Patent Application
20230399518
The present disclosure relates to a paint color material, a method for producing a coated product, and a method for producing a coated product.
As a paint color material, there has been known a color material that develops a structural color different from a pigmentary color caused by light absorption. The structural color is generally a color generated by interference or scattering of visible light caused by the structure of a color material. Therefore, the color material that develops the structural color is advantageous in that discoloration due to sunlight is less likely to occur as compared with a general organic-based pigment, dye, or the like, and an environmental load is less likely to occur as compared with a general organic-based pigment, inorganic-based pigment, or the like. For example, Patent Literature 1 discloses a composition containing particles having a core-shell structure and capable of forming a film with a structural color.
As described above, the structural color has various advantages. Therefore, there has been a demand for a technique that can obtain an unprecedented and novel color using a structural color.
The present disclosure can be implemented as the following forms.
(1) A paint color material including color material particles that each include a core portion and a pigmentary layer being formed around the core portion and containing an iron tannate, and that each have a particle diameter corresponding to a wavelength of a structural color, in which the paint color material develops a color by the pigmentary layer and the structural color.
According to such a mode, the paint color material develops a novel color by the pigmentary layer and the structural color.
(2) The paint color material according to (1), further including a liquid portion, in which the color is adjustable depending on a liquid property of the liquid portion.
According to such a mode, the paint color material develops a novel color that can be adjusted depending on the liquid property of the liquid portion.
(3) The paint color material according to (1), in which the paint color material is a paint color material to be applied onto a support, and the color is adjustable depending on an applied thickness.
According to such a mode, by changing the applied thickness of the paint color material, an intensity ratio of reflected light of the structural color to reflected light of the pigmentary layer can be changed, and the color can be freely changed. Therefore, the paint color material develops a novel color that can be adjusted depending on the applied thickness.
(4) The paint color material according to (3), in which the color is adjustable depending on a water absorbing property of the support in addition to the applied thickness.
According to such a mode, the paint color material develops a novel color that can be adjusted depending on the water absorbing property of the support in addition to the applied thickness.
(5) A method for producing a paint color material developing a color by a pigmentary color and a structural color, the method including: a first step of obtaining a mixed liquid containing color material particles by alternately adding and mixing a liquid obtained by suspending core particles each having a uniform particle diameter in a solution containing Fe and a liquid containing tannic acid into a liquid containing water as a main component, the color material particles each including a core portion formed by the core particle and a pigmentary layer that is formed around the core portion and contains an iron tannate, and each having a particle diameter corresponding to a wavelength of the structural color; and a second step of washing the color material particles.
According to such a mode, a paint color material that develops a novel color by the pigmentary color of the pigmentary layer and the structural color can be produced.
(6) The production method according to (5), in which in the mixed liquid, a ratio of the number of moles of the Fe to the number of moles of the core particles is 5.41×10−4 or more, and a ratio of the number of moles of the tannic acid to the number of moles of the core particles is 3.61×10−4 or more.
According to such a mode, the pigmentary layer can be more effectively formed around each of the core particles.
(7) The production method according to (5) or (6), in which a pH of the mixed liquid is adjusted to 7.0 or more prior to the second step.
According to such a mode, the color developed by the pigmentary layer of the paint color material can be adjusted, and storage stability of the paint color material can be improved.
(8) The production method according to any one of (5) to (7), further including a third step of, after the second step, additionally forming a pigmentary layer around each of the color material particles by alternately adding and mixing a liquid obtained by suspending the color material particles in a solution containing Fe and a liquid containing tannic acid into a liquid containing water as a main component.
According to such a mode, the thickness of the pigmentary layer of each of the color material particles can be increased. The thickness of the pigmentary layer of each of the color material particles can be adjusted by adjusting the number of times the third step is executed.
(9) A method for producing a coated product, the method including: a step of applying, onto a support, a paint containing particles that each include a core portion and a pigmentary layer being formed around the core portion and containing an iron tannate, and that each have a particle diameter corresponding to a wavelength of a structural color; and a step of adjusting a thickness of the paint onto the support to adjust a color developed by the pigmentary layer and the structural color.
According to such a mode, a coated product that develops a novel color which is adjusted depending on the applied thickness of the paint color material can be produced.
A. First embodiment: A paint color material according to a first embodiment includes color material particles that each include a core portion and a pigmentary layer being formed around the core portion and containing an iron tannate, and that have a particle diameter corresponding to a wavelength of a structural color. Accordingly, the paint color material develops a color by the pigmentary layer and the structural color. The structural color is a color generated by interference or scattering of visible light caused by the structure of the color material. Therefore, in a color material that develops a structural color, discoloration due to sunlight is less likely to occur as compared with a general organic-based pigment or dye.
The color material particles included in the paint color material have a so-called core-shell shape, with the pigmentary layer as a shell portion. That is, the color material particle is formed by integrating the core portion and the pigmentary layer being formed around the core portion. In the present embodiment, a spherical silica (SiO2) particle having a uniform particle diameter is used as the core portion. A transparent or translucent material having a low Haze value is preferably used as the core portion. The Haze value is an index indicating a fog-degree of a material, and can be measured in accordance with JISK7136: 2000.
