JP2002179754A - Soft polyurethane foam, method for producing the same, electro-conductive roller using the same and electrophotographic device using the electro-conductive roller - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an electro-conductive polyurethane foam having a steady electric resistance not affected by surrounding environment, and to provide its production method and its use. SOLUTION: This soft polyurethane foam is obtained by reacting an isocyanate compound with a polyol under the condition that a compound salt solution comprising an equivalent mixture composed of either combination of ammonium thiocyanate and ferrous chloride, sodium thiocyanate and ferrous chloride, potassium thiocyanate and ferrous chloride, ammonium formate and ferrous chloride, ammonium formate and ferric chloride, ammonium thiocyanate and ferrous bromide, sodium thiocyanate and ferrous bromide, potassium thiocyanate and ferrous bromide, and ammonium formate and ferrous bromide is added in a specified amount or more to the polyol. Using the soft polyurethane foam, an electro-conductive roller for an electrophotographic device or the like can be made.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a conductive soft foamed polyurethane whose electric resistance does not depend on the environment. More specifically, the present invention is directed to the production of a conductive soft foamed polyurethane in which the electric resistance value of these rolls hardly changes even if the temperature or humidity around the charging roll or the transfer roll, which is composed of the soft foamed polyurethane, changes. A flexible foamed polyurethane obtained by the method,
The present invention relates to a conductive roll using the flexible foamed polyurethane and an electrophotographic apparatus using the conductive roll.

[0002]

2. Description of the Related Art When a soft foamed polyurethane is used for a conductive roll such as a charging roll and a transfer roll of an electrophotographic apparatus, it is recognized that a change in electric resistance due to an environmental change (temperature and humidity) occurs. The use of soft foamed polyurethane for rolls and the like causes various obstacles.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a conductive soft foamed polyurethane whose electric resistance hardly changes even when the temperature or humidity changes, a flexible foamed polyurethane obtained by the production method, An object of the present invention is to provide a conductive roll using the flexible foamed polyurethane and an electrophotographic apparatus using the conductive roll.

[0004]

Accordingly, the present invention provides a mixed salt solution of an equivalent mixture of ammonium thiocyanate and ferrous chloride, a mixed salt solution of an equivalent mixture of sodium thiocyanate and ferrous chloride with respect to a polyol, Equivalent mixed mixed salt solution of potassium and ferrous chloride, equivalent mixed mixed salt solution of ammonium formate and ferrous chloride, equivalent mixed mixed salt solution of ammonium formate and ferric chloride, ammonium thiocyanate and ferrous bromide Equivalent mixed complex salt solution, sodium thiocyanate and ferrous bromide equivalent mixed salt solution, potassium thiocyanate and ferrous bromide equivalent mixed salt solution, and ammonium formate and ferrous bromide equivalent mixture The isocyanate compound is reacted with the polyol under a condition in which a solution selected from the group consisting of the complex salt solution is added in a predetermined amount or more to form a soft foamed polyurethane. It is set to be produced down.

Further, in the present invention, the soft foamed polyurethane is used in a conductive roll such as a charging roll and a transfer roll for an electrophotographic apparatus.

Further, the present invention provides a photosensitive member, a latent image forming means,
In an electrophotographic apparatus having a unit for developing the formed latent image and a unit for transferring the developed image to a transfer material, using the conductive roll described above as the latent image forming unit when charging the photosensitive member. I do.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Table 1 shows an example of a change in electrical resistance of a foamed polyurethane due to environmental changes (temperature and humidity) for a flexible foamed polyurethane and an elastomer.

[0008]

[Table 1] In the table, it is confirmed that the electric resistance changes over two orders due to changes in the environment (15 ° C. × 10% to 30 ° C. × 80%), and the electric resistance decreases as the temperature and humidity increase. Shows a tendency to. In general-purpose rubber (natural rubber including foamed polyurethane, SBR, chloroprene rubber, etc.), regardless of polar rubber or non-polar rubber, the electrical resistance value tends to decrease with increasing temperature ¹⁾ .

1) Edited by the Society of Polymer Science, Department of Polymer Engineering Vo
l. 7. "Rubber properties and processing" Jinjinshokan, Showa 42
Published first edition on February 15, 2002, p. 346, FIG. 7.50, FIG. 7.51, "Volume resistivity temperature characteristics of non-polar and polar rubbers" From this, it can be seen that even foamed polyurethane shows a tendency for electric resistance to decrease with temperature. Is considered to depend on the molecular structure of the polyol constituting the foamed polyurethane. However, it is very difficult to prevent by changing the molecular structure of the polyol. Therefore, paying attention to the fact that water is used as a foaming agent in soft foamed polyurethane, if an inorganic compound soluble in water is dissolved in water and then added to the polyol, the electrolyte has a certainty of the transport number,
The study was conducted based on the idea that there must be something that could reduce the change in electrical resistance due to environmental changes. Subsequent research revealed that these compounds had disadvantages such as high price and deliquescent, so this time, by compounding the compounds to overcome those disadvantages, It has overcome disadvantages. In addition, we paid attention to the fact that water was used for the flexible foamed polyurethane, but also in the elastomer, electric resistance change due to environmental change occurred over two orders, and foaming was caused by adding water. Although it cannot be avoided, it was confirmed that the change in electrical resistance due to environmental changes can be reduced. Commercially available polyols, prepolymers and isocyanate compounds can be used, and the mixing ratio of the soft foamed polyurethane to the elastomer is illustrated below. (1) Flexible foamed polyurethane: Daiichi Kogyo Seiyaku Co., Ltd. Polyol H-9246-3 104.0 parts Water 1 part Isocyanate H-9241-B 34.1 parts (2) Elastomer: Uniroyal Corporation Prepolymer B635 100 parts Isocyanate A120 82.5 parts Moreover, the saturation solubility of the inorganic compound used this time, the compounding ratio,
The mass per volume and the like are as follows. (1) Saturated solubility at 25 ° C (1) FeCl ₂ 0.65 g / ml (2) FeCl ₃ 1.83 g / ml (3) FeBr ₂ 0.075 g / ml (4) NH ₄ SCN 1.76 g / ml (5) NaSCN 1.50 g / ml (6) KSCN 2.40 g / ml (7) NH ₄ COOH 1.14 g / ml (2) Relationship between the above capacity and mass (1) FeCl ₂ 1.38 g / ml (2) FeCl ₃ 1.84 g / ml (3) FeBr ₂ 1.32 g / ml (4) NH ₄ SCN 1.40 g / ml (5) NaSCN 1.58 g / ml (6) KSCN 1.74 g / ml (7) NH ₄ COOH 1.39 g / ml (3) equivalent mixing the mixed ratio _{(1) NH 4 SCN / FeCl} 2 NH 4 SCN saturated aqueous 1g mixing ratio composite salt equivalent mixed composite salt solution of the complex salt solution is mixed at a ratio of FeCl ₂ saturated aqueous solution 2.25 g.

