JP3324383B2 - Development roll - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an electrophotographic copying machine,
It relates to a developing roll used for a printer or the like.

[0002]

2. Description of the Related Art Generally, copying by an electrophotographic copying machine is performed as follows. That is, a document image is formed as an electrostatic latent image on a photosensitive drum rotating about an axis, and toner is adhered to the image to form a toner image. Next, copying is performed by transferring the toner image to copy paper.
In this case, in order to form an electrostatic latent image on the surface of the photosensitive drum, the surface of the photosensitive drum is charged in advance, and a document image is projected on the charged portion through an optical system and irradiated with light. 2. Description of the Related Art An electrostatic latent image is formed by canceling the charge of a part. As a method for charging the surface of the photosensitive drum prior to the formation of the electrostatic latent image, recently, a roll charging method for charging the surface of the photosensitive drum by directly contacting a charging roll with the surface of the photosensitive drum has been adopted. . Further, as a method of forming a toner image on the electrostatic latent image formed on the surface of the photosensitive drum in this manner, a method using a developing roll (contact developing method) is employed. That is, toner adheres to the surface of the frictionally charged developing roll, and the toner flies from the developing roll toward the electrostatic latent image on the surface of the photosensitive drum, thereby forming a toner image on the surface of the photosensitive drum. This toner image is
The copy is performed by being fixed on the copy paper.

As shown in FIG. 3, the developing roll 4 generally has a cylindrical or solid conductive shaft 14 (in the figure, a cylindrical sleeve 12 and an end cap 13 for closing the openings at both ends thereof). Is formed) and a conductive resin layer 15 formed on the outer peripheral surface thereof. For example, in a tank in which a coating liquid composed of a material for forming the conductive resin layer 15 is stored. , The cylindrical sleeve 1
2 is repeatedly immersed and dried, and is obtained by fitting and fixing the end caps 13 in the openings at both ends.

As the developing roll used in the electrophotographic copying machine, for example, a low-hardness conductive polyurethane roll obtained by reacting a polyol in which a conductive material such as a conductive whisker is mixed with a polyisocyanate is used. It has been proposed (JP-A-3-187732, JP-A-5-323777).

[0005]

In such a developing roll, it is important to uniformly and surely apply the toner to the entire outer peripheral surface thereof and to transport the toner to the photosensitive drum in order to obtain a high-quality image. Has become. That is, in general, a developing roll has a conductive property that frictionally charges the toner to the opposite polarity to the toner in order to attach the toner to the roll surface and transport the toner to the developing area. Preventing the toner from adhering to the roll surface is required as an important characteristic. However, although the developing roll as described above is set to have a low hardness so as not to damage the contacting photoconductor (photosensitive drum), it is necessary to prevent the toner from adhering to the surface of the developing roll. However, it is not satisfactory in that it has good toner transportability. That is, in the conventional developing roll, the initial image characteristics tend to decrease as the number of images output by using a copying machine increases.

The present invention has been made in view of such circumstances, and has as its object to provide a developing roll capable of preventing toner from adhering and providing good image characteristics for a long period of time.

[0007]

To achieve the above object, according to an aspect of the present onset Ming, a roll more or two or more layers to the outer periphery of the shaft body is formed, most of the layers The developing roll in which the outer layer is formed of the following (β) and a polymer material (α) containing a charge controlling agent is used as the first layer.
It shall be the subject matter of the present invention.

(Α) A repeating unit (A) represented by the following general formula (A), a repeating unit (B) represented by the following general formula (B), and a repeating unit represented by the following general formula (C) Represented by the repeating unit (C), wherein the repeating unit (A)
A polycarbonate copolymer in which the content of each of the repeating unit (B) and the repeating unit (C) is set so as to satisfy all of the following formulas (1), (2) and (3).

[0009]

Embedded image [In the above formula (A), R ₁ , R ₂ , R ₃ , R ₄ , R
₅ and R ₆ are an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a substituted aryl group having 6 to 12 carbon atoms, or a C _{6 to} 12 And may be the same or different from each other. Also, R ₇ and R
₈ is a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a substituted aryl group having 6 to 12 carbon atoms or an unsubstituted aryl group having 6 to 12 carbon atoms, They may be the same or different. A is an integer of 0 to 4, and b is an integer of 0 to 4. X
Is a substituted alkylene group having 1 to 6 carbon atoms or 1 to 6 carbon atoms.
6 unsubstituted alkylene groups, wherein n is an integer of 1 to 6. Further, p is a positive number, q is 0 or a positive number, p
+ Q is less than 200. ]

Embedded image

Embedded image [In the above formula (C), Y is a single bond, -O-, -C
O -, - S -, - SO -, - SO 2 -, - CR 11 R 12 -
(However, R ₁₁ and R _{12 each} represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, A substituted or unsubstituted aryl group having 6 to 12 carbon atoms, which may be the same or different from each other.), A substituted cycloalkylidene group having 5 to 11 carbon atoms, An unsubstituted cycloalkylidene group, an α, ω-alkylene group having 2 to 10 carbon atoms or a fluorenylidene group, which may be the same or different. R ₉ and R _{10 each} represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or a substituted aryl group having 6 to 12 carbon atoms. Alternatively, it is an unsubstituted aryl group having 6 to 12 carbon atoms, which may be the same or different. And c is an integer of 0 to 4 and d is 0 to
4 is an integer. However, R ₁₁ and R ₁₂ are not simultaneously a methyl group, and c and d are not simultaneously 0. ]

[0010]

[Expression 7] 0.5 ≦ (A) / [(A) + (B) + (C)] ≦ 0.9 (1)

0 ≦ (B) / [(A) + (B) + (C)] ≦ 0.5 (2)

0 ≦ (C) / [(A) + (B) + (C)] ≦ 0.5 (3) [In the expressions (1), (2) and (3), (A)
Is the content of the repeating unit (A), (B) is the content of the repeating unit (B), and (C) is the content of the repeating unit (C). However, (A) + (B) + (C) = 1. (Β) A conductive agent having a particle size of 0.01 to 0.5 μm.

Further , one or two or more layers may be provided on the outer periphery of the shaft body.
Is a roll on which the layers of
The outermost layer is made of the above (β) and charcoal having a particle size of 0.5 to 20 μm.
Formed from the above polymer material (α) containing elementary particles
The developed roll is referred to as a second gist.

That is, the present invention provides a series of researches for obtaining a developing roll capable of maintaining a good image characteristic by preventing a toner from adhering to the roll surface for a long period of time. Stacked. As a result, when the outermost surface of the developing roll is formed using a polycarbonate copolymer, which is a special polymer material containing a conductive agent (β) having a specific particle size, the polycarbonate copolymer becomes a toner. , The occurrence of toner filming can be prevented. Moreover, by using the conductive agent (β) having the above specific particle size, the conductive agent exerts a static elimination effect, controls the roll conductivity, and realizes better image characteristics. Heading reached the present invention.