The pigmentary layer includes iron tannate and develops a pigmentary color caused by iron tannate. The pigmentary color is a color generated by absorption of light in a certain wavelength range and reflection of light in an unabsorbed wavelength range in a certain substance. A general organic-based or inorganic-based pigment or dye develops the pigmentary color. The iron tannate is known to be produced by, for example, a reaction between an iron salt such as iron (III) chloride and tannic acid. The iron tannate is known to develop different colors depending on a liquid property. Specifically, the iron tannate is dimerized to develop a bluish purple color under conditions of pH of 3.0 to 6.0, and is trimerized to develop a reddish brown color under conditions of pH of 7.0 or more. Accordingly, the pigmentary layer develops a strong bluish color under acidic conditions, and develops a strong reddish color under neutral or basic conditions.
As described above, the color material particles each have a particle diameter corresponding to a wavelength of the structural color. For example, when the paint color material is applied onto a support, the color material particles are arranged with periodicity onto the support. The paint color material develops a structural color having a wavelength corresponding to the particle diameter of each color material particles by the arrangement of the color material particles. For example, in the case where a colloidal crystal with a face-centered cubic lattice is formed by arranging the color material particles, a wavelength λ of the structural color, an average refractive index n a of the colloidal crystal, and a particle diameter D of each of the color material particles have a relationship of the following equation (1).
λ=1.633naD (1)
The average refractive index na is determined by a refractive index ni and a volume fraction Φi of a component i constituting the colloidal crystal, as shown in the following equation (2).
n
a
2
=Σn
i
2Φi (2)
Hereinafter, a state where the paint color material is applied onto the support is also referred to as an “application state”.
The particle diameter of the color material particle is determined by the size of the core portion and the thickness of the pigmentary layer. For example, in the present embodiment, the particle diameter of the color material particle is a value obtained by summing the particle diameter of the silica particle constituting the core portion and the thickness of the pigmentary layer. Therefore, by adjusting the diameter of the core portion and the thickness of the pigmentary layer, the particle diameter of the color material particle can be adjusted, and a desired structural color in the application state can be developed.
As in the first embodiment, in the case where the paint color material develops the structural color by the arrangement of the color material particles, a period of a structure of a portion that develops the structural color is short, and angle dependence of the color of the color material is low. On the other hand, for example, in the case where the color material develops a structural color by a portion formed in a thin film shape having a uniform film or a multi-layer film shape, the period of the structure of the portion that develops the structural color is long. In this case, the structure of the portion that develops the structural color is close to a so-called thin film interference model or multi-layer interference model, so that the angle dependence of the color material increases. In the case where the color material has high angle dependence, the color of the color material is likely to visually vary depending on an angle at which the color material is viewed and a direction in which the color material is irradiated with light.
The paint color material may further include a liquid portion in addition to the color material particles described above. The liquid portion may be, for example, any liquid such as water, and is preferably, for example, a liquid that does not cause loss of the structural color of the paint color material or the pigmentary color of the pigmentary layer due to a chemical reaction with the color material particles or the pigmentary layer. In the case where the paint color material includes the liquid portion, by changing a liquid property of the liquid portion, the color developed by iron tannate contained in the pigmentary layer described above can be changed, and the color developed by the paint color material can be changed. In addition, the paint color material may include, for example, an additive for improving storage stability of the paint.
The paint color material is used by being applied onto a support. For example, the paint color material including the liquid portion is applied onto a glass material serving as a support by spin coating, and dried to thereby obtain a coated product in which the paint color material is applied onto the support. As the support, for example, various materials having any shape such as a ceramic material, a metal material, a resin material, paper, and cloth in addition to the glass material can be used. The application of the paint color material onto the support may be performed by any method as long as the finished coated product develops the structural color, and may be performed, for example, by dropping or spraying the paint color material onto the support, or by using a writing brush, a brush or the like, in addition to the spin coating.
Further, in step S140, a fourth liquid and a fifth liquid are prepared. The fourth liquid is a suspension obtained by suspending color material particles in a solution containing Fe as a solute. The fifth liquid is a solution containing tannic acid, similar to the second liquid. In step S140, specifically, a suspension obtained by suspending the first color material particles washed in step S130 in a solution containing Fe is prepared as the fourth liquid. Then, in step S150, the fourth liquid and the fifth liquid are alternately added into and mixed with a sixth liquid containing water as a main component, similar to the third liquid. By executing step S150, a second mixed liquid containing second color material particles formed by additionally forming the pigmentary layer around each of the first color material particles is obtained. Thereafter, in step S160, the second color material particles obtained in step S150 are washed in the same manner as the first color material particles are washed in step S130. Step S120 may be referred to as a first step, step S130 may be referred to as a second step, step S150 may be referred to as a third step, and step S160 may be referred to as a fourth step.
