KR101398514B1 - Coating composition comprising aniline terminated waterborne polyurethane and poly(3,4-ethylenedioxythiophene)/polystyrene sulfonate - Google Patents

Abstract

The present invention relates to a process for preparing a coating composition containing polyurethane-water-dispersible polyurethane having an aniline end group and poly-3,4-ethylenedioxythiophene doped with polystyrene sulfonate. The coating composition is prepared by preparing a prepolymer prepared from polycarbonate thiol, diisocyanate and dimethylolpropionic acid, and then capping the terminal isocyanate group in the main chain of the prepolymer with aniline to prepare a prepolymer having an aniline end group, A coating composition prepared by preparing a water dispersible polyurethane composition having an aniline end group and mixing the water dispersible polyurethane composition having an aniline end group with poly-3,4-ethylenedioxythiophene doped with polystyrene sulfonate It is confirmed that the antistatic property and the electric conductivity are superior to the conductive coating composition prepared by using the conventional water-dispersible polyurethane composition or poly-3,4-ethylenedioxythiophene doped with polystyrene sulfonate.

Description

[0001] The present invention relates to a coating composition containing an aniline terminated water-dispersible polyurethane and a poly-3,4-ethylenedioxythiophene / polystyrenesulfonate, and a coating composition comprising the aniline terminated waterborne polyurethane and poly (3,4-ethylenedioxythiophene)

The present invention relates to a coating composition excellent in antistatic property and electrical conductivity and containing a water-dispersible polyurethane having an aniline end group and poly-3,4-ethylenedioxythiophene / polystyrenesulfonate.

As static electricity is transferred to an object in contact with electrons on the trajectory farthest from the nucleus of the surface atom of the insulator in the event of collision, peeling, or friction due to contact with another object, And the other material is generated by being charged with (+) charge by losing electrons. That is, it is known that electrons generated between two materials move and charge is accumulated on the surface without leakage, forming static electricity [Non-Patent Documents 1 and 2]. Disruptions caused by static electricity in industrial sites such as semiconductor factories, petrochemical factories, and precision machinery factories cause malfunction, quality deterioration of production robots, and burnout and explosion due to discharge spark, The generation of static electricity in many airplanes and operating rooms can cause a great accident [Non-Patent Document 3]. In order to prevent such an electrostatic phenomenon, it is possible to reduce the generation rate of electric charges by adding a quadrivalent ammonium salt, an ionic compound, a surfactant, a carbon black, a carbon nanotube, a conductive polymer, There have been a lot of studies on the prevention of electrification which increase the number of the electrodes [Non-patent Documents 4 to 5].

Among the conductive polymers, polythiophene has attracted much attention among conductive polymers due to its high electrical conductivity and thermal stability. Poly (3,4-ethylenedioxythiophene), PEDOT, which has an ethylenedioxy group in polythiophene, has an optical inhibition largely due to the electron donating effect of ethylene dioxy group band gap is low and has transparency in the visible light region. In addition, many studies have been carried out in the fields where the antistatic function is high and the chemical stability and electrical stability are high, which can be utilized [Non-patent Documents 6 to 7]. Particularly, poly-3,4-ethylenedioxythiophene / polystyrenesulfonate (PEDOT / PSS) doped with a water-soluble dopant polystyrene sulfonate (PSS) is dispersible in water, (Organic light emitting diodes) and the like [Non-Patent Document 8].

Polyurethane (PU) is a urethane group formed by the reaction of a polyol having two or more hydroxyl groups (OH) and a diisocyanate group having two isocyanate groups at the molecular end, NHCOO-] _n . ≪ / _RTI > This polyurethane can control various physical properties according to the content of soft segment and hard segment. Therefore, polyurethane can be applied to various fields such as coatings such as paints, rubber, leather, fiber, Have been widely used [Non-Patent Documents 9 to 11].

However, organic solvents such as benzene, toluene and xylene are mainly used in the production of polyurethane because of the high hydrophobicity of the polyol. The oil-based polyurethane produced by this method is a volatile organic compound ), Which not only presents the danger of fire, but also causes air pollution. Therefore, recently, in the synthesis of polyurethane, polar carboxyl groups or sulfonate-type polar ion groups have been introduced to induce them into ionomers, and hydrophobic polyurethanes are stably dispersed in water, Studies have been actively conducted on waterborne polyurethane dispersions (WPUD) [Non-Patent Documents 12 to 13].

