JPS59231552A - Developing method - Google Patents

Abstract

PURPOSE:To form an image having stable image quality with good fidelity in a developing method of an electrostatic latent image using a one-component type nonmagnetic toner by using a toner compounded with specific fine silica powder. CONSTITUTION:A layer of an insulating nonmagnetic toner 5 is formed on a toner carrying body 2 disposed apart at a prescribed space from an electrostatic latent image holding body 1 more thinly than said space by a coating means 4 (a symbol 3 denotes a hopper and 6 a biasing power source for development) and the electrostatic latent image on the body 1 is developed by transferring selectively the toner onto said body. The insulating nonmagnetic toner compounded with about 0.01-20wt% the fine powder obtd. by treating the fine silica powder formed by vapor phase oxidation of a silicon halide compd. with a silane coupling agent (e.g.; gamma-aminopropyltriethoxysilane) and subjecting further the powder to a hydrophobing treatment so as to attain 30-80 degree of hydrophobicity (methanol titration test method) is used in the above-mentioned method.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for developing an electrostatic image formed on the surface of an electrostatic image carrier, and particularly a method for developing an electrostatic image formed by forming a thin and uniform layer of insulating non-magnetic toner on a toner carrier. It's about how to do it.

Conventionally, the following methods are known for developing an electrostatic image on the surface of an electrostatic image carrier using component-based nonmagnetic toner. The first method consists of a movable toner carrying means that carries and conveys toner gold and supplies it to a latent image (electrostatic) holder, a toner replenishing means, and a movable toner that receives toner from this toner replenishing means. A movable application means for applying toner to the carrying means, which has a fiber pusher for carrying toner on its surface, and is in contact with the movable toner carrying means and in the same direction as the movable toner carrying means at this abutting portion. The movable toner carrying means is also provided with a movable coating means that moves at high speed, and the movable coating means uniformly coats toner on the surface of the movable toner carrying means to form a toner coating layer, and this coating layer is electrostatically applied. Dive 1
In this method, development is performed by bringing the image close to the image area.

The second method involves transferring a rotatable magnetic roller 2 which adsorbs a magnetic carrier for charging component-based non-magnetic toner particles to form a magnetic brush, and transferring the toner particles from the roller. #Equipped with a developing roller for developing the electrostatic image on the electrostatic 1st station holder, a gap between the electrostatic 1st holder and the developing roller is maintained in the developing section, and the gap length is determined by the toner application on the developing roller. This is a method in which the electrostatic image is developed by setting the thickness to be larger than the Akane thickness.

The third method is to pump up the toner under the toner carrier stored in the toner storage means onto the toner carrier, and then apply vibrations to only the pumped up portion of the toner to make it Y6-like, thereby increasing the surface of the toner carrier. In this method, a toner layer of a predetermined thickness is formed on the toner, and an electrostatic image on the electrostatic image holder is developed by placing the toner carrier carrying the toner layer on its surface against an electrostatic image holder. .

However, these methods are methods in which +e +t& non-magnetic toner is supported on a carrier by non-magnetic force in a developing section, and is produced. The forces for supporting non-ampholytic toner are mainly HP'jt, air, attraction, and physical adhesion force. There are many disadvantages compared to developing methods using insulating magnetic toners, such as the fact that many toners are not evenly applied to the carrier in a relatively thin layer. A so-called soil build-up occurs in which toner is deposited on non-image areas.Furthermore, even if it is applied thinly and evenly, the amount of toner adhering to the dust area of the image is insufficient, resulting in an image with low density.Furthermore, more toner is applied thinly and evenly. Even if applied evenly, the toner can produce very poor images with low fidelity and low toner strength.Furthermore, repeated use of large amounts of toner can result in decreased image density and poor quality images. In addition, many toners have the disadvantage that they sometimes lead to a decrease in image density when exposed to environmental changes such as high temperature and high humidity, low temperature and low humidity, and other times they suffer from soil strength/iron resistance. Was.

In addition, in the development method using component magnetic toner, since a large amount of magnetic powder is contained within the magnetic toner particles,
Compared to non-magnetic toners, it not only has a higher Mi flfj, but also has more beautiful colors than other toners.

An object of the present invention is to provide a new developing method using an absolutely non-staining toner which has improved the above-mentioned drawbacks. That is, the purpose of the present invention is to.

To provide a developing method with high fidelity and stable image quality. Furthermore, it is an object of the present invention to provide a new developing method using an insulating non-acupuncture toner that eliminates the ground force phenomenon and provides a high-resolution image with uniform density and sufficient density in one quadrant of the image.

