JP5072616B2 - Method for producing composition for forming antistatic film - Google Patents

Description

The present invention relates to a method for producing a composition for forming an antistatic film.
The composition produced according to the present invention is used for forming an antistatic film. The antistatic film, a support having a controlled surface resistivity to a certain range of the semiconductor region, specifically, a copying machine, a facsimile, a component used in an image forming apparatus using an electrostatic action, such as a printer Used to configure .

Conventionally, fixing members of image forming apparatuses such as copiers, facsimiles, and printers have been required to be subjected to antistatic treatment in order to prevent an offset phenomenon in which toner is electrostatically attached. Proposals have been made. For example, in Japanese Patent Laid-Open No. 63-8777, carbon black is added to silicon rubber of a pressure roller to improve conductivity, and further, grounding is performed through a cored bar to prevent charging. Japanese Patent Application Laid-Open No. 63-55579 proposes making the fixing roller conductive and grounding it to prevent electrification. Japanese Patent Laid-Open No. 6-314047 proposes a fixing unit pressure roller in which a resistance value is controlled by adding a specific amount of carbon black to silicon rubber. Japanese Patent Application Laid-Open No. 7-77859 proposes a conductive roller using, as a base layer, rubber added with an ion conductive component whose volume resistivity is controlled to 10 ⁶ to 10 ⁹ Ω · cm. In JP-A-2-49055, JP-A-2-49056, and JP-A-6-73286, a conductive roller of an electrophotographic copying machine in which a resistance value is controlled by using a π-electron conjugated conductive polymer. Materials have been proposed.
Japanese Patent Laid-Open No. 63-8679 JP-A-63-55579 JP-A-6-314047 Japanese Unexamined Patent Publication No. 7-77859 JP-A-2-49055 JP-A-2-49056 JP-A-6-73286

  However, the methods described in Japanese Patent Application Laid-Open Nos. 63-8777 and 63-55579 have a problem that the paper itself is discharged because the conductivity is too good, and so-called transfer missing occurs. This phenomenon occurs in a particularly humid environment, and there is a problem of humidity dependency. In other words, this type of material is required to be controlled within a range where conductivity is required and not to depend on the use environment.

In the technique of Japanese Patent Laid-Open No. 6-314047, the conductivity of the entire material is controlled to an appropriate value. However, when the conductivity of a rubber material is controlled by adding a conductive material such as carbon black, it is not necessarily uniform at the micro level. Therefore, it cannot meet the demand for precise image formation. In addition, the conductive roller disclosed in JP-A-7-77859 has a complicated structure because an electrode layer, a resistance adjusting layer, and a protective layer are formed on a base layer made of an ion conductive elastic body.
In the case of a rubber material that is made conductive by adding an electron conductive component such as carbon black or metal powder or an ion conductive component such as an ammonium salt, the resistance value is likely to change due to a subtle variation in the amount added, It may be difficult to control the resistance value of a desired semiconductor region.

  JP-A-2-49055, JP-A-2-49056, and JP-A-6-73286 propose a material in which a π-electron conjugated conductive polymer is mixed with a matrix resin in order to solve the above problems. However, each time the fixing device design is changed, these methods require the composition and physical properties of the rubber material itself, which is not efficient and economical. It is rare.

As a result of intensive research to solve the problems of the prior art, a support whose surface is coated with a composition containing a π-electron conjugated conductive polymer and a resin component as conductive components exhibits desired characteristics. As a result, the present invention has been made. Since the π-electron conjugated conductive polymer is electronically conductive, it has a feature that the conductivity is less dependent on humidity and is suitable for this application. If a π-electron conjugated conductive polymer soluble in an organic solvent and / or water is selected and used, it can be uniformly mixed with various coating resins at a micro level.
That is, the present invention provides a method for producing a composition for forming an antistatic film comprising a π-electron conjugated conductive polymer and a resin component as conductive components .

（式中、ＸはＳ，Ｏ，Ｓｅ，ＴｅまたはＮＲ⁵ である。Ｒ¹およびＲ² はそれぞれ独立にＨ、炭素数１〜２０の直鎖状または分岐状の飽和もしくは不飽和のアルキル基、アルコキシ基、アルキルカルボン酸基、もしくはアルキルスルホン酸基、またはハロゲン、ニトロ基、アミノ基、トリハロメチル基、カルボキシル基、もしくはスルホン酸基を表す。Ｒ⁵は炭素数１〜１０の直鎖状もしくは分岐状の飽和もしくは不飽和のアルキル基、アルキルカルボン酸基、もしくはアルキルスルホン酸基、または炭素数６〜１０の置換もしくは非置換のアリール基を表す。Ｒ¹およびＲ²のアルキル基は互いに任意の位置で結合して環状鎖構造を形成してもよい。Ｒ¹ 、Ｒ² およびＲ⁵ のアルキル基、アルコキシ基、アルキルカルボン酸基、もしくはアルキルスルホン酸基にはカルボニル、エーテル、エステル、チオエーテル、スルホン酸エステル、アミド、スルホンアミド、スルホン結合を任意に含んでもよい。
ただし、Ｒ¹およびＲ²のアルキル基が互いに結合して環状鎖構造を形成して、一般式（I）で表される化学構造を有する繰り返し単位が下記一般式（II）

