WO2019199059A1 - Decorative member - Google Patents

Abstract

The present application relates to a decorative member comprising a light reflection layer and a light absorption layer provided on the light reflection layer, wherein the light absorption layer includes an area in which the thickness (t(x)) of the light absorption layer gradually increases in any one direction (x) that is vertical to the thickness direction (z) of the light absorption layer.

Description

Decoration

This application is subject to the Korean Patent Application No. 10-2018-0041562 filed with the Korean Patent Office on April 10, 2018 and the Korean Patent Application No. 10-2018-0100613 filed with the Korean Patent Office on August 27, 2018. Claiming benefit, the entire contents of which are incorporated herein.

The present application relates to a decorative member.

In cosmetic containers, various mobile devices, and home appliances, product design, for example, color, shape, and pattern play a big role in adding value to customers. Product preference and price also depend on the design.

For example, in the case of a cosmetic compact container, various colors and colors are implemented in various ways and applied to a product. There is a method of giving a color to the case material itself and a method of attaching a decor film that implements color and shape to the case material to give a design.

The expression of color in the existing deco film was intended to be implemented through printing, deposition, and the like. When expressing heterogeneous colors on a single surface, it should be printed two or more times, and when it is desired to apply a variety of colors to a three-dimensional pattern, it is practically difficult to implement. In addition, the existing deco film is fixed in color depending on the viewing angle, even if there is a slight change is limited to the degree of difference in color.

[Preceding technical literature]

[Patent Documents]

Patent Document 1: Republic of Korea Patent Publication No. 10-2010-0135837

The present application provides a decorative member.

The present application includes a light reflecting layer and a light absorbing layer provided on the light reflecting layer, wherein the light absorbing layer has a thickness t of the light absorbing layer in one direction (x) perpendicular to the thickness direction (z) of the light absorbing layer. It provides a decorative member comprising an area where x)) increases.

The decorative member according to the exemplary embodiment of the present specification includes a region in which thickness is increased, so that the appearing color has a gradation effect.

In addition, the decorative member according to an exemplary embodiment of the present specification by gradually changing the thickness of the light absorbing layer, the color appearing has a gradation effect.

In addition, light is absorbed by the incident path and the reflection path when the external light is incident through the light absorption layer, and the external light is reflected on the surface of the light absorption layer and the surface of the light reflection layer. The constructive and destructive interference phenomena occur between the reflected light and the reflected light on the surface of the light reflection layer. Specific colors may be expressed through the phenomenon of light absorption, constructive interference, and destructive interference in the incident path and the reflective path as described above. Therefore, a specific color may be realized according to the reflectance spectrum according to the material of the light reflection layer and the composition of the light absorption layer. In addition, since the color to be expressed has a thickness dependency, it is possible to change the color according to the thickness even when having the same material configuration.

1, 2 and 5 to 12 show a decorative member according to an embodiment of the present disclosure.

3 shows a method of distinguishing a light absorption layer and a light reflection layer.

4 illustrates the principle of interference of light in the light absorption layer and the light reflection layer.

Hereinafter, this specification is demonstrated in detail.

In this specification, the term “or” means “and / or” when it includes any or all of the listed items, unless otherwise defined.

In the present specification, the term "layer" means covering 70% or more of the area in which the layer exists. It means preferably covering at least 75%, more preferably at least 80%.

In this specification, the "thickness" of a layer means the shortest distance from the lower surface of the layer to the upper surface.

In the present specification, "light absorbing layer" and "light reflecting layer" is a layer having relative properties to each other, the light absorbing layer means a layer having a higher light absorption than the light reflecting layer, the light reflecting layer is in the light absorbing layer Compared to this may mean a layer having a high light reflectivity.

The light absorption layer and the light reflection layer may each be composed of a single layer, or may be composed of two or more layers.

In the present specification, the light absorption layer and the light reflection layer are named according to their function. For light having a specific wavelength, a layer that reflects light relatively much may be represented by a light reflection layer, and a layer that reflects light relatively little may be represented by a light absorption layer.

In the present specification, "color expression layer" means a configuration including a light absorption layer and a light reflection layer.

2 illustrates a laminated structure of a decoration member according to an exemplary embodiment of the present specification. 2 shows a decorative member further comprising a base 101. 2 shows that the substrate 101 is provided on the opposite side of the surface of the light reflection layer 201 opposite to the light absorption layer 301, but between the light reflection layer 201 and the light absorption layer 301; Alternatively, the light absorbing layer 301 may be provided on an opposite side of the surface of the light absorbing layer 301 facing the light reflecting layer 201, and the description may be omitted.

3, the light absorption layer and the light reflection layer will be described. In the decorative member of FIG. 3, each layer is laminated in the order of L _i-1 layer, L _i layer, and L _{i + 1} layer based on the direction of light input, and between the L _i-1 layer and the L _i layer. Interface I _i is located at, and interface I _{i + 1} is located between the L _i layer and the L _{i + 1} layer.

When irradiating light having a specific wavelength in a direction perpendicular to each layer so that thin film interference does not occur, the reflectance at the interface Ii may be expressed by Equation 1 below.

[Equation 1]

In Equation 1, n _i (λ) denotes a refractive index according to the wavelength λ of the i-th layer, and k _i (λ) denotes an extinction coefficient according to the wavelength λ of the i-th layer. Means. The extinction coefficient is a measure that can define how strongly the target material absorbs light at a particular wavelength, as defined above.

By applying Equation 1 above, when the sum of reflectances for each wavelength at the interface I _i calculated at each wavelength is R _i , R _i is represented by Equation 2 below.

[Equation 2]

Hereinafter, the decorative member including the light reflection layer and the light absorption layer described above will be described.

An exemplary embodiment of the present specification includes a light reflecting layer and a light absorbing layer provided on the light reflecting layer, wherein the light absorbing layer is formed in one direction (x) perpendicular to the thickness direction (z) of the light absorbing layer. A decorative member is provided that includes an area of increasing thickness t (x).