Another object of the present invention is to provide a developing method using an insulating non-magnetic toner that has excellent durability such as continuous use characteristics.

Another object of the present invention is to develop a method of using a loquat non-acupuncture toner that is stable against environmental changes such as high temperature and high humidity, and low temperature and low humidity.
The objective is to provide a method for displaying images.

Another object of the present invention is to provide a method for producing the above-mentioned image, which provides an image having a clear hue.

The developing method of the present invention is characterized by the fact that an electrostatic image carrier holding a holder on the bottom surface and a toner carrier carrying insulating non-magnetic toner on the entire surface are separated by a certain gap in the image area. A fine silica powder produced by vapor phase oxidation of a silicon halide compound, which after being heat treated at a temperature of 400°C or higher, has the general formula 8% (R is an alkoxy group or a chlorine atom, m is an integer of 1 to 3, Y is a carbonized scale group containing at least one or more of an amino group, a vinyl group, a glycidoxy group, a mercapto group, a methacrylic group, or a ureido group, and n is an integer of 3 to 1) treated with a 7-rank cutting agent shown in
The degree of hydrophobicity measured by methanol titration test is 30
A non-magnetic toner containing a ridge powder that has been hydrophobized so as to have a value in the range of 80 is supported on a toner carrier 6 to a thickness as thin as the gap, and the toner is applied in a developing section. The method of transferring the toner to the holder and developing it lies in the method.

In the above-mentioned developing method of the present invention, it is preferable that the toner carrier and the static image be formed in the developing area as necessary. i. It is preferable to apply a father current and/or a direct current bias between the ridge holder and the ridge holder.

The inventors of the present invention have investigated various development methods using conventionally known non-magnetic toners, and have found that, in order to solve the above-mentioned drawbacks, they are more effective than developing methods using magnetic toners. Is it denser than the electrostatic charge weight of the toner on the toner carrier? I found out that 11J is important.

In other words, in a developing method that uses non-magnetic toner, for example, if the amount of charge is low, the toner will not be uniformly coated on the toner carrier, and development will not be possible, and if the amount of charge is increased, Even if the toner is applied evenly, if the value is not appropriate, the toner will be raw. Conversely, if the value is not appropriate, the electrostatic attraction between the toner and the toner carrier will be too strong. This makes it difficult for the toner to transfer to the static image holder, resulting in a decrease in image quality and the appearance of low-quality images. Furthermore, for the same reason, the quality of the image is greatly affected by oxidation of the toner charge amount due to repeated use or environmental changes. Therefore, it is extremely important to ensure that the amount of charge remains constant.

In addition, the physical adhesion force between the toner and the toner carrier clearly affects the transfer of the toner from the toner carrier, for example, the degree of freedom of each toner is small and the toner application density in a single layer of toner on the toner carrier. If this is large, the resulting image density will result in a low-resolution, low-quality image, so it is extremely important to prevent the physical adhesion from increasing.

The present invention provides a method for developing an insulating non-magnetic toner by supporting it on a toner carrier in a developing section by non-magnetic force, by using a toner containing specific silica fine powder. It is something to be achieved.

The silica fine powder produced by vapor phase oxidation of a silicon halogen compound used in the present invention is so-called dry process silica or heated silica, and is produced by a conventionally known technique. For example, this method utilizes the thermal decomposition reaction of silica tetrachloride gas in a hydrogen flame, and the basic reaction formula is as follows.

5iCt4+2H2+0□→5lo2+4) lctAlso,
In this manufacturing process, for example, aluminum chloride or
By using another metal halide compound such as titanium chloride together with a silicon halide compound, it is also possible to obtain a composite fine powder of silica and other metal oxides, and the present invention also includes these.

The particle size is desirably within the range of o, ooi to 2μ as an average particle size, particularly preferably 0.002μ.
It is preferable to use fine powder gold within the range of ~0.2μ.

Examples of commercially available silica fine powders include those available under the following trade names.

AERO8IL 130 (Japan Aerosil Co., Ltd.) 200 AERO8IL 300 (Japan Aerosil Co., Ltd.) 380 T600 MOX 80 MQX 170 COK 84 Cab-0-8iA M-5 (CABOT
MS-7 S75 S-5 E)l-5 Wacker f(DK N 20(
WACi (ER-CHEMIE V 15GMB)
Company I) N20g 30 40 D-CFine 5ilica (Dow Corning Company) Fransol (Franai Company 1) Examples of adding these silica fine powders to toner are known. However, such substances are not necessarily sufficient in terms of stability, and addition of such silica changes chargeability, making it unsuitable for toners that require positive charge control. The fine silica powder used in the present invention is obtained by heat-treating the fine powder at a temperature of 1,400°C or higher.The heat treatment may be performed, for example, by placing the fine powder in an electric furnace at a temperature of 400°C or higher for an appropriate period of time. It is best to leave it for 10 minutes to 10 hours. There are no particular restrictions on the heat treatment method, and any method can be used as long as it does not significantly deteriorate the properties of the toner. In addition, direct heat treatment is preferably performed at 4500 to 1500°C.
In particular, it is preferably 500 to 100 OC. Heat treatment of these fine powders is sometimes found to be effective in maintaining stability against environmental changes.

