JP2003207930A - One-component toner for full color and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide one-component toner for full color which does not cause scattering, the tailing of fixation, faulty fixation, fogging in the latter half of an endurance test, the soiling of an electrifying member, offset, filming, and dripping, and makes color reproducibility excellent. <P>SOLUTION: The toner is used in an image forming apparatus having a thermal fixing device for thermally fixing a developed image on recording material by a heating body fixed at a proper position and a pressure member oppositely press-contacting with the heating body and bringing the recording material into contact with the heating body across a heat resistant fixing thin film. The melt viscosity MI of the toner by a melt indexer is 3 to 40, the toner includes an additive A and an additive B including different in organic elements respectively, and its value obtained by a following calculational expression in measurement by a particle analyzer is 5 to 60% (a counted number that three elements of carbon, the additive A, and the additive B derived from the toner synchronize/the total counted number of synchronizing particles)×100(%). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner used in a recording method using an electrophotographic method, an electrostatic recording method or the like. More specifically, the present invention relates to a full-color one-component toner used in a copying machine, a printer, or a fax machine, in which a toner image is previously formed on an electrostatic latent image carrier and then transferred onto a transfer material to form an image, and an image forming method.

[0002]

2. Description of the Related Art In recent years, devices using electrophotography have been applied to conventional copying machines as well as devices such as printers and fax machines. In particular, in printers and fax machines, since it is necessary to reduce the size of the copying machine, a toner cartridge centering on the developing device and a drum cartridge centering on the photoconductor are often used.

As the developing method used for the toner cartridge, there are many one-component developing methods. In the one-component developing method, the toner is charged by the friction between the toner control member and the toner particles and the friction between the toner carrier and the toner particles, and at the same time, a thin coating is applied on the toner carrier so that the toner carrier and the latent image carrier are separated from each other. This is a method in which the electrostatic latent image on the latent image carrier is developed by developing the electrostatic latent image on the latent image carrier so as to visualize it as a toner image.

Unlike the two-component developing method, the one-component developing method does not require carrier particles such as glass beads, iron powder, and ferrite, so that the developing device itself can be made compact and lightweight. Further, in the two-component developing method, it is necessary to keep the toner concentration in the developer constant, so that a device for detecting the toner concentration and replenishing a required amount of toner is required, which leads to an increase in size and weight of the developing device. Also in this respect, the one-component developing method is advantageous for downsizing and weight saving.

In recent years, there has been a demand for power saving in consideration of the environment, and in order to shorten the time from turning on the switch of the copying machine or printer to outputting the first image, the film Fusers are beginning to be used. This is because the fixing roller does not need to be heated before outputting an image as in the conventional roller type fixing device, so not only the power consumption is reduced but also the heat loss due to fixing with a film is small. The time to get the first one can also be shortened.

However, with the recent trend toward higher image quality and full color, the problems that were not so problematic in the past have been highlighted.

One of them is a problem called scattering. This is a phenomenon in which an outline portion of an image or a character portion (hereinafter referred to as an edge portion) is jaggedly roughened by toner scattered during fixing.

It has also been found that a phenomenon called "fixing tailing" is likely to occur in a film fixing device because fixing is performed by rapid heating.

Further, it has been found that the recent increase in speed tends to cause defective fixing in a film fixing device in which it is difficult to apply strong pressure during fixing.

Further, with the spread of full-color images, color reproducibility closer to natural color has been demanded.

To solve these problems by adjusting the adhesion state of the external additive of the toner, Japanese Patent Laid-Open No. 2000-2000 has been proposed.
Although various attempts have been made such as JP-A-310874, JP-A-2000-310876, and JP-A-2001-22118, fog in a non-image area occurs in the latter half of the durability test, and a charging member. There was some pollution. Further, the scattering, the trailing of the fixing, and the fixing failure when the film fixing device is used are insufficient for improvement.

[0012]

DISCLOSURE OF THE INVENTION The object of the present invention is to scatter, fixing tailing, fixing failure, fog in the latter half of the durability test,
It is an object of the present invention to provide a full-color one-component toner and an image forming method in which color reproducibility is excellent without causing contamination, offset, filming, or fluffing of a charging member.

[0013]

The above object can be achieved by the present invention described below.

That is, according to the present invention, at least a heating body fixed at an appropriate position and a pressure member for contacting the heating body with the heating body to bring the recording material into close contact with the heating body through a heat-resistant fixing thin film. A toner used in an image forming apparatus having a heat fixing device that heat-fixes a visible image on a recording material by a melt index MI.
Is 3 to 40, each contains an external additive A and an external additive B containing different inorganic elements, and the value of the following calculation formula is 5 to 60% in the measurement with a particle analyzer. It relates to a one-component toner. (Count number in which three elements of toner-derived carbon, external additive A and external additive B are synchronized / total number of synchronized particles) × 100
(%)

Further, according to the present invention, at least a heating member fixed at an appropriate position, and a pressing member for bringing the recording material into close contact with the heating member through a heat-resistant fixing thin film by facing the heating member against each other. According to the image forming method having a heat fixing device that heat-fixes the visible image on the recording material, the image is fixed in the order of black, cyan, magenta, and yellow from the bottom layer of the transfer material, and the toner is melted by the melt indexer. The toner has a viscosity MI of 3 to 40, toners containing an external additive A and an external additive B containing different inorganic elements, and the value of the above calculation formula is 5 to 60% when measured by a particle analyzer. The present invention relates to an image forming method characterized by using the full-color one-component toner.

