JP2012210311A - Ornament and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ornament having a high-quality colloid crystal with suppressed arrangement turbulence in a short time, with suppressed contraction of a surface and exhibiting a clear structure color.SOLUTION: The method of manufacturing the ornament includes: a first step of applying a dispersion liquid (A) containing a silica dioxide colloid to a substrate whose surface is coated with a metal-containing material, and drying the substrate to obtain a particle arrangement body in which a silica dioxide particle in the silica dioxide colloid is arranged; a second step of applying a dispersion liquid (B) containing resin and water or an organic solvent to the particle arrangement body, and drying the liquid to obtain a particle embedding body in which the particle arrangement body is embedded with the resin; and a third step of peeling the particle embedded body off the substrate to obtain the ornament made of the particle embedded body.

Description

  The present invention relates to a decorative article and a manufacturing method thereof.

  It is known to use colloidal crystals that can obtain Bragg reflection by regularly arranging them as photonic members, reflectors, and the like, and research on obtaining such colloidal crystals has been made (for example, Patent Document 1). reference).

  In addition, as disclosed in Patent Document 2 and Patent Document 3, colloidal crystals that express structural colors are obtained by arranging monodisperse particles using a liquid medium containing a temporary fixing monomer and a main fixing monomer. There is a manufacturing method in which after the formation, the step of polymerizing the temporarily fixing monomer and the step of polymerizing the main fixing monomer are sequentially performed.

  Further, as disclosed in Patent Document 4, the particle concentration based on the volume fraction is between 5 and 70%, and the monodisperse particle solution in a colloidal crystal state is given a shear flow. A colloid having a tissue with excellent three-dimensional uniformity after the dispersed particle solution is flowed in a uniaxial direction parallel to the substrate surface in a space between two parallel substrate surfaces facing in parallel. There are manufacturing methods for forming crystals.

JP 2005-279633 A JP 2010-138303 A JP 2010-138304 A JP 2002-028471 A

  However, in the invention described in Patent Document 1, the man-hour for producing the colloidal crystal is large and the productivity is sometimes low.

  In the inventions described in Patent Document 2 and Patent Document 3, there are a hydrophilic monomer gelation step, a solvent and hydrophilization monomer substitution step, and a hydrophilic monomer polymerization step along with the colloidal particle arrangement. Disturbances are likely to occur, and there are cases where man-hours are large and productivity is poor.

  Moreover, since the invention described in Patent Document 4 generates shear flow in the cell and takes it out, it takes time for the process, resulting in poor productivity.

  In any of Patent Documents 1 to 4, the particle arrangement is easily disturbed, and the silicon dioxide particles and the resin are not bonded to each other, or the silicon dioxide particles are not melt-bonded to each other and become brittle. In some cases, structural colors were not exhibited.

In view of the above problems, the present invention applies the dispersion liquid (A) containing a silicon dioxide colloid on a substrate coated with a metal-containing material on the surface, and dries the silicon dioxide particles in the silicon dioxide colloid. A first step of obtaining an array of particle arrays, and a dispersion (B) containing a resin and water or an organic solvent is applied onto the particle array and dried, whereby the particle array is made of the resin. A second step of obtaining an embedded particle embedded body, and a third step of obtaining an ornament made of the particle embedded body by peeling the particle embedded body from the substrate.

  According to the method for producing a decorative article of the present invention, it is possible to provide a decorative article having a high quality colloidal crystal in which disorder of arrangement is suppressed in a short time, and a clear structural color in which surface shrinkage is suppressed. .

  Therefore, a roll-to-roll method or a single-wafer coating method can be utilized, and the disorder of the particle arrangement can be suppressed and a decorative product can be produced with high productivity.

  As a result, it is possible to produce a decorative article having a glittering particle embedding body in which a particle array made of silicon dioxide is embedded with a resin, and if further baked at 400 to 1000 ° C., the resin component is thermally decomposed to produce carbon dioxide. An ornament made only of silicon can be produced.