で表される化学構造を有する繰り返し単位に該当するものを除く。
一般式（II）において、ＸはＳ，Ｏ，Ｓｅ，ＴｅまたはＮＲ^６ である。Ｒ³およびＲ⁴ はそれぞれ独立にＨ、炭素数１〜２０の直鎖状または分岐状の飽和もしくは不飽和のアルキル基、アルコキシ基、アルキルカルボン酸基、もしくはアルキルスルホン酸基、またはハロゲン、ニトロ基、アミノ基、トリハロメチル基、カルボキシル基、もしくはスルホン酸基を表す。Ｒ^６は炭素数１〜１０の直鎖状もしくは分岐状の飽和もしくは不飽和のアルキル基、アルキルカルボン酸基、もしくはアルキルスルホン酸基、または炭素数６〜１０の置換もしくは非置換のアリール基を表す。Ｒ³ およびＲ⁴ のアルキル基は互いに任意の位置で結合して環状鎖構造を形成してもよい。Ｒ³ 、Ｒ⁴ およびＲ^６ のアルキル基、アルコキシ基、アルキルカルボン酸基、もしくはアルキルスルホン酸基にはカルボニル、エーテル、エステル、チオエーテル、スルホン酸エステル、アミド、スルホンアミド、スルホン結合を任意に含んでもよい）
で表される化学構造のうちの少なくとも一種を繰り返し単位として含む重合体であることを特徴とする帯電防止膜形成用組成物の製造方法。
1) A method for producing an antistatic film-forming composition comprising a step of dissolving or dispersing a π-electron conjugated conductive polymer in a solution containing a resin component,
The resin component is at least one of polyurethane, polyester, acrylic resin, polyamide, epoxy resin, alkyd resin, phenol resin, and polysiloxane;
The π-electron conjugated conductive polymer has the following general formula (I)

Wherein X is S, O, Se, Te or NR ^5. R ¹ and R ² are each independently H, a linear or branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms. , An alkoxy group, an alkylcarboxylic acid group, or an alkylsulfonic acid group, or a halogen, nitro group, amino group, trihalomethyl group, carboxyl group, or sulfonic acid group, wherein R ⁵ is a straight chain having 1 to 10 carbon atoms. or branched, saturated or unsaturated alkyl group, an alkyl carboxylic acid or alkyl sulfonic acid, or an alkyl group .R ¹ and R ² representing a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, each other It may be bonded at any position to form a cyclic chain structure: an alkyl group, an alkoxy group, an alkylcarboxylic acid group, or an alkyl group of R ¹ , R ² and R ⁵ The sulfonic acid group may optionally contain a carbonyl, ether, ester, thioether, sulfonic acid ester, amide, sulfonamide, or sulfone bond.
However, the alkyl group represented by R ¹ and R ² is bonded to each other to form a cyclic chain structure, and the repeating unit having the chemical structure represented by the general formula (I) is represented by the following general formula (II)

Except those corresponding to repeating units having a chemical structure represented by
In the general formula (II), X is S, O, Se, Te or NR ⁶ . R ³ and R ⁴ are each independently H, a linear or branched, saturated or unsaturated alkyl group, alkoxy group, alkylcarboxylic acid group, or alkylsulfonic acid group having 1 to 20 carbon atoms, or halogen, nitro Represents a group, an amino group, a trihalomethyl group, a carboxyl group, or a sulfonic acid group. R ⁶ represents a linear or branched saturated or unsaturated alkyl group, alkyl carboxylic acid group, or alkyl sulfonic acid group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. To express. The alkyl groups of R ³ and R ⁴ may be bonded to each other at an arbitrary position to form a cyclic chain structure. The alkyl group, alkoxy group, alkylcarboxylic acid group, or alkylsulfonic acid group of R ³ , R ^4, and R ⁶ optionally includes a carbonyl, ether, ester, thioether, sulfonic acid ester, amide, sulfonamide, sulfone bond May be)
A method for producing a composition for forming an antistatic film, wherein the polymer comprises at least one of the chemical structures represented by formula (1) as a repeating unit.

  2) The step of dissolving or dispersing the π-electron conjugated conductive polymer in the solution containing the resin component dissolves or disperses the π-electron conjugated conductive polymer in a solvent, and then the obtained solution Or the manufacturing method of the composition for antistatic film formation including the process of adding a dispersion liquid to the solution containing this resin component.

  3) The antistatic film-forming composition has a surface resistance value of 1 × 10 after removal of the solvent. ⁹  ~ 1x0 ¹³ A method for producing an antistatic film-forming composition capable of forming an antistatic film of Ω / □.

By using a support having an antistatic film formed of the antistatic film forming composition obtained Ri by the present invention as a fixing member of the image forming apparatus, it is possible to avoid the offset phenomenon, yet is small humidity dependency Therefore, it will not be affected by the usage environment. In addition, since the antistatic treatment layer on the surface of the fixing member is uniform, it is possible to form a very precise image. Furthermore, since an antistatic effect can be obtained simply by forming a film on the surface of the existing fixing member support, there is no need for a new material design, which is efficient and economical.

