JPH11272068A - Regulating member of developer layer and image forming method and device using the member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a developer layer regulating member which stabilizes electrification and carrying of a toner for a long time, which causes no fog or irregular density and which gives stable image density without producing image defects such as stripes due to deposition or sticking of a toner on an electrifying member, and to provide a device and a method to form stable images by using this regulating member. SOLUTION: This developer layer regulating member 5 to form a thin layer of a developer on a developer carrying body 3 is produced by forming a coating layer containing at least one kind of compd. expressed by the formula of G-D-F on the surface of a base body. In the formula, G represents a subunit which form an inorg. network, D represents a flexible org. subunit and F represents a subunit containing tertiary amino groups. The coating layer is preferably a coating film essentially comprising silicon oxide which is produced from a material containing at least one kind of compd. expressed by the formula and a bifunctional or tetrafunctional silicon compd. In the image forming method and the device using this developer layer regulating member 5, a nonmagnetic one-component toner is preferably used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a developer layer regulating member used in a one-component developing system, and a method and an apparatus for forming an image using the same.

[0002]

2. Description of the Related Art As dry development methods of various electrostatic copying systems that are currently in practical use, a two-component development system using a carrier such as toner and iron powder and a one-component toner development system using no carrier are known. Have been. However, in the two-component developing method, the developer deteriorates due to toner particles adhering to the carrier surface, and only the toner is consumed and the concentration ratio of the toner in the developer decreases. There is a drawback that the developing device becomes large due to the provision of a density adjusting device or the like that keeps the toner constant, but the one-component developing method does not use a carrier, and thus does not have the above-described problem, and can reduce the size of the device. Because of its advantages, it is becoming the mainstream of the development system.

One-component toner developing systems include a magnetic one-component developing system using magnetic toner and a non-magnetic one-component developing system using non-magnetic toner. This magnetic one-component developing method uses a developer carrier having a magnetic field generating means such as a magnet inside, holds a magnetic toner containing a magnetic substance such as magnetite inside, and reduces the thickness by a layer regulating member. It is used for development, and has recently been put to practical use in small printers and the like. On the other hand, in the non-magnetic one-component developing method, a toner supply roll or the like is pressed against a developer carrier, and toner is held on the developer carrier by electrostatic force and supplied.
The toner is developed by forming a thin layer of toner with a layer regulating member, and has the advantage of being able to cope with colorization because it does not use a colored magnetic material. It has become possible to reduce the weight and cost, and in recent years, it has begun to be put to practical use in small full-color printers and the like.

In the two-component developing system, a carrier is used as a means for charging and conveying the toner. The toner and the carrier are sufficiently stirred and mixed in the developing device.
Since the toner is transported to the developer carrier and developed, stable charging and transport can be maintained even during use for a relatively long time, and high-speed development can be easily supported. In the one-component developing method, stable charging such as a carrier, since there is no transport means, when using for a long time or performing high-speed development, poor charging or poor transport is likely to occur,
At present, there are still many issues to be improved.

That is, in the one-component developing system, after the toner is conveyed onto the developer carrier, the toner is thinned by the layer regulating member and developed, but the toner, the developer carrier, and the layer regulating member are developed. Since the chances of contact charging and frictional charging with a charging member such as are limited to a very short time, the amount of the toner is likely to be insufficiently charged or the amount of the oppositely charged toner is likely to be increased as compared with the two-component developing method using a carrier. Toner requires a faster charging speed and an appropriate amount of charging.
In addition, in the one-component developing method, deterioration of the toner caused by external stress due to repeated use and contamination of the charging member by the toner particles and external additives have a great effect on the charging and developing property of the toner. In order to maintain the charge and the layer formation, it is necessary to design a toner and a charging member in combination with a stress resistance.

Conventionally, a metal sleeve such as aluminum or SUS stainless steel or an elastic sleeve in which a conductive agent such as carbon is dispersed in silicone rubber, NBR, EPDM, or the like has been used as a developer carrier. As the regulating member, an elastic blade such as urethane rubber or silicone rubber, or a metal blade such as SUS stainless steel or phosphor bronze is used. However, these charging members have low charging ability per se, so it is not only difficult to adjust the initial toner charging, but also the amount of low charging toner and reverse polarity toner increases due to toner deterioration and contamination of the charging member due to long-term use. As a result, problems such as fog and low image density tended to occur.

In order to improve the above-mentioned problem, many methods have been proposed, for example, in which a material having a charging polarity opposite to that of the toner is dispersed in the resin on the surface of the charging member to impart strong charging to the toner. (JP-A-61-118765, JP-A-61-122658, JP-A-61-1
No. 22660). According to these methods, although the initial charging characteristics of the toner are certainly improved and an image of good image quality is obtained, the problem of non-uniform charging distribution due to poor dispersion or the generation of a toner of the opposite polarity still cannot be solved. If used continuously for a long period of time, the toner and its additives, etc., are likely to electrostatically adhere to the surface of the charging member, especially the layer regulating member, and not only hinder the charging of the toner but also cannot maintain a uniform layer formation. And generate streaks on the image. These have been major obstacles particularly in a non-magnetic one-component developing method in which a toner does not contain a magnetic substance.

In order to solve these problems, Japanese Patent Application Laid-Open No. 2-150873 proposes a layer regulating member treated with a fluorine-containing coupling agent and a nitrogen-containing coupling agent. The treatment with the agent has limitations and is not fully satisfactory.
Japanese Patent Application Laid-Open No. 8-69173 proposes a metal regulating member having a ten-point average roughness Rz / toner diameter of 0.05 to 0.8 in the surface of the regulating member. Generally, it is preferable that the surface of the regulating member is slightly rough to improve the cleaning property of the surface, but this regulating member is still insufficient for suppressing the adhesion of toner.

Japanese Patent Application Laid-Open No. 9-50178 discloses that
It has been proposed to remove the adhered toner by dispersing the abrasive substance in the resin layer on the surface of the developing sleeve.In this method, although a certain amount of adhered toner can be removed, since the abrasive substance is present on the surface, Filming of the toner occurs on the surface due to the surface roughness. Further, if filming is prevented by the worn resin layer, there is a problem that the electrical resistance design and the charging application design of the resin layer are greatly restricted, and the stability is reduced when used repeatedly. Furthermore, Japanese Patent Application Laid-Open No. 9-265236 proposes to use a fluorine compound for the charging member, but a film containing the fluorine compound has insufficient mechanical strength and is easily worn. Therefore, the surface is roughened by abrasion, and the surface roughness triggers toner adhesion, or the abrasion is too large to change the linear pressure of the regulating member.
There are problems such as lowering of the charge of the toner, and the problem is not sufficiently improved.

[0010]

In recent years, as the demand for printers has increased, the size, speed, and cost of devices have been advanced, and there has been a demand for devices with higher reliability and longer life. I have. The present invention has been made in view of the above-mentioned circumstances, and has an object to solve those problems. That is, an object of the present invention is to stabilize the charging and conveyance of the toner for a long period of time so that fog and density unevenness do not occur, and the toner to a charging member such as a developer carrying member and a developer layer regulating member is controlled. It is an object of the present invention to provide a developer layer regulating member used in a one-component developing system capable of obtaining a stable image density in which streaks are not generated on an image due to adhesion or sticking of the toner. Another object of the present invention is to provide a one-component image forming apparatus having high reliability, which can be adapted to miniaturization, high speed, and low cost, and can be used stably for a long period of time, and an image using the same. It is to provide a forming method.

[0011]

According to the present invention, as a result of intensive studies to solve the above-mentioned problems, a specific network is formed at a portion of the developer layer regulating member which comes into contact with the developer carrier. By providing a coating layer containing a compound, a good charge is imparted to the developer (toner), and it is possible to prevent toner particles and their additives from adhering or sticking to the surface of the layer regulating member, and to provide a long term The present inventors have found that a uniform toner layer can be stably formed on the developer carrying member over the entire area, and have completed the present invention.