(2) NaSCN / FeCl ₂ NaSCN saturated aqueous solution 1
Mix with 1.80 g of a saturated aqueous solution of FeCl ₂ per g.

(3) KSCN / FeCl ₂ 1 g of KSCN saturated aqueous solution
, And a mixture of 2.41 g of a saturated aqueous solution of FeCl ₂ .

(4) NH ₄ COOH / FeCl _{2 The} mixed solution of 1.85 g of a saturated aqueous solution of FeCl ₂ is mixed with 1 g of a saturated aqueous solution of NH ₄ COOH.

(5) FeCl ₃ / NH ₄ COOH The mixture is mixed at a ratio of 1.87 g of a saturated aqueous solution of NH ₄ COOH to 1 g of a saturated aqueous solution of FeCl ₃ .

(6) NH ₄ SCN / FeBr ₂ Mix 1/4 g of a saturated aqueous solution of NH ₄ SCN with 24.63 g of a saturated aqueous solution of FeBr ₂ .

(7) NaSCN / FeBr ₂ NaSCN saturated aqueous solution 1
Mix with 19.71 g of a saturated aqueous solution of FeBr ₂ per g.

(8) KSCN / FeBr ₂ 1 g of KSCN saturated aqueous solution
And 26.97 g of a saturated aqueous solution of FeBr ₂ .

(9) NH ₄ COOH / FeBr _{2 The} mixed solution of 19.26 g of a saturated aqueous solution of FeBr ₂ is mixed with 1 g of a saturated aqueous solution of NH ₄ COOH. (4) Relationship between volume and mass of equivalent mixed complex salt solution (1) NH ₄ SCN / FeCl ₂ equivalent mixed salt solution 1.38 g / ml (2) NaSCN / FeCl ₂ equivalent mixed salt solution 1.53 g / ml (3 ) KSCN / FeCl ₂ equivalent mixed salt solution 1.59 g / ml (4) NH ₄ COOH / FeCl ₂ equivalent mixed salt solution 1.29 g / ml (5) NH ₄ COOH / FeCl ₃ equivalent mixed salt solution 1.41 g / ml (6) NH ₄ SCN / FeBr ₂ equivalent mixed salt solution 1.33 g / ml (7) NaSCN / FeBr ₂ equivalent mixed salt solution 1.43 g / ml (8) KSCN / FeBr ₂ equivalent mixed salt solution 1.44 g / ml (9) NH ₄ COOH / FeBr ₂ equivalent mixed salt solution 1.27 g / ml The reaction conditions (temperature, stirring, etc.) and casting conditions for producing the soft foamed polyurethane by reacting the polyol with the isocyanate compound are usually It is used and is not particularly limited.

Further, a conductive roll such as a charging roll and a transfer roll is used in an electrophotographic apparatus. The soft foamed polyurethane described above is used for these conductive rolls.

Next, the usage of the conductive roll will be described.

In FIG. 1, reference numeral 1 denotes a rotating drum type electrophotographic photosensitive member as a member to be charged (hereinafter referred to as a photosensitive drum).
And is driven to rotate at a predetermined peripheral speed (process speed) in the clockwise direction indicated by the arrow. 1a is the photosensitive drum 1
The conductive drum substrate 1b made of aluminum or the like is a photosensitive layer formed on the outer peripheral surface of the drum substrate 1a.

Reference numeral 2 denotes a contact charging roll (a kind of conductive roll). In this embodiment, a roll body (charging roll) which is disposed substantially parallel to the surface of the photosensitive drum 1 and pressed against the photosensitive drum 1 with a predetermined pressing force. ), The photosensitive drum 1 is driven to rotate.

Reference numeral 3 denotes a power supply for applying a voltage to the charging roll 2. By applying a predetermined voltage from the power supply to the metal core 2a of the charging roll 2, the peripheral surface of the rotating photosensitive drum 1 has a predetermined polarity and potential. It is charged by a contact charging method.

The surface of the photosensitive drum 1 which has been uniformly primary-charged to a predetermined potential by the charging roll 2 is subjected to laser beam scanning exposure 4 of target image information by a laser scanner (image exposure means) (not shown), and a developing unit 5. The steps of toner development and transfer of the formed toner image to the transfer material 7 by the transfer means 6 are sequentially performed, and the transfer material 7 that has been transferred from the surface of the photosensitive drum 1 after receiving the toner image is introduced into a fixing means (not shown). It is output as an image formed product (print). After the transfer of the toner image, the surface of the photosensitive drum 1 is cleaned by a cleaning device 8 to remove contaminants adhering to untransferred toner, and is repeatedly used for image formation.

[0024]

EXAMPLE 1 An equivalent amount of ammonium thiocyanate having a saturation solubility of 1.76 g / ml at 25 ° C. and a ferrous chloride solution having a saturation solubility of 0.65 g / ml at 25 ° C. were mixed. 0.276 g of equivalent mixed salt solution (based on polyol: 0.
92% by mass) was mixed with 30 g of polyol H-9246-3, and 0.1 ml of water was added. Then, a specified amount of isocyanate was weighed, stirred and mixed, and then t14 mm × W100
The mixture was cast into a plate having a size of mm × 1140 mm and cured at 60 ° C. for 15 minutes to obtain a molded body. 15 ° C. × 10%, 23.5
The electric resistance value when left for 3 days or more under the environmental conditions of 30 ° C. × 55% and 30 ° C. × 80% is as shown in Table 2, and the electric resistance of 23.5 ° C. × 55% shown in Table 1 Value 3.5
23.5 ° C in Table 2 when compared with 6 × 10 ¹⁰ (Ωcm)
The electrical resistance value of × 55% was low at 2.43 × 10 ⁸ (Ωcm), the sample showed conductivity, and the electrical resistance change due to environmental change was of the order of one order.

