# Patent

## Title
Decorative member

## Abstract

A decoration element including: a color developing layer including a light reflective layer and a light absorbing layer provided on the light reflective layer; and a substrate provided on a surface of the color developing layer. The substrate comprises a pattern layer, and the light absorbing layer comprises an aluminum oxynitride (AlaObNc).

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a U.S. national stage of international application No. PCT/KR2018/015936, filed Dec. 14, 2018, and claims priority to and the benefits of Korean Patent Application No. 10-2017-0173250, filed with the Korean Intellectual Property Office on Dec. 15, 2017, and Korean Patent Application No. 10-2018-0088855, filed with the Korean Intellectual Property Office on Jul. 30, 2018, the entire contents of which are incorporated herein by reference.
TECHNICAL FIELD
The present application relates to a decoration element including a color developing layer.
BACKGROUND
For various cosmetic containers, mobile devices and electronic products, product designs such as colors, shapes and patterns play a major role in providing values of products to customers in addition to product functions. Product preferences and prices are also dependent on designs.
As for cosmetic compact containers as one example, various colors and color senses are obtained using various methods and used in products. A method of providing colors to a case material itself or a method of providing designs by attaching a deco film implementing colors and shapes to a case material may be included.
In existing deco films, attempts have been made to develop colors through methods such as printing and deposition. When expressing heterogeneous colors on a single surface, printing needs to be conducted two or more times, and implementation is hardly realistic when to apply various colors to a three-dimensional pattern. In addition, existing deco films have fixed colors depending on a viewing angle, and even when there is a slight change, the change is limited to just a difference in the color sense.
SUMMARY
The present application is directed to providing a decoration element including a color developing layer.
One embodiment of the present specification provides a decoration element comprising a color developing layer comprising a light reflective layer and a light absorbing layer provided on the light reflective layer; and a substrate provided on one surface of the color developing layer and comprising a pattern layer,
wherein the light absorbing layer comprises an aluminum oxynitride (AlaObNc), and
when a transmission X-ray analysis on an any one point of the light absorbing layer, ω represented by the following Equation 1 is 0.8 or less.




  
    
      
        ω
        =
        
          
            (
            
              T
              X
            
            )
          
          ×
          
            (
            
              σ
              X
            
            )
          
        
      
    
    
      
        [
        
          Equation
          ⁢
          
            
          
          ⁢
          1
        
        ]
      
    
  
  
    
      
        Tx
        =
        
          
            {
            
              
                T
                1
              
              -
              
                
                  [
                  
                    
                      T
                      1
                    
                    
                      T
                      0
                    
                  
                  ]
                
                ×
                
                  T
                  0
                
              
            
            }
          
          ×
          
            
              (
              
                T
                0
              
              )
            
            
              -
              1
            
          
        
      
    
    
      
        [
        
          Equation
          ⁢
          
            
          
          ⁢
          2
        
        ]
      
    
  
  
    
      
        
          σ
          X
        
        =
        
          
            3
            ⁢
            a
          
          
            
              2
              ⁢
              b
            
            +
            
              3
              ⁢
              c
            
          
        
      
    
    
      
        [
        
          Equation
          ⁢
          
            
          
          ⁢
          3
        
        ]
      
    
  




In Equation 1, Tx is represented by Equation 2, and σx is represented by Equation 3,
in Equation 2, T1 is a thickness of the light absorbing layer comprising any one point of the light absorbing layer on which the transmission X-ray analysis is performed,



 
  [
  
   
    T
    1
   
   
    T
    0
   
  
  ]
 



is a maximum integer that is not greater than




 
  
   
    T
    1
   
   
    T
    0
   
  
  ,
 



and T0 is 100 nm,

when T1 is m*T0, Tx is 1, when T1 is not m*T0, Tx satisfies Equation 2, and m is an integer of 1 or greater, and
in Equation 3, a means an element content ratio of aluminum (Al), b means an element content ratio of oxygen (O), and c means an element content ratio of nitrogen (N).
A decoration element according to one embodiment of the present specification is capable of displaying waim tone colors by comprising a light absorbing layer comprising an aluminum oxynitride and having each element content adjusted to a specific ratio.
The present application provides a decoration element having dichroism displaying different colors depending on a viewing direction and having improved visibility of the dichroism.



BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 illustrates a decoration element according to an exemplary embodiment.
FIG. 2 illustrates a method of distinguishing a light absorbing layer and a light reflective layer.
FIG. 3 illustrates one point of a light absorbing layer and a thickness of the light absorbing layer comprising the same.
FIG. 4 illustrates a principle of light interference in a light absorbing layer and a light reflective layer.
FIG. 5 to FIG. 9 illustrate decoration elements according to exemplary embodiments.
FIGS. 10A and 10B, 11A to 11C, 12A to 12E and 13A to 13E illustrate laminated structures of a decoration element according to various exemplary embodiments.
FIG. 14 to FIG. 22 illustrate various shapes of a pattern layer.
FIG. 23A illustrates a pattern layer surface having a plurality of convex portions being arranged in an inversed phase structure of 180 degrees, and FIG. 23B illustrates the change in an image or logo color depending on a viewing angle.
FIGS. 24, 25, 26A and 26B illustrate upper surface structures of light absorbing layers of a decoration element according to various exemplary embodiments.
FIG. 27 to FIG. 30 are images of various decoration elements.
FIGS. 31A to 311 illustrate an upper surface structure of a light absorbing layer of a decoration element according to another exemplary embodiment.
FIG. 32 and FIG. 33 illustrate the distribution of warm color tones and cool color tones.
FIG. 34 shows thickness-dependent changes in the color of a decoration element of an experimental example.
FIG. 35 is a graph of Equation 2A.



DETAILED DESCRIPTION
Hereinafter, the present specification will be described in detail.
In the present specification, “or” represents, unless defined otherwise, a case of selectively or all comprising those listed, that is, a meaning of “and/or”.
In the present specification, a “layer” means covering 70% or more of an area where the corresponding layer is present. It means covering preferably 75% or more, and more preferably 80% or more.
In the present specification, a “thickness” of a certain layer means a shortest distance from a lower surface to an upper surface of the corresponding layer.
In the present specification, colors displayed by a decoration element may be defined by spectral characteristics of a light source, reflectance of an object, and color visual efficiency of an observer.
For objective color expression, colors need to be measured in a standard light source and a standard observer, and colors are expressed in a coordinate of color space. Colors of a decoration element may be displayed by a CIE Lab (L*a*b*) coordinate or a LCh coordinate providing visually uniform color space. L* represents brightness, +a* represents redness, −a* represents greenness, +b* represents yellowness and −b* represents blueness, and C* and h* will be described later. In the color space, a total color difference depending on an observation position may be expressed as ΔE·ab=√{square root over ((ΔL)2+(Δa)2+(Δb)2)}.
The colors may be measured using a spectrophotometer (CM-2600d, manufactured by Konica Minolta, Inc.), and reflectance of a sample may be measured through a spectrophotometer and reflectance for each wavelength may be obtained, and from this, spectral reflectance graph and a converted color coordinate may be obtained. Herein, data are obtained at an 8-degree viewing angle, and, in order to see dichroism of a decoration element, measurements are made in a horizontal direction and a vertical direction with respect to the decoration element.
The viewing angle is an angle formed by a straight line (d1) in a normal direction of a color developing layer surface of a decoration element and a straight line (d2) passing through the spectrophotometer and a point of the sample to measure, and generally has a range of 0 degrees to 90 degrees.
Having a viewing angle of 0 degrees means measuring in the same direction as a normal direction of a color developing layer surface of a decoration element.
In the present specification, a “light absorbing layer” and a “light reflective layer” are layers having properties relative to each other, and the light absorbing layer may mean a layer having higher light absorbance compared to the light reflective layer, and the light reflective layer may mean a layer having higher light reflectivity compared to the light absorbing layer.
The light absorbing layer and the light reflective layer may each be formed in a single layer, or in a multilayer of two or more layers.
In the present specification, the light absorbing layer and the light reflective layer are named by their functions. For light having a specific wavelength, a layer reflecting light relatively more may be expressed as the light reflective layer, and a layer reflecting light relatively less may be expressed as the light absorbing layer.
FIG. 1 illustrates a laminated structure of a decoration element according to one embodiment of the present specification. FIG. 1 illustrates a decoration element comprising a color developing layer (100) and a substrate (101). The color developing layer (100) comprises a light reflective layer (201) and a light absorbing layer (301). FIG. 1 illustrates a structure in which the substrate (101) is provided on the light absorbing layer (301) side of the color developing layer (100), however, the substrate may also be provided on the light reflective layer (201) side.
Through FIG. 2, the light absorbing layer and the light reflective layer are described. In the decoration element of FIG. 2, each layer is laminated in order of a Li−1 layer, a Li layer and a Li+1 layer based on a light entering direction, an interface Ii is located between the Li−1 layer and the Li layer, and an interface Ii+1 is located between the Li layer and the Li+1 layer.
When irradiating light having a specific wavelength in a direction perpendicular to each layer so that thin film interference does not occur, reflectance at the interface Ii may be expressed by the following Mathematical Equation 1.



 
  
   
    
     
      
       
        
         
          
           [
           
            
             
              n
              i
             
             (
             λ
             )
            
            -
            
             
              n
              
               i
               -
               1
              
             
             (
             λ
             )
            
           
           ]
          
          2
         
         +
        
       
      
      
       
        
         
          [
          
           
            
             k
             i
            
            (
            λ
            )
           
           -
           
            
             k
             
              i
              -
              1
             
            
            (
            λ
            )
           
          
          ]
         
         2
        
       
      
     
     
      
       
        
         
          
           [
           
            
             
              n
              i
             
             (
             λ
             )
            
            +
            
             
              n
              
               i
               -
               1
              
             
             (
             λ
             )
            
           
           ]
          
          2
         
         +
        
       
      
      
       
        
         
          [
          
           
            
             k
             i
            
            (
            λ
            )
           
           +
           
            
             k
             
              i
              -
              1
             
            
            (
            λ
            )
           
          
          ]
         
         2
        
       
      
     
    
   
   
    
     [
     
      Mathematical
      ⁢
         
      Equation
      ⁢
         
      1
     
     ]
    
   
  
 



In Mathematical Equation 1, ni(λ) means a refractive index depending on the wavelength (λ) of the ith layer, and ki(λ) means an extinction coefficient depending on the wavelength (λ) of the ith layer. The extinction coefficient is a measure capable of defining how strongly a subject material absorbs light at a specific wavelength, and the definition is the same as a definition to provide later.
Using Mathematical Equation 1, when a sum of reflectance for each wavelength at the interface Ii calculated at each wavelength is Ri, Ri is as in the following Mathematical Equation 2.



