JP2008129444A - Conductive roller - Google Patents

Conductive roller Download PDF

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JP2008129444A
JP2008129444A JP2006316000A JP2006316000A JP2008129444A JP 2008129444 A JP2008129444 A JP 2008129444A JP 2006316000 A JP2006316000 A JP 2006316000A JP 2006316000 A JP2006316000 A JP 2006316000A JP 2008129444 A JP2008129444 A JP 2008129444A
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polyol
roller
polyol component
resistance value
component
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JP5129953B2 (en
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Ryuta Tanaka
隆太 田中
Kenichi Isayama
賢一 諌山
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Bridgestone Corp
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Bridgestone Corp
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductive roller which is less in environmental change in the resistance value of a roller and also less in resistance variation within a single roller. <P>SOLUTION: The conductive roller has an elastic roller formed from a polyurethane having a sea-island structure obtained by mixing and reacting: a polyol component (A) containing polyol blended with at least carbon black as a conductive agent; a polyol component (B) containing polyol incompatible with the polyol component (A) and blended with an ion conductive agent as a conductive agent; and an isocyanate component containing polyisocyanate. In the conductive roller, an environmental change in a resistance value (i.e., a difference between the resistance value in the environment in which a temperature is 10°C and a relative humidity is 15% and the resistance value in the environment in which a temperature is 28°C and a relative humidity is 85%) is ≤1.5 digits. Additionally, resistance variation (a difference between the maximum and minimum values of the resistance value when the roller is rotated one time under the environment in which a temperature is 10°C and a relative humidity is 15%) is ≤0.15 digits. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、導電性ローラ、特に複写機、ファクシミリ、プリンタ等の電子写真複写装置に使用する導電性ローラに関するものである。   The present invention relates to a conductive roller, and more particularly to a conductive roller used in an electrophotographic copying apparatus such as a copying machine, a facsimile machine, and a printer.

複写機、ファクシミリ、プリンタ等の電子写真複写装置には、通常、ポリウレタン等からなる弾性層を備え、該弾性層にイオン性導電剤やカーボンブラック等の導電剤を配合することによって導電性を付与した導電性ローラが使用されている。当該導電性ローラにおいて、導電剤としてイオン性導電剤を単独で配合した場合、環境条件の変化による該ローラの抵抗値の変動(抵抗値の環境変動)が大きくなるため、ローラに導電性を付与する手段として、導電剤としてカーボンブラックを単独で配合する手法(特許文献1)や、イオン性導電剤とカーボンブラックの両方を配合する手法(特許文献2)が採られてきた。   An electrophotographic copying apparatus such as a copying machine, a facsimile machine, or a printer is usually provided with an elastic layer made of polyurethane or the like, and conductivity is imparted to the elastic layer by adding a conductive agent such as an ionic conductive agent or carbon black. Conductive rollers are used. In the conductive roller, when an ionic conductive agent is blended alone as the conductive agent, the resistance of the roller varies due to changes in environmental conditions (environmental fluctuation of the resistance), thus imparting conductivity to the roller. As a means to do this, a method of blending carbon black alone as a conductive agent (Patent Document 1) and a method of blending both an ionic conductive agent and carbon black (Patent Document 2) have been adopted.

特開平8−166732号公報JP-A-8-166732 特開平7−33977号公報JP 7-33977 A

しかしながら、カーボンブラックを単独でローラに配合した場合には、当該ローラ1本内での抵抗値のバラツキ(抵抗バラツキ)が大きくなるため、画像ムラが生じ、また、ロット間でのローラの抵抗値の変動が大きくなるという問題点がある。また、イオン性導電剤とカーボンブラックの両方を配合する方法では、低温・低湿環境下でのローラ1本内で抵抗値バラツキが大きくなり、それによって画像ムラが生じるという問題点がある。   However, when carbon black is blended alone into a roller, the variation in resistance value (resistance variation) within the roller increases, resulting in image unevenness, and the roller resistance value between lots. There is a problem that fluctuations of In addition, the method of blending both an ionic conductive agent and carbon black has a problem in that the resistance value variation increases in one roller in a low temperature and low humidity environment, thereby causing image unevenness.

そこで、本発明は、上記従来技術の問題点を解決し、ローラの抵抗値の環境変動が小さく、かつローラ1本内での抵抗バラツキが小さい導電性ローラを提供することを目的とする。   SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a conductive roller in which the environmental variation of the resistance value of the roller is small and the resistance variation within one roller is small.

