JPH0815909A - Toner and its production - Google Patents

Abstract

PURPOSE:To obtain a full-color toner having satisfactory fixability, color mixing property and triboelectric chargeability, maintaining anti-offsetting property even in the case of repetitive fixation on paper and ensuring high image density by kneading a 1st bonding resin with paste contg. an insoluble colorant, removing the volatile component and kneading the resultant kneaded material with a 2nd bonding component. CONSTITUTION:A 1st bonding resin having 7-30% cloud value of a dispersion of the resin is kneaded with paste contg. 5-25wt.% insoluble colorant and the volatile component is removed. A 2nd binder is added to the resultant kneaded material and they are kneaded to obtain the objective toner for full-color copying. The heating temp. in the 1st kneading process is preferably set within the range of 80-160 deg.C so as to improve anti-offsetting property and to attain high image quality. A heating kneader, a Henschel mixer, a uniaxial extruder, a biaxial extruder or a kneader extruder is used as a kneading device.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color toner,
In particular, the present invention relates to a toner having a wide color reproducibility of a color image, a high image density, and difficult to fuse, and a method for producing the toner.

[0002]

2. Description of the Related Art In recent years, full-color copying machines have been rapidly developed, and digitalized full-color copying machines have begun to be put on the market. Color image formation by full-color electrophotography generally involves color reproduction using three primary color toners of three colors, yellow, magenta, and cyan, or four colors in which black is added.

The general method is to first form an electrostatic latent image on the photoconductive layer by passing light from the original through a color separation light transmitting filter having a complementary color relationship with the color of the toner. Next, the toner is held on the support through a development and transfer process. Next, the above-mentioned steps are sequentially performed a plurality of times, the toners are superposed on the same support while matching the registration, and the final full-color image is obtained by fixing only once.

In the color electrophotographic method, in which a plurality of toner layers of different colors are superposed on the same support as the fixing step by carrying out the development a plurality of times as described above, the fixing characteristic that the color toner should have is It is a very important factor. That is,
The fixed color toner is required to have moderate gloss and luster by suppressing irregular reflection by toner particles as much as possible.

Further, each toner must be a color toner having a wide color reproducibility, in which an upper toner layer has transparency so as not to interfere with color development of toner layers having different color tones therebelow. As color toners that can satisfy these requirements, the present applicants have disclosed those in Japanese Patent Application Laid-Open Nos. 50-82442 and 51-
JP-A-144625 and JP-A-59-57256 disclose a combination of a novel binder resin for color toner and a colorant.

The color toners described above have a considerably sharp melt property, and when combined with a silicone rubber roller capable of applying silicone oil, the toner shape changes to a state close to complete melting at the time of fixing, Good gloss and color reproducibility are obtained.

These effects mean that, as the fixing property of the toner, the viscosity is more important than the elasticity in the viscoelastic property of the binder resin. That is, when heated, the toner behaves more as a viscous material, the thermal melting property is increased, and gloss is also obtained.

However, such a binder resin design with an emphasis on viscosity inevitably reduces intermolecular agglomeration at the time of heat melting, and also increases toner adhesion to the heat roller when passing through the fixing device. become. These cause a high temperature offset phenomenon. In particular, when a silicone rubber roller is used as a fixing roller, if it is used repeatedly regardless of whether or not the release oil is applied, a high temperature offset is likely to occur due to an essential decrease in the releasability of the surface of the silicone rubber roller.

In the silicone rubber roller, some releasability can be maintained due to the smoothness and cleanliness of the silicone oil impregnated inside the silicone rubber and the surface of the roller at the beginning of use. However, when a color image with a large image area such as a color image and a much larger holding amount on a support such as plain paper is copied as compared with a white / black copy image, the oil in the silicone rubber is naturally depleted. However, the roller surface also becomes rough, and the releasability of the roller gradually decreases. The speed of deterioration of this releasability reaches several times that of black and white copying.

Further, since the toner itself has almost no elasticity as described above, it is useless for the offset resistance effect. For these reasons, toner coating or granular deposits are formed on the surface of the fixing roller after copying only a few thousand to tens of thousands of sheets, and the upper layer of the image surface is stripped off when passing through the heat roller.
So-called high temperature offset occurs.

Although various measures have been attempted for toners in order to solve or alleviate the above problems, further improvement is desired. For example, JP-A-55-60960, JP-A-57-208559, and JP-A-58-1195.
No. 3, JP-A-58-14144, JP-A-SHO-60
As described in JP-A-123852, a method of adding a low-molecular weight polyethylene, polypropylene, wax, higher fatty acid or the like, which is a releasable component, to the toner is also used in order to increase the releasability of the toner. While these methods are effective in preventing offset, if they are contained in a large amount so as to exert sufficient effect in offset resistance, the compatibility with the main binder resin of the toner deteriorates, and the color of these toners is When an OHP image is formed, its transparency is impaired, charging characteristics become unstable, and durability is deteriorated.

Further, JP-A-47-12334, JP-A-57-37353, and JP-A-57-208559.
Japanese Patent Laid-Open Publication No. 2003-242242, a monomer component containing an etherified bisphenol monomer, a dicarboxylic acid monomer, a trivalent or higher polyhydric alcohol monomer, and / or a trivalent or higher polyvalent carboxylic acid monomer. A toner containing as a binder a polyester composed of a non-linear copolymer obtained from the above has been proposed. However, such a technique is known in which a polyester containing an aetherized bisphenol monomer and a dicarboxylic acid monomer is added to form a trivalent polyester. Offset prevention in the toner by including as a binder the polyester obtained by crosslinking with a large amount of monomer components containing the above polyhydric alcohol monomer and / or polyhydric carboxylic acid monomer having 3 or more valences It has high performance.

However, in such a toner,
Its softening point is a little high, and therefore good low temperature fixing is difficult, and when it is used for full color copying, it is at a practically practical level with respect to high temperature offset resistance.
As described above, there are problems with the fixability and sharp melt properties,
The color mixture and the color reproducibility due to the superposition of full-color toners using the polyester are not desired.

Further, JP-A-57-109825, JP-A-62-78568, and JP-A-62-78569.
JP-A No. 59-7960 and JP-A No. 59-29256 by the applicant of the present invention, a dicarboxylic acid monomer containing an etherified bisphenol monomer and a long-chain aliphatic hydrocarbon is used. Body and other dicarboxylic acid monomers, and trihydric or higher polyhydric alcohol monomers and / or 3
A non-linear copolymer obtained from a monomer component containing a polyvalent carboxylic acid monomer having a valence of 3 or more and having 3 carbon atoms in its side chain.
Although a toner containing a polyester having a saturated or unsaturated aliphatic hydrocarbon group of 22 as a binder has been disclosed, these polyester resins are mainly intended for high-speed copying toner and have viscoelastic properties of the resin. That is, contrary to the above-mentioned viscosity-oriented polyester, the elasticity is enhanced and the high temperature offset to the roller is remarkably reduced. Then, at the time of fixing, the pressure and heating of the heat roller are increased as much as possible, and the toner is pressed in a semi-molten state between the fibers of the transfer paper to perform pressure heating and fixing to achieve the object. .

Therefore, it is hardly possible to say that the toner layer necessary for color copying melts to form a continuous film and obtain a smooth surface, and the fixed toner exists in the state of particles on the transfer paper and is obtained. The color image is dull and has poor saturation. Further, in the case of an OHP image, the light is scattered and diffused on the surface of the toner particles and almost no light is transmitted, which makes it practically unusable.

