used.

In addition, particularly for color toners, the following characteristics are strongly desired.

(1) The fixed toner must be almost completely melted to the extent that the shape of the toner particles cannot be discerned, so that it does not diffusely reflect light and interfere with color reproduction.

(2) The colored toner must have transparency that does not interfere with toner layers of different tones below the toner layer.

(3) Each of the constituent toners must have well-balanced hue and spectral reflection characteristics and sufficient saturation.

From this point of view, many studies have been made regarding binder resins, but to date no toner has been developed that satisfies all of the above characteristics. Today, polyester-based resins are often used as color binder resins in this technical field, but toners made of polyester-based resins are generally easily affected by temperature and humidity. Problems such as insufficient charge amount occur under humid conditions, and there is an urgent need to develop color toners that have a stable f'fFN amount even in a wide range of environments.

[Problems to be Solved by the Invention] An object of the present invention is to provide a color toner for electrostatic charge development that solves the above-mentioned problems.

In other words, the purpose of the present invention is to solve the problem (
<An object of the present invention is to provide a color toner for electrostatic charge development which always has stable triboelectric charging properties.

A further object of the present invention is to provide a color toner for electrostatic charge development that has clear image characteristics without fog and has excellent durability and stability.

[Means and effects for solving the problem] The characteristics are that in a color toner containing at least non-magnetic colorant-containing resin particles and an external additive, the external additive has a particle diameter of 20 to 800 mμ; Specific electrical resistance 106-1015
Ωcm, and are organic resin particles that are charged to the opposite polarity to the colorant-containing resin particles when frictionally charged with iron powder,
[b] Organic resin particles having 30% by weight or more of the structure of formula 1) as a component and having at least one or more of the structures represented by formula 2) or formula 3). It's in color toner.

Formula 1) %Formula% (In the formula, R4 is a hydrogen atom or a linear or branched alkyl group of 01 to C6, R2 is a hydrogen atom or a C1 to C1
□ represents a straight chain or branched alkyl group. ) Formula 2) (In the formula, A represents a C1 to C6 linear or branched alkylene group, phenylene group, or substituted phenylene group.) Formula 3) %Formula% (In the formula, A is the same as in Formula 2 .

As a result of intensive studies on the environmental stability of the chargeability of color developers for electrostatic charge development, the present inventors found that as an external additive, the particles have a particle size of 20 to 800 mμ and have a polarity opposite to that of the colorant-containing resin particles.
It has been discovered that a toner containing organic resin particles having a specific electrical resistance of 106 to 1015 Ωcm has extremely excellent charging stability in various environments and provides good images without fogging.

The reason for this is that the charge-up caused by excessive rubbing between the binder resin and the carrier used in the present invention is neutralized by the organic resin particles described above.

Furthermore, by adding the organic resin particles, the charging of the toner is accelerated, and extremely stable charging characteristics are achieved from the initial stage.

Although the reason for this is not yet clear, it is inferred as follows. That is, at the beginning of rubbing between the carrier and the toner, the organic resin particles are strongly attracted to the carrier side and are electrically charged rather than the colorant-containing resin particles. Therefore, charging of the colorant-containing resin particles of opposite polarity is accelerated. On the other hand, after the toner has risen, it is more strongly attracted to the colorant-containing resin particles than the carrier and has a function of neutralizing excessive charge. , and saturation charge level can be maintained satisfactorily and stably in various environments.

In order to make the above effect even more effective, the particle size of the organic resin particles should be 20 to 800 mμ, and the specific electrical resistance should be 106 to 800 mμ.
It needs to be 1015 Ωcm.

If the particle size exceeds 800 mμ, non-uniform dispersion or separation of particles will occur, while if it is smaller than 20 mμ, the colorant will be too strongly adsorbed or embedded in the colorant-containing resin particles, impeding the effect. Good charging properties can be obtained by setting the particle size within the range of 20 to 800 mμ.

Furthermore, if the specific electrical resistance is greater than 1015 Ωcm, the degree of agglomeration of the organic resin particles will increase, the mixing property will decrease, and at the same time the organic resin particles themselves will be charged up, flying together with the toner to non-image areas and causing fog. This may lead to negative effects such as carrier spending. On the other hand, if it is smaller than 106 Ωcm, the toner charge amount decreases especially under high temperature conditions, resulting in fogging, scattering, leakage phenomenon during development, and image defects.

In the present invention, in order to reliably exhibit its performance and have stable negative f-electrification, it is preferably contained in an amount of 01 to 5.0% by weight based on the colorant-containing resin particles.

Furthermore, the organic resin particles of the present invention are also suitable for reducing the diameter of toner.

