JP3449215B2 - Metal fine piece with embossed pattern and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to embossed metal fine particles used as a material for hologram pigments and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, a metal fine piece having an embossed pattern has been known as a material for a hologram pigment whose color changes depending on a viewing angle. For example, Tokuhyo Hiradai 50-5023
No. 01 publication also discloses a method for producing such a metallic flaky pigment with an embossed pattern. According to this conventional example, on the embossed pattern formed on the surface of the carrier sheet, the embossed pattern is followed, a raised release surface is formed, and a metal film is adhered on the release surface. Make the metal film form an embossed pattern,
The release surface is then solubilized and the metal coating is removed from the carrier sheet. This embossed metallic film is crushed to obtain an embossed metallic flakes.

[0003]

However, in the above-described conventional manufacturing method, no protective film is formed on the embossed metal film, and the metal film is embossed at the stage of refining the metal film. The pattern may disappear. In addition, the surface on which the embossed pattern is formed may be damaged. Therefore, it cannot be said that the technique is practically established as a method for producing a metal fine piece with an embossed pattern.

The present invention has been made in view of the above conventional problems, and an object of the present invention is to provide an embossed metal fine piece which is easy to manufacture and has high scratch resistance, and a method for manufacturing the same.

[0005]

In order to achieve the above object, according to the present invention, a metal alkoxide and an alkoxy compound are used.
Substituted metal alkoxide in which some of the radicals are replaced by organic
And consisting of a substituted metal alkoxide of metal alkoxy
A mixed solution having a mixing ratio of 10 to 90% to
Apply the sol obtained by hydrolysis and dehydration condensation to the upper and lower surfaces of the carrier layer.
Coating to form a first coating layer
And imparting an embossed pattern to the first coating layer
And a step of applying the embossed pattern to the first core.
Baking the coating layer and the baked first
Forming a metal thin film on the coating layer;
A second coat is formed by coating the metal thin film with the sol.
The step of forming a coating layer and the second coating layer
The method is characterized by including a step of firing and a step of removing the supporting layer .

Further , an embossed pattern is applied to the metal thin film.
Process and at least a thin metal film with an embossed pattern
Also on one side of the metal alkoxide and the alkoxyl group
A substituted metal alkoxide partially substituted with an organic group, or
To a metal alkoxide of a substituted metal alkoxide
Prepare a mixed solution with a mixing ratio of 10 to 90% and add
Coating, coating the sol obtained by dehydration condensation
And a step of forming an insulating layer .

Further , an embossed pattern is applied to the metal thin film.
Adhesive tape to the process and the metal thin film with embossed pattern
The metal thin film with adhesive tape.
Process, metal alkoxide, and part of the alkoxyl group
A substituted metal alkoxide in which is an organic group,
Mixed with substituted metal alkoxides
Preparing a mixed solution having a ratio of 10 to 90%, hydrolysis,
Immerse the fixed metal thin film in the sol obtained by dehydration condensation.
And forming a coating layer on the metal thin film
And are included.

Further, the step of applying an embossed pattern to the metal thin film and the step of applying an acid to the surface of the metal thin film provided with the embossed pattern.
And the step of converting the metal alkoxide and alkoxyl group
A substituted metal alkoxide partially substituted with an organic group, or
To a metal alkoxide of a substituted metal alkoxide
Prepare a mixed solution with a mixing ratio of 10 to 90% and add
Solution, dehydration condensation sol obtained on the oxidized surface
Forming a coating layer by coating .

[0009]

[0010]

[0011]

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention (hereinafter referred to as embodiments) will be described below with reference to the drawings.

Embodiment 1. FIG. 1A shows an example of particles of a pigment for metallic coating used for metallic coating applied to vehicle coating. The size of the pigment particles used for metallic coating is about 2 as the average diameter φ.
The thickness is 0 μm and the thickness t is about 0.1 to 0.3 μm. This is because if the pigment particles are too large, they will look like dust on the painted surface. Therefore,
Even if a holographic pigment is used to paint a vehicle,
It is considered preferable to form an embossed pattern on the metallic pigment as shown in (a). An example of the embossed pattern in this case is shown in FIG. As the embossed pattern, it is considered that the pitch P is 1 μm or less and the height 1 of the unevenness is 0.2 μm or less.