Further, the above polycarbonate copolymer is
By blending the charge controlling agent together with the conductive agent (β) having the above specific particle diameter, the chargeability of the toner of the roll itself can be improved, and the required characteristics of the developing roll can be satisfied.

Further, the above-mentioned polycarbonate copolymer is blended with the conductive agent (β) having the above-mentioned specific particle size and carbon-based particles having a large particle size of 0.5 to 20 μm to form a roll surface. Can be set to a predetermined roughness, and good toner transportability can be provided.

[0015]

Next, an embodiment of the present invention will be described.

As an example of the developing roll of the present invention, as shown in FIG. 1, an innermost layer 21 is formed along the outer periphery of a conductive shaft 14 comprising a cylindrical sleeve 12 and end caps 13 closing both ends thereof. The intermediate layer 22 is formed on the outer peripheral surface, and the outermost layer 23 is formed on the outer peripheral surface.

As the conductive shaft 14, any conventionally known conductive shaft may be used. For example, a metal core made of a solid metal body may be used in addition to the hollow metal cylinder shown in FIG. And, as the metal material, aluminum, stainless steel and the like can be mentioned.

The material for forming the innermost layer 21 formed on the outer periphery of the shaft body 14 and the intermediate layer 22 formed on the outer peripheral surface thereof is not particularly limited, either. Is also good. For example, as the material for forming the innermost layer 21, ethylene-propylene-diene rubber (EPDM), styrene-butadiene rubber (SBR),
Examples thereof include those obtained by blending carbon black with silicone rubber, polyurethane-based elastomer, or the like.

The material for forming the intermediate layer 22 includes:
For example, EPDM, SBR, nitrile rubber, hydrogenated nitrile rubber, polyurethane elastomer, polyester, N-methoxymethylated nylon, carbon black, metal oxide, quaternary ammonium salt, borate, lithium perchlorate, etc. And a mixture of the above conductive agents. A conventionally known method is also applied to the method for preparing each of the materials for forming the innermost layer 21 and the intermediate layer 22. To give an example, first, a material (compound-like) for forming the innermost layer 21 can be prepared by kneading the above components with a kneading machine such as a kneader. The material for forming the intermediate layer 22 (coating liquid) can be prepared by kneading the above components with a ball mill or a roll, adding a solvent to the mixture, and mixing and stirring.

The outermost layer 23 formed on the outer peripheral surface of the intermediate layer 22 is formed using a special polymer material (α) containing a conductive agent (β) having a specific particle size.

The special polymer material (α) includes a repeating unit (A) represented by the following general formula (A) and a repeating unit (B) represented by the following general formula (B): A polycarbonate copolymer comprising a repeating unit (C) represented by the following general formula (C), and the polycarbonate copolymer has toner non-adhesiveness.

[0022]

Embedded image [In the above formula (A), R ₁ , R ₂ , R ₃ , R ₄ , R
₅ and R ₆ are an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a substituted aryl group having 6 to 12 carbon atoms, or a C _{6 to} 12 And may be the same or different from each other. Also, R ₇ and R
₈ is a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a substituted aryl group having 6 to 12 carbon atoms or an unsubstituted aryl group having 6 to 12 carbon atoms, They may be the same or different. A is an integer of 0 to 4, and b is an integer of 0 to 4. X
Is a substituted alkylene group having 1 to 6 carbon atoms or 1 to 6 carbon atoms.
6 unsubstituted alkylene groups, wherein n is an integer of 1 to 6. Further, p is a positive number, q is 0 or a positive number, p
+ Q is less than 200. ]

[0023]

Embedded image

[0024]

Embedded image [In the above formula (C), Y is a single bond, -O-, -C
O -, - S -, - SO -, - SO 2 -, - CR 11 R 12 -
(However, R ₁₁ and R _{12 each} represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, A substituted or unsubstituted aryl group having 6 to 12 carbon atoms, which may be the same or different from each other.), A substituted cycloalkylidene group having 5 to 11 carbon atoms, An unsubstituted cycloalkylidene group, an α, ω-alkylene group having 2 to 10 carbon atoms or a fluorenylidene group, which may be the same or different. R ₉ and R _{10 each} represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or a substituted aryl group having 6 to 12 carbon atoms. Alternatively, it is an unsubstituted aryl group having 6 to 12 carbon atoms, which may be the same or different. And c is an integer from 0 to 4;
4 is an integer. However, R ₁₁ and R ₁₂ are not simultaneously a methyl group, and c and d are not simultaneously 0. ]

In the polycarbonate copolymer comprising the repeating unit (A), the repeating unit (B) and the repeating unit (C), the repeating unit (A), the repeating unit (B) and the repeating unit (C) Must satisfy all the relationships of the following formulas (1), (2) and (3).

[0026]

[Expression 10] 0.5 ≦ (A) / [(A) + (B) + (C)] ≦ 0.9 (1)

0 ≦ (B) / [(A) + (B) + (C)] ≦ 0.5 (2)

0 ≦ (C) / [(A) + (B) + (C)] ≦ 0.5 (3) [In the equations (1), (2) and (3), (A)
Is the content of the repeating unit (A), (B) is the content of the repeating unit (B), and (C) is the content of the repeating unit (C). However, (A) + (B) + (C) = 1. ]

That is, based on the total weight of the repeating unit (A), the repeating unit (B) and the repeating unit (C),
The repeating unit (A) is set in the range of 50 to 90% by weight (hereinafter abbreviated as "%"). Preferably it is 50-80%. If the content of the repeating unit (A) is less than 50%, the elastic modulus of the polycarbonate copolymer is too high, which may adversely affect the photosensitive drum. If it exceeds 90%, the softening temperature of the polycarbonate copolymer decreases. However, this is because the mechanical strength of the surface protective layer becomes insufficient.

Therefore, the total content of the repeating unit (B) and the repeating unit (C) is 10 to 50 with respect to the total weight of the repeating unit (A), the repeating unit (B) and the repeating unit (C). %.
Preferably it is 20 to 50%.

The content of each of the repeating unit (B) and the repeating unit (C) is 0 to 50 with respect to the total weight of the repeating unit (A), the repeating unit (B) and the repeating unit (C). Set to%. Preferably 5 each
~ 35%. However, in this case, the total content of the repeating unit (B) and the repeating unit (C) is, as described above, the repeating unit (A) and the repeating unit (B).
And 10 to 50 with respect to the total weight of the repeating unit (C).
%.

