JPH02294667A - Method for fixing toner image for full color - Google Patents

Abstract

PURPOSE:To prevent high-temperature offset from occurring by providing a means for setting a blank paper ejecting direction nearer to a pressurizing roller side than the vertical direction to a line combining the centers of a fixing roller and a pressurizing roller when the blank paper is allowed to pass as a fixing device. CONSTITUTION:The fixing roller and the pressurizing roller are the thermal roller fixing device having a rubber-like elastic layer on the core bar. When the blank paper is allowed to pass, the paper ejecting direction is set nearer to the pressurizing roller side than the vertical direction to the line combining of the centers of the fixing roller and the pressurizing roller. A way the hardness of the pressurizing roller is made higher than that of the fixing roller or a way the diameter of the fixing roller is made larger than that of the pressurizing roller or the like is mentioned as the method. Furthermore, by attaching a heating device not only to the fixing roller side but also the the pressurizing roller side, 'rotation in consort' is reduced as compared with the case that the heating device is attached only to the fixing roller side. Thus, the offset does not occur even after an image producing test, for example, the printing resisting test of 30000 sheets.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an electrophotographic toner, and more particularly to a method for fixing a full-color toner image in which the durability of a fixing roller is significantly improved.

[Prior Art] Conventionally, as an electrophotographic method, US Pat.
Although a number of methods are known, as described in Japanese Patent No. 24748, in general, a photoconductive substance is used to form an electrical latent image on a photoreceptor by various means, and then the latent image is The image is developed using toner, and if necessary, the toner image is transferred to a transfer material such as paper, and then fixed by heating or pressure to obtain a copy.

Furthermore, various developing methods are known in which an electrical latent image is visualized using toner.

For example, the magnetic brush method described in U.S. Pat. No. 2,874,063, the cascade development method described in U.S. Pat.
A large number of developing methods are known, such as the Jambi Shigou brush developing method described in No. 70 and the liquid developing method. Toners used in these developing methods have conventionally been fine powders in which dyes and pigments are dispersed in natural or synthetic resins.
Furthermore, it is also known to use a developing fine powder to which a third substance is added for its own purpose.

In recent years, there has been a rapid shift from monochrome copying machines to full-color copying machines, and two-color copying machines and digitalized full-color copying machines are also being released in the market. Color image formation using full-color electrophotography generally uses three primary colors: yellow, magenta. All colors are reproduced using three color toners (cyan) or four colors including black. The general method is to first form an electrostatic latent image on a photoconductive layer by passing light from an original through a color-separating light transmitting filter having a complementary color to the toner color. The toner is then held on the support through development and transfer steps. The above-described steps are then repeated several times in sequence, and the toners are superimposed on the same support while registering, and a final full-color image is obtained by fixing only once.

In color electrophotography, which requires multiple development steps and the overlapping of several toner layers of different colors on the same support in the fixing process, the fixing properties that color toners should have are extremely important. This is an important element.

That is, the fixed color toner needs to suppress diffused reflection due to toner particles as much as possible and have appropriate gloss and luster.

In addition, the color toner must have transparency that does not interfere with toner layers of different tones located below the toner layer, and must have a wide color reproducibility.

As a color toner that satisfies these requirements, the present applicants have published Japanese Patent Application Laid-Open No. 50-62442 and Japanese Patent Application Laid-open No. 511-N462.
Publication No. 5. JP-A-59-57251i has disclosed a novel combination of a color binder resin and a colorant.

The color toners described above have considerable sharp melting properties, and upon fixing, the shape of the toner changes to a state close to complete melting, resulting in favorable gloss and color reproducibility. However, offset resistance is still not sufficient.

Fixing rollers can be roughly divided into silicone rubber rollers and Teflon-coated rollers, but especially when using silicone rubber rollers as fixing rollers, the wood-like silicone rubber surface may peel off due to repeated use, regardless of whether or not the molding oil is applied. Due to the decrease in moldability, high temperature offset is more likely to occur. In the silicone rubber roller, a certain degree of mold releasability can be maintained at the initial stage of use due to the smoothness and cleanliness of the roller surface. However, as color copies continue to be copied, where the image area is large and the amount of toner retained on the support is much larger than that of black and white copies, the releasability of the roller gradually decreases. The speed at which this mold releasability deteriorates is several times that of black and white copying. As a result, a toner film or granular deposits are not formed on the roller surface after only a few thousand to tens of thousands of copies, or a so-called high-temperature offset occurs in which the upper layer of toner on the image surface is peeled off when the heated roller passes. .

On the other hand, Teflon-coated rollers have excellent durability, but they tend to spread the toner under pressure, and therefore have the disadvantage of reducing the resolution of copied images and making background stains more noticeable. .

In order to improve these defects, lOO~30
There is one coated with a PFA (barfluoroalkoxy resin) tube of 0 μm (Japanese Patent Publication No. 58-43740). When these rollers are used, the reduction in resolution of copied images due to toner spreading is improved. However, in general, when a Teflon Co. 1 type roller is used as a fixing roller, a pressure roller whose outer circumferential surface of a core metal is coated with a relatively thick layer of elastic material such as rubber is generally used.

In this case, contrary to what is shown in Figure 1, the direction in which the paper is ejected from the fixing roller after being fixed is perpendicular to the line connecting the centers of the fixing roller and the pressure roller is on the fixing roller side. There is.

