JP2009083183A - Optical membrane laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical membrane laminate equipped with a light absorbing layer low in the transmittance of visible light, having metal gloss sufficiently large in reflection brightness and reflection chroma, and providing a light absorbing function. <P>SOLUTION: The optical membrane laminate 1 is constituted by providing an optical membrane layer 3 on a base material 2, and is characterized in that the optical membrane layer 3 has the light absorbing layer comprising at least one layer selected from high refractive index membrane layers 4 and 7, a low refractive index membrane layer 5 and a pure metal membrane layer 6. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an optical thin film laminate, a decorative member, and a decorative molded product, and in particular, has a light absorption layer, has a low visible light transmittance, and has a high gloss and / or high reflection chroma. The present invention relates to an optical thin film laminate.

Conventionally, there is an optical thin film laminate having an optical thin film layer obtained by laminating a high refractive index thin film layer and a low refractive index thin film layer a plurality of times on a base material (for example, see Patent Document 1).
In such an optical thin film laminate, visible light in the optical thin film layer can be obtained by using a material having a zero extinction coefficient in the visible light region as a material for the high refractive index thin film layer and the low refractive index thin film layer. The light absorptance of the region can be reduced, and the light loss in the optical thin film layer can be reduced.

In addition, such optical thin film laminates have conventionally been used in, for example, automobile members, vehicle members, household appliance members, mobile phone members, portable game machine members, personal computer members, PDA (Personal Digital Assistant) members, audio product members, It is used for decorative members such as car navigation members, office supplies members, sporting goods members, miscellaneous goods members, glasses / sunglasses members, camera members, optical article members, and measuring instrument members.
JP 2005-248276 A

However, since the conventional optical thin film laminate has the following disadvantages, it may not be able to sufficiently meet various surface decorating requirements when used as a decorating member.
That is, an optical thin film laminate using a material having an extinction coefficient of zero in the visible light region cannot make the achromatic color of reflection and transmission black. In an optical thin film laminate using a material having an extinction coefficient of zero in the visible light region, the achievable reflection and transmission achromatic color is silver, and the specular gloss increases as the reflectance increases.

  In addition, in an optical thin film laminate using a material having a zero extinction coefficient in the visible light region, there is a limit in increasing the lightness and saturation of CIELAB (based on JIS Z 8729). This is because the refractive index of a practical material having an extinction coefficient of zero in the visible light region is between 1.4 and 2.4, and between the low refractive index thin film layer material and the high refractive index thin film layer material. This is because the difference in refractive index cannot be made larger.

  In addition, as a method of increasing the brightness and saturation of an optical thin film laminate using a material with an extinction coefficient of zero in the visible light region, the number of high refractive index thin film layers and low refractive index thin film layers is increased. There is a way. However, in this method, various problems as described below occur as the number of stacked layers is increased. That is, an increase in the number of processes, an increase in production cost, occurrence of curling of the base material and film cracking / peeling, an increase in difficulty of reproducibility of optical characteristics, and the like.

The present invention has been made in view of such circumstances, and an object of the present invention is to provide an optical thin film laminate having a metallic luster with low visible light transmittance and high reflection brightness and / or reflection saturation. To do.
In addition, the present invention provides a decorative member excellent in surface decorating properties provided with the optical thin film laminate of the present invention, and a decorative molded product excellent in surface decorating properties using the optical thin film laminate of the present invention. The purpose is to provide.

  In order to solve the above problems, the optical thin film laminate of the present invention is provided with an optical thin film layer on a substrate, and the optical thin film layer comprises a high refractive index thin film layer, a low refractive index thin film layer, and a pure metal thin film. It is characterized by comprising at least one light absorbing layer selected from the layers.

  Moreover, in said optical thin film laminated body, the extinction coefficient in wavelength 550nm of the said light absorption layer shall be 0.01 or more.

  In the optical thin film laminate, the high refractive index thin film layer has a refractive index at a wavelength of 550 nm of 1.75 or more, and the low refractive index thin film layer has a refractive index at a wavelength of 550 nm of less than 1.75. It can be assumed that

  Moreover, in the above optical thin film laminate, the optical thin film layer may be formed by a vacuum film forming method.

In order to solve the above problems, the decorative member of the present invention is characterized by comprising the optical thin film laminate according to any one of the above.
Moreover, the decorative molded product of the present invention is formed by molding the optical thin film laminate according to any one of the above.

In the optical thin film laminate of the present invention, an optical thin film layer is provided on a substrate, and the optical thin film layer is at least one selected from a high refractive index thin film layer, a low refractive index thin film layer, and a pure metal thin film layer. Since the light absorption layer is provided, the light absorption function of the light absorption layer can reduce the transmittance of visible light and increase the reflection brightness and / or the reflection saturation. As a result, the optical thin film laminate of the present invention is excellent in surface decorating properties having a metallic luster with a large reflection brightness and / or reflection saturation.
Moreover, since the optical thin-film laminated body of this invention is used for the decorating member and decorating molded product of this invention, it becomes the thing excellent in the surface decorating property.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
FIG. 1 is a cross-sectional view showing an example of the optical thin film laminate of the present invention. An optical thin film laminate 1 shown in FIG. 1 is obtained by providing an optical thin film layer 3 on a substrate 2.

