JPH11352731A - Electrophotographic carrier and developer using that - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrophotographic carrier having a high mechanical strength, excellent adhesion property of a coating resin layer to a carrier core and causing no fixing of a toner component, and to provide an electrophotographic developer comprising the carrier described above and a toner. SOLUTION: This electrophotographic carrier is produced by coating a carrier core with a coating resin containing a polycarbonate resin having a repeating unit expressed by the formula. The electrophotographic developer consists of the carrier described above and a toner. In the formula, R, R<1> are each an alkyl group, aryl group or the like, X, X' are each an alkylene group or the like, a is 0 or 1, na is 0 or 1, nb, nc are each 1 or 2 (the sum of na to nc is 3), n1 to n4 are each 0 or integers >=1, however, the sum of n1 to n4 is 0 to 450.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic carrier and an electrophotographic developer using the same. More specifically, the present invention relates to an electrophotographic carrier used for developing an electrostatic latent image in an image forming method utilizing an electrophotographic method, and an electrophotographic developer using the carrier as one component.

[0002]

2. Description of the Related Art In electrophotography, an electrostatic latent image is formed on a photoreceptor or an electrostatic recording medium by various means, and toner is adhered to the electrostatic latent image to develop the electrostatic latent image. The way to do it is generally done. The electrostatic latent image can be developed using a one-component developer such as a one-component magnetic jumping development system or a one-component non-magnetic contact development system, or by dispersing a small amount of magnetic carrier in insulating non-magnetic toner. A method using a two-component developer is known.

The granular carrier used in the two-component developer imparts an appropriate amount of positive or negative charge to the toner by mixing with the toner and frictionally charging each other. In order to prevent filming of the toner on the surface of the carrier, to form a uniform surface state, to adjust the charge amount, and to improve the durability of the developer, a resin is applied to the core material, which is a magnetic material. in use.

[0004] By the way, the carrier coated with the resin as described above, while being used as an electrophotographic developer,
In addition to a change in electric characteristics and a change in environment dependence due to abrasion due to agitation friction, there is a problem in that toner components adhere to the carrier resin coating layer and charge deterioration due to peeling of the coating resin layer occurs. Various proposals have been made as a method for solving such a problem. For example, Japanese Unexamined Patent Publication
Japanese Patent Publication No. 239256 proposes a carrier using an aromatic polycarbonate resin containing 2,2-bis (4-hydroxyphenyl) propane as a main component as a carrier coating layer having excellent durability. The resin has a problem that it is difficult to form a uniform resin coating because of its high crystallinity.

Japanese Patent Application Laid-Open No. 6-282113 proposes a carrier in which a resin coating layer is formed using a polycarbonate-polydiorganosiloxane copolymer in order to reduce the surface energy of the carrier coating layer. In this case, however, there is a problem in that the adhesiveness between the core material and the coating resin layer is not sufficient, and the amount of toner component adhered to the carrier increases with time during use.

Furthermore, Japanese Patent Application Laid-Open No. 10-10791 proposes a carrier coated with a polycarbonate resin having an alkoxysilane in a side chain. In this case, the core material and the resin coating layer are formed by the action of the alkoxysilane. Is improved, but the mechanical strength is low and the durability is not sufficient because the main chain of the polycarbonate polymer is composed of an aliphatic chain.

[0007]

An object of the present invention is to provide an electrophotographic carrier which is excellent in mechanical strength, has good adhesiveness to a carrier core material and does not adhere toner components, and an electrophotographic carrier containing the carrier. An object is to provide a photographic developer.

[0008]

The present inventors have made various studies to solve the above-mentioned problems, and as a result, as a coating resin for the carrier core material, a polycarbonate resin having a repeating unit having a specific chemical structure has been used. The inventors have found that the carrier used exhibits excellent performance in practical properties, and have completed the present invention based on these findings.

That is, the gist of the present invention is as follows. (1) In an electrophotographic carrier having a resin coating layer provided on magnetic particles, the resin coating layer is formed of a resin containing a polycarbonate resin having a repeating unit (1) represented by the following general formula [1]. A carrier for electrophotography, wherein the carrier is made.

[0010]

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[In the formula (1), R is the same or different, substituted or unsubstituted alkyl group having 1 to 6 carbon atoms which does not contain an aliphatic unsaturated bond, or a substituted or unsubstituted alkyl group having 6 to 12 carbon atoms. An aryl group, R ¹ is each independently a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, or substituted with 6 to 12 carbon atoms. Or an unsubstituted aryl group, X is each independently an alkylene group having 2 or more carbon atoms or an alkyleneoxyalkylene group having 2 or more carbon atoms, X ′ is each independently an alkylene group having 2 or more carbon atoms, A is an alkyleneoxyalkylene group having 2 or more carbon atoms or an oxygen atom, a is independently an integer of 0 to 4, na is 0 or 1, nb is 1 or 2, nc is 1 or (However, na + nb + nc = 3
And nb is the number of repeating units bonded to a silicon atom), and n1, n2, n3 and n4 are each independently an integer of 0 or 1 or more (provided that n1 + n2 + n
3 + n4 = 0 to 450). (2) The polycarbonate resin according to the above (1), wherein the polycarbonate resin comprises a repeating unit (1) represented by the general formula [1] and a repeating unit (2) represented by the following general formula [2]. Electrophotographic carrier.

[0012]

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[In the formula [2], R ² is independently a halogen atom, a vinyl group, an allyl group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkyl group having 6 to 12 carbon atoms. An aryl group, a substituted or unsubstituted cycloalkyl group having 3 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms, a is , Each independently 0-
And Y is a single bond, -O-, -CO-,-
S -, - SO -, - SO 2 -, - CR 3 R 4 - ( provided that, R ^3, R ⁴ are each independently a hydrogen atom, a carbon number 1 to 1
0 substituted or unsubstituted alkyl group, 6 to 12 carbon atoms
A substituted or unsubstituted aryl or trifluoromethyl group), a substituted or unsubstituted cycloalkylidene group having 5 to 11 carbon atoms, a substituted or unsubstituted α, ω-alkylene group having 2 to 12 carbon atoms, A 9,9-fluorenylidene group, a 1,8-menthanediyl group, a 2,8-menthanediyl group, a substituted or unsubstituted pyradylidene group, and a substituted or unsubstituted arylene group having 6 to 24 carbon atoms. (3) The carrier for electrophotography according to the above (1) or (2), wherein the resin coating layer contains a charge control agent and / or conductive particles. (4) The carrier for electrophotography according to any one of (1) to (3), and a toner mixed at a ratio of 2 to 40% by weight based on the total amount of the carrier and the toner. Developer for electrophotography.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The magnetic particles used as a core material of the electrophotographic carrier of the present invention are not particularly limited, and those known as components of a two-component developer for electrophotography may be used. it can. Specific examples of such a carrier core material include, for example, metal oxides such as ferrite and magnetite, and metals such as iron, nickel and cobalt. In addition, these metal oxides and metals, copper,
Alloys or mixtures with metals such as zinc, antimony, aluminum, lead, tin, bismuth, beryllium, manganese, magnesium, tungsten, zirconium, and vanadium can be used. Further, a mixture of the ferrite or magnetite with a metal oxide such as iron oxide, titanium oxide, or magnesium oxide, a nitride such as chromium nitride or vanadium nitride, or a carbide such as silicon carbide or tungsten carbide may be used. Further, ferromagnetic ferrite may be used. These may be used alone or as a mixture of two or more.

Next, the shape of the carrier core material is not particularly limited, and may be any shape such as a spherical shape and an irregular shape. Also, the particle size may be within a normally used range, and preferably 20 to 100.
μm. If the particle size is less than 20 μm, the carrier may adhere to or be scattered from the electrostatic latent image carrier (generally, the photoreceptor).
If the thickness exceeds 00 μm, carrier streaks and the like may occur, which may cause deterioration in image quality.

In the polycarbonate resin forming a coating layer on the surface of the carrier core material, the repeating unit constituting the polycarbonate resin is a polycarbonate polymer comprising a repeating unit (1) represented by the general formula [1], or It is a polycarbonate copolymer comprising a repeating unit (1) represented by the general formula [1] and a repeating unit (2) represented by the general formula [2], and its polymer chain is linear or branched. And may have any of a ring-shaped structure. Among these, a polycarbonate copolymer is preferable.

More specifically, the polycarbonate resin composed of the repeating units represented by the formulas [1] and [2] will be described in more detail below. Examples of the substituted alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a 2-butyl group, a t-butyl group, a pentyl group, and a hexyl group. Examples of the substituted or unsubstituted aryl group include phenyl, naphthyl, biphenyl, tolyl, and styryl groups. In addition, R ¹ shown in the same formula
Examples of the substituted or unsubstituted alkyl group having 1 to 6 carbon atoms represented by are a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a 2-butyl group and a t-
Examples thereof include a butyl group, a pentyl group, and a hexyl group. Examples of the substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, and 2- Butoxy group, t-butoxy group, pentyloxy group, hexyloxy group and the like. Examples of the substituted or unsubstituted aryl group having 6 to 12 carbon atoms include a phenyl group, a tolyl group, a styryl group, a biphenylyl group, and a naphthyl group. And the like. Examples of the alkylene group having 2 or more carbon atoms represented by X and X ′ in the formula include an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group. Examples of the oxyalkylene group include a methyleneoxymethylene group and an ethyleneoxyethylene group.