The heat-treated silica fine powder used in the phenomenon method of the present invention has the general formula % (R is an alkoxy group or a chlorine atom, m is an integer of 1 to 3, Y is an amine group, a vinyl group, a glycidoxy group, a mercapto group, Hydrophobicity treated with a silane coupling agent represented by a hydrocarbon group containing at least one or more of Kyo, methacrylic group, and ureido group, where n is an integer of 3 to 1) and measured by methanol titration test. The degree of oxidation is 30~
It is hydrophobized to show a value in the range of 80. A developer used in the developing method of the present invention can be obtained by incorporating the treated silica fine powder into a toner.

The silane coupling agent used in the present invention has the general formula %. , methacrylic group, or ureido group.
Hydrocarbon group containing a species or two or more structures, n Fi3~
1 mk! The compound represented by i) 1 □ is an adduct represented by the following chemical formula.

As a compound with vinyl group ff1f H2C=CH8iCL.

H2C=CH8i (QC21-15).

)12C=CfiCH2S ict.

H2C= C11CI(2S i (CH,)CA2n
2c = cactt2s t (Ct-t, ) 2
ct) I2C=CI-1CH2Si(OC2■(5)3
1(2C=CH8i (QC2H40CI(ρ5(H2
C=CHCH2)2SiCt2 (H2C=CH)2Si(OC2H5)2(H2C=C
H)3S 1Oc2)15I(2C=CH<)-CH2
CM2S i (OCH,)3 etc. are good, and as a compound containing a glycidoxy group, CH2-Cf
(CH20CH2C1(2C1(2S i (OCI(
3) 3! CH2-CHCH20CH2CH2CH2CH2SiCH3(
OC2H5)2CI(2-CHCf120CH20f(
2Cfi2S i (CH3) 2QC2H5 As one containing a mercapto group, f(SCH2CH2CH2S i (QC)l, )
5H8Cf(2Cf(2C)I2S i (QC2)1
5) 6. In the past, 6 (H5C)2C= C-C00CH2CH2Ck12S contained a methacrylic group.
1Ct2CM.

(H3C)2C= C-C00CH2CH2C1(2S
i (OCH3).

CH3)12C=C-C00CI(2C1(2(J2S L
(OCR,) 5萱CH3 ureido groups include H2NC0NCII2CK2Cj-128i (OC2
H5).

can be mentioned.

'A particularly preferred silane coupling agent for use in the present invention is a compound containing an amine group and is represented by the following structural formula.

H2NC)12CH2CH2S i (OCR,)5H
2NCH2CH2CH2SiiOC2115).

CH5 H2NCH2CH2CH2Sl(OCH3)2CH.

F12Net(2C1(2NHCi(2CH20H2S
t (OCH3)2H2NCONHCf(2CH2C1
(2S i (OC2f(5).

H2NC) I2CH2NHCH2CH2CH2S i
(OCf(3).

H2N0I(2C)12NHC)12C)12NHC)
12Ci (2C12S i (001(5) 3H5C
20COCH2CH2NHCH2CH2CH2S1(O
CH3)3H5C20COCH2CH2NHCI-12
CH2NHCII2CH2CH28i (OCH,)
3H5C20COCH2C1 (2NHCH2C112N
l(CH2C)12NHCf(2Ci(2NH・・CH
2CH2C1(2S i (OCR,) 3H, COC
OCH2CM2MCt(2CM2NHCH2C0C0C
H2Ci (OCH3) 31(2N(ySi(OCH
3) 6 C>NHCH2CH2C1(28i (OCf13)6
H2NCH2CH2NHCH2-C>-CH2CH,,
S i (OCH3)3H2NCH2-C> Cn2c
n2s i (QC)I3)3H2NCH2CI(2N
HCH2(ΣC1(2CH2S i (OCH5)5(
u3co), s1ct12cH2Ct(2-Nu
-CH2H,CN)IcH2Ci(2C1(28i (
QC2H5).

