JP2000136287A - Composition for roller and roller therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition useful for various rollers of an electronic copying machine or printer, capable of directly providing an alcohol-soluble nylon layer, etc., without treating with a primer, etc., by compounding a specific vinyl-based polymer. SOLUTION: This composition contains a vinyl-based polymer containing at least one alkenyl group in a molecule, preferably having a ratio, which is the ratio of the weight-average molecular weight to the number-average molecular weight measured by gel permeation chromatography, of <18, and preferably having a number-average molecular weight of 500-100,000. The vinyl-based polymer preferably has the aklenyl group at the molecular end. The composition is preferably obtained by subjecting a vinyl-based monomer, such as an acrylic ester monomer, to atom-transfer radical polymerization to form a vinyl-based polymer having a halogen atom at the molecular end, and replacing the halogen atom with a substituting group having the alkenyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to various rollers and paper feeding rollers which can be used in contact with a photosensitive member of an electronic copying machine or a printer which performs copying or printing using, for example, electrostatic force. TECHNICAL FIELD The present invention relates to a composition for a roller used for producing a composition and the like, and a roller produced using the composition.

[0002]

2. Description of the Related Art For example, in an electronic copying machine, toner is attracted and attracted to a photosensitive member on which an electrostatic latent image corresponding to a document image is formed by electrostatic force, and the toner is transferred to a fed sheet. Then, the original image is copied onto the paper by thermally fusing the toner carried on the paper.

That is, in the above-mentioned electronic copying machine, copying is performed by going through processes of charging, exposure, development, transfer, fixing, cleaning, and static elimination. At each predetermined position around the
Various rollers are provided in contact with the photoreceptor or separated by a certain distance. For the production of the roller, conductive polyurethane foam, chloroprene rubber, and EP rubber are often used.

However, in particular, the rollers used in the respective processes of charging, developing, transferring, and cleaning are often used so as to come into contact with the photoreceptor, and a roller made of the above-mentioned material is used for the above-mentioned application. In such a case, migrating substances such as unreacted monomers, oligomers, and other non-reactive additives contained in the roller migrate to the photoreceptor and become contaminated, resulting in an unclear image.

In order to solve the above-mentioned problems, the roller is used by coating the surface of the roller with a nylon-based material or covering it with a heat-shrinkable tube. Further, in order to control the specific resistance of the roller, the surface of the roller is similarly coated with a semiconductive material.

However, in the case of the conventional roller, since the coating of the surface layer alone cannot provide a sufficient adhesive force as described above, the roller surface is treated in advance with a primer, or a conductive and highly adhesive material such as epichlorohydrin is used. It is coated after being covered with rubber, but the adhesive layer is provided between the conductive roller and the surface coating layer or heat shrink tube, so the characteristics of the roller tend to vary and the cost increases. is there.

[0007]

SUMMARY OF THE INVENTION In view of the above situation, the present invention provides a composition for a roller for an electronic copying machine or printer, which can directly provide an alcohol-soluble nylon layer or the like without performing a primer treatment or the like. The purpose is to gain.

[0008]

That is, the present invention is a composition for a roller for use in an electronic copying machine or a printer, comprising a vinyl polymer (A) having at least one alkenyl group in a molecule. The present invention is also a roller manufactured using the above-mentioned composition for a roller. Hereinafter, the present invention will be described in detail.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the roller composition of the present invention, a vinyl polymer (A) having at least one alkenyl group in the molecule is used. The number of alkenyl groups contained in the component (A) must be at least one in one molecule, but is preferably 1.1 to 4 on average per molecule.
The alkenyl group may be present at either the side chain or the terminal of the molecule, but is preferably present at the terminal of the molecule in order to obtain good rubber elasticity.

The main chain of the component (A) is made of a vinyl polymer, but the monomer constituting the main chain of the vinyl polymer is not particularly limited, and various monomers can be used. The vinyl monomer used for producing the main chain of the vinyl polymer of the present invention is not particularly limited, and various types can be used. For example, (meth) acrylic acid, methyl (meth) acrylate, (meth)
Ethyl acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, (Meta)
Acrylic acid-n-pentyl, (meth) acrylic acid-n-
Hexyl, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, (meth) acrylic acid-
n-octyl, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, phenyl (meth) acrylate, toluyl (meth) acrylate, ( Benzyl meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate,
2-hydroxyethyl (meth) acrylate, (meth)
2-hydroxypropyl acrylate, stearyl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene (meth) acrylate Oxide adduct, trifluoromethylmethyl (meth) acrylate, 2- (meth) acrylate
Trifluoromethylethyl, (meth) acrylic acid-2-
Perfluoroethylethyl, (meth) acrylic acid-2-
Perfluoroethyl-2-perfluorobutylethyl,
2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, (meth) acrylic acid-
2-perfluoromethyl-2-perfluoroethylmethyl, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexyl (meth) acrylate (Meth) acrylic acid monomers such as decylethyl; styrene monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof; perfluoroethylene, perfluoropropylene, vinylidene fluoride, etc. Fluorine-containing vinyl monomers;
Vinyltrichlorosilane, vinylmethyldichlorosilane, vinyldimethylchlorosilane, vinylmethylmethoxysilane, vinyltrimethylsilane, divinyldichlorosilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl-1,1,3,3-tetramethyl Disiloxane, trivinylmethylsilane, tetravinylsilane, allyltrichlorosilane, allylmethyldichlorosilane, allyldimethylchlorosilane, allyldimethylmethoxysilane, allyltrimethylsilane, diallyldichlorosilane, diallylmethoxysilane, diallyldimethylsilane, γ-methacryloyloxypropyl Silicon-containing vinyl monomers such as trimethoxysilane and γ-methacryloyloxypropylmethyldimethoxysilane; maleic anhydride Acid, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl and dialkyl esters of fumaric acid; maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide , Stearylmaleimide, phenylmaleimide, cyclohexylmaleimide, and other maleimide monomers; acrylonitrile, methacrylonitrile, and other nitrile group-containing vinyl monomers; acrylamide, methacrylamide, and other amide group-containing vinyl monomers; vinyl acetate, vinyl propionate, pivalin Vinyl acid, vinyl benzoate,
Vinyl esters such as vinyl cinnamate; alkenes such as ethylene and propylene; conjugated dienes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, allyl chloride;
Allyl alcohol and the like can be mentioned. These may be used alone or a plurality of them may be copolymerized. In the above expression format, for example, (meth) acrylic acid means acrylic acid and / or methacrylic acid.

Among the vinyl polymers (A) having at least one alkenyl group, (meth) acrylic monomers obtained by synthesizing at least 40% by weight of (meth) acrylic acid monomers among the above-mentioned monomers can be obtained. ) Acrylic polymers are more preferred in terms of physical properties. Among the (meth) acrylic acid-based monomers, (meth) acrylic acid ester monomers are more preferable, and acrylic acid ester monomers are more preferable. Further, a main chain obtained by polymerizing a styrene monomer is also preferable.

The number average molecular weight of the vinyl polymer (A) having at least one alkenyl group is not particularly limited, but is preferably in the range of 500 to 100,000, more preferably 3000 to 40,000. When the molecular weight is 500 or less, the intrinsic characteristics of the vinyl polymer are hardly exhibited, and when the molecular weight is 100,000 or more,
Handling becomes difficult.

The molecular weight distribution of the vinyl polymer (A) having at least one alkenyl group, that is, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by gel permeation chromatography. There is no particular limitation on. However, it is preferable that the molecular weight distribution is narrow in order to keep the viscosity of the composition for a roller low and to facilitate the handling, and to obtain sufficient cured physical properties. The value of the molecular weight distribution is preferably less than 1.8, more preferably 1.7 or less, still more preferably 1.
It is 6 or less, more preferably 1.5 or less, further preferably 1.4 or less, and further preferably 1.3 or less.

The vinyl polymer (A) having at least one alkenyl group can be obtained by various polymerization methods, and the method is not particularly limited. However, it is preferable to use a radical polymerization method from the viewpoint of the versatility of the monomer or the ease of control, and it is possible to directly introduce an alkenyl group by the radical polymerization method or convert it into an alkenyl group by one or several steps of reaction. A more preferred method is to obtain a vinyl polymer having at least one alkenyl group by obtaining a vinyl polymer having a specific functional group and then converting the specific functional group to an alkenyl group.

In a radical polymerization method used in a method for synthesizing a vinyl polymer having a specific functional group containing an alkenyl group, a specific functional group is prepared by using an azo compound, a peroxide or the like as a polymerization initiator. Classified into “general radical polymerization method”, which simply copolymerizes a monomer having a polymer with a vinyl monomer, and “controlled radical polymerization method”, which can introduce a specific functional group at a controlled position such as the terminal. it can.

The “general radical polymerization method” is a simple method and can be used in the present invention. However, in this method, since a monomer having a specific functional group is stochastically introduced into the polymer, it is necessary to use a considerably large amount of this monomer when trying to obtain a polymer having a high functionalization rate. On the contrary, when used in a small amount, there is a problem that the ratio of the polymer into which the specific functional group is not introduced becomes large. In addition, since it is a free radical polymerization, there is a problem that the molecular weight distribution of the polymer is wide and only a polymer having a relatively high viscosity can be obtained.

