KR20040040357A - Composition for preparing conductive non-foaming polyurethane resin, conductive non-foaming polyurethane shaped form and conductive non-foaming roll comprising the composition - Google Patents

Abstract

PURPOSE: Provided are a conductive non-foamable polyurethane molded article having low environmental dependence and good mechanical strength while maintaining excellent conductivity, a conductive non-foamable roll comprising the same and a composition therefor. CONSTITUTION: The composition for preparing a conductive non-foamable polyurethane resin comprises (A) an isocyanate group-containing compound, (B) an active hydrogen-containing compound and (C) additives containing (c-1) lithium bis(trifluoromethanesulfonyl)imide represented by the formula 1: Li(CF3SO2)2N and/or lithium tris(trifluoromethanesulfonyl)methane represented by the formula 2: Li(CF3SO2)3C and (c-2) carbon black as necessary components. The composition is reacted to obtain a conductive non-foamable polyurethane molded article having a density of 800 to 1300 kg/m3 at 25 deg.C as measured by JIS K6 300 standards.

Description

COMPOSITION FOR PREPARING CONDUCTIVE NON-FOAMING POLYURETHANE RESIN, CONDUCTIVE NON-FOAMING POLYURETHANE SHAPED FORM AND CONDUCTIVE NON-FOAMING ROLL COMPRISING THE COMPOSITION}

The present invention relates to conductive non-foamed polyurethane moldings and conductive non-foamed rolls excellent in conductivity, environmental dependence, durability, and the like, and to compositions thereof.

In recent years, it has become important to impart conduction performance to resins from the viewpoint of high quality and high speed processing, for example in electrophotographic applications. In order to achieve this, conventionally, the method of apply | coating antistatic agents, such as surfactant, to the surface of a resin molded article, or kneading antistatic agent in resin is known. However, the former method has a problem in its practicality as a conductive resin that maintains a constant conduction performance for a long time in that the conduction performance is significantly lowered when the humidity performance is dependent on the conduction performance or when it elapses for a long time. In addition, the latter method has a problem such that the antistatic agent kneaded into the surface of the molded article or the heat resistance is low, the color is yellow to brown or the conduction performance is lower than the former method.

Here, although polyurethane is low in electrical insulation compared with other resin by the structure, since the degree is not practically large, the method which uses polyurethane as resin and gives antistatic performance to polyurethane is performed. Conventionally, such methods include addition of carbon black, conductive fillers, coating or addition of surfactants, and addition of alkali metal salts such as perchloric acid, thiocyanic acid or nitric acid (for example, Patent Document 1: Japanese Patent Laid-Open No. 1988). -43951 (in particular, from the upper left to the upper right of the second page) and a method for adding a special quaternary ammonium salt (for example, Patent Document 2: Japanese Patent Laid-Open No. 1992-298518 (in particular, pages 2 to 5)) Is known.

However, when a conventional surfactant is used, sufficient conductivity cannot be imparted, and since a long time passes, the conductivity is considerably lowered or a humidity dependency occurs, which leads to practical limitations. In addition, when carbon black or conductive filler is added, it is scattered when added to the polyurethane raw material, or the viscosity of the raw material increases, which causes problems in formability. In addition, when alkali metal salts are added to perchloric acid, there is a problem in industrial production because of poor solubility in polyols or heat generation upon dissolution. In addition, since the quaternary ammonium salt may be colored by heating, when it is going to color in a desired color, there exists a restriction.

As a method of solving such a series of problems, a method of adding lithium bis (trifluoromethanesulfonyl) imide and / or lithium tris (trifluoromethanesulfonyl) methane in polyurethane has been proposed (for example, a patent). Document 3: See Japanese Patent Laid-Open No. 2002-146178 (especially pages 2 to 3). According to this method, it is thermally stable while maintaining excellent conductivity, has no dependence on the environment, can prevent coloring such as bleed out, and can be easily colored, an additive for producing the conductive polyurethane, and It is described with the intention of providing a method for producing a conductive polyurethane.