The developer layer regulating member of the present invention is for forming a thin layer of a developer on a developer carrier, and has a compound represented by the following general formula (I) on the surface of a substrate. A coating layer containing at least one of the following. GDF (I) (wherein, G is an inorganic network-forming subunit, D is a flexible organic subunit, and F is a tertiary amino group-containing subunit.) The coating layer of the agent layer regulating member is a coating mainly composed of silicon oxide obtained from a material containing at least one compound represented by the general formula (I) and a bifunctional or tetrafunctional silicon compound. Preferably, there is.

The image forming apparatus according to the present invention comprises means for forming an electrostatic latent image on a latent image holding member, and a one-component toner on the developer holding member by bringing a developer layer regulating member into contact with the developer holding member. An image forming apparatus having a means for forming a thin layer of a toner, a means for visualizing an electrostatic latent image with toner, a means for transferring a toner image onto a transfer member, and a means for heating and fixing a developer image. A layer regulating member includes the above-described developer layer regulating member.

According to the image forming method of the present invention, there is provided a step of forming an electrostatic latent image on a latent image holding member, wherein a developer layer regulating member is brought into contact with the developer holding member to form a one-component toner on the developer holding member. A step of forming a thin layer, a step of forming a toner image by visualizing the electrostatic latent image with the toner, a step of transferring the obtained toner image onto a transfer body, and heating and fixing the transferred toner image In the image forming method having the steps, the above-mentioned developer layer regulating member is used as the developer layer regulating member. In the image forming method of the present invention, it is preferable to use a one-component non-magnetic toner.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to the drawings. The developer layer regulating member of the present invention includes a latent image forming step of forming an electrostatic latent image on a latent image holding member, a contact of the developer layer regulating member with the developer carrying member, and a thin layer on the developer carrying member. A developing step of using the formed toner to visualize the electrostatic latent image on the latent image holding member, a transferring step of transferring the toner image on the latent image holding member to a transfer member, and heating the toner image on the transfer member It is used in an image forming method and an apparatus having a fixing step for fixing, and is used, for example, in a one-component image forming apparatus shown in FIG.

FIG. 1 shows an example of the image forming apparatus of the present invention, and is a schematic configuration diagram of a one-component non-magnetic image forming apparatus. In FIG. 1, a latent image holding member 1 is charged by a roll charger 2 and is exposed to a laser beam (not shown) to form an electrostatic latent image. The developer carrier 3 is disposed so as to face the latent image carrier 1, and the developer layer regulating blade 5 is formed so as to form a thin layer of toner on the surface thereof.
Are provided so as to come into contact with each other at a constant pressure. For example, a DC voltage and an AC voltage are applied to the developer carrier 3 and the developer supply roll 4 (or the developer supply brush). Reference numeral 6 denotes a transfer roll, 7 denotes a cleaner, 8 denotes a fixing device, 9 denotes a developer, 10 denotes a developing device, and 11 denotes a transfer member.

In the latent image forming step, a conventionally known method can be applied, and an electrostatic latent image is formed on a latent image holding member such as a photosensitive layer or a dielectric layer by electrophotography or electrostatic recording. To form As the photosensitive layer of the latent image holding member used in the present invention, any known organic or amorphous silicon-based photosensitive layer can be used. When the latent image holding member is cylindrical, it can be obtained by a known manufacturing method such as extruding aluminum or an aluminum alloy and then processing the surface. It is also possible to use a belt-like latent image holding member.

In the developing step, a thin layer of toner is formed on a rotating cylindrical body used as a developer carrying member (developing roll) by a layer regulating member, and is transported to a developing nip. The developing roll is in contact with the latent image holding member that holds the electrostatic latent image in the developing unit or is disposed with a certain gap therebetween, and applies a bias voltage between the developing roll and the latent image holding member. While developing the electrostatic latent image with toner. In the magnetic one-component development, a rotating cylinder having a magnet built therein is used as a developer carrier, and toner having a magnetic material is transported and held by a magnetic force. In non-magnetic one-component development,
For example, a urethane sponge, a conductive polypropylene or acrylic brush, a toner supply roll, or the like is pressed against the developer carrier to supply the toner onto the developer carrier.

The developer carrier used in the present invention includes an elastic sleeve in which a conductive agent such as carbon is dispersed in silicone rubber, NBR, EPDM or the like, aluminum, SUS or the like.
A sleeve or metal obtained by drawing metal or ceramics such as stainless steel, or a substrate that has been subjected to surface treatment such as oxidation or metal plating, polishing, or blasting to control the transportability and chargeability of the toner. These bases are coated with a resin such as an acrylic resin or a phenol resin or a resin mixture obtained by dispersing a charge control agent, a conductive agent, a lubricant or the like on these resins, and a plastic sleeve obtained by integrally molding these. .

The regulation of the toner layer is performed by bringing the developer layer regulating member into contact with the surface of the developer carrier. The developer layer regulating member of the present invention uses an elastic blade of silicone rubber, urethane rubber or the like or a metal blade of SUS stainless steel, phosphor bronze or the like as a base material, and has the surface of the general formula (I) By forming a film containing at least one of the compounds represented by the formula, good chargeability can be imparted to the toner, and the toner particles and additives thereof adhere or adhere to the surface of the layer regulating member even after long-term use. In this case, good layer formation and good chargeability could be continuously obtained. In the present invention, the curable compound represented by the general formula (I) is contained in the coating layer so that when the coating layer is formed and dried, or when the coating layer passes through a high-humidity chamber, charging is imparted. Sexual substance itself,
Alternatively, a network is formed with the binder resin component and the like, and a very hard film is formed, so that a film having stable characteristics can be obtained.

Further, a coating mainly composed of silicon oxide formed by adding a bifunctional, trifunctional or tetrafunctional silicon compound to the compound represented by the above general formula (I) has a much higher quality. It becomes a film having hardness, and the dispersion state in the obtained film becomes uniform and good. The reason for this is that a silicon oxide film obtained using a bifunctional or trifunctional or tetrafunctional silicon compound as a main component is a huge polymer compound in which siloxane bonds of Si—O—Si spread in a three-dimensional network. Therefore, it is extremely hard and has excellent scratch resistance, abrasion resistance and heat resistance, and also has the function that silicone resin has essentially low surface energy and stain resistance. It is assumed that this is due to It is also considered that one factor is that the toner component adheres and the coating layer surface is less deteriorated due to scratches and abrasion even after long-term use.

Furthermore, since the above-mentioned coating has an appropriate conductivity due to silanol groups remaining in the siloxane network as compared with those of other plastics, it has a low temperature and low humidity, especially as seen in conventional plastic coatings. Electrostatic adhesion to the layer regulating member due to charge-up of the toner in the environment is prevented, and the toner is given an appropriate negative charging property, so that the difference between the toner charge in the low-temperature low-humidity environment and the high-temperature high-humidity environment is obtained. Can also be reduced. The compound represented by the general formula (I) has a high affinity with the bifunctional, trifunctional, and tetrafunctional silicon compounds due to its structure, disperses well, and forms a uniform dispersed film. Since the toner can be formed, a uniform charge can be imparted to the toner, and the hardness of the coating film is improved by dispersing the compound.

Although the developer layer regulating member of the present invention can be applied to magnetic one-component development and non-magnetic one-component development, it is more effective to use it for non-magnetic one-component development in which the toner does not contain a magnetic substance. This means that in the case of a magnetic toner, the magnetic material exposed on the toner surface is effective to some extent to mechanically scrape off the toner components attached to the charging member surface, but the toner charging in a low temperature and low humidity environment is not effective. This is considered to be due to the fact that charge-up is more difficult than when magnetic toner is used.

In the present invention, the compound used in the coating layer of the developer layer regulating member is represented by the following general formula (I). GDF (I) In the general formula (I), G is an inorganic network-forming subunit, D is a flexible organic subunit, and F is a tertiary amino group-containing subunit.