(Base material)
The material of the base material 2 is not particularly limited as long as it has transparency, and examples thereof include plastic, glass, or a composite material of these.
Examples of plastic materials include polyester, polyamide, polyimide, polypropylene, polyethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetal, polyvinyl alcohol, polyurethane, polyethyl methacrylate, polycarbonate, polystyrene, polyphenylene sulfite, and polyethersulfide. Hong, polyethersulfone, polyolefin, polyarylate, polysulfone, polyparaxylene, polyetheretherketone, polyethylene terephthalate, polyethylene naphthalate, polyphenyl oxide, triacetylcellulose, cellulose acetate, silicon resin, fluororesin, acrylic resin, phenol Resin, epoxy resin, ABS resin, ABS alloy, etc. Not intended to be constant. The plastic material may contain a known additive, for example, an ultraviolet absorber, a plasticizer, a lubricant, a colorant, an antioxidant, a flame retardant and the like.
Examples of the glass material include, but are not limited to, soda lime glass, borosilicate glass, quartz glass, Pyrex (registered trademark) glass, alkali-free glass, lead glass, and the like.

Moreover, the shape of the base material 2 is not specifically limited, For example, it can be set as plate shape, roll shape, etc.
The thickness of the base material 2 is appropriately selected according to the intended use, and is usually 5 μm or more and 10 mm or less.

  The surface of the substrate 2 is preferably smooth. Further, the surface of the substrate 2 may be subjected to a surface treatment as necessary before the optical thin film layer 3 is formed. Examples of the surface treatment method here include corona treatment method, vapor deposition treatment method, electron beam treatment method, high frequency discharge plasma treatment method, sputtering treatment method, ion beam treatment method, atmospheric pressure glow discharge plasma treatment method, alkali treatment method. And an acid treatment method.

(Optical thin film layer)
The optical thin film layer 3 constituting the optical thin film laminate 1 shown in FIG. 1 includes a high refractive index thin film layer 4, a low refractive index thin film layer 5, a pure metal thin film layer 6, and a high refractive index thin film layer from the side close to the substrate 2. 7 four layers are sequentially laminated. The optical thin film layer 3 includes a light absorption layer made of at least one selected from the high refractive index thin film layers 4 and 7, the low refractive index thin film layer 5, and the pure metal thin film layer 6.

In the optical thin film laminate 1 shown in FIG. 1, the light absorption function of the optical thin film layer 3 is such that at least one of the four layers constituting the optical thin film layer 3 has a light extinction coefficient of 0. It is obtained by setting it as the light absorption layer which is 01 or more. When the extinction coefficient is 0.01 or more, a sufficient light absorption function can be obtained. On the other hand, when the extinction coefficient is less than 0.01, the light transmittance is excellent. Therefore, each of the four layers constituting the optical thin film layer 3 is a thin film having a light absorption function (that is, a light absorbing layer), or any of the four layers constituting the optical thin film layer 3 is selected. Whether the layer is a transparent thin film excellent in light transmittance can be determined by the value of the extinction coefficient of the material used.
The extinction coefficient at a wavelength of 550 nm of the light absorption layer is preferably 7 or less. When the extinction coefficient exceeds 7, there is a possibility that the light transmittance becomes insufficient and cannot be applied to various uses.

  The optical constants of the refractive index and extinction coefficient of the material constituting the optical thin film layer 3 are determined by spectroscopic ellipsometry, using the samples of the high refractive index thin film layers 4 and 7, the sample of the low refractive index thin film layer 5, It can be obtained by measuring the change in the polarization state of the light reflected from the surface of the sample of the metal thin film layer 6.

(High refractive index thin film layer)
The high refractive index thin film layers 4 and 7 shown in FIG. 1 have a refractive index of 1.75 or more at a light wavelength of 550 nm. When the high refractive index thin film layers 4 and 7 are excellent in light transmittance, the high refractive index thin film layers 4 and 7 having an extinction coefficient in the visible light region of less than 0.01 are used. .