However, the surface specific resistance of the test piece of conductive polyurethane obtained by this method is 5 × 10 ⁶ to 7 × 10 ⁸ (Ω / sq) as described in the examples of the publication, for example 1 × 10 ⁵ It is still insufficient to provide for the field of electrophotographic applications that need to have a conduction performance on the order of 9 × 10 ⁷ (Ω / sq).

Furthermore, in addition to the necessity to have such excellent conduction performance as described above as provided to the field of electrophotographic use, it is also used under conditions such as high temperature and high humidity, or low temperature and low humidity, and the change of the conduction performance is Very little, that is, very low environmental dependence is particularly required in recent years, and conductive polyurethanes are desired which can be applied to this demand.

Further, as provided in the field of electrophotographic use, it is also required to have excellent mechanical strength that does not show defects such as deformation even when repeatedly used over a long period of time, in particular, less deformation by long-term use.

SUMMARY OF THE INVENTION In order to solve the above problems, an object of the present invention is to provide a conductive non-foamed polyurethane molded product and a conductive non-foamed roll, and to produce them, while maintaining extremely high conductivity and at the same time having low environmental dependence and excellent mechanical strength such as deformation. It is to provide a composition for.

As a result of intensive research, the present inventors found that the above problems can be solved by a composition for producing a conductive polyurethane resin composed of (A) an isocyanate group-containing compound, (B) an active hydrogen-containing compound, and (C) a specific additive. The present invention has been completed.

That is, the present invention is shown in the following [1] to [10]:

[1] A composition for producing a conductive non-foaming polyurethane resin, comprising (A) an isocyanate group-containing compound, (B) an active hydrogen-containing compound, and (C) an additive, wherein the (C) additive is represented by the following general formula (1) Characterized in that it contains lithium bis (trifluoromethanesulfonyl) imide and / or lithium tris (trifluoromethanesulfonyl) methane represented by the following formula (2) and (c-2) carbon black as essential components: Composition for preparing the conductive non-foaming polyurethane resin;

[2] The composition for producing a conductive non-foaming polyurethane resin according to the above [1], wherein the (A) isocyanate group-containing compound is an isocyanate group terminal prepolymer;

[3] the composition for producing a conductive non-foaming polyurethane resin according to the above [1] or [2], wherein the ratio of (c-1) to (c-2) is from 99: 1 to 3:97 (mass ratio);

[4] The composition for producing a conductive non-foamable polyurethane resin according to any one of the above [1] to [3], wherein the use ratio of (C) to the total of (A) and (B) is 0.2 to 8.0% by mass;

[5] The density at 25 ° C measured based on JIS K6300, obtained by reacting the composition for producing a conductive non-foamable polyurethane resin according to any one of [1] to [4], is 800 to 1300 kg / m ³ Conductive non-foamed polyurethane moldings;

[6] The conductive non-foaming material of the above [5], wherein the surface resistance at a temperature of 10 to 30 ° C. and a relative humidity of 15 to 85%, measured based on JIS K6911, is 1 × 10 ⁴ to 1 × 10 ⁷ Ω at a voltage of 500V. Polyurethane moldings;

[7] The conductive non-foaming polyurethane molded product according to the above [5] or [6], having a A hardness of 10 to 55 ° measured based on JIS K7312;

[8] The conductive non-foamed polyurethane molded article according to any one of [5] to [7], wherein the compressive permanent strain is less than 1.2% measured at 70 ° C. for 22 hours based on JIS K6301;

[9] Among the above-mentioned [5] to [8], in which the loss of wear at 1000 revolutions is less than 200 mg in 1 kg of grindstone H-22 measured by a taper type wear test based on JIS K7312. The conductive non-foamed polyurethane molding according to any one of claims; And

[10] A conductive non-foaming roll, comprising the conductive non-foaming polyurethane molded product according to any one of [5] to [9].

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

First, the composition for manufacturing the conductive polyurethane resin of the present invention will be described.

In this invention, although it is preferable to contain one or more isocyanate groups in one molecule as (A) isocyanate group containing compound, it is more preferable to contain two or more isocyanate groups.

