JP2003241415A - Toner, image forming device and process cartridge - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner free from melt sticking on a photoreceptor and giving a favorable image even for a long-term use. <P>SOLUTION: The toner contains at least a binder resin and a coloring material. In the binder resin, the mass composition ratio of polyester monomers to vinyl monomers ranges from 50/50 to 90/10. The contact angel of the toner with water ranges from 90° to 130°. The toner contains a hydrocarbon wax having 60° to 130° melting point defined by the endothermic peak temperature during elevation of temperature in a DSC (Differential Scanning Colorimeter). The surface layer of the photoreceptor contains a polyallylate resin, a fluorine- based comb-like graft polymer and fluorocarbon resin particles. The above toner and the photoreceptor are combined in an image forming device. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner used in a recording method using electrophotography, an electrostatic recording method, an electrostatic printing method or a toner jet recording method, an image forming apparatus using the toner, and The present invention relates to a process cartridge attached to an image forming apparatus and used.

[0002]

Although many are known as electrophotographic methods, generally, the outer peripheral surface of a photoconductor (electrostatic latent image bearing member) having a photoconductive layer on its surface is corona charged, roller charged,
On the outer peripheral surface of the photoconductor, by uniformly charging it by a charging means such as a fur brush charge or a magnetic brush charge, and then exposing the copy image of the copy object with a laser or an LED according to the reflected light or the modulation symbol. Form an electrostatic latent image on the
Further, the electrostatic charge image is developed with toner, and the toner image is transferred to a transfer material such as paper, if necessary, and then the toner image is fixed on the transfer material by heating, pressure, heating and pressurizing, or solvent vapor. I will get it.

At this time, the photoreceptor is required to have sensitivity, electrical characteristics, and optical characteristics according to the electrophotographic process to be applied. In particular, a photoreceptor that is repeatedly used is directly applied with an electrical / mechanical external force such as charging, image exposure, toner development, transfer and cleaning, and therefore durability against them is also required. Specifically, durability against electrical deterioration due to ozone and nitrogen oxides during charging, mechanical deterioration such as electrical discharge during charging, abrasion or scratches on the surface due to rubbing of the cleaning member, and electrical deterioration. Sex is required. In particular, organic photoreceptors composed of a relatively soft material, unlike inorganic photoreceptors, have poor durability against mechanical deterioration, and therefore, there is a strong demand for improvement thereof.

In recent years, a polycarbonate resin having bisphenol A as a skeleton has been attracting attention as a resin which is often used for a surface layer and has good wear properties and electric characteristics, but it has not yet been possible to solve all the above problems. However, various improvements have been tried.

Among them, as a method of effectively preventing mechanical deterioration and increasing durability, a method of reducing the friction coefficient of the surface of the photoconductor by allowing a fluororesin powder to exist in the surface layer of the photoconductor. Is mentioned. With this configuration, the sliding property with the cleaning member becomes smooth, and the force applied to the surface of the photoconductor can be weakened.

Further, in recent years, energy saving and resource saving have come to be demanded even in copying machines and printers. As one of the energy-saving measures in an electrophotographic apparatus, there is an attempt to save power in a fixing device that fixes toner on paper. Along with this, low-melting-point toners capable of low-temperature fixing have become mainstream. However, since such a toner has a low viscosity, the phenomenon that the toner is fused on the photoconductor is apt to occur depending on the environmental conditions and the development conditions, and accordingly, an image defect occurs, or a cleaning member or the like slides the toner. Rubbing sometimes caused scratches on the photoconductor.

In addition, digitalization of copying machines and printers
As the image quality becomes higher, the toner particle size is becoming smaller. As a result, the surface area of the toner is increased, the width of the charge amount distribution is increased, and there is a problem that fog, which is a core of fusion of the photoreceptor, is likely to occur.

Conventionally, vinyl polymers such as polyester resins and styrene resins have been mainly used as the binder resin.

The vinyl polymer is excellent in pulverizability during the production of toner particles and can easily be made into a high molecular weight compound, so that it is possible to obtain a polymer excellent in high temperature offset resistance. Or, if you lower the glass transition temperature,
There arises a problem that developability and blocking resistance deteriorate. On the other hand, when the polyester resin is used as the binder resin, it has excellent low-temperature fixability,
On the other hand, it has a drawback that an offset phenomenon is likely to occur at a high temperature. In order to improve this, an attempt has been made to increase the molecular weight or intentionally generate a gel component to control the viscoelasticity characteristics, but there is a problem that the low temperature fixing property and the deterioration of pulverizability at the time of toner manufacturing are deteriorated. Will occur.

Further, in order to enhance the releasing effect, many methods of adding a releasing agent such as wax have been studied. However, if added in a large amount, the dispersion in the toner is deteriorated, which affects the charge amount of the toner and causes image defects such as fog. Further, since such a toner has a low viscosity, the toner adheres around the fog on the photoconductor as a nucleus, which causes a problem such as an image defect.

As described above, various improvements have been attempted. However, in the recent situation of further speeding up and energy saving, a toner and an image forming that solve all of these problems are formed. In reality, there is no device or process cartridge.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner, an image forming apparatus and a process cartridge which solves all the above problems.

That is, it is an object of the present invention to prevent toner from being fused on a photosensitive member and to obtain a good image even in long-term durability, an image forming apparatus using the toner, and the image forming apparatus. It is to provide a process cartridge to be attached to and used.

[0014]

A first aspect of the present invention is a toner used in the second image forming apparatus of the present invention, which has at least a binder resin and a colorant, and the binder resin is at least a polyester resin. And a vinyl-based resin, the mass composition ratio of the polyester-based monomer and the vinyl-based monomer contained in the resin is 50/50 to 90/10, and the contact angle of the toner with water is 90 to 130 °. The toner is characterized by.

The second aspect of the present invention is to charge the electrostatic latent image bearing member; to form an electrostatic latent image on the charged electrostatic latent image bearing member; Developing the electrostatic latent image with toner held on a toner carrier to form a toner image; and transferring the toner image on the electrostatic latent image carrier to a transfer material. And the electrostatic latent image carrier is an electrophotographic photoreceptor having a photosensitive layer on a conductive substrate, and the surface layer of the photoreceptor has the following formula (1)

[0016]

[Chemical 4]

[0017] wherein, X is -CR ¹³ R ¹⁴ - (R ¹³ and R
¹⁴ is each independently a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms), and optionally substituted 1 to 1 having 5 to 11 carbon atoms.
-Cycloalkylene group, α, ω-alkylene group having 2 to 10 carbon atoms, single bond, -O-, -S-, -SO- or-
SO ₂ −. R ^{1 to} R ¹² are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group,
It is an aryl group or an alkylene group, and n is an integer. ] An image forming apparatus comprising a polymer having a structural unit represented by the above, and using the first toner of the present invention as the toner.

A third aspect of the present invention is a detachable process cartridge used by being attached to the second image forming apparatus of the present invention, which comprises an electrostatic latent image carrier having the above-mentioned specific surface layer, toner and toner. At least a developing device having a toner carrier is provided.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below.

According to the study by the present inventor, the releasability between the surface of the photoconductor and the toner is important in order to prevent the toner fusion to the photoconductor (electrostatic latent image carrier). .

In the present invention, the contact angle of the toner with water is used as an index of releasability. This contact angle represents the hydrophobicity of the toner, and it is considered that a highly hydrophobic toner has a small surface free energy and a high releasability.
This contact angle is greatly affected by the compatibility between the binder resin and other internal additives such as a release agent. In the present invention, by using a resin containing a highly polar polyester resin as a binder resin and a vinyl resin having a low polarity, it is possible to improve the compatibility with other internal additives and control the contact angle. Has been achieved.

The toner of the present invention has a contact angle with water of 90.
To 130 °, preferably 100 to 125 °. When the contact angle is smaller than 90 °, the adhesive force between the photoconductor and the toner increases, and fusion is likely to occur.
Further, offsetting to the fixing member and the cleaning member is likely to occur. When the contact angle of the toner is larger than 130 °, the viscosity of the toner becomes high, and even a photoreceptor having excellent mechanical strength as in the present invention may be scratched by rubbing of a cleaning member or the like. Not good.

The binder resin of the present invention contains at least a polyester resin and a vinyl resin, and the mass composition of the polyester monomer and the vinyl monomer contained in the binder resin is 50/50 to 90/10. , Preferably 60/40 to 85/15. Within this range, the contact angle of the toner can be controlled within the range defined by the present invention. When the amount of the polyester-based monomer is less than 50%, not only the hydrophobicity increases and the contact angle tends to be larger than the required value, but also the viscosity increases and the low temperature fixability deteriorates. Further, when the amount of the polyester-based monomer is more than 90%, the hydrophilicity becomes high, the contact angle becomes small, and the toner adheres to the photoconductor.

The binder resin of the present invention contains two kinds of polyester resin and vinyl resin.
It is particularly preferable to contain a hybrid resin component in which both are partially reacted. In this hybrid resin, since two types of resins having originally poor compatibility are uniformly dispersed, the characteristics of both resins can be utilized and the contact angle of the toner can be easily controlled. Further, since the hybrid resin is also excellent in compatibility with other internal additives, even if the toner particles are made small in particle size, the toner does not deteriorate due to long-term durability and the durability used in the image forming apparatus of the present invention is improved. When used in combination with the photoconductor, it is possible to suppress the occurrence of image defects and the like for a long period of time.

The polyester-based monomer used in the present invention includes the following.

As the alcohol component, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol,
1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, the following (1-
1) a bisphenol derivative represented by the formula and the following (1
-2) The diols represented by the formula are mentioned.

