JP3463719B2 - Electrostatic image developing toner, developer and image forming method - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner and a developer used for developing an electrostatic latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method or the like.

[0002]

BACKGROUND OF THE INVENTION A number of electrophotographic methods are known, but generally, an electrostatic charge image is formed on a photoconductor made of a photoconductive material, and then the electrostatic charge image is charged. This is carried out by developing with toner, transferring the toner image to a recording material such as paper, if necessary, and then fixing the toner image by heating, pressure, solvent vapor or the like to obtain a copied image.

Various means are used to obtain the above-mentioned copied image. For example, a negatively-charged electrostatic latent image formed on a photoconductor is developed by a normal development method to obtain a copied image. A means of developing a positively charged electrostatic latent image formed on a photoconductor by a reversal development method to obtain a copied image is used.
In order to obtain a copied image by these means, a developer containing a positively charged toner is widely used as the developer.

Various means are also used to fix the obtained toner image, but since the heat efficiency is high and it is possible to fix at a high speed, a heat roller using a heating roller is used. The fixing method is widely used.

When the heat roller fixing method is used for fixing, the requirements for the toner are as follows: (1) the toner can be reliably fixed at a low temperature, and (2) the melted toner does not transfer to the heat roller at the time of fixing, that is, Conditions such as excellent offset resistance are required.

Further, in order to form a clear copy image even when used for a long period of time, the toner chargeability does not change greatly under the use environment condition or the storage environment condition, and the toner does not agglomerate and is powdered. It is also required that it can be stably stored as a body, that is, that it has excellent storage stability.

To meet the requirements of the above (1) and (2), JP-A-55-90509, JP-A-63-214760, JP-A-63-216063 and JP-A-63-63 are provided. No. 217356 to JP-A No. 63-217364 discloses a technique using a metal-crosslinked resin and an offset preventive agent.

When a metal-crosslinked resin is used for the toner, the metal crosslink bond of the resin has a smaller bonding force than a covalent bond and is easily broken by heating, so that the resin can be melted at a low temperature, and the paper can be melted. Since it adheres well to recording materials such as, it can be fixed at low temperature. Further, since the resin has an appropriate viscoelasticity due to the metal cross-linking, the offset resistance of the toner can be improved.

However, the metal-crosslinked resin has a polar group such as a carboxyl group as a reactive group for forming a metal crosslink, and therefore, when this is used as a resin component of the toner, the hydrophilicity of the toner is reduced. Became big,
As a result, when the environment changes, the chargeability of the toner changes greatly, so that it is not always possible to obtain an image having a constant level.

Further, the polyolefin or the like contained in the toner as an offset preventing agent has a characteristic that the negative chargeability is very strong, which is disadvantageous in obtaining a toner having a positive charge.

Further, in the electrophotographic method, when the toner image formed on the photoconductor is transferred onto the recording material, not all the toner is transferred onto the recording material, and about 10 to 20% by weight of the toner is transferred. It remains on the photoconductor. The toner remaining on the photoconductor (transfer residual toner) interferes with the subsequent formation of an electrostatic charge image on the photoconductor, so it is removed and collected by the cleaning process, and is discharged outside the system as so-called waste toner. Monkey

Considering environmental pollution, it is preferable to reuse these waste toners without discarding them. As a technique for reusing the waste toner, Japanese Patent Laid-Open No. 60-217367 discloses that an electrostatic charge image formed on a photoconductor is developed to form a toner image, and the toner image is transferred to a transfer body. There is described an image forming method including a step of removing a toner remaining on a photoconductor using a cleaning device and returning the removed toner to a toner replenishing device or a developing device for repeated use. By using such an image forming method, the toner can be effectively used without producing any waste toner. In addition, by adopting such technology,
Another merit is the compactness of the machine.

However, when a developer comprising a toner containing the above-mentioned metal-crosslinked resin and an offset preventing agent and a carrier is used, the toner remaining on the photoconductor is recovered and reused by the above means. The drawbacks brought about by the toner containing the metal-crosslinked resin and the offset preventive agent remarkably occur, and the developer cannot be recovered and reused for a long period of time and the life of the developer is shortened.

[0014]

SUMMARY OF THE INVENTION Accordingly, the object of the present invention is to provide excellent fixability at low temperature and anti-offset property, to be rapidly applied with a proper amount of positive charge, and to stably provide a proper amount for a long period of time. An object of the present invention is to provide an electrophotographic toner that maintains a positive charge and is free from toner scattering and image fog.

Another object of the present invention is to fix the toner at a low temperature,
Offset resistance is excellent, and a proper amount of positive charge is quickly applied, and the carrier surface is not contaminated.
An object of the present invention is to provide a developer for developing an electrostatic charge image, which stably maintains an appropriate amount of positive charge for a long period of time and is free from toner scattering and image fog, and an image forming method.

[0016]

The above objects of the present invention are as follows: (1) Colored particles containing a metal-crosslinked styrene-acrylic acid ester copolymer are added to an organopolyamine having an ammonium functional group at the terminal represented by the following formula 2. Characterized by adding inorganic fine particles treated with siloxane
Toner for developing electrostatic images.

[0017]

[Chemical 5] [In the formula, Y and Z are each a substituted or unsubstituted carbon atom number 1
~ 8 represents an alkyl group or an aryl group. A and B
Is a hydrogen atom, a substituted or unsubstituted C1-4 carbon atom, respectively.
Alkyl group or group having ammonium salt structure
Represents However, at least one of A and B is
It is a group having a ammonium salt structure. n is an integer of 5 to 400
Represent ] (2) Metal cross-linked styrene-acrylic acid ester
The polymer is (a) styrene monomer, (b) acrylic acid.
Ester-based monomer or methacrylic acid ester-based monomer
And (c) a monomer represented by the following formula 1 is copolymerized
Of the copolymer obtained by crosslinking with a polyvalent metal salt
The electrostatic charge according to (1) above, which is a compound
Toner for image development.

[0018]

[Chemical 6] [In the formula, R ₁ represents a hydrogen atom or a methyl group, and L 1
Is 3 or more carbon atoms having an ester bond in the molecular chain
Represents a divalent linking group. ] (3) Metal cross-linked styrene-acrylic acid ester copolymer
The colored particles containing the polymer are polyolefin and fat.
Characterized by containing acid amide or fatty acid ester
For developing the electrostatic charge image according to the above (1) or (2)
toner. (4) Polyolefin and fatty acid amide or fatty acid
For the colored particles containing ester, the formula described in (1) above
Olga having an ammonium functional group at the terminal represented by 2
Made by adding inorganic fine particles treated with nopolysiloxane
A toner for developing an electrostatic charge image, which is characterized in that (5) A developer for developing an electrostatic image, comprising the toner for developing an electrostatic image according to any one of (1) to (4) and a carrier. (6) The developer for developing an electrostatic charge image according to the above (5), wherein the carrier is a carrier having a magnetic core coated with a resin. (7) The developer for developing an electrostatic charge image according to the above (6), wherein the carrier in which the magnetic core is coated with a resin has 30 atomic% or more of fluorine atoms in the surface region. (8) The resin is a fluorinated acrylate resin or a fluorinated methacrylate resin containing a repeating unit represented by the following formula 12, a vinylidene fluoride resin, a hexafluoropropylene resin, or a vinylidene fluoride / hexafluoropropylene resin. The developer for electrostatic image development according to (7) above, which is a polymer resin.

[0019]

[Chemical 7] [In the formula, R represents a hydrogen atom or a methyl group, and Rf represents an alkyl group substituted with a fluorine atom. ] (9) The resin contains 75 or more repeating units represented by the following formula 13.
(7) or above, characterized by being a fluorinated methacrylate resin having a weight% or more, or a copolymer resin of vinylidene fluoride and hexafluoropropylene
The developer for developing an electrostatic charge image according to (8) .

[0020]

[Chemical 8] [In the formula, Rf represents an alkyl group substituted with a fluorine atom. (10) The electrostatic charge image formed on the photoreceptor is developed with a developer including at least a toner and a carrier to form a toner image, and the toner image is transferred to a transfer material, and then a cleaning device is used. the toner remaining on the photoreceptor is removed Te, the removed toner, an image forming method having the step of repeated use is returned to the toner replenishing device or a developing device, a developer, the above-mentioned (5) to (9) Noi
Image forming method which comprises using an electrostatic charge image developer Zurekani described. Can be achieved by

The present invention will be described in detail below.

First, a metal-crosslinked styrene-acrylic copolymer (hereinafter referred to as "metal-crosslinked St-") contained in the colored particles.
Also referred to as "Ac copolymer resin". ) Will be described.

In the metal-crosslinked St-Ac copolymer resin, the monomer for forming the basic skeleton of the styrene-acrylic copolymer is a styrene-based monomer and an acrylate-based monomer or methacrylic acid. It is preferable to use at least one selected from ester monomers. A carboxyl group is preferable as the reactive group for forming a metal cross-linkage, and in order to introduce a carboxyl group into the basic skeleton of the styrene-acrylic copolymer, a monomer having a carboxyl group, for example, a monomer having a carboxyl group, for example, is introduced. ,
Copolymerization may be performed using a monomer selected from acrylic acid or methacrylic acid or a derivative having a carboxyl group derived from these.

As the above-mentioned monomer having a carboxyl group, a half-ester compound obtained by an esterification reaction of an acrylic acid ester or a methacrylic acid ester having a hydroxyl group or a derivative thereof with a dicarboxylic acid compound is preferably used.

When the above-mentioned half-ester compound is used to introduce a carboxyl group into the basic skeleton of the styrene-acrylic copolymer, the carboxyl group can be introduced at a position that has a small influence on the main chain structure, and steric hindrance is small. Since a chemical structure is obtained, when a metal crosslink is formed, the reaction between the polyvalent metal compound forming the metal crosslink and the carboxyl group proceeds efficiently to form an ionic bond, and a resin having a good crosslink Can be obtained.

Examples of the styrenic monomer that can be used to obtain the styrene-acrylic copolymer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene and p-methylstyrene. -Ethylstyrene, 2,3-dimethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-
Butyl styrene, pn-hexyl styrene, pn-
Octyl styrene, pn-nonyl styrene, pn-
Examples thereof include decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene, p-chloro styrene and 3,4-dichloro styrene. Of these, styrene is particularly preferably used.

These monomers may be used alone or in combination of two or more.

The styrene content is 50 to 95% of that of the copolymer.
It is preferably in the weight%. By using styrene in the above range, high pulverization efficiency can be obtained in the pulverization step of toner production, and the toner having a desired particle size can be efficiently obtained.

Examples of acrylic acid ester monomers that can be used to obtain a styrene-acrylic copolymer include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and acrylic. Acid isobutyl, n-hexyl acrylate, n-octyl acrylate, n-nonyl acrylate, n-acrylate
Decyl, n-dodecyl acrylate, n-lauryl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, etc. Examples of the monomer include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, and methacrylic acid. Acid n-decyl, n-dodecyl methacrylate, n-lauryl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, 2-chloroethyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethyl methacrylate Ruaminoechiru, and the like.

