CN109613637A - Decorating film - Google Patents

Decorating film Download PDF

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Publication number
CN109613637A
CN109613637A CN201710939113.1A CN201710939113A CN109613637A CN 109613637 A CN109613637 A CN 109613637A CN 201710939113 A CN201710939113 A CN 201710939113A CN 109613637 A CN109613637 A CN 109613637A
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index material
refractive index
material layer
layer
cosine
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CN109613637B (en
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于甄
张国臻
夏振
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Zhangjiagang Kangdexin Optronics Material Co Ltd
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Zhangjiagang Kangdexin Optronics Material Co Ltd
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/08—Mirrors
    • G02B5/0816—Multilayer mirrors, i.e. having two or more reflecting layers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention provides a kind of decorating films.The reflection membrane system of decorating film includes the refractive material portion of hollow out, and refractive material portion includes that at least one film structure is │ (α1Hβ1Lα2Hβ2L...αmHβmL) the membrane stack of │, wherein H indicates high refractive index material layer, and L indicates low refractive index material layer, and n, m are positive integer, and 3 < n≤150,3 < m≤50, m≤n, the α in the same membrane stack1, α2..., αmAnd βm..., β2, β1Meet the same gradation law on the same cosine waveform or sinusoidal waveform each independently；For low-index material unit α i-th highiHβiL, 1≤i≤n, αiIndicate that i-th of high refractive index material layer optical thickness accounts for the multiple of λ/4, βiIndicate that i-th of low refractive index material layer optical thickness accounts for the multiple of λ/4, λ is the supervisory wavelength of membrane stack.The pattern color that the refractive material portion of decorating film is shown is sharp keen.

Description

Decorating film
Technical field
The present invention relates to optic film structure fields, in particular to a kind of decorating film.
Background technique
In-mold decoration forming technology is widely used in the appearance members such as electronic product, household electrical appliances, locomotive, it is known that mould it is built-in When decorations forming technique is used in production with the mirror surface or color changeable effect for dazzling beautiful shell, it is necessary to be coated with one layer or more in substrate surface The metal or pigment figure layer of layer, and if desired reach the effect for changing different colours according to different perspectives, with greater need for Multideck The mode of plating is made, but the poor ductility of the coat of metal formed is deposited, so that the qualification of in-mold decoration forming technique Rate is low, can not promote whole product quality.
In order to solve the defect of the above-mentioned coat of metal, the principle of interference that the prior art is generated based on multi-layer optical film is utilized Multi-layer optical film also becomes a kind of effective decorative means as decorating film, although multi-layer optical film is sent out with visual angle change color Changing, but the color-gamut presented is poor, albefaction is serious, color does not have apparent identity, therefore its decorative effect It is difficult to reach the decorative effect of the coat of metal.
Summary of the invention
The main purpose of the present invention is to provide a kind of decorating films, to solve the decoration of multi-layer optical film in the prior art The problem of effect difference.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of decorating film, comprising: transparent substrate Layer has opposite first surface and second surface；Membrane system is reflected, the first surface and/or second of transparent substrate layer is set On surface, reflection membrane system includes the refractive material portion of hollow out, and each high low-index material unit includes a high-index material Layer and a paired low refractive index material layer, refractive material portion include that at least one film structure is │ (α1Hβ1Lα2Hβ2L...αmHβmL) the membrane stack of │, wherein H indicates high refractive index material layer, and L indicates low refractive index material layer, and n, m are positive integer, And 3 < n≤150,3 < m≤50, m≤n, the α in the same membrane stack1, α2..., αmAnd βm..., β2, β1Each independently Meet the same gradation law on the same cosine waveform or sinusoidal waveform；For low-index material unit α i-th highiHβiL, 1≤i≤n, αiIndicate that i-th of high refractive index material layer accounts for λ/4 along optical thickness on the direction vertical with transparent substrate layer Multiple, βiIndicate that i-th of low refractive index material layer accounts for the multiple of λ/4, λ along optical thickness on the direction vertical with transparent substrate layer For the supervisory wavelength of membrane stack.