[0016]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS As a result of intensive studies by the present inventor, at least a heating member fixed at an appropriate position and a recording material is abutted against the heating member by a heat-resistant fixing thin film and the recording material In an image forming apparatus having a heat fixing device that heats and fixes a visible image on a recording material by a pressure member that is brought into close contact with a heating body, the melt viscosity MI by the melt indexer is 3 to 40, and different inorganic elements are used. Using a toner containing the external additive A containing the external additive B and the toner containing the external additive B, the following calculation formula (count number in which three elements of carbon derived from the toner, the external additive A, and the external additive B are synchronized / Synchronous particle total count number) x 100
By using a full-color one-component toner having a (%) value of 5 to 60%, scattering, fixing tailing, poor fixing, fogging in the latter half of the endurance test, and charging member contamination can be prevented. Found.

The details will be described below.

FIG. 1 shows an example of an exploded perspective view of a fixing device according to the present invention. 1 is a fixing film, 2 is a stay, 3 is a pressure roller, 4 is an electrode portion, 5 is a stay fixing member, and 6 is a spring.

A heater holder is fixed to the stay 2, and an alumina substrate on which a resistance material is printed is adhered and fixed to the heater holder. In this fixing device, when the resistance material is energized, the alumina substrate is instantly heated, and the amount of heat necessary for fixing can be applied to the recording material at the nip portion.

The toner used in the present invention is used in full color. Although the present toner can obtain the above-mentioned effects even when used in monochrome, the harmful effects such as splattering, fixing tailing, fixing failure, fog in the latter half of the durability test, charging member contamination, and color reproducibility in the system of the present invention can be obtained. Since this is a problem that has become prominent in the constitution, the present toner having these improving effects is preferably used in a full-color machine. In addition, the color order to be fixed at that time is preferably black, cyan, magenta, and yellow from the viewpoint of the transfer material from the viewpoints of fixability, color developability, and color reproducibility. The effect of improving color reproducibility in the invention may not be exhibited.

In the present invention, the melt index (hereinafter abbreviated as MI) of the toner has a value of 3 to 40 (g / 10 minutes).
Is preferable from the viewpoint of fixability. When MI is less than 3, not only fixing failure may occur, but also low temperature offset may occur. Further, if MI is greater than 40, high temperature offset may occur, which is not preferable. And it is more preferably 5 to 30 (g / 10 minutes).

In the present invention, the toner uses at least two kinds of external additives each containing a different inorganic element. These at least two kinds of external additives need to have different charging orders so that they are divided into positive and negative when they come into contact with each other, which improves scattering and fixing tailing. The reason for this improvement is not clear, but the positively charged external additive acts like a microcarrier to stabilize the chargeability of the toner, and therefore changes in chargeability due to the surrounding environment and charging due to toner deterioration It is considered possible to minimize the change in sex.

The synchronism rate of these two external additives and the three elements of the toner base particles is preferably 5 to 60%. If the synchronization rate is less than 5%, it will be difficult to balance the chargeability of the toner, and not only scattering, fixing tailing, and fog in the latter half of the durability cannot be improved, but also charging due to a free external additive. Contamination of parts may become severe. Further, if the synchronization rate is more than 60%, fixing failure may occur, and fluidity is likely to decrease even in the latter half of the endurance test, and toner leakage and fluffing during machine startup are likely to occur.

Of these, more preferably 1 of 2 elements
The element is Si, which is preferable from the viewpoint of improving fluidity and imparting chargeability to the toner. Also, using Ti as one of the two elements is effective for controlling the charging property by a microcarrier-like function and maintaining the fluidity in the latter half of the durability test. Further, it is effective to use Mg as one of the two elements because the same effect as described above can be expected.

In the present invention, the toner is MI as described above.
By controlling the synchronization rate of the three elements, the adhesion state of the external additive to the toner can be stabilized all the time. Therefore, it is possible to maintain good chargeability even in the latter half of the durability test, and suppress scattering and tailing during fixing.

In the present invention, when the wax is contained in the toner, 1% by mass or more and 15% by mass or less is preferable because the fixing property and the charging property are not impaired. More preferably 1.
It is 5 mass% or more and 13.0 mass% or less.

In the present invention, the circularity of the toner is 0.9.
It is preferably 50 or more and less than 0.995 because it is easy to uniformly control the charging property. Toner circularity is 0.95
If it is less than 0, the chargeability of the toner tends to vary, and the effect of maintaining uniform charging according to the present invention may not appear. If the circularity is 0.995 or more, cleaning failure may occur.

In the present invention, the circularity is the equivalent circle diameter of the number of toner particles measured by a flow type particle image measuring device.
It is measured in a circularity scattergram, and in the present invention, it was measured using "FPIA-1000 type" (manufactured by Toa Medical Electronics Co., Ltd.) and calculated using the following formula. Circularity = circumference with the same projected area as the particle image / perimeter of the particle projected image

Here, the "particle projection area" is the area of the binarized toner particle image.

As a specific measuring method, 10 ml of ion-exchanged water from which impure solids and the like have been removed beforehand is prepared in a container, and a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant into the water. Then, 0.02 g of a measurement sample is further added and uniformly dispersed. As a means for dispersing, an ultrasonic disperser "UH-50 type" (manufactured by SMT) equipped with a titanium alloy chip of 5Φ as a vibrator was used, and dispersion treatment was performed for 5 minutes to obtain a dispersion liquid for measurement. To do. At that time, the dispersion is appropriately cooled so that the temperature of the dispersion does not exceed 40 ° C.