FIG. 2 shows a cross-sectional view of the embossed metal fine piece according to the present embodiment in which the above-mentioned embossed pattern is formed. In FIG. 2, an organic / inorganic composite material layer 12 as a protective layer is formed above and below the metal thin film 10 on which the embossed pattern of irregularities is formed. With such a configuration, when the metal thin film 10 on which the embossed pattern is formed is miniaturized, the organic / inorganic composite material layer 12 acts as a protective layer and can prevent the embossed pattern from disappearing. Therefore, the metal thin film 10 can be easily miniaturized. Further, the hardness of the organic / inorganic composite material layer 12 can be appropriately adjusted to improve the scratch resistance of the metal fine pieces with an embossed pattern.

The organic / inorganic composite material layer 12 described above is M
(OR) _n (M is a metal and R is an organic group) and a substituted metal alkoxide RM (O) in which a part of the alkoxyl group is substituted with an organic group.
R) _n-1 is mixed, alcohol, water, acid, etc. are mixed to prepare a solution, which is hydrolyzed and dehydrated and condensed to obtain a sol for an organic / inorganic composite material layer. It is formed by using the dip method.

The mixing ratio of the substituted metal alkoxide to the metal alkoxide is 10 to 90% in terms of molar ratio. More preferably, it is 20 to 80%. When the molar ratio of the substituted metal alkoxide becomes small, the organic / inorganic composite material layer 12 becomes hard, and when the molar ratio becomes large, it becomes soft. Therefore,
When it is desired to particularly enhance the scratch resistance of the organic / inorganic composite material layer 12, it is preferable that the mixing ratio of the substituted metal alkoxide to the metal alkoxide is 30% or less in terms of molar ratio.

FIG. 3 shows a method for manufacturing an embossed metal fine piece according to this embodiment. In FIG.
First, a water-soluble film such as a PVA film is used as a supporting layer, and the upper and lower surfaces thereof are dip-coated with the organic / inorganic composite material layer 12 by the sol-gel method. The embossed pattern is transferred to the organic / inorganic composite material layer 12 by a press and then fired. A roll press or the like can be used for the transfer of the embossed pattern by a press. In addition, as the embossed pattern original plate used in the pressing step, one having an embossed pattern formed in advance is used. In this case, when it is desired to increase the transfer efficiency of the embossed pattern from the embossed pattern original plate to the organic / inorganic composite material layer 12 and increase the reflection strength peculiar to the hologram, the mixing ratio of the substituted metal alkoxide to the metal alkoxide used is set. 70% or more, organic / inorganic composite material layer 1
It is preferable to keep 2 soft.

Next, a metal thin film 10 is formed on the organic / inorganic composite material layer 12 to which the embossed pattern is transferred by metal vapor deposition or plating, and further the organic / inorganic composite material layer 12 is formed thereon. And bake. As a result, two metal piece samples in which the metal thin film 10 with the embossed pattern is protected above and below the carrier layer by the organic / inorganic composite material layer 12 are formed. When this is immersed in water, the carrier layer is dissolved in water, and the two metal piece samples are separated from above and below one carrier layer. By crushing this and making it fine, the metal fine piece with an embossed pattern according to the present embodiment can be obtained.

In the thus obtained metal fine piece with embossed pattern, the thickness of the organic / inorganic composite material layer 12 is set to 0.1 μm or more. This makes it possible to sufficiently function as a protective layer. In order to prevent the organic / inorganic composite material layer 12 from peeling off the film after the film formation, the viscosity of the sol for the organic / inorganic composite material layer is 2.3.
It is preferable that the pressure is not more than mPa · s.

In the embossed pattern press transfer step shown in FIG. 3, the organic / inorganic composite material layer 12 having the embossed pattern is formed.
In order to improve the transfer efficiency to the supporting layer, it is preferable that the pressing pressure is not absorbed by the carrier layer. For this purpose, it is conceivable to form the carrier layer by using a rigid material such as metal or glass instead of a soft material such as PVA film. However, in this case, for example, ultrasonic waves or the like must be used as a method for separating the metal piece sample formed on the surface of the supporting layer from the supporting layer. Therefore, as compared with the case where a PVA film or the like is used as the supporting layer, the separation of the metal piece sample becomes slightly difficult. Therefore, in order to facilitate the separation of the carrier layer and the sample and to improve the transfer efficiency of the embossed pattern to the organic / inorganic composite material layer 12 by pressing, on a substrate formed of a hard material such as metal or glass. It is preferable that a water-soluble film such as a PVA film is coated on and used as a carrier layer.