H2N((J12CH2NH)2CH2C1(2CH2
Examples include S i (OCH3)3H3C-Nf(CONH3 C31(6St(OCf(,)3).Alcoquine groups in the above compounds may be chlorine atoms.These may be used alone or in a mixture of two or more. may be used in the system.

In addition, in order to perform the hydrophobization treatment so that the degree of hydrophobization required for the silica fine powder used in the present invention, that is, the degree of hydrophobization measured by a methanol titration test is in the range of 30 to 80, conventional methods are required. A known hydrophobization method is used to form an organosilicon compound that reacts with or physically adsorbs to fine silica powder.
It is applied by chemical treatment such as n. In a preferred method, the vapor phase of the silicon halide compound is treated with an organosiliconized compound after the silica fine powder produced by chemical reaction is treated with the above-mentioned silane coupling agent, or simultaneously with the treatment with the 7-rank soling agent. Examples of the active silicon compounds are hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethylsilane, trimethyldichlorosilane, methyltrichlorucrane, allyldimethylchlorosilane, allyl phenyldichloro Silane, benzyldimethylchlorosilane, bromomethyltrichlorosilane, α-chloroethyltrichlorsilane, p-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, chloromethyltrimethylchlorosilane, triorganosilylmercaptan, e.g. trimethyl7 Lymercabutane, triorganosilylacrylate, such as vinylnomethylacetoki77ran, furthermore, dimethylethoxysilane, trimethyldimethoxysilane, hexamethyllephoxy7.1
．． 3-divinyltetramethyldisiloxane, l,3-zophenyltetramethersosiloxane, and 2 to 12 70 gythane units per molecule, each with one St attached to the terminally located unit. There is dimethylpolysiloxane which has few hydroxyl groups.

These can be used singly or in a mixture of two or more types.

The preferred ratio of the silane coupling agent compound and the hydrophobizing agent to the 7-liquid fine powder is 15:8.
The total amount of silane coupling agent and hydrophobization treatment is preferably 0.1 to 5 to 85:15, based on the silica fine powder.
It is preferable that the amount is ~30wt%, preferably 0.5~20wt%.

The degree of hydrophobicity of the final treated silica bale powder is 30 to 30 as measured by methanol titration test.
A preferred developer for use in the development method of the present invention is obtained when it is hydrophobized to exhibit a value in the range of 80.

Here, the methanol titration test is an experimental test for confirming the degree of hydrophobization of the silica fine powder having a hydrophobized surface gold. The "pamethanol titration test" specified herein for evaluating the degree of hydrophobization of treated silica fine powder is carried out as follows.
F 'ii' 50 ml of water in an Erlenmeyer flask with a capacity of 250 + u
Add to m1. Methanol is titrated from the burette until all of the silica is wetted. At this time, the solution in the flask is constantly stirred with a magnetic stirrer. The end point is observed when the entire amount of fine silica powder is suspended in the liquid, and the degree of hydrophobization is expressed as the percentage of methanol in the liquid mixture of methanol and water when the end point is reached.

Further, the applied amount of these treated silica fine powders is fully effective when applied in an amount of 0.01 to 20% with respect to the toner MN, and is especially excellent when applied in an amount of 0.1 to 3%. It exhibits positive chargeability with excellent stability.

A preferred form of addition is 0. It is preferable that the treated silica fine powder having an amount of 01 to 3 is attached to the surface of the toner particles.

As the binder resin for the toner used in the developing method of the present invention, a six-strand material resin conventionally known as a toner binder resin for electrophotography is used.

For example, polystyrene, polystyrene/butatsuene copolymer, styrene copolymer such as styrene/acrylic copolymer, polyethylene, polyethylene vinyl acetate copolymer,
Ethylene copolymerization such as polyethylene vinyl alcohol copolymerization, phenolic resin, epoxy resin, allyl 7-thalerate resin, polyamide resin, polyester resin, male, acid resin, etc. Furthermore, there are no particular restrictions on the manufacturing method of any of the resins.

This is because conventionally, resins prepared by emulsion polymerization or the like tend to contain impurities and are difficult to use, but the present invention allows them to be easily used, and the range of resin selection is greatly expanded. This is also a great effect of the present invention.

As the coloring material used in the toner, conventionally known coloring materials such as carbon black and dye pigments can be used, and all the conventionally known dyes as positive load control agents can be mixed with the treated silica fine powder used in the present invention. Can be used in combination.

Hereinafter, the present invention will be explained in detail based on an example of the actual/A aspect using the drawings.

