JPH01185659A - Toner for developing electrostatic latent image and production thereof - Google Patents

Abstract

PURPOSE:To obtain a toner having good light transmittability and heat resistance by providing a shell layer consisting of a charge control agent and vinyl resin on the surface of core particles consisting of a coloring agent and polyester resin and specifying the softening points of the polyester and vinyl resins. CONSTITUTION:The shell layer consisting of the charge control agent and the vinyl resin is laminated on the outside surface of the core particles consisting of the coloring agent and the polyester resin. The polyester resin to be used for the core particles is a linear polyester resin and the softening point thereof is 80-150 deg.C. The flocculation of a toner takes place in the production process when the softening point is below 80 deg.C. Complete melting is not possible and light transmittability is degraded when said point exceeds 150 deg.C. The softening point of the vinyl resin is 80-150 deg.C and the glass transition point thereof is 55-70 deg.C. Heat resistance is degraded when the softening point is below 55 deg.C and the light transmittability is deteriorated when said point exceeds 70 deg.C. The toner having the excellent light transmittability, heat resistance and shape stability is thereby obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a toner for developing electrostatic latent images. Specifically, the present invention provides a method for developing electrostatic latent images in electrophotography, electrostatic recording, and electrostatic printing, which exhibits sufficient translucency for OHP or full-color use, and provides clear projected images or colored images. The present invention relates to a toner for developing electrostatic latent images.

(Prior art) Development of electrostatic latent images in electrophotography, electrostatic recording, and electrostatic printing involves electrostatically adsorbing triboelectrically charged toner to an electrostatic latent image formed on a photoreceptor. This is done by visualizing the results.

As a method for charging the toner used in developing such an electrostatic latent image, in a two-component development method, it is known that charging is imparted by mixing and stirring with a substance generally called a carrier. It is also known that in the -component development method, charge is imparted by contact with a developing sleeve, a toner regulating blade, or the like. In either method, if the toner is not uniformly charged, problems occur during development and transfer. Conventionally, in order to improve the chargeability of toner, a charge control agent having a triboelectric charge series opposite to that of the carrier or blade material has been added as a component of the toner. ing.

For example, toners have conventionally been manufactured by the so-called pulverization method, in which a thermoplastic resin is mixed with a colorant and a charge control agent, melt-kneaded, cooled and solidified, and then pulverized and classified to obtain toner particles. It is being Also known are those obtained by a suspension method in which a charge control agent is mixed and dispersed together with a polymerizable monomer, a polymerization initiator, a colorant, etc., and polymerized in water. However, in all of these toners, the charge control agent exists inside the toner particles, and only a small amount of the added amount is present on the surface. For this reason, the distribution of the amount of charge on the toner becomes wide, and this causes problems such as toner scattering and fogging. Furthermore, in the case of toner produced by the pulverization method, the degree of variation in the charge amount distribution of the toner varies depending on whether each composition of the toner is uniformly dispersed. Therefore, it is an important issue to uniformly disperse each toner composition in each toner.

In recent years, toners for developing electrostatic latent images have been made into composite structures for the purpose of separating functions or improving surface properties in order to respond to higher definition, higher image quality, and diversifying toner functions and uses. Various toners have also been proposed.

For example, JP-A-59-37553 discloses a toner obtained by mixing JM resin for binding and a coloring agent and heat-treating the mixture in a hot air stream. Since the coloring agent that adheres to the surface is carbon black or magnetic powder, moisture resistance and charge stability cannot be obtained. Furthermore, JP-A No. 61-210368 discloses a toner in which a coloring agent is attached and fixed on the surface of a spherical resin using a binder crumb, but the binder resin and coloring agent are mixed on the surface of the spherical resin. As a result, the colorant is poorly dispersed and does not adhere uniformly to the surface of the spherical resin, making it impossible to obtain sufficient image density. Gender will be greatly influenced. Furthermore, JP-A-62-209541 discloses a toner characterized by fixing a charge control agent on the surface of a magnetic or non-magnetic toner by mechanical strain. Expensive charge control agents can be used effectively by having them exist only on the surface of the toner, but colorants, magnetic powder, etc. contained in magnetic or non-magnetic toners are present on the toner surface, and this is similar to the above. However, charging stability could not be obtained.

Furthermore, JP-A No. 61-275767 discloses a layer consisting of a magnetic material and/or a coloring agent on the surface of the core particle, and at least one monomer selected from fluorine-containing monomers, amino group-containing monomers, and nitro group-containing monomers. A toner is shown in which capsule layers made of a polymer of monomers containing are sequentially laminated. In this toner, the chargeability is imparted by the above-mentioned polar resin, and since the outermost surface is formed by the polar resin, the chargeability of the toner particles themselves can be made uniform. . However, polar resins do not provide sufficient chargeability, and the amount of charge of polar resins generally increases gradually in proportion to the stirring time, and the build-up of charge is slow. When actually used in an apparatus, toner is sequentially replenished according to the amount of toner consumed, and when toner with different stirring times is mixed, the charge amount distribution becomes extremely wide.
If used continuously for a long period of time, there is a high possibility that problems such as toner scattering and fogging may occur.

Furthermore, Japanese Patent Publication No. 59-38583 discloses a toner in which a coating layer made of microparticles formed by emulsion polymerization is wet-formed on the surface of core particles.
No. 226162 discloses a toner in which fine resin particles are wet-adhered to the surface of a colored thermoplastic resin and then heat-treated.

In these toners, the surface properties are improved by wet-forming a coating layer made of microscopic resin particles, and the surface is roughened to increase the surface area and friction coefficient, which improves chargeability. This is an attempt to improve. In addition, since the toner has such surface properties, the fluidity and cleaning properties of the toner are improved.

However, although the charging property can be improved to some extent by improving the surface properties,
In the toner shown in No. 38583, it is said that it is preferable to add a characteristic imparting agent such as a charge control agent to the core particles, and in such an embodiment, as described above, the distribution of the charge control agent in the core particles is greatly affected. There is a large possibility that the charge amount distribution of the toner will become wide depending on the amount of charge.

Furthermore, in these toners, the fine resin particles that wet-cover the surface of the core particles adhere to the core particles while retaining their particle shape, as is clear from the electron micrograph shown in JP-A No. 62-226162. is being
Therefore, the coating layer formed from the fine resin particles does not completely cover the surface of the core particles (that is, it is not dense). Because of this, even if a charge control agent is added to the minute resin particles in a toner with such a structure, there is a strong possibility that stable chargeability will not be obtained due to the influence of the coloring agent, magnetic powder, etc. in the core particles. In particular, when the toner is stored or used under severe temperature conditions, the components constituting the core particles leak into the toner surface through the gaps between the minute resin particles, causing an even greater effect. Incidentally, when the core particle component leaches out onto the toner surface in this way, a problem arises in that the toner particles also coagulate together.