That is, when the toner is made smaller in diameter, the number of contact points between the toner and the carrier increases, making carrier spending more likely to occur, and the number of contact points between the toner and the toner increases, making it easier to cause toner blocking. On the other hand, 20 to 800 mμ
The spherical organic resin particles of appropriate size serve as a good spacer and have a good effect. For toner blocking, the material of the opposite polarity resin particles has a Tg higher than that of the toner resin.
It is even more effective to use one with a high value. Such organic resin particles are proposed in Japanese Patent Laid-Open No. 1-113762 as a means of preventing the developer from melting into the drum. Furthermore, as mentioned above, there are several examples of adding resin particles of opposite polarity to toner, such as in Japanese Patent Application Laid-open No. 54-45135 and Japanese Patent Publication No. 52-3225.
No. 6 proposes the addition of colorless resin particles smaller than the toner particle size.

However, in these examples, the toner and the opposite polarity resin particles behave separately, and during development, the toner adheres to the latent image area, while the opposite polarity resin particles adhere to the background area.

In other words, the opposite polarity resin particles function to promote charging of the toner. However, the present invention is characterized in that it uses resin particles of opposite polarity that are sufficiently small compared to the toner particle size, and that they are ultimately strongly attached to the toner and behave as one.

Further, in the past, reverse polarity resin particles have been used for the purpose of assisting charging of magnetic toner, which is difficult to provide with a large amount of charge. In contrast, the present invention is characterized in that it is actively used for non-magnetic color toners that tend to be excessively charged.

Further, the organic resin particles in the present invention have an amine (sulfonate)-type and/or sulfobetaine-type facial ionic group as a constituent component.

Formula 2) (In the formula, A represents a C1-C6 linear or branched alkylene group, phenylene group, or substituted phenylene group.) Formula 3) %Formula% (In the formula, A is the same as in Formula 2. ) One method for introducing these structures into organic resin particles is to use a polymer compound containing an amino (sulfonic) acid type amphoteric ionic group of the above formula. An epoxy resin can be used as a dispersion stabilizer or an emulsifier in Japanese Patent No. 40522, and an acrylic resin can be used in Japanese Patent No. 54-24357. This method not only introduces the structure of the above formula, but also provides stable dispersion without the disadvantages of conventional emulsifiers, such as the emulsifier remaining in the product and deteriorating its original physical properties. can create a state. Examples of resins having an amino(sulfonic) acid type amphoteric ionic group and a sulfobetaine group that are used as dispersion stabilizers or emulsifiers include the following.

The polyester resin containing an aminosulfonic acid type zwitterionic group has the following formula as the alcohol component in the reaction component: [Formula % Formula %] [In the formula, R4 has at least one hydroxyl group, and 10- or - 01-C20 alkyl group that may contain cOo-, R5 is a hydrogen atom, C1-
A C20 alkyl group, an alkyl group or a cyclic group having at least one hydroxyl group and/or sulfonic acid group, and A represents a C1-C6 straight or branched alkylene group, phenylene group or substituted phenylene group. ] A hydroxyl group-containing aminosulfonic acid type zwitterionic compound represented by is used in an amount of 0.05 to 50% by weight based on the total reaction components, and a polybasic acid compound and, if necessary, a polyhydric alcohol and/or oxirane are used. It is obtained by reacting with a compound. Examples of hydroxyl group-containing aminosulfonic acid type zwitterionic compounds include hydroxyethyltaurine, dihydroxyethyltaurine, dihydroxyprobyltaurine, and the like.

The epoxy resin containing an aminosulfonic acid type zwitterionic group has the following formula: % formula % [wherein R6, R, represents hydrogen or a methyl group]. An epoxy resin having a terminal group represented by the formula: Ra N HR9S O3M [wherein R8 is hydrogen or a C3-C20 alkyl group or a substituted alkyl group, R9 is an 01-c8 alkylene or substituted alkylene group, M represents an amine, an alkali metal or ammonia. It is produced by reacting an aminosulfonate of ] and then treating the reaction product with an acid.

Examples of aminosulfonic acid salts of the formula % include alkali metal salts such as taurine, 2-aminopropanesulfonic acid, 3-aminobutanesulfonic acid, 1-amino-2-methylpropanesulfonic acid, and N-ethyltaurine. , amine salts and ammonium salts.

The acrylic resin containing an aminosulfonic acid type zwitterionic group has the formula % formula % [wherein R1 is a substituent containing a radically polymerizable ethylenically unsaturated group, and R2 is H or various It is a substituent mainly composed of cI to C2° hydrocarbons that may contain substituents, R3 is a substituent mainly composed of C1 to C8 hydrocarbons, and B is a -COOH group or -3o3H It is the basis. ] At least 1 f! selected from the polymerizable amino acid compounds represented by f! It is obtained by polymerizing or copolymerizing 1,000 ml of

The sulfobetaine type zwitterionic group is described, for example, in JP-A-53-
As disclosed in Publication No. 72090, the formula R1゜R [wherein R1゜ is a hydrogen atom or a methyl group, RII and RI2 are the same or different and are an alkyl group of 01 to C6, A2 is 0 or NH, m, and nl is the same or different and represents an integer of 1 to 12; or [wherein R13 is a hydrogen atom or a methyl group, R14 is a hydrogen atom or a C5 to C3 alkyl group, 1 is an integer of 0 to 6, and R2 is an integer of 1 to 6; , and A2 have the same meanings as above. ] A resin obtained by polymerizing or copolymerizing the compound shown below is used as a dispersion stabilizer or a surfactant.