When an organic material, rather than an organic / inorganic composite material, is used as a material for sandwiching the metal thin film 10 described above, the film elasticity is too large and the embossed pattern transferred in the press transfer process is maintained. Difficult to do. Alternatively, there is a problem that a complicated process is required to maintain the formed embossed pattern. Further, since the organic material has low hardness, there is a problem that the film is easily damaged. On the other hand, when an inorganic material is used,
Since the hardness is too high, it is extremely difficult to transfer the embossed pattern by pressing. Therefore, hologram-like reflection cannot be produced.

These problems can be solved by using the organic / inorganic composite material layer 12 as described above. That is, by appropriately adjusting the mixing ratio of the substituted metal alkoxide to the metal alkoxide, it is possible to form a film having appropriate elasticity and hardness, so that it is possible to improve the hologram-like reflection strength and scratch resistance. . In order to obtain a good balance between the hologram-like reflection strength and scratch resistance of the organic / inorganic composite material layer 12, the molar ratio of the substituted metal alkoxide to the metal alkoxide is, for example, about 30 to 70%. Is preferred.

Examples of the embossed metal fine pieces according to this embodiment will be described below.

Example 1. Tetraethoxysilane (TEOS) was used as the metal alkoxide, and methyltriethoxysilane (MTEOS) was used as the substituted metal alkoxide. These and ethanol (EtOH), water (H ₂ O),
Hydrochloric acid (HCl) was mixed in the respective proportions (molar ratios) shown below.

TEOS: MTEOS: EtOH: H
₂ O: HCl = 0.5: 0.5: 6: 11: 0.1 The mixed solution was aged, and the viscosity of the sol was 2.0 mPa.
When s was reached, a stainless steel substrate was dip-coated to form an organic / inorganic composite material layer. At this time,
The pulling rate was adjusted to change the film thickness of the organic / inorganic composite material layer between 0.05 and 0.3 μm.

Further, Ni having an embossed pattern on the surface
A plate was pressed onto this organic / inorganic composite material layer to transfer an embossed pattern. After that, the organic / inorganic composite material layer on which the embossed pattern was transferred, which was formed on the stainless steel substrate, was baked in a baking furnace. Furthermore, an Al layer is formed on this organic / inorganic composite material layer by vapor deposition, and the above-mentioned sol is dip-coated on the organic / inorganic composite material layer to the same thickness as the layer to which the embossed pattern has been transferred to form an organic / inorganic composite material layer. After forming, it was fired to obtain a metal piece sample.

FIG. 4 shows the results obtained by measuring the 12-degree reflection at each film thickness using the metal piece sample prepared as described above.
Shown in. In FIG. 4, the horizontal axis represents the film thickness of the organic / inorganic composite material layer, and the vertical axis represents the average reflectance of 12 degree reflection. As can be seen from FIG. 4, when the film thickness of the organic / inorganic composite material layer is 0.1 μm or less, it is considered that the embossed pattern is not effectively transferred, and the reflectance is extremely low. There is. Therefore, it is considered that the thickness of the organic / inorganic composite material layer is preferably 0.1 μm or more.

Example 2. An organic / inorganic composite material layer was formed in the same manner as in Example 1 while changing the mixing ratio of MTEOS to TEOS, and the relationship between each film thickness and the peeled area was examined. This result is shown in FIG. In FIG.
The horizontal axis represents the film thickness of the organic / inorganic composite material layer, and the vertical axis represents the peeled area for each film thickness. As can be seen from FIG. 5, when the MTEOS amount is 10%, the film thickness is from around 500 nm, and when it is 50%, the film thickness is 800 n.
From around m, when 90%, the film peeling becomes remarkable from around 1000 nm.