Hereinafter, the present invention will be described in detail.
In the π-electron conjugated conductive polymer compound containing a repeating unit having the chemical structure represented by the general formulas (I) and (II) , the substituents of R ¹ , R ² , R ³ and R ⁴ are respectively Independently H, alkyl group, alkoxy group, alkylcarboxylic acid group, or alkylsulfonic acid group, or halogen, nitro group, amino group, trihalomethyl group, carboxyl group, or sulfonic acid group, but alkyl group, alkoxy group The alkylcarboxylic acid group and the alkylsulfonic acid group have 1 to 20 carbon atoms, may be linear or branched, and may be saturated or unsaturated. More specifically, examples of the alkyl group include methyl, ethyl, propyl, allyl, isopropyl, butyl, tert-butyl, 1-butenyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and the like as alkoxy groups. Is methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, methoxyethoxy, 2- (2-methoxyethoxy) Ethoxy, etc., halogen, fluoro, chloro, bromo, etc., alkyl carboxylic acid group, methyl carboxylic acid, 2-ethyl carboxylic acid, 3-propyl carboxylic acid, 4-butyl carboxylic acid, 5-pentyl carboxylic acid, -Hexylcarboxylic acid, 7-heptylcarboxylic acid, 8-octylcarboxylic acid, 9-nonylcarboxylic acid, 10-decylcarboxylic acid, 11-undecylcarboxylic acid, 12-dodecylcarboxylic acid, 2-ethenylcarboxylic acid, 3 -(1-propenyl) carboxylic acid, 3- (2-propenyl) carboxylic acid, 4- (3-butenyl) carboxylic acid, 5- (4-propenyl) carboxylic acid, 6- (5-hexenyl) carboxylic acid, 7 -(6-heptenyl) carboxylic acid, 8- (7-octenyl) carboxylic acid, dimethylmethylcarboxylic acid, 2- (1-methyl) ethylcarboxylic acid, 2- (2-methyl) ethylcarboxylic acid, 2- (1 , 1-dimethyl) ethyl carboxylic acid, 2- (2,2-dimethyl) ethyl carboxylic acid, 3- (1-methyl) propyl carboxylic acid, 3- (2-methyl) ) Propyl carboxylic acid, 3- (3-methyl) propyl carboxylic acid, 3- (1,1-dimethyl) propyl carboxylic acid, 3- (2,2-dimethyl) propyl carboxylic acid, 3- (3,3-dimethyl) ) Alkylsulfonic acid groups such as propylcarboxylic acid, methylsulfonic acid, 2-ethylsulfonic acid, 3-propylsulfonic acid, 4-butylsulfonic acid, 5-pentylsulfonic acid, 6-hexylsulfonic acid, 7-heptylsulfone Acid, 8-octylsulfonic acid, 9-nonylsulfonic acid, 10-decylsulfonic acid, 11-undecylsulfonic acid, 12-dodecylsulfonic acid, 2-ethenylsulfonic acid, 3- (1-propenyl) sulfonic acid, 3- (2-propenyl) sulfonic acid, 4- (3-butenyl) sulfonic acid, 5- (4-propenyl) sulfonic acid, 6- 5-hexenyl) sulfonic acid, 7- (6-heptenyl) sulfonic acid, 8- (7-octenyl) sulfonic acid, dimethylmethylsulfonic acid, 2- (1-methyl) ethylsulfonic acid, 2- (2-methyl) Ethylsulfonic acid, 2- (1,1-dimethyl) ethylsulfonic acid, 2- (2,2-dimethyl) ethylsulfonic acid, 3- (1-methyl) propylsulfonic acid, 3- (2-methyl) propylsulfone Acid, 3- (3-methyl) propylsulfonic acid, 3- (1,1-dimethyl) propylsulfonic acid, 3- (2,2-dimethyl) propylsulfonic acid, 3- (3,3-dimethyl) propylsulfone An acid etc. are mentioned.

In the general formulas (I) and (II), X is a heteroatom such as S, O, Se, Te, or a group represented by NR ⁵ or NR ⁶ . R ⁵ and R ⁶ represent an alkyl group, an alkyl carboxylic acid group, an alkyl sulfonic acid group, or an aryl group, and the alkyl group, the alkyl carboxylic acid group, and the alkyl sulfonic acid group have 1 to 10 carbon atoms, It may be linear or branched and may be saturated or unsaturated. The aryl group has 6 to 10 carbon atoms and may be substituted or unsubstituted. Further, R ⁵ and R ⁶ may optionally contain carbonyl, ether, ester, thioether, sulfonate ester, amide, sulfone bond. Examples of the substituent of the substituted aryl group include alkyl groups such as methyl and ethyl, alkoxy groups such as methoxy and ethoxy, halogen atoms such as fluoro, chloro and bromo, trifluoromethyl and cyano groups. More specific examples of R ⁵ and R ⁶ are methyl, ethyl, propyl, allyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, methoxyethyl, ethoxyethyl, methyl carboxylic acid, ethyl carboxylic acid, 3-propyl carboxylic acid. Acid, 4-butylcarboxylic acid, 5-pentylcarboxylic acid, 6-hexylcarboxylic acid, methylsulfonic acid, ethylsulfonic acid, 3-propylsulfonic acid, 4-butylsulfonic acid, 5-pentylsulfonic acid, 6-hexylsulfone Examples include groups such as acid, acetonyl, acetyl, phenyl, tolyl, and xylyl.