In the present invention, the poly-3,4-ethylenedioxythiophene / polystyrene sulfonate composition and the water-dispersible polyurethane were mixed to prepare a coating composition excellent in antistatic function. In particular, a polyurethane prepolymer is prepared from a poly (carbonate diol), a diisocyanate and dimethylol propionic acid (DMPA), and the polyisocyanate prepolymer has a terminal isocyanate Capped with aniline to synthesize an aniline terminated waterborne polyurethane having an aniline terminal group and then mixed with poly-3,4-ethylenedioxythiophene / polystyrenesulfonate to obtain a coating film The surface resistivity of the antistatic coating composition of the present invention was remarkably reduced and thus an antistatic coating composition of new type excellent in electric conductivity and the like could be produced.

Park, H. S., Park, D. W. and Kim, W.J., Studies on the Durable Antistatic Agent of Sulfated Polyacrylate and Additives, Korean Chem. Eng. Res., 28 (4), 403-410 (1990). Kim, S. J., Kim, H. K., Keun, J.H. and Park, H.S., Synthesis and Characterization of Water-soluble Polyamine Durable Antistatic Agent, J. Korean Ind. Eng. Chem., 5 (3), 466-477 (1994). Hwang, Y. H., Sung, K.C. and Park, H.S., Antistatic Agents for Plastics, J. Korean Oil Chemists'Soc., 19 (1), 1-9 (2002). Ha, J. W. and Whang, K. H., Formulation of a Thermally Curable Coating Composition with Anti-Static Function, J. Korean Ind. Eng. Chem., 12 (1), 27-33 (2001). Lee, J. K., Choi, H. O., Kim, E. B., Kim, S. Y. and Ju C. D., Surface Resistance and Tensile Strength of Polyester Resin by Antistatic Agents, Korean Chem. Eng. Res., 48 (5), 638-642 (2010). Kim, K. Y., Seo, K. I., and Chung, I., J., A Study on Polymerization of Conductive Polymer PEDOT / PSSA and Its Electrical Properties, Theories and Applications of Chem. Eng., 4 (2), 3833 (1998). Lee, W.J. and Kim, Y.J., Preparation of Polycarbonate / Polyaniline Conducting Composites and Their Electrical Properties, J. Korean Ind. Eng. Chem., 10 (2), 287-292 (1999). Park, CM, Kim, TY, Kim, WJ, Kim, YS and Suh, KS, Solvent Effects on the Charge Transport Behavior in Poly (3,4-ethylenedioxythiophene) Synthesized with Iron (III) ), 29 (4), 363-368 (2005). Kim, W., Lee, M., G. and Song, K. C., Preparation of Silylated Waterborne Polyurethane / Silica Nanocomposites Using Colloidal Silica, Korean Chem. Eng. Res., 48 (5), 561-567 (2010). 48 (4), 434 (1995), and the preparation and properties of aminosilane terminated waterborne polyurethane, ibid., 43 (4) -439 (2010). 49 (4), 411 (2007), pp. 413-427. The Effect of Addition of Pentaerythritol Triacrylate on the Properties of Waterborne Polyurethane, ibid., Shin, YT, Hong, MG, Choi, JJ, Lee, WK, Yoo, -416 (2011). (4), (4), (4), (4), (4), (4), and (5), the waterborne polyurethane / silica nanocomposites using Tetraethylorthosilicate, ibid. 428-433 (2010). Kim, BS, Lee, WK, Yoo, BW, Lee, MG and Song, KC, Effect of Types of Acrylate Monomers on the Properties of Waterborne Polyurethane Dispersion, 548-553 (2011). ASTM D 3359, Standard Test Methods for Measuring Adhesion by Tape Test, ASTM International, 927-929 (1997).

It is an object of the present invention to provide a coating composition containing a water dispersible polyurethane having an aniline end group and poly-3,4-ethylenedioxythiophene / polystyrenesulfonate.

The present invention relates to a water-dispersible polyurethane having an aniline end group and a coating composition containing poly-3,4-ethylenedioxythiophene doped with polystyrene sulfonate.

The water dispersible polyurethane composition having an aniline end group has a structure in which an isocyanate group in the side chain of the polyurethane prepolymer is capped with aniline. As the amount of aniline added increases, the average particle diameter of the water-dispersed polyurethane increases and the transmittance Is decreased.

The water-dispersible polyurethane having an aniline end group is obtained by reacting an isocyanate group-containing polyurethane prepolymer prepared by mixing diisocyanate, polycarbonate diol and dimethylol propionic acid dissolved in 1-methyl-2-pyrrolidinone, Aniline to prepare a polyurethane prepolymer having an aniline end group, neutralizing the resulting polyurethane prepolymer, and then dispersing the polyurethane prepolymer having the neutralized aniline end group with water.

The polyurethane prepolymer having an aniline terminal group is prepared by mixing 0.001 to 0.05 mol of a diisocyanate, 0.02 to 0.08 mol of a polycarbonate diol and 0.001 to 0.06 mol of dimethylolpropionic acid dissolved in 1-methyl-2-pyrrolidinone To an isocyanate group-containing polyurethane prepolymer by adding 0.005 to 0.05 mol of aniline.