The decorative member according to the exemplary embodiment of the present specification includes an area in which the thickness of the light absorbing layer increases, and thus, the gradation effect according to the interference phenomenon of light may be more variously represented. In addition, since the color gradually changes with the change in the thickness of the light absorbing layer, and the color change does not change rapidly, the viewer who sees the decorative member can feel the natural color change. 1 illustrates an example of a decorative member. The decorative member provided with the light absorption layer which gradually increases in thickness on the light reflection layer was shown. Referring to FIG. 1, a gradation light absorbing layer in which the thickness of the light absorbing layer gradually increases from point A to point H may be identified.

In the present specification, the thickness direction z of the light absorbing layer may be a normal direction of a surface of the light absorbing layer that faces the light reflecting layer.

In the present specification, any one direction x perpendicular to the thickness direction z of the light absorbing layer may mean any one direction on a surface of the light absorbing layer that faces the light reflecting layer. Alternatively, the light absorbing layer may be a direction parallel to a length direction of a width having the longest length of the light absorbing layer, in one direction on a surface of the light absorbing layer that faces the light reflecting layer.

The thickness of the light absorption layer may be adjusted by changing the deposition rate of the light absorption layer material deposited according to each region. For example, the S1 region of FIG. 1 may have a deposition rate of 0% to 10%, and the S7 region may have an average deposition rate of 80% to 90%.

The thickness of the region where the thickness t (x) of the light absorbing layer is gradually increased may be achieved by adjusting the distance between the deposition material T and the target M to be deposited. For example, as shown in FIG. 12, since the S7 region of the light reflection layer is close to the deposition material, the light absorption layer of the S7 region is formed thick, and the S1 region of the light reflection layer is far from the deposition material and thus the light absorption layer of the S1 region. Is formed thin.

In one embodiment of the present specification, a region in which the thickness t (x) of the light absorbing layer is increased is a region in which the thickness of the light absorbing layer is gradually increased; A region in which the thickness of the light absorption layer continuously increases; And at least one of regions where the thickness of the light absorbing layer is discontinuously increased.

In the present specification, the region where the thickness of the light absorbing layer gradually increases includes a section in the thickness direction of the light absorbing layer including a point where the thickness of the light absorbing layer is the smallest and a point where the thickness of the light absorbing layer is the largest. It means that the thickness of the light absorbing layer increases along the direction of the point where the thickness of the light absorbing layer is the smallest of the thickness of the light absorbing layer.

In one embodiment of the present specification, the light absorbing layer includes one or more regions where the thickness gradually increases. 5 illustrates a structure in which the thickness of the light absorption layer 301 is gradually increased.

In an exemplary embodiment of the present specification, the light absorbing layer includes at least one region having an inclined surface having an inclination angle greater than 0 degrees and less than 90 degrees, and at least one or more of the areas having the inclined surface have a progressive thickness of the light absorbing layer. Has an increasing structure. 5 illustrates a structure of a light absorption layer including a region having an inclined surface at an upper surface thereof. In the region G and H of FIG. 5, the upper surface of the light absorption layer has an inclined surface, and the thickness of the light absorption layer gradually increases.

The region in which the thickness of the light absorbing layer continuously increases means a region including only the region in which the thickness increases toward one direction x perpendicular to the thickness direction z of the light absorbing layer.

The region in which the thickness of the light absorbing layer is discontinuously increased means a region including a region in which the thickness does not increase toward one direction x perpendicular to the thickness direction z of the light absorbing layer.

In an exemplary embodiment of the present specification, the thickness t (x) of the light absorption layer may be 10 nm or more and 300 nm or less, 10 nm or more and 200 nm or less, preferably 10 nm or more and 150 nm or less.

In one embodiment of the present specification, the value calculated by the following formula A may be 0.01 or more and 2 or less, 0.05 or more and 1.5 or less, preferably 0.1 or more and 1.2 or less.

Equation A

In Equation A, t0 is a minimum thickness of a region where the thickness t (x) of the light absorbing layer is increased, and t1 is a maximum of a region where the thickness t (x) of the light absorbing layer is increased. Thickness. When satisfying the numerical range, the color appearing as the thickness change of the light absorbing layer appears with a gradation effect.

In one embodiment of the present specification, the value calculated by the following equation (B) is 0.1 or more and 5 or less, 0.2 or more and 4 or less, or 0.5 or more and 3.5 or less.

Equation B

In Equation B, h0 is the minimum value of h *, and h1 is the maximum value of h *, when the h * value of the Lch coordinate at each point in one direction (x) of the light absorption layer is measured and displayed in a graph. to be. When satisfying the numerical range, the color appearing as the thickness change of the light absorbing layer appears with a gradation effect.

In one embodiment of the present specification, the light absorbing layer may be a single layer or a multilayer of two or more layers.

The light absorption layer may be made of a material having an extinction coefficient k at a wavelength of 400 nm, preferably 380 to 780 nm, that is, a material having an extinction coefficient greater than 0 and 4 or less, preferably 0.01 to 4.

In one embodiment of the present specification, the light absorption layer is indium (In), titanium (Ti), tin (Sn), silicon (Si), germanium (Ge), aluminum (Al), copper (Cu), nickel ( Ni), vanadium (V), tungsten (W), tantalum (Ta), molybdenum (Mo), neodymium (Nb), iron (Fe), chromium (Cr), cobalt (Co), gold (Au) and silver ( Ag) one or two or more materials selected from Ag, oxides thereof; Nitrides thereof; Oxynitrides thereof; It may also include one or two or more materials of carbon and carbon composites.