The weight ratio of the repeating unit (B) to the repeating unit (C) is not particularly limited. However, by increasing the weight ratio of the repeating unit (C), the repeating unit (C) can be used for coating at the time of forming the outermost layer. It is possible to improve the solubility in a solvent and the heat resistance.

The polycarbonate copolymer may be linear, branched, or cyclic. Further, the above-mentioned polycarbonate copolymer may contain each of the repeating unit (A), the repeating unit (B) and the repeating unit (C) by one kind alone, or may contain two or more kinds. Further, a mixture of polycarbonate copolymers composed of different repeating units may be used.

Incidentally, the above polycarbonate copolymer is:
As long as the object of the present invention is not hindered, the mixture may have other repeating units other than those described above, or may be a mixture in which other polycarbonate components and additives are appropriately added and blended.

The polycarbonate copolymer used in the present invention has a concentration of 0.5 g / methylene chloride as a solvent.
dl solution at 20 ° C. [η _sp / c]
0.1-3.0 dl / g, preferably 0.3-2.0 d
1 / g. That is, the reduced viscosity is 0.1 dl
If it is less than / g, the mechanical strength of the outermost layer may be low. If it exceeds 3.0 dl / g, the solution viscosity and the melt viscosity of the polycarbonate copolymer may be high, and the workability in forming the outermost layer may be remarkable. May drop.

In the repeating unit (A) of the polycarbonate copolymer represented by the general formula (A), preferred examples of R _{1 to} R ₆ include a methyl group, an ethyl group and a phenyl group. Preferred examples of the structure of the two phenylene groups in the repeating unit (A) include a substituent R ₇
And those without R ₈ , ie, a and b are 0
And the like. X is preferably, for example, an ethylene group, a trimethylene group or the like. The number of repetitions n of X is preferably 1.

Further, p + q, which indicates the degree of polymerization of the polysiloxane unit in the repeating unit (A), is closely related to the composition ratio of the polycarbonate copolymer, and it is difficult to unambiguously define it. Below, preferably 20
~ 50. That is, when p + q exceeds 200,
This is because when the polycarbonate copolymer is used, the mechanical strength of the outermost layer may decrease.

Preferred examples of the repeating unit (A) include those of the following structural formulas.

[0037]

Embedded image

Preferred examples of R ₉ and R _{10 in} the repeating unit (C) represented by the general formula (C) include a methyl group and a phenyl group.
Further, a repeating unit (C) in which at least one of c and d indicating the number of repetitions of R ₉ and R ₁₀ is 0, that is, a repeating unit in which at least one of two phenylene groups has no substituent is also mentioned as a preferable example. Can be Further, R
The substitution positions of ₉ and R ₁₀ are preferably each located at the meta position with respect to Y.

Preferred examples of Y in the repeating unit (C) include an isopropylidene group, a hexafluoroisopropylidene group, a diphenylmethylene group, a 1-phenylethylidene group, a cyclohexylidene group, a single bond and the like .

Preferred examples of the repeating unit (C) include those of the following structural formulas.

[0041]

Embedded image

The polycarbonate copolymer is, for example, a dihydroxy compound (a) represented by the following general formula (a) and a 2,2-bis (4-hydroxy compound represented by the following general formula (b): It can be produced by reacting at least one of phenyl) propane and a dihydroxy compound (b) represented by the following general formula (c) with a carbonate-forming compound.

[0043]

Embedded image [In the above formula (a), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R
_6, R ₇ and _{R 8, b, X, n} , p, q are the same as the general formula (A). ]

[0044]

Embedded image

[0045]

Embedded image [In the above formula (c), Y, R ₉ and R ₁₀ , c and d are the same as those in the general formula (C). ]

This reaction is carried out using various carbonyl halides such as phosgene as a carbonate-forming compound, haloformates such as a chloroformate compound or a carbonate compound in the presence of a suitable acid-binding agent. It is carried out by a method such as performing a polycondensation reaction, or performing a transesterification reaction using bisaryl carbonates as the carbonate-forming compound.

Specific examples of each of R _{1 to} R _{6 in} the general formulas (A) and (a) include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n
-Butyl group, 1-methylpropyl group, 2-methylpropyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, heptyl group, octyl group, nonyl group, decyl Group,
Undecyl group, dodecyl group, cyclohexyl group, phenyl group, tolyl group, xylyl group, trimethylphenyl group,
Examples include an ethylphenyl group, a naphthyl group, a methylnaphthyl group, a biphenylyl group and the like.

Specific examples of R ₇ and R ₈ include, for example, fluorine atom, chlorine atom, bromine atom,
Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, 1-methylpropyl group, 2-methylpropyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl Groups, isohexyl, cyclohexyl, phenyl, tolyl, xylyl, trimethylphenyl, ethylphenyl, naphthyl, methylnaphthyl, biphenylyl and the like.

Specific examples of X include, for example, a butylene group such as a methylene group, an ethylene group, a propylene group, a trimethylene group and a tetramethylene group, a heptylene group such as a heptamethylene group, and a hexylene group such as a hexamethylene group. Is raised.

As the dihydroxy compound (a) represented by the general formula (a), for example, a compound having the following structural formula is preferably used. These dihydroxy compounds (a) may be used alone or in combination of two or more.

[0051]