Examples of the material for the high refractive index thin film layers 4 and 7 include lead telluride (PbTe) (refractive index 1.75, extinction coefficient 2.90), yttrium trioxide (Y ₂ O ₃ ) (refractive index 1. 79, extinction coefficient 0), thorium dioxide (ThO ₂ ) (refractive index 1.80, extinction coefficient 0), bismuth trioxide (Bi ₂ O ₃ ) (refractive index 1.91, extinction coefficient 0), three Gadolinium oxide (Gd ₂ O ₃ ) (refractive index 1.93, extinction coefficient 0), lanthanum trioxide (La ₂ O ₃ ) (refractive index 1.95, extinction coefficient 0), praseodymium oxide (Pr ₆₎ O ₁₁₎ (refractive index 1.95, the number attenuation coefficient 0), hafnium dioxide _(HfO 2) (refractive index 1.99, extinction coefficient 0) trioxide neodymium _{(Nd 2 O} 3) _(refractive index 2.00 , Extinction coefficient 0), silicon monoxide (SiO) (refractive index 2.00, extinction coefficient 0. 03), tin dioxide (SnO ₂ ) (refractive index 2.00, extinction coefficient 0), zinc monoxide (ZnO) (refractive index 2.00, extinction coefficient 0), antimony trioxide (Sb ₂ O ₃ ) (Refractive index 2.04, extinction coefficient 0), indium trioxide (In ₂ O ₃ ) and tin dioxide (SnO ₂ ) mixture (ITO) (refractive index 2.05, extinction coefficient 0.01), Silicon mononitride (SiN) (refractive index 2.06, extinction coefficient 0), zirconium dioxide (ZrO ₂ ) (refractive index 2.06, extinction coefficient 0), tantalum pentoxide (Ta ₂ O ₅ ) (refractive index 2.14, extinction coefficient 0), cerium dioxide (CeO ₂ ) (refractive index 2.20, extinction coefficient 0), chromium trioxide (Cr ₂ O ₃ ) (refractive index 2.24, extinction coefficient 0. 07), niobium pentoxide (Nb ₂ O ₅ ) (refractive index 2.27, extinction coefficient 0), titanium dioxide (TiO ₂ ) (refractive index 2.32, extinction coefficient 0), zinc monosulfide (ZnS) (refractive index 2.35, extinction coefficient 0), silicon monoxide (SiC) (refractive index 2.66, Extinction coefficient 0), zinc selenide (ZnSe) (refractive index 2.69, extinction coefficient 0.02), antimony trisulfide (Sb ₂ S ₃ ) (refractive index 3.00, extinction coefficient 0), germanium (Ge) (refractive index 3.95, extinction coefficient 1.98), silicon (Si) (refractive index 4.08, extinction coefficient 0.04), or a mixture thereof. The chemical composition of these compounds may or may not match the stoichiometric composition.
In the materials of the high refractive index thin film layers 4 and 7, the refractive index and the extinction coefficient described in parentheses are values at a light wavelength of 550 nm.

  The materials of the high-refractive index thin film layer 4 and the high-refractive index thin film layer 7 shown in FIG. 1 may or may not be the same. The layer 4 and the high refractive index thin film layer 7 can be appropriately selected according to the purpose.

(Low refractive index thin film layer)
The low refractive index thin film layer 5 shown in FIG. 1 has a refractive index of less than 1.75 at a light wavelength of 550 nm. When the low refractive index thin film layer 5 is excellent in light transmittance, the low refractive index thin film layer 5 having an extinction coefficient in the visible light region of less than 0.01 is used.

Examples of the material for the low refractive index thin film layer 5 include titanium mononitride (TiN) (refractive index 1.25, extinction coefficient 2.10), thiolite (Na ₅ A ₁₃ F ₁₄ ) (refractive index 1.33, Extinction coefficient 0), sodium monofluoride (NaF) (refractive index 1.34, extinction coefficient 0), cryolite (Na ₃ AlF ₆ ) (refractive index 1.35, extinction coefficient 0), difluoride Magnesium (MgF ₂ ) (refractive index 1.38, extinction coefficient 0), lithium monofluoride (LiF) (refractive index 1.39, extinction coefficient 0), calcium difluoride (CaF ₂ ) (refractive index 1 .43, extinction coefficient 0), silicon dioxide (SiO ₂ ) (refractive index 1.46, extinction coefficient 0), strontium difluoride (SrF ₂ ) (refractive index 1.46, extinction coefficient 0), two barium fluoride _(BaF 2) (refractive index 1.48, the number attenuation coefficient 0), trifluoride Itte Biumu _(YbF 3) (refractive index 1.52, extinction coefficient 0), a nitride of tungsten and titanium _{(TiN x W} y) (refractive index 1.54, extinction coefficient 1.52), tetrafluoride thorium ( ThF ₄ ) (refractive index 1.56, extinction coefficient 0), hafnium tetrafluoride (HfF ₄ ) (refractive index 1.57, extinction coefficient 0), lanthanum trifluoride (LaF ₃ ) (refractive index 1. 58, extinction coefficient 0), neodymium trifluoride (NdF ₃ ) (refractive index 1.60, extinction coefficient 0), cerium trifluoride (CeF ₃ ) (refractive index 1.64, extinction coefficient 0), Aluminum trioxide (Al ₂ O ₃ ) (refractive index 1.67, extinction coefficient 0), magnesium monoxide (MgO) (refractive index 1.74, extinction coefficient 0), or a mixture thereof It is done. The chemical composition of these compounds may or may not match the stoichiometric composition.
In the material of the low refractive index thin film layer 5 described above, the refractive index and the extinction coefficient described in parentheses are values at a light wavelength of 550 nm.

