JP6995308B2 - Manufacturing method of black gloss paint, black gloss coating film and black gloss paint - Google Patents

Description

Application of Article 30, Paragraph 2 of the Patent Law Annual Meeting of the Imaging Society of Japan (119 times in total) "Imaging Conference JAPAN 2017" Proceedings Publisher: Japan Imaging Society Publication date: June 20, 2017

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

Piano black paint, which has a jet-black color tone and gives off luster, is used for piano painting and painting of high-class furniture and high-class kitchens. A mixture of polyester resin and carbon black is used as the paint.

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

Japanese Patent Application Laid-Open No. 2014-21231

In the conventional polyester resin / carbon black mixed paint, carbon black must be dispersed in the resin solution, which requires a complicated dispersion step. Further, the gloss is not developed only by applying the paint to the painted surface, and it is necessary to smooth the coating film by polishing and then polish it with a buff and a compound to give the gloss. It is said that it is a highly difficult technique that takes more than ten years to learn.

Therefore, an object of the present invention is to provide a material for a black glossy paint, a black glossy paint, and a black glossy paint film, which can form a black glossy coating film by a simple process.

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

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

Further, according to another aspect of the present invention, the method for producing a black glossy paint is a step of dissolving 3-butoxythiophene and ferric perchlorate in an acetonitrile solution and an oligomer by mixing the acetonitrile solution. It has a step of synthesizing and a step of dissolving the oligomer in nitromethane.

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

According to the present invention, unlike the conventional paint in which polyester and carbon black are mixed and dispersed, the paint can be manufactured only by stirring without the trouble of dispersion. Further, the 3-butoxythiophene polymer that gives the black gloss film of the present invention develops a black gloss just by painting and drying, unlike the conventional paint in which polyester and carbon black are mixed and dispersed. That is, unlike the conventional method, it does not require a special technique of smoothing by polishing after painting and drying and developing gloss by buffing.

It is a figure which shows the digital microscope image observed from the oblique of the polymer. It is a figure which shows the digital microscope image observed from the upper part of a polymer membrane. It is a figure which shows the coating film formed from 3-methoxythiophene (a), 3-ethoxythiophene (b), 3-propoxythiophene (c), 3-butoxythiophene oligomer. It is a figure which shows the color measurement 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 membrane (d) of methoxythiophene (a), ethoxythiophene (b), propoxythiophene (c) and butoxythiophene. It is a figure which shows the angle (2θ) of the diffraction peak of each oligomer film, and the lamella interlayer distance and stacking distance calculated from the angle. It is a figure which shows the Edge-on lamella structure (a) and Face-on lamella (b) structure.

As a result of diligent studies, the inventors have found that by mixing a general-purpose resin and a 3-methoxythiophene polymer, the coating film exhibits a jet-black piano black color. This 3-methoxythiophene polymer is dissolved alone in a solvent and applied to obtain a golden glossy film. 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 gloss coating film was formed alone without mixing a general-purpose resin. It turned out to be.

A digital microscope image taken with a ruler so as to be perpendicular to the obtained film (Fig. 1) and a digital microscope image taken by irradiating the ring illumination of the digital microscope perpendicular to the film (Fig. 1). FIG. 2) is shown. In FIG. 1, the scale of the ruler is reflected, and in FIG. 2, the specular reflection image of the ring illumination is observed, and it can be seen that the specular reflection characteristic is high. In addition, a * and b * of the polymer film were measured using a device manufactured by Konica Minolta (spectrophotometer CM-600d) (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 tones, they are small values that are extremely close to a * = 0 and b * = 0, and it was confirmed that the color tones are very close to black in terms of color measurement.

Unlike conventional paints in which polyester and carbon black are mixed and dispersed, the 3-butoxythiophene polymer that gives the black glossy coating film of the present invention dissolves in a solvent in a molecular form, so there is no need to ask for dispersion and a simple stirring frame. The paint can be manufactured only by itself. Further, since it can be used as a paint by itself, it does not require a resin to be added, and is not limited to a solvent (solvent) for dissolving the added resin, and has an advantage that the selection range of the solvent (solvent) is widened.

Further, the 3-butoxythiophene polymer that gives the black gloss coating film of the present invention develops a black gloss just by painting and drying, unlike the conventional paint in which polyester carbon black is mixed and dispersed. That is, unlike the conventional method, it does not require a special technique of smoothing by polishing after painting and drying and developing gloss by buffing.

1. 1. Experimental method Oligomers were synthesized by mixing acetonitrile solutions in which 3-alkoxythiophene and ferric perchlorate were dissolved in a nitrogen atmosphere. The obtained oligomer was dissolved in nitromethane, and a film was formed on a glass substrate by a casting method. The physical characteristics 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 was performed by taking an external image with a digital microscope (KEYENCE, VHX-5000), measuring the normal reflection spectrum based on a vapor-deposited aluminum substrate (Nippon Spectroscopy, MSV-370), and using a laser microscope (KEYENCE, VK-). The surface texture (roughness) was measured by 9700), and the color was measured using a spectrophotometer (Konica Minolta, CM-600d).

