JPH03276163A - Cyan developer - Google Patents

Abstract

PURPOSE:To reproduce the low saturation black of a full-color image and to improve the transparency and fastness of cyan by blending two kinds of specified binding resins in a prescribed ratio and using two kinds of specified colorants. CONSTITUTION:This developer contains a toner contg. polyester resin (A) and styrene-acrylic resin (B) obtd. by copolymerizing a copolymerizable monomer contg. an amino group such as diethylaminoethyl methacrylate as binding resins in (55:45)-(95:5) weight ratio of A:B and further contg. C.I. Pigment Blue 15:3 (C) and C.I. Pigment Green 7 (D) as colorants. The ring and ball softening point of both the resins A, B has been regulated to <=120 deg.C. The pref. amt. of the colorant C used is 4.0-0.5 pt. wt. per 100 pts. wt. of the resins A, B, that of the colorant D is 4.0-0.5 pt. wt. and the pref. total amt. of the colorants C, D is 5.0-2.0 pts. wt.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a developer for developing electrostatic images, and more specifically, for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc. The present invention relates to a color developer, particularly a positively chargeable cyan developer.

[Prior art and problems to be solved by the invention] Conventional electrophotographic methods include U.S. Pat.
As described in specifications such as No. 97691 and No. 2357809, a photoconductive insulating layer is uniformly charged (charging step), and then the layer is exposed to light (exposure step), so that the charge of the exposed portion is increased. An electrostatic latent image is formed by dissipating the electrostatic latent image, and the electrostatic latent image is made visible by attaching a colored, charged fine powder called toner (development process). It consists of a step of transferring the image onto a transfer material such as transfer paper (transfer step) and then permanently fixing it by heating, pressure, or other appropriate means (fixing step).

The developing methods applied to these electrophotographic methods are broadly divided into dry developing methods and wet developing methods. The former method further includes a method using a one-component developer and a method using a two-component developer, and the present invention relates to a two-component dry developer.

Two-component dry developers include a magnetic brush development method using a magnetic powder carrier, a cascade development method using a somewhat coarse bead carrier, etc., depending on the type of system for conveying the toner. Color developers are also basically produced using the electrophotographic method described above: [Charging] → [Exposure] → [Development] → [
A color image is formed by repeating the transfer process several times and fixing the image. However, in the exposure process, exposure is performed by exposing with a color separation filter or by writing an image read by a scanner with a laser or the like.

As toners applied to these developing methods, fine powders in which colorants such as dyes and pigments are dispersed in natural or synthetic thermoplastic resins have been used. Examples of synthetic resin systems include mixing and dispersing various additives such as colorants, charge control agents, and waxes in binder resins such as styrene-acrylic copolymer (polystyrene) resins, polyester resins, and epoxy resins. Particles obtained by pulverizing the particles to a particle size of about 1 to 30 ρ are used as toner. In the case of a system using a two-component dry developer, the toner is usually mixed with carrier particles such as glass beads or iron powder, and at that time, the toner is held on the carrier by electrostatic attraction generated by friction, resulting in an electrostatic latent image. transported to the surface. The charging property of the toner is determined by the charging polarity of the electrostatic latent image, and a clear positive or negative polarity and an appropriate amount of charge are required. In order to store a desired charge in the toner, it is possible to utilize the triboelectric properties of the carrier and its surface material and the resin that is a component of the toner.
Alternatively, it is unsatisfactory because it is difficult to quickly reach the desired amount of charge.

In such a case, the image obtained by development is likely to have background fog and become unclear. Therefore, in order to quickly impart the desired amount of charge to the toner,
Addition of a substance called a charge control agent to control chargeability has been carried out. For positive charging, compounds having an electron-donating group such as nigrosine dyes are effective, and for negative charging, electron-accepting organic complexes such as oil-soluble metal-containing dyes are widely used. Since nigrosine dyes generally have poor compatibility with resins, they are often used as modified products with oleic acid, stearic acid, etc.