On the other hand, the “controlled radical polymerization method” further comprises
`` Chain transfer agent method '', in which a vinyl polymer having a functional group at the end is obtained by performing polymerization using a chain transfer agent having a specific functional group, and the polymer growing terminal grows without termination reaction etc. By doing so, it can be classified as a "living radical polymerization method" in which a polymer having a molecular weight almost as designed is obtained.

The "chain transfer agent method" is capable of obtaining a polymer having a high degree of functionalization and can be used in the present invention. However, a chain having a considerably large amount of a specific functional group based on the initiator can be used. Since a transfer agent is required, there are economical problems including processing. Also, similar to the above “general radical polymerization method”,
Since it is a free radical polymerization, there is also a problem that only a polymer having a wide molecular weight distribution and a high viscosity can be obtained.

Unlike these polymerization methods, the "living radical polymerization method" is a radical polymerization which is difficult to control because the polymerization rate is high and a termination reaction is likely to occur due to coupling between radicals. It is difficult for the reaction to occur, and a polymer having a narrow molecular weight distribution (Mw / Mn
Is about 1.1 to 1.5), and the molecular weight can be freely controlled by the charging ratio of the monomer and the initiator. Therefore, the `` living radical polymerization method '' has a narrow molecular weight distribution and can obtain a polymer having a low viscosity, and can introduce a monomer having a specific functional group into almost any position of the polymer, It is more preferable as a method for producing the vinyl polymer having the specific functional group.

In the narrow sense of living polymerization,
This refers to polymerization in which the molecular chain grows while the terminal always keeps activity.In general, the pseudo-polymer in which the terminal is inactivated and the terminal that is activated grows in an equilibrium state. Living polymerization is also included. The definition in the present invention is also the latter.

The "living radical polymerization method" has been actively studied by various groups in recent years. Examples thereof include, for example, Journal of American Chemical Society (J. Am. Chem. Soc.), 19
1994, Vol. 116, p. 7943, using a cobalt porphyrin complex, Macromolecules, 1994, 2
7, "Atom Transfer Radical Polymerization" using a radical scavenger such as a nitroxide compound as shown in page 7228, or using an organic halide or the like as an initiator and a transition metal complex as a catalyst.
al Polymerization: ATRP).

Among the "living radical polymerization methods", the "atom transfer radical polymerization method" in which an organic halide or a sulfonyl halide compound or the like is used as an initiator and a vinyl monomer is polymerized using a transition metal complex as a catalyst is described above. In addition to the features of the `` living radical polymerization method, '' a polymer having a halogen or the like at the end which is relatively advantageous for a functional group conversion reaction is obtained, and the degree of freedom in designing initiators and catalysts is large. Is more preferable as a method for producing a vinyl polymer having The atom transfer radical polymerization method is described in, for example, Matyjaszewski et al., Journal of American Chemical Society (JA).
m. Chem. Soc. ) 1995, 117, 56
14 pages, Macromolecules
ules) 1995, 28, 7901, Science 1996, 272, 866.
Page, WO96 / 30421, WO97 / 1824
No. 7 or Sawamoto et al., Macromolecules, 1995,
28, page 1721 and the like.

The initiator used in the polymerization is particularly limited.
Not specified, for example, organic halides, especially active
Organic halides (eg, halogen at the α-position
Compounds having a halogen at the benzyl position
Compound) or a sulfonyl halide compound
No. When these compounds are used as initiators
Is a vinyl polymer having a halogen at the polymer end
Obtainable. This terminal halogen is obtained by the method described below.
The alkenyl terminal
A benzyl-based polymer can be obtained. Such an initiator
To give a concrete example, C₆ H_Five -CH_Two X, C₆ H_Five −
C (H) (X) CH_Three , C₆ H_Five -C (X) (CH_Three )_Two 
(Where C₆ H_Five Represents a phenyl group. X is chlorine,
Represents bromine or iodine. ); R^Three -C (H) (X) -CO
_Two R^Four , R^Three -C (CH_Three) (X) -CO_Two R^Four , R^Three −
C (H) (X) -C (O) R^Four , R^Three -C (CH_Three) (X)
-C (O) R^Four (Where R^Three And R^Four Are the same or
Differently, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,
Aryl group having 6 to 20 primes or aral having 7 to 20 carbon atoms
Represents a kill group. X represents chlorine, bromine or iodine
You. ); R^Three -C₆ H_Four -SO _Two X (where R^Three Is the water
Elemental atom, alkyl group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
Represents an aryl group or an aralkyl group having 7 to 20 carbon atoms.
You. X represents chlorine, bromine or iodine. )
It is.

As the initiator, an organic halide or a sulfonyl halide compound having a functional group other than the functional group that initiates polymerization can be used. In this case, a polymer having a functional group derived from the functional group contained in the initiator at one main chain terminal and a halogen at the other terminal is produced. Examples of the functional group include an alkenyl group, a crosslinkable silyl group, a hydroxyl group, an epoxy group, an amino group, an amide group, and a carboxyl group.

The organic halide having an alkenyl group is not limited, and examples thereof include those having a structure represented by the general formula (3). ^{R 5 R 6 C (X)} -R 7 -R 8 -C (R 2) = CH 2 (3) ( wherein, R ² is hydrogen or a methyl group, R ^5, R ⁶ is hydrogen or a carbon A monovalent alkyl group having 1 to 20 carbon atoms, a monovalent aryl group having 6 to 20 carbon atoms, or 7 to 20 carbon atoms
R ⁷ is -C (O) O- (ester group), -C (O) O- (ester group)
(O)-(keto group) or o-, m-, p-phenylene group, R ⁸ is a direct bond, or a divalent organic group having 1 to 20 carbon atoms and containing at least one ether bond. Is also good,
X is chlorine, bromine, or iodine) Specific examples of the substituents R ⁵ and R ⁶ include hydrogen, methyl, ethyl, n-propyl, isopropyl, butyl, pentyl, and hexyl. . R ⁵ and R ⁶ may be linked at the other end to form a cyclic skeleton.

The organic halide having an alkenyl group further includes a compound represented by the general formula (4). ^{_{H 2 C = C (R 2}} ) -R 8 -C (R 5) (X) -R 9 -R 6 (4) ( ^{wherein, R 2, R 5, R} 6, R 8 are as defined above. R ⁹
Is a direct bond, -C (O) O- (ester group), -C
(O)-(keto group) or an o-, m-, p-phenylene group. X is the same as above. ) R ⁸ is a direct bond or a divalent organic group having 1 to 20 carbon atoms (which may contain one or more ether bonds). In the case of a direct bond, a halogen is bonded. It is a halogenated allylic compound with a vinyl group bonded to carbon. in this case,
Since the carbon-halogen bond is activated by the adjacent vinyl group, R ⁹ does not necessarily have to have a C (O) O group or a phenylene group, and may be a direct bond. When R ⁷ is not a direct bond, R ⁹ may be a C (O) O group or a C
An (O) group and a phenylene group are preferred.

Specific examples of the sulfonyl halide compound having an alkenyl group include: o-, m-, p-CH ₂ ＣＨCH— (CH ₂ ) _n —C ₆ H
_{4 -SO 2 X, o-, m-} , p-CH 2 = CH- (CH 2) n -O-C
₆ H ₄ —SO ₂ X (in each formula, X is chlorine, bromine, or iodine, and n is an integer of 0 to 20).

The organic halide having a crosslinkable silyl group is not particularly limited, and examples thereof include those having a structure represented by the general formula (5). ^{R 5 R 6 C (X)} -R 7 -R 8 -C (H) (R 2) CH 2 - [Si (R 10) 2-b (Y) b O] m -Si (R 11) 3- _a (Y) _a (5) (wherein, R ² , R ⁵ , R ⁶ , R ⁷ , R ⁸ and X are the same as above, and R ¹⁰ and R ¹¹ are all alkyl groups having 1 to 20 carbon atoms. An aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ′ ₃ SiO— (R ′
To 20 monovalent hydrocarbon groups, wherein three R's may be the same or different), and R ¹⁰ or R ¹¹ is two When present, they may be the same or different. Y represents a hydroxyl group or a hydrolyzable group;
When two or more are present, they may be the same,
It may be different. a represents 0, 1, 2, or 3, and b represents 0, 1, or 2. m is an integer of 0-19. However, it is assumed that a + mb ≧ 1 is satisfied.)

Further examples of the organic halide having a crosslinkable silyl group include those having a structure represented by the general formula (6). ^{_{(R 11) 3-a (}} Y) a Si- [OSi (R 10) 2-b (Y) b] m -CH 2 -C (H) (R 2) -R 8 -C (R 5) ( ^{X) -R 9 -R 6 (6} ) ( ^{wherein, R 5, R 6, R} 8, R 9, R 9, R 10, R 11,
a, b, m, X and Y are the same as above)

An organic halide having a hydroxyl group,
Alternatively, the sulfonyl halide compound is not particularly limited, and examples thereof include the following. HO— (CH ₂ ) _n —OC (O) C (H) (R) (X) (in the above formula, X is chlorine, bromine, or iodine;
R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and n is an integer of 1 to 20)

The organic halide having an amino group or the sulfonyl halide compound is not particularly limited.
The following are exemplified. _{H 2 N- (CH 2) n} -OC (O) C (H) (R)
(X) (In the above formula, X is chlorine, bromine, or iodine;
R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, and n is an integer of 1 to 20)

The organic halide having an epoxy group or the sulfonyl halide compound is not particularly limited, and examples thereof include the following.