 
  
   
    
     
      R
      i
     
     =
     
      
       
        ∑
        
         λ
         =
         
          380
          ⁢
            
          nm
         
        
        
         λ
         =
         
          780
          ⁢
            
          nm
         
        
       
       
        
         
          
           
            
             
              
               [
               
                
                 
                  n
                  i
                 
                 (
                 λ
                 )
                
                -
                
                 
                  n
                  
                   i
                   -
                   1
                  
                 
                 (
                 λ
                 )
                
               
               ]
              
              2
             
             +
            
           
          
          
           
            
             
              [
              
               
                
                 k
                 i
                
                (
                λ
                )
               
               -
               
                
                 k
                 
                  i
                  -
                  1
                 
                
                (
                λ
                )
               
              
              ]
             
             2
            
           
          
         
         
          
           
            
             
              
               [
               
                
                 
                  n
                  i
                 
                 (
                 λ
                 )
                
                +
                
                 
                  n
                  
                   i
                   -
                   1
                  
                 
                 (
                 λ
                 )
                
               
               ]
              
              2
             
             +
            
           
          
          
           
            
             
              [
              
               
                
                 k
                 i
                
                (
                λ
                )
               
               +
               
                
                 k
                 
                  i
                  -
                  1
                 
                
                (
                λ
                )
               
              
              ]
             
             2
            
           
          
         
        
        ⁢
        Δ
        ⁢
        λ
       
      
      
       
        ∑
        
         λ
         =
         
          380
          ⁢
            
          nm
         
        
        
         λ
         =
         
          780
          ⁢
            
          nm
         
        
       
       
        Δ
        ⁢
        λ
       
      
     
    
   
   
    
     [
     
      Mathematical
      ⁢
         
      Equation
      ⁢
         
      2
     
     ]
    
   
  
 



Hereinafter, a decoration element comprising the light reflective layer and the light absorbing layer described above will be described.
One embodiment of the present specification provides a decoration element comprising a color developing layer comprising a light reflective layer and a light absorbing layer provided on the light reflective layer; and a substrate provided on one surface of the color developing layer and comprising a pattern layer,
wherein the light absorbing layer comprises an aluminum oxynitride (AlaObNc), and
when a component analysis is performed through a transmission X-ray analysis on an any one point of the light absorbing layer, ω represented by the following Equation 1 is 0.8 or less.



 
  
   
    
     ω
     =
     
      
       (
       
        T
        X
       
       )
      
      ×
      
       (
       
        σ
        X
       
       )
      
     
    
   
   
    
     [
     
      Equation
      ⁢
         
      1
     
     ]
    
   
  
 




 
  
   
    
     Tx
     =
     
      
       {
       
        
         T
         1
        
        -
        
         
          [
          
           
            T
            1
           
           
            T
            0
           
          
          ]
         
         ×
         
          T
          0
         
        
       
       }
      
      ×
      
       
        (
        
         T
         0
        
        )
       
       
        -
        1
       
      
     
    
   
   
    
     [
     
      Equation
      ⁢
         
      2
     
     ]
    
   
  
 




 
  
   
    
     
      σ
      X
     
     =
     
      
       3
       ⁢
       a
      
      
       
        2
        ⁢
        b
       
       +
       
        3
        ⁢
        c
       
      
     
    
   
   
    
     [
     
      Equation
      ⁢
         
      3
     
     ]
    
   
  
 



In Equation 1, Tx is represented by Equation 2, and σx is represented by Equation 3,
in Equation 2, T1 is a thickness of the light absorbing layer comprising any one point of the light absorbing layer on which the component analysis is performed,



 
  [
  
   
    T
    1
   
   
    T
    0
   
  
  ]
 



is a maximum integer that is not greater than




 
  
   
    T
    1
   
   
    T
    0
   
  
  ,
 



and T0 is 100 nm,

when T1 is m*T0, Tx is 1, when T1 is not m*T0, Tx satisfies Equation 2, and m is an integer of 1 or greater, and
in Equation 3, a means an element content ratio of aluminum (Al), b means an element content ratio of oxygen (O), and c means an element content ratio of nitrogen (N). For example, when the content of the aluminum (Al), the content of the oxygen (O) and the content of the nitrogen (N) at the one point are 57.5%, 9.8% and 39.7%, respectively, a, b and c may be expressed as 0.575, 0.098 and 0.397, respectively.
In the present specification, the content ratio of a specific element may mean an atomic percent (at %) of a specific element at any one point of the light absorbing layer on which the component analysis is performed.
In the decoration element according to one embodiment of the present specification, warm colors (warm tone) may be observed through the light absorbing layer by the light absorbing layer comprising an aluminum oxynitride (AlaObNc), adjusting a content ratio of each element of the aluminum oxynitride, and adjusting a thickness of the light absorbing layer to a specific range. Herein, the relation between the content ratio of each element of the aluminum oxynitride and the thickness of the light absorbing layer may be expressed as ω, a warm tone parameter, represented by Equation 1. The warm tone parameter may be expressed as ωw. The subscript w of ωw means a warm tone.
In one embodiment of the present specification, ω represented by Equation 1 with respect to any one point (x) of the light absorbing layer may be 0.8 or less, greater than or equal to 0 and less than or equal to 0.75, greater than or equal to 0.1 and less than or equal to 0.75, or greater than or equal to 0.1 and less than or equal to 0.7. When satisfying the above-mentioned numerical range, warm colors (warm tone) may be observed through the light absorbing layer, and among the warm colors, a color that a user wants may be readily displayed.
In the present specification, the ‘any one point of the light absorbing layer’ may mean any one point on a surface of or inside the light absorbing layer.
In one embodiment of the present specification, Tx is a thickness parameter represented by Equation 2. As the light absorbing layer thickness changes, warm colors (warm tone) or cool colors (cool tone) appear alternately, and color changes appear with the thickness having a certain period (T0). Herein, Tx may mean a ratio of the light absorbing layer thickness (T1) at any one point with respect to the certain period (T0) of the light absorbing layer thickness. For example, when the certain period (T0) of the thickness is 100 nm, the Tx value when the light absorbing layer has a thickness of 10 nm, 110 nm and 210 nm is the same as 0.1.
In one embodiment of the present specification, Equation 2 may be represented by the following Equation 2A.



 
  
   
    
     
      
       f
       ⁡
       (
       
        T
        1
       
       )
      
      =
      
       
        
         T
         1
        
        
         T
         0
        
       
       ⁢
       
        (
        
         0
         <
         
          T
          1
         
         ≤
         
          T
          0
         
        
        )
       
      
     
     ⁢
     
     
      
       f
       ⁡
       (
       
        T
        1
       
       )
      
      =
      
       f
       ⁡
       (
       
        
         T
         1
        
        +
        
         n
         ×
         
          T
          0
         
        
       
       )
      
     
    
   
   
    
     [
     
      Equation
      ⁢
         
      2
      ⁢
      A
     
     ]
    
   
  
 



In Equation 2A, Tx is a function value according to T1 of the function represented by f(T1), n is a positive integer of 1 or greater, T1 is a thickness of the light absorbing layer comprising any one point of the light absorbing layer on which the component analysis is performed, and T0 is 100 nm.
Equation 2A represents a periodic function f(T1) by a thickness (T1) of the light absorbing layer. It means having the same f(T1) value by a period T0. This is shown in FIG. 35. According to FIG. 35, f(T1) appearing in a range of (0<T1≤T0) repeatedly appears having a certain period (T0). For example, f(0.5T0) when T1=0.5T0 and f(1.5T0) when T1=0.5T0+T0 have the same value of 0.5.
In Equation 2, T1 is a thickness of the light absorbing layer comprising any one point of the light absorbing layer. T1 means, when selecting any one point of the light absorbing layer, a thickness of the light absorbing layer comprising the one point. When observing a cross-section of the light reflective layer through a scanning electron microscope (SEM) and the like, an interface may be identified between the light reflective layer and the light absorbing layer, and it may be identified that a layer comprising an aluminum oxynitride (AlON) is the light absorbing layer through a component analysis. Herein, any one point of the light absorbing layer is selected, and a thickness of the light absorbing layer comprising the any one point may be calculated to be used as T1.
In one embodiment of the present specification, a, b and c are the same as or different from each other, and may each have a value of greater than 1 and less than 1.
In one embodiment of the present specification, a+b+c may be 1.
The thickness T1 may mean, in a cross-section in a direction perpendicular to a surface direction of the light absorbing layer while comprising any one point of the light absorbing layer, a length in the surface direction of the light absorbing layer.
FIG. 3 shows a method of determining one point and a thickness of the light absorbing layer. When selecting any one point (red dot of FIG. 3) of the light absorbing layer, a content ratio parameter represented by Equation 3 is calculated through a component analysis on this point, and a width of a line segment perpendicular to a surface direction of the light absorbing layer among light segments passing through this point is calculated to calculate the thickness (T1).
In addition, T1 may be achieved by controlling a process pressure used in deposition, a flow rate of a reactive gas with respect to a plasma gas, a voltage, a deposition time or a temperature when forming the light absorbing layer.
In Equation 2,



 
  [
  
   
    T
    1
   
   
    T
    0
   
  
  ]
 



is a maximum integer that is not greater than




 
  
   
    T
    1
   
   
    T
    0
   
  
  .
 



[x] is a Gaussian symbol generally used in the field to which this technology belongs or in the mathematical field, and means a maximum integer that is not greater than x.

In the decoration element of the present disclosure, a cool tone or a warm tone repeatedly appears with a certain period depending on changes in the thickness of the light absorbing layer. Herein, T0 may be expressed as a “period of a light absorbing layer thickness in which a warm tone repeatedly appears”.
In one embodiment of the present specification, the thickness T1 of the light absorbing layer is 100 nm or less, and Tx may be represented by the following Equation 2-1.

Tx=T1/T0  [Equation 2-1]

In Equation 2-1, T1 and T0 have the same definitions as in Equation 2.
In Equation 3, a means an element content ratio of aluminum (Al), b means an element content ratio of oxygen (O), and c means an element content ratio of nitrogen (N). The element content ratio of each element of the light absorbing layer may be measured using methods generally used in the art, and an X-ray photoelectron spectroscopy (XPS) method or electron spectroscopy for chemical analysis (ESCA, Thermo Fisher Scientific Inc.) may be used.
In the present specification, the transmission X-ray analysis may be the X-ray photoelectron spectroscopy method.
In one embodiment of the present specification, the thickness parameter Tx may be greater than or equal to 0.01 and less than or equal to 0.5, preferably greater than or equal to 0.1 and less than or equal to 0.5, and more preferably greater than or equal to 0.2 and less than or equal to 0.5. When satisfying the above-mentioned numerical range, warm colors (warm tone) may be more clearly observed in the decoration element.
In one embodiment of the present specification, the content ratio parameter σx may be greater than or equal to 1.1 and less than or equal to 1.9, preferably greater than or equal to 1.2 and less than or equal to 1.8, and more preferably greater than or equal to 1.2 and less than or equal to 1.7. When satisfying the above-mentioned numerical range, warm colors (warm tone) may be more clearly observed in the decoration element. The ratio between these elements may be achieved by controlling a gas fraction when depositing the aluminum oxynitride.
Specifically, after performing qualitative analyses by conducting a survey scan in light absorbing layer surface and thickness directions using an X-ray photoelectron spectroscopy (XPS) method or electron spectroscopy for chemical analysis (ESCA, Thermo Fisher Scientific Inc.), a quantitative analysis is performed with a narrow scan. Herein, the qualitative analysis and the quantitative analysis are performed by obtaining the survey scan and the narrow scan under the condition of the following Table 1. Peak background uses a smart method.