The chemical structure represented by the general formula (I) thienylene, furylene, Sereniren, Terurire emissions, N - include substituted pyrrolylene skeleton. As the chemical structure represented by the general formula (II) isothianaphthenylene, isobenzofuran flip Ren, isobenzofuran selenides two Ren, isobenzofuran Tel relay emissions, N - include substituted isoindolylene skeleton.

In the present invention, the atomic groups represented by the symbols R ¹ to R ⁴ and X are completely independent of each other.

In general, a π-electron conjugated conductive polymer exhibits conductivity by an operation called doping that oxidizes or reduces a part of the π-electron conjugated structure. The π-electron conjugated conductive polymer used in the present invention cannot be defined unconditionally because its intrinsic conductivity varies depending on the structure, but it is preferable to perform the doping operation. As a doping method, either normal chemical doping or electrochemical doping may be used (see “Basics and Applications of Conducting Polymers—Synthesis / Physical Properties / Evaluation / Applied Technologies”). ). Further, by performing a doping operation, the π-electron conjugated conductive polymer compound includes an ionic species called a dopant. The types of dopant include halogen element ions such as iodine, bromine and chlorine, group 15 element halide ions such as PF ⁶⁻ , SbF ⁶⁻ , AsF ⁶⁻ and SbCl ⁶⁻ , and group 13 elements such as BF ^4−. Protonic acid anions such as halide ions, sulfuric acid, fluorosulfuric acid, chlorosulfuric acid, trifluoroacetic acid, trifluoromethanesulfonic acid, nitric acid, perchloric acid, polyacrylic acid, polymethacrylic acid, polystyrene sulfonic acid, polyvinyl sulfonic acid, poly Anion of polyelectrolyte such as phosphoric acid can be mentioned. In addition to these ionic species, electron acceptors such as quinones are also used as dopants.

Among the π-electron conjugated conductive polymers used in the present invention, those having a carboxylic acid group, an alkyl carboxylic acid group, a sulfonic acid group, or an alkyl sulfonic acid group as a substituent are called so-called self-doped polymers and have a dopant. It is a compound that develops conductivity without being added. Since these π-electron conjugated conductive polymers do not require a doping operation, they are useful in that they can be used easily.
The π-electron conjugated conductive polymer used in the present invention may be soluble or insoluble in an organic solvent and / or water, but is soluble for uniform mixing at a micro level. It is preferable that

  The resin mixed with the π-electron conjugated conductive polymer used in the present invention is selected to have good adhesion to the support. When the support is a rubber material, it has good adhesion to the rubber material of the base material, has flexibility to follow the rubber material, and does not impair the releasability required when used as a fixing roller Further, any material having heat resistance up to 200 ° C. may be used. Examples thereof include polyurethane, polyester, acrylic resin, polyamide, epoxy resin, alkyd resin, phenol resin, polysiloxane, and the like.

The antistatic film-forming composition produced according to the present invention is a liquid material in which a π-electron conjugated conductive polymer and a resin component are dissolved or dispersed, and the conductive polymer and the resin component are dissolved or dispersed in a solvent. As long as the method and the order of dissolution or dispersion are any method and order, the liquid material may be formed. In particular, a method in which a π-electron conjugated conductive polymer is dissolved or dispersed in a solution containing a resin component, or a π-electron conjugated conductive polymer is dissolved or dispersed in a solvent and then mixed with a solution containing a resin component. The method is preferred.

  The solvent that dissolves the resin component is a solvent that can dissolve the resin component at a desired concentration at room temperature or moderate heating, and can be the same or homogeneously mixed with the solvent that dissolves or disperses the π-electron conjugated conductive polymer. Any solvent can be used without particular limitation. For example, water, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, acetone, 2-butanone, methanol, ethanol, Isopropanol, n-butanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol Call dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, acetonitrile, propylene carbonate, tetrahydrofuran, benzene, toluene, xylene, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, dichloromethane, chloroform, carbon tetrachloride and the like. These solvents are used alone or in combination of two or more. The concentration of the resin component varies depending on the type of the resin component, the type of the solvent, and the desired film thickness of the antistatic film, and is not generally determined. It is. Although the temperature at the time of melt | dissolving a resin component in a solvent changes with kinds of solvent, the range of room temperature-100 degreeC is preferable normally.

