JP2019038943A - Black gloss coating material, black gloss coating film and method for producing black gloss coating material - Google Patents

Abstract

To provide a material for a black gloss coating material capable of forming a black coating film by a simple process, to provide a black gloss coating material and to provide a black gloss coating film.SOLUTION: The method for producing a black gloss coating material comprises a step of dissolving 3-butoxy thiophene and ferric perchlorate into an acetonitrile solution, a step of mixing the acetonitrile solution to synthesize an oligomer and a step of dissolving the oligomer into nitromethane. The black gloss coating film contains 3-butoxy thiophene polymer in which the 3-butoxy thiophene has edge-on lamellar structure. It is desirable that the interlayer distance of the lamellar structure is 1.5 nm to 1.6 nm.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a black gloss paint, a black gloss paint film, and a method for producing a black gloss paint.

  Piano black paint with a lacquer black color is applied to piano paint, high-quality furniture, and high-quality kitchen paint. As the paint, a mixture of polyester resin and carbon black is used.

  The following Patent Document 1 describes a black paint containing carbon black, a binder resin, and the like.

JP2014-21231A

  In a conventional polyester resin / carbon black mixed paint, since carbon black must be dispersed in a resin solution, a complicated dispersion process is required. Moreover, gloss is not manifested only by applying to the painted surface with a paint, and it is necessary to smoothen the coating film by polishing, and then polish it with a buff and a compound to obtain gloss. It is said to be a highly difficult technology that takes ten years to learn.

  Accordingly, an object of the present invention is to provide a black gloss paint material, a black gloss paint, and a black gloss paint film that can form a black paint film by a simple process.

  In order to solve the above-described problems, according to one aspect of the present invention, the black glossy paint contains a 3-butoxythiophene polymer.

  According to another aspect of the present invention, the black glossy coating film contains a 3-butoxythiophene polymer, and the 3-butoxythiophene has a lamellar structure. Furthermore, it is desirable that the interlayer distance of the lamellar structure is 1.5 nm or more and 1.6 nm or less.

  According to another aspect of the present invention, there is provided a method for producing a black luster paint comprising a step of dissolving 3-butoxythiophene and ferric perchlorate in an acetonitrile solution, and mixing the acetonitrile solution with an oligomer. It has the process of synthesize | combining and the process of melt | dissolving the said oligomer in nitromethane.

  According to another aspect of the present invention, a black gloss paint is prepared by dissolving 3-butoxythiophene and ferric perchlorate in an acetonitrile solution, and synthesizing an oligomer by mixing the acetonitrile solution. And a step of dissolving the oligomer in nitromethane.

  According to the present invention, unlike a conventional coating material in which polyester and carbon black are mixed and dispersed, it is not necessary to carry out dispersion, and the coating material can be produced by simple stirring. Further, the 3-butoxythiophene polymer that gives the black glossy film of the present invention, unlike a conventional paint in which polyester and carbon black are mixed and dispersed, exhibits black gloss only by being applied and dried. That is, unlike the conventional method, it does not require special techniques for smoothing by polishing and gloss development by buffing after painting and drying.

It is a figure which shows the digital microscope image observed from the diagonal of a polymer. It is a figure which shows the digital microscope image observed from the upper direction of a polymer film. It is a figure which shows the coating film formed from 3-methoxythiophene (a), 3-ethoxythiophene (b), 3-propoxythiophene (c), and 3-butoxythiophene oligomer. It is a figure which shows the colorimetry result of the oligomer (d) of methoxythiophene (a), ethoxythiophene (b), propoxythiophene (c), and butoxythiophene. It is a figure which shows the reflection spectrum of the oligomer (d) of methoxythiophene (a), ethoxythiophene (b), propoxythiophene (c), and butoxythiophene. It is a figure which shows the XRD pattern of the oligomer film | membrane (d) of methoxythiophene (a), ethoxythiophene (b), propoxythiophene (c), and butoxythiophene. It is a figure which shows the angle (2 (theta)) of the diffraction peak of each oligomer film | membrane, the lamella interlayer distance calculated from the angle, and a stacking distance. It is a figure which shows Edge-on lamella structure (a) and Face-on lamella (b) structure.

  As a result of intensive studies, the inventors have found that the coating film exhibits a jet black piano black color by mixing a general-purpose resin and a 3-methoxythiophene polymer. When this 3-methoxythiophene polymer is dissolved alone in a solvent and coated, a glossy film with a golden tone is obtained. And this time, when the substituent bonded to the 3-position of thiophene was changed to a 3-butoxy group instead of the 3-methoxy group to form a polymer, a black glossy coating film was formed independently without mixing a general-purpose resin. Turned out to be.