As the (A) isocyanate group-containing compound, for example, diphenylmethane diisocyanate (hereinafter abbreviated as "MDI"), polyphenylene polymethylene polyisocyanate, triylene diisocyanate (hereinafter abbreviated as "TDI"), xylene diisocyanate, Tetramethylxylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate (hereinafter abbreviated as "HDI"), naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, etc., and these isocyanate groups Some of the isocyanate groups of the containing compound may be modified by biuret, allophanate, carbodiimide, uretonimine, oxazolidone, amide, imide, isocyanurate, uretdione and the like. These can use together single or 2 types or more as needed.

In the present invention, from the viewpoint of improving the durability of the obtained molded article, it is preferable to select one of MDI, TDI, and HDI alone or in plural for the compound (A) isocyanate group.

In the present invention, the (A) isocyanate group-containing compound from the viewpoint of reducing the heat of reaction during the production of the molded article, improving the resin mixing property during the molding, and industrially and stably easily obtaining the molded article of the present invention. As an isocyanate group terminal prepolymer obtained by reacting a part of the above-mentioned (A) isocyanate group-containing compound and a part of the (B) active hydrogen-containing compound described below beforehand before production of a molded article is preferably used.

In this case, as the active hydrogen-containing compound (B), which is previously reacted with the (A) isocyanate group-containing compound, in view of the fact that the performance intended by the present invention is better obtained in terms of compression set, hardness, wear resistance, and the like. In view of the fact that the polyether polyol is preferably selected, an isocyanate group terminal prepolymer having excellent workability at the time of molding can be obtained, such as being able to maintain compatibility and liquidity with other resins. Preferably, polyether polyols having a number average molecular weight of 500 to 10000, preferably 800 to 8000, in particular 1000 to 4000, are selected.

The isocyanate group content per molecule of the isocyanate group terminal prepolymer is 2 to 30% by mass, preferably 4 to 15% by mass, and particularly preferably 6 to 10% by mass. If the content of isocyanate groups per molecule is less than 2% by mass, the obtained prepolymer is not preferable because defects such as deterioration of mixing property at the time of forming high viscosity occur. In addition, when the content of isocyanate groups per molecule exceeds 30% by mass, it is not preferable because a defect that becomes unsuitable for the intended use of the present invention occurs, such as an increase in the heat of reaction during the production of the molded product, resulting in increased bubbles. Can not do it.

In the present invention, the average number of functional groups of the (A) isocyanate group-containing compound is preferably from 2.0 to 4.0, particularly preferably from 2.0 to 3.0, from the viewpoint of obtaining a molded product that can withstand the intended use of the present invention. If the average number of functional groups is less than 2.0, it is not preferable because the molded article obtained is likely to cause defects which cause unnecessary deformation over time. Moreover, when the average number of functional groups exceeds 4.0, it is unpreferable since the defect which a defect arises in the molded object obtained easily occurs.

In the present invention, the (A) isocyanate group-containing compound preferably has a viscosity at 75 ° C. of 20 to 4000 mPa · s, from the viewpoint of easily and industrially easily obtaining a molded product intended by the present invention, and 50 to It is especially preferable that it is 3000 mPa * s. When the viscosity exceeds 4000 mPa · s, it is not preferable because a defect that causes mixing defects during the production of the molded product is likely to occur.

In the present invention, the active hydrogen-containing compound (B) may contain at least one functional group containing active hydrogen in one molecule, but preferably contains two or more functional groups containing active hydrogen.

Examples of the active hydrogen-containing compound (B) include low molecular weight polyols having a molecular weight of less than 500, low molecular polyamines, low molecular amino alcohols, and polymer polyols having a number average molecular weight of 500 or more. These can be used individually or in mixture of 2 or more types.

As the low molecular polyol, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4- Butanediol, 1,6-hexanediol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, hydrogenated bisphenol A, glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose, di Glycerin and the like.

As the low molecular polyamine, for example, tetramethylenediamine, hexamethylenediamine, trilenediamine, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, diethyltri Amine, dibutyl triamine, dipropylene triamine, etc. are mentioned.