Further, R ^{2 to} R shown in the above formula [2]
Examples of the substituted or unsubstituted alkyl group having 1 to 10 carbon atoms represented by ⁴ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a 2-butyl group,
t-butyl group, pentyl group, hexyl group, heptyl group,
An octyl group, a nonyl group, a decyl group;
Examples of the substituted or unsubstituted aryl group having from 12 to 12 include a phenyl group, a tolyl group, a styryl group, a biphenylyl group, and a naphthyl group, and a substituted or unsubstituted cycloalkyl group having 3 to 12 carbon atoms represented by R ^2. As the cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, and the like,
Examples of the substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, 2-butoxy, t-butoxy, pentyloxy, and hexyl. Oxy groups and the like, and the substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms includes a phenoxy group, a tolyloxy group, a styryloxy group, a naphthyloxy group,
And a biphenyloxy group. Examples of the substituted or unsubstituted cycloalkylidene group having 5 to 11 carbon atoms represented by Y represented by the same formula include a cyclopentylidene group, a cyclohexylidene group, a cycloheptylidene group, a cyclooctylidene group, and a cyclononylidene group. Group, cyclodecylidene group, cycloundecylidene group, 3,3,5-trimethyl-1,1-cyclohexylidene group and the like, and as a substituted or unsubstituted α, ω-alkylene group having 2 to 12 carbon atoms, Examples thereof include an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, and a dodecamethylene group. Examples of the substituted or unsubstituted arylene group having 6 to 24 carbon atoms represented by Y include p-phenylene group, m-phenylene group, o-phenylene group, naphthylene group, biphenylene group, terphenylene group, and quarterphenylene group. , Anthracenylene group,
And a birenylene group.

When the copolymer is composed of the repeating unit (1) and the repeating unit (2), the molar ratio of the repeating unit (1) [(1) / ((1) + (2)) 〕But,
0.0001 or more, preferably 0.001 to
Those having a range of 0.6 are preferably used. When the molar ratio is less than 0.0001, the effect of reducing the surface energy of the copolymer due to the introduction of the siloxane unit as the copolymer component is hardly obtained. This polycarbonate resin may have one or more of the above-mentioned repeating units (1) and (2).

In addition to the repeating units (1) and (2), structural units other than those defined by the above formulas (1) and (2) may be used in the polycarbonate resin so long as the object of the present invention is not impaired. Or a unit having a polyester structure, a polyurethane structure, a polyether structure, a polyepoxide structure, or a polyformal structure.

As the polycarbonate resin, those having a weight average molecular weight in the range of 10,000 to 150,000, preferably 30,000 to 100,000 can be suitably used. This weight average molecular weight is 100
If it is less than 00, the surface hardness of the coating layer formed using the same may be low, and sufficient durability may not be obtained. If the weight average molecular weight is more than 150,000, the viscosity of the coating liquid for forming the coating layer becomes too high, and the resin dissolution stability is lowered. It is not preferable because it is easy to invite.

The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the polycarbonate resin [Mw /
[Mn] is preferably 5.0 or less, more preferably 4.0 or less. The value of [Mw / Mn] is 5.
If a material having a molecular weight distribution exceeding 0 is used, unevenness of resin coating on the carrier surface may be caused. Next,
Regarding the method for producing a polycarbonate resin having the above-mentioned repeating unit, for example, using a phosgene as a carbonate-forming compound, in the presence of a suitable acid binder and a solvent, dihydric phenol and dihydroxy having a siloxane structural unit What is necessary is just to employ | adopt the method of making it react with a compound. In this case, the reaction temperature is 0 to 150 ° C., preferably 5 to 40 ° C., and the reaction pressure may be any one of reduced pressure, normal pressure, and pressurized, but it is appropriate to carry out the reaction under a pressure of about the self-pressure of the reaction system. The reaction time varies depending on the type of the raw material and the reaction temperature, but is 0.5 minute to 10 hours, preferably 1 minute to 2 hours. Alternatively, a method in which bisaryl carbonate is used as the carbonate-forming compound to produce the compound by a transesterification method may be employed.

The dihydroxy compound having a dihydric phenol or siloxane structural unit used as a raw material may be used alone or in combination of two or more. At the time of these reactions, the reaction may be performed by adding a terminal terminator or a branching agent as necessary. Examples of the dihydric phenol include 4,4′-dihydroxybiphenyl, 3,3′-difluoro-4,4′-dihydroxybiphenyl,
4'-dihydroxy-3,3'-dimethylbiphenyl,
4,4'-dihydroxybiphenyls such as 4,4'-dihydroxy-2,2'-dimethylbiphenyl and 4,4'-dihydroxy-3,3'-dicyclohexylbiphenyl; bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) phenylmethane, bis (3
-Methyl-4-hydroxyphenyl) methane, bis (3
-Nonyl-4-hydroxyphenyl) methane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, bis (3,5-dibromo-4-hydroxyphenyl) methane, bis (3-chloro-4-hydroxyphenyl) ) Methane, bis (3-fluoro-4-hydroxyphenyl) methane, bis (2-tert-butyl-4-hydroxyphenyl) phenylmethane, bis (2-hydroxyphenyl) methane, 2-hydroxyphenyl-4-hydroxyphenyl ) Methane, bis (2-hydroxy-4)
Methylphenyl) methane, bis (2-hydroxy-4-
Methyl-6-tert-butylphenyl) methane, bis (2-hydroxy-4,6-dimethylphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane,
1,2-bis (4-hydroxyphenyl) ethane, 1,
1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-methylphenyl) -1-phenylethane, 1,1-bis (4-hydroxy-3-phenylphenyl) ) -1-Phenylethane, 2- (4-hydroxy-3-methylphenyl) -2
-(4-hydroxyphenyl) -1-phenylethane,
1,1-bis (2-tert-butyl-4-hydroxy-3-methylphenyl) ethane, 1-phenyl-1,1
-Bis (3-fluoro-4-hydroxyphenyl) ethane, 1,1-bis (2-hydroxy-4-methylphenyl) ethane, 2,2-bis (4-hydroxyphenyl)
Propane, 1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (2-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2 , 2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2
-Bis (3-sec-butyl-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 2,2
-Bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2, 2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-
Bis (2-tert-butyl-4-hydroxy-5-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5 -Difluorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (3-bromo-
4-hydroxy-5-chlorophenyl) propane, 2,
2-bis (4-hydroxyphenyl) -1,1,1,
3,3,3-hexafluoropropane, 2,2-bis (2-hydroxy-4-sec-butylphenyl) propane, 2,2-bis (2-hydroxy-4,6-dimethylphenyl) propane, 2-bis (4-hydroxyphenyl) butane, 2,2- (3-methyl-4-hydroxyphenyl) butane 1,1-bis (4-hydroxyphenyl) -2-methylpropane, 1,1-bis (2 -T
tert-butyl-4-hydroxy-5-methylphenyl) -2-methylpropane, 1,1-bis (2-butyl-4-hydroxy-5-methylphenyl) butane, 1,
1-bis (2-tert-butyl-4-hydroxy-5
-Methylphenyl) butane, 1,1-bis (2-methyl-4-hydroxy-5-tert-pentylphenyl)
Butane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) butane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 1,
1-bis (4-hydroxyphenyl) -3-methylbutane, 3,3-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl ) Heptane, 2,2-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) heptane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (4-hydroxyphenyl) Nonane, 2,2-bis (4
-Hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4
-Hydroxyphenyl) cyclohexane, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, 1,1-bis (3- Cyclohexyl-4-hydroxyphenyl) cyclohexane,
1,1-bis (3-phenyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane,
1,1-bis (3-methyl-4-hydroxyphenyl)
Bis (hydroxyphenyl) alkanes such as -3,3,5-trimethylcyclohexane; bis (4-hydroxyphenyl) ether such as bis (4-hydroxyphenyl) ether and bis (3-fluoro-4-hydroxyphenyl) ether Bis (4-hydroxyphenyl) sulfides such as bis (4-hydroxyphenyl) sulfide and bis (3-methyl-4-hydroxyphenyl) sulfide; bis (4-hydroxyphenyl) sulfoxide, bis (3-methyl- Bis (4-hydroxyphenyl) sulfoxides such as 4-hydroxyphenyl) sulfoxide; bis (4-hydroxyphenyl)
Bis (4-hydroxyphenyl) sulfones such as sulfone, bis (3-methyl-4-hydroxyphenyl) sulfone, bis (3-phenyl-4-hydroxyphenyl) sulfone; bis (such as 4,4′-dihydroxybenzophenone) 4-hydroxyphenyl) ketones;
9,9-bis (4-hydroxyphenyl) fluorene,
9,9-bis (3-methyl-4-hydroxyphenyl)
Bis (hydroxyphenyl) fluorenes such as fluorene and 9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene; dihydroxy-p-terphenyls such as 4,4 "-dihydroxy-p-terphenyl;
Dihydroxy-p-quarterphenyls such as 4,4 ″ ′-dihydroxy-p-quarterphenyl;
5-bis (4-hydroxyphenyl) pyrazine, 2,5
-Bis (4-hydroxyphenyl) -3,6-dimethylpyrazine, 2,5-bis (4-hydroxyphenyl)-
Bis (hydroxyphenyl) pyrazines such as 2,6-diethylpyrazine; 1,8-bis (4-hydroxyphenyl) menthane, 2,8-bis (4-hydroxyphenyl) menthane, 1,8-bis (3- Bis (hydroxyphenyl) menthanes such as methyl-4-hydroxyphenyl) menthane and 1,8-bis (4-hydroxy-3,5-dimethylphenyl) menthane; 1,4-bis [2
-(4-hydroxyphenyl) -2-propyl] benzene, 1,3-bis [2- (4-hydroxyphenyl)-
And bis [2- (4-hydroxyphenyl) -2-propyl] benzenes such as 2-propyl] benzene.