Further, in the above-mentioned same membrane stack, for low-index material unit α i-th highiHβiL, high refractive index material The optical thickness of the bed of material is αi*λ/4, the optical thickness of low refractive index material layer are βi*λ/4, the refractive index of high refractive index material layer For NH, the physical thickness of high refractive index material layer is DH, then there is NH*DH=αi*λ/4；The refractive index of low refractive index material layer is NL, the physical thickness of low refractive index material layer is DL, then there is NL*DL=βi* λ/4 wherein, α1, α2..., αmAnd βm..., β2, β1Meet each independently selected from range 0~2 π the same sinusoidal waveform or cosine waveform upper left semifocal chord (such as 0~ String between pi/2), lower-left semifocal chord (such as string between pi/2~π), upper right semifocal chord (such as string between the pi/2 of π~3) and bottom right Same gradation law on semifocal chord (string between 3 pi/2s~2 π).
Further, when above-mentioned decorating film is using 455nm as supervisory wavelength, αi, βiValue range exist: 0.01≤αi≤ 3.2,0.01≤βi≤ 3.2, it is preferable that 0.05≤αi≤ 2.8,0.05≤βi≤2.8；Preferably, 0.1≤αi≤ 2.8,0.1≤ βi≤2.8；It is further preferable that 0.2≤αi≤ 2.7,0.2≤βi≤2.7。
Further, the quantity of the high low-index material unit of above-mentioned membrane stack accounts for the high low-refraction in refraction materials portion The 60~99% of the total quantity of material cell.
Further, the physical thickness of above-mentioned high refractive index material layer be 1~400nm, preferably 10~150nm, preferably The physical thickness of low refractive index material layer is 1~400nm, preferably 10~150nm.
Further, the refractive index of above-mentioned high refractive index material layer is 1.5~5.0, preferably 1.65~3.0, low refraction The refractive index of rate material layer is 1.1~1.5, preferably 1.25~1.48.
Further, the refraction materials of above-mentioned high refractive index material layer and low refractive index material layer are formed each independently Selected from MgF2、CaF2, transition metal fluorides, ZnO, TiO2、TiN、In2O3、SnO3、Cr2O3、ZrO2、Ta2O5、LaB6、NbO、 Nb2O3、Nb2O5、SiO2、SiC、Si3N4、Al2O3, fluorine resin, in the resin containing hollow silica any one or it is more Kind.
Further, total number of plies of above-mentioned high refractive index material layer and low refractive index material layer is 12~60.
Further, the optical admittance of above-mentioned high low-index material unit is greater than 1.5 or 1 < A < 1.2, decorating film energy Enough width range reflection wavelengths with 20~50nm are in 380~1200nm range light.
Further, above-mentioned reflection membrane system further includes transparent levelling blanket, and the sky in refractive material portion is arranged in transparent levelling blanket Making the surface for reflecting the separate transparent substrate layer of membrane system in gap is plane, and preferably the shape in refractive material portion is lines, figure Or text.
Further, above-mentioned reflection membrane system further includes one or more layers adhesive layer, and the adjacent membrane stack in part passes through adhesive layer Bonding.
Further, above-mentioned adhesive layer be OCA glue-line or PSA glue-line, preferably adhesive layer with a thickness of 0.005~0.2mm.
Further, above-mentioned transparent substrate layer be pet layer, COP layers, COC layers, CPI layers, PMMA layers, PEN layers, PC layers or TAC layer, preferably clear substrate layer with a thickness of 1~50 μm.
Further, light absorber, preferably light absorption are additionally provided in above-mentioned refractive material portion or in transparent substrate layer Agent is arranged at least partly high refractive index material layer and/or at least partly low refractive index material layer or refractive material portion is also wrapped One or more layers light absorption oxidant layer is included, light absorption oxidant layer is adjacent with part high refractive index material layer and low refractive index material layer to be set It sets.
Further, above-mentioned light absorber is selected from inorganic light absorber, organic light absorber and organic and inorganic compound light combination and inhales Any one or more in agent is received, preferably inorganic light absorber is metal oxide or metallic salt, wherein metal oxide It is copper, chromium, iron or cadmium with the metal in metallic salt, preferably organic light absorber is phthalocyanine, porphyrin or azo, organic and inorganic compound Light combination absorbent is phthalocyanine metal chelate, porphyrin metal chelate or azo-metal chelate.