The inorganic network-forming subunit (G) is selected from materials capable of forming a network of inorganic compounds. Examples of the material include an inorganic compound containing a compound of a trivalent or higher polyvalent element capable of forming a network structure by hydrolysis and condensation reaction.
Halides, acid halides, hydroxides, alkoxides or esters of elements such as Si, Al, Ti, Cu, Fe, Se and Te are used.
A silicon compound capable of forming a siloxane bond of i-O-Si is preferable, and more preferably a silicate ester residue other than Y in the compound represented by the following general formula (III). —Y—SiR ¹ _(3-a) (OR ² ) _a (III) In the general formula (III), R ¹ is a hydrogen atom, an alkyl group or an unsubstituted aryl group, and R ² is a hydrogen atom, an alkyl group Or a trialkylsilyl group. a is 1, 2
Or 3.

The flexible organic subunit (D) is a group represented by Y in the compound represented by the general formula (III), and comprises the inorganic network forming subunit (G) and the tertiary An organic group having two or more reactive groups bonded to the amino group-containing subunit (F) and capable of imparting flexibility, and for example, may have a substituent 2
Is a monovalent saturated or unsaturated aliphatic hydrocarbon, aromatic hydrocarbon or araliphatic hydrocarbon group.
_x H _2x - _(x an integer of _{1~15), - C x 'H} 2x' -2 -
(X 'is an integer of 2 to 15), -Cx _{" H2x" -4-} (x "
Is an integer of 2 to 15) or a substituted or unsubstituted divalent aryl group, or a divalent saturated group containing at least one selected from -CH = N-, -O- and -COO-, or Unsaturated aliphatic hydrocarbons, aromatic hydrocarbons or araliphatic hydrocarbon groups are preferred.

Further, as the tertiary amino group-containing subunit (F), any tertiary amino group-containing compound capable of imparting a negative charge can be used, but it is particularly preferably used in the present invention. Examples thereof include residues of a tertiary amino group-containing compound represented by the following general formula (II).

[0028]

Embedded image In the general formula (II), Ar _{1 to} Ar ₄ are each independently a substituted or unsubstituted aryl group;
₅ is an unsubstituted aryl or arylene group,
_{One to} four groups in r _{1 to} Ar ₅ have a substituent represented by the above-mentioned G-D-. k is 0 or 1.

The above general formula (I) used in the present invention
Tables 1 to 37 show specific examples of the compounds represented by In the table, Me means a methyl group, Et means an ethyl group,
Further, X in the columns of Ar _{1 to} Ar ₅ indicates that the silyl group shown in the column X of the table is substituted. (Monofunctional triphenylamine)

[Table 1]

[0030]

[Table 2]

[0031]

[Table 3]

[0032]

[Table 4]

[0033]

[Table 5]

[0034]

[Table 6]

[0035]

[Table 7]

[0036]

[Table 8]

[0037]

[Table 9]

[0038]

[Table 10]

(Monofunctional benzidine)

[Table 11]

[0040]

[Table 12]

[0041]

[Table 13]

(Bifunctional triphenylamine)

[Table 14]

[0043]

[Table 15]

[0044]

[Table 16]

[0045]

[Table 17]

[0046]

[Table 18]

[0047]

[Table 19]

[0048]

[Table 20]

[0049]

[Table 21]

(Bifunctional benzidine)

[Table 22]

[0051]

[Table 23]

[0052]

[Table 24]

[0053]

[Table 25]

[0054]

[Table 26]

[0055]

[Table 27]

[0056]

[Table 28]

[0057]

[Table 29]

(Trifunctional triphenylamine)

[Table 30]

[0059]

[Table 31]

[0060]

[Table 32]

[0061]

[Table 33]

[0062]

[Table 34]

(4-functional benzidine)

[Table 35]

[0064]

[Table 36]

[0065]

[Table 37]

The coating layer in the present invention is used in combination with the compound represented by the above general formula (I) as a raw material for forming a coating mainly composed of silicon oxide having a network structure of higher hardness. It is preferred to use bifunctional to tetrafunctional silicon compounds. Examples of the bifunctional silicon compound used in the present invention include an alkali silicate (alkali silicate) composed of silicic acid (SiO ₂ ) and an alkali (Na ₂ O, K ₂ O, Li ₂ O, etc.), aqueous colloidal silica (aqueous silica gel) ), Organosilica gel using an alcohol such as methyl alcohol, ethyl alcohol and isopropyl alcohol, an organic solvent such as toluene and tetrahydrofuran as a dispersion medium, tetrafunctional halogenated silane such as carbon tetrachloride, orthosilicic acid [Si (OH) ₂ ], Tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetra-sec-butoxysilane, tetra-te
Condensation products (organic silicates) such as monomers of alkyl esters of orthosilicic acid such as rt-butoxysilane or dimers and trimers obtained by hydrolysis and condensation reactions thereof
And the like.

As the trifunctional silicon compound, R ³ —Si
-L ₃ (wherein, R ³ is a hydrogen atom or an aliphatic or aromatic hydrocarbon, preferably an alkyl group having 1 to 6 carbon atoms. L is a chlorine atom or a methoxy group, an ethoxy group, etc. And a condensation product obtained by hydrolysis and condensation of the organosilicon compound represented by the formula (1), which is a reactive group chemically bonded to an inorganic material by hydrolysis such as an alkoxy group having 1 to 4 carbon atoms. Specific examples of the organic silicon compound include methyltrichlorosilane and methyltrimethoxysilane. Also, K-Si-L
₃ (where K is a vinyl group, an epoxy group, a methacryl group,
An organic group having a reactive group chemically bonded to an organic material such as an amino group or a mercapto group, L has the same meaning as described above. Or a condensation product obtained by hydrolysis and condensation of the silane coupling agent. Specific examples of the silane coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, γ- Glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacrylic Roxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyltri Tokishishiran, .gamma.-aminopropyltriethoxysilane, N-beta (aminoethyl) .gamma.-aminopropyltrimethoxysilane, N-beta
(Aminoethyl) γ-aminopropylmethyldimethoxysilane and the like are used.

The bifunctional silicon compound is a compound represented by the following general formula (a).

Embedded image (Wherein, R ⁴ and R ⁵ may be the same or different and are a hydrogen atom or an aliphatic or aromatic hydrocarbon, preferably an alkyl group having 1 to 6 carbon atoms, or a vinyl group,
L, an organic group having a reactive group chemically bonded to an organic material such as an epoxy group, a methacryl group, an amino group, and a mercapto group, has the same meaning as described above. ) And a silane coupling agent represented by the hydrolysis / condensation product thereof and a condensation product obtained by the hydrolysis and condensation reaction thereof. Specific examples thereof include 3-glycidoxypropylmethyldimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane,
Examples include phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylvinyldimethoxysilane, phenylvinyldiethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane.

In order to obtain the coating liquid used for forming the coating layer of the present invention, water and a catalyst as a curing agent are added to a material composition containing the above-mentioned materials as a main component.
Hereinafter, the method will be described.

In the present invention, the degree of hydrolysis and the degree of condensation of the coating liquid used for forming the coating layer vary depending on the amount of water used. Usually, the amount of water to be added is preferably in the range of 1 to 20% by weight based on the silicon compound. If the amount of water added is less than 1% by weight, the film cannot be formed.
If the amount is more than 10% by weight, it takes time to cure or the curing is insufficient.

Examples of the catalyst used in the coating agent include acidic catalysts, aminosilanes, quaternary ammonium salts of inorganic or organic acids, amine salts of inorganic or organic acids,
One or more compounds selected from organic tin compounds and the like can be mentioned. As the acidic catalyst, there are organic acids and inorganic acids, for example, a dilute solution of formic acid, acetic acid, oxalic acid, chloroacetic acid, hydrochloric acid, phosphoric acid, sulfuric acid, etc. is used,
These acids can be used as a mixture of two or more kinds.
The addition amount of the catalyst, the above-mentioned catalyst alone or two or more,
It is used at a concentration in the range of 50 to 1500 ppm based on the solid content in the composition solution. If the amount is less than the lower limit, the effect of adding the catalyst is not recognized.

In the present invention, a diorganopolysiloxane having both molecular ends blocked with hydroxyl groups as represented by the following general formula (b) is produced from the above-mentioned bifunctional silicon compound and trifunctional silicon compound. However, those containing this as a main component are also suitable as a coating agent.