To measure the shape of the toner, the flow type particle image measuring device is used, and the toner particle concentration at the time of measurement is 3000.
The concentration of the dispersion liquid is readjusted to be about 10,000 particles / μl, and 1,000 or more toner particles are measured. After the measurement, this data is used to determine the average circularity of the toner.

The method for producing the toner base of the present invention is not particularly limited. First, the method for producing the toner of the present invention in the suspension polymerization method will be described below.

First, wax, polar resin, colorant, charge control agent, polymerization initiator, and other additives are added to the polymerizable monomer and uniformly dissolved or dispersed by a homogenizer, an ultrasonic disperser or the like. The monomer system is dispersed in an aqueous phase containing a dispersion stabilizer by a usual stirrer, homogenizer, homomixer or the like. At this time, preferably, the stirring speed and time are adjusted so that the droplets of the monomer have a desired size of the developer particles, and granulation is performed. After that, stirring may be performed to the extent that the particle state is maintained and the particles are prevented from settling by the action of the dispersion stabilizer. The polymerization temperature is preferably 40 ° C. or higher, generally 50 ° C. to 90 ° C. In addition, the temperature may be raised in the latter half of the polymerization reaction, and further, in order to remove unreacted polymerizable monomers, by-products, etc. that cause odor during fixing of the developer, in the latter half of the reaction or at the end of the reaction. Part of the aqueous medium may be distilled off.
After completion of the reaction, the produced developer particles are washed, collected by filtration and dried. In the suspension polymerization method, usually monomer system 1
It is preferable to use 300 parts by mass to 3000 parts by mass of water as a dispersion medium with respect to 00 parts by mass.

The particle size distribution and particle size of the toner can be controlled by adjusting the pH of the system at the time of granulation, changing the kind and amount of the sparingly water-soluble inorganic salt or dispersant acting as a protective colloid, and mechanically. It can be carried out by controlling the apparatus conditions, for example, the peripheral speed of the rotor, the number of passes, the stirring conditions such as the shape of stirring blades, the shape of the container or the solid content concentration in the aqueous solution.

The polymerizable monomer used in the present invention includes styrene, o- (m-, p-) methylstyrene, m
-(P-) Styrene-based monomers such as ethylene styrene;
Methyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, ( (Meth) acrylic acid ester monomers such as 2-ethylhexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and diethylaminoethyl (meth) acrylate; butadiene, isoprene, cyclohexane, (meth) acrylonitrile, acrylic acid Monomers such as amides are preferably used.

The polar resin added during the polymerization is
Styrene (meth) acrylic acid copolymers, maleic acid copolymers, polyester resins and epoxy resins are preferably used.

As the wax used in the present invention, paraffin wax, polyolefin wax, Fischer-Tropsch wax, amide wax, higher fatty acid, ester wax and derivatives thereof, or graft / block compounds thereof are preferably used. To be

The charge control agent used in the present invention includes
Known compounds can be used, but a charge control agent that does not inhibit polymerization and has no solubilized product in an aqueous system is particularly preferable. As specific compounds, negative compounds such as salicylic acid, naphthoic acid, dicarboxylic acids, metal compounds of their derivatives, polymer compounds having sulfonic acid in the side chain, boron compounds, urea compounds, silicon compounds, calixarene, etc. are used. As a positive system, a quaternary ammonium salt, a polymer type compound having the quaternary ammonium salt in its side chain, a guanidine compound, an imidazole compound or the like is preferably used. The charge control agent is preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

The polymerization initiator used in the present invention includes
For example, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutylnitrile,
1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-
Azo-based polymerization initiators such as dimethylvaleronitrile and azobisisobutylnitrile, benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroxyperoxide, 2,
Peroxide-based polymerization initiators such as 4-dichlorobenzoyl peroxide and lauroyl peroxide are used.

The amount of the polymerization initiator added varies depending on the desired degree of polymerization, but it is generally used in an amount of 0.5 to 20% by mass based on the monomer. Although the type of the polymerization initiator varies slightly depending on the polymerization method, it may be used alone or in combination with reference to the 10-hour half-life temperature.

As the dispersant used when the suspension polymerization is used, for example, as an inorganic oxide, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide is used. , Magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina, magnetic material, ferrite and the like. Examples of organic compounds include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose,
A sodium salt of carboxymethyl cellulose, starch or the like is used by dispersing it in an aqueous phase.

These dispersants are preferably used in an amount of 0.2 to 2.0 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

As these dispersants, commercially available products may be used as they are, but in order to obtain finely dispersed particles having a uniform particle size, the inorganic compound is produced by high-speed stirring in a dispersion medium. You can also For example, in the case of calcium phosphate, a dispersant suitable for the suspension polymerization method can be obtained by mixing an aqueous sodium phosphate solution and an aqueous calcium chloride solution under high speed stirring.

In order to make these dispersants finer,
You may use together 0.001-0.1 mass part surfactant. Specifically, commercially available nonion, anion, cationic surfactants can be used, for example, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, Calcium oleate is preferably used.

In the toner of the present invention, in addition to black colorants such as carbon black and magnetite as colorants,
Any pigment and / or dye such as the yellow / magenta / cyan colorants shown below can be used.