As the polycarbonate diol, polyhexamethylene carbonate diol may preferably be used.

In preparing the isocyanate group-containing polyurethane prepolymer, a catalyst can be used. As the catalyst, dibutyltin dilaurate and stainus octoate can be used, and 0.00001 to 0.0001 mol can be used.

The diisocyanate may be at least one compound selected from the group consisting of 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4-diphenylmethane diisocyanate, toluene diisocyanate and 4,4-dicyclohexylmethane diisocyanate have.

The isocyanate group-containing polyurethane prepolymer may be prepared by reacting dimethylisopropionic acid in diisocyanate, polycarbonate diol and 1-methyl-2-pyrrolidinone at 50 to 100 ° C for 1 to 5 hours. In the polyurethane prepolymer having an isocyanate group, the molar ratio of the isocyanate group to the hydroxyl group of the polyhexamethylene carbonate diol is preferably 1: 1.0 to 1.5.

In addition, a chain extender may be added before the neutralization reaction of the polyurethane prepolymer having an aniline end group. As the chain extending agent, at least one compound selected from the group consisting of ethylenediamine, 1,6-hexanediol, diethylenetriamine, hydrazine, isophoronediamine, morpholine and 1,4-butanediol may be used. By adding an extender and reacting, the polymerization reaction of the composition can be enhanced. The chain extender may be added in an amount of 0.001 to 0.03 mol and reacted for 0.5 to 2 hours.

The neutralizing agent used in the neutralization reaction of the polyurethane prepolymer having an aniline terminal group is characterized by being at least one compound selected from triethylamine, potassium hydroxide and ammonia. By using a neutralizing agent when preparing the polyurethane prepolymer, the carboxyl group formed by adding dimethylol propionic acid can be neutralized. The neutralizing agent can be reacted at 30 to 70 ° C for 0.5 to 3 hours.

In the coating composition containing the water-dispersible polyurethane having an aniline end group and poly-3,4-ethylenedioxythiophene doped with polystyrene sulfonate, the water-soluble polyurethane and polystyrene sulfonate-doped poly-3,4 - ethylene dioxythiophene may preferably be from 1: 0.1 to 0.3 (w / w). Preferably, poly (3,4-ethylenedioxythiophene) doped with polystyrene sulfonate is reacted with the water dispersible polyurethane having an aniline end group at room temperature for 0.5 to 2 hours to mix. The poly-3,4-ethylenedioxythiophene doped with polystyrene sulfonate is liquid, odorless, dark blue in color, and well dispersed in water. The poly-3,4-ethylenedioxythiophene doped with polystyrene sulfonate may be dispersed in water, preferably 0.5 to 5%, and dispersed in water.

Thus, the process for producing a coating composition containing poly-3,4-ethylenedioxythiophene doped with a water-dispersible polyurethane having an aniline end group and a polystyrene sulfonate of the present invention is preferably a method comprising:

Mixing a diisocyanate, a polycarbonate diol and dimethylol propionic acid dissolved in 1-methyl-2-pyrrolidinone to prepare an isocyanate group-containing polyurethane prepolymer;

Adding aniline to the isocyanate group-containing polyurethane prepolymer to prepare a polyurethane prepolymer having an aniline terminal group;

Adding a chain extender to the polyurethane prepolymer having the aniline terminal group;

Adding a neutralizing agent to a polyurethane prepolymer having an aniline terminal group to which the chain extender is added;

Dispersing a polyurethane prepolymer having an aniline end group to which the neutralizing agent is added to prepare a water dispersible polyurethane having an aniline end group; And

And adding poly-3,4-ethylenedioxythiophene doped with polystyrene sulfonate to the water dispersible polyurethane having an aniline end group.

In addition, the method for producing the coating composition may further comprise,

0.001 to 0.05 mol of diisocyanate, 0.02 to 0.08 mol of polycarbonate diol and 0.001 to 0.06 mol of dimethylolpropionic acid dissolved in 1-methyl-2-pyrrolidinone to prepare a polyurethane prepolymer having an isocyanate group ;

Adding 0.005 to 0.05 mol of aniline to the isocyanate group-containing polyurethane prepolymer to prepare a polyurethane prepolymer having an aniline terminal group;

Adding 0.001 to 0.03 mol of a chain extender to the polyurethane prepolymer having an aniline terminal group;

Adding 0.005 to 0.07 mol of a neutralizing agent to the polyurethane prepolymer having an aniline terminal group added with the chain extender;

Preparing a water dispersible polyurethane having an aniline terminal group by adding water to the polyurethane prepolymer having an aniline end group to which the neutralizing agent has been added, And

Adding poly-3,4-ethylenedioxythiophene doped with polystyrene sulfonate to the water dispersible polyurethane having an aniline end group at a mixing ratio of 1: 0.1 to 0.3 (w: w) have.