Embedded image

Examples of the dihydroxy compound (c) represented by the general formula (c) include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, and 1,2-bis (4-hydroxyphenyl) ethane, 2,2-bis (3-methyl-4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 4,4-bis (4-hydroxyphenyl) heptane, 1,1-bis (4-hydroxyphenyl) -1,1-diphenylmethane, , 1-bis (4-hydroxyphenyl) -1-phenylethane,
1,1-bis (4-hydroxyphenyl) -1-phenylmethane, bis (4-hydroxyphenyl) ether,
Bis (4-hydroxyphenyl) sulfide, bis (4
-Hydroxyphenyl) sulfone, 1,1-bis (4-
Hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-
Bis (3-methyl-4-hydroxyphenyl) propane, 2- (3-methyl-4-hydroxyphenyl) -2
-(4-hydroxyphenyl) -1-phenylmethane,
Bis (3-methyl-4-hydroxyphenyl) sulfide, bis (3-methyl-4-hydroxyphenyl) sulfone, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, bis (3-methyl-4 -Hydroxyphenyl) methane, 1,1-bis (2-butyl-4)
-Hydroxyphenyl) butane, 2,2-bis (2-methyl-4-hydroxyphenyl) propane, 1,1-bis (2-tert-butyl-4-hydroxy-3-methylphenyl) ethane, 1,1- Bis (2-tert-butyl-4-hydroxy-5-methylphenyl) propane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) butane, 1,1-bis (2
-Tert-butyl-4-hydroxy-5-methylphenyl) isobutane, 1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) heptane,
1,1-bis (2-tert-butyl-4-hydroxy-5-methylphenyl) -1-phenylmethane, 1,1
-Bis (2-tert-amyl-4-hydroxy-5-
Methylphenyl) butane, bis (3-chloro-4-hydroxyphenyl) methane, bis (3,5-dibromo-4)
-Hydroxyphenyl) methane, 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 (3,5-difluoro-4)
-Hydroxyphenyl) propane, 2,2-bis (3,
5-dichloro-4-hydroxyphenyl) propane,
2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (3-bromo-4-hydroxy-5-chlorophenyl) propane, 2,2-bis (3,5-dichloro -4-hydroxyphenyl) butane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) butane, 1-phenyl-1,1-bis (3-
Fluoro-4-hydroxyphenyl) ethane, bis (3
-Fluoro-4-hydroxyphenyl) ether, 1,
1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxybiphenyl, 4,4'-dihydroxy-3,3'-dimethylbiphenyl, 4,4'-dihydroxy-2,2'- Dimethylbiphenyl, 4,4'-dihydroxy-3,3'-dicyclohexylbiphenyl, 3,3'-difluoro-4,
4'-dihydroxybiphenyl, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 1,1-bis (3-phenyl- 4-hydroxyphenyl) cyclohexane, bis (3-phenyl-4-hydroxyphenyl) sulfone, 4,4'-dihydroxybenzophenone, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 9,9-bis (4 -Hydroxyphenyl) fluorene and the like. These dihydroxy compounds (c) are used alone or in combination of two or more.

Among the above dihydroxy compounds (c), particularly preferred are, for example, 1,1-bis (4-hydroxyphenyl) -1,1-diphenylmethane, 1,1-bis (4-hydroxyphenyl)- 1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-methyl-4-
Hydroxyphenyl) propane, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 4,
4'-dihydroxybiphenyl, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-
Bis (4-hydroxyphenyl) hexafluoropropane is mentioned.

The carbonic acid ester forming compounds include:
The reaction of performing polycondensation using a carbonyl dihalide, a haloformate, a carbonate compound or the like in the presence of an acid binder is usually performed in a solvent.

The use ratio of the above-mentioned carbonate-forming compound is appropriately set in consideration of the reaction stoichiometry (equivalent ratio). When a gaseous carbonate-forming compound such as phosgene is used, a method of blowing it into the reaction system is preferable.

Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide.
Examples thereof include alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof.

The proportion of the acid bond used is also appropriately set in consideration of the reaction stoichiometry (equivalent ratio), similarly to the above-mentioned carbonate-forming compound. Specifically, two equivalents or a slight excess of the acid binder relative to the total number of moles of the dihydroxy compounds (a), (b), and (c) used (normally, one mole corresponds to two equivalents) It is preferable to use

The solvent is not particularly limited as long as it is used for producing a known polycarbonate. Specific examples include hydrocarbon solvents such as xylene and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. These may be used alone or in combination of two or more. In addition, interfacial polycondensation may be performed using two different solvents that do not dissolve each other.

In order to promote the polycondensation reaction, a catalyst such as a tertiary amine such as triethylamine or a quaternary ammonium salt is used.
It is preferable to carry out the reaction by adding a molecular weight regulator (terminal terminator). Also, if necessary, sodium sulfite,
A small amount of an antioxidant such as hydrosulfide may be added. The reaction is usually performed at 0 to 150 ° C, preferably 5 to 4 ° C.
It is performed at a temperature in the range of 0 ° C. The reaction pressure may be any of reduced pressure, normal pressure, and pressurized pressure. Usually, the reaction is preferably performed at normal pressure or about the self-pressure of the reaction system. The reaction time is appropriately set depending on the reaction temperature and the like, but is usually about 0.5 minute to 10 hours, preferably about 1 minute to 2 hours.

First, a dihydroxy compound (a),
A two-step method is used in which a part of the reaction raw materials composed of (b) and (c) is reacted with a carbonate-forming compound to form an oligomer, and then the remaining reaction raw materials are added to complete the polycondensation. You can also. According to such a two-step method, the control of the reaction is easy and the molecular weight can be controlled with high accuracy.

In the case of using the transesterification of the above dihydroxy compounds (a), (b) and (c) with bisaryl carbonate, the reaction may be carried out by a melt polycondensation method,
Solid phase polycondensation method and the like can be mentioned. When performing the above-mentioned melt polycondensation method, the above-mentioned monomers are mixed and reacted in a molten state at a high temperature under reduced pressure. The reaction is usually 150-350
C., preferably at a temperature in the range of 200 to 300C. When the above solid phase polycondensation method is performed, the above monomers are mixed, and the mixture is heated in a solid state to a temperature equal to or lower than the melting point of the produced polycarbonate copolymer to perform polycondensation. In any case, at the final stage of the reaction, the degree of reduced pressure is preferably set to 1 mmHg or less, and phenols derived from the bisaryl carbonate generated by the transesterification are distilled out of the system. The reaction time depends on the reaction temperature and the degree of pressure reduction, but is usually about 1 to 4 hours. The reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon. If necessary, the above-mentioned molecular weight regulator, antioxidant and the like may be added.

To set the reduced viscosity [η _sp / c] of the obtained polycarbonate copolymer in the above range, for example, selection of the reaction conditions, adjustment of the amount of the terminal terminator,
It can be achieved by various methods such as adjusting the amount of the branching agent used. In some cases, the obtained polycarbonate copolymer is appropriately subjected to at least one of a physical treatment (mixing, fractionation, etc.) and a chemical treatment (polymer reaction, cross-linking treatment, partial decomposition treatment, etc.) to obtain a desired product. It is a reduced viscosity polycarbonate copolymer.

Examples of the terminal stopper include phenol, α
-Naphthol, β-naphthol, o-methylphenol, m-methylphenol, p-methylphenol, p
-Ethylphenol, p-propylphenol, p-butylphenol, p- (t-butyl) phenol, p-
Phenylphenol, o-chlorophenol, m-chlorophenol, p-chlorophenol, o-bromophenol, m-bromophenol, p-bromophenol, o-methoxyphenol, m-methoxyphenol, p-methoxyphenol, p- Ethoxyphenol, o-aminophenol, m-aminophenol, p
-Aminophenol, p-cyanophenol, p-nitrophenol, p- (perfluorononyl) phenol, p- (perfluorohexyloxy) phenol,
p- (perfluorobutyl) phenol, 4-verfluorodecyl-2,3,5,6-tetrafluorophenol, 3-methyl-4- (perfluorononyl) phenol, p- (2-1H, 1H-per Fluorotridecyloxy-1,1,1,3,3,3-hexafluoro-2-
Propyl) phenol, 3,5-bis (perfluorohexyloxycarbonyl) phenol, p-1H, 1H
-Perfluorooctyloxyphenol, perfluorodecyl p-hydroxybenzoate, (p-hydroxybenzyl) perfluorodecane, 2H, 2H, 9H-perfluorononane and the like.

