KR100329213B1 - Composition for Preparing Conductive Polyurethanes - Google Patents

Abstract

The present invention relates to a composition for producing a conductive polyurethane, and more particularly, to antistatic properties, chargeability, latent image printability, corrosiveness, used in elastomers, foams, adhesives, coating agents, paints, ink binders, binders for magnetic recording media, etc. and the improved electromagnetic shielding characteristics, such as classical Figure (the volume resistivity value of 10 ⁴ - 10 ⁸ Ωcm) relates to the manufacture of polyurethane compositions. That is, in the present invention, a highly conductive polyurethane can be produced by adding a conductive metal composed of only a transition metal salt or a metal salt and a solution thereof to a polyurethane raw material.

Description

Composition for Preparing Conductive Polyurethanes

The present invention relates to a composition for producing a conductive polyurethane. More specifically, high-conductivity (volume of antistatic properties, chargeability, latent image printability, corrosiveness, and electromagnetic shielding properties, which are used in elastomers, foams, adhesives, coating agents, paints, ink binders, and binders for magnetic recording media, etc.) are improved. the resistivity 10 ⁴ - 10 ⁸ Ωcm) relates to polyurethane compositions.

In particular, the present invention is a high-conductivity suitable for use in conductive rollers that electrostatically control the contacted object such as toner carrying rollers, charging rollers, developing rollers, transfer rollers, and cleaning rollers used in electrostatic recording or electrophotographic printers. It relates to a composition for producing a polyurethane.

A method of imparting conductivity to polyurethane resins has been widely researched and developed to date.

For example, Japanese Patent Laid-Open No. 7-33977 (published Feb. 1995) discloses a conductive imparting material and an ion conducting material according to an electronic conducting device to produce a conductive polyurethane elastomer that has a uniform resistance and is relatively stable against environmental changes. Although a method of mixing and dispersing conductivity-imparting materials by a mechanism is described, it is described that incompatible conductive materials are added to the polyurethane resin matrix, so that such incompatible conductive materials are transferred to the surface to contaminate the surface and lose conductivity. There is a problem.

Japanese Patent Application Laid-Open No. 9-278862 (published Oct. 28, 1997) discloses a volume specific resistance value at a glass transition temperature of 30 ° C. or lower by reacting an aliphatic long chain polyol with an organic polyisocyanate or an aliphatic long chain polyol with an organic polyisocyanate and a chain extender. 10 ¹¹ - 50 ¹⁰ can be produced Ωcm polyurethane resin, and thus can take advantage of the polyurethane resin produced in the adhesive that there is described a which electrostatic properties by improving the polyol structure of the polyurethane raw material and chargeability And an attempt to improve latent image printability and the like.

In addition, Japanese Patent Laid-Open No. 9-324117 (published Dec. 16, 1997) discloses a polyurethane composition containing a conductive surfactant and a cyclic oligosaccharide, or a polyurethane composition further containing conductive carbon. This is also an attempt to improve the structure of polyurethane.

On the other hand, US Patent No. 5,639,847 (June 17, 1997) discloses a solution and a dispersant comprising a metal salt or transition metal salt capable of imparting ionic conductivity, a flame retardant and / or a polyol, in order to prepare a conductive polyurethane. A method of preparing a conductive polyurethane by mixing a conductive quasi-solution after mixing is described. A nonionic surfactant, which is a dispersant, must be used to stabilize the transition metal and improve solubility.

The present invention solves the problems of the prior art described above, it is to be found that the conductivity can be further improved compared to the conventional polyurethane by the selection of a suitable solution rather than the polyurethane structure change method that was applied to improve the conductivity. The present invention has been reached.

The present invention provides a composition for producing a highly conductive polyurethane having a uniform resistance value and relatively stable conductivity against environmental changes, and improved antistatic properties, chargeability, latent image printability, corrosion resistance, and electromagnetic wave shielding properties. Its purpose is to provide.