[0073]

Embedded image (Wherein, R ⁶ and R ⁷ may be the same or different and each represents an unsubstituted or substituted monovalent hydrocarbon group;
Is an integer greater than or equal to. In the general formula (b), specific examples of R ⁶ and R ⁷ include an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, a cycloalkyl group such as a cyclohexyl group, a vinyl group or an allyl group. Aryl groups such as alkenyl group, phenyl group or tolyl group, aralkyl groups such as benzyl group or phenylethyl group, and groups in which hydrogen atoms of these groups are substituted with halogen atoms, for example, chloromethyl group, 3,3,3 -Trifluoropropyl group and the like. In addition, these diorganopolysiloxanes
The viscosity at 25 ° C. is 10 to 1000 cSt, especially 10
Since p is preferably in the range of 300 cSt, p in the formula (b) is preferably in the range of 3 to 50. At this time, the above-mentioned trifunctional silicon compound can be used simultaneously as a cross-linking agent in this diorganopolysiloxane, taking into account the film-forming speed and the pot life (the period during which the composition does not gel during storage). The above catalyst may be appropriately added.

In the present invention, when the compound represented by the general formula (I) is dispersed and mixed in the coating liquid, the compounding ratio (weight ratio) of the above functional silicon compound and the compound represented by the general formula (I) ) Is preferably used in the range of 1000: 1 to 1: 1 and more preferably 1000: 5 to 2: 1. These dispersion methods include a ball mill dispersion method,
Known methods such as an attritor dispersion method and a sand mill dispersion method can be applied. Further, the solvent is used in an amount of 5 to 10000 parts by weight, preferably 7 to 50 parts by weight, based on 100 parts by weight of the functional silicon compound as the raw material of the coating and the compound of the formula (I).
Can be used at 0 parts by weight.

The silicon oxide film thus obtained is
Although it is very hard and has excellent wear resistance and abrasion resistance, it has a drawback that cracks easily occur due to volume condensation during the curing process. Therefore, when forming a coating film, it is important to set an appropriate hydrolysis rate, catalyst type, reaction / curing time, curing temperature, and the like. In order to increase the adhesion to the base material or the coating strength, if necessary, flake or fibrous fine powder such as mica, talc, asbestos, zinc powder, aluminum powder, etc. And various pigments such as carbon powder, carbon black, graphite, and iron oxide.

Further, as a method for increasing the adhesion to the substrate and the film strength, a graft polymer is formed by forming an organic polymer having a hydroxyl group in a molecule such as polyvinyl alcohol, polyester resin, epoxy ester resin, phenol resin and the like. Or a three-component graft polymer obtained by adding a silane coupling agent thereto, or a difunctional or trifunctional silicon compound thereof and a silicone resin, an acryl-silicone resin, an acrylic resin, an epoxy resin, a phenol resin, or butyral. Resin, melamine-
Acrylic resin, melamine-alkyd resin, acrylic-
A method of increasing the resin hardness and coating strength by mixing with a resin such as an epoxy resin or an acrylic-urethane resin may be used. However, when the ratio of the resin to be mixed is high, necessary properties other than the film strength are reduced. Therefore, when the composite is formed, the weight ratio of the bifunctional or trifunctional silicon compound in the entire composite film is reduced. It is preferably at least 20%, preferably at least 40%, more preferably at least 60%.

The thus-obtained film containing silicon oxide as a main component is very hard and has excellent abrasion resistance and abrasion resistance. Therefore, when a film is formed, it is important to set an appropriate hydrolysis rate, a catalyst type, a reaction and curing time, a curing temperature, and the like. Also, for the purpose of increasing the adhesion to the base material or the coating strength, etc., if necessary, scaly or fibrous fine powder such as mica, talc, asbestos, zinc powder, aluminum powder, etc. Various pigments such as metal powder such as powder, carbon black, graphite, iron oxide and the like can be appropriately added.

Further, as a method for improving the adhesiveness to the substrate and the film strength, a graft polymer is formed by forming an organic polymer having a hydroxyl group in a molecule such as polyvinyl alcohol, polyester resin, epoxy ester resin and phenol resin. Or a three-component graft polymer to which a silane coupling agent is added, or a bifunctional or trifunctional silicon compound and a silicone resin, an acrylic-silicone resin, an acrylic resin,
Epoxy resin, phenolic resin, butyral resin, melamine-acrylic resin, melamine-alkyd resin, acryl-epoxy resin, acrylic-urethane resin and the like to increase the resin hardness and film strength by mixing the resin and the like. . By the way, when the ratio of the resin to be mixed is high, necessary properties other than the film strength are reduced. Therefore, when the composite is formed, the weight ratio of the bifunctional or trifunctional silicon compound in the total composite film is 20%. % Or more, preferably 40% or more, more preferably 60% or more.

For the purpose of assisting the charge of the toner or controlling the resistance, resin powder such as PMMA, melamine, nylon, silicone, a charge control agent such as a metal azo dye complex and a quaternary ammonium salt, and a styrene-acrylic resin. Charge control resins such as polymers and polyesters; inorganic fine powders such as silica, titania, tin oxide, zinc oxide, magnesium oxide, ferrite, and magnetite; conductive powders such as carbon black and graphite; and semiconductive agents such as molybdenum disulfide. Etc. can be included in the coating.

In the present invention, the developer layer regulating member (hereinafter, referred to as a “layer regulating member”) on which the coating containing silicon oxide as a main component is formed is provided with a toner suitable for a developing area by a developer carrier. By transporting the toner amount, a more uniform toner layer is formed on the developer carrying member, and is brought into contact with the developer carrying member at a certain pressure. In this case, the amount of toner can be controlled by various conditions of the developing machine, but the position of the layer regulating member that is in contact with the developer carrier is important.

In the present invention, it is preferable that a position within 3 mm from the tip of the free end (unfixed side) of the layer regulating member is brought into contact with the developer carrying member. This is because the closer the contact position of the layer regulating member is to the free end, the more the proper amount of toner can be transported even if the contact is made at a lower pressure. When the contact pressure can be set low, the pressure applied to the toner is reduced, and the long-term storage property and fluidity of the toner are improved, so that the inorganic fine powder or the organic fine powder added to the toner surface is released from the toner. In addition, the burial in the toner is reduced, and it can withstand repeated use for a long time.

The reason why the closer the position of the layer regulating member in contact with the developer carrying member to the free end, the more appropriate amount of toner can be conveyed by low pressure contact is considered as follows. Generally, the toner excessively adheres to the developer carrying member in the developing machine due to the adhesive force between the toners and the mechanical pressure by the elastic roll. An excess amount of this excess toner is scraped off by the layer regulating member, and the toner that has passed through the region (nip) pressed by the developer carrier and the layer regulating member moves to the developing region. On the other hand, the scraped toner must move in a narrow space (prenip portion) sandwiched between the developer carrier and the layer regulating member in a direction opposite to the direction in which the developer carrier moves. However, since the movement of this space becomes a so-called reverse flow, it is involved in the movement of the toner on the developer carrying member and tries to move in the nip direction again. It is estimated that the smaller the space of the pre-nip portion, the smaller the amount of toner to be caught, so that the closer the contact position is to the free end, the more the amount of toner can be conveyed with a relatively low contact pressure. Is done.

In the layer regulating member of the present invention, even when the layer regulating member is brought into contact with the developer carrier at a position within 3 mm from the free end, the coating mainly composed of silicon oxide formed on the layer regulating member is
It is kept smooth without cracks or voids. Therefore, the surface of the layer regulating member forming the pre-nip portion is also smooth, and there is no disturbance in the movement of the toner, there is no fusion of the toner, and a uniform toner layer can be maintained for a long time, and white streaks appear on the printed image. The effect of not being generated is obtained.