In one embodiment of the present specification, the light absorption layer is indium (In), titanium (Ti), tin (Sn), silicon (Si), germanium (Ge), aluminum (Al), copper (Cu), nickel ( Ni), vanadium (V), tungsten (W), tantalum (Ta), molybdenum (Mo), neodymium (Nb), iron (Fe), chromium (Cr), cobalt (Co), gold (Au) and silver ( Ag) one or two or more materials selected from Ag or oxides thereof; Nitrides thereof; Or a single layer or multiple layers comprising oxynitride thereof. As a specific example, the light absorption layer includes one or two or more selected from copper oxide, copper nitride, copper oxynitride, aluminum oxide, aluminum nitride, aluminum oxynitride, and molybdenum titanium oxynitride.

In one embodiment of the present specification, the light absorbing layer includes silicon (Si) or germanium (Ge).

In one embodiment of the present specification, the light absorption layer made of silicon (Si) or germanium (Ge) has a refractive index (n) of 0 to 8, 0 to 7 at a wavelength of 400nm, the extinction coefficient (k) is More than 0 and 4 or less, preferably 0.01 to 4, and may be 0.01 to 3 or 0.01 to 1.

In one embodiment of the present specification, the light absorption layer includes one or two or more selected from copper oxide, copper nitride, copper oxynitride, aluminum oxide, aluminum nitride, aluminum oxynitride, and molybdenum titanium oxynitride. In this case, the light absorption layer may have a refractive index n of 1 to 3, for example, 2 to 2.5 at a wavelength of 400 nm, and an extinction coefficient k of greater than 0 and 4 or less, preferably 0.01 to 2.5, preferably 0.2 to 2.5. , More preferably, 0.2 to 0.6.

In one embodiment of the present specification, the light absorption layer is AlOxNy (x> 0, y> 0).

In one embodiment of the present specification, the light absorption layer may be AlOxNy (0 ≦ x ≦ 1.5, 0 ≦ y ≦ 1).

In an exemplary embodiment of the present specification, the light absorption layer is AlOxNy (x> 0, y> 0), and the number of each atom satisfies the following equation with respect to 100% of the total atoms.

In one embodiment of the present specification, the light absorption layer may be made of a material having an extinction coefficient (k) at a wavelength of 400 nm, preferably 380 to 780 nm, for example, the light absorption layer / light reflection layer is CuO / Cu, CuON / Cu, CuON / Al, AlON / Al, AlN / Al / AlON / Cu, AlN / Cu or the like.

According to an exemplary embodiment, the difference in thickness of each region of the light absorption layer is 2 to 200 nm, and may be determined according to a desired color difference.

In one embodiment of the present specification, the light absorption layer has a refractive index (n) of 0 to 8 at a wavelength of 400nm, it may be 0 to 7, may be 0.01 to 3, may be 2 to 2.5. . The refractive index n may be calculated as sin θa / sin θb (θa is the angle of light incident on the surface of the light absorption layer, and θb is the angle of refraction of light inside the light absorption layer).

In one embodiment of the present specification, the light absorption layer has a refractive index n of 0 to 8 at a wavelength of 380 to 780 nm, preferably 0 to 7, may be 0.01 to 3, 2 to 2.5 days Can be.

In one embodiment of the present specification, the light absorption layer has a extinction coefficient k at a wavelength of 400 nm greater than 0 and 4 or less, preferably 0.01 to 4, 0.01 to 3.5, may be 0.01 to 3, , 0.1 to 1. The extinction coefficient (k) is -λ / 4πI (dI / dx) (wherein the path unit length (dx) in the light absorption layer, for example, the reduction fraction dI / I of light intensity per meter, multiplied by λ / 4π, Where λ is the wavelength of light.

In one embodiment of the present specification, the light absorption layer has a extinction coefficient k in the wavelength range of 380 nm to 780 nm, greater than 0 and 4 or less, preferably 0.01 to 4, 0.01 to 3.5, 0.01 to 3.5 3, and may be 0.1 to 1. Since the extinction coefficient k is in the above range in the entire visible light wavelength range of 400 nm, preferably 380 nm to 780 nm, it may serve as a light absorbing layer within the visible light range.

As described above, the principle of expressing the color of the light absorbing layer having a specific extinction coefficient and refractive index and the principle of color expression of a decorative member expressing color by adding a dye to a conventional substrate are different. For example, when using a method of absorbing light by adding a dye to the resin, and using a material having an extinction coefficient as described above, the spectrum of absorbing light is different. When dye is added to the resin to absorb light, the absorption wavelength band is fixed, and only a phenomenon in which the amount of absorption changes with a change in coating thickness occurs. In addition, in order to obtain a desired light absorption amount, a thickness change of at least several micrometers or more is required to adjust the light absorption amount. On the other hand, in a material having an extinction coefficient, even if the thickness varies on the scale of several or tens of nanometers, the wavelength band of absorbing light changes.

In addition, when a dye is added to the conventional resin, only a specific color by the dye is expressed, and thus various colors cannot be exhibited. On the other hand, the light absorption layer of the present invention by using a specific material rather than a resin, there is an advantage that can be displayed in a variety of colors by the interference phenomenon of light without the addition of a dye.

According to the above embodiments, the light absorption layer absorbs light at the incident path and the reflection path of the light, and the light is reflected at the surface of the light absorbing layer and at the interface between the light absorbing layer and the light reflecting layer, respectively, so that the two reflected light beams reinforce or cancel each other. Will be

In the present specification, the light reflected from the surface of the light absorbing layer may be represented by the surface reflected light, the light reflected from the interface between the light absorbing layer and the light reflecting layer. Figure 4 shows a schematic diagram of such a principle of action. Although the structure in which the base material 101 is provided in the light reflection layer 201 side in FIG. 4 is illustrated, it is not limited to such a structure, The position of the base material 101 may be arrange | positioned in another position.

In one embodiment of the present specification, the light reflecting layer is not particularly limited as long as it is a material capable of reflecting light, but the light reflectance may be determined according to the material, for example, color is easily implemented at 50% or more. Light reflectance can be measured using an ellipsometer.