(Pure metal thin film layer)
Examples of the material of the pure metal thin film layer 6 include silver (Ag) (refractive index 0.055, extinction coefficient 3.32), gold (Au) (refractive index 0.331, extinction coefficient 2.32), Copper (Cu) (refractive index 0.670, extinction coefficient 2.86), aluminum (Al) (refractive index 0.834, extinction coefficient 6.03), palladium (Pd) (refractive index 1.64, extinction coefficient) Extinction coefficient 3.85), nickel (Ni) (refractive index 1.87, extinction coefficient 3.32), rhodium (Rh) (refractive index 1.97, extinction coefficient 5.02), platinum (Pt) ( Refractive index 2.13, extinction coefficient 3.71), tantalum (Ta) (refractive index 2.48, extinction coefficient 1.83), titanium (Ti) (refractive index 2.54, extinction coefficient 3.34). ), Iron (Fe) (refractive index 2.89, extinction coefficient 3.35), chromium (Cr) (refractive index 3.12, extinction coefficient 4.42) Tungsten (W) (refractive index 3.24, extinction coefficient 2.49), molybdenum (Mo) (refractive index 3.79, extinction coefficient 3.51) or the like, or, mixtures thereof.
In the material of the pure metal thin film layer 6, the refractive index and the extinction coefficient described in parentheses are values at a light wavelength of 550 nm.
Pure metal thin film layer materials can also be classified for convenience as high refractive index thin film layer materials or low refractive index thin film layer materials depending on the refractive index, but when the material is pure metal, it is classified as a pure metal thin film layer material. To classify.

The high refractive index thin film layers 4 and 7, the low refractive index thin film layer 5 and the pure metal thin film layer 6 constituting the optical thin film layer 3 shown in FIG. 1 are formed by vapor deposition, sputtering, plasma CVD (Chemical Vapor Deposition). The film is preferably formed by a vacuum film formation method such as an ion plating method or an ion beam assist method.
When the optical thin film layer 3 is formed by a vacuum film forming method, it is possible to form a thin film that becomes the optical thin film layer 3 while maintaining the surface shape of the substrate 2. In the vacuum film forming method, the size of the thin film forming material to be deposited is atoms / molecules in the order of angstroms. For this reason, for example, even when the optical thin film layer 3 is formed on the base material 2 having fine unevenness of the order of micrometers, the surface of the base material 2 is uniform without filling the unevenness on the base material 2. A thin film to be the optical thin film layer 3 with a thickness of is deposited. Therefore, it becomes the optical thin film laminated body 1 which was excellent in the surface decorating property without the color unevenness holding the uneven | corrugated shape on the base material 2. FIG.

  An optical thin film laminate 1 shown in FIG. 1 is provided with an optical thin film layer 3 on a substrate 2, and the optical thin film layer 3 comprises high refractive index thin film layers 4 and 7, a low refractive index thin film layer 5, and a pure metal thin film. Since the light absorption layer which consists of at least 1 type selected from the layer 6 is provided, the outstanding light absorption function is obtained and it is possible to make the transmittance | permeability of visible light low.

  Further, the optical thin film laminate 1 shown in FIG. 1 has an extinction coefficient of 0.01 or more at a wavelength of 550 nm of the light absorption layer, and in addition, the high refractive index thin film layers 4 and 7 at a wavelength of 550 nm. When the refractive index is 1.75 or more and the refractive index at a wavelength of 550 nm of the low refractive index thin film layer 5 is less than 1.75, the high refractive index thin film layers 4 and 7 forming the optical thin film layer 3 are low. Since the difference in refractive index of the refractive index thin film layer 5 can be made larger, the reflection brightness and / or reflection saturation can be further increased.

  Moreover, since the optical thin film layered body 1 shown in FIG. 1 has the optical thin film layer 3 formed by a vacuum film forming method, a thin film that forms the optical thin film layer 3 with a uniform thickness on the surface of the substrate 2. As a result, the surface decoration without color unevenness is excellent.

In addition, the optical thin film laminated body of this invention is not limited to the example mentioned above.
For example, the light absorption layer constituting the present invention may be at least one selected from a high refractive index thin film layer, a low refractive index thin film layer, and a pure metal thin film layer. The number of layers constituting the film may be one layer or two or more layers, and the number of layers is not limited.
In addition, the optical thin film layer constituting the present invention only needs to have a light absorption layer, and may be composed of one layer that also serves as the light absorption layer, or two or more layers are laminated. There is no limit to the number of layers.

The optical thin film laminate of the present invention includes an automobile member, a vehicle member, a household appliance member, a mobile phone member, a portable game machine member, a personal computer member, a PDA member, an audio product member, a car navigation member, an office supplies member, a sport. It is preferably used as a decorative member for an article member, a miscellaneous goods member, a glasses / sunglass member, a camera member, an optical article member, a measuring instrument member or the like.
That is, by molding the optical thin film laminate of the present invention, decorative molded products that are the various decorative members described above are obtained.