In the present invention, when the amount of the tetrafunctional silicon compound used among the above-mentioned bifunctional to tetrafunctional silicon compounds used as a raw material of the film is increased, the film becomes Si—O—Si Are more densely formed, have higher hardness, and have improved scratch resistance. However, it is not preferable to use the tetrafunctional silicon compound in a certain amount or more. This is because, when a coating solution is applied thickly to form a thick film, a difference occurs in the reaction rate between the surface and the inside of the coating layer when the coating solution is solidified by a dealcoholization reaction, and the film formed after the reaction is formed. It is considered that cracks and cracks occur due to differences in volume shrinkage and the like. Therefore, when a tetrafunctional silicon compound is used, it is desirable that the total weight of the tetrafunctional silicon compound in the entire composite coating is 10% or less.

As the coating method for forming the film of the present invention, known coating methods such as spray coating and dip coating are used.
In order to stabilize the layer formation for a long period of time,
It is preferably in the range of 20 μm, preferably 3 to 10 μm. Further, it is preferable that the surface of the coating is formed uniformly and smoothly. In addition, since the tip of the base material on which the layer regulating member acts is at an acute angle, it is necessary that the coating liquid is not applied to the free end of the layer regulating member. When applied to the layer regulating member including the tip, the thickness near the tip of the free end becomes thick, and there is a problem that cracks and cracks are formed near the tip.

The transfer step in the present invention includes contact-type transfer in which a transfer roller and a transfer belt are pressed against a latent image holding member to transfer a toner image to a transfer member, and non-contact transfer in which a toner image is transferred to a transfer member using a corotron. Known methods such as a method in which a toner image is once transferred to a mold, a belt-like or cylindrical intermediate transfer body, and then transferred to another transfer body are used.

The cleaning step is a step of removing the toner remaining on the latent image holding member without being transferred in the transfer step by a cleaner. When the amount of untransferred toner is small, a cleaner-less operation is possible. When the cleaning step is provided, a known one such as blade cleaning, brush cleaning or roller cleaning is used, and elastic cleaning such as silicone rubber or urethane rubber is used for blade cleaning. In the fixing step, the toner image transferred to the transfer body is fixed by a fixing device. As the fixing means, a heat fixing method using a heat roll is preferably used.

The toner used in the present invention contains at least a binder resin and a magnetic substance in a magnetic toner, and contains at least a binder resin and a colorant in a non-magnetic toner. As the binder resin of the toner,
Polystyrene, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyethylene, polypropylene, polyester, polyurethane Known materials such as epoxy resin, silicone resin, polyamide, modified rosin, and paraffin wax can be used, and among them, styrene-acrylic copolymer and polyester are preferably used.

In recent years, with the progress of colorization, a binder resin having a low softening point has been frequently used from the viewpoint of improving the smoothness and transparency of a fixed image. Have a problem that they easily fuse with a charging member and easily hinder the chargeability of toner and layer formation. In particular, in the present invention, a binder resin having a softening point of 90 to 120 ° C. and a low softening point is used. The effect is great when there is. Here, the softening point means a temperature at a melt viscosity of 10 ⁴ Pa · s (10 ⁵ poise) measured with a flow tester (manufactured by Shimadzu Corporation, nozzle 1 × 1 mm, load 10 kg).

Examples of colorants for toner include carbon black, aniline blue, calcoil blue, chrome yellow, ultramarine blue, Dupont oil red, quinoline yellow, methylene blue chloride, copper phthalocyanine, malachite green oxalate, lamp black, and the like. Rose Bengal, C.I. I. Pigment Red 48: 1, C.I. I. Pigment Red 122,
C. I. Pigment Red 57: 1, C.I. I. Pigment Yellow 97, C.I. I. Pigment Yellow 1
2, C.I. I. Pigment Yellow 17, C.I. I. Pigment Yellow 180, C.I. I. Pigment Blue 15: 1, C.I. I. Known ones such as CI Pigment Blue 15: 3 can be used.

As the magnetic material, any conventionally known magnetic material can be used. For example, metals such as iron, cobalt and nickel or alloys thereof, Fe ₃ O ₄ , γ-F
e ₂ O ₃ , metal oxides such as cobalt-added iron oxide, MnZ
Ferrites such as n ferrite and NiZn ferrite are exemplified. These magnetic substances are usually used by adding 30 to 70% by weight.

Further, a release agent may be added to the toner used in the present invention for the purpose of improving gloss and offset resistance. As the release agent, a paraffin having 8 or more carbon atoms, a polyolefin, or the like is preferable. For example, paraffin wax, paraffin latex, microcrystalline wax, carnauba wax, or polypropylene,
Polyethylene and the like are used, and these are used alone or in combination. Furthermore, in order to assist toner charging,
A charge control agent can be added. Examples of the charge control agent when used as a negatively charged toner include azo complex salt dyes such as chromium and iron, complex compounds such as chromium, zinc, aluminum and boron of salicylic acid and charge control resins. Known compounds such as quaternary ammonium salts can be used.

Further, the toner may include fine particles of a fluidizing agent for imparting appropriate fluidity and chargeability to the developer, conductive powder for improving the charge exchange property, and improving the cleaning property and the photosensitive member. An additive such as a lubricant or an abrasive for preventing black spots, white spots, white spots, comets, filming, etc. due to the adhesion of toner or external additives to the talc may be mixed. Examples of the fluidizing agent fine particles used include hydrophobic silica, hydrophobized fine particles titanium oxide, inorganic fine powders such as alumina, organic fine powders such as fatty acids or their derivatives or metal salts, fluororesins, acrylic resins or styrene resins. Resin fine powder such as resin, cerium oxide, magnetite and the like can be mentioned, and these can be used alone or in combination.

The volume average particle diameter of the toner is 4
To 12 μm, more preferably 5 to 10 μm. When the volume average particle size is less than 4 μm, the fluidity is remarkably reduced, so that a sufficient layer cannot be formed, and fog and dart are easily caused. On the other hand, 12
If it is larger than μm, not only the resolution is lowered and high image quality cannot be obtained, but also the charge amount per unit weight of the developer is reduced, so that the layer formation maintenance is poor and fog and dirt are easily generated.

The toner used in the present invention can be produced by any known method. For example, kneading and grinding methods,
That is, after premixing the binder resin, the colorant, and the charge control agent added as necessary, the mixture is melt-kneaded in a kneader, the obtained kneaded material is cooled and pulverized, and then classified. A method in which external additive fine particles are added to and mixed with the toner particles obtained by the above method, a polymer toner obtained by suspension polymerization or emulsion polymerization, or the like is used.

[0096]

The present invention will be described below in more detail with reference to examples. The compounds in the table represented by the general formula (I) can be synthesized as follows.

Synthesis Example 1 [Synthesis of Compound (13)] In a 500 ml two-necked flask purged with nitrogen, 25 g of 3-iodopropyltrimethoxysilane was placed, and toluene was added.
Dissolved in 00 ml. Then, 27 g of triphenylphosphine was added. Then, after heating and refluxing for 7 hours with stirring, the precipitated crystals were washed well with toluene, and the solvent was removed under reduced pressure to obtain 36.5 g of a phosphonium salt.
(Melting point: 102.0 to 102.5 ° C., white crystals) Next, 30 g of the above phosphonium salt was placed in a 1000 ml two-necked flask purged with nitrogen, and dissolved in 600 ml of anhydrous dimethylformamide. Next, the reaction system was changed to -5.
C., 2.1 g of sodium hydride was added, and the mixture was stirred for 15 minutes. Thereafter, with stirring, 10.2 g of N- (4-formylphenyl) -N- (3,4-dimethylphenyl) biphenyl-4-amine was added, and the temperature was gradually raised to room temperature, followed by stirring for 2 hours. After completion of the reaction, 20 ml of methanol was added, and the reaction mixture was further poured into 3 liters of ice water and extracted with toluene. After removing the solvent from this solution under reduced pressure, the residue was purified by column chromatography on silica gel (solvent: toluene) to obtain 12 g of compound (13). (Pale yellow oily substance)