For example, the production of the paint color material may be ended at a time point when step S130 is completed without executing steps from step S140 to step S160 shown in
In the first mixed liquid obtained in step S120, it is preferred that a ratio of the number of moles of Fe to the number of moles of the core particles is 5.41×10−4 or more, and a ratio of the number of moles of tannic acid to the number of moles of the core particles is 3.61×10−4 or more. Therefore, in the first embodiment, in the first mixed liquid, it is preferred that Fe/SiO2, which is the ratio of the number of moles of Fe to the number of moles of silica, is 5.41×10−4 or more, and TA/SiO2, which is the ratio of the number of moles of tannic acid to the number of moles of silica, is 3.61×10−4 or more. Accordingly, the pigmentary layer can be more effectively formed around each of the core particles. The Fe/SiO2 and TA/SiO2 in the first mixed liquid can be adjusted, for example, by adjusting the number of moles of silica and the number of moles of Fe in the first liquid, the number of moles of tannic acid in the second liquid, and a mixing amount of the first liquid and the second liquid.
In the production method shown in
The paint color material according to the present embodiment described above includes the color material particles that each include the core portion and the pigmentary layer including iron tannate, and that each have a particle diameter corresponding to a wavelength of the structural color. Therefore, the paint color material develops a novel color by the pigmentary layer and the structural color. Since the paint color material according to the first embodiment develops the color by the pigmentary layer and the structural color, the paint color material is less likely to lose color due to sunlight or the like, for example, as compared with a color material that develops only a pigmentary color such as a general organic-based pigment or dye. Further, since the color developed by the pigmentary layer is more likely to be discolored due to the sunlight or the like than the structural color, for example, the change in color over time in a coated product may be obtained, and the change in color over time can be used as an index of aging. In addition, by using, for example, silica or a material such as glass containing silica as a main component, as the material forming the core portion, an environmental load due to a color material can be reduced, and a novel color of the color material can be implemented as compared with a general organic-based or inorganic-based pigment.
In the first embodiment, the paint color material includes the liquid portion, and the color can be adjusted depending on the liquid property of the liquid portion. Therefore, the paint color material develops a novel color that can be adjusted depending on the liquid property of the liquid portion.
The method for producing a paint color material according to the first embodiment includes the first step of obtaining the first mixed liquid containing the first color material particles by alternately adding and mixing the first liquid obtained by suspending the core particles each forming the core portion in the solution containing Fe and the second liquid containing tannic acid into the third liquid containing water as a main component, and the second step of washing the first color material particles. Therefore, a paint color material that develops a novel color by the pigmentary layer and the structural color can be produced.
In the method for producing a paint color material according to the first embodiment, in the first mixed liquid, the molar ratio of Fe to the core particles is 5.41×10−4 or more, and the molar ratio of tannic acid to the core particles is 3.61×10−4 or more. Therefore, the pigmentary layer can be more effectively formed around each of the core particles.
In the method for producing a paint color material according to the first embodiment, in the first step, the pH of the first mixed liquid is adjusted to 7.0 or more. Therefore, the color developed by the pigmentary layer of the paint color material can be adjusted, and storage stability of the paint color material can be improved.
The method for producing a paint color material according to the first embodiment includes the third step of additionally forming the pigmentary layer around each of the color material particles by alternately adding and mixing the fourth liquid obtained by suspending the color material particles in the solution containing Fe and the fifth liquid containing tannic acid into the sixth liquid containing water as a main component. Therefore, the thickness of the pigmentary layer of the color material particles can be increased.
The thickness of the pigmentary layer of each of the color material particles can be adjusted by adjusting the number of times the third step is executed.
B. Second embodiment: A paint color material according to a second embodiment includes particles that each include a core portion and a pigmentary layer being formed around the core portion and containing an iron tannate, and that each have a particle diameter corresponding to a wavelength of a structural color. The paint color material develops a color by the pigmentary layer and the structural color. The structural color is a color generated by interference or scattering of visible light caused by the structure of the color material. Therefore, in a color material that develops a structural color, discoloration due to sunlight is less likely to occur as compared with a general organic-based pigment or dye.
In the paint color material according to the second embodiment, by changing an applied thickness when the paint color material is applied onto a support, an intensity ratio between reflected light of the structural color and reflected light by the pigmentary layer can be changed, and the color developed by the paint color material can be freely changed. That is, the color developed by the paint color material can be adjusted depending on the applied thickness. Accordingly, even in the case where the same paint color material is used, the color can be made different depending on the applied thickness, and therefore, for example, a difference in color developed by the paint color material can be easily obtained by making a coating method, a tool used for coating, or the like different and making the applied thickness of the paint color material different.
The particles contained in the paint color material each have a so-called core-shell shape, with the pigmentary layer as a shell portion. That is, the particle is formed by integrating the core portion and the pigmentary layer formed around the core portion. Hereinafter, the particles each including the pigmentary layer formed around the core portion in the present embodiment are also referred to as color material particles. In the present embodiment, a spherical silica particle having a uniform particle diameter is used as the core portion. A transparent or translucent material having a low Haze value is preferably used as the core portion. The Haze value is an index indicating a fog-degree of a material, and can be measured in accordance with JISK7136: 2000.
The pigmentary layer includes iron tannate and develops a pigmentary color caused by iron tannate. The pigmentary color is a color generated by absorption of light in a certain wavelength range and reflection of light in an unabsorbed wavelength range in a certain substance. A general organic-based or inorganic-based pigment or dye develops the pigmentary color. The iron tannate is known to be produced by, for example, a reaction between an iron salt such as iron (III) chloride and tannic acid. The iron tannate is known to develop different colors depending on a liquid property. Specifically, the iron tannate is dimerized to develop a bluish purple color under conditions of pH of 3.0 to 6.0, and is trimerized to develop a reddish brown color or a reddish purple color under conditions of pH of 7.0 or more.