As described above, many of the conventionally known toners have various problems as described above, particularly problems in chargeability, and further improvements are desired.

Furthermore, when considering the use of such a toner as a translucent color toner, in addition to these problems, other problems as shown below arise.

That is, in developing the electrostatic latent image as described above, the visualized image is further exposed to an overhead projector (
When projecting an image using an optical projection device such as an OHP, it is necessary to show chromaticity on the projection surface.
Also, three-color separation exposure and subtractive color method Three primary colors (or four colors including black)
When making a so-called full-color copy in which the colors of the original image are reproduced by combining color toners (colors), it is necessary to reproduce various intermediate colors, and in both cases, it is necessary to form a toner layer with high fixation and brightness. In order to increase transparency, it is necessary to uniformly melt the resin contained in the toner as a fixing resin, and the resin used as a fixing agent must be a sharp melt with low viscosity, so it must have a low molecular weight and It is said to have a narrow molecular weight distribution.

However, synthetic resins with such characteristics are -
Problems arise such as being brittle to JR and having poor fixability to paper and OHP sheets. Among various synthetic resins, polyester resins have polar groups (-CO○H groups, -OH groups), etc., so they are advantageous in terms of fixability to paper and ○HP sheets, and are relatively good. However, when a polyester resin is used in a toner with a conventionally known structure such as the one described above, the environmental resistance is poor due to the influence of the polar group, and charging resistance is particularly high at high temperatures. Sexual stability was an issue.

Incidentally, such polyester resins are combined with expensive solid silicone varnish to improve environmental resistance, and various organic pigments are blended into pulverized toners (Japanese Patent Publication No. 53-47174).
No. 53-47175, No. 53-47176) have also been proposed, but even in such toners, the problem of environmental resistance caused by the polar groups of polyester-based soap has not been essentially improved. Moreover, various problems with the pulverized toner as described above naturally remain.

(Problem M to be Solved by the Invention) Therefore, it is an object of the present invention to provide a new toner for developing electrostatic latent images which solves the above-mentioned problems. A further object of the present invention is to provide a toner for developing electrostatic latent images that can exhibit excellent light transmittance and, at the same time, has excellent fixing properties and environmental resistance. Another object of the present invention is to provide a toner for developing electrostatic latent images that has stable chargeability and at the same time has uniform chargeability among particles. The present invention further provides charging properties, development amount, cleaning properties, etc. that fully correspond to higher definition in terms of line reproducibility, higher image quality in terms of texture, halftone reproducibility, gradation, resolution, etc. The object of the present invention is to provide a toner for developing electrostatic latent images having powder properties such as fluidity.

(Means for Solving the Problems) The above objects consist of a core particle consisting of at least a coloring agent and a polyester resin, and an outer shell consisting of at least a charge control agent and a vinyl resin, the outer surface of the core particle being coated with a film. A toner for developing an electrostatic latent image composed of a layer, wherein the polyester resin has a softening point of 80 to 150°C.
is a linear polyester resin, and the vinyl resin has a softening point of 80 to 150°C and a glass transition point of 55 to 7.
This is achieved by using an electrostatic latent image developing toner characterized by a temperature of 0°C.

The above objectives also include a process of electrostatically adhering vinyl resin fine particles to the surface of core particles consisting of at least a colorant and a polyester resin, and a process of melting the surface of the adhered fine particles by mechanical shearing force to form a film. This is achieved by a method for producing a toner for developing an electrostatic latent image, which is characterized by comprising the steps of: forming an outer shell layer, and melting and fixing a charge control agent on the outer shell layer.

Hereinafter, the present invention will be explained in more detail based on embodiments.

In the toner for developing electrostatic latent images of the present invention, the core particles are composed of at least a colorant and a polyester resin, and optionally contain other toner property improving agents such as a release agent and a charge control agent. Is possible.

Further, the structure of the core particles is not particularly limited as long as it contains at least a colorant and a polyester resin component, and various embodiments may be used. Mixed inside,
The entire core particle may be made of this colorant-containing polyester resin, or the core particle may be formed by forming a colorant layer containing a colorant on the surface of a base particle made of a polyester resin that does not contain a colorant. is also possible.

Note that the toner of the present invention is a color toner, and considering the fact that a wide variety of measures are required regarding the addition of a coloring agent depending on the intended use, the model of use, etc., the core particles are configured in the latter manner. This can be said to be preferable from the viewpoint of manufacturability and cost efficiency.

Further, the core particles are not particularly limited as long as they can be obtained by a conventionally known method for producing polyester resin toner particles, such as a pulverization method, a suspension method, a spray dry method, etc. A wet granulation method may be used.

More specifically, when using the pulverization method, core particles can be obtained by mixing and kneading a coloring agent and the like with a polyester resin, and then pulverizing and classifying the mixture.

Note that it is also possible to spheroidize the particles thus obtained by subjecting them to heat treatment or the like. Alternatively, it is possible to obtain core particles by pulverizing and classifying the polyester resin as it is, subjecting it to spheroidization treatment if necessary, and forming a coloring agent layer on the surface of the base particles thus obtained. can.

When using the suspension method, the polyester resin is melted with or without a coloring agent, suspended in an aqueous medium, and granulated; when using the spray try method, the polyester resin component is The polyester resin component alone or together with a colorant is dissolved in a solvent and then spray-dried and granulated. In either case, if necessary, a colorant layer is added to the surface of the resulting particles in the same manner as in the above case. is formed into a core particle.

In addition, when attempting to obtain core particles by forming a colorant layer containing a colorant on the surface of the base particles as described above,
The coloring agent alone is attached to the surface of the base particles formed in the above manner using van der Waals force and electrostatic force in a wet or dry manner, and then fixed to the base particles by heat or mechanical impact force. It can also be
Alternatively, it is also possible to adhere and immobilize the coloring agent together with the thermoplastic resin fine particles, or to adhere and immobilize the synthetic resin fine particles containing the colorant.

However, the method for producing the core particles used in the toner for developing electrostatic latent images of the present invention is of course not limited to the method exemplified above.

In the present invention, the polyester resin used to constitute the core particle includes various polyester resins synthesized from a polyol component and a polybasic acid component, such as those shown below, and which are partially cross-linked. However, in order to exhibit good melting properties during fixing and form a highly transparent toner layer, linear polyester resins are preferably used. In particular, those having a softening point of 80 to 150°C, preferably 80 to 130°C are desirable.

That is, if the softening point is less than 80°C, toner aggregation will occur during the manufacturing process, and if the softening point exceeds 150°C, it will not be completely melted during fixing, resulting in poor translucency.