Synthesis Example 2 [Synthesis of Compound (3)] A 200 ml eggplant-shaped flask was charged with 6 g of the compound (13) obtained in Synthesis Example 1, and 20 ml of tetrahydrofuran was added.
1 and 20 ml of ethanol. Then, 5% P
0.1 g of dC was added, the atmosphere was replaced with dry hydrogen, and the reaction was carried out at room temperature for 15 hours with the mouth of the flask connected to a dry hydrogen supply source. After completion of the reaction, Pd-C was filtered, the solvent was removed under reduced pressure, and then column purification was performed on silica gel (solvent: toluene), followed by recrystallization (solvent: toluene / hexane = 1/5). 4.2 g of compound (3) were obtained. (Melting point 71.5-72 ° C, colorless transparent crystal)

Synthesis Example 3 Synthesis of Compound (155) 15.9 g of the phosphonium salt synthesized in Example 1 was placed in a two-necked flask purged with nitrogen, and dissolved in 300 ml of anhydrous dimethylformamide. Next, the reaction system was cooled to −5 ° C., and 1.5 g of sodium hydride was added, followed by stirring for 15 minutes. Then, with stirring, 3,3'-dimethyl-N,
6.0 g of N'-bis (4-formylphenyl) -N, N'-bis (3,4-dimethylphenyl) -1,1'-biphenyl-4,4'-diamine are added, and the temperature is gradually raised to room temperature. And stirred for 2 hours. After completion of the reaction, 30 ml of methanol was added, and the reaction mixture was further poured into 3 liters of ice water, extracted with toluene, and the solvent was removed under reduced pressure.
Column purification (solvent: toluene) with silica gel gave 6.9 g of compound (155). (Pale yellow oily substance)

Synthesis Example 4 [Synthesis of Compound (145)] The compound (155) obtained in Synthesis Example 3 in an eggplant-shaped flask
6.3 g was added and dissolved in 20 ml of tetrahydrofuran and 20 ml of ethanol. Then, 5% Pd-C0.
2 g was added, the atmosphere was replaced with dry hydrogen, and the reaction was carried out at room temperature for 15 hours with the mouth of the flask connected to a dry hydrogen supply source.
After completion of the reaction, Pd-C was filtered, the solvent was removed under reduced pressure, and then column purification was performed on silica gel (solvent: hexane / ethyl acetate = 1/1) to obtain 5.9 g of compound (145). (Pale yellow oily substance)

Synthesis Example 5 [Synthesis of Compound (60)] N- (4-formylphenyl) -N- (3,4-dimethylphenyl) biphenyl-
10 g of 4-amine was added and dissolved in 100 ml of toluene. Next, 1 g of molecular sieve 4A and 0.5 g of paratoluenesulfonic acid were added. Thereafter, while stirring, 13 g of 4-aminopropyltrimethoxysilane was added in 1 g.
After dropping over 0 minutes and stirring at room temperature for 5 hours, 200 m
The mixture was poured into 1 l of water, extracted with toluene, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 13.2 g of compound (60). (Pale yellow oily substance)

Synthesis Example 6 [Synthesis of Compound (165)] In a two-necked flask purged with nitrogen, 3,3'-dimethyl-N,
10 g of N'-bis (4-formylphenyl) -N, N'-bis (3,4-dimethylphenyl) -1,1'-biphenyl-4,4'-diamine was added, and toluene 100 m
l. Then, molecular sieve 4A1g
And 1 g of paratoluenesulfonic acid. Thereafter, while stirring, 12 g of 4-aminopropyltrimethoxysilane
Was added dropwise over 10 minutes, and the mixture was stirred at room temperature for 5 hours.
The mixture was poured into 0 ml of water, extracted with toluene, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 11 g of compound (165). (Pale yellow oily substance)

Example 1 (Preparation of Layer Control Member 1) A flask equipped with a stirrer, a thermometer and a reflux condenser was charged with methyltrimethoxysilane 1
00 parts by weight, 100 parts by weight of dimethyldimethoxysilane,
80 parts by weight of isopropyl alcohol and 20 ethanol
3 parts by weight of ion-exchanged water was added to the basic composition consisting of parts by weight, 1 part by weight of nitric acid was further added, and the mixture was mixed at 25 ° C. for 1 hour to prepare a coating agent. . 20 g of this coating agent and 5 g of compound (3)
-8 g of a solution dissolved in 90 g of butanone was mixed to obtain a coating liquid (1) for forming a layer regulating member. Using the obtained coating liquid (1), 8 mm from the tip of the free end of the surface of a plate-like body having a 1 mm-thick urethane rubber stuck on a 0.15 mm-thick SUS stainless steel substrate
Is spray-coated in an atmosphere of 25 ° C. and 50 RH%, dried in an atmosphere of 25 ° C. and 50 RH% for 24 hours, and further dried and cured at 100 ° C. for 3 hours to form a film having a thickness of about 5 μm. A layer regulating member (1) having a coating layer was obtained.
The state of the film of the obtained coating layer was good, and there was no crack or crack.

(Preparation of Non-Magnetic One Component Toner 1) 92 parts of polyester resin (terephthalic acid / bisphenol A ethylene oxide adduct weight average molecular weight Mw: 12,000, Tg: 65 ° C., softening point: 100 ° C.) Copper phthalocyanine blue pigment 5 Part Charge control agent: Bontron E84 (manufactured by Orient Chemical Industry Co., Ltd.) 3 parts After premixing the above materials with a Henschel mixer,
The mixture was kneaded by a twin-screw extruder at a set temperature of 140 ° C., a screw rotation speed of 300 rpm, and a supply speed of 150 kg / h. After cooling, the mixture was coarsely pulverized, finely pulverized with a jet mill, and further classified with an air classifier to obtain toner particles having a volume average particle diameter D50 of 7.3 μm. Next, 100 parts by weight of the obtained toner particles were treated with 0.8 part by weight of silica treated with dimethyl silicone oil having an average particle diameter of 12 nm and rutile-type titanium oxide 1.0 treated with hydrophobization with decyltrimethoxysilane having an average particle diameter of 15 nm. Were mixed with a Henschel mixer to prepare a non-magnetic one-component toner (1).

The non-magnetic one-component image forming apparatus shown in FIG.
As the layer regulating blade 5, the layer regulating member (1) was attached. The position of the layer regulating member (1) in contact with the developer carrier was 2 mm from the tip of the free end. Also,
An image was formed using a non-magnetic one-component toner (1). In this image forming apparatus, the surface of aluminum is sandblasted to have an average surface roughness Ra of 0.5 μm.
m, and a developer supply roll (developer supply brush) 4 in which carbon black is dispersed in an acrylic resin. The developer support 3 holds a latent image. The body 1 was arranged with a gap of 150 μm. The latent image holder 1 is charged by a roll charger 2 and then exposed to laser light to form an electrostatic latent image. A DC voltage and a developer voltage are applied to the developer carrier 3 and the developer supply roll 4. An AC voltage was applied to develop the electrostatic latent image. The toner layer was formed on the developer carrier 3 by bringing the layer regulating blade 5 into contact with the developer carrier 3 at a constant linear pressure. The peripheral speed of the latent image holder 1 is 80 mm / s, and the peripheral speed of the developer carrier 3 is 120 mm / s.
/ S. Note that a transfer roll was used for transferring the toner, a blade-type cleaner was used for cleaning, and a heat roller fixing device was used for fixing. Using the above apparatus, a print test of 10,000 sheets was performed in a high-temperature and high-humidity environment (28 ° C., 85% RH) and a low-temperature and low-humidity environment (10 ° C., 15% RH). In any environment,
High-quality images with sufficient image density, no background fog, and no streaks on the images were continuously obtained. When the layer regulating member (1) was examined after the test, no toner was found to adhere.