[0027]

[Chemical 5]

Examples of the acid component include benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and phthalic anhydride or their anhydrides; alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or their anhydrides. Further, succinic acid substituted with an alkyl group or alkenyl group having 6 to 18 carbon atoms or an anhydride thereof; unsaturated dicarboxylic acid such as fumaric acid, maleic acid, citraconic acid, itaconic acid or an anhydride thereof. .

The polyester resin used in the present invention is a trivalent or higher polyvalent carboxylic acid or its anhydride and / or
Alternatively, it is preferably a polyester resin containing a trihydric or higher polyhydric alcohol. Examples of trivalent or higher polycarboxylic acids or anhydrides thereof include 1,2,4-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid and pyromellitic acid. Examples thereof include acid anhydrides and lower alkyl esters thereof, and examples of trihydric or higher polyhydric alcohols include 1,2,3-propanetriol, trimethylolpropane, hexanetriol, and pentaerythritol. In the binder resin according to the present invention, an aromatic alcohol that is highly stable due to environmental changes is particularly preferable, and examples thereof include 1,2,4-benzenetricarboxylic acid and its anhydride.

Next, the vinyl-based monomers used in the present invention include the following.

Styrene: o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene,
pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p -Methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene,
Styrene and its derivatives such as m-nitrostyrene, o-nitrostyrene and p-nitrostyrene; ethylenically unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene and isoprene; vinyl chloride, Vinyl halides such as vinylidene chloride, vinyl bromide and vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate. , Isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate. Α-methylene aliphatic monocarboxylic acid esters such as: methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate Acrylic acid esters such as stearyl acrylate, 2-chloroethyl acrylate and phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether: vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone Vinyl ketones such as; N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl compounds such as N-vinyl pyrrolidone; vinyl naphthalene; acrylonitrile, methacrylonitrile And acrylic acid or methacrylic acid derivatives such as acrylamide.

Further, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenylsuccinic acid, fumaric acid and mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenylsuccinic anhydride Unsaturated dibasic acid anhydrides such as: maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl ester Half ester of unsaturated basic acid such as half ester, alkenyl succinic acid methyl half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester; unsaturated basic acid ester such as dimethyl maleic acid, dimethyl fumaric acid; acrylic Α, β-unsaturated acid anhydrides such as methacrylic acid, crotonic acid and cinnamic acid; anhydrides of the α, β-unsaturated acids and lower fatty acids; alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, these Monomers having a carboxyl group such as acid anhydrides and monoesters thereof.

Further, acrylic acid or methacrylic acid esters such as 2-hydroxyl ethyl acrylate, 2-hydroxyl ethyl methacrylate and 2-hydroxyl propyl methacrylate, 4- (1-hydroxy-)
1-methylbutyl) styrene, 4- (1-hydroxy-)
Mention may be made of monomers having a hydroxyl group such as 1-methylhexyl) styrene.

Further, in the toner of the present invention, the vinyl resin contained in the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups, but it is used in this case. Examples of the cross-linking agent include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; diacrylate compounds linked by an alkyl chain such as ethylene glycol diacrylate;
1,3-butylene glycol diacrylate, 1,4-
Examples include butanediol diacrylate, 1,5-pentanediol acrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and those in which the acrylate of the above compounds is replaced with methacrylate; Examples of the diacrylate compounds linked by an alkyl chain include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate. , And those in which the acrylates of the above compounds are replaced by methacrylates; diaclays chained by a chain containing an aromatic group and an ether bond. Examples of the compounds include polyoxyethylene (2) -2,2-bis (4hydroxyphenyl) propanediacrelate, polyoxyethylene (4) -2,2-bis (4hydroxyphenyl) propanediacrylate, and the above. The acrylate of the compound of the above is replaced by methacrylate; examples of the polyester type diacrylate compounds include, for example, MA
NDA (manufactured by Nippon Kayaku Co., Ltd.) is listed.

As the polyfunctional crosslinking agent, pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate,
Oligoester acrylates and those obtained by replacing the acrylates of the above compounds with methacrylates; triallyl cyanurate and triallyl trimellitate.

These crosslinking agents are used in an amount of 0.01 to 10 with respect to 100 parts by weight of the non-crosslinked vinyl monomer component.
Parts by mass (more preferably 0.03 to 5 parts by mass) can be used.

Among these crosslinkable monomers, fixability,
From the standpoint of anti-offset property, examples of compounds preferably used for the binder resin include aromatic divinyl compounds (particularly divinylbenzene) and diacrylate compounds linked by a chain containing an aromatic group and an ether bond.

Examples of the polymerization initiator used when producing the vinyl resin of the present invention include 2,2'-azobisisobutyronitrile and 2,2'-azobis (4-methoxy-2,4). -Dimethylvaleronitrile), 2,2 '
-Azobis (2,4-dimethylvaleronitrile), 2,
2'-azobis (2-methylbutyronitrile), dimethyl-2,2'-azobisisobutyrate, 1,1'-azobis (1-cyclohexanecarbonitrile), 2-
(Carbamoylazo) -isobutyronitrile, 2,2 '
-Azobis (2,4,4-trimethylpentane), 2-
Phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2-azobis (2-methylpropane),
Ketone peroxides such as methylethylketone peroxide, acetylacetone peroxide, cyclohexanone peroxide, 2,2-bis (t-butylperoxy) butane, t-butylhydroperoxide, cumene hydroperoxide, 1,1,3,3. 3-
Tetramethylbutyl hydroperoxide, di-t-
Butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, α, α′-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, Three
5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-trioyl peroxide, di-isopropyl peroxydicarbonate, di-
2-ethylhexyl peroxydicarbonate, di-n
-Propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, dimethoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t-butylperoxide Oxyacetate, t-butylperoxyisobutyrate, t-butylperoxyneodecanoate, t-butylperoxy2-ethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, t-butyl peroxyisopropyl carbonate,
Di-t-butylperoxyisophthalate, t-butylperoxyallyl carbonate, t-amylperoxy 2-ethylhexanoate, di-t-butyl peroxyhexahydroterephthalate, di-t-butylperoxyazelate Is mentioned.

Furthermore, when the binder resin contains a hybrid resin component, a vinyl resin component and /
Alternatively, it is preferable to include a monomer component capable of reacting with both resin components in the polyester resin component. Among the polyester-based monomers, those that can react with the vinyl-based resin include, for example, phthalic acid, maleic acid, citraconic acid,
Examples thereof include unsaturated dicarboxylic acids such as itaconic acid and anhydrides thereof. Examples of the vinyl-based monomer capable of reacting with the polyester resin component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

The above hybrid resin can be obtained by carrying out a polymerization reaction of one or both of the resins in the presence of a polymer containing a monomer component capable of reacting with the above vinyl resin and polyester resin.

Examples of the method for producing the binder resin used in the toner of the present invention include the following production methods (1) to (6).

(1) A method in which a vinyl resin, a polyester resin, and a hybrid resin are separately produced and then blended, and the blending is performed by dissolving and swelling in an organic solvent (for example, xylene), and then distilling off the organic solvent. Preferably, it is produced by adding a wax in this blending process. The hybrid resin is synthesized by separately producing a vinyl resin and a polyester resin, dissolving and swelling in a small amount of an organic solvent, adding an esterification catalyst and alcohol, and heating the mixture to carry out a transesterification reaction. Ester compounds can be used.

(2) A method for producing a polyester type unit and a hybrid resin in the presence of the vinyl type polymerization unit after the production. The hybrid resin is produced by reacting a vinyl-based polymerization unit (a vinyl-based monomer can be added if necessary) with a polyester-based monomer (alcohol, carboxylic acid) and / or polyester. Also in this case, an organic solvent can be appropriately used. Preferably, wax is added in this step.

(3) After manufacturing the polyester unit,
It is a method for producing a vinyl-based polymerization unit and a hybrid resin in the presence of this. The hybrid resin is produced by reacting a polyester-based unit (a polyester-based monomer can be added if necessary) with a vinyl-based monomer and / or a vinyl-based polymerization unit. Preferably, wax is added in this step.

(4) After the vinyl-based polymerization unit and the polyester-based unit are produced, a vinyl-based monomer and / or a polyester-based monomer (alcohol, carboxylic acid) is added in the presence of these polymer units to produce a hybrid resin. . Also in this case, an organic solvent can be appropriately used. Preferably, wax is added in this step.

(5) After the production of the hybrid resin, a vinyl-based monomer and / or a polyester-based monomer (alcohol, carboxylic acid) is added to carry out addition polymerization and / or polycondensation reaction to thereby effect the vinyl-based polymerization unit and the polyester-based polymerization. Manufacture the unit. In this case, the hybrid resin may be the one manufactured by the manufacturing method of the above (2) to (4), or the one manufactured by a known manufacturing method as needed. Furthermore, an organic solvent can be appropriately used.
Preferably, wax is added in this step.

(6) Vinyl-based polymerization unit, polyester-based unit and hybrid resin component by mixing vinyl-based monomer and polyester-based monomer (alcohol, carboxylic acid, etc.) and continuously performing addition polymerization and polycondensation reaction To manufacture. Furthermore, an organic solvent can be appropriately used. Preferably, wax is added in this step.

In the above production methods (1) to (5), the vinyl-based polymerization unit and / or the polyester-based unit may be a polymer unit having a plurality of different molecular weights and crosslinking degrees.

Among the above production methods (1) to (6), particularly the production method (3) makes it easy to control the molecular weight of the vinyl-based polymerization unit and control the production of the hybrid resin component. In addition, it is preferable to add wax because the dispersion state can be controlled.

The binder resin as described above may be used alone, or two or more kinds of binder resins having different softening points may be mixed and used. Such a system is preferable because the molecular weight distribution of the toner can be designed relatively easily and a wide fixing area can be provided.