According to another aspect of the present invention, a kind of decorating film, the representation of the decorating film are provided are as follows: Sub │ (α1Hβ1L α2Hβ2L...αmHβmL)N0│ Air, wherein Sub represents transparent substrate layer and decorating film, │ (α1Hβ1Lα2Hβ2L...αmHβmL)N0│ Indicate membrane stack, membrane stack is engraved structure, and Air represents atmosphere, and H is high refractive index material layer, and L is low refractive index material layer；One High refractive index material layer and a matching low refractive index material layer form one high low-index material unit, and m is certainly So number, and 3 m≤50 <；N0 indicates the quantity of membrane stack, 1≤N0 < 10；For low-index material unit α i-th highiHβiL, 1 ≤ i≤n, αiIndicate that i-th of high refractive index material layer accounts for times of λ/4 along optical thickness on the direction vertical with transparent substrate layer Number, βiIndicate that i-th of low refractive index material layer accounts for the multiple of λ/4 along optical thickness on the direction vertical with transparent substrate layer；α1, α2..., αmAnd βm..., β2, β1The middle part for meeting the same gradation law on same sinusoidal waveform is sinusoidal alternation area； α1, α2..., αmAnd βm..., β2, β1In to be unsatisfactory for the part of same gradation law on same sinusoidal waveform be sinusoidal excellent Change area or α1, α2..., αmAnd βm..., β2, β1The middle part for meeting the same gradation law in same cosine waveform is Cosine alternation area；α1, α2..., αmAnd βm..., β2, β1In be unsatisfactory for the portion of same gradation law in same cosine waveform It is divided into cosine optimization area, wherein the high refractive index material layer and low refractive index material layer in sinusoidal alternation area or cosine alternation area The sum of quantity accounts for 60~99% of the sum of quantity of high refractive index material layer and low refractive index material layer in membrane stack.
Further, the α in above-mentioned cosine alternation area1, α2..., αmThe upper left semifocal chord for meeting cosine waveform is incremented by, β1, β2..., βmThe upper right semifocal chord for meeting cosine waveform successively decreases, and cosine optimization area is located at the both ends in cosine alternation area, and cosine optimizes α in area1, α2..., αmWith one-to-one β1, β2..., βmDifference be less than and the α in cosine alternation area1With β1Difference And αmWith βmDifference；Or the α in cosine alternation area1, α2..., αmThe lower-left semifocal chord for meeting cosine waveform is incremented by, β1, β2..., βmThe bottom right semifocal chord for meeting cosine waveform successively decreases, and cosine optimization area is located at the both ends in cosine alternation area, and cosine optimizes α in area1, α2..., αmWith one-to-one β1, β2..., βmDifference be less than and the α in cosine alternation area1With β1Difference And αmWith βmDifference.
Further, the α in above-mentioned sinusoidal alternation area1, α2..., αmThe upper left semifocal chord for meeting institute's sine and cosine waveform is incremented by, β1, β2..., βmThe upper right semifocal chord for meeting sinusoidal waveform successively decreases, and sinusoidal optimization area is located at the both ends in sinusoidal alternation area, and sinusoidal excellent Change the α in area1, α2..., αmWith one-to-one β1, β2..., βmDifference be less than and the α in sinusoidal alternation area1With β1Difference Value and αmWith βmDifference；Or the α in sinusoidal alternation area1, α2..., αmThe lower-left semifocal chord for meeting sinusoidal waveform is incremented by, β1, β2..., βmThe bottom right semifocal chord for meeting sinusoidal waveform successively decreases, and sinusoidal optimization area is located at the both ends in sinusoidal alternation area, and sinusoidal optimization α in area1, α2..., αmWith one-to-one β1, β2..., βmDifference be less than and the α in sinusoidal alternation area1With β1Difference And αmWith βmDifference.
Further, the high low-index material number of unit in above-mentioned each membrane stack is repaired by waveform compensation coefficient factor Decorations, factor are equal to α1, α2..., αmAnd βm..., β2, β1The cosine waveform respectively formed accounts for complete a quarter waveform Ratio, and work as α1, α2..., αmAnd βm..., β2, β1Independently meet upper left semifocal chord waveform, lower-left semifocal chord waveform, upper right semifocal chord Factor is 1, when factor is less than 1, each film when the complete a quarter waveform of one of waveform and bottom right semifocal chord waveform The high low-index material number of unit of compensation in heap is less than or equal to the 1- of the high low-index material number of unit of membrane stack Factor times, and compensate in high low-index material unit, the optical thickness coefficient and low-refraction material of high refractive index material layer The optical thickness coefficient of the bed of material and and the deviation of the optical thickness coefficient in its cosine waveform for compensating be less than ± 20%.
Further, it is additionally provided with light absorber in above-mentioned membrane stack or transparent substrate layer, preferably light absorber setting exists At least partly high refractive index material layer and/or at least partly in low refractive index material layer or membrane stack further includes one or more layers light Absorber layer, light absorption oxidant layer are disposed adjacent with part high refractive index material layer and low refractive index material layer.