The thickness of the organic / inorganic composite material layer is set to 0.
The sample prepared on the glass substrate in the same manner as in Example 1 while having a thickness of 3 μm and varying the amount of MTEOS was evaluated for 12-degree reflection and scratch resistance of the film. Scratch resistance is JIS-R
According to 3212, a Taber abrasion test was performed, and the haze value after 100 rotations was measured. The result is shown in FIG. The horizontal axis of FIG. 6 shows the amount of MTEOS (TEO of MTEOS
The mixing ratio to S) and the vertical axis indicate the average reflectance and the haze value at 12-degree reflection. From FIG. 6, M
It can be seen that when the TEOS amount is 20% or less, the average reflectance sharply decreases, and when the TEOS amount is 80% or more, the haze value sharply increases and the scratch resistance of the film decreases. Also, MTEOS
It can be seen that when the amount is 30% or less, the haze value becomes particularly low, and the scratch resistance of the film is improved. Furthermore, M
It can be seen that the average reflectance is particularly high when the TEOS amount is 70% or more. This is because the organic-inorganic composite material layer becomes hard when the mixing ratio of MTEOS as the substituted metal alkoxide becomes low, and becomes soft when the mixing ratio becomes large. The increase in the MTEOS amount increases the reflection intensity because the organic groups (CH ₃ ) in the inorganic (SiO ₂ ) increase, the elasticity of the film increases, and the embossed pattern can be deeply transferred. .

From the above, the mixing ratio (molar ratio) of MTEOS to TEOS is 20 to 80 as described above.
% Is considered to be suitable. In this range,
The mixing ratio may be selected so that suitable characteristics can be obtained according to the application of the embossed metal fine piece.

In Example 1, a stainless steel substrate is used as the carrier layer, but when a water-soluble film such as a PVA film is used, the haze value does not change but the average reflectance decreases by 5 to 10%. I understood. Further, when the PVA film was coated on the stainless steel substrate to form the carrier layer, the decrease in average reflectance was only 2 to 3%.

In FIG. 7, M is used for each of a stainless steel (SUS) substrate, polyvinyl alcohol (PVA), and a PVA film coated on the SUS substrate as the supporting layer.
The measurement result of the average reflectance of 12 degree reflection with respect to the mixing ratio of TEOS is shown. As can be seen from FIG. 7, there is a slight difference in the average reflectance depending on the carrier layer used. However, at this level, it is considered that there is no practical problem.

Example 3. The mixing ratio of MTEOS to TEOS was changed to 10, 50, and 90% to prepare a sol by the same method as in Example 1, and the viscosity was adjusted to adjust each viscosity and the film thickness of the organic / inorganic composite material layer. I investigated the relationship. The result is shown in FIG. In FIG. 8, the horizontal axis shows the viscosity of the sol and the vertical axis shows the film thickness. Considering the results shown in FIG. 8 and the results shown in FIG. 5, it is appropriate that the viscosity of the sol is 2.3 mPa · s or less in order to prevent the film peeling from becoming extremely large. Conceivable.

Embodiment 2. 9 to 13 show each step of Embodiment 2 of the method for producing an embossed metal fine piece according to the present invention. As shown in FIG. 9, first, an embossed pattern original plate 1 is formed by using a pressing method or a rolling method.
The metal thin film 10 is pressed by 4. As a result, FIG.
As shown in, the emboss pattern is transferred to the metal thin film 10.

In this way, as shown in FIG. 11, a transparent and hard coating layer 16 is formed on at least one surface of the metal thin film 10 to which the embossed pattern is transferred.
As the coating layer 16, for example, the organic / inorganic composite material layer described in the first embodiment is suitable. Further, the following bifunctional silane or trifunctional silane is also effective.

[0036]

[Chemical 1] Further, when the coating layer 16 is formed on the surface of the metal thin film 10, it is also preferable to oxidize the surface of the metal thin film 10 by irradiating ultraviolet rays or the like. Thereby, the bonding force between the metal thin film 10 and the coating layer 16 can be improved. Therefore, the peeling of the coating layer 16 can be prevented in the step of miniaturizing the metal thin film 10, and the metal thin film 10 can be prevented from warping or waviness.

The metal thin film 10 shown in FIG. 11 is attached to one side of the embossed pattern original plate 14. In this way, the embossed pattern original plate 14 is attached,
The metal thin film 10 having one surface coated with the coating layer 16 is subjected to an ultrasonic cleaning machine as shown in FIG. 12 while being attached to the embossed pattern original plate 14. As a result, the metal thin film 10 is peeled off from the embossed pattern original plate 14 and pulverized together with the coating layer 16. The metal thin film 10 crushed in this way can be classified with a sieve or the like to obtain a metal fine piece with an embossed pattern according to the present embodiment (FIG. 13).