As described above, the color material particles each have a particle diameter corresponding to a wavelength of the structural color. For example, when the paint color material is applied onto a support, the color material particles are arranged with periodicity onto the support. The paint color material develops a structural color having a wavelength corresponding to the particle diameter of each of the color material particles by the arrangement of the color material particles. For example, in the case where a colloidal crystal with a face-centered cubic lattice is formed by arranging the color material particles, a wavelength λ of the structural color, an average refractive index n a of the colloidal crystal, and a particle diameter D of each color material particles have a relationship of the following equation (3).
λ=1.633naD (3)
The average refractive index na is determined by a refractive index ni and a volume fraction Φi of a component i constituting the colloidal crystal, as shown in the following equation (4).
n
a
2
=Σn
i
2Φi (4)
Hereinafter, a state where the paint color material is applied onto the support is also referred to as an “application state”.
The particle diameter of the color material particle is determined by the size of the core portion and the thickness of the pigmentary layer. For example, in the second embodiment, the particle diameter of the color material particle is a value obtained by summing the particle diameter of the silica particles constituting the core portion and the thickness of the pigmentary layer. Therefore, by adjusting the diameter of the core portion and the thickness of the pigmentary layer, the particle diameter of the color material particle can be adjusted, and a desired structural color in the application state can be developed.
As in the second embodiment, in the case where the paint color material develops the structural color by the arrangement of the color material particles, a period of a structure of a portion that develops the structural color is short, and angle dependence of the color of the color material is low. On the other hand, for example, in the case where the color material develops a structural color by a portion formed in a thin film shape having a uniform film or a multi-layer film shape, the period of the structure of the portion that develops the structural color is long. In this case, the structure of the portion that develops the structural color is close to a so-called thin film interference model or multi-layer interference model, so that the angle dependence of the color material increases. In the case where the color material has high angle dependence, the color of the color material is likely to visually vary depending on an angle at which the color material is viewed and a direction in which the color material is irradiated with light.
The paint color material is used by being applied onto a support. As the support, for example, various materials such as a glass material, a ceramic material, a metal material, a resin material, paper, and cloth in any shape can be used.
The color developed by the paint color material may be adjusted depending on a water absorbing property of the support onto which the paint color material is applied in addition to the applied thickness. The water absorbing property of the support may be adjusted, for example, depending on a material of the support, or may be adjusted by subjecting the support to a treatment such as coating.
The thickness of the paint color material onto the support may be adjusted, for example, after coating in step S2320 or after drying in step S2330. By adjusting the water absorbing property of the support prepared in step S2310, the color developed by the paint color material in the application state can be adjusted depending on the water absorbing property of the support.
The paint color material according to the present embodiment described above includes the color material particles that each include the core portion and the pigmentary layer containing iron tannate, and that each have a particle diameter corresponding to a wavelength of the structural color. Accordingly, by changing the applied thickness of the paint color material, the intensity ratio between the reflected light of the structural color and the reflected light of the pigmentary layer can be changed, and the color can be freely changed. Therefore, the paint color material develops a novel color that can be adjusted depending on the applied thickness. Since the paint color material according to the present embodiment develops the color by the pigmentary layer and the structural color, the paint color material is less likely to lose color due to sunlight or the like, for example, as compared with a color material that develops only a pigmentary color such as a general organic-based pigment or dye. Further, since the color developed by the pigmentary layer is more likely to be discolored due to the sunlight or the like than the structural color, for example, the change in color over time in a coated product may be obtained, and the change in color over time can be used as an index of aging. In addition, by using, for example, silica or a material such as glass containing 50 mass % or more of silica as the material forming the core portion, an environmental load due to a color material can be reduced, and a novel color developed by the color material can be implemented as compared with a general organic-based and inorganic-based pigment.
In the second embodiment, the color developed by the paint color material is adjusted depending on the water absorbing property of the support in addition to the applied thickness. Therefore, the paint color material develops a novel color that can be adjusted depending on the water absorbing property of the support in addition to the applied thickness.
C. Experimental results according to the first embodiment:
Each of samples was prepared by the following method. A silica particle aqueous suspension manufactured by Fuji Chemical Industries Co., Ltd. was used as a silica particle aqueous suspension that is a raw material for silica particles serving as core particles. Specifically, a silica particle aqueous suspension having a density of 1.168 g/cm3 and containing 26.3 mass % of silica particles each having a particle diameter of 268.3 nm was used in the preparation of the sample 1-1 and the sample 1-2, a silica particle aqueous suspension having a density of 1.163 g/cm3 and containing 25.7 mass % of silica particles each having a particle diameter of 268.3 nm was used in the preparation of the sample 1-16 and the sample 1-17, a silica particle aqueous suspension having a density of 1.125 g/cm3 and containing 20.5 mass % of silica particles each having a particle diameter of 268.3 nm was used in the preparation of the sample 1-5, the sample 1-9, the sample 1-10, the sample 1-13, the sample 1-14, and the sample 1-24, and a silica particle aqueous suspension having a density of 1.171 g/cm3 and containing 26.8 mass % of silica particles each having a particle diameter of 322.4 nm was used in the preparation of the sample 1-6 to the sample 1-8, the sample 1-11, the sample 1-12, the sample 1-15, and the sample 1-18 to the sample 1-23. The average particle diameter of the silica particles was calculated based on measurement results of a particle size distribution by a dynamic light scattering method. Specifically, a median diameter (D50) of the silica particles calculated based on the measurement results by the dynamic light scattering method was used as the average particle diameter. The average particle diameter of the silica particles contained in the silica particle aqueous suspension used to prepare each color material was used as the average particle diameter of the core portion of each color material. As the second liquid, a tannic acid aqueous solution whose concentration is adjusted by adding pure water to tannic acid (molecular weight: 1701.19) manufactured by Kishida Chemical Co., Ltd. as a raw material of tannic acid was used.