[0033]

Embedded image

(In the above formula, X is chlorine, bromine or iodine, R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 to 20 carbon atoms.
Aralkyl group, n is an integer of 1 to 20)

Further, the polymerization can be carried out using an organic halide or a sulfonyl halide compound having two or more starting points as an initiator. In such a case, a vinyl polymer having two or more halogens in one molecule is produced. To specifically illustrate the initiator having the above two starting points,

[0036]

Embedded image

(Wherein C ₆ H ₄ represents a phenylene group; X represents chlorine, bromine or iodine; R is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or Represents an aralkyl group having 7 to 20 carbon atoms, and n is 0 to 2
Represents an integer of 0. );

[0038]

Embedded image

(Wherein X represents chlorine, bromine or iodine)
You. n represents an integer of 0 to 20. C ₆ H_Four The pheny
Represents a len group. ) And the like.

Examples of the transition metal complex used as a catalyst for the above atom transfer radical polymerization include Group 7 and Group 8 of the Periodic Table,
A complex having a Group 9 element, a Group 10 element, or a Group 11 element as a central metal can be used. Preferred are 0-valent copper, 1
Complex of divalent copper, divalent ruthenium, divalent iron or divalent nickel. Among them, a copper complex is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, and the like. is there. When a copper compound is used, 2,2'-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine and the like for enhancing the catalytic activity Can be added. Tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ )
Are also suitable as catalysts. When a ruthenium compound is used as a catalyst, aluminum alkoxides can be added as an activator. Further, bis (triphenylphosphine) complex of divalent iron (FeCl ₂ (PPh ₃ )
₂ ) Bivalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ) and divalent nickel bistributylphosphine complex (NiBr ₂ (PB
u ₃ ) ₂ ) are also suitable as catalysts.

There are no particular restrictions on the vinyl monomer used in this polymerization, and any of those already exemplified can be suitably used.

The above polymerization reaction can be carried out without a solvent or in various solvents. Examples of the solvent include hydrocarbon solvents such as benzene and toluene; ether solvents such as diethyl ether, tetrahydrofuran, diphenyl ether, anisole and dimethoxybenzene; halogenated hydrocarbon solvents such as methylene chloride, chloroform and chlorobenzene; acetone , Methyl ethyl ketone, methyl isobutyl ketone and the like; ketone solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol and tert-butyl alcohol; nitrile solvents such as acetonitrile, propionitrile and benzonitrile; acetic acid Ester solvents such as ethyl and butyl acetate; and carbonate solvents such as ethylene carbonate and propylene carbonate. These can be used alone or in combination of two or more. Also, an emulsion or supercritical fluid C
Polymerization can also be performed in a system using O ₂ as a medium.

The polymerization can be carried out at a temperature in the range of 0 to 200 ° C., preferably in the range of room temperature to 150 ° C.

The vinyl polymer (A) having at least one alkenyl group can be obtained by the following method, but is not limited thereto. (Aa) a compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule as shown in the following general formula (7) when synthesizing a vinyl polymer by radical polymerization. As a second monomer. ^{_{H 2 C = C (R 2}} ) -R 12 -R 13 -C (R 2) = CH 2 (7) ( wherein, two R ² represents a hydrogen or a methyl group, be the same or different from each other R ¹² is —C (O) O
-, or o-, m-, shows a p- phenylene group, R ¹³
Represents a direct bond or a divalent organic group having 1 to 20 carbon atoms, and may contain one or more ether bonds. There is no restriction on the timing of reacting a compound having both a polymerizable alkenyl group and a low polymerizable alkenyl group in one molecule. In particular, in the case of living radical polymerization, where a rubber-like property is expected, the polymerization reaction is not required. It is preferable to react as a second monomer at the end of the reaction or after the completion of the reaction of a predetermined monomer.

(Ab) When a vinyl polymer is synthesized by living radical polymerization, for example, 1,5-hexadiene, 1,7-octadiene, 1, A method of reacting a compound having at least two alkenyl groups having low polymerizability such as 9-decadiene.

(Ac) The vinyl polymer having at least one highly reactive carbon-halogen bond includes various organic compounds having an alkenyl group such as organotin such as allyltributyltin and allyltrioctyltin. A method in which a halogen is substituted by reacting a metal compound.

(Ad) A vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with a stabilized carbanion having an alkenyl group as shown in the general formula (8) to form a halogen. How to replace. ^{M + C - (R 14)} (R 15) -R 16 -C (R 2) = CH 2 (8) ( wherein, R ² is the same, R ^14, R ¹⁵ together carbanion C ^- stable Or one of them is the above-described electron-withdrawing group and the other is hydrogen or a carbon atom having 1 to 10 carbon atoms.
Represents an alkyl group or a phenyl group. R ¹⁶ represents a direct bond or a divalent organic group having 1 to 10 carbon atoms, and may contain one or more ether bonds. M ⁺ represents an alkali metal ion or a quaternary ammonium ion)
Examples of the electron withdrawing group for R ¹⁴ and R ¹⁵ include —CO ₂ R and —C
Those having the structure of (O) R and -CN are particularly preferred.

(Ae) An enolate anion is prepared by reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with a simple metal such as zinc or an organometallic compound. An alkenyl group-containing electrophilic compound such as an alkenyl group-containing compound having a leaving group such as a halogen or an acetyl group, a carbonyl compound having an alkenyl group, an isocyanate compound having an alkenyl group, and an acid halide having an alkenyl group. How to react.

(Af) The vinyl polymer having at least one highly reactive carbon-halogen bond may be, for example, an oxyanion having an alkenyl group represented by the general formula (9) or (10) or a carboxy group. A method in which a halogen is substituted by reacting a rate anion. ^{_{H 2 C = C (R 2}} ) -R 17 -O - M + (9) ( wherein, R ^2, M ⁺ is the same .R ¹⁷ in the 1 to 2 carbon atoms
H ₂ C ＝ C (R ² ) —R ¹⁸ —C (O) O ⁻ M ⁺ (10) (wherein R is a divalent organic group which may contain one or more ether bonds) ² , and M ⁺ are the same as described above, and R ¹⁸ is a direct bond or a divalent organic group having 1 to 20 carbon atoms, which may contain one or more ether bonds).

The method for synthesizing the above-mentioned vinyl polymer having at least one highly reactive carbon-halogen bond is not particularly limited. For example, in the radical polymerization, as described in JP-A-4-132706, For example, a method using a halide such as carbon tetrachloride, ethylene chloride, carbon tetrabromide, or methylene bromide as a chain transfer agent (chain transfer agent method); an organic halogen having at least one highly reactive carbon-halogen bond. Radical polymerization of a vinyl monomer using a halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst (atom transfer radical polymerization). Since the polymers obtained by the above two methods each have a carbon-halogen bond at the terminal, it is preferable as a method for obtaining a vinyl polymer having an alkenyl group at the terminal, but it is easy to control the molecular weight, the molecular weight distribution and the like. From a certain point, the latter atom transfer radical polymerization method is more preferable.

The vinyl polymer having at least one alkenyl group (A) can be obtained from a vinyl polymer having at least one hydroxyl group, and the following exemplified methods can be used, but the present invention is not limited to these. It is not done. (Ag) A method in which a base such as sodium methoxide is allowed to act on a hydroxyl group of a vinyl polymer having at least one hydroxyl group to react with a alkenyl group-containing halide such as allyl chloride. (Ah) A method of reacting an alkenyl group-containing isocyanate compound such as allyl isocyanate. (Ai) A method of reacting an alkenyl group-containing acid halide such as (meth) acrylic acid chloride in the presence of a base such as pyridine. (Aj) A method of reacting an alkenyl group-containing carboxylic acid such as acrylic acid in the presence of an acid catalyst. (A-k) A diisocyanate compound is reacted, and the remaining isocyanate group is reacted with a general formula (11): CH ₂ ＣC (R ¹ ) —C (O) —R ¹⁹ —OH (11) (where R ¹ is R ¹⁹ is 2 of 2-20 carbon atoms
Represents a valent organic group. ), For example, a method of reacting 2-hydroxypropyl methacrylate; and the like.

In the present invention, when a halogen is not directly involved in the method for introducing an alkenyl group such as (Aa) and (Ab), a vinyl polymer is synthesized by a living radical polymerization method. Is preferred. The method (Ab) is more preferable because the control is easier.