The coating layer 1 shown in FIG.
In order to form 6 on the surface of the metal thin film 10, the metal thin film 10 still attached to the embossed pattern original plate 14 is immersed in a coating liquid such as an organic / inorganic composite material solution, but is pulled out from the coating liquid. When the metal thin film 1
0 may be deformed by the viscosity and surface tension of the liquid. As a result, the surface of the metal thin film 10 is slightly warped or undulated. When such waviness occurs, there is a problem that the interference color when used as a pigment is weakened.
Since the metal thin film 10 is only pressed against the embossed pattern original plate 14 by the pressure at the time of pressing, it is impossible to stop the minute movement of the metal thin film 10, so that such undulation occurs. Therefore, a tape is attached on the metal thin film 10 attached to the surface of the embossed pattern original plate 14 after pressing, and the metal thin film 10 is peeled off from the embossed pattern original plate 14 by peeling off the tape. After that, it is also preferable to immerse the whole tape in the coating liquid to form the coating layer 16 on the surface of the metal thin film 10. After forming the coating layer 16, the tape is immersed in a solvent to separate it from the metal thin film 10. In such a method, since the metal thin film 10 is fixed by the adhesive force of the tape when the coating layer 16 is formed,
It is possible to suppress warpage and undulation even when subjected to a force due to the viscosity and surface tension of the coating liquid. Thereby, the interference color of the metal fine piece with an embossed pattern can be improved.

A specific example of the method for producing the embossed metal fine piece according to this embodiment will be described below as an example.

Example 4. The Ni originals used as the embossed pattern original 14 are arranged on the upper and lower sides, and an aluminum foil having a thickness of 1 μm as the metal thin film 10 is sandwiched therebetween. In this state, the aluminum foil was pressed with a Ni original plate at a pressure of 600 MPa at room temperature to transfer the embossed pattern to the upper and lower surfaces of the aluminum foil.

The aluminum foil to which the embossed pattern was transferred showed an optical effect of diffraction and had an embossed optical pattern on its surface.

Since the aluminum foil pressed with the Ni original plate remains attached to one of the original plates as described above, the aluminum foil was immersed in the organic / inorganic composite material solution together with the original plate. It was pulled out from the liquid and the coating liquid was attached to the surface of the aluminum foil. This was further kept at room temperature for 1 hour, and then heated at 80 ° C. for 1 hour to fix the coated liquid to form a coating layer 16.

Coating layer 16 obtained as described above
The aluminum foil formed on the surface is still attached to the Ni original plate. Therefore, the aluminum foil in the state of being attached to this original plate was immersed in acetone, and ultrasonic waves were applied for 150 minutes by an ultrasonic cleaning machine (homogenizer). In this way, the aluminum foil attached to the original plate was peeled off from the original plate and pulverized to form flakes. The flakes were classified by a sieve to obtain a metal fine piece with an embossed pattern (hereinafter referred to as a hologram pigment) having a particle diameter of 25 to 45 μm. FIG. 14 shows an electron micrograph of the pigment thus obtained. From this, it was confirmed that the coating layer of about 1 μm was coated on one surface of the aluminum foil of 1 μm in thickness.

Holographic pigment prepared as described above 0.0
5g, acrylic melamine resin 150cc, thinner 5
It was mixed with 0 cc to make it clear. The clear containing the hologram pigment was applied onto the color base of the coated plate by a spray gun. After coating, the coating was held at 140 ° C. for 20 minutes to fix the coating. After application to the coated plate, each flake on the coated plate exhibited a diffractive optical effect with an embossed diffractive pattern on its surface. As a result, the obtained coated plate was able to create a unique iridescent effect.

When the aluminum foil is dipped in the organic / inorganic composite material solution to form the coating layer 16 in the above-described step, the surface of the aluminum foil is oxidized by an ultraviolet irradiation device and then the coating layer 16 is formed. Then, the bonding strength between the coating layer 16 and the aluminum foil increases. Therefore, it is possible to prevent the coating layer 16 from peeling off from the aluminum foil in the subsequent steps. Accordingly, even in the process of applying ultrasonic waves to crush the metal thin film 10, the metal thin film 10 is protected by the coating layer 16, and the hologram pigment is less likely to warp or swell. As a result, the interference color of the hologram pigment could be strengthened. The results are shown in Table 1.