Among these various dihydric phenols,
2,2-bis (4-hydroxyphenyl) propane,
1,1-bis (4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxy-3 -Methylphenyl) propane, 2,2-bis (4-hydroxy-3-phenylphenyl) propane, 4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl)
Sulfone, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 3,3-bis (4-hydroxyphenyl) pentane, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene , Bis (4-hydroxyphenyl) ether, 4,4'-dihydroxybenzophenone and the like are preferable.

As the dihydroxy compound having a siloxane structural unit, a dihydroxy compound represented by the following general formula [3] is used.

[0026]

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(R, R ¹ , X, X ′, a,
na, nb, nc, n1, n2, n3 and n4 all have the same meaning as in the above formula [1]. The following are specific examples of these dihydroxy compounds.

[0028]

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[0029]

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As the terminal terminator, a monovalent carboxylic acid and its derivative or a monovalent phenol can be used. For example, p-tert-butyl-phenol, p
-Phenylphenol, p-cumylphenol, p-allylphenol, o-allylphenol, m-aminophenol, vinylphenol, eugenol, isoeugenol, p-perfluorononylphenol, p-
(Perfluorononylphenyl) phenol, p- (perfluoroxylphenyl) phenol, p-tert
-Perfluorobutylphenol, 1- (P-hydroxybenzyl) perfluorodecane, p- [2- (1H,
1H-perfluorotridodecyloxy) -1,1,
1,3,3,3-hexafluoropropyl] phenol, 3,5-bis (perfluorohexyloxycarbonyl) phenol, perfluorododecyl p-hydroxybenzoate, p- (1H, 1H-perfluorooctyloxy) phenol 2,2H, 2H, 9H-perfluorononanoic acid, 1,1,1,3,3,3-tetrafluoro-2
-Propanol and the like are preferably used. The addition ratio of these terminal stoppers is 0.1 to 30 as a copolymer composition ratio.
Mol%, more preferably 1 to 10 mol%. If this ratio exceeds 30 mol%, the surface hardness may be lowered when the resin coating layer is formed, and this ratio may be 0.1%. If it is less than mol%, the viscosity of the coating liquid may be too high.

Specific examples of the branching agent include phloroglysin, pyrogallol, 4,6-dimethyl-2,4,6
-Tris (4-hydroxyphenyl) -2-heptene,
2,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) -3-heptene, 2,4-dimethyl-2,
4,6-tris (4-hydroxyphenyl) heptane,
1,3,5-tris (2-hydroxyphenyl) benzene, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) ethane, tris (4-hydroxy Phenyl) phenylmethane, 2,2-bis [4,4-bis (4-hydroxyphenyl) cyclohexyl] propane, 2,4-bis [2-bis (4-hydroxyphenyl) -2-propyl] phenol, 2, 6-bis (2-hydroxy-5-
Methylbenzyl) -4-methylphenol, 2- (4-
(Hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane, tetrakis (4-hydroxyphenyl) methane, tetrakis [4- (4-hydroxyphenylisopropyl) phenoxy] methane, 2,4-dihydroxybenzoic acid, trimesic acid , Cyanuric acid, 3,3-
Bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole, 3,3-bis (4
-Hydroxyaryl) oxindole, 5-chloroisatin, 5,7-dichloroisatin, 5-bromoisatin and the like.

The addition amount of these branching agents is 30 mol% or less, preferably 5 mol% or less in the copolymer composition ratio, and if it exceeds 30 mol%, the viscosity of the coating liquid may become too high. Examples of the carbonate-forming compound include various carbonyl halides such as phosgene, haloformates such as chloroformate, and carbonate compounds. The proportion of these carbonate-forming compounds used may be appropriately adjusted in consideration of the stoichiometric ratio of the reaction.

Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, lithium hydroxide and cesium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, and organic compounds such as pyridine. A base or a mixture thereof can be used. The proportion of the acid binder used may be appropriately adjusted in consideration of the stoichiometric ratio of the reaction. Specifically, one equivalent or more, preferably 1 to 5 equivalents of an acid binder may be used per 1 mol of hydroxyl groups of the starting dihydric phenol.

Examples of the solvent include aromatic hydrocarbons such as toluene and xylene; methylene chloride, chloroform;
1-dichloroethane, 1,2-dichloroethane, 1,
1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,
Halogenated hydrocarbons such as 2,2-tetrachloroethane, pentachloroethane and chlorobenzene, and acetophenone are used.

Examples of the catalyst include tertiary amines such as trimethylamine, triethylamine, tributylamine, N, N-dimethylcyclohexylamine, pyridine and dimethylaniline, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, tributylbenzylammonium chloride, and the like. Quaternary ammonium salts such as trioctylmethylammonium chloride, tetrabutylammonium chloride and tetrabutylammonium bromide, and quaternary phosphonium salts such as tetrabutylphosphonium chloride and tetrabutylphosphonium bromide are preferred.

Next, a resin coating layer is formed on the surface of the carrier core material using the polycarbonate resin obtained as described above. In this case, the resin coating amount varies depending on the density and the particle size of the carrier core material, but is 1 to the entire carrier.
0% by weight or less, preferably 5% by weight or less. Since this resin coating amount indirectly defines the thickness of the resin coating layer of the carrier core material, if it exceeds 10% by weight, the resin coating layer becomes too thick, and the uniform resin coating layer is formed. In addition to the above, there arise problems that the resin coating layer is peeled off and resistance controllability becomes difficult. If the resin coating layer is too thick, when it is used as a developer, the charge amount increases, the resin coating layer peels off due to agitation in the machine, and the image density decreases and fine lines are reduced. This leads to deterioration of reproducibility. Therefore, it is preferable that the resin coating amount is such that the coating resin layer completely covers the surface of the carrier core material.

The formation of the polycarbonate resin coating layer can be carried out by a fluidized bed type wet method using a device such as a spiral coater or a spray dry, or a stirring dry type wet method using a universal mixing stirrer. In the polycarbonate resin coating layer, conductive fine particles, fine particles having charge control ability are dissolved or dispersed together with the coating resin solution and added to obtain a carrier having further improved conductivity and charge control ability. it can.

As such conductive fine particles, known fine particles may be blended in a usual amount. Specific examples of the conductive fine particles include carbon black, graphite,
Carbides such as silicon carbide; conductive magnetic powders such as magnetite and ferrite; metal powders such as titanium black and copper powder;
Metal oxides such as zinc oxide and tin oxide can be used. Among them, zinc oxide, tin oxide, conductive titania, and the like are particularly suitable for a carrier for forming a color image because they have excellent whiteness. The average particle diameter of these conductive fine particles is preferably 0.01 to 5.0 μm.

As the fine particles having charge control ability, known particles may be blended in a usual amount. Specific examples of the fine particles include toner external additives such as silica and titania, and polymethyl methacrylate. Examples include resin, resin fine particles such as styrene-acrylic copolymer resin, quaternary ammonium salts, and nigrosine-based metal complexes. These fine particles having charge control ability have an average particle diameter of 0.01 to
Those having a thickness of 5.0 μm are preferred.

Further, other resins can be used in combination with the polycarbonate resin coating layer as long as the performance as a coating carrier is not impaired. In this case, the coating layer may have a two-layer structure with another resin, or may be used in a completely mixed state. With respect to the conductive properties of the carrier obtained in this manner, the optimum value varies depending on the developing system using the carrier, but generally, in a resistance measurement at room temperature, 10 ² to 10 ¹⁴ Ω.
-Those showing a value of cm are preferred. This electric resistance value is 1
When the value is less than 0 ² Ω · cm, carrier development or fogging may occur. When the value exceeds 10 ¹⁴ Ω · cm, image quality may be deteriorated such as a decrease in image density. Here, the measurement of the electric resistance value is performed by providing electrodes having an area of 5 cm ^{2 on} the upper and lower surfaces of a carrier layer having a thickness of 0.5 cm, applying a load of 1 kg, and applying a load of 1 to 500 between the two electrodes.
A voltage of V was applied, the value of the current flowing to the bottom was measured and converted from this value to calculate the electrical resistance.

Next, as a toner used as a compounding component of the developer in the present invention, a toner produced by a known method can be used. For example, a toner produced by subjecting a monomer such as a vinyl compound to a suspension polymerization method, a pulverization method, a microcapsule method, a spray drying method, a mechanochemical method, or the like can be used. The average particle size of these toners is 20 μm or less, preferably 5 to 15 μm.
It is.

In addition to the binder resin and the colorant which are usually used, other additives such as a charge control agent, a lubricant, an anti-offset agent,
A compound containing a fixing improving aid or the like can be used. In addition, a magnetic material can be added to form a magnetic toner. In this case, it is effective for improving the developing characteristics and preventing the toner from scattering in the machine. Further, a fluidizing agent may be externally mixed to improve the fluidity.

Examples of the binder resin used here include polystyrene resins such as polystyrene, styrene / butadiene copolymer and styrene / acrylic copolymer, polyethylene, ethylene / vinyl acetate copolymer and ethylene / vinyl alcohol copolymer. Such an ethylene copolymer, an epoxy resin, a phenol resin, an acrylic phthalate resin, a polyamide resin, a polyester resin, a maleic acid resin, and the like can be used.