The toner of the present invention preferably contains 10 to 50% by mass of THF (tetrahydrofuran) insoluble matter. When the THF insoluble content is less than 10% by mass, the viscosity of the toner becomes small and the toner tends to adhere. Further, when it is 50% by mass or more, not only the contact angle of the toner with water becomes large, but also
The low-temperature fixability deteriorates, and the load in the melt-kneading process during toner production is large, which causes a problem in productivity.

The toner of the present invention preferably has a weight average particle diameter of 4 to 10 μm from the viewpoint of image density and resolution.

The toner of the present invention has a softening point of 80 to 180 ° C., preferably 90 to 150 ° C., as measured by a Koka type flow tester. When the softening point of the toner is higher than 180 ° C., the low temperature fixability deteriorates. On the other hand, when the temperature is lower than 80 ° C., not only high temperature offset is likely to occur, but also fusion to the photoconductor occurs.

If desired, the toner of the present invention may contain one or more waxes as a releasing agent, and the wax is measured by a differential scanning calorimeter (DSC). The melting point defined by the endothermic peak temperature at the time of temperature increase is preferably 60 to 130 ° C. Melting point 6
When the temperature is 0 ° C. or lower, the viscosity of the toner is lowered and the toner is apt to adhere to the photoconductor, and when the melting point is 130 ° C. or higher, the low temperature fixability is deteriorated.

The wax is preferably added in an amount of 1 to 30 parts by mass with respect to 100 parts by mass of the binder resin. 1
When the amount is less than the amount by mass, the desired releasing effect is not sufficiently obtained, and when the amount is more than 30 parts by mass, the dispersion in the toner is poor and the toner adheres to the photosensitive member or the toner such as the carrier or the sleeve. Contamination of the surface of the carrier occurs and the toner image deteriorates, which becomes a practical problem.

Since the binder resin according to the present invention contains a vinyl polymer unit and a polyester unit in the resin chain, it is possible to uniformly disperse various kinds of waxes. Aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax and paraffin wax;
Oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax; block copolymers of these aliphatic hydrocarbon waxes; waxes containing fatty acid ester as a main component such as carnauba wax, sazol wax and montanic acid ester wax A fatty acid ester such as deoxidized carnauba wax partially or wholly deoxidized. Further, saturated straight chain fatty acids such as palmitic acid, stearic acid, montanic acid, or long-chain alkylcarboxylic acids having a longer-chain alkyl group; unsaturated fatty acids such as plurnic acid, eleostearic acid, and valinaric acid. Stearin alcohol, aralkyl alcohol, behenyl alcohol, carnaubayl alcohol,
Saturated alcohols such as ceryl alcohol, melysyl alcohol, or long-chain alkyl alcohols having a long-chain alkyl group; polyhydric alcohols such as sorbitol: calcium stearate, calcium laurate, zinc stearate, magnesium stearate Fatty acid metal salts (generally called metal soaps); waxes obtained by grafting aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid; fatty acids such as behenic acid monoglyceride and polyhydric alcohols. A partial esterified product of the above; a methyl ester compound having a hydroxyl group obtained by hydrogenation of vegetable oils and fats. In the present invention, a hydrocarbon wax is particularly preferable in terms of ease of dispersion in toner and high releasability.

The wax may be added at the time of melt-kneading during the production of toner, or may be added during the production of resin.

The toner of the present invention may be a magnetic toner or a non-magnetic toner. In the case of a magnetic toner, it is preferable to use the following magnetic materials for reasons such as chargeability, fluidity, and uniformity of copy density.

Magnetic materials used also as colorants include iron oxides such as magnetite, maghemite, and ferrite, and magnetic iron oxides containing other metal oxides; Fe, C
o, metals such as Ni, or these metals and Al,
Co, Pb, Mg, Ni, Sn, Zn, Sb, Be, B
Examples thereof include alloys with metals such as f, Cd, Ca, Mn, Se, Ti, W and V, and mixtures thereof. Conventionally, triiron tetraoxide (Fe ₃ O _4), iron sesquioxide (γ-Fe ₂
O ₃ ), iron zinc oxide (ZnFe ₂ O ₄ ), yttrium iron oxide (Y ₃ Fe ₅ O ₁₂ ), cadmium iron oxide (Cd ₃ Fe ₂
O ₄ ), iron gadolinium oxide (Gd ₃ Fe ₅ O ₁₂ ), iron oxide copper (CuFe ₂ O ₄ ), lead iron oxide (PbFe ₁₂ O ₁₉ ),
Iron oxide nickel (NiFe ₂ O ₄ ), iron oxide neodymium (N
dFe ₂ O ₃ ), iron oxide barium (BaFe ₁₂ O ₁₉ ), iron oxide magnesium (MgFe ₂ O ₄ ), iron manganese oxide (MnFe ₂ O ₄ ), iron oxide lanthanum (LaFeO ₃ ),
Iron powder (Fe), cobalt powder (Co), nickel powder (N
i) etc. are known. The above-mentioned magnetic materials are used alone or in combination of two or more. A particularly preferred magnetic material is ferric tetroxide or ferric sesquioxide fine powder.

These magnetic materials have an average particle size of 0.05 to 2
In μm, the magnetic characteristics under application of 795.8 kA / m are coercive force (Hc) 1.6 to 12.0 kA / m and saturation magnetization (σs).
50 to ²⁰⁰ Am ² / kg (preferably 50 to 100 A)
m ² / kg) and remanent magnetization (σr) of ^{2 to} 20 Am ² / kg are preferable.

The magnetic substance is preferably added in an amount of 10 to 200 parts by mass with respect to 100 parts by mass of the binder resin.

When the toner of the present invention is used as a non-magnetic toner, any suitable pigment or dye can be used as a colorant.

As the dye, C.I. I. Direct Red 1, C.I. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I. Mordant Red 30, C.I. I. Direct Blue 1, C.I.
I. Direct Blue 2, C.I. I. Acid Blue 9,
C. I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Modant To Blue 7, C.I. I. Direct Green 6, C.I.
I. Basic Green 4, C.I. I. There are Basic Green 6 etc. Examples of pigments include yellow lead, cadmium yellow, mineral fast yellow, navel yellow, naphthol yellow S, Hansa yellow G, permanent yellow NCG, tartrazine lake, red lead yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, benzidine orange G. , Cadmium red, Permanent red 4R, Watching red calcium salt, Eosin lake, Brilliant carmine 3
B, manganese purple, fast violet B, methyl violet lake, navy blue, cobalt blue, alkali blue lake, Victoria blue lake, phthalocyanine blue, fast sky blue, indanthrene blue BC, chrome green, chromium oxide, pigment green B, malachite. Green Rake, Final Yellow Green G, etc.

When the toner of the present invention is used as a toner for forming a full-color image, the following colorants are listed. Examples of magenta color pigments include C.I. I. Pigment Red 1-19, 21-23, 30-32, 37-4
1, 48-55, 57, 58, 60, 63, 64, 6
8, 81, 83, 87-90, 112, 114, 12
2, 123, 163, 202, 206, 207, 20
9, C.I. I. Pigment violet 19, C.I. I. Butt Red 1, 2, 10, 13, 15, 23, 29, 3
5 and the like.

The above magenta pigment may be used alone, but it is more preferable to use a dye and a pigment together to improve the sharpness from the viewpoint of the image quality of a full color image. Examples of magenta dyes include C.I. I. Solvent Red 1,
3, 8, 23-25, 27, 30, 49, 81-84,
100, 109, 121, C.I. I. Disperse Red 9, C.I. I. Solvent Violet 8, 13, 14,
21, 27, C.I. I. Oil soluble dyes such as Disperse Violet 1, C.I. I. Basic Red 1, 2, 9, 1
2-15, 17, 18, 22-24, 27, 29, 3
2, 34-40, C.I. I. Basic Violet 1,
Basic dyes such as 3, 7, 10, 14, 15, 21, 25 and 28 are mentioned.

As the color pigment for cyan, C.I. I. Pigment Blue 2, 3, 15 to 17, C.I. I. Bat Blue 6, C.I. I. 1 to 5 phthalimidomethyl groups in Acid Blue 45 or a phthalocyanine skeleton having the following structure
For example, individually substituted copper phthalocyanine pigment.

[0067]

[Chemical 6]

As the coloring pigment for yellow, C.I. I. Pigment Yellow 1-7, 10-17, 23, 35, 7
3, 83, C.I. I. Butt Yellow 1, 3, 20, and the like.

The coloring agent is based on 100 parts by mass of the binder resin.
0.1 to 60 parts by mass is preferable, and more preferably 0.5.
˜50 parts by mass.

The chargeability of the toner of the present invention may be either positive or negative, but since the binder resin itself has a high negative chargeability,
It is preferably a negatively chargeable toner.

A charge control agent may be used in the toner of the present invention, if necessary, in order to further stabilize the charge amount. As the negative charge control agent, for example, an organometallic complex or a chelate compound is effective, and examples thereof include:
Monoazo metal complexes; acetylacetone metal complexes; metal complexes of aromatic hydroxycarboxylic acids or aromatic dicarboxylic acids and their metal salts, anhydrides, esters and phenol derivatives such as bisphenol.

As the positive charge control agent, a modified product of nigrosine and a fatty acid metal salt or the like; tributylbenzylammonium-1-hydroxy-4-naphthosulfonate,
Quaternary ammonium salts such as tetrabutylammonium tetrafluoroborate, and onium salts such as phosphonium salts which are analogs thereof, and lake pigments thereof;
Triphenylmethane dyes and lake pigments thereof (as a laker, phosphotungstic acid, phosphomolybdate, phosphotungsten molybdate, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanine compounds, etc.); higher fatty acids Metal salts of dibutyltin oxide, dioctyltin oxide and dicyclohexyltin oxide; dibutyltin borate, dioctyltin borate, and organotin borate such as dicyclohexyltin borate. These may be used alone or in combination of two or more.