The conductive agent (β) contained in the above polycarbonate copolymer has a particle size of 0.01 to 0.5 μm.
Is used. Specifically, c-TiO ₂ , c-ZnO, carbon black, c-SnO ₂ , iron oxide, potassium titanate, and the like set to the above particle diameters can be mentioned. These conductive agents are used alone or in combination of two or more. Above all, c-ZnO, c-TiO ₂ , c-SnO ₂
It is preferable to use Here, “c−” means having conductivity. That is, since the charge stays with the use of the developing roll, it becomes possible to control the conductivity by blending the above-mentioned conductive agent (β) and set an appropriate charging range. It is preferable to set the electric resistance of the outermost layer in the range of 1 × 10 ² to 8 × 10 ¹¹ Ω · cm, more preferably 5 × 10 ^{8 to} 5 by the combination of the conductive agent (β).
× 10 ¹⁰ Ω · cm.

The content of the conductive agent (β) is 100 parts by weight of the polycarbonate copolymer (hereinafter abbreviated as “parts”).
Is preferably set to 5 to 250 parts, more preferably 5 to 180 parts. That is, if the content of the conductive agent (B) is less than 5 parts, the effect of imparting conductivity cannot be obtained, and if it exceeds 250 parts, the polycarbonate copolymer tends to be hard and brittle. .

Further, in the first aspect of the present invention,
Is a polymer material (alpha) which is the outermost layer formation material, the conductive agent with (beta), Ru contain a charge control agent. By including the charge control agent, the toner charging property of the developing roll can be improved, and one of the required characteristics of the developing roll can be satisfied. As the charge control agent, specifically, quaternary ammonium salts, borates,
Examples thereof include azine-based (nigrosine-based) compounds, azo compounds, oxynaphthoic acid-based metal complexes, and surfactants (anionic, cationic, and nonionic). These charge control agents may be used alone or in combination of two or more.

The content of the charge control agent is preferably set to 0.01 to 5 parts, more preferably 1 to 3 parts, based on 100 parts of the polycarbonate copolymer. That is, when the content of the charge control agent is less than 0.01 part, the effect on the toner chargeability is small, and when the content exceeds 5 parts,
This is because there is a tendency that tackiness appears or physical properties are inferior.

According to a second aspect of the present invention , the polymer material (α), which is the outermost layer forming material, contains carbon-based particles having a large particle diameter together with the conductive agent (β).
You . The carbon-based particles have a particle size of 0.5 to 20 μm.
That it is set in a range of Ru was found using. More preferably, the particle size is 1 to 10 μm. By including the carbon-based particles, it is possible to form the outermost layer of the roll to a desired surface roughness. That is, the carbon-based particles are used to form the outermost layer of the developing roll to a desired surface roughness. FIG. 2 is a schematic cross-sectional view of a developing roll surface formed using the polymer material (α) containing the carbon-based particles together with the conductive agent (β). Thus, the conductive agent (β) having a small particle size and the carbon-based particles 3 having a large particle size are dispersed in the polycarbonate copolymer 1 which is a matrix component. By the dispersion, the roll surface is formed to have a desired surface roughness. It is not preferable to use, for example, particles having an insulating property instead of the carbon-based particles having a conductive property, since the developing roll becomes excessively charged. Therefore, in the present invention, the above-described large-diameter carbon-based particles having conductivity are used as the particles contained for forming the surface roughness.

The surface of the outermost layer of the developing roll formed by using the carbon-based particles has a surface roughness (Ra).
Is preferably formed on a rough surface having fine irregularities so as to be 0.3 to 0.9 μm. Particularly preferably, the surface roughness (Ra)
0.4 to 0.6 μm. By setting such surface roughness, good toner transportability can be obtained. The surface roughness (Ra) is in accordance with JIS B 0
601-1982 is the center line average roughness (Ra) shown by the definition and display of the surface roughness. The surface roughness (Ra) is measured using a stylus electric magnifying surface roughness measuring device (JIS B 0605-1994).

Specific examples of the carbon-based particles include those produced by baking a thermosetting resin such as a phenol resin in a reducing gas atmosphere, coal tar, coal tar pitch, petroleum heavy oil, and the like. 350-50 bitumen
Small spheres produced by heating at 0 ° C., those obtained by plating plastic fine particles, natural graphite, artificial graphite and the like can be mentioned. These carbon-based particles may be used alone or in combination of two or more.

The content of the carbon-based particles is preferably set to 1 to 30 parts, more preferably 2 to 15 parts, based on 100 parts of the polycarbonate copolymer.
That is, if the content of the carbon-based particles is less than 1 part, the surface of the coating film cannot be roughened, and if it exceeds 30 parts, the electrical resistance sharply decreases, which tends to cause leakage, decrease in physical properties, and increase in hardness. Because it can be done.

In the present invention, the polymer material (α), which is the outermost layer forming material, contains both the above-mentioned charge controlling agent and the carbon-based particles having a large particle diameter together with the above-mentioned conductive agent (β). You may make it contain. As described above, by using both the charge control agent and the carbon-based particles having a large particle diameter, the effect of improving the toner charging property of the developing roll can be obtained,
The roll surface can be formed to have a desired surface roughness, and a desired amount of appropriately charged toner can be sent to the photoreceptor. In this case, the contents of the charge control agent and the carbon-based particles having a large particle diameter are the same as the above-mentioned set amounts.

In the present invention, the polymer material (α), which is the outermost layer forming material, may be filled together with the conductive agent (β), the charge controlling agent, and the carbon-based particles having a large particle size, if necessary. Agents, stabilizers, ultraviolet absorbers, antistatic agents, reinforcing agents, lubricants, release agents, dyes, pigments, flame retardants, oils, and the like can be appropriately blended.

Next, the outermost layer forming material of the developing roll used in the present invention can be prepared by using the above-mentioned materials, for example, by the following method.

That is, first, the polycarbonate copolymer is kneaded in an internal mixer (for example, a Banbury mixer). To this, the above-mentioned conductive agent (β), and further, if necessary, a charge control agent and large-sized carbon-based particles are added,
Continue kneading. This kneaded material is dissolved in a solvent to prepare a coating solution. Examples of the solvent include tetrahydrofuran, ethyl acetate, methyl ethyl ketone, methanol, toluene, isopropyl alcohol, methyl cellosolve, dimethylformamide and the like. These may be used alone or in combination of two or more.