The half-ester compound preferably used for introducing a carboxyl group into the basic skeleton of the styrene-acrylic copolymer is, for example, an acrylic acid ester or methacrylic acid ester having a hydroxyl group or a derivative thereof and a dicarboxylic acid compound. The dicarboxylic acid compound used for the esterification reaction includes malonic acid, succinic acid, aliphatic dicarboxylic acids such as glutaric acid, and aromatic dicarboxylic acids such as phthalic acid. . The dicarboxylic acid compound may have a substituent such as a halogen atom, a lower alkyl group or an alkoxy group. Further, the dicarboxylic acid compound may be an acid anhydride.

Examples of acrylic acid ester, methacrylic acid ester having hydroxyl group or derivatives thereof include, for example, acrylic acid or methacrylic acid, a compound obtained by adding 1 mol or 2 mol or more of alkylene oxide such as ethylene oxide or propylene oxide, acryl. Examples thereof include hydroxyalkyl esters obtained by subjecting an acid or methacrylic acid to a dihydric alcohol such as propylene glycol in an esterification reaction.

As a preferable half-ester compound, a half-ester compound represented by the following formula 1 can be mentioned.

[0033]

[Chemical 9] [In the formula, R ₁ represents a hydrogen atom or a methyl group, and L 1
Represents a divalent linking group having an ester bond in the molecular chain and having 3 or more carbon atoms. Among the half ester compounds represented by the formula 1, more preferable half ester compounds include:
The half ester compound represented by the following formulas 3-6 is mentioned.

[0034]

[Chemical 10] [Wherein R ¹¹ and R ¹² represent a hydrogen atom or a methyl group, and m
Represents an integer of 1 to 14, and n represents an integer of 0 to 8. ]

[0035]

[Chemical 11] [Wherein R ¹¹ and R ¹² represent a hydrogen atom or a methyl group, and h
Represents an integer of 1 to 14, X represents a halogen atom, a lower alkyl group or an alkoxy group, and p represents an integer of 0 to 3. ]

[0036]

[Chemical 12] [In the formula, R ¹¹ represents a hydrogen atom or a methyl group, and j is 3
Represents an integer of 6 and k represents an integer of 0 to 8. ]

[0037]

[Chemical 13] [In the formula, R ¹¹ represents a hydrogen atom or a methyl group, and i is 3
Represents an integer of 6 to 6, Y represents a halogen atom, a lower alkyl group or an alkoxy group, and p represents an integer of 0 to 3. Among the half ester compounds represented by the formulas 3 to 6, the half ester compound represented by the formula 3 is preferable.

Specific examples of the half-ester compound represented by the above formula 1 include succinic acid monoacryloyloxyethyl ester, succinic acid monoacryloyloxypropyl ester, glutaric acid monoacryloyloxyethyl ester, and phthalic acid monoacryloyloxy ester. Ethyl ester, phthalic acid monoacryloyloxypropyl ester, succinic acid monomethacryloyloxyethyl ester, succinic acid monomethacryloyloxypropyl ester, glutaric acid monomethacryloyloxyethyl ester, phthalic acid monomethacryloyloxyethyl ester, phthalic acid monophthalic acid Examples thereof include methacryloyloxypropyl ester.

The proportion of the acrylic acid ester monomer or methacrylic acid ester monomer used in the basic skeleton of the styrene-acrylic copolymer is preferably 5 to 50% by weight of the copolymer.

The amount of the half ester compound used is
It is preferably 0.5 to 30% by weight of the copolymer.

By selecting the above content ratio, it is possible to impart good offset resistance and storage stability to the toner.

As the polyvalent metal element for crosslinking to obtain the metal-crosslinked St-Ac copolymer resin, Cu, Ag and B are used.
e, Mg, Ca, Sr, Ba, Zn, Cd, Al, T
i, Ge, Sn, V, Cr, Mo, Mn, Fe, Ni,
Co, Zr, Se, etc. can be mentioned.

Among these various polyvalent metal elements,
Alkaline earth metals (Be, Mg, Ca, Sr, Ba) and zinc group elements (Zn, Cd) are preferable, and Mg and Zn are particularly preferable.

Examples of the polyvalent metal compound used for metal-crosslinking the St-Ac copolymer resin include, for example, fluorides, chlorides, chlorates, bromides and iodides of the above metals.
Oxide, hydroxide, sulfide, sulfite, sulfate, selenide, telluride, nitride, nitrate, phosphide, phosphinate, phosphate, carbonate, orthosilicate, acetate,
Examples thereof include oxalates, lower alkyl metal compounds such as methyl compounds and ethyl compounds, and the like. Among these, acetates of the above metals and oxides of the above metals are particularly preferable.

The amount of the polyvalent metal compound used for the metal cross-linking cannot be unconditionally specified because it varies depending on the kind and the amount of the monomer constituting the styrene-acrylic copolymer, but for example, styrene. -The acrylic copolymer is composed of a styrene-based monomer, an acrylic acid ester-based monomer or a methacrylic acid ester-based monomer, and a half-ester compound, and has a low molecular weight component in the styrene-acrylic copolymer. And a high molecular weight component, the amount is about 0.1 to 1 mol with respect to 1 mol of the half-ester compound charged.

To obtain a metal-crosslinked St-Ac copolymer resin by reacting a styrene-acrylic copolymer with a polyvalent metal compound, for example, a styrene-acrylic copolymer obtained by polymerizing by a solution polymerization method is used. To the solution containing the coalesce, mix the polyvalent metal compound or the dispersion solution of the polyvalent metal compound,
It is preferable that the temperature is raised and desolvation is performed for about 1 to 3 hours, and this temperature is maintained for 1 hour or more while the temperature in the reaction system reaches about 150 to 180 ° C. to complete the reaction. Further, after performing the solvent removal in the above, roll mill, kneader,
The reaction may be completed by melt-kneading with an extruder or the like. Further, in some cases, the polyvalent metal compound may be allowed to be present in the reaction system together with the solvent before the polymerization for obtaining the styrene-acrylic copolymer is started.

In the metal-crosslinked St-Ac copolymer resin, the carboxyl group of the copolymer and the polyvalent metal atom are bonded by a much looser ionic bond than the covalent bond, and this ionic bond causes The crosslinked structure of is formed.

The styrene-acrylic copolymer is preferably one having a molecular weight distribution which can be divided into at least two groups of a low molecular weight polymer component and a high molecular weight polymer component. By designing the molecular weight so as to have such a molecular weight distribution, it is possible to further improve low-temperature fixability, offset resistance, and storage stability, and at the same time prevent generation of toner fine powder. be able to.

For the colored particles containing the metal-crosslinked St-Ac copolymer resin, other resin can be used together with the metal-crosslinked St-Ac copolymer resin. These resins are not particularly limited, and various conventionally known resins can be used. For example, styrene resin, acrylic resin, styrene / acrylic resin, polyester resin, styrene / ptadiene resin, etc. are used.

The colorant for obtaining the colored particles is not particularly limited, and various conventionally known materials can be used. Examples of these colorants include carbon black, nigrosine dye, aniline blue, chalco oil blue, chrome yellow, ultramarine blue, DuPont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, malachite green oxalate, and rose bengal. To be These colorants are
Usually, it is 1 for the metal-crosslinked St-Ac copolymer resin.
It is preferable to use ˜20% by weight.

Next, the polyolefin, fatty acid amide and fatty acid ester contained in the colored particles will be described.

The polyolefin may be an unmodified polyolefin, or may be a modified polyolefin modified by having a blocked portion or modified by grafting.

The polyolefin portion of the unmodified polyolefin and the modified polyolefin is a homopolymer type obtained from a single olefin monomer, or a plurality of olefin monomers, or an olefin monomer and another monomer copolymerizable therewith. It may be of any type of copolymer type obtained by polymerization.

Examples of the olefin monomer include ethylene, propylene, butene-1, pentene-1, 3-
Methyl-1-butene, 3-methyl-1-pentene and all other olefin monomers can be mentioned.
Examples of other monomers copolymerizable with the olefin monomer include vinyl ethers such as vinyl methyl ether, vinyl esters such as vinyl acetate, haloolefins such as vinyl fluoride, and methyl acrylate. Alternatively, various ones such as acrylic acid esters or methacrylic acid esters such as methyl methacrylate, acrylic acid derivatives such as acrylonitrile, organic acids such as acrylic acid, and the like can be mentioned.

As the copolymer type polyolefin,
For example, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-vinyl acetate copolymer,
Ethylene-vinyl methyl ether copolymer, ethylene-
Examples thereof include propylene-vinyl acetate copolymer. When a monomer other than the olefin monomer is used as the comonomer component, it is preferable to use the olefin monomer in an amount of 80 mol% or more.

Examples of the modifying component in the modified polyolefin include aromatic vinyl monomers such as 1-phenylpropene, styrene, methylstyrene, p-ethylstyrene and pn-butylstyrene, such as methyl acrylate and ethyl acrylate. Alternatively, acrylic acid esters or methacrylic acid esters such as methyl methacrylate and ethyl methacrylate are used. In the modified polyolefin, the content of the modifying component is preferably 0.1 to 15% by weight, more preferably 1 to 10% by weight based on the modified polyolefin. By setting the content of the modifying component in the above range, the affinity with the binder resin can be increased without impairing the releasing effect.

The polyolefin used preferably has a low softening point. Specifically, JISK 2531-19
The softening point measured by the ring and ball method specified in 60 is 80 to 18
A polyolefin having a temperature of 0 ° C. is preferable, and a softening point of 9 is particularly preferable.
A polyolefin having a temperature of 0 to 160 ° C. is preferable.

The polyolefins that can be used in the present invention are commercially available, and commercially available polyolefins that can be particularly preferably used include, for example, "Viscor 660P" and "Viscor 550P" (above, Sanyo Kasei Co., Ltd.). Kogyo Co., Ltd., “Polyethylene 6A” (Allied Chemical Co.), “High Wax 400P”, “High Wax 100P”, “High Wax 200P”, “High Wax 220P”, “High Wax 320P”, “High Wax”
2203A "," High Wax 4202E "(all manufactured by Mitsui Petrochemical Co., Ltd.)," Hoechst Wax PE520 "," Hoechst Wax PE130 ", and" Hoechst Wax PE190 "(all manufactured by Hoechst).

Polyolefin is a resin component 10 of colored particles.
It is preferable to use 2 parts by weight or more with respect to 0 parts by weight,
Particularly, it is preferable to use 2 to 10 parts by weight. By containing the polyolefin in the above range, the releasing effect can be exhibited without lowering the fluidity of the toner.

As the fatty acid amide used in the present invention, for example, an alkylenebis fatty acid amide represented by the following formula 7 is preferable.

[0061]

[Chemical 14] [In the formula, R ²¹ and R ²² represent a saturated or unsaturated aliphatic hydrocarbon group having 10 or more carbon atoms. R ²³ and R ²⁴ represent a hydrogen atom or —OCR ²⁵ (R ²⁵ represents a saturated or unsaturated aliphatic hydrocarbon group). R ²¹ and R ²² , R ²³ and R
²⁴ may be the same as or different from each other. n
Represents a positive integer. The above-mentioned alkylene bis fatty acid amides are commercially available. Examples of commercially available products include “bisamide”, “Diamid 200 bis”, and “Lubron E”.
(Above, manufactured by Nippon Hydrogen Industrial Co., Ltd.), "Plastflow" (manufactured by Nitto Kagaku), "Alflo H50S", "Alflo V"
-60 "(above, NOF Corporation)," Amide-6L ",
"Amide-7S", "Amide-6H" (above, Kawaken Fine Chemicals Co., Ltd.), "Armorax-EBS"
(Made by Lion Armor), "Hoechst Wax C"
(Manufactured by Hoechst Japan), "Nobco Wax-22D
S "(manufactured by Nobuco Chemical Co., Ltd.)," Adva Wax-28
0 "(manufactured by Advance)," Kaowax-EB "
(Manufactured by Kao Corporation) and “Parisin-285” (manufactured by Bakercaster Oil Co.). As the fatty acid amide of the present invention, it is particularly preferable to use "Hoechst wax C" among the above-mentioned commercially available products.