A fluidity improver may be used in the toner of the present invention. As the fluidity improver, any fluidity improver can be used as long as the fluidity can be increased by externally adding the toner particles before and after the addition. For example, vinylidene fluoride fine powder, fluororesin powder such as polytetrafluoroethylene fine powder, wet process silica, fine powder silica such as dry process silica, silica as a silane coupling agent,
Examples include titanium coupling agents and treated silica that has been surface-treated with silicone oil. A preferred fluidity improver is a fine powder produced by vapor phase oxidation of a silicon halogen compound, which is so-called dry process silica or fumed silica, and is produced by a conventionally known technique. . For example, the thermal decomposition oxidation reaction of silicon tetrachloride gas in oxygen and hydrogen is utilized, and the basic reaction formula is as follows.

SiCl ₄ + 2H ₂ + O ₂ → SiO ₂ + 4HCl

In this manufacturing process, it is also possible to obtain a fine composite powder of silica and another metal oxide by using another metal halogen compound such as aluminum chloride or titanium chloride together with a silicon halogen compound. Also included as silica. The average particle diameter of the particles is preferably in the range of 0.001 to 2 μm, and particularly preferably 0.002 to 0.2.
It is preferable to use silica fine powder in the range of μm.

Examples of commercially available silica fine powders produced by vapor phase oxidation of a silicon halogen compound include those commercially available under the following trade names. AEROSiL (Nihon Aerosil Forest) 130 200 300 380 TT600 MOX170 MOX80 COK84 Ca-O-SiL (CABOT Co.) M-5 MS-7 MS-75 HS-5 EH-5 Wacker HDK N 20 (WACKER-CH).
(EMIE GNBH) V15 N20E T30 T40 D-C Fine Silica (Dow Corning Co.
Company) Francol (Francil)

Furthermore, it is preferable to use a treated silica fine powder obtained by subjecting the silica fine powder produced by the vapor phase oxidation of the silicon halogen compound to a hydrophobic treatment. The treated silica fine powder is particularly preferably one obtained by treating the silica fine powder so that the hydrophobicity titrated by the methanol titration test shows a value in the range of 30 to 80.

As a method for hydrophobizing, it is imparted by chemically treating with an organic silicon compound or the like which reacts with or physically adsorbs on the fine silica powder. The preferred method is
A silica fine powder produced by vapor phase oxidation of a silicon halogen compound is treated with an organosilicon compound. As such an organosilicon compound, hexamethyldisilazane,
Trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β -Chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, 1-
Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane and 2 to 12 siloxane units per molecule, each of which is located at the terminal unit Si
Examples thereof include dimethylpolysiloxane containing a hydroxyl group bonded to. These are used alone or in a mixture of two or more.

The inorganic fine powder may be treated with silicone oil, or may be treated in combination with the above hydrophobic treatment.

A preferred silicone oil is 25
Those having a viscosity at 30 ° C. of 30 to 1000 centistokes are used, and for example, dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene modified silicone oil, chlorophenyl silicone oil, fluorine modified silicone oil and the like are particularly preferable.

The method for treating silicone oil is, for example, a method in which silica fine powder treated with a silane coupling agent and silicone oil are directly mixed using a mixer such as a Henschel mixer; A method of spraying silicone oil on the above; or a method of dissolving or dispersing the silicone oil in an appropriate solvent and then adding fine silica powder and mixing to remove the solvent. Silicone oil treated silica has a silica content of 200 in inert gas after the silicone oil treatment.
It is more preferable that the coating on the surface is stabilized by heating to a temperature of not less than 0 ° C (more preferably not less than 250 ° C).

Aminopropyltrimethoxysilane having a nitrogen atom, aminopropyltriethoxysilane, dimethylaminopropyltrimethoxysilane, diethylaminopropyltrimethoxysilane, dipropylaminopropyltrimethoxysilane, dibutylaminopropyltrimethoxysilane, monobutylamino Propyltrimethoxysilane, dioctylaminopropyldimethoxysilane, dibutylaminopropyldimethoxysilane, dibutylaminopropylmonomethoxysilane, dimethylaminophenyltriethoxysilane, trimethoxysilyl-γ
-Propylphenylamine, trimethoxysilyl-γ-
A silane coupling agent such as propylbenzylamine may be used alone or in combination. As a preferable silane coupling agent, hexamethyldisilazane (HMD
S).

In the present invention, those treated by a method of treating silica with a coupling agent and then treating with silicone oil, or a method of treating silica with a coupling agent and silicone oil simultaneously are preferable.

The fluidity-improving agent has a specific surface area of 30 m ² / g or more, preferably 5 as measured by BET method by nitrogen adsorption.
Those of 0 m ² / g or more give good results. The fluidity improver may be used in an amount of 0.01 to 8 parts by mass, preferably 0.1 to 4 parts by mass based on 100 parts by mass of the toner particles.

If necessary, external additives other than the chargeability improver may be added to the toner of the present invention.

For example, resin fine particles or inorganic fine particles which act as a charging aid, a conductivity-imparting agent, a fluidity-imparting agent, an anti-caking agent, a release agent, a lubricant, an abrasive and the like. As such a substance, for example, a lubricant such as Teflon (registered trademark), zinc stearate, polyvinylidene fluoride, and polyvinylidene fluoride are preferable. Alternatively, abrasives such as cerium oxide, silicon carbide, and strontium titanate are preferable, and strontium titanate is particularly preferable. Alternatively, fluidity-imparting agents such as titanium oxide and aluminum oxide, among which hydrophobic ones are particularly preferable. Alternatively, a small amount of anti-caking agent, conductivity-imparting agent such as carbon black, zinc oxide, antimony oxide, tin oxide, etc., or fine particles of opposite polarity can be used as a developing property improver.

The resin fine particles, the inorganic fine powder or the hydrophobic inorganic fine powder mixed with the toner is preferably used in an amount of 0.1 to 5 parts by mass with respect to 100 parts by mass of the toner.

The toner of the present invention can be mixed with a carrier and used as a two-component developer. The current value of the carrier is preferably 20 to 200 μA by adjusting the degree of unevenness of the carrier surface and the amount of resin to be coated.

As the resin for coating the surface of the carrier, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, acrylic acid ester copolymer, methacrylic acid ester copolymer, silicone resin,
Fluorine-containing resin, polyamide resin, ionomer resin,
A polyphenylene sulfide resin or the like or a mixture thereof can be used.

As the magnetic material of the carrier core, oxides such as ferrite, iron-excessive ferrite, magnetite and γ-iron oxide, metals such as iron, cobalt and nickel, or alloys thereof can be used. The elements contained in these magnetic materials include iron, cobalt, nickel, aluminum, copper, lead, magnesium, tin,
Examples thereof include zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten and vanadium.

To prepare the toner of the present invention, first, a binder resin, a colorant and / or a magnetic material, a release agent, a charge control agent or other additives are mixed with a mixer such as a Henschel mixer or a ball mill. Mix well. The mixture is melted and kneaded using a kneader such as a kneader or an extruder to make the resins compatible with each other, and the solidified product is crushed after cooling and solidification of the melt-kneaded product, and the crushed product is classified according to the present invention. Toner can be obtained. Further, a toner having a fluidity improver and / or other external additive on the surface of toner particles is obtained by thoroughly mixing the fluidity improver and / or other external additive with a toner by a mixer such as a Henschel mixer. You can

Tables 1 to 5 below show devices generally used as toner manufacturing devices, but the devices are not limited to these.

[0093]

[Table 1]

[0094]

[Table 2]

[0095]

[Table 3]

[0096]

[Table 4]

[0097]

[Table 5]

Next, the methods for measuring the physical properties of the toner and raw materials of the present invention are shown below. The examples described below are also based on this method.

(1) Measurement of contact angle of toner with water Measuring device: FACE contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd.) Measuring temperature: 23 to 25 ° C. Measuring humidity: Relative humidity 40 to 60% Sample preparation: about 10 g Of the toner is compressed and molded at a pressure of 2.0 × 10 ⁷ Pa for 2 minutes to have a diameter of 25 mm and a thickness of about 10 m.
A disk-shaped sample of m is prepared. This is a glass sample bottle (for example, snap cup No.
30) and put on a Teflon (registered trademark) sheet on a hot plate heated to 100 to 120 ° C. for 5 minutes.
A pressure of 5-10 × 10 ⁵ Pa is applied for about 10 minutes. When the toner is softened and melted, it is cooled to room temperature, the glass sample bottle is broken, and the melted and molded product of the toner is taken out. This is sequentially polished with # 280 → # 800 → # 1500 polishing paper to obtain a diameter of 25 mm and a thickness of 5
A disc-shaped sample of mm is used. The contact angle measurement surface shall be visually finished without scratches. It should be noted that ion-exchanged water or commercially available purified water is used for the measurement, and the contact angle of each sample is measured 5 times, and the average value thereof is used as the contact angle of the toner.

(2) Measurement of tetrahydrofuran (THF) insoluble matter 0.5 to 1.0 g of a sample is weighed (W ₁ g), and a cylindrical filter paper (for example, No. 86R manufactured by Toyo Roshi Kaisha, Ltd.) is put into a Soxhlet extractor. After extraction with 200 ml of THF as a solvent for 10 hours and evaporating the soluble component solution extracted with the solvent, the product is vacuum dried at 100 ° C. for several hours, and the amount of the THF soluble component is weighed (W ₂ g). The weight of the combustion residual ash in the toner is calculated (W ₃ g). The combustion ash content is determined by the following procedure. Accurately weighed sample were placed about 2.0g magnetic crucible beforehand accurately weighed 30 ml, precisely weighed the weight of the sample (W _a g). Put the crucible in the electric furnace for about 900
After heating at 0 ° C. for 3 hours, allowing to cool in an electric furnace, allowing to cool in a desiccator at room temperature for 1 hour or more, the crucible weight is precisely weighed. From this, the combustion residual ash content (W _b g) is obtained.

