SOLUTION COMPOSITION COMPRISING CONDUCTIVE POLYMER

Abstract

A solution composition comprising a conductive polymer, a resin, and a solvent is described. The solution composition has an acid value of 0.0 to 14.5 mgKOH/g or a base value of 0.0 to 1.0 mgHCl/g. The solution composition may be applied to a surface such as a steel surface and dried to obtain a film. The obtained film may be used for rust inhibition.

Claims

1. A solution composition, comprising: a conductive polymer; a resin; and a solvent, wherein the solution composition has an acid value of 0.0 to 14.5 mgKOH/g or having a base value of 0.0 to 1.0 mgHCl/g.

2. The solution composition of claim 1, wherein the conductive polymer is a polyaniline-based polymer.

3. The solution composition of claim 2, wherein the polyaniline-based polymer is a substituted or unsubstituted polyaniline doped with a dopant.

4. The solution composition of claim 1, having a viscosity of 1000 cP or higher or 80000 cP or lower at 25° C.

5. The solution composition of claim 1, having a viscosity of 1000 cP or higher or 60000 cP or lower at 25° C.

6. The solution composition of claim 3, wherein the dopant is a sulfosuccinate derivative.

7. The solution composition according to of claim 1, wherein the resin is a thermosetting resin.

8. The solution composition of claim 7, wherein the thermosetting resin is at least one resin selected from the group consisting of an alkyd resin, an unsaturated polyester, a polyester, a melamine resin, a polyisocyanate, an acrylic resin, a phenol resin, a polyamine, a polyurethane, and an epoxy resin.

9. The solution composition of claim 7, wherein the thermosetting resin is a polyurethane or an epoxy resin.

10. A film obtained from the solution composition of claim 1.

11. A metallic component comprising the film of claim 10.

12. The metallic component of claim 11, further comprising a steel material which is coated with the film.

Description

EXAMPLES

Example 1

[0082] (1) Preparation of Polyaniline Doped with Dopant (Polyaniline Complex)

[0083] 35.0 g of Aerosol OT (sodium di(2-ethylhexyl)sulfosuccinate, purity: 75% or higher, manufactured by FUJIFILM Wako Pure Chemical Corporation) and 1.47 g of Sorbon T-20 (a nonionic emulsifier having a polyoxyethylene sorbitan fatty acid ester structure, manufactured by Toho Chemical Industry Co., Ltd.) were dissolved in 600 mL of toluene to prepare a solution.

[0084] The resulting solution was put into a 6 L separable flask placed under a nitrogen stream, and 22.2 g of aniline was added thereto. Then, 1800 mL of 1 mol/L phosphoric acid aqueous solution was added thereto, and the solution was cooled to 5° C. The solution had two liquid phases of toluene and water.

[0085] Immediately after the temperature of the solution became 5° C., the solution was stirred at 390 rotations per minute. To the solution after stirring, a solution of ammonium persulfate, in which 65.7 g of ammonium persulfate was dissolved in 600 mL of 1 mol/L phosphoric acid, was added dropwise over a period of 2 hours using a dropping funnel under stirring. For 18 hours from the start of the dropwise addition, the solution was stirred while keeping the internal temperature of the solution at 5° C. Then, the solution temperature was increased up to 40° C. and was stirred for an additional 1 hours. After stirring, the solution was left to separate into two phases. The aqueous phase was separated and the organic phase was collected.

[0086] To the obtained organic phase, 1500 mL of toluene was added, and the mixture was washed once with 600 mL of 1 mol/L phosphoric acid and 3 times with 600 mL of ion-exchanged water. The insoluble matter was removed by filtration using a #5C filter paper to obtain a toluene solution of a polyaniline complex.

[0087] The obtained toluene solution was transferred to an evaporator, and the volatiles were distilled off under reduced pressure while being warmed in a hot water bath at 60° C., to obtain 43.0 g of a powdery polyaniline complex (molecular weight: 60000).

[0088] The weight-average molecular weight of the polyaniline was 60000. The molecular weight was determined by the polystyrene conversion method using a gel permeation chromatography (GPC).

[0089] The dopant ratio of the polyaniline complex [(number of moles of dopant doped into polyaniline)/(number of moles of monomer unit of polyaniline)] was 0.63.

[0090] The dopant ratio was calculated from the number of moles of dopant and the number of moles of monomer units of the polyaniline in the polyaniline complex. Specifically, the number of moles of sulfur atoms derived from the dopant and the number of moles of nitrogen atoms derived from the monomer unit of the polyaniline were quantified by an organic element analytical method, and the dopant ratio was calculated by taking the ratio of these values.