Examples of compounds represented by the above formula include NN-dimethyl-N-methacryloxyethyl-N-(3-sulfopropyl)-ammonium betaine, N,N-dimethyl-
Examples include N-methacrylamidopropyl-N-(3-sulfopropyl)-ammonium hetaine and 1-(3-sulfopropyl)-2-vinylpyridinium hetaine.

Further, as a method for introducing the above-mentioned structure, at least one kind selected from the polymerizable amino acid compounds represented by the following formula can be copolymerized with an acrylic monomer as a polymerizable monomer.

Formula: R2 R1-N-R3-B [In the formula, R5 is a substituent containing a radically polymerizable ethylenically unsaturated group, and B is a -COOH group or -
It is 5o3H. ] Specific examples of the above monomers obtained by the addition reaction between hensyl halide and a primary or secondary aminosulfonic acid compound include N-(vinylbenzyl)taurine, N-methyl-N-(vinylbenzyl)taurine,
Examples include N-(isopropenylbenzyl)taurine and N-(isopropenylbenzyl)taurine. In addition, compounds such as N-(2-hydroxy-3-allyloxypropyl) taurine, 2-[N-(2- Examples include hydroxy-3-allyloxypropyl)kotaurine, N-(2-hydroxy-3-allyloxypropyl)alanine, and the like.

After the polymerization reaction, the particles constituting the opposite polarity resin particles used as an additive in the present invention are expressed by the following formula 1)% formula% (wherein R1 is a hydrogen atom or a straight chain or branched alkyl group of Cl-C5). group, R2 is a hydrogen atom or C1-CI2
represents a straight-chain or branched alkyl group. ) Addition-polymerizable unsaturated carboxylic acids such as acrylic acid and methacrylic acid, which have a structure of : In order to adjust electrical properties, thermal properties, etc., it can be copolymerized with addition-polymerizable unsaturated carbonic acids having structures other than those described above, their rust conductors, or other polymerizable molecules.

A specific example is the following 1,000.

First, as addition polymerizable unsaturated carboxylic acids, acrylic acid,
Methacrylic acid, α-ethyl acrylic acid, crotonic acid, α
- Addition-polymerizable unsaturated aliphatic monocarboxylic acids such as methylcrotonic acid, α-ethylcrotonic acid, incrotonic acid, tiglic acid, ungellic acid, or maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid addition-polymerizable unsaturated aliphatic dicarboxylic acids such as dihydromuconic acid and dihydromuconic acid.

Furthermore, metal salts of these carboxylic acids can also be used, and this metal salt formation can be carried out after the completion of polymerization.

Further, examples thereof include esterified products of the above-mentioned addition polymerizable unsaturated carboxylic acid and alcohols such as alkyl alcohols, halogenated alkyl alcohols, alkoxyalkyl alcohols, aralkyl alcohols, and alkenyl alcohols. Specific examples of the above alcohol include methyl alcohol, ethyl alcohol, propyl alcohol,
Alkyl alcohols such as butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, dodecyl alcohol, tetradecyl alcohol, hexadecyl alcohol: Halogenated alkyl alcohols that partially halogenate these alkyl alcohols; Methoxyethyl alcohol Alkoxyalkyl alcohols such as , ethoxyethyl alcohol, ethoxyethoxyethyl alcohol, methoxypropyl alcohol, and ethoxypropyl alcohol; Aralkyl alcohols such as benzyl alcohol, phenylethyl alcohol, and phenylpropyl alcohol; Alkenyl alcohols such as allyl alcohol and crotonyl alcohol. It will be done.

In addition, amides and nitriles derived from the addition-polymerizable unsaturated carbonic acid: ethylene, propylene, butene,
Aliphatic monoolefins such as isobutylene; vinyl chloride, vinyl bromide, vinyl iodide, 1,2-dichloroethylene, 1,2-dibromoethylene, 1,2-short ethylene, isopropenyl chloride, bromide Isopropenyl, allyl chloride, allyl bromide, vinylidene chloride, vinyl fluoride,
Halogenated aliphatic olefins such as vinylidene fluoride, 1
．． 3-butadiene, 1,3-pentadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2,4-hexadiene, 3-methyl-2,4
Conjugated diene aliphatic diolefins such as -hexadiene can be mentioned.