The alkylenebis fatty acid amides are generally
As the number of carbon atoms of the aliphatic hydrocarbon group and the length of the alkylene chain increase, the melting point increases, but the low temperature fixability of the toner,
From the viewpoint of cohesiveness, those having a melting point in the range of 100 to 180 ° C are preferable, and those having a melting point in the range of 130 to 160 ° C are particularly preferable. Therefore, the number of carbon atoms in the alkylene chain connecting nitrogen atoms is preferably 5 or less.

The fatty acid ester used in the present invention is preferably a fatty acid ester having a melting point of 30 to 130 ° C. or a partially saponified product thereof. Specific examples of these fatty acid esters include polyhydric alcohol esters of fatty acids, higher alcohol esters of fatty acids, partial esters of fatty acids and polyhydric alcohols, mixed esters, and the like. Among these, the higher alcohol ester of fatty acid is particularly preferable as the fatty acid ester used in the present invention.

The above-mentioned higher alcohol esters of fatty acids are commercially available. Examples of the commercially available products include "Spalm acetyl" (manufactured by NOF Corporation), "Hoechst Wax E",
“Hoechst wax OP” (above, manufactured by Hoechst Japan) and the like can be mentioned. In particular, "Hoechst wax E" can be preferably used.

The average particle diameter of the colored particles is usually 1 to 30 μm, preferably 5 to 20 μm in terms of volume average particle diameter. The volume average particle diameter of the colored particles is the Coulter counter T
It was measured with an A-II type (manufactured by Coulter, Inc.) using an aperture of 100 μm.

Next, the equation 2 used in the present invention is represented by
Organopolysiloxane (hereinafter having an ammonium functional group at the end to be simply an ammonium functional group at the terminal
It may be referred to as an organopolysiloxane. The inorganic fine particles treated with ( ) will be described.

In the present invention, by using the inorganic fine particles treated with the organopolysiloxane having an ammonium functional group at the terminal, the positive chargeability of the inorganic fine particles is increased, and when the inorganic fine particles are added to the colored particles to form a toner, An appropriate amount of positive charge can be quickly applied and the positive charge can be stably maintained.

When the inorganic fine particles treated with the organopolysiloxane having an ammonium functional group only in the side chain are used, the above effect is not observed, whereas the treatment with the organopolysiloxane having an ammonium functional group at the end is performed. The reason why the above effect is obtained when the above-mentioned inorganic fine particles are used has not been clarified in detail, but it can be estimated as follows.

That is, when an organopolysiloxane having an ammonium functional group only in its side chain is used for treating the inorganic fine particles, the ammonium functional group is present only in the side chain of the organopolysiloxane molecule. In addition, when the inorganic fine particles are treated, the ammonium functional group approaches a polar group such as a hydroxyl group on the surface of the base inorganic fine particles, which facilitates coordination, and as a result, the positively charged property of the ammonium functional group is not sufficiently exhibited. It is presumed that.
On the other hand, when the ammonium functional group is present at the end of the organopolysiloxane, the ammonium functional group does not selectively approach the polar group on the surface of the inorganic fine particles and is coordinated, so that the ammonium functional group is not present in the inorganic fine particles. It is presumed that it is possible to exist on the surface.

By allowing the ammonium functional group to exist on the outermost surface of the inorganic fine particles, the positive charging property of the ammonium functional group can be sufficiently involved in triboelectric charging, and the positive charging property of the inorganic fine particles is increased. When added as a toner, an appropriate amount of positive charge can be quickly applied, and the positive charge can be stably maintained, and the toner can form an electrostatic charge image formed on the electrostatic image support. When used as a developer for developing, it is considered that a high-definition image with high image density and no image fog can be obtained for a long period of time without toner scattering.

The organopolysiloxane having an ammonium functional group at the terminal used in the present invention can be obtained by modifying the terminal group of the organopolysiloxane so that at least one of the terminals has an ammonium functional group.

In the present invention, the term "terminal" means the end of the organopolysiloxane molecular chain, not the end of the side chain of the organopolysiloxane molecular chain.

The powder represented by the following formula 2 used in the present invention
Organopolysiloxaes with ammonium functional groups at the ends
Will be described in more detail.

[0074]

[Chemical 15] [In the formula, Y and Z are each a substituted or unsubstituted carbon atom number 1
~ 8 represents an alkyl group or an aryl group. A and B
Each represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a group having an ammonium salt structure. However, at least one of A and B is a group having an ammonium salt structure. n represents an integer of 5 to 400 . Furthermore, as the organopolysiloxane used in the present invention, those represented by the following formulas 8 and 9 are preferable.

[0075]

[Chemical 16] In Formula 8 and Formula 9, Y and Z each represent a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or an aryl group (for example, a phenyl group), and R ¹ has 1 to 1 carbon atoms.
8 represents an alkylene group or an arylene group (for example, a phenylene group), and R ² , R ³ and R ⁴ are a hydrogen atom, an aryl group (for example, a phenyl group), an alkyl group having 1 to 30 carbon atoms, an amino group. An alkyl group having 1 to 30 carbon atoms, an aryl group having an amino group (eg, a phenyl group), an alkyl group having 1 to 30 carbon atoms having an ammonium salt structure, or an aryl group having an ammonium salt structure (eg, A phenyl group), and R ⁵ has 1 carbon atom
To R 4, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X ⁻ represents a counter anion (eg, halogen ion, sulfo ion).
a, b, c and d represent an integer of 1 to 3. However, a
+ B = 3 and c + d = 3. n is an integer of 5 to 400 . In addition, R ^{1 to} R ⁶ may have an arbitrary substituent such as an alkyl group and an aryl group.

In equations 8 and 9

[0077]

[Chemical 17] For example, the following may be mentioned.

[0078]

[Chemical 18]

[0079]

[Chemical 19]

[0080] In the present invention, the organopolysiloxane may be used any viscosity, preferably those kinematic viscosity at 25 ° C. is 5 to 500 mm ² / sec, more 10 to 100 mm ² / Better is something in the range of seconds
Good By setting the kinematic viscosity of the organopolysiloxane and the degree of polymerization of the diorganosiloxane unit within the above ranges, the treatment of the inorganic fine particles can be achieved without impairing the fluidity.

The organopolysiloxane having an ammonium functional group at the terminal used in the present invention can be produced by a conventionally known method. For example, a silanol group at the terminal of the organopolysiloxane molecular chain is reacted with an organoalkoxysilylammonium compound, and in some cases, a silanol group at the terminal of the organopolysiloxane molecular chain is treated with an organoalkoxysilylamine compound and a hydrogen halide. It can be produced by reacting in the presence of an acid and an acid such as other inorganic or organic acid.

The organoalkoxysilylammonium compound can be produced by a known method, for example, by reacting an alkoxysilylalkylhalogenide or an alkoxysilylalkylsulfonate with an amine, particularly a tertiary amine.
Further, the organoalkoxysilylamine compound can also be produced by a known method, and a part thereof can be obtained as a commercial product.

The positive charge imparting property can be controlled by variously changing the reaction ratio between the above-mentioned organoalkoxysilylammonium compound or organoalkoxysilylamine compound and dimethylpolysiloxane having silanol groups at both ends.

The inorganic fine particles to be treated with the organopolysiloxane having an ammonium functional group at the end of the present invention include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, Examples thereof include fine particles of chromium oxide, cerium oxide, antimony trioxide, tin oxide, zirconium oxide, silicon carbide and the like. These can be used alone or as a mixture.

The above-mentioned base inorganic fine particles can be used regardless of whether they are produced by a dry method or a wet method.

Examples of the dry method include a method of producing inorganic fine particles by vapor-phase oxidation of a halide of a metal element or a semimetal, for example, a halogen by utilizing a thermal decomposition oxidation reaction in oxygen or hydrogen. It is a method for producing inorganic fine particles from a compound gas, and the reaction formula is shown as follows.

MX _n +1/2 nH ₂ +1/4 nO ₂ →
MO _{1 / 2n} + nHCl In this reaction formula, M represents a metal atom or a metalloid atom, X represents a halogen atom, and n represents a positive integer.

When inorganic fine particles are produced by the dry method, SiCl ₄ ,
By using TiCl ₄ , AlCl ₃ and BaCl ₂ , fine particles of SiO ₂ , TiO ₂ , Al ₂ O ₃ and BaO can be obtained respectively. In the case of vapor phase oxidation, a corresponding compound oxide can be obtained by mixing and using a halide.

Examples of the wet method include a method of using an aqueous solution of sodium silicate and decomposing it with an acid and / or an alkali salt to produce inorganic fine particles.

As the base inorganic fine particles, silica, alumina and titanium oxide are preferable because they have an appropriate electric resistance. Furthermore, silica fine particles produced by the dry method are more preferable in that they have an appropriate electric resistance. Further, the term "silica" includes not only silicon dioxide (silica) but also silicates such as aluminum silicate, sodium silicate, magnesium silicate, potassium silicate, calcium silicate, and zinc silicate. It is preferable that the content of SiO ₂ is 85% by weight or more.

As the inorganic fine particles used for the treatment with the organopolysiloxane having an ammonium functional group at the terminal, those having a number average primary particle diameter of 3 to 500 nm are used in order to improve the fluidity of the toner. It is more preferably in the range of 5 to 100 nm.
Here, the number average primary particle diameter refers to the number average particle diameter of the primary particles (particles in the state of being separated into individual unit particles) of the inorganic fine particles present in the form of fine particles, for example, a transmission electron microscope ( The TEM image can be obtained by importing it into an image analysis device.

In the base inorganic fine particles used in the present invention, the surface of the base inorganic fine particles may be appropriately treated with a hydrophobizing agent in order to reduce the influence of the chargeability fluctuation caused by the base inorganic fine particles themselves due to environmental changes. preferable.

When the inorganic fine particles used in the present invention are subjected to a hydrophobizing treatment with a hydrophobizing agent before being treated with the organopolysiloxane having an ammonium functional group at the terminal, the adsorption of water on the surface of the inorganic fine particles can be remarkably suppressed. As a result, it is possible to make the fluctuation of the charging characteristic due to the fluctuation of the humidity extremely small.

By hydrophobizing the surface of the inorganic fine particles with a hydrophobizing agent, the hydroxyl groups present on the surface of the inorganic fine particles are modified to a non-polar group, and then treated with an organopolysiloxane having an ammonium functional group at the end. , The ammonium functional group present at the end of the organopolysiloxane is prevented from selectively approaching and coordinating with the polar group present on the surface of the inorganic fine particles, and the ammonium functional group can be present on the outermost surface. The positive chargeability of the ammonium functional group can be remarkably exhibited.

As described above, by performing the hydrophobizing treatment with the hydrophobizing agent before the treatment with the organopolysiloxane having an ammonium functional group at the terminal, a proper amount of positive charge can be rapidly imparted to the toner, and Since the positive charge can be stably maintained even when the humidity environment changes, even in various usage environments, there is no toner scattering in the apparatus and there is no image fog, and high-definition images with high image density can be obtained. Can be obtained.