  A digital microscope image (FIG. 1) photographed with a ruler set perpendicular to the obtained film and a digital microscope image photographed by irradiating the ring illumination of the digital microscope perpendicularly to the film ( FIG. 2) is shown. In FIG. 1, the scale of the ruler is reflected, and in FIG. 2, a regular reflection image of the ring illumination is observed, and it can be seen that a high regular reflection characteristic is exhibited. Further, a * and b * of the polymer film were measured using a device (Spectrocolorimeter CM-600d) manufactured by Konica Minolta (measurement conditions: 10 ° C. field of view, light source D65, measurement diameter 8 mm). As a result, the values of a * and b * were 5.5 and 3.1, respectively. Although these values are black color tones, they are small values very close to a * = 0 and b * = 0, and it was confirmed that the color tones are very close to black.

  The 3-butoxythiophene polymer that gives the black glossy coating film of the present invention is different from the conventional paint in which polyester and carbon black are mixed and dispersed, and is dissolved in a solvent in a molecular form. The paint can be manufactured only by it. Moreover, since it can be used as a paint alone, a resin to be added is unnecessary, and it is not limited to a solvent (solvent) that dissolves the added resin, and there is an advantage that a selection range of the solvent (solvent) is widened.

  Further, the 3-butoxythiophene polymer that gives the black glossy coating film of the invention is different from the conventional paint in which polyester carbon black is mixed and dispersed, and exhibits black gloss only by applying and drying. That is, unlike the conventional method, it does not require special techniques for smoothing by polishing and gloss development by buffing after painting and drying.

1. Experimental Method An oligomer was synthesized by mixing an acetonitrile solution in which 3-alkoxythiophene and ferric perchlorate were dissolved in a nitrogen atmosphere. The obtained oligomer was dissolved in nitromethane and formed on a glass substrate by a casting method. The physical properties of the coating film were evaluated by specular reflection spectrum measurement and thin film X-ray diffraction measurement. As 3-alkoxythiophene, 3-methoxythiophene (a), 3-ethoxythiophene (b), 3-propoxythiophene (c), and 3-butoxythiophene (d) were used.

  Evaluation of the prepared coating film is based on appearance imaging using a digital microscope (KEYENCE, VHX-5000), specular reflection measurement based on a deposited aluminum substrate (JASCO, MSV-370), laser microscope (KEYENCE, VK- 9700) and surface color (roughness) measurement and colorimetry using a spectrocolorimeter (Konica Minolta, CM-600d).

  Cyclic voltammetry measurement was performed using an electrochemical analyzer (ALS Japan Inc., Model 600A), indium tin oxide coated glass (ITO) as the working electrode, and Pt plate as the counter electrode.

  The orientation of oligomer molecules in the coating film was examined by thin film X-ray diffraction measurement (XRD).

2. 2. Results and Discussion 2.1 Appearance Observation images of the obtained four coating films of alkoxythiophene oligomer having a metallic luster are shown in FIG. Images (a), (b), (c) and (d) show photographs of coating films formed from oligomers of methoxythiophene, ethoxythiophene, propoxythiophene and butoxythiophene, respectively. It was found that the color tone changes due to the difference in the alkyl chain length of the alkoxy group, and the appearance of gold color tone with methoxy group, copper color tone with ethoxy group, magenta gloss color with propoxy group, and black gloss color with butoxy group is realized. In addition, it can be seen that the film surface has a high regular reflection characteristic by observing a ruler scale reflected on the side surface of the sample. Therefore, next, color measurement and specular reflection spectrum measurement of the film were performed.

3.2 Color measurement of coating film FIG. 4 shows the color measurement results of oligomers (d) of methoxythiophene (a), ethoxythiophene (b), propoxythiophene (c) and butoxythiophene. For colorimetry, a D65 light source was used, and the results were expressed in the (L *, a *, b *) color system. For comparison, the colorimetric results of the gold deposited film (e) and the copper deposited film (f) are also shown. Looking at the a * b * values, it can be seen that the methoxythiophene oligomer film is closest to the gold color, the ethoxy oligomer film is closer to metallic copper, and the propoxy, butoxy and alkyl chain lengths become closer to the origin, i.e., black. It was.