As the low molecular amino alcohol, for example, monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-methyl diethanolamine, N-ethylethanolamine, Nn-butylethanolamine, Nn-butyldiethanolamine, N -(β-aminoethyl) ethanolamine, N- (β-aminoethyl) isopropanolamine, etc. are mentioned.

Examples of the polymer polyol include dibasic acids such as polyether polyol, hydroxyl group-containing amine polyether, polyoxyethylene monoalkyl ether, azipic acid and phthalic anhydride, and glycols and triols such as ethylene glycol, diethylene glycol and trimethylolpropane. Lactone-based polyols, polycarbonate polyols, acrylic polyols, polybutadiene-based polyols, novolac resins and resol resins obtained by ring-opening polymerization of cyclic ester monomers such as various polyester polyols and ε-caprolactam obtained by dehydration condensation reactions. So-called polymer polyol etc. which radical-polymerized vinyl-type monomers, such as an acrylonitrile and styrene, among the phenolic polyols, such as these, and a polyol, are mentioned. Of these, polyether polyols are particularly preferred.

In the present invention, all of the above-mentioned active hydrogen-containing compounds may be used. However, as described above, these (B) active hydrogen-containing compounds may be used in view of the reduction of the heat of reaction during the production of the molded product or the improvement of the mixing properties of the resin during the molding. (A) It is preferable to use for the preparation of the isocyanate group terminal prepolymer obtained by reacting before isoform with the isocyanate group-containing compound prior to production of the molded article, and to use it in the form of reacting with the prepolymer during production of the molded article.

In the present invention, the average number of functional groups of the active hydrogen-containing compound (B) is preferably from 2.0 to 4.0, particularly preferably from 2.0 to 3.0, from the viewpoint of obtaining a molded article that can withstand the intended use of the present invention. If the average number of functional groups is less than 2.0, it is not preferable because the molded article obtained is likely to cause defects which cause unnecessary deformation over time. Moreover, when the average number of functional groups exceeds 4.0, it is unpreferable since the defect which a defect arises in the molded object obtained easily occurs.

Further, in the present invention, the number average molecular weight of the active hydrogen-containing compound (B) is 500 to 10000, more preferably 800 to 8000, particularly from the viewpoint of making the hardness of the obtained molded product suitable for the intended use of the present invention. It is preferable that it is 1000-5000. When the number average molecular weight is less than 500, the hardness of the obtained molded article is unnecessarily high, which is not preferable because a defect that becomes unsuitable for the intended use of the present invention tends to occur. Moreover, when the number average molecular weight exceeds 10000, it is not preferable because the molded article obtained tends to produce defects which cause unnecessary deformation over time.

In the present invention, the additive (C) is at least lithium bis (trifluoromethanesulfonyl) imide represented by the following general formula (1) and / or lithium tris (trifluoromethanesulfonyl) methane represented by the following general formula (2) and ( c-2) must include carbon black:

Formula 1

Formula 2

The biggest characteristic of this invention is that both (c-1) and (c-2) are used together at least as an additive (C). When only (c-1) is included and (c-2) is not included as an additive (C), the resistance value and hardness which this invention requires are not obtained. In addition, when (C) only contains (c-2) as an additive and does not contain (c-1), the environmental dependence that the resistance falls under high temperature and high humidity or the resistance rises under low temperature and low humidity becomes remarkable, and the molded article obtained Mechanical failures, particularly poor compression set and wear resistance, are caused.

Lithium bis (trifluoromethanesulfonyl) imide represented by the formula (1) or lithium tris (trifluoromethanesulfonyl) methane represented by the formula (2) is, for example, 'Sanconol' manufactured by Sanko Chemical Industries, Ltd. It is available as a series.

In this invention, when using together (c-1) and (c-2), the ratio is preferably in the range of 99: 1 to 3:97 (mass ratio), and is 90:10 to 50:50 (mass ratio). Range is particularly preferred. By using together in this range, the low environmental dependence and stable resistance value which this invention requires can be obtained.