(W _b / W _a ) × 100 = combustion residual ash content (mass%) From this content, the weight of the combustion residual ash in the sample can be determined. The THF insoluble matter is calculated from the following formula.

THF insoluble matter = {(W _1- (W ₃ + W ₂ ))
/ (W ₁ -W ₃ )} × 100 (mass%) In the case of a binder resin, the THF insoluble content may be calculated from the following formula.

THF insoluble matter = {(W ₁ -W ₂ ) / W ₁ } ×
100 (mass%)

An example of a Soxhlet extraction device is shown in FIG. The THF 1 contained in the container 2 is heated by the heater 8 and vaporized, and the vaporized THF is guided to the cooler 6 through the pipe 7. The cooler 5 is constantly cooled by cooling water 6. The THF liquefied by being cooled by the cooler 5 accumulates in the reservoir 9 having a cylindrical filter paper, and when the liquid level of the THF becomes higher than that of the middle tube 4, the THF is discharged from the reservoir 9 into the container 2. The toner 3 contained in the cylindrical filter paper is extracted by circulating THF.

(3) Measurement of particle size distribution Measuring apparatus: Coulter Multisizer IIe (manufactured by Beckman Coulter, Inc.) As the electrolytic solution, primary sodium chloride is used to prepare a 1% NaCl aqueous solution. For example, ISOTON R-II (manufactured by Beckman Coulter, Inc.) can be used. As a measuring method, a surfactant as a dispersant in 100 to 150 ml of the electrolytic aqueous solution,
Preferably, 0.1 to 5 ml of alkylbenzene sulfonate is added, and 2 to 20 mg of the measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the volume and number of toner particles having a particle size of 2 μm or more are measured by the measuring device using a 100 μm aperture as an aperture. The volume distribution and number distribution were calculated. Then, the weight average particle diameter (D4) and the number average particle diameter (D1) according to the present invention (the median value of each channel is used as a representative value for each channel) are determined.

(4) Wax Melting Point Measuring Method The wax melting point is measured according to ASTM D3418-82 using a differential scanning calorimeter (DSC), DSC-7 (manufactured by Perkin Elmer Co., Ltd.).

The measurement sample is 2 to 10 mg, preferably 5 m
Weigh g accurately. This is put in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a temperature rising rate of 10 ° C./min at a normal temperature and normal humidity in a measurement temperature range of 30 to 200 ° C. The endothermic peak of the main peak of the DSC curve in the temperature range of 30 to 200 ° C. obtained in the second heating process is analyzed.

(5) Toner softening point measuring method: Measured by a Koka type flow tester according to JIS K 7210. The specific measuring method is shown below. While heating a 1 cm ³ sample at a temperature rising rate of 6 ° C./min using a Koka type flow tester (manufactured by Shimadzu Corporation), a load of 20 kg / cm ² was applied by a plunger, and a nozzle having a diameter of 1 mm and a length of 1 mm. Is extruded, thereby drawing a plunger drop amount (flow amount) -temperature curve. When the height of the S-shaped curve is h, h / 2
The temperature corresponding to (the temperature at which half the resin flows out) is the softening point.

Next, the photosensitive member used in the image forming apparatus of the present invention will be described. However, unless otherwise specified, the scope of the present invention is not intended to be limited thereto.

The surface layer of the photoreceptor of the present invention is represented by the following formula (1).
It contains a polymer having a structural unit represented by.

[0111]

[Chemical 7]

In the formula, X is —CR ¹³ R ¹⁴ — (R ¹³ and R ¹⁴
Are each independently a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms), and optionally substituted 1,1 to 5 carbon atoms.
A cycloalkylene group, an α, ω-alkylene group having 2 to 10 carbon atoms, a single bond, -O-, -S-, -SO- or -S.
O ₂ −. R ^{1 to} R ¹² are each independently a hydrogen atom,
It is a halogen atom, an optionally substituted alkyl group, an aryl group or an alkylene group, and n is an integer.

The halogen atom is a fluorine atom,
Examples thereof include chlorine atom and bromine atom, examples of alkyl group include methyl group, ethyl group and propyl group, examples of aryl group include phenyl group and naphthyl group, and examples of alkylene group include methylene group and dimethylene group. And trimethylene group and the like. In addition, examples of the substituent that these may have include the halogen atom, the alkyl group, and the aryl group as described above.

By having this arylate structure, the surface layer has increased rigidity and improved mechanical strength. Further durability can be provided by adding fluorine resin particles thereto. Further, by having the fluorine-based resin particles in the film, internal stress can be relieved considerably, and solvent cracks can be prevented. As described above, by combining the photoconductor having a small surface free energy and the toner as described above, a further releasing effect can be exhibited.

Specific examples of the structural unit represented by the above formula (1) are shown below, but the present invention is not limited to these.

[0116]

[Chemical 8]

[0117]

[Chemical 9]

Preferred examples include the structural unit examples 1, 6 and 8, and the structural unit example 8 is particularly preferred.

The polymer having a constitutional unit represented by the formula (1) used in the present invention is a terephthalic acid chloride and an isophthalic acid chloride for increasing the solubility of the bisphenol represented by the following formula (2). Interfacial polymerization can be carried out by stirring the mixture in a solvent / water system under alkali.

[0120]

[Chemical 10]

[0121] In the above formulas, X is -CR ¹³ R ¹⁴ - (R ¹³ and R ¹⁴ are each independently a hydrogen atom, a trifluoromethyl group, an alkyl group or an aryl group having 6 to 12 carbon atoms having 1 to 6 carbon atoms Which has 5 to 11 carbon atoms which may be substituted,
It is a 1-cycloalkylene group, an α, ω-alkylene group having 2 to 10 carbon atoms, a single bond, —O—, —S—, —SO— or —SO ₂ —. R ^{1 to} R ⁸ are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group,
It is an aryl group or an alkylene group.

The ratio of terephthalic acid chloride to isophthalic acid chloride is determined in consideration of the solubility of the polymer, and there is no established theory. However, 30 mol of either chloride
It should be noted that the solubility of the synthesized polymer is extremely lowered when the content is less than 100%. Usually, it is preferable to synthesize at a ratio of 1/1.

In the electrophotographic photosensitive member according to the present invention, even a polymer having the same constitutional unit represented by the formula (1) may have two or more different constitutional units represented by the formula (1). It may be a copolymer consisting of

Further, copolymers may be prepared with other general bisphenols such as bisphenol Z, bisphenol A, bisphenol C and bisphenol AF in consideration of solubility at the time of polymerization. However, in this case, equation (1)
The structural unit represented by is 20 to 90 mol of the total polymer.
% Present, more preferably 50-99 m
ol%.

Further, other binder resin may be added if necessary. Examples of other binder resins include thermoplastic resins such as polycarbonate resin, acrylic resin, polyester resin, polyamide resin, polyvinyl acetate resin, and polyvinyl butyral resin; thermosetting resins such as polyurethane resin, phenol resin, and epoxy resin; Curing resin etc. are mentioned.

Examples of the material for the fluorine-based resin particles include tetrafluoroethylene resin, trifluoroethylene chloride resin, hexafluoroethylene propylene resin, vinyl fluoride resin, vinylidene fluoride resin and difluorodichloroethylene resin. One of these may be used alone, or two or more thereof may be mixed. Further, it may be mixed with other antiwear agents and lubricants.

The particle size and molecular weight of the fluorine-based resin particles can be selected as appropriate and are not particularly limited.

The ratio of the fluororesin particles in the surface layer is appropriately selected depending on the kind of the fluororesin particles and the constitution of the photosensitive layer. If the amount of addition is large, the light transmittance is lowered, the sensitivity is lowered, and the light of image exposure is scattered to cause bleeding in the image. On the other hand, if the addition amount is too small, it is easily worn and the effect of the present invention cannot be sufficiently obtained. It is generally 0.1 to 50% by mass, particularly preferably 0.5 to 40% by mass, based on the total solid content of the surface layer. Further, additives such as dispersion aids can be added as necessary.

Among the dispersing aids for the fluorine-based resin particles, particularly preferable ones are fluorine-based comb-type graft polymers. The fluorine-based comb-type graft polymer has a molecular weight of 100 having a polymerizable functional group at one end of each molecular chain.
It is obtained by copolymerizing a macromonomer composed of an oligomer having a relatively low molecular weight of about 0 to 10000 and a fluoropolymerizable monomer, and the fluoropolymer has a backbone and the macromonomer polymer hangs in a branch shape. It has a structure.

The macromonomer is selected such that the resin to which the graft polymer is added has an affinity, and for example, a polymer or copolymer of acrylic acid ester, methacrylic acid ester, styrene compound or the like is used.

On the other hand, as the fluorine-based polymerizable monomer,
Hereinafter, one or more polymerizable monomers having a fluorine atom in the side chain as in (3) to (7) are used, but the invention is not limited thereto.

[0132]

[Chemical 11]

In the above formula, R ¹⁵ represents a hydrogen atom or a methyl group. R ¹⁶ is a hydrogen atom, a halogen atom, an alkyl group,
It represents an alkoxy group or a nitrile group, and may be a combination of several kinds thereof. n is an integer of 1 or more, m is an integer of 1 to 5, k is an integer of 1 to 4, and m + k = 5.

The content of the fluorine-based comb-type graft polymer is suitably 0.01 to 10% by mass based on the total solid content of the surface layer based on the solid content measurement, and particularly 0.02 to 2
Mass% is preferred. If it is less than 0.01% by mass, the effect of improving the dispersibility is not sufficient. On the other hand, if it exceeds 10% by mass, the graft polymer is present not only on the surface of the coating film but also in the bulk. The problem results in the accumulation of residual charge during repeated electrophotographic processes.