In the present invention, as a hydrophobizing agent that can be used, a compound that can easily react with a hydroxyl group existing on the surface of the inorganic fine particles and bond an organic group to oxygen of the hydroxyl group is used. . Generally, as a hydrophobic treatment agent, a silane compound represented by the following formula 10,
Examples thereof include a silane coupling agent such as a disilazane compound and a titanium-based coupling agent such as a titanium compound represented by the following formula 11, and among these, a silane coupling agent is preferably used.

[0097]

[Chemical 20] In the above formula 10, R ⁷ represents a halogen atom or an alkoxy group having 1 to 5 carbon atoms, and R ⁸ represents 1 to 1 carbon atoms.
5 represents an alkyl group, R ⁹ represents a substituted or unsubstituted alkyl group, an aryl group, an alkylaryl group or an arylalkyl group, and n represents a positive integer of 1 to 3.

[0098]

[Chemical 21] In the above formula 11, R ⁷ represents a halogen atom or an alkoxy group having 1 to 5 carbon atoms, and R ⁸ represents 1 to 1 carbon atoms.
5 represents an alkyl group, R ⁹ represents a substituted or unsubstituted alkyl group, an aryl group, an alkylaryl group or an arylalkyl group, and n represents a positive integer of 1 to 3.

Specific examples of the silane coupling agent include:
For example, halogenated silane compounds such as methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, methyltribromosilane, dimethyldibromosilane, trimethylbromosilane, diethyldichlorosilane, allyldimethylchlorosilane, and allylphenyldichlorosilane, and hexyltrimethoxysilane. , Octyltrimethoxysilane, dioctyldimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane and other alkoxysilane compounds, and hexamethyldisilazane, hexaethyldisilazane, hexapropyldisilazane and other disilazane compounds. . Any of these can be preferably used, and among these, dimethyldichlorosilane, octyltrimethoxysilane, and hexamethyldisilazane are particularly preferable because of easy reaction with the hydroxyl group on the surface of the inorganic fine particles and availability at low cost.

In order to perform the hydrophobic treatment on the base inorganic fine particles by using the hydrophobic treatment agent, the inorganic fine particles are made into a cloud shape by stirring or the like, and the hydrophobic treatment agent which is made into a solution using alcohol or the like is sprayed or It is possible to use a conventionally known method such as a dry process in which a vaporized hydrophobizing agent is brought into contact with the reaction to cause a reaction, or a wet treatment in which inorganic particles are dispersed in a solvent and a hydrophobizing agent is dropped to react.

Treatment of the base inorganic fine particles with the hydrophobic treatment agent is preferably such that the surface thereof has an appropriate hydrophobicity, and the hydrophobicity of 30 to 70%, which is a measure of wettability to methanol, is 30% to 70%. It is preferable that the treatment is performed within the range. By setting the degree of hydrophobicity of the base inorganic fine particles in the above range, the moisture resistance of the base inorganic fine particles is appropriately improved, and when the base inorganic fine particles are treated with the organopolysiloxane having an ammonium functional group at the end, The adhesion of organopolysiloxanes having ammonium functional groups is increased.

When the degree of hydrophobicity of the base inorganic fine particles is less than 30%, the moisture resistance of the inorganic fine particles is not sufficient, the chargeability tends to change due to environmental changes, and the degree of hydrophobicity is 70%. When it exceeds the above range, the adhesion between the organopolysiloxane having an ammonium functional group at the terminal and the base inorganic fine particles is deteriorated, and the long-term positive charge is likely to be insufficient.

The degree of hydrophobicity of the above-mentioned inorganic fine particles is calculated as follows. <Calculation of Hydrophobicity> 50 ml of distilled water is placed in an Erlenmeyer flask, and 0.200 g of inorganic fine particles to be measured is precisely weighed and added. While stirring with a magnetic stirrer, methanol is dripped from a buret whose tip is immersed in a liquid until the inorganic fine particles become wet. When the inorganic fine particles are completely wet with the solution, the dropping of methanol is terminated, the amount of dropped methanol is read, and the hydrophobicity is calculated by the following formula.

Hydrophobicity (%) = [a / (50 + a)] × 100 a; Amount of dropped methanol (milliliter) Treatment of inorganic fine particles with an organopolysiloxane having an ammonium functional group at a terminal On the other hand, it is preferable to use 1 to 50% by weight, preferably 3 to 40%, of an organopolysiloxane having an ammonium functional group at the terminal. By setting the amount within the above range, a preferable positive charge imparting property can be imparted without impairing the fluidity of the treated inorganic fine particles.

The treatment of the base inorganic fine particles with the organopolysiloxane having an ammonium functional group at the end is performed by dissolving the organopolysiloxane having an ammonium functional group at the end in an alcohol, for example, an alcohol having 1 to 5 carbon atoms. Can be carried out by treating the base inorganic fine particles. The alcohol used for dissolution is preferably methanol, ethanol, isopropanol or a mixture thereof. This treatment includes a method of spraying the above-mentioned alcohol solution on the base inorganic fine particles and drying, or a method of immersing the base inorganic fine particles in the alcohol solution and drying.

The concentration of the organopolysiloxane having an ammonium functional group at the end in the solution used for the treatment is
Generally 1-90% by weight, depending on solubility and properties
And preferably 10 to 50% by weight.

The treatment of the matrix inorganic fine particles with the organopolysiloxane having an ammonium functional group at the terminal is
After mixing, the ambient temperature is preferably 20 to 250 ° C, more preferably 80 to 220 ° C. By setting the atmosphere temperature of the treatment within the above range, the crosslinking of the organopolysiloxane having an ammonium functional group at the terminal proceeds properly, and the base inorganic fine particles are firmly and uniformly coated.

Although the processing time depends on the ambient temperature, it is usually
10 minutes to 6 hours. The preferable treatment time is 0.5 to 6 hours when the ambient temperature is in the range of 80 to 220 ° C. Any suitable equipment can be used for the treatment, for example a circulating air drying chamber, a heating mixer or a disc dryer.

It also has an ammonium functional group at the end.
Inorganic fine particles treated with organopolysiloxane are optional
BE with a surface area of
T specific surface area 10 to 400 m² / G is preferred, 50
~ 350m² The range of / g is more preferable. BET ratio
Surface area is 10m²If less than / g, the fluidity of the toner is secured.
Becomes difficult and also 400m²Air when exceeding / g
Depending on the moisture content in the
It tends to be unstable. The BET specific surface area is
Micromeritics manufactured by ICROMERITICS
It was measured with a Flow Soap II Model 2300.

The inorganic fine particles treated with the organopolysiloxane having an ammonium functional group at the terminal according to the present invention are added to colored particles containing at least a binder resin and a colorant to be used as a toner. The proportion of the fine particles added is preferably 0.1 to 5% by weight, more preferably 0.1 to 4% by weight, based on the colored particles.

When the content of the inorganic fine particles treated with the organopolysiloxane having an ammonium functional group at the end of the present invention is less than 0.1% by weight, the fluidity and positive chargeability of the toner are not sufficient, and as a result, However, the triboelectric chargeability of the toner becomes poor, and it becomes impossible to apply a proper amount of positive charge to the toner, and toner scattering and image fog are likely to occur. Further, the content ratio of the inorganic fine particles treated with the organopolysiloxane having an ammonium functional group at the end is 5
If it is more than wt%, a part of the inorganic fine particles treated with the organopolysiloxane having an ammonium functional group at the end is released from the colored particles. When the toner adheres to the sleeve, the regulation blade, or the photoconductor, the triboelectric chargeability of the toner is impaired, the toner cannot be applied with an appropriate amount of positive charge, and toner scattering or image fog occurs. There is. Further, in some cases, the positive charge is excessively applied to the toner, so that the image density is lowered.

Styrene-acrylic resin fine particles having a number average primary particle diameter of 0.1 to 2.0 μm or higher fatty acid metal salt such as zinc stearate may be added to the toner as a cleaning aid.

When a magnetic toner is obtained, magnetic particles are contained in the colored particles. As the magnetic particles, particles such as ferrite magnetite having an average primary particle diameter of 0.1 to 2.0 μm are used. The addition amount of these magnetic particles is 20 to 70% by weight in the colored particles.

If necessary, various additives such as a metal complex dye, a nigrosine dye, a quaternary ammonium compound and other charge control agents may be added to the toner. Inorganic particles or organic particles other than the inorganic particles of the present invention may be added to the toner.

The toner of the present invention can be used as a one-component developer, but can also be used as a two-component developer by mixing with a carrier, for example, a carrier having a magnetic core coated with a resin.

In the present invention, when the inorganic fine particles treated with the organopolysiloxane having an ammonium functional group at the terminal are used for the toner, a relatively high charge amount can be imparted to the toner, and toner scattering and image fogging can be prevented. In a two-component developer that uses the carrier as a frictional charge imparting member, the electrostatic binding force of the carrier increases, and if the developer is used for a long period of time, the toner that cannot participate in the development receives mechanical stress and the carrier surface is Contamination is caused and the function of the carrier as a triboelectric charging member is diminished.

These drawbacks can be solved by using a carrier in which a magnetic core having fluorine atoms in the surface region of 30 atom% or more is coated with a resin. By these, the contamination of the carrier surface is sufficiently suppressed, the positive charge can be stably applied to the toner for a long period of time, and a high-definition image with high image density without toner scattering or image fog can be obtained. .

The fluorine atom content in the surface region was measured by using an X-ray electron spectroscopic analyzer "ESCA-1000" (manufactured by Shimadzu Corporation).

The method of surface analysis by ESCA is disclosed in
No. 2-87157, the element number% of the measurement element existing on the surface of the material (here, the fluorine-containing resin coating the surface of the core material) is measured.

In the present invention, the element number% of the fluorine atom thus obtained is defined as the fluorine atom content rate (atomic%). Furthermore, specific measurement conditions and measurement elements are shown below. The element ratio is calculated from the obtained area intensity of each element. -Embodiment of ESCA measurement device: ESCA-1000 (manufactured by Shimadzu Corporation) Measurement conditions: X-ray = Mg anode type (using 1253.6 eV) Acceleration = 10 kV, 30 mA resolution = 31.5 eV Measurement element: carbon (C1s) , Nitrogen (N1s), oxygen (O1s), fluorine (F1s), silicon (2p) iron (Fe2p2 / 3), copper (Cu2p2 / 3), zinc (Zn 2p2 / 3) ESCA surface analyzer is particularly limited But not
For example, ESCALAB210, ESCALAB200R (above produced by VG), ESCA-850, ESCA-1000 [above produced by Shimadzu Corporation], PHI560 (above produced by Philips) and the like can be mentioned.

The means for making the fluorine atom in the surface region of the carrier in which the magnetic core is coated with a resin be 30 atomic% or more is not particularly limited, but it is preferable to coat with a fluorine-containing resin. The resin used alone contains 30 atomic% fluorine atoms in the surface area of the carrier.
It may be a resin that can be the above, or by itself, the fluorine atom in the surface region of the carrier is 30
Even if the content cannot be set to be at least 30 at%, any resin can be used as long as the surface area of the resin-coated carrier can be at least 30 at%. The resin coating the magnetic core is preferably a fluorinated resin containing a repeating unit represented by the following formula 12, and more preferably a fluorinated resin containing a repeating unit represented by the following formula 13.