For example, when the toner according to the present invention is used as a full-color toner, the followings are listed.

Examples of magenta color pigments include C.I. I. Pigment Red 1,2,3,4,5,6,7,8,9,1
0,11,12,13,14,15,16,17,1
8, 19, 21, 22, 23, 30, 31, 32, 3
7, 38, 39, 40, 41, 48, 49, 50, 5
1, 52, 53, 54, 55, 57, 58, 60, 6
3,64,68,81,83,87,88,89,9
0,112,114,122,123,163,20
2,206,207,209; C.I. I. Pigment Violet 19; C.I. I. Bat red 1, 2, 10, 1
3,15,23,29,35.

The pigment may be used alone, but it is more preferable from the viewpoint of the image quality of a full-color image to improve the sharpness by using a dye and a pigment in combination.

Examples of magenta dyes include C.I. I.
Solvent Red 1,3,8,23,24,25,2
7, 30, 49, 81, 82, 83, 84, 100, 1
09, 121; C.I. I. Disperse Red 9; C.I.
I. Solvent Violet 8,13,14,21,2
7; C.I. I. Oil soluble dyes such as Disperse Violet 1, C.I. I. Basic Red 1, 2, 9, 12, 1
3,14,15,17,18,22,23,24,2
7, 29, 32, 34, 35, 36, 37, 38, 3
9, 40; C.I. I. Basic violet 1,3
7,10,14,15,21,25,26,27,28
And basic dyes such as

As the color pigment for cyan, C.I. I. Pigment Blue 2, 3, 15, 16, 17; C.I. I. Bat Blue 6; C.I. I. Acid Blue 45, a copper phthalocyanine pigment having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton can be mentioned.

As the coloring pigment for yellow, C.I. I. Pigment Yellow 1,2,3,4,5,6,7,10,1
1, 12, 13, 14, 15, 16, 17, 23, 6
5, 73, 83; C.I. I. Bat yellow 1,3,20
Etc.

Next, a method of manufacturing the toner by the pulverization method will be described.

As the binder resin used in the pulverized toner of the present invention, polystyrene, poly-α-methylstyrene, styrene-propylene copolymer, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene -Vinyl acetate copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid acrylic copolymer, vinyl chloride resin, polyester resin, epoxy resin, phenol resin, polyurethane resin and the like can be used alone or in combination. Among them, styrene-acrylic, styrene-methacrylic copolymer resin, and polyester resin are preferable.

When the pulverized toner of the present invention is controlled to have a positive charging property, a modified product thereof with a fatty acid metal salt or the like; tributylbenzyldiammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate Such as quaternary ammonium salts, and onium salts such as phosphonium salts which are analogs thereof; amine and polyamine compounds; metal salts of higher fatty acids; acetylacetone metal complexes; dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide, and other diamines. Organotin oxide; dibutyltin borate, dioctyltin borate, diorganotin borate such as dicyclohexyltin borate, etc. are added. Further, in the case of controlling to negative chargeability, an organic metal complex and a chelate compound are effective, and a monoazo metal complex, an acetylacetone metal complex, an aromatic hydroxycarboxylic acid, and an aromatic dicarboxylic acid type metal complex can be used. The amount used is 0.1 to 15 parts by mass, preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the binder resin.

A wax is added to the pulverized toner of the present invention to prevent fixing offset. For example, an aliphatic hydrocarbon wax such as low molecular weight polyethylene, low molecular weight polypropylene, paraffin wax, Fischer-Tropsch wax or an oxide thereof; a wax containing an aliphatic ester as a main component such as carnauba wax or montanic acid ester wax, or one of them. Examples include those obtained by deoxidizing a part or all of them. In addition, saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, and valinaric acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubayl alcohol, ceryl alcohol. , Saturated alcohols such as melicyl alcohol; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide; saturated fatty acid bisamides such as methylenebisstearic acid amide; unsaturated fatty acid amides such as ethylene bisoleic acid amide Aromatic bisamides such as N, N'-distearylisophthalic acid amide; Fatty acid metal salts such as zinc stearate; Waxes obtained by grafting aliphatic hydrocarbon waxes with vinyl monomers such as styrene; Be A partial esterified product of a fatty acid such as henic acid monoglyceride and a polyhydric alcohol; a methyl esterified product having a hydroxyl group obtained by hydrogenation of vegetable oils and the like can also be used.

Next, the binder resin, wax, charge control agent, colorant and the like are thoroughly mixed by a mixer such as a Henschel mixer or a ball mill, and then a heat kneader such as a heating roll, kneader or extruder is used. Melt and knead to disperse or dissolve the charge control agent and colorant in the mutually compatible resins, cool and solidify, mechanically pulverize to the desired particle size, and further classify to obtain a sharp particle size distribution. To Alternatively, after cooling and solidification, the finely pulverized product obtained by colliding with a target under a jet stream is spheroidized by heat or mechanical impact force.

The toner base material of the present invention manufactured as described above can be used by externally adding an inorganic fine powder such as silica, alumina or titania. Inorganic fine powder is preferably a specific surface area (BET) is 5m ² / g~500m ² / g. Further, the surface-treated product of the inorganic fine powder can be used as an external additive. Examples of the surface treatment agent include a silane coupling agent, a silylating agent, a titanium coupling agent, and a silicone oil, but preferably a silane coupling agent, a silylating agent, and a silicone oil are used. You may use together.