In forming such a surface layer, generally, the above-mentioned fluororesin particles are dispersed in the above-mentioned binder resin, a charge transporting material and a solvent are added thereto to prepare a coating solution, which is coated by a coating means. A photoconductor is prepared. As the solvent used at this time, a solvent having good solubility in the binder resin and the charge transport material and good dispersibility of the fluorine-based resin particles is selected. Particularly good examples are ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone and cyclohexanone; ethers such as diethyl ether and tetrahydrofuran; esters such as ethyl acetate and butyl acetate; hydrocarbons such as toluene and benzene; chlorobenzene. And halogenated hydrocarbons such as dichloromethane.

Further, as a method for preparing the above coating liquid, the fluorine resin particles, the charge transporting material and the binder resin may be simultaneously dispersed with the solvent. Alternatively, a coating liquid may be prepared by preparing a dispersion liquid in which the fluorine-based resin particles and the binder resin are previously dispersed, and mixing the dispersion liquid with the binder resin and the charge transport material dissolved in advance. In the preparation of the coating liquid for the electrophotographic photosensitive member used in the present invention, or the fluorinated resin particle dispersion liquid, simple stirring and mixing may be used, but if necessary, a dispersing means such as a ball mill, a roll mill, a sand mill and a high pressure homogenizer may be used. Good. Ideally, the dispersed particle size is close to the intrinsic primary particle size of the fluororesin particles used and has a uniform distribution.

The constitution of the electrophotographic photosensitive member used in the present invention will be described below.

The photoreceptor of the present invention may be a single layer type in which the photosensitive layer contains the charge transport material and the charge generating material in the same layer, or may be a laminated type in which the charge transport layer and the charge generating layer are separated. The laminated type is preferable in terms of electrophotographic characteristics.

The conductive support to be used may be any one having conductivity, and examples thereof include metals such as aluminum and stainless steel, metals provided with a conductive layer, paper and plastic, and the shape is a sheet or a cylinder. And so on.

When the image input such as LBP is laser light, a conductive layer may be provided for the purpose of preventing interference fringes due to scattering or covering scratches on the support. This can be formed by dispersing conductive powder such as carbon black and metal particles in a binder resin. The thickness of the conductive layer is 5 to 10 μm, preferably 10 to 30 μm.

An intermediate layer having an adhesive function is provided thereon. Examples of the material of the intermediate layer include polyamide, polyvinyl alcohol, polyethylene oxide, ethyl cellulose, casein, polyurethane and polyether urethane. These are dissolved in a suitable solvent and applied. The thickness of the intermediate layer is 0.05 to 5 μm, and preferably 0.
3-1 μm is suitable.

A charge generation layer is formed on the intermediate layer.
Examples of the charge generating substance used in the present invention include selenium-tellurium, pyrylium, thiapyrylium dyes, phthalocyanine, anthanthrone, dibenzpyrenequinone, trisazo, cyanine, disazo, monoazo, indigo, quinacridone and asymmetric quinocyanine pigments. To be In the case of the function-separated type, the charge generation layer comprises a homogenizer, ultrasonic dispersion, ball mill, vibrating ball mill, sand mill, attritor, roll mill, and liquid collision type high speed with 0.3 to 4 times the amount of the charge generation substance as the binder resin and solvent. Disperse well with a method such as a disperser, apply the dispersion,
It is formed by drying. The thickness of the charge generation layer is 5 μm or less, preferably 0.1 to 2 μm.

The charge transport layer is mainly formed by coating and drying a coating material in which a charge transport material and the binder resin of the present invention are dissolved in a solvent. Examples of charge transport materials used include triarylamine compounds, hydrazone compounds,
Examples thereof include stilbene compounds, pyrazoline compounds, oxazole compounds, triallylmethane compounds and thiazole compounds.

These are combined with 0.5 to 2 times the amount of binder resin and coated and dried to form a charge transport layer. The thickness of the charge transport layer is 5 to 40 μm, preferably 15 to 30
μm is suitable.

FIG. 2 shows an example of an electrophotographic apparatus which is an image forming apparatus of the present invention using the photoconductor thus prepared. The apparatus of the present invention is suitable for using a cylindrical photosensitive member, but the present invention is not limited to this, and the photosensitive member may have a desired shape such as an endless belt.

The developing means 11 contains the toner 12 of the present invention. The toner 12 is a magnetic toner or a non-magnetic toner. In image forming apparatuses other than the apparatus shown in FIG.
A developing means using a two-component developer having a toner and a carrier may be used. The photoconductor 13 according to the present invention is charged by a charging unit (for example, a charging roller which is a contact charging unit, a charging brush, a charging blade, etc.) 20 to which a voltage is applied by the bias applying unit 22, and is exposed (for example, a laser beam). Alternatively, an electrostatic charge image is formed on the photoconductor 13 by the light 15 of the halogen lamp). A developing sleeve 16 including a toner applying blade (for example, elastic blade, magnetic blade, etc.) 18 and a magnetic field generating means (for example, magnet) 19.
The electrostatic toner image is developed with the magnetic toner 12 housed in the developing means 11 having the. For the development, a regular development method or a reversal development method is used. In the developing section, the bias applying means 21 applies an alternating bias, a pulse bias and / or a DC bias to the developing sleeve 16 as necessary. When the transfer material P is conveyed and reaches the transfer section,
By charging the transfer material P while pressing it from the back surface (the side opposite to the photoconductor 13 side) of the transfer material P by the transfer means (for example, transfer roller, transfer belt, etc.) 14 to which the voltage is applied by the bias applying means 22, The toner image on the surface of the photoconductor 13 is electrostatically transferred onto the transfer material P. In some cases, the toner image on the photoconductor 13 is transferred to an intermediate transfer body (for example, an intermediate transfer drum, an intermediate transfer belt, etc.) not shown,
The toner image may be transferred from the intermediate transfer member to the transfer material P.

The toner image on the transfer material P separated from the photoconductor 13 is heated and pressed by a heating and pressing means (for example, a fixing device in which a pressing roller is pressed against a fixed heating element via a heat resistant sheet or a heating and pressing device). It is fixed on the transfer material P by a roller fixing device or the like) 24. The toner remaining on the photoconductor 13 after the transfer step is removed from the surface of the photoconductor 13 by a cleaning unit (for example, a cleaning blade, a cleaning roller, a cleaning brush, etc.) 17, if necessary. After the cleaning, the photosensitive member 13 is repeatedly charged by the charging unit 20 from the charging step.

The photosensitive member 13, which is the member to be charged and the electrostatic image holding member, rotates in the direction of the arrow. The developing sleeve 16 having a non-magnetic cylinder which is a toner carrier rotates so as to move in the same direction as the photoconductor 13 in the developing section. Inside the developing sleeve 16, a multi-pole permanent magnet (magnet roll) as a magnetic field generating means 19 is fixedly supported. The magnetic toner 12 contained in the developing means 11 is applied to the surface of the developing sleeve 16 by the applying blade 18.
The toner particles are tribo-charged by friction with the surface of the coating blade 18 and / or the developing sleeve 16. A toner layer (for example, a thickness of 1
0 to 300 μm) is uniformly applied to the surface of the developing sleeve 16. In the developing unit, the developing sleeve 16 has, for example, an AC bias f of 200 to 4000 Hz and V _pp.
Is applied at 500 to 3000V.

Upon transfer of toner particles in the developing section,
The toner particles are transferred to the electrostatic image by the electrostatic force on the surface of the photoconductor and the action of the AC bias or the pulse bias.

Further, FIG. 3 is a schematic sectional view of the process cartridge taken out from the main body of the image forming apparatus. The process cartridge includes a developing means 11 and a toner carrier (developing sleeve 16), that is, the developing means 11 and the photoconductor 1.
3 and at least one is made into a cartridge, and the process cartridge is an image forming apparatus main body (for example, a copying machine,
It is formed so as to be attachable to and detachable from a laser beam printer or the like. Reference numerals in FIG. 3 are the same as those in FIG.

[0151]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

(1) Production of Resin (Production of Resin A) terephthalic acid 600 parts by weight trimellitic anhydride 600 parts by weight fumaric acid 330 parts by weight PO-BPA 1050 parts by weight EO-BPA 450 parts by weight 189 parts by mass of Wax 1 shown in No. 6 was charged in a four-necked flask together with an esterification catalyst, and a decompression device, a water separation device, a nitrogen gas introducing device, a temperature measuring device, and a stirring device were attached, and 1
While stirring at a temperature of 30 ° C., vinyl monomers (621 parts by mass of styrene, 2-ethylhexyl acrylate 13
A mixture of 6 parts by mass and 0.13 parts by mass of divinylbenzene) was added dropwise from the dropping funnel over 4 hours. 130
The mixture was aged for 3 hours while being kept at ℃, and heated to 230 ℃ to carry out the reaction. After completion of the reaction, the resin was taken out from the container, cooled and pulverized to obtain a resin A.

[0153]

[Table 6]

(Production of Resins B to G) Resins B to G were obtained in the same manner as in the production method of the resin A except that the monomers shown in Table 7 were changed.

(Production of Resin H) Polyester resin H was obtained by polycondensing the monomers shown in Table 7.

(Production of Resin I) 100 parts by mass of xylene was charged into a reaction vessel equipped with a reflux tube, a stirrer, a nitrogen introducing tube, a thermometer, a dropping device and a pressure reducing device, and then 1394 parts by mass of styrene and acrylic acid were added. 436 parts by mass of butyl, 550 parts by mass of monobutyl maleate and 158 parts by mass of di-t-butyl peroxide as a polymerization initiator were added, and the mixture was heated to a reflux temperature while nitrogen was bubbled through and kept for 12 hours. Then, xylene was distilled off under reduced pressure to obtain a vinyl resin I.