When an alkenyl group is introduced by converting a halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond, an organic halogen having at least one highly reactive carbon-halogen bond may be used. Halide, or a sulfonyl halide compound as an initiator,
Obtained by radical polymerization of a vinyl monomer using a transition metal complex as a catalyst (atom transfer radical polymerization method).
At least one highly reactive carbon-halogen bond at the terminal
It is preferable to use a vinyl polymer having two or more vinyl polymers. The method (Af) is more preferable because the control is easier.

Examples of the method for producing a vinyl polymer having at least one hydroxyl group include the following methods, but are not limited to these methods. (Ba) When a vinyl polymer is synthesized by radical polymerization, for example, a compound having both a polymerizable alkenyl group and a hydroxyl group in one molecule as shown in the following general formula (12) is used as a second monomer As a reaction. H ₂ C ＝ C (R ² ) —R ¹² —R ¹³ —OH (12) (wherein R ² , R ¹² and R ¹³ are the same as above) A polymerizable alkenyl group and a hydroxyl group in one molecule There is no limitation on the timing of reacting the compound having the above. Particularly, in the case of living radical polymerization, when a rubber-like property is expected, the reaction is carried out as the second monomer at the end of the polymerization reaction or after the completion of the reaction of a predetermined monomer. Is preferred.

(Bb) When a vinyl polymer is synthesized by living radical polymerization, at the end of the polymerization reaction or after completion of the reaction of a predetermined monomer, for example, an alkenyl such as 10-undecenol, 5-hexenol, or allyl alcohol is used. A method of reacting alcohol. (Bc) A method of radically polymerizing a vinyl monomer using a large amount of a hydroxyl group-containing chain transfer agent such as a hydroxyl group-containing polysulfide disclosed in JP-A-5-262808. (Bd) For example, JP-A-6-239912, JP-A-8-
283310. A method of radically polymerizing a vinyl monomer using hydrogen peroxide or a hydroxyl group-containing initiator as shown in 283310. (Be) A method of radically polymerizing a vinyl monomer by using an excess of alcohols as described in, for example, JP-A-6-11612.

(Bf) For example, JP-A-4-132706
A method of introducing a hydroxyl group into a terminal by hydrolyzing or reacting a halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond with a hydroxyl group-containing compound by a method such as that described in US Pat.

(Bg) A vinyl polymer having at least one highly reactive carbon-halogen bond is reacted with a stabilized carbanion having a hydroxyl group as shown in the general formula (13) to substitute halogen. how to. ^{M + C - (R 14)} (R 15) -R 16 -OH (13) ( wherein, R ^14, R ¹⁵ together carbanion C ^- or an electron withdrawing group stabilizing, or one of the electronic And the other is hydrogen or an alkyl group having 1 to 10 carbon atoms or a phenyl group, and R ¹⁶ is a direct bond or 1 carbon atom.
Represents a divalent organic group of from 10 to 10, and may contain one or more ether bonds. M ⁺ represents an alkali metal ion or a quaternary ammonium ion.) The electron-withdrawing groups for R ¹⁴ and R ¹⁵ include —CO ₂ R and —C
Those having the structure of (O) R and -CN are particularly preferred.

(Bh) An enolate anion is prepared by reacting a vinyl polymer having at least one highly reactive carbon-halogen bond with a simple metal such as zinc or an organometallic compound. A method of reacting aldehydes or ketones later.

(Bi) A vinyl polymer having at least one highly reactive carbon-halogen bond may be added to a hydroxyl group-containing oxyanion or carboxylate represented by the general formula (14) or (15). A method in which halogen is substituted by reacting an anion. ^{HO-R 20 -O - M +} (14) ( wherein, R ²⁰ are the same as the divalent organic group which may contain one or more ether bonds .M ⁺ is the C20 ) HO—R ²⁰ —C (O) O ⁻ M ⁺ (15) (wherein R ²⁰ and M ⁺ are the same as above).

In the present invention, when a halogen is not directly involved in a method for introducing a hydroxyl group such as (Ba) to (Be), a vinyl polymer is synthesized by a living radical polymerization method. Is preferred. The method (Bb) is more preferable because the control is easier.

When a hydroxyl group is introduced by converting a halogen of a vinyl polymer having at least one highly reactive carbon-halogen bond, an organic halide,
Alternatively, a vinyl-based compound having at least one highly reactive carbon-halogen bond at a terminal obtained by radically polymerizing a vinyl-based monomer using a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst (atom transfer radical polymerization method). Preferably, a polymer is used. The method (Bi) is more preferable because the control is easier.

According to the first aspect, the roller composition of the present invention comprises, in addition to the component (A), a curing agent (B) having at least two hydrosilyl groups in a molecule, and a hydrosilylation catalyst. (C) is further contained. In this embodiment, the component (A) is a component that is cured by a hydrosilylation reaction with the component (B), and has at least one alkenyl group in the molecule. To cure.

The alkenyl group in the first embodiment is a group represented by the following general formula. CH ₂ ＣＲCR ² − (wherein R ² is hydrogen or a methyl group)

The curing agent having at least two hydrosilyl groups in the molecule as the component (B) used in the composition for a roller according to the first aspect of the present invention has at least one curing agent in the molecule as the component (A). It is a component that acts as a curing agent for a vinyl polymer having two alkenyl groups. Component (B) has at least 2, preferably 2 to 50, more preferably 2 to 20, more preferably 2 to 15, and especially 3 to 3, components in the molecule.
Since it has 12 hydrosilyl groups, each hydrosilyl group reacts with the alkenyl group present in the molecule of component (A) and cures. When the number of the hydrosilyl groups is 2
When the number is less than the number, the curing rate when the composition of the present invention is cured by the hydrosilylation reaction becomes slow, and the curing failure often occurs. When the number of the hydrosilyl groups is more than 50, the stability of the curing agent (B), that is, the stability of the composition of the present invention is deteriorated. It tends to remain inside and cause voids and cracks.

The term "having one hydrosilyl group" refers to Si
H means one H. In the case of SiH ₂ , it has two hydrosilyl groups.
Is better in terms of curability when bonded to different Si, and is also preferable in terms of rubber elasticity.

The molecular weight of the component (B) is preferably 30,000 or less in terms of number average molecular weight (Mn) from the viewpoint of the dispersibility and the roller workability of the component (E) to be used, if necessary. , Even less than 20,000, especially 15,
000 or less is preferable. Considering the reactivity and compatibility with the component (A), 300 to 10,000 is more preferable.

There is no particular limitation on the structure of the component (B) as described above. For example, the general formula (2): R ²¹ X _a (2) (wherein X is a group containing at least one hydrosilyl group, ²¹ is a monovalent to tetravalent hydrocarbon group having 2 to 150 carbon atoms,
a is an integer selected from 1 to 4, provided that when X contains only one hydrosilyl group, a is 2 or more) and contains a hydrosilyl group having an average molecular weight of 30,000 or less. Specific examples include hydrocarbon-based curing agents.

In the general formula (2), X represents at least one
Represents a group containing a drosilyl group.
Is, for example, -SiH_n (CH_Three )_3-n , -SiH_n (C
_Two H_Five ) _3-n , -SiH_n (C₆ H_Five )_3-n (More than
n = 1-3), -SiH_Two (C₆H₁₃) And other silicon sources
A hydrosilyl group containing only one child,

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A hydrosilyl group containing two or more silicon atoms, such as

[0071]

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[0072]

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[0073]

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And the like, and hydrosilyl groups derived from various chain, branched, and cyclic polyvalent hydrogen siloxanes. In the formula, m units and p units, n units and q units, m units and p units and x units, n units and q units, It is described that y units, m units and n units, and further, m units, n units, p units, and q units are connected by block bonding. However, these may be block bonds or random bonds. The same applies to the following description.

Of the various hydrosilyl groups described above,
Since the hydrosilyl group-containing hydrocarbon-based curing agent as the component (B) is less likely to impair compatibility with other organic polymers, the molecular weight of the portion constituting the hydrosilyl group is 5
It is preferably at most 00, and in consideration of the reactivity of the hydrosilyl group, the following is preferred.

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The above groups are also referred to as groups represented by the formula (8).

In the general formula (2), R ²¹ has 2 to 150 carbon atoms.
And a group consisting of a polymer. As a specific example,

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[0080]

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(These are described in, for example, JP-A-3-95266). Specific examples of the group in which R ²¹ is a polymer include ethylene, propylene, 1-butene, isobutylene and the like. A polymer obtained by polymerizing an olefinic compound having 2 to 6 carbon atoms as a main monomer, having one to four bonds, homopolymerizing a diene-based compound such as butadiene, isoprene, or the like; And hydrogenated after copolymerization with a diene compound, and those having 1 to 4 bonds. Among the hydrocarbon-based curing agents represented by the general formula (2) having R ²¹ and X as described above, R ²¹ is a hydrocarbon group having 5 to 20 carbon atoms, and X is a group represented by the formula (8). Combination of cases raises reactivity,
It is preferable from the viewpoint of obtaining a good network structure and the compatibility with the component (A).

Among these, it is preferable that R ²¹ is a hydrocarbon group having 5 to 12 carbon atoms from the viewpoint that the raw material can be easily obtained. Among the groups represented by X, the cyclic polysiloxane compound is preferred. Is preferred from the viewpoint that the compatibility with the component (A) is further improved. The compound obtained by this combination is preferable as the hydrocarbon-based curing agent. As a specific example, for example,

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And the like.