As a monomer for obtaining a polyester resin, polyol components include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1゜3-butanediol 1 .2.3-butanediol, 1.5-bentanediol, 1.6-hexanediol, neopentyl glycol, 2-ethyl 1°3-hexanediol, 2,2.4-trimethyl-
1,3-bentanediol, 1,4-bis(2-hydroxymethyl)cyclohexane, 2,2-bis(4-hydroxypropoxyphenyl)propane, bisphenol A, hydrogenated bisphenol A, polyoxyethylated bisphenol A, etc. Examples of polybasic acid components include maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,4-benzenetricarboxylic acid, and 1,2,5-benzenetricarboxylic acid. Saturated carboxylic acids, phthalic acid, terephthalic acid, isophthalic acid, succinic acid, adipic acid, malonic acid, sebacic acid, 1,2.4-cyclohexanetricarboxylic acid, 1
, 2.5-cyclohexanetricarboxylic acid, 1.2.4
-butanetricarboxylic acid, 1,3-dicarboxy-2-
Examples include saturated carboxylic acids such as methyl-2-methylcarboxypropane and tetra(methylcarboxy)methane, and acid anhydrides thereof and esters with lower alcohols may also be used. Specifically, for example, anhydrous Examples include maleic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, dimethyl terephthalate, and the like. In addition, the polyester resin used in the present invention is not limited to the one obtained by polymerizing a combination of one type each of the polyol component and other basic acid component as described above, but it may be one obtained by polymerizing using multiple types of each. In particular, unsaturated carboxylic acids and saturated carboxylic acids, or polycarboxylic acids and polycarboxylic acid anhydrides are often combined as polybasic acid components.

As the coloring agent used for the core particles in the toner for developing electrostatic latent images of the present invention, various pigments and dyes of various colors as shown below can be used.

Yellow pigments include C,1,10316 (Naphthol Yellow S), C,1,11710 (Hansa Yellow 10G)
C,1,11660 (Hansa Yellow 5G), C,1,
11670 (Hanzaero-3G>, C, 1, 11680
(Panza Yellow G), C, 1, 11730 (Hansa Yellow GR), C.

1.11735 (Hansa Yellow A), C, 1,1174
0 (Hansa Yellow RN), C, 1,12710 (Hansa Yellow R), C, 1,12720 (Pigment Yellow L
), C,1,21090 (benzidine yellow), C,1
, 121095 (Benzidine Yellow G), C, 1, 21
100 (Benzidine Yellow GR), C, 1, 20040
(Permanent Yellow NCG), C, 1, 21220 (
Palkan Fast Yellow 5>, C, 1, 21135 (Parkan Fast Yellow R), etc.

Red pigments include C,1,12055 (Stalin I), C,1,12075 (permanent orange),
C, 1, 12175 (Resol Fast Orange 3GL
), C, 1, 12305 (Permanent Orange GTR
), C, 1, 11725 (Hansa Yellow 3R), C, I
, 21165 (Palcan Fast Orange GG), C,
I.

21110 (Benzidine Orange G), C,I.

12120 (Permanent Red 4R), C, I.

1270 (Rose Red), C, 1, 12085 (Fire Red), C, 1, 12315 (Brilliant Fast Scarlet), C, 1, 12310 (Permanent Red F2R), C, I.

12335 (Permanent Red F4R), C.

1.12440 (Permanent Red FRL), C,
1,12460 (Permanent Red FRLL), C,
1,12420 (permanent red F4RH), C,
1, (12450 (Light Fast Red Toner B)
, C, 1, 12490 (Permanent Aimin FB),
C, 1,15850 (Brilliant Carmine 6B>, etc.).

Examples of blue pigments include C, 1,74100 (metal-free phthalocyanine blue), C, 1,74160 (phthalocyanine blue), and C, 1,74180 (fast sky blue).

These colorants can be used alone or in combination, but in an amount of 1 to 10 parts by weight, more preferably 2 to 5 parts by weight, based on 400 parts by weight of the resin contained in the toner particles.
It is preferable to use parts by weight. That is, if the amount is more than 10 parts by weight, the fixing properties and translucency of the toner will deteriorate, while if it is less than 1 part by weight, the desired image density may not be obtained.

In the toner for developing electrostatic latent images of the present invention, the core particles comprising at least the above-mentioned polyester resin and the colorant are those in which the entire core particle is made of the polyester-based resin containing the colorant as described above. Alternatively, various embodiments can be taken, such as one in which a coloring agent layer is formed on the surface of base particles made of a polyester resin that does not contain a colorant, but in any embodiment, the particle size of the core particle is 5 to 20 μm, More preferably, it is 6 to 15 μm.

That is, if the particle size of the core particles is less than 5 μm, it becomes difficult to retain the colorant required for image density.
In addition, the final toner particle size may be smaller than necessary, which may cause problems such as toner aggregation or toner scattering or fog due to insufficient or uneven charge amount.On the other hand, core particles If the particle size exceeds 20 μm, the final toner particle size will be larger than necessary, and there is a risk that high definition and high visibility cannot be achieved.

Therefore, in the electrostatic latent image developing materials 1 to 1 of the present invention, the core particles having the above-mentioned structure have their outer surfaces coated with an outer shell layer consisting of at least a charge control agent and a vinyl resin. ing.

As described above, in the toner for developing electrostatic latent images of the present invention, the polyester-based jM resin constituting the core particles is -COO
Due to the presence of polar groups such as H groups and -〇H groups, environmental resistance, especially at high humidity, is poor, and in order to form a toner layer with high transparency after fixing, it is necessary to use a toner with a low softening point. Polyester resin is considered to be a material that is brittle and has low heat resistance, but because the outer shell layer is formed by coating the core particles, polyester resin is not exposed to the external environment. , there is no influence on charging properties etc. due to resin modification. In addition, even if the polyester resin contained in the core particles melts due to the heat applied during storage or use, there is no risk of core material components leaching out onto the surface of the toner particles, and there is no risk of toner agglomeration due to the molten resin or leaching of the core material. The influence of material components on charging properties is eliminated. Furthermore, even if a shearing force that would destroy polyester resin alone occurs during agitation to impart chargeability, the particle size will change due to cracks in the shell layer covered by the vinyl resin-containing outer shell layer. There is no possibility that this will occur, and stable chargeability and developability will be exhibited.

Furthermore, by forming the outer shell layer that coats the core particle in this way, charge polarity, chargeability, developability, etc. can be controlled by the structure of the outer shell layer without being affected by the structure of the core particle existing inside. This is because even if the type of colorant contained in the core particles changes, stable and uniform chargeability can be imparted to each toner particle. In addition, by localizing the charge control agent in the outer shell layer, which is the outermost surface of the toner particles, effective charge control can be performed with an extremely small amount of charge control agent, and even if a colored charge control agent is used, color The image is clear and there is no color turbidity, and even if the particle size is made smaller as image quality becomes higher, sufficient chargeability can be imparted.