Further, the present applicants have proposed a new polyester resin excellent in high temperature offset resistance and applicable to color copying in JP-A-2-73366 and JP-A-1-224767, but The resin is
Although it is superior to the conventional resin for color toner, the effect of preventing the offset to the fixing roller is exhibited at most about 20,000 copies repeatedly, and the offset prevention effect of the black and white toner is 100,000 sheets or more. It is sufficient, and in view of having printing durability and offset resistance of several hundred thousand sheets at present, it is preferable to further improve the performance.
In terms of electrification, the roller has a large difference in electrification amount between a low-temperature low-humidity environment and a high-temperature high-humidity environment, and a color image after repeated copying tends to have a slightly lower density on the low-humidity side. On the side, toner scattering and fog may occur.

Further, JP-A-62-195676, JP-A-62-195678, and JP-A-62-1956.
Japanese Patent Publication No. 80 discloses polyester resins in which the ratio of the hydroxyl value to the acid value is specified, but these polyester resins are also intended for high-speed fixing,
According to the study of the present inventors, the color toner using the resin has not reached the point where sufficient color mixing property is obtained.

As a problem peculiar to color copying, at least 3
The color balance of the color toners, preferably four color toners, must be in harmony, and it is meaningless to discuss the fixing characteristics and color reproducibility of only one color. It is necessary to design and select the resin in consideration of matching and balance.

In principle, if there are three primary colors, yellow, magenta, and cyan, almost all colors can be reproduced by the subtractive color mixing method, and therefore, the full-color copying machines currently on the market. Is configured to use color toners of three primary colors in an overlapping manner. By this, theoretically all color tones should be able to be realized in all density ranges, but in reality, it is still improved with respect to the spectral reflection characteristics of the toner, the mixing property at the time of overlapping and fixing the toner, the decrease in saturation, etc. Have a point.

When black is obtained by superimposing three colors, a toner layer three times as much as that of a monochromatic color is formed on the transfer paper, and further it is difficult for the offset resistance. Further, when the toner is manufactured and used as a non-magnetic one-component toner, that is, a one-component toner having no carrier, using a conventional resin that attaches importance to viscosity, further problems will occur. A commonly used developing device is, for example, one as shown in FIG.

The specific structure will be described below. The developing device is provided with an opening portion facing the photosensitive drum 111, and is provided with a developing chamber 101 for storing non-magnetic one-component toner (hereinafter referred to as non-magnetic toner). The developing chamber accommodates a conductive developing sleeve 103 that conveys the non-magnetic toner toward the photosensitive drum. Developing sleeve 103
Is disposed in the developing chamber so that a part of the outer peripheral surface thereof projects outward from the opening.

The developing sleeve 103 is held with a gap of 50 to 500 μm from the photosensitive drum 111, and a developing region for supplying the non-magnetic toner carried on the developing sleeve 103 toward the photosensitive drum is formed. . Further, in the developing chamber 101, the coating roller 10 for supplying the non-magnetic toner conveyed by the conveying means 108 to the developing sleeve 103.
7 are accommodated.

A DC bias is applied to the developing sleeve 103.
An AC bias or a developing bias in which AC is superimposed on DC is applied. The developing bias is the bias power source 10
It is generated from 5. A blade 109 is disposed above the developing sleeve 103 to regulate the layer thickness of the non-magnetic toner carried on the developing sleeve. The blade is attached to the developing chamber 101. Below the developing sleeve 103, a blowout preventing sheet 106 for preventing blowout of the non-magnetic toner from the lower portion of the developing chamber to the outside is provided.

At the time of development, the conveying means 108 conveys the non-magnetic toner toward the roller 107, and the non-magnetic toner is applied to the developing sleeve 103 by the applying roller 107. The developing sleeve 103 is rotated in the direction shown by the arrow in the figure, and the non-magnetic toner carried on the developing sleeve 103 is regulated to a predetermined layer thickness by the blade 109 and then sent to the developing area. In the developing area, an electric field is formed by the developing bias, and the force of the electric field causes the non-magnetic toner to fly toward the portion of the photosensitive drum where the latent image is formed.

As described above, the toner flying to the photosensitive drum 111 is transferred from the photosensitive drum to the transfer body, and the transfer body is subjected to a fixing process, whereby a transfer body on which an image is formed can be obtained. . At this time, if the binder resin of the non-magnetic toner has a weak intermolecular force and has a sharp melt property, the non-magnetic toner carried on the developing sleeve 103 for a long time may cause friction with the surface of the developing sleeve 103. The friction between the blade 109 and the developing sleeve 103 and the application roller 107 causes the toner to be fused on the developing sleeve 103 due to being compressed, sliding, rubbing, etc., and the contact portion between the blade 109 and the developing sleeve 103. The toner fusion to the toner and the toner fusion to the contact portion between the developing sleeve 109 and the coating roller 107 occur during the repeated copying of only a few thousand sheets or a few hundred sheets.

Further, the toner enters the connecting portion between the end portion of the developing sleeve 103 and the developing device main body, and the toner is heated and melted and solidified to stop the rotation of the developing sleeve 103. May be distorted, and in extreme cases, the developing device may be destroyed.
On the other hand, the demand for the quality of full-color copied images is increasing more and more. For general users who consider printing, full-color copy images are not yet at a satisfactory level, and they want a level closer to printing and a level closer to photography.

That is, a solid image in a wide image area in a copied image, the uniformity of a halftone image, a toner having an image density output covering a wide dynamic range from high density to low density, and transparency of a print sequence. OH
P, the transparency of the image and the toner used for the image, and the like. The shortest and preferred method to meet these requirements is to first improve the dispersibility of the colorant present in the toner.

In JP-A-61-117565 and JP-A-61-156054, a binder resin, a colorant, a charge control agent and the like are previously dissolved in a solvent and the solvent is removed to obtain a toner. However, it is difficult to control the dispersibility of the charge control agent, the solvent remains in the final product toner and gives an unpleasant odor, and the solvent is an aromatic system such as xylene or toluene. In the case of a solvent or the like, or a ketone-based solvent such as methyl ethyl ketone or acetone, there is a problem that not only odor but also bad influence on the human body.

Further, in Japanese Patent Laid-Open No. 61-91666,
Although a method for producing a toner using a halogen-based solvent is disclosed, the halogen-based solvent has strong toxicity and strong polarity, so that there are drawbacks such as limiting the colorant used.
In addition, JP-A-4-39671 and JP-A-4-3967.
Japanese Patent Laid-Open No. 2-249752 and Japanese Patent Laid-Open No. 4-242752 disclose a method for producing a toner while applying heat and pressure in a kneader. The method is more preferable for dispersing a colorant, but the toner is not preferable. The molecular chain of the constituent binder resin is broken by a strong kneading load, and the partial reduction of the molecular weight in the polymer is promoted. Therefore, high temperature offset is likely to occur in the fixing process. In particular, in color copying, since the toners of three or four colors are laminated and fixed, the latitude of high temperature offset resistance is much more severe than that of black and white toner, and slight molecular breakage in the polymer occurs. This easily causes high temperature offset.

[0030]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to provide good fixing property and color mixing property in full-color copying, have sufficient triboelectrification property, and have high glossiness which remarkably enhances image quality. High temperature offset is sufficiently prevented, fixing temperature range is wide, anti-offset property is maintained by repeated fixing paper passing, and toner fusion to parts inside the developing device, such as developing sleeve, blade, coating roller, etc. (EN) A toner and a method for producing a toner, which are free from sticking, have good dispersibility of a colorant, have high tinting strength, can obtain high image density, and have high saturation and excellent transparency.