The outermost layer forming material of the developing roll can be produced by the following method in addition to the above-mentioned method.

That is, first, the polycarbonate copolymer is dissolved in a solvent. This solvent is the same as described above. Then, the conductive agent (β), a charge controlling agent and carbon-based particles having a large particle diameter are blended in the dissolved polycarbonate copolymer according to the purpose, and dispersed by a ball mill or the like. Then, a coating liquid is prepared by stirring.

Next, the developing roll of the present invention as shown in FIG. 1 is produced, for example, as follows.

That is, first, using the materials for forming the innermost layer 21 and the intermediate layer 22 prepared as described above, the shaft is formed in accordance with a conventional method (a die forming method, a dipping method, a spraying method, a roll coating method, etc.). An innermost layer 21 and an intermediate layer 22 are formed on the outer periphery of the body 14 in this order to produce a roll base.

On the other hand, the material for forming the outermost layer of the developing roll (coating solution) is prepared, and the intermediate layer 22 of the roll base is prepared.
Is coated with the above coating liquid. This coating method is not particularly limited, and a conventional method such as a dipping method, a spray method, and a roll coating method can be applied. Then, after coating, drying and heat treatment (conditions: 60
To 170 ° C.) to evaporate and remove the solvent in the coating liquid. In this manner, a developing roll having a three-layer structure as shown in FIG. 1 can be manufactured. In this developing roll, the thickness of each layer is appropriately determined. For example, the thickness of the innermost layer 21 is preferably set in a range of 2 to 10 mm, and particularly preferably 3 mm.
６6 mm. The thickness of the intermediate layer 22 is 1 to 90.
The thickness is preferably set in the range of μm, particularly preferably 5 to 10 μm. The thickness of the outermost layer 23 is preferably set to 10 to 100 μm, and particularly preferably 20 to 50 μm.

The electric resistance of the outermost layer 23 is preferably set in the range of 1 × 10 ² to 8 × 10 ¹¹ Ω · cm, more preferably 5 × 10 ^{8 to} 5 ×, as described above.
10 ¹⁰ Ω · cm.

Further, as an example of the developing roll of the present invention,
Although the three-layer structure shown in FIG. 1 has been described, the layers formed on the outer periphery of the shaft body 14 are not necessarily three layers, and are formed in an appropriate number of layers. However, the outermost layer (in the case of a single layer, the layer) must be formed of the polymer material (A) containing the above specific component (the outermost layer forming material).

Next, examples will be described together with comparative examples.

First, prior to the Examples and Comparative Examples, a core bar [diameter 10 mm, stainless steel (SUS30)
4))), a material obtained by adding carbon black to liquid silicone rubber as an innermost layer forming material, and a material obtained by adding carbon black to hydrogenated nitrile rubber as an intermediate layer forming material were prepared.

Then, an innermost layer and an intermediate layer were formed on the outer periphery of the shaft body according to the above-mentioned method to prepare a roll base.

Next, two types of polycarbonate copolymers A and B were prepared.

[Preparation of Polycarbonate Copolymer A] As a raw material monomer, 59.3 g of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) was used.
(0.26 mol) was dissolved in 550 ml of an 8% aqueous sodium hydroxide solution. The resulting solution and 250 ml of methylene chloride were introduced into a baffled reactor, and phosgene gas was introduced at 950 m
Blowing was performed at a rate of 1 / min for 15 minutes. After allowing the reaction solution to stand, the organic layer was separated to obtain a methylene chloride solution of an oligomer of bisphenol A having a degree of polymerization of 2 to 4 and a molecular terminal having a chloroformate group.

To this oligomer solution, 129.6 g (0.036 mol) of a dihydroxy compound represented by the following structural formula and 205 ml of methylene chloride were introduced into a baffled reactor, and the mixture was stirred at about 10 ° C. A homogeneous solution was obtained.

[0089]

Embedded image

Next, 0.15 g of p-tert-butylphenol as a terminal stopper and 1,1-bis (4-hydroxyphenyl) -1,1-diphenylmethane (bisphenol T) as a post-addition monomer were added to the obtained solution.
P) 150 ml of an 8% aqueous sodium hydroxide solution in which 4.22 g (0.012 mol) was dissolved and 5 ml of a 10% aqueous triethylamine solution were added, and the mixture was maintained at about 10 ° C. and vigorously stirred to carry out a polycondensation reaction. After completion of the reaction, the organic layer was diluted by adding 1 liter of methylene chloride, washed with water, diluted hydrochloric acid and water in that order, and then poured into methanol to obtain 154.5 g of a polycarbonate copolymer.

The concentration of the thus obtained polycarbonate copolymer in methylene chloride as a solvent was 0.5 g / d.
The reduced viscosity [η _sp / c] at 20 ° C. of the 1
It was 78 dl / g, and it was confirmed by < ¹ > H-NMR spectrum analysis that it consisted of the following repeating units.

[0092]

Embedded image

The content of the repeating unit containing the polydimethylsiloxane structure in the above polycarbonate copolymer was 64% by weight, the content of the repeating unit having the bisphenol A structure was 33% by weight, and the content of the bisphenol TP structure was 33% by weight. The content of the repeating unit was 3% by weight.

[Preparation of Polycarbonate Copolymer B] 63.8 g of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) as a raw material monomer
(0.28 mol) and 2,2-bis (3-phenyl-
4-hydroxyphenyl) propane (bisphenol P
H) 7.6 g (0.02 mol) was dissolved in 550 ml of a 6% aqueous potassium hydroxide solution. The resulting solution and 250 ml of methylene chloride were introduced into a baffled reactor,
Phosgene gas was blown in at a rate of 950 ml / min for 15 minutes while vigorously stirring at about 0 ° C. After allowing this reaction solution to stand, the organic layer was separated and the degree of polymerization was 2-4.
And the composition ratio of the bisphenol A structure having a chloroformate group at the molecular end to the bisphenol PH structure is about 10:
A methylene chloride solution of the co-oligomer 1 was obtained.

To this co-oligomer solution, 124.4 g (0.04 mol) of a dihydroxy compound represented by the following structural formula and 400 ml of methylene chloride were introduced into a baffled reactor, and the mixture was maintained at about 10 ° C. and stirred. Thus, a uniform solution was obtained.