More specifically, the optical thin film laminate of the present invention can be used by being bonded onto a display screen made of liquid crystal or the like provided in, for example, a mobile phone, a PDA, a smartphone, or a portable game machine. By providing the optical thin film laminate of the present invention on the screen of the display, for example, when the display is extinguished, the liquid crystal display screen is hidden by the light absorption function of the optical thin film laminate and the liquid crystal element cannot be seen. It can be set as the display which can visually recognize the image displayed on the screen of the liquid crystal display through the optical thin film laminated body.
Moreover, you may coat | cover the optical thin film laminated body of this invention not only on the screen of a display but the housing | casing which comprises the circumference | surroundings of a display. In this case, for example, when the display is turned off, the appearance texture of the display screen and the appearance texture of the housing can be approximated, and the display screen design and the housing design can be unified. it can. That is, it is possible to make the image appear on the screen of the display and be visible only when the display is lit.

  Furthermore, when the optical thin film laminate of the present invention is used as a decorating member for a casing portion of a device that transmits and receives radio waves such as a mobile phone, a television, a radio, and a car navigation, the base material constituting the optical thin film laminate It is preferable to use a dielectric material for the optical thin film layer. By using a dielectric material for the base material and / or optical thin film layer, attenuation and disturbance of antenna transmission / reception sensitivity due to reflection / scattering of radio waves can be avoided, and visible light transmittance is low, An optical thin film laminate having a metallic luster having a high reflection brightness and / or reflection saturation can be provided.

Examples of the present invention will be specifically described below.
[Example 1]
As shown below, a high refractive index thin film layer 4, a low refractive index thin film layer 5, a pure metal thin film layer 6, a high refractive index thin film layer on a colorless and transparent polyethylene terephthalate film having a thickness of 100 μm as the base material 2 The optical thin film layer 3 formed by sequentially laminating four layers 7 was formed to obtain the optical thin film laminate 1 shown in FIG.

First, titanium dioxide (TiO ₂ ) was deposited on the substrate 2 by a vacuum vapor deposition method using an electron beam to form a high refractive index thin film layer 4 having a physical film thickness of 95 nm.
Next, silicon dioxide (SiO ₂ ) was deposited on the high refractive index thin film layer 4 by a vacuum vapor deposition method using an electron beam to form a low refractive index thin film layer 5 having a physical film thickness of 85 nm.
Thereafter, nickel (Ni) was deposited on the low refractive index thin film layer 5 by a vacuum vapor deposition method using an electron beam to form a pure metal thin film layer 6 which is a light absorption layer having a physical film thickness of 8.5 nm. .
Subsequently, on the pure metal thin film layer 6, titanium dioxide (TiO ₂₎ is deposited by a vacuum deposition method using an electron beam, to form a high refractive index thin film layer 7 of the physical thickness 20 nm, the optical thin film layer 3 was completed to complete the optical thin film laminate 1 of Example 1 shown in FIG.

Thereafter, the reflection lightness and the reflection hue / saturation of the optical thin film laminate 1 thus obtained were measured. The measurement procedure is as follows.
First, the entire surface of the substrate 2 opposite to the side on which the optical thin film layer 3 of the optical thin film laminate 1 was formed was painted with a black paint so as not to cause unevenness. Then, the base material 2 painted with the black paint was held over light, and it was confirmed whether light leaked through the base material 2.
Then, the surface of the base material 2 that was not blacked (the surface on which the optical thin film layer 3 of the base material 2 was formed) was used as a measurement light source of a U-4000 type self-recording spectrophotometer (manufactured by Hitachi, Ltd.). It was installed. At this time, it was installed so that the measurement light was incident on the surface of the substrate 2 at an angle of 5 ° with respect to the vertical line on the surface of the substrate 2 on which the optical thin film layer 3 was formed.

Then, a photometer is installed in the direction of the light regularly reflected on the surface of the substrate 2 and at a position where the 2 ° field of view is obtained, and the spectral reflectance in the visible light region (380 to 780 nm) is measured. Tristimulus values X, Y, and Z defined in Z 8701 were determined. Tristimulus values X, Y, and Z were calculated at 5 nm intervals. Subsequently, using the obtained tristimulus values, the lightness L *, hue / saturation a *, and b * of the L * a * b * color system (CIELAB) defined in JIS Z 8729 are obtained for the D65 light source. It was.
As a result, as shown in Table 1, L * was 29.4, a * was 0.1, and b * was 0.0.

Next, the luminous average transmittance Y was measured.
First, the side on which the optical thin film layer 3 of the optical thin film laminate 1 was formed was placed toward the measurement light source of a U-4000 type self-recording spectrophotometer (manufactured by Hitachi, Ltd.). At this time, it was installed so that the measurement light was incident on the surface of the substrate 2 at an angle of 5 ° with respect to the vertical line on the surface of the substrate 2 on which the optical thin film layer 3 was formed.
Then, a photometer is installed in the direction of the light transmitted through the substrate 2 and at a position where the 2 ° field of view is set, and the spectral transmittance in the visible light region (380 to 780 nm) is measured, and is defined in JIS Z 8701. Tristimulus values X, Y, and Z were determined. Tristimulus values X, Y, and Z were calculated at 5 nm intervals.
As a result, as shown in Table 1, the luminous average transmittance Y for the D65 light source was 37.3%.