In this invention, the range of 0.2-8.0 mass% is preferable, and, as for the introduction amount of (C) additive with respect to the sum total of (A) isocyanate group containing compound and (B) active hydrogen containing compound, the range of 0.3-5.0 mass% is Particularly preferred. If the amount of the (C) additive to the total is out of the range of 0.2 to 8.0% by mass, it is not preferable in that it is difficult to obtain the required resistance and mechanical properties.

In the present invention, in addition to the compounds described above as the (A) isocyanate group-containing compound, (B) active hydrogen-containing compound and (C) additive, a known urethanization catalyst, foaming agent, ultraviolet absorber, antioxidant, anti-coloring agent, Fluorescent dye, dispersible dye, lubricant, surfactant, etc. can be used together.

The following describes in detail the conductive non-foaming polyurethane moldings obtained from the composition in the present invention.

In the present invention, (c-1) lithium bis (trifluoromethanesulfonyl) imide represented by the formula (1) and / or lithium tris (trifluoromethanesulfonyl) methane represented by the formula (2) is known. It is preferable to introduce | transduce by the method of mixing and disperse | distributing to (B) active hydrogen containing compound previously by the prescribed method.

In the present invention, the conductive non-foamable polyurethane molding is a known mixture and / or injection of (A) an isocyanate group-containing compound, (B) and (c-1) mixed dispersion, and (c-2) carbon black. A necessary amount is respectively mix | blended by the method, it inject | pours into a mold, a defoaming process is performed by a well-known method, For example, it can obtain by reaction hardening in a mold for 30 to 300 minutes preferably in the temperature range of 60-130 degreeC. .

In carrying out the reaction curing in the present invention, it is preferable to mix the isocyanate group to the active hydrogen group at a ratio of 0.60 to 1.20 to 1.00 (mass ratio), and the isocyanate group to the active hydrogen group of 0.70 to 1.10 to 1.00 (mass ratio) It is more preferable to mix | blend in a ratio.

The molded article thus obtained is preferably a non-foamed phase having a density of 800 to 1300 kg / m ³ at 25 ° C. measured on the basis of JIS K6300.

The molded article obtained in the present invention preferably has a surface resistance of 1 × 10 ⁴ to 1 × 10 ⁷ Ω at a voltage of 500V at a temperature of 10 to 30 ° C. and a relative humidity of 15 to 85%, measured based on JIS K691 1. In addition, the molded article obtained in the present invention also has excellent characteristics in which the change in surface resistance value due to environmental changes such as low temperature low humidity and high temperature high humidity is very small as shown in Examples described later.

It is preferable that the molded article obtained in the present invention has a high density and elasticity, in terms of mechanical properties, having an A hardness of 10 to 55 ° measured based on JIS K7312.

In addition, the molded article obtained in the present invention preferably has a compression set of less than 1.2% measured for 22 hours at 70 ° C based on JIS K6301.

In addition, it is preferable that the molded article obtained in the present invention has excellent wear characteristics in which the loss of wear at 1000 rotations is 200 mg or less in 1 kg of grindstone H-22 measured by a tapered abrasion test based on JIS K7312. Do.

In the present invention, the conductive non-foamable polyurethane molded article is an excellent molded article having high durability in terms of mechanical properties such as hardness, compression set, wear resistance, and the like, while having excellent conductive performance not affected by environmental changes. Because of their excellent performance, the use of the conductive non-foamed polyurethane moldings of the present invention can be preferably used in areas requiring conductivity in electrophotographic articles, in particular areas that must withstand long term continuous use. Especially, it can use especially preferably as a conductive non-foaming roll which electrically adjusts a to-be-contacted object, such as a roll for toner conveyance, a developing roll, a transfer roll, a cleaning roll, etc. in an electrophotographic, electrostatic printer, etc.

Example

Hereinafter, the composition for producing the conductive non-foamed polyurethane resin of the present invention, the overall physical properties of the conductive non-foamed polyurethane molded product and the conductive non-foamed roll made of the composition will be described in more detail, for example. In addition, of course, this invention should not be interpreted as being limited to these Examples.