[0122]

[Chemical formula 22] [In the formula, R represents a hydrogen atom or a methyl group, and Rf represents an alkyl group substituted with a fluorine atom. ]

[0123]

[Chemical formula 23]

[In the formula, Rf represents an alkyl group substituted with a fluorine atom. As the alkyl group substituted with a fluorine atom represented by Rf, an alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom is preferable, and further 3
Alkyl groups substituted with 5 to 5 fluorine atoms are preferred.
Specific examples of the alkyl group substituted with a fluorine atom represented by the _{Rf, -CF 3, -CF 2 CF} 2 H, -CF 2
CF ₃ may be mentioned.

The resin used for coating the carrier in the present invention is, for example, a fluorinated acrylate resin,
Fluorinated methacrylate resin, copolymer of fluorinated methacrylate and methacrylic acid ester, fluorinated styrene resin, copolymer of fluorinated styrene and styrene, trifluoroethylene resin, tetrafluoroethylene resin (PTFE), vinylidene fluoride Examples thereof include resins (PVdF), hexafluoropropylene resins (PHFP), and copolymers of vinylidene fluoride with trifluoroethylene, tetrafluoroethylene or hexafluoropropylene.

Further, these resins are commercially available, and these commercially available resins such as NEOFLON VDF V
P-850 (made by Daikin Industries, Ltd.), FORAFLO
N 1000 VLD, KYNER 450, KYNER 461, K
It is also possible to use YNER SL, KYNERADS (above, manufactured by Elf Atchem).

Of these, preferred resins are fluorinated methacrylate resins, copolymers of fluorinated methacrylate and methacrylic acid, vinylidene fluoride resins (P
VdF), a hexafluoropropylene resin, a copolymer of vinylidene fluoride and tetrafluoroethylene, a copolymer of vinylidene fluoride and hexafluoropropylene, and more preferably a monomer having a fluorine atom of 3 to 5 is used. Fluorinated methacrylate resin thus obtained, copolymer of fluorinated methacrylate having 3 to 5 fluorine atoms and methyl methacrylate or ethyl methacrylate, vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride It is a copolymer with hexafluoropropylene.

These resins may be used alone or in combination of two or more kinds.

If necessary, various additives such as a dispersion aid and a resistance control agent can be added to the carrier.

The carrier of the present invention can be manufactured by various conventionally known methods.

A resin-coated carrier in which the surface of magnetic material particles such as iron and ferrite is coated with a resin is prepared by dissolving the resin in an appropriate organic solvent to prepare a coating solution, and using this coating solution, an immersion method and a dry method are used. After forming a coating layer on the surface of the magnetic material particles by a method such as a spray method or a fluidized bed method, a method generally called a wet method of producing by further applying heat or leaving it, or when forming a resin coating layer It can be produced by a method generally called a dry method without using a solvent.

Further, the magnetic powder dispersion type carrier obtained by melt-kneading the magnetic material and the resin, pulverizing and classifying the magnetic material particles such as iron and ferrite and the resin and, if necessary, the dispersion aid. It can be produced by uniformly mixing the agent and various property-improving agents, melt-kneading, pulverizing and classifying.

The particle size of the magnetic carrier is 30 in terms of volume average particle size.
It is preferably in the range of to 150 μm.

The volume average particle size of the carrier is measured by using a laser diffraction particle size distribution measuring device "HELOS" (manufactured by JEOL Ltd.). The particles to be measured were dispersed by placing the particles to be measured, a surfactant and water (dispersion medium) in a 50 cc beaker and treating them with an ultrasonic homogenizer having an output of 150 W for 120 seconds.

The toner of the present invention can be used to visualize an electrostatic latent image in the commonly used electrophotographic method, electrostatic recording method, electrostatic printing method and the like. In electrophotography, for example, after an electrostatic latent image is formed on a photoconductor, the electrostatic latent image is visualized by a powdery developer in a developing device, and the obtained visible image is transferred paper or the like. Transfer to another transfer material. The powder remaining on the photoconductor is cleaned, and the visible image formed on the transfer material is fixed. As the photoconductor, a generally known photoconductive photoconductor having a tubular or sheet shape can be used, and examples thereof include a selenium-tellurium photoconductor, a selenium-arsenic photoconductor, an amorphous silicon photoconductor, and an organic photoconductor. Although it is possible to use a body and other conventionally known photoconductors, amorphous silicon photoconductors and organic photoconductors can be preferably used in consideration of durability, environmental compatibility, and ease of disposal of the photoconductor. .

As a preferable fixing method for fixing a toner image, for example, a heat roll fixing method and a fixing method (SURF fixing method) in which heat fixing is performed via a fixing film material which moves in contact with a fixedly installed heating body. However, the toner of the present invention is suitable for fixing by these fixing methods.

The hot roll fixing method is a fixing method in which a transfer material carrying a toner image is passed between a rotating fixing roller and a pressure-bonding roller in pressure contact with the fixing roller to fix the toner image on the transfer material. Yes, specifically, on the surface tetrafluoroethylene, polytetrafluoroethylene-
Between an upper roller with a heat source inside a metal cylinder made of iron, aluminum, etc. coated with a material with excellent releasability such as perfluoroalkoxy vinyl ether copolymer, and a lower roller made of silicone rubber, etc. In this method, the transfer material is passed through so that the toner image contacts the upper roller, and the toner material is heated and fixed.

A linear heater is used as a heat source for the upper roller, and the surface temperature of the upper roller is heated to about 120 to 200 ° C. Upon fixing, pressure is applied between the upper roller and the lower roller to deform the lower roller and form a so-called nip. The formed nip width is preferably 1 mm to 10 mm, more preferably 1.5 mm to 7 mm. When the nip width is narrow, heat cannot be uniformly applied to the toner,
Fixing unevenness is likely to occur, and when the nip width is wide, melting of the resin is promoted, causing a problem of excessive fixing offset. 40 mm / sec.-40 transfer material for fixing
It is preferable to move at a speed of 0 mm / sec.

As the heating element used in the latter SURF fixing method, a fixed linear heating element having a low heat capacity is used. The line-shaped heating element with low heat capacity has a thickness of 0.2 m.
m ~ 5.0mm, preferably 0.5mm ~ 3.5mm, width 10mm ~ 15mm, longitudinal length 240mm ~ 400mm alumina substrate 1.0mm ~ 2.5mm width applied to form an electrical resistor It is heated by energizing from both ends of the electric resistor. A pulse of 100 V and a cycle of 25 msec. Is used as the heating power source, and the amount of energy released is changed by changing the pulse width to control the heating temperature.

In the linear heating element, when the surface temperature of the electric resistor detected by the temperature sensor is T ₁ , the surface temperature T ₂ of the fixing film material moving on the electric resistor is lower than T _1. Become. The surface temperature T ₁ of the electric resistor is preferably 120 ° C. to 220 ° C., and the surface temperature T ₂ of the fixing film material in contact with the electric resistor is 0.5 ° C. to 10 ° C. from the temperature of T _1.
It is preferably low. Further, the surface temperature T ₃ of the fixing film material at the position where the fixing film material is separated from the surface of the fixed toner is preferably almost equal to T ₂ .

The fixing film material has a thickness of 10 μm to 3 μm.
5 μm heat-resistant film, for example, a film made of polyester, polyperfluoroalkoxy vinyl ether, polyimide, polyester imide, a release material layer made by adding a conductive material to a fluororesin such as Teflon is used as an endless film coated with 5 μm to 15 μm. . The total thickness of the endless film is generally 15 μm to 50 μm. The endless film is driven by a driving roller and a driven roller, and is transported without wrinkles and twists.

For heating and fixing, a pressure roller arranged at a position facing the linear heating element is used. As the pressure roller, a roller having a rubber elastic layer having high releasability such as silicon rubber is used. The transfer material having a toner image is passed such that the toner image side is in contact with the endless film, is pressed by a pressure roller that rotates in pressure contact, and is heated and fixed by the heating body through the endless film. The pressure applied by the pressure roller is generally 2 kg to 30 kg in total pressure. Transfer material is 40 mm / sec. To 400 mm / sec.
It is preferable to move at a speed of.

Further, instead of the endless film, an end fixing film wound around a feeding shaft may be used, and the end film may be fixed while being wound around the winding shaft.
Alternatively, a simple cylindrical one without a supporting roller such as a driving roller may be used.

In any of the fixing methods, it is possible to provide a mechanism for preventing the toner from adhering to the fixing device and a mechanism for cleaning the adhered toner. Examples of these mechanisms include a mechanism for supplying fluorine-based silicone oil to the upper roller or the fixing film, and a mechanism for cleaning the upper roller or the fixing film with a pad, roller, web, etc. impregnated with the fluorine-based silicone oil.

Next, the electrostatic charge image formed on the photoconductor of the present invention is developed with a developer consisting of toner and carrier to form a toner image, and the toner image is transferred to a transfer material and then cleaned. An image forming method will be described with reference to the drawings, which includes a step of removing toner remaining on a photoconductor using an apparatus and returning the removed toner to a toner replenishing apparatus or a developing apparatus for repeated use.

In the present invention, in the above image forming method, the colored particles containing the metal-crosslinked styrene-acryl copolymer resin, the polyolefin and the fatty acid amide or the fatty acid ester, which have been described in detail above, are added. It is preferable to use a toner to which inorganic fine particles treated with an organopolysiloxane having an ammonium functional group at the end are added and a resin-coated carrier in which a magnetic core having fluorine atoms in the surface region of 30 atom% or more is coated with a resin.

FIG. 1 is a diagram showing an example of an image forming apparatus capable of carrying out the image forming method of the present invention.

In FIG. 1, reference numeral 14 is an electrostatic charge image carrier, which has the shape of a rotating drum. Around the electrostatic image carrier 14, a charger 1, an exposure optical system 2, a developing device 12, a transfer device 5, a separator 6, and a cleaning device 15 are arranged in this order from the upstream side to the downstream side in the rotation direction. Has been done. Reference numeral 10 is a fixing device, and 11 is a toner supply box.

In FIG. 1, the surface of the electrostatic charge image carrier 14 is charged to a uniform potential by the charger 1, and then the surface of the electrostatic charge image carrier 14 is imagewise exposed by the exposure optical system 2. An electrostatic charge image is formed. The electrostatic charge image is developed by the developer contained in the developing device 12 to form a toner image. This toner image is electrostatically transferred onto the recording material P by the transfer device 5, and is fixed by the fixing device 10 to form a fixed image.

The residual toner remaining on the electrostatic image carrier 14 without being transferred is cleaned and collected by the pad 9 in the cleaning device 15. The electrostatic image carrier 14 that has been cleaned and the residual toner has been removed is used to form the next image.

The toner collected in the cleaning device 15 is returned by a toner recycling system (not shown), mixed with new toner from the toner supply box 11, and reused.

2 and 3 are views for explaining an example of the toner recycling system.