In addition, as charge control agents for positive charging, fatty acid amines, quaternary ammonium salts, Fenschwarz) IBW
, Sudan Cheeksharz BBC.

Brilliant Spirit, etc., but many of these charge control agents are derived from dyes and pigments, have complicated structures, and many have strong coloring properties. In the case of chromatic toners, colored compounds cannot be used, so colorless or light-colored charge control agents are being considered;
There is nothing that surpasses the performance of pigments, and although it is unsatisfactory, dyes and pigments are currently being used.

These charge control agents are usually mixed with a thermoplastic resin, dispersed by hot melt kneading, finely pulverized, and adjusted to a suitable particle size as necessary before use. Although these dyes and pigments used as charge control agents have no choice but to be used for charge control, many problems arise because of this.

Firstly, its molecular structure is complex and its properties are not constant, making it susceptible to deterioration due to hot melt kneading and changes in performance due to temperature and humidity conditions.As the number of copies increases, the quality and characteristics of electrophotographic images deteriorate. This tends to cause a decrease in The second problem is that it is extremely difficult to uniformly disperse these charge control agents in a thermoplastic resin, which causes a difference in the amount of frictional charge between the toner particles obtained by pulverization, resulting in a decrease in image quality. It is to invite.

Thirdly, many of the charge control agents are hydrophilic, and due to poor dispersion in these resins, they are easily exposed on the surface of the toner particles. Therefore, under high temperature conditions, the charge control agent absorbs moisture and reduces the amount of charge on the toner. The image quality deteriorates, making it impossible to obtain high-quality images. Fourth
However, there is a problem in that most of the dyes and pigments that are generally known as charge control agents are chromatic or dark colored, and cannot be incorporated into toners that have a vivid, desired color. . Fifth, when toner mixed with a charge control agent is used for a long period of time, the charge control agent may adhere to the surface of the photoreceptor or may promote adhesion of the toner to the photoreceptor, which is bad for electrostatic latent image formation. There are many things that have negative effects on the cleaning process of copying machines, such as damaging the photoconductor surface or cleaning blade due to filming, or accelerating wear of these parts. .

As described above, when a charge control agent is used in a toner, the amount of charge generated on the surface of the toner particles varies during the process of generating frictional charging between toner particles or between a toner and a carrier. As a result, development fog,
Problems such as toner scattering and carrier contamination are likely to occur. In addition, this problem becomes more noticeable when a large number of copies are made, making the product practically unsuitable for use.

Furthermore, under high humidity conditions, not only the quality of the toner image deteriorates, but also the transfer efficiency to the transfer paper decreases significantly, making the toner image unusable. Further, since charge control agents cause a number of undesirable problems in both black toner and color toner, efforts have been made to avoid these problems. For example, Japanese Patent Application Laid-Open No. 60-112051 discloses that a specific polyester resin and a copolymerizable monomer having a tertiary amino group are combined with a hydrophobic copolymer to avoid the offset phenomenon in the heat roller constant fixing method. By using a copolymer resin of monomers as a binder resin and combining it with a carrier coated with a vinyl chloride-vinyl acetate copolymer resin, it can be charged uniformly and sufficiently positively without using conventional charge control agents. A developer toner is disclosed. This toner has a composition ratio of a polyester resin, a copolymerizable monomer having a tertiary amino group, and a hydrophobic copolymerizable monomer of 10 to 50% by weight and 50 to 90% by weight,
Further, the ring and ball softening point of each resin is limited to a range of 100 to 180°C. However, the softening point is 12
If the temperature is higher than 0°C, when used as a full-color developer, the transparency will be impaired and clear images will not be obtained. That is, the purpose of the invention in the above-mentioned publication is, as stated, related to an offset avoidance means, and cannot solve the above-mentioned problems related to color toners.