[0025]

[Table 2] Similarly, the saturated solubility at 25 ° C. is determined by mixing 0.138 g (based on 0.46% by mass of polyol) of an equivalent mixed salt solution obtained by mixing equivalent amounts of the ammonium thiocyanate and ferrous chloride solutions described above with polyol H. -9246-3,3
After mixing with 0 g, water (0.2 ml) was added, a specified amount of isocyanate was weighed, stirred, mixed, and then t14 mm × W
Cast into a 100 mm x 140 mm plate, 60 ° C
After curing for 15 minutes, a molded product was obtained. 15 ° C x 10%,
Table 3 shows the electrical resistance values when left for 3 days or more under the conditions of 23.5 ° C. × 55% and 30 ° C. × 80%.

[0026]

[Table 3] From Table 3, the electric resistance value at 23.5 ° C. × 55% is 1.
01 × 10 ¹⁰ (Ωcm), no conductivity was observed,
In addition, the change in electrical resistance due to environmental changes (15 ° C. × 10% to 30 ° C. × 80%) is on the order of two. Mixed equivalent mixed salt solution 0.2
It is clear that adding 76 g (based on 0.92% by mass of the polyol) to 30 g of the polyol is a lower limit condition for suppressing a change in electric resistance due to an environmental change. Similarly, the saturated solubility at 25 ° C. is 0.69 g of an equivalent mixed salt solution (equivalent to 2.3 of polyol) obtained by mixing equivalent amounts of ammonium thiocyanate and ferrous chloride solutions as described above.
% By mass) was mixed with 30 g of polyol H-9246-3, a specified amount of isocyanate was weighed, stirred and mixed, and then cast into a plate having a size of t14 mm × W100 mm × l 140 mm and cast at 60 ° C. × 15. After curing for minutes, a molded article was obtained. 15 ° C x 10%, 23.5 ° C x 55%, 30 ° C x 8
Table 4 shows the electrical resistance values when left for 3 days or more under each environmental condition of 0%.

[0027]

[Table 4] From Table 4, the electric resistance value of 23.5 ° C. × 55% is 1.22 ×
10 ⁸ (Ωcm), conductivity was observed, and the change in electrical resistance due to environmental changes (temperature, humidity) was on the order of 1 order. It is clear that this is also effective in reducing the change in electrical resistance due to environmental changes. It is.

Example 2 Equivalent mixture of sodium thiocyanate having a saturation solubility of 1.50 g / ml at 25 ° C. and a ferrous chloride solution having a saturation solubility of 0.65 g / ml at 25 ° C. 0.306 g of mixed complex salt solution (based on polyol 1.0
2% by mass) was mixed with 30 g of polyol H-9246-3, and 0.1 ml of water was added. Then, a specified amount of isocyanate was weighed, stirred and mixed, and t14 mm × W100 m
It was cast into a plate having a size of mx140 mm and cured at 60 ° C. for 15 minutes to obtain a molded product. 15 ° C x 10%, 23.5 ° C
Table 5 shows the electrical resistance values when left for 3 days or more under the conditions of × 55% and 30 ° C. × 80%.

[0029]

[Table 5] From Table 5, the electric resistance value at 23.5 ° C. × 55% is 4.96.
× 10 ⁸ (Ωcm), conductivity is recognized, and the change in electrical resistance due to environmental changes (temperature, humidity) is on the order of 1 order, and it is also effective in reducing the change in electrical resistance due to environmental changes. it is obvious. Similarly, an equivalent mixed complex salt solution obtained by mixing equivalent amounts of a sodium thiocyanate solution and a ferrous chloride solution having a saturation solubility at 25 ° C. as described above is 0.1%.
53 g (based on 0.51% by mass of polyol) of polyol H
-9246-3, after mixing with 30 g, adding 0.2 ml of water, weighing a specified amount of isocyanate, stirring and mixing, casting the mixture in a plate having a size of t14 mm × W100 mm × l 140 mm, and heating at 60 ° C. After curing for 15 minutes, a molded product was obtained. 15 ° C x 10%, 23.5 ° C x 55%, 30 ° C x 8
Table 6 shows the electrical resistance values in the state where the sample was left for 3 days or more under each condition of 0%.

[0030]

[Table 6] From Table 6, the electric resistance at 23.5 ° C. × 55% is 2.
18 × 10 ¹⁰ (Ωcm), and no conductivity was observed. The change in electric resistance due to the environmental change is of the order of 2 and no decrease in the change in electric resistance is recognized. From this, the conditions shown in Table 5, that is, an equivalent mixed complex salt solution obtained by mixing equivalent amounts of sodium thiocyanate and ferrous chloride solutions are also used.
It is clear that adding 306 g (1.02% by mass based on polyol) to 30 g of polyol H-9246-3 is a lower limit condition for reducing a change in electric resistance due to an environmental change. Similarly, the saturated solubility at 25 ° C. is determined by mixing 0.765 g (based on 2.55% by mass of polyol) of an equivalent mixed salt solution obtained by mixing equivalent amounts of sodium thiocyanate and ferrous chloride solutions as described above. After mixing to 30 g, a specified amount of isocyanate was weighed, stirred and mixed, cast into a plate having a size of t14 mm × W100 mm × l 140 mm, and cured at 60 ° C. × 15 minutes to obtain a molded product. 15 ° C x 10%, 23.5 ° C x 55%, 30 ° C x
Table 7 shows the electrical resistance values in the state of being left for 3 days or more under each condition of 80%.

[0031]

[Table 7] From Table 7, the electric resistance value of 23.5 ° C. × 55% is 3.25 ×.
10 ⁸ (Ωcm), conductivity was observed, and the change in electrical resistance due to environmental changes was of the order of one. It is clear that this is also effective in reducing the change in electrical resistance due to environmental changes.