Further, above-mentioned decorating film further includes transparent levelling blanket, and transparent levelling blanket is arranged in the gap of engraved structure And the surface of the separate transparent substrate layer of the surface of the separate transparent substrate layer of membrane stack and transparent levelling blanket forms a plane, It is preferred that engraved structure is lines, figure or text.
It applies the technical scheme of the present invention, the distance between adjacent high refractive index layer and adjacent low refractive index material layer The distance between that is, the distance of wall, and according to Fabry-Perot interference principle, the distance of wall is λ/4 Interference reaches cosine wave property that is maximum, and transmitting according to the duality principle of light when multiple, and the period of cosine becomes larger, because This is │ (α by the way that film structure is arranged in reflection membrane system1Hβ1Lα2Hβ2L...αmHβmL) the membrane stack of │, due to the height folding of membrane stack The optical thickness coefficient (such as α and β) for penetrating rate material layer and low refractive index material layer follows the regular alternation of cosine waveform, i.e., adjacent The distance between high refractive index layer and the distance between adjacent low refractive index material layer the regular alternation of cosine waveform is presented, Will make the interference effect of specific wavelength is enhanced, then the wavelength band that corresponding respective indices of refraction forms interference will be presented The trend to narrow, i.e., the range of light wavelengths that the membrane stack can make reflectivity sharp change occur largely narrow, to occur The effect of narrowband reflection；And since the membrane stack of the application is engraved structure, thus it is shown that the pierced pattern shape of membrane stack, When facing the decorating film, it is based on narrowband reflection effect, which has bright-colored sharp keen appreciation effect, when viewing angle is inclined When shifting, pattern color changes, and the rear pattern color changed is still more sharp keen, to realize decoration effect more outstanding Fruit, can be applied to the decoration of building materials, household electrical appliances 3C Product, and realize identification decorative effect outstanding.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present invention, and of the invention shows Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 shows the schematic diagram of the section structure for the decorating film that a kind of preferred embodiment according to the present invention provides；
Fig. 2 shows the schematic diagram of the section structure for the decorating film that another preferred embodiment according to the present invention provides；
Fig. 3 shows the schematic diagram of the section structure for the decorating film that another preferred embodiment according to the present invention provides；
Fig. 4 shows the decorating film using Essential Macleod Film Design software to embodiment 1 according to the present invention Light reflective properties simulation test figure；
Fig. 5 shows the transmissivity optical system for testing system structure diagram of according to embodiments of the present invention 2 decorating film；
The knot for the light reflectivity that the transmittance test result that Fig. 6 shows according to embodiments of the present invention 2 decorating film obtains Fruit figure；
Fig. 7 shows the decorating film using Essential Macleod Film Design software to embodiment 3 according to the present invention Light reflective properties simulation test figure；
Fig. 8 shows the decorating film using Essential Macleod Film Design software to embodiment 4 according to the present invention Light reflective properties simulation test figure；
Fig. 9 shows the decorating film using Essential Macleod Film Design software to embodiment 5 according to the present invention Light reflective properties simulation test figure；
Figure 10 shows the decoration using Essential Macleod Film Design software to embodiment 6 according to the present invention The simulation test figure of the light reflective properties of film；And
Figure 11 shows the decoration using Essential Macleod Film Design software to embodiment 7 according to the present invention The simulation test figure of the light reflective properties of film.
Wherein, the above drawings include the following reference numerals:
10, transparent substrate layer；20, refractive material portion；21, high refractive index material layer；22, low refractive index material layer；23, it glues Tie layer；24, light absorption oxidant layer；30, transparent levelling blanket.
W1, tungsten lamp；D1, deuterium lamp；M1~M10, reflecting mirror；G, grating；S1, entrance slit；S2, exit slit；C, chopping the light tune Device processed；R, reference light colorimetric pool；S, sample light colorimetric pool；PMT, photomultiplier tube.
Specific embodiment
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase Mutually combination.The present invention will be described in detail below with reference to the accompanying drawings and embodiments.