For this reason, even if the fixed image passes through the nip where the fixing roller and the pressure roller are in contact, it is dragged by the fixing roller, causing a so-called "tangle" phenomenon and offset. This can be prevented. For this reason, there is a method of attaching a separation piece for paper ejection, but this separation piece is in contact with the fixing roller and can cause scratches or leave streaks on the image surface, especially for photos with a large image area. When copying full-color images such as images, the image quality will be significantly degraded.

Various measures have been attempted for fixing devices and toner to solve or alleviate this problem, but it cannot be said that a sufficient solution has been achieved yet.

As the fixing device, a material with excellent surface releasability is used. Alternatively, methods such as applying oil to the rollers have been devised, and most of the thermal roller fusers of copying machines that are currently not commercially available use some form of oil application. However, applying a large amount of oil to improve mold releasability causes undesirable problems such as oil stains on the sheet and increased cost.

In addition, in order to increase releasability, low molecular weight polyethylene or wax that melts sufficiently when heated is added to the toner, but although it is effective in preventing offset, the addition of large amounts may cause color toner problems. Adverse effects such as impairing the transparency of the Of{P image, making the charging characteristics unstable, and decreasing durability are also observed, and it is difficult to say that it is sufficient.

In addition, a problem unique to color copying is that the color balance of at least three color toners, preferably four colors, must be harmonious, and therefore each color must be balanced in terms of fixing characteristics and color reproducibility. It must be something. In principle, yellow is one of the three primary colors. If there are three colors, magenta and cyan, it should be possible to reproduce almost all colors using the subtractive color mixing method.Therefore, current full-color copying machines on the market are configured to use 3yX color toners superimposed. It becomes. Ideally, this would allow any color to be achieved in any density range;
In reality, there are still issues to be improved, such as the spectral reflection characteristics of toner, color mixing when toner is plated and fixed, and a decrease in chroma.

When obtaining black by combining three colors, three times as many toner layers are formed on the transfer paper as in the case of a single color, as described above, and offset resistance is also difficult to obtain.

However, the inventors of the present invention have carried out intensive research to complement improvements in color toners and fixing devices, and have discovered the following.

That is, when a pigment colorant is used for color toner,
Contamination of the fixing roller is significantly reduced compared to those using dye-based colorants. Therefore, the durability of the fixing roller is also improved. However, when only pigment-based colorants are used, especially for magenta toner, the resulting images have low saturation and poor color reproducibility.

Regarding magenta toner and fixing properties, the present applicant published JP-A-82
-45555-7, by using a rhodamine-based basic dye alone or together with M14, it is possible to significantly improve the dye offset on the silicone rubber fixing roller compared to the rhodamine-based oil-soluble dye. showed that.

However, as a result of detailed studies by the present inventors, the use of rhodamine-based basic dyes alone forms salts that easily dissociate in water, resulting in poor charging characteristics and being affected by environmental factors such as temperature and humidity. I realized that I would be greatly affected by this. Furthermore, although it is possible to increase the saturation with a toner that uses a combination of pigment and dye, it has drawbacks because it is a combination system.

This is because the dye and pigment used have poor affinity, so they repel each other in the binder resin during the dispersion process, making it difficult to make the color tone uniform. In addition, since the compatibility of each dye and pigment with the binder resin is not uniform, both dyes and pigments will not be in the same dispersion state at the same time.
The pigment may be poorly dispersed, or the dispersion time may be too long, making it easy for the dye to separate. If a toner with colorants unevenly distributed in this way is used as a toner, it will have poor charging characteristics for electrophotography, cause fogging, contamination due to toner scattering inside the machine, and even reduce the transparency of the 011P image. I also understood that. Furthermore, in the examples of JP-A-62-15555-7, a phenol resin is used as a charge control agent, and a combination system of rhodamine-based basic dye and pigment is used as a coloring agent, and dyeing offset on a silicone rubber roller is shown. It was shown that this does not occur at all.

However, as mentioned above, toner with poor colorant dispersion and poor charging properties has a tendency to aggregate, and especially during development, the toner adheres to the surroundings of the carrier, causing the carrier to be developed along with the toner. A phenomenon called "carrier pull" occurs.

Therefore, the present inventors conducted extensive research and found that by using a dye treated with phenolic resin in a pigment-dye combination system, dye migration could be prevented, and color reproducibility and fixing properties would be good. This led to the invention of color toner.

This is presumed to be due to the following reasons.

The composition of the magenta toner in the present invention is disclosed in Japanese Patent Application Laid-Open No. 62-1
Although it is similar to the example of No. 5555-7, there is a case where a toner is obtained by kneading a dye that has been treated with a phenol resin in advance with a pigment, a binder resin, etc. The dispersion state of the colorant is completely different from the case where a toner is obtained by kneading resins all at once. Although this is not clear, it is thought that the interaction between the phenolic resin and the dye changes depending on the presence of the pigment and binder resin. This is because, as shown in the comparative example, no effect of improving fixing properties was observed by adding phenolic resin, indicating that simply adding phenolic resin during kneading is not effective. As a result, as mentioned above, even if the system is a combination of pigment and dye and contains phenolic resin, those with poor dispersion will
A phenomenon called "carrier pulling" occurs, and when this carrier passes through the fusing device, especially in the case of silicone rubber rollers, the carrier becomes embedded in the rubber, which ultimately shortens the life of the fusing roller. It turns out. Therefore, the properties of the toner will be completely different depending on whether the dye is pretreated with a phenolic resin or not.