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

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

2. 2. Results and Discussion 2.1 Appearance Fig. 3 shows observation images of the obtained four types of alkoxythiophene oligomer-coated films having a metallic luster. 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 changed depending on the difference in the alkyl chain length of the alkoxy group, and the methoxy group achieved a golden tone, the ethoxy group achieved a copper tone, the propoxy group achieved a magenta glossy color, and the butoxy group achieved a black glossy color. Further, it can be seen that the film surface has a high specular reflection characteristic by seeing the reflection of the scale of the ruler leaning against the side surface of the sample. Therefore, next, the color of the film and the specular reflection spectrum were measured.

3.2 Color measurement of coating film Fig. 4 shows the color measurement results of methoxythiophene (a), ethoxythiophene (b), propoxythiophene (c) and butoxythiophene oligomer (d). A D65 light source was used for color measurement, and the results were represented by a (L *, a *, b *) color system. In addition, for comparison, the color measurement results of the gold-deposited film (e) and the copper-deposited film (f) are also shown. Looking at the a * b * values, it was found that the methoxythiophene oligomer membrane is closest to gold, the ethoxy oligomer membrane is closer to metallic copper, and propoxy, and as the butoxy and alkyl chain lengths increase, it becomes closer to the origin, that is, black. rice field.

3.3 Specular reflection spectrum Next, the specular reflection spectrum of the obtained coating film was measured. FIG. 5 shows the reflection spectra of methoxythiophene (a), ethoxythiophene (b), propoxythiophene (c) and butoxythiophene oligomer (d). The spectrum of the gold-deposited film (dotted line) is also shown for comparison. The reflection spectrum of the methoxythiophene oligomer film (a) has a lower reflectance than the gold-deposited film, but its general shape and rising wavelength are similar, and it can be seen that the color tone is golden. Further, it can be seen that the hue and reflectance of the coating film are significantly changed by changing the oligomer, and the rising wavelength of the specular reflection spectrum is red-shifted as the number of carbon atoms of the alkoxy group of the raw material increases.

The causes of the difference in reflectance and color tone due to the above-mentioned alcohol group are the difference in electron donating property of the alkoxy group, the difference in conjugation length due to the difference in polymerization degree, and the concentration of polaron / bipolaron which is a chromophore, that is, the dope rate. Differences, and differences in molecular orientation. Therefore, when these four factors were examined, it was determined that the contribution of the difference in molecular orientation was the largest, and the results will be described below.

3.4 X-ray diffraction measurement (XRD)
Thin film XRD measurement was performed to examine the orientation structure of the oligomer molecules in the coating film. FIG. 6 shows the XRD pattern of the oligomer membrane (d) of methoxythiophene (a), ethoxythiophene (b), propoxythiophene (c) and butoxythiophene. Although the substituent is different from that of the oligomer molecule in this study, 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. It is known that a signal and a signal corresponding to the stacking distance between molecules forming lamellas in the high angle region may be observed. By analogy with this previously reported, it can be seen that the signal of 2θ <10 ° seen in the four patterns in FIG. 6 corresponds to the lamella interlayer distance, and the signal near 2θ = 25 ° corresponds to the stacking distance. FIG. 7 shows the angle (2θ) of the diffraction peak of each oligomer film, and the lamella interlayer distance and stacking distance calculated from the angle. Considering that the measurement method of X-ray diffraction is Out-of-Plane measurement and the lattice plane almost parallel to the sample surface is evaluated, the signal of 2θ <10 ° is shown in FIG. 8 (a). The presence of edge-on lamellae is indicated, and the signal at 2θ = 25 ° (approximately 25 °) indicates the presence of face-on lamellae as shown in FIG. 8 (b). With this in mind, the most striking facts derived from FIG. 6 are that the lamella interlayer distance increases as the alkyl chain length of the alkoxy group increases, and that as the lamella interlayer distance increases, 2θ = for a signal of 2θ <10 °. The proportion of signals at 25 ° (almost 25 °) increases. And it is considered that this difference in ratio is one of the factors that caused the difference in color tone and reflectance.

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

INDUSTRIAL APPLICABILITY The present invention can be industrially used as a method for producing a black glossy paint, a black glossy coating film, and a black glossy paint.

Claims (6)

A black glossy paint containing 3-butoxythiophene polymer as a solute and nitromethane as a solvent . The black glossy paint according to claim 1, wherein the 3-butoxythiophene polymer is doped with an anion. A black glossy coating film containing a 3 -butoxythiophene polymer, wherein the 3-butoxythiophene has a lamellar structure. The black glossy coating film according to claim 3, wherein the 3-butoxythiophene polymer is doped with an anion. The black glossy coating film according to claim 3 or 4, wherein the interlayer distance of the lamellar structure is 1.5 nm or more and 1.6 nm or less. 3 -A black glossy paint having a step of dissolving 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. Manufacturing method .

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