FIG. 1 shows a static image '4' using the insulating non-magnetic toner specified in the present invention. An example of an embodiment of a latent developing method and a developing device is shown. In the figure, reference numeral 1 denotes a cylindrical electrostatic image holder, on which an electrostatic latent image is completely formed by, for example, a known electrophotographic method such as the Carlson method or the NP method. The magnetic non-magnetic toner 5 is transferred to the toner carrier 2.
Developing is carried out with toner 5 applied by a blood cloth means 4 which regulates the thickness of one layer of toner on top. The toner carrier 2 is a cylindrical developing roller made of stainless steel.

The developing roller may be made of aluminum or other metals. Further, a metal roller coated with resin or the like may be used in order to triboelectrically charge the toner to a desired polarity.Furthermore, this developing roller may be made of an electrically conductive non-metallic material. Although not shown in the drawings, spacer rollers made of high-density polyethylene are inserted into the shafts of both ends of the toner carrier 2. By applying this spacer roller to both ends of the 131I electrostatic image holder 1 and fixing the developing device, the distance between the electrostatic image holder 1 and the toner carrier 2 can be adjusted by coating the toner on the toner carrier 2. Set and hold the toner to a thickness greater than one layer.

This interval is for example 100μ to 500μ, preferably 15
It is 0μ to 300μ. If this interval is too thick, it will be silent d1
The electrostatic force exerted on the non-magnetic toner coated on the toner carrier 2 by the electrostatic latent on the holder 1 becomes weaker, the image quality deteriorates, and it becomes difficult to visualize fine lines in particular by development. If this gap is not provided, there is a risk that the toner applied on the toner carrier 2 will be compressed and aggregated between the toner carrier 2 and the electrostatic image holder 1. Reference numeral 6 denotes a developing bias power source, which is capable of applying a voltage between the conductive toner carrier 2 and the back electrode of the electrostatic image holder l. This developing bias voltage is as described in Japanese Patent Application No. 53-92108.

FIG. 2 is a diagram showing another example of the embodiment.

In the figure, 1 is an electrostatic image carrier, 2 is a toner carrier,
Reference numeral 5 indicates the insulating non-magnetic toner specified in the present invention, 3 indicates a hopper, 9 indicates a cleaning blade, and 10 indicates a toner supply member. 16 is a vibration member, 17 is a vibration generating means, 16a is a permanent magnet, 16b is a support spring, 17a is an iron core, and 17b is a winding wire. By applying alternating current to the winding 17b, the vibration member 16
The tray is vibrated at an appropriate amplitude and frequency to form a uniform l-toner cloth layer on the toner carrier 2 rotating at a constant speed, and the toner is applied to the entire toner carrier 2 and electrostatic image carrier 1. A gap larger than the thickness of the layer is maintained to allow the non-magnetic toner to fly onto the electrostatic image and develop it. The vibration of the vibrating member 16 may be at any level as long as it does not come into direct contact with the toner carrier 2, but it is preferable to control the frequency and amplitude so that the toner coating layer has a uniform thickness of about 5 to 100 μm. . or,
Toner carrier 2 and O'i! It is also possible to apply an alternating current or/and direct current developing/guinea pressure between the filter and the retaining special body 1.

FIG. 3 is a diagram showing another example of the embodiment. In the same figure, 1 is an electrostatic image carrier, 2 is a toner carrier, 3 is a developer container, and 5 is an insulating non-magnetic toner specified in the present invention. , 6 is a developing bias power source, 9 is a toner cleaning member, 35 is a coating roller, 36 is a fiber brush fixed on the moat surface, and 40 is a coating bias mechanism IIA. The toner 5 is uniformly coated on the toner carrier 2 by fully rotating the hollow cloth roller 35 and conveyed by the brush 36, and the electrostatic one-image holder 1 is coated with the toner 5.
I will fly it to Naruha and develop it. The gap between the toner carrier 2 and the application roller ~35 is adjusted W4 so as to form a uniform layer of toner of about 5 to 100μ on the toner carrier 2, and the cloth earing power supply 40 for VCmC is used to uniformly apply the toner. A bias voltage may also be applied. The gap between the electrostatic image carrier 1 and the toner carrier 2 is set to be larger than the thickness of the above-mentioned toner layer, and '$1. s, a developer bias may be applied from the developer bias power supply 6.

FIG. 4 is a diagram showing another example of the embodiment.