Examples of the coloring agent include known dyes and pigments, for example, carbon black, phthalocyanine blue, induslen blue, peacock blue, permanent red, red bengala, alizarin lake, chrome green, malachite green lake, methyl violet lake,
Hansa Yellow, Permanent Yellow and titanium oxide can be used.

Examples of the charge control agent include positive charge control agents such as nigrosine, a nigrosine base, a triphenylmethane compound, polyvinylpyridine, and a quaternary ammonium salt;
Metal complexes of alkyl-substituted salicylic acids, such as di-te
A negative charge control agent such as a chromium complex salt or a zinc complex salt of rt-butylsalicylic acid can be used. As the lubricant, Teflon, zinc stearate, polyvinylidene fluoride and the like can be used, and as the anti-offset agent and fixing aid, a low-molecular-weight, polyolefin wax such as polypropylene or a modified product thereof can be used. . And as the magnetic material, magnetite,
Ferrite, iron, nickel and the like can be used, and as a fluidizing agent, silica, titanium oxide, aluminum oxide and the like can be used.

Next, the mixing ratio of the carrier and the toner in the developer of the present invention is 2 to 40% by weight, preferably 3 to 30% by weight of the total amount of the carrier and the toner.
%, More preferably 4 to 25% by weight. If the mixing ratio of the toner is less than 2% by weight, the charge amount of the toner becomes too high to obtain a sufficient image density, and if it exceeds 40% by weight, a sufficient charge amount cannot be obtained. In-flight scattering and fogging on images occur.

The developer of the present invention comprises a two-component system and 1.5
It is used in a component-based development type electrophotographic system, for example, a copying machine (analog, digital, monochrome, color), a printer (monochrome, color), a facsimile, and the like. When this developer is applied, it can be used in various image forming methods, exposure methods, developing methods (apparatus), and electrophotographic processes of a toner density control method. The carrier and the toner may be used after adjusting the particle size, magnetic force, electric resistance value, and charge amount of the toner.

[0048]

[Example 1]

(1) Production of polycarbonate copolymer resin 2,2-bis (4-hydroxyphenyl) propane 74
g of a solution of 550 ml of a 6% by weight aqueous sodium hydroxide solution and 250 ml of methylene chloride are mixed and stirred, and while cooling, at 20 ° C., phosgene gas is introduced into the solution at 950 ml / sec. At a rate of 15 minutes.

Next, the resulting reaction solution was allowed to stand and the organic phase was separated to obtain a methylene chloride solution of a polycarbonate oligomer having a degree of polymerization of 2 to 5 and having a chloroformate group at a molecular terminal. Obtained. Then, methylene chloride was further added to the methylene chloride solution of the oligomer to make the total amount 450 ml, and the mixture was mixed with 150 ml of an 8% by weight aqueous sodium hydroxide solution, and 12.3 g of 4,4'-biphenol was added thereto. And 1.0 g of a dihydroxy compound having a siloxane structure represented by the following formula and 3.0 g of a molecular weight regulator, p-tert-butylphenol.

[0050]

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Then, while vigorously stirring the mixed solution, 2 ml of a 7% by weight aqueous solution of triethylamine was added as a catalyst to the mixture at 28 ° C.
The reaction was carried out under stirring for hours. After completion of the reaction, the reaction product was diluted with 1 liter of methylene chloride, then twice with 1.5 liters of water, 1 liter of 0.01N hydrochloric acid and 1 liter of water.
Washed twice in liter order. The obtained organic phase was put into methanol, and the precipitated solid was filtered and then dried to obtain 90 g of a polycarbonate copolymer resin.

The polycarbonate copolymer resin thus obtained was prepared by using methylene chloride as a solvent and adjusting its concentration to 0.5 g.
/ Reduced viscosity measured at 20 ° C. as deciliter [ηs
p / c] was 0.77 deciliter / g. The reduced viscosity was measured using an automatic viscosity measuring machine [VMR-042] manufactured by Rigosha Co., Ltd. with an automatic viscosity Ubbelohde improved viscometer [RM type].

Further, the chemical structure and copolymer composition of this polycarbonate copolymer resin were determined by ¹ H-NMR and ²⁹ S-NMR.
Determined by i-NMR spectrum. As a result, ¹ H
In the NMR spectrum, peaks derived from 2,2-bis (4-hydroxyphenyl) propane were observed at 1.7 ppm and 7.1 to 7.3 ppm, and 4,4′-biphenol was observed at 7.6 ppm. Was observed. And 0-0.1 ppm, 0.6
The peaks derived from the dihydroxy compound having the siloxane structure were observed at ppm and 0.87 ppm. In the ²⁹ Si-NMR spectrum, -6
Peaks were observed at 4 ppm, -21 ppm and 7.8 ppm, and the copolymer composition was calculated from the intensity ratio of these peaks. As a result, the chemical structure and copolymer composition of the polycarbonate copolymer resin were as shown below.

[0054]

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(2) Production of a polycarbonate resin-coated carrier The polycarbonate resin produced in the above (1) was
It was dissolved in methylene chloride as a solvent to prepare a coating solution having a concentration of 10% by weight. This coating liquid was applied to a carrier core material having an average particle size of 6
It was applied to a 0 μm ferrite particle by a spiral coater. Next, the ferrite particles coated with this coating solution were dried, subjected to a 125 μm sieving process and an airflow classification process, and simultaneously crushed and removed of fine powder to obtain a target polycarbonate resin-coated carrier. The polycarbonate resin-coated carrier obtained here had a polycarbonate resin amount of 0.98% by weight. The measurement of the resin amount was calculated from the heat loss up to 1000 ° C. by thermal analysis.

(3) Preparation of Developer A toner to be used by mixing with the polycarbonate resin-coated carrier produced in (2) above was produced by the following method.

2,2-bis (4-hydroxyphenyl)
Carbon black (Cabot; BPL) per 100 parts by weight of polyester resin made from propane
8 parts by weight and a dye (manufactured by Orient Chemical Industries; E-8
4) After thoroughly mixing 5 parts by weight with a ball mill,
This was kneaded with three kneading rolls heated to 140 ° C. Then, after allowing the kneaded material to cool to room temperature,
The toner was obtained by coarsely pulverizing with a feather mill and finely pulverizing with a jet mill.

Next, the toner obtained here is added to the carrier so as to be 5% by weight with respect to the total weight of the above-mentioned polycarbonate resin-coated carrier and the toner, and then mixed so as to be uniformly dispersed and developed. Agent was obtained.

(4) Evaluation of Performance of Carrier Coated with Polycarbonate Resin Using the developer obtained in the above (3), an initial printing test and a 10,000-sheet printing durability test were performed using a printer. In the initial print test, the density of the solid portion and the background portion of the printed paper were measured with a Macbeth densitometer,
The image density and background fog were evaluated.

Next, in the 10,000-sheet printing durability test, high temperature and high humidity (temperature 33 ° C., humidity 85%),
Next, the charge amount under three environments in the order of medium temperature and humidity (temperature 25 ° C., humidity 60%), low temperature and low humidity (temperature 10 ° C., humidity 30%), and the charge amount after printing 10,000 sheets (temperature 25 ° C.) , Humidity 6
0%). The charge amount was measured using a charge amount measuring device (Model TB-200) manufactured by Toshiba Chemical Corporation. The initial charge amount was measured by mixing 0.5 g of the toner and 9.5 g of the carrier in a polybin having an internal volume of 50 ml, stirring the mixture for 1 hour with a ball mill, and then blowing at a pressure of 0.8 kg / cm ² (G ), Blow time 50 seconds, 50
The test was performed under the condition of using a 0 mesh stainless steel wire mesh. In addition, the measurement of the charge amount after printing 10,000 sheets was performed by extracting 10 g of the developer from the charge amount measuring device, and using this, a blow pressure of 0.8 kg / cm ² (G) and a blow time of 50 seconds, 5 seconds.
The test was performed under the condition of using a 00 mesh stainless steel wire mesh.
Table 1 shows the results of the performance evaluation of these carriers. In the column of background fog in Table 1, a mark with no fog was indicated by 、, a mark with practical use was indicated by ○, a mark with practical use was indicated by △, and a mark with impractical was indicated. Is marked with x.

Further, the developer subjected to the 10,000-sheet printing durability test was observed under an electron microscope, and the state of adhesion of the toner to the carrier and the state of peeling of the polycarbonate resin coating on the carrier surface were observed. Second result
It is shown in the table. In Table 2, in the column of the toner adhesion state, the very good one from the initial stage to the end of the durability test is indicated by ◎.
A mark, a mark that is sufficiently good in practical use was marked with a circle, a mark with some difficulty in durability was marked with a mark, and a mark with a practical problem was marked with a cross. In addition, the indication of the column of the coating resin peeling state is indicated by ◎ when there is no peeling from the initial stage to after the endurance test, and when there is slight peeling after the endurance test but there is no practical problem,
Those which had peeling after the durability test and had poor durability were indicated by a triangle.

Table 2 shows the results obtained by measuring the state of embedding of external additives on the carrier surface of the developer having undergone the 10,000-sheet printing durability test by photoelectron measurement and judging from the peak intensity. The indication of the column of the embedded state of the external additive in Table 2 indicates that the peak of the external additive is 1 atom.
%, Those with peaks of 1 to 3 atom% are marked with ○, and those with peaks exceeding 3 atom% are marked with △.