Furthermore, the absorption rate (%) was calculated | required using the formula shown below. In the formula shown below, the reflectance (%) is a value at a wavelength of 550 nm in the spectral reflectance measured in advance as shown above. The spectral reflectance used to determine the absorptance is determined by measuring the optical thickness of the optical thin film stack 1 without painting the surface of the base 2 opposite to the side on which the optical thin film layer 3 of the optical thin film stack 1 is formed. The side on which the thin film layer 3 was formed was installed facing the measurement light source of a U-4000 type self-recording spectrophotometer (manufactured by Hitachi, Ltd.). The transmittance (%) is a value at a wavelength of 550 nm in the spectral transmittance measured in advance as shown above.
Absorptivity (%) = 100% -Transmittance (%)-Reflectance (%)
As shown in Table 1, the absorptance of the optical thin film laminate 1 was 56.2%.

[Example 2]
As shown below, the optical thin film layer 3 shown in FIG. 2 is formed by forming an optical thin film layer 3 in which a pure metal thin film layer 6 is laminated on a colorless and transparent polyethylene terephthalate film having a thickness of 100 μm as the base material 2. Body 1 was obtained.

  That is, nickel (Ni) is deposited on the substrate 2 by a vacuum evaporation method using an electron beam to form a pure metal thin film layer 6 which is a light absorption layer having a physical film thickness of 7 nm, and the optical thin film layer 3 is formed. The optical thin film laminate 1 of Example 2 shown in FIG. 2 was completed.

Thereafter, the reflection brightness and the reflection hue / saturation of the optical thin film laminate 1 thus obtained were measured in the same manner as in Example 1. As a result, as shown in Table 1, L * was 55.8, a * was 0.5, and b * was 3.2.
Further, the luminous average transmittance Y was measured in the same manner as in Example 1. As a result, as shown in Table 1, the luminous average transmittance Y was 43.9%.
Further, the absorptance was determined in the same manner as in Example 1. As a result, as shown in Table 1, the absorptance of the optical thin film laminate 1 was 31.1%.

[Example 3]
As shown below, a pure metal thin film layer 6, a high refractive index thin film layer 4, a low refractive index thin film layer 5, and a high refractive index thin film layer are formed on a colorless and transparent polyethylene terephthalate film having a thickness of 100 μm as the base material 2. The optical thin film layer 3 formed by sequentially laminating the four layers 7 was formed to obtain the optical thin film laminate 1 shown in FIG.

First, nickel (Ni) was deposited on the base material 2 by a vacuum vapor deposition method using an electron beam to form a pure metal thin film layer 6 as a light absorption layer having a physical film thickness of 18.5 nm.
Subsequently, titanium dioxide (TiO ₂ ) was deposited on the pure metal thin film layer 6 by a vacuum evaporation method using an electron beam to form a high refractive index thin film layer 4 having a physical film thickness of 140 nm.
Next, silicon dioxide (SiO ₂ ) was deposited on the high refractive index thin film layer 4 by a vacuum vapor deposition method using an electron beam to form a low refractive index thin film layer 5 having a physical film thickness of 125 nm.
Thereafter, titanium dioxide (TiO ₂ ) is deposited on the low refractive index thin film layer 5 by a vacuum vapor deposition method using an electron beam to form a high refractive index thin film layer 7 having a physical film thickness of 60 nm. 3 was completed, and the optical thin film laminate 1 of Example 3 shown in FIG. 3 was completed.

Thereafter, the reflection brightness and the reflection hue / saturation of the optical thin film laminate 1 thus obtained were measured in the same manner as in Example 1. As a result, as shown in Table 1, L * was 70.7, a * was 42.0, and b * was −0.7.
Further, the luminous average transmittance Y was measured in the same manner as in Example 1. As a result, as shown in Table 1, the luminous average transmittance Y was 19.0%.
Further, the absorptance was determined in the same manner as in Example 1. As a result, as shown in Table 1, the absorptance of the optical thin film laminate 1 was 41.6%.

[Example 4]
As shown below, three layers of a high refractive index thin film layer 4, a low refractive index thin film layer 5, and a high refractive index thin film layer 7 are sequentially formed on a colorless and transparent polyethylene terephthalate film having a thickness of 100 μm as the base material 2. A laminated optical thin film layer 3 was formed to obtain an optical thin film laminate 1 shown in FIG.

First, titanium dioxide (TiO ₂ ) was deposited on the substrate 2 by a vacuum vapor deposition method using an electron beam to form a high refractive index thin film layer 4 having a physical film thickness of 150 nm.
Next, titanium mononitride (TiN) is deposited on the high refractive index thin film layer 4 by a vacuum vapor deposition method using an electron beam to form a low refractive index thin film layer 5 which is a light absorption layer having a physical film thickness of 70 nm. did.
Thereafter, titanium dioxide (TiO ₂ ) is deposited on the low refractive index thin film layer 5 by a vacuum vapor deposition method using an electron beam to form a high refractive index thin film layer 7 having a physical film thickness of 145 nm. 3 was completed, and the optical thin film laminate 1 of Example 4 shown in FIG. 4 was completed.