The sample 1-1, the sample 1-2, and the sample 1-7 to the sample 1-24 were prepared according to the method for producing a paint color material shown in
In the preparation of the sample 1-2, the sample 1-14, and the sample 1-15, prior to step S130, 0.2 mL of a 1 mol/L sodium hydroxide aqueous solution is added to the first mixed liquid obtained in step S120 to adjust the pH of the first mixed liquid. The pH immediately after adding sodium hydroxide was 8.0 in the sample 1-2 and the sample 1-14, and was 8.1 in the sample 1-15. In the preparation of the sample 1-13, prior to step S130, 0.5 ml of a 0.1 mol/L phosphate pH 7.0 buffer was added to the first mixed solution obtained in step S120, followed by stirring to adjust the pH of the first mixed liquid. In the sample 1-13, the pH immediately after adding the buffer was 7.2. In the preparation of the sample 1-24, after step S130, 0.5 ml of a 0.1 mol/L phosphate pH 7.0 buffer was added to the aqueous suspension of the color material particles prior to the measurement of the “pH after washing” described above. In the sample 1-24, the pH immediately after adding the buffer was 7.2. The pH 7.0 buffer was prepared by mixing 30.5 ml of 0.2 mol/L disodium hydrogen phosphate and 19.5 ml of 0.2 mol/L sodium dihydrogen phosphate, and further adding 50 ml of pure water thereto.
In the preparation of the sample 1-1, the sample 1-2, and the sample 1-7 in which the number of times of the pigmentary layer formation was 3, a suspension obtained by suspending the first color material particles obtained in step S130 in water was further prepared, and the prepared suspension of the color material particles and an iron (III) chloride hexahydrate aqueous solution similar to that in step S110 were mixed using a vortex to prepare the fourth liquid of step S140. Thereafter, similar to steps S120 and S130, steps S150 and S160 were performed to additionally form a pigmentary layer around each of the first color material particles. A tannic acid aqueous solution similar to the second liquid was used as the fifth liquid, and pure water similar to the third liquid was used as the sixth liquid. After step S160, the steps similar to step S140 to step S160 were executed again to additionally form a pigmentary layer, and the total number of times of the pigmentary layer formation was set to 3. In the sample 1-2, the pH of the mixed liquid was adjusted to 8.0 in step S150 and the step similar to step S150, which was executed again after step S160, similar to after completion of step S120. In the sample 1-1, the sample 1-2, and the sample 1-7, after completion of the third pigmentary layer formation, the obtained color material particles were suspended in 5.0 ml of water, the color of the color material particles in the suspension was visually observed, and the observed color was defined as the “color in suspension state” shown in
The sample 1-3 and the sample 1-4 were prepared by mixing an iron (III) chloride hexahydrate aqueous solution with the second liquid. Specifically, 0.05 ml of the iron (III) chloride hexahydrate aqueous solution in which a concentration of iron (III) chloride hexahydrate was 40 g/L and 0.6 ml of the second liquid in which a concentration of tannic acid was 13 g/L were added into 25 ml of pure water, and mixed by stirring using a stirrer to thereby obtain an iron tannate liquid as the color material. The Fe molar concentrations and the TA molar concentrations of the sample 1-3 and the sample 1-4 shown in
As the sample 1-5, a silica aqueous suspension having a density of 1.125 g/cm3 and containing 20.5 mass % of silica particles each having a particle diameter of 268.3 nm was used. As the sample 1-6, a silica aqueous suspension having a density of 1.171 g/cm3 and containing 26.8 mass % of silica particles each having a particle diameter of 322.4 nm was used. In the sample 1-5 and the sample 1-6, the color of the silica particles in the silica aqueous suspension was visually observed, and the observed color was defined as the “color in suspension state” shown in
The average particle diameter of the color material particles contained in the sample 1-1, the sample 1-7, and the sample 1-8 was calculated by the same method as that for the average particle diameter of the core portions. By subtracting the particle diameter of the core portions from the measured average particle diameter of the color material particles, the thickness of the pigmentary layer formed around the core portion can be calculated.
Suspensions each obtained by suspending the sample 1-1 to the sample 1-15 in pure water were applied onto supports, respectively, and dried to thereby obtain coated products of the sample 1-1 to the sample 1-15. In the production of the coated product, a plurality of coated products having different applied thicknesses were prepared by adjusting the amount of the color material applied. In the sample 1-1 to the sample 1-4, a white porous plate manufactured by Nikkato Corporation was used as the support. In the sample 5 to the sample 1-15, a transparent slide glass manufactured by Matsunami Glass Ind., Ltd. was used as the support. The color of each sample in the application state was visually observed.