In the figure, 1 is rf! 2 is a toner carrier, 5 is a one-component non-magnetic toner specified in the present invention, 43 is a developer container, 4B is a magnetic roller, 49 is its non-magnetic sleeve, 50 is a magnet, 52 is a magnetic brush, Reference numeral 53 indicates a one-component non-magnetic toner or a two-component developing agent in which a non-magnetic toner and a magnetic carrier are mixed. By magnetically holding the magnetic carrier on the non-magnetic sleeve 49 and turning it into a bluff, and rotating the non-magnetic sleeve 49, the toner or developer 5
A uniform layer 5 of toner is formed by drawing up the toner 3 with the carrier brush and contacting it onto the toner carrier 2. At this time, since the carrier is held on the magnetic roller 48 by magnetic force, it does not move onto the toner carrier 2. Next, the toner is developed by flying from the toner carrier 2 onto the electrostatic image holder 1. The gap between the magnetic roller 48 and the toner carrier 2 is adjusted so that the thickness of one layer of toner on the toner carrier 2 is about 5 to 100 μm. The gap between the toner carrier 2 and the 1f cartridge holding member 1 may be made larger than the thickness of the toner, and a developing bias voltage may be applied to the toner carrier 2.

FIG. 5 shows yet another row of embodiments. In the same figure, 1 is an image holder; 21, 1. A toner carrier, 3 is a hopper, 6 is a developer bias power supply, 5 is a single-component non-magnetic toner specified in the present invention, 50 is a fixed magnet, 52
numeral 58 indicates a magnetic brush made of carrier and toner mixture, and numeral 58 indicates a blade for toner thickness. A magnetic brush 52 formed on the toner carrier 2 is circulated by rotating the toner carrier 2, and the toner in the hopper 3 is thoroughly loaded and uniformly coated in a thin layer on the toner carrier 2. The one-component non-magnetic toner 5' on the toner carrier 2 is produced by aligning the toner carrier 2 and the electrostatic image carrier l with a gap greater than the thickness of one toner layer.
f: Flying development onto the static image on the static image holder 1. The thickness of one layer of toner is controlled by the size of the magnetic bluff 52, that is, the amount of carrier, and the regulating blade 58. Silence '1! f,
The gap between the 1 m holder 1 and the toner carrier 2 is set larger as the toner is thicker. Developing power supply 6 allows
It is also possible to apply IA.

[Example-1] Materials consisting of 100 parts by weight of styrene-BiviA copolymer, 10 parts by weight of phthalocyanine pigment, and 10 parts by weight of penzoquanamine-formaldehyde condensate were thoroughly mixed in a blender and then heated to 150°C. It was mixed with 2 nerols. After allowing the kneaded mixture to cool completely.

After coarsely pulverizing with a cutter mill, pulverizing with a pulverizer using a Noet air flow, and further fractionating with a wind dispersion machine to obtain fine powder with a particle size of 5 to 20 μ◇ Next, 7 Lili fine powder Body Aerosi/I/z o o (manufactured by Nippon Aerosil Co., Ltd.) Silica powder produced by heat treatment at 80°C for 1 hour. Placed in a closed Henschel mixer heated to -70°C, and subjected to silane cassilling against the silica. γ-Aminoglopyltriethoxysilane diluted with alcohol was added dropwise so that the treatment amount was 9 cents per 100ml, and the mixture was stirred at commercial speed. Obtained fc powder f: 12
After drying at 0°C, the silica was placed in a hydrogen shell mixer and sprayed with 10% by weight of trimethylcyclosilane to the silica. Stirred at high speed for 2 hours at room temperature, The mixture was further stirred at 80°C for 24 hours, and then the mixer was opened to atmospheric pressure.
I was further dried at low speed at atmospheric pressure for 5 hours at 60°C. The degree of hydrophobicity was 58. The treated silica powder was mixed in a Henschel mixer at a ratio of 0.6 elb/III to the fine powder, and a toner was prepared.

On the other hand, 100 parts by weight of zinc oxide, 20'N'it parts of styrene-butanoene copolymer, n-butyl methacrylate v-)4
A mixture consisting of 0Ji parts, 120ffi of toluene, and 4jmit parts of 1% Rose Bengal methanol bath solution was mixed in a T-ball mill for 6 hours. This is 0.05 +
Dry thickness of m-thick aluminum plate is ・40μ
The photoreceptor was coated with a wire knife so as to have the following properties, and the solvent was evaporated with warm air to produce a zinc oxide powder-based photoreceptor in the form of a drum. This photoreceptor was subjected to a corona discharge of 16 kV to uniformly charge the entire surface, and then an original image was irradiated to form an electrostatic latent image.

The toner was placed in a developing device as shown in FIG. 1, and developed using the electrostatic layer formed above. In this case, the toner carrier 2 is a stainless steel cylindrical sleeve with an outer diameter of 50 aaa, and the distance between the photosensitive drum surface and the sleeve surface is 0.25 m.
m, and an alternating current of 400)1zlooOV and a direct current bias of -150v were applied to the sleeve.