In one embodiment of the present specification, the light reflection layer may be a metal layer, a metal oxide layer, a metal nitride layer, a metal oxynitride layer, or an inorganic layer. The light reflection layer may be composed of a single layer, or may be composed of two or more multilayers.

In one embodiment of the present specification, the light reflection layer is indium (In), titanium (Ti), tin (Sn), silicon (Si), germanium (Ge), aluminum (Al), copper (Cu), nickel ( Ni), vanadium (V), tungsten (W), tantalum (Ta), molybdenum (Mo), neodymium (Nb), iron (Fe), chromium (Cr), cobalt (Co), gold (Au) and silver ( One or two or more materials selected from Ag); Oxides thereof; Nitrides thereof; Oxynitrides thereof; carbon; And one or two or more materials selected from the group consisting of carbon composites.

In one embodiment of the present specification, the light reflection layer may include two or more alloys selected from the above materials, oxides, nitrides or oxynitrides thereof.

In one embodiment of the present specification, the light reflection layer may be manufactured by using an ink including carbon or a carbon composite to implement a high resistance reflective layer. Carbon or carbon composites include carbon black and CNT.

In one embodiment of the present specification, the ink including the carbon or carbon composite material may include the above-described material or an oxide, nitride, or oxynitride thereof, for example, indium (In), titanium (Ti), and tin (Sn). ), Silicon (Si), germanium (Ge). Aluminum (Al), Copper (Cu), Nickel (Ni), Vanadium (V), Tungsten (W), Tantalum (Ta), Molybdenum (Mo), Neodymium (Nb), Iron (Fe), Chromium (Cr), One or two or more oxides selected from cobalt (Co), gold (Au), and silver (Ag) may be included. After printing the ink containing the carbon or carbon composite, a curing process may be further performed.

In the exemplary embodiment of the present specification, when the light reflection layer includes two or more kinds of materials, two or more kinds of materials may be formed by one process, for example, deposition or printing. A method of first forming a layer and then further forming a layer thereon with one or more materials can be used. For example, after indium or tin is deposited to form a layer, the ink containing carbon may be printed and cured to form a light reflection layer. The ink may further include an oxide such as titanium oxide and silicon oxide.

In one embodiment of the present specification, the thickness of the light reflection layer may be determined according to a desired color in the final structure, for example, 1 nm or more, preferably 25 nm or more, such as 50 nm or more, preferably 70 nm or more.

(materials)

In one embodiment of the present specification, the decorative member is an opposite surface of the surface facing the light absorbing layer of the light reflection layer; Between the light reflection layer and the light absorption layer; Or a substrate provided on an opposite side of the surface of the light absorption layer that faces the light reflection layer. For example, an opposite side of the surface of the light reflection layer 201 that faces the light absorption layer 301 (Fig. 6 (a)); Alternatively, the substrate may be provided on an opposite surface (FIG. 6B) of the light absorption layer 301 opposite to the light reflection layer 201.

In one embodiment of the present specification, the substrate may include a plastic injection molding or glass substrate for a cosmetic container. More specifically, the plastic injection molding is polypropylene (PP), polystyrene (PS), polyvinylacetate (PVAc), polyacrylate (polyacrylate), polyethylene terephthalate (PET), polyvinyl chloride (PVC), polymethyl meta At least one of methacrylate (PMMA), ethylene-vinyl acetate copolymer (EVA), polycarbonate (PC), polyamide, and styrene-Acrylonitrile copolymer (SAN) But it is not limited thereto.

In addition, the plastic injection molding may be a plastic injection molding in the form of a flat plate without bending (a specific pattern), or may be a plastic injection molding having a bending (specific pattern).

The plastic injection molding can be produced by a plastic molding method. The plastic molding methods include compression molding, injection molding, air blow molding, thermoforming, hot melt molding, foam molding, roll molding reinforced plastic molding, and the like. In the case of the compression molding, a molding method is performed by putting a material into a mold and heating and applying pressure. This is the oldest molding method and can be mainly used for molding a thermosetting resin such as a phenol resin. The injection molding is a molding method which pushes the plastic melt into a transporter and fills the mold through a nozzle. The injection molding may be performed by molding both a thermoplastic resin and a thermosetting resin, and may be said to be the most commonly used molding method. SAN is currently used as a cosmetic case. The air blow molding is a method of molding a product by inserting a plastic parison in the center of the mold and injecting air, and the manufacturing method of the product is very fast by forming a plastic bottle or a small container.

In one embodiment of the present specification, the glass substrate may use a glass having a transmittance of 80% or more.

In one embodiment of the present specification, the thickness of the substrate may be selected as needed, for example, may have a range of 50 to 200㎛.

In one embodiment of the present specification, the decoration member may be manufactured by forming a light reflection layer on the substrate, and a light absorption layer provided on the light reflection layer. More specifically, the decorative member may sequentially form a light absorption layer and a light reflection layer on the substrate using a deposition process, and the like, and sequentially form the light reflection layer and the light absorption layer on the substrate using a deposition process or the like. But it is not limited thereto.

(Color film)

In one embodiment of the present specification, the opposite surface of the surface of the light reflection layer facing the light absorbing layer; Between the light reflection layer and the light absorption layer; Or a color film provided on a surface opposite to a surface of the light absorption layer that faces the light reflection layer. The color film may serve as a substrate. For example, it can be used as a color film by adding dyes or pigments to those that can be used as substrates.

In one embodiment of the present specification, the color film is L * a * b on the color coordinates CIE L * a * b * of the color development layer when the color film is present as compared with the case where the color film is not provided. If color difference (DELTA) E ^* ab which is distance in space of ^* is made to exceed 1, it will not specifically limit.

The color can be represented by CIE L * a * b *, and the color difference can be defined using a distance (ΔE ^* ab) in L * a * b * space. Specifically, in the range of 0 <ΔE ^* ab <1, the observer cannot recognize the color difference (Refer to Machine Graphics and Vision 20 (4): 383-411). Therefore, in the present specification, the color difference according to the addition of the color film may be defined as ΔE ^* ab> 1.