As a result of intensive studies to achieve the above object, in the present invention, a highly conductive polyurethane is prepared by injecting a conductive mixture consisting of a transition metal salt or a metal salt and a solution thereof into a polyurethane raw material known in the art as a composition material for forming a polyurethane. I found it possible. The highly conductive polyurethanes produced according to the invention have a resistance value of about 1 × 10 ⁴ to 1 × 10 ⁸ Ω · cm.

Transition metal salts and metal salts used to obtain a composition for preparing a highly conductive polyurethane according to the present invention are materials capable of imparting conductivity by an ion conducting mechanism, and the transition metal salts include metal salts such as lithium, sodium, potassium, and the like, and complexes thereof. Or metal salts such as calcium and barium, and complex compounds thereof or complexes thereof, and more specifically Li ^{+ 3} , Na ⁺ , Na ⁺ , LiCF ₃ SO ₃ , NaClO ₄ , LiClO ₄ , LiAsF ₆ , LiBF ₄ , NaSCN, KSCN, and the like. Metal salts of group 1 of the periodic table, such as K ⁺ , electrolytes such as salts of NH ₄ , metal salts of group 2 of the periodic table, such as Ca ⁺⁺ and Ba ⁺⁺ such as Ca (ClO ₄ ) ₂ , CuCl ₂ , CuBr ₂ , and Cu (CH ₃ COO) ₂ , FeCl _2, FeCl _3, FeBr _2, FeBr ₃ , Fe (CH ₃ COO) ₃ , ZnCl ₂ , Zn (CH ₃ COO) _2, and the like are used alone or in a mixture thereof.

Solution was used to prepare a highly conductive polyurethane-producing composition according to the invention _{LiCF 3 SO 3, NaClO 4,} LiClO 4, LiAsF 6, LiBF 4, NaSCN, KSCN , such as Li ^+, Na ^+, K ^+, etc. for the electrolyte, Ca (ClO ₄₎ of periodic table group 2, such as Ca ^++, Ba ^++, etc. of the _second metal salt, ZnCl _2, and so on, such as a metal salt, or a salt of NH ₄ in the periodic table group 1, 1,3- Dioxolane-2-one (1,3-dioxolan-2-one) or 4-methyl-1,3-dioxolan-2-one (4-methyl-1,3-dioxolan-2-one) And about 1-30 g of the metal salt to 100 g of the solution to prepare a conductive solution. In addition, the conductive liquid prepared as described above is used by mixing about 15-60 g with respect to 100 g of polyol. Therefore, the usage-amount of a metal salt is 0.15-18 g with respect to 100 g of polyols.

Meanwhile, CuCl ₂ , CuBr ₂ , Cu (CH ₃ COO) ₂ , FeCl _2, FeCl _3, FeBr _2, FeBr ₃ , Fe (CH ₃ COO) ₃ , ZnCl ₂ , Zn (CH ₃ COO) _2, etc. When used alone or in mixtures thereof, 1,3-dioxolan-2-one or 4-methyl-1,3-dioxolan-2-one (4- A mixture of methyl-1,3-dioxolan-2-one) and tri (haloalkyl) phosphate is used as a solution. Specific examples of tri (haloalkyl) phosphate include tri (chloroethyl) phosphate, tri (β-chloroisopropyl) phosphate, and the like.

At this time, 1-30 g of the metal salt was dissolved in 100 g of a tri (haloalkyl) phosphate solution to prepare a primary conductive solution, and then 1,3-dioxoran-2-one and 4-methyl-1 One dissolved solution selected from, 3-dioxoran-2-one is mixed with about 7-70g of 100g of the primary conductive solution to prepare a secondary conductive solution. The secondary conductive solution prepared as described above is used by mixing about 3-30 g with respect to 100 g of polyol. Therefore, the usage-amount of a metal salt is 0.1-10 g with respect to 100 g of polyols.

If the amount is more than the added amount, there is a problem that the mechanical properties such as hardness, wear, and the like of the conductive polyurethane is lowered. If the amount is less than the amount, the conductivity is lowered.