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete Site preparation description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Below Description only actually at least one exemplary embodiment be it is illustrative, never as to the present invention and its application or make Any restrictions.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creative work premise Under every other embodiment obtained, shall fall within the protection scope of the present invention.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root According to exemplary embodiments of the present invention.As used herein, unless the context clearly indicates otherwise, otherwise singular Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
As the application background technique is analyzed, decorating film in the prior art, decorative effect is difficult to reach metal-plated The decorative effect of layer, using the gamut differences of the optical device of decorating film, albefaction is serious, role's product effect is poor, asks to solve this Topic, this application provides a kind of decorating films, and as illustrated in fig. 1 and 2, which includes transparent substrate layer 10 and reflect membrane system, thoroughly Bright substrate layer 10 has opposite first surface and second surface；The first surface of transparent substrate layer 10 is arranged in reflection membrane system And/or on second surface, reflection membrane system includes the refractive material portion 20 of hollow out, and refractive material portion 20 includes n stacked height Refraction materials unit, each high low-index material unit include that a high refractive index material layer 21 and paired one are low Refractive index material 22, refractive material portion 20 include that at least one film structure is │ (α1Hβ1Lα2Hβ2L...αmHβmL) the film of │ Heap, wherein H indicates high refractive index material layer 21, and L indicates low refractive index material layer 22, and n, m are positive integer, and 3 < n≤150,3 < m≤50, m≤n, the α in the same membrane stack1, α2..., αmAnd βm..., β2, β1Meet the same cosine each independently Same gradation law on waveform or sinusoidal waveform；For low-index material unit α i-th highiHβiL, 1≤i≤n, αiTable Show that the optical thickness along the direction vertical with transparent substrate layer 10 of i-th of high refractive index material layer 21 accounts for the multiple of λ/4, βiIt indicates I-th of low refractive index material layer 22 optical thickness along the direction vertical with transparent substrate layer 10 accounts for the multiple of λ/4, and λ is membrane stack Supervisory wavelength.
It should be noted that the above-mentioned sinusoidal waveform of the application and cosine waveform are standard sine waveform in coordinate system and remaining The variation tendency (being only limitted to variation tendency, specific value is not limited by quadrant and positive and negative values) of string waveform, i.e. sinusoidal waveform packet Include symmetrically arranged upper semifocal chord and lower semifocal chord, upper semifocal chord includes upper left semifocal chord and upper right semifocal chord, lower semifocal chord include lower-left semifocal chord and Bottom right semifocal chord；Cosine waveform includes symmetrically arranged left semifocal chord and right semifocal chord, and left semifocal chord is the string that successively decreases, and right semifocal chord is to be incremented by string, Left semifocal chord includes upper left semifocal chord and lower-left semifocal chord, and right semifocal chord includes upper right semifocal chord and bottom right semifocal chord.
Since the difference that cosine waveform and sinusoidal waveform are phase generates.In order to express easily, below only with regard to cosine Waveform is illustrated.Currently in order to realizing narrowband reflection, the prior art is dedicated to increasing high refractive index material layer in reflection membrane system The selection of design and refractive material with the low refractive index material layer number of plies, present inventor have been surprisingly found that under study for action, when The thickness change of high refractive index material layer and low refractive index material layer for reflection peak bandwidth there are directly related property, be based on this Present inventor has made intensive studies the thickness change rule of high refractive index material layer and low refractive index material layer, concurrently The regular alternation that the optical thickness coefficient of existing high refractive index material layer 21 and low refractive index material layer 22 follows cosine waveform is formed Cosine membrane stack to reduce reflection peak bandwidth have effect outstanding.Action principle therein, inventor think:
According to Fabry-Perot (Fabry-Perot) principle of interference, when the frequency of incident light meets its resonance condition, Its transmission spectrum will appear very high peak value, correspond to very high transmissivity.Assuming that interference strength is distributed:
I in formula0For incident intensity；R is the energy reflectivity of reflecting surface；Phase difference of the δ between adjacent two coherent light, and enters Penetrate that light inclination angle is related, R+T=1 (R is the surface reflectivity of membrane system, and T is transmissivity).The distance between adjacent high refractive index layer And the distance between adjacent low refractive index material layer that is, wall distance, and according to Fabry-Perot interference original Reason, interference reaches cosine baud that is maximum, and transmitting according to the duality principle of light when the distance of wall is the multiple of λ/4 Property, the period of cosine becomes larger, therefore by reflection membrane system setting film structure be │ (α1Hβ1Lα2Hβ2L...αmHβmL) the membrane stack of │, due to the high refractive index material layer 21 of membrane stack and the optical thickness coefficient (such as α and β) of low refractive index material layer 22 The regular alternation for following cosine waveform, i.e., between the distance between adjacent high refractive index layer and adjacent low refractive index material layer Distance the regular alternation of cosine waveform is presented, the interference effect of specific wavelength will be made to be enhanced, then corresponding corresponding Refractive index forms the trend that the wavelength band of interference narrows presentation, i.e. the membrane stack can make reflectivity the wavelength of light of sharp change occur Range largely narrows, to the effect of narrowband reflection occur, and then avoids reflection bandwidth optics device caused greatly Part gamut differences, albefaction be serious, role's product effect difference defect, and since the membrane stack of the application is engraved structure, shows The pierced pattern shape of membrane stack out is based on narrowband reflection effect when facing the decorating film, which has bright-colored sharp keen Appreciation effect, when viewing angle offset when, pattern color changes, and change rear pattern color it is still more sharp keen, from And decorative effect more outstanding is realized, it can be applied to the decoration of building materials, household electrical appliances 3C Product, and realize identification dress outstanding Adorn effect.Meanwhile according to the variation of membrane stack number, there is corresponding variation in narrowband reflection peak number mesh.