The coating composition containing the water dispersible polyurethane having an aniline end group and the poly-3,4-ethylenedioxythiophene doped with polystyrenesulfonate according to the present invention can be applied to a conventional water-dispersible polyurethane composition or polystyrene sulfonate-doped A conductive film, a conductive garment, a support sheet for a conductive sheet, a flooring made of a conductive sheet, an electronic sheet, and the like, which are superior in antistatic property and electrical conductivity to the coating composition prepared by using poly-3, 4-ethylenedioxythiophene. A material film, a heat radiation sheet, a heat sheet, a sheet for shoes, an insole sheet for shoes, and the like.

1 is a FT-IR spectrum analysis result of a polyurethane prepolymer, wherein a) is a FT-IR spectrum analysis result of a polyurethane prepolymer obtained by reacting polycarbonate diol, isophorone diisocyanate and dimethylol propionic acid for 3 hours , b) and c) are FT-IR spectrum analysis results of the polyurethane prepolymer having an aniline terminal obtained by reacting the polyurethane prepolymer with aniline for 1 hour or 2 hours.
2 shows the results of measurement of transmittance for water-dispersible polyurethanes A0, A1, A2, and A3 having an aniline end group using a spectrophotometer (UV-Visible spectrometer, UV-2450, Shimadzu).
Fig. 3 shows the results of analysis of the average particle size of the water-dispersible polyurethane composition having an aniline end group using a particle size analyzer.
4 shows the result of measuring the surface resistance of the coating film of the coating composition prepared by varying the addition amount of the water dispersible polyurethane composition having an aniline terminal group and poly-3,4-ethylenedioxythiophene doped with polystyrene sulfonate Conductivity confirmation).
Figure 5 shows a comparison of the coating compositions (A3-P0, A3-P1, A3-P2, A3-P3, A3-P4 and A3-P4) containing poly-3,4-ethylenedioxythiophene doped with a water dispersible polyurethane and polystyrene sulfonate A3-P5).

Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the embodiments described herein but may be embodied in other forms. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art.

≪ Example 1: Preparation of material for producing coating >

To prepare the coating composition of the present invention, an aliphatic isophthalone diisocyanate (98%, Aldrich) was used as a diisocyanate, and a polycarbonate diol, polyhexamethylene carbonate diol (1000 g / mol, Asahi Kasei ) Was used as a polyol. Dimethylolpropionic acid (98%, Aldrich) was used as the anionic group added for water dispersion, and 1-methyl-2-pyrrolidinone as a solvent for dissolving dimethylolpropionic acid. 2-pyrolidinone, NMP, 99%, Aldrich) was used. Triethylamine (TEA, 99.5%, Aldrich) was used as a neutralizing agent for dimethylolpropionic acid.

Also, dibutyltin dilaurate (DBTL, 95%, Aldrich) was used as a catalyst. An aniline (99.5%, Aldrich) having an aromatic structure was used for capping the residual isocyanate group of the obtained polyurethane prepolymer. 1,4-butanediol (1,4-BD, 99%, Aldrich) was used as a chain extender. Conductive polymers to be mixed with the water-dispersible polyurethane coating composition having an aniline terminal group include poly (3,4-ethylenedioxythiophene) doped with poly (styrene sulfonate) Poly (3,4-ethylenedioxythiophene) / polystyrene (PEDOT / PSS, Baytron P Al 4083, manufactured by Bayer Co.) was used in the form of poly (3,4-ethylenedioxythiophene) Cymel 327 (CYTEC INC, USA), a melamine-based curing agent, was used as an additive to improve the curing speed and surface hardness of the coating film. The above reagents were used without purification and chemical treatment.

≪ Example 2: Preparation of coating composition containing water-dispersible polyurethane having an aniline end group and poly-3,4-ethylenedioxythiophene / polystyrene sulfonate >

Example  2-1. Polyurethane having an isocyanate group Prepolymer  Produce

A 500 ml four-necked round flask equipped with a thermometer, a condenser, a constant temperature water tank and a stirrer was charged with isophorone diisocyanate, dimethyolpropionic acid obtained by dissolving polyhexamethylene carbonate diol and 1-methyl-2-pyrrolidinone, Dibutyl tin dilaurate as an acid catalyst and then reacted at 75 ° C and 500 rpm for 3 hours to prepare an isocyanate group-containing polyurethane prepolymer. At this time, the molar ratio of the isocyanate group to the hydroxyl group of the polyhexamethylene carbonate diol was fixed at 1.3.