本発明者らは、上記問題点を解決すべく鋭意検討した結果、導電剤として少なくともカーボンブラックを分散させたポリオールを含むポリオール成分と、該ポリオール成分と相溶しにくく、導電剤としてイオン導電剤を分散させたポリオールを含むポリオール成分と、ポリイソシアネートを含むイソシアネート成分とを混合、反応させることによって得られる海島構造を有するポリウレタンからなる弾性層を備えるローラを製造することによって、イオン導電剤の特徴であるローラの抵抗値の均一性と、カーボンブラックの特徴である環境条件の変化により抵抗値が変動しないという特性を持つ導電性ローラを得、本発明を完成させた。   As a result of intensive studies to solve the above problems, the present inventors have found that a polyol component containing at least a carbon black dispersed as a conductive agent and an ionic conductive agent as a conductive agent are hardly compatible with the polyol component. Features of an ion conductive agent by producing a roller having an elastic layer made of polyurethane having a sea-island structure obtained by mixing and reacting a polyol component containing a polyol in which a polyol is dispersed and an isocyanate component containing a polyisocyanate Thus, a conductive roller having characteristics that the resistance value does not fluctuate due to the uniformity of the resistance value of the roller and the change in environmental conditions that is characteristic of carbon black was obtained, and the present invention was completed.

すなわち、本発明の導電性ローラは、導電剤として少なくともカーボンブラックを配合したポリオールを含むポリオール成分(A)と、該ポリオール成分(A)と相溶しにくく、導電剤としてイオン導電剤を配合したポリオールを含むポリオール成分(B)と、ポリイソシアネートを含むイソシアネート成分とを反応させることによって得られる海島構造を有するポリウレタンからなる弾性層を備える導電性ローラにおいて、抵抗値の環境変動(温度10℃、相対湿度15%の環境での抵抗値と、温度28℃、相対湿度85%の環境での抵抗値との差)が1.5桁以内であり、抵抗バラツキ(温度10℃、相対湿度15%の環境下でローラを1回転させたときの抵抗値の最大値と最小値との差)が0.15桁以内であることを特徴とする。   That is, the conductive roller of the present invention is incompatible with the polyol component (A) containing a polyol in which at least carbon black is blended as a conductive agent, and blended with an ionic conductive agent as the conductive agent. In a conductive roller having an elastic layer made of polyurethane having a sea-island structure obtained by reacting a polyol component (B) containing a polyol and an isocyanate component containing a polyisocyanate, the environmental fluctuation of the resistance value (temperature 10 ° C., The difference between the resistance value in an environment with a relative humidity of 15% and the resistance value in an environment with a temperature of 28 ° C and a relative humidity of 85% is within 1.5 digits, and the resistance varies (environment with a temperature of 10 ° C and a relative humidity of 15%) The difference between the maximum value and the minimum value of the resistance value when the roller is rotated once is within 0.15 digits.

本発明の導電性ローラの好適例においては、導電剤を配合していない前記ポリオール成分(A)に前記イソシアネート成分を反応させることによって得られるポリウレタンの抵抗値が導電剤を配合していない前記ポリオール成分(B)に前記イソシアネート成分を反応させることによって得られるポリウレタンの抵抗値より高いことを特徴とする。   In a preferred example of the conductive roller of the present invention, the polyol having a resistance value of polyurethane obtained by reacting the isocyanate component with the polyol component (A) not containing a conductive agent does not contain a conductive agent. The resistance value of the polyurethane obtained by reacting the isocyanate component with the component (B) is higher.

本発明の導電性ローラの他の好適例においては、前記ポリオール成分(A)に含まれるポリオールと、前記ポリオール成分(B)に含まれるポリオールとの質量比での比率が3:7〜7:3であることを特徴とする。   In another preferred embodiment of the conductive roller of the present invention, the ratio by mass ratio of the polyol contained in the polyol component (A) and the polyol contained in the polyol component (B) is from 3: 7 to 7: It is 3, It is characterized by the above-mentioned.

本発明の導電性ローラの他の好適例においては、前記カーボンブラックのDBP吸油量が100ml/100g以下であることを特徴とする。   In another preferred embodiment of the conductive roller of the present invention, the carbon black has a DBP oil absorption of 100 ml / 100 g or less.