Other examples include styrene and its conductors, such as alkyl styrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene, octylstyrene. Styrene, fluorostyrene, chlorostyrene,
Examples include halogenated styrenes such as bromostyrene, dipromostyrene, and iodostyrene, as well as nitrostyrene, acetylstyrene, methoxystyrene, and the like.

Further examples include vinyl acetates, vinyl ethers, and nitrogen-containing vinyl compounds such as vinyl carbazole, vinyl pyridine, and vinyl pyrrolidone.

The fine powder according to the present invention may be obtained by polymerizing one or more of these monomers.

The resin particles of opposite polarity used in the present invention are not limited to the use of only one type, but a plurality of types may be used in combination.

Further, methods for producing the opposite polarity resin particles used in the present invention include a spray try method, a suspension polymerization method, a sheet polymerization method, a mechanical crushing method, and the like.

The opposite polarity resin particles may be subjected to particle surface treatment as necessary. Surface treatment methods include surface treatment with metals such as iron, nickel, cobalt, copper, zinc, gold, and silver by vapor deposition or plating, or metal oxides such as the above metals, magnetic materials, and conductive zinc oxide. It is also possible to fix substances by ion adsorption or external addition, or to support organic compounds capable of triboelectricity such as pigments or dyes, polymer resins, etc. by coating or external addition.

Furthermore, the molecular weight distribution of the reverse polarity resin particles used in the present invention is as follows:
The peak molecular weight must be in the range of 10,000 to 5,000,000, preferably in the range of 120,000 to 1,000,000.

If the peak molecular weight is larger than 5 million, it will adversely affect the fixing properties of the color toner, and if it is smaller than 10,000, the magnetic particles may be contaminated or the blocking resistance may be deteriorated.

In the present invention, the above-described organic resin particles and a fluidity improver may be used in combination. In particular, hydrophobic inorganic oxides are most suitable as flow improvers. In other words, the hydrophobic inorganic oxide serves to supplement the opposite polarity resin particles in terms of chargeability and fluidity. Therefore, the BET specific surface area is som2/g
If it is not more than that, it will not work properly. More preferably, it is 150 m2/g or more.

As such a hydrophobic inorganic oxide, it is particularly preferable to use treated silica fine powder obtained by hydrophobicizing silica fine powder produced by gas phase oxidation of a silicon halide compound. Among the treated silica fine powders, it is particularly preferred that the silica fine powders be treated so that the degree of hydrophobicity as measured by a methanol titration test is in the range of 30 to 80.

Hydrophobization is achieved by chemical treatment with an organosilicon compound that reacts with fine silica powder or physically adsorbs it.

In a preferred method, fine silica powder produced by vapor phase oxidation of a silicon halide is treated with an organosilicon compound.

Examples of such suitable organosilicon compounds are hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane,
Allyl phenylcyclosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, ρ-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, Vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyljethoxysilane,
Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, and Si containing 2 to 12 siloxane units per molecule, one each for the terminally located unit. There are dimethylpolysiloxanes containing hydroxyl groups bonded to . These are 1 ft! Alternatively, it is used in a mixture of 2 ff4 or more.

Commercially available products include Taranox-500 (Talco),
Examples include AEROSIL R-972 (Japan Aerosil Co., Ltd.). The amount added is 0.3 to 2% based on the colorant-containing resin particles.

The amount added is also related to the particle size distribution of the resin particles described later, but if it is less than 0.3% by weight, it will be difficult to achieve adequate fluidity, and if it is more than 2% by weight, problems such as toner scattering and fogging will occur. is likely to occur.

A charge control agent may be added to the toner according to the present invention in order to stabilize charge characteristics. In this case, a colorless or light-colored charge control agent that does not affect the color tone of the toner is preferred. Examples of the negative charge control agent include organometallic complexes such as metal complexes of alkyl M jh salicylic acid (for example, chromium complexes or zinc complexes of di-tert-butylsalicylic acid). When the negative charge control agent is added to the toner, 0.1 to 10 parts by weight per 100 parts by weight of the binder resin;
It is preferable to add 0.5 to 8 parts by weight.

When preparing a two-component development side by mixing with the toner according to the present invention, the mixing ratio is 2 as the toner concentration in the developer.
~10% by weight, preferably 3-9% by weight usually gives good results. If the toner concentration is less than 2% by weight, the image density will be too low to be practical, and if it exceeds 10% by weight, fogging and in-machine scattering will increase and the useful life of the developer will be shortened.

As the coloring agent used in the present invention, a wide variety of known dyes and pigments can be used, such as phthalocyanine blue, industhrene blue, peacock blue, permanent red, lake red, rhodamine lake, banza yellow, permanent yellow, and henjin yellow. The content thereof is 12 parts by weight or less, preferably 0.5 to 9 parts by weight, based on 100 parts by weight of the binder resin so as to sensitively reflect the transparency of the OHP film.