[0031]

The above object can be achieved by the present invention described below. That is, in the present invention, in a toner containing at least a binder resin and a colorant, at least a first binder resin having a resin dispersion having a haze value of 7 to 30% and an insoluble colorant in an amount of 5 to 25% by weight. %, A kneaded product obtained by kneading a paste containing the same to remove volatile components, a toner having toner particles obtained via a step of kneading with a second binder resin, And a first kneading step of kneading the first binder resin and a paste containing an insoluble colorant in an amount of 5 to 25% by weight to remove volatile components, and the obtained kneaded product is used as a second binder resin. And a second kneading step of kneading.

[0032]

The reason why the toner of the present invention obtains preferable characteristics is presumed as follows. That is, at least one molecule of the crosslinking monomer component is regularly introduced into a linear polymer chain in which 20 to 30 units are repeated, and weak crosslinking is formed. And, although it is a weak crosslink, the whole polymer is constituted as one three-dimensional polymer. As a result, the offset resistance is much improved depending on the mixture of the mere linear polymers. Moreover, such a cross-linking level is within a range that does not hinder the easy mobility of the binder resin due to heat.

By using a toner in which the monomer components constituting the binder resin, the composition and the amount thereof are extremely limited, and a toner is used, a full-color image with good color mixture and color reproducibility can be obtained, and offset resistance can be obtained. I try not to cause any adverse effects. In the above-mentioned weakly crosslinked condensate, the amount of the crosslinking monomer component and the amount of the linear monomer component are determined so as to keep a balance, and if the amount of the linear monomer is too large, an abnormal sharp melt property occurs, and However, if it is too small, the glossiness and saturation of the color image decrease.

In order to preferably disperse the colorant in such a binder resin, in the conventional method of kneading by pressurizing at a high temperature, the molecular chain of the binder resin is easily cut and the offset resistance is improved. To improve the quality of full-color images
The intended effect on the color toner design cannot be fully exerted. Therefore, in the present invention, when the toner is manufactured, the heating temperature T in the first kneading step is 80 ° C. ≦ T.
It is limited to the range of ≤160 ° C. This is because the kneading is not performed at a high temperature and the load is not too low.

Further, the colorant is dispersed at normal pressure without applying pressure during kneading. This means that if kneading is performed while applying pressure, even if the heating temperature is set low, the same state as when kneading at a substantially high temperature will appear, and a great load will be applied to the kneaded product. , Will promote the breakage of the molecular chain in the binder resin. In the present invention, in order to remove the volatile solvent constituting the paste, it is more preferable to carry out kneading under a slightly reduced pressure condition rather than pressurization or normal pressure because the solvent can be rapidly removed. .

Further, in the first kneading step, the content of the colorant is set to 25% by weight or less with respect to the weight of the paste, and an appropriate dispersion amount is set efficiently and effectively. If it exceeds 25% by weight, a high temperature higher than the setting of the present invention is required during kneading for dispersing the colorant, or a powerful screw or paddle structure is required for the pressure heating kneading or kneading device. All of these are not possible because the polymer chains forming the binder resin are easily broken. On the other hand, if the content of the colorant is less than 5% by weight, the content of the colorant is too small, and the effect of the production method of the present invention cannot be sufficiently obtained.

In addition, the paste in the present invention refers to a state in which the colorant is present in the colorant manufacturing process without any drying process. In other words, the colorant particles are in the state of almost primary particles and are present in an amount of 5 to 25% by weight based on the total paste. The remaining 95 in the paste
.About.75 wt.% Is accounted for by the majority of volatile solvents, with some minimum wt% or less of dispersants, auxiliaries etc. being minimum if necessary.

The volatile solvent is a solvent that evaporates by general heating, for example, an aromatic solvent such as toluene, xylene and chlorobenzene, a ketone solvent such as methyl ethyl ketone and acetone, an alcohol solvent such as methanol and ethanol. Examples of the solvent include ether solvents such as methyl cellosolve and butyl cellosolve, and water. In the present invention, water is a solvent that is particularly preferably used and ecologically preferable.

The insoluble colorant in the present invention is a colorant which is insoluble in the volatile solvent in the paste and can be dispersed in a paste form. For example, when water is selected as the volatile solvent, all water-insoluble colorants are insoluble colorants. Moreover, when xylene is selected as the volatile solvent,
Oil-soluble dyes that are soluble in xylene are generally unsuitable in the present invention. The reason for this is that when the heat-kneading is performed together with the binder resin in a viscous solution state in which the colorant is dissolved in a solvent, the kneading load is not so great that the dispersion of the colorant in the binder resin becomes insufficient. . For this reason, it is essential that the paste be in a state in which an appropriate load is applied when it is kneaded with the binder resin.

As described above, the present invention provides a binder resin which can satisfy both offset resistance and full-color high image quality, and, while maintaining its characteristics, a high content of the colorant in the binder resin in the production method. Both of the efficient and effective dispersion can be achieved by dust. Examples of the kneading device used in the present invention include a heating kneader, a Henschel mixer, a single-screw extruder, a twin-screw extruder, and a kneader-ruder, and a particularly preferable embodiment is a heating kneader.

[0041]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the preferred embodiments. Colorants suitable for the purposes of the present invention include the following pigments or dyes. In the present invention, C.I. I. Disperse Yellow 164; C.I. I. Solvent Yellow 77 and C.I.
I. Colorants such as Solvent Yellow 93 cannot be prized.

Examples of dyes include C.I. I. Direct Red 1; C.I. I. Direct Red 4; C.I. I. Acid Red 1; C.I. I. Basic Red 1; C.I.
I. Modern Red 30; C.I. I. Direct Blue 1;
C. I. Direct Blue 2; C.I. I. Acid Blue 9; C.I. I. Acid Blue 15; C.I. I. Basic Blue 3; C.I. I. Basic Blue 5; C.I. I. Mordant Blue 7 and the like can be mentioned.

Examples of the pigment include Naphthol Yellow S, Hansa Yellow G, Permanent Yellow NCG, Permanent Orange GTR, Pyrazolone Orange, Benzidine Orange G, Permanent Red 4R, Watching Red Calcium Salt, Brilliant Carmine 38, Fast Bio Red B, Methyl. Vio red lake, phthalocyanine blue, fast sky blue, indanthrene blue BC and the like can be mentioned. Disazo yellow, an insoluble azo pigment, and copper phthalocyanine are preferably used as the pigment, and basic dyes and oil-soluble dyes are suitable as the dye.

Particularly preferably, C.I. I. Pigment Yellow 17; C.I. I. Pigment Yellow 15; C.I. I. Pigment Yellow 13; C.I. I. Pigment Yellow 1
4; C.I. I. Pigment Yellow 12; C.I. I. Pigment Red 5; C.I. I. Pigment Red 3; C.I. I.
Pigment Red 2; C.I. I. Pigment Red 6;
C. I. Pigment Red 7; C.I. I. Pigment Blue 15; C.I. I. Pigment Blue 16 or a copper phthalocyanine pigment in which the phthalocyanine skeleton having the following structural formula (I) is substituted with 2 to 3 substituents.