本発明によれば、ローラの抵抗バラツキが小さく、環境条件の変化による抵抗値の変動が小さい導電性ローラを提供し得るという有利な効果を奏する。   According to the present invention, there is an advantageous effect that it is possible to provide a conductive roller in which the resistance variation of the roller is small and the resistance value varies little due to a change in environmental conditions.

以下に、本発明の詳細を説明する。本発明の導電性ローラは、導電剤として少なくともカーボンブラックを配合したポリオールを含むポリオール成分(A)と、該ポリオール成分(A)と相溶しにくく、導電剤としてイオン導電剤を配合したポリオールを含むポリオール成分(B)と、ポリイソシアネートを含むイソシアネート成分とを反応させることによって得られる海島構造を有するポリウレタンからなる弾性層を備える導電性ローラにおいて、抵抗値の環境変動(温度10℃、相対湿度15%の環境での抵抗値と、温度28℃、相対湿度85%の環境での抵抗値との差)が1.5桁以内であり、抵抗バラツキ(温度10℃、相対湿度15%の環境下でローラを1回転させたときの抵抗値の最大値と最小値との差)が0.15桁以内であることを特徴とする。   Details of the present invention will be described below. The conductive roller of the present invention comprises a polyol component (A) containing a polyol containing at least carbon black as a conductive agent and a polyol containing an ionic conductive agent as a conductive agent that is hardly compatible with the polyol component (A). In a conductive roller having an elastic layer made of polyurethane having a sea-island structure obtained by reacting a polyol component (B) containing polyisocyanate and an isocyanate component containing polyisocyanate, the environmental fluctuation of the resistance value (temperature 10 ° C., relative humidity) The difference between the resistance value in a 15% environment and the resistance value in an environment with a temperature of 28 ° C and a relative humidity of 85% is within 1.5 digits, and there is resistance variation (temperature of 10 ° C and relative humidity of 15%) The difference between the maximum and minimum resistance values when the roller is rotated once is within 0.15 digits.

本発明の導電性ローラの弾性層は、導電剤として少なくともカーボンブラックを配合したポリオールを含むポリオール成分(A)と、該ポリオール成分(A)と相溶しにくく、導電剤としてイオン導電剤を配合したポリオールを含むポリオール成分(B)と、ポリイソシアネートを含むイソシアネート成分とを反応させることによって得られる海島構造を有するポリウレタンからなる。前記ポリオール成分(A)及び前記ポリオール成分(B)は混合が容易であるため、きれいな海島構造を形成することができる。   The elastic layer of the conductive roller of the present invention is incompatible with the polyol component (A) containing a polyol containing at least carbon black as a conductive agent and the polyol component (A), and contains an ionic conductive agent as the conductive agent. It consists of a polyurethane having a sea-island structure obtained by reacting a polyol component (B) containing a prepared polyol with an isocyanate component containing a polyisocyanate. Since the polyol component (A) and the polyol component (B) are easily mixed, a clean sea-island structure can be formed.

ここで、ポリオール成分(A)及びポリオール成分(B)のうち、配合量が多いポリオール成分由来のポリウレタン部分が海部となり、配合量が少ないポリオール成分由来のポリウレタン部分が島部となる。ポリオール成分(A)及びポリオール成分(B)の配合量が同量である場合には、どちらのポリオール成分由来のポリウレタン部分が海部となってもよい。このような海島構造を弾性層に持たせることで、ローラの抵抗バラツキを小さくし、かつローラの抵抗値の環境変動を小さくすることができる。   Here, among the polyol component (A) and the polyol component (B), the polyurethane portion derived from the polyol component with a large blending amount becomes the sea portion, and the polyurethane portion derived from the polyol component with the small blending amount becomes the island portion. When the blending amount of the polyol component (A) and the polyol component (B) is the same amount, the polyurethane portion derived from either polyol component may be the sea portion. By giving such an island structure to the elastic layer, it is possible to reduce the resistance variation of the roller and to reduce the environmental variation of the resistance value of the roller.