If necessary, additives may be mixed into the toner of the present invention within a range that does not impair the properties of the toner. Examples of such additives include lubricants such as Teflon, zinc stearate, and polyvinylidene fluoride; Or a fixing aid (for example, low molecular weight polyethylene, low molecular weight polypropylene)
etc.

In producing the toner of the present invention, the constituent materials are thoroughly kneaded using a thermal kneading machine such as a hot roll, kneader, or extruder, and then obtained by mechanical crushing and classification, or by adding color to the binder resin solution. After dispersing materials such as agents,
Method to obtain by spray drying or should constitute a binder resin! Various methods can be applied, such as a polymerization toner production method in which a toner is obtained by mixing a predetermined material with #mer and then polymerizing the emulsified suspension.

In the color 1 to toner of the present invention, the weight average particle size of the 1-toner is 6 to 10 μm, and the toner particles having a particle size of 5111T1 or less are 15 to 40% by number and 12.7 to 1
6. Toner particles containing 0.1 to 5.0% by weight of Ottm, 1.0% by weight or less of 16 shims or more, and having a particle size of 6.35 to 10.1 μm have a particle size distribution that satisfies the following formula. The effect is more pronounced when

The toner having the above particle size distribution can faithfully reproduce the latent image formed on the photoreceptor, and has excellent reproducibility of halftone dots and minute latent images such as digital ones.
Provides an image with excellent gradation and resolution, especially in highlight areas. Furthermore, it maintains high image quality even when copying or printing is continued, and even in the case of high-density images, it is possible to perform good development with less toner consumption than conventional non-magnetic toner, making it economical. This has advantages in terms of flexibility and miniaturization of the copying machine or printer main body.

Let me explain in more detail. Non-magnetic toner particles with a particle size of 5 μm or less account for 15 to 40 percent of the total number of particles, more preferably 2
0 to 35% by number is good. If the number of non-magnetic toner particles with a particle size of 5 μm or less is less than 15%, there will be less non-magnetic toner particles effective for high image quality, and especially as the toner is used for continuous copying or printing, the effective non-magnetic toner particles will become less effective. As the magnetic toner particle component decreases, the balance of the particle size distribution of the non-magnetic toner as shown in the present invention may deteriorate, and the image quality may gradually deteriorate. If it exceeds 40% by number, non-magnetic toner particles tend to aggregate with each other, resulting in toner agglomerates larger than the original particle size, resulting in rough image quality and decreased resolution. Or, the density difference between the edge part and the inside of the latent image is large (the image tends to be hollow).

Also, 12.7-16. OLLm range of particles is 0.1~
The content is preferably 5.0% by weight, preferably 0.2-3
．． 0% by weight is good. If it is more than 5.0% by weight, the image quality will deteriorate and more development than necessary, that is, too much toner will be applied, leading to an increase in toner consumption (on the other hand, 0.1% by weight).
If the weight percentage is not swirled, there is a possibility that the image density will be lowered due to the lowered fluidity.

In addition, the amount of non-magnetic toner particles having a particle size of 16 μm or more is preferably 1.0% by weight or less, more preferably 0.6% by volume or less, and if it is more than 1.0% by weight, fine line reproduction may be hindered. Not only that, but during transfer, coarse toner particles of 16 μm or more protrude from the thin layer surface of the toner particles developed on the photoreceptor, resulting in a gap between the photoreceptor and the transfer paper via the toner layer. If the delicate adhesion state becomes irregular, it may cause fluctuations in transfer conditions, which is likely to be a factor in generating defective transferred images. The weight average diameter of the non-magnetic color toner is 6 to 1.0 ILm, preferably 7 to 9 μm.
is good, and this value is inseparable from each component mentioned above.
It is impossible to think like that. Weight average particle size 6μ
If it is less than m, in applications with a high image area ratio such as graphic images, the amount of toner applied on the transfer paper is small, which tends to cause problems such as low image density. This is considered to be due to the same reason as the reason why the density inside the edge portion of the latent image decreases as described above.

If the weight average particle diameter is 10 μm or more, the resolution will not be good, and even if copying is good at the beginning, image quality will tend to deteriorate with continued use.

Furthermore, although the particle size distribution can be measured by various methods, in the present invention it was measured using a Coulter counter.

In other words, the measuring device is Coulter counter TA.
-4 type (manufactured by Coulter) and an interface (manufactured by Nikkaki) that outputs number distribution 1 volume distribution and CX-1
A personal computer (manufactured by Canon) is connected, and a 1% NaCρ aqueous solution is prepared using primary sodium chloride as the electrolyte.