Characteristics required as a color developer include color performance and transparency. Regarding color performance, each of the three primary color toners must have good spectral reflection characteristics in order to faithfully reproduce the colors of the original. On the other hand, transparency requires that light passes through a plurality of toner layers in which a plurality of toners of different colors are superimposed, and that a composite color reproducibility can be obtained. In addition to simply color reproduction, it is also necessary to have excellent transparency of the OHP projected image of the toner image transferred and fixed to the transveneer lens for the OHP projector (OHP), in other words, it is necessary to have good spectral transmittance. It is. Although known organic pigments and dyes are used as colorants for color toners, each of them has many drawbacks. Organic pigments generally have higher fastness to heat and light than dyes, but even those with relatively good spectral reflection properties have strong hiding power because they exist in a dispersed state as pigment particles in the toner layer, and dispersed particles Due to light scattering, the hue of images in reflection and transmission changes, and the spectral transmittance is low, making the projected image of the leaf P dark and low in saturation.

On the other hand, dyes are dissolved in the toner layer or exist in a more finely dispersed state than pigments, so the vividness of colors and
Although it has excellent transparency and coloring power, it has the disadvantage that it tends to fade due to heat and light.

The charging property of toner is determined by the charging polarity of the electrostatic latent image, and a clear positive or negative polarity and an appropriate amount of charge are required. However, the colorant, which is an essential component of color developers, has a normal charge. Dyes that are not used as control agents also have some functional groups, that is, electron-donating groups and electron-accepting groups, which can be a hindrance in designing the charge amount of toner, or when used repeatedly. This is an obstacle to obtaining a stable charge amount transition.

The colorant used in cyan toner is
-47176 Publication, Special Publication No. 63-56536,
Dyes and pigments such as those described in JP-A No. 63-74074 have been proposed, but none of these dyes and pigments has been able to satisfy all of the above characteristics. There is a strong need in the art for improved cyan toners.

The object of the present invention is to provide a color developer which overcomes the above-mentioned problems, and more particularly to provide a cyan developer which provides an improved full-color image that reproduces extremely desaturated blacks through image superimposition. There is a particular thing.

Another object of the present invention is to provide a cyan developer that reproduces colors faithful to originals and has excellent transparency. Still another object of the present invention is to provide a cyan developer that has high fastness to heat and light and is capable of providing full-color images with high saturation. Still another object of the present invention is to provide a developer that enables faithful development and transfer of electrostatic latent images, that is, no background fogging during development, no toner scattering around edges, and high image density. The developer has excellent midtone reproducibility.

Still another object of the present invention is to provide a developer which maintains its initial characteristics even when the developer is used for a long period of time, has no toner aggregation, and has excellent storage stability.

[Means to solve the problem]

The present inventors have made extensive studies in view of the current state of the prior art as described above, and as a result have found a cyan developer that overcomes the above-described drawbacks and have arrived at the present invention.

That is, the present invention provides a dry developer formed by mixing a carrier and a toner, in which the binder resin, which is the main component of the toner, is
It consists of a polyester resin (A) and a styrene-acrylic resin (B) obtained by copolymerizing a copolymerizable monomer containing an amino group, and the weight ratio of resin (A) and resin (8) is A):(B) is in the range of 55:45 to 95:5, and the softening point (ring and ball method) of the resins (A) and (B) is 1
20°C or less, and the colorant mixed with the binder resin is C
,r, Pigment Blue15:3 and C,1,P
igment Green 7.

The binder resin which is the main component of the cyan developer of the present invention is a styrene-acrylic resin (A) made by copolymerizing a polyester resin (A) and a copolymerizable monomer containing an amino group.
B), and the weight ratio of resin (A) and resin (B) (
8) : (B) is in the range of 55:45 to 95:5, and the softening point of the resins (A) and (B) (ring and ball method JIS
K-2207) is 120°C or less. For cyan developers, transparency is required as a resin property, and it is important that the resin has sharp melt properties. Binder resins that meet these requirements have a glass transition temperature (Tg) from the viewpoint of storage stability.
is 55° C. or higher, and the binder resin used in the cyan developer preferably has a high affinity with organic pigments and dyes and has a chemical structure that is dispersible or soluble.