There is no particular limitation on the method for producing the hydrosilyl group-containing hydrocarbon-based curing agent (B), and any method may be used. For example, (i) SiCl
LiAlH ₄ , NaBH ₄
To reduce the SiCl groups in the curing agent to Si
(Ii) a functional group X ^{1 in the} molecule
Reacting a hydrocarbon compound having the formula (I) with a compound having both a functional group Y ¹ and a hydrosilyl group that react with the functional group X ^{1 in the} molecule, and (iii) a method for reacting a hydrocarbon compound containing an alkenyl group. A method of selectively hydrosilylating a polyhydrosilane compound having at least two hydrosilyl groups to leave the hydrosilyl groups in the molecule of the hydrocarbon compound even after the reaction.

Of the above methods, the method (iii) can be suitably used because the manufacturing process is generally simple. In this case, two or more of the hydrosilyl groups of some of the polyhydrosilane compounds may react with the alkenyl group of the hydrocarbon-based compound to increase the molecular weight. Even if it is used as a component (B), there is no problem.

As the component (B), a polysiloxane-based curing agent can also be used. Specific examples include the following linear and cyclic polyorganohydrogensiloxanes (including modified polyoxyalkylenes, modified styrenes, modified olefins, and the like).

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(M and n are integers, 10 ≦ m + n ≦ 50, 2
≦ m, 0 ≦ n, R is a methyl group, and the molecular weight is 100 to 10,
000 polyoxyalkylene group or 2-20 carbon atoms
May contain one or more phenyl groups. When a plurality of Rs are included, they need not be the same. )

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(M and n are integers, 10 ≦ m + n ≦ 50, 2
≦ m, 0 ≦ n, R is a methyl group, and the molecular weight is 100 to 10,
000 polyoxyalkylene group or 2-20 carbon atoms
And may contain one or more phenyl groups. When a plurality of Rs are included, they need not be the same. )

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(M and n are integers, 3 ≦ m + n ≦ 20, 2 ≦
m ≦ 19, 0 ≦ n ≦ 18, R is methyl group, molecular weight is 10
The polyoxyalkylene group may have 0 to 10,000 or a hydrocarbon group having 2 to 20 carbon atoms and may contain one or more phenyl groups. When a plurality of Rs are included, they need not be the same. )

In order to further improve the compatibility with the component (A), it is preferable that R has a phenyl group. Further, from the viewpoint of availability, -CH ₂ -CH ₂ -C ₆
H _5, are _{-CH 2 -CH (CH 3) -C} 6 H 5, also,
Storage stability point from -CH ₂ -CH of (CH ₃₎ -C ₆ H
₅ is preferred.

In the first embodiment of the present invention, a hydrosilylation catalyst which is the component (C) is used together with the components (A) and (B). The hydrosilylation catalyst as the component (C) is not particularly limited, and specific examples thereof include a radical initiator such as an organic peroxide and an azo compound, and a transition metal catalyst.

The radical initiator is not particularly limited, and various radical initiators can be used. Illustratively, di-t-butyl peroxide, 2,5-dimethyl-
2,5-di (t-butylperoxy) hexane, 2,5
-Dimethyl-2,5-di (t-butylperoxy) -3
Dialkyl peroxides such as -hexyne, dicumyl peroxide, t-butylcumyl peroxide, α, α'-bis (t-butylperoxy) isopropylbenzene; benzoyl peroxide, p-chlorobenzoyl peroxide, m-chlorobenzoyl peroxide, 2,
Diacyl peroxides such as 4-dichlorobenzoyl peroxide and lauroyl peroxide; perbenzoic acid-t-
Peroxyesters such as butyl and the like; peroxydicarbonates such as diisopropyl percarbonate and di-2-ethylhexyl percarbonate; 1,1-di (t-butylperoxy) cyclohexane, 1,1-di (t-butylperoxy) −3,
And peroxyketals such as 3,5-trimethylcyclohexane.

The transition metal catalyst is not particularly limited, and examples thereof include platinum alone, platinum solid dispersed in a carrier such as alumina, silica and carbon black, chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde. And platinum compounds such as a complex with a ketone, a platinum-olefin complex, a platinum / phosphite complex, and a platinum (0) -divinyltetramethyldisiloxane complex. Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ , RhCl ₃ ,
RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl ₃ , PdCl _{2
· H 2 O, NiCl 2,} TiCl 4 , and the like.
These catalysts may be used alone or in combination of two or more. Of the above hydrosilylation catalysts, transition metal catalysts are preferred, and platinum compounds are more preferred.

The roller composition according to the first aspect of the present invention comprises:
It is prepared from the components (A) to (C). Component (A) and component (B) are used in a proportion such that the hydrosilyl group in component (B) is 0.2 per mole of alkenyl group in component (A).
It is preferably used in an amount of from 5.0 to 5.0 mol, more preferably from 0.4 to 2.5 mol, from the viewpoint of rubber elasticity. Also,
The amount of the hydrosilylation catalyst used as the component (C) is as follows:
(A) 10 ^-1 to 1 based on 1 mol of the alkenyl group in the component.
0 ^-6 used in a molar range.

The roller composition of the present invention as described above may contain, if necessary, carbon black or metal fine powder for imparting conductivity, a quaternary ammonium base, a carboxylic acid group, a sulfonic acid group, or a sulfuric acid. Ester group, organic compound or polymer containing a phosphate ester group, etc., ether ester amide or ether amide imide polymer, ethylene oxide-epihalohydrin copolymer,
A compound having a conductive unit represented by a methoxypolyethylene glycol acrylate polymer or a compound imparting conductivity such as an organic antistatic agent such as a polymer compound (component (E)), and improving processability and cost. Fillers, storage stabilizers, plasticizers, ultraviolet absorbers, lubricants, pigments, and the like.

As the carbon black, for example, those having an average particle size of about 15 to 19 mμ are preferably used.
Specific examples include EC carbon obtained by a pyrolysis method.

As the metal fine powder, for example, a metal powder having an average particle diameter of about 0.1 μm to 3 μm is preferably used, and specific examples include Ni powder.

The quaternary ammonium base (for example,

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[0104] group, etc.), other carboxylic acid group (-COOH group, -COONa group also include carboxylate such as -COOK group), another sulfonic acid group (-SO ₃ H group, -SO ₃ Na group, sulfonic acid groups such as —SO ₃ K group), and sulfate group (—OSO ₃ Na,
A group such as —OSO ₃ K), a phosphate group (—OPO
Organic compounds containing a group) such as ₃ K ₂ or as the polymer include quaternary ammonium chloride, 4
Quaternary ammonium sulfate, quaternary ammonium base-containing organic compounds such as quaternary ammonium nitrates, quaternary ammonium base-containing polymers such as polyvinylbenzyl-type cations and polyacrylic acid-type cations,
Carboxylic acid group-containing organic compounds such as alkali metal salts of higher fatty acids, carboxylic acid group-containing polymers such as ionomers, sulfonic acid group-containing organic compounds such as alkyl sulfonates and alkylbenzene sulfonates, polyvinyl benzyl sulfonates, polyacrylic sulfonates, etc. Sulfonic acid group-containing polymers, organic compounds having a sulfuric acid ester group such as alkyl sulfate, and organic compounds having a phosphoric acid ester group such as alkyl phosphate.

Other than the above compounds, amphoteric organic antistatic agents such as alkyl betaine type, alkyl imidazoline type and alkyl alanine type, polyoxyethylene alkylamine, polyoxyethylene alkylamide,
Nonionic organic antistatic agents such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, glycerin fatty acid ester and sorbitan fatty acid ester can also be used. The ether ester amide or ether amide imide polymer has a group represented by an ether bond and an ester amide bond or an ether bond ester amide bond in the polymer,
It imparts conductivity as a whole polymer. Also,
The ethylene oxide-epihalohydrin copolymer is obtained by copolymerizing epihalohydrin such as epichlorohydrin and ethylene oxide. further,
The methoxypolyethylene glycol acrylate is a polymer of an ester of methoxypolyethylene glycol and acrylic acid.

Among the organic antistatic agents, for example, a quaternary ammonium base, an acrylic oligomer containing a carboxylic acid group or a sulfonic acid group, a maleimide copolymer, an acrylimide copolymer, or a polyetheresteramide, Polyether amide imide, ethylene oxide-epihalohydrin copolymer, methoxy polyethylene glycol acrylate oligomer and the like are preferably used. When the organic antistatic agent is a polymer, it is preferably in a liquid state, so that the average molecular weight is preferably in a range in which the organic antistatic agent is in a liquid state.

The amount of the component (E) which imparts conductivity to the roller composition of the present invention, which comprises the components (A) to (C), is not particularly limited.
Usually, about 0.01 to the total amount of the components (A) to (C).
And the specific resistance of the cured product is 10 ³ Ω · 10 ¹⁰ Ω ·
cm. When carbon black or metal powder is used as the component (E), the specific resistance is usually set to 10 ³ to 10 ⁶ Ω · cm. Also,
When the organic antistatic agent as described above is added to the roller composition of the present invention comprising the components (A) to (C), the amount of the organic antistatic agent is about 0 to the total amount of the components (A) to (C). .5-
30%. In this case, the specific resistance is 10 ⁷ to 10 ¹⁰
It is mainly used to make Ω · cm.