Example  2-2. aniline Horse short  Have Prepolymer  Produce

When the polyurethane prepolymer of Example 2-1 was prepared, the remaining isocyanate group remaining in the prepolymer was capped with aniline by adjusting the addition amount of aniline under the conditions shown in Table 1 and reacting at 50 ° C for 2 hours to obtain an aniline terminal group (This step was omitted in the case of A0 in Table 1 below). ≪ tb > < TABLE >

Example  2-3. aniline Horse short  Preparation of water-dispersible polyurethane having

Thereafter, 1,4-butanediol was added as a chain extender and reacted at 50 DEG C for 1 hour. Then, dimethylol propionic acid was added under the conditions shown in Table 1 to prepare carboxyl (COOH, carboxyl acid ) Was neutralized at 50 ° C for 1 hour to neutralize it. After that, 120 g of distilled water was added and dispersed at 1,000 rpm for 20 minutes to obtain aniline To prepare a water-dispersible polyurethane having a terminal group.

Condition mol soft
Segment
Hard segment
Capping agent chain
Extenders
catalyst
corrector
Polyhexamethylene carbonate diol (PCD) Isophorone
Diisocia
Nate
(IPDI)
Dimethylol
Propionic acid
(DMPA)
aniline
(aniline)
1,4-
Butanediol
(1,4-BD)
Dibutyltin
Dilaurate
(DBTL)
tree
Ethylamine
(TEA) A0
(Comparison group)
0.052
0.0117
0.038
0.0000
0.027
0.000045
0.038 A1 0.052 0.0117 0.038 0.013 0.020 0.000045 0.038 A2 0.052 0.0117 0.038 0.017 0.018 0.000045 0.038 A3 0.052 0.0117 0.038 0.026 0.014 0.000045 0.038

Example  2-4. aniline Horse short  Water-dispersible polyurethane and Poly -3,4- Ethylene dioxythiophene / Polystyrene sulfonate  Preparation of coating compositions containing

When the water dispersible polyurethane composition having an aniline end group (A0 to A3, A0 is a comparative group) is produced, a water dispersible polyurethane composition having an aniline end group and poly-3,4-ethylenedioxythiophene / polystyrenesulfonate The mixture was mixed for 1 hour under the conditions shown in Table 2 below, and 1 g of a melamine crosslinking agent (Cymel 327) was added to prepare an antistatic coating solution.

Condition Weight (g)
A0
A1
A2
A3 Poly-3,4-ethylenedioxy
Thiophene / polystyrenesulfonate
(PEDOT / PSS) A0-P0 10 - - - 0 A0-P1 10 - - - 1.0 A0-P2 10 - - - 1.5 A0-P3 10 - - - 2.0 A0-P4 10 - - - 2.5 A0-P5 10 - - - 3.0 A0-P6 10 - - - 3.5 A1-P0 - 10 - - 0 A1-P1 - 10 - - 1.0 A1-P2 - 10 - - 1.5 A1-P3 - 10 - - 2.0 A1-P4 - 10 - - 2.5 A1-P5 - 10 - - 3.0 A1-P6 - 10 - - 3.5 A2-P0 - - 10 - 0 A2-P1 - - 10 - 1.0 A2-P2 - - 10 - 1.5 A2-P3 - - 10 - 2.0 A2-P4 - - 10 - 2.5 A2-P5 - - 10 - 3.0 A2-P6 - - 10 - 3.5 A3-P0 - - - 10 0 A3-P1 - - - 10 1.0 A3-P2 - - - 10 1.5 A3-P3 - - - 10 2.0 A3-P4 - - - 10 2.5 A3-P5 - - - 10 3.0 A3-P6 - - - 10 3.5

waterborne polyurethane and poly (3,4-ethylenedioxythiophene) / polystyrene) is shown in the following Reaction Scheme 1.

[Reaction Scheme 1]

< Example  3. Aniline Horse short  A water-dispersible polyurethane coating composition having an aniline Horse short  Water-dispersible polyurethane and Poly -3,4-ethylene Dioxythiophene / Polystyrene sulfonate  &Lt; tb &gt; &lt;

Example  3-1. FT - IR ( Fourier transform spectroscopy ) Polyurethane through spectroscopic analysis Prepolymer  aniline Capping  Confirm

The polyurethane prepolymer in the reaction steps of Examples 2-1 and 2-2 was thinly coated on a potassium bromide (KBr) plate to confirm whether or not an aniline was capped in the polyurethane prepolymer, and then FT-IR (FTIR- 8400S, Shimadzu) was used to measure the progress of the reaction between the main functional group and the isocyanate group, which is shown in Fig.