Furthermore, the present inventors have discovered that in a fixing device consisting of a fixing roller and a pressure roller, when a blank sheet is passed through, the paper is ejected in a direction perpendicular to a line connecting the centers of the fixing roller and the pressure roller. By placing it on the roller side,
It has been found that it is possible to prevent "tangling" of the fixed image surface caused by the fixing roller.

By using this fixing device and the power toner,
It has been found that it is possible to obtain copied images with good color reproducibility and to dramatically extend the durability of the fixing roller.

[Problems to be Solved by the Invention] In view of the above-mentioned problems, an object of the present invention is to provide a method for fixing full-color toner images that exhibits good fixing properties and color mixing properties in full-color copying.

Another object of the present invention is to provide a method for fixing full-color toner images having sufficient triboelectric charging properties.

Another object of the present invention is to provide a method for fixing full-color toner images that significantly improves image quality and gloss.

Another object of the present invention is to provide a method for fixing a full-color toner image that has excellent durability and is resistant to carrier waste even during repeated copying. Another object is to provide a fixing method that sufficiently prevents high temperature offset and has a wide fixable temperature range.

Another object of the present invention is to provide a fixing method that maintains offset resistance even when the fixing sheet is passed repeatedly.

[Means and effects for solving the problems] The present invention is characterized by the magenta toner. In a method for fixing a full-color toner image formed by multicolor electrophotography using at least two of cyan toner, yellow toner, and black toner, the magenta toner is treated with a quinacridone pigment and a phenol resin. a toner having polyester resin particles containing a xanthine dye and a flow improver; the cyan toner is a toner having a flow improver and polyester resin particles containing a copper phthalocyanine blue pigment; the yellow toner is a toner having polyester resin particles containing an azo yellow pigment and a flow improver; the black toner is a toner having a flow improver and a polyester resin containing carbon black as a coloring agent; and a fixing roller and a flow improver. The pressure roller is a heat roller fixing device with a rubber-like elastic layer on its core, and the paper discharge direction when passing blank paper is a line connecting the centers of the fixing roller and the pressure roller. The present invention provides a method for fixing a full-color toner image, in which the full-color toner image is fixed using a fixing device that is arranged so as to be closer to the pressure roller than in the vertical direction.

The present invention will be specifically explained in detail below.

The composition of the polyester resin for full strength toner used in the present invention is as follows.

That is, such a composition is 45 to 55 mo1% of the total components.
is the alcohol component, and 55 to 45 moρ% is the acid component.

Alcohol components include ethylene glycol, brobylene glycol, l3-butanediol, l,4-butanediol, 2,3-butanediol, diethylene glycol. Triethylene glycol. I,5-pentanediol, I,6-hexanediol, neobentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, and bisphenol derivatives represented by the formula (Al); (wherein R is is an ethylene or brobylene group, x and y are each an integer of 1 or more, and x
The average value of +y is 2 to 10) Also, diols represented by formula (B): Diols such as glycerin. Examples include polyhydric alcohols such as sorbitol and sorbitan. In addition, examples of divalent carboxylic acids containing 1% or more of 501Ilo in the total acid components include phthalic acid. Terephthalic acid, isophthalic acid. Benzenedicarboxylic acids or their anhydrides such as phthalic anhydride; succinic acid. Adivic acid, sebacic acid. Alkyl dicarboxylic acids such as azelaic acid or their anhydrides; succinic acid or its anhydride substituted with an alkyl group having 6 to 18 carbon atoms; fumaric acid, maleic acid,
Examples include unsaturated dicarboxylic acids such as citraconic acid and itaconic acid, or their anhydrides, and examples of trivalent or higher carboxylic acids include trimellitic acid, biromellitic acid, penzophenonetetracarboxylic acid, and their anhydrides. can be mentioned.

The alcohol component of the polyester resin particularly preferred for carrying out the present invention is a bisphenol bladder conductor represented by the above formula (^), and the acid component is phthalic acid. Terephthalic acid. Isophthalic acid or its anhydride; dicarboxylic acids such as succinic acid, rhodecenylsuccinic acid or its anhydride, fumaric acid, maleic acid, and maleic anhydride. Examples include tricarboxylic acids such as trimellitic acid or its anhydride.

This is because polyester resins obtained with these acid dialcohols exhibit sharp melting characteristics, good color mixing properties as toners for full color and hot roller fixing, and excellent anti-offset properties.

Furthermore, the glass transition temperature of the polyester resin obtained here is 50 to 75°C, preferably 55 to 65°C, and the number average molecular ffiMn is 1.500 to 7,000, preferably 2,000 to 5,000. Average molecular weight M
l1 6,000 to 150,000 preferably 10,
000 to 100,000 is desirable. In addition, its acid value is 90 or less, preferably 50 or less, 011
It is desirable that the value is 50 or less, preferably 30 or less. This is because when the number of terminal groups in the molecular chain increases, the environmental dependence of the toner's charging characteristics becomes more severe when it is made into a toner. The magenta quinacridone pigment and xanthine dye used in the present invention are as follows. Typical examples of quinacridone pigments include the following: C. I. Basic Violet 11-1
There are U etc. Among them ■. C.I. Pigment Re
d 122 is particularly suitable as a magenta colorant.