The composition of the present invention comprising the components (A) to (C) as described above, and if necessary, a composition to which components such as the component (E) are added, for example, a SUS shaft at the center. By casting, injection, extrusion molding, etc. in a mold provided with, and heating and curing at a temperature of 30 to 150 ° C., preferably 80 to 140 ° C. for 1 hour to 10 seconds, preferably 20 to 1 minute, It can be formed into various rollers that can be used in contact with a photoconductor of an electronic copying machine or a printer or various rollers that feed paper.
After semi-curing, post-curing may be performed.

According to the second aspect of the present invention, the alkenyl group contained in the vinyl polymer as the component (A) is a polymerizable carbon-carbon double bond. Preferably, the alkenyl group is represented by the following general formula (1). CH ₂ ＣC (R ¹ ) —C (O) O— (1) (wherein, R ¹ is a hydrogen atom, a methyl group, —CN, or a C 1-20 carbon atom which may contain an oxygen atom. Represents a monovalent hydrocarbon group.)

In the general formula (1), specific examples of R ¹ are not particularly limited, and include, for example, —H, —CH ₃ , —CH
_{2 CH 3, - (CH 2} ) n CH 3 (n represents an integer of _{2~19), - C 6 H 5} , -CH 2 OH, but -CN, and the like, preferably -H, -CH ₃

In this embodiment, a cross-linking reaction proceeds by polymerization of the polymerizable carbon-carbon double bond to obtain a cured product. However, a polymerization initiator is added as the component (D), and heating or light irradiation is performed. By performing the above, polymerization can be rapidly performed. Examples of the component (D) include a thermal initiator and a photopolymerization initiator.

The thermal initiator is not particularly limited, and includes an azo initiator, a peroxide, a persulfate, and a redox initiator. Suitable azo initiators include, but are not limited to, 2,2'-azobis (4-methoxy-
2,4-dimethylvaleronitrile) (VAZO 33),
2,2'-azobis (2-amidinopropane) dihydrochloride (VAZO 50), 2,2'-azobis (2,4-dimethylvaleronitrile) (VAZO 52), 2,2'-azobis (isobutyro) Nitrile) (VAZO 64), 2,2'-
Azobis-2-methylbutyronitrile (VAZO 67),
1,1-Azobis (1-cyclohexanecarbonitrile) (VAZO 88) (All DuPont Chemical)
al), 2,2'-azobis (2-cyclopropylpropionitrile), and 2,2'-azobis (methylisobutyrate) (V-601) (available from Wako Pure Chemical Industries). Can be

Suitable peroxide initiators include, but are not limited to, benzoyl peroxide, acetyl peroxide, lauroyl peroxide, decanoyl peroxide, dicetyl peroxydicarbonate, di (4-t- Butylcyclohexyl) peroxydicarbonate (Perkadox)
16S) (available from Akzo Nobel), di (2-ethylhexyl) peroxydicarbonate, t
-Butyl peroxypivalate (Luppersol 1
1) (available from Elf Atochem), t-butylperoxy-2-ethylhexanoate (Trig
onox 21-C50) (available from Akzo Nobel), and dicumyl peroxide.

Suitable persulfate initiators include, but are not limited to, potassium persulfate, sodium persulfate, and ammonium persulfate. Suitable redox (redox) initiators include, but are not limited to, combinations of the above persulfate initiators with reducing agents such as sodium metabisulfite and sodium bisulfite; Examples include systems based on tertiary amines, such as systems based on benzoyl peroxide and dimethylaniline; and systems based on organic hydroperoxides and transition metals, such as systems based on cumene hydroperoxide and cobalt naphthate. Other initiators include, but are not limited to, tetraphenyl 1,1,2,2-
Pinacol such as ethanediol is exemplified.

Preferred thermal radical initiators are selected from the group consisting of azo initiators and peroxide initiators. More preferred are 2,2'-azobis (methylisobutyrate), t-butylperoxypivalate,
And di (4-tert-butylcyclohexyl) peroxydicarbonate, and mixtures thereof.

The thermal initiator used in the present invention is present in a catalytically effective amount, and such amount is not limited,
Typically, about 0.01 to 5 parts by weight, more preferably about 0.02 parts by weight, based on 100 parts by weight of the total amount of the polymer (A) and the other monomer and oligomer mixture added.
It is 5 to 2 parts by weight. It is also possible to use a mixture as the above-mentioned thermal initiator, and usually, the total amount of the polymer (A) and the monomer and oligomer mixture added to the other is 10%.
When it is 0 parts by weight, about 0.01 to 5 parts by weight, more preferably about 0.025 to 2 parts by weight can be added.

There is no particular limitation on the photopolymerization initiator.
Photo-radical initiators and photo-anion initiators are preferred, for example, acetophenone, propiophenone, benzophenone, xanthol, fluorein, benzaldehyde,
Anthraquinone, triphenylamine, carbazole,
3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 4-methoxyacetophen, 3-bromoacetophenone, 4-allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone 4,4'-dimethoxybenzophenone,
4-chloro-4'-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-
Chloro-8-nonyl xanthone, benzoyl, benzoin methyl ether, benzoin butyl ether, bis (4-dimethylaminophenyl) ketone, benzyl methoxy ketal, 2-chlorothioxanthone and the like can be mentioned. These initiators may be used alone or in combination with other compounds. Specifically, a combination with an amine such as diethanolmethylamine, dimethylethanolamine, and triethanolamine, further combined with an iodonium salt such as diphenyliodonium chloride, and a combination with a dye and an amine such as methylene blue. Can be

As the near-infrared light polymerization initiator, a near-infrared light-absorbing cationic dye may be used. As a near-infrared light-absorbing cationic dye, it is excited with light energy in the range of 650 to 1500 nm, for example, as disclosed in
It is preferable to use a near-infrared light-absorbing cationic dye-borate anion complex or the like disclosed in JP-A-1402 and JP-A-5-194609, and it is more preferable to use a boron sensitizer in combination.

The addition amount of the photopolymerization initiator may be an amount that only slightly activates the system. The amount of the photopolymerization initiator is not particularly limited, but is preferably 0.001 to 10 parts by weight based on 100 parts by weight of the polymer of the composition.

If necessary, the above-mentioned compound (E) for imparting conductivity can be added to the composition for rollers according to the second embodiment of the present invention. For compositions for rollers,
The amount of the component (E), which imparts conductivity, is not particularly limited, but is usually about 0.01 to 30% of the component (A). It is added so as to be 10 ³ to 10 ¹⁰ Ω · cm.

When carbon black or metal powder is used as the component (E), the specific resistance is usually 10 ³
It is to ~10 ⁶ Ω · cm. When an organic antistatic agent is added as the component (E), the specific resistance should be 10 ⁷ to 10 ¹⁰ Ω ·
cm), and is preferably added in an amount of about 0.5 to 30% based on the component (A).

If necessary, a polymerizable monomer and / or oligomer may be added to the roller composition of the second embodiment of the present invention. As the polymerizable monomer and / or oligomer, a monomer and / or oligomer having a radical polymerizable group, or a monomer and / or oligomer having an anion polymerizable group is preferable. Examples of the radical polymerizable group include a (meth) acryl group, a styrene group, an acrylonitrile group, a vinyl ester group, an N-vinylpyrrolidone group, an acrylamide group, a conjugated diene group, a vinyl ketone group, and a vinyl chloride group. Among them, those having a (meth) acryl group similar to the polymer of the present invention are preferable. Examples of the anionic polymerizable group include (meth) acrylic group, styrene group, acrylonitrile group, N
-A vinylpyrrolidone group, an acrylamide group, a conjugated diene group, a vinyl ketone group, and the like. Among them, those having a (meth) acryl group similar to the polymer of the present invention are preferable.

Specific examples of the above monomers include (meth) acrylate monomers, cyclic acrylates, N-
Examples include vinylpyrrolidone, styrene-based monomers, acrylonitrile, N-vinylpyrrolidone, acrylamide-based monomers, conjugated diene-based monomers, and vinyl ketone-based monomers. Examples of (meth) acrylate monomers include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, and compounds of the following formulas. it can.

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[0125]

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As the styrene monomer, styrene, α
-Methylstyrene and the like; acrylamide-based monomers include acrylamide and N, N-dimethylacrylamide; conjugated diene-based monomers include butadiene and isoprene; and vinylketone-based monomers include methylvinylketone and the like.