さらに、本発明の導電性ローラは、抵抗値の環境変動(温度10℃、相対湿度15%の環境での抵抗値と、温度28℃、相対湿度85%の環境での抵抗値との差)が1.5桁以内であり、抵抗バラツキ(温度10℃、相対湿度15%の環境下でローラを1回転させたときの抵抗値の最大値と最小値との差)が0.15桁以内であることを特徴とする。ここで、抵抗値の環境変動は、温度10℃、相対湿度15%の環境(以下、L/L環境と呼ぶ)でのローラの抵抗値と温度28℃、相対湿度85%の環境(以下、H/H環境と呼ぶ)でのローラの抵抗値との差であり、L/L環境及びH/H環境での抵抗値は、それぞれL/L環境下及びH/H環境下でφ30mmのアルミドラム上でローラを回転させ、低電流制御にて10μAを流したときの電流値より算出したものである。また、抵抗バラツキは、L/L環境下でφ30mmのアルミドラム上でローラを1回転させ、ローラに1000Vの電圧を印加した時のローラの抵抗値の最大値と最小値との差である。   Furthermore, the conductive roller of the present invention has an environmental variation in resistance value (difference between a resistance value in an environment having a temperature of 10 ° C. and a relative humidity of 15% and a resistance value in an environment having a temperature of 28 ° C. and a relative humidity of 85%). Is within 1.5 digits, and the resistance variation (difference between the maximum and minimum resistance values when the roller is rotated once in an environment with a temperature of 10 ° C and a relative humidity of 15%) is within 0.15 digits. Features. Here, the environmental fluctuation of the resistance value is the resistance value of the roller in the environment of 10 ° C and relative humidity of 15% (hereinafter referred to as L / L environment), the environment of 28 ° C and relative humidity of 85% (hereinafter referred to as This is the difference between the roller resistance value in the H / H environment) and the resistance value in the L / L environment and H / H environment is 30 mm in aluminum in the L / L environment and H / H environment, respectively. This is calculated from the current value when a roller is rotated on the drum and 10 μA is passed under low current control. Further, the resistance variation is the difference between the maximum value and the minimum value of the resistance value when the roller is rotated once on a φ30 mm aluminum drum in an L / L environment and a voltage of 1000 V is applied to the roller.

ここで、環境変動が1.5桁以内の範囲内にないと、ローラの環境変動に対応する大容量の電源が必要となり、プリンターのコストアップとなる。また、抵抗バラツキが0.15桁以内の範囲内にないと、ハーフトーン画像や黒ベタ画像を印字した場合に、濃度ムラが発生する。   Here, if the environmental fluctuation is not within the range of 1.5 digits or less, a large-capacity power supply corresponding to the environmental fluctuation of the roller is required, which increases the cost of the printer. If the resistance variation is not within the range of 0.15 digits, density unevenness occurs when a halftone image or a solid black image is printed.

本発明の導電性ローラにおいては、導電剤を配合していないポリオール成分(A)にイソシアネート成分を反応させることによって得られるポリウレタンの抵抗値が導電剤を配合していないポリオール成分(B)にイソシアネート成分を反応させることによって得られるポリウレタンの抵抗値より高いことが好ましい。導電剤を配合していないポリオール成分(A)にイソシアネート成分を反応させることによって得られるポリウレタンの抵抗値が、導電剤を配合していないポリオール成分(B)にイソシアネート成分を反応させることによって得られるポリウレタンの抵抗値と同等であるか、又は低い場合、ローラ抵抗バラツキが大きくなる恐れがある。具体的には、導電剤を配合していないポリオール成分(A)にイソシアネート成分を反応させることによって得られるポリウレタンの抵抗値は、導電剤を配合していないポリオール成分(B)にイソシアネート成分を反応させることによって得られるポリウレタンの抵抗値より1桁以上高いことが好ましい。   In the conductive roller of the present invention, the resistance value of the polyurethane obtained by reacting the isocyanate component with the polyol component (A) not containing the conductive agent is isocyanate to the polyol component (B) not containing the conductive agent. It is preferably higher than the resistance value of the polyurethane obtained by reacting the components. The resistance value of the polyurethane obtained by reacting the isocyanate component with the polyol component (A) not containing the conductive agent is obtained by reacting the isocyanate component with the polyol component (B) not containing the conductive agent. When the resistance value is equal to or lower than that of polyurethane, the roller resistance variation may increase. Specifically, the resistance value of polyurethane obtained by reacting an isocyanate component with a polyol component (A) not containing a conductive agent is obtained by reacting an isocyanate component with a polyol component (B) containing no conductive agent. It is preferable that it is higher by one digit or more than the resistance value of the polyurethane obtained.