Above-mentioned supervisory wavelength is determined with the lambda1-wavelength of the use environment of membrane stack, for example selects 550nm as visible The supervisory wavelength of light can specifically be selected, herein not using 750nm as the supervisory wavelength of infrared light according to the prior art It repeats again.
As long as the variation of the optical thickness coefficient of above-mentioned high refractive index material layer 21 and low refractive index material layer 22 follows just Same gradation law on string waveform or cosine waveform, can be realized narrowband reflection and decorative effect, excellent in the application one kind In the embodiment of choosing, in the same membrane stack, for low-index material unit α i-th highiHβiL, high refractive index material layer 21 Optical thickness is αi*λ/4, the optical thickness of low refractive index material layer 22 are βi*The refractive index of λ/4, high refractive index material layer 21 is NH, the physical thickness of high refractive index material layer 21 is DH, then there is NH*DH=αi*λ/4；The refractive index of low refractive index material layer 22 For NL, the physical thickness of low refractive index material layer 22 is DL, then there is NL*DL=βi*λ/4；Wherein, α1, α2..., αmWith βm..., β2, β1Each independently meet selected from range 0~2 π the same sinusoidal waveform and cosine waveform upper left semifocal chord, Same gradation law on lower-left semifocal chord, upper right semifocal chord and bottom right semifocal chord.Above-mentioned each optical thickness coefficient is abided by within the above range The waveform changing rule of four semifocal chords of the same string wave is followed, the difference of obtained optical thickness is in relatively narrow range, energy Play above-mentioned narrowband effect preferably；It and is not in half-wave hole common in optical thin film design (in optical filter Often there is a reflection peak at half of the reflection with central wavelength, commonly referred to as in bandpass region in practical preparation Half-wave hole, also having it is referred to as that the half-wave of optical filter falls).
It is easier to the physical thickness realized in order to obtain and controls total physical thickness of decorating film, decorating film is prison with 455nm When controlling wavelength, αi, βiValue range exist: 0.01≤αi≤ 3.2,0.01≤βi≤ 3.2, preferably 0.05≤αi≤ 2.8,0.05 ≤βi≤ 2.8, further preferred 0.1≤αi≤ 2.8,0.1≤βi≤2.8；It is more highly preferred to 0.2≤αi≤ 2.7,0.2≤βi≤ 2.7。
In the decorating film design of the application, in order to enable reflection membrane system and hardness, the adhesion of transparent substrate layer 10 etc. More preferably, the high low-index layer of transition can be set generally before membrane stack is set in transparent substrate layer 10, or in order to improve Transition zone can be also arranged in the adaptability of adjacent membrane stack, the height in order to guarantee the narrow bandization effect of membrane stack, in preferably above-mentioned membrane stack The quantity of low-index material unit accounts for the 60~99% of the total quantity of the high low-index material unit in refraction materials portion.
In view of the application requirement of the decorating film of the application, the physical thickness of preferably above-mentioned high refractive index material layer 21 is 1 ~400nm, preferably 10~150nm, the preferably physical thickness of low refractive index material layer 22 be 1~400nm, preferably 10~ 150nm。
The refractive index size of above-mentioned high refractive index material layer 21 and low refractive index material layer 22 can be with reference in the prior art Making the size of the refraction materials of reflectance coating, the refractive index of high refractive index material layer 21 is 1.5~5.0, preferably 1.65~ 3.0, the refractive index of low refractive index material layer 22 is 1.1~1.5, preferably 1.25~1.48.