Further, representative examples of the xanthine dye used in the present invention include the following.

All of ■ to ■ have a clear bluish pink color.

■． ■Because it is a basic dye, it has some hygroscopicity.
Furthermore, considering the compatibility with the resin, in the present invention,
It is oil-soluble, has excellent compatibility with resins, has high coloring power, and has a strong C.I. I. Solvent Red 49. is especially common. Further, the phenol resin for quinanthene dye treatment used in the present invention has the following heptanomer composition.

Examples of phenols include phenol, cresol, xylenol, alkylphenol, paraphenylphenol, bisphenol A, etc.Aldehydes include formaldehyde, paraformaldehyde, etc. Hexamethylenetetramine. All known ones such as furfural can be used.

Among these, it is particularly preferable to use a phenol resin, which is a condensate of tart-butylphenol and formaldehyde, because the dye is dispersed in a good state.

The method of treating the xanthine dye with the phenol resin in the present invention is as follows: (1) The xanthine dye and the phenol resin are mixed in a two-mouth Lumir or Banbury mixer. (2) Dissolve the phenol resin in a suitable solvent, dissolve or disperse the xanthine dye therein, and then remove the solvent.
(3) A method of dissolving and decomposing a xanthine dye in a mixture of phenol and formaldehyde, adding an alkali and heating to make it three-dimensional, (4) A method of dissolving and dispersing a xanthine dye in a mixture of phenol and formaldehyde, An example of this method is to prepare a novolac resin under an acid catalyst and then cure it by adding a crosslinking agent such as hexamethylenetetramine.

The xanthine dye treated with the phenol resin by these methods is dried and pulverized, and then melt-kneaded with a polyester resin as a binder resin to be uniformly dispersed.

Further, in the present invention, when treating a xanthine dye with a phenol resin, a quinacridone pigment can also be dispersed and treated in the same manner as the xanthine dye. Furthermore, in the present invention, when a xanthine dye is treated with a phenol resin, the polyester resin can also be melted or dissolved when the quinanthene dye is melted, dissolved, or dispersed.

The copper phthalocyanine blue pigment used in the present invention includes C.I. I. Pigment Blue 15, C. I. Pigment Blue-16, C. I. Pigment Blue 17 or ■
These include copper phthalocyanine pigments in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton having the structure shown by the formula.

■． Copper phthalocyanine pigment n+al ~ 5 As the azo yellow pigment used in the present invention, c. r.
Pigment Yellow 1, C. I. Pigment Yellow 2, C. I. Pigment Yellow 3, C. I. Pigment Yellow 4. C. I. Pigment yellow 5, C
．． I. pigment yellow a, c. r. Pigment Yellow 7, CA. pigment yellow to, C. I. Pigment Yellow 11, C. I. Pigment Yellow 12,C. I. Pigment Yellow 13, C. I. Pigment Yellow 14, C. I. Pigment Yellow 1.5, C. Examples include L Pigment Yellow 17. The content is O} For yellow toner, which sensitively reflects the transparency of IP film, binder resin 1
The amount is 12 parts by weight or less, preferably 0.5 to 7 parts by weight.

If it exceeds 12 parts by weight, the reproducibility of green and red, which are mixed colors of yellow, and human skin tones in images will be poor. For other magenta and cyan color toners,
The amount is desirably 15 parts by weight or less, more preferably 0.1 to 9 parts by weight, based on 100 parts by weight of the binding resin.

In particular, for black toners that use two or more colorants in combination, adding a total colorant amount of 20 parts by weight or more will not only tend to cause the carrier to be spent, but also cause the colorant to be present in large numbers on the toner surface. Excessive exposure also increases concerns about toner adhesion to the drum and fixing performance. Therefore, the amount of the colorant is preferably 3 to 15 parts by weight per 100 parts by weight of the binder resin.

The particle size of carbon black used as a colorant for black toner is 50 to 70 mμ, preferably 50 to 60 mμ.
μ. Toner containing carbon black with a particle size of less than 501 has a yellowish chromaticity, and not only is it impossible to obtain a sharp black color, but it is also extremely difficult to disperse carbon black, which is exposed on the toner surface. Carbon black becomes non-uniform.

Therefore, the adhesion of the fluidity improver deteriorates and the fluidity is significantly reduced, making it impossible to obtain a good amount of triboelectric charge, resulting in fogging and toner scattering. In addition, the particle size is 70m
If it exceeds μ, the blackness of the carbon black is low.
An image with vivid black color cannot be obtained.

In addition, the oil absorption rate of this carbon black is 50 to 100.
cc/100g, preferably 60 to 80cc/
It is 100g. When the oil absorption exceeds 100cc/100g, the carbon black structure becomes longer.
As the conductivity increases, the amount of triboelectric charging of the toner decreases, causing fogging and scattering. Also, the oil absorption amount is 50cc/
If it is less than IOOg, high image density cannot be obtained.