In the present invention, U.S. Patent No. transition has not been used in the 5,639,847 arc metal salt, that is, _{LiCF 3 SO 3, NaClO 4,} LiClO 4, LiAsF 6, LiBF 4, Li + , such as NaSCN, KSCN, Na ^+, K ^+, such as the periodic table 1 an electrolyte of a metal salt, or as salt of an NH ₄ group, Ca (ClO ₄₎ of the periodic table, such as Ca ^++, Ba ^++, etc. to use the metal salt of a ₂ of the second group it more different transition metals for the preparation of the conductive liquid Has the advantage of being used. In the present invention, in the case of the metal salt disclosed in US Patent No. 5,639,847, a low molecular material of 1,3-dioxolan-2-one and tri (haloalkyl) phosphate are used together as a solution for dissolving metal ions. In addition, there is an effect that can effectively dissolve the metal ions without using a dispersant, and thus the resistance value of the conductive polyurethane according to the present invention prepared while controlling the addition amount of the conductive liquid is about 10 ⁴ Ωcm-10 ⁸ The value of Ω · cm is shown.

In the present invention, by adding a 1,3-dioxolane-2-one-based low molecular material as the dissolution solution, the conductivity of the conductive liquid as well as the conductive polyurethane prepared using the same improved at least two times or more.

In the present invention, the polyol as a raw material used for producing the conductive polyurethane is as follows. Generally polyether polyols, polyester polyols and polyetherpolyester polyols, copolymers of these two polyols, are used as polyols used in the production of flexible polyurethane foams or polyurethane elastomers, and also unsaturated monomers such as ethylene groups in the polyols. General polyols, such as polymer polyol which superposed | polymerized, are used. And diisocyanates include toluene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI) and polymers thereof, aliphatic polyisocyanates having 2-18 carbon atoms, 8- Aromatic polyisocyanates of 15 and mixtures or modifications thereof are used, and the prepolymers are made of ester polyols and those made of ether polyols. In addition, methylene diamine and toluene diamine are used as a curing agent used in the production of polyurethane molds.

And various seniors, various polyurethane synthesis catalysts, various surfactants and other various additives used in the production of polyurethanes.

Areas where conductive polyurethanes prepared using the compositions of the present invention may be applied include conductive polyurethane elastomers, conductive polyurethane adhesives, conductive polyurethane fibers, conductive polyurethane foams, conductive polyurethane molded products and other conductive polyurethanes. There are products.

Hereinafter, although an Example is described in order to demonstrate this invention more concretely, this invention is not limited to this.

Example

Example 1

The conductive liquid was dissolved by stirring 1000 g of lithium perchlorate (Aldrich Chemical, USA) for 1 hour in 4000 g of 4-methyl-1,3-dioxolan-2-one, manufactured by NISSO PETROCHEMICAL INDUSTRIES CO. LTD. Prepared.

Example 2

A conductive liquid was prepared in the same manner as in Example 1 except that sodium perchlorate (Aldrich Chemical, USA) was used instead of lithium perchlorate.

Example 3

A conductive solution was prepared by stirring 1000 g of zinc chloride (Duksan Chemical, Korea) for 1 hour in 5000 g of 4-methyl-1,3-dioxolane-2-one.

Example 4

500 g of FeCl ₂ (Duksan Chemical, Korea) was mixed with 5000 g of tri (β-chloroethyl) phosphate (Akzo Corp., USA), followed by 1800 g of 4-methyl-1,3-dioxolan-2-one. It was stirred for 3 hours to dissolve to prepare a conductive liquid.

Example 5-8

The conductive liquid prepared in Example 1-4 was mixed with 328 g of polyester polyol HT-5636 (Gangnam Hwaseong, Korea) having a molecular weight of 1500-2000, and then F-2200 (Gangnam of MDI prepolymer having a molecular weight of 1500-2000). Hwaseong, South Korea) 272g to prepare a polyurethane, but the amount of the conductive liquid was adjusted so that the concentration of the metal salt in the polyurethane as shown in Table 1 below. The resistance value of the polyurethane thus prepared was measured and shown in Table 1 below.