The above-mentioned resin-ril silicone paint, acrylic epoxy paint, polyamide paint, epoxy paint, alkyd resin paint, phenol resin paint, silicon paint and the like can be mentioned and can be suitably used. Preferably, Nippon Polyurethane Industry Co., Ltd. “Nipporan” series, Dainippon Ink Chemical Co., Ltd. “Beckosol” series, “Acridic” series, “Barnock” series, “Spenlite” series, “Fluonate” series, "Priofen" series, "Rakkamide" series, "Epiclon" series, "Kanekazemulac" series manufactured by Kaneka Chemical Co., Ltd., "Polyflex" series, Daiichi Kogyo Seiyaku Co., Ltd., "Nippon Paint Co., Ltd." NIPPE SILICON TOP ”series,“ NITPOLAN 5109 ”,“ 5110 ”,“ 5111 ”,“ Same ”made by Nippon Polyurethane Industry Co., Ltd. 5115, 5124, 5128, 5120, 5120 135, 5137, 5138, 5189, 5232, 5232, 5236, 5199, 5230, 5233, 5195, Japan “Beccosol A-7600”, “M-7612-53”, “47-623”, “M-7605-55”, “M-7605-55MV”, “M” manufactured by Ink Chemical Co., Ltd. -7605-55HV "," M-7608-55 "," M-761-55 "," M-7615-60 "," M-7630-80 "," M-763-80 " , “M-7652-55”, “Acridic A-405”, “A-409”, “46-544”, “A-433”, “A-418”, “52- 101 "," 54-172-60 "," A-430-6 ""A-412-70S","A-413-70S","A-606-50S","A-801","A-801-P","56-719".",AU-1042","A-832","48-261","A-807","A-817","55-129","BU-955"."A-826","A-825-HV","DU-589","A-808","A-809","56-898","A-823"."FU-409","A-814","A-810-45","A-834","52-666","52-668","52-668","44-" 127 "," A-811 "," 52-614 "," A-911 "," A-914 "," A-915 "," Fluonate K-7 " 00 ”,“ K-702 ”,“ K-703 ”,“ K-704 ”,“ Priofen 5010 ”,“ 5030-40K ”,“ TD-447 ”,“ Rakkamide N-153 ” “IM-65”, “TD-966”, “TD-966-H”, “TD-973”, “B-201”, “TD-961”, “TD-971”, “ 15-202 "," Bernock DM-651 "," DM-652 "," DM-653 "," 9-434-2 "," DM-691-IM "," DM-675 ""DM-677""12-406""16-416""16-411""DF-407""18-472" Kaneka Chemical Co., Ltd. “Kanekazem Lac” manufactured by Daiichi Kogyo Seiyaku Co., Ltd. “Polyflex MT”, “SL- “3”, “MH”, “UF”, “WP-1”, “WP-2”, “WP-4”, “WP-5”, “WP-7”, “ "WP-8", "Same WP-9", "Same 90H", "Same FL-83", "Same FL-87", "Same NS", "Same NR", "Same NW", "Same PR""SamePR-42","SameNY-35","SameNY-40U","SameNY-20","SameM-50","SameBD-1","SameBD-2","SameN-100","SameN-120".
When the π-electron conjugated conductive polymer of the present invention is dissolved or dispersed in a solution containing a resin component, the mixing ratio of the π-electron conjugated conductive polymer depends on the type of π-electron conjugated conductive polymer and the resin. It varies depending on the type and the desired antistatic performance of the film, and is generally not determined, but is usually 1 to 20% by weight based on the resin component.

  In addition, as a solvent for dissolving or dispersing a π-electron conjugated conductive polymer, which is used when the π-electron conjugated conductive polymer is dissolved or dispersed in a solvent and then mixed with a solution containing a resin component, It is a solvent that can dissolve or disperse the π-electron conjugated conductive polymer at a desired concentration at room temperature or moderate heating, and it is not particularly limited as long as it is the same or homogeneously mixed with the solvent that dissolves the resin component. Are, for example, water, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, acetone, 2-butanone, methanol, ethanol, isopropanol, ethylene glycol, ethylene glycol monomethyl ether , Ethylene glycol dimethyl ether, ethylene glycol monoethyl ether , Ethylene glycol diethyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, acetonitrile, propylene carbonate, tetrahydrofuran, benzene, toluene, xylene, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, Examples include dichloromethane, chloroform, carbon tetrachloride and the like. These solvents are used alone or in combination of two or more. The concentration of the π-electron conjugated conductive polymer varies depending on the type of the π-electron conjugated conductive polymer and the type of the solvent and is not generally determined, but is usually 0.1 to 80% by weight, preferably 5 to 5%. 50 weight percent. Although the temperature at which the π-electron conjugated conductive polymer is dissolved in a solvent varies depending on the type of the solvent, it is usually preferably in the range of room temperature to 150 ° C.

  In the production of the antistatic film-forming composition of the present invention, the resin component is dissolved in a solvent, the π-electron conjugated conductive polymer is dissolved or dispersed in a solution containing the resin component, and the π-electron conjugated conductive polymer is used. The method of dissolving or dispersing in a solvent, or mixing a solution or dispersion of a π-electron conjugated conductive polymer with a solution containing a resin component may be any method as long as a uniform liquid is obtained. However, for example, a method using a normal mixing device such as a mechanical stirring device, a magnetic stirrer, a ball mill, a paint shaker, or a mortar can be used.