The carbon black contained in the resin binds to the binder resin 1.
00, [2.1 to 10.0 parts by weight, preferably 3.0 to 6.0 parts by weight, per 1 part by weight. If the carbon black content is less than 2.1 parts by weight, high image density cannot be obtained, solid area uniformity decreases, and ro. If the amount of offi is exceeded, a sufficient amount of 1% F current cannot be obtained.

In measuring the physical properties of the carbon black, the particle size was measured by directly and selectively counting the particle size in a scanning electron micrograph.

The method for measuring oil absorption is as described below. 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. In this case, a colorless or light-colored negative charge control agent that does not affect the color tone of the toner is preferred. Examples of negative charge control agents include organic gold R complexes such as gold R complexes of alkyl-substituted salicylic acids (eg, chromium complexes or zinc complexes of tertiary butyl salicylic acid). When a negative charge control agent is added to the toner, it is added in an amount of 0.000 parts by weight per 100 parts by weight of the binder resin.
It is good to add 1-10 parts by weight, preferably 0.5-8 parts by weight.

Particle size distribution of the classified products of magenta toner, cyan toner, yellow toner, and black toner obtained using the above-mentioned materials (colorant-containing resin particles without flow improvers such as silica, aluminum oxide, and titanium oxide, which will be described later). The volume average particle size is 4.0 to 16.0 μm1 based on the quality of the copied image.
Preferably 6.0 to 14.0 μm, number average distribution 5.
04 μm or less is 50% or less, preferably 40% or less, 20.2 μm or more in the volume average distribution is 9% or less, preferably 5% or less, and the ratio α of the volume average particle size to the number average particle size is (α; volume average particle size/number average particle size) is 1
．． It is desirable that it be 7 or less, preferably 1.4 or less.

As the fluidity improver used in the present invention, any fluidity improver can be used as long as the fluidity improves when added to the colorant-containing resin particles when comparing before and after addition.

For example, fluororesin powders such as pinylidene fluoride fine powder, polytetrafluoroethylene fine powder, etc.; or fatty acid metal salts such as zinc stearate, calcium stearate, lead stearate, etc.; or metal oxides such as aluminum oxide, oxidized aluminum, etc. titanium, zinc oxide powder, etc.; or powdered silica, that is, wet-processed silica, dry-processed silica, and treated silica in which these silicas are surface-treated with a silane coupling agent, a titanium coupling agent, silicone oil, etc.

A preferred flow improver is a fine powder produced by vapor phase oxidation of a silicon halide compound, so-called dry process silica or fumed silica, which is produced by conventionally known techniques. For example, it utilizes the thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame, and the basic reaction formula is as follows.

SiCf, + 2 82+ 02→Si02+ 4 H
GR Also, preferred flow improvers include aluminum oxide and titanium oxide, which are obtained in the same manner as in the above manufacturing process.

The particle size is 0.001 to 2 μm as the average primary particle size.
It is desirable that it be within the range of 0.0, particularly preferably 0.0
It is best to use fine powder within the range of 0.02 to 0.2 μm. Commercially available silica fine powders produced by vapor phase oxidation of silicon halogen compounds used in the present invention include those commercially available under the following trade names, for example.

^EROSIL 130 (
Nippon Aerosil Co., Ltd.) 200 TT600 MOX170 vox ao COκ 84 Ca-0-SiL (CA [lOcho Go. Co., Ltd.) M- 5 MS- 7 MS-75 1 {S- 5 EH- 5 Wacker HDK N 20 (WACKER
-Cl {EMIE GMBI1) V15 N20E T30 T40 D-G Fine Silica (Dow Corning Go.) Fransol (FrancsH) Furthermore, the silica fine powder produced by vapor phase oxidation of the silicon halogen compound was subjected to hydrophobization treatment. It is more preferable to use treated silica fine powder.

Among the treated silica fine powders, it is particularly preferred that the silica fine powders be treated so that the degree of hydrophobicity as measured by a methanol titration test is in the range of 30 to 80.

Hydrophobization is achieved by reaction with fine silica powder or chemical treatment with organic silicon compounds that physically adsorb. In a preferred method, fine silica powder produced by vapor phase oxidation of a silicon halide is treated with an organosilicon compound.

Examples of such organosilicon compounds are hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane,
Allyl phenyldichlorosilane, benzyldimethylchlorosilane, promomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, ρ-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylbutane, trimethylsilylbutane, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane,
Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane and siloxane having 2 to 12 siloxitin units per molecule, each having one molecule at the terminal position. Examples include dimethylborisiloxane containing a hydroxyl group bonded to Si. These can be used alone or in a mixture of two or more. The particle size of the treated silica fine powder is 0.003-0.
It is preferable to use one in the range of 1 μm.

Commercially available products include Taranox 500 (Talco),
Eight EHOSTL R-972 (Japan Aerosil Co., Ltd.)
and so on. The amount added to the colorant-containing resin particles is as follows:
oo 0.0 parts by weight. Ol to 10 parts by weight, preferably 0.1 to 5 parts by weight. If the amount is less than 0.0 parts of Ol, there is no effect on improving fluidity, and 10 parts of Ol! Exceeding the limit will promote fogging, smearing of letters, and scattering inside the aircraft. As for the fixing device used in the present invention, when a blank sheet of paper is passed through, the paper can be printed in green if the paper is ejected in a green direction that is closer to the pressure roller than in a direction perpendicular to the line connecting the centers of the fixing roller and the pressure roller. It can be used for inventions. Examples of ways to make the paper ejection direction be on the pressure roller side are: (1) Making the pressure roller harder than the fixing roller (methods to increase the pressure roller hardness include:
(i) A method in which the hardness of the elastic body attached to the core bar is higher than that of the fixing roller; (11) When using the same elastic body as the fixing roller, by making it thinner than the elastic layer thickness of the fixing roller. There is a method of making it hard as a roller. ) ■ Make the diameter of the fixing roller larger than the diameter of the pressure roller.