Example 3 Equivalent mixture of potassium thiocyanate having a saturation solubility of 2.40 g / ml at 25 ° C. and a ferrous chloride solution having a saturation solubility of 0.65 g / ml at 25 ° C. 0.318 g of mixed complex salt solution (based on polyol 1.0
6% by mass) was mixed with 30 g of polyol H-9246-3, and after adding 0.1 ml of water, a specified amount of isocyanate was weighed, stirred and mixed, and then t14 mm × W100 m
It was cast into a mx140 mm plate-shaped mold and cured at 60 ° C for 15 minutes to obtain a molded product. 15 ° C. × 10%, 23.5
Table 8 shows the electrical resistance values when left for 3 days or more under each environmental condition of 30 ° C. × 55% and 30 ° C. × 80%.

[0033]

[Table 8] According to Table 8, the electric resistance value at 23.5 ° C. × 55% is 3.56.
× 10 ⁸ (Ωcm), the sample showed conductivity, and the change in electrical resistance due to environmental changes was of the order of one. It is clear that the sample was also effective in reducing the change in electrical resistance due to environmental changes. is there. Similarly, the saturated solubility at 25 ° C. is determined by adding an equivalent mixed complex salt solution obtained by mixing an equivalent amount of potassium thiocyanate and ferrous chloride solutions as described above.
After mixing 159 g (based on 0.53 mass% of polyol) with 30 g of polyol H-9246-3, adding 0.2 ml of water, weighing a specified amount of isocyanate, stirring and mixing, t14 mm × W100 mm × It was poured into a plate having a size of 140 mm and cured at 60 ° C. for 15 minutes to obtain a molded product. 15 ° C x 10%, 23.5 ° C x 55%, 30 ° C x 8
Table 9 shows the electrical resistance values in the state of being left for 3 days or more under each environmental condition of 0%.

[0034]

[Table 9] From Table 9, the electric resistance value at 23.5 ° C. × 55% is 2.
It is 96 × 10 ¹⁰ (Ωcm), and no conductivity is observed. Further, the change in electric resistance due to the environmental change is of the order of two, and no decrease in the change in electric resistance due to the environmental change is recognized. Based on this, the conditions shown in Table 8, that is, 0.318 g of an equivalent mixed salt solution (1.06% by mass of polyol) obtained by mixing equivalent amounts of potassium thiocyanate and ferrous chloride solutions are added to 30 g of the polyol. Is a lower limit condition for showing conductivity and reducing a change in electric resistance due to an environmental change. Similarly, the saturated solubility at 25 ° C. is determined by adding 0.795 g (based on 2.65 mass% of polyol) of an equivalent mixed salt solution obtained by mixing an equivalent amount of potassium thiocyanate and ferrous chloride solutions as described above. After mixing to 30 g, a specified amount of isocyanate was weighed, stirred and mixed, and then t14 mm × W100 mm
The molded product was obtained by casting in a plate of 140 mm × 100 mm and curing at 60 ° C. for 15 minutes. 15 ° C x 10%, 23.5 ° C
Table 10 shows the electrical resistance values when left for 3 days or more under the conditions of × 55% and 30 ° C. × 80%.

[0035]

[Table 10] From Table 10, the electric resistance value at 23.5 ° C. × 55% is 1.16 × 10 ⁸ (Ωcm), the conductivity is recognized, and the electric resistance change due to the environmental change is one order. It is clear that it is also effective in reducing the change in electric resistance due to the change.

Example 4 Ammonium formate having a saturated solubility at 25 ° C. of 1.14 g / ml and a saturated solubility at 25 ° C. of 0.6
After mixing 0.258 g of an equivalent mixed salt solution (0.86% by mass of polyol) obtained by mixing an equivalent amount of a ferrous chloride solution of 5 g / ml with 30 g of polyol H-9246-3,
After adding 0.1 ml of water, a specified amount of isocyanate was weighed, stirred and mixed, and then t14 mm × W100 mm × l
It was poured into a 140 mm plate and cured at 60 ° C. for 15 minutes to obtain a molded product. 15 ° C x 10%, 23.5 ° C x 5
Table 11 shows the electrical resistance values when left for 3 days or more under the conditions of 5% and 30 ° C. × 80%.

[0037]

[Table 11] From Table 11, the electric resistance value of 23.5 ° C. × 55% is 5.45.
× 10 ⁸ (Ωcm), conductivity was observed, and the change in electrical resistance due to environmental changes was of the order of one. It is clear that this is also effective in reducing the change in electrical resistance due to environmental changes. Similarly, the saturated solubility at 25 ° C. is determined by adding 0.129 g (based on 0.43% by mass of polyol) of an equivalent mixed salt solution obtained by mixing equivalent amounts of ammonium formate and ferrous chloride as described above with polyol H-9246. -3,3
After mixing with 0 g, 0.2 ml of water was added, and a specified amount of isocyanate was weighed, stirred and mixed, and then t14 mm × W
Cast into a 100 mm x 140 mm plate, 60 ° C
After curing for 15 minutes, a molded product was obtained. 15 ° C x 10%,
Table 12 shows the electric resistance values in the state of being left for 3 days or more under the conditions of 23.5 ° C. × 55% and 30 ° C. × 80%.

[0038]

[Table 12] From Table 12, the electrical resistance at 23.5 ° C. × 55% is 2.89 × 10 ¹⁰ (Ωcm), and no conductivity is observed. Further, the change in electric resistance due to the environmental change is of the order of two, and no decrease in the change in electric resistance due to the environmental change is recognized. From this, the conditions shown in Table 11, that is, 0.258 g of an equivalent mixed salt solution obtained by mixing equivalent amounts of ammonium formate and ferrous chloride (0.86% by mass based on polyol)
Is added to 30 g of polyol H-9246-3, which is a lower limit condition for showing conductivity and reducing a change in electric resistance due to an environmental change. Also 2
The saturated solubility at 5 ° C. is determined by mixing 0.645 g (based on 2.15 mass% of polyol) of an equivalent mixed salt solution obtained by mixing equivalent amounts of ammonium formate and ferrous chloride as described above with 30 g of the polyol. After weighing, stirring and mixing a specified amount of isocyanate, t14 mm × W100
mm × l 140 mm plate-shaped mold, 60 ° C × 15
After curing for minutes, a molded article was obtained. 15 ° C × 10%, 23.
Table 13 shows the electric resistance values in the state of being left for 3 days or more under the conditions of 5 ° C. × 55% and 30 ° C. × 80%.