Example Conductive liquid Consumption of Conductive Liquid (g) Amount of metal salt in the conductive liquid (g) Concentration of Metal Salts in Polyurethane (wt%) Resistance value (ohm-cm) Example 5 Example 1 0 0 0.0 * 3 × 10 ¹³ 94 19 2.7 5 × 10 ⁶ 118 24 3.3 8 × 10 ⁵ Example 6 Example 2 0 0 0.0 * 3 × 10 ¹³ 150 30 4.0 7 × 10 ⁶ 160 32 5.1 9 × 10 ⁵ Example 7 Example 3 0 0 0.0 * 3 × 10 ¹³ 100 17 2.4 8 × 10 ⁷ 142 24 3.2 6 × 10 ⁶ Example 8 Example 4 0 0 0.0 * 3 × 10 ¹³ 102 7 1.0 7 × 10 ⁶ 127 9 1.2 5 × 10 ⁵

* Controlled as no metal salt included.

Table 2 shows the results of comparing the resistance values of the conductive polyurethane prepared using Example 5-8 with those of Table II of Example 13 of US Pat. No. 5,639,847.

Example 5 Example 6 Example 7 Example 8 U.S. Patent Table 2 U.S. Patent Table 2 MPC addi (g) * for 100 g polyol * 3.3 5.1 3.2 1.2 9.0 24.0 Resistance value (ohm-cm) 8 × 10 ⁵ 9 × 10 ⁵ 6 × 10 ⁶ 5 × 10 ⁵ 1.5 × 10 ⁸ 6.9 × 10 ⁷

* Means the addition amount of metal salt.

It can be seen from Table 2 that the conductivity of the polyurethane produced using the composition according to the present invention is smaller than that of the U.S. patent to further improve conductivity.

In the present invention, more various transition metals may be used in the preparation of the conductive liquid, and a low molecular material of 1,3-dioxolane-2-one system alone or tri (halo) may be used as a dissolution solution for dissolving metal ions. By using in combination with alkyl) phosphate, it is possible to effectively dissolve the metal ions without using a dispersant, as well as further improve the conductivity of the polyurethane.

Claims (5)

Metal salts of group 1 of the periodic table selected from the group consisting of LiCF ₃ SO ₃ , NaClO ₄ , LiClO ₄ , LiAsF ₆ , LiBF ₄ , NaSCN and KSCN, salts of NH ₄ , Ca (ClO ₄ ) ₂ , ZnCl ₂ or these 1-30 g of a mixture of 1,3-dioxolan-2-one (1,3-dioxolan-2-one) or 4-methyl-1,3-dioxolan-2-one (4-methyl-1 , 3-dioxolan-2-one) 15-60 g of a conductive liquid prepared by dissolving in 100 g of a polyol is prepared by mixing a composition for producing a highly conductive polyurethane, characterized in that. CuCl ₂ , CuBr ₂ , Cu (CH ₃ COO) ₂ , FeCl _{2 ,,} FeCl _{3 ,,} FeBr _{2 ,,} FeBr ₃ , Fe (CH ₃ COO) ₃ , ZnCl ₂ , Zn (CH ₃ COO) ₂ or their Dissolving 1-30 g of the mixture in 100 g of a tri (haloalkyl) phosphate solution to prepare a primary conductive solution; 1,3-dioxolan-2-one or 4-methyl-1,3-dioxolan-2-one (4-methyl) based on 100 g of the first conductive liquid Preparing a secondary conductive liquid prepared by mixing 7-70 g of 1,3-dioxolan-2-one); And 3-30 g of the secondary conductive solution to 100 g of a polyol. The composition of claim 2, wherein the tri (haloalkyl) phosphate is tri (chloroethyl) phosphate or tri (β-chloroisopropyl) phosphate. delete delete