In order to produce an antistatic film by using the antistatic film-forming composition produced as described above and produce a support having an antistatic film, the composition is applied or sprayed on the support. Alternatively, the solvent may be removed after the support is immersed in the composition.
Taking the case where the support is rubber as an example, the method for applying the antistatic film-forming composition to the surface of the rubber material is a normal dip coat depending on the form of the target rubber material and the target film thickness. Bar coating, applicator coating, spin coating, brush coating, spraying, and the like can be used. Moreover, although the drying and hardening method of a coating film changes with kinds of the resin composition and coating material to be used, in order to dry and harden in a short time, it is good to heat at 60-150 degreeC. In addition, an appropriate curing agent may be added as necessary as long as the physical properties are not significantly adversely affected.

A method of forming an antistatic film from the compositions according to the invention, not only a method by coating or spraying or dipping using the antistatic film forming composition containing the above described solvents, [pi electron conjugated conductive polymer and the resin The composition for forming an antistatic film containing the components may be heat-pressed on the surface of the support to be antistatically treated. For example, there may be mentioned a method in which such a conductive polymer and a resin component are dissolved or melt-mixed and a composition for forming an antistatic film formed into a film is heat-pressed to the support surface.

  The film thickness of the antistatic film varies depending on the target surface resistance value and the material of the support serving as the base material, that is, mechanical and electrical characteristics, and thus cannot be generally limited, but is preferably 0.1 to 500 μm, Preferably it is 1-100 micrometers. When the film thickness is smaller than 0.1 μm, it is easily influenced by the physical properties of the substrate, and it becomes difficult to control the characteristics. Moreover, when the film thickness is larger than 500 μm, it is difficult to form a film having a uniform film thickness.

The surface resistance value of the antistatic film is preferably 1 × 10 ⁹ to 1 × 10 ¹³ Ω / □. When the support is a fixing roller or a transfer roller, if the surface resistance is less than 1 × 10 ⁹ Ω / □, the static electricity of the paper is released and the toner does not come off. On the other hand, if it is greater than 1 × 10 ¹³ Ω / □, the toner may be repelled and not transferred to the roller or repelled.

The support used is not limited, and examples thereof include a polymer molded body such as a thermoplastic polymer molded body and a thermosetting polymer molded body, and a molded body having rubber elasticity. In addition to rollers, belts, rings, tubes, spheres, flat plates, etc., the shape may be any shape depending on the individual application.
Taking a rubber material used as a fixing roller as an example, the material is required for use as a fixing roller, such as hardness, nip properties, and other mechanical properties, and up to 200 ° C. required for toner heat fixing. There is no particular limitation as long as the heat resistance is satisfied, and examples thereof include rubber materials such as butyl rubber, butadiene rubber, isoprene rubber, chloroprene rubber, SBR, NBR, EPR, silicon rubber, fluorine rubber, and urethane rubber. These rubber materials may contain additives in order to control various properties such as mechanical properties and electrical properties. In addition, in order to stably obtain the surface resistance value of 10 ⁹ to 10 ¹² Ω / □, the inherent surface resistance value of the rubber material as the base material is 1 × 10 ⁹ Ω / □ or more. preferable. Examples of the roller that can be used as the support of the present invention include a fixing roller, an image forming apparatus roller such as a transfer roller, a cleaning roller, and a charging roller, and a copy paper conveyance roller.

  The rubber material coated with the resin composition containing the π-electron conjugated conductive polymer of the present invention is characterized in that the variation in surface resistance due to humidity is small by using the electron-conductive π-electron conjugated conductive polymer. Have The fluctuation is within an order of magnitude within the range of 5% to 80% humidity.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the technical scope of the present invention is not limited by these examples.
[Example 1] (Reference Example)
100 g of polyurethane paint “Nipporan 5137” (manufactured by Nippon Polyurethane Industry Co., Ltd.) and 3.0 g of poly (1,3-isothianaphthenylene-5-sulfonic acid) previously added and mixed with 12.0 g of water Were mixed using a ball mill (80 rpm, 1 hour).
The coating composition obtained by the above method was applied on an insulating butyl rubber plate (10 × 10 cm) having a surface resistance of 3 × 10 ¹⁵ Ω / □ using a bar coater so as to have a film thickness of 10 μm. . The surface resistance value of the coating film was 1 × 10 ¹¹ Ω / □ under high humidity (85%) and 6 × 10 ¹¹ Ω / □ under low humidity (10%). : Measured with HR probe).

[Example 2] (Reference Example)
The preparation method and coating method are the same as in Example 1 except that the amount of poly (1,3-isothianaphthenylene-5-sulfonic acid) added is 1.5 g and the amount of water is 7.5 g. The surface resistance value was 3 × 10 ¹² Ω / □ under high humidity and 8 × 10 ¹² Ω / □ under low humidity.