It is the photograph substitute figure which observed the particle | grain embedding body in Example 1 in one Embodiment of this invention from the upper surface by SEM. It is the photograph substitute figure which carried out the SEM observation of the particle array in Example 2 in one Embodiment of this invention from the upper surface. It is the photograph substitute figure which carried out the SEM observation of the particle array in Example 3 in one Embodiment of this invention from the upper surface. It is the photograph substitute figure which carried out the SEM observation of the particle array in Example 4 in one Embodiment of this invention from the upper surface. It is the photograph substitute figure which carried out the SEM observation of the particle array in Example 5 in one Embodiment of this invention from the upper surface. FIG. 5 is a photo-substituting diagram in which the particle array in Comparative Example 1 is observed from the upper surface by SEM. FIG. 5 is a photograph substitute diagram in which the particle array in Comparative Example 2 is observed by SEM from the upper surface. FIG. 5 is a photograph substitute diagram in which the particle array in Comparative Example 3 is observed by SEM from the upper surface. It is the graph which measured the reflective color tone for the ornament of the Example in this invention, and the comparative example with the angle-change colorimeter. It is a schematic diagram of the particle embedding body in one Embodiment of this invention. It is a schematic diagram of the particle array in one embodiment of the present invention. It is a schematic diagram of the particle array in one embodiment of the present invention.

  Hereinafter, an embodiment of the present invention will be specifically described.

  In the method for producing a decorative article of this embodiment, a dispersion liquid (A) containing a silicon dioxide colloid is applied to a substrate having a surface coated with a metal-containing material, and dried, whereby silicon dioxide particles in the silicon dioxide colloid are obtained. A first step of obtaining a particle array in which particles are arranged, and a dispersion (B) containing a resin and water or an organic solvent is applied on the particle array and dried to embed the particle array in the resin The second step of obtaining the particle embedding body and the third step of obtaining the decorative article made of the particle embedding body by peeling the particle embedding body from the substrate.

  A resin film or the like is preferably used as the substrate. As the metal-containing material, a material containing at least one of aluminum, copper, stainless steel, chromium, and nickel is used.

For example, a substrate coated with a metal-containing material is formed by sticking a metal-containing material foil on a resin film or depositing a metal-containing material on a resin film. The thickness of the metal foil is 0.1 to 100 μm. In the case of sputtering or the like, the metal foil is deposited with a thickness of 0.1 to 1 μm.

  Further, for example, the metal-containing material may be formed by vapor-depositing at least one of silicon dioxide and aluminum oxide on a resin film, and may be vapor-deposited with a thickness of 0.1 to 1 μm using sputtering or the like.

  In the first step, as the solvent of the dispersion liquid (A), water, alcohols such as methyl alcohol, ethyl alcohol, n-propanol, iso-propanol, terpineol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, One or more mixtures of acetates such as butyl acetate, ethers such as diethyl ether and dimethyl ether, ethyl carbitol and methyl carbitol can be selected and used.

  A commercially available product may be used as the silicon dioxide colloid in such a dispersion (A), and the concentration is suitably 0.1 to 20% by mass.

  The resin in the dispersion (B) can be selected from acrylic resin, polyester resin, nitrocellulose, ethylcellulose, polyvinyl butyral, and the like.

  Use of these materials is preferable in that the shape retention of the decorative article 1 is improved.

  Those having a weight average molecular weight of 1,000 to 10,000,000 are preferable. If a weight average molecular weight is 1000 or more, it can reduce that the arrangement | sequence of a particle array approaching an oligomer collapses. On the other hand, if the weight average molecular weight is several million or less, it can be reduced that the molecular weight becomes high and the dissolution in a solvent becomes difficult.

  Examples of the organic solvent for the dispersion (B) include water, alcohols such as methyl alcohol, ethyl alcohol, n-propanol, iso-propanol, and terpineol, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ethyl acetate, and butyl acetate. One kind or a mixture of a plurality of acetate esters such as diethyl ether and dimethyl ether, ethyl carbitol, methyl carbitol and the like can be selected and used.

  And as a density | concentration of resin in such a dispersion liquid (B), it is appropriate to set it as 0.1-20 mass%.

  Application methods of dispersion liquid (A) and dispersion liquid (B) include bar coating, doctor blade, die coating, curtain coating, gravure coating, spray, spin coating, dip coating, screen printing, gravure printing, flexographic printing, etc. Can be arbitrarily selected.