As a measuring method, 0.1 to 5 mp2 of a surfactant, preferably an alkylbenzenesulfonate salt, is added as a dispersant to 100 to 150 mρ of the electrolytic aqueous solution, and 2 to 20 mg of the measurement sample is added. The electrolyte in which the sample was suspended was dispersed in an ultrasonic disperser for about 1 to 3 minutes, and then
With the counter TA-n type, the aperture is 100
The volume distribution and number distribution of particles of 2 to 40 μm were calculated by measuring the number of toner particles using a μm aperture. Then, according to the present invention, the weight-based weight average diameter (D,) obtained from the volume distribution (the median value of each channel is taken as the representative value for each channel) 1 The amount of coarse powder on the weight basis obtained from the volume distribution (], the number of fine powders (5,041xm or less) based on the number distribution was determined from the number distribution of 5 particles of 66.0 μm or more.

As the binding substance used in the colorant-containing resin particles of the present invention, various resin materials conventionally known as toner binding resins for electrophotography are used.

For example, styrene copolymers such as borisdyrene, styrene/butadiene copolymer, styrene/acrylic copolymer, ethylene copolymers such as polyethylene, ethylene/vinyl acetate copolymer, and ethylene/vinyl alcohol copolymer. , phenolic resin, epoxy resin, acrylic phthalate resin, polyamide resin, polyester resin,
Maleic acid resin, etc. Furthermore, there are no particular restrictions on the manufacturing method of any of the resins.

Among these resins, the effects of the present invention are particularly great when a polyester resin having a high negative charging ability is used. In other words, polyester resin has excellent fixing properties and color
Although it is suitable for toner, it has a strong negative charging ability and tends to be excessively charged. However, when polyester resin is used in the structure of the present invention, the disadvantages are improved and an excellent toner can be obtained.

In particular, the following formula (wherein R is ethylene or propylene group, Xl,
Each Y is an integer of 1 or more, and the average value of Xly is 2 to 1O. ) as a diol component, and a carboxylic acid component consisting of a bivalent or higher carboxylic acid, its acid anhydride, or its lower alkyl ester (e.g., fumaric acid, maleic acid, maleic anhydride, phthalate). A polyester resin obtained by cocondensation polymerization with terephthalic acid, trimellitic acid, pyromellitic acid, etc.) is more preferable because it has sharp melting characteristics.

In the present invention, an electrically insulating resin is used as the coating resin on the carrier surface, but it is appropriately selected depending on the toner material and the carrier core material. In the present invention, at least one monomer selected from at least acrylic acid (or its ester) monomer and methacrylic acid (or its ester) monomer is used to improve adhesion to the surface of the carrier core material. It is necessary to contain In particular, when polyester resin particles with high negative charging ability are used as a toner material, it is preferable to further copolymerize with a styrene monomer in order to stabilize charging, and the copolymerization weight ratio of the styrene monomer is is preferably 5 to 70% by weight.

The average molecular weight of the above copolymer is determined to be a number average molecular weight of 10.
00-35,000 preferably 1.7,000-24,
000. Weight average molecular weight is 25,000 to 100,00
0, preferably 49,000 to 55,000.

Examples of styrene monomers that can be used in the present invention for the coating resin of the carrier core material include styrene monomers, chlorostyrene monomers, a-methylstyrene monomers, styrene-chlorostyrene monomers, and acrylic monomers such as: Examples include acrylic acid ester monomers (methyl acrylate monomer, ethyl acrylate monomer, butyl acrylate monomer, octyl acrylate monomer, phenyl acrylate monomer, 2-ethylhexyl acrylate monomer), etc.
Examples include methacrylic acid ester monomers (methyl methacrylate monomer, ethyl methacrylate monomer, butyl methacrylate monomer, phenyl methacrylate monomer).

The carrier core material (magnetic particles) used in the present invention includes, for example, surface-oxidized or unoxidized metals such as iron, nickel, copper, zinc, cobalt, manganese, chromium, rare earths, and their alloys or oxides. Can be used. Moreover, there are no special restrictions on the manufacturing method.

The measurement method of the present invention will be described below.

(1) Frictional charge measurement: The measurement method will be explained in detail using drawings.

FIG. 1 is an explanatory diagram of a device for determining the tribocharge amount of toner. First, a mixture of toner and carrier whose weight ratio is 1:19 or 1:99 in the case of an external additive is placed in a metal measuring container 2 with a 500-mesh screen 3 at the bottom. 50-1.00 m
Place in a polyethylene bottle with a capacity of about 10 to 40 g.
The mixture (developer) is shaken by hand for about 0.5 to 1.5 seconds.
g and put on the metal lid 4. Measurement container 2 at this time
Let the total weight of the scale be W, (g). Next, bow sucker 1
(At least the portion in contact with the measurement container 2 is an insulator), suction is applied from the suction lower, and the air volume control valve 6 is adjusted to set the pressure of the vacuum gauge 5 to 250 mmAq. In this state, suction is performed for a sufficient period, preferably 2 minutes, to remove the toner by suction. The potential of the electrometer 9 at this time is assumed to be ■ (volt). here 8
is a capacitor and has a capacitance of C (μF). In addition, the weight of the entire measurement container after suction is weighed and is defined as Wz (g).