The applied thicknesses of the sample 1-1 and the sample 1-2 were calculated using cross-sectional scanning electron microscope (SEM) images of the coated products, respectively. Specifically, four cross-sectional SEM images were observed for each coated product, a thickness of a portion excluding the support was measured at 2 points for each SEM image, and an average value of thicknesses measured at 8 points was calculated to thereby calculate the applied thickness of the coated product.
The reflectance spectrum of the sample 1-1 to the sample 1-4 in the application state was measured using a USB 2000 Miniature Fiber Optic Spectrometer, which is a small fiber optical spectrometer, manufactured by Ocean Optics, Inc. Specifically, the sample was irradiated with white light such that an incident angle thereof was perpendicular to the sample, and a relative reflectance spectrum was measured. As a reference sample for the relative reflectance spectrum measurement, a standard white plate of PTFE was used. As a white light source, a halogen lamp was used.
The average particle diameter of the color material particles of the sample 1-1 was 286.7 nm. The average particle diameter of the color material particles of the sample 1-7 was 373.6 nm. The average particle diameter of the color material particles of the sample 1-8 was 338.6 nm. It is considered that in the sample 1-1, the sample 1-7, and the sample 1-8, iron tannate was adsorbed around the silica particles serving as the core particles, so that the pigmentary layer containing iron tannate was formed around the core portion, and the color material particles having an average particle diameter larger than the average particle diameter of the core portions were formed. The average particle diameters of the color material particles of the sample 1-7 and the sample 1-8 were larger than the average particle diameter of the color material particles of the sample 1-1, respectively. It is considered that the average particle diameters of the core portions of the sample 1-7 and the sample 1-8 were larger than the average particle diameter of the core portions of the sample 1-1, so that the average particle diameters of the color material particles of the sample 1-7 and the sample 1-8 were larger than the average particle diameter of the color material particles of the sample 1-1.
Further, the average particle diameter of the color material particles of the sample 1-7 was larger than the average particle diameter of the color material particles of the sample 1-8. It is considered that since the number of times of the pigmentary layer formation of the sample 1-8 was 1, and the number of times of the pigmentary layer formation of the sample 1-7 was 3, the pigmentary layer was formed thicker in the sample 1-7 than in the sample 1-8. Thus, the thickness of the pigmentary layer of the paint color material can be adjusted by adjusting the number of times of the pigmentary layer formation. The particle diameter of the color material particles can be adjusted by adjusting the thickness of the pigmentary layer.
As shown in
The sample 1-1, the sample 1-2, the sample 1-9, the sample 1-10, the sample 1-13, and the sample 1-14, in which the particle diameter of the core portions was 268.3 nm, had a stronger greenish color in the application state than in the suspension state. In these samples, the more the amount of the color material applied, the stronger the greenish color in the application state. On the other hand, the sample 1-7, the sample 1-8, the sample 1-11, the sample 1-12, and the sample 1-15, in which the particle diameter of the core portions was 322.4 nm, had a stronger reddish color in the application state than in the suspension state. In these samples, the more the amount of the color material applied, the stronger the reddish color in the application state. The sample 1-5 and the sample 1-6 developed a green color and a red color, respectively, in the application state. The sample 1-3 and the sample 1-4 developed a bluish purple color and a reddish brown color in the application state, respectively, similar to that in the suspension state.
It is considered that in the sample 1-1, the sample 1-2, and the sample 1-7 to the sample 1-15, the color material particles were arranged with a period in the application state, so that the structural color was developed in addition to the pigmentary color developed by the pigmentary layer. It is considered that, in these samples, the more the amount of the color material applied, the larger the applied thickness, the more the portion where the particles were arranged with a period in the thickness direction, and the stronger the structural color relatively with respect to the pigmentary color. It is considered that since the sample 1-5 and the sample 1-6 include no pigmentary layer, they only developed the structural color. It is considered that since the sample 1-3 and the sample 1-4 include no color material particles, they did not develop any structural color in the application state, and developed the same color as that in the suspension state.
As described above, the particle diameter of the color material particles contained in the sample 1-7 and the sample 1-8 was larger than the particle diameter of the color material particles contained in the sample 1-1. Further, since a difference between the method for preparing the sample 1-1 and the method for preparing the sample 1-2 is only the presence or absence of pH adjustment, the average particle diameter of the color material particles of the sample 1-2 is considered to be about the same as the average particle diameter of the color material particles of the sample 1-1. Therefore, it is considered that the sample 1-7 and the sample 1-8 developed a red structural color having a wavelength longer than that of the structural colors of the sample 1-1 and the sample 1-2, corresponding to the particle diameter of the color material particles. Similarly, it is considered that, since in other samples including a core portion having a particle diameter of 322.4 nm, the particle diameter of the color material particles is larger than that of the sample including a core portion having a particle diameter of 268.3 nm, a red structural color was developed. Accordingly, in the paint color material, for example, a relationship between the wavelength of the structural color and the particle diameter of the color material particle is examined in advance by experiments, and the particle diameter of the color material particle is adjusted such that a desired structural color is developed, whereby a desired structural color can be developed.