3.3 Regular reflection spectrum Next, regular reflection spectrum measurement of the obtained coating film was performed. FIG. 5 shows the reflection spectra of methoxythiophene (a), ethoxythiophene (b), propoxythiophene (c) and butoxythiophene oligomer (d). For comparison, the spectrum of the gold deposited film (dotted line) is also shown. The reflection spectrum of the methoxythiophene oligomer film (a) has a lower reflectance than that of the gold vapor deposition film, but its outline and rise wavelength are similar, and it can be seen that the color tone is gold. Moreover, it can be seen that the hue and reflectance of the coating film change significantly by changing the oligomer, and the rising wavelength of the regular reflection spectrum is red-shifted as the number of carbon atoms of the alkoxy group of the raw material increases.

  The reason for the difference in reflectance and color tone due to the above alkoxy group is that the difference in electron donating property of alkoxy group, the difference in conjugation length due to the difference in polymerization degree, the concentration of polaron / bipolaron as chromophore, that is, the doping rate Differences and molecular orientations can be mentioned. Therefore, when these four factors were examined, it was judged that the contribution of the difference in molecular orientation was the largest, so the results will be described below.

3.4 X-ray diffraction measurement (XRD)
Thin film XRD measurement was performed to investigate the orientation structure of oligomer molecules in the coating film. FIG. 6 shows XRD patterns of oligomer films (d) of methoxythiophene (a), ethoxythiophene (b), propoxythiophene (c), and butoxythiophene. The polyalkylthiophene film has a lamellar crystal region surrounded by an amorphous region, and its X-ray diffraction pattern corresponds to the lamellar interlayer distance in the low angle region, although the substituent is different from the oligomer molecule of this study. It is known that a signal and a signal corresponding to a stacking distance between molecules forming a lamella in a high angle region may be observed. By analogy with this report, it can be seen that signals of 2θ <10 ° seen in the four patterns of FIG. 6 correspond to the lamellar interlayer distance, and signals around 2θ = 25 ° correspond to the stacking distance. FIG. 7 shows the diffraction peak angle (2θ) of each oligomer film and the lamellar interlayer distance and stacking distance calculated from the angles. Considering that the measurement method of X-ray diffraction is Out-of-Plane measurement and evaluating a lattice plane almost parallel to the sample surface, a signal of 2θ <10 ° is approximately shown in FIG. 8 (a). The signal of 2θ = 25 ° (approximately 25 °) indicates the presence of a face-on lamella as shown in FIG. 8 (b), indicating the presence of an edge-on lamella. Considering this, the most remarkable facts derived from FIG. 6 are that the lamellar interlayer distance increases as the alkyl chain length of the alkoxy group increases, and that 2θ = 10 for signals of 2θ <10 ° as the lamellar interlayer distance increases. The signal ratio at 25 ° (approximately 25 °) is increased. This difference in ratio is considered to be one of the factors that caused the difference in color tone and reflectance.

4. Summary The color tone of the coating film changed greatly by changing the number of carbon atoms in the side chain of 3-alkoxythiophene. As the carbon number increased, golden, copper and black glossy films were obtained. In agreement with this observation result, the rising wavelength of the reflectance of the coating film was red-shifted as the carbon number of the alkoxy group in the side chain was longer. Therefore, in order to investigate the cause of this color change, the X-ray diffraction measurement of the alkoxythiophene oligomer coating film was performed. As a result, oligomeric molecules form a lamellar structure in the coating film, the lamellar interlayer distance increases with increasing carbon number of the alkyl chain, and the increase in the interlayer distance increases the ratio of fiss on lamella to edge on lamella. I understood it. Therefore, it was considered that this difference in interlayer distance was one of the causes of the difference in color tone of the coating film.

  INDUSTRIAL APPLICABILITY The present invention is industrially applicable as a method for producing a black gloss paint, a black gloss paint film and a black gloss paint.

Claims (5)

  Black gloss paint containing 3-butoxythiophene polymer.   A black glossy coating film comprising a 3-butoxythiophene polymer, wherein the 3-butoxythiophene has a lamellar structure.   The black glossy coating film according to claim 2, wherein an interlayer distance of the lamellar structure is 1.5 nm or more and 1.6 nm or less.   A black gloss paint comprising a step of dissolving 3-butoxythiophene and ferric perchlorate in an acetonitrile solution, a step of synthesizing an oligomer by mixing the acetonitrile solution, and a step of dissolving the oligomer in nitromethane. Production method.   A black gloss paint produced by the method according to claim 4.