  The drying condition of the dispersion (A) depends on the substrate, but is preferably in the range of 20 to 200 ° C. from the viewpoint of the arrangement of the silicon dioxide colloid. If it is 20 degreeC or more, drying will become enough and disturbance of a particle arrangement | sequence can be reduced. On the other hand, if it is 200 degrees C or less, the disorder | damage | failure of the particle | grain arrangement | sequence by insufficient durability of a board | substrate can be reduced.

  The drying conditions for the dispersion (B) are preferably in the range of 20 to 200 ° C., although depending on the type of solvent. If it is 20 degreeC or more, drying will become enough and generation | occurrence | production of the stickiness of the surface can be reduced. On the other hand, if it is 200 degrees C or less, the disorder | damage | failure of the particle | grain arrangement | sequence by generation | occurrence | production of bumping of a solvent can be reduced.

  A drying method in which hot air is not directly applied to the film surface during drying is preferable.

  As for the substrate, it is preferable that the contact angle of the dispersion A on the resin film on which the metal foil is formed or the metal is deposited is 90 ° or less. If the contact angle is 90 ° or less, liquid repellency to the substrate is reduced, and a smooth coated surface is easily obtained.

  When the refractive index (N1) of the resin of the dispersion B is the refractive index of silicon dioxide (N2) in the particle embedding body 3, N1 is N2-0.01 or less or a value exceeding N2 + 0.01. Resins are preferred. If the refractive index is not in the range of N2-0.01 to N2 + 0.01, the refractive index of the silicon dioxide particles and the refractive index of the resin can be separated, so that the structural color is easily shown.

  In addition, when baking at 400-1000 degreeC and removing resin by baking, since it becomes only the particle array 2, there is no problem.

  Furthermore, in the method for manufacturing a decorative article of the present embodiment, the particle diameter of silicon dioxide in the dispersion (A) is controlled within a range of 0.01 to 10 μm.

  In particular, the particle diameter is preferably 0.05 to 0.5 μm. If it is 0.01 μm or more, it becomes easy to obtain a structural color in the near ultraviolet to visible to near infrared region, while if it is 10 μm or less, light scattering in the visible region is reduced, and the white turbidity of the decorative article 1 can be reduced. .

  The CV value representing the particle size distribution of the silicon dioxide colloid is preferably 10% or less, more preferably 5% or less, and particularly preferably 3% or less.

  Here, the CV value is calculated from CV value (%) = ((standard deviation) / (average particle size)) × 100 using the standard deviation in the number-based particle size distribution and the value of the above average particle size. Is.

  As shown in FIGS. 1 to 9, the average particle diameter is 50,000 times as large as a photo of silicon dioxide colloidal particles 5 (hereinafter also simply referred to as silicon dioxide particles 5) using a scanning electron microscope (manufactured by JEOL Ltd.). Is obtained by measuring the maximum length of each of the 100 silicon dioxide particles 5 in the two photographic images and calculating the number average value.

  Here, the “maximum length” refers to the maximum distance between two points between two arbitrary points on the circumference of the silicon dioxide particles 5. When the silicon dioxide particles 5 are photographed as aggregates, the maximum length of primary particles forming the aggregates is measured.

  After the second step, the particle embedding body 3 as shown in FIG. 1 is obtained. In the third step, for example, a method such as peeling the particle embedding body 3 from the substrate with a brush is used.

  Furthermore, the method for manufacturing a decorative article according to the present embodiment includes a fourth step in which the particle embedded body peeled off from the substrate is baked at 400 to 1000 ° C. after the third step.

  The firing conditions at this time are carried out by maintaining the temperature in the atmosphere for 4 to 8 hours.

(Decoration)
In the decorative article of the present embodiment, silicon dioxide particles and a resin are bonded to each other.

  For example, as shown in FIG. 11, since the silicon dioxide particles are bonded by resin only at the portions in contact with each other, the Bragg diffraction can be maintained and an excellent structural color can be obtained.

  Furthermore, the decorative article of this embodiment is one in which silicon dioxide particles are melt bonded.

  For example, as shown in FIG. 12, since the silicon dioxide particles are bonded by melting only at the portions where they are in contact with each other, the Bragg diffraction can be maintained and an excellent structural color can be obtained.