Thereafter, the reflection brightness and the reflection hue / saturation of the optical thin film laminate 1 thus obtained were measured in the same manner as in Example 1. As a result, as shown in Table 1, L * was 60.8, a * was 44.0, and b * was 3.7.
Further, the luminous average transmittance Y was measured in the same manner as in Example 1. As a result, as shown in Table 1, the luminous average transmittance Y was 6.9%.
Further, the absorptance was determined in the same manner as in Example 1. As a result, as shown in Table 1, the absorption rate of the optical thin film laminate 1 was 69.1%.

[Example 5]
As shown below, a pure metal thin film layer 6, a high refractive index thin film layer 4, a low refractive index thin film layer 5, and a high refractive index thin film layer are formed on a colorless and transparent polyethylene terephthalate film having a thickness of 100 μm as the base material 2. The optical thin film layer 3 formed by sequentially laminating the four layers 7 was formed to obtain the optical thin film laminate 1 shown in FIG.

First, on the base material 2, aluminum (Al) was deposited by the vacuum evaporation method using an electron beam, and the pure metal thin film layer 6 which is a light absorption layer with a physical film thickness of 8 nm was formed.
Subsequently, titanium dioxide (TiO ₂ ) was deposited on the pure metal thin film layer 6 by a vacuum vapor deposition method using an electron beam to form a high refractive index thin film layer 4 having a physical film thickness of 90 nm.
Next, silicon dioxide (SiO ₂ ) was deposited on the high refractive index thin film layer 4 by a vacuum vapor deposition method using an electron beam to form a low refractive index thin film layer 5 having a physical film thickness of 60 nm.
Thereafter, titanium dioxide (TiO ₂ ) is deposited on the low refractive index thin film layer 5 by a vacuum vapor deposition method using an electron beam to form a high refractive index thin film layer 7 having a physical film thickness of 30 nm. 3 was completed, and the optical thin film laminate 1 of Example 5 shown in FIG. 3 was completed.

Thereafter, the reflection brightness and the reflection hue / saturation of the optical thin film laminate 1 thus obtained were measured in the same manner as in Example 1. As a result, as shown in Table 1, L * was 63.6, a * was -2.9, and b * was -42.3.
Further, the luminous average transmittance Y was measured in the same manner as in Example 1. As a result, as shown in Table 1, the luminous average transmittance Y was 38.4%.
Further, the absorptance was determined in the same manner as in Example 1. As a result, as shown in Table 1, the absorptance of the optical thin film laminate 1 was 27.9%.

[Example 6]
As shown below, a pure metal thin film layer 6, a high refractive index thin film layer 4, a low refractive index thin film layer 5, and a high refractive index thin film layer are formed on a colorless and transparent polyethylene terephthalate film having a thickness of 100 μm as the base material 2. The optical thin film layer 3 formed by sequentially laminating the four layers 7 was formed to obtain the optical thin film laminate 1 shown in FIG.

First, chromium (Cr) was deposited on the base material 2 by a vacuum vapor deposition method using an electron beam to form a pure metal thin film layer 6 as a light absorption layer having a physical thickness of 9 nm.
Subsequently, zinc monosulfide (ZnS) was deposited on the pure metal thin film layer 6 by a vacuum evaporation method using an electron beam to form a high refractive index thin film layer 4 having a physical film thickness of 65 nm.
Next, magnesium difluoride (MgF ₂ ) was deposited on the high refractive index thin film layer 4 by a vacuum evaporation method using an electron beam to form a low refractive index thin film layer 5 having a physical film thickness of 85 nm.
Thereafter, zinc monosulfide (ZnS) is deposited on the low refractive index thin film layer 5 by a vacuum vapor deposition method using an electron beam to form a high refractive index thin film layer 7 having a physical film thickness of 50 nm. 3 was completed, and the optical thin film laminate 1 of Example 5 shown in FIG. 3 was completed.

Thereafter, the reflection brightness and the reflection hue / saturation of the optical thin film laminate 1 thus obtained were measured in the same manner as in Example 1. As a result, as shown in Table 1, L * was 65.0, a * was -2.1, and b * was -40.9.
Further, the luminous average transmittance Y was measured in the same manner as in Example 1. As a result, as shown in Table 1, the luminous average transmittance Y was 22.8%.
Further, the absorptance was determined in the same manner as in Example 1. As a result, as shown in Table 1, the absorptance of the optical thin film laminate 1 was 44.8%.

[Example 7]
As shown below, a low-refractive-index thin film layer 5, a high-refractive-index thin-film layer 4, a low-refractive-index thin-film layer 8, and a high-refractive-index thin film are formed on a colorless and transparent polyethylene terephthalate film having a thickness of 100 μm as the substrate 2. The optical thin film layer 3 in which the four layers 7 were sequentially laminated was formed to obtain the optical thin film laminate 1 shown in FIG.