Further, in the present invention, the following inorganic powder may be added in order to improve developability and durability. Metal oxides such as magnesium, zinc, aluminum, cerium, cobalt, iron, zirconium, chromium, manganese, strontium, tin, antimony; complex metal oxides such as calcium titanate, magnesium titanate, strontium titanate; barium sulfate, Metal salts such as calcium carbonate, magnesium carbonate, aluminum carbonate;
Clay minerals such as kaolin; Phosphoric acid compounds such as apatite;
Silicon compounds such as silica, silicon carbide, and silicon nitride; carbon powders such as carbon black and graphite.

The following organic particles and composite particles may be added for the same purpose. Resin particles such as polyamide resin particles, silicone resin particles, silicone rubber particles, urethane particles, melamine-formaldehyde particles, and acrylic particles; rubber, wax, fatty acid compounds, resins, etc. and metals,
Composite particles composed of inorganic particles such as metal oxides, metal salts and carbon black; Fluorine resins such as polyethylene fluoride and polyvinylidene fluoride; Fluorine compounds such as carbon fluoride;
Fatty acid metal salts such as zinc stearate; fatty acid derivatives such as fatty acids and fatty acid esters; molybdenum sulfide, amino acids and amino acid derivatives.

The melt index (MI) of the toner of the present invention is preferably in the range of 3 to 40 g / 10 min.
0 g / 10 minutes is more preferable. Melt index is 4
If it is higher than 0 g / 10 minutes, wrapping around the fixing device or high-temperature offset may occur. Further, when used in a non-magnetic one-component developing system, rubbing between the toner carrier and the developing blade. In this case, the toner particles are significantly fused to the upper surface of the developing blade, and the fused material causes coating unevenness in the toner coat layer on the carrier, which results in development unevenness and streaks on the image, which is not preferable. If the melt index is less than 3 g / 10 minutes, the fixing temperature becomes too high, which may cause fixing failure. Further, cold offset is likely to occur, which is not preferable. To keep these balances good, the melt index is preferably in the range of 3 to 40 g / 10 minutes,
30 g / 10 minutes is more preferable. Therefore, when the melt index is within the range of the present invention, hot offset / cold offset is reduced, and even if an image is displayed for a long period of time, there is no image disturbance such as splattering or fixing tailing, and a good image can be obtained. I can.

Here, the melt index (MI (13
5 ° C., 2.2 kg)) is measured according to the Japanese Industrial Standard Thermoplastic Flow Test Method JIS K7210.
According to the description of, the measurement is performed by the manual cutting method under the following measurement conditions. At this time, the measured value is converted into a 10-minute value. Measurement temperature: 135 ° C. Load: 2.2 kg (21.6 N) Sample filling amount: 5-10 g

The method for measuring the synchronization / asynchronization of the external additive is as follows:
As a toner analysis method, the Annual Meeting of the Electrophotographic Society (95 times in total), "Japan Hardcopy '97" paper collection, "New External Evaluation Method-Toner Analysis by Particle Analyzer", Toshiyuki Suzuki, Toshio Takahara, Electrophotography It is preferable to use the toner analysis method disclosed by the academic society, July 9-11, 1997.

In this toner analysis method, the toner particles are introduced into the plasma to excite the toner particles, and the emission spectrum associated with the excitation is detected to perform the analysis.

According to this analysis method, it is possible to simultaneously detect the emission spectra associated with the excitation of a plurality of elements,
Furthermore, the periodicity of the emission spectrum can be measured.

The elements contained in the same particle generate an excitation light emission spectrum (synchronous spectrum) at the same period, while the element existing as a single substance such as the external additive free substance is not synchronized with the toner base. Produces an excitation emission spectrum (asynchronous spectrum) by itself. The relative synchronism / synchronism of the excitation and emission spectra derived from each of these elements was determined to determine the synchronism / asynchronism with respect to the toner base at that time.

In the present application, the count (number) of emission spectra accompanying excitation of carbon atoms derived from the mother particles and the count (number) of emission spectra associated with excitation of Si atoms derived from, for example, silica as an external additive. Based on the synchronization difference, the toner particles in synchronization are made to be the toner particles to which the external additive is attached,
Asynchronous toner particles were used as toner particles to which no external additive was attached. Then, the ratio of the number of counts in which three or more elements were synchronized was calculated from the total number of counts of synchronized particles in which two or more elements were synchronized.

As a concrete measuring method, Yokogawa Electric Co., Ltd.
Using PT1000 manufactured by C, after measuring under the following conditions, C
The synchronism of the emission spectrum count of Si atoms based on the atoms was measured by applying the following equation.

<< Measurement condition of PT1000 manufactured by Yokogawa Electric Co., Ltd. >> C-detection number in one measurement: 500 to 2500-Noise cut level: 1.5 or less-Sort time: 20 digits-Gas: O ₂ 0.1%, He gas-Analysis wavelength: C atom: 247.860 nm Si atom: 288.160 nm Ti atom: 334.900 nm Mg atom: 285.210 nm-Channel used: C atom: 1 or 2 Si atom: 1 Or 2 Ti atom: 1 to 4 Mg atom: 1 or 2

Incidentally, the adjustment of the synchronization ratio of the external additives depends on the type of external additives used, the amount of external additives, the charging characteristics, hardness, cohesiveness, particle size, etc. of each external additive. Therefore, it is adjusted by various methods, but in the present invention, it is adjusted by the order of external addition by dry external addition after the preparation of the matrix, the external addition time, the external addition strength, the temperature during external addition, and the sieving after external addition.