TABLE 1







Element
Scan Section Binding Energy
Step Size





















Narrow (Snapshot)
20.89 
eV
0.1 eV



Survey
−10 eV to 1350 
eV
  1 eV










In addition, the component analysis may be performed by preparing a light absorbing layer slice having the same composition of the light absorbing layer before laminating the decoration element. Alternatively, when the decoration element has a structure of substrate/pattern layer/light reflective layer/light absorbing layer, an outermost edge of the decoration element may be analyzed using the method described above. In addition, the light absorbing layer may be visually identified by observing a photograph of a cross-section of the decoration element. For example, when the decoration element has a structure of substrate/pattern layer/light reflective layer/light absorbing layer, the presence of an interface between each layer is identified in a photograph of a cross-section of the decoration element, and an outermost layer corresponds to the light absorbing layer.
In one embodiment of the present specification, a hue-angle h* in CIE L*Ch color space of the light absorbing layer may be in a range of 315° to 360° and 0° to 150°, a range of 320° to 360° and 0° to 105°, or a range of 320° to 360° and 0° to 100°.
When the Hue-angle h* is in the above-mentioned range, a warm tone may be observed from the decoration element. A warm tone means satisfying the above-mentioned numerical range in CIE L*Ch color space. Colors corresponding to a warm tone are shown in FIG. 32 and colors corresponding to a cool tone are shown in FIG. 33.
In one embodiment of the present specification, the light absorbing layer may have L of 0 to 100 or 30 to 100 in CIE L*Ch color space.
In one embodiment of the present specification, the light absorbing layer may have C of 0 to 100, 1 to 80 or 1 to 60 in CIE L*Ch color space.
In the present specification, the CIE L*Ch color space is CIE Lab color space, and herein, cylinder coordinates C* (chroma, relative color saturation), a distance from L axis, and h* (hue-angle, hue-angle in CIE Lab hue circle) are used instead of a* and b* of Cartesian coordinates.
In one embodiment of the present specification, the light absorbing layer preferably has a refractive index (n) of 0 to 8 at a wavelength of 400 nm, and the refractive index may be from 0 to 7, may be from 0.01 to 3, and may be from 2 to 2.5. The refractive index (n) may be calculated by sin θa/sin θb (θa is an angle of light incident on a surface of the light absorbing layer, and θb is a refraction angle of light inside the light absorbing layer).
In one embodiment of the present specification, the light absorbing layer preferably has a refractive index (n) of 0 to 8 in a wavelength range of 380 nm to 780 nm, and the refractive index may be from 0 to 7, may be from 0.01 to 3, and may be from 2 to 2.5.
In one embodiment of the present specification, the light absorbing layer has an extinction coefficient (k) of greater than 0 and less than or equal to 4 at 400 nm, and the extinction coefficient is preferably from 0.01 to 4, may be from 0.01 to 3.5, may be from 0.01 to 3, and may be from 0.1 to 1. The extinction coefficient (k) is −λ/4πI (dI/dx) (herein, a value multiplying λ/4π with dI/I, a reduced fraction of light intensity per a path unit length (dx), for example 1 m, in the light absorbing layer, and herein, λ is a wavelength of light).
In one embodiment of the present specification, the light absorbing layer has an extinction coefficient (k) of greater than 0 and less than or equal to 4 in a wavelength range of 380 nm to 780 nm, and the extinction coefficient is preferably from 0.01 to 4, may be from 0.01 to 3.5, may be from 0.01 to 3, and may be from 0.1 to 1. The extinction coefficient (k) is in the above-mentioned range at 400 nm, preferably in the whole visible wavelength region of 380 nm to 780 nm, and therefore, a role of the light absorbing layer may be performed in the visible range.
A principle of a light absorbing layer having such specific extinction coefficient and refractive index developing colors and a principle of color development of a decoration element developing colors by adding a dye to an existing substrate are different. For example, using a method of absorbing light by adding a dye to a resin, and using a material having an extinction coefficient as described above lead to different light absorption spectra. When absorbing light by adding a dye to a resin, an absorption wavelength band is fixed, and only a phenomenon of varying an absorption amount depending on the changes in the coating thickness occurs. In addition, in order to obtain a target light absorption amount, changes in the thickness of at least a few micrometers or more are required to adjust the light absorption amount. On the other hand, in materials having an extinction coefficient, a wavelength band absorbing light changes even when the thickness changes by a several to tens of nanometer scale.
In addition, when adding a dye to an existing resin, only specific colors by the dye are developed, and therefore, various colors may not be displayed. On the other hand, by the light absorbing layer of the present disclosure using a specific material instead of a resin, an advantage of displaying various colors is obtained by an interference phenomenon of light without adding a dye.
According to the embodiments, light absorption occurs in an entering path and a reflection path of light in the light absorbing layer, and by the light reflecting on each of a surface of the light absorbing layer and an interface of the light absorbing layer (301) and the light reflective layer (201), the two reflected lights go through constructive or destructive interference. In the present specification, the light reflected on the surface of the light absorbing layer may be expressed as surface reflected light, and the light reflected on the interface of the light absorbing layer and the light reflective layer may be expressed as interface reflected light. A mimetic diagram of such a working principle is illustrated in FIG. 4. FIG. 4 illustrates a structure in which a substrate (101) is provided on a light reflective layer (201) side, however, the structure is not limited to such a structure, and as for the substrate (101) location, the substrate may be disposed on other locations.
In one embodiment of the present specification, the light absorbing layer may be a single layer, or a multilayer of two or more layers.
In one embodiment of the present specification, the light absorbing layer may further comprise one, two or more selected from the group consisting of metals, metalloids, and oxides, nitrides, oxynitrides and carbides of metals or metalloids. The oxides, nitrides, oxynitrides or carbides of metals or metalloids may be formed under a deposition condition and the like set by those skilled in the art. The light absorbing layer may also comprise the same metals, metalloids, alloys or oxynitrides of two or more types as the light reflective layer.
In one embodiment of the present specification, the thickness (T1) of the light absorbing layer may be determined depending on target colors in a final structure, and for example, may be greater than or equal to 1 nm and less than or equal to 300 nm, greater than or equal to 1 nm and less than or equal to 50 nm, greater than or equal to 101 nm and less than or equal to 150 nm, and greater than or equal to 201 nm and less than or equal to 250 nm.
In one embodiment of the present specification, the light reflective layer is not particularly limited as long as it is a material capable of reflecting light, however, light reflectance may be determined depending on the material, and for example, colors are readily expressed at 50% or greater of light reflectance. Light reflectance may be measured using an ellipsometer.
In one embodiment of the present specification, the light reflective layer may be a metal layer, a metal oxide layer, a metal nitride layer, a metal oxynitride layer or an inorganic material layer. The light reflective layer may be formed in a single layer, or may also be formed in a multilayer of two or more layers.
In one embodiment of the present specification, the light reflective layer may be a single layer or a multilayer comprising one, two or more types of materials selected from the group consisting of one, two or more types of materials selected from among 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 (Nd), iron (Fe), chromium (Cr), cobalt (Co), gold (Au) and silver (Ag); oxides thereof; nitrides thereof; oxynitrides thereof; carbon; and carbon composites.
In one embodiment of the present specification, the light reflective layer may comprise alloys of two or more selected from among the above-mentioned materials, or oxides, nitrides or oxynitrides thereof.
In one embodiment of the present specification, the light reflective layer may allow highly resistant reflective layer by being prepared using an ink comprising carbon or carbon composites. Carbon black, CNT and the like may be included as the carbon or carbon composites.
In one embodiment of the present specification, the ink comprising carbon or carbon composites may comprise above-described materials, or oxides, nitrides or oxynitrides thereof, and for example, oxides of one, two or more types of selected from among 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 (Nd), iron (Fe), chromium (Cr), cobalt (Co), gold (Au) and silver (Ag) may be included. A curing process may be further carried out after printing the ink comprising carbon or carbon composites.
In one embodiment of the present specification, when the light reflective layer comprises two or more types of materials, the two or more types of materials may be formed using one process, for example, a method of deposition or printing, however, a method of first forming a layer using one or more types of materials, and then additionally forming a layer thereon using one or more types of materials may be used. For example, a light reflective layer may be formed by forming a layer through depositing indium or tin, then printing an ink comprising carbon, and then curing the result. The ink may further comprise oxides such as titanium oxides or silicon oxides.
In one embodiment of the present specification, the thickness of the light reflective layer may be determined depending on target colors in a final structure, and for example, may be 1 nm or greater, 25 nm or greater, 50 nm or greater, and preferably 70 nm or greater.
(Light Absorbing Layer Structure)
In one embodiment of the present specification, the light absorbing layer may have various shapes by adjusting a deposition condition and the like when forming the light absorbing layer.
In one embodiment of the present specification, the light absorbing layer comprises two or more points with different thicknesses.
In one embodiment of the present specification, the light absorbing layer comprises two or more regions with different thicknesses.
In one embodiment of the present specification, the light absorbing layer may comprise an inclined surface.
Examples of the structure according to the embodiment are illustrated in FIG. 5 and FIG. 6. FIG. 5 and FIG. 6 illustrate a structure in which a light reflective layer (201) and a light absorbing layer (301) are laminated (substrate not included). According to FIG. 5 and FIG. 6, the light absorbing layer (301) has two or more points with different thicknesses. According to FIG. 5, thicknesses in A point and B point are different in the light absorbing layer (301). According to FIG. 6, thicknesses in C region and D region are different in the light absorbing layer (301).
In one embodiment of the present specification, the light absorbing layer comprises one or more regions in which an upper surface has an inclined surface with an inclined angle of greater than 0 degrees and less than or equal to 90 degrees, and the light absorbing layer comprises one or more regions having a thickness different from a thickness in any one region having the inclined surface. In the inclined surface, an angle formed by any one straight line included in an upper surface of the light absorbing layer and a straight line parallel to the light reflective layer may be defined as the inclined angle. For example, an inclined angle of the upper surface of the light absorbing layer of FIG. 5 may be approximately 20 degrees.
Surface properties such as an upper surface slope of the light reflective layer may be the same as an upper surface of the light absorbing layer. For example, by using a deposition method when forming the light absorbing layer, the upper surface of the light absorbing layer may have the same slope as the upper surface of the light reflective layer. However, the upper surface slope of the light absorbing layer of FIG. 5 is different from the upper surface slope of the light reflective layer.
FIG. 7 illustrates a structure of a decoration element having a light absorbing layer in which an upper surface has an inclined surface. The structure is a structure laminating a substrate (101), a light reflective layer (201) and a light absorbing layer (301), and thickness t1 in E region and thickness t2 in F region are different in the light absorbing layer (301). Reference numeral 401 may be a color film.
FIG. 7 relates to a light absorbing layer having inclined surfaces facing each other, that is, having a structure with a triangle cross-section. In the structure of the pattern having inclined surfaces facing each other as in FIG. 7, a thickness of the light absorbing layer may be different in two surfaces of the triangle structure even when progressing deposition under the same condition. Accordingly, a light absorbing layer having two or more regions with different thicknesses may be formed using just one process. As a result, developed colors may become different depending on the thickness of the light absorbing layer. Herein, the thickness of the light reflective layer does not affect changes in the color when it is a certain thickness or greater.
FIG. 7 illustrates a structure in which a substrate (101) is provided on a light reflective layer (201) side, however, the structure is not limited thereto, and as described above, the substrate (101) may also be disposed on other locations.
In addition, in FIG. 7, the surface adjoining the light reflective layer (201) of the substrate (101) is a flat surface, however, the surface adjoining the light reflective layer (201) of the substrate (101) may have a pattern having the same slope as an upper surface of the light reflective layer (201). This is shown in FIG. 8. This may cause a difference in the thickness of the light absorbing layer due to a difference in the slope of the pattern of the substrate. However, the present disclosure is not limited thereto, and even when the substrate and the light absorbing layer are prepared to have different slopes using different deposition methods, the dichroism described above may be obtained by having the thickness of the light absorbing layer being different on both sides of the pattern.