The sample 1-5 and the sample 1-6 had a stronger whitish color in the application state than the sample 1-1, the sample 1-2, and the sample 1-7 to the sample 1-15 in the application state. It is considered that, in the sample 1-5 and the sample 1-6, only the silica particles including no pigmentary layer were contained, so that the reflected light of the structural color of the sample 1-5 and the sample 1-6 in the application state was multiple-scattered, and there was no color developed by the pigmentary layer, and thus a strong whitish color was observed. On the other hand, it is considered that since the sample 1-1, the sample 1-2, and the sample 1-7 to the sample 1-15 each include the pigmentary layer, multiple scattering of the reflected light of the structural color of these samples in the application state was prevented, and the color developed by the reflected light of the pigmentary color and the reflected light of the structural color, which is stronger than that of the sample 1-5 and the sample 1-6, was observed.
As shown in
As shown in
The sample 1-16 had a white color in the suspension state. It is considered that, in the preparation of the sample 1-16, since Fe/SiO2 and TA/SiO2 in the first mixed solution were smaller than those in the other samples, the pigmentary layer was hardly formed around the each of silica particles serving as the core particles. As shown in
As described above, the method for preparing sample 1-13 and the method for preparing sample 1-24 are the same in that the pH is adjusted with a buffer, but the timing of pH adjustment is different. The sample 1-24 had a reddish purple color in the suspension state after washing, but the pigmentary layer gradually peeled off from the core portion over time, and after 7 days, the color of the color material turned a white color. The sample 1-13 had a reddish purple color in the suspension state after washing similar to the sample 1-24, and the color of the color material remained the reddish purple color even after 7 days. Therefore, in the event of adjusting the pH in the production of the paint color material, it is preferred to adjust the pH of the first mixed solution prior to the second step in order to enhance the storage stability of the paint color material.
According to the experimental results described above, it is confirmed that the paint color material including the particles that each include the core portion and the pigmentary layer being formed around the core portion and containing iron tannate develops a novel color by the pigmentary layer and the structural color.
D. Experimental results according to the second embodiment: Various color materials were prepared for experiments. The prepared color material was applied onto a support to prepare a coated product as a sample, and a reflectance spectrum of the prepared coated product was measured to verify the effect of the embodiment described above.
Five kinds of color materials A to E were prepared as the color materials. The color material A to the color material C were prepared according to the production method shown in
In the preparation of the color material A, first, 0.05 mL of an iron (III) chloride hexahydrate aqueous solution in which a concentration of iron (III) chloride hexahydrate was 40 g/L and 0.55 mL of a silica particle aqueous suspension were mixed using a vortex to prepare the liquid a of step S2110. Prior to the preparation of the liquid a, the silica particle aqueous suspension was irradiated with ultrasonic waves for 90 minutes to improve the dispersibility of silica microparticles in the silica particle aqueous suspension. As the liquid b, 0.6 mL of a tannic acid aqueous solution in which a concentration of tannic acid was 13 g/L was prepared. Next, in step S2120, using a syringe, 1 drop (about 0.03 mL) of the liquid a and 1 drop (about 0.03 mL) of the liquid b were alternately added in a total of 0.6 mL of each liquid into 25 mL of pure water, and mixed by stirring using a stirrer to prepare the mixed liquid of the liquid a and the liquid b, thereby obtaining the color material particles. After completion of step S2120, the pH of the mixed liquid was adjusted to 8.0 by adding 0.2 mL of a 1 mol/L sodium hydroxide aqueous solution to the mixed liquid. Thereafter, in step S2130, first, the mixed liquid was centrifuged, and the supernatant generated by the centrifugation was discarded to obtain a residue containing the color material particles. Next, the color material particles were washed by repeating an operation of mixing the residue with pure water by a vortex, further centrifuging the suspension obtained by mixing, and discarding the supernatant generated by centrifugation.
Further, a 0.55 mL suspension was prepared by suspending the color material particles obtained in step S2130 in water, and the prepared color material suspension and an iron (III) chloride hexahydrate aqueous solution similar to that in step S2110 were mixed using a vortex to prepare the liquid c in step S2210 shown in
In the preparation of the color material B, the same procedure as that for the color material A was performed, except that the pH adjustment was not performed after completion of step S2120 and after completion of step S2220. In the preparation of the color material B, the pH after completion of step S2120 and after completion of step S2220 was 5.0. In the preparation of the color material C, in step S2110, 0.05 mL of an iron (III) chloride hexahydrate aqueous solution in which a concentration of iron (III) chloride hexahydrate was 40 g/L and 0.55 mL of a silica particle aqueous suspension were mixed using a vortex to prepare the liquid a. In step S2210, a 0.55 mL suspension was prepared by suspending the color material obtained in step S2130 in water, and the prepared suspension of the color material and an iron (III) chloride hexahydrate aqueous solution similar to that in step S2110 were mixed using a vortex to prepare the liquid c. In the preparation of the color material C, similar to the preparation of the color material B, pH adjustment was not performed after the completion of step S2120 and after completion of step S2220. In the preparation of the color material C, similar to the preparation of the color material B, the pH after completion of step S2120 and after completion of step S2220 was 5.0. In the preparation of the color material C, the same procedure as that in the preparation of the color material B were performed for portions not specifically described.