In addition, since the charge control agent is used to impart chargeability, the charge builds up quickly, making it possible to obtain a stable charge distribution without being affected by differences in stirring time, resulting in improved image quality. This is advantageous due to the improvement in

In the toner for developing electrostatic latent images of the present invention, the charge control agent contained in the outer shell layer may be present as a mixture in the vinyl resin constituting the outer shell layer, or may be present on the surface of the outer shell layer. Alternatively, it can exist in both. In addition, the outer shell layer is composed of at least a charge control agent and a vinyl resin, but if necessary, a fluidizing agent or a cleaning aid such as silica, titanium oxide, aluminum oxide, metal soap, etc. may be added to the outer shell layer. can do.

In this way, the outer shell layer is formed by coating the outer surface of the core particle. Microparticles and charge control agent microparticles, or vinyl resin microparticles containing charge control agent) are mechanically mixed in an appropriate blending ratio and uniformly distributed around the core particle by the action of van der Waals force and electrostatic force. A preferred method is to attach the microparticles to the substrate and then soften the microparticles by a local temperature increase caused by, for example, a mechanical impact force to form a film. According to this method, even if the vinyl resin contained in the outer shell layer has a higher softening point than the polyester resin contained in the core particles,
It is possible to easily form an outer shell layer that coats the outer surface of the core particle. In addition, the outer shell layer formed by such a method does not substantially change the shape of the core particle, and its surface properties depend on the composition, physical properties (particle size, thermal properties, and The smoothness and surface roughness can be changed by selecting the gelling component (gelling component, etc.), and by appropriately selecting the treatment conditions and number of treatments. From the viewpoint of properties such as fluidity, cleanability, and chargeability of the toner particles, it is desirable that the toner particles be spherical and have minute irregularities on the surface. With this formation method,
For example, in order to successfully form an outer shell layer on the outer surface of a core particle of 5 to 20 μm, the resin fine particles for forming the outer shell layer should have an average particle diameter of 0.05 to 3 μm, preferably 0.1 to 3 μm.
1 μm, and the coefficient of variation of particle size distribution is 20% or less,
Preferably, 15% or less is used. Powders with an average particle diameter smaller than 0.05 μm are difficult to manufacture, and powders with an average particle diameter larger than 3 μm or a coefficient of variation larger than 20% make it difficult to coat the surface of the core particles with a film. Furthermore, it is desirable to use spherical microparticles in the coating film formation process.

The above coefficient of variation in particle size is a measure of variation in particle size (
%), and the standard deviation (σ
) divided by the average particle diameter, and is determined as follows. That is, first, a photograph is taken with a scanning electron microscope, 100 particles are selected at random, and their particle diameters are measured. Based on this measurement result, the standard deviation (σ
) and the average particle size. The standard deviation (σ) used in the present invention is the value obtained by dividing the square of the difference from the average value of each measured value by (n-1) when n particle diameters are measured. expressed as a square root. That is, it is expressed by the following equation.

However, Xl, X2...Xl are the measured values of the particle diameter of the sample particles, and X is the average value of each of the n measured values.

The standard deviation (σ) obtained in this way is calculated as the average particle diameter (
r) and multiplied by 100 was used as the coefficient of variation.

x 100 Also, the shape factor SFI, which is described in the following examples as a numerical value representing sphericity, is the difference between the major axis/minor axis of the particle (
It is used as a parameter to indicate the external surface area of the powder and the large roughness of the particle surface, and is defined by the formula shown below. Note that each value shown in this specification was measured by an image analyzer (Luzex 5000, manufactured by Nippon Regulator Co., Ltd.).

(In the formula, area indicates the average value of the projected area of the powder, and length indicates the average value of the maximum length in the projected image of the powder.) Therefore, the closer the toner particle shape is to a pearl, the more The value of the shape factor SF1 is close to 100.

In addition, devices that can be suitably used in such a method include the Vibe Blade Dization System (Nara Kikai Seisakusho), which applies the impact method in high-speed airflow, and the Ongmil (Nara Kikai Seisakusho).
(manufactured by Hosokawa Micron ■), Mechano Mill (manufactured by Kaida Seiko ■)
and so on.

In addition, in the embodiment in which the charge control agent is attached to the surface of the outer shell layer, the charge control agent is attached to the surface of the outer shell layer formed as described above by the action of van der Waals force and electrostatic force as described above, and then machined in the same manner. It may be melted and fixed by an impact force or the like.

However, it is of course not limited to this method.

In the toner for developing electrostatic latent images of the present invention, the vinyl resin contained in the outer shell layer covering the core particles is not particularly limited, and may be a homopolymer or copolymer of various vinyl monomers as shown below; Blends of these polymers can be used, but preferred are styrene polymers, styrene-(meth)acrylic copolymers, etc., which have stable heat resistance and at the same time exhibit sharp melt properties during fixing. Therefore, its physical properties include a number average molecular weight Mn of 3,000 to 90,000 and a molecular weight distribution of Mw/
Mn 3.0 or less, glass transition point 55-70°C2
It is desired that the softening point is 80 to 150°C. That is, if the glass transition point is less than 55°C, the heat resistance (cohesiveness during storage) will decrease, and if it exceeds 70°C, the translucency will deteriorate. Also, the softening point is 80°C
If the temperature is less than 150°C, cohesiveness becomes a problem, and if it exceeds 150°C, the light transmittance deteriorates.

Examples of vinyl monomers include styrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, and p-tert-butylstyrene. , p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene, p-methoxystyrene, p-phenyl styrene, p
Examples include styrene and its derivatives such as -chlorostyrene and 3,4-dichlorostyrene, among which styrene is most preferred. Examples of other vinyl monomers include ethylene, propylene, butylene, imbutylene, ethylenically unsaturated monoolefins, vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride and other vinyl halides, and vinyl acetate. , vinyl esters such as vinyl propionate, vinyl benzoate, vinyl butyrate, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, acrylic 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isobutyl methacrylate, isobutyl methacrylate, propyl methacrylate,
α- such as isobutyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylamine ethyl methacrylate, diethylamine ethyl methacrylate, etc.
Methylene aliphatic monocarphonic acid esters, (meth)acrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, and vinyl isobutyl ether, vinyl methyl ketone, and vinyl Examples include vinyl ketones such as xyl ketone and methyl isopropenyl ketone, N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, and N-vinylpyrrolidone, and vinylnaphthalenes.