In one embodiment of the present specification, the light absorbing layer comprises one or more regions with a gradually changing thickness. FIG. 9 illustrates a structure in which a thickness of the light absorbing layer (301) layer gradually changes.
In one embodiment of the present specification, the light absorbing layer comprises one or more regions in which an upper surface has an inclined surface with an inclined angle of greater than 0 degrees and less than or equal to 90 degrees, and at least one or more of the regions having an inclined surface has a structure in which a thickness of the light absorbing layer gradually changes. FIG. 9 illustrates a structure of a light absorbing layer comprising a region in which an upper surface has an inclined surface. In FIG. 9, both G region and H region have a structure in which an upper surface of the light absorbing layer has an inclined surface, and a thickness of the light absorbing layer gradually changes.
In the present specification, the structure in which a thickness of the light absorbing layer changes means that a cross-section in a thickness direction of the light absorbing layer comprises a point having a smallest thickness of the light absorbing layer and a point having a largest thickness of the light absorbing layer, and a thickness of the light absorbing layer increases along the direction of the point having a smallest thickness of the light absorbing layer with respect to the point having a largest thickness of the light absorbing layer. Herein, the point having a smallest thickness of the light absorbing layer and the point having a largest thickness of the light absorbing layer may mean any point of on an interface of the light absorbing layer with the light reflective layer.
In one embodiment of the present specification, the light absorbing layer comprises a first region having a first inclined surface with an inclined angle in a range of 1 degree to 90 degrees, and may further comprise two or more regions in which an upper surface has an inclined surface with a different slope direction or a different inclined angle from the first inclined surface, or an upper surface is horizontal. Herein, thicknesses in the first region and the two or more regions may all be different from each other in the light absorbing layer.
(Substrate)
In one embodiment of the present specification, the decoration element comprises a substrate provided on one surface of the color developing layer and comprising a pattern layer.
In one embodiment of the present specification, the decoration element comprises a substrate (101) provided on any one or more of a surface facing the light absorbing layer (301) of the light reflective layer (201); or a surface facing the light reflective layer of the light absorbing layer. For example, the substrate may be provided on a surface opposite to the surface facing the light absorbing layer of the light reflective layer (FIG. 10A); or a surface opposite to the surface facing the light reflective layer of the light absorbing layer (FIG. 10B).
In one embodiment of the present specification, the substrate may comprise a plastic injection molded article or a glass substrate for a cosmetic container. More specifically, the plastic injection molded article may comprise one or more types of polypropylene (PP), polystyrene (PS), polyvinyl acetate (PVAc), polyacrylate, polyethylene terephthalate (PET), polyvinyl chloride (PVC), polymethyl methacrylate (PMMA), an ethylene-vinyl acetate copolymer (EVA), polycarbonate (PC), polyamide and a styrene-acrylonitrile copolymer (SAN), but is not limited thereto.
In addition, the plastic injection molded article may be a plate-type plastic injection molded article without curves (specific pattern), or may be a plastic injection molded article having curves (specific pattern).
The plastic injection molded article may be prepared using a plastic molding method. The plastic molding method comprises compression molding, injection molding, air blow molding, thermoforming, hotmelt molding, foaming molding, roll molding, reinforced plastic molding and the like. The compression molding is a molding method of placing a material into a mold, heating the result, and applying a pressure thereto, and, as the longest molding method, this may be mainly used in molding thermal curable resins such as phenol resins. The injection molding is a molding method of pushing out a plastic melt using a transporting device, and filling a mold therewith through a nozzle, and this method may mold both thermoplastic resins and thermal curable resins, and is a molding method used the most. The resin used as a cosmetic case is SAN. The air blow molding is a method of molding a product while placing a plastic parison in the center of a mold and injecting air thereto, and, as a molding method of making plastic bottles or small containers, the speed of manufacturing a product is very fast.
In one embodiment of the present specification, glass having transmittance of 80% or greater may be used as the glass substrate. In one embodiment of the present specification, the substrate thickness may be selected as needed, and for example, may have a range of 50 μm to 200 μm.
In one embodiment of the present specification, the decoration element may be prepared using a step of forming a light reflective layer on the substrate and a light absorbing layer provided on the light reflective layer. More specifically, in the decoration element, the light absorbing layer and the light reflective layer may be consecutively formed on the substrate using a deposition process or the like, or the light reflective layer and the light absorbing layer may be consecutively formed on the substrate using a deposition process or the like, however, the method is not limited thereto.
(Color Film)
In one embodiment of the present specification, the color developing layer further comprises a color film.
In one embodiment of the present specification, the decoration element further comprises a color film on a surface opposite to the surface facing the light reflective layer of the light absorbing layer; between the light absorbing layer and the light reflective layer; or on a surface opposite to the surface facing the light absorbing layer of the light reflective layer. The color film may also perform a role of a substrate. For example, those that may be used as a substrate may be used as a color film by adding a dye or a pigment thereto.
In one embodiment of the present specification, the color film is not particularly limited as long as it has a color difference ΔE*ab, a distance in space of L*a*b* in a color coordinate CIE L*a*b* of the color developing layer, of greater than 1 when the color film is present compared to when the color film is not provided.
Colors may be expressed by CIE L*a*b*, and a color difference may be defined using a distance (ΔE*ab) in the L*a*b* space. Specifically, the color difference is ΔE·ab=√{square root over ((ΔL)2+(Δa)2+(Δb)2)}, and within a range of 0<ΔE*ab<1, an observer may not recognize the color difference [reference document: Machine Graphics and Vision 20(4):383-411]. Accordingly, a color difference obtained by the color film addition may be defined by ΔE*ab>1 in the present specification.
FIG. 11A illustrates a structure in which a light reflective layer (201), a light absorbing layer (301) and a color film (401) are consecutively laminated, FIG. 11B illustrates a structure in which a light reflective layer (201), a color film (401) and a light absorbing layer (301) are consecutively laminated, and FIG. 11C illustrates a structure in which a color film (401), a light reflective layer (201) and a light absorbing layer (301) are consecutively laminated.
In one embodiment of the present specification, when the substrate is provided on a surface opposite to the surface facing the light absorbing layer of the light reflective layer, and the color film is located on a surface opposite to the surface facing the light absorbing layer of the light reflective layer, the color film may be provided between the substrate and the light reflective layer; or on a surface opposite to the surface facing the light reflective layer of the substrate. As another example, when the substrate is provided on a surface opposite to the surface facing the light reflective layer of the light absorbing layer, and the color film is located on a surface opposite to the surface facing the light reflective layer of the light absorbing layer, the color film may be provided between the substrate and the light absorbing layer; or on a surface opposite to the surface facing the light absorbing layer of the substrate.
In one embodiment of the present specification, the substrate is provided on a surface opposite to the surface facing the light absorbing layer of the light reflective layer, and the color film is further provided. FIG. 12A illustrates a structure in which the color film (401) is provided on a surface opposite to the light reflective layer (201) side of the light absorbing layer (301), FIG. 12B illustrates a structure in which the color film (401) is provided between the light absorbing layer (301) and the light reflective layer (201), FIG. 12C illustrates a structure in which the color film (401) is provided between the light reflective layer (201) and the substrate (101), and FIG. 12D illustrates a structure in which the color film (401) is provided on a surface opposite to the light reflective layer (201) side of the substrate (101). FIG. 12E illustrates a structure in which the color films (401a, 401b, 401c, 401d) are provided on a surface opposite to the light reflective layer (201) side of the light absorbing layer (301), between the light absorbing layer (301) and the light reflective layer (201), between the light reflective layer (201) and the substrate (101), and on a surface opposite to the light reflective layer (201) side of the substrate (101), respectively, however, the structure is not limited thereto, and 1 to 3 of the color films (401a, 401b, 401c, 401d) may not be included.
In one embodiment of the present specification, the substrate is provided on a surface opposite to the surface facing the light reflective layer of the light absorbing layer, and the color film is further provided. FIG. 13A illustrates a structure in which the color film (401) is provided on a surface opposite to the light absorbing layer (301) side of the substrate (101), FIG. 13B illustrates a structure in which the color film (401) is provided between the substrate (101) and the light absorbing layer (301), FIG. 13C illustrates a structure in which the color film (401) is provided between the light absorbing layer (301) and the light reflective layer (201), and FIG. 13D illustrates a structure in which the color film (401) is provided on a surface opposite to the light absorbing layer (301) side of the light reflective layer (201). FIG. 13E illustrates a structure in which the color films (401a, 401b, 401c, 401d) are provided on a surface opposite to the light absorbing layer (201) side of the substrate (101), between the substrate (101) and the light absorbing layer (301), between the light absorbing layer (301) and the light reflective layer (201), and on a surface opposite to the light absorbing layer (201) side of the light reflective layer (201), respectively, however, the structure is not limited thereto, and 1 to 3 of the color films (401a, 401b, 401c, 401d) may not be included.
In the structures such as FIG. 12B and FIG. 13C, the light reflective layer may reflect light entering through the color film when the color film has visible light transmittance of greater than 0%, and therefore, colors may be obtained by laminating the light absorbing layer and the light reflective layer.
In the structures such as FIG. 12C, FIG. 12D and FIG. 13D, light transmittance of the colors developed from the color film of the light reflective layer (201) may be 1% or greater, preferably 3% or greater and more preferably 5% or greater so that changes in the color difference obtained by the color film addition may be recognized. This is due to the fact that light transmitted in such a visible light transmittance range may be mixed with colors obtained by the color film.
In one embodiment of the present specification, the color film may be provided as one sheet, or as a laminate of 2 sheets or more that are the same or different types.
As the color film, those capable of developing target colors by combining with colors developed from the laminated structure of the light reflective layer and the light absorbing layer described above may be used. For example, color films expressing colors by one, two or more types of pigments and dyes being dispersed into a matrix resin may be used. Such a color film may be formed by directly coating a composition for forming a color film on a color film-providable location, or a method of preparing a color film by coating a composition for forming a color film on a separate substrate or using a known molding method such as casting or extrusion, and then disposing or attaching the color film on a color film-providable location may be used. As the coating method, wet coating or dry coating may be used.
The pigment and the dye capable of being included in the color film may be selected from among those capable of obtaining target colors from a final decoration member, and known in the art, and one, two or more types among pigments and dyes such as red-based, yellow-based, purple-based, blue-based or pink-based may be used. Specifically, dyes such as perinone-based red dyes, anthraquinone-based red dyes, methane-based yellow dyes, anthraquinone-based yellow dyes, anthraquinone-based purple dyes, phthalocyanine-based blue dyes, thioindigo-based pink dyes or isoxindigo-based pink dyes may be used either alone or as a combination. Pigments such as carbon black, copper phthalocyanine (C.I. Pigment Blue 15:3), C.I. Pigment Red 112, Pigment blue or isoindoline yellow may be used either alone or as a combination. As such dyes or pigments, those commercially available may be used, and for example, materials manufactured by Ciba ORACET or Chokwang Paint Ltd. may be used. Types of the dyes or pigments and colors thereof are for illustrative purposes only, and various known dyes or pigments may be used, and more diverse colors may be obtained therefrom.
As the matrix resin included in the color film, materials known as materials of transparent films, primer layers, adhesive layers or coating layers may be used, and the matrix resin is not particularly limited to these materials. For example, various materials such as acryl-based resins, polyethylene terephthalate-based resins, urethane-based resins, linear olefin-based resins, cycloolefin-based resins, epoxy-based resins or triacetylcellulose-based resins may be selected, and copolymers or mixtures of the materials illustrated above may also be used.