Blending weight ratio of resin (A) and resin (B) (A): (B
) is 55:45 to 95:5, more preferably 65
: In the range of 35 to 90:10. If the ratio of the resin (B) is less than 5, the amount of charge on the toner will be insufficient or the toner will be negatively charged. Furthermore, if the ratio of resin (B) is more than 45, the polyester resin loses its ability to disperse or dissolve dyes and pigments, and when used in cyan toner, the color saturation is low.
This is undesirable because it becomes dull and furthermore, the OHP projected image becomes dark.

In addition, the softening point (SP) of each resin (8) and (B) is 120
Must be below °C. If SP exceeds this range, the molecular weight of the binder resin becomes too large and the sharp dissolution property is impaired due to the entanglement of polymer chains, resulting in a lack of transparency and a dull-toned image with low chroma, which is undesirable.

On the other hand, regarding colorants, C, 1, Pigment B
lue15: 3 and C, 1, Pigment Green
By using 7 in combination, color fading due to heat and light can be reduced and the hue can be corrected, making it possible to obtain an excellent cyan developer.

In addition, by mixing dyes and pigments, or pigments and pigments of the same hue with the binder resin, clear and high-density images can be obtained, and images fixed on OHP transparent ranges have high spectral transmission characteristics. It can be made to have good projection properties.

Furthermore, according to the present invention, it is possible to obtain a cyan developer that is less affected by temperature and humidity environments and always has stable charging properties. In addition, it is possible to use no dye, or to use it in an extremely small amount, and as a result, it is possible to significantly improve dye fleets, filming on photoresists, and spending on carriers. It is possible to obtain a highly durable cyan developer that maintains its initial performance even when the developer is used for a long period of time.

A more preferred embodiment of the present invention is obtained by specifying the blending ratio of the colorant.

That is, C.1, Pigment Blue 15:3 and C.1. I. In a system used in combination with PigmentGreen 7, the total amount of colorant per 100 parts by weight of binder resin is 5.
．． 0 to 2.0 parts by weight, and C,1,Pigme
nt Blue 15:3 in an amount of 4.0 to 0.5 parts by weight, more preferably 3.0 to 1.0 parts by weight, C,I.

Pigment Green 7 in an amount of 4.0 to 0.5 parts by weight, more preferably 3.0 to 1.0 parts by weight.

When the ratio of C, I, Pigment Blue L5:3 is more than 4.0 parts by weight, the reddish blue becomes stronger;
If it is less than 0.5 parts by weight, it becomes difficult to obtain the desired image density.

Further, when the proportion of C,1,Pigment Green 7 is more than 4.0 parts by weight, the greenish taste becomes strong, while on the other hand, when the proportion of C,1,Pigment Green 7 is more than 4.0 parts by weight, the greenish color becomes strong.
If it is less than 5 parts by weight, it tends to be difficult to obtain the desired image density.

The polyester resin (A) used as the binder resin of the present invention is synthesized by a condensation reaction between a polyhydric carboxylic acid and a polyhydric alcohol. Examples of polyhydric carboxylic acids include carboxylic acids such as fumaric acid, maleic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, succinic acid, and adipic acid, their anhydrides, or lower alkyl esters thereof. can. Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, neopentyl glycol, and polyoxyethylene (2,2)-2,2'-bis(4-hydroxyphenyl)propane. , polyoxypropylene (2,2
)=2,2"-bis(4-hydroxyphenyl)propane, hydrogenated bisphenol A, glycerin, etc. can be used. Monocarboxylic acids and monoalcohols can also be added if necessary.