[0039]

[Table 13] From Table 13, the electric resistance value at 23.5 ° C. × 55% is 3.39 × 10 ⁸ (Ωcm), and the conductivity is recognized. Also, the change in electric resistance due to environmental changes is of the order of one, and it is clear that it is also effective in reducing the change in electric resistance due to environmental changes.

Example 5 Ammonium formate having a saturated solubility at 25 ° C. of 1.14 g / ml and a saturated solubility at 25 ° C. of 1.8
0.0705 g of an equivalent mixed salt solution obtained by mixing an equivalent amount of a ferric chloride solution of 3 g / ml (to 0.235 of polyol)
% By mass) with 30 g of polyol H-9246-3, and after adding 0.25 ml of water, a specified amount of isocyanate was weighed, stirred and mixed, and then t14 mm × W100 m
It was cast into a plate having a size of mx140 mm and cured at 60 ° C. for 15 minutes to obtain a molded product. 15 ° C x 10%, 23.5 ° C
Table 14 shows the electrical resistance values when left for 3 days or more under the conditions of × 55% and 30 ° C. × 80%.

[0041]

[Table 14] From Table 14, the electric resistance at 23.5 ° C. × 55% is 6.98.
× 10 ⁹ (Ωcm), conductivity was observed, and the change in electrical resistance due to environmental changes was of the order of one. It is clear that this is also effective in reducing the change in electrical resistance due to environmental changes. Similarly, the saturated solubility at 25 ° C. is determined by adding 0.0353 g (based on 0.118 mass% of polyol) of an equivalent mixed salt solution obtained by mixing equivalent amounts of ammonium formate and ferric chloride as described above with polyol H-9246. −
After mixing with 3, 30 g, adding water (0.275 ml), weighing a specified amount of isocyanate, stirring and mixing, and then adding t1
A 4 mm × W100 mm × l 140 mm plate was cast and cured at 60 ° C. for 15 minutes to obtain a molded article. 15 ℃
Table 15 shows the electrical resistance values when left for 3 days or more under the conditions of × 10%, 23.5 ° C. × 55%, and 30 ° C. × 80%.
Shown in

[0042]

[Table 15] From Table 15, the electrical resistance at 23.5 ° C. × 55% is 2.11 × 10 ¹⁰ (Ωcm), and no conductivity is observed. The change in electric resistance due to the environmental change is of the order of two, and the decrease in the electric resistance change due to the environmental change is not recognized. From this, the conditions shown in Table 14, that is, 0.0705 g (based on 0.235 mass% of polyol) of an equivalent mixed salt solution obtained by mixing equivalent amounts of ammonium formate and ferric chloride solution were added to 30 g of polyol H-9246-3. It is evident that the addition of C is the lower limit condition for showing conductivity and reducing the change in electrical resistance due to environmental changes. Similarly, 0.705 g of an equivalent mixed salt solution obtained by mixing equivalent amounts of ammonium formate and ferric chloride having the same saturated solubility at 25 ° C. as described above was added to polyol H-9246-3,
After mixing with 30 g (based on 2.35% by mass of polyol), a specified amount of isocyanate was weighed, stirred, mixed, and then mixed with t1.
A 4 mm × W100 mm × l 140 mm plate was cast and cured at 60 ° C. for 15 minutes to obtain a molded article. 15 ℃
Table 16 shows the electric resistance values when left for 3 days or more under the conditions of × 10%, 23.5 ° C. × 55%, and 30 ° C. × 80%.
Shown in

[0043]

[Table 16] According to Table 16, the electric resistance value of 23.5 ° C. × 55% is 5.71.
× 10 ⁹ (Ωcm), conductivity was observed, and the change in electrical resistance due to environmental changes was of the order of one. It is clear that this is also effective in reducing the change in electrical resistance due to environmental changes.

Example 6 An equivalent amount of ammonium thiocyanate having a saturation solubility of 1.76 g / ml at 25 ° C. and a ferrous bromide solution having a saturation solubility of 0.075 g / ml at 25 ° C. were mixed. 0.266 g of an equivalent mixed complex salt solution (based on 0.887% by mass of polyol) was added to polyol H-9246-3, 3
After mixing with 0 g, water (0.1 ml) was added, and a specified amount of isocyanate was weighed, stirred and mixed, and then t14 mm × W
Cast into a 100 mm x 140 mm plate, 60 ° C
After curing for 15 minutes, a molded product was obtained. 15 ° C x 10%,
Table 17 shows the electrical resistance values in the state of being left for 3 days or more under the environmental conditions of 23.5 ° C. × 55% and 30 ° C. × 80%.

[0045]

[Table 17] According to Table 17, the electric resistance at 23.5 ° C. × 55% is 1.39 × 10 ⁸ (Ωcm), the conductivity is recognized, and the electric resistance change due to the environmental change is one order. It is clear that it is also effective in reducing the change in electric resistance due to the change. Similarly, the saturated solubility at 25 ° C. is determined by using an equivalent mixed salt solution of 0.1 equivalent by mixing an equivalent amount of the ammonium thiocyanate and ferrous bromide solutions as described above.
After mixing 33 g (based on 0.443 mass% of polyol) with 30 g of polyol H-9246-3, adding 0.2 ml of water, weighing a specified amount of isocyanate, stirring and mixing, t14 mm × W100 mm × It was poured into a plate having a size of 140 mm and cured at 60 ° C. for 15 minutes to obtain a molded product. 15 ° C x 10%, 23.5 ° C x 55%, 30 ° C x 8
Table 18 shows the electrical resistance values in the state where the sample was left for 3 days or more under each condition of 0%.