また、本発明の導電性ローラにおいては、前記ポリオール成分(A)に含まれるポリオールと、前記ポリオール成分(B)に含まれるポリオールの質量比での比率が3:7〜7:3であるのが好ましい。ポリオール成分(A)の比率が3以下の場合、希望する環境変動値が得られず、7より大きい場合は、カーボンブラックを単独で配合した場合と同様に抵抗バラツキが大きくなる。   In the conductive roller of the present invention, the ratio by mass ratio of the polyol contained in the polyol component (A) and the polyol contained in the polyol component (B) is from 3: 7 to 7: 3. Is preferred. When the ratio of the polyol component (A) is 3 or less, the desired environmental fluctuation value cannot be obtained, and when it is greater than 7, the resistance variation becomes large as in the case where carbon black is blended alone.

上記ポリオール成分(A)に含まれるポリオールとしては、ポリテトラメチレングリコール、ポリイソプレンポリオール、ポリブタジエンポリオール等が挙げられる。これらの中でも、コストメリット、作業性の観点から、ポリテトラメチレングリコール、ポリブタジエンポリオールが好ましい。   Examples of the polyol contained in the polyol component (A) include polytetramethylene glycol, polyisoprene polyol, and polybutadiene polyol. Among these, polytetramethylene glycol and polybutadiene polyol are preferable from the viewpoint of cost merit and workability.

上記ポリオール成分(B)に含まれるポリオールとしては、ポリプロピレングリコール、ポリエチレングリコール等が挙げられる。これらの中でも、環境変動をより低くする観点から、ポリプロピレングリコールが好ましい。これらのポリオールを含むポリオール成分(B)は、上記ポリオール成分(A)と相溶しにくい。また、上記に列挙したポリオール成分(A)に含まれるポリオールの抵抗値は上記に列挙したポリオール成分(B)に含まれるポリオールの抵抗値よりも高い。   Examples of the polyol contained in the polyol component (B) include polypropylene glycol and polyethylene glycol. Among these, polypropylene glycol is preferable from the viewpoint of lowering environmental fluctuation. The polyol component (B) containing these polyols is hardly compatible with the polyol component (A). Moreover, the resistance value of the polyol contained in the polyol component (A) listed above is higher than the resistance value of the polyol contained in the polyol component (B) listed above.

上記イソシアネート成分に含まれるポリイソシアネートとしては、MDI、TDI等すべてのポリイソシアネートが挙げられる。これらの中でも、フォーム物性、作業性の観点から、液状の変性MDIが好ましい。   Examples of the polyisocyanate contained in the isocyanate component include all polyisocyanates such as MDI and TDI. Among these, liquid modified MDI is preferable from the viewpoint of foam physical properties and workability.

本発明の導電性ローラにおいては、上記ポリオールを含むポリオール成分(A)に導電剤として少なくともカーボンブラックを配合することによって、ポリオール成分(A)に導電性を付与し、上記ポリオールを含むポリオール成分(B)に導電剤としてイオン導電剤を配合することによって、ポリオール成分(B)に導電性を付与する。上記ポリオール成分(A)に配合するカーボンブラックとしては、FT級、MT級サーマルブラック、SRF級オイルファーネスブラック等が挙げられる。これらの中でも、抵抗バラツキの均一性の観点から、FT級サーマルブラックが好ましい。   In the conductive roller of the present invention, by adding at least carbon black as a conductive agent to the polyol component (A) containing the polyol, the polyol component (A) is imparted with conductivity, and the polyol component containing the polyol ( By adding an ionic conductive agent as a conductive agent to B), conductivity is imparted to the polyol component (B). Examples of the carbon black to be blended with the polyol component (A) include FT grade, MT grade thermal black, SRF grade oil furnace black and the like. Among these, FT grade thermal black is preferable from the viewpoint of uniformity of resistance variation.

なお、本発明の導電性ローラにおいては、上記カーボンブラックのDBP吸油量が100ml/100g以下であることが好ましく、60ml/100g以下であることがより好ましい。本発明に使用するカーボンブラックのDBP吸油量が上記範囲であることによって、抵抗バラツキを制御したローラを生産することができる。また、上記カーボンブラックの配合量は、上記ポリオール成分(A)及び上記ポリオール成分(B)に含まれるポリオールの総和100質量部に対して8〜12質量部とするのが好ましい。   In the conductive roller of the present invention, the carbon black has a DBP oil absorption of preferably 100 ml / 100 g or less, and more preferably 60 ml / 100 g or less. When the DBP oil absorption amount of the carbon black used in the present invention is in the above range, a roller with controlled resistance variation can be produced. Moreover, it is preferable that the compounding quantity of the said carbon black shall be 8-12 mass parts with respect to 100 mass parts of sum total of the polyol contained in the said polyol component (A) and the said polyol component (B).