First, titanium mononitride (TiN) was deposited on the base material 2 by a vacuum vapor deposition method using an electron beam to form a low refractive index thin film layer 5 which is a light absorption layer having a physical film thickness of 30 nm.
Subsequently, titanium dioxide (TiO ₂ ) was deposited on the low refractive index thin film layer 5 by a vacuum vapor deposition method using an electron beam to form a high refractive index thin film layer 4 having a physical film thickness of 95 nm.
Next, titanium mononitride (TiN) is deposited on the high refractive index thin film layer 4 by a vacuum vapor deposition method using an electron beam to form a low refractive index thin film layer 8 which is a light absorption layer having a physical film thickness of 20 nm. did.
Then, on the low refractive index thin film layer 8 of titanium dioxide (TiO ₂₎ is deposited by a vacuum deposition method using an electron beam, to form a high refractive index thin film layer 7 of a physical thickness of 90 nm, the optical thin film layer 3 was completed to complete the optical thin film laminate 1 of Example 5 shown in FIG.

Thereafter, the reflection brightness and the reflection hue / saturation of the optical thin film laminate 1 thus obtained were measured in the same manner as in Example 1. As a result, as shown in Table 1, L * was 71.7, a * was -33.3, and b * was -1.4.
Further, the luminous average transmittance Y was measured in the same manner as in Example 1. As a result, as shown in Table 1, the luminous average transmittance Y was 16.7%.
Further, the absorptance was determined in the same manner as in Example 1. As a result, as shown in Table 1, the absorptance of the optical thin film laminate 1 was 34.0%.

[Example 8]
As shown below, a pure metal thin film layer 6, a high refractive index thin film layer 4, a low refractive index thin film layer 5, and a high refractive index thin film layer are formed on a colorless and transparent polyethylene terephthalate film having a thickness of 100 μm as the base material 2. The optical thin film layer 3 formed by sequentially laminating the four layers 7 was formed to obtain the optical thin film laminate 1 shown in FIG.

First, nickel (Ni) was deposited on the base material 2 by a vacuum vapor deposition method using an electron beam to form a pure metal thin film layer 6 as a light absorption layer having a physical film thickness of 8.5 nm.
Subsequently, titanium dioxide (TiO ₂ ) was deposited on the pure metal thin film layer 6 by a vacuum vapor deposition method using an electron beam to form a high refractive index thin film layer 4 having a physical film thickness of 130 nm.
Next, silicon dioxide (SiO ₂ ) was deposited on the high refractive index thin film layer 4 by a vacuum vapor deposition method using an electron beam to form a low refractive index thin film layer 5 having a physical film thickness of 80 nm.
Thereafter, titanium dioxide (TiO ₂ ) is deposited on the low refractive index thin film layer 5 by a vacuum vapor deposition method using an electron beam to form a high refractive index thin film layer 7 having a physical film thickness of 80 nm. 3 was completed, and the optical thin film laminate 1 of Example 5 shown in FIG. 3 was completed.

Thereafter, the reflection brightness and the reflection hue / saturation of the optical thin film laminate 1 thus obtained were measured in the same manner as in Example 1. As a result, as shown in Table 1, L * was 76.3, a * was -0.6, and b * was 50.8.
Further, the luminous average transmittance Y was measured in the same manner as in Example 1. As a result, as shown in Table 1, the luminous average transmittance Y was 26.4%.
Further, the absorptance was determined in the same manner as in Example 1. As a result, as shown in Table 1, the absorptance of the optical thin film laminate 1 was 21.5%.

It is sectional drawing which showed an example of the optical thin film laminated body of this invention. It is sectional drawing which showed another example of the optical thin film laminated body of this invention. It is sectional drawing which showed another example of the optical thin film laminated body of this invention. It is sectional drawing which showed another example of the optical thin film laminated body of this invention. It is sectional drawing which showed another example of the optical thin film laminated body of this invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Optical thin film laminated body, 2 ... Base material, 3 ... Optical thin film layer, 4 ... High refractive index thin film layer, 5 ... Low refractive index thin film layer, 6 ... Pure metal thin film layer, 7 ... High refractive index thin film layer, 8 ... low refractive index thin film layer.

Claims (6)

An optical thin film layer is provided on the substrate,
An optical thin film laminate, wherein the optical thin film layer includes a light absorption layer made of at least one selected from a high refractive index thin film layer, a low refractive index thin film layer, and a pure metal thin film layer.   2. The optical thin film laminate according to claim 1, wherein the light absorption layer has an extinction coefficient of 0.01 or more at a wavelength of 550 nm. The high refractive index thin film layer has a refractive index of 1.75 or more at a wavelength of 550 nm,
The optical thin film laminate according to claim 1 or 2, wherein the low refractive index thin film layer has a refractive index of less than 1.75 at a wavelength of 550 nm.   The optical thin film laminate according to any one of claims 1 to 3, wherein the optical thin film layer is formed by a vacuum film forming method.   A decorative member comprising the optical thin film laminate according to any one of claims 1 to 4.   A decorative molded product obtained by molding the optical thin film laminate according to any one of claims 1 to 4.

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