Examples of the polyfunctional monomers include neopentyl glycol polypropoxy diacrylate, trimethylolpropane polyethoxy triacrylate, bisphenol F polyethoxy diacrylate, and bisphenol A
Polyethoxy diacrylate, dipentaerythritol polyhexanolide hexaacrylate, tris (hydroxyethyl) isocyanurate polyhexanolide triacrylate, tricyclodecane dimethylol diacrylate 2- (2-acryloyloxy-1,1-dimethyl) )
-5-ethyl-5-acryloyloxymethyl-1,3
-Dioxane, tetrabromobisphenol A diethoxy diacrylate, 4,4-dimercaptodiphenyl sulfide dimethacrylate, polytetraethylene glycol diacrylate, 1,9-nonanediol diacrylate, ditrimethylolpropane tetraacrylate and the like.

Examples of the oligomer include epoxy acrylate resins such as bisphenol A type epoxy acrylate resin, phenol novolak type epoxy acrylate resin, cresol novolak type epoxy acrylate resin, COOH group-modified epoxy acrylate resin, polyol (polytetramethylene glycol, ethylene Polyester diol of glycol and adipic acid, ε-caprolactone-modified polyester diol, polypropylene glycol, polyethylene glycol, polycarbonate diol, hydroxyl-terminated hydrogenated polyisoprene, hydroxyl-terminated polybutadiene, hydroxyl-terminated polyisobutylene, etc.) and organic isocyanates (tolylene diisocyanate, isophorone) Diisocyanate, diphenylmethane diisocyanate, hexamethyl Diisocyanates, xylylene diisocyanates, etc.) to obtain hydroxyl-containing (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and pentaerythritol triacrylate. Examples thereof include a urethane acrylate resin obtained by the reaction, a resin in which a (meth) acryl group is introduced into the above polyol via an ester bond, and a polyester acrylate resin.

These monomers and oligomers are selected according to the polymerization initiator used and the curing conditions. Further, the number average molecular weight of the monomer and / or oligomer having a (meth) acrylic group is preferably 2,000 or less, and more preferably 1,000 or less because of good compatibility.

The roller composition according to the second aspect of the present invention may optionally contain a filler, a storage stabilizer, a plasticizer, an ultraviolet absorber, a lubricant, a pigment, etc. for improving workability and cost. May be.

The method for curing the roller composition according to the second aspect of the present invention is not particularly limited, but heating and light irradiation are performed depending on the nature of the polymerization initiator (D).
In the case of light irradiation, for example, a high-pressure mercury lamp, a low-pressure mercury lamp,
Irradiation of light or an electron beam by an electron beam irradiation device, a halogen lamp, a light emitting diode, a semiconductor laser, or the like is performed.

By curing the roller composition according to the second aspect of the present invention by the above method, various rollers which can be used in contact with a photosensitive member of an electronic copying machine or a printer or various rollers which feed paper. Can be molded into After semi-curing, post-curing may be performed. In particular, in the case of a composition using a photopolymerization initiator, a molded article can be obtained by short-time light or electron beam irradiation.

The rollers formed by curing the roller compositions according to the first and second aspects of the present invention have good adhesiveness, so that the surface can be coated with a nylon-based material or covered with a heat-shrinkable tube. In this case, it can be used without prior primer treatment or coating with epichlorohydrin rubber like a conventional roller made of polyurethane or the like. As a result, variations in roller characteristics due to the intermediate layer are suppressed, and manufacturing costs can be reduced.

The manufactured roller has a specific resistance of 10
³ to 10 ¹⁰ Ω · cm, especially 10 ³ to 10 ⁶ Ω · cm when using carbon black, and 10 ⁷ to 10 ¹⁰ Ω · cm when using an organic antistatic agent. Can also be.

A roller (polymer protective layer) made of nylon, acrylic resin, fluororesin, urethane resin, silicone resin or the like to which an organic antistatic agent or a small amount of carbon black is added is applied to the roller manufactured as described above. It may be formed.

The surface layer has a thickness of 15 to 300 μm, preferably 30 to 200 μm, and is formed by coating or coating as a tube.

The specific resistance of the surface layer is 10 ⁷ to 10 ¹¹ Ω
Cm, preferably 10 ⁷ to 10 ⁹ Ω · cm, and when used for charging the photoreceptor, the resistance between the shaft and the surface is 0.1 to 100 MΩ, preferably 1 to 30 MΩ.
MΩ is 100 to 1 when used for toner transfer.
000 MΩ is used. When used for a non-magnetic toner developing roller, the roller is adjusted so as to have a roller resistance of 0.01 to 10 MΩ.

[0141]

EXAMPLES Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to the following examples. "Parts" and "%" in the following Examples and Comparative Examples
Represents “parts by weight” and “% by weight”, respectively. In the following examples, "number average molecular weight" and "molecular weight distribution (ratio of weight average molecular weight to number average molecular weight)" were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC). However, a GPC column packed with a polystyrene crosslinked gel and chloroform as a GPC solvent were used.

(Production Example 1)Alkenyl terminated poly (ac
Synthesis of butyl acrylate)  10 L separable flask with reflux tube and stirrer
Was charged with CuBr (28.0 g, 0.20 mol)
Then, the inside of the reaction vessel was replaced with nitrogen. Acetonitrile (55
9 mL) and stirred in an oil bath at 70 ° C. for 40 minutes.
Was. To this, butyl acrylate (1.00 kg), 2, 5
-Diethyl dibromoadipate (117 g, 0.325
mol), pentamethyldiethylenetriamine (1.7
mL, 1.41 g, 8.1 mmol) (hereinafter tria
(Designated as min) was added to initiate the reaction. Heat at 70 ° C
While stirring, butyl acrylate (4.00 kg) is continuously applied
Was dripped. Triamine during dropping of butyl acrylate
(8.5 mL, 7.06 g, 0.041 mol)
Added. 370 minutes after the start of the reaction, 1,7-octa
Diene (1.57L, 1.17kg, 10.65mo
l), triamine (20.4 mL, 16.8 g, 97.
2 mol), followed by heating and stirring at 70 ° C. for 220 minutes.
did. The reaction mixture was diluted with toluene and activated alumina
After passing through the ram, the volatiles are distilled off under reduced pressure to polymerize.
A body [1] was obtained. The number average molecular weight of the polymer is 21,300,
The molecular weight distribution was 1.36.

The polymer [1] (732 g) and potassium benzoate (2 g) were placed in a 10 L separable flask equipped with a reflux tube.
5.5 g), N, N-dimethylacetamide (700 m
l) was added and heated and stirred at 100 ° C. for 12 hours under a nitrogen stream. After removing N, N-dimethylacetamide under reduced pressure by heating, the mixture was diluted with toluene. The solids insoluble in toluene (KBr and excess potassium benzoate) were filtered through an activated alumina column. The volatile component of the filtrate was distilled off under reduced pressure to obtain a polymer [2].

In a 2 L round-bottom flask equipped with a reflux tube, polymer [2] (732 g), aluminum silicate (150 g, Kyowa Chemical Co., Ltd., 700 PEL), and toluene (4.0 g) were added.
L), and the mixture was heated and stirred at 100 ° C. for 3 hours under a nitrogen stream. After removing the aluminum silicate by filtration, toluene in the filtrate was distilled off under reduced pressure to obtain alkenyl-terminated poly (butyl acrylate) (hereinafter, referred to as polymer [3]). The number average molecular weight of the polymer [3] was 21,800, and the molecular weight distribution was 1.31. The average number of alkenyl groups introduced per molecule of polymer [3] was determined by ¹ H NMR to be 3.4.

(Production Example 2)Acryloyl-terminated poly (A
Synthesis of butyl acrylate)  10 L separable flask with reflux tube and stirrer
Was charged with CuBr (28.0 g, 0.20 mol)
Then, the inside of the reaction vessel was replaced with nitrogen. Acetonitrile (55
9 mL) and stirred in an oil bath at 70 ° C. for 40 minutes.
Was. To this, butyl acrylate (1.00 kg), 2, 5
-Diethyl dibromoadipate (117 g, 0.325
mol), pentamethyldiethylenetriamine (1.7
mL, 1.41 g, 8.1 mmol) (hereinafter tria
(Designated as min) was added to initiate the reaction. Heat at 70 ° C
While stirring, butyl acrylate (4.00 kg) is continuously applied
Was dripped. Triamine during dropping of butyl acrylate
(8.5 mL, 7.06 g, 0.041 mol)
Added. The reaction mixture was diluted with toluene and activated alumina
After passing through the column, the volatile components are distilled off under reduced pressure to obtain B
An r-terminal polymer (hereinafter referred to as polymer [4]) was obtained.
Number average molecular weight of polymer [4] is 19,500, molecular weight distribution
Was 1.17.

The above polymer [4] (300 g) was treated with N, N-
After dissolving in dimethylacetamide (300 mL),
Potassium acrylate (7.34 g: t-butoxy potassium)
(Synthesized by reacting acrylic acid with
Then, the mixture was heated and stirred at 70 ° C. for 3 hours under a nitrogen atmosphere. this
Dilute the mixture with 500 mL of toluene and wash several times with warm water
did. Organic layer_Two SO_Four Dried with activated alumina
After passing through the column, the toluene is distilled off under reduced pressure.
Acryloyl-terminated polymer (hereinafter referred to as polymer [5]
U). The number average molecular weight of the polymer [5] is 2020
0, molecular weight distribution was 1.19. Polymer [5] one minute
The average number of acryloyl groups introduced per child ¹ H N
It was 2.1 as determined by MR analysis.