In FIGS. 2 and 3, 12 is a developing device,
13 is a developing sleeve, 14 is an electrostatic image carrier, 15 is a cleaning device, 16 is a first toner conveying screw,
Reference numeral 17 is a second toner carrying screw, 18 is a third toner carrying screw, 19 is a distributor, and 20 is a toner supply box. In FIG. 2, the toner collected by the cleaning device 15 is the first toner carrying screw 16,
The toner is transported by the second toner transport screw 17 and the third toner transport screw 18, and is collected in the distributor 19 provided for the recycled toner and provided in the developing device 12. Each of the first toner carrying screw 16, the second toner carrying screw 17, and the third toner carrying screw 18 has a spiral blade provided inside the rotation shaft, and the toner collected by the rotation of the blade is Be transported. Distributor 1
The toner collected in 9 is used again for developing the electrostatic image. New toner is supplied from the toner supply box 20.

In FIG. 3 as well, as in the case of FIG. 2, the toner collected by the leaning device 14 is conveyed by the first toner conveying screw 16, the second toner conveying screw 17, and the third toner conveying screw 18. However, in FIG. 3, the first toner conveying screw 1
6, the toner conveyed by the second toner conveying screw 17 and the third toner conveying screw 18 is mixed with new toner in the toner replenishing box 20 and then supplied to the developing device.

In the above description, the photoconductive photosensitive member described above can be used as the electrostatic charge image carrier 14, and the fixing device 10 can use the thermal roll fixing method and S described above.
A fixing device that fixes by the URF fixing method can be used.

[0156]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the following description, all “parts” indicate “parts by weight”.

Example 1 <Production of Inorganic Fine Particles> -Production of Inorganic Fine Particles 1- 20 parts of the following silane coupling agent (S-1), a kinematic viscosity at 25 ° C. of 55 mm ² / sec and a degree of polymerization n = 80 parts of dimethylpolysiloxane (A) having silanol groups at both ends, which is 50, was reacted in a 37% hydrochloric acid aqueous solution at 35 ° C., and a kinematic viscosity at 25 ° C. was 50 mm ² / sec. Organopolysiloxane having functional group (A)
Got

[0158]

[Chemical formula 24]

Next, 80 parts of silica fine particles (B) having a hydrophobization degree of 38% were hydrophobized on the surface of the silica fine particles (A) having a number average primary particle diameter of 7 nm into a mixer. After adding 5 parts of 25% ammonia water to 25 ° C., 20 parts by weight of the organopolysiloxane (A) having an ammonium functional group at the terminal synthesized above was placed in a mixer and added to methanol / isopropanol (40/60). ) Spray the dissolved solution into the mixed solvent and
Stir for minutes. After that, the solvent was removed at a set temperature of 130 ° C. under a nitrogen atmosphere in an air dryer to obtain inorganic fine particles 1 treated with an organopolysiloxane whose terminal was modified with an ammonium functional group.

-Production of Inorganic Fine Particles 2- In the production of the inorganic fine particles 1, the kinematic viscosity at 25 ° C. was 110 mm ² / sec instead of dimethylpolysiloxane (A).
Synthesized in the same manner as the organopolysiloxane (A) except that dimethylpolysiloxane having a silanol group at both ends and a degree of polymerization of n = 100 was used, and the kinematic viscosity at 25 ° C. was 100 mm ² / sec. Inorganic fine particles 2 were obtained in the same manner except that the organopolysiloxane having an ammonium functional group was used instead of the organopolysiloxane (A).
Got

-Production of Inorganic Fine Particles 3- In the production of the inorganic fine particles 1, the kinematic viscosity at 25 ° C. was 540 mm ² / sec instead of dimethylpolysiloxane (A),
Synthesized in the same manner as organopolysiloxane (A) except that dimethylpolysiloxane having a silanol group at both ends and having a degree of polymerization of n = 300 was used, and the kinematic viscosity at 25 ° C. was 500 mm ² / sec. Inorganic fine particles 3 were obtained in the same manner except that the organopolysiloxane having an ammonium functional group was used instead of the organopolysiloxane (A).
Got

-Production of Inorganic Fine Particles 4- In the production of inorganic fine particles 1, the kinematic viscosity at 25 ° C. was 10 mm ² / sec instead of dimethylpolysiloxane (A).
Synthesized in the same manner as the organopolysiloxane (A) except that dimethylpolysiloxane having a silanol group at both ends and having a degree of polymerization of n = 10 was used, and the kinematic viscosity at 25 ° C. was 5 mm ² / sec. Inorganic fine particles 4 were obtained in the same manner except that the organopolysiloxane having an ammonium functional group was used instead of the organopolysiloxane (A).
Got

-Production of Inorganic Fine Particles 5- In the production of inorganic fine particles 1, the surface of silica fine particles having a number average primary particle diameter of 7 nm was treated with dimethyldichlorosilane in place of silica fine particles (B), and the degree of hydrophobicity was 30. Inorganic fine particles 5 were obtained in the same manner except that the silica fine particles (%) were used.

-Production of Inorganic Fine Particles 6- In the production of inorganic fine particles 1, the surface of silica fine particles having a number average primary particle diameter of 7 nm was treated with dimethyldichlorosilane in place of silica fine particles (B), and the degree of hydrophobicity was 50. Inorganic fine particles 6 were obtained in the same manner except that the silica fine particles (%) were used.

-Production of Inorganic Fine Particles 7- In the production of inorganic fine particles 1, the surface of silica fine particles having a number average primary particle diameter of 7 nm was treated with hexamethyldisilazane in place of silica fine particles (B). Inorganic fine particles 7 were obtained in the same manner except that 62% of silica fine particles were used.

-Production of Inorganic Fine Particles 8- In the production of inorganic fine particles 1, the silica fine particles (B) were replaced with silica fine particle surfaces having a number average primary particle diameter of 7 nm, which were treated with octyltrimethoxysilane. 56
Inorganic fine particles 8 were obtained in the same manner except that the silica fine particles (%) were used.

-Production of Inorganic Fine Particles 9- In the production of inorganic fine particles 1, the surface of silica fine particles having a number average primary particle diameter of 16 nm was treated with dimethyldichlorosilane in place of silica fine particles (B), and the degree of hydrophobicity was 42. Inorganic fine particles 9 were obtained in the same manner except that the silica fine particles (%) were used.

-Production of Inorganic Fine Particles 10- In the production of the inorganic fine particles 1, the surface of silica fine particles having a number average primary particle diameter of 16 nm was treated with hexamethyldisilazane in place of the silica fine particles (B). Inorganic fine particles 10 were obtained in the same manner except that 70% of silica fine particles were used.

-Production of Inorganic Fine Particles 11- Inorganic fine particles 11 were obtained in the same manner as in the production of the inorganic fine particles 1 except that silica fine particles having a number average primary particle diameter of 100 nm were used instead of the silica fine particles (A). .

-Production of Inorganic Fine Particles 12- In the production of the inorganic fine particles 1, instead of the silane coupling agent (S-1), the following silane coupling agent (S-
Organopolysiloxane (A) having a kinematic viscosity at 25 ° C. of 40 mm ² / sec and having an ammonium functional group at the end, which was synthesized in the same manner as organopolysiloxane (A) except that 2) was used, Inorganic fine particles 12 were obtained in the same manner except that they were used instead of).

[0171]

[Chemical 25]

-Production of Inorganic Fine Particles 13- In the production of the inorganic fine particles 1, instead of the silane coupling agent (S-1), the following silane coupling agent (S-
3) except for using it was synthesized in the same manner as the organopolysiloxane (A), kinematic viscosity of 46 mm ² / s at 25 ° C., an organopolysiloxane having an ammonium functional group at the terminal, the organopolysiloxane (A Inorganic fine particles 13 were obtained in the same manner except that they were used instead of the above).

[0173]

[Chemical formula 26]

-Production of Inorganic Fine Particles 14- In the production of the inorganic fine particles 1, the use ratio of the silica fine particles (B) and the organopolysiloxane (A) when the silica fine particles (B) is treated with the organopolysiloxane (A) is Inorganic fine particles 1 in the same manner except that silica fine particles (B) / organopolysiloxane (A) = 60/40.
Got 4.

-Production of Inorganic Fine Particles 15- In the production of the inorganic fine particles 1, the use ratio of the silica fine particles (B) and the organopolysiloxane (A) when the silica fine particles (B) are treated with the organopolysiloxane (A). , Silica fine particles (B) / organopolysiloxane (A) = 97/3
Got 5.

-Production of Inorganic Fine Particles 16- In the production of the inorganic fine particles 1, the surface of alumina fine particles having a number average primary particle diameter of 20 nm was hydrophobized with hexamethyldisilazane in place of the silica fine particles (B). Inorganic fine particles 16 were obtained in the same manner except that alumina fine particles having a hydrophobicity of 63% were used.

-Production of Inorganic Fine Particles 17- In the production of inorganic fine particles 1, the surface of titanium oxide fine particles having a number average primary particle diameter of 50 nm was hydrophobized with hexamethyldisilazane in place of silica fine particles (B). Inorganic fine particles 17 were obtained in the same manner except that titanium oxide fine particles having a hydrophobicity of 66% were used.

-Production of Inorganic Fine Particles 18- In the production of the inorganic fine particles 1, the kinematic viscosity at 25 ° C. was 55 mm ² / sec in place of the organopolysiloxane (A).
Inorganic fine particles 18 were obtained in the same manner except that dimethylpolysiloxane having a silanol group at both ends and having a degree of polymerization of n = 50 was used.

-Production of Inorganic Fine Particles 19- In the production of the inorganic fine particles 1, instead of the organopolysiloxane (A), 15 parts of octyltrimethoxysilane and 25 parts of
Synthesized by reacting 85 parts of dimethylpolysiloxane having silanol groups at both ends with a kinematic viscosity of 55 mm ² / sec at ℃ at a polymerization degree of n = 50 in a 37% hydrochloric acid aqueous solution at 35 ° C. Inorganic fine particles 19 were obtained in the same manner except that an organopolysiloxane having a kinematic viscosity at 48 ° C. of 48 mm ² / sec and a terminal modified with octyltrimethoxysilane was used.

-Production of Inorganic Fine Particles 20- In the production of the inorganic fine particles 1, it was synthesized by subjecting dimethyldimethoxysilane and a silane coupling agent (S-3) to a copolycondensation reaction in place of the organopolysiloxane (A). , The kinematic viscosity at 25 ℃ is 52mm ² / sec,
Inorganic fine particles 20 were obtained in the same manner except that an organopolysiloxane having a degree of polymerization of n = 50 and having an ammonium functional group only in the side chain represented by the following formula was used.

[0181]

[Chemical 27]

Table 1 shows the contents of the constitution of the inorganic fine particles 1 to 20. Table 2 shows the hydrophobicity, bulk density and triboelectric charge of the inorganic fine particles 1-20. The number average primary particle diameter and the degree of hydrophobization are obtained by the above-mentioned methods, and the bulk density and the triboelectric charge amount are measured as follows.

<Bulk Density> This is a value measured according to ISO787 / 11 and is a value obtained by dividing the mass of the material by the volume after tapping.

<Frictional charge> A value measured by a blow-off method. 50 g of iron oxide powder (Type X-28, manufactured by Dowa Iron Powder Mining Co., Ltd.) and 0.5 g of inorganic fine particles were put in a polyethylene bottle. The values are measured with TB-200 manufactured by Toshiba Chemical Co., Ltd. after stirring for 30 minutes with a ball mill (108 rpm type).