  Specifically, the particle embedding body 3 (see FIG. 10) is one in which a resin is filled between particles regularly formed in the surface direction and the thickness direction, and is one in the direction in which light is incident. It has a configuration in which particles are regularly arranged in the direction. If this is fired at 400 to 1000 ° C., it becomes a decorative article without resin as shown in FIG. 11 and FIG.

  The structural color expressed in the decorative article of the present invention is expressed by light that is defined and selectively reflected based on the observation angle of the particle array 2.

  The light selectively reflected in the particle array 2 is light having a wavelength represented by λ = 2nD (sin θ) as Equation (1) based on Bragg's law and Snell's law.

  In the formula (1), λ is the peak wavelength of the structural color, n is the refractive index of the particle array 2 represented by the following formula (2), D is the interval in the perpendicular direction of the silicon dioxide particles, and θ is the perpendicular of the display member. And the observation angle.

  The refractive index n of the particle array 2 is n = {na · c} + {nb · (1-c)} in the formula (2), where na is the refractive index of the silicon dioxide particles 5 and nb is the refraction of the matrix. The ratio c is the volume ratio of the silicon dioxide particles 5 in the particle array 2. Here, the peak wavelength λ of the structural color is measured using a variable angle colorimeter “Color Robo III” (manufactured by Color Techno System).

  The thickness of the particle array 2 is preferably 0.01 to 30 μm, for example. If the thickness is 0.1 μm or more, the intensity of the reflected light can be increased, and if it is 50 μm or less, peeling from the substrate can be reduced during coating.

  In addition, Formula (1) and Formula (2) are approximate formulas, and in practice, they may not completely match these calculated values.

  The period number of the particle layer of the particle array 2 needs to be at least 1 or more, preferably 5 to 200. If the number of periods is within this range, the particle array 2 can exhibit a structural color.

  The structural color expressed in the particle embedding body 3 and the particle array 2 is not limited to a color having a peak wavelength in the visible region, but may be a color (light) having a peak wavelength in the ultraviolet region or the infrared region.

(Evaluation method)
As a method for confirming the particle arrangement, samples are prepared by the methods described below, and the results of the respective SEM observation results (manufactured by JEOL) are shown in FIGS.

  As the reflection color tone measurement, FIG. 9 shows the result of using a color robot III (manufactured by Color Techno System) for each sample, and the measurement conditions are an incident angle of 30 °, a D65 light source, a 10 ° field of view, and a black drawing paper as a sample stage. In FIG. 9, the vertical axis a and the horizontal axis b are a value and b value in the L * a * b color system, and are defined in JIS Z 8729 in the Japanese Industrial Standard.

(Sample preparation)
Hereinafter, specific examples of the present invention will be described, but the present invention is not limited thereto.

<Example 1>
As a dispersion (A), an aqueous dispersion of silicon dioxide particles (30% by mass) having a particle size of 270 nm (CV value 2%) was applied to an Al-deposited PET film at a thickness of 25 μm by a bar coater at 100 mm / second, and hot air circulation was performed. The sample was dried at 100 ° C. for 10 minutes by a type dryer and cooled to room temperature.

  Next, an ethyl cellulose (4% by mass) terpineol solution as a dispersion (B) was applied at a wet film thickness of 25 μm at 100 mm / second by a bar coater, and dried at 100 ° C. for 10 minutes by a hot air circulation dryer.

  By rubbing the film surface with a brush, the coating film was peeled off to obtain a sample.

<Example 2>
As a dispersion (A), an aqueous dispersion of silicon dioxide particles (30% by mass) having a particle size of 270 nm (CV value 2%) was applied to an Al-deposited PET film at a thickness of 25 μm by a bar coater at 100 mm / second, and hot air circulation was performed. The sample was dried at 100 ° C. for 10 minutes by a type dryer and cooled to room temperature.

  Next, an ethyl cellulose (4% by mass) terpineol solution as a dispersion (B) was applied at a wet film thickness of 25 μm at 100 mm / second by a bar coater, and dried at 100 ° C. for 10 minutes by a hot air circulation dryer.

  By rubbing the film surface with a brush, the coating film was peeled off, and the particle embedding body was put in a mullite crucible and fired at 760 ° C. for 6 hours to obtain a sample.