[Synthesis of Isocyanate Group Terminal Prepolymer]

Synthesis Example

The reactor was equipped with a stirrer, a thermometer, and a nitrogen gas introduction tube at a compounding ratio shown in Table 1 below, and reacted for 3 hours at 60 ° C. under a nitrogen atmosphere while stirring.

The raw material composition and the isocyanate group content (NCO content) of the obtained isocyanate group terminal prepolymer are shown in Table 1 below.

Synthesis Example P-1 P-2 P-3 P-4 P-5 P-6 Prepolymer Isocyanate (mass part) MDI 313 313 337 TDI 225 242 HDI 218 Polyol (mass part) GP-3000 687 775 782 663 758 PTG-3000TF 687 NCO content (mass%) 7.6 7.6 7.6 7.6 8.5 8.5 Viscosity (mPas / 75 ° C) 470 1500 300 350 300 220 MDI: Diphenylmethane diisocyanate ("Mionate MT" made by Nippon Polyurethane Industry Co., Ltd.) TDI: Toluene diisocyanate ("T-80" made by Nippon Polyurethane Industry Co., Ltd.) HDI: Hexamethylene diisocyanate ( Japan Polyurethane Industry Co., Ltd.) GP-3000: Polyether polyol (Sanyo Chemical Co., Ltd. product, number average molecular weight 3000, hydroxyl value 56 mgKOH / g) PTG-3000TF: Polyether polyol (Hodogaya Chemical Industry) Product, number average molecular weight 3000, hydroxyl value 56mgKOH / g)

Examples 1 to 14 and Comparative Examples 1 and 2

The polyols and additives (except for carbon black) shown in Tables 2 to 4 below were mixed to obtain mixed dispersions. Then, the mixed dispersion, the isocyanate group terminal prepolymer obtained in the synthesis example, and carbon black were mixed based on the blending ratios shown in Tables 2 to 4 below. After the mixture was sufficiently stirred until the mixture was completely uniform, defoaming treatment was performed until foaming was collected at a vacuum pressure of 10 Torr or lower. Thereafter, the mixture was poured into a mold, followed by curing reaction at 80 ° C. for 30 minutes, followed by demolding to obtain a plate-shaped conductive non-foamed polyurethane molded product. After the mold was cured at room temperature for 24 hours after demolding, the density, (final) hardness, (surface) resistance, compression set, and wear resistance of the molded product were measured for each molded product.

The results are shown in Tables 2 to 4 below.

Example One 2 3 4 5 6 7 Composition (mass part) ① Prepolymer P-1 1000 1000 1000 1000 1000 1000 1000 ② Polyol PTG-1000SN 860 860 860 860 860 860 860 ③Additive A 56 28 11 33 78 111 Additive B 28 56 ④ carbon black 37 37 37 7 22 52 74 Compounding ratio (③ + ④) / (① + ②) 0.05 0.05 0.05 0.01 0.03 0.07 0.10 ③: ④ 60:40 60:40 60:40 60:40 60:40 60:40 60:40 Isocyanate group / hydroxyl group (mass ratio) 1.05 1.05 1.05 1.05 1.05 1.05 1.05 Form Properties Density (kg / m ³ ) 1020 1020 1020 1020 1020 1020 1020 Final hardness 50 50 51 56 52 50 49 Resistance value (Ω) Condition: 10 ℃ × 15% RH 6 × 10 ⁵ 5 × 10 ⁵ 5 × 10 ⁵ 2 × 10 ⁷ 9 × 10 ⁵ 2 × 10 ⁵ 5 × 10 ⁴ 20 ℃ × 55% RH 3 × 10 ⁵ 3 × 10 ⁵ 2 × 10 ⁵ 7 × 10 ⁶ 6 × 10 ⁵ 9 × 10 ⁴ 9 × 10 ³ 30 ℃ × 85% RH 9 × 10 ⁴ 9 × 10 ⁴ 8 × 10 ⁴ 4 × 10 ⁶ 1 × 10 ⁵ 5 × 10 ⁴ 5 × 10 ³ Compression set strain (%) 0.3 0.3 0.6 0.3 0.5 0.4 3.0 Abrasion resistance (friction loss: mg) 70 65 60 65 70 80 90