Furthermore, by attaching the heating device not only to the fixing roller side but also to the pressure roller side, it is possible to significantly reduce the "entanglement" compared to a case where the heating device is attached only to the fixing roller side.

As a fixing device incorporating these methods, for example, a fixing roller with a silicone rubber elastic body and an RTV or L
To reduce the swelling of the rubber caused by the roller or fixing oil of TV J ¥1713, HTVi is provided in the lower layer, and nTV or LTV is provided in the upper layer to improve wetting with the fixing oil.
The rubber hardness (
JTS-^) is 30 to 70 degrees, preferably 35 to 60 degrees (in the case of two layers, when the two layers are combined), and the layer thickness is 0.5 to 5 IIlffl, preferably 1.0 to 3. 5m
The pressure roller has a hardness of 40 degrees or more, preferably 50 degrees or more, and may be made of silicone rubber, fluororubber, or Teflon coated.

In addition, for the purpose of improving fixing oil resistance and abrasion resistance, the fixing roller may have a two-layer structure such as silicone rubber-fluororubber system, silicone rubber or fluororubber-Teflon coat system, or silicone rubber or fluorine rubber. It is also possible to use a material having a three-layer structure such as Muteflon coat silicone rubber, but in this case as well, it is important that the hardness falls within the above-mentioned range.

The diameter of the fixing roller cannot be made too large because copying machines are required to be smaller. Furthermore, if the constant roller diameter is made small, the nip cannot be sufficiently maintained, and the toner will not be sufficiently melted, resulting in poor color mixing, or the fixing speed will have to be lowered to improve color mixing. Therefore, the diameter of the fixing roller and pressure roller is 40 to 8
h+aφ is appropriate. Below, each measurement method in the present invention will be described.

(1) Measurement of glass transition temperature Tg In the present invention, measurement is performed using a differential thermal analysis measuring device (DSC measuring device), DSC-7 (manufactured by Birkin Elmer). Precisely weigh 5 to 20 mg of the sample to be measured, preferably IOm3. This is placed in an aluminum van, and using an empty aluminum van as a reference, the measurement is carried out at room temperature at a temperature increase rate of 10° C./min within the measurement temperature range of 30° C. to 200° C.

In this temperature raising process, a main endothermic peak in the temperature range of 40 to 100°C is obtained.

The intersection point between the line at the midpoint of the baseline before and after the endothermic peak appears and the differential thermal curve is defined as the glass tipping temperature Tg in the present invention.

(2) Measurement of molecular weight distribution In the present invention, high performance liquid chromatography (JASCO TRI ROTAR-VT HPL manufactured by JASCO Corporation)
Csystem). The column is Toso TSκ3el-2000, -30 manufactured by Toyo Soda Kogyo Co., Ltd.
00, -4000, -5000, and the solvent was TI
IF was used. The Detector is manufactured by Showa Denko Sh.
odex RISE-51, and the measurement conditions were Flo
W rate is 1.0 mf/min, column temperature is 40
℃, TnJvo1. I did it with a 75μ spear. The molecular weight of the sample was calculated from the relationship between the logarithm value of the inspection line and the count number, which was prepared using several types of monodisperse polystyrene keyaki quasi-samples, to determine the molecular weight distribution of the sample.

As a standard boristyrene sample for preparing the i-line, for example, Pressure Chtmical Co. or manufactured by Toyo Soda Kogyo Co., Ltd. with a molecular weight of 6X10', 2.1x
lO', 4 x lo'. 1.75 x 10',
5. lx 10'. 1.1x 10'3.9X 10
', 8.6X 10', 2 X 10', 4.
It is appropriate to use a standard polystyrene sample of 48 x 10' and at least about 1O point.

(3) As the particle size distribution measuring device, Coulter Counter TA-II type (manufactured by Coulter Co., Ltd.) is used, and an interface (manufactured by Nikkakiki) and CX-
1 Connect a personal computer (manufactured by Canon) and prepare a 1% NaCi+aqueous solution using primary sodium chloride as an electrolyte.

As a measurement method, 100 to 150 mil of the electrolytic aqueous solution
0.1 to 5 ml of a surfactant, preferably an alkylbenzene sulfonate, as a dispersant is added therein, and further 0.5 to 50 mg of the measurement sample is added.

The electrolytic solution in which the sample was suspended was separated for about 1 to 3 minutes using an ultrasonic disperser, and the particle size was determined to be 2 to 40 μm using the Coulter Counter T^-II type using a 100 μm aquarium. Measure the distribution and find the volume average distribution and number average distribution.