[0046]

[Table 1] Even when the surface of the aluminum foil is not oxidized, a sufficiently good interference color can be obtained as a hologram pigment. However, when the surface of the aluminum foil was subjected to oxidation treatment, the interference color was further intensified, and the interference color of the hologram pigment was in a very good state. The double circles in Table 1 indicate this.

Further, as described above, when the coating layer 16 is formed on the surface of the aluminum foil, the aluminum foil is fixed once by attaching it to a tape rather than the state where the aluminum foil is still attached to the original plate. It is possible to suppress warping or waviness of the aluminum foil by immersing it in the organic / inorganic composite material solution after that. Thus, Table 2 shows the results when the tape was used in forming the coating layer 16.

[0048]

[Table 2] In Table 2 as well, ⊚ indicates that the interference color was intensified as compared with the case where the tape was not used, and was extremely good as the interference color of the hologram pigment. However, even when no tape is used, a sufficiently good hologram pigment has been obtained.

Embodiment 3. 15 to 18 show each step of Embodiment 3 of the method for producing an embossed metal fine piece according to this embodiment. In FIG. 15, a metal thin film 10 is formed on the surface of the embossed pattern original plate 14 by using a plating method. As a result, the embossed pattern of the embossed pattern original plate 14 is transferred to the metal thin film 10.

In this way, the transparent and hard coating layer 16 is formed on the metal thin film 10 formed on the surface of the embossed pattern original plate 14. This coating layer 16
As described above, as described in the second embodiment, an organic / inorganic composite material layer or a bifunctional silane or a trifunctional silane can be used. In this case also, the metal thin film 10
It is also preferable to form the coating layer 16 after oxidizing the surface of the film by ultraviolet irradiation or the like.

In this way, the embossed pattern original plate 1
Metal thin film 10 and coating layer 1 formed on 4
1 attached to the embossed pattern original plate 14 as shown in FIG.
Sonicate as shown in 7. Thereby, ultrasonic waves are applied to separate and crush the metal thin film 10 whose one surface is coated with the coating layer 16 from the embossed pattern original plate 14. The crushed metal thin film 10 is classified by a sieve or the like to obtain a hologram pigment (FIG. 18). As described above, by coating at least one surface of the metal thin film 10 with the coating layer 16, it is possible to suppress warpage and undulation that occur in the metal thin film 10 during pulverization and the like. As a result, the interference color of the hologram pigment can be strengthened.

As in the second embodiment, the metal thin film 10
When the coating layer 16 is formed on the surface of the metal thin film 1 from the surface of the embossed pattern original plate 14 after plating.
It is also preferable that 0 is attached to the tape and released from the mold, and then the tape is immersed in the coating liquid. As a result, it is possible to further prevent the metal thin film from warping or waviness due to the viscosity or surface tension of the coating liquid.

A specific example of the method for producing the embossed metal fine piece according to this embodiment will be described below as Example 5.

Example 5. NiSO ₄ .6H ₂ O, NiCl ₂ having an embossed pattern surface and a Ni original plate used as an embossed pattern original plate as a negative electrode and a positive electrode as Ni
Plating was performed on the Ni original plate using a plating bath composed of 6H ₂ O and H ₃ BO ₄ . By plating for 1 minute under the conditions of a plating bath temperature of 50 ° C. and a current value of 2 A / dm ² , N
A Ni plating film having a thickness of 1.0 μm was formed on the i master plate. The Ni-plated film exhibited an optical effect of diffraction and had an embossed optical pattern on its surface. In this way, the Ni plating film as it was attached on the Ni original plate was immersed in the organic-inorganic composite material solution together with the original plate. Next, this was pulled out from the liquid, and the coating liquid was attached to the surface of the Ni plating film. After it was kept at room temperature for 1 hour, it was heated at 80 ° C. for 1 hour to fix the coating liquid and form the coating layer 16.

Coating layer 1 thus obtained
Since the Ni-plated film with 6 adheres to the original plate as it is, it was immersed in acetone in this state and ultrasonic waves were applied by an ultrasonic cleaning machine (homogenizer). In this way, ultrasonic waves were applied for 5 hours and 30 minutes in acetone,
The Ni plating film attached to the original plate was peeled off and pulverized into flakes. The flakes were classified by a sieve to obtain a hologram pigment having a particle diameter of 25 to 45 μm. Figure 1
9 shows the electron micrograph. From this, it was confirmed that a coating film of about 1 μm was coated on one surface of the Ni plating film having a thickness of 1 μm.