Example 8 9 10 11 12 13 14 Composition (mass part) ① Prepolymer P-1 1000 1000 P-2 1000 P-3 1000 P-4 1000 P-5 1000 P-6 1000 ② Polyol PTG-1000SN 860 860 860 860 926 926 G-1500 660 EXCENOL5030 660 GP-3000 74 74 ③Additive A 70 84 70 56 56 60 60 ④ carbon black 23 9 46 37 37 40 40 Compounding ratio (③ + ④) / (① + ②) 0.05 0.05 0.05 0.05 0.05 0.05 0.05 ③: ④ 75:25 90:10 60:40 60:40 60:40 60:40 60:40 Isocyanate group / hydroxyl group (mass ratio) 1.05 1.05 1.06 1.05 1.05 1.05 1.05 Form Properties Density (kg / m ³ ) 1020 1020 1010 1020 1020 1010 1010 Final hardness 48 45 55 45 40 51 44 Resistance value (Ω) Condition: 10 ℃ × 15% RH 7 × 10 ⁵ 9 × 10 ⁵ 2 × 10 ⁵ 5 × 10 ⁴ 6 × 10 ⁵ 6 × 10 ⁵ 1 × 10 ⁵ 20 ℃ × 55% RH 4 × 10 ⁵ 6 × 10 ⁵ 8 × 10 ⁵ 4 × 10 ⁴ 2 × 10 ⁵ 4 × 10 ⁵ 4 × 10 ⁴ 30 ℃ × 85% RH 1 × 10 ⁵ 4 × 10 ⁵ 3 × 10 ⁵ 1 × 10 ⁴ 8 × 10 ⁴ 1 × 10 ⁵ 2 × 10 ⁴ Compression set strain (%) 0.4 0.8 0.3 1.0 0.3 0.5 1.1 Abrasion resistance (friction loss: mg) 65 60 65 60 70 65 60

Comparative example One 2 Composition (mass part) ① Prepolymer P-1 1000 1000 ② Polyol PTG-1000SN 860 860 ③Additive A 93 ④ carbon black 93 Compounding ratio (③ + ④) / (① + ②) 0.05 0.05 ③: ④ 100: 0 0: 100 Isocyanate group / hydroxyl group (mass ratio) 1.05 1.05 Form Properties Density (kg / m ³ ) 1020 1030 Final hardness 50 51 Resistance value (Ω) Condition: 10 ℃ × 15% RH 5 × 10 ⁷ 1 × 10 ³ 20 ℃ × 55% RH 1 × 10 ⁷ 5 × 10 ² 30 ℃ × 85% RH 7 × 10 ⁶ 9 × 10 ¹ Compression set strain (%) 0.3 5.0 Abrasion resistance (friction loss: mg) 60 360

In Tables 2 to 4, PTG-1000SN is a polyether polyol (manufactured by Hodogaya Chemical Co., Ltd., number average molecular weight 1000, hydroxyl value 112 mgKOH / g), and G-1500 is a polyether polyol (Asahiddenka Industry). Product, the number average molecular weight 3000, the hydroxyl value is 112 mgKOH / g), EXCENOL5030 is a polyether polyol (product of Asahi Glass Co., Ltd., the number average molecular weight 5000, the hydroxyl value is 33 mgKOH / g), GP -3000 is a polyether polyol (manufactured by Sanyo Chemical Co., Ltd., number average molecular weight 3000, hydroxyl value is 56 mgKOH / g), and additive A is a lithium bis (trifluoromethanesulfonyl) imide compound and a polyether polyol And additive B are a mixture of a lithium tris (trifluoromethanesulfonyl) methane compound and a polyether polyol (manufactured by Sanko Chemical Industry Co., Ltd.).

The measurement methods for density, final hardness, resistance, compression set and wear resistance of moldings are as follows:

Density was measured by the density in 25 degreeC based on JISK6300.

The final hardness is cured the molded product at room temperature for 24 hours after demolding, and then put into an oven at 120 ° C. for 1 hour, after cure, and then aged at room temperature of 25 ° C. and 60% humidity for 7 days. ), And hardness measurement was performed using a JIS A hardness tester based on JIS K7312.