<Example 3>
As a dispersion (A), an aqueous dispersion of silicon dioxide particles (30% by mass) having a particle size of 270 nm (CV value 2%) was applied onto a SiO2 vapor-deposited PET film at a thickness of 25 μm by a bar coater at a rate of 100 mm / sec. The sample was dried at 100 ° C. for 10 minutes by a type dryer and cooled to room temperature.

  Next, an ethyl cellulose (4% by mass) terpineol solution as a dispersion (B) was applied at a wet film thickness of 25 μm at 100 mm / second by a bar coater, and dried at 100 ° C. for 10 minutes by a hot air circulation dryer.

  By rubbing the film surface with a brush, the coating film was peeled off, and the particle embedding body was put in a mullite crucible and fired at 760 ° C. for 6 hours to obtain a sample.

<Example 4>
As a dispersion (A), an aqueous dispersion of silicon dioxide particles (30% by mass) having a particle size of 270 nm (CV value 2%) was applied onto a SiO2 vapor-deposited PET film at a thickness of 25 μm by a bar coater at a rate of 100 mm / sec. The sample was dried at 100 ° C. for 10 minutes by a type dryer and cooled to room temperature.

Next, a water-based polyester resin (30% by mass) was applied as a dispersion liquid (B) at a wet film thickness of 25 μm at 100 mm / second by a bar coater, and dried at 100 ° C. for 10 minutes by a hot air circulation dryer.

  By rubbing the film surface with a brush, the coating film was peeled off, and the particle embedding body was put in a mullite crucible and fired at 760 ° C. for 6 hours to obtain a sample.

<Example 5>
As a dispersion liquid (A), a silicon dioxide particle aqueous dispersion liquid (30 mass%) having a particle diameter of 225 nm (CV value 2%) was applied with a bar coater at 100 mm / second onto a SiO2 vapor-deposited PET film with a wet film thickness of 25 μm and hot air circulation. It dried at 100 degreeC with the type dryer for 10 minutes, and cooled to room temperature.

  Next, an ethyl cellulose (4% by mass) terpineol solution as a dispersion (B) was applied at a wet film thickness of 25 μm at 100 mm / second by a bar coater, and dried at 100 ° C. for 10 minutes by a hot air circulation dryer.

  By rubbing the film surface with a brush, the coating film was peeled off, and the particle embedding body was put in a mullite crucible and fired at 760 ° C. for 6 hours to obtain a sample.

<Comparative Example 1>
As a dispersion (A), an aqueous dispersion of silicon dioxide particles (30% by mass) having a particle size of 270 nm (CV value 2%) was applied with a wet film thickness of 25 μm onto a PET film coated with water-repellent silicon at 100 mm / second by a bar coater. Then, it was dried at 100 ° C. for 10 minutes by a hot air circulation dryer and cooled to room temperature.

  Next, an ethyl cellulose (4% by mass) terpineol solution as a dispersion (B) was applied at a wet film thickness of 25 μm at 100 mm / second by a bar coater, and dried at 100 ° C. for 10 minutes by a hot air circulation dryer.

  By rubbing the film surface with a brush, the coating film was peeled off, and the particle embedding body was put in a mullite crucible and fired at 760 ° C. for 6 hours to obtain a sample.

<Comparative example 2>
As a dispersion (A), a solution obtained by adding 5% by mass of a water-based polyester resin (30% by mass) to an aqueous dispersion (30% by mass) of silicon dioxide particles having a particle size of 270 nm (CV 2%) is deposited with Al at 100 mm / second by a bar coater. A wet film thickness of 25 μm was applied onto a PET film, dried at 100 ° C. for 10 minutes with a hot air circulating dryer, and cooled to room temperature.

  Next, an ethyl cellulose (4% by mass) terpineol solution as a dispersion (B) was applied at a wet film thickness of 25 μm at 100 mm / second by a bar coater, and dried at 100 ° C. for 10 minutes by a hot air circulation dryer.

  By rubbing the film surface with a brush, the coating film was peeled off, and the particle embedding body was put in a mullite crucible and fired at 760 ° C. for 6 hours to obtain a sample.