[0070]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples.

Example 1 First, a polymerized toner was prepared by the following procedure.

In 700 g of ion-exchanged water, 0.1 mol /
Add 500 g of Na ₃ PO ₄ aqueous solution at 50 ° C.
After heating to TK homomixer (made by Tokushu Kika Kogyo)
And was stirred at 10,000 rpm. 72 g of a 1.0 mol / liter CaCl ₂ aqueous solution was gradually added to this to obtain an aqueous medium containing Ca ₃ (PO ₄ ) ₂ .

The following formulation was heated to 60 ° C., and using a TK type homomixer (made by Tokushu Kika Kogyo), 9,000 rpm
Were uniformly dissolved and dispersed. -Styrene 160 parts by mass-n-butyl acrylate 40 parts by mass-C. I. Pigment Blue 15: 3 14 parts by mass, aluminum salicylate compound 2 parts by mass, saturated polyester 15 parts by mass, stearyl stearate 28 parts by mass, divinylbenzene 0.4 parts by mass

Polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) (5 parts by mass) was dissolved therein to prepare a polymerizable monomer composition.

The above polymerizable monomer composition was charged into the above aqueous medium and stirred at 60 ° C. under nitrogen atmosphere using a TK homomixer at 8,300 rpm to obtain the polymerizable monomer composition. Granulated.

Then, while stirring with a paddle stirring blade, the temperature was raised to 70 ° C. in 2 hours, and after 4 hours, the heating rate was 40 ° C./Hr.
The temperature was raised to 80 ° C. and the reaction was carried out for 5 hours. After the completion of the polymerization reaction, the residual monomer was distilled off under reduced pressure, and after cooling, hydrochloric acid was added to dissolve the calcium phosphate salt and filtered, and the particle diameter was adjusted by classification to obtain cyan toner base particles 1. .

To 100 parts by mass of the cyan toner base particles, 0.2 parts by mass of the external additive B was mixed at 2000 rpm for 5 minutes while maintaining the temperature of the Henschel mixer in the tank at 40 ° C., and then the temperature in the tank up to 10 ° C. While maintaining cooling, 1.5 parts by mass of the external additive A was mixed at 2000 rpm for 10 minutes,
The toner of the present invention was obtained by passing through a sieve having openings of 38 μm.

The weight average particle diameter of the toner was 6.6 μm, the average circularity was 0.965, the MI was 9.1 g / 10 minutes, and the three-element synchronization ratio was 32.5%.

A commercially available color laser printer LBP2040 (manufactured by Canon Inc.) was modified into the film fixing device described in the present application, and the toner carrying member was an elastic roller having a base layer of NBR. At this time, it was set so as to contact the latent image carrier and evaluated. The cyan cartridge of the above modified machine was filled with 150 g of toner, and a continuous printing test of 10,000 sheets was performed at a printing ratio of 2%. In each test, a solid black pattern, a solid white pattern, and a halftone image were printed as samples at the initial and 10000th sheets, and the images at that time were also confirmed. When the evaluation was performed with four colors, images were formed in the order of black, cyan, magenta, and yellow from the bottom layer of the transfer material.

Regarding each of the evaluation items, regarding the offset, A was that neither hot offset nor cold offset occurred, B was not generated in the image, and C was even generated even in the image. 1 for fog
Images after continuous printing of 0000 sheets are evaluated. If the fog is less than 1%, A is 1% or more and less than 3%, B is 3% or more 5
If it is less than%, it is ranked C, and if it is 5% or more, it is ranked D.
By the way, the fog value was obtained by measuring the reflected light on a solid white image with a reflectometer (manufactured by Tokyo Denshoku Co., Ltd.). Regarding filming, images after continuous printing of 10,000 sheets are evaluated, and if the number of prints by filming per 10 cm ² is less than 1, it is ranked A, if 1 or more and less than 3 is B, and if it is 3 or more, it is C. Divided.

Regarding the roughness of the edge portion due to scattering, the line image with a printing rate of 4% was continuously printed in a normal temperature and normal humidity environment, and then the photographic image was visually evaluated with a magnifying glass. Minor occurrence is B,
C is for the splatter that can be clearly seen, and D is a severe fog that can be confirmed without using a magnifying glass.

The fixing tailing was evaluated in the same manner as above.

Regarding the fixing failure, a rubbing test was conducted 10 times with a load of 250 g on solid black and halftone images, and the initial density at that time and the density after the test were measured with a Macbeth reflection densitometer RD918. Depending on the difference, A is less than 0.05, B is 0.05 or more and less than 0.1, and 0.
C was defined as 1 or more and less than 0.15, and D was defined as 0.15 or more.

Regarding the contamination of the charging member, A means that there was no contamination, and B means that the contamination did not appear in the image.
The case where the contamination appeared even in the image was designated as C. Further, regarding the fluffing of the toner, A means that it did not occur at all, A means that it did not appear in the image even if there was contamination inside the machine, and C that appeared even in the image.

Regarding the color reproducibility, if the color is dull or has a better color mixture than the image directly produced by a commercially available color laser printer LBP2040 (manufactured by Canon Inc.), it is A, and if it is equivalent, B is dull or a color mixture is recognized. If so, it was set to C.