The color material D and the color material E were prepared by mixing an iron (III) chloride hexahydrate aqueous solution and the liquid b. Specifically, 0.05 ml of an iron (III) chloride hexahydrate aqueous solution in which a concentration of iron (III) chloride hexahydrate was 40 g/L and 0.6 ml of the second liquid in which a concentration of tannic acid was 13 g/L were added into 25 ml of pure water, and mixed by stirring using a stirrer to obtain the color material. In the preparation of the color material D, after the completion of the adjustment of the mixed liquid was completed, 0.2 mL of a 1 mol/L sodium hydroxide aqueous solution was added into the mixed liquid to adjust the pH of the mixed liquid to 8.0. In the preparation of the color material E, the pH adjustment of the mixed liquid was not performed, and the pH of the mixed liquid after the adjustment of the mixed liquid was 5.0. In the production of the color material D and the production of the color material E, no washing step was performed.
The average particle diameter of the color material particles contained in the color material B and the color material C was calculated by the same method as that for the average particle diameter of the core portions. By subtracting the particle diameter of the core portions from the measured average particle diameter of the color material particles, the thickness of the pigmentary layer formed around the core portion can be calculated.
The reflectance spectrum of the coated product was measured using a USB 2000 Miniature Fiber Optic Spectrometer, which is a small fiber optical spectrometer, manufactured by Ocean Optics, Inc. Specifically, the sample was irradiated with white light such that an incident angle thereof was perpendicular to the sample, and a relative reflectance spectrum was measured. A PTFE standard white plate WS-1 manufactured by Ocean Photonics was used as a reference sample in the relative reflectance spectrum measurement. As a white light source, a halogen lamp was used. In the sample 2-4 using the transparent glass as the support, the measurement was performed by placing the sample on white drawing paper. A reflected light intensity ratio was calculated based on the measured reflectance spectrum. The reflected light intensity ratio is a ratio of the reflected light intensity of the structural color to the reflected light intensity of the color developed by the pigmentary layer.
The applied thickness of the coated product was calculated using a cross-sectional scanning electron microscope (SEM) image of the coated product. Specifically, four cross-sectional SEM images were observed for each coated product, a thickness of a portion excluding the support was measured at 2 points for each SEM image, and an average value of thicknesses measured at 8 points was calculated to thereby calculate the applied thickness of the coated product.
The average particle diameter of the color material particles of the color material B was 286.7 nm, and the average particle diameter of the color material particles of the color material C was 373.6 nm. It is considered that, in the color material B and the color material C, iron tannate was adsorbed to the silica particles as the core portions, so that the pigmentary layer containing iron tannate was formed around each of the core portions, and color material particles having an average particle diameter larger than the average particle diameter of the core portions were formed. The average particle diameter of the color material particles of the color material C was larger than the average particle diameter of the color material particles of the color material B. It is considered that the number of times of pigmentary layer additional formation is the same for the color material C and the color material B, so that the average particle diameter of the color material particles of the color material C is larger than the average particle diameter of the color material particles of the color material B due to the average particle diameter of the core portions.
As shown in
The sample 2-3 using the color material C and the sample using the color material A or the color material B had different structural color hues. As described above, the particle diameter of each of the color material particles contained in the color material C was larger than the particle diameter of each of the color material particles contained in the color material B. As described above, since the difference between the method for preparing the color material A and the method for preparing the color material B is only the presence or absence of pH adjustment, the average particle diameter of the color material particles of the color material A is considered to be about the same as the average particle diameter of the color material particles of the color material B. Therefore, it is considered that the sample 2-3 developed a red structural color having a wavelength longer than that of the samples using the color material A and the color material B, corresponding to the particle diameter of each of the color material particles. Accordingly, in the paint color material, for example, a relationship between the wavelength of the structural color and the particle diameter of the color material particle is examined in advance by experiments, and the particle diameter of the color material particle is adjusted such that a desired structural color is developed, whereby a desired structural color can be developed.
In the sample 2-1 shown in
In the sample 2-5 shown in
By referring to the experimental results as shown in
According to the experimental results described above, it is confirmed that the paint color material containing the particles that each include the core portion and the pigmentary layer being around the core portion and containing iron tannate develops a novel color that can be adjusted depending on the applied thickness.
The present disclosure is not limited to the above-described embodiments, and can be implemented by various configurations without departing from the gist of the present disclosure. For example, the technical features in the embodiments corresponding to the technical features in the aspects described in “Brief Summary” can be appropriately replaced or combined in order to solve a part or all of the problems described above or in order to achieve a part or all of the effects described above. Any of the technical features may be omitted as appropriate unless the technical feature is described as essential herein.
The present application is based on a Japanese Patent Application 2020-178523 filed on Oct. 26, 2020 and a Japanese Patent Application 2020-178525 filed on Oct. 26, 2020, the contents of which are incorporated herein by reference.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2020-178523 | Oct 2020 | JP | national |
| 2020-178525 | Oct 2020 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2021/038765 | 10/20/2021 | WO |