(Example 1)Roller composition and roller
Creation (1)  100 parts of polymer [3], α-methylstyrene-modified polyphenol
Dromethylsiloxane (SiH value 3.70 mmol /
g) 6.29 parts, carbon black (# 55G, Asahi Car)
15 parts, antioxidant (Irganox 101)
0, Ciba Specialty Chemicals) 1 copy, 0 value
1,1,3,3-tetramethyl-1,3-divinyl of platinum
Rudisiloxane complex (1.32 × 10^-Fourmol / ml;
(Xylene solution) 0.075 ml, and degassing under reduced pressure
did. The viscosity of the obtained composition was 130 Pa · s.
Was. Put this around the 8mm diameter SUS shaft
An injection pressure of 1.0 is applied to a mold capable of forming a layer of about 4 mm.
It was injected at room temperature using a liquid injection molding machine at MPa. So
After that, the mold is allowed to stand at 160 ° C for 30 minutes to cure.
As a result, a roller made of a semiconductive rubber elastic body was obtained.
Was done.

(Example 2)Roller composition and roller
Creation (2)  100 parts of polymer [5], carbon black (# 55G,
15 parts, p-methoxyphenol 0.1
Parts (0.5 parts were added as a 20% ethyl acetate solution),
Perhexa 3M (1,1-di- (t-butyl)
Peroxy) -3,3,5-trimethylcyclohexa
And Nippon Oil & Fats Co., Ltd.), and degassing under reduced pressure.
Was. The viscosity of the obtained composition was 110 Pa · s.
Was. Put this around the 8mm diameter SUS shaft
Liquid injection molding machine in a mold that can form a layer of about 4 mm
Was injected using. This mold is placed in an environment of 150 ° C. for 30 minutes.
After curing by standing for a minute,
The resulting roller was obtained. Raws obtained in Examples 1-2
Evaluation of hardness, roller resistance, outer diameter accuracy and contamination of photoconductor
The results are shown in Table 1.

The JIS hardness is JIS K6253-1.
It was measured in accordance with 993. Asker C hardness was measured using an Asker C type rubber hardness tester manufactured by Kobunshi Keiki. The roller resistance value was measured by applying a load of 500 g (1 kg in total) to both ends of the shaft, placing the shaft on a metal plate, and measuring the resistance between the shaft and the plate when 100 V DC was applied. The outer diameter was measured with a laser outer diameter measuring device. The evaluation of the photoconductor contamination was performed by using an OPC (organic photoconductor) removed from a commercially available laser beam printer at 5
With a load of 00g (1kg in total) pressed against
After leaving still in an environmental tester at 40 ° C. × 90% for 7 days, the OPC was removed, the external appearance of the OPC was observed, and the image was returned to a laser beam printer for image evaluation.

[0150]

[Table 1]

As shown in Table 1, from the composition of this example, a roller having low hardness and excellent outer diameter dimensional accuracy without post-processing was obtained. Also, since it does not contain unreacted oligomers or low-molecular substances, there is no bleeding phenomenon, so that the photoreceptor and the intermediate transfer body are not contaminated, and development, charging,
Very high reliability when used as a transfer roller or cleaning roller.

The roller of this embodiment has a roller resistance of 1
Was from 0 ⁶ Ω 10 ⁹ Ω, but the type and amount of carbon black, or by the addition of a dispersing agent, can control the resistance value. In addition, the surface of the obtained roller is coated with a surface layer of nylon resin, acrylic resin, fluorine resin, urethane resin, silicone resin, etc. It is possible to control. By forming a surface layer according to the purpose, it can be used for various rollers.

As described above, the composition containing the acrylic polymer of this example as a main component is in a liquid state at room temperature, so that it is excellent in workability of compounding a conductive material and the like, and has a high curing speed. Injection molding is possible and excellent in moldability. Also,
Since the viscosity is low in the first place, there is no need to add non-reactive diluents or plasticizers to lower the viscosity. There is no migration of contaminants to the product, and it has excellent heat resistance.
Even if it is used for a long time as a charging roller or the like, a highly reliable roller can be obtained without deterioration of image quality due to contamination of the photoreceptor and the intermediate transfer member.

[0154]

According to the present invention, there is no contamination of the photoreceptor made of a semiconductive rubber elastic material containing a vinyl polymer, particularly an acrylic polymer, which is excellent in weather resistance and long-term reliability. Excellent rollers are obtained. Since crosslinking is performed by addition-type curing of the alkenyl-terminated polymer and radical curing of the polymerizable carbon-carbon double bond group, the curing speed is high and the moldability is excellent.

[Brief description of the drawings]

FIG. 1 is a side view of a shaft used for manufacturing a roller in Examples 1 and 2.

FIG. 2 is a side view of the rollers manufactured in Examples 1 and 2.

FIG. 3 is a cross-sectional view of a roller manufactured in Examples 1 and 2.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 33/00 F16C 13/00 A F16C 13/00 G03G 15/02 101 G03G 15/02 101 15/08 501D 15/08 501 15/16 103 15/16 103 C08F 8/00 21/10 C08K 5/54 // C08F 8/00 G03G 21/00 312

Claims (29)

[Claims] 1. A roller composition for use in an electronic copying machine or printer, comprising a vinyl polymer (A) having at least one alkenyl group in the molecule. 2. The roller composition according to claim 1, wherein the vinyl polymer (A) has an alkenyl group at a molecular terminal. 3. The roller composition according to claim 1, wherein the main chain of the vinyl polymer (A) is produced by living radical polymerization of a vinyl monomer. 4. The roller composition according to claim 3, wherein the main chain of the vinyl polymer (A) is produced by atom transfer radical polymerization of a vinyl monomer. 5. The vinyl polymer (A) is prepared by (1) producing a vinyl polymer having a halogen atom at a terminal by atom transfer radical polymerization, and (2) converting the halogen atom to an alkenyl group. The roller composition according to claim 4, which is produced by converting the compound into a substituent having the same. 6. The roller composition according to claim 1, wherein the main chain of the vinyl polymer (A) is obtained by polymerizing a (meth) acrylic acid monomer. 7. The roller composition according to claim 6, wherein the (meth) acrylic acid-based monomer is a (meth) acrylic acid ester monomer. 8. The roller composition according to claim 7, wherein the (meth) acrylate monomer is an acrylate monomer. 9. The roller composition according to claim 1, wherein the main chain of the vinyl polymer (A) is obtained by polymerizing a styrene monomer. 10. The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the vinyl polymer (A) measured by gel permeation chromatography (Mw / Mn).
The roller composition according to any one of claims 1 to 9, wherein the value of the roller composition is less than 1.8. 11. The vinyl polymer (A) having a number average molecular weight in the range of 500 to 100,000.
0. The composition for a roller according to any one of 0. 12. The roller according to claim 1, further comprising a curing agent (B) having at least two hydrosilyl groups in the molecule, and a hydrosilylation catalyst (C). Composition. 13. The roller composition according to claim 1, wherein the alkenyl group is a polymerizable carbon-carbon double bond. 14. The roller composition according to claim 13, wherein the alkenyl group is represented by the following general formula (1). CH ₂ ＣC (R ¹ ) —C (O) O— (1) (wherein, R ¹ is a hydrogen atom, a methyl group, —CN, or a C 1-20 carbon atom which may contain an oxygen atom. Represents a monovalent hydrocarbon group.) 15. The roller composition according to claim 13, further comprising a polymerization initiator (D). 16. The roller composition according to claim 15, wherein the polymerization initiator (D) is a thermal initiator. 17. The composition for a roller according to claim 15, wherein the polymerization initiator (D) is a photo-radical polymerization initiator. 18. The composition for a roller according to claim 15, wherein the polymerization initiator (D) is a photoanionic polymerization initiator. 19. A compound (E) for imparting conductivity.
The composition for a roller according to any one of claims 1 to 18, comprising: 20. The composition for a roller according to claim 19, wherein the compound (E) for imparting conductivity is carbon black. 21. The roller composition according to claim 19, wherein the compound (E) for imparting conductivity is an organic antistatic agent. 22. A roller having a specific resistance of 10 ³ to 1
The composition for a roller according to any one of claims 1 to 21, wherein the composition is 0 ¹⁰ Ω · cm. 23. A roller having a specific resistance of 10 ³ to 1
0 rollers composition according to any one of becomes ⁶ Omega · cm claims 1-21. 24. The obtained roller has a specific resistance of 10 ⁷ to 1
The composition for a roller according to any one of claims 1 to 21, wherein the composition is 0 ¹⁰ Ω · cm. 25. A roller produced by using the composition for a roller according to claim 1. Description: 26. The roller according to claim 25, manufactured by thermosetting. 27. The roller according to claim 25, manufactured by photocuring. 28. The roller according to claim 25, wherein a polymer protective layer having a thickness of 30 to 200 μm is provided on the surface. 29. The polymer protective layer has a specific resistance of 10 ⁷ to 10.
29. The roller according to claim 28, which has a resistance of ^11? Cm.