Furthermore, a styrene-acrylic copolymerizable monomer is used as a raw material for the styrene-acrylic resin (B) obtained by copolymerizing the amino group-containing copolymerizable monomer used as the binder resin of the present invention. As a body, styrene, 0-methylstyrene,
Styrenic monomers such as m-methylstyrene, p-methylstyrene, α-methylstyrene, methyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, n-butyl methacrylate, methacrylic acid 1so-butyl, 2-ethylhexyl methacrylate,
Examples include esters of acrylic acid and methacrylic acid such as lauryl methacrylate, and in addition to the necessary G, other copolymerizable monomers can also be used in combination.

Copolymerizable monomers containing amino groups include dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropylacrylamide, dimethylaminopropylmethacrylamide, p-dimethylaminostyrene. , N-vinylpyridine, N
- Monomers such as vinylpyrrolidone can be used.

As the carrier used in the present invention, well-known carriers can be used, and specifically, iron, ferrite, steel, magnetite,
Examples include magnetic materials such as nickel, and carrier materials whose surfaces are coated with various resins. Furthermore, particularly suitable carrier coating agents for use in the cyan developer of the present invention include fluororesins and silicone resins.

The fluororesin is preferably a fluororesin in which the proportion of fluorine atoms among the monovalent atoms bonded to the carbon main chain and side chains is 80 mol % or more. Such fluororesins include poly(tetrafluoroethylene-vinylidene fluoride), poly(tetrafluoroethylene-fluoropropyl vinyl ether), copolymers of 2-perfluorooctylethyl methacrylate and n-butyl methacrylate, and poly(tetrafluoroethylene-vinylidene fluoride), Examples include fluoroethylene-hexafluoropropylene) alone and in mixtures.

Further, as the silicone resin, a silicone resin that cures at room temperature is preferable, and a silicone resin that cures at room temperature after being coated on a carrier is particularly preferable.

The room temperature curable silicone resin is a silicone resin having the chemical structure shown in the following formula, such as KR-114.
, KR-220, KR-251, KR-255 (all manufactured by Shin-Etsu Chemical Co., Ltd.).

R+ R+ R→0-5i→
- or →o-8i÷-±0-S i÷R2R30 →0-5i÷R1 (However, in the formula, R3 to R4 are a hydrogen atom, a hydroxyl group, a lower alkoxyl group having 1 to 4 carbon atoms, a methyl group, or (It is a phenyl group.) [Examples] The present invention will be explained below using specific examples. However, the present invention is not limited to the following examples. Further, the numbers in the composition ratios shown below are expressed in parts by weight unless otherwise specified.

Examples of manufacturing a carrier particularly suitable for the present invention and synthesis examples of a binder resin used in the present invention are also shown below.

<Carrier manufacturing example> Manufacturing example 1 1000 parts of iron powder manufactured by Nippon Tetsuko Co., Ltd. (TS Sea 300) was fluidized in a fluidized bed, heated to 80°C, and mixed with 5% water.
After spraying 10 parts (in terms of resin content) of a fluororesin (Daicel Chemical Industries, Ltd., Daiflon ND-4) diluted to
A coated carrier (1) was obtained by heat treatment with Cl2O for a minute.

Production example 2 Ferrite particles (F-100) manufactured by Nippon Iron Powder Co., Ltd. 100
0 part was heated and maintained at 60°C while fluidized in a fluidized bed, and 10 parts (resin content equivalent) of silicone resin (manufactured by Shin-Etsu Silicone Co., Ltd., KR-251) dissolved at 5% in toluene was sprayed, and then After drying for 20 minutes, heat treatment was performed at 200°C for 130 minutes in an electric furnace to form a coated carrier (2).
I got it.

<Synthesis Example of Binder Resin> Synthesis Example I 149.1 parts of propylene glycol, 52.1 parts of ethylene glycol, and 410.2 parts of dimethyl terephthalate were subjected to a condensation reaction, and further 55.3 parts of trimellitic acid anhydride was added and reacted. A polyester resin (1) having a softening point (SP) of 104.5°C and a glass transition point (Tg) of 62.4°C was obtained.