The vinyl resin used in the outer shell layer may be obtained by any polymerization method such as bulk polymerization, suspension polymerization, emulsion polymerization, or solution polymerization. Furthermore, as mentioned above, when forming an outer shell layer by attaching microparticles around a core particle by the action of van der Waals force and electrostatic force and then forming a film by mechanical shearing force, etc., The method of forming such fine particles is not particularly limited, and may include a crushing method in which resin lumps obtained by various polymerization methods are crushed and classified into fine particles, emulsion polymerization of the monomers mentioned above, suspension polymerization, etc. A granulation polymerization method in which fine particles are formed through cloudy polymerization seed polymerization or soap-free polymerization, a suspension method in which vinyl resin is melted and suspended in a non-solvent medium, and granulated, or a vinyl resin is dissolved in a solvent and then sprayed. Known methods such as a wet granulation method such as a spray dry method for drying and granulation may be used. In either method, a charge control agent may be added as necessary to obtain charge control agent-containing resin particles.

In addition, the amount of vinyl resin forming the outer shell layer is 10
5 to 20 parts by weight, preferably 8 to 15 parts by weight relative to 0 parts by weight
It is a heavy building. In other words, if the amount of vinyl resin forming the outer shell layer is less than 5 parts by weight, it becomes difficult to completely cover the core particles with the outer shell layer, and the polyester resin forming the core particles leaches out, leading to toner aggregation. Otherwise, the colorant component may be exposed on the surface of the toner particles and inhibit stable and uniform charging properties.On the other hand, if it exceeds 20 parts by weight, it may be difficult to form a uniform outer shell layer. This is because there is a risk that the particle size distribution of the toner may be expanded or the particle shape may be changed, resulting in deterioration of characteristics such as charging characteristics and development amount.

The charge control agent contained in the outer shell layer is not particularly limited, and various organic or inorganic agents may be used as long as they can impart positive or negative charges through triboelectric charging.

As a positive charge control agent, for example, nigrosine base EX
(manufactured by Orient Chemical Industry ■), quaternary ammonium salt P
-51 (manufactured by Orient Chemical Industry ■), Nigrosine Bontron N-01 (manufactured by Orient Chemical Industry ■), Sudan Chief Schwarz BB (Solvent Black 3: C
o1or Index 26150), Fettschwarz HBN (C, I, NO, 26150), Brilliant Spirits Schwarz TN (manufactured by Farpen Fabricken Beyer), Zabon Schwarz X (manufactured by Farberke Hoechst), and further alkoxylated amines, Alkylamide, molybdate chelate pigments, etc. may be mentioned, and negative charge control agents include, for example, oil black (Color Index 26150).
, Oil Black BY (manufactured by Orient Chemical Industry ■),
Bontron S-22 (manufactured by Orient Chemical Industry ■), salicylic acid metal complex E-81 (manufactured by Orient Chemical Industry ■),
Thioindigo pigment, sulfonylamine derivative of copper phthalocyanine, Spiron Black TRH (manufactured by Hodogaya Chemical Co., Ltd.), Bondron 5-34 (Orient Chemical Co., Ltd.)
), Nigrosine SO (manufactured by Orient Kagaku Kogyo ■), Ceres Schwarz (R) G (manufactured by Hualpen Fabriken Bayer), Cromorgen Schwarz ETOO (
C, I, NO, 14645), Azo Oil Black (R) (manufactured by National Aniline), and the like.

These charge control agents can be used alone or in combination, but the amount of charge control agent added to the outer shell layer is 0.00 parts by weight per 100 parts by weight of the vinyl resin forming the outer shell layer. 001 to 10 parts by weight, preferably 0.0
It is 1 to 5 parts by weight.

That is, if the amount added is less than o, ooi parts by weight, the amount of charge control agent present on the surface of the toner particles is small.
If the amount of charge of the 1-ner is insufficient and, on the other hand, the 10-layer overlapping section is used, the charge control agent will peel off from the outer shell layer, become spent on the surface of the carrier, or be mixed into the developer, reducing the printing life. This is because there is a risk of deteriorating the quality.

(Example) Hereinafter, the present invention will be explained in more detail with reference to Examples.

Production example of styrene-acrylic resin microparticles 1 3 with a stirrer, condenser, inert gas introduction tube, and thermometer installed
70 parts by weight of styrene monomer and 25 parts by weight of n-butyl methacrylate were added as a dispersion in a four-bottle flask.
parts by weight, using 5 parts by weight of n-butyl acrylate and 1.5 parts by weight of hendiyl peroxide as a polymerization initiator, and as a dispersion medium, 1000 cc of distilled water and an appropriate amount of fully saponified polyvinyl alcohol (degree of polymerization of about 1000>2% and/or For the solution, add 1% sodium dodecylbenzenesulfonate.
These were mixed in a liquid tank, and mixed and dispersed at 1200 Orpm using a Tokushu Kika Kogyo (rTK Auto Homo Mixer manufactured by...) as a mixing and dispersing means, increasing the rotational speed of the turbine step by step from 150 Orpm. This dispersion mixture was heated at 80°C for 55 minutes while continuing to stir at the final rotation speed.
Polymerization was carried out by heating for a period of time.

After the polymerization was completed, it was filtered using a centrifugal dehydrator and washed 8 times with pure water.
Vacuum dried and crushed to produce styrene with a particle size of 0.4 μm, number average molecule 1Mn10000, molecular weight distribution Mw/Mn=2.4, glass transition point 60°C, softening point 120°C, coefficient of variation 14%, shape factor SF1113. Acrylic resin microparticles were obtained.

Production Example 2 of Styrene-Acrylic Resin Microparticles In Production Example 1 of Styrene-Acrylic Resin Microparticles, 60 parts by weight of styrene monomer, 30 parts by weight of n-butyl methacrylate, 5 parts by weight of ethyl acrylate, and 5 parts by weight of cyclohexyl methacrylate were added as raw materials. Styrene was produced in the same manner except that 2 parts by weight of benzoyl peroxide was used as a polymerization initiator and the final rotational speed of the turbine was changed to 1200 rpm.
Acrylic resin microparticles were obtained. The obtained microparticles had a number average molecular weight of 1Mn4000 and a molecular weight distribution Mw/Mn=2.
1. Glass transition point 58°C5 Softening point 95°C, coefficient of variation 1
0%, shape factor SFI 108, and particle size 0.4 μm.

Sunalene Acrylic 1) Minimum Resin Value of S Preparation Example 3 In Production Example 1 of Styrene-Acrylic Resin Fine Particles, the raw materials used were 90 parts by weight of styrene monomer, 10 parts by weight of n-butyl methacrylate, and 2 parts by weight of polymerization initiator benzoyl peroxide.
Styrene-acrylic resin microparticles were obtained in the same manner except that parts by weight were used. The obtained microparticles had a number average molecule ff1Mn8500 and a molecular weight distribution Mw/Mn=2
, 9, Glass transition point 75°C2 Softening point 165°C1 Coefficient of variation 10%, Shape coefficient spi 106 particle size 0.4
It was μm.