In one embodiment of the present specification, the decorative member has a dichroism of ΔE * ab> 1.

FIG. 7 illustrates a decorative member including a color film, and a structure in which a light reflection layer 201, a light absorption layer 301, and a color film 401 are sequentially stacked in FIG. 7A. b) a structure in which the light reflection layer 201, the color film 401 and the light absorption layer 301 are sequentially stacked, and the color film 401, the light reflection layer 201, and the light absorption layer in FIG. The structure in which 301 is sequentially stacked is illustrated.

In one embodiment of the present specification, the substrate is provided on an opposite side of the surface of the light reflection layer that faces the light absorbing layer, and the color film is located on the opposite side of the surface of the light reflection layer that faces the light absorbing layer. When the color film is between the substrate and the light reflection layer; Or it may be provided on the opposite side of the surface facing the light reflection layer of the substrate. As another example, when the substrate is provided on the opposite side of the surface of the light absorbing layer opposite to the light reflecting layer, and the color film is located on the opposite side of the surface of the light absorbing layer opposite to the light reflecting layer, The color film is between the substrate and the light absorption layer; Or it may be provided on the opposite side of the surface facing the light absorbing layer of the substrate.

In one embodiment of the present specification, the substrate is provided on an opposite surface of the light reflection layer opposite to the light absorption layer, and a color film is further provided. 8A illustrates a structure in which a color film 401 is provided on the opposite side of the light reflection layer 201 side of the light absorption layer 301, and in FIG. 8B, the color film 401 includes a light absorption layer 301. ) And the light reflection layer 201, the structure of the color film 401 is provided between the light reflection layer 201 and the substrate 101 in Figure 8 (c), the color in Figure 8 (d) The structure with which the film 401 was provided in the opposite surface by the side of the light reflection layer 201 of the base material 101 is shown. In (e) of FIG. 9, color films 401a, 401b, 401c, and 401d respectively have opposite surfaces on the side of the light reflection layer 201 of the light absorption layer 301, between the light absorption layer 301 and the light reflection layer 201, respectively. The structure provided between the reflective layer 201 and the base 101 and on the opposite side of the light reflection layer 201 side of the base 101 is illustrated, but is not limited thereto. Color films 401a, 401b, 401c, 1-3 of the 401d) may be omitted.

In one embodiment of the present specification, the substrate is provided on the opposite side of the surface of the light absorption layer facing the light reflection layer, and a color film is further provided. FIG. 9A illustrates a structure in which the color film 401 is provided on the opposite side of the light absorbing layer 301 side of the substrate 101. In FIG. 9B, the color film 401 is formed of the substrate 101. The structure provided between the light absorbing layer 301, the structure in which the color film 401 is provided between the light absorbing layer 301 and the light reflection layer 201 in Figure 9 (c), the color film in Figure 9 (d) The structure 401 is shown on the opposite side of the light absorption layer 301 side of the light reflection layer 201. In (e) of FIG. 9, color films 401a, 401b, 401c, and 401d respectively have opposite surfaces on the light absorbing layer 301 side of the substrate 101, between the transparent substrate 101 and the light absorbing layer 301, respectively. The structure provided between the absorption layer 301 and the light reflection layer 201 and on the opposite side of the light absorption layer 301 side of the light reflection layer 201 is illustrated, but is not limited thereto. Color films 401a, 401b, 1 to 3 of 401c and 401d may be omitted.

8 (b) and 9 (c) have a structure in which the light incident layer may reflect light incident through the color film when the visible light transmittance of the color film is greater than 0%. Color can be implemented accordingly.

In the structures shown in FIGS. 8 (c), 8 (d) and 9 (d), the light of the color expressed from the curling film of the light reflection layer 201 so that the color difference change due to the addition of the color film can be recognized. It is preferred that the transmittance is at least 1%, preferably at least 3%, more preferably at least 5%. This is because the light transmitted in the visible light transmittance range may be mixed with the color by the color film.

In one embodiment of the present specification, the color film may be provided in a state in which one or more kinds or two or more kinds are stacked.

The color film may be used in combination with the color expressed from the laminated structure of the light reflection layer and the light absorption layer described above to express a desired color. For example, a color film in which one or two or more of pigments and dyes are dispersed in a matrix resin and exhibit color can be used. The color film as described above may be formed by coating the composition for forming a color film directly at a position where the color film may be provided, or coating the composition for forming a color film on a separate substrate, or known molding such as casting or extrusion After manufacturing the color film using the method, a method of arranging or attaching the color film at a position where the color film may be provided may be used. The coating method may be wet coating or dry coating.

Pigments and dyes that may be included in the color film may be selected from those known in the art as to achieve the desired color from the final decorative member, red, yellow, purple, blue, pink 1 type, or 2 or more types of pigments and dyes, such as a series, can be used. Specifically, perinone-based red dye, anthraquinone-based red dye, methine-based yellow dye, anthraquinone-based yellow dye, anthraquinone-based violet dye, phthalocyanine-based blue dye, thioindigo-based pink dye, iso Dyes such as isoxindigo-based pink dyes may be used alone or in combination. Carbon black, copper phthalocyanine (C.I. Pigment Blue 15: 3), C.I. Pigments such as Pigment Red 112, Pigment blue, and Isoindoline yellow may be used alone or in combination. As the dye or pigment as described above, commercially available ones may be used, and for example, a material such as Ciba ORACET Co., Ltd. and Kwang Paint Co. may be used. The types of dyes or pigments and their colors are only examples, and various known dyes or pigments may be used, thereby realizing more various colors.