1 (a) is a FT-IR spectrum analysis result of a polyurethane prepolymer (prepolymer of Example 2-1) obtained by reacting a polyhexamethylene carbonate diol, isophorone diisocyanate and dimethylolpropionic acid for 3 hours, The results are shown for the A1 polyurethane prepolymer added with 0.0075 mol of aniline prepared in Example 2-2. 1 (b) and 1 (c) show FT-IR spectrum analysis results of the polyurethane prepolymer having an aniline end (prepolymer of Example 2-2) obtained by reacting the polyurethane prepolymer with aniline for 1 hour and 2 hours. In Fig. 1 a) in the band from -CO -NH stretching peak, 1,700cm ^-1 in the vicinity of the -C = O band, -CH ₂ bands in the region 2,900cm ^-1, 1,100cm ^-1 vicinity near 3,300cm ^-1, A peak for an isocyanate group was confirmed at around 2,260 cm ^-1 , indicating that a polyurethane prepolymer was synthesized. Further, in (b) and (c) of FIG. 1, as the reaction time after the addition of the aniline increases, the peak intensity with respect to the isocyanate group in the vicinity of 2,260 cm ^-1 becomes weak, so that the isocyanate group of the polyurethane prepolymer side chain is capped with aniline have.

Example  3-2. aniline Horse short  Determination of the transmittance of the water-dispersible polyurethane composition having

A water-dispersible polyurethane composition having an aniline terminal group was spin-coated on a polycarbonate substrate and then thermally cured at 120 ° C for 30 minutes to prepare a coating film. The coating film was measured with a UV-Visible spectrometer (UV-2450, Shimadzu) at 600 nm. The transmittance of the coated film was measured and the measurement results are shown in FIG.

As shown in FIG. 2, the transmittance of the water-dispersible polyurethanes A0, A1, A2, and A3 having an aniline terminal group was measured. As the amount of aniline added increased, the turbidity increased in the visible light region. It was determined that the greater the amount of aniline added during the synthesis, the more the aniline was capped in the polyurethane main chain, thereby reducing the transmittance of the water-dispersible polyurethane having an aniline end group.

Example  3-3. Water-soluble polyurethane containing no aniline and aniline Horse short  Of the water-dispersible polyurethane Check the size

Dynamic light scattering (DLS) was performed to confirm the particle size of the water dispersible polyurethane compositions A1, A2 and A3 having an aniline end group and A0 which is a water dispersible polyurethane composition containing no aniline of Example 2-3 (Nicomp, model 380, USA), and the results of the analysis are shown in FIG.

As shown in Fig. 3, the average particle diameter of pure water-dispersible polyurethane A0 was 13 nm, while the water-dispersible A1, A2 and A3 polyurethane compositions having aniline ends had average particle diameters of 25 nm, 33 nm and 40 nm As the amount of aniline added increases, the average particle size increases. It was analyzed that the more aniline added during the synthesis, the more the aniline was capped in the polyurethane main chain, the size of the formed particles increased, and the average particle size of the water-dispersible polyurethane having an aniline end group was also increased. As the particle size increases, as the amount of aniline having an aromatic structure increases, the water-dispersed polyurethane The average particle size increases and the proportion of the hard segment in the polyurethane structure also increases, resulting in excellent abrasion resistance of the coating film.

Example  3-4. Water-dispersible polyurethanes and Poly -3,4- Ethylene dioxythiophene / Polystyrene sulfonate  Identify pencil hardness, adhesion, and film thickness of coating compositions containing

In order to confirm the shape of the pencil hardness and the adhesion of the coating composition of the present invention, the coating composition of Example 2-4 was spin-coated on a polycarbonate substrate and then thermally cured at 120 ° C for 30 minutes to form a coating film .

The pencil hardness was measured to push the hardened layer Put the pencil for pencil hardness measured in a pencil hardness tester (CT-PC1, CORE TECH, Korea) caught by 45 ^o angle, while applying a constant load (1kg). The pencil used was a Mitsubishi pencil, and a pencil indicating the strength of H-9H, F, HB, B-6B and the like was used.

In order to confirm the adhesive force, the method disclosed in ASTM D 3359 (Non-Patent Document 14) was referred to. For this purpose, a 100 mm square was cut out with a cutter at 11 mm intervals with a cutter at intervals of 1 mm, a 3M tape was closely adhered to the cured coating layer, and the coating was peeled off several times with a constant force. Was observed. 5B for 100, 3B for more than 85, 4B for more than 85, 2B for over 65, 1B for over 35, and 0B for less than 35.

In order to measure the thickness of the coated film, the thickness of the cured film was measured based on the thickness of the polycarbonate substrate before coating using a film thickness meter (Model-S112, Japan).