[0045] [Wherein X ₁ , X ₂ , X ₃ and X ₄ are Or H. However, the case where all of X _{1 to} X ₄ are H is excluded. ]

As the dye, C.I. I. Solvent Red 49; C.I. I. Solvent Red 52; C.I. I. Solvent Red 109; C.I. I. Basic Red 12;
C. I. Basic Red 1; C.I. I. Basic red 3b and the like can be mentioned. The content of the dye or pigment is 12 parts by weight or less, and preferably 0.5 to 7 parts by weight, based on 100 parts by weight of the binder resin for the yellow toner that sensitively reflects the light transmittance of the OHP film. Parts by weight.

When it exceeds 12 parts by weight, the reproducibility of green and red, which are mixed colors of yellow, and human skin color as an image is poor. For other magenta and cyan color toners, 1 for 100 parts by weight of the binder resin
It is 5 parts by weight or less, more preferably 0.1 to 9 parts by weight. It is also preferable to add a charge control agent to the toner according to the present invention in order to stabilize the negative charge characteristics. At this time, a colorless or pale-colored negative charge control agent that does not affect the color tone of the toner is preferable.

When the toner of the present invention is used as a two-component toner, a suitable carrier is required. As these carriers, for example, surface-oxidized or non-oxidized metals such as iron, nickel, copper, zinc, cobalt, manganese, chromium, rare earths, their alloys or oxides, and magnetic ferrites can be used. Moreover, there is no particular limitation in the manufacturing method. A system in which the surface of the carrier is coated with a resin or the like is particularly preferable. As the method, any conventionally known method such as a method of dissolving or suspending a coating material such as a resin in a dissolving agent and applying it to a carrier, and adhering it to the carrier, or a method of simply mixing with a powder can be applied. .

The substance adhered to the surface of the carrier varies depending on the toner material, and examples thereof include polytetralfluoroethylene, monochlorotrifluoroethylene polymer, polyvinylidene fluoride, silicone resin, polyester resin, styrene resin, acrylic resin, It is suitable to use polyamide, polyvinyl butyral, nigrosine, amino acrylate resin, basic dye and its lake, fine silica powder, fine alumina powder, metal complex or metal salt of dialkylsalicylic acid, alone or in combination.

Treatment of the carrier with the above solid material
The carrier may be appropriately determined so as to satisfy the above conditions, but generally, the total amount is preferably 0.1 to 30% by weight (more preferably 0.5 to 20% by weight) based on the carrier.
The average particle size of these carriers is 20 to 100 μm, preferably 25 to 75 μm, and more preferably 25 to 65 μm.

A particularly preferred carrier is C
It is a ternary ferrite carrier of u-Zn-Fe,
The surface thereof may be a resin such as a fluorinated resin and a styrene resin alone or in combination, for example, polyvinylidene fluoride,
Styrene-methylmethacrylate resin, polytetrafluoroethylene, styrene-methylmethacrylate resin, fluorocopolymer, etc., alone or in a mixture in a suitable suitable ratio, 0.01 to 5% by weight, preferably Is a coated magnetic ferrite carrier having the above-mentioned average particle size in which the carrier is coated at a ratio of 0.1 to 1% by weight, and the carrier particles of 250 mesh pass and 350 mesh on are 70% by weight or more.

The above-mentioned fluorine-based copolymer is a vinylidene fluoride-tetrafluoroethylene copolymer (10:90).
To 90:10), and examples of the styrene-based copolymer include styrene-2-ethylhexyl acrylate copolymer (20:80 to 80:20) and styrene-acrylic acid 2
-Ethylhexyl-methyl methacrylate copolymer (20
.About.60: 5 to 30:10 to 50). The coated ferrite carrier has a sharp particle size distribution,
With respect to the toner of the present invention, preferable triboelectrification properties are obtained, and there is an effect of improving electrophotographic characteristics.

When a two-component developer is prepared by mixing with the toner according to the present invention, the mixing ratio is 1% by weight to 15% by weight, preferably 2% by weight as the toner concentration in the developer.
Good results are usually obtained with a weight percentage of 13 to 13%. If the toner concentration is less than 1% by weight, the image density will be low, and if it exceeds 15% by weight, fog and in-machine scattering will increase, and the useful life of the developer tends to be shortened.

The fluidity improver used in the present invention may be any one as long as it can be added to the colorant-containing resin particles to increase the fluidity before and after the addition. For example, hydrophobic colloidal silica fine powder,
Examples thereof include colloidal silica fine powder, hydrophobic titanium oxide fine powder, titanium oxide fine powder, hydrophobic alumina fine powder, alumina fine powder and mixed powder thereof. When the toner of the present invention is used as a one-component non-magnetic toner, the above-mentioned magnetic carrier is not used, and the above-mentioned fluidity improver and the like are appropriately added and used.

Examples of the monomer component of the binder resin used in the present invention include styrene, chlorostyrene, α-methylstyrene, propylene, butadiene, styrene chloride,
Maleic acid, acrylic acid, methyl acrylate, butyl acrylate, propyl acrylate, octyl acrylate,
Examples thereof include phenyl acrylate, methyl methacrylate, butyl methacrylate, propyl methacrylate, ethyl methacrylate, phenyl methacrylate and acrylonitrile.

Other cross-linkable monomer components include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; diacrylate compounds linked by an alkyl chain such as ethylene glycol diacrylate and 1,3-. Butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-
Pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentylglycol diacrylate, and acrylates of the above compounds replaced by methacrylates; diacrylate compounds linked by an alkyl chain containing an ether bond, for example, , Diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate,
Dipropylene glycol diacrylate, and acrylates of the above compounds replaced by methacrylates;
Diacrylate compounds linked by a chain containing an aromatic group and an ether bond, for example, polyoxyethylene (2)-
2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate,
And those obtained by replacing the acrylate of the above compounds with methacrylate.

As the polyfunctional cross-linking agent, pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate, and acrylates of the above compounds are replaced with methacrylate. Triaryl cyanurate, triallyl trimellitate and the like.

In the present invention, the binder resin preferably used is a polyester resin, and examples of the divalent acid component constituting the polyester resin include terephthalic acid, isophthalic acid and phthalic acid as aromatic dicarboxylic acids. Acid, diphenyl-p, p'-dicarboxylic acid,
Naphthalene-2,6-dicarboxylic acid, diphenylmethane-p, p'-dicarboxylic acid, benzophenone-4,4 '
-Dicarboxylic acid, 1,2-diphenoxyethane-p,
P′-dicarboxylic acid or the like can be used, and as other acids, maleic acid, fumaric acid, glutaric acid, cyclohexanedicarboxylic acid, succinic acid, malonic acid, adipic acid, mesaconic acid, itaconic acid, citraconic acid, sebacic acid ,
Examples thereof include anhydrides of these acids and lower alkyl esters.

Examples of the acid or alcohol having an alkyl substituent or an alkenyl substituent used for synthesizing the polyester resin used in the toner of the present invention include, for example, n-dodecenyl group, isododecenyl group, n-dodecyl group, isododecyl group, Maleic acid having an isooctyl group, fumaric acid, glutaric acid, succinic acid, malonic acid, adipic acid and ethylene glycol, 1,3-propylene diol, tetramethyl glycol, 1,4-butylene diol, 1,
5-pentyl diol etc. are mentioned.

As the dihydric alcohol, (R ′ is an alkylene group having 2 to 5 carbon atoms, X and Y are positive numbers, and 2 ≦ X + Y ≦ 6), for example, polyoxypropylene (2,2)-
2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (6)-
2,2-bis (4-hydrokiphenyl) propane, polyoxypropylene (13) -2,2-bis (4-hydroxyphenyl) propane and the like can be mentioned.