Production example 4 of styrene-acrylic resin microparticles In production example 1 of styrene-acrylic resin microparticles, the charged raw materials were 50 parts by weight of styrene monomer, 30 parts by weight of 11-butyl methacrylate, 1 to 20 parts by weight of ethyl acrylate, and 1 to 20 parts by weight of ethyl acrylate. Styrene-acrylic resin microparticles were obtained in the same manner except that 0.3 parts by weight of benzoyl peroxide was used. The obtained microparticles had a number average molecular weight Mn of 7000
, molecular weight distribution Mw/Mn=2.6, glass transition point 50°C
, softening point 95℃, coefficient of variation 8%, shape factor SFl 1
08 with a particle size of 0.3 μm.

Production example 1 of polyester resin particles Polyester resin (manufactured by Kao ■, NE-38) was used as a dispersion liquid.
2>30g was dissolved in a mixed solvent of toluene and methylene chloride (7:3), and the dispersion medium was 10 g of distilled water.
Using an appropriate amount of completely saponified polyvinyl alcohol (degree of polymerization of about 1000 > 2% and 1% of sodium dodecylbenzenesulfonate added to 00cc), mix them in a liquid tank and use Tokushu Kika Kogyo ■ as a mixing and dispersing means. Using the rTK autohomogen mixer, set the turbine to 150 rpm.
Increase the rotation speed step by step from 500o rpm.
Mixing and dispersion was performed. This dispersion mixture was heated at 80°C for 3 hours while stirring at the final rotation speed to evaporate the solvent, filtered with a centrifugal dehydrator, washed 8 times with pure water, dried in vacuum, and crushed. , polyester resin particles (2) having an average particle size of 11 μm were obtained.

Polyester Standing 2 Polyester resin (manufactured by Kao Corporation, NE-382) was coarsely pulverized with a feather mill, then pulverized with a fine pulverizer using a jet stream, and further classified by air to obtain polyester with an average particle size of 12 μm. Resin particles (■) were obtained.

Polyester resin particles obtained as above 1
00 parts by weight and phthalocyanine pigment (CI74160) 3
Put the weight part into a 100 Henschel mixer and mix at 1500 r.
The mixture was mixed and stirred for 2 minutes at a rotational speed of am to adhere the pigment to the surface of the polymer particles. Next, using Nara Machinery Hybridization System NII S-1 type, 9. OOOr
pm for 3 minutes to immobilize the pigment on the surface of the polymer particles.

Further, 100 parts by weight of the pigment-treated polymer particles and 10 parts by weight of the microparticles obtained in Production Example 1 of the styrene-acrylic resin particles were subjected to the same treatment as above, and styrene-acrylic resin particles were treated in the same manner as above.
An acrylic resin coating layer was provided. Further, to 100 parts by weight of the polymer particles obtained here, a negative charge control agent chromium complex dye Spiron Black TRH (Hodogaya Chemical Co., Ltd.)
By subjecting 0.5 parts by weight of 0.5 parts by weight of 0.5 parts by weight of 0.5 parts of Spiron Black TRH to the toner surface to adhere to the toner surface, the toner of Example 1, toner a with an average particle size of 11.9 μm, was prepared.
I got it.

Gosu: Nori also 1 The average particle of the toner of Example 2 was prepared by using the same composition and production method as in Production Example a of Senkan Toner, except that the pigment was replaced with 3 parts by weight of Brilliant Carmine 6B (CI 15850). A toner b having a diameter of 12.0 μrn was obtained.

Toner Production Example C Using the same composition and production method as in Toner Production Example a except that the pigment was replaced with 3 parts by weight of benzidine yellow (CI 21090), the toner of Example 3 with an average particle size of 11.9 μm was produced. Toner C was obtained.

In toner production example a, the negative charge control agent was replaced with the positive charge control agent P-51 (manufactured by Orient Chemical Industry Co., Ltd.) 1.0.
Using the same composition and manufacturing method except for replacing 1 part by weight,
A toner d of Example 4 having an average particle size of 12.0 μm was obtained.

Toner production example e In toner production example a, in addition to the phthalocyanine pigment triple layer, 5 parts by weight of the microparticles obtained in production example 2 of styrene-acrylic resin microparticles were colored. Using the same composition and manufacturing method except for using it as a agent layer forming material, the toner of Example 5 with an average particle size of 11
．． A toner e of 6 μm was obtained.

Toner production example f Phthalocyanine pigment (CI7
4160) was added at a composition ratio of 10 parts by weight and placed in a Henschel mixer and mixed and stirred at a rotational speed of 1500 rpm for 2 minutes to adhere the phthalocyanine pigment to the surface of the resin microparticles. Next, Nara Machinery Hybridization System NH3-1
The pigment was fixed on the surface of the polymer particles by treatment using a mold at 9000 ppm for 3 minutes. The toner of Example 6 (13° 1 μm) was prepared in the same manner as in toner production example a except that 15 parts by weight of the obtained h7',-colorant-containing particles were used as a colorant-forming material and 15 parts by weight was changed to a phthalocyanine additive. A toner f was obtained.

Banjouji! Using the same composition and manufacturing method as in toner production example a, except that the core particles were replaced with polyester resin particles (2),
Toner g having an average particle size of 13.1 μm, which is the toner of Example 7, was obtained.

Toner production example h In toner production example a, the same composition and production method were used except that the particles obtained in production example 2 were used instead of the styrene-acrylic resin fine particles obtained in production example 1. , Toner h having an average particle size of 12.0 μrn, which is the toner of Example 8, was obtained.

Toner production example i In toner production example a, the same composition and production method were used, except that the styrene-acrylic resin fine particles were replaced with the non-produced particles in production example 1, and the non-produced particles in production example 3 were used. , toner j of Comparative Example 1 with an average particle size of 12.1 μm
I got it.

Toner production example j In toner production example a, the same composition and production method were used except that the particles obtained in production example 4 were used instead of the styrene-acrylic resin microparticles for the particles obtained in production example 1. , toner j of Comparative Example 2 with an average particle size of 12.0 μm
I got it.

Polyester I is an example of toner production! <Manufactured by Kao, NE-382)
100 Weight 1L part Phthalocyanine pigment (C1
74160) 2.5 Weight L
After thoroughly mixing the above materials in a ball mill, 130
The mixture was kneaded on three rolls heated to °C. After cooling the kneaded material, it was coarsely pulverized with a feather mill, then pulverized with a fine pulverizer using a jet stream, and further classified by air to obtain an average particle size of 1.
Polyester resin particles of 2 μm were obtained.