The refraction materials for forming the high refractive index material layer 21 and low refractive index material layer 22 with above-mentioned refractive index can To be selected in common refraction materials from the prior art, high refractive index material layer 21 and low refractive index material layer are formed 22 refraction materials are each independently selected from MgF2、CaF2, transition metal fluorides, ZnO, TiO2、TiN、In2O3、SnO3、 Cr2O3、ZrO2、Ta2O5、LaB6、NbO、Nb2O3、Nb2O5、SiO2、SiC、Si3N4、Al2O3, fluorine resin, contain hollow titanium dioxide Any one or more in the resin of silicon.
In addition, in order to improve reflectance coating to the reflectivity of target wavelength, preferably high refractive index material layer 21 and low-refraction Total number of plies of material layer 22 is 12~60.
Preferably, the optical admittance of above-mentioned high low-index material unit is greater than 1.5 or 1 < A < 1.2, and decorating film can With the width range reflection wavelength of 20~50nm in 380~1200nm range light (A indicates optical admittance).
In addition, preferably above-mentioned reflection membrane system further includes transparent flat in order to improve the application stability of the decorating film of the application The table for reflect the separate transparent substrate layer of membrane system in the gap in refractive material portion 20 is arranged in flood 30, transparent levelling blanket 30 Face is plane.Certainly, it if being not provided with the transparent levelling blanket 30, since the physical thickness of membrane stack is nanoscale, is answering The negative effect of used time is nor it is obvious that can realize that protection is made to the membrane stack of hollow out after being provided with transparent levelling blanket 30 With improving the application stability and service life of decorating film.The decorating film of the application can decorate out lines effect, various figures Shape, text and other effects, therefore the shape in preferably refractive material portion 20 is lines, figure or text.
Each high refractive index material layer 21 and low refractive index material layer 22 in the reflection membrane system of the application can be using coatings Or sputtering mode formed, be limited to production method, when the number of plies of high refractive index material layer 21 and low refractive index material layer 22 compared with When more, can in different transparent substrate layers 10 setting unit high refractive index material layer 21 and low refractive index material layer 22, Then again by two transparent substrate layers 10 high refractive index material layer 21 and low refractive index material layer 22 be combined, i.e., as scheme Shown in 2, preferably above-mentioned reflection membrane system further includes one or more layers adhesive layer 23, and the adjacent membrane stack in part is viscous by adhesive layer 23 Knot.After gluing, extra transparent substrate layer 10 can retain or remove, and preferably remove it.
In order to avoid adhesive layer 23 to generate unnecessary influence to light as far as possible, preferably above-mentioned adhesive layer 23 is OCA glue Layer or PSA glue-line, further preferred adhesive layer 23 with a thickness of 0.005~0.2mm.Make it both be able to satisfy bonding to require, there is guarantor Demonstrate,prove its enough light transmittance.
In a kind of preferred embodiment of the application, above-mentioned transparent substrate layer 10 is pet layer, COP layers, COC layers, CPI Layer, PMMA layers, PEN layers, PC layers or TAC layer；Preferably clear substrate layer 10 with a thickness of 1~50 μm.Certainly, above-mentioned transparent substrate The hard substrates such as layer 10 or glass may be implemented to fill when selecting the flexible materials such as pet layer as transparent substrate layer 10 Adorn the flexibility of film.
In above-mentioned refractive material portion 20 or in substrate layer it is additionally provided with light absorber, to realize to specific wavelength into one Step absorbs.There are many set-up modes of the light absorber, for example light absorber is arranged at least partly high refractive index material layer 21 And/or at least partly in low refractive index material layer 22, high refractive index material layer 21 and/or low-refraction are dispersed by light absorber In material layer 22, on the basis of not increasing the thickness of reflection membrane system additionally, narrow-band absorption effect is realized.Or by above-mentioned light absorption Agent is arranged in individual structure sheaf, such as preferably as shown in figure 3, refractive material portion 20 further includes one or more layers light absorber Layer 24, light absorption oxidant layer 24 is disposed adjacent with part high refractive index material layer 21 and low refractive index material layer 22.By light absorber It is produced in individual light absorption oxidant layer 24, increases light absorber dosage and the flexibility of position is set.
Above-mentioned light absorber is mainly derived from existing light absorber material, for example preferred light absorber is inhaled selected from inorganic light Any one or more in agent, organic light absorber and organo-mineral complexing light absorber is received, preferably inorganic light absorber is Metal oxide or metallic salt, wherein the metal in metal oxide and the metallic salt be copper, chromium, iron or cadmium, preferably Organic light absorber is phthalocyanine, porphyrin or azo, and organo-mineral complexing light absorber is phthalocyanine metal chelate, porphyrin metal chela Close object or azo-metal chelate.