(Production of Comparative Resins a and b) Comparative Resins a and b were obtained in the same manner as in the production method of Resin A except that the monomers shown in Table 7 were changed.

[0158]

[Table 7]

(2) Production of Toner (Production of Toner 1) Resin A 100 parts by mass Magnetic iron oxide 100 parts by mass (average particle size: 0.2 μm, Hc: 9.5 kA / m, σ
s: 81 Am ² / kg, σr: 11 Am ² / kg) Al salicylic acid Al complex 0.5 parts by mass The above mixture was melt-kneaded with a twin-screw extruder heated to 130 ° C., and the cooled mixture was coarsely roughened with a hammer mill. Crushed. The coarsely pulverized product was finely pulverized with a jet mill, and the obtained fine powder was classified with an air classifier to obtain a magnetic toner.

To 100 parts by weight of this magnetic toner, the hydrophobic toner was added.
Ill-treated silica (BET: 140m ²) 1.0 part by mass
Externally added with a Henschel mixer to obtain Toner 1.

(Production of Toners 2 to 8) Toners 2 to 8 were obtained in the same manner as in the production method of Toner 1, except that the raw materials shown in Table 8 were changed.

(Production of Toners 9 to 11) Comparative Toners 9 to 11 were obtained in the same manner as in the production method of Toner 1, except that the raw materials shown in Table 8 were changed.

[0163]

[Table 8]

(3) Manufacture of Photoreceptor (Manufacture of Photoreceptor 1) An aluminum cylinder having a diameter of 30 mm 254 mm was used as a support, and coating materials composed of the following materials were applied to the support by a dipping method, and the temperature was 140 ° C. for 30 minutes. It was heat-cured to form a conductive layer having a thickness of 15 μm. Conductive pigment: SnO ₂ coated barium sulfate 10 parts by mass Resistance adjusting pigment: Titanium oxide 2 parts by mass Binder resin: Phenol resin 6 parts by mass Leveling material: Silicone oil 0.001 parts by mass Solvent: Methanol / methoxypropanol = 0. 2 / 0.8 20 parts by mass

Next, a solution prepared by dissolving 3 parts by mass of N-methoxymethylated nylon and 3 parts by mass of copolymerized nylon in a mixed solvent of 65 parts by mass of methanol and 30 parts by mass of n-butanol was applied onto the surface by a dipping method. Then, an intermediate layer having a thickness of 0.5 μm was formed.

Next, the Bragg angle 2 of the X-ray diffraction of CuKα
4 parts by mass of oxytitanium phthalocyanine (TiOPc) having a strong peak at θ ± 0.2 ° of 9.0 °, 14.2 °, 23.9 ° and 27.1 ° and polyvinyl butyral (trade name: S-REC BM2, 2 parts by mass of Sekisui Chemical Co., Ltd. and 60 parts by mass of cyclohexanone were dispersed for 4 hours by a sand mill using φ1 mm glass beads,
100 parts by mass of ethyl acetate was added to prepare a charge generation layer dispersion liquid. Apply this by dipping method, thickness 0.3μ
m charge generating layer was formed.

Next, as a step of preparing the fluororesin particle dispersion, 25 parts by mass of tetrafluoroethylene resin powder (trade name: Lubron L-2, manufactured by Daikin Industries, Ltd.) 25 parts by mass of a polymer having structural unit example 8 (Weight average molecular weight: 110000) Fluorine-based comb type graft polymer 1 part by mass (trade name: GF-300, manufactured by Toa Gosei Co., Ltd.) After fully mixing 75 parts by mass of monochlorobenzene, a sand mill apparatus using φ1 mm glass beads was used. The dispersion was carried out for 4 hours to prepare a fluororesin particle dispersion liquid.

The polymer having the structural unit example 8 was prepared by dissolving 0.01 mol of a predetermined biphenol, 0.8 g of sodium hydroxide and 1 g of tetramethylammonium chloride in 100 ml of water and charging the mixture in a 1 liter mixer.
To 30 ml of 2-dichloroethane, terephthalic acid chloride of 0.
005 mol and isophthalic acid chloride 0.005 mol
Was dissolved in the solution, stirred at a high speed for 10 minutes, and allowed to stand for 2 hours. Then, 1,2-dichloroethane solution was recovered, and a large amount of hexane was added to the solution to recover it as a polymer. It should be noted that the product used was one that had been subjected to a purification step of washing with water after recovery, dissolution with chloroform, and dropping of methanol.

Next, 9 parts by mass of an amine compound having the following structural formula,

[0170]

[Chemical 12]

1 part by mass of amine compound having the following structural formula

[0172]

[Chemical 13]

And 10 parts by mass of a polymer having the structural unit example 8 and 12.5 parts by mass of the fluororesin particle dispersion.
30 parts by weight of monochlorobenzene and 70 parts of dichloromethane
It was dissolved in a mixed solvent of parts by mass. The content of the fluororesin particles with respect to the solid content is 10% by mass.

This coating composition was applied by the dipping method, and the coating was applied at 120 ° C. for 2 hours.
And dried to form a charge transport layer having a thickness of 25 μm.
A photoconductor 1 as shown in was obtained.

(Production Example 2 of Photoreceptor) In Production Example 1 of the photoreceptor, instead of the polymer having the constitutional unit example 8, a polymer having the constitutional unit example 1 (weight average molecular weight: 9000) was used.
Photosensitive member 2 was obtained in the same manner except that (0) was used.

(Production Example 3 of Photoreceptor) In the same manner as in Production Example 1 of a photoreceptor, a conductive layer and a charge generation layer were formed on a support of an aluminum cylinder.

Next, 9 parts by mass of an amine compound having the following structural formula,

[0178]

[Chemical 14]

1 part by mass of amine compound having the following structural formula

[0180]

[Chemical 15]

Then, 10 parts by mass of a polymer containing the monomer of Structural Unit Example 6 was dissolved in a mixed solvent of 30 parts by mass of monochlorobenzene and 70 parts by mass of dichloromethane. This coating material is applied on the above charge generation layer by a dipping method, and the coating is applied at 120 ° C. for 1 hour.
After being dried for an hour, a charge transporting layer having a thickness of 25 μm was formed to obtain a photoconductor 3.

(Production Example 4 of Photoreceptor) A photoreceptor 4 for comparative example was obtained in the same manner as in Example 1 except that the binder resin shown in Table 9 was used for the charge transport layer.

[0183]

[Table 9]

[0184]

[Chemical 16]

(4) Embodiment (Structure of Image Forming Apparatus) (Embodiment 1) Digital copying machine "GP20" manufactured by Canon Inc.
The image forming apparatus 1 including the photoconductor 1 shown in Table 9 in “F” and performing image formation using the toner 1 was obtained. The following evaluation was performed using this image forming apparatus.

Image Output Test A 200,000-sheet paper passing test was conducted on the obtained image forming apparatus, and a solid black / white image was periodically output during the endurance test to fuse the toner onto the photoreceptor and Image defects due to the occurrence of scratches on the photoconductor were evaluated. Further, the scratches on the drum after the durability were visually evaluated, and the comprehensive results are shown in Table 10.

The evaluation results in Table 10 were judged according to the following criteria.

(Fusion of drum) ⊚: Excellent (not generated) ◯: Good (several points are seen on the photosensitive member, but not generated on the image) Δ: No problem (several points visually on the image) Pochi is seen, but there is no problem in practical use) ×: There is a problem (a lot of spots can be confirmed on the image, there is a problem) (Drum scratch) ○: Good (not generated) Δ: No problem (slightly observed when observed well) (Amount that can be seen) ×: There is a problem (level that can be clearly confirmed by visual inspection)

Low Temperature Fixability Test After obtaining an unfixed image with the above image forming apparatus, an external fixing device (a fixing device of a copying machine "GP20F" manufactured by Canon Inc.) is taken out, and an external drive and a temperature control device for the fixing device are attached. A fixing image is obtained by changing the fixing temperature by using a process speed modified to 200 mm / sec. The density decrease rate was measured by measuring the density before and after the rubbing when a load of 4900 N / m ² (50 g / cm ² ) was rubbed on the obtained image 5 times. The temperature at which the density reduction rate is 20% or less is the minimum fixing temperature.

The evaluation results in Table 10 were judged according to the following criteria.

[0191] ⊚: Excellent (less than 145 ° C.) ◯: Good (145 to less than 150 ° C) Δ: No problem (150 to less than 160 ° C) ×: There is a problem (160 ° C or higher)

High Temperature Offset Test After an unfixed image is obtained by the above image forming apparatus, the fixing temperature is changed using the same external fixing device as in the above test, and the unfixed image is passed. At that time, it was visually determined that the toner was offset on the fixing roller, and the temperature generated was defined as the high temperature offset generation temperature.

The evaluation results in the table were judged according to the following criteria.

◯: Good (not generated at less than 240 ° C.) Δ: No problem (slightly generated at 220 to less than 240 ° C., no problem in practical use) ×: Problematic (clearly generated at less than 220 ° C., practical As a result of performing the above-mentioned evaluations, very good results were obtained as shown in Table 10.

(Examples 2 to 8) In Example 1, Table 1
Image forming apparatuses 2 to 8 were obtained in the same manner except that the toner and the photoconductor shown in 0 were changed. In addition, as a result of performing evaluation in the same manner as in Example 1, good results as shown in Table 10 were obtained.

(Comparative Examples 1 to 5) In Example 1, Table 1
Comparative image forming apparatuses 1 to 5 were obtained in the same manner except that the toner and the photoconductor shown in 0 were changed. Moreover, as a result of performing the evaluation in the same manner as in Example 1, the results shown in Table 10 were obtained.

[0197]

[Table 10]

[0198]

As described above, according to the toner and the image forming apparatus of the present invention, the toner which prevents the toner from being fused on the photoconductor and can obtain a good image even in the long-term durability, and An image forming apparatus can be provided.