ポリオール成分(B)に配合するイオン導電剤としては、テトラエチルアンモニウム、テトラブチルアンモニウム、ドデシルトリメチルアンモニウム(例えばラウリルトリメチルアンモニウム)、ヘキサデシルトリメチルアンモニウム、オクタデシルトリメチルアンモニウム(例えばステアリルトリメチルアンモニウム)、ベンジルトリメチルアンモニウム、変性脂肪酸ジメチルエチルアンモニウム、ラウロイルアミノプロピルジメチルエチルアンモニウム等の第4級アンモニウム塩、リチウム、ナトリウム、カリウム、カルシウム、マグネシウム等のアルカリ金属やアルカリ土類金属等の、過塩素酸塩、塩素酸塩、塩酸塩、臭素酸塩、ヨウ素酸塩、ホウフッ化水素酸塩、硫酸塩、アルキル硫酸塩、カルボン酸塩、スルホン酸塩、トリフルオロメチル硫酸塩などが挙げられる。これらの中でも、ポリプロピレングリコールへの相溶性の観点から、過塩素酸ナトリウム、過塩素酸リチウムが好ましい。   Examples of the ionic conductive agent to be blended with the polyol component (B) include tetraethylammonium, tetrabutylammonium, dodecyltrimethylammonium (eg, lauryltrimethylammonium), hexadecyltrimethylammonium, octadecyltrimethylammonium (eg, stearyltrimethylammonium), benzyltrimethylammonium, Quaternary ammonium salts such as denatured fatty acid dimethylethylammonium and lauroylaminopropyldimethylethylammonium, perchlorates, chlorates, such as alkali metals and alkaline earth metals such as lithium, sodium, potassium, calcium and magnesium, Hydrochloride, bromate, iodate, borofluoride, sulfate, alkyl sulfate, carboxylate, sulfonate, trifluoro Such as methyl sulfate and the like. Among these, sodium perchlorate and lithium perchlorate are preferable from the viewpoint of compatibility with polypropylene glycol.

なお、ポリオール成分(A)には、導電剤として、上記カーボンブラックに加えて、ポリオール成分(B)に配合する導電剤として上記に列挙したイオン導電剤を配合してもよい。ポリオール成分(A)に配合するイオン導電剤の種類は、ポリオール成分(B)に配合するイオン導電剤と同じか、又は異なっていてもよい。   The polyol component (A) may be blended with the ionic conductive agents listed above as the conductive agent to be blended with the polyol component (B) in addition to the carbon black. The kind of ionic conductive agent mix | blended with a polyol component (A) may be the same as that of the ionic conductive agent mix | blended with a polyol component (B), or may differ.

上記ポリオール成分(A)と上記ポリオール成分(B)には、さらに触媒を添加するのが好ましい。該触媒は、ポリオール成分(A)又はポリオール成分(B)のいずれか一方に添加してもよく、また、両方に添加してもよい。該触媒は、ウレタン化反応用の触媒であり、例えばアミン系の触媒、有機金属触媒等が挙げられる。これらの触媒は単独で用いてもよく、また、2種以上組み合わせて用いてもよい。   It is preferable to further add a catalyst to the polyol component (A) and the polyol component (B). The catalyst may be added to either the polyol component (A) or the polyol component (B), or may be added to both. The catalyst is a catalyst for urethanization reaction, and examples thereof include amine-based catalysts and organometallic catalysts. These catalysts may be used alone or in combination of two or more.

上記ポリオール成分(A)、上記ポリオール成分(B)には、他にも、本発明の効果を損なわない範囲内で無機炭酸塩等の充填剤、シリコーン製泡剤や各種界面活性剤等の製泡剤、フェノールやフェニルアミン等の酸化防止剤、低摩擦化剤、電荷調整剤などを添加することができる。   In addition to the polyol component (A) and the polyol component (B), other fillers such as inorganic carbonates, silicone foaming agents, various surfactants and the like can be used without departing from the effects of the present invention. Foaming agents, antioxidants such as phenol and phenylamine, low friction agents, charge control agents and the like can be added.