Hologram pigment 0.1 prepared as described above
g, acrylic melamine resin 150 cc, thinner 50
It was made clear by blending with cc. The clear containing the hologram pigment was applied onto the color base of the coated plate by a spray gun. After coating, the coating was held at 140 ° C. for 20 minutes to fix the coating on the coated plate.

After being coated in this manner, the coating material on the coated plate exhibited the optical effect of diffraction, and the surface thereof had an embossed diffraction pattern. As a result, the obtained coated plate was able to create a unique iridescent effect.

Coating layer 1 on the Ni plating film described above
Before forming No. 6, the surface of the Ni plating film was oxidized by ultraviolet irradiation. As a result, the bonding strength between the Ni plating film and the coating layer 16 is increased, and it is possible to prevent the coating layer 16 from peeling off from the Ni plating film in the subsequent pulverization process, and prevent the Ni plating film from waviness and the like. I was able to strengthen the interference color. This is the same as the effect described in the second embodiment.

As in the second embodiment, before the coating layer 16 is formed on the Ni-plated film, if the Ni-plated film is fixed on the tape and the Ni-plated film is fixed and then immersed in the coating liquid, the viscosity of the coating liquid can be reduced. Ni by surface tension
It is possible to prevent the plating film from warping or waviness.
Therefore, also by this, the interference color can be further improved.

[0060]

As described above, according to the present invention, the organic / inorganic composite material layer is coated on both sides of the metal thin film on which the embossed pattern is formed, and this serves as a protective layer to eliminate the embossed pattern. The metal piece can be easily miniaturized without using.

By adjusting the mixing ratio of the substituted metal alkoxide to the metal alkoxide, both scratch resistance and reflectance can be achieved.

Furthermore, since the embossed pattern can be directly applied to the organic / inorganic composite material layer by pressing, the production is easy. Further, in this case, since the sample can be formed on both sides of the supporting layer at the same time, efficient production is possible.

Also, by embossing the pattern directly onto the metal thin film by pressing and forming the organic / inorganic composite material layer on at least one surface of the metal thin film, the metal with the embossing pattern having strong and strong interference color can be easily formed. Fine pieces can be produced.

Further, when the organic / inorganic composite material layer is formed on the surface of the fine metal piece, if the metal thin film is fixed with an adhesive tape in advance, the metal thin film is formed during coating by the viscosity and surface tension of the coating liquid. Warpage and undulation that occur can be suppressed. Thereby, the interference color can be further strengthened.

Further, by pre-oxidizing the surface of the metal thin film covering the organic / inorganic composite material layer, the binding force between the metal thin film and the organic / inorganic composite material can be improved.
As a result, it is possible to prevent the organic / inorganic composite material layer from peeling off in the crushing step or the like, and it is possible to suppress the occurrence of warpage or waviness of the metal thin film. Thereby, the interference color can be further improved.

[Brief description of drawings]

FIG. 1 is an explanatory diagram showing an example in which an embossed pattern is formed on the surface of a metallic coating pigment.

FIG. 2 is a cross-sectional view of a metal fine piece with an embossed pattern according to the first embodiment of the present invention.

FIG. 3 is an explanatory view showing a method for manufacturing a metal fine piece with an embossed pattern according to the first embodiment of the present invention.

FIG. 4 is a diagram showing a relationship between a film thickness of an organic / inorganic composite material layer and an average reflectance.

FIG. 5 is a diagram showing a relationship between a film thickness of an organic / inorganic composite material layer and a peeled area.

FIG. 6 is a diagram showing the relationship between the amount of MTEOS and the average reflectance.

FIG. 7 is a diagram showing the relationship between the amount of MTEOS and the average reflectance for each supporting layer.

FIG. 8 is a diagram showing the relationship between the viscosity and film thickness of a sol that is a raw material for an organic / inorganic composite material layer.

FIG. 9 is an explanatory diagram of the steps of Embodiment 2 of the method for producing an embossed metal fine piece according to the present invention.

FIG. 10 is an explanatory diagram of the steps of Embodiment 2 of the method for producing embossed metal fine pieces according to the present invention.