[0046]

[Table 18] From Table 18, the electric resistance at 23.5 ° C. × 55% is 1.81 × 10 ¹⁰ (Ωcm), and no conductivity is observed. The change in electric resistance due to the environmental change is of the order of two, and the decrease in the electric resistance change due to the environmental change is not recognized. Based on this, the conditions shown in Table 17, that is, 0.266 g of an equivalent mixed complex salt solution obtained by mixing equivalent amounts of ammonium thiocyanate and ferrous bromide solutions (based on 0.88
(7% by mass) to 30 g of polyol H-9246-3 is clearly the lower limit condition for showing conductivity and reducing the change in electric resistance due to environmental changes.
Similarly, 0.665 g (2.22% by mass based on polyol) of an equivalent mixed salt solution obtained by mixing equivalent amounts of ammonium thiocyanate and ferrous bromide solutions having the above-mentioned saturated solubility at 25 ° C. was added to polyol H. -9246-3, 30
g, weigh a specified amount of isocyanate, stir,
After mixing, t14mm × W100mm × l 140m
m, and cured at 60 ° C. for 15 minutes to obtain a molded product. 15 ° C. × 10%, 23.5 ° C. × 55%, 30
Table 19 shows the electric resistance values in the state of being left for 3 days or more under each condition of ° C x 80%.

[0047]

[Table 19] From Table 19, the electric resistance value at 23.5 ° C. × 55% is 1.00 × 10 ⁸ (Ωcm), the conductivity is recognized, and the electric resistance change due to the environmental change is one order. It is clear that it is also effective in reducing the change in electric resistance due to the change.

Example 7 Equivalent amounts of sodium thiocyanate having a saturation solubility of 1.50 g / ml at 25 ° C and a ferrous bromide solution having a saturation solubility of 0.075 g / ml at 25 ° C were mixed. 0.286 g of the equivalent mixed complex salt solution (based on polyol 0.
953% by mass) of polyol H-9246-3, 30 g
, After adding 0.1 ml of water, weighing a specified amount of isocyanate, stirring and mixing, t14mm × W10
0mm × 1 Pour into 140mm plate-shaped mold, 60 ℃ × 1
After curing for 5 minutes, a molded article was obtained. 15 ° C x 10%, 2
Table 20 shows the electric resistance values in the state of being left for 3 days or more under the conditions of 3.5 ° C. × 55% and 30 ° C. × 80%.

[0049]

[Table 20] From Table 20, the electric resistance value at 23.5 ° C. × 55% is 3.48 × 10 ⁸ (Ωcm), the conductivity is recognized, and the electric resistance change due to the environmental change is one order. It is clear that it is also effective in reducing the change in electric resistance due to the change. Similarly, the saturated solubility at 25 ° C. can be determined by using an equivalent mixed salt solution of 0.14 in which sodium thiocyanate and ferrous bromide solution as described above are mixed in equivalent amounts.
3 g (based on 0.477% by weight of polyol) of polyol H
-9246-3, after mixing with 30 g, adding 0.2 ml of water, weighing a specified amount of isocyanate, stirring and mixing, casting the mixture in a plate having a size of t14 mm × W100 mm × l 140 mm, and heating at 60 ° C. After curing for 15 minutes, a molded product was obtained. 15 ° C x 10%, 23.5 ° C x 55%, 30 ° C x 8
Table 21 shows the electrical resistance values in the state where the samples were left for 3 days or more under each condition of 0%.

[0050]

[Table 21] According to Table 21, the electric resistance at 23.5 ° C. × 55% is 2.19 × 10 ¹⁰ (Ωcm), and no conductivity is observed. The change in electric resistance due to the environmental change is of the order of two, and the decrease in the electric resistance change due to the environmental change is not recognized. From this, the conditions shown in Table 20, that is, 0.256 g of an equivalent mixed salt solution prepared by mixing equivalent amounts of sodium thiocyanate and ferrous bromide solutions (based on 0.953 against polyol)
(% By mass) to polyol H-9246-3 (30 g) is a lower limit condition for showing conductivity and reducing a change in electric resistance due to an environmental change. Similarly, 0.715 g of an equivalent mixed salt solution prepared by mixing equivalent amounts of sodium thiocyanate and ferrous bromide solutions having the above-mentioned saturated solubility at 25 ° C. (based on 2.3 of polyol)
8% by mass) was mixed with 30 g of polyol H-9246-3, and a specified amount of isocyanate was weighed, stirred and mixed, and then poured into a plate having a size of t14 mm × W100 mm × 1 and 140 mm, and heated at 60 ° C. × After curing for 15 minutes, a molded article was obtained. 15 ° C x 10%, 23.5 ° C x 55%, 30 ° C x 8
Table 22 shows the electrical resistance values in the state of being left for 3 days or more under each condition of 0%.

[0051]

[Table 22] From Table 22, the electric resistance value at 23.5 ° C. × 55% is 1.23 × 10 ⁸ (Ωcm), the conductivity is recognized, and the electric resistance change due to environmental change is one order. It is clear that it is also effective in reducing the change in electric resistance due to the change.

Example 8 Equivalent amounts of potassium thiocyanate having a saturation solubility of 2.40 g / ml at 25 ° C. and a ferrous bromide solution having a saturation solubility of 0.075 g / ml at 25 ° C. were mixed. 0.288 g of equivalent mixed salt solution (based on polyol: 0.
96% by mass) was mixed with 30 g of polyol H-9246-3, and 0.1 ml of water was added. Then, a specified amount of isocyanate was weighed, stirred and mixed, and t14 mm × W100
The mixture was cast into a plate having a size of mm × 1140 mm and cured at 60 ° C. for 15 minutes to obtain a molded body. 15 ° C. × 10%, 23.5
Table 23 shows the electrical resistance values when left for 3 days or more under the conditions of ° C × 55% and 30 ° C × 80%.

[0053]

[Table 23] From Table 23, the electric resistance at 23.5 ° C. × 55% is 3.58 × 10 ⁸ (Ωcm), the conductivity is recognized, and the electric resistance change due to environmental change is one order. It is clear that it is also effective in reducing the change in electric resistance due to the change. Similarly, the saturated solubility at 25 ° C. is determined by mixing an equivalent mixture of a potassium salt of thiocyanate and a ferrous bromide solution as described above in an equivalent amount of 0.144.
g (based on 0.48% by mass of polyol) with polyol H-9
After mixing with 246-3 and 30 g, 0.2 ml of water was added.
After weighing a specified amount of isocyanate, stirring and mixing,
It was poured into a plate having a size of t14 mm × W100 mm × l 140 mm and cured at 60 ° C. for 15 minutes to obtain a molded body. 1
Table 24 shows the electrical resistance values of the samples that were left for 3 days or more under the conditions of 5 ° C. × 10%, 23.5 ° C. × 55%, and 30 ° C. × 80%.