As the matrix resin included in the color film, materials known as materials such as a transparent film, a primer layer, an adhesive layer, and a coating layer may be used, and are not particularly limited thereto. For example, various materials such as acrylic resins, polyethylene terephthalate resins, urethane resins, linear olefin resins, cycloolefin resins, epoxy resins, triacetyl cellulose resins, and the like may be selected, and copolymers of the above exemplified materials or Mixtures may also be used.

When the color film is disposed closer to the position for observing the decorative member than the light reflection layer or the light absorption layer, for example, (a), (b), (a), (b) and (c) of FIG. In such a structure, the color film has a light transmittance of 1% or more, preferably 3% or more, and more preferably 5% or more of the color expressed from the light reflection layer, the light absorption layer, or the laminated structure of the light reflection layer and the light absorption layer. desirable. As a result, the color expressed from the color film and the color expressed from the light reflection layer, the light absorbing layer, or a laminated structure thereof may be combined together to achieve a desired color.

The thickness of the color film is not particularly limited, and if the desired color can be represented, one of ordinary skill in the art can select and set the thickness. For example, the thickness of the color film may be 500 nm to 1 mm.

(Protective layer)

In one embodiment of the present specification, the surface facing the light absorption layer of the light reflection layer; Between the light reflection layer and the light absorption layer; Alternatively, the light absorbing layer may further include a protective layer on any one or more of the surfaces facing the light reflection layer. That is, the protective layer serves to protect the decorative member by being provided between each layer of the decorative member or at the outermost side of the decorative member.

In the present specification, "protective layer" means a layer capable of protecting other layers of the decorative member, unless otherwise defined. For example, it is possible to prevent deterioration of other layers in a moisture or heat resistant environment. Or an inorganic layer of the light absorption layer or the light reflection layer due to external factors; Alternatively, scratching of the pattern layer is effectively suppressed, so that the dichroism of the decorative member can be effectively expressed.

In one embodiment of the present specification, the protective layer includes aluminum oxynitride. Since the protective layer includes aluminum oxynitride (AlON), the function of the protective layer to be described later may be increased as compared with the case where the protective layer does not contain aluminum oxynitride (AlON). In addition, when adjusting the ratio of each element of the aluminum oxynitride, the protective function can be further improved, which will be described later.

In the present specification, the aluminum oxynitride may be AlOxNy (0 ≦ x ≦ 1.5, 0 ≦ y ≦ 1.0, x + y> 0.8), preferably 0 ≦ x ≦ 1.0, 0.1 ≦ y ≦ 1.0, x + y> 0.8), more preferably 0 ≦ x ≦ 1.0, 0.5 ≦ y ≦ 1.0, and x + y> 0.8. When the numerical range is satisfied, light transmittance is high and a certain level of abrasion resistance and fastness can be effectively protected without changing the expression color even if the temperature or humidity changes. In addition, the decorative member including the protective layer has the effect of improving the moisture resistance heat resistance. The ratio of each element can be measured by measuring method of X-ray photoelectron spectroscopy (XPS). In addition, the ratio between the elements can be achieved by adjusting the gas fraction during aluminum oxynitride deposition.

In an exemplary embodiment of the present specification, the number of scratches generated when the wear resistance is evaluated by reciprocating 10 times at 27 rpm at a load of 3 g or less on a protective layer surface at a load of 3 g or less, preferably 2 or less It may be: More preferably, zero scratches, that is, scratches may not occur. The criteria for evaluating scratches may be used to evaluate scratches d2, which is 1/3 or more of the operation length d1 of the crack generating device such as steel wool, which is applied to generate scratches on the surface of the protective layer during the abrasion resistance test. For example, when the operation length of the crack generator applied to the surface of the protective layer is 3 cm, scratches with a length of 1.2 cm are evaluated with scratches, and scratches with 0.8 cm less than 1/3 are not evaluated with scratches. The driving length d1 of the crack generator may be adjusted according to the overall size of the decorative member.

When satisfying the numerical range, it is possible to effectively protect the light absorption layer and the light reflection layer to prevent the problem of color appearance and fluctuations.

The friction resistance evaluation is a fastness rubbing tester (Product name: KPD-301, manufacturer: Gibae ENT) installed steel wool (steel wool 100% oil free, Briwax products used) and then load 1rpm with a load of 1g It can be calculated by counting the number of scratches evaluated by scratches occurring in 10 round trip conditions.

In one embodiment of the present specification, the light transmittance of the protective layer may be 90% or more and 100% or less, preferably 95% or more and 100% or less at a wavelength of 550 nm. The measurement method is measured in the transmittance measurement mode using a spectrophotometer (Solidspec. 3700, Shimazu). In order to exclude the influence of the substrate, the transmittance of the substrate is 100%, and the light transmittance of the protective layer is measured in comparison with this. When the numerical range is satisfied, the transparency of the protective layer may be good and the optical properties of the decorative member may be excellently maintained.

In one embodiment of the present specification, the thickness of the protective layer may be 5 nm or more and 30 nm or less, 10 nm or more and 20 nm or less. The thickness may be achieved by adjusting a process pressure, a flow rate of a reactive gas, a voltage, a deposition time, and a temperature used for deposition when forming a protective layer. When the numerical range is satisfied, the protective effect of the protective layer may be increased, and the light transmittance of the protective layer may be prevented from being impaired.

In the present specification, the protective layer is a layer that is distinguished from the substrate, the light absorbing layer, or the light reflecting layer, and may be confirmed whether the protective layer is present through an etching process or component analysis.

Specifically, using a X-ray photoelectron spectroscopy (XPS) or an electron spectroscopy for Chemical Analysis (ESPA, Thermo Fisher Scientific Inc.) to perform a survey scan in the protective layer surface and thickness direction After qualitative analysis, quantitative analysis is performed by narrow scan. At this time, a qualitative and quantitative analysis is performed by obtaining a survey scan and a narraw scan under the following conditions. Peak background uses the smart method.