The amount of triboelectric charge (μc/g) of this toner is calculated as shown below.

(However, the measurement conditions are 23°C and 60% RH.) The carrier used for the measurement is 250 mesh bath 350
A coated ferrite carrier of the present invention containing mesh carrier particles of 70 to 90% by weight is used.

(2) Volume specific resistance ■Bellet (20mmφX2-3mm thickness) 10tX3
Made by pressure molding for 0 seconds.

■Leave this pellet in an environmental chamber at 22°C and 55% RH for 24 hours.

■TR-8601, HIGHMECO manufactured by Takeda Riken Co., Ltd.
The resistance value is measured by changing the electric field using the HMM ET E R, and the value in lkv/cm is read from the data plot.

[Examples] The present invention will be described in detail below with reference to Examples and drawings. In addition, all % and parts indicate weight % and parts by weight.

h) A 11 400 parts of deionized water was added to a 2ρ separable flask equipped with a stirrer, a thermometer, an N2 inlet tube, and a condenser dropping port, and the temperature was raised to 80°C. After adding 2.2 parts of an aqueous solution prepared by dissolving 0.2 parts of dimethylethanolamine and 2 parts of AlBN in 20 parts of deionized water and allowing it to stand for 10 minutes, N,N-diethyl-N- prepared separately from the aqueous solution was added. A mixture of 10 parts of methacryloxyethyl-N-(3-sulfopropyl)-ammonium-betaine dissolved in 50 parts of deionized water, and 100 parts of methyl methacrylate, 70 parts of styrene, and 15 parts of ethylene glycol dimethacrylate was added. It was dripped over 3 hours.

After dropping, keep at the same temperature for 2 hours until the average particle size is 60 mμ.
An emulsion was obtained. Water was removed from this using a freeze dryer to produce sulfobetaine-containing acrylic resin particles.

Using the same synthesis apparatus as in Synthesis Example 1, 500 parts of deionized water and 15 parts of N-saikutadecyl-2-alanine were added and heated at 80°C.
The temperature rose to . 2 parts of an aqueous solution of 0.3 parts of dimethylethanolamine and 5 parts of AIBN1 dissolved in 50 parts of deionized water.
It dripped over time. 10 minutes after the first dropwise addition of the aqueous solution, 100 parts of methyl methacrylate, n-
A mixed solution of 40 parts of butyl acrylate, 50 parts of styrene, 7 parts of diethylaminopropyl methacrylamide, and 20 parts of ethylene glycol dimethacrylate was added dropwise over 2 hours. After that, the reaction was completed by keeping at the same temperature for 3 hours.
An emulsion with an average particle size of 75 mμ was obtained. Water was removed from this in a freeze dryer to produce acrylic resin particles containing an amino acid type zwitterionic group, an amino group, and a carboxyl group.

13 80 parts of methyl methacrylate, 20 parts of n-butyl acrylate, 4 parts of dimethylaminoethyl methacrylate, 200 parts of distilled water, 0.6 parts of potassium persulfate, 4 parts of polyoxyethylene nonylphenol, 1 part of sodium lauryl sulfate (emulsifier) ) was polymerized at 80°C for 4 hours.

After the polymerization reaction is completed, the reaction solution is cooled to room temperature, and using an ultrafiltration device and a freeze dryer, acrylic resin particles without amino (sulfonic) acid type and sulfobetaine type zwitterionic groups are obtained by emulsion polymerization. Obtained. The average particle size of this product was 58 mμ.

Thoroughly pre-mix with a Henschel mixer, 3
The mixture was melt-kneaded at least twice using this roll mill, cooled, and then coarsely ground to about 1 to 2 mm using a hammer mill, and then finely ground using an air jet type pulverizer.

Furthermore, the obtained finely ground product was classified and a particle size distribution of 2 to 10 μm was selected so as to have the particle size distribution of the present invention, thereby obtaining colorant-containing resin particles.

100 parts of the above colorant-containing resin particles have a particle diameter of 60 μm, a specific electrical resistance of 3×10”Ωcm, and a weight average molecular fillo
ooo was combined with 1.0 part of the acrylic resin particles of Synthesis Example 1 to prepare a cyan toner.

This cyan toner is Met.