本発明の導電性ローラは、上記ポリオール成分(A)、上記ポリオール成分(B)、上記イソシアネート成分を機械的攪拌により混合し、例えば、中心部に金属製のシャフトを配置した所望の形状の金型内へ注入後、加熱硬化させることによって製造することができる。   In the conductive roller of the present invention, the polyol component (A), the polyol component (B), and the isocyanate component are mixed by mechanical stirring, for example, a gold having a desired shape in which a metal shaft is arranged at the center. It can manufacture by heat-hardening after injection | pouring in a type | mold.

以下に、実施例を挙げて本発明をさらに詳しく説明するが、本発明は下記の実施例に何ら限定されるものではない。   Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

表1に示す配合処方に従い、表2に示す配合量のポリテトラメチレングリコール(PTMG)をポリオール成分(A)に、表2に示す配合量のポリプロピレングリコール(PPG)をポリオール成分(B)に配合し、さらに、表2に示す種類及び配合量のカーボンブラックを表2に示す通りにポリオール成分(A)及びポリオール成分(B)に配合して、各実施例及び比較例に用いるポリオール成分(A)及びポリオール成分(B)を得た。得られたポリオール成分(A)、ポリオール成分(B)、表1に示すイソシアネート成分を乾燥空気とともに機械的攪拌により混合し、発泡させ、得られた混合物を直径6mmの金属製シャフトを組み込んだ内径18mmの筒形状の金型へ注入し、90℃で3時間加熱硬化させた。得られたローラを脱型して、研磨し、外径16mmの導電性ローラを得た。実施例1〜5及び比較例1〜8の導電性ローラを得た。得られた導電性ローラのポリウレタン弾性層の断面を電子顕微鏡で観察したところ、比較例7及び8以外の実施例及び比較例のローラの弾性層は海島構造を有していた。また、ポリオール成分(A)に使用したポリオール(ポリテトラメチレングリコール、PTMG)は、該ポリオールに触媒及びイソシアネート成分を混合し、反応させて得られるポリウレタンの抵抗値がポリオール成分(B)に使用したポリオール(ポリプロピレングリコールPPG)に触媒及びイソシアネート成分を混合し、反応させて得られるポリウレタンの抵抗値よりも高いものである。得られた各実施例及び各比較例の導電性ローラの環境変動及び抵抗バラツキを測定した。測定結果を表2に示す。   In accordance with the formulation shown in Table 1, the amount of polytetramethylene glycol (PTMG) shown in Table 2 is added to the polyol component (A), and the amount of polypropylene glycol (PPG) shown in Table 2 is added to the polyol component (B). Further, the types and blending amounts of carbon black shown in Table 2 were blended into the polyol component (A) and the polyol component (B) as shown in Table 2, and the polyol component (A used in each Example and Comparative Example) ) And polyol component (B). The obtained polyol component (A), polyol component (B), and isocyanate component shown in Table 1 were mixed with dry air by mechanical stirring and foamed, and the resulting mixture had an inner diameter incorporating a metal shaft having a diameter of 6 mm. It was poured into an 18 mm cylindrical mold and cured by heating at 90 ° C. for 3 hours. The obtained roller was removed from the mold and polished to obtain a conductive roller having an outer diameter of 16 mm. The electroconductive roller of Examples 1-5 and Comparative Examples 1-8 was obtained. When the cross section of the polyurethane elastic layer of the obtained conductive roller was observed with an electron microscope, the elastic layers of the rollers of Examples and Comparative Examples other than Comparative Examples 7 and 8 had a sea-island structure. In addition, the polyol (polytetramethylene glycol, PTMG) used for the polyol component (A) was mixed with a catalyst and an isocyanate component in the polyol and reacted to obtain a resistance value of polyurethane used for the polyol component (B). The resistance value of the polyurethane obtained by mixing and reacting a polyol (polypropylene glycol PPG) with a catalyst and an isocyanate component is higher. Environmental fluctuations and resistance variations of the obtained conductive rollers of each Example and each Comparative Example were measured. The measurement results are shown in Table 2.