<Comparative Example 3>
As a dispersion liquid (A), a silicon dioxide particle aqueous dispersion liquid (30% by mass) having a particle diameter of 270 nm (CV value 2%) was directly applied onto a PET film at a wet film thickness of 25 μm by a bar coater at 100 mm / sec. Drying at 100 ° C. for 10 minutes with a drier, rubbing the film surface with a brush, peeling the coating film, placing it in a mullite crucible, and baking at 760 ° C. for 6 hours gave a particle array. .

(Evaluation results)
In Example 1, as shown in FIG. 1, it can be seen that the resin is filling the gap at the same time as the particle arrangement is made, and the structure is stable. As shown in FIG. It was confirmed that it changed depending on the angle and mainly changed from green to blue-green.

  In Examples 2 to 4, as shown in FIGS. 2 to 4, it was confirmed that the particles were arranged and at the same time the sintering proceeded to the hanging structure. As shown in FIG. 9, it was confirmed that the reflection color tone changed depending on the angle and changed mainly from green to blue-green.

  As seen in FIG. 5, Example 5 has an initial particle size smaller than those of Examples 1 to 4, but it was confirmed that the particle size was not substantially changed even after firing. In addition, it was confirmed that sintering was progressing to the hanging structure at the same time as the particle arrangement was made. As can be seen in FIG. 9, it was confirmed that the reflection color tone changed depending on the angle and mainly changed around blue.

  In Comparative Example 1, the dispersion liquid (A) is repelled on the substrate surface during coating to form liquid droplets and becomes a white powder when dried, resulting in an array in which the particles are disordered as shown in FIG. No structural color was shown.

  In Comparative Example 2, since the resin inhibits the particles assembled by self-organization, a dense arrangement cannot be obtained as shown in FIG. 7, and as a result, only a weak color tone was shown.

  In Comparative Example 3, although the particle arrangement is uniform, the colloidal crystal state is broken when it is peeled off by rubbing with a brush, and therefore, the colloidal crystal state is destroyed as shown in FIG. Not shown.

  In addition, according to the sample preparation method of Example 1, the evaluation result of the relationship between various combinations of a metal containing material and a resin sheet and playability is shown in Table 1.

  ○ indicates that the color playability can be confirmed, × indicates the part that is partially cloudy and the color playability cannot be confirmed, and xx indicates that wrinkle is generated and the color playability cannot be confirmed.

  Thus, although the dependence of the material of the resin film is hardly seen, the metal-containing material has a great influence on the structural color (playability). In addition, about the other Example and comparative example in Table 1, the result containing having combined a metal containing material and a board | substrate like Table 1 according to the conditions of Example 1 is shown.

1: Decoration 2: Particle array 3: Particle embedding 4: Resin 5: Silicon dioxide particles

Claims (7)

First, a dispersion (A) containing silicon dioxide colloid is applied onto a substrate coated with a metal-containing material on the surface and dried to obtain a first particle array in which silicon dioxide particles in the silicon dioxide colloid are arranged. Process,
A second step of obtaining a particle embedding body in which the particle array is embedded with the resin by applying a dispersion (B) containing a resin and water or an organic solvent on the particle array and drying the dispersion. When,
And a third step of obtaining a decorative article made of the particle embedded body by peeling the particle embedded body from the substrate.   The method for manufacturing a decorative article according to claim 1, wherein a material containing at least one of aluminum, copper, stainless steel, chromium, and nickel is used as the metal-containing material.   The method for producing a decorative article according to claim 1 or 2, wherein a particle diameter of silicon dioxide in the dispersion (A) is controlled within a range of 0.01 to 10 µm.   The method for producing a decorative article according to any one of claims 1 to 3, wherein at least one of acrylic resin, polyester resin, nitrocellulose, ethylcellulose, and polyvinyl butyral is used as the resin in the dispersion (B).   The manufacturing method of the ornament in any one of Claims 1-4 including the 4th process of baking the said particle | grain embedding body peeled from the said board | substrate at 400-1000 degreeC after the said 3rd process.   A decorative article manufactured by the method for manufacturing a decorative article according to any one of claims 1 to 5, wherein the silicon dioxide particles and the resin are bonded to each other. A decorative article produced by the method of manufacturing a decorative article according to claim 5,
A decorative article in which the silicon dioxide particles are melt bonded.