Synthesis example ■ Polyoxypropylene (2,2) -2,2'-bis(
350.0 parts of 4-hydroxyphenyl)propane, 116.0 parts of maleic acid, and 0.2 parts of hydroquinone monomethyl ether were subjected to a condensation reaction, and sp was 98.6°C1Tg.
A polyester resin (2) having a temperature of 60.5°C was obtained.

Synthesis example ■ 5.0 parts of dodecyl mercaptan, 120.0 parts of styrene, 70 parts of n-butyl methacrylate in 60.0 parts of toluene.
．． 0 parts, diethylaminoethyl methacrylate 10.0
After adding 4.0 parts of α,α azobisisobutyronitrile as a polymerization initiator and carrying out polymerization and aging reaction, toluene was removed by topping to obtain a styrene-acrylic resin (1).

The resin had an sp of 104.5°C and a Tg of 62.3°C.

Synthesis example ■ 3.0 parts of dodecyl mercaptan in 60.0 parts of xylene
parts, styrene 170.0 parts, 2-ethylhexyl acrylate 20.0 parts, dimethylaminoethyl acrylate) 1
0.0 parts of α, α゛-azobisdimethyl cracked nitrile was added as a polymerization initiator to polymerize, and after an aging reaction, the xylene was removed to form a styrene-acrylic resin (2). I got it.

The resin had an sp of 106.2°C and a Tg of 68.8"C.

Example-1 Polyester resin (2) 80 parts, 0 parts, styrene-acrylic resin (2) 20 parts, 0 parts, Chromofine
Blue 4920 (Dainichiseika Chemical Co., Ltd. C, 1, Pig+
nent Blue 15:3) 2.5 copies, Fast
gen Green S (Dainippon Ink Co., Ltd. C.I.P.
igmentGreen 7) After mixing 1.0 part, melt-knead with a twin-screw extruder kneader, and mix with a cutter mill to 2 mm.
Coarsely grind to the following size and then use an air jet mill for 5~20ρ
It was crushed and classified into an average of 10 pieces. A cyan toner was prepared by mixing 0.2 parts of hydrophobic silica R974 (manufactured by Nippon Aerosil Co., Ltd.) with 100 parts of the fine particles using a high-speed mixer. 50 parts of this cyan toner and 950 parts of coat carrier (1) ■
A developer was obtained by mixing with a mold blender.

When the developability of this developer was evaluated using a commercially available general-purpose copying machine, the initial charge amount by blow-off method was 16.
5 pc/g, clear, fog-free, and high image density (Macbeth densitometer RI -9144 ID=1.62) was obtained. Further, even after 10,000 sheets were continuously copied, an image of good quality comparable to the initial image without fog, with a charge amount of 17.6 μc/g and an ID of 1.54, was obtained. Also, 0) IP receipt copying, upper and lower silicone roll fixing machine (temperature 160°C, circumferential speed 50 n+m/5e)
The image fixed in c) had good transparency, and the image projected by OHP had a good cyan color and good transparency. In addition, the solid part of the copy image was divided into two parts, one part was stored in a cool and dark place, and the other part was stored in a Sun 5hine
Ultraviolet rays from a carbon arc were irradiated in a WeatherMeter at 45°C. After irradiating with ultraviolet rays for 5 hours, use a colorimeter (NO-1001) manufactured by Nihon Heavy Industries Co., Ltd.
The color difference (ΔE) was determined based on the leaf shape). The result is ΔE=4.
6, and there was little fading.