[Example 3] (Embodiment of the present invention)
The addition amount, the preparation method, and the coating method are the same as in Example 1 except that poly [2,5-thienylene-3- (3-propanesulfonic acid)] is used as the π-electron conjugated conductive polymer. The surface resistance value was 1 × 10 ¹² Ω / □ under high humidity and 7 × 10 ¹² Ω / □ under low humidity.

[Example 4] (Reference Example)
An addition amount, a preparation method, and a coating method, except that poly (1,4-iminophenylene) doped with HCl is used as the π-electron conjugated conductive polymer, and water in Example 1 is changed to N-methyl-2-pyrrolidone. Is the same as in Example 1. The surface resistance value was 2 × 10 ¹⁰ Ω / □ under high humidity and 9 × 10 ¹⁰ Ω / □ under low humidity.

[Example 5] (Embodiment of the present invention)
An addition amount, a preparation method, and a coating method, except that poly (3-octyl-2,5-thienylene) containing iodine as a dopant is used as a π-electron conjugated conductive polymer and water in Example 1 is changed to ethyl acetate. Is the same as in Example 1. The surface resistance value was 8 × 10 ¹¹ Ω / □ under high humidity and 3 × 10 ¹² Ω / □ under low humidity.

[Example 6] (Embodiment of the present invention)
Addition except that poly (N-octyl-2,5-pyrrolylene) containing a perchlorate anion as a dopant is used as the π-electron conjugated conductive polymer and the water in Example 1 is N-methyl-2-pyrrolidone The amount, preparation method and coating method are the same as in Example 1. The surface resistance value was 6 × 10 ¹⁰ Ω / □ under high humidity and 3 × 10 ¹¹ Ω / □ under low humidity.

[Example 7] (Reference Example)
The amount of addition, the preparation method, and the coating method are the same as in Example 1 except that “Nipporan 5120” is used as the polyurethane paint and the film thickness is 20 μm. The surface resistance value was 8 × 10 ¹⁰ Ω / □ under high humidity and 4 × 10 ¹¹ Ω / □ under low humidity.

[Example 8] (Reference Example)
“Acridic A-606-50S” (Dainippon Ink Chemical Co., Ltd.) 100 g as an acrylic resin coating, poly (1,3-isothianaphthenylene-5-sulfonic acid) as a π-electron conjugated conductive polymer The preparation method and coating method are the same as in Example 1 except that 2.50 g (7.50 g of water is added in advance as in Example 1) is used. The surface resistance value was 1.5 × 10 ¹¹ Ω / □ under high humidity and 4 × 10 ¹¹ Ω / □ under low humidity.

[Example 9] (Reference Example)
The addition amount, the preparation method, and the coating method are the same as in Example 1 except that 100 g of “Kanekazemulac” (manufactured by Kaneka Chemical Co., Ltd.) is used as the acrylic silicone resin. The surface resistance value was 2 × 10 ¹² Ω / □ under high humidity and 6.5 × 10 ¹² Ω / □ under low humidity.

[Example 10] (Reference Example)
Poly (1,4-iminophenylene) using 100 g of “Racamide TD-966-H” (Dainippon Ink Chemical Co., Ltd.) as the polyamide resin and polystyrenesulfonic acid as a dopant as the π-electron conjugated conductive polymer The preparation method and the coating method are the same as in Example 1 except that 6.00 g (15.00 g of water is added in advance as in Example 1) was used. The surface resistance value was 7 × 10 ⁹ Ω / □ under high humidity and 2 × 10 ¹⁰ Ω / □ under low humidity.

[Example 11] (Reference Example)
Using the composition prepared in Example 1, an antistatic film having a thickness of about 20 μm was formed on a fixing device roller of a copying machine “PC-10” (manufactured by Canon Inc.). As a result of performing a 2000-sheet printing test, no offset phenomenon occurred when the paper was not processed. Also, there were no problems such as paper wrapping.

[Example 12] (Reference Example)
100 g of acrylic silicone paint “Kanekazemulac” (manufactured by Kaneka Chemical Co., Ltd.) as the resin component, 2.50 g of poly (1,3-isothianaphthenylene-5-sulfonic acid) as the π-electron conjugated conductive polymer (In advance, 7.50 g of water was added and mixed), and both were mixed using a ball mill (80 rpm, 1 hour). A polyacetal plate (10 × 10 cm, surface resistance value: 2 × 10 ¹⁴ Ω / □), which is a thermoplastic resin, is used as a support, and the obtained composition is applied onto the support so that the film thickness becomes 20 μm. It applied using. After the coating film was heated and dried at 100 ° C. for 1 hour, the surface resistance was measured and found to be 4 × 10 ¹⁰ Ω / □ under high humidity and 9 × 10 ¹⁰ Ω / □ under low humidity.

[Example 13] (Reference Example)
The addition amount and the preparation method are the same as in Example 1 except that “Nipporan 5111” is used as the polyurethane resin. A melamine resin plate (10 × 10 cm, surface resistance value: 8 × 10 ¹⁵ Ω / □), which is a thermosetting resin, is used as a support, and the film thickness of the obtained composition is 10 μm on the support. Application was performed using an applicator. After the coating film was heated and dried at 120 ° C. for 2 hours, the surface resistance value was measured and found to be 8 × 10 ¹⁰ Ω / □ under high humidity and 3 × 10 ¹¹ Ω / □ under low humidity.