Then, a powder image 'fc was transferred while irradiating a direct current corona of -7 kV from the back side of the transfer paper to obtain a copied image. Fixing was carried out using a commercially available plain paper (M (trade name, NP-5000, manufactured by Canon)).

The resulting transferred image had a sufficiently high specularity of 1.46, had no fogging, had no toner scattering 9 around the image, and was a good image with high resolution. Durability was continuously examined using the above toner, and the transferred images after 10,000 copies were completely uncolored compared to the initial images.

In addition, when the environmental conditions were set to t-35℃ and 85%, the image density was 1.40, a value that was almost unchanged from normal temperature and humidity, and a clear t-color image was obtained with no fogging or scattering, and it was durable. There was almost no change from 10,000 sheets to 30,000 sheets. When the transfer image was obtained at 10C and 10% low temperature and low humidity, the image density was 1.47.
Even the solid black areas were developed and transferred extremely smoothly, resulting in an excellent image with no sharp 9 or hollow areas. Kaya conducted a durability test in continuous and listening mode under these environmental conditions, and the density fluctuation was ±0.2 up to 910,000 sheets, which was practically acceptable.

[Comparative Example 1] A toner was obtained in the same manner as in Example 1 except that it was not treated with Aerosil 200'1i-r-aminoprobyltrinitochrysanthemum 7ran and trimethylcyclosilane, and development and transfer were performed. Comparative Example 2 A developer was obtained in the same manner as in Example 1, except that no treatment was performed with trimethylcyclosilane, and an image was obtained in the same manner. At room temperature and humidity, there was little fog, but the image density was low at 0.72, the line drawings were scattered, and the black areas were noticeably rough. Durability f: When investigated, the density decreased to 0.58 after 5,000 sheets were printed. 35
When an image was obtained under the conditions of 85% humidity and 85% humidity, the image density was as low as 0.60, and the image density was found to be unsuitable for public use due to increased fogging, blurring, and roughness. 10℃, humidity l
When a painter was obtained under the condition of 0%, the image density was 0.70.
There were low dropouts, fogging, roughness, and transfer defects were noticeable. The density was 0.37 after about 500 images, probably because one continuous image was extracted, making it impractical.

[Comparative Example 3] The same procedure as in Example 1 was carried out except that t of dimethyldichlorosilane was changed to 0.1% by weight based on the silica. The degree of hydrophobicity of silica at this time is 14
At normal temperature and humidity, good image peeling can be obtained up to 10,000 sheets, and the toner weight per unit volume of one layer of toner9 does not change.
The initial image density is 1.2 i, and when 95,000 sheets are printed, it is 0.
70, and fog also increased. After being stored for one month under conditions of 10°C and 10% humidity, we tested it in this environment and found that the initial image density was as high as 1.4 and good results were obtained; however, coating defects occurred after 5000 sheets. Image density is 0.6
It dropped to 2.

[Example 2] γ-Aminopropyltriethoxysilane iN, N-Nomethylaminobuenyltriethoxysilane was carried out in almost the same manner as in Example 1, and the coating was stable and good. The results were obtained. The degree of hydrophobicity of the silica at this time was 74.

[Example 3] The coating was carried out in almost the same manner as in Example 1 except that γ-aminoglobiltriethoxylane was replaced with aminoethylaminomethylphenethyltrimethoxysilane, and the coating was stable and good results were obtained. . At this time, the hydrophobization rate of 7 liters was 48 O. [Example-4] The process was carried out in the same manner as in Example 1 except that the heat treatment temperature of Aerosil 200 was changed to 500°C. The results were obtained.

[Example 5] The toner of Example 1 was put into the apparatus shown in FIG. 2, and the vibrating member 16'i was vibrated at a frequency of about 50 Hz and an amplitude of 0.2 mm, and the toner carrier 2 was set at a circumferential speed of 120 m. /sec, a uniform toner coating layer with a thickness of about 50 μm is formed on the toner carrier, and the toner carrier 2 and the electrostatic fabric holder l are opposed to each other with a gap of about 300 μm to form a toner coating layer on the toner carrier. The carrier 2 has a frequency of 100 to several kilohertz.

Similar good results were obtained when a bias alternating current field with a negative peak value of -660 to -1200V and a normal peak value of +400 to +800V was applied. On the other hand, when the toners of Comparative Examples 1 to 3 were examined as described above, the defects described in Comparative Examples 1 to 3 were noticeable.