Example 2 (1) Production of Polycarbonate Resin-Coated Carrier The polycarbonate resin obtained in Example 1 was dissolved in methylene chloride so as to have a concentration of 10% by weight.
Next, as a charge control agent, a phenol condensation resin (F-12, manufactured by Orient Chemical Co., Ltd.) was dissolved to a concentration of 0.1% by weight to prepare a carrier resin coating solution.
Next, using a spiral coater, the average particle size was 60 μm.
This carrier resin coating solution was applied to the ferrite particles. Further, after the drying treatment, a 125 μm sieving treatment and an airflow classification treatment were performed, and crushing and fine powder removal were performed to obtain a polycarbonate resin-coated carrier. The ratio of the resin-coated portion of the obtained resin-coated carrier was 1.03% by weight. (2) Preparation of developer A developer was obtained in the same manner as (3) of Example 1 except that the polycarbonate resin-coated carrier obtained in (1) was used. (3) Performance evaluation of polycarbonate resin-coated carrier The performance of the polycarbonate resin-coated carrier was evaluated in the same manner as in (1) of Example 1, except that the developer obtained in the above (2) was used. The results are shown in Tables 1 and 2.

Example 3 (1) Production of Polycarbonate Resin-Coated Carrier The polycarbonate resin obtained in Example 1 was dissolved in methylene chloride so as to have a concentration of 10% by weight.
Next, carbon black (MA100, manufactured by Mitsubishi Chemical Corporation) as conductive fine particles was dispersed therein to a concentration of 0.1% to prepare a carrier resin coating solution. Next, an average particle size of 60
The above-mentioned carrier resin coating solution was applied to ferrite particles of μm. Further, after the drying treatment, a 125 μm sieving treatment and an airflow classification treatment were performed, and crushing and fine powder removal were performed to obtain a polycarbonate resin-coated carrier. The ratio of the resin-coated portion of the obtained resin-coated carrier was 1.15% by weight. (2) Preparation of developer A developer was obtained in the same manner as (3) of Example 1 except that the polycarbonate resin-coated carrier obtained in (1) was used. (3) Performance evaluation of polycarbonate resin-coated carrier The performance of the polycarbonate resin-coated carrier was evaluated in the same manner as in (1) of Example 1, except that the developer obtained in the above (2) was used. The results are shown in Tables 1 and 2.

Example 4 (1) Production of Polycarbonate Resin Coated Carrier 10 g of the polycarbonate resin obtained in Example 1 was dissolved in 1 liter of methylene chloride to prepare a carrier resin coating solution. Then, in an all-purpose mixing stirrer, an average particle size of 6
1 kg of 0 μm ferrite particles were added, and subsequently, the whole amount of the carrier coating solution prepared here was added thereto, and while stirring, the whole amount of methylene chloride as a solvent was removed under reduced pressure.
Next, after drying this, it was subjected to a 125 μm sieving treatment and airflow classification treatment, followed by crushing and removal of fine powder to obtain a polycarbonate resin-coated carrier. Here, the ratio of the resin-coated portion of the obtained resin-coated carrier was 0.9.
It was 9% by weight. (2) Preparation of developer A developer was obtained in the same manner as (3) of Example 1 except that the polycarbonate resin-coated carrier obtained in (1) was used. (3) Performance evaluation of polycarbonate resin-coated carrier The performance of the polycarbonate resin-coated carrier was evaluated in the same manner as in (1) of Example 1, except that the developer obtained in the above (2) was used. The results are shown in Tables 1 and 2.

Example 5 (1) Production of Polycarbonate Copolymer Resin In place of the dihydroxy compound having a siloxane structure used in Example 1, 145 g of a dihydroxy compound having a siloxane structure represented by the following formula was used. 4,
A polycarbonate copolymer resin was produced in the same manner as in Example 1 except that 4′-biphenol was not used.

[0067]

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The reduced viscosity of the obtained polycarbonate copolymer resin was 0.63 deciliter / g, and the structure and copolymer composition of this polycarbonate copolymer resin were as follows in the ¹ H-NMR spectrum. 7p
pm and 7.1-7.3 ppm peaks derived from 2,2-bis (4-hydroxyphenyl) propane,
0.1 ppm, 0.6 ppm and 0.87 ppm of the peak derived from the dihydroxy compound having the siloxane structure, and -64 in the ²⁹ Si-NMR spectrum.
ppm, -21 ppm and 7.8 ppm, and the result of calculating the copolymer composition from the intensity ratio of these peaks,
The chemical structure and copolymer composition of this polycarbonate copolymer resin were found to be as shown below.

[0069]

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(2) Production of Polycarbonate Resin-Coated Carrier A polycarbonate resin-coated carrier was obtained in the same manner as in (1) of Example 1, except that the polycarbonate resin obtained in the above (1) was used. Here, the ratio of the resin-coated portion of the obtained resin-coated carrier was 1.35% by weight. (3) Preparation of developer A developer was obtained in the same manner as in (3) of Example 1, except that the polycarbonate resin-coated carrier obtained in (2) was used. (4) Performance evaluation of the polycarbonate resin-coated carrier The performance of the polycarbonate resin-coated carrier was evaluated in the same manner as in (4) of Example 1, except that the developer obtained in the above (3) was used. The results are shown in Tables 1 and 2.

Example 6 (1) Production of Polycarbonate Copolymer Resin In place of the dihydroxy compound having a siloxane structure used in Example 1, 430 g of a dihydroxy compound having a siloxane structure represented by the following formula was used. 4,
A polycarbonate copolymer resin was produced in the same manner as in Example 1 except that 4′-biphenol was not used.

[0072]

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The reduced viscosity of the polycarbonate copolymer resin obtained here was 0.52 deciliter / g, and the structure and copolymer composition of this polycarbonate copolymer resin were as shown in ¹ H-NMR spectrum. 7p
pm and 7.1-7.3 ppm peaks derived from 2,2-bis (4-hydroxyphenyl) propane,
0.1 ppm, 0.6 ppm and 0.87 ppm of the peak derived from the dihydroxy compound having the siloxane structure, and -64 in the ²⁹ Si-NMR spectrum.
ppm, -21 ppm and 7.8 ppm, and the result of calculating the copolymer composition from the intensity ratio of these peaks,
The chemical structure and copolymer composition of this polycarbonate copolymer resin were found to be as shown below.

[0074]

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(2) Production of polycarbonate resin-coated carrier A polycarbonate resin-coated carrier was obtained in the same manner as in (1) of Example 1, except that the polycarbonate resin obtained in the above (1) was used. Here, the ratio of the resin-coated portion of the obtained resin-coated carrier was 1.22% by weight. (3) Preparation of developer A developer was obtained in the same manner as in (3) of Example 1, except that the polycarbonate resin-coated carrier obtained in (2) was used. (4) Performance evaluation of the polycarbonate resin-coated carrier The performance of the polycarbonate resin-coated carrier was evaluated in the same manner as in (4) of Example 1, except that the developer obtained in the above (3) was used. The results are shown in Tables 1 and 2.

Example 7 (1) Production of Polycarbonate Copolymer Resin In place of the dihydroxy compound having a siloxane structure used in Example 1, 164 g of a dihydroxy compound having a siloxane structure represented by the following formula was used. 4,
A polycarbonate copolymer resin was produced in the same manner as in Example 1 except that 4′-biphenol was not used.

[0077]

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The reduced viscosity of the obtained polycarbonate copolymer resin was 0.63 deciliter / g, and the structure and copolymer composition of this polycarbonate copolymer resin were as follows in the ¹ H-NMR spectrum. 7p
pm and 7.1-7.3 ppm peaks derived from 2,2-bis (4-hydroxyphenyl) propane,
0.1 ppm, 0.6 ppm and 0.87 ppm of the peak derived from the dihydroxy compound having the siloxane structure, and -64 in the ²⁹ Si-NMR spectrum.
ppm, -21 ppm and 7.8 ppm, and the result of calculating the copolymer composition from the intensity ratio of these peaks,
The chemical structure and copolymer composition of this polycarbonate copolymer resin were found to be as shown below.

[0079]

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(2) Production of Polycarbonate Resin-Coated Carrier A polycarbonate resin-coated carrier was obtained in the same manner as in (1) of Example 1, except that the polycarbonate resin obtained in the above (1) was used. Here, the ratio of the resin-coated portion of the obtained resin-coated carrier was 0.89% by weight. (3) Preparation of developer A developer was obtained in the same manner as in (3) of Example 1, except that the polycarbonate resin-coated carrier obtained in (2) was used. (4) Performance evaluation of the polycarbonate resin-coated carrier The performance of the polycarbonate resin-coated carrier was evaluated in the same manner as in (4) of Example 1, except that the developer obtained in the above (3) was used. The results are shown in Tables 1 and 2.

Example 8 (1) Production of Polycarbonate Copolymer Resin The amount of the dihydroxy compound having a siloxane structure used in Example 1 was 48.2 g, and the amount of 4,4′-biphenol was 8.3 g. A polycarbonate copolymer resin was produced in the same manner as in Example 1 except that the above conditions were changed.

The reduced viscosity of the polycarbonate copolymer resin obtained here was 0.75 deciliter / g, and the structure and copolymer composition of this polycarbonate copolymer resin were as shown in the ¹ H-NMR spectrum of 1. 7p
pm and 7.1-7.3 ppm peaks derived from 2,2-bis (4-hydroxyphenyl) propane,
0.1 ppm, 0.6 ppm and 0.87 ppm of the peak derived from the dihydroxy compound having the siloxane structure, and -64 in the ²⁹ Si-NMR spectrum.
ppm, -21 ppm and 7.8 ppm, and the result of calculating the copolymer composition from the intensity ratio of these peaks,
The chemical structure and copolymer composition of this polycarbonate copolymer resin were found to be as shown below.