Element	Scan section binding energy	Step size
Narrow (Snapshot)	20.89 eV	0.1 eV
Survey	-10 to 1350 eV	1 eV

In addition, when the structure of the decorative member is a substrate / (other layer) / protective layer, the outermost of the decorative member can be etched using an oxygen plasma and analyzed by the above method. Alternatively, the protective layer may be visually confirmed by observing a cross-sectional photograph of the decorative member. For example, when the structure of the decorative member is a substrate / light reflection layer / light absorbing layer / protective layer, it can be seen that an interface exists between each layer in the cross-sectional photograph of the decorative member, and the outermost layer corresponds to the protective layer. In one embodiment of the present specification, the light reflection layer, the light absorption layer and the protective layer may be by a method of depositing an inorganic layer.

In one embodiment of the present specification, the method of depositing the inorganic layer may be by a reactive sputtering method. Reactive sputtering is a method in which energetic ions (eg, Ar ⁺ ) impinge on a target material, and at this time, the separated target material is deposited on the convex or concave surface of the pattern layer. In this case, the base pressure may be 1.0 × 10 ⁻⁵ Torr or less, 6.0 × 10 ⁻⁶ Torr or less, preferably 3.0 × 10 ⁻⁶ Torr or less.

In one embodiment of the present specification, the reactive sputtering method may be performed in a chamber including a plasma gas and a reactive gas. The plasma gas may be an argon (Ar) gas. In addition, the reactive gases required for forming the inorganic layer are oxygen (O ₂ ) and nitrogen (N ₂ ), which are gases for providing oxygen or nitrogen atoms, and are distinguished from plasma gases.

In one embodiment of the present specification, in the method of depositing the inorganic layer, the flow rate of the plasma gas may be 10 sccm or more and 300 sccm or less, preferably 20 sccm or more and 200 sccm or less. The sccm means Standard Cubic Centimeer Per minute.

In one embodiment of the present specification, the process pressure p1 in the chamber may be 1.0 mTorr to 10.0 mTorr, preferably 1.5 mTorr to 6.0 mTorr. If the process pressure during sputtering is higher than the above range, the Ar particles present in the chamber increase, and the particles of zinc oxide emitted from the target collide with the Ar particles to lose energy, thereby decreasing the growth rate of the thin film. On the other hand, if too low process pressure is maintained, the energy loss of the target particles by the Ar particles decreases, but the disadvantage is that the particles having high energy may damage the substrate or the quality of the inorganic layer.

In one embodiment of the present specification, the method of depositing an inorganic layer is performed by a reactive sputtering method, and the fraction of the reactive gas to the plasma gas is 30% or more and 70% or less, preferably 40% or more and 70% or less. More preferably, it may be 50% or more and 70% or less. The fraction of the reactive gas may be calculated as (Q _{reactive gas} / (Q _{plasma process gas} + Q _{reactive gas} ) * 100%). The Q _{reactive gas} may mean a flow rate of the _{reactive gas} in the chamber, and the Q _{plasma process gas} may be a flow rate of the _{plasma process gas} in the chamber.

In one embodiment of the present specification, the driving power of the reactive sputtering method may be 100W or more and 500W or less, preferably 150W or more and 300W or less.

In one embodiment of the present specification, the voltage applied in the reactive sputtering method may be 350V or more and 500V. The range of the voltage may be adjusted according to the state of the target, the process pressure, the driving power (process power) or the fraction of the reactive gas.

In one embodiment of the present specification, the deposition temperature of the reactive sputtering method may be 20 ° C or more and 300 ° C or less. When deposited at a temperature lower than the above range, there is a problem in that the crystallinity of the thin film growth is deteriorated due to insufficient energy necessary for crystal growth of particles falling off the target and arriving at the substrate. There may be a problem that the thin film growth rate is lowered due to evaporation or re-evaporation.

In one embodiment of the present specification, the decorative member is a case of a decor film or a mobile device. Moreover, the adhesive layer is further included as needed.

Hereinafter, the present application will be described in detail with reference to Examples, but the scope of the present specification is not limited by the following Examples.

Example 1

On the indium light reflecting layer, a silicon light absorbing layer was formed by gradually increasing the thickness of the light reflecting layer toward the longest direction through the oblique deposition method.

At this time, the minimum thickness t0 of the region where the thickness of the light absorbing layer was increased was 50 nm, and the maximum thickness t1 of the region where the thickness of the light absorbing layer was increased was 60 nm.

Example 2

On the indium light reflecting layer, a silicon light absorbing layer was formed by gradually increasing the thickness of the light reflecting layer toward the longest direction through the oblique deposition method.

At this time, the minimum thickness t0 of the region where the thickness of the light absorbing layer was increased was 30 nm, and the maximum thickness t1 of the region where the thickness of the light absorbing layer was increased was 40 nm.

Example 3

On the indium light reflecting layer, a silicon light absorbing layer was formed by gradually increasing the thickness of the light reflecting layer toward the longest direction through the oblique deposition method.

At this time, the minimum thickness t0 of the region where the thickness of the light absorbing layer was increased was 10 nm, and the maximum thickness t1 of the region where the thickness of the light absorbing layer was increased was 20 nm.

Comparative Example 1

The same method as in Example 1 was performed except that a light absorbing layer having a predetermined thickness having no inclination was formed. At this time, the thickness of the light absorption layer was constant at about 10 nm.

Comparative Example 2

The same method as in Example 1 was performed except that a light absorbing layer having a predetermined thickness having no inclination was formed. At this time, the thickness of the light absorption layer was constant at about 20nm.

Evaluation example

As a result of forming a PET substrate or a protective layer (AlON or SiOx) on the decorative members of the prepared examples and comparative examples, and visually observed, it can be seen that the decorative member of the embodiment exhibits a gradation effect of varying colors. However, it was confirmed that the decorative member of the comparative example does not appear in various colors. This is shown in FIGS. 10 and 11. The face-up structure of FIG. 11 means a lamination structure of "light absorption layer / light reflection layer / substrate", and the face-down structure of FIG. 11 means a lamination structure of "protective layer / light absorption layer / light reflection layer / substrate". .