[0054]

[Table 24] From Table 24, the electrical resistance at 23.5 ° C. × 55% is 2.11 × 10 ¹⁰ (Ωcm), and no conductivity is observed. Further, the change in electric resistance due to the environmental change is of the order of two, and the decrease in the change in electric resistance due to the environmental change is not recognized. From this, the conditions shown in Table 23, that is, 0.288 g (based on 0.96% by mass of polyol) of an equivalent mixed salt solution obtained by mixing equivalent amounts of potassium thiocyanate and ferrous bromide were added to polyol H-9246-3. , 30 g is a lower limit condition for showing conductivity and reducing a change in electric resistance due to an environmental change. Similarly, 0.72 g (based on 2.40% by weight of polyol) of an equivalent mixed salt solution obtained by mixing equivalent amounts of potassium thiocyanate and ferrous bromide solutions having the above-mentioned saturated solubility at 25 ° C. was added to polyol H. -9246-3, after mixing into 30 g,
After weighing a specified amount of isocyanate, stirring and mixing,
It was poured into a plate having a size of t14 mm × W100 mm × l 140 mm and cured at 60 ° C. for 15 minutes to obtain a molded body. 1
Table 25 shows the electrical resistance values when left for 3 days or more under the conditions of 5 ° C. × 10%, 23.5 ° C. × 55%, and 30 ° C. × 80%.

[0055]

[Table 25] According to Table 25, the electric resistance value at 23.5 ° C. × 55% is 1.27 × 10 ⁸ (Ωcm), the conductivity is recognized, and the electric resistance change due to the environmental change is one order. It is clear that it is also effective in reducing the change in electric resistance due to the change.

Example 9 Ammonium formate having a saturation solubility at 25 ° C. of 1.14 g / ml and a saturation solubility of 0.04 at 25 ° C.
0.254 g of an equivalent mixed salt solution obtained by mixing an equivalent amount of a ferrous bromide solution of 75 g / ml (based on 0.847
% By mass) was mixed with 30 g of polyol H-9246-3, and 0.1 ml of water was added. Then, a specified amount of isocyanate was weighed, stirred and mixed, and then t14 mm × W100 mm
The molded product was obtained by casting in a plate of 140 mm × 100 mm and curing at 60 ° C. for 15 minutes. 15 ° C x 10%, 23.5 ° C
Table 26 shows the electrical resistance values when left for 3 days or more under the conditions of × 55% and 30 ° C. × 80%.

[0057]

[Table 26] From Table 26, the electric resistance value at 23.5 ° C. × 55% is 4.88 × 10 ⁹ (Ωcm), the conductivity is recognized, and the electric resistance change due to the environmental change is one order. It is clear that it is also effective in reducing the change in electric resistance due to the change. Similarly, the saturated solubility at 25 ° C. is 0.127 g of an equivalent mixed salt solution obtained by mixing equivalent amounts of the ammonium formate and ferrous bromide solutions as described above.
(Based on 0.423% by mass of polyol) with polyol H-9
After mixing with 246-3 and 30 g, 0.2 ml of water was added,
After weighing a specified amount of isocyanate, stirring and mixing,
It was poured into a plate having a size of t14 mm × W100 mm × l 140 mm and cured at 60 ° C. for 15 minutes to obtain a molded body. 1
Table 27 shows the electrical resistance values when left for 3 days or more under the conditions of 5 ° C. × 10%, 23.5 ° C. × 55%, and 30 ° C. × 80%.

[0058]

[Table 27] From Table 27, the electric resistance at 23.5 ° C. × 55% is 2.08 × 10 ¹⁰ (Ωcm), and no conductivity is observed. The change in electric resistance due to the environmental change is of the order of two, and the decrease in the electric resistance change due to the environmental change is not recognized. From this, the conditions shown in Table 26, that is, 0.254 g (based on 0.847% by mass of polyol) of an equivalent mixed salt solution obtained by mixing equivalent amounts of ammonium formate and ferrous bromide were added to polyol H-9246-3. It is clear that the addition to 30 g is the lower limit condition for showing conductivity and reducing the change in electric resistance due to environmental changes. Similarly, 0.635 g of an equivalent mixed salt solution obtained by mixing equivalent amounts of ammonium formate and ferrous bromide having the same saturated solubility at 25 ° C. as described above (based on 2.12% by mass of polyol).
Was mixed with 30 g of polyol H-9246-3, a specified amount of isocyanate was weighed, stirred and mixed, and then t1
A 4 mm × W100 mm × l 140 mm plate was cast and cured at 60 ° C. for 15 minutes to obtain a molded article. 15 ℃
Table 28 shows the electric resistance values when left for 3 days or more under the conditions of × 10%, 23.5 ° C. × 55%, and 30 ° C. × 80%.
Shown in From Table 28, the electric resistance value at 23.5 ° C. × 55% is 2.76 × 10 ⁹ (Ωcm), the conductivity is recognized, and the electric resistance change due to the environmental change is one order. It is clear that it is also effective in reducing the change in electric resistance due to the change.

[0059]

[Table 28] Example 10 An example of a urethane elastomer is illustrated. Prepolymer B, a urethane elastomer manufactured by Uniroyal (US)
635 and isocyanate A120, and the compounding ratio is as described above. Equivalent mixing of 50 g of this prepolymer with an equivalent mixture of ferrous chloride having a saturation solubility of 0.65 g / ml at 25 ° C. and an ammonium thiocyanate solution having a saturation solubility of 1.76 g / ml at 25 ° C. 0.69 g of composite salt solution (1.38% by mass based on prepolymer)
, A specified amount of isocyanate was weighed, stirred and mixed, and then t14 mm × W100 mm × l 140 mm
And cured at 100 ° C. for 3 hours to obtain a molded product. Since the aqueous solution was added to this molded article, a foaming phenomenon occurred, and the molded article became a molded article containing bubbles. However, the physical properties showed a normal elastomer state. After obtaining this compact, 1
Table 29 shows the electrical resistance values when left for 3 days or more under environmental conditions of 5 ° C × 10%, 23.5 ° C × 55%, and 30 ° C × 80%. From Table 29, the electric resistance value at 23.5 ° C. × 55% is 3.00 × 10 ⁷ (Ωcm), the conductivity is recognized, and the electric resistance change due to environmental change is 0 order. It is clear that it is also effective in reducing the electric resistance change due to the change. As described above, not only in the case of the flexible foamed polyurethane but also in the case of the elastomer type polyurethane, the conductivity is exhibited by adding the equivalent mixed salt solution as described above, and the effect of reducing the change in electric resistance due to environmental changes is recognized. Is clear.