When the color film is disposed closer to the location observing a decoration member than the light reflective layer or the light absorbing layer as in, for example, the structures of FIGS. 12(a) and (b), and FIGS. 13(a), (b) and (c), light transmittance of the colors developed by the color film from the light reflective layer, the light absorbing layer or the laminated structure of the light reflective layer and the light absorbing layer may be 1% or greater, preferably 3% or greater and more preferably 5% or greater. As a result, target colors may be obtained by combining colors developed from the color film and colors developed from the light reflective layer, the light absorbing layer or the laminated structure thereof.
The thickness of the color film is not particularly limited, and those skilled in the art may select and set the thickness as long as it is capable of obtaining target colors. For example, the color film may have a thickness of 500 nm to 1 mm.
(Pattern Layer)
In one embodiment of the present specification, the substrate comprises a pattern layer, and the pattern layer is provided adjacent to the color developing layer.
In the present specification, the pattern layer being provided adjacent to the color developing layer may mean the pattern layer being in direct contact with the color developing layer. For example, the pattern layer may be in direct contact with the light reflective layer of the color developing layer, or the pattern layer may be in direct contact with the light absorbing layer of the color developing layer.
In one embodiment of the present specification, the pattern layer comprises a convex portion or concave portion shape having an asymmetric-structured cross-section.
In one embodiment of the present specification, the pattern layer comprises a convex portion shape having an asymmetric-structured cross-section.
In one embodiment of the present specification, the pattern layer comprises a concave portion shape having an asymmetric-structured cross-section.
In one embodiment of the present specification, the pattern layer comprises a convex portion shape having an asymmetric-structured cross-section and a concave portion shape having an asymmetric-structured cross-section.
In the present specification, the “cross-section” means a surface when cutting the convex portion or concave portion in any one direction. For example, the cross-section may mean, when placing the decoration member on the ground, a surface when cutting the convex portion or concave portion in a direction parallel to the ground or a direction perpendicular to the ground. In the surface of the convex portion or concave portion shape of the pattern layer of the decoration member according to the embodiment, at least one of the cross-sections in a direction perpendicular to the ground has an asymmetric structure.
In the present specification, the “asymmetric-structured cross-section” means a structure in which a figure formed with the borders of the cross-section does not have line symmetry or point symmetry. Line symmetry refers to having a property of overlapping when mirroring a certain figure centering on a straight line. Point symmetry refers to, when a certain figure rotates 180 degrees based on one point, having a symmetrical property completely overlapping the original figure. Herein, the borders of the asymmetric-structured cross-section may be a straight line, a curved line or a combination thereof.
In one embodiment of the present specification, in the convex portion or concave portion shape having an asymmetric-structured cross-section, at least one cross-section comprises two or more sides having different inclined angles, different curvatures, or different side shapes. For example, when two sides among the sides forming at least one cross-section have different inclined angles, different curvatures, or different side shapes, the convex portion or concave portion has an asymmetric structure.
As described above, the decoration member may develop dichroism by the convex portion or concave portion having an asymmetric-structured cross-section included in the surface of the pattern layer. Dichroism means different colors being observed depending on a viewing angle. Colors may be expressed by CIE L*a*b*, and a color difference may be defined using a distance (ΔE*ab) in the L*a*b* space. Specifically, the color difference is ΔE·ab=√{square root over ((ΔL)2+(Δa)2+(Δb)2)}, and within a range of 0<ΔE*ab<1, an observer may not recognize the color difference [reference document: Machine Graphics and Vision 20(4):383-411]. Accordingly, dichroism may be defined by ΔE*ab>1 in the present specification.
In one embodiment of the present specification, the color developing layer has dichroism of ΔE*ab>1. Specifically, a color difference ΔE*ab, a distance in L*a*b* space in a color coordinate CIE L*a*b* of the color developing layer, may be greater than 1.
In one embodiment of the present specification, the decoration element has dichroism of ΔE*ab>1. Specifically, a color difference ΔE*ab, a distance in L*a*b* space in a color coordinate CIE L*a*b* of the whole decoration element, may be greater than 1.
In one embodiment of the present specification, the shape of the convex portion or concave portion comprises a first inclined surface and a second inclined surface having different inclined angles.
In one embodiment of the present specification, in the shape of the convex portion or concave portion, at least one cross-section comprises a first inclined side and a second inclined side having different inclined angles. Shapes of the first inclined side and the second inclined side are the same as or different from each other, and are each a straight-line shape or a curved-line shape.
In one embodiment of the present specification, the borders of the asymmetric-structured cross-section are a straight line, a curved line or a combination thereof.
FIG. 14 presents the first inclined side and the second inclined side having a straight-line shape. Each convex portion shape comprises a first area (D1) comprising a first inclined side and a second area (D2) comprising a second inclined side. The first inclined side and the second inclined side have a straight-line shape. An angle (c3) formed by the first inclined side and the second inclined side may be from 75 degrees to 105 degrees. An angle (c1) formed by the first inclined side and the ground (substrate) and an angle (C2) formed by the second inclined side and the ground are different. For example, a combination of c1 and c2 may be 20 degrees/80 degrees, 10 degrees/70 degrees or 30 degrees/70 degrees.
FIGS. 15A and 15B illustrate the first inclined side or the second inclined side having a curved-lien shape. The cross-section of the pattern layer has a convex portion shape, and the cross-section of the convex portion shape comprises a first area (E1) comprising a first inclined side and a second area (E2) comprising a second inclined side. Any one or more of the first inclined side and the second inclined side may have a curved-line shape. For example, the first inclined side and the second inclined side may both have a curved-line shape, or the first inclined side may have a straight-line shape, and the second inclined side may have a curved-line shape. When the first inclined side has a straight-line shape and the second inclined side has a curved-line shape, the angle c1 may be larger than the angle c2. FIGS. 15A and 15B illustrate the first inclined side having a straight-line shape and the second inclined side having a curved-line shape. The angle formed by the inclined side having a curved-line shape with the ground may be calculated from, when drawing an arbitrary straight line from a point where the inclined side touching the ground to a point where the first inclined side adjoins the second inclined side, an angle formed by the straight line and the ground. The curved-line-shaped second inclined side may have a different curvature depending on the pattern layer height, and the curved line may have a radius of curvature. The radius of curvature may be 10 times or less than the width (E1+E2) of the convex portion shape. FIG. 15A shows a radius of curvature of the curved line being twice the width of the convex portion shape, and FIG. 15B shows a radius of curvature of the curved line being the same as the width of the convex portion shape. A ratio of the part (E2) having a curvature with respect to the width (E1+E2) of the convex portion may be 90% or less. FIGS. 15A and 15B illustrate a ratio of the part (E2) having a curvature with respect to the width (E1+E2) of the convex portion being 60%.
In the present specification, the inclined angle of the inclined side may be treated the same as the inclined angle of the inclined surface.
In the present specification, unless mentioned otherwise, the “side” may be a straight line, but is not limited thereto, and a part or all may be a curved line. For example, the side may comprise a structure of a part of an arc of a circle or oval, a wave structure or a zigzag.
In the present specification, when the side comprises a part of an arc of a circle or oval, the circle or oval may have a radius of curvature. The radius of curvature may be defined by, when converting an extremely short section of a curved line into an arc, the radius of the arc.
In the present specification, the inclined angle of the convex portion may mean an angle formed by an inclined surface of the convex portion and a horizontal surface of the pattern layer. Unless particularly mentioned otherwise in the present specification, the first inclined surface may be defined as a left inclined surface of the convex portion, and the second inclined surface may mean a right inclined surface of the convex portion in the drawings.
In the present specification, unless particularly mentioned otherwise, the first inclined side may be defined as a left inclined side of the convex portion and the second inclined side may be defined as a right inclined side of the convex portion in the drawing.
In the present specification, unless mentioned otherwise, the “inclined side” means, when placing the decoration member on the ground, a side having an angle formed by a side with respect to the ground being greater than 0 degrees and less than or equal to 90 degrees. Herein, when the side is a straight line, an angle formed by the straight line and the ground may be measured. When the side comprises a curved line, an angle formed by, when placing the decoration member on the ground, the ground and a straight line connecting a point of the side closest to the ground and a point of the side farthest from the ground in a shortest distance may be measured.
In the present specification, unless mentioned otherwise, the “inclined surface” means, when placing the decoration member on the ground, a surface having an angle formed by a surface with respect to the ground being greater than 0 degrees and less than or equal to 90 degrees. Herein, when the surface is a flat surface, an angle formed by the flat surface and the ground may be measured. When the surface comprises a curved surface, an angle formed by, when placing the decoration member on the ground, the ground and a straight line connecting a point of the surface closest to the ground and a point of the surface farthest from the ground in a shortest distance may be measured.
In the present specification, unless mentioned otherwise, the “inclined angle” is an angle formed by, when placing the decoration member on the ground, the ground and a surface or side forming the pattern layer, and is greater than 0 degrees and less than or equal to 90 degrees. Alternatively, it may mean an angle formed by the ground and a segment (a′-b′) made when connecting a point (a′) where a surface or side forming the pattern layer adjoins the ground and a point (b′) where a surface or side forming the pattern layer is farthest from the ground.
In the present specification, unless mentioned otherwise, the “curvature” means a degree of changes in the slope of the tangent at continuous points of a side or surface. As the change in the slope of the tangent at continuous points of a side or surface is larger, the curvature is high.
In the present specification, the convex portion may be a convex portion unit shape, and the concave portion may be a concave portion unit shape. The convex portion unit shape or the concave portion unit shape means a shape comprising two inclined sides (first inclined side and second inclined side), and is not a shape comprising three or more inclined sides. When referring to FIG. 18, the convex portion (P1) of the circle C1 is one convex portion unit shape comprising a first inclined side and a second inclined side. However, the shape included in the circle C2 comprises two convex portion unit shapes. The first inclined side may be defined as a left inclined side of the convex portion or concave portion, and the second inclined side may mean a right inclined side of the convex portion or concave portion.
In one embodiment of the present specification, an angle formed by the first inclined side and the second inclined side may be in a range of 80 degrees to 100 degrees. Specifically, the angle may be 80 degrees or greater, 83 degrees or greater, 86 degrees or greater or 89 degrees or greater, and may be 100 degrees or less, 97 degrees or less, 94 degrees or less or 91 degrees or less. The angle may mean an angle of a vertex formed by the first inclined side and the second inclined side. When the first inclined side and the second inclined side do not form a vertex with each other, the angle may mean an angle of a vertex in a state forming a vertex by virtually extending the first inclined side and the second inclined side.
In one embodiment of the present specification, a difference between the inclined angle of the first inclined side and the inclined angle of the second inclined side of the may be in a range of 30 degrees to 70 degrees in the convex portion. The difference between the inclined angle of the first inclined side and the inclined angle of the second inclined side may be, for example, 30 degrees or greater, 35 degrees or greater, 40 degrees or greater or 45 degrees or greater, and may be 70 degrees or less, 65 degrees or less, 60 degrees or less or 55 degrees or less. Having the difference between the inclined angles of the first inclined side and the second inclined side in the above-mentioned range may be advantageous in terms of obtaining direction-dependent color expression. In other words, when a difference in the inclined angle of the inclined side is in the above-mentioned range, thicknesses of the light absorbing layers each formed on the first inclined side and the second inclined side may become different, and as a result, dichroism may become greater when looking at the decoration element from the same direction (refer to the following Table 2).