Other dihydric alcohols include, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol,
Diols such as 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol and 1,4-butenediol, 1,4-bis (hydroxymethyl)
Cyclohexane, bisphenol, hydrogenated bisphenol A and the like can be mentioned.

Examples of trivalent or higher polycarboxylic acids include trimellitic acid, pyromellitic acid, cyclohexanetricarboxylic acids, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,
2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methylenecarboxylic propane, 1,3-dicarboxylic-2
-Methyl-2-methylenecarboxylic propane, tetra (methylenecarboxylic) methane, 1,2,7,8-octitanium tetracarboxylic acid and their anhydrides.

Examples of trihydric or higher polyols include sorbitol, 1,2,3,6-hexanetetol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose, 1, 2,4-mesitatriol, glycerin, 2-
Methyl propanetriol, 2-methyl-1,2,4-
Examples include butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trihydroxymethylbenzene.

Particularly preferred polyester resins include
A polyester resin produced from a monomer composition containing at least the following components (a), (b), (c) and (d), and having a hydroxyl value of 10 to 20.
And the weight average molecular weight is 13,000 to 20,000.
And the number average molecular weight is 5,000 to 8,000, and the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is 2 to 3.5.

(A) a divalent aromatic acid component (a) selected from isophthalic acid, terephthalic acid and its derivatives, 25 to 35 mol% of the total amount of monomers, and (b) trimellitic acid and its derivatives. The selected trivalent aromatic acid component (b) is 2 to 4 mol% of the total amount of the monomers, and (c) a divalent acid component (c) selected from at least dodecenylsuccinic acid, octylsuccinic acid and its anhydride. ) Is 1 of the total amount of monomers
2-18 mol% and (d) 45-60 mol% of the propoxylated and / or ethoxylated etherified diphenyl component (d) of the total monomer amount.

The production conditions of the above-mentioned polyester resin, which is an embodiment of this particularly preferable binder resin, are changed from the production conditions of the conventional polyester resin so that the molecular weight distribution of the polyester resin is as sharp and narrow as possible. I am preparing. It is important to make the molecular chain distribution of the polyester resin uniform within a narrow range in order to achieve both color mixing properties and offset resistance in the color toner. That is, in a condensate having a short molecular chain with a small molecular weight, the molecular main chain easily moves by heating, and conversely, a condensate with a long molecular chain having a high molecular weight hardly moves with its thermal energy. When the imbalance exists in the polyester resin, when a color toner using the resin passes through a fixing roller at a low temperature, the low-molecular weight condensate rapidly melts and exhibits a behavior of fixing and color mixing. In addition, a phenomenon occurs in which the polymer condensate is almost insoluble.

On the other hand, when a temperature high enough to melt the high molecular weight binder is applied to the fixing roller, the low molecular weight binder behaves as an adhesive having no elasticity at all, which causes a factor of high temperature offset. Therefore, particularly in full-color toners, the ratio of the weight average molecular weight to the number average molecular weight can be as high as possible in order to increase the intermolecular aggregation of the polyester resin constituting the toner while having a relatively sharp melt property. It needs to be small. This is a more important property than discussed with black and white toners.

The first binder resin and the second binder resin used in the present invention may be the above-mentioned binder resins synthesized so as to conform to the present invention, and may be used in combination at appropriate times. The same resin may be used as the first and second binder resins. (1) Method for measuring haze value of resin dispersion: The haze value of this resin dispersion is an important factor supporting the novelty and inventive step of the present invention. That is, it is a basis for determining whether or not the binder resin has a transitional character with a degree of crosslinking having the characteristics of both the linear resin and the non-linear crosslinked resin, which is the gist of the present invention. .

That is, the degree of cross-linking which has been generally referred to heretofore is, as disclosed by the present applicants in JP-A-63-223662, the corresponding binder resin is dispersed in a tetrahydrofuran solvent, and Soxhlet extraction is carried out to about 6 It was carried out for about an hour, and the tetrahydrofuran insoluble content was determined from the results, and this was used as a parameter indicating the degree of crosslinking of the binder resin. This method is effective when the binder resin has a very high degree of cross-linking, and the binder resin for toners is mainly used for high-speed copying machines. It is essential to use a pressure heating fixing roller which has high-temperature offset resistance and supplies high pressure and high temperature in order to maintain the fixing property. The binder resin of the present invention is of course completely dissolved by this measuring method having a strong dissolving power, and the degree of crosslinking cannot be measured.

The applicant of the present invention filed Japanese Patent Application No. 2-33269.
In Japanese Patent Laid-Open No. 1-1990, a method capable of measuring a weaker degree of crosslinking than the above-mentioned measuring method and a toner having a characteristic of having a weaker crosslinking are proposed, but the method also intends the present invention. When such a binder resin is measured, it is completely dissolved, and the apparent degree of crosslinking does not exist.

However, when the binder resin of the present invention is used for a color toner, it is obvious that the color mixing property is excellent and the high temperature offset resistance is beyond the conventional level. However, the inventors of the present invention have
The present invention has been completed by devising a new method for measuring the degree of crosslinking, and confirming that a binder resin satisfying the method can achieve the object of the present invention.

The method will be described below. Prepare a mixed solvent of xylene and isopropyl alcohol. The mixing ratio of xylene and isopropyl alcohol is
Adjust within the range of 1: 1 to 3: 1. Preferably 2.5:
It is 1. A binder resin as a sample is added to the above mixed solvent so that the concentration thereof is 5% by weight, and 0.2 to 2 is added by a turbula mixer.
Disperse for minutes, preferably 0.5 to 1 minute. This resin dispersion is filled in a transparent glass absorption cell having a haze value of 2% or less, preferably 1% or less.

A model 1001DP turbidimeter (manufactured by Nippon Denshoku) or a SEP-T-SB photoelectric meter (manufactured by Nippon Seimitsu Co., Ltd.) was equipped with the absorption cell filled with the dispersion liquid, and the total transmittance (T%) was measured. ) And diffuse transmittance (D%), and the haze value of the resin is calculated based on the following formula. Haze value (%) = D / T × 100

The smaller the value of this haze value, the more transparent it means that there is no opaque portion in the mixed solvent, that is, there are no aggregates insoluble in the solvent, in other words, weak crosslinked products. On the contrary, a large haze value means that there are many components forming opacity, that is, the degree of crosslinking in the resin is high. Conventional crosslinkable polyesters show considerable crosslinkability, and are disclosed in JP-A-57-37353, JP-A-57-208559, and JP-A-57-1.
The resins proposed in Japanese Patent Application Laid-Open No. 09825 and Japanese Patent Application Laid-Open No. 62-195677 are far beyond the scope of the present invention.
The haze value showed a large value and was unsuitable for use as a color toner.

(2) Measurement of weight average molecular weight (Mw) and number average molecular weight (Mn): In the present invention, HLC-8.
Mw and Mn are measured using 02A type (made by Toyo Soda Co., Ltd.). Column is TSKgel G manufactured by Toyo Soda Kogyo Co., Ltd.
MH6 × 2 is used and THF is used as a solvent. The detector uses RI (refractive index), and the sample has a concentration of 0.5% by weight.
Then, the injection amount is 200 microliters. The molecular weight of the sample is calculated from the relationship between the logarithmic value and the count number of a calibration curve prepared from several kinds of monodisperse polystyrene standard samples having the molecular weight distribution of the sample.