Example 2 (Preparation of Layer Control Member 2) Except that the amount of the silicon compound in the basic compound of Example 1 was changed to 140 parts by weight of methyltrimethoxysilane and 60 parts by weight of dimethyldimethoxysilane. A coating agent was prepared in the same manner as in Example 1, and sealed for one month and stored. This coating agent 20
g and 10 g of the compound (3) were mixed to obtain a coating liquid (2) for forming a layer regulating member. Using the obtained coating liquid (2), a SUS stainless steel substrate having a thickness of 0.15 mm and urethane rubber having a thickness of 1 mm adhered thereto, within a range of 5 mm from the free end of the surface of the plate-like body. , 25
After spray coating in an atmosphere of 50 ° C.
The coating was dried in an atmosphere of 50 ° C. and 50% RH for 24 hours, and further dried and cured at 100 ° C. for 3 hours to obtain a layer regulating member (2) having a coating having a thickness of about 8 μm. The state of the obtained coating film was good, with no cracks or cracks. The layer regulating member (2) was attached to the same image forming apparatus as in Example 1, and a print test was performed in the same manner as in Example 1 using the same non-magnetic one-component toner. The position of the layer regulating member (2) was 1 mm from the tip of the free end. In any environment, a high-quality image having sufficient image density, no background fog, and no streak on the image was continuously obtained. When the layer regulating member (2) was examined after the completion of the print test, no sticking of the toner was observed.

Example 3 A coating liquid (3) for forming a layer regulating member was obtained in the same manner as in Example 2 except that 10 g of the compound (13) was used instead of 10 g of the compound (3). Using the obtained coating liquid (3), a 1 mm-thick urethane rubber was stuck on a 0.15 mm-thick SUS stainless steel substrate within a range of 8 mm from the tip of the free end of the plate-like body surface. , 25 ℃, 50R
After spray coating under H% atmosphere, 25 ° C, 50R
It was dried in an atmosphere of H% for 24 hours, and further dried and cured at 100 ° C. for 3 hours to obtain a layer regulating member (3) having a coating having a thickness of about 6 μm. The state of the obtained coating film was good, with no cracks or cracks. The layer regulating member (3) is attached to the same image forming apparatus as in the first embodiment,
A print test was performed in the same manner as in Example 1 using the same non-magnetic one-component toner. The position of the layer regulating member (3) was 0.5 mm from the tip of the free end.
In any environment, a high-quality image having sufficient image density, no background fog, and no streak on the image was continuously obtained. When the layer regulating member (3) was examined after the test was completed, no adhesion of the toner was observed.

Example 4 A coating liquid (4) for forming a layer regulating member was obtained in the same manner as in Example 2 except that 10 g of the compound (3) was replaced by 4 g of the compound (13). Using the obtained coating liquid (4), within a range of 10 mm from the tip of the free end of the surface of the plate-like body having a 1 mm-thick urethane rubber stuck on a 0.15 mm-thick SUS stainless steel substrate 25 ° C, 50
After spray coating in an atmosphere of RH%, the temperature is 25 ° C, 50
Dry under an atmosphere of RH% for 24 hours, and further at 100 ° C.
For 3 hours to obtain a layer regulating member (4) having a coating having a thickness of about 4 μm. The state of the obtained coating film was good, with no cracks or cracks. The layer regulating member (4) is attached to the same image forming apparatus as in the first embodiment,
The same print test as in Example 1 was performed using the same non-magnetic one-component toner. The position of this layer regulating member (4)
It was 2.5 mm from the tip of the free end. In any environment, a high-quality image having sufficient image density, no background fog, and no streak on the image was continuously obtained. When the layer regulating member (4) was examined after the test was completed, no toner adhesion was observed.

Example 5 In Example 2, 10 g of the compound (155) was mixed instead of 10 g of the compound (3). Using the coating liquid (5) for forming the layer-regulating member, the surface of the layer-regulating blade on which urethane rubber is stuck on a SUS substrate prepared for the same non-magnetic one-component image forming apparatus as in Example 1 , 25
Spray coating was performed in an atmosphere at 50 ° C. and 50% RH. This application is in a range of 8 mm from the tip of the free end. Next, 2
Dry under an atmosphere of 5 ° C. and 50% RH for 24 hours.
The coating was dried and cured at 00 ° C. for 3 hours to obtain a layer regulating member (5) having a coating having a thickness of about 10 μm. The state of the obtained coating film was good without cracks and cracks. The layer regulating member (5) was attached to the same image forming apparatus as in Example 1, and the same print test as in Example 1 was performed using the same non-magnetic one-component toner. At this time, the position where the layer regulating member (5) contacts the developer carrier is 1 mm from the tip of the free end.
Was in the position. In any environment, high-quality images having sufficient image density, no background fog, and no streaks were obtained continuously. When the layer regulating member (5) was examined after the test was completed, no toner was fixed.

Example 6 In Example 2, 10 g of the compound (145) was mixed instead of 10 g of the compound (3). Using the coating liquid (6) for forming the layer-regulating member, the surface of a layer-regulating blade having urethane rubber adhered to a SUS substrate prepared for the same non-magnetic one-component image forming apparatus as in Example 1 , 25
Spray coating was performed in an atmosphere at 50 ° C. and 50% RH. This application is in a range of 8 mm from the tip of the free end. Next, 2
Dry under an atmosphere of 5 ° C. and 50% RH for 24 hours.
The coating was dried and cured at 00 ° C. for 3 hours to obtain a layer regulating member (6) having a coating having a thickness of about 12 μm. The state of the obtained coating film was good without cracks and cracks. The layer regulating member (6) was attached to the same image forming apparatus as in Example 1, and the same print test as in Example 1 was performed using the same non-magnetic one-component toner. At this time, the position where the layer regulating member (6) contacts the developer carrier is 1 mm from the tip of the free end.
Was in the position. In any environment, high-quality images having sufficient image density, no background fog, and no streaks were obtained continuously. Examination of the layer regulating member (6) after the end of the test revealed that toner was not fixed.

Example 7 In Example 2, 10 g of the compound (60) was mixed instead of 10 g of the compound (3). The coating liquid (7) for forming a layer-regulating member was applied at 25 ° C. to the surface of a layer-regulating blade having urethane rubber adhered to a SUS substrate prepared for the same non-magnetic one-component image forming apparatus as in Example 1. , 50%
Spray coating was performed under an atmosphere of RH. This application is in a range of 8 mm from the tip of the free end. Next, 25 ℃, 50
% RH atmosphere for 24 hours.
After drying and curing for a time, a layer regulating member (7) having a film having a thickness of about 5 μm was obtained. The state of the obtained film is crack,
There was no crack and it was good. The layer regulating member (7)
The same print test as in Example 1 was performed using the same non-magnetic one-component toner attached to the same image forming apparatus as in Example 1. At this time, the position where the layer regulating member (7) came into contact with the developer carrying member was a position 1 mm from the tip of the free end. In any environment, high-quality images having sufficient image density, no background fog, and no streaks were obtained continuously. After the test, the layer regulation member (7)
As a result, no fixation of the toner was observed.

Example 8 In Example 2, 10 g of the compound (165) was mixed instead of 10 g of the compound (3). Using this coating liquid (8) for forming a layer regulating member, urethane rubber was stuck on a SUS substrate prepared for the same non-magnetic one-component image forming apparatus as in Example 1 to apply 25% of the surface of the layer regulating blade. ℃,
Spray coating was performed under an atmosphere of 50% RH. This application is in a range of 8 mm from the tip of the free end. Next, 25
C. and 50% RH in an atmosphere for 24 hours.
After drying and curing at 0 ° C. for 3 hours, a layer regulating member (8) having a coating having a thickness of 3 μm was obtained. The state of the obtained coating film was good without cracks and cracks. The layer regulating member (8) is attached to the same image forming apparatus as in the first embodiment,
The same print test as in Example 1 was performed using the same non-magnetic one-component toner. At this time, the position where the layer regulating member (8) came into contact with the developer carrier was 1 mm from the free end. In any environment, high-quality images having sufficient image density, no background fog, and no streaks were obtained continuously. When the layer regulating member (8) was examined after the test was completed, no adhesion of the toner was observed.

Comparative Example 1 A silicone resin SR2410 (manufactured by Dow Corning Toray Co., Ltd.) was applied to the same plate as in Example 1 by dip coating so as to have a thickness of 3 μm, and then cured at 150 ° C. for 3 hours.
A layer regulating member (5) was obtained. Using this, the same print test as in Example 1 was performed. The position of the layer regulating member (5) was 2 mm from the tip of the free end. In the print test, streaks appeared on the image when the number of sheets exceeded 3,000 sheets in a high-temperature and high-humidity environment, and when the number of sheets exceeded 1500 in a low-temperature and low-humidity environment. Worsened. After the test, the layer regulation member (5)
As a result, it was found that a large amount of toner was fixed to the nip portion of the blade surface in contact with the developing sleeve.