Color measurement can be performed using a spectrophotometer (CM-2600d, manufactured by Konica Minolta Co., Ltd.). The spectrophotometer can reflect the reflectance of the sample and indicate the reflectance for each wavelength. have. At this time, data was obtained at an 8-degree viewing angle, and the Lch coordinates were measured by measuring the horizontal and vertical directions with respect to the decorative member to see the dichroism of the decorative member.

The CIE Lch color space is the CIE Lab color space, where cylindrical coordinates c * (saturation, relative color saturation, L *, instead of a *, b * of Cartesian Coordinates). (Distance from L axis) and h * (hue angle, hue angle on CIE Lab color wheel) were used.

The Lch coordinates of the light absorbing layer of each example were measured at the smallest point t0 and the largest point of the thickness t1. The Lch coordinates of the light absorbing layer of each comparative example were measured, and the results are shown in Table 2 below. Indicated. Since the light absorption layer of the comparative example had a constant thickness, the same Lch coordinate value was found in the entire light absorption layer.

Point	thickness	Lch coordinates
		Example 1	Example 2	Example 3	Comparative Example 1	Comparative Example 2
T1	60 nm	75, 34, 49	-	-	-	-
T0	50 nm	82, 31, 87	-	-	-	-
T1	40 nm	-	81, 15, 109	-	-	-
T0	30 nm	-	70, 12, 217	-	-	-
T1	20 nm	-	-	36, 54, 316	-	36, 54, 316
T0	10 nm	-	-	76, 62, 83	76, 62, 83	-

The decorative members according to Examples 1 to 3 were observed and shown in FIGS. 10 and 11, respectively. The decorative members according to Examples 1 to 3 may exhibit a gradation effect of gradually changing colors, and various colors appearing at the largest and smallest points of the light absorbing layer of each decorative member may also appear. .

On the other hand, in Comparative Examples 1 and 2, the light absorption layer thickness is constant, it is confirmed that the color appearing in the light absorption layer is constant.

From the above results, it was confirmed that the gradation effect was obtained when the thickness of the light absorbing layer had a gradually changing structure. In addition, when changing the maximum and minimum thickness of the light absorbing layer, it was confirmed that the color appears.

Claims (13)

1. Light reflection layer and

   It includes a light absorption layer provided on the light reflection layer,

   The light absorbing layer includes a region in which a thickness t (x) of the light absorbing layer increases in one direction (x) perpendicular to the thickness direction z of the light absorbing layer.
2. The method according to claim 1, wherein the thickness of the light absorbing layer (t (x)) is increased in the area of the thickness of the light absorbing layer gradually increases; A region in which the thickness of the light absorption layer continuously increases; And at least one of regions in which the thickness of the light absorbing layer is discontinuously increased.
3. The decorative member according to claim 1, wherein the thickness t (x) of the light absorption layer is 10 nm or more and 300 nm or less.
4. The decorative member according to claim 1, wherein the value calculated by the following formula A is 0.01 or more and 2 or less:

   Equation A

   

   In Equation A, t0 is a minimum thickness of a region where the thickness t (x) of the light absorbing layer is increased, and t1 is a maximum of a region where the thickness t (x) of the light absorbing layer is increased. Thickness.
5. The decorative member according to claim 1, wherein the value calculated by the following formula B is 0.1 or more and 5 or less:

   Equation B

   

   In Equation B, h0 is the minimum value of h *, and h1 is the maximum value of h *, when the h * value of the Lch coordinate at each point in one direction (x) of the light absorption layer is measured and displayed in a graph. to be.
6. The method of claim 1, wherein the light absorption layer is indium (In), titanium (Ti), tin (Sn), silicon (Si), germanium (Ge), aluminum (Al), copper (Cu), nickel (Ni), vanadium (V), tungsten (W), tantalum (Ta), molybdenum (Mo), neodymium (Nb), iron (Fe), chromium (Cr), cobalt (Co), gold (Au) and silver (Ag) One or two or more materials, oxides thereof; Nitrides thereof; Oxynitrides thereof; A decorative member that is a single layer or a multilayer comprising one or two or more materials of carbon and a carbon composite material.
7. The decorative member according to claim 1, wherein the light absorption layer has a refractive index of 0 to 8 at a wavelength of 400 nm.
8. The decorative member according to claim 1, wherein the light absorption layer has an extinction coefficient greater than 0 and 4 or less at a wavelength of 400 nm.
9. The method of claim 1, wherein the light reflection layer is indium (In), titanium (Ti), tin (Sn), silicon (Si), germanium (Ge), aluminum (Al), copper (Cu), nickel (Ni), vanadium (V), tungsten (W), tantalum (Ta), molybdenum (Mo), neodymium (Nb), iron (Fe), chromium (Cr), cobalt (Co), gold (Au) and silver (Ag) One or two or more materials, oxides thereof; Nitrides thereof; Oxynitrides thereof; A decorative member that is a single layer or a multilayer comprising one or two or more materials of carbon and a carbon composite material.
10. The light emitting layer of claim 1, further comprising: an opposite surface of a surface of the light reflection layer that faces the light absorption layer; Between the light reflection layer and the light absorption layer; Or a substrate provided on an opposite side of the surface of the light absorbing layer that faces the light reflecting layer.
11. The light emitting layer of claim 1, further comprising: an opposite surface of a surface of the light reflection layer that faces the light absorption layer; Between the light reflection layer and the light absorption layer; Or a color film provided on a surface opposite to a surface of the light absorption layer that faces the light reflection layer.
12. The decorative member according to claim 1, which has a dichroism of ΔE * ab> 1.
13. The decorative member according to any one of claims 1 to 12, wherein the decorative member is a case of a decor film or a mobile device.

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