As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical C
o. Made or manufactured by Toyo Soda Kogyo Co., Ltd. has a molecular weight of 6 × 10
² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ ,
5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ ,
It is suitable to use those of 8.6 × 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ , and to use at least about 10 standard polystyrene samples.

(3) Measurement of hydroxyl value: JAS K007
It is measured by the following method according to the method shown in. 20
Precisely weigh 6 g of the sample in a 0 ml Erlenmeyer flask in units of 1 mg,
A mixed solution of acetic anhydride / pyridine = 1/4 is added with 5 ml hole pipette, and further 25 ml of pyridine is added with a measuring cylinder. Attach a condenser to the Erlenmeyer flask mouth, 1
React for 90 minutes in an oil bath at 00 ° C. Distilled water 3
Add ml from the top of the condenser, shake well, and leave for 10 minutes. The Erlenmeyer flask is pulled up from the oil bath with the condenser attached and allowed to cool. When the temperature reaches about 30 ° C., the condenser and the flask are washed with a small amount of acetone (about 10 ml) from the upper port of the condenser. Add 50 ml of THF with a graduated cylinder and use an alcohol solution of phenolphthalein as an indicator for N
50 ml with a / 2KOH-THF solution (scale interval 0.1 ml)
Neutralization titration using the burette of. Immediately before the end point of neutralization, 25 ml of neutral alcohol (methanol / acetan = 1/1
(Volume ratio) and titrate until the solution has a deep red color. At the same time, perform a blank test.

Then, the hydroxyl value is determined according to the following formula. Hydroxyl value (mgKOH / g) = [(B−A) × f × 2
8.05] / S + C where A: ml number of N / 2KOH-THF solution required for this test B: ml number of N / 2KOH-THF solution required for blank test f: For N / 2KOH-THF solution Titer S: Amount of sample (g) C: Acid value or alkali value. However, the acid value is positive and the alkali value is negative. The average of the two measurements is used.

(4) Gloss (glossiness) measuring method: VG-1
Using a 0 type gloss meter (manufactured by Nippon Denshoku Co., Ltd.), each solid image used for chromaticity measurement is measured as a sample. For the measurement, first, the voltage is set to 6 V by a constant voltage device. Then, the projection angle and the reception angle are adjusted to 60 °. Using the 0-point adjustment and standard plate, after the standard setting, the sample image is placed on the sample table, three white papers are overlaid and measured, and the numerical value shown on the display is read in%.

The production method for obtaining the polyester resin of the present invention is, for example, as follows. First, a linear condensate is formed, and in the process, the molecular weight is adjusted so as to be 1.5 to 3 times the target acid value and hydroxyl value, and more slowly than before so that the molecular weight becomes uniform, and As the condensation reaction proceeds gradually, for example, the reaction is carried out at a lower temperature for a longer time than before, or the esterification agent is decreased.
Alternatively, the reaction is controlled by using an esterifying agent having low reactivity, or by combining these methods.
Then, under the conditions, a cross-linking acid component and, if necessary, an esterifying agent are further added to react with each other to form a three-dimensional condensate. The temperature is further raised, and the reaction is allowed to proceed slowly for a long time so that the molecular weight distribution becomes uniform, the crosslinking reaction proceeds, the reaction is terminated when the hydroxyl value falls to a target value, and the polyester resin used in the present invention is obtained.

[0081]

The present invention will be described in detail with reference to the following examples. Example 1 A cyan color toner was obtained according to the following formulation amount and manufacturing method. Styrene-butyl acrylate-methyl acrylate copolymer 100 parts by weight Paste containing 25% by weight of copper phthalocyanine pigment (disubstituted product) having structural formula (1) (solvent is 75% by weight of water) 80 parts by weight As the first kneading step, the formulation is first charged in a kneader and heated while mixing. Maximum temperature (necessarily determined by the boiling point of the solvent in the paste, in this case 1
When the temperature reaches 00 ° C), the mixture is heated and melted and kneaded for about 45 minutes to distill off water in the paste. Then, the temperature was raised to 150 ° C., and the mixture was heated and melted and kneaded for about 30 minutes to complete the process. After cooling, the kneaded product was taken out.

Next, based on the following formulation, a cyan toner was obtained through a second kneading step. 50 parts by weight of the above kneaded material Polyester resin consisting of terephthalic acid, trimellitic acid and propoxylated bisphenol 88 parts by weight Chromium complex (charge control agent) 2 parts by weight The production method is as follows: After mixing, the temperature is set to 130 ° C. with a twin-screw extrusion kneader, melt kneading is performed, and after cooling, coarse crushing is performed to about 1 to 2 mm using a hammer mill, and then 40 μm or less with a fine crusher using an air jet method. Finely pulverized to a particle size of. Further, the finely pulverized product thus obtained is classified, and selected so that the volume average diameter in the particle size distribution is 8.2 μm to obtain 2 classified products. For the purpose of improving fluidity and imparting charging characteristics, S
0.8 parts by weight of the i-compound treated titanium oxide fine powder was externally added to 100 parts by weight of the classified product, and 0.5 part by weight of acrylic resin particles (average diameter 50 μm) was further added to obtain a cyan color toner.

Further, with respect to 5.0 parts by weight of this color toner, a Cu-Zn-Fe ferrite carrier coated with about 0.35% by weight of methyl methacrylate homopolymer was mixed so as to make the total amount 100 parts by weight, and developed. I used it as an agent. The toner concentration in the developer was 5.0% by weight. Figure 2
A copying test was conducted using a color electrophotographic apparatus having the OPC photosensitive drum shown. At this time, the fixing roller used in the fixing device 7 had a single layer of HTV silicone rubber layer, and the pressure roller surface was made of silicone rubber. An initial image was obtained using this method, and the color tone was vivid with excellent saturation.

Furthermore, a cyan image which faithfully reproduces the original without fog was obtained even after printing of 50,000 sheets. Further, the conveyance in the copying machine and the detection of the developer concentration were good, and a stable image concentration was obtained. Even when the fixing temperature was set at 160 ° C. and repeated copying of 50,000 sheets, offset to the fixing roller did not occur at all. Further, in order to compare and examine the high temperature offset amount, a new fixing roller is provided in the fixing device 7. The driving of the silicone oil-impregnated web was stopped, and in that state, an image having an area ratio of 20% was used as an original, and 5,000 sheets were repeatedly copied. Then, in order to quantify the toner adhered to the web, so-called high-temperature offset toner, the portion was measured with a Macbeth reflection densitometer, and the density was 0.3.

In this method, if the high temperature offset amount is large,
The reflection density value of the toner-attached web increases and decreases when it is small, so that the high temperature offset is quantified. Also, low temperature and low humidity (15 ℃
The charge amount was measured in each environment of 10% RH) and high temperature and high humidity (32.5 ° C. 85% RH), but it became extremely environmentally independent, and the charge amount ratio by that environment was 1.35. It was

As a method of evaluating a color copied image, there is a method of determining the quality of a color image by measuring the gloss (glossiness) of the image surface. That is, the higher the gloss value is, the smoother the image surface is, and it is judged that the color quality is high and the saturation is high. On the contrary, when the gloss value is low, the dull image surface with the poor saturation is judged to be rough. In Example 1, the value was 18%. Also, the contrast potential 3
The image density at 00V was extremely high at 1.85 (Macbeth reflection density), and the transparency of the OHP image was also good.