[0083]

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(2) Production of Carrier Coated with Polycarbonate Resin A polycarbonate resin-coated carrier was obtained in the same manner as in (2) of Example 1, except that the polycarbonate resin obtained in the above (1) was used. Here, the ratio of the resin-coated portion of the obtained resin-coated carrier was 0.95% by weight. (3) Preparation of developer A developer was obtained in the same manner as in (3) of Example 1, except that the polycarbonate resin-coated carrier obtained in (2) was used. (4) Performance evaluation of the polycarbonate resin-coated carrier The performance of the polycarbonate resin-coated carrier was evaluated in the same manner as in (4) of Example 1, except that the developer obtained in the above (3) was used. The results are shown in Tables 1 and 2.

Example 9 (1) Production of Polycarbonate Copolymer Resin The amount of the dihydroxy compound having a siloxane structure used in Example 1 was 9.6 g, and the amount of 4,4′-biphenol was 11.8 g. A polycarbonate copolymer resin was produced in the same manner as in Example 1 except that the above conditions were changed.

The reduced viscosity of the polycarbonate copolymer resin obtained here was 0.77 deciliter / g, and the structure and copolymer composition of this polycarbonate copolymer resin were as shown in ¹ H-NMR spectrum. 7p
pm and 7.1-7.3 ppm peaks derived from 2,2-bis (4-hydroxyphenyl) propane,
0.1 ppm, 0.6 ppm and 0.87 ppm of the peak derived from the dihydroxy compound having the siloxane structure, and -64 in the ²⁹ Si-NMR spectrum.
ppm, -21 ppm and 7.8 ppm, and the result of calculating the copolymer composition from the intensity ratio of these peaks,
The chemical structure and copolymer composition of this polycarbonate copolymer resin were found to be as shown below.

[0087]

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(2) Production of a polycarbonate resin-coated carrier A polycarbonate resin-coated carrier was obtained in the same manner as in (2) of Example 1, except that the polycarbonate resin obtained in the above (1) was used. Here, the ratio of the resin-coated portion of the obtained resin-coated carrier was 1.01% by weight. (3) Preparation of developer A developer was obtained in the same manner as in (3) of Example 1, except that the polycarbonate resin-coated carrier obtained in (2) was used. (4) Performance evaluation of the polycarbonate resin-coated carrier The performance of the polycarbonate resin-coated carrier was evaluated in the same manner as in (4) of Example 1, except that the developer obtained in the above (3) was used. The results are shown in Tables 1 and 2.

Example 10 (1) Production of Polycarbonate Copolymer Resin The amount of the dihydroxy compound having a siloxane structure used in Example 1 was changed to 144.7 g.
A polycarbonate copolymer resin was produced in the same manner as in Example 1 except that 4′-biphenol was not used.

[0090] The reduced viscosity of the obtained polycarbonate copolymer resin here is 0.51 dl / g, The structure and the copolymer composition of the polycarbonate copolymer resin, 1 in ¹ H-NMR spectrum. 7p
pm and 7.1-7.3 ppm peaks derived from 2,2-bis (4-hydroxyphenyl) propane,
0.1 ppm, 0.6 ppm and 0.87 ppm of the peak derived from the dihydroxy compound having the siloxane structure, and -64 in the ²⁹ Si-NMR spectrum.
ppm, -21 ppm and 7.8 ppm, and the result of calculating the copolymer composition from the intensity ratio of these peaks,
The chemical structure and copolymer composition of this polycarbonate copolymer resin were found to be as shown below.

[0091]

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(2) Production of Polycarbonate Resin-Coated Carrier A polycarbonate resin-coated carrier was obtained in the same manner as in (1) of Example 1, except that the polycarbonate resin obtained in the above (1) was used. Here, the ratio of the resin-coated portion of the obtained resin-coated carrier was 0.98% by weight. (3) Preparation of developer A developer was obtained in the same manner as in (3) of Example 1, except that the polycarbonate resin-coated carrier obtained in (2) was used. (4) Performance evaluation of the polycarbonate resin-coated carrier The performance of the polycarbonate resin-coated carrier was evaluated in the same manner as in (4) of Example 1, except that the developer obtained in the above (3) was used. The results are shown in Tables 1 and 2.

Example 11 (1) Production of Polycarbonate Copolymer Resin The amount of the dihydroxy compound having a siloxane structure used in Example 1 was 0.1 g, and the amount of 4,4′-biphenol was 12.3 g. A polycarbonate copolymer resin was produced in the same manner as in Example 1, except for changing the above.

The reduced viscosity of the polycarbonate copolymer resin obtained here was 0.77 deciliter / g, and the structure and copolymer composition of this polycarbonate copolymer resin were as shown in ¹ H-NMR spectrum. 7p
pm and 7.1-7.3 ppm peaks derived from 2,2-bis (4-hydroxyphenyl) propane,
0.1 ppm, 0.6 ppm and 0.87 ppm of the peak derived from the dihydroxy compound having the siloxane structure, and -64 in the ²⁹ Si-NMR spectrum.
ppm, -21 ppm and 7.8 ppm, and the result of calculating the copolymer composition from the intensity ratio of these peaks,
The chemical structure and copolymer composition of this polycarbonate copolymer resin were found to be as shown below.

[0095]

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(2) Production of a polycarbonate resin-coated carrier A polycarbonate resin-coated carrier was obtained in the same manner as in (1) of Example 1, except that the polycarbonate resin obtained in the above (1) was used. Here, the ratio of the resin-coated portion of the obtained resin-coated carrier was 0.97% by weight. (3) Preparation of developer A developer was obtained in the same manner as in (3) of Example 1, except that the polycarbonate resin-coated carrier obtained in (2) was used. (4) Performance evaluation of the polycarbonate resin-coated carrier The performance of the polycarbonate resin-coated carrier was evaluated in the same manner as in (4) of Example 1, except that the developer obtained in the above (3) was used. The results are shown in Tables 1 and 2.

Example 12 (1) Production of Polycarbonate Copolymer Resin The amount of the dihydroxy compound having a siloxane structure used in Example 1 was 1.0 g, and the amount was 4,4 ′.
-Instead of biphenol, 2,2-bis (3-phenyl-
A polycarbonate copolymer resin was produced in the same manner as in Example 1 except that 25.1 g of 4-hydroxyphenyl) propane was used.

The reduced viscosity of the polycarbonate copolymer resin obtained here was 0.77 deciliter / g, and the structure and copolymer composition of this polycarbonate copolymer resin were as shown in ¹ H-NMR spectrum. 7p
6.8 ppm at 7.1-7.3 ppm derived from 2,2-bis (4-hydroxyphenyl) propane, 6.8
ppm peak derived from 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 0-0.1 pp
m, peaks derived from the dihydroxy compound having the siloxane structure of 0.6 ppm and 0.87 ppm, and -64 ppm,-in the ²⁹ Si-NMR spectrum.
From the results of calculating the copolymer composition from the peaks at 21 ppm and 7.8 ppm and the intensity ratio of these peaks, the chemical structure and copolymer composition of the polycarbonate copolymer resin are as follows:
It was found to be as shown below.

[0099]

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(2) Production of a polycarbonate resin-coated carrier A polycarbonate resin-coated carrier was obtained in the same manner as in (1) of Example 1, except that the polycarbonate resin obtained in the above (1) was used. Here, the ratio of the resin-coated portion of the obtained resin-coated carrier was 0.97% by weight. (3) Preparation of developer A developer was obtained in the same manner as in (3) of Example 1, except that the polycarbonate resin-coated carrier obtained in (2) was used. (4) Performance evaluation of the polycarbonate resin-coated carrier The performance of the polycarbonate resin-coated carrier was evaluated in the same manner as in (4) of Example 1, except that the developer obtained in the above (3) was used. The results are shown in Tables 1 and 2.

Example 13 (1) Production of Polycarbonate Copolymer Resin In place of the dihydroxy compound having a siloxane structure used in Example 1, 10.6 g of the dihydroxy compound having a siloxane structure used in Example 7 was used. And,
Example 1 was repeated except that 13.0 g of 4,4'-dihydroxybenzophenone was used instead of 4,4'-biphenol.
As above, a polycarbonate copolymer resin was produced.

The reduced viscosity of the obtained polycarbonate copolymer resin was 0.75 deciliter / g, and the structure and copolymer composition of the polycarbonate copolymer resin were as follows in ¹ H-NMR spectrum. 7p
pm and 7.1-7.3 ppm peaks derived from 2,2-bis (4-hydroxyphenyl) propane, 7.3
~ 7.5 ppm of peaks derived from 4,4'-dihydroxybenzophenone, 0-0.1 ppm, 0.6 ppm
And 0.87 ppm of a peak derived from the dihydroxy compound having the siloxane structure, and ²⁹ Si-NMR.
-64 ppm, -21 ppm and 7.
From the result of calculating the copolymer composition from the peak of 8 ppm and the intensity ratio of these peaks, it was confirmed that the chemical structure and the copolymer composition of this polycarbonate copolymer resin were as shown below.