These volume average distributions were obtained. From the number average distribution, obtain the volume average particle diameter, number average particle diameter, 5.04 μm or less for the number average distribution, and 20.2 μm or more for the volume average distribution. (4) Measurement of oil absorption (DBP method) Oil absorption is measured in accordance with ASTM method 0 2414-79. Turn on the absorbometer cock, completely fill the automatic burette system with DBP (dibutyl phthalate) so that no air bubbles remain, and set the device specifications to the following conditions. ■Spring tension 2.68kg/ca+■Rotor rotation speed 125 rpm■Torque limit switch scale 5■Dunbar valve 0.1
50 ■ DBP dropping speed 4 mj/sin After adjusting the DBP dropping speed by actual measurement, put a certain amount of dry sample into the absorbometer mixing chamber, set the burette counter to point O, and set the switch to automatic to start dropping. do. When the torque reaches the set point (5 in this case), the limit switch is activated and the dripping stops automatically.Read the scale (V) on the bullet counter at that time and calculate the oil absorption amount using the following formula. ■ OA=-XIOO W 0^: Oil absorption ffi (mj/100g) V; Amount of DBP used up to the end point (limit switch operating point)
ll) W: Weight of dry sample (g) [Example] The present invention will be explained in detail with reference to Examples below.

Polyester resin obtained by condensing raw bropoxidized bisphenol and fumaric acid (M Q = 3,000, M
w = 17.000, Tg = 57℃, acid value =
9.0, OH value=17) A full color toner was obtained using 100 parts by weight of the colorant and charge control agent in the prescribed amounts shown in Table 1 below.

It was used as a color toner. The manufacturing method was the master badge method.

First, a polyester resin and an amount of 6 times the amount of the coloring agent mentioned above were melted and kneaded in a Miki roll mill, and after cooling, they were crushed into pieces of 1 mm or less in a hammer mill to obtain a colored resin for a master hatch. Next, add polyester resin to the predetermined amount. Weigh the charge control agent and colored resin for masterbatch,
Preliminary mixing was performed using a Henschel mixer. Thereafter, the mixture was melt-kneaded in a three-roll mill, cooled, and then coarsely ground to approximately 1 to 210,111 particles using a hammer mill, and then finely ground to a particle size of 30 μm or less using an air jet type pulverizer.

Furthermore, the obtained finely pulverized material was classified, and for magenta toner, the volume average particle size was 8.02 μm, and the number average particle size was 6.
, 20 μm (therefore, α = 1.29), 30.0% of the number average distribution is 5.04 μm or less, and 20,
2 μm or more was adjusted to 0.0%. Regarding other toners,
The particle size distribution is shown in Table 2. To 100 parts by weight of each classified product, 0.5 parts by weight of silica fine powder treated with hexamethyldisilazane as a fluidity improver and 0.2 parts by weight of aluminum oxide fine powder were externally added to form a carrier. is styrene-2-edylhexyl acrylate-methyl methacrylate (copolymerization weight ratio 50:20:30)
A developer was prepared using a Cu-Zn-Fe based ferrite carrier (average particle size: 40 Pm; 250 mesh bath, 400 mesh on, 83% by weight) coated with 0.5% by weight of toner so that the toner concentration of each color was 5% by weight. .

Using these developers and toners, an image reproduction test was conducted using a modified Canon full color copying machine CLC-1 (with a modified fixing device). As a fixing roller, RTV/}I
TV silicone rubber double layer, rubber layer thickness 3.0mm
A fixing roller having a hardness of 40 degrees and a diameter of 40 mm was used as the pressure roller, and a fluororubber roller having a hardness of 50 degrees, a layer thickness of 1 mm, and a diameter of 40 mm was used as the pressure roller. A heating device was also attached to the pressure roller side.

In addition, in the blank paper passing test, the paper ejection direction was toward the pressure roller.

As a result of the image output test, there was no offset to the fixing roller even after printing 250,000 sheets in full color mode, and the original color chart was faithfully reproduced without fog, and the black image area had good concealment properties. A vivid full-color image with excellent deep black was obtained.

5) Expenses: Jubropoxidized bisphenol, ethoxylated bisphenol. Polyester resin obtained by condensing terephthalic acid and trimellitic acid (Mn = 3,500, M w
= 19,000, Tg = 59°C, acid value = ■0,
OH value = 20) The above prescription amount (
A toner classified product having a particle size distribution shown in Table 4 was prepared in the same manner as in Example 1 using the colorant and charge control agent shown in Table 3). As a fluidity improver, 0.5 parts by weight of silica fine powder treated with hexamethyldisilazane was externally added to 100 parts by weight of each classified toner product to prepare a full color 1.toner.

The carrier was a 50:50 mixture of vinylidene fluoride-tetrafluoroethylene copolymer (copolymerization weight ratio 8.2) and styrene-acrylic 2-ethylhexy-methyl methacrylate (copolymerization ratio 45:20:35). Cu- coated with 0.7 fifi% at m amount ratio of
Zn-Fe-based ferrite carrier (average particle size 49 μm2
50 mesh pass 400 mesh on 91.0% by weight)
A developer was prepared so that the toner concentration of each color was 9% by weight.

Using these developer and toner, and using the same fixing device as in Example 1, a Canon full color copying machine CLC-
An image output test was conducted using 1.