TABLE 2









Difference in



Inclined Angle of



First Inclined Side



and



Second Inclined Side











Side of First Inclined Side
Side of Second Inclined Side
















L1*
a1*
b1*
L2*
a2*
b2*
ΔE*ab


















0
25.6
1.2
−1.3
23.8
1.4
−1.8
1.9


10
25.6
1.2
−1.3
24.0
1.4
−2.6
2.1


20
25.6
1.2
−1.3
24.9
0.8
−2.4
1.4


30
34.6
1.1
−5.7
23.8
1.1
−1.1
11.7


40
34.0
1.1
−5.7
23.8
1.1
−1.1
11.2


50
38.1
0.8
−6.3
24.0
1.1
−1.1
15.0


60
39.2
1.2
−6.9
23.8
1.1
−1.1
16.5









In one embodiment of the present specification, the cross-section of the convex portion or concave portion shape may be a polygonal shape of triangle or square. FIG. 16 presents the convex portion shape being a square shape. The square shape may be a general square shape, and is not particularly limited as long as an inclined angle of each inclined side is different. The square shape may be a shape left after partially cutting a triangle. For example, a trapezoid in which one pair of opposite sides is parallel, or a square shape in which a pair of opposite sides parallel to each other is not present may be included. The convex portion shape comprises a first area (F1) comprising a first inclined side, a second area (F2) comprising a second inclined side and a third area (F3) comprising a third inclined side. The third inclined side may or may not be parallel to the ground. For example, when the square shape is a trapezoid, the third inclined side is parallel to the ground. Any one or more of the first inclined side to the third inclined side may have a curved-line shape, and descriptions on the curved-line shape are the same as the descriptions provided above. The combined length of F1+F2+F3 may be defined as a pitch of the convex portion shape, and a description on the pitch is the same as the description provided above.
FIG. 19 presents a method of determining the shape of the convex portion shape. For example, the convex portion shape may have a shape removing a specific area of the ABO1 triangle shape. A method of determining the removed specific area is as follows. Details on the inclined angles c1 and c2 are the same as the descriptions provided above.
1) An arbitrary point P1 on an AO1 segment dividing the AO1 segment in a ratio of L1:L2 is set.
2) An arbitrary point P2 on a BO1 segment dividing the BO1 segment in a ratio of m1:m2 is set.
3) An arbitrary point O2 on an AB segment dividing the AB segment in a ratio of n1:n2 is set.
4) An arbitrary point P3 on an O1O2 segment dividing the O2O1 segment in a ratio of o1:o2 is set.
Herein, the ratios of L1:L2, m1:m2, n1:n2 and o1:o2 are the same as or different from each other, and may be each independently from 1:1000 to 1000:1.
5) The area formed by the P1O1P2P3 polygon is removed.
6) The shape formed by the ABP2P3P1 polygon is employed as the cross-section of the convex portion.
The convex portion shape may be modified to various forms by adjusting the ratios of L1:L2, m1:m2, n1:n2 and o1:o2. For example, the height of the pattern may increase when the L1 and m1 increase, and the height of the concave portion formed on the convex portion may decrease when the o1 increases, and by adjusting the ratio of n1, the position of the lowest point of the concave portion formed on the convex portion may be adjusted to be closer to any one side of the inclined sides of the convex portion.
When the ratios of L1:L2, m1:m2 and o1:o2 are all the same, the cross-section shape may be a trapezoidal shape (FIG. 20A). The height of the trapezoid (ha, hb) may vary by adjusting the ratio of L1:L2. For example, FIG. 20A illustrates a convex portion shape prepared when the L1:L2 ratio is 1:1, and FIG. 20B illustrates a convex portion shape prepared when the L1:L2 ratio is 2:1, and the m1:m2 ratio is 1:1 and the o1:o2 ratio is 1:8.
In one embodiment of the present specification, the convex portion or concave portion shape comprises two or more of the convex portion or concave portion shapes. By having two or more of the convex portion or concave portion shapes as above, dichroism may become greater. Herein, the two or more convex portion or concave portion shapes may have a form of repeating identical shapes, however, shapes different from each other may be included. This is shown in FIGS. 21, 22, 23A and 23B.
FIG. 21 illustrates two or more convex portion shapes that are different from each other being alternately arranged. A shape in which a second convex portion (P2) having a smaller height compared to the convex portion is disposed between the convex portions (P1) may be obtained. Hereinafter, the convex portion stated prior to the second convex portion may be referred to as a first convex portion.
FIG. 22 illustrates a concave portion being included between two or more convex portion shapes. The pattern layer surface may have a shape further comprising a concave portion (P3) having a smaller height compared to the convex portion on a tip portion (pointed part) of the convex portion (P1). Such a decoration element may exhibit an effect of an image color softly changing depending on a viewing angle.
As illustrated in FIGS. 23A and 23B, each shape may be arranged in an inversed phase structure. Like this, the pattern layer comprises a convex portion or concave portion shape, and each of the shapes may be arranged in an inversed phase structure.
Specifically, as illustrated in FIG. 23A, the pattern layer surface may have a shape of a plurality of convex portions being arranged in an inversed phase structure of 180 degrees. Specifically, the pattern layer surface may comprise a first area (C1) in which the second inclined surface has a larger inclined angle compared to the first inclined surface, and a second area (C2) in which the second inclined surface has a larger inclined angle compared to the first inclined surface. In one example, the convex portion included in the first area may be referred to as a first convex portion (P1), and the convex portion included in the second area may be referred to as a fourth a convex portion (P4). As for heights, widths, inclined angles and an angle formed by the first and the second inclined surfaces of the first convex portion (P1) and the fourth convex portion (P4), descriptions provided in the convex portion (P1) section may be used in the same manner.
As illustrated in FIG. 23B, it may be constituted that any one area of the first area and the second area corresponds to an image or a logo, and the other area corresponds to a background part. Such a decoration element may exhibit an effect of an image or logo color softly changing depending on a viewing angle. In addition, a decorative effect of colors of an image or logo part and a background part looking switched depending on a viewing direction.
The first area and the second area may each comprise a plurality of convex portions. Widths and the number of convex portions of the first area and the second area may be properly controlled depending on the size of a target image or logo.
In one embodiment of the present specification, the pattern layer comprises two or more convex portion shapes, and may further comprise a flat portion (G1) in all or a part between each convex portion shape.
As illustrated in FIGS. 17A and 17B, a flat portion may be included between each convex portion of the pattern layer. The flat portion means an area where a convex portion is not present. Other than the pattern layer further comprising a flat portion, descriptions on the remaining constituents (D1, D2, c1, c2, c3, first inclined side and second inclined side) are the same as the descriptions provided above. Meanwhile, the combined length of D1+D2+G1 is defined as a pitch of the pattern, which is different from the width of the pattern described above.
A height (H1) of the convex portion (P1) may be from 5 μm to 30 μm. Having the convex portion height in the above-mentioned range may be advantageous in a production process aspect. In the present specification, the convex portion height may mean a shortest distance between the highest part and the lowest part of the convex portion based on the horizontal surface of the pattern layer. As for the descriptions relating to the height of the convex portion, the same numerical range may also be used in the depth of the concave portion described above.
A width (W1) of the convex portion (P1) may be from 10 μm to 90 μm. Having the convex portion width in the above-mentioned range may be advantages in a process aspect in processing and forming a pattern. The width of the convex portion (P1) may be, for example, 10 μm or greater, 15 μm or greater, 20 μm or greater or 25 μm or greater, and may be 90 μm or less, 80 μm or less, 70 μm or less, 60 μm or less, 50 μm or less, 40 μm or less or 35 μm or less. The descriptions relating to the width may be used in the concave portion described above as well as the convex portion.
A distance between the convex portions (P1) may be from 0 μm to 20 μm. The distance between the convex portions in the present specification may mean, in two adjacent convex portions, a shortest distance between a point where one convex portion ends and a point where another convex portion starts. When properly maintaining the distance between the convex portions, a phenomenon of a reflection area looking dark due to shading when a relatively bright color is to be obtained may be improved when looking at the decoration element from an inclined surface side of the convex portion having a larger inclined angle. Between the convex portions, a second convex portion with a smaller height compared to the convex portion may be present as to be described later. The descriptions relating to the distance may be used in the concave portion described above as well as the convex portion.
A height (H2) of the second convex portion (P2) may be in a range of 1⁄5 to 1⁄4 of the height (H1) of the first convex portion (P1). For example, a height difference (H1-H2) between the first convex portion and the second convex portion may be from 10 μm to 30 μm. A width (W2) of the second convex portion may be from 1 μm to 10 μm. Specifically, the width (W2) of the second convex portion may be 1 μm or greater, 2 μm or greater, 3 μm or greater, 4 μm or greater or 4.5 μm or greater, and may be 10 μm or less, 9 μm or less, 8 μm or less, 7 μm or less, 6 μm or less or 5.5 μm or less.
In one embodiment of the present specification, the second convex portion may have two inclined surfaces (S3, S4) having different inclined angles. An angle (a4) formed by the two inclined surfaces of the second convex portion may be from 20 degrees to 100 degrees. Specifically, the angle (a4) may be 20 degrees or greater, 30 degrees or greater, 40 degrees or greater, degrees or greater, 60 degrees or greater, 70 degrees or greater, 80 degrees or greater or 85 degrees or greater, and may be 100 degrees or less or 95 degrees or less. An inclined angle difference (a6−a5) between both inclined surfaces of the second convex portion may be from 0 degrees to 60 degrees. The inclined angle difference (a6−a5) may be 0 degrees or greater, 10 degrees or greater, 20 degrees or greater, 30 degrees or greater, 40 degrees or greater or 45 degrees or greater, and may be 60 degrees or less or 55 degrees or less. The second convex portion having a dimension in the above-mentioned range may be advantageous in terms of forming bright color by increasing light inflow from a side surface having a large inclined surface angle.
In one embodiment of the present specification, a height (H3) of the concave portion (P3) may be from 3 μm to 15 μm. Specifically, a height (H3) of the concave portion (P3) may be 3 μm or greater, and may be 15 μm or less, 10 μm or less or 5 μm or less. The concave portion may have two inclined surfaces (S5, S6) having different inclined angles. An angle (a7) formed by the two inclined surfaces of the concave portion may be from 20 degrees to 100 degrees. Specifically, the angle (a7) may be 20 degrees or greater, 30 degrees or greater, 40 degrees or greater, 50 degrees or greater, 60 degrees or greater, 70 degrees or greater, 80 degrees or greater or 85 degrees or greater, and may be 100 degrees or less or 95 degrees or less. An inclined angle difference (a9−a8) between both inclined surfaces of the concave portion may be from 0 degrees to 60 degrees. The inclined angle difference (a9−a8) may be 0 degrees or greater, 10 degrees or greater, 20 degrees or greater, 30 degrees or greater, 40 degrees or greater or 45 degrees or greater, and may be 60 degrees or less or 55 degrees or less. The concave portion having a dimension in the above-mentioned range may be advantageous in terms that a color sense may be added on the inclined surface.
In one embodiment of the present specification, the convex portion or concave portion shape on the pattern layer surface may be a cone-shaped convex portion protruding outward from the surface of the pattern layer or a cone-shaped concave portion caved-in inward from the surface of the pattern layer.
In one embodiment of the present specification, the cone shape comprises a shape of a circular cone, an oval cone or a polypyramid. Herein, the shape of the bottom surface of the polypyramid comprises a triangle, a square, a star shape having 5 or more protruding points, and the like. According to one embodiment, when the pattern layer has a cone-shaped convex portion shape when placing the decoration element on the ground, at least one of vertical cross-sections of the convex portion shape with respect to the ground may have a triangular shape. According to another embodiment, when the pattern layer has a cone-shaped concave portion shape when placing the decoration element on the ground, at least one of vertical cross-sections of the concave portion shape with respect to the ground may have an inverted triangular shape.
In one embodiment of the present specification, the cone-shaped convex portion or the cone-shaped concave portion shape may have at least one asymmetric-structured cross-section. For example, when observing the cone-shaped convex portion or concave portion from a surface side of the convex portion or concave portion shape, having two or less identical shapes present when rotating 360 degrees based on the vertex of the cone is advantageous in developing dichroism. FIG. 24 illustrates images when observing the cone-shaped convex portion shape from a surface side of the convex portion shape, and a) all illustrates a symmetric-structured cone shape, and b) illustrates an asymmetric-structured cone shape.
When placing the decoration element on the ground, the symmetric-structured cone shape has a structure in which a cross-section in a direction parallel to the ground (hereinafter, referred to as horizontal cross-section) is a circle or a regular polygon having the same side lengths, and the vertex of the cone is present on a vertical line with respect to the cross-section of the center of gravity of the horizontal cross-section with respect to the ground. However, the cone shape having an asymmetric-structured cross-section has a structure in which, when observing from a surface side of the cone-shaped convex portion or concave portion shape, the position of the vertex of the cone is present on a vertical line of a point that is not the center of gravity of the horizontal cross-section of the cone, or has a structure in which the horizontal cross-section of the cone is an asymmetric-structured polygon or oval. When the horizontal cross-section of the cone is an asymmetric-structured polygon, at least one of the sides and the angles of the polygon may be designed to be different from the rest.
For example, as in FIG. 25, the position of the vertex of the cone may be changed. Specifically, when designing the vertex of the cone to be located on a vertical line of the center of gravity (O1) of the horizontal cross-section of the cone with respect to the ground when observing from a surface side of the cone-shaped convex portion as in the first drawing of FIG. 25, 4 identical structures may be obtained when rotating 360 degrees based on the vertex of the cone (4-fold symmetry). However, the symmetric structure is broken by designing the vertex of the cone on a position (O2) that is not the center of gravity (O1) of the horizontal cross-section with respect to the ground. When employing a length of one side of the horizontal cross-section with respect to the ground as x, migration distances of the vertex of the cone as a and b, a height of the cone shape, a length of a line vertically connecting from the vertex of the cone (O1 or O2) to the horizontal cross-section with respect to the ground, as h, and an angle formed by the horizontal cross-section and a side surface of the cone as θn, cosine values for Surface 1, Surface 2, Surface 3 and Surface 4 of FIG. 25 may be obtained as follows.