Example 2 A magenta toner was obtained in the same manner as in Example 1 with the following formulation amounts. First kneading step Polyester resin consisting of fumaric acid and ethoxylated bisphenol 80 parts by weight C.I. I. Pigment Red 122 25% by weight water paste 100 parts by weight

Second kneading step Kneaded product from the first kneading step 40 parts by weight Polyester resin consisting of terephthalic acid, trimellitic acid and ethoxylated-propoxylated bisphenol 198 parts by weight Chromium complex 2 parts by weight Repeated copying as in Example 1. The endurance test was carried out according to the above, but there was no offset to the fixing roller, and the transparency of the OHP image was excellent. The maximum image density (Dmax) at this time was 1.90. Table 1 shows the results.

Comparative Example 1 Polyester resin comprising terephthalic acid, trimellitic acid and propoxylated bisphenol 100 parts by weight Water paste containing 30% by weight of copper phthalocyanine pigment (disubstituted product) having the structural formula (1) 16. 7 parts by weight Chromium complex 4 parts by weight The total amount of the above formulation was charged in a kneader and heated while applying heat and pressure. When the temperature reaches 100 ° C., water is distilled off while heating and pressurizing. After distilling off the water, the temperature is raised to 150 ° C., and the mixture is kneaded by heating under pressure for 15 minutes to obtain a kneaded product, which is then pulverized and classified. Then, a cyan toner was obtained. Evaluation was performed in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 2 A water paste containing 30% by weight of a copper phthalocyanine pigment (disubstituted product) having the structural formula (1) was used, except that 5.0 parts by weight of a fine powder pigment having the same structure was dried and pulverized. ,
Other than that, kneading was carried out using a twin-screw extruder with the same formulation amount as in Comparative Example 1. After that, pulverization and classification were performed to obtain a cyan toner. Next, the same evaluation as in Example 1 was performed, and the results are shown in Table 1.
Shown in

Table 1

(Production Example-1 of polyester resin) 2 mol of terephthalic acid, 1.09 mol of dodecenyl succinic anhydride,
Polyoxypropylene (2.2) -2,2-bis (4-
Hydroxyphenyl) propane (3.4 mol) and dibutyltin oxide (0.01 g) were placed in a glass 2-liter four-necked flask, equipped with a thermometer, a stir bar, a condenser and a nitrogen inlet tube, and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised with stirring, and the reaction was allowed to proceed at 170 ° C. for 5 hours, then 19
The temperature was raised to 0 ° C. and the reaction was carried out for 4 hours. The hydroxyl value of the polyester resin produced at this time was 59.8.

Thereafter, 0.2 mol of trimellitic anhydride and 0.08 g of dibutyltin oxide were added, and the mixture was reacted at 190 ° C. for another 3 hours, further heated to 200 ° C. and reacted for 5 hours to complete the reaction, A polyester resin (1) used in the present invention was obtained. At that time, the hydroxyl value was 16.8, the glass transition temperature was 64 ° C, and the weight average molecular weight was 16.0.
The number average molecular weight was 5,900 and the ratio was 2.7.

(Production Example-2 of Polyester Resin) 1.8 mol of isophthalic acid, 1.16 mol of octylsuccinic acid and polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane 3. 34 mol of Production Example-1
The reaction was conducted in a nitrogen atmosphere in the same manner as in. Then, 0.13 mol of trimellitic anhydride and 0.09 g of dibutyltin oxide were added and the reaction was carried out at 180 ° C. for 5 hours to obtain a polyester resin (2) used in the present invention. The hydroxyl value of this resin is 14.7, the glass transition temperature is 62 ° C., the weight average molecular weight (Mw) is 17,000, and the number average molecular weight (Mn).
6,300, and Mw / Mn was about 2.7.

(Production Example-3 of polyester resin) 5 mol of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 2 mol of terephthalic acid,
3 mol of trimellitic anhydride and 0.05 g of dibutyltin oxide were reacted at 220 ° C. in a nitrogen atmosphere using the same device as in Production Example-1 to obtain a crosslinked polyester resin (3). Mw / of the obtained crosslinked polyester resin
Mn was clearly above 3.5.

(Production Example-4 of Polyester Resin) Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 2 mol, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl)
2.1 moles of propane, 2 moles of terephthalic acid, 1.6 moles of dodecenylsuccinic acid and 0.46 moles of trimellitic acid were reacted at 250 ° C. for 8 hours using the same apparatus as in Production Example-1 to give a polyester resin (4). Got The hydroxyl value of this resin was 20.4, the weight average molecular weight was 110,000, and the number average molecular weight was 5,540, and the ratio was 16.2. The glass transition temperature was 61.5 ° C.

(Production Example 5 of polyester resin) 5.0 mol of polyoxypropylene (2.5) -2,2-bis (4-hydroxyphenyl) propane was placed in a four-necked flask, and a stirrer, a condenser, A thermometer and a gas introduction tube were set and placed in the mantle heater. After purging the inside of the reaction vessel with nitrogen gas, when the contents were heated to 50 to 60 ° C., 3.0 mol of terephthalic acid and succinic acid substituted with a C ₁₂ alkenyl group (C ₁₆ H ₃₀ O ₄ ) 1.5 mol and 0.35 mol trimellitic acid were added.

The mixture system was heated to 210 ° C. with stirring.
After about 5 hours while removing water of reaction, the reaction product was cooled to room temperature. As the reaction conditions, the total amount of the monomer components was charged at once, the reaction temperature was high, and the reaction time was short, so the molecular weight distribution was broader than that of the polyester resin used in the present invention, and the average molecular weight was low. became. In connection with this, the hydroxyl value was as high as 32. At this time, the weight average molecular weight was 12,500 and the number average molecular weight was 3,070, and the ratio was 4.07.

(Production Example of Polyester Resin-6) Production Example of Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 5 mol, fumaric acid 4.5 mol and hydroquinone 0.1 g Using a device similar to -1, polyester resin (6) was obtained by reacting at 220 ° C in a nitrogen stream. Hydroxyl value 3 of the obtained resin (6)
2, the weight average molecular weight (Mw) was 18,700, the number average molecular weight (Mn) was 3,270, and Mw / Mn was about 5.7.

Example 3 A cyan color toner was obtained according to the following formulation amount and production method. Polyester resin (1) of Production Example-1 100 parts by weight Paste containing 25% by weight of copper phthalocyanine pigment (disubstituted product) having structural formula (1) (solvent is 75% by weight of water) 100 parts by weight As the first kneading step, the formulation is first charged in a kneader and heated while mixing. Maximum temperature (necessarily determined by the boiling point of the solvent in the paste, in this case 1
When the temperature reaches 00 ° C), the mixture is heated and melted and kneaded for about 45 minutes to distill off water in the paste. Then, the temperature was raised to 150 ° C., and the mixture was heated and melted and kneaded for about 30 minutes to complete the process. After cooling, the kneaded product was taken out.

Next, based on the following formulation, a cyan toner was obtained through a second kneading step. 50 parts by weight of the above kneaded material 150 parts by weight of the polyester resin of Production Example-1 150 parts by weight of chromium complex (charge control agent) 4 parts by weight The production method is as follows. The mixture was melt-kneaded at a temperature of 130 ° C. with a machine, cooled, roughly crushed to about 1 to 2 mm with a hammer mill, and then finely pulverized to a particle size of 40 μm or less with an air jet type fine pulverizer. Further, the finely pulverized product thus obtained is classified, and selected so that the volume average diameter in the particle size distribution is 8.2 μm, to obtain a 2-class product, and for the purpose of improving fluidity and imparting charging characteristics, Si
0.8 parts by weight of the compound-treated titanium oxide fine powder was externally added to 100 parts by weight of the classified product, and 0.5 part by weight of acrylic resin fine particles (average diameter 50 μm) was further added to obtain a cyan color toner.