[0185]

[Table 1]

[0186]

[Table 2]

<< Production of Colored Particles >>-Production of Colored Particles 1 (for the Present Invention) -72 parts of styrene, 10 parts of methyl methacrylate, 14 parts of butyl acrylate, 4 parts of monoacryloyloxyethyl succinate and 0.5 part of zinc oxide were used. Thus, a resin obtained by metal-crosslinking a styrene-acrylic copolymer having a bimodal molecular weight distribution, a weight average molecular weight Mw of 170,000 and a number average molecular weight Mn of 9,000 was produced.

Next, 100 parts of the above resin and 10 parts of carbon black (Black Pearls L, manufactured by Cabot Corporation) were premixed with a stirring type mixer, and then melt-kneaded with a biaxial kneader. After cooling, fine pulverization was performed with a jet mill, and the finely pulverized product was further classified with a classifier to produce colored particles 1 having a volume average particle size of 9.0 μm.

-Production of Colored Particles 2 (for the Present Invention) -Using 82 parts of styrene, 14 parts of butyl acrylate, 4 parts of monoacryloyloxyethyl isophthalate and 0.6 part of magnesium oxide, a bimodal molecular weight distribution is obtained. , Weight average molecular weight Mw is 186,000, number average molecular weight Mn is 10,000
A resin obtained by metal-crosslinking the above styrene-acrylic copolymer was produced.

Next, 100 parts of the above resin and 10 parts of carbon black (Black Pearls L, manufactured by Cabot Corporation) were premixed with a stirring type mixer and then melt-kneaded with a biaxial kneader. After cooling, fine pulverization was performed with a jet mill, and the finely pulverized product was classified with a classifier to produce colored particles 2 having a volume average particle diameter of 9.0 μm.

<< Production of Toner >> In accordance with the combination shown in Table 3, 100 parts of the above-mentioned colored particles 1 to 2 were mixed with 1 part of the inorganic fine particles.
~ 1.0 part of and 20 parts of zinc stearate added,
Toners 1-34 (invention) and toners 35-40 (comparative) were prepared by mixing for 10 minutes with a stir mixer.

[0192]

[Table 3]

<Production of Carrier> -Production of Carrier 1-Copolymer of the following fluorine atom-containing monomer (5FM) and methyl methacrylate (MMA) (monomer ratio: 5FM /
A coating solution was prepared by dissolving 20 parts of MMA = 80/20) in 100 parts of a mixed solvent of acetone / methyl ethyl ketone [mixing ratio 1: 1 (volume)]. Using a fluidized bed coating device, 200 parts of spherical magnetite particles having a volume average particle diameter of 60 μm were coated with this coating liquid to obtain a carrier 1 having a fluorine atom content of 38 atom% in the surface region.

[0194]

[Chemical 28]

—Production of Carrier 2— 10 parts of a vinylidene fluoride / hexafluoropropylene copolymer (monomer ratio: vinylidene fluoride / hexafluoropropylene = 80/20) and 10 parts of polymethylmethacrylate (Mw = 50,000) were used as 100 parts. A coating solution was prepared by dissolving in 1 part of dimethylformamide. Using a fluidized bed coating device, 200 parts of spherical magnetite particles having a volume average particle diameter of 60 μm were coated with this coating liquid to obtain a carrier 2 having a fluorine atom content in the surface region of 94 atom%.

<< Production of Developer >> According to the combinations shown in Table 4, 94 parts by weight of each of the above carriers and each of the above toners 6
Parts were mixed to prepare developers 1-40.

[0197]

[Table 4]

<< Copy Test >> The electrostatic latent image formed on the organic photoconductor is developed by a forward development method using a developer,
After forming a toner image and transferring this toner image to a transfer material, the toner image is heat-rolled and fixed on the transfer material under the following conditions, and the toner remaining on the photoconductor is removed using a cleaning device. An electrostatic recording device that can be used was used.

<Conditions for heat roll fixing> As a heat roll fixing device, as a top roller, a cylindrical surface having a diameter of 30 mm and having a surface covered with a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer and a heater built in the central portion Was used as the lower roller, and a roller having a diameter of 30 mm and made of silicon rubber whose surface was similarly coated with tetrafluoroethylene-perfluoroalkyl ether copolymer was used as the lower roller. Further, as a cleaning mechanism, a pad impregnated with polydimethylsiloxane was attached and used.

For fixing, a linear pressure of 0.8 kg / cm, a nip width of 4.3 mm,
The printing linear velocity was set to 250 mm / sec. Also,
The temperature of the upper roller surface was set to 190 ° C.

In the above electrostatic recording apparatus, the above developers 1 to 40 were used as developers, and a high temperature and high humidity environment (environmental temperature 30 ° C.,
After copying 50,000 copies in relative humidity 80%), repeat the cycle of copying 50,000 copies in low temperature and low humidity environment (environmental temperature 10 ° C, relative humidity 20%) twice, totaling 200,000 copies Was copied, and the toner charge amount (toner Q / M), the maximum image density (Dmax), the background fog (Fog), and the degree of toner scattering in the apparatus were evaluated as follows.

<< Evaluation of Toner Charge Amount (Toner Q / M) >>
The developer to be measured is carried on a rotatable cylindrical developer carrier equipped with magnetic poles fixed inside, and the developer carrier is placed at a distance of 2.0 mm from the developer carrier. Install a bronze plate.

While rotating the developer carrier, between the developer carrier and the phosphor bronze plate, 800 V as a DC component, AC
A voltage of 2 kV (pp) is applied as a component to form an electric field between them, and the toner in the developer is moved to the phosphor bronze plate.

Toner electrostatically attached to the phosphor bronze plate is blown off using compressed air to separate it from the phosphor bronze plate.

At that time, the electric charge [Q (μC)] flowing in through the phosphor bronze plate was measured by an electrometer, and the weight of the phosphor bronze plate before and after the toner adhered was measured using an electronic balance. The weight [m (g)] of the toner adhered to was calculated, and the toner charge amount (μC / g) was calculated by the following formula and evaluated.

[0206]

[Equation 1]

<< Evaluation of Maximum Image Density (Dmax) >> The optical density on a copied image was measured using a Macbeth densitometer (RD-918 type).
Was measured using.

<< Evaluation of Fog of Background Part >> The optical density of the background part was measured using a Macbeth densitometer (RD-918 type). When the average of the measured values at the five measurement locations was 0.1 or more, it was determined that the background fogging occurred.

<< Evaluation of Degree of Toner Scattering in Apparatus >> A double-sided tape was attached to three places on the upper wall of the image forming apparatus to perform copying, and the scattered toner was collected. After completion of copying, the double-sided tape was peeled off, and the number of adhered particles per 1 cm ² was calculated up to two decimal places from the SEM photograph image of the toner adhered to the double-sided tape. When the number of adhered particles per 1 cm ² exceeded 50.0, it was determined that toner scattering in the apparatus occurred.

The obtained results are shown in Tables 5, 6 and 7.

[0211]

[Table 5]

[0212]

[Table 6]

[0213]

[Table 7]

As is clear from Table 5, Table 6 and Table 7,
When the developers 1 to 34 are used, the positive chargeability of the toner is good, and the fluctuation of the charging characteristics due to the fluctuation of humidity can be made very small. No fogging of the image background or toner scattering in the apparatus was observed even when copying was performed, and a good copied image could always be obtained. Also, the copied image obtained after copying 200,000 copies had high image density and high definition.

The results show that the inorganic fine particles have good positive charge imparting property and positive charge retaining property.

On the other hand, in the case of using the developers 35 and 38, since the inorganic fine particles treated with the organopolysiloxane not modified with the organic group having the ammonium functional group at the end are used, the inorganic fine particles are The positive charge imparting property of the toner is extremely small, and after copying 20,000 copies, toner scattering in the apparatus increased, and image fog occurred at the time of copying 30,000 copies.

When the developers 36 and 39 are used,
Since the inorganic fine particles treated with the organopolysiloxane modified with an organic group having no ammonium functional group at the end are used, the positive charge imparting property of the inorganic fine particles is very small, and 20,000 copies are reproduced. After doing
Toner scattering in the apparatus increased, and image fog occurred at the time of copying 30,000 copies.

Furthermore, when the developers 37 and 40 are used, since the inorganic fine particles treated with the organopolysiloxane having an ammonium functional group in the side chain are used,
Although the inorganic fine particles have a certain degree of positive charge imparting property, they are still not sufficient. After copying 60,000 copies, toner scattering in the apparatus increases, and image fog occurs at the time of copying 80,000 copies. It has happened.

Example 2 <Production of colored particles> -Colored particles 3 (for the present invention) -72 parts of styrene, 10 parts of methyl methacrylate and 14 parts of butyl acrylate were used to have a bimodal molecular weight distribution,
Weight average molecular weight Mw is 170,000, number average molecular weight Mn is 9,0
00 styrene-acrylic copolymer resin was produced.

Next, 100 parts of the above resin, 10 parts of carbon black (Black Pearls L, manufactured by Cabot Corporation),
After pre-mixing 4 parts of polypropylene (Viscor 660P, manufactured by Sanyo Chemical Industry Co., Ltd.) and 3 parts of alkylenebis fatty acid amide (Hoechst wax C, manufactured by Hoechst Japan Co., Ltd.) with a stirring mixer, biaxial Melt and knead with a kneader, cool, and then finely pulverize with a jet mill.
0 μm colored particles 3 were produced.

-Colored particles 4 (for the present invention) -Using 82 parts of styrene and 14 parts of butyl acrylate, it has a bimodal molecular weight distribution and a weight average molecular weight Mw of 186,00.
A styrene-acryl copolymer resin having a number average molecular weight Mn of 0 and 10,000 was produced.

Next, 100 parts of the above resin, 10 parts of carbon black (Black Pearls L, manufactured by Cabot Corporation),
After preliminarily mixing 4 parts of polypropylene (Viscor 660P, manufactured by Sanyo Chemical Industry Co., Ltd.) and 3 parts of alkylenebis fatty acid amide (Hoechst wax C, manufactured by Hoechst Japan Co., Ltd.) with a stirring mixer, biaxial Melt and knead with a kneader, cool, and then finely pulverize with a jet mill.
0 μm colored particles 4 were produced.

<< Production of Toner >> In accordance with the combination shown in Table 8, 100 parts of the above colored particles 3 or 4 was used in Example 1.
1.0 part of the inorganic fine particles 1 to 20 and 0.1 part of zinc stearate described in 1 above are mixed and mixed for 10 minutes by a stirring type mixer, and toners 41 to 74 (invention) and toners 75 to 80 are added.
(Comparative) was produced.

[0224]

[Table 8]

<< Manufacture of Developer >> According to the combinations shown in Table 9, 94 parts by weight of the carrier described in Example 1 and 6 parts of each of the above toners were mixed to manufacture developers 41 to 80.

[0226]

[Table 9]

<< Copy Test >> The above-mentioned developer 4 is used as a developer.
A copy test was performed in the same manner as in Example 1 except that Nos. 1 to 80 were used. As in Example 1, the toner charge amount (toner Q / M), the maximum image density (Dmax), and the background fog ( Fog) and the degree of toner scattering in the apparatus were evaluated. The results obtained are shown in Tables 10, 11 and 12.

[0228]

[Table 10]

[0229]

[Table 11]

[0230]

[Table 12]

As is clear from Tables 10, 11, and 12, when the developers 41 to 74 are used, the positive chargeability of the toner is good, and the variation of the charging characteristics due to the variation of humidity is extremely reduced. Therefore, even when copying 200,000 copies under various environmental conditions, no fog on the image background or toner scattering in the apparatus was observed, and good copy images were always obtained. . Also, the copied image obtained after copying 200,000 copies had high image density and high definition.