The external additives are listed in Table 1, the toner composition and physical properties are listed in Table 2, and the evaluation results are listed in Table 3.

[Example 2] Instead of the external additive B, the external additive D
Evaluation was made in the same manner as in Example 1 except that was used. As described above, Table 1 shows the list of external additives, Table 2 shows the constitution and physical properties of the toner, and Table 3 shows the evaluation results.

Example 3 Evaluations were made in the same manner as in Example 2 except that the aluminum salicylate compound added was 5 parts by mass and the external additive C was used in place of the external additive A. As described above, Table 1 shows the list of external additives, Table 2 shows the constitution and physical properties of the toner, and Table 3 shows the evaluation results.

[Example 4] Instead of the external additive B, the external additive F
Evaluation was performed in the same manner as in Example 1 except that was used. As described above, Table 1 shows the list of external additives, Table 2 shows the constitution and physical properties of the toner, and Table 3 shows the evaluation results.

Example 5 Evaluations were made in the same manner as in Example 1 except that the aluminum salicylate compound added was 5 parts by mass and the external additive F was used in place of the external additive A. As described above, Table 1 shows the list of external additives, Table 2 shows the constitution and physical properties of the toner, and Table 3 shows the evaluation results.

Example 6 Evaluations were made in the same manner as in Example 2 except that the aluminum salicylate compound added was 5 parts by mass and the external additive F was used in place of the external additive A. As described above, Table 1 shows the list of external additives, Table 2 shows the constitution and physical properties of the toner, and Table 3 shows the evaluation results.

Example 7 100 parts by mass of styrene-butyl acrylate copolymer C.I. I. Pigment Yellow 93 7 parts by mass, behenyl behenate 3.5 parts by mass, aluminum salicylate compound 2 parts by mass After the above materials were premixed, melt kneading was performed by a twin-screw kneading extruder set at 125 ° C. After cooling the kneaded product, it is roughly pulverized, finely pulverized by a pulverizer using a jet stream, further classified by an air classifier, and finally a hybridization system (Nara Kikai Seisakusho)
Spheroidizing treatment was performed at 8300 rpm for 5 minutes. Evaluation was performed in the same manner as in Example 1 except that the toner base was used.

The particle diameter of the toner was 6.9 μm, the average circularity was 0.945, the MI was 27.3 g / 10 minutes, and the three-element synchronization ratio was 51.3%.

The list of the external additives is shown in Table 1, the constitution and physical properties of the toner are shown in Table 2, and the evaluation results are shown in Table 3.

[Example 8] Evaluation was made in the same manner as in Example 1 except that the amount of stearyl stearate used was 1.9 parts by mass. As described above, Table 1 shows the list of external additives, Table 2 shows the constitution and physical properties of the toner, and Table 3 shows the evaluation results.

Example 9 Evaluations were made in the same manner as in Example 1 except that the amount of stearyl stearate used was 47.4 parts by mass. As described above, Table 1 shows the list of external additives, Table 2 shows the constitution and physical properties of the toner, and Table 3 shows the evaluation results.

Example 10 Evaluation was carried out in the same manner as in Example 2 except that the external additive F was used in place of the external additive A and the external additive G was used in place of the external additive B. did. As described above, Table 1 shows the list of external additives, Table 2 shows the constitution and physical properties of the toner, and Table 3 shows the evaluation results.

[Embodiment 11] Evaluation was carried out in the same manner as in Embodiment 1 except that images were formed in the order of yellow, magenta, cyan and black from the lowermost layer of the transfer material. The list of external additives is shown in Table 1, and the composition and physical properties of toner are shown in Table 2.
Table 3 shows the evaluation results.

[Example 12] Evaluation was carried out in the same manner as in Example 10 except that image formation was performed in the order of magenta, cyan, black, and yellow from the lowermost layer of the transfer material. The list of external additives is shown in Table 1, and the composition and physical properties of toner are shown in Table 2.
Table 3 shows the evaluation results.

Example 13 Divinylbenzene was added to 0.3
Mass part, and the pigment is C.I. I. Pigment Blue instead of C.I. I. Evaluation was performed in the same manner as in Example 1 except that Pigment Red 122 was used. As described above, Table 1 shows the list of external additives, Table 2 shows the constitution and physical properties of the toner, and Table 3 shows the evaluation results.

Example 14 Divinylbenzene was added to 0.5
Mass part, and the pigment is C.I. I. Example 1 except that carbon black was used instead of pigment blue
It evaluated similarly to. As described above, Table 1 shows the list of external additives, Table 2 shows the constitution and physical properties of the toner, and Table 3 shows the evaluation results.

[Comparative Example 1] Evaluation was made in the same manner as in Example 1 except that only A was used as the external additive. The list of external additives is shown in Table 1, and the composition and physical properties of toner are shown in Table 2.
Table 3 shows the evaluation results.

[Comparative Example 2] Evaluation was carried out in the same manner as in Example 1 except that the aluminum salicylate compound added was 5 parts by mass, and the external additive used was only C and the external additive was the same as external additive A. did. As described above, Table 1 shows the list of external additives, Table 2 shows the constitution and physical properties of the toner, and Table 3 shows the evaluation results.

[Comparative Example 3] Evaluation was carried out in the same manner as in Example 1 except that the aluminum salicylate compound added was 5 parts by mass and the external additive used was only D and the external additive was added in the same manner as the external additive A. did. As described above, Table 1 shows the list of external additives, Table 2 shows the constitution and physical properties of the toner, and Table 3 shows the evaluation results.