[0060]

[Table 29]

[0061]

According to the present invention, there can be obtained a conductive soft foamed polyurethane in which the electric resistance does not change or hardly changes even when the temperature or humidity changes. Further, conductive rolls such as charging rolls for electrophotographic devices and transfer rolls are manufactured from the polyurethane. Further, an electrophotographic apparatus including the conductive roll can be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram of an example of an electrophotographic apparatus using a conductive roll of the present invention.

[Explanation of symbols]

 Reference Signs List 1 photosensitive drum 1a conductive drum base 1b photosensitive layer 2 charging roll (conductive roll) 2a cored bar 2b elastic layer 2c surface layer 3 voltage application power supply 4 laser beam scanning exposure 5 developing device 6 transfer means 7 transfer material 8 cleaning device

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) F16C 13/00 G03G 15/02 101 G03G 15/02 101 15/16 103 15/16 103 C08G 101: 00) // (C08G 18/09 18/08 101: 00) 101: 00) F term (reference) 2H003 BB11 CC05 2H032 AA05 3J103 AA02 AA12 FA30 GA02 GA57 GA58 GA60 HA04 HA18 HA48 4J002 CK021 DD077 DD087 DG026 EG026 GM00 4J034 CA03 HA01 JA24 KB05 MA01 MA12 NA03 QB07 QC01 QD03 RA11

Claims (12)

[Claims] 1. 25 ° C. with respect to 100 parts by mass of a polyol.
Ammonium thiocyanate having a saturation solubility of 1.76 g / ml in water and a saturation solubility of 0.20 at 25 ° C.
A method for producing a soft foamed polyurethane, comprising reacting an isocyanate compound with the polyol under a condition of adding at least 0.92 parts by mass of a mixed salt solution of ferrous chloride equivalent to 65 g / ml. 2. 25 ° C. based on 100 parts by mass of a polyol.
Sodium thiocyanate having a saturation solubility of 1.50 g / ml in water and a saturation solubility of 0.60 at 25 ° C.
A method for producing a soft foamed polyurethane, comprising reacting an isocyanate compound with the polyol under a condition of adding 1.02 parts by mass or more of a mixed salt solution of ferrous chloride equivalent to 5 g / ml. 3. 25 ° C. with respect to 100 parts by mass of a polyol.
Potassium thiocyanate having a saturation solubility of 2.40 g / ml in water and a saturation solubility of 0.65 at 25 ° C.
A method for producing a soft foamed polyurethane, comprising reacting an isocyanate compound with the polyol under the condition of adding 1.06 parts by mass or more of an equivalent mixed salt solution of a ferrous chloride solution of g / ml. 4. 25 ° C. based on 100 parts by mass of a polyol
Ammonium formate with a saturation solubility of 1.14 g / ml in water and 0.65 g /
ml of an equivalent mixed salt solution of a ferrous chloride solution.
A method for producing a soft foamed polyurethane, comprising reacting an isocyanate compound with the polyol under the condition of adding 86 parts by mass or more. 5. 25 ° C. with respect to 100 parts by mass of a polyol.
Ammonium formate having a saturation solubility of 1.14 g / ml in water and 1.83 g /
0.1 ml of an equivalent mixed salt solution of a ferric chloride solution.
A method for producing a soft foamed polyurethane, comprising reacting an isocyanate compound and the polyol under the condition of adding 235 parts by mass or more. 6. 25 ° C. with respect to 100 parts by mass of a polyol.
Ammonium thiocyanate having a saturation solubility of 1.76 g / ml in water and a saturation solubility of 0.20 at 25 ° C.
A method for producing a soft foamed polyurethane, comprising reacting an isocyanate compound with the polyol under the condition of adding 0.887 parts by mass or more of an equivalent mixed salt solution of a ferrous bromide solution of 075 g / ml. 7. 25 ° C. with respect to 100 parts by mass of a polyol.
Sodium thiocyanate having a saturation solubility of 1.50 g / ml in water and a saturation solubility of 0.05 at 25 ° C.
A method for producing a soft foamed polyurethane, comprising reacting an isocyanate compound with the polyol under a condition of adding 0.953 parts by mass or more of an equivalent mixed salt solution of a ferrous bromide solution of 75 g / ml. 8. 25 ° C. with respect to 100 parts by mass of a polyol.
Potassium thiocyanate having a saturation solubility of 2.40 g / ml in water and a saturation solubility of 0.07 g at 25 ° C.
A method for producing a soft foamed polyurethane, comprising reacting an isocyanate compound with the polyol under the condition of adding 0.96 parts by mass or more of an equivalent mixed salt solution of a ferrous bromide solution of 5 g / ml. 9. 25 ° C. with respect to 100 parts by mass of a polyol.
Ammonium formate with a saturation solubility of 1.14 g / ml in water and 0.075 g of a saturation solubility at 25 ° C.
A method for producing a soft foamed polyurethane, comprising reacting an isocyanate compound with the polyol under the condition of adding 0.847 parts by mass or more of an equivalent mixed salt solution of a ferrous bromide solution at a concentration of 0.1 / ml. 10. A soft foamed polyurethane produced by the method according to claim 1. 11. A conductive roll comprising the soft foamed polyurethane of claim 10. 12. An electrophotographic apparatus comprising a photoconductor, a latent image forming unit, a unit for developing the formed latent image, and a unit for transferring the developed image to a transfer material, wherein the latent image is charged when the photoconductor is charged. An electrophotographic apparatus using the conductive roll according to claim 11 as an image forming unit.