The resistance value was measured using the R8340A digital ultrahigh resistance / microammeter made from ADVANTEST company based on JISK6911 under each atmospheric condition shown in each table | surface. In addition, the voltage at the time of measurement was set to 500V.

The compression set was evaluated for 22 hours at 70 ° C. by a method based on JIS K6301.

Abrasion resistance was measured by a tapered abrasion test based on JIS K7312. In addition, the grindstone used at the time of a measurement was "H-22", and measured the loss of abrasion at the time of 1000 rotations in 1 kg of load.

Example 15

According to the composition of Example 1, the conductive non-foaming roll was produced in the same aspect as that used for a commercially available laser beam printer. As a result of setting and evaluating this roll as a transfer roll used for constant current control in the said laser beam printer, the favorable image was obtained.

According to the composition for producing a conductive non-foaming polyurethane resin of the present invention, the surface resistance at a temperature of 10 to 30 ° C. and a relative humidity of 15 to 85% measured based on JIS K6911 is 1 × 10 ⁴ to 1 × 10 at a voltage of 500 V. Conductive, non-foamed polyurethane moldings with excellent conduction performance of ⁷ Ω can be obtained.

The conductive non-foamed polyurethane molding of the present invention maintains the excellent conductivity described above, and has very excellent performance with little change in conductivity due to environmental difference, that is, low environmental dependence. In addition, the conductive non-foamable polyurethane molding of the present invention is also excellent in mechanical properties such as compression set and wear resistance at the same time, has a very excellent effect to withstand long-term use. Therefore, the molded article can be suitably used as a conductive roll for electrically controlling a contacted object, such as a toner conveying roll, a developing roll, a transfer roll, a cleaning roll, and the like, particularly in an electrophotographic or electrostatic printer.

Claims (10)

A composition for producing a conductive non-foaming polyurethane resin comprising (A) an isocyanate group-containing compound, (B) an active hydrogen-containing compound, and (C) additive, wherein (C) the additive is (c-1) lithium bis represented by the following formula (1) (Trifluoromethanesulfonyl) imide and / or a lithium tris (trifluoromethanesulfonyl) methane represented by the following formula (2) and (c-2) carbon black as essential components Compositions for the preparation of foamed polyurethane resins: Formula 1 Formula 2 The method of claim 1, (A) A composition for producing a conductive non-foaming polyurethane resin wherein the isocyanate group-containing compound is an isocyanate group terminal prepolymer. The method according to claim 1 or 2, A composition for producing a conductive non-foaming polyurethane resin having a ratio of (c-1) to (c-2) of 99: 1 to 3:97 (mass ratio). The method according to any one of claims 1 to 3, A composition for producing a conductive non-foaming polyurethane resin, wherein the use ratio of (C) to the total of (A) and (B) is 0.2 to 8.0% by mass. A conductive non-foamed poly with a density of 800 to 1300 kg / m ³ at 25 ° C., measured based on JIS K6300, obtained by reacting the composition for producing a conductive non-foamed polyurethane resin according to any one of claims 1 to 4. Urethane moldings. The method of claim 5, wherein A conductive non-foaming polyurethane molding having a surface resistance of 1 × 10 ⁴ to 1 × 10 ⁷ Ω at a voltage of 500 V measured at a temperature of 10 to 30 ° C. and a relative humidity of 15 to 85%, measured based on JIS K6911. The method according to claim 5 or 6, A conductive non-foaming polyurethane molding having an A hardness of 10 to 55 °, measured according to JIS K7312. The method according to any one of claims 5 to 7, Conductive non-foaming polyurethane molding having a compression set of less than 1.2% measured at 70 ° C. for 22 hours according to JIS K6301. The method according to any one of claims 5 to 8, A conductive non-foaming polyurethane molded product having a wear loss of 1000 mg or less at 200 revolutions in 1 kg of grindstone H-22 measured by a taper type abrasion test based on JIS K7312. A conductive non-foaming roll comprising a conductive non-foaming polyurethane molding according to any one of claims 5 to 9.