The above phthalocyanine-containing polyester resin particles 90
Parts by weight and 1 part by weight of 10 parts by weight of the microparticles obtained in Production Example 1 of the styrene-acrylic resin particles were mixed and stirred for 2 minutes at a rotation speed of 250 Orpm in a 109 Henschel mixer.
Furthermore, Nara Mechanical Hybridization System NH3
A styrene-acrylic resin coating layer was provided by processing in Type-1 at 9.000 rpm for 3 minutes. Furthermore, 0.3 parts by weight of the negative charge control agent E-81 (manufactured by Orient Chemical Industry Co., Ltd.) was added to 100 parts by weight of the polymer particles obtained here in the same manner as above, and E-81 was added to the toner. The average particle size of the toner of Example 9 was 14.
A toner k of 1 μm was obtained.

Kukanifu Seika Jll.

In Toner Production Example K, the same composition and production method were used except that the pigment was replaced with 2.5 parts by weight of Brillian 1 Hecarmine 6B (CI 15850) to produce the toner of Example 10 with an average particle size of 14.2 μm. I got toner k.

Toner Production Example M Toner Production Example K was prepared using the same composition and production method as in Toner Production Example K except that 2.5 parts by weight of benzidine yellow (CI 21090) was used to produce the toner of Example 11 with an average particle diameter of 14. , 3 μm toner m was obtained.

92 parts by weight of terephthalic acid, 8 parts by weight of succinic acid, 18 parts by weight of ethylene glycol, 82 parts by weight of neopentyl glycol, and 0.43 parts by weight of dumbbell acetate were charged into a reaction vessel.
The ester reaction was carried out at 80 to 220°C for 3 hours, and then the pressure in the reaction system was reduced to 6 mmHg, and then further reduced to 0.
．． The reaction was carried out at 240°C for 30 minutes at 5 mmHg or less.

The obtained polyester resin had a number average molecular weight of 2700,
The glass transition point was 5°1°C, the softening point was 85°C, and the acid value was 46.

The above polyester resin 100 parts by weight Phthalocyanine pigment (CI ?4160)
2.5 Heavy ffi parts The above material was subjected to the same treatment as in the toner production example to obtain phthalocyanine-containing polyester resin particles having an average particle size of 11 μm.

The above phthalocyanine-containing polyester resin particles 90
Parts by weight and 10 parts by weight of the fine particles obtained in Production Example 2 of Styrene-Acrylic Resin Particles were subjected to the same treatment as in Toner Production Example to form a styrene-acrylic resin coating layer. Furthermore, 0.00% of the negative charge control agent E-84 (manufactured by Orient Chemical Industry Co., Ltd.) was added to 100 parts by weight of the polymer particles obtained here.
2 parts by weight of E-81 was treated in the same manner as in the toner production example to make E-81 adhere to the toner surface to obtain toner n having an average particle size of 13.2 μm, which is the toner of Example 12.

Toner Production Example 0 The toner of Example 13 with an average particle diameter of 14.2μ was prepared in the same manner as in the Toner Production Example except that polyester resin Vylon 300 (manufactured by Toyobo ■, softening point 123°C) was used.
Toner 0 of m was obtained.

Toner Production Example P In Toner Production Example K, the negative charge control agent was replaced with the positive charge control agent P-51 (manufactured by Orient Chemical Industry Co., Ltd.) 1.0
Using the same composition and manufacturing method except for changing parts by weight,
A toner p of Example 14 having an average particle size of 14.0 μm was obtained.

In Production Example K of Σ22 Ketsu Fudo Naru Yutona, the same composition and production method were used except that the particles obtained in Production Example 3 were used instead of the styrene-acrylic resin microparticles in Production Example 1. Using this method, toner q of Comparative Example 3 having an average particle size of 13.8 mm was obtained.

Toner Production Example R In Toner Production Example K, the same composition and production method were used except that the particles obtained in Production Example 4 were used instead of the styrene-acrylic resin fine particles obtained in Production Example 1. , a toner of Comparative Example 4, 1henerr, having an average particle size of 14.0 μm was obtained.

1 to Toner Production Example S Toner S having an average particle size of 12.0 μrn, which is the toner of Comparative Example 5, was obtained using the same method as in Toner Production Example K except that the styrene-acrylic resin layer was not formed. .

Toner Production Example L Toner of Comparative Example 6 with an average particle size of 14.2μ was prepared in the same manner as in the Toner Production Example except that polyester resin Vylon 103 (manufactured by Toyobo Co., Ltd., softening point 158°C) was used.
Toner S of m was obtained.

30g of the polyester resin and pigment kneaded product obtained in the toner production example was mixed with toluene-methylene chloride (7:
3) was dissolved in the mixed solvent, and the dispersion medium was 1000 cc of distilled water with an appropriate amount of 2% fully saponified polyvinyl alcohol (degree of polymerization approximately 1000) and 1% sodium dodecylbenzenesulfonate. , mix them in a liquid tank, and use a Tokushu Kika Kogyo (Tai-made rTK Auto Homo Mixer) as a mixing and dispersing means.
5 while increasing the rotation speed step by step from 50 orpm.
Mixing and dispersion was carried out at 000 ppm. This dispersion mixture was heated at 80°C for 3 hours while stirring at the final drum rotation speed to evaporate the solvent, filtered with a centrifugal dehydrator, washed 8 times with pure water, dried in vacuum, and dissolved. It was crushed to obtain polyester resin particles with an average particle size of 11 μm.

The above phthalocyanine-containing polyester resin particles 90
Parts by weight and Production Example 1 of the above styrene-acrylic 1N fat particles
10 parts by weight of the microparticles obtained were placed in a 109 Henschel mixer and mixed and stirred at a rotation speed of 250 rpm for 2 minutes.
Furthermore, Nara Mechanical Hybridization System NH3
-1 type at 9.00 rpm for 3 minutes to provide a styrene-acrylic resin coating layer. Furthermore, 0.3 parts by weight of the negative charge control agent E-81 (manufactured by Orient Chemical Industry Co., Ltd.) was added to 1 part by weight of 100 parts of the polymer particles obtained here, and E-81 was added by the same treatment as above. The average particle size of the toner of Example 5 is 12.
．． A toner U of 9 μm was obtained.

Preparation of Carrier In the evaluation of the characteristics described below, the carrier that is mixed with the toner prepared as described above to form the developer is a binder type carrier obtained as follows.

magnetite
500 parts by weight fBL-3P, Titanium Industries Ml
) Sunalene-acrylic copolymerization 111
100 Heavy Ji Department (Prioride ACL,
Gutdeyer Chemical II) Silica #200
2 parts by weight (Nippon Aerosil II) The above ingredients were thoroughly mixed in a super mixer, kneaded in a single-screw extrusion kneader, cooled and coarsely pulverized, pulverized in a hammer mill to an average particle size of 50 μm, and divided into coarse powder and The fine powder was classified to obtain carriers with an average size of 40 μm. When you measure the specific gravity, it is 3.
．． It was 3g/cm3.