Further, with respect to 5.0 parts by weight of this color toner, styrene-methyl methacrylate (copolymer weight ratio 6
5:35) coated with about 0.35% by weight of Cu-
A Zn-Fe-based ferrite carrier was mixed in a total amount of 100 parts by weight to prepare a developer. The toner concentration in the developer was 5.0% by weight. A copying test was conducted using a color electrophotographic apparatus having the OPC photosensitive drum shown in FIG. At this time, the fixing roller used in the fixing device 7 is 1
There was a single layer of HTV silicone rubber layer having a thickness of mm, and the pressure roller surface was 3 mm of HTV silicone rubber. An initial image was obtained using this method, and the color tone was vivid with excellent saturation.

Further, a cyan image which faithfully reproduces the original without fog was obtained even after printing 60,000 sheets. Further, the conveyance in the copying machine and the detection of the developer concentration were good, and a stable image concentration was obtained. Even when the fixing temperature was set to 160 ° C. and 60,000 sheets were repeatedly copied, offset to the fixing roller did not occur at all. Further, in order to compare and examine the amount of high temperature offset, a new fixing roller is used and the fixing device
Prepared for. The driving of the silicone oil-impregnated web was stopped, and in that state, an image having an area ratio of 20% was used as an original, and 5,000 sheets were repeatedly copied. Then, in order to quantify the toner adhered to the web, so-called high-temperature offset toner, the portion was measured with a Macbeth reflection densitometer, and the density was 0.3.

In this method, if the high temperature offset amount is large,
The reflection density value of the toner-attached web increases and decreases when it is small, so that the high temperature offset is quantified. Also, low temperature and low humidity (15 ℃
The charge amount was measured in each environment of 10% RH) and high temperature and high humidity (32.5 ° C. 85% RH), but it became extremely environmentally independent, and the charge amount ratio by that environment was 1.35. It was

As a method of evaluating a color copied image, there is a method of determining the quality of a color image by measuring the gloss (glossiness) of the image surface. That is, the higher the gloss value is, the smoother the image surface is, and the glossier the color quality is, and the lower the gloss value is, the more dull the image surface is. In Example 1, the value was 21%. Also, the contrast potential 3
The image density at 00V was 1.95 (Macbeth reflection density), which was extremely high, and the transparency of the OHP image was also good.

Example 4 In the color electrophotographic apparatus shown in FIG. 2, cyan was the same as in Example 1 except that the developing device 2-1 was replaced with a non-magnetic one-component toner developing device as shown in FIG. The toner was used to repeatedly copy 5.0 thousand sheets under high temperature and high humidity, but there was no fusion to the developing sleeve 103, the blade 109, and the coating roller 107, and the image density was 1.80 at a potential contrast of 300V. A high Dmax was obtained. or,
Neither scattering nor fog occurred due to the decrease in the charge amount of the toner.

Example 5 A magenta toner was obtained in the same manner as in Example 1 with the following formulation amounts. First Kneading Step Polyester Resin (2) of Production Example-2 80 parts by weight C.I. I. Pigment Red 122 20% by weight water paste 100 parts by weight

Second Kneading Step Kneaded product by the first kneading step 40 parts by weight Polyester resin (1) of Production Example-1 160 parts by weight Chromium complex 2 parts by weight As in Example 1, a durability test by repeated copying was conducted. There was no offset to the fixing roller, and the transparency of the OHP image was excellent. The maximum image density (Dmax) at this time was 1.88. Table 1 shows the results.

Comparative Examples 3 to 5 Cyan toners were obtained using polyester resins (3), (4) and (6) under the same production conditions as in Example 3. Next, in the same manner as in Example 4, a durability test was conducted using the non-magnetic one-component toner. Table 1 shows the results.

Comparative Example 6 Polyester Resin (2) of Production Example-2 100 parts by weight Water paste containing 30% by weight of copper phthalocyanine pigment (disubstituted product) having the structural formula (1) 16.7 parts by weight Chromium complex 4 parts by weight The total amount of the above formulation was charged into a kneader and heated while applying heat and pressure. When the temperature reaches 100 ° C., water is distilled off while heating and pressurizing. After distilling off the water, the temperature is raised to 150 ° C., and the mixture is kneaded by heating under pressure for 15 minutes to obtain a kneaded product, which is then pulverized and classified. Then, a cyan toner was obtained. Evaluation was performed in the same manner as in Example 4, and the results are shown in Table 2.

Table 2

[0112]

According to the present invention as described above, good fixing properties and color mixing properties are exhibited, sufficient triboelectrification properties are exhibited, glossiness that remarkably enhances image quality is high, and high temperature offset is sufficiently prevented. The fixing temperature range is wide, and the offset resistance is maintained even after repeated fixing paper passes, and there is no toner fusion to the parts inside the developing device, that is, the parts such as the developing sleeve, the blade, and the application roller. Good dispersibility,
A toner having high tinting strength, high image density, high saturation, and excellent transparency is provided.

[0113]

[Brief description of drawings]

FIG. 1 is a diagram illustrating a commonly used developing device.

FIG. 2 is a diagram illustrating a color electrophotographic apparatus.

[Description of sign]

 1: Photosensitive drum 2: Rotational development unit 2-1 to 4: Development device 3: Replenishing hopper 4: Toner transport cable 6: Transfer drum 10: Heating and pressure roller fixing device 17: Cleaning unit

Claims (6)

[Claims] 1. In a toner containing at least a binder resin and a colorant, at least the haze value of the resin dispersion liquid is 7.
~ 30% of the first binder resin and the insoluble colorant 5 ~
25% by weight of a paste is kneaded to remove the volatile components, and the obtained kneaded product has toner particles obtained via a step of kneading with a second binder resin. toner. 2. The first binder resin comprises the following component (a):
A polyester resin produced from a monomer composition containing at least (b), (c) and (d), wherein the polyester resin has a hydroxyl value of 10 to 20 and a weight average molecular weight of 13,000 to. 20,000, the number average molecular weight is 5,000 to 8,000, and the weight average molecular weight (Mw) / number average molecular weight (Mn) ratio is 2 to 3.5. toner. (A) 25-35 mol% of divalent aromatic acid component (a) selected from isophthalic acid, terephthalic acid and its derivatives, and (b) trimellitic acid and its derivatives A trivalent aromatic acid component (b) is 2 to 4 mol% of the total amount of the monomer, and (c) a divalent acid component (c) selected from dodecenylsuccinic acid, octylsuccinic acid and an anhydride thereof is the total monomer. 12-18 mol% of the total amount, and (d) the propoxylated and / or ethoxylated etherified bisphenol component (d) is 45-6 of the total monomer amount.
0 mol%. 3. The toner according to claim 1, which is a non-magnetic one-component toner. 4. The first binder resin and the insoluble colorant in an amount of 5 to 5
It has a first kneading step of kneading a paste containing 25% by weight to remove volatile components, and a second kneading step of kneading the obtained kneaded material with a second binder resin. Method for producing toner. 5. The haze value of the resin dispersion of the first binder resin is
The method for producing a toner according to claim 4, wherein the amount is 7 to 30%. 6. The method for producing a toner according to claim 4, wherein the first kneading step comprises only heat-melt kneading.