Example-2 70.0 parts of polyester resin (1), 30.0 parts of styrene-acrylic resin (1), Lionol Blue F
G-7330 (C, 1, Pig+I manufactured by Toyo Ink Manufacturing Co., Ltd.
Ient Blue '15: 3N, 5th part, Cyani
ne Green 5310 (C.I.P manufactured by Dainichiseika Chemical Co., Ltd.
Example-1 using 5 parts of igmentGreen 7N
A cyan toner was produced using the same process. 30 parts of this cyan toner and 970 parts of coat carrier (2) were mixed in a ■ type blender to obtain a developer. This developer was used as an example.
When evaluated in the same manner as 1, the initial charge amount was 17.4p.
c/g, clear and fog-free images with I[l of 1.46 were obtained, and after 10,000 copies were continuously copied, the amount of charge was 16.
A fog-free image of 6 pc/g, 10:1.50, and comparable to the initial image was obtained, and when the fixed image was projected onto an OHP sheet, it exhibited a good cyan color and had good transparency. Further, the color difference after irradiation with ultraviolet rays for 5 hours was 8E=3.7, and no fading was observed.

The amount of charge after the developer was left in an environment of 35'C/80% RH for 24 hours was 12.6 μc/g, and a clear image without fogging was obtained.

Example-3 75.0 parts of polyester resin (1), 25.0 parts of styrene-acrylic resin (2), Fastgen Blue
GBK (Dainippon Ink Co., Ltd. C, 1, pigmen L
Blue 15:3) 1.0 copy, Fastgen G
A cyan toner was produced using 2.0 parts of reen S in the same process as in Example-1. 50 parts of this cyan toner and 950 parts of coat carrier (1) were mixed in a ■ type blender to obtain a developer. When this developer was evaluated in the same manner as in Example-1, an image with an initial charge amount of 16.6 μc/g, clear and fog-free, and an ID of 1.54 was obtained.
After continuous copying of 0,000 sheets, the amount of charge was 16.2pc/g,
A fog-free image with an ID of 1.60 was obtained that was comparable to the initial image, and when the fixed image was projected onto an OHP sheet, it exhibited a good cyan color and had good transparency. Further, the color difference after irradiation with ultraviolet light for 5 hours was 8E=2.9, and no fading was observed.

Example-4 Polyester resin (2) 65,0 parts, styrene-acrylic resin (1) 35.0 parts, Lionol Blue
FG-73302, 5 copies, Lionol Green
Y-101 (C, 1, Pigmen manufactured by Toyo Ink Manufacturing Co., Ltd.
A cyan toner was produced in the same manner as in Example-1 using 1.5 parts of Green 7). This cyan toner 5
Part 0 and uncoated carrier (TEFV-2 manufactured by Nippon Tetsuko Co., Ltd.)
00/300) and 950 parts of the developer were mixed using a type B L/7 goo to obtain a developer. When this developer was evaluated in the same manner as in Example-1, an image with an initial charge amount of 13.6 pc/g, a clear and fog-free image, and an ID of 1.62 was obtained.
After continuous copying of 0 sheets, the amount of charge is 14.1pc/g, 10
A fog-free image of 1.67 was obtained, comparable to the initial image, and when the fixed image was projected onto the leaf P sheet, it exhibited a good cyan color and had good transparency. Further, the color difference after irradiation with ultraviolet rays for 5 hours was ΔE=5.2, and no fading was observed.

Comparative Example-1 Chromofine Blue 492 as colorant
A cyan toner was produced in the same manner as in Example-1 except that 03.0 parts of the cyan toner was used. 50 parts of this cyan toner and 950 parts of coat carrier (1) were mixed in a ■ type blender to obtain a developer. When this developer was evaluated in the same manner as in Example-1, the initial charge amount was 16.5 ttc/g.
, clear, fog-free, and high image density (ID=1.62
) images were obtained. Furthermore, even after 10,000 sheets were continuously copied, the charge amount was 17.6 pc/g and 10 was 1.54, which was a good quality image that was comparable to the initial image, but the hue was quite reddish. It took on a blue color.