 
  
   
    cos
    ⁢
    
     (
     Θ1
     )
    
   
   =
   
    
     (
     
      x
      2
     
     )
    
    
     sqrt
     (
     
      
       h
       2
      
      +
      
       
        (
        
         x
         2
        
        )
       
       2
      
     
     )
    
   
  
  ⁢
  

  
   
    cos
    ⁢
    
     (
     Θ2
     )
    
   
   =
   
    
     (
     
      x
      2
     
     )
    
    
     sqrt
     (
     
      
       h
       2
      
      +
      
       
        (
        
         x
         2
        
        )
       
       2
      
     
     )
    
   
  
  ⁢
  

  
   
    cos
    ⁢
    
     (
     Θ3
     )
    
   
   =
   
    
     (
     
      
       x
       2
      
      -
      a
     
     )
    
    
     sqrt
     (
     
      
       h
       2
      
      +
      
       
        (
        
         
          x
          2
         
         -
         a
        
        )
       
       2
      
     
     )
    
   
  
  ⁢
  

  
   
    cos
    ⁢
    
     (
     Θ4
     )
    
   
   =
   
    
     (
     
      
       x
       2
      
      -
      b
     
     )
    
    
     sqrt
     (
     
      
       h
       2
      
      +
      
       
        (
        
         
          x
          2
         
         -
         b
        
        )
       
       2
      
     
     )
    
   
  
 



Herein, θ1 and θ2 are the same, and therefore, there is no dichroism. However, θ3 and θ4 are different, and |θ3-θ4| means a color difference between two colors (ΔE*ab), and therefore, dichroism may be obtained. Herein, |θ3-θ4|>0. As above, how much the symmetric structure is broken, that is, a degree of asymmetry, may be represented quantitatively using an angle formed by the horizontal cross-section with respect to the ground and a side surface of the cone, and the value representing such a degree of asymmetry is proportional to a color difference of dichroism.
FIGS. 26A and 26B illustrate surfaces having a convex portion shape in which the highest point has a line shape. FIG. 26A illustrates a pattern having a convex portion developing no dichroism and FIG. 26B illustrates a pattern having a convex portion developing dichroism. An X-X′ cross-section of FIG. 26A is an isosceles triangle or an equilateral triangle, and a Y-Y′ cross-section of FIG. 26B is a triangle having different side lengths.
In one embodiment of the present specification, the pattern layer has a surface of a convex portion shape in which the highest point has a line shape or a concave portion shape in which the lowest point has a line shape. The line shape may be a straight-line shape or a curved-line shape, and may comprise both a curve and a straight line, or a zigzag shape. This is illustrated in FIG. 27 to FIG. 29. When observing the surface of the convex portion shape in which the highest point has a line shape or the concave portion shape in which the lowest point has a line shape from a surface side of the convex portion or concave portion shape, having only one identical shape when rotating 360 degrees based on the center of gravity of the horizontal cross-section with respect to the ground of the convex portion or the concave portion is advantageous in developing dichroism.
In one embodiment of the present specification, the pattern layer has a surface of a convex portion or concave portion shape in which a cone-type tip portion is cut. FIG. 30 illustrates images obtaining, when placing a decoration element on the ground, an inversed trapezoidal concave portion in which a cross-section perpendicular to the ground is asymmetric. Such an asymmetric cross-section may have a trapezoidal or inversed trapezoidal shape. In this case, dichroism may also be developed by the asymmetric-structured cross-section.
In addition to the structures illustrated above, various surfaces of convex portion or concave portion shapes, as illustrated in FIGS. 31A to 311, may be obtained.
In the present specification, unless mentioned otherwise, the “surface” may be a flat surface, but is not limited thereto, and a part or all may be a curved surface. For example, the shape of a cross-section in a direction perpendicular to the surface may comprise a structure of a part of an arc of a circle or oval, a wave structure or a zigzag.
In one embodiment of the present specification, the pattern layer comprises a symmetric-structured pattern. As the symmetric structure, a prism structure, a lenticular lens structure and the like are included.
In one embodiment of the present specification, the decoration element comprises a pattern layer comprising a convex portion or concave portion shape having an asymmetric-structured cross-section on a surface facing the light reflective layer of the light absorbing layer; between the light absorbing layer and the light reflective layer; or a surface facing the light absorbing layer of the light reflective layer.
In one embodiment of the present specification, the pattern layer has a flat portion on a surface opposite to the convex portion or concave portion shape-formed surface, and the flat portion may be formed on a substrate. As the substrate layer, a plastic substrate may be used. As the plastic substrate, triacetyl cellulose (TAC); cycloolefin copolymers (COP) such as norbornene derivatives; poly(methyl methacrylate) (PMMA); polycarbonate (PC); polyethylene (PE); polypropylene (PP); polyvinyl alcohol (PVA); diacetyl cellulose (DAC); polyacrylate (Pac); polyether sulfone (PES); polyetheretherketon (PEEK); polyphenylsulfone (PPS), polyetherimide (PEI); polyethylene naphthalate (PEN); polyethylene terephthalate (PET); polyimide (PI); polysulfone (PSF); polyarylate (PAR), amorphous fluorine resins or the like may be used, however, the plastic substrate is not limited thereto.
In one embodiment of the present specification, the pattern layer may comprise a thermal curable resin or an ultraviolet curable resin. As the curable resin, photocurable resins or thermal curable resins may be used. As the photocurable resin, ultraviolet curable resins may be used. Examples of the thermal curable resin may comprise silicone resins, silicon resins, furan resins, polyurethane resins, epoxy resins, amino resins, phenol resins, urea resins, polyester resins, melamine resins or the like, but are not limited thereto. Typical examples of the ultraviolet curable resin may comprise acrylic polymers such as polyester acrylate polymers, polystyrene acrylate polymers, epoxy acrylate polymers, polyurethane acrylate polymers or polybutadiene acrylate polymers, silicone acrylate polymers, alkyl acrylate polymers or the like, but are not limited thereto.
In one embodiment of the present specification, a color dye may be further included inside or on at least one surface of the pattern layer. Comprising a color dye on at least one surface of the pattern layer may, for example, mean a case of comprising a color dye in the substrate layer described above provided on a flat portion side of the pattern layer.
In one embodiment of the present specification, as the color dye, anthraquinone-based dyes, phthalocyanine-based dyes, thioindigo-based dyes, perinone-based dyes, isoxindigo-based dyes, methane-based dyes, monoazo-based dyes, 1:2 metal complex-based dyes and the like may be used.
In one embodiment of the present specification, when comprising the color dye inside the pattern layer, the dye may be added to the curable resin. When further comprising the color dye below the pattern layer, a method of coating a layer comprising the dye above or below the substrate layer may be used.
In one embodiment of the present specification, the color dye content may be, for example, from 0 wt % to 50 wt %. The color dye content may determine transmittance and a haze range of the pattern layer or the decoration element, and the transmittance may be, for example, from 20% to 90%, and the haze may be, for example, from 1% to 40%.
In one embodiment of the present specification, the color developing layer may give metal texture and depth of color when looking at the decoration element. The color developing layer allows an image of the decoration element to be seen in various colors depending on the viewing angle. This is due to the fact that the wavelength of light passing the pattern layer and reflected on an inorganic material layer surface changes depending on the wavelength of incident light.
The color developing layer may have the same convex portion or concave portion as the surface of the pattern layer described above. The color developing layer may have the same slope as the surface of the pattern layer described above.
In one embodiment of the present specification, the decoration element comprises a protective layer provided between the substrate and the color developing layer; a surface facing the substrate of the color developing layer; or a surface facing the color developing layer of the substrate.
In one embodiment of the present specification, the decoration element comprises a protective layer provided any one or more of between the substrate and the pattern layer, between the pattern layer and the light reflective layer, between the light reflective layer and the light absorbing layer, and on a surface opposite to the surface facing the light reflective layer of the light absorbing layer. In other words, the protective layer performs a role of protecting the decoration element by being provided between each layer of the decoration element or at an outermost part of the decoration element.
In the present specification, unless defined otherwise, the “protective layer” means a layer capable of protecting other layers of the decoration element. For example, deterioration of an inorganic material layer may be prevented under a humidity resistant or heat resistant environment. Alternatively, scratching on an inorganic material layer or a pattern layer by external factors is effectively suppressed enabling the decoration element to effectively develop dichroism.
In the present specification, unless defined otherwise, the ‘inorganic material layer’ means a light absorbing layer or a light reflective layer.
In the present specification, an example of the decoration element structure comprising the protective layer is as follows.
For example, a structure of substrate/protective layer/pattern layer/light reflective layer/light absorbing layer/protective layer or substrate/protective layer/pattern layer/light absorbing layer/light reflective layer/protective layer may be included.
In one embodiment of the present specification, the protective layer comprises an aluminum oxynitride. By the protective layer comprising an aluminum oxynitride (AlON), functions of the protective layer to describe later may be enhanced compared to when the protective layer does not comprise an aluminum oxynitride (AlON). In addition, functions of protection may be further enhanced when adjusting a ratio of each element of the aluminum oxynitride.
In one embodiment of the present specification, by further comprising the protective layer, the decoration element suppresses damages on the pattern layer and the organic material layer even when being left unattended under a high temperature and high humidity environment, and therefore, excellent decorative effects may be maintained even under a harsh environment.
The decoration element of the present specification may be used in known subjects requiring the use of a decoration element. For example, they may be used without limit in portable electronic devices, electronic goods, cosmetic containers, furniture, building materials and the like.
A method of using the decoration element in portable electronic devices, electronic goods, cosmetic containers, furniture, building materials and the like is not particularly limited, and known methods known as a method of using a deco film in the art may be used. The decoration member may further comprise a gluing layer as necessary. In another example, the decoration element may be used in portable electronic devices or electronic goods by direct coating. In this case, a separate gluing layer for attaching the decoration element to the portable electronic devices or the electronic goods may not be required. In another example, the decoration element may be attached to portable electronic devices or electronic goods using a gluing layer as a medium. As the gluing layer, an optically clear adhesive tape (OCA tape) or an adhesive resin may be used. As the OCA tape or the adhesive resin, OCA tapes or adhesive resins known in the art may be used without limit. As necessary, a peel-off layer (release liner) may be further provided for protecting the gluing layer.
In one embodiment of the present specification, the light reflective layer and the light absorbing layer may each be formed on a substrate or a pattern of a pattern layer of the substrate using a sputter method, an evaporation method, a vapor deposition method, a chemical vapor deposition (CVD) method, wet coating and the like. Particularly, the sputter method has straightness, and therefore, a difference in the deposition thicknesses of both inclined surfaces of the convex portion may be maximized by tilting a position of a target.
In one embodiment of the present specification, the light reflective layer and the light absorbing layer may each be formed using a reactive sputtering method. Reactive sputtering is a method in which ions having energy (for example, Ar−) impacts a target material, and the target material come off herein is deposited on a surface to deposit. Herein, the base pressure is 1.0×10−5 torr or less, 6.0×10−6 torr or less, and 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 comprising a plasma gas and a reactive gas. The plasma gas may be argon (Ar) gas. In addition, the reactive gas required to form the inorganic material layer is oxygen (O2) and nitrogen (N2), and, as a gas for providing an oxygen or nitrogen atom, is distinguished from the plasma gas.
In one embodiment of the present specification, the plasma gas may have a flow rate of greater than or equal to 10 sccm and less than or equal to 300 scan, and preferably greater than or equal to 20 scan and less than or equal to 200 scan. The scan means a standard cubic centimeter per minute.
In one embodiment of the present specification, a process pressure (p1) in the chamber may be from 1.0 mtorr to 10.0 mtorr, and preferably from 1.5 mtorr to 10.0 mtorr. When the process pressure is greater than the above-mentioned range during the sputtering, Ar particles present inside the chamber increase, and particles emitted from a target collide with the Ar particles losing energy, which may decrease a growth rate of the thin film. When the process pressure is maintained too low on the other hand, an energy loss of the aluminum oxynitride particles caused by the Ar particles decreases, however, there is a disadvantage in that a substrate may be damaged due to particles having high energy, or qualities of the protective layer may decrease.
In one embodiment of the present specification, the reactive gas may have a fraction of greater than or equal to 30% and less than or equal to 70%, preferably greater than or equal to 40% and less than or equal to 70%, and more preferably greater than or equal to 50% and less than or equal to 70% with respect to the plasma gas. The reactive gas fraction may be calculated by (Qreactive gas/(Qplasma process gas+Qreactive gas)*100%). The Qreactive gas may mean a flow rate of the reactive gas inside the chamber, and Qplasma process gas may be a flow rate of the plasma process gas inside the chamber. When satisfying the above-mentioned numerical range, the atomic ratio of the aluminum oxynitride described above may be adjusted to a target range.
In one embodiment of the present specification, the reactive sputtering method may have driving power of greater than or equal to 100 W and less than or equal to 500 W, and preferably greater than or equal to 150 W and less than or equal to 300 W.
In one embodiment of the present specification, a range of the voltage applied in the reactive sputtering method may be greater than or equal to 350 V and less than or equal to 500 V. The voltage range may be adjusted depending on 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 reactive sputtering method may have a deposition temperature of higher than or equal to 20° C. and lower than or equal to 300° C. When depositing at a temperature lower than the above-mentioned range, there is a problem in that particles come off from the target and reaching the substrate have insufficient energy required for crystal growth decreasing crystallinity of thin film growth, and at a temperature higher than the above-mentioned range, particles come off from the target evaporate or re-evaporate causing a problem of reducing a thin film growth rate.
Hereinafter, the present application will be specifically described with reference to examples, however, the scope of the present specification is not limited by the following examples.
EXAMPLE AND COMPARATIVE EXAMPLE
Comparative Example 1
A prism-shaped pattern layer having each inclined angle of 20 degrees/70 degrees was formed by coating an ultraviolet curable resin on a PET substrate. After that, a color developing layer comprising a light absorbing layer and a light reflective layer was formed on the pattern layer using a reactive sputtering method.
Specifically, a 60 nm light absorbing layer having a composition of the following Table 3 was formed by using a reactive sputtering method and adjusting a nitrogen gas flow rate to 1.5% to 13.0% compared to an argon gas flow rate. After that, In having a thickness of 70 nm was deposited on the light absorbing layer using a sputtering method to form a light reflective layer.
Comparative Example 2
A decoration element was prepared in the same manner as in Comparative Example 1 except that flow rates of the oxygen gas and the nitrogen gas were each adjusted to 12.8% compared to the argon gas flow rate. In addition, the light absorbing layer thickness was adjusted to 80 nm.
Comparative Example 3
A decoration element was prepared in the same manner as in Comparative Example 1 except that flow rates of the oxygen gas and the nitrogen gas were each adjusted to 13% compared to the argon gas flow rate. In addition, the light absorbing layer thickness was adjusted to 100 nm.
Example 1
A decoration element was prepared in the same manner as in Comparative Example 1 except that flow rates of the oxygen gas and the nitrogen gas were each adjusted to 13% compared to the argon gas flow rate. In addition, the light absorbing layer thickness was adjusted to 20 nm.
Example 2
A decoration element was prepared in the same manner as in Comparative Example 1 except that flow rates of the oxygen gas and the nitrogen gas were each adjusted to 13% compared to the argon gas flow rate. In addition, the light absorbing layer thickness was adjusted to 40 nm.
Example 3
A decoration element was prepared in the same manner as in Comparative Example 1 except that flow rates of the oxygen gas and the nitrogen gas were each adjusted to 13% compared to the argon gas flow rate. In addition, the light absorbing layer thickness was adjusted to 50 nm.
Light absorbing layer thicknesses, thickness parameters, and component ratios at each location of the examples and the comparative examples were measured and shown in the following Table 3.