The results for the pencil hardness, adhesion and coating film thickness are shown in Table 3.

Condition Pencil hardness Adhesion Film Thickness (㎛) A0-P0 2B 5B 13 A0-P1 2B 5B 13 A0-P2 2B 5B 10 A0-P3 2B 5B 11 A0-P4 3B 5B 12 A0-P5 3B 5B 10 A0-P6 5B 2B 8 A1-P0 2B 5B 13 A1-P1 2B 5B 13 A1-P2 2B 5B 10 A1-P3 2B 5B 11 A1-P4 3B 5B 12 A1-P5 3B 5B 10 A1-P6 5B 2B 8 A2-P0 2B 5B 14 A2-P1 2B 5B 12 A2-P2 2B 5B 10 A2-P3 2B 5B 11 A2-P4 3B 5B 12 A2-P5 3B 5B 11 A2-P6 5B 2B 8 A3-P0 2B 5B 15 A3-P1 2B 5B 14 A3-P2 2B 5B 12 A3-P3 2B 5B 13 A3-P4 3B 5B 12 A3-P5 3B 5B 11 A3-P6 5B 2B 8

As shown in Table 3, the samples to which the added amount of poly-3,4-ethylenedioxythiophene / polystyrenesulfonate was added in an amount of 3.0 g or less showed pencil hardness of 2B to 3B. However, Showed low pencil hardness of (A0-P6, A0-P6, A1-P6, A1-P6, A2-P6, A2-P6, A3-P6, A3-P6) This is probably due to an increase in the content of the conductive polymer having a low mechanical strength in the coating solution. Also, there was no difference in pencil hardness according to the change in the amount of aniline added (A0 to A3).

The adhesion of poly-3,4-ethylenedioxythiophene / polystyrenesulfonate added to 3.0g or less of the coated film was 5B, but the added amount of over 3.5g was 2B Respectively.

The samples added with poly-3,4-ethylenedioxythiophene / polystyrenesulfonate of 3.0 g or less had thicknesses of coating films of 10 μm or more, but samples added in an excess amount of 3.5 g or more were less than 10 μm . From the above results, it was found that the mixing ratio of the water-dispersed polyurethane having an aniline terminal group and poly-3,4-ethylenedioxythiophene / polystyrenesulfonate was preferably 1: 0.1-0.3 (w: w) I could.

Example  3-5. Water-dispersible polyurethanes and Poly -3,4- Ethylene dioxythiophene / Polystyrene sulfonate  Determination of the surface resistance of the coating compositions containing (electrically conductive)

In order to confirm the surface resistance of the coating film surface of the coating composition of the present invention, the coating composition of Example 2-4 was spin-coated on a polycarbonate substrate and then thermally cured at 120 ° C for 30 minutes to form a coating film . The surface resistance was measured using a surface resistance meter (SIMCO, ST-3, Japan) under the condition of constant temperature and humidity maintained, and it is shown in FIG.

4, when poly-3,4-ethylenedioxythiophene / polystyrenesulfonate was mixed with the pure water-dispersible polyurethane coating composition (A0), poly-3,4-ethylenedioxythiophene / polystyrene When the addition amount of poly-3,4-ethylenedioxythiophene / polystyrenesulfonate was more than 2.0 g, the surface resistance was reduced to some extent . On the other hand, when poly-3,4-ethylenedioxythiophene / polystyrenesulfonate is mixed with the water dispersible polyurethane coating composition (A1, A2, A3) having an aniline terminal group, / Polystyrene sulfonate, the surface resistance was greatly decreased. However, it was found that the change of the aniline addition amount did not greatly affect the surface resistance of the water dispersible polyurethane coating composition samples having an aniline end group, and thus showed almost constant electric conductivity. As a result, it was found that the composition of the present invention is excellent in electric conductivity and antistatic effect (antistatic effect increases when surface resistance is low). (A0-P6, A0-P6, A1-P6, A1-P6, A2-P6 and A3-P6) were added in an amount exceeding 3.5 g of the poly-3,4-ethylenedioxythiophene / polystyrene sulfonate. A2-P6, A3-P6, A3-P6) Surface resistance could not be confirmed because the coatings were not good due to poor physical properties such as hardness and adhesion.

Example  3-6. Water-dispersible polyurethanes and Poly -3,4- Ethylene dioxythiophene / Polystyrene sulfonate  Determination of the transmittance of coating compositions containing

A3, which is a water-dispersible polyurethane composition having an aniline terminal group, and poly-3,4-ethylenedioxythiophene / polystyrene sulfonate, P0 to P5, (A3-P0, A3-P1, A3-P2, A3-P3, A3-P4 and A3-P5) containing a cyanophene / polystyrenesulfonate was spin-coated on a polycarbonate substrate, The coating film was thermally cured at 120 ° C for 30 minutes. Then, using a spectrophotometer (UV-Visible spectrometer, UV-2450, Shimadzu) The transmittance of the coated film was measured, and the measurement result was shown in FIG.