Comparative Example 2 A cyan toner was produced in the same manner as in Example 2 except that 40.0 parts of polyester resin (1) and 1160.0 parts of styrene-acrylic resin were used.
and 970 parts of coat carrier (2) were mixed in a ■ type blender to obtain a developer. When this developer was evaluated in the same manner as in Example-1, the initial charge amount was 22.8 pc/g.
, clear and fog-free images with an ID of 1.44 were obtained, and the charge amount was 23.1pc/ even after 10,000 continuous copies.
An image with g, 10 of 1.37 was obtained, and a clear image without fog was obtained. However, when the 0) IP receipt fixed image was projected, it exhibited a grayish cyan color and had poor transparency. Also, the color difference after 5 hours of UV irradiation is ΔE
= 3.9, and no fading was observed.

Comparative Example-3 75.0 parts of polyester resin (+), 25.0 parts of styrene-acrylic resin (2), Fastgen Blue
A cyan toner was produced using 6.0 parts of GBK in the same process as in Example-1. 30 parts of this cyan toner and 970 parts of coat carrier (2) were mixed in a ■ type blender to obtain a developer. When this developer was evaluated in the same manner as in Example-1, an image with an initial charge amount of 12.8 pc/g, a clear and fog-free image, and an ID of 1.64 was obtained.
Even after continuous copying, a clear image without fog was obtained with a charge amount of 13.1 pc/g and an ID of 1.57.

However, the developer was stored at 35°C/80%RH for 2 hours.
After being left for 4 hours, the amount of charge decreased to 8.6 pc/g, fogging occurred on the entire surface, and the image quality was extremely low. The color difference after irradiation with ultraviolet light for 5 hours was ΔE=4.3, and no fading was observed.

Comparative Example-4 Polyester resin (2) 100.0 parts, Bontron P
52 (manufactured by Orient Chemical Co., Ltd., charge control agent) 3.0 parts, F
astgen Blue GBK 2.5 parts, Cyan
A cyan toner was produced in the same manner as in Example 1, except that 1.5 parts of Ine Green was used. 30 parts of this cyan toner and 970 parts of coat carrier (2) were mixed in a ■ type blender to obtain a developer. Ta. When this developer was evaluated in the same manner as in Example 1, the initial charge amount was 13.
．． 8 μc/g, clear and fog-free images with an ID of 1.62 were obtained, but after continuous copying of 10,000 sheets, images with a charge amount of 1091 μc/g and 10 of 1.57 with a lot of fog were obtained. . Also, the developer before continuous copying is
The amount of charge after being left in a C/80%RH environment for 24 hours is 8
．． It was 6 μC/g, there were capris all over the surface, and the image quality was extremely low.

〔Effect of the invention〕

As described above, by using the positively chargeable dry cyan developer of the present invention, it was possible to obtain a full-color image with unprecedented clarity. Furthermore, the image developed into an OHP (transparent range) had good transparency, and the light transmission image showed vivid color development.

Claims (1)

[Claims] 1. In a dry developer formed by mixing a carrier and a toner, the binder resin, which is the main component of the toner, is composed of a polyester resin (A) and a copolymerizable monomer containing an amino group. styrene-acrylic resin (B) formed by copolymerizing polymers, and the weight ratio of resin (A) and resin (B) (A): (B
) is in the range of 55:45 to 95:5, the softening points (ring and ball method) of the resins (A) and (B) are 120°C or less, and the colorant mixed with the binder resin is in the range of C.I. I. PigmentB
lue15:3 and C. I. PigmentGreen7
A cyan developer characterized by comprising: 2. The blending ratio of the colorant to 100 parts by weight of the binder resin is C. I. PigmentBlue15:3 is 4.0~
0.5 parts by weight and C. I. 2. The cyan developer according to claim 1, wherein Pigment Green 7 is in the range of 4.0 to 0.5 parts by weight, and the total amount of both colorants is 5.0 to 2.0 parts by weight. 3. The carrier according to claim 1 or 2, wherein the carrier is coated with a fluororesin in which the proportion of fluorine atoms among the monovalent atoms bonded to the carbon chain is 80 mol% or more. Cyan developer. 4. The carrier is coated with room temperature curing silicone resin,
The cyan developer according to claim 1 or 2, wherein the cyan developer is heat-treated at at least 180°C.