[Example 6] Toner assembly, toner holding body 2 and application row 2 shown in Example 2
The gap of 35 is about 2 centimeters, and the length of the bamboo fiber brush 36 is about 3 Il.
Insert into the phenomenon device shown in FIG. 3 and set as lI11,
The gap between the roller 2 and the electrostatic roller holder was maintained at 300μ, and a single layer of toner of about 80μ was formed on the developing roller, and the peak value of the voltage at a frequency of 200Hz ±45 was formed as a mud wave.
Adding DC component 250v to 0v, peak voltage value +7
When developing with 00v and -200v applied, similar good polished rice was obtained.

[Example 7] The toner of Example 3 was prepared in the manner shown in Fig. 4 in which the gap between the toner carrier 2 and the Oa':A roller 48 was set to be about 2 mm, and the maximum gap of the magnetic brush 52 was about 4 mm. into the developing device shown, and set the gap between the developing roller and the static-1 urine holder to 300 μm.
A single layer of toner of approximately 80μ was formed on the developing roller, and as an AC waveform, a DC component of 250Vt was added to the peak 1 section of the rBL number of 200 Hz voltage ±450V, and the voltage peaks Ii + 700V and -200V'i5 were applied. Similar good results were obtained when the phenomenon occurred.

[Example 8] Toner 20 of Example 1. pi is mixed in advance with 20 g of fairy powder carrier, and the mixture is applied to a fifth plate in which the gap between the blade 58 and the toner carrier 2 is set to be about 250 μ.
The toner is placed in the developing device shown in the figure, the gap between the machine 1 seeking roller and the static formation 1 image holder is kept at 300μ, and the toner of about 80μ is formed on the t-current roller as a δ-semata flow liquid type at a frequency of 200μ.
Hz voltage peak value ±450VK flow component 250V
Similar good results were obtained by applying peak voltages of +700V and -200V for development.

The feature of the current method of the present invention constructed in this way is that it is possible to obtain an insulating non-magnetic toner image with a high level of strength, and it is also a high-quality image that does not deteriorate due to long-term use. It can be used for long periods of time. In addition, there is almost no decrease in the amount of charge due to environmental changes such as temperature and humidity, and it is possible to be served by a woman's autonomy. Furthermore, clear color images of each color can be obtained. Another feature is that there is no selectivity between the silica fine powder used in the present invention and the resin.
It can be combined with any resin, allowing a wide selection of applicable toner compositions. For example, it can be used for pressure fixable toners and capsule toners in addition to heat-fixable toners.

[Brief explanation of the drawing]

FIGS. 1 to 5 are sectional views showing different types of developing apparatuses used for carrying out the developing method according to the present invention. l... Electrostatic image holder, 2... Toner carrier,
3... Hotnozo-14... Toner coating 4F means, 5.
. . .-component non-disgusting toner, 6 . . . phenomenon bias pressure source, 9 . . . toner cleaning blade, lO . . . toner supply member, 16 . . . vibration member, 17 . . . vibration generation. Means, 35... Fall Δ110-ra, 36... Fiber brush, 40... Bias power source for application, 48... Magnetic roller, 49... Non-magnetic sleeve, 50... Permanent magnet, 52 . . . Magnetic brush, 53 . . . -component non-magnetic toner or a two-component developer mixed with the non-magnetic toner and magnetic carrier, 58 . . Regulating blade. Figure 1 Figure 2

Claims (2)

[Claims] (1) An electrostatic one-image holder that holds electrostatic @ on its surface,
An insulating non-magnetic toner (T) is a fine silica powder produced by vapor phase oxidation of silicon halogen/compound by disposing the toner carrier supported on the surface of the insulating non-magnetic toner and the toner supporting member on the surface thereof in a developing section facing each other with a certain gap. Heat treated at temperatures above 7”
After C, the general formula % formula % (R is an alkoxy group or a chlorine atom, m is an integer of 1 to 3 (D is an integer, Y is at least one of an amino group, a vinyl group, a green/doxy group, a mercapto group, a methacryl group, and a ureido group) 1
or a hydrocarbon group containing two or more types, n is an integer of 3 to 1) treated with a silane cassilling agent, and the degree of hydrophobicity measured by a methanol titration test is a value in the range of 30 to 800 An insulating non-magnetic toner containing hydrophobized fine silica powder is supported on a toner carrier to a thin thickness across the gap as shown in FIG. Developing by transferring it to the body f: Characteristic developing method. (2) The developing method according to claim (1), wherein in the developing section, an alternating current and /i or direct current bias is applied between the toner carrier and the electrostatic image holder.