Comparative Example 2 In Example 1, 5 g of the compound (3) was obtained by adding N- (4-formylphenyl) -N- (3,4-dimethylphenyl)
A coating solution (6) for forming a layer regulating member was obtained in the same manner as in Example 1, except that 4 g of biphenyl-4-amine was used. Using the obtained coating liquid (6), the same plate-shaped body as in Example 1 was spray-coated so as to have a film thickness of 5 μm, dried and cured to obtain a layer regulating member (6). Using this, the same print test as in Example 1 was performed. The position of the layer regulating member (6) was 2 mm from the tip of the free end. In the print test, a slight fog was seen in the background from the beginning, and streaks appeared on the image from the time when the 1000th sheet was exceeded in a high-temperature and high-humidity environment and when the number of sheets exceeded 500 sheets in a low-temperature and low-humidity environment. However, the reduction in image density and the fogging of the background portion gradually deteriorated. When the layer regulating member was examined after the test was completed, it was found that a large amount of toner had adhered to the developing sleeve and the contact nip portion.

COMPARATIVE EXAMPLE 3 A plate-like member having a SUS stainless steel substrate having a thickness of 0.15 mm and a urethane rubber having a thickness of 1 mm adhered thereto and having no coating layer on the surface thereof was used as a layer regulating member (7). ) And a print test was performed in the same manner as in Example 1. The position where the layer regulating member (7) came into contact with the developer carrying member was 1.5 mm from the tip of the free end.
Under a high-temperature and high-humidity environment, the fogging of the background portion deteriorated from the time when the number of sheets exceeded 3,000, but no streaks appeared on the image. Further, in a low-temperature and low-humidity environment, the background portion was often fogged from the beginning, and when the number of sheets exceeded 1,000, dirt became severe and the test was stopped. When the layer regulating member was examined after the test was completed, the adhesion of the toner was small.

Table 38 shows the results of the tests of Examples 1 to 8 and Comparative Examples 1 to 3. The image quality evaluation method and evaluation criteria are as follows. (Image quality evaluation method) <Image density> X-ri, a density measuring device manufactured by X-rite
Measured by te404A. <Fog> The background portion was observed with a 50-fold loupe, and the sensory evaluation was performed. The evaluation criteria are as follows. ○:
Not at all, Δ: slightly, ×: considerably. <Streak on Image> An image obtained by developing the entire surface of the toner on A4 size paper was evaluated by counting the number of streaks.
：: 5 or less; Δ: 6 to 10; ×: 11 or more. <Comprehensive evaluation> ：: Good in all items,
×: A problem occurs in practical use.

[0117]

[Table 38]

[0118]

As described above, the developer layer regulating member of the present invention has a high hardness negative charge imparting coating layer having a network formed on the surface thereof, so that the toner is not fixed and the toner is charged and the layer is formed. Stable and less dependent on the environment for charging, high image density can be obtained over a long period of time, and low developability, background fogging and Streaks can be prevented, and a high-quality image can be stably formed.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram of an example of a one-component image forming apparatus of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Latent image holding body, 2 ... Roll charger, 3 ... Developer carrier, 4 ... Developer supply roll, 5 ... Layer regulating blade, 6 ...
Transfer roll, 7 ... cleaner, 8 ... fixing device.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Kotaro Yoshihara 1600 Takematsu, Minamiashigara-shi, Kanagawa Prefecture Inside Fuji Xerox Co., Ltd. (72) Inventor Rieko Kataoka 1600 Takematsu, Minamiashigara-shi, Kanagawa Fuji Xerox Co., Ltd. (72) Inventor Katsumi Nukata 1600 Takematsu, Minami Ashigara, Kanagawa Prefecture Inside Fuji Xerox Co., Ltd. (72) Inventor Kazuhiro Koseki 1600 Takematsu, Minami Ashigara City, Kanagawa Prefecture Inside Fuji Xerox Co., Ltd. Address Fuji Xerox Co., Ltd.

Claims (13)

[Claims] 1. A developer layer regulating member for forming a thin layer of a developer on a developer carrier, comprising: at least one compound represented by the following general formula (I) on a surface of a substrate: A developer layer regulating member provided with a coating layer containing the same. GDF (I) (wherein, G is an inorganic network-forming subunit, D is a flexible organic subunit, and F is a tertiary amino group-containing subunit.) 2. The compound according to claim 1, wherein F in the compound represented by the general formula (I) is a residue of a tertiary amino group-containing compound represented by the following general formula (II). The developer layer regulating member according to the above. Embedded image [In the formula, Ar _{1 to} Ar ₄ each independently represent a substituted or unsubstituted aryl group, Ar ₅ represents an unsubstituted aryl group or an arylene group, and _{1 to 1 of} Ar _{1 to} Ar ₅ The four groups are substituents represented by G-D- (provided that
G and D have the same meaning as described above. )have. k is 0 or 1. ] 3. The developer according to claim 1, wherein G—D— in the compound represented by the general formula (I) is a compound represented by the following general formula (III). Layer regulating member. —Y—SiR ¹ _(3-a) (OR ² ) _a (III) wherein R ¹ represents a hydrogen atom, an alkyl group or an unsubstituted aryl group, and R ² represents a hydrogen atom, an alkyl group or a trialkyl Shows a silyl group. Y represents a divalent group. a is an integer of 1 to 3. Where Y corresponds to G and SiR
¹ _(3-a) (OR ² ) _a corresponds to D. ] 4. Y in the silane compound represented by the general formula (III) is -C _x H _2x- (x is an integer of 1 to 15),-
_{C x 'H 2x'-2 -} (x' is an integer of 2~15), - C _{x "
H2x "-4-} (x" is an integer of 2 to 15) or a substituted or unsubstituted divalent aryl group, or -CH =
At least one selected from N-, -O- and -COO-
The developer layer regulating member according to any one of claims 1 to 3, wherein the member is a divalent aliphatic, aromatic, or araliphatic hydrocarbon group containing a seed. 5. The coating layer is a coating mainly composed of silicon oxide obtained from a material containing at least one compound represented by the general formula (I) and a bifunctional or tetrafunctional silicon compound. The developer layer regulating member according to any one of claims 1 to 4, wherein: 6. The developer layer regulating member according to claim 1, wherein the coating layer is provided on a surface of the elastic body. 7. The developer layer regulating member according to claim 1, wherein the thickness of the coating layer is in a range of 2 to 20 μm. 8. The developer layer regulating member according to claim 1, wherein the substrate is urethane rubber. 9. A means for forming an electrostatic latent image on a latent image holding member, and a thin layer of one-component toner is formed on the developer holding member by bringing a developer layer regulating member into contact with the developer holding member. An image forming apparatus comprising: means for visualizing an electrostatic latent image with a developer; means for transferring a toner image onto a transfer member; and means for heating and fixing the toner image. Item 10. An image forming apparatus comprising the developer layer regulating member according to any one of Items 1 to 8. 10. The position where the developer layer regulating member abuts on the developer carrier is 3 m from the free end of the developer layer regulating member.
The image forming apparatus according to claim 9, wherein m is within m. 11. The image forming apparatus according to claim 9, wherein the developer carrier is made of metal, ceramics, or plastics. 12. A step of forming an electrostatic latent image on a latent image holding member, wherein a developer layer regulating member is brought into contact with the developer holding member and a one-component toner formed in a thin layer on the developer holding member is used. An image forming method having a step of visualizing the electrostatic latent image on the latent image holding member, a step of transferring the obtained toner image onto a transfer body, and a step of heating and fixing the transferred developer image. An image forming method, wherein the developer layer regulating member according to any one of claims 1 to 8 is used as the developer layer regulating member. 13. The image forming method according to claim 12, wherein the developer is a non-magnetic toner.