[0096]

Embedded image

Then, 0.15 g of p-tert-butylphenol, 250 ml of an 8% aqueous potassium hydroxide solution and 5 ml of a 10% aqueous triethylamine solution were added to the obtained solution as a terminal stopper, and the mixture was vigorously stirred at about 10 ° C. To carry out a polycondensation reaction. After completion of the reaction, the organic layer was diluted by adding 1 liter of methylene chloride, washed with water, diluted hydrochloric acid and water in that order, and then poured into methanol to obtain 165.5 g of a polycarbonate copolymer.

The thus obtained polycarbonate copolymer had a concentration of 0.5 g / d using methylene chloride as a solvent.
The reduced viscosity [η _sp / c] at 20 ° C. of the 1
It was 69 dl / g, and it was confirmed by ¹ H-NMR spectrum analysis that it consisted of the following repeating units.

[0099]

Embedded image

The content of the repeating unit containing the polydimethylsiloxane structure in the above polycarbonate copolymer was 61% by weight, the content of the repeating unit having the bisphenol A structure was 33% by weight, and the content of the bisphenol PH structure was 33% by weight. The content of the repeating unit was 6% by weight.

[0101]

Examples 1 to 15 The outermost layer was formed on the outer peripheral surface of the above-mentioned roll substrate by the above-mentioned method. That is, the polycarbonate copolymers A and B produced above were kneaded using a Banbury mixer. The respective materials shown in Tables 1 and 2 below were added thereto at the ratios shown in the same table, and kneading was continued. The kneaded product was dissolved in a solvent (tetrahydrofuran / methyl ethyl ketone) to prepare a coating solution. Using this coating solution, an outermost layer was formed on the outer peripheral surface of the roll base by the above-mentioned method (coating method: roll coating method) to produce a target developing roll. The thickness of the innermost layer of the developing roll is 5 mm, the thickness of the intermediate layer is 7 μm, and the thickness of the outermost layer is 30 μm.

[0102]

[Table 1]

[0103]

[Table 2]

[0104]

Comparative Examples 1 and 2 Materials shown in Table 3 below were prepared, and rolls were manufactured using these materials. That is, as the polyol, a low-branched polyol (Nipporan N-403, manufactured by Nippon Polyurethane Industry Co., Ltd.) which is a condensation polymerization ester of diethylene glycol, trimethylolpropane, and adipic acid is used.
2, average functional group number 2.35, hydroxyl value 60) were used.
100 parts of this polyol was heated to 40 ° C., 1 part of Ketjen Black was added in Comparative Example 1, and 10 parts of titanium oxide whiskers were added in Comparative Example 2, and the mixture was premixed with a mixer, and then mixed at room temperature for 2 days. Cured. Next, this mixture was heated to 70 to 80 ° C. and kneaded with a paint roll to disperse Ketjen Black or whiskers in the polyol. The polyol composition thus obtained has a viscosity of 3000 cps at 100 ° C.

Then, the polyol composition was heated at 140 ° C.
And stirred under a reduced pressure of 10 to 20 mmHg for dehydration and drying. The temperature of the mixture was adjusted to 110 to 120 ° C., and a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., mixing ratio by weight of 80/2) was added to 100 parts of the polyol.
(0, TDI-80) and stirred vigorously for 2 minutes, then poured into a mold heated to 110 ° C. and cured for 2 hours. Thereafter, secondary crosslinking was performed at 110 ° C. for 24 hours to obtain a roll made of a low-hardness conductive polyurethane.

[0106]

[Table 3]

Examples 1 to 15 thus obtained,
For each of the developing rolls of Comparative Examples 1 and 2, the surface roughness of the outermost layer surface and the electric resistance of the outermost layer were measured. Also,
The image quality evaluation of the copied image and the occurrence of toner filming were measured and evaluated according to the following methods. The results are shown in Tables 4 to 8 below.

[Surface Roughness] For the outermost layer surface of each developing roll, the arithmetic average roughness was measured using a stylus electric magnifying surface roughness meter (JISB 0605-1994).

[Electrical Resistance] For each developing roll, the electrical resistance of the outermost layer was measured by the following method. That is, a 10 mm square electrode (with a guard) was provided on the outermost layer surface with a silver paste, and the resistance between the electrode and the shaft was measured according to the method of JIS K 6911.

[Evaluation of Image Quality of Copied Image] The developing roll was incorporated in an electrophotographic copying machine, and copying was actually performed. Then, the image quality of the copied image was visually evaluated at the beginning of copying and after copying 30,000 sheets. That is, print the characters,
A sample in which fine lines were clearly copied without any problem in the copied image was rated as "O", and a sample in which blurring or fogging occurred was rated as "x". Note that blurring refers to a thing in which a thin line is interrupted, and fogging refers to a thing in which toner has flown to a place where there is no image. When toner filming occurred, evaluation was made separately for a portion where toner filming occurred and a portion where toner filming did not occur.

[Toner Filming] In a portion where the toner is thickly attached to the surface of the developing roll, the chargeability is deteriorated, and a defective copy image occurs. Specifically, if a part of the toner component adheres to the surface of the developing roll with a thickness of 1 μm or more, the image is significantly deteriorated. Therefore, the toner adhesion is 1
The case where the thickness was equal to or more than μm was regarded as occurrence of toner filming.

[0112]

[Table 4]

[0113]

[Table 5]

[0114]

[Table 6]

[0115]

[Table 7]

[0116]

[Table 8]

From the results shown in Tables 4 to 8, all the products of the Examples were not only image quality evaluated at the initial copy, but also obtained good copy images after 30,000 copies. Obviously, a copied image free from toner filming can be obtained. On the other hand, in Comparative Examples 1 and 2, there was no problem with the image quality at the beginning of copying, but after copying 30,000 sheets, problems (fading and fogging) occurred and toner filming occurred. .

[0118]

As described above, the developing roll of the present invention
The outermost layer is formed using the specific polycarbonate copolymer containing a conductive agent (β) having a particle size of 0.01 to 0.5 μm and a charge control agent . Since the polycarbonate copolymer has non-adhesiveness to the toner, occurrence of toner filming is prevented. In addition, by using the conductive agent (β) having the above specific particle size, the conductive agent exerts a static elimination effect to control the conductivity of the roll, thereby maintaining better image characteristics.
As described above, the developing roll of the present invention can provide good image characteristics for a long period of time by preventing toner from adhering.

Further, the above polycarbonate copolymer is
By blending a charge control agent together with the conductive agent (β) having the specific particle size, the chargeability of the toner of the roll itself can be improved.

Further, by blending the above-mentioned polycarbonate copolymer with the conductive agent (β) having the above-mentioned specific particle size and carbon-based particles having a large particle size of 0.5 to 20 μm, the roll surface is improved. Can be set to a predetermined roughness, and good toner transportability can be provided.

[Brief description of the drawings]

FIG. 1 is a sectional view showing an example of a developing roll of the present invention.