As a result, even after printing 1,000,000 sheets in full color mode, there is no offset to the fixing roller, the original color chart is faithfully reproduced without fogging, and the black image area has a deep and deep color with excellent concealment. A vivid full-color image with black color was obtained.

Medical] C1 mutual fixing roller is made of silicone rubber (HTV), Teflon film coat (tetrafluoroethylene resin), silicone rubber (
LTV) three-layer structure, layer thickness 2.0+ms+,
Hardness 50 degrees. A roller with a diameter of [ihmφ] was used, and the pressure roller had a two-layer structure of fluororubber and Teflon coat (tetrafluoroethylene resin), with a layer thickness of 1.01 mm.
Q1, hardness 60 degrees. A roller with a diameter of 60 mm was used. A heating device was also attached to the pressure roller side. In a blank sheet feeding test using this fixing device, the sheet was ejected in the direction of the pressure roller. This fixing device was attached to a Canon full color copying machine CLC-1, and an image reproduction test was conducted using the toner and developer of Example 1.

As a result, even after printing 200,000 sheets in full color mode, there is no offset to the fixing roller and the original color chart is faithfully reproduced without fogging, and the black image area has a deep black color with excellent concealment properties. A vivid full-color image was obtained. The large 31i {M4 fixing roller is made of two layers of RTV/HTV silicone rubber, and the layer thickness is 2. Omm. Hardness 45 degrees, roller diameter 8
The pressure roller used is one with a two-layer structure of silicone rubber (ITν) and fluorine rubber, with a layer thickness of 1
．． Omm+, hardness 50 degrees. A roller with a diameter of 60 mm was used. A heating device was also attached to the pressure roller side. In a blank sheet feeding test using this fixing device, the sheet was ejected in the direction of the pressure roller. This fixing device was attached to a Canon full color copying machine CLC-1, and an image reproduction test was conducted using the toner and developer of Example 1. As a result, even after printing 30,000 sheets in full color mode, there is no offset to the fixing roller at all, and the original color chart is faithfully reproduced without fogging, and the black image area has a depth with excellent concealment. A vivid full-color image with black color was obtained.

mIL± As a colorant for magenta toner, C.I. I. A classified magenta toner was prepared in the same manner as in Example 1 except that 1.2 fi parts of Basic Violet 10 was used (volume average particle size: 8.38 μm, number average particle size: 6.28 μm (
α=1.33), number average distribution 5.04μl or less29
．． 1%, volume average distribution 20.2 μm or more 0.0%). As for other colors, those used in Example 1 were used.

After this, an image reproduction test was conducted in the same manner as in Example 1.

As a result, when we observed the fixing roller after printing on 5,000 sheets using a full color saw, we found that the carrier was embedded in the fixing roller due to the "carrier pull" phenomenon. Furthermore, after printing 4,000 sheets, the surface of the fixed image was rough compared to the initial image. Comparative Example 2 Fluororubber-Teflon coat (4
Double-layered (fluorinated ethylene resin) with hardness of 70 degrees. IW
Using a roller with a thickness of 1.0 mm and a roller diameter of 60 mmφ,
The pressure roller is made of a single layer of silicone rubber (IITV) with a hardness of 55 degrees and a layer thickness of 5. hm, roller diameter 6
A one with a diameter of 0 mm was used. The heating device was attached only to the fixing roller side. In a blank sheet feeding test using this fixing device, the sheet was ejected in the direction of the fixing roller.

This fixing device was installed on Canon's full color copier CLC-1.
An image reproduction test was conducted using the toner and developer of Example 1.

As a result, a so-called ``offset jam'' occurred in which the image was wrapped around the fixing roller from the first sheet, and a printing durability test was not possible.

[Effects of the Invention] As explained above, the present invention is suitable for full color! - Due to the method of fixing the color image, it is possible to obtain a full-color image that faithfully reproduces the original color chart without offset and without fog even after an image reproduction test, for example, after printing 30,000 sheets.

Furthermore, in the black image area, a deep black color with excellent concealment properties can be obtained.

Furthermore, the toner conveyance within the copying machine is good, and a stable image density can be obtained, and a good image with almost no fogging or toner scattering can be obtained.

[Brief explanation of the drawing]

In order to explain the features of the present invention, Fig. 1 shows an example in which the paper is ejected in a direction perpendicular to a line connecting the center lines of the fixing roller and the pressure roller, toward the pressure roller. It is.

Claims (1)

[Claims] (1) In a method for fixing a full-color toner image formed by multicolor electrophotography using at least two of magenta toner, cyan toner, yellow toner, and black toner, the magenta toner is a quinacridone pigment. The cyan toner is a toner having polyester resin particles containing a xanthine dye treated with a phenolic resin and a flow improver, and the cyan toner is a toner having polyester resin particles containing a copper phthalocyanine blue pigment and a flow improver. The yellow toner is a toner having polyester resin particles containing an azo yellow pigment and a flow improver, and the black toner is a toner having a flow improver and a polyester resin containing carbon black as a colorant. is a heated roller fixing device in which the fixing roller and the pressure roller have a rubber-like elastic layer on the core metal, and the paper ejection direction is along the line connecting the centers of the fixing roller and the pressure roller. A method for fixing a full-color toner image, characterized in that the full-color toner image is fixed using a fixing device that is positioned closer to the pressure roller than in the vertical direction.