Figure 2008129444
Figure 2008129444

*1 重量平均分子量1000のポリテトラメチレングリコール.
*2 重量平均分子量5000のポリプロピレングリコール.
*3 ジメチルポリシロキサン−ポリオキシアルキレン共重合物(水酸基価32).
*4 ルプラネートMB301.
*5 各実施例及び比較例のPTMG及びPPGの配合量を表2に示す.
* 1 Polytetramethylene glycol with a weight average molecular weight of 1000.
* 2 Polypropylene glycol with a weight average molecular weight of 5000.
* 3 Dimethylpolysiloxane-polyoxyalkylene copolymer (hydroxyl value 32).
* 4 Lupranate MB301.
* 5 Table 2 shows the blending amounts of PTMG and PPG in each example and comparative example.

Figure 2008129444
Figure 2008129444

*6 DBP吸油量30ml/100g.
*7 デンカブラック(DBP吸油量125ml/100g).
* 6 DBP oil absorption 30ml / 100g.
* 7 Denka Black (DBP oil absorption: 125ml / 100g).

表2より、各実施例のローラでは、環境変動及び抵抗バラツキの両方が規定する範囲内、すなわち、環境変動が1.5桁以内で、抵抗バラツキが0.15桁以内であり、環境変動が小さく、かつ抵抗バラツキも小さいことが分かる。これに対して、各比較例のローラでは、環境変動及び抵抗バラツキのうちいずれか一方が上記の規定する範囲を越えていた。   From Table 2, the roller of each example is within the range specified by both environmental fluctuation and resistance variation, that is, environmental fluctuation is within 1.5 digits, resistance variation is within 0.15 digits, environmental fluctuation is small, and resistance is It can be seen that the variation is small. On the other hand, in the roller of each comparative example, either one of the environmental variation and the resistance variation exceeded the range specified above.

Claims (4)

導電剤として少なくともカーボンブラックを配合したポリオールを含むポリオール成分(A)と、該ポリオール成分(A)と相溶しにくく、導電剤としてイオン導電剤を配合したポリオールを含むポリオール成分(B)と、ポリイソシアネートを含むイソシアネート成分とを混合し、反応させることによって得られる海島構造を有するポリウレタンからなる弾性層を備える導電性ローラにおいて、環境変動(温度10℃、相対湿度15%の環境での抵抗値と、温度28℃、相対湿度85%の環境での抵抗値との差)が1.5桁以内であり、抵抗バラツキ(温度10℃、相対湿度15%の環境下でローラを1回転させたときの抵抗値の最大値と最小値との差)が0.15桁以内であることを特徴とする導電性ローラ。   A polyol component (A) containing a polyol blended with at least carbon black as a conductive agent, a polyol component (B) containing a polyol blended with an ionic conductive agent as a conductive agent that is hardly compatible with the polyol component (A), and In a conductive roller equipped with an elastic layer made of polyurethane with a sea-island structure obtained by mixing and reacting with an isocyanate component containing polyisocyanate, the environmental fluctuation (resistance value in an environment with a temperature of 10 ° C and a relative humidity of 15% And the difference between the resistance value in an environment with a temperature of 28 ° C and a relative humidity of 85% are within 1.5 digits, and the resistance variation (when the roller is rotated once in an environment with a temperature of 10 ° C and a relative humidity of 15%) A conductive roller characterized in that the difference between the maximum and minimum resistance values is within 0.15 digits. 導電剤を配合していない前記ポリオール成分(A)に前記イソシアネート成分を反応させることによって得られるポリウレタンの抵抗値が導電剤を配合していない前記ポリオール成分(B)に前記イソシアネート成分を反応させることによって得られるポリウレタンの抵抗値より高いことを特徴とする請求項1記載の導電性ローラ。   The polyurethane component obtained by reacting the isocyanate component with the polyol component (A) not blended with a conductive agent reacts the isocyanate component with the polyol component (B) not blended with a conductive agent. The conductive roller according to claim 1, wherein the resistance value is higher than the resistance value of the polyurethane obtained by the above. 前記ポリオール成分(A)に含まれるポリオールと、前記ポリオール成分(B)に含まれるポリオールとの質量比での比率が3:7〜7:3であることを特徴とする請求項1記載の導電性ローラ。   The ratio according to mass ratio of the polyol contained in the polyol component (A) and the polyol contained in the polyol component (B) is from 3: 7 to 7: 3. Sex roller. 前記カーボンブラックのDBP吸油量が100ml/100g以下であることを特徴とする請求項1記載の導電性ローラ。   The conductive roller according to claim 1, wherein the carbon black has a DBP oil absorption of 100 ml / 100 g or less.
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