[0103]

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(2) Production of a polycarbonate resin-coated carrier A polycarbonate resin-coated carrier was obtained in the same manner as in (1) of Example 1, except that the polycarbonate resin obtained in the above (1) was used. Here, the ratio of the resin-coated portion of the obtained resin-coated carrier was 1.00% by weight. (3) Preparation of developer A developer was obtained in the same manner as in (3) of Example 1, except that the polycarbonate resin-coated carrier obtained in (2) was used. (4) Performance evaluation of the polycarbonate resin-coated carrier The performance of the polycarbonate resin-coated carrier was evaluated in the same manner as in (4) of Example 1, except that the developer obtained in the above (3) was used. The results are shown in Tables 1 and 2.

[Example 14] The 2,2-
Instead of bis (4-hydroxyphenyl) propane,
9,9-bis (3-methyl-4-hydroxyphenyl)
Using 123.2 g of fluorene, 164.0 g of the dihydroxy compound having a siloxane structure used in Example 7 was used in place of the dihydroxy compound having a siloxane structure used in Example 1, and 4,4′-biphenol was not used. Except for the above, a polycarbonate copolymer resin was produced in the same manner as in Example 1.

[0106] The reduced viscosity of the obtained polycarbonate copolymer resin here is 0.48 dl / g, The structure and the copolymer composition of the polycarbonate copolymer resin, 2 in the ¹ H-NMR spectrum. Fifteen
ppm and 7.8 ppm of 9,9-bis (3-methyl-
4-hydroxyphenyl) peaks derived from fluorene, 0-0.1 ppm, 0.6 ppm and 0.87 ppm
From the results of calculating the copolymer composition from the peaks derived from the dihydroxy compound having the above siloxane structure and the peaks at -64 ppm, -21 ppm and 7.8 ppm in the ²⁹ Si-NMR spectrum, and the intensity ratio of these peaks, It was recognized that the chemical structure and copolymer composition of the copolymer resin were as shown below.

[0107]

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(2) Production of polycarbonate resin-coated carrier A polycarbonate resin-coated carrier was obtained in the same manner as in (2) of Example 1, except that the polycarbonate resin obtained in the above (1) was used. Here, the ratio of the resin-coated portion of the obtained resin-coated carrier was 1.02% by weight. (3) Preparation of developer A developer was obtained in the same manner as in (3) of Example 1, except that the polycarbonate resin-coated carrier obtained in (2) was used. (4) Performance evaluation of the polycarbonate resin-coated carrier The performance of the polycarbonate resin-coated carrier was evaluated in the same manner as in (4) of Example 1, except that the developer obtained in the above (3) was used. The results are shown in Tables 1 and 2.

Example 15 (1) Production of polycarbonate copolymer resin In place of the dihydroxy compound having a siloxane structure used in Example 1, 10.6 g of the dihydroxy compound having a siloxane structure used in Example 5 was used.
A polycarbonate copolymer resin was produced in the same manner as in Example 1 except that 9.1 g of bis (4-hydroxyphenyl) ether was used instead of 4,4′-biphenol.

The reduced viscosity of the polycarbonate copolymer resin obtained here was 0.62 deciliter / g, and the structure and copolymer composition of this polycarbonate copolymer resin were as shown in ¹ H-NMR spectrum. 7p
pm and 7.1-7.3 ppm peaks derived from 2,2-bis (4-hydroxyphenyl) propane, 7.0
ppm derived from bis (4-hydroxyphenyl) ether, 0-0.1 ppm, 0.6 ppm and 0.1 ppm.
87 ppm of a peak derived from the dihydroxy compound having the above siloxane structure, and -64 ppm, -21 ppm and 7.8 pp in a ²⁹ Si-NMR spectrum.
From the result of calculating the copolymer composition from the peak of m and the intensity ratio of these peaks, it was confirmed that the chemical structure and the copolymer composition of this polycarbonate copolymer resin were as shown below.

[0111]

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(2) Production of Carrier Coated with Polycarbonate Resin A carrier coated with polycarbonate resin was obtained in the same manner as in (2) of Example 1, except that the polycarbonate resin obtained in (1) was used. Here, the ratio of the resin-coated portion of the obtained resin-coated carrier was 0.96% by weight. (3) Preparation of developer A developer was obtained in the same manner as in (3) of Example 1, except that the polycarbonate resin-coated carrier obtained in (2) was used. (4) Performance evaluation of the polycarbonate resin-coated carrier The performance of the polycarbonate resin-coated carrier was evaluated in the same manner as in (4) of Example 1, except that the developer obtained in the above (3) was used. The results are shown in Tables 1 and 2.

[Example 16] (1) Production of polycarbonate copolymer resin Instead of 2,2-bis (4-hydroxyphenyl) propane used in Example 1, 1,1-bis (4-hydroxyphenyl) was used. Example 1 using 90.0 g of cyclohexane
In the same manner as in Example 1 except that 146.0 g of the dihydroxy compound having a siloxane structure used in Example 5 was used in place of the dihydroxy compound having a siloxane structure used in Example 5, and that 4,4′-biphenol was not used. Thus, a polycarbonate copolymer resin was produced.

The reduced viscosity of the obtained polycarbonate copolymer resin was 0.57 deciliter / g, and the structure and copolymer composition of this polycarbonate copolymer resin were as follows in the ¹ H-NMR spectrum. 5p
pm and 2.3 ppm, 7.2 ppm, 7.3 ppm,
Peak derived from 1,1-bis (4-hydroxyphenyl) cyclohexane, 0 to 0.1 ppm, 0.6 ppm
And 0.87 ppm of a peak derived from the dihydroxy compound having the siloxane structure, and ²⁹ Si-NMR.
-64 ppm, -21 ppm and 7.
From the result of calculating the copolymer composition from the peak of 8 ppm and the intensity ratio of these peaks, it was confirmed that the chemical structure and the copolymer composition of this polycarbonate copolymer resin were as shown below.

[0115]

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(2) Production of a polycarbonate resin-coated carrier A polycarbonate resin-coated carrier was obtained in the same manner as in (2) of Example 1, except that the polycarbonate resin obtained in the above (1) was used. Here, the ratio of the resin-coated portion of the obtained resin-coated carrier was 0.97% by weight. (3) Preparation of developer A developer was obtained in the same manner as in (3) of Example 1, except that the polycarbonate resin-coated carrier obtained in (2) was used. (4) Performance evaluation of the polycarbonate resin-coated carrier The performance of the polycarbonate resin-coated carrier was evaluated in the same manner as in (4) of Example 1, except that the developer obtained in the above (3) was used. The results are shown in Tables 1 and 2.

[Example 17] (1) Production of polycarbonate copolymer resin In place of the dihydroxy compound having a siloxane structure used in Example 1, 30 g of the dihydroxy compound having a siloxane structure used in Example 6 was used, and 1,1-bis (4
A polycarbonate copolymer resin was produced in the same manner as in Example 1 except that 15.8 g of (-hydroxyphenyl) diphenylmethane was used.

The reduced viscosity of the polycarbonate copolymer resin obtained here was 0.68 deciliter / g, and the structure and copolymer composition of this polycarbonate copolymer resin were as shown in ¹ H-NMR spectrum. 7p
pm and 7.1-7.3 ppm peaks derived from 2,2-bis (4-hydroxyphenyl) propane, 7.1
~ 7.3 ppm of peaks derived from 1,1-bis (4-hydroxyphenyl) diphenylmethane, 0-0.1 p
pm, 0.6 ppm and 0.87 ppm of peaks derived from the dihydroxy compound having the siloxane structure, and -64 ppm in a ²⁹ Si-NMR spectrum.
From the results of calculating the copolymer composition from the peaks at −21 ppm and 7.8 ppm and the intensity ratio of these peaks, it was confirmed that the chemical structure and copolymer composition of this polycarbonate copolymer resin were as shown below.

[0119]

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(2) Production of polycarbonate resin-coated carrier A polycarbonate resin-coated carrier was obtained in the same manner as in (1) of Example 1, except that the polycarbonate resin obtained in the above (1) was used. Here, the ratio of the resin-coated portion of the obtained resin-coated carrier was 1.02% by weight. (3) Preparation of developer A developer was obtained in the same manner as in (3) of Example 1, except that the polycarbonate resin-coated carrier obtained in (2) was used. (4) Performance evaluation of the polycarbonate resin-coated carrier The performance of the polycarbonate resin-coated carrier was evaluated in the same manner as in (4) of Example 1, except that the developer obtained in the above (3) was used. The results are shown in Tables 1 and 2.

Example 18 (1) Production of Polycarbonate Copolymer Resin 30 g of a dihydroxy compound having a siloxane structure used in Example 6 was used in place of the dihydroxy compound having a siloxane structure used in Example 1, and 2,2-bis (4) instead of 4,4'-biphenol
-Hydroxyphenyl) propane was used in the same manner as in Example 1 except that 14.5 g of propane was used to produce a polycarbonate copolymer resin.

The reduced viscosity of the obtained polycarbonate copolymer resin was 0.68 deciliter / g, and the structure and copolymer composition of this polycarbonate copolymer resin were as shown in ¹ H-NMR spectrum. 7p
pm and 7.1-7.3 ppm peaks derived from 2,2-bis (4-hydroxyphenyl) propane,
0.1 ppm, 0.6 ppm and 0.87 ppm of the peak derived from the dihydroxy compound having the siloxane structure, and -64 in the ²⁹ Si-NMR spectrum.
ppm, -21 ppm and 7.8 ppm, and the result of calculating the copolymer composition from the intensity ratio of these peaks,
The chemical structure and copolymer composition of this polycarbonate copolymer resin were found to be as shown below.