The results show that the inorganic fine particles have good positive charge imparting property and positive charge retaining property.

On the other hand, in the case of using the developers 75 and 78, since the inorganic fine particles treated with the organopolysiloxane not modified with the organic group having the ammonium functional group at the end are used, the inorganic fine particles are The positive charge imparting property of the toner is extremely small, and after copying 20,000 copies, toner scattering in the apparatus increased, and image fog occurred at the time of copying 30,000 copies.

When developers 76 and 79 are used,
Since the inorganic fine particles treated with the organopolysiloxane modified with an organic group having no ammonium functional group at the end are used, the positive charge imparting property of the inorganic fine particles is very small, and 20,000 copies are reproduced. After doing
Toner scattering in the apparatus increased, and image fog occurred at the time of copying 30,000 copies.

Further, when the developers 77 and 80 are used, since the inorganic fine particles treated with the organopolysiloxane having an ammonium functional group in the side chain are used,
Although the inorganic fine particles have a certain degree of positive charge imparting property, they are still not sufficient. After copying 60,000 copies, toner scattering in the apparatus increases, and image fog occurs at the time of copying 80,000 copies. It has happened.

Example 3 <Production of colored particles> -Production of colored particles 5 (for the present invention) -72 parts of styrene, 10 parts of methyl methacrylate, 14 parts of butyl acrylate, 4 parts of monoacryloyloxyethyl succinate, 0.5 part of zinc oxide. Parts were used to produce a resin in which a styrene-acryl copolymer having a weight average molecular weight Mw of 170,000 and a number average molecular weight Mn of 9,000 was crosslinked with a metal having a bimodal molecular weight distribution.

Next, 100 parts of the above resin, 10 parts of carbon black (Black Pearls L, manufactured by Cabot),
After pre-mixing 4 parts of polypropylene (Viscor 660P, manufactured by Sanyo Chemical Industry Co., Ltd.) and 3 parts of alkylenebis fatty acid amide (Hoechst wax C, manufactured by Hoechst Japan Co., Ltd.) with a stirring mixer, biaxial Melt and knead with a kneader, cool, and then finely pulverize with a jet mill.
0 μm colored particles 5 were produced.

-Production of Colored Particles 6 (for the Present Invention) -Using 82 parts of styrene, 14 parts of butyl acrylate, 4 parts of monoacryloyloxyethyl isophthalate and 0.6 part of magnesium oxide, a bimodal molecular weight distribution is obtained. , Weight average molecular weight Mw is 186,000, number average molecular weight Mn is 10,000
A resin obtained by metal-crosslinking the above styrene-acrylic copolymer was produced.

Next, 100 parts of the above resin, 10 parts of carbon black (Black Pearls L, manufactured by Cabot),
After preliminarily mixing 4 parts of polypropylene (Viscor 660P, manufactured by Sanyo Chemical Industry Co., Ltd.) and 3 parts of alkylenebis fatty acid amide (Hoechst wax C, manufactured by Hoechst Japan Co., Ltd.) with a stirring mixer, biaxial Melt and knead with a kneader, cool, and then finely pulverize with a jet mill.
0 μm colored particles 6 were produced.

<< Production of Toner >> In accordance with the combination shown in Table 13, 100 parts of the colored particles 5 or 6 produced as described above were added to 1.0 parts of the inorganic fine particles 1 to 20 described in Example 1.
Parts and 0.1 part of zinc stearate were added and mixed for 10 minutes with a stirrer mixer to produce toners 81-120.

[0241]

[Table 13]

<Production of Carrier> -Production of Carrier 3-A copolymer of the following fluorine atom-containing monomer (5FM) and methyl methacrylate (MMA) (monomer ratio: 5FM /
A coating solution was prepared by dissolving 20 parts of MMA = 40/60) in 100 parts of a mixed solvent of acetone / methyl ethyl ketone [mixing ratio 1: 1 (volume)]. Using a fluidized bed coating device, 200 parts of spherical magnetite particles having a volume average particle diameter of 60 μm were coated with this coating liquid to prepare a carrier 3 for comparison having a fluorine atom content rate of 22 atom% in the surface region.

[0243]

[Chemical 29]

<< Production of Developer >> According to the combination shown in Table 14, 94 parts by weight of Carriers 1 and 2 or Carrier 3 described in Example 1 and 6 parts of each toner described above are mixed to prepare developers 81 to 120. Was manufactured.

[0245]

[Table 14]

<< Copy Test >> The above developer 8 is used as a developer.
A copying test was performed in the same manner as in Example 1 except that Nos. 1 to 120 were used, and in the same manner as in Example 1, the toner charge amount (toner Q / M), the maximum image density (Dmax), and the background fog ( Fog) and the degree of toner scattering in the apparatus were evaluated. The results obtained are shown in Tables 15, 16 and 17.

[0247]

[Table 15]

[0248]

[Table 16]

[0249]

[Table 17]

As is clear from Tables 15, 16, and 17, when the developers 81 to 114 are used, the positive chargeability of the toner is good, and the fluctuation of the charging characteristics due to the fluctuation of humidity is made extremely small. Therefore, even when copying 200,000 copies under various environmental conditions, no fog on the image background or toner scattering in the apparatus was observed, and good copy images were always obtained. . Also, the copied image obtained after copying 200,000 copies had high image density and high definition.

The results show that the inorganic fine particles have good positive charge imparting property and positive charge retaining property.

On the other hand, in the case of using the developers 115 and 118, since the inorganic fine particles treated with the organopolysiloxane not modified with the organic group having the ammonium functional group at the end are used, the inorganic fine particles are The positive charge imparting property of the toner is extremely small, and after copying 20,000 copies, toner scattering in the apparatus increased, and image fog occurred at the time of copying 30,000 copies.

In the case of using the developers 116 and 119, since the inorganic fine particles treated with the organopolysiloxane modified with an organic group having no ammonium functional group at the end are used, the inorganic fine particles are The positive charge imparting property of the toner is very small, and after copying 20,000 copies, toner scattering in the apparatus increased, and image fog occurred at the time of copying 30,000 copies.

Further, in the case of using the developers 117 and 120, since the inorganic fine particles treated with the organopolysiloxane having an ammonium functional group in the side chain are used, the inorganic fine particles have a certain degree of positive charge imparting property. It is still not enough, and after copying 60,000 copies, toner scattering in the apparatus increases, and image fog occurs at the time of copying 80,000 copies.

[0255]

INDUSTRIAL APPLICABILITY The toner of the present invention is excellent in fixability and anti-offset property at low temperature, and is quickly imparted with an appropriate amount of positive charge, and is stable for a long period of time with an appropriate amount of positive charge. It is possible to provide an image free from toner scattering and image fog. Further, the developer for developing an electrostatic charge image of the present invention does not cause contamination of the carrier surface, maintains a proper amount of positive charge stably over a long period of time, and gives an image free from toner scattering and image fog. be able to.

[Brief description of drawings]

FIG. 1 is a diagram showing an example of an image forming apparatus capable of performing an image forming method of the present invention.

FIG. 2 is a diagram illustrating a toner recycling system of the present invention.

FIG. 3 is a diagram for explaining another toner recycling system of the present invention.

[Explanation of sign]

1; charger 2; exposure optical system 5: Transfer device 6; Separator 10: Fixing device 11: Toner supply box 12: Developing device 14; Electrostatic charge image carrier 15; Cleaning device 16: First toner conveying screw 17: Second toner conveying screw 18; Third toner conveying screw 19; Distributor 20: Toner supply box

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-2-110474 (JP, A) JP-A-2-217863 (JP, A) JP-A-2-110572 (JP, A) JP-A-3- 225351 (JP, A) JP 2-110473 (JP, A) JP 1-120567 (JP, A) JP 4-67047 (JP, A) JP 63-46469 (JP, A) JP 64-66667 (JP, A) JP 62-229158 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03G 9/08-9/113

Claims (10)

(57) [Claims] 1. A colored particle containing a metal-crosslinked styrene-acrylic acid ester copolymer is represented by the following formula 2.
A toner for developing an electrostatic charge image, which is obtained by adding inorganic fine particles treated with an organopolysiloxane having an ammonium functional group to a terminal thereof. [Chemical 1] [In the formula, Y and Z are each a substituted or unsubstituted carbon atom number 1
~ 8 represents an alkyl group or an aryl group. A and B
Is a hydrogen atom, a substituted or unsubstituted C1-4 carbon atom, respectively.
Alkyl group or group having ammonium salt structure
Represents However, at least one of A and B is
It is a group having a ammonium salt structure. n is an integer of 5 to 400
Represent ] 2. A metal-crosslinked styrene-acrylic acid ester copolymer comprising (a) a styrene monomer, (b) an acrylic acid ester monomer or a methacrylic acid ester monomer, and (c). The toner for developing an electrostatic image according to claim 1 , which is a compound obtained by crosslinking a copolymer obtained by copolymerizing a monomer represented by the following formula 1 with a polyvalent metal salt. . [Chemical 2] [In the formula, R ₁ represents a hydrogen atom or a methyl group, and L 1
Represents a divalent linking group having an ester bond in the molecular chain and having 3 or more carbon atoms. ] 3. A metal crosslinked styrene - colored particles containing acrylic acid ester copolymer, an electrostatic charge image according to claim 1 or 2, characterized in that it contains a polyolefin and fatty acid amides or fatty acid esters Toner for development. 4. A colored particle containing a polyolefin and a fatty acid amide or a fatty acid ester, the method according to claim 1.
A toner for developing an electrostatic charge image, characterized in that inorganic fine particles treated with an organopolysiloxane having an ammonium functional group at the terminal represented by the above formula 2 are added. 5. A method according to claim 1 electrostatic image developer comprising the electrostatic image developing toner and carrier according to any one of 4. 6. The developer for developing an electrostatic charge image according to claim 5, wherein the carrier is a carrier having a magnetic core coated with a resin. 7. The developer for developing an electrostatic charge image according to claim 6, wherein the carrier in which the magnetic core is coated with a resin has 30 atomic% or more of fluorine atoms in the surface region. 8. The resin is a fluorinated acrylate resin or fluorinated methacrylate resin containing a repeating unit represented by the following formula 12, or a vinylidene fluoride resin,
The developer for developing an electrostatic image according to claim 7, which is a hexafluoropropylene resin or a copolymer resin of vinylidene fluoride and hexafluoropropylene. [Chemical 3] [In the formula, R represents a hydrogen atom or a methyl group, and Rf represents an alkyl group substituted with a fluorine atom. ] 9. The resin is a fluorinated methacrylate resin having a repeating unit represented by the following formula 13 in an amount of 75% by weight or more, or a copolymer resin of vinylidene fluoride and hexafluoropropylene. Item 7 or
Or the developer for developing an electrostatic charge image according to item 8 . [Chemical 4] [In the formula, Rf represents an alkyl group substituted with a fluorine atom. ] 10. A toner image is formed by developing an electrostatic charge image formed on a photoconductor with a developer including at least a toner and a carrier, and the toner image is transferred to a transfer material. The toner remaining on the photoconductor is removed by using the image forming method, and the removed toner is returned to the toner replenishing device or the developing device and repeatedly used .
An image forming method comprising using the developer for developing an electrostatic charge image according to any one of claims.