Example 1-15 and Comparative Example 1 thus obtained
The properties of toners a to U of Nos. 6 to 6 were evaluated as described below. In addition, each of toners a to t is 100
After-treatment was performed with 20.1 parts by weight of colloidal silica R-972 (manufactured by Nippon Aerosil ■) based on parts by weight, and used for evaluation of properties.

Charge amount (Q/M> and scattering amount) Here, 2 g of surface-treated toner and 28 g of the carrier shown above were placed in a 50 cc plastic bottle and placed on a rotating stand for 12 hours.
In order to investigate the rise in the charge amount of the toner when rotated at 0 Orpm, the charge amount after stirring for 3 minutes, 10 minutes, and 30 minutes was measured, and the amount of scattering at that time was also investigated. Similarly, the toner and carrier were placed in a polyethylene bottle and stored at 35° C. and 85% relative humidity for 24 hours, after which the amount of charge and the amount of scattering were measured, and the moisture resistance was also investigated.

The amount of scattering was measured using a digital dust meter P51 (model 2 (manufactured by Somede Kagaku Co., Ltd.). The dust meter and the magnet roll were installed at a distance of 10 marks, and 2 g of developer was placed on the magnet roll. After setting, attach the magnet to 2000
The toner particles generated when the RAM is rotated are read as dust by the powder deafness meter, and the number of counts per minute is c.
Displayed in pm.

Table 1 shows the measurement results of the amount of charge and the amount of scattering.

The specified toner shown in Image Output Evaluation Table 2 and the above carrier were used
A two-component developer was prepared by mixing the carrier at a ratio of 7/93. Using this developer, Examples 1 to 3.5 to 13
and 15, EP-5702 (for Comparative Examples 1 to 6)
For Examples 4 and 14 (manufactured by Minolta Camera Co., Ltd.), the fixing device of EP-47oz (manufactured by Minolta Camera Co., Ltd.) was modified to have an oil coating method, and the initial image output evaluation (and A printing durability test) was conducted, and various image evaluations shown in Table 2 were performed.

1) Image blur As described above, images were printed using the above-mentioned copying machine using various toner and carrier combinations. Regarding fog on images, toner fog on white background images was evaluated and ranked. A rank of Δ or higher is practically usable, but a rank of 0 or higher is desirable.

2) Printing durability test 100,000 sheets using the above EP-5702 for Examples 1 to 3.5 to 13 and 15 and Comparative Examples 1 to 6, and EP-4702 for Examples 4 and 14. A printing durability test was conducted. At this time, the toner charge amount and fog were evaluated.

3) Fixing property test The image was developed three times on paper and an OHP sheet using the copying machine described above, and the fixing property was evaluated at an adhesion amount of 4 mg/cm 2 . The fixing strength is ◎ if the image does not become distorted even after 20 times or more of rubbing using a sand eraser, Q if 15 to 20 times.
5 to 15 times was defined as Δ, and less than that was defined as X. The results are shown in Table 3.

4) Transparency and Translucency Transparency and translucency were respectively measured on the fixed images on paper and OI-IP sheet obtained in the above fixability test. Transparency was evaluated by visual observation of the cloudiness of the image, and translucency was evaluated by visual observation of the vividness of colors in the projected image when projected with an OHP projector. The results are shown in Table 3.

Table 3 Evaluation Results Examples 1 to 15 Rise in charge amount, toner scattering amount, environmental stability (moisture resistance) for the above toners a to h, ni to p, and +1 toners.
, a printing durability test, and a fixation test were conducted, and Table 1 shows that
As shown in Tables 2 and 3, good results were obtained for all of the compounds 1 to 3.

Comparative Example 1 When the above-described toner i was subjected to the same fixing test I as in the example, only poor results were obtained in terms of transparency and translucency. (See Table 3) Comparative Example 2 When the toner j was subjected to the same printing durability test as in the example, it was found that as the printing durability shown in Table 2 was carried out, the amount of charge decreased and toner scattering was also reduced. It increased dramatically.

Comparative Example 3 When the above-mentioned toner q was subjected to the same fixing test as in the example, only poor light transmittance results were obtained. (See Table 3) Comparative Example 4 When the above toner r was subjected to the same printing durability test as in the example, as shown in Table 2,
The amount of charge decreased, the amount of toner scattering increased dramatically, and blocking occurred in the developer after 20,000 sheets, forcing us to cancel the printing durability test.

Comparative Example 5 When the above-mentioned Toner S was subjected to the same moisture resistance test as in the Example, as shown in Table 1, the amount of charge was significantly reduced and the amount of toner scattering was also significantly increased.

Comparative Example 6 When the above-mentioned toner t was subjected to the same fixing test as in the example, only poor light transmittance was obtained. (See Table 3) (Effects of the Invention) As described above, the toner for developing electrostatic latent images of the present invention has the following properties:
A toner for developing an electrostatic latent image, comprising a core particle made of at least a colorant and a polyester resin, and an outer shell layer made of at least a charge control agent and a vinyl resin and coated on the outer surface of the core particle. The polyester resin is a linear polyester resin with a softening point of 80 to 150°C, and the vinyl resin has a softening point of 80°C.
Since it is characterized by a glass transition temperature of 0°C to 150°C and a glass transition point of 55°C to 70°C, it exhibits excellent translucency for OHP and full color applications, and can obtain clear colored images. can. In addition, despite having such excellent translucency, it also has excellent heat resistance, environmental resistance, and shape stability, and has a stable and uniform charge amount, and the charge builds up quickly. In addition, even when used continuously for a long period of time, it exhibits stable developability without causing problems such as toner aggregation, fogging on images, or toner scattering.

Claims (4)

[Claims] (1) For electrostatic latent image development, consisting of a core particle made of at least a colorant and a polyester resin, and an outer shell layer made of at least a charge control agent and a vinyl resin and coated on the outer surface of the core particle. In the toner, the polyester resin is a linear polyester resin with a softening point of 80 to 150°C, and the vinyl resin has a softening point of 80 to 150°C and a glass transition point of 55 to 70°C. A toner for developing electrostatic latent images. (2) The toner for developing electrostatic latent images according to claim 1, wherein the charge control agent is fused and fixed on the outer shell layer. (3) The toner for developing electrostatic latent images according to claim 1, wherein the vinyl resin is fine particles with a coefficient of variation of less than 20%. (4) A step of electrostatically adhering vinyl resin fine particles to the surface of a core particle consisting of at least a colorant and a polyester resin, and an outer shell layer formed by melting the surface of the adhered fine particles by mechanical shearing force. A method for producing a toner for developing an electrostatic latent image, comprising a step of forming a charge control agent and a step of melting and fixing a charge control agent on the outer shell layer.