[Brief description of drawings]

FIG. 1 is a diagram showing a Soxhlet extraction apparatus diagram.

FIG. 2 is a schematic cross-sectional view of an example of an electrophotographic apparatus that is an image forming apparatus of the present invention.

FIG. 3 is a schematic cross-sectional view of an example of a process cartridge.

[Explanation of symbols]

1 THF 2 containers 3 toner 4 Middle tube 5 cooler 6 cooling water 7 tubes 8 heater 9 Reservoir 11 Developing means 12 toner 13 Photoconductor 14 Transfer means 15 exposure 16 Development sleeve 17 Cleaning means 18 Toner coating blade 19 Magnetic field generating means 20 charging means 21-23 Bias applying means 24 Heating / pressurizing means P transfer material

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03G 5/05 104 G03G 5/05 104B 5/147 502 5/147 502 9/083 9/08 331 9 / 087 321 9/09 361 9/097 101 346 (72) Inventor Yusuke Hasegawa 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Masaaki Taya 3-chome Shimomaruko, Ota-ku, Tokyo No. 2 Canon Inc. F-term (reference) 2H005 AA01 AA02 AA06 AA08 AA21 CA02 CA08 CA12 CA14 CA16 CA25 CB13 DA02 EA03 EA07 EA10 2H068 AA13 AA14 BB27 BB31 BB61 FA03 FA27 FC15

Claims (33)

[Claims] 1. A step of charging an electrostatic latent image carrier; a step of forming an electrostatic latent image on the charged electrostatic latent image carrier; a toner image formed on the electrostatic latent image carrier. In order to develop the electrostatic latent image with a toner held on a toner carrier, and a step of transferring the toner image on the electrostatic latent image carrier to a transfer material. The latent electrostatic image bearing member is an electrophotographic photosensitive member having a photosensitive layer on a conductive substrate, and the surface layer of the photosensitive member has the following formula (1): [In the formula, X is —CR ¹³ R ¹⁴ — (R ¹³ and R ¹⁴ are each independently a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms) ,
1,1-cycloalkylene group having 5 to 11 carbon atoms which may be substituted, α, ω-alkylene group having 2 to 10 carbon atoms, single bond, —O—, —S—, —SO— or —SO ₂ − R ^{1 to} R ¹² are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an aryl group or an alkylene group, and n is an integer. ] A toner used in an image forming apparatus containing a polymer having a constitutional unit represented by: wherein the toner contains at least a binder resin and a colorant, and the binder resin contains at least a polyester resin and a vinyl resin. Containing a resin and the mass composition ratio of the polyester monomer and the vinyl monomer contained in the resin is 50/50 to 90.
/ 10 and the contact angle of the toner with water is 90 to 130 °. 2. The toner according to claim 1, wherein a contact angle of the toner with water is 100 to 125 °. 3. The mass composition ratio of the polyester-based monomer and the vinyl-based monomer contained in the binder resin is 60/40.
Or 85/15.
The toner according to. 4. The toner according to claim 1, wherein the binder resin contains a hybrid resin component in which a polyester monomer and a vinyl monomer are partially reacted. 5. A polyester-based unit of the binder resin is a trivalent or higher polyvalent carboxylic acid or its anhydride and / or
5. The toner according to claim 1, which has a structure crosslinked with a polyhydric alcohol having a valence of 3 or more. 6. The differential scanning calorimeter (DS)
The toner according to any one of claims 1 to 5, further comprising a wax having a melting point of 60 to 130 ° C defined by the endothermic peak temperature at the time of temperature increase measured in C). 7. The toner according to claim 6, wherein the wax is a hydrocarbon wax. 8. The toner according to claim 1, wherein the toner contains a magnetic substance as a colorant. 9. The toner according to claim 1, wherein the toner contains a negatively chargeable charge control agent. 10. The toner according to any one of claims 1 to 9, wherein a silica fine powder that has been hydrophobized is externally added to the toner. 11. The toner according to claim 10, wherein the fine silica powder is treated with silicone oil. 12. The toner according to claim 1, wherein the surface layer of the photoconductor further contains fluorine resin particles. 13. The fluororesin particles are selected from tetrafluoroethylene resin, trifluoroethylene chloride resin, hexafluoroethylene propylene resin, vinyl fluoride resin, vinylidene fluoride resin, and 2-fluorodichloroethylene. 13. The toner according to claim 12, comprising at least one of the following: 14. The image forming apparatus using a photoconductor in which the content of the fluorine-based resin particles is 0.1 to 50 mass% with respect to the total solid content of the surface layer. Item 14. The toner according to Item 12 or 13. 15. The surface layer of the photoconductor contains a fluorine-type comb-type graft polymer.
15. The toner according to any one of 14 to 14. 16. A step of charging an electrostatic latent image carrier; a step of forming an electrostatic latent image on the charged electrostatic latent image carrier; a toner image being formed on the electrostatic latent image carrier. In order to develop the electrostatic latent image with a toner held on a toner carrier, and a step of transferring the toner image on the electrostatic latent image carrier to a transfer material. The latent image carrier is an electrophotographic photoreceptor having a photosensitive layer on a conductive substrate, and the surface layer of the photoreceptor has the following formula (1): [In the formula, X is —CR ¹³ R ¹⁴ — (R ¹³ and R ¹⁴ are each independently a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms) ,
1,1-cycloalkylene group having 5 to 11 carbon atoms which may be substituted, α, ω-alkylene group having 2 to 10 carbon atoms, single bond, —O—, —S—, —SO— or —SO ₂ − R ^{1 to} R ¹² are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an aryl group or an alkylene group, and n is an integer. ] An image forming apparatus containing a polymer having a structural unit represented by the above, wherein the toner contains at least a binder resin and a colorant, and the binder resin contains at least a polyester resin and a vinyl resin. The mass composition ratio of the polyester-based monomer and the vinyl-based monomer contained in the resin is 50/50 to 90.
/ 10, and the contact angle of the toner with water is 90 to 130 °. 17. The contact angle of the toner with water is 100.
The image forming apparatus according to claim 16, wherein the image forming apparatus has an angle of from 125 ° to 125 °. 18. The mass composition ratio of the polyester-based monomer and the vinyl-based monomer contained in the binder resin is 60/4.
The image forming apparatus according to claim 16 or 17, wherein the image forming apparatus has a size of 0 to 85/15. 19. The image forming apparatus according to claim 16, wherein the binder resin contains a hybrid resin component in which a polyester monomer and a vinyl monomer are partially reacted. 20. A polyester-based unit of the binder resin is a trivalent or higher polyvalent carboxylic acid or an anhydride thereof and / or
20. The image forming apparatus according to claim 16, which has a structure crosslinked with a polyhydric alcohol having a valence of 3 or more. 21. The differential scanning calorimeter (DS)
21. The image forming apparatus according to claim 16, further comprising a wax having a melting point of 60 to 130 ° C. defined by the endothermic peak temperature at the time of temperature increase measured in C). 22. The image forming apparatus according to claim 21, wherein the wax is a hydrocarbon wax. 23. The image forming apparatus according to claim 16, wherein the toner contains a magnetic material as a colorant. 24. The image forming apparatus according to claim 16, wherein the toner contains a negatively chargeable charge control agent. 25. The image forming apparatus according to claim 16, wherein the toner is externally added with silica fine powder which has been subjected to a hydrophobic treatment. 26. The image forming apparatus according to claim 25, wherein the silica fine powder is treated with silicone oil. 27. The image forming apparatus according to claim 26, wherein the surface layer of the photoconductor further contains fluorine resin particles. 28. The fluororesin particles are made of tetrafluoroethylene resin, trifluoroethylene chloride resin, hexafluoroethylene propylene resin, vinyl fluoride resin, vinylidene fluoride resin, or difluorodichloroethylene resin. The image forming apparatus according to claim 27, wherein the image forming apparatus comprises at least one selected. 29. The image forming apparatus according to claim 27, wherein the content of the fluorine-based resin particles is 0.1 to 50 mass% with respect to the total solid content of the surface layer. 30. The surface layer according to claim 16, wherein the surface layer contains a fluorine-type comb-type graft polymer.
9. The image forming apparatus according to any one of 9 above. 31. A step of charging an electrostatic latent image carrier; a step of forming an electrostatic latent image on the charged electrostatic latent image carrier; a toner image being formed on the electrostatic latent image carrier. To develop the electrostatic latent image with the toner held on the toner carrier; and to transfer the toner image on the electrostatic latent image carrier to a transfer material. A detachable process cartridge to be used by attaching, comprising at least an electrostatic latent image carrier and a developing means having a toner and a toner carrier, the electrostatic latent image carrier being provided on a conductive substrate. An electrophotographic photosensitive member having a photosensitive layer, wherein the surface layer of the photosensitive member is represented by the following formula (1): [In the formula, X is —CR ¹³ R ¹⁴ — (R ¹³ and R ¹⁴ are each independently a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms) ,
1,1-cycloalkylene group having 5 to 11 carbon atoms which may be substituted, α, ω-alkylene group having 2 to 10 carbon atoms, single bond, —O—, —S—, —SO— or —SO ₂ − R ^{1 to} R ¹² are each independently a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an aryl group or an alkylene group, and n is an integer. ] A polymer having a structural unit represented by the above formula is contained, and the toner contains at least a binder resin and a colorant, and the binder resin contains at least a polyester resin and a vinyl resin, and is contained in the resin. The mass composition ratio of the polyester monomer and the vinyl monomer is 50/50 to 90.
/ 10 and the contact angle of the toner with water is 90 to 130 °. 32. The process cartridge according to claim 31, wherein the surface layer of the photoconductor further contains fine particles of fluororesin. 33. The process cartridge according to claim 31 or 32, wherein the toner is the toner according to any one of claims 2 to 11.