[Comparative Example 4] Evaluation was carried out in the same manner as in Example 1 except that the external addition order of the external additive A and the external additive B was reversed and the temperature during external addition was kept at 10 ° C. did. As described above, Table 1 shows the list of external additives, Table 2 shows the constitution and physical properties of the toner, and Table 3 shows the evaluation results.

[Comparative Example 5] Evaluation was carried out in the same manner as in Example 1 except that the external additive B was 0.4 parts and the external addition time was 10 minutes. As described above, Table 1 shows the list of external additives, Table 2 shows the constitution and physical properties of the toner, and Table 3 shows the evaluation results.

[Comparative Example 6] Evaluation was made in the same manner as in Example 1 except that the amount of divinylbenzene was changed to 0.6 part by mass. As described above, Table 1 shows the list of external additives, Table 2 shows the constitution and physical properties of the toner, and Table 3 shows the evaluation results.

[Comparative Example 7] Evaluation was made in the same manner as in Example 1 except that 0.2 part by mass of divinylbenzene was used. As described above, Table 1 shows the list of external additives, Table 2 shows the constitution and physical properties of the toner, and Table 3 shows the evaluation results.

[Comparative Example 8] Evaluation was carried out in the same manner as in Comparative Example 1 except that the color order of the images was changed from the bottom layer of the transfer material to yellow, magenta, cyan, and black. As described above, Table 1 shows the list of external additives, Table 2 shows the constitution and physical properties of the toner, and Table 3 shows the evaluation results.

[0110]

[Table 1]

[0111]

[Table 2]

[0112]

[Table 3]

[0113]

As described above, according to the present invention,
The visible image on the recording material is heat-fixed by a heating member fixed at an appropriate position and a pressing member that is pressed against the heating member to bring the recording material into close contact with the heating member via a heat-resistant fixing thin film. In an image forming apparatus having a heating and fixing device, it is possible to improve the scattering, fixing trailing, and fixing failure when using a film fixing device, and to prevent fog in the latter half of durability, contamination of charging members, offset, filming, and fluffing. It was possible to obtain a full-color one-component toner in which the color reproducibility was improved without any occurrence.

[Brief description of drawings]

FIG. 1 is a schematic view of a fixing device according to the present invention.

[Explanation of symbols]

1 fixing film 3 pressure roller

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kenichi Nakayama             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation F-term (reference) 2H005 AA06 AA08 AA15 AA21 CA14                       CB07 CB13 EA07 EA10 FA07                 2H033 AA02 AA09 BA11 BA12 BA26                       BE03

Claims (12)

[Claims] 1. A recording material comprising at least a heating body fixed at an appropriate position and a pressing member which is brought into pressure contact with the heating body to bring the recording material into close contact with the heating body through a heat-resistant fixing thin film. A toner used in an image forming apparatus having a heat fixing device that heat-fixes the above-described visible image, wherein the melt viscosity MI by a melt indexer is 3 to 40, and the external additive A and the external additive A containing different inorganic elements are used. Additive B
And a value of the following calculation formula in the measurement with a particle analyzer is 5 to 60%. (Count number in which three elements of toner-derived carbon, external additive A and external additive B are synchronized / total number of synchronized particles) × 100
(%) 2. An external additive A or B used for the toner.
The one-component toner for full color according to claim 1, wherein one of the inorganic elements is Si. 3. An external additive A or B used for the toner.
The one-component toner for full color according to claim 1 or 2, wherein one of the inorganic elements is Ti. 4. An external additive A or B used for the toner.
4. The full-color one-component toner according to claim 1, wherein one of the inorganic elements is Mg. 5. The toner according to claim 1, wherein the average circularity of the toner is 0.950 or more and less than 0.995.
The one-component toner for full color according to any one of 1. 6. The full-color one-component toner according to claim 1, wherein the wax content of the toner is 1% by mass or more and 15% by mass or less. 7. A recording material comprising at least a heating body fixed at an appropriate position and a pressing member which is brought into pressure contact with the heating body to bring the recording material into close contact with the heating body through a heat-resistant fixing thin film. In an image forming method having a heat fixing device that heat-fixes the upper visible image, the image is transferred from the lowermost layer of the transfer material to black, cyan, magenta,
The toner is fixed in the order of yellow, the toner has a melt viscosity MI of 3 to 40 by a melt indexer, and the toner contains toners containing an external additive A and an external additive B each containing a different inorganic element. An image forming method, wherein a full-color one-component toner having a value of the following calculation formula of 5 to 60% in the measurement by an analyzer is used. (Count number in which three elements of toner-derived carbon, external additive A and external additive B are synchronized / total number of synchronized particles) × 100
(%) 8. An external additive A or B used for the toner.
The image forming method according to claim 7, wherein one of the inorganic elements is Si. 9. An external additive A or B used for the toner.
9. The image forming method according to claim 7, wherein one of the inorganic elements is Ti. 10. The image forming method according to claim 7, wherein the inorganic element of either the external additive A or B used in the toner is Mg. 11. The image forming method according to claim 7, wherein the average circularity of the toner is 0.950 or more and less than 0.995. 12. The toner has a wax content of 1% by mass.
12. The image forming method according to claim 7, wherein the content is 15% by mass or less.