[Example 14] (Reference Example)
After adding 3 wt% of poly (1,3-isothianaphthenylene-5-sulfonic acid) to a polyurethane resin “Tuftane” (manufactured by Goodrich Chemical) and melt-kneading, it was formed into a film having a thickness of 50 μm by an extrusion method. . A urethane rubber plate (10 × 10 cm, thickness 0.3 cm, surface resistance value: 1 × 10 ¹⁵ Ω / □) was covered with the obtained film, and the film was pressure-bonded using a hot press apparatus. When the surface resistance value was measured, it was 7.5 × 10 ¹¹ Ω / □ under high humidity and 1 × 10 ¹² Ω / □ under low humidity.

[Example 15] (Reference Example)
Polyamide: Nylon 12 (film grade) is used as a resin component, and 5 wt% of poly (1,3-isothianaphthenylene-5-sulfonic acid) is added to produce a film having a thickness of 50 μm as in Example 14. did. The obtained film was thermocompression bonded to the urethane rubber plate surface in the same manner as in Example 14. The surface resistance value was 3 × 10 ¹¹ Ω / □ under high humidity and 1 × 10 ¹² Ω / □ under low humidity.

[Example 16] (Reference Example)
Polypropylene (film grade) was used as the resin component, 5 wt% of poly (1,3-isothianaphthenylene-5-sulfonic acid) was added, and a film having a thickness of 50 μm was produced in the same manner as in Example 14. The obtained film was thermocompression bonded to the urethane rubber plate surface in the same manner as in Example 14. The surface resistance value was 2.5 × 10 ¹² Ω / □ under high humidity and 6 × 10 ¹² Ω / □ under low humidity.

Claims (3)

A method for producing an antistatic film-forming composition comprising a step of dissolving or dispersing a π-electron conjugated conductive polymer in a solution containing a resin component,
The resin component is at least one of polyurethane, polyester, acrylic resin, polyamide, epoxy resin, alkyd resin, phenol resin, and polysiloxane;
The π-electron conjugated conductive polymer has the following general formula (I)

Wherein X is S, O, Se, Te or NR ^5. R ¹ and R ² are each independently H, a linear or branched saturated or unsaturated alkyl group having 1 to 20 carbon atoms. , An alkoxy group, an alkylcarboxylic acid group, or an alkylsulfonic acid group, or a halogen, nitro group, amino group, trihalomethyl group, carboxyl group, or sulfonic acid group, wherein R ⁵ is a straight chain having 1 to 10 carbon atoms. or branched, saturated or unsaturated alkyl group, an alkyl carboxylic acid or alkyl sulfonic acid, or an alkyl group .R ¹ and R ² representing a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, each other It may be bonded at any position to form a cyclic chain structure: an alkyl group, an alkoxy group, an alkylcarboxylic acid group, or an alkyl group of R ¹ , R ² and R ⁵ The sulfonic acid group may optionally contain a carbonyl, ether, ester, thioether, sulfonic acid ester, amide, sulfonamide, or sulfone bond.
However, the alkyl group represented by R ¹ and R ² is bonded to each other to form a cyclic chain structure, and the repeating unit having the chemical structure represented by the general formula (I) is represented by the following general formula (II)

Except those corresponding to repeating units having a chemical structure represented by
In the general formula (II), X is S, O, Se, Te or NR ⁶ . R ³ and R ⁴ are each independently H, a linear or branched, saturated or unsaturated alkyl group, alkoxy group, alkylcarboxylic acid group, or alkylsulfonic acid group having 1 to 20 carbon atoms, or halogen, nitro Represents a group, an amino group, a trihalomethyl group, a carboxyl group, or a sulfonic acid group. R ⁶ represents a linear or branched saturated or unsaturated alkyl group, alkyl carboxylic acid group, or alkyl sulfonic acid group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. To express. The alkyl groups of R ³ and R ⁴ may be bonded to each other at an arbitrary position to form a cyclic chain structure. The alkyl group, alkoxy group, alkylcarboxylic acid group, or alkylsulfonic acid group of R ³ , R ^4, and R ⁶ optionally includes a carbonyl, ether, ester, thioether, sulfonic acid ester, amide, sulfonamide, sulfone bond May be)
A method for producing a composition for forming an antistatic film, wherein the polymer comprises at least one of the chemical structures represented by formula (1) as a repeating unit.

  The step of dissolving or dispersing the π-electron conjugated conductive polymer in the solution containing the resin component dissolves or disperses the π-electron conjugated conductive polymer in a solvent, and then the obtained solution or dispersion is The manufacturing method of the composition for antistatic film formation of Claim 1 including the process added to the solution containing a resin component. The composition for forming an antistatic film is capable of forming an antistatic film having a surface resistance value of 1 × 10 ⁹ to 1 × 10 ¹³ Ω / □ after removal of the solvent. Manufacturing method of antistatic film forming composition.