(2) Preparation of Solution Composition

[0091] 1 g of the polyaniline complex obtained in (1) above was weighed and charged into 9 g of propylene glycol monobutyl ether with stirring to obtain a 10% by mass polyaniline complex solution. Subsequently, 90 mL of DAIFERAMINE (manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd., a y-butyrolactone solution of 30% by mass polyurethane) which is a resin solution, was added to the polyaniline complex solution, and the mixture was stirred for 5 minutes at 2000 rpm using a planetary centrifugal stirrer (manufactured by THINKY CORPORATION, ARE-250) to prepare a solution composition.

[0092] The acid value or base value of the obtained solution composition was determined using a potentiometric titration method. AT-500 manufactured by KYOTO ELECTRONICS MANUFACTURING CO., LTD. was used as the measuring device, and an inflection point of the obtained potential difference was defined as an end point. The acid value was determined by the following expression using potassium hydroxide as the titrant.

Acid value (mgKOH/g)=(V1−V0)×N×f×M/S

[0093] In the expression, V1 is the titration amount (mL) in this test, V0 is the titration amount (mL) in the blank test, N is the concentration (mol/L) of the titrant, f is the factor of the titrant (1.010), M is the molar mass (g/mol) of the titrant, and S is the sample mass (g).

[0094] The base value was measured in the same manner as the acid value, except that hydrochloric acid was used as the titrant.

[0095] The measurement results are shown in Table 1.

[0096] As well, the viscosity of the resulting solution composition was measured using a digital viscometer at 25° C. DV2T manufactured by Brookfield Corporation was used as the measuring device to measure the viscosity at a rotational speed of 1 rpm. The measurement results are shown in Table 1.

[0097] (3) Film Formation

[0098] The solution composition obtained in (2) above was sucked up with an eyedropper and applied to an SPC steel plate using a film coater (manufactured by TESTER SANGYO CO., LTD., PI-1210). Then, the applied plate was dried for 2 hours at 80° C. in air to obtain a metallic component having a film thickness of 30 pm.

[0099] The obtained metallic component with a film was subjected to an environmental cycle test under the following conditions, and the rust generation was observed.

[0100] Brine spraying: NaCl solution (concentration: 5% by mass) at 35° C. sprayed for 2 hours Drying: Dried in air at a temperature of 60° C. and humidity of 20 to 30 RH % for 4 hours Wetting: Allowed to stand for 2 hours in air at a temperature of 50° C. and humidity of 95 RH % or more. The above brine spraying, drying and wetting were set to 1 cycle, and 30 cycles (10 days) were performed. The percentage of the area of rust covering the sample surface was measured for the sample after the environmental cycle test.

[0101] The results are shown in Table 1.

TABLE-US-00001 TABLE 1 Molecular Dopant Resin Acid Base Area ratio weight of PANI Dopant ratio used value value of rust Viscosity Thickness Example 1 60000 AOT 0.63 PU  9.8 —  2%   20000 24.8 Example 2 60000 AOT 0.32 PU  2   —  2%   10000 19.9 Example 3 20000 NSA 0.53 PU  3   —  2%   11000 24.5 Example 4 20000 NSA 0.26 PU  1.2 —  2%   29000 20.2 Example 5  5000 NSA 0.53 PU  5.5 —  2%    2100 19.5 Example 6  5000 NSA 0.26 PU  2   —  2%    1900 19.6 Example 7 20000 — 0   PU — 0.5  5%    7500 22.6 Example 8 20000 phosphoric acid 0.15 PU  2.5 —  3%    4000 20.2 Example 9 60000 AOT 0.63 EP  7.5 —  1%   15000 19.8 Example 10 75000 NSA 0.96 PU 12.2 — 30%   75000 17.4 Example 11 20000 NSA 0.96 PU 12.7 — 20%   59000 27.6 Example 12  5000 NSA 0.96 PU 14.1 — 10%    4000 27.0 Example 13 60000 AOT 0.63 PU  9.8 —  5%   20000 20.0 Example 14 60000 AOT 0.63 PU  9.8 —  7%   20000 20.0 Example 15 60000 AOT 0.63 PU  9.8 —  1%   20000 20.0 Comp. Ex. 1 60000 AOT 0.63 PU 15   — 40% >90000 20.2 Comp. Ex. 2  5000 NaOH 0.32 PU — 3.5 55%    3000 25.3 Comp. Ex. 3 Not blended — — —  2   — 80%   15000 24.3 In the table, AOT means Aerosol OT, NSA means naphthalene sulfonic acid, PU means polyurethane, and EP means epoxy. The unit of the acid value is “mgKOH/g,” the unit of the base value is “mgHCl/g,” the unit of the viscosity is “cP,” and the unit of the thickness is “μm.”