[0123]

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(2) Preparation of polycarbonate resin-coated carrier A polycarbonate resin-coated carrier was obtained in the same manner as in (2) of Example 1, except that the polycarbonate resin obtained in the above (1) was used. Here, the ratio of the resin-coated portion of the obtained resin-coated carrier was 0.95% by weight. (3) Preparation of developer A developer was obtained in the same manner as in (3) of Example 1, except that the polycarbonate resin-coated carrier obtained in (2) was used. (4) Performance evaluation of the polycarbonate resin-coated carrier The performance of the polycarbonate resin-coated carrier was evaluated in the same manner as in (4) of Example 1, except that the developer obtained in the above (3) was used. The results are shown in Tables 1 and 2.

Example 19 (1) Production of Polycarbonate Copolymer Resin Instead of 2,2-bis (4-hydroxyphenyl) propane used in Example 1, 81.0 g of bis (4-hydroxyphenyl) sulfone Using 10.6 g of the dihydroxy compound having a siloxane structure used in Example 7 in place of the dihydroxy compound having a siloxane structure used in Example 1, and using 2,2-bis instead of 4,4′-biphenol (4-hydroxyphenyl) sulfone 1
A polycarbonate copolymer resin was produced in the same manner as in Example 1 except that 6.0 g was used.

The reduced viscosity of the polycarbonate copolymer resin obtained here was 0.74 deciliter / g, and the structure and copolymer composition of this polycarbonate copolymer resin were determined in the ¹ H-NMR spectrum as 8. 0p
pm peak derived from bis (4-hydroxyphenyl) sulfone, 0-0.1 ppm, 0.6 ppm and 0.8 ppm
7 ppm of a peak derived from the dihydroxy compound having the siloxane structure, and -64 ppm, -21 ppm and 7.8 ppm in a ²⁹ Si-NMR spectrum.
From the results of the calculation of the copolymer composition from the peaks and the intensity ratio of these peaks, it was confirmed that the chemical structure and copolymer composition of this polycarbonate copolymer resin were as shown below.

[0127]

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(2) Production of a polycarbonate resin-coated carrier A polycarbonate resin-coated carrier was obtained in the same manner as in (1) of Example 1, except that the polycarbonate resin obtained in the above (1) was used. Here, the ratio of the resin-coated portion of the obtained resin-coated carrier was 0.99% by weight. (3) Preparation of developer A developer was obtained in the same manner as in (3) of Example 1, except that the polycarbonate resin-coated carrier obtained in (2) was used. (4) Performance evaluation of the polycarbonate resin-coated carrier The performance of the polycarbonate resin-coated carrier was evaluated in the same manner as in (4) of Example 1, except that the developer obtained in the above (3) was used. The results are shown in Tables 1 and 2.

Example 20 (1) Production of polycarbonate copolymer resin In place of 2,2-bis (4-hydroxyphenyl) propane used in Example 1, 2,2-bis (3-methoxy-
4-hydroxyphenyl) 1,1,1,3,3,3-hexafluoropropane using 129 g of dihydroxy compound having a siloxane structure used in Example 7 in place of the dihydroxy compound having a siloxane structure used in Example 1 Using 10.6 g of compound, 25 g of 2,2-bis (3-methoxy-4-hydroxyphenyl) 1,1,1,3,3,3-hexafluoropropane was used instead of 4,4′-biphenol. Otherwise, the procedure of Example 1 was followed to produce a polycarbonate copolymer resin.

The reduced viscosity of the obtained polycarbonate copolymer resin was 0.68 deciliter / g, and the structure and copolymer composition of this polycarbonate copolymer resin were as described in ¹ H-NMR spectrum. 7p
pm, peak derived from 2,2-bis (3-methoxy-4-hydroxyphenyl) 1,1,1,3,3,3-hexafluoropropane, 0-0.1 ppm, 0.6 pp
m and 0.87 ppm of a peak derived from the dihydroxy compound having the siloxane structure, and ²⁹ Si-NM.
From the results of calculating the copolymer composition from the peaks at −64 ppm, −21 ppm and 7.8 ppm in the R spectrum and the intensity ratio of these peaks, the chemical structure and copolymer composition of the polycarbonate copolymer resin are as shown below. It was recognized that there was.

[0131]

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(2) Production of a polycarbonate resin-coated carrier A polycarbonate resin-coated carrier was obtained in the same manner as in (2) of Example 1, except that the polycarbonate resin obtained in the above (1) was used. Here, the ratio of the resin-coated portion of the obtained resin-coated carrier was 1.06% by weight. (3) Preparation of developer A developer was obtained in the same manner as in (3) of Example 1, except that the polycarbonate resin-coated carrier obtained in (2) was used. (4) Performance evaluation of the polycarbonate resin-coated carrier The performance of the polycarbonate resin-coated carrier was evaluated in the same manner as in (4) of Example 1, except that the developer obtained in the above (3) was used. The results are shown in Tables 1 and 2.

Comparative Example 1 (1) Production of Polycarbonate Resin-Coated Carrier The coating resin was prepared in the same manner as in Example except that a polydimethylsiloxane-polycarbonate copolymer having the following repeating unit and a weight average molecular weight of 30,000 was used. A resin-coated carrier was obtained in the same manner as in 1 (2). Here, the ratio of the resin-coated portion of the obtained resin-coated carrier was 0.96.
% By weight.

[0134]

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(2) Preparation of developer A developer was obtained in the same manner as (3) of Example 1, except that the polycarbonate resin-coated carrier obtained in (1) was used. (3) Performance evaluation of polycarbonate resin-coated carrier The performance of the polycarbonate resin-coated carrier was evaluated in the same manner as in (1) of Example 1, except that the developer obtained in the above (2) was used. The results are shown in Tables 1 and 2.

Comparative Example 2 (1) Production of a Carrier Coated with a Polycarbonate Resin A polycarbonate resin having the following repeating units and a weight average molecular weight of 30,000 was used as the resin for the coating, except that (2) of Example 1 was used. Similarly, a resin-coated carrier was obtained. Here, the ratio of the resin-coated portion of the obtained resin-coated carrier was 0.99% by weight.

[0137]

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(2) Preparation of developer A developer was obtained in the same manner as in (3) of Example 1, except that the carrier coated with the polycarbonate resin obtained in (1) was used. (3) Performance evaluation of polycarbonate resin-coated carrier The performance of the polycarbonate resin-coated carrier was evaluated in the same manner as in (1) of Example 1, except that the developer obtained in the above (2) was used. The results are shown in Tables 1 and 2.

[0139]

[Table 1]

[0140]

[Table 2]

[0141]

The carrier for electrophotography of the present invention has high mechanical strength and high adhesiveness between the carrier core material and its coating layer, so that it has excellent durability and does not adhere toner components. When an electrostatic latent image is developed using a developer obtained by blending a specific amount of toner with the electrophotographic carrier, a clear image without background fog can be obtained.

──────────────────────────────────────────────────の Continued on front page (51) Int.Cl. ⁶ Identification code FI G03G 9/10 361

Claims (4)

[Claims] 1. An electrophotographic carrier having a resin coating layer provided on magnetic particles, wherein the resin coating layer contains a polycarbonate resin having a repeating unit (1) represented by the following general formula [1]. An electrophotographic carrier, characterized by being formed of: Embedded image [In the formula [1], R is the same or different, substituted or unsubstituted alkyl group having 1 to 6 carbon atoms or substituted or unsubstituted aryl group having 6 to 12 carbon atoms, which does not contain an aliphatic unsaturated bond. R ¹ is independently a halogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, or a substituted or unsubstituted having 6 to 12 carbon atoms. Is an aryl group of
X is each independently an alkylene group having 2 or more carbon atoms or an alkyleneoxyalkylene group having 2 or more carbon atoms;
X ′ is each independently an alkylene group having 2 or more carbon atoms, an alkyleneoxyalkylene group having 2 or more carbon atoms or an oxygen atom, a is each independently an integer of 0 to 4, na
Is 0 or 1, nb is 1 or 2, nc is 1 or 2 (where na + nb + nc = 3),
n1, n2, n3 and n4 are each independently 0 or an integer of 1 or more (provided that n1 + n2 + n3 + n4 = 0 to 45)
0). ] 2. The polycarbonate resin according to claim 1, wherein the polycarbonate resin comprises a repeating unit (1) represented by the general formula [1] and a repeating unit (2) represented by the following general formula [2]. Electrophotographic carrier. Embedded image [In the formula [2], R ² is independently a halogen atom, a vinyl group, an allyl group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms. A substituted or unsubstituted cycloalkyl group having 3 to 12 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms, and a are each independently Is an integer of 0 to 4, and Y is a single bond, -O-, -CO-, -S-, -SO
—, —SO ₂ —, —CR ³ R ⁴ — (where R ³ , R ⁴
Are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms or a trifluoromethyl group); A substituted or unsubstituted cycloalkylidene group, a substituted or unsubstituted α, ω-alkylene group having 2 to 12 carbon atoms, a 9,9-fluorenylidene group,
1,8-menthanediyl group, 2,8-menthanediyl group, substituted or unsubstituted pyradylidene group, having 6 to 6 carbon atoms
And 24 substituted or unsubstituted arylene groups. ] 3. The electrophotographic carrier according to claim 1, wherein the resin coating layer contains a charge control agent and / or conductive particles. 4. A carrier comprising the carrier for electrophotography according to claim 1, and a toner mixed at a ratio of 2 to 40% by weight based on the total amount of the carrier and the toner. Electrophotographic developer.