5, A3-P0, which is a sample to which no poly-3,4-ethylenedioxythiophene / polystyrenesulfonate was added, exhibited an average transmittance of 90%, but poly-3,4-ethylenedioxythiophene / The permeability of the coated film decreased with increasing the amount of poly (3,4 - ethylenedioxythiophene / polystyrenesulfonate) added to polystyrene sulfonate added samples. This is probably due to the increase in the amount of PEDOT / PSS added to the coating solution.

Claims (9)

A water-dispersible polyurethane having an aniline end group and poly-3,4-ethylenedioxythiophene doped with polystyrene sulfonate. The method according to claim 1,
Wherein the coating composition is a coating comprising a water-dispersible polyurethane having an aniline end group and a poly-3,4-ethylenedioxythiophene doped with polystyrene sulfonate in a mixing ratio of 1: 0.1 to 0.3 (w: w) Composition. 3. The method according to claim 1 or 2,
The water dispersible polyurethane having an aniline terminal group is preferably used in an amount of from 0.001 to 0.05 mol of a diisocyanate, 0.02 to 0.08 mol of a polyhexamethylene carbonate diol and 0.03 to 0.07 mol of 1-methyl-2-pyrrolidinone, mol of dimethylol propionic acid to an isocyanate group-containing polyurethane prepolymer, 0.005 to 0.05 mol of aniline is added to prepare a polyurethane prepolymer having an aniline end group, and the polyurethane prepolymer is selected from triethylamine, potassium hydroxide and ammonia By weight of a polyurethane prepolymer having an aniline terminal group, and neutralizing the neutralized agent with 0.005 to 0.07 mol of at least one neutralizing agent. 3. The method according to claim 1 or 2,
Wherein the poly-3,4-ethylenedioxythiophene doped with polystyrene sulfonate is a conductive polymer doped with poly-3,4-ethylenedioxythiophene with polystyrene sulfonate. The method of claim 3,
The water-dispersible polyurethane having an aniline end group is preferably a group consisting of ethylenediamine, 1,6-hexanediol, diethylenetriamine, hydrazine, isophoronediamine, morpholine and 1,4-butanediol And 0.001 to 0.03 mol of at least one chain extender selected from the group consisting of: &lt; RTI ID = 0.0 &gt; 3. The method according to claim 1 or 2,
The water-dispersible polyurethane having an aniline end group has a structure in which an isocyanate group of the side chain of the polyurethane prepolymer is capped with aniline, the average particle diameter increases with an increase in the amount of aniline, and the transmittance decreases in the visible light region Composition. The method of claim 3,
The diisocyanate is at least one compound selected from the group consisting of 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4-diphenylmethane diisocyanate, toluene diisocyanate and 4,4-dicyclohexylmethane diisocyanate. &Lt; / RTI &gt; The method of claim 3,
Wherein the isocyanate group-containing polyurethane prepolymer is a water-dispersible polyurethane having an aniline end group, wherein the polyurethane prepolymer having an isocyanate group is prepared by adjusting a molar ratio of an isocyanate group and a hydroxyl group of a polyhexamethylene carbonate diol to 1: 1.0 to 1.5. . 0.001 to 0.05 mol of diisocyanate, 0.02 to 0.08 mol of polycarbonate diol and 0.001 to 0.06 mol of dimethylolpropionic acid dissolved in 1-methyl-2-pyrrolidinone to prepare an isocyanate group-containing polyurethane prepolymer ;
Adding 0.005 to 0.05 mol of aniline to the isocyanate group-containing polyurethane prepolymer to prepare a polyurethane prepolymer having an aniline terminal group;
Adding 0.001 to 0.03 mol of a chain extender to the polyurethane prepolymer having an aniline terminal group;
Adding 0.005 to 0.07 mol of a neutralizing agent to the polyurethane prepolymer having an aniline terminal group added with the chain extender;
Preparing a water dispersible polyurethane having an aniline terminal group by adding water to the polyurethane prepolymer having an aniline end group to which the neutralizing agent has been added, And
Adding poly-3,4-ethylenedioxythiophene doped with polystyrene sulfonate to the water-dispersible polyurethane having an aniline terminal group at a mixing ratio of 1: 0.1 to 0.3 (w: w);
And a poly-3,4-ethylenedioxythiophene doped with polystyrene sulfonate, wherein the water-dispersible polyurethane has an aniline end group.

Images