Example 2

[0102] A solution composition was prepared and evaluated in the same manner as in Example 1, except that the amount of Aerosol OT used was changed to 17.8 g. The results are shown in Table 1.

Example 3

[0103] After dissolving 2.22 g of polyaniline (manufactured by Sigma-Aldrich Co. LLC, molecular weight: 20000) in 40 mL of N-methylpyrrolidone, 137 g of naphthalene sulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the solution, and the mixture was stirred to obtain a polyaniline complex.

[0104] Preparation of the solution composition, film formation and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1.

Example 4

[0105] A solution composition was prepared and evaluated in the same manner as in Example 3, except that the amount of naphthalene sulfonic acid used was changed to 0.67 g. The results are shown in Table 1.

Example 5

[0106] A solution composition was prepared and evaluated in the same manner as in Example 3, except that 2.22 g of polyaniline (manufactured by Sigma-Aldrich Co. LLC, molecular weight: 5000) was used, and the amount of naphthalene sulfonic acid used was changed to 1.37 g. The results are shown in Table 1.

Example 6

[0107] A solution composition was prepared and evaluated in the same manner as in Example 5, except that the amount of naphthalene sulfonic acid used was changed to 0.67 g. The results are shown in Table 1.

Example 7

[0108] A solution composition was prepared and evaluated in the same manner as in Example 3, except that no naphthalene sulfonic acid was used. The results are shown in Table 1.

Example 8

[0109] A solution composition was prepared and evaluated in the same manner as in Example 3, except that 0.18 g of phosphoric acid having a concentration of 99% was used in place of naphthalenesulfonic acid. The results are shown in Table 1.

Example 9

[0110] A solution composition was prepared and evaluated in the same manner as in Example 1, except that 90 mL of an epoxy resin solution (ARAKYD 9205, manufactured by Arakawa Chemical Industries, Ltd., a solution containing 40% by mass of epoxy) was used in place of DAIFERAMINE (a γ-butyrolactone solution of 30% by mass polyurethane) which is a resin solution. The results are shown in Table 1.

Example 10

[0111] A polyaniline complex was obtained in the same manner as in Example 3, except that polyaniline (REGULUS, molecular weight: 75000), manufactured by KAKEN SANGYOU CORPORATION, was used, and the amount of naphthalene sulfonic acid added was changed to 2.48 g. Preparation of the solution composition, film formation and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1.

Example 11

[0112] After dissolving 2.22 g of polyaniline (manufactured by Sigma-Aldrich Co. LLC, molecular weight: 20000) in 40 mL of N-methylpyrrolidone, 2.48 g of naphthalene sulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the solution, and the mixture was stirred to obtain a polyaniline complex. Preparation of the solution composition, film formation and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1.

Example 12

[0113] After dissolving 2.22 g of polyaniline (manufactured by Sigma-Aldrich Co. LLC, molecular weight: 5000) in 40 mL of N-methylpyrrolidone, 2.48 g of naphthalene sulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the solution, and the mixture was stirred to obtain a polyaniline complex. Preparation of the solution composition, film formation and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1.

Example 13

[0114] A metalic component with a film was obtained and evaluated in the same manner as in Example 1, except that an aluminum plate (A6061) was used in place of the SPC steel plate. The results are shown in Table 1.

Example 14

[0115] A metallic component with a film was obtained and evaluated in the same manner as in Example 1, except that a galvanized steel plate was used in place of the SPC steel plate. The results are shown in Table 1.

Example 15

[0116] A metallic component with a film was obtained and evaluated in the same manner as in Example 1, except that a tin-plated copper plate was used in place of the SPC steel plate. The results are shown in Table 1.

Comparative Example 1

[0117] A solution composition was prepared and evaluated in the same manner as in Example 1, except that the amount of Aerosol OT used was changed to 200 g. The results are shown in Table 1.

Comparative Example 2

[0118] A solution composition was prepared and evaluated in the same manner as in Example 5, except that 5 g of sodium hydroxide was used in place of naphthalenesulfonic acid. The results are shown in Table 1.

Comparative Example 3

[0119] A film was formed and evaluated in the same manner as in Example 1, except that DAIFERAMINE (a γ-butyrolactone solution of 30% by mass polyurethane) which is a resin solution was used in place of the polyaniline complex solution. The results are shown in Table 1.

[0120] Although only some exemplary embodiments and/or examples of this invention have been described in detail above, those skilled in the art will readily appreciate that many modifications are possible in the exemplary embodiments and/or examples without materially departing from the novel teachings and advantages of this invention. Accordingly, all such modifications are intended to be included within the scope of this invention.

[0121] The documents described in the specification and the specification of Japanese application(s) on the basis of which the present application claims Paris convention priority are incorporated herein by reference in its entirety.