To 5 parts of this cyan toner, a copolymer (number average molecular weight 21,250, weight average molecular weight 52,360) consisting of 50% styrene, 20% methyl methacrylate, and 30% 2-ethylhexyl acrylate with a weight average particle size of 45 μm, 3
5 μm or less 4.2%, 35-40 μm, 9.5%, 34
Cu-Zn-Fe with particle size distribution of μm or more 0.2%
A 0.5% carrier coated on a ferrite carrier was mixed in a total amount of 100 parts to prepare a developer.

When this developer was used in a commercially available plain paper color copying machine (Color Laser Copier 500 manufactured by Canon), the development contrast was set at 270V, and the image was produced at 23°C/65%, and the resulting image was as follows. The density was high (1.50), and it was clear with no fog.
I made 0 copies, but the density drop during that time was 0.05
The image size was small, and the fog and sharpness were the same as the initial image. In addition, when the development contrast was set to 330■ at low temperature and low humidity (20°C, 10% RH) and the image was printed, the image density was as high as 1.46. This suggests that it was effective.

Furthermore, when images were produced under high temperature and high humidity conditions (30° C./80%) with the development contrast set at 250 V, a very stable and good image was obtained with an image density of 1.53.

Further 23℃/60%RH120℃/10%, 30℃/8
Even in the initial image after being left in each environment for 1 month at 0%,
All (no abnormalities were observed.

As external additives, 0.5 parts of the acrylic resin particles of Synthesis Example 1 used in Example 1, and 0.5 parts of silica fine powder treated with hexamethyldisilazane (BET specific surface area 230 m''/g) were used.
Image printing was carried out in the same manner as in Example 1 except that 5 parts were used, and the result was 1.32 to 1.4923°C/6 at 20°C/10%.
Under 5% 1.43-1.5230℃/Under 80% 1
．． Although the environmental characteristics were slightly lower than in Example 1 (51 to 1.61), good results were obtained.

The procedure was the same as in Example 1, except that 0.8 part of the acrylic resin particles shown in Synthesis Example 2 having a specific electrical resistance of 2X]O'', a weight average molecular weight of 150,000, and a particle size of 75 mu was used as an external additive. A cyan toner was used. When image formation was carried out in the same manner as in Example 1 using the above cyan toner, the results were 1.42 to 1,4723°C/6 at 20°C/10%.
Under 5% 1.45-1.5030℃/Under 80% 1
．． A good result of 48 to 1.52, which is almost the same as in Example 1, was obtained.

Man-hours ■U In Example 1, image printing was carried out in the same manner as in Example 1 except that acrylic particles were not used.
Fog occurred below 0%, and the image density also decreased.

L Soft Soil 1 Image printing was carried out in the same manner as in Example 1 except that the acrylic resin particles shown in Synthesis Example 3 were used instead of the acrylic resin particles in Synthesis Example 1.
Fog and toner scattering occurred from about 0 sheets onwards.

Image formation was carried out in the same manner as in Example 1, except that instead of the acrylic resin particles in Synthesis Example 1, particles having the same composition as Synthesis Example 1 but with different polymerization conditions and a particle size of 900 mμ were used. However, fogging occurred at 20°C/10%.

[Effects of the Invention] According to the present invention, by adding the above-mentioned external additives, charging performance is improved and good images without fog can be obtained.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram of a measuring device used to determine the amount of charge.

Claims (2)

[Claims] (1) In a color toner containing at least non-magnetic colorant-containing resin particles and an external additive, the external additive has: [a] a particle size of 20 to 800 mμ and a specific electrical resistance of 10^6 to 1
0^1^5 Ωcm, and is an organic resin particle that is charged to the opposite polarity to the colorant-containing resin particle when frictionally charged with iron powder, [b] 30% by weight of the structure of formula 1) as its component A color toner characterized in that it is an organic resin particle having the above structure and having at least one of the structures represented by formulas 2) and 3). Formula 1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 is a hydrogen atom or a straight chain or branched alkyl group of C_1 to C_5, R_2 is a hydrogen atom or C
Represents a straight chain or branched alkyl group of _1 to C_1_2. ) Formula 2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, A is a C_1 to C_6 linear or branched alkylene group, phenylene group, or substituted phenylene group ) Formula 3) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, A is the same as Formula 2.) (2) The weight average diameter of the toner is 6 to 10 μm, and 5 μm.
15 to 40% by number of toner particles having a particle size of m or less,
12.7-16.0 μm is 0.1-5.0% by weight, 16
Contains 1.0% by weight or less of micrometers or more, 6.35 to 10
．． Toner particles of 1 μm meet the following formula 9≦V×@d@_4/N≦14 [where V: weight % of toner particles having a particle size of 6.35 to 10.1 μm N: 6.35 to 10.1 μm The color toner according to claim 1, wherein the number % of toner particles having a particle size is: @d@_4: average weight diameter of all toner particles].