FIG. 2 is an enlarged schematic cross-sectional view of the outermost layer surface of the developing roll of the present invention.

FIG. 3 is a sectional view of a conventional developing roll used in an electrophotographic copying machine.

[Explanation of symbols]

 12 cylindrical sleeve 13 end cap 14 conductive shaft 21 innermost layer 22 intermediate layer 23 outermost layer

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Akihiko Kaji 3600, Gezu, Kita-gaiyama, Komaki-shi, Aichi Prefecture Tokai Rubber Industries Co., Ltd. (56) References JP-A-7-320201 (JP, A) Hei 7-70423 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) G03G 15/08 501

Claims (3)

(57) [Claims] 1. A roll having one or two or more layers formed on the outer periphery of a shaft body, wherein the outermost layer of these layers is a polymer containing the following (β) and a charge control agent: A developing roll formed of the material (α). (Α) a repeating unit (A) represented by the following general formula (A), a repeating unit (B) represented by the following general formula (B), and a repeating unit represented by the following general formula (C) The content of the repeating unit (A), the repeating unit (B) and the repeating unit (C) is defined by the following formulas (1), (2) and (3). Is set to satisfy all of the above. Embedded image [In the above formula (A), R ₁ , R ₂ , R ₃ , R ₄ , R
₅ and R ₆ are an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a substituted aryl group having 6 to 12 carbon atoms, or a C _{6 to} 12 And may be the same or different from each other. Also, R ₇ and R
₈ is a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a substituted aryl group having 6 to 12 carbon atoms or an unsubstituted aryl group having 6 to 12 carbon atoms, They may be the same or different. A is an integer of 0 to 4, and b is an integer of 0 to 4. X
Is a substituted alkylene group having 1 to 6 carbon atoms or 1 to 6 carbon atoms.
6 unsubstituted alkylene groups, wherein n is an integer of 1 to 6. Further, p is a positive number, q is 0 or a positive number, p
+ Q is less than 200. [Chemical formula 2] Embedded image [In the above formula (C), Y is a single bond, -O-, -C
O -, - S -, - SO -, - SO 2 -, - CR 11 R 12 -
(However, R ₁₁ and R _{12 each} represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, A substituted or unsubstituted aryl group having 6 to 12 carbon atoms, which may be the same or different from each other.), A substituted cycloalkylidene group having 5 to 11 carbon atoms, An unsubstituted cycloalkylidene group, an α, ω-alkylene group having 2 to 10 carbon atoms or a fluorenylidene group, which may be the same or different. R ₉ and R _{10 each} represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or a substituted aryl group having 6 to 12 carbon atoms. Alternatively, it is an unsubstituted aryl group having 6 to 12 carbon atoms, which may be the same or different. And c is an integer of 0 to 4 and d is 0 to
4 is an integer. However, R ₁₁ and R ₁₂ are not simultaneously a methyl group, and c and d are not simultaneously 0. 0.5 ≦ (A) / [(A) + (B) + (C)] ≦ 0.9 (1) 0 ≦ (B) / [(A) + (B) + (C)] ≦ 0.5 (2) 0 ≦ (C) / [(A) + (B) + (C)] ≦ 0.5 (( 3) [In formulas (1), (2) and (3), (A)
Is the content of the repeating unit (A), (B) is the content of the repeating unit (B), and (C) is the content of the repeating unit (C). However, (A) + (B) + (C) = 1. (Β) A conductive agent having a particle size of 0.01 to 0.5 μm. 2. One or two or more layers on the outer periphery of a shaft body
Formed on the outermost one of these layers.
The layer is made of the following (β) and carbon having a particle size of 0.5 to 20 μm.
Formed by a polymer material (α) containing system particles
A developing roll. (Α) a repeating unit represented by the following general formula (A)
(A) and a repeating unit represented by the following general formula (B)
(B) and a repeating unit represented by the following general formula (C)
(C), the repeating unit (A),
The content ratio of the unit (B) and the repeating unit (C) is as follows:
Satisfies all the relations of equation (1), equation (2) and equation (3)
Polycarbonate copolymer set as follows. Embedded image [In the above formula (A), R ₁ , R ₂ , R ₃ , R ₄ , R
₅ and R ₆ are an alkyl group having 1 to 12 carbon atoms, a fluoroalkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a substituted aryl group having 6 to 12 carbon atoms, or a C _{6 to} 12 And may be the same or different from each other. Also, R ₇ and R
₈ is a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, a substituted aryl group having 6 to 12 carbon atoms or an unsubstituted aryl group having 6 to 12 carbon atoms, They may be the same or different. A is an integer of 0 to 4, and b is an integer of 0 to 4. X
Is a substituted alkylene group having 1 to 6 carbon atoms or 1 to 6 carbon atoms.
6 unsubstituted alkylene groups, wherein n is an integer of 1 to 6. Further, p is a positive number, q is 0 or a positive number, p
+ Q is less than 200. [Chemical formula 5] Embedded image [In the above formula (C), Y is a single bond, -O-, -C
O -, - S -, - SO -, - SO 2 -, - CR 11 R 12 -
(However, R ₁₁ and R _{12 each} represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, A substituted or unsubstituted aryl group having 6 to 12 carbon atoms, which may be the same or different from each other.), A substituted cycloalkylidene group having 5 to 11 carbon atoms, An unsubstituted cycloalkylidene group, an α, ω-alkylene group having 2 to 10 carbon atoms or a fluorenylidene group, which may be the same or different. R ₉ and R _{10 each} represent a halogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, or a substituted aryl group having 6 to 12 carbon atoms. Alternatively, it is an unsubstituted aryl group having 6 to 12 carbon atoms, which may be the same or different. And c is an integer of 0 to 4 and d is 0 to
4 is an integer. However, R ₁₁ and R ₁₂ are not simultaneously a methyl group, and c and d are not simultaneously 0. 0.5 ≦ (A) / [(A) + (B) + (C)] ≦ 0.9 (1) 0 ≦ (B) / [(A) + (B) + (C)] ≦ 0.5 (2) 0 ≦ (C) / [(A) + (B) + (C)] ≦ 0.5 (( 3) [In formulas (1), (2) and (3), (A)
Is the content of the repeating unit (A), (B) is the content of the repeating unit (B), and (C) is the content of the repeating unit (C). However, (A) + (B) + (C) = 1. (Β) A conductive agent having a particle size of 0.01 to 0.5 μm. 3. The method according to claim 1, wherein the polymer material (α) is (β) or (β) .
The developing roll according to claim 1, further comprising carbon-based particles having a particle size of 0.5 to 20 μm in addition to the charge control agent .