FIG. 11 is an explanatory diagram of a process of Embodiment 2 of the method for manufacturing an embossed metal fine piece according to the present invention.

FIG. 12 is an explanatory diagram of the steps of Embodiment 2 of the method for producing a metal fine piece with an embossed pattern according to the present invention.

FIG. 13 is an explanatory view of a process of Embodiment 2 of the method for producing an embossed metal fine piece according to the present invention.

FIG. 14 is an electron micrograph of a hologram pigment obtained by a second embodiment of a method for producing embossed metal fine particles according to the present invention.

FIG. 15 is an explanatory view showing a process of a third embodiment of a method for producing a metal fine piece with an embossed pattern according to the present invention.

FIG. 16 is an explanatory view showing a process of a third embodiment of a method for producing an embossed metal fine piece according to the present invention.

FIG. 17 is an explanatory view showing a process of a third embodiment of the method for manufacturing an embossed metal fine piece according to the present invention.

FIG. 18 is an explanatory view showing a process of a third embodiment of the method for producing a metal fine piece with an embossed pattern according to the present invention.

FIG. 19 is an electron micrograph of a hologram pigment manufactured by Embodiment 3 of the method for manufacturing embossed metal fine particles according to the present invention.

[Explanation of symbols]

10 metal thin film, 12 organic / inorganic composite material layer, 14
Original embossed pattern, 16 coating layers.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yukio Okouchi 1 Toyota Town, Toyota City, Aichi Prefecture Toyota Motor Co., Ltd. (72) Inventor Hiroyuki Kimoto 1 Toyota Town, Toyota City, Aichi Prefecture Toyota Motor Co., Ltd. (72) Inventor Masatsugu Nakanishi, Toyota Town, Toyota City, Aichi Prefecture, Toyota, Ltd. (56) References Japanese Patent Laid-Open No. 10-88026 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09C 1/62 C09C 3/04

Claims (4)

(57) [Claims] 1. A mixed solution comprising a metal alkoxide and a substituted metal alkoxide in which a part of an alkoxyl group is substituted with an organic group, and a mixed solution having a mixing ratio of the substituted metal alkoxide to the metal alkoxide of 10 to 90% is prepared. And then coating the sol obtained by hydrolysis and dehydration condensation on the upper and lower surfaces of the carrier layer to form a first coating layer, and a step of applying an embossed pattern to the first coating layer, Baking the first coating layer provided with an embossed pattern, forming a metal thin film on the baked first coating layer, and coating the sol on the metal thin film to form a second layer. A step of forming the coating layer, a step of baking the second coating layer, and a step of removing the carrier layer. Method of manufacturing a Nbosu textured metal fine pieces. 2. A step of applying an embossed pattern to a metal thin film, and a metal alkoxide and a substituted metal alkoxide in which a part of the alkoxyl group is replaced with an organic group on at least one surface of the metal thin film provided with the embossed pattern. And consists of
A step of preparing a mixed solution in which the mixing ratio of the substituted metal alkoxide to the metal alkoxide is 10 to 90%, and coating a sol obtained by hydrolysis and dehydration condensation to form a coating layer. And a method for producing a metal fine strip with an embossed pattern. 3. A step of applying an embossed pattern to the metal thin film, a step of pressing an adhesive tape against the metal thin film provided with the embossed pattern, and fixing the metal thin film with the adhesive tape, a metal alkoxide and an alkoxyl group A substituted metal alkoxide partially substituted with an organic group, and the mixing ratio of the substituted metal alkoxide to the metal alkoxide is 10 to 10.
A mixed solution of 90% is prepared, and the fixed metal thin film is dipped in a sol obtained by hydrolysis and dehydration condensation to form a coating layer on the metal thin film. A method for producing a metal fine strip with an embossed pattern. 4. A step of providing an embossed pattern on a metal thin film, a step of oxidizing the surface of a metal thin film provided with an embossed pattern, a metal alkoxide, and a substituted metal in which a part of an alkoxyl group is replaced with an organic group. An alkoxide, and the mixing ratio of the substituted metal alkoxide to the metal alkoxide is 10 to
An embossed pattern, which comprises: forming a coating layer by coating a sol obtained by preparing a mixed solution of 90%, hydrolysis and dehydration condensation on the oxidized surface. A method for producing fine metal strips with metal.