TABLE 3








Light 
Thickness 
Component Ratio at Each Location (AlaObNc)
















Absorbing Layer
Parameter Tx
σx 



ω Value 



Thickness (T1)
(Equation 2)
(Equation 3)
a (*10−2)
b (*10−2)
c(*10−2)
(Equation 1)

















Example 1
20 nm
0.2
1.2
57.5
9.8
39.7
0.24


Example 2
40 nm
0.4
1.3
58.6
6.9
39.7
0.52


Example 3
50 nm
0.5
1.4
58.6
3.0
39.2
0.7


Comparative Example 1
60 nm
0.6
1.4
58.5
2.0
39.3
0.84


Comparative Example 2
80 nm
0.8
1.4
58.6
1.9
39.2
1.12


Comparative Example 3
100 nm 
1
1.4
58.6
1.7
39.3
1.4









Evaluation Example (Evaluation on Color)
Component ratios of the decoration elements prepared in the examples and the comparative examples were analyzed, and colors appearing by each thickness were observed, and recorded in the following Table 4.












TABLE 4









h*





L*Ch
Value
Color









Example 1
91, 11, 95
 95°
Warm Tone



Example 2
65, 48, 77
 77°




Example 3
47, 21, 9
 9°




Comparative Example 1
48, 21, 283
283°
Cool Tone



Comparative Example 2
68, 12, 235
235°




Comparative Example 3
77, 9, 134
134°










In the decoration elements of Examples 1 to 3, wait colors appeared, however, cool colors appeared in Comparative Examples 1 to 3. Through this, it was identified that warm colors appeared when changing the thickness even when the compositions (AlON) of the light absorbing layers were the same.
From the results, it was identified that warm tone colors appeared when ω represented by Equation 1 was 0.8 or less, however, cool tone colors appeared when ω was greater than 0.8.

## Claims

1. A decoration element comprising:
a color developing layer comprising a light reflective layer and a light absorbing layer provided on the light reflective layer; and
a substrate provided on a surface of the color developing layer,
wherein the substrate comprises a pattern layer,
wherein the light absorbing layer comprises an aluminum oxynitride (AlaObNc); and
wherein ω represented by the following Equation 1 is 0.8 or less:




 
  
   
    
     ω
     =
     
      
       (
       
        T
        X
       
       )
      
      ×
      
       (
       
        σ
        X
       
       )
      
     
    
   
   
    
     [
     
      Equation
      ⁢
         
      1
     
     ]
    
   
  
 




 
  
   
    
     Tx
     =
     
      
       {
       
        
         T
         1
        
        -
        
         
          [
          
           
            T
            1
           
           
            T
            0
           
          
          ]
         
         ×
         
          T
          0
         
        
       
       }
      
      ×
      
       
        (
        
         T
         0
        
        )
       
       
        -
        1
       
      
     
    
   
   
    
     [
     
      Equation
      ⁢
         
      2
     
     ]
    
   
  
 




 
  
   
    
     
      σ
      X
     
     =
     
      
       3
       ⁢
       a
      
      
       
        2
        ⁢
        b
       
       +
       
        3
        ⁢
        c
       
      
     
    
   
   
    
     [
     
      Equation
      ⁢
         
      3
     
     ]
    
   
  
 


wherein ω is a relation between a content ratio of each element of the aluminum oxynitride and a thickness of the light absorbing layer at any one point of the light absorbing layer;
wherein in Equation 1, Tx is represented by Equation 2, and σx is represented by Equation 3;
wherein in Equation 2, T1 (nm) is the thickness of the light absorbing layer comprising the any one point of the light absorbing layer, T0 is 100 nm, and




 
  [
  
   
    T
    1
   
   
    T
    0
   
  
  ]
 



is a maximum integer that is not greater than



 
  
   
    T
    1
   
   
    T
    0
   
  
  ;
 



with the proviso that when T1 is m*T0, Tx is 1 and when T1 is not m*T0, Tx satisfies Equation 2, and m is an integer of 1 or greater;
wherein in Equation 3, a is an element content ratio of aluminum (Al), b is an element content ratio of oxygen (O), and c is an element content ratio of nitrogen (N), wherein the element content ratio is an atomic percent (at %) of an element at the any one point of the light absorbing layer;
wherein the pattern layer comprises a convex portion or a concave portion;
wherein each of the convex portion and the concave portion has an asymmetric cross-section;
wherein in each of the convex portion and the concave portion having an asymmetric cross-section, at least one cross-section comprises a first inclined side and a second inclined side having different inclined angles; and
wherein an angle formed by the first inclined side and the second inclined side is in a range of 80° to 100°.

2. The decoration element of claim 1, wherein Tx is greater than or equal to 0.01 and less than or equal to 0.5.

3. The decoration element of claim 1, wherein σx is greater than or equal to 1.1 and less than or equal to 1.9.

4. The decoration element of claim 1, wherein a hue-angle h* in CIE L*Ch color space of the light absorbing layer ranges from 315° to 360° and 0° to 150°.

5. The decoration element of claim 1, wherein the light reflective layer is a single layer or a multilayer comprising one or more materials selected from the group consisting of 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 (Nd), iron (Fe), chromium (Cr), cobalt (Co), gold (Au), silver (Ag), oxides thereof, nitrides thereof, oxynitrides thereof, carbon and carbon composites.

6. The decoration element of claim 1, wherein the light absorbing layer has a refractive index of 0 to 8 at a wavelength of 400 nm.

7. The decoration element of claim 1, wherein the light absorbing layer has an extinction coefficient of greater than 0 and less than or equal to 4 at a wavelength of 400 nm.

8. The decoration element of claim 1, wherein the light absorbing layer comprises two or more points with different thicknesses.

9. The decoration element of claim 1, wherein the color developing layer further comprises a color film.

10. The decoration element of claim 1, wherein the light absorbing layer has dichroism when a color difference ΔE*ab of the color developing layer is greater than 1, and wherein the color difference ΔE*ab is a difference in color coordinates L*a*b* in a color coordinate CIE L*a*b* of the color developing layer.

11. The decoration element of claim 1, wherein the substrate comprises a plastic injection molded article or a glass substrate.

12. The decoration element of claim 11, wherein the plastic injection molded article comprises one or more materials selected from the group consisting of polypropylene (PP), polystyrene (PS), polyvinyl acetate (PVAc), polyacrylate, polyethylene terephthalate (PET), polyvinyl chloride (PVC), polymethyl methacrylate (PMMA), an ethylene-vinyl acetate copolymer (EVA), a polycarbonate (PC), a polyamide and a styrene-acrylonitrile copolymer.