In another typical embodiment of the application, a kind of decorating film is provided, can refer to Fig. 1, the decorating film Representation are as follows: Sub │ (α1Hβ1Lα2Hβ2L...αmHβmL)N0│ Air, wherein Sub represents transparent substrate layer 10, │ (α1Hβ1Lα2H β2L...αmHβmL)N0│ indicates membrane stack, and membrane stack is engraved structure, Air represents atmosphere, and H is high refractive index material layer 21, and L is low Refractive index material 22；One high refractive index material layer 21 and a matching low refractive index material layer shape 22 are at a height Low-index material unit, m are natural number, and 3 < m < 50；N0 indicates the quantity of membrane stack, 1≤N0 < 10；It is high for i-th Low-index material unit αiHβiL, 1≤i≤n, αiIndicate i-th of high refractive index material layer 21 along vertical with transparent substrate layer 10 Direction on optical thickness account for the multiples of λ/4, βiIndicate i-th of low refractive index material layer 22 along vertical with transparent substrate layer 10 Optical thickness accounts for the multiple of λ/4 on direction, and λ is the supervisory wavelength of membrane stack；α1, α2..., αmAnd βm..., β2, β1Middle satisfaction The part of same gradation law on same sinusoidal waveform is sinusoidal alternation area；α1, α2..., αmAnd βm..., β2, β1In not The part for meeting the same gradation law on same sinusoidal waveform is sinusoidal optimization area or α1, α2..., αmAnd βm..., β2, β1The middle part for meeting the same gradation law in same cosine waveform is cosine alternation area；α1, α2..., αmAnd βm..., β2, β1In to be unsatisfactory for the part of same gradation law in same cosine waveform be that cosine optimizes area, wherein sine is passed The sum of high refractive index material layer and the low refractive index material layer quantity for becoming area or cosine alternation area account for high-index material in membrane stack Layer and the 60~99% of the sum of low refractive index material layer quantity.
According to Fabry-Perot (Fabry-Perot) principle of interference, when the frequency of incident light meets its resonance condition, Its transmission spectrum will appear very high peak value, correspond to very high transmissivity.Assuming that interference strength is distributed:
I in formula0For incident intensity；R is the energy reflectivity of reflecting surface；Phase difference of the δ between adjacent two coherent light, and enters Penetrate that light inclination angle is related, R+T=1 (R is the surface reflectivity of membrane system, and T is transmissivity).Between adjacent high refractive index material layer Distance and the distance between adjacent low refractive index material layer are that is, the distance of wall, and according to Fabry-Perot Luo Gan Principle is related to, interference reaches cosine wave that is maximum, and transmitting according to the duality principle of light when the distance of wall is the multiple of λ/4 The period of characteristic, cosine becomes larger, therefore by being │ (α in setting film structure1Hβ1Lα2Hβ2L..αmHβmL) the decoration of │ Film, due to the high refractive index material layer 21 of decorating film and the optical thickness coefficient (such as α and β) of low refractive index material layer 22 follow it is remaining The regular alternation of string waveform, i.e., the distance between adjacent high refractive index layer and the distance between adjacent low refractive index material layer The regular alternation that cosine waveform is presented, will make the interference effect of specific wavelength be enhanced, then corresponding respective indices of refraction The trend that the wavelength band of interference narrows presentation is formed, i.e. the decorating film can make reflectivity the range of light wavelengths of sharp change occur Largely narrow, to the effect of narrowband reflection occur, and since the membrane stack of the application is engraved structure, shows The pierced pattern shape for showing membrane stack is based on narrowband reflection effect when facing the decorating film, which has bright-colored sharp The appreciation effect of benefit, when viewing angle offset, pattern color changes, and the rear pattern color changed is still more sharp keen, To realize decorative effect more outstanding, the decoration of building materials, household electrical appliances 3C Product can be applied to, and realize identification outstanding Decorative effect.Meanwhile according to the variation of membrane stack number in decorating film, there is corresponding variation in narrowband reflection peak number mesh.
In a preferred embodiment of the present application, the α in cosine alternation area1, α2..., αmMeet the upper left of cosine waveform Semifocal chord is incremented by, β1, β2..., βmThe upper right semifocal chord for meeting cosine waveform successively decreases, and cosine optimization area is located at the two of cosine alternation area End, and the α in cosine optimization area1, α2..., αmWith one-to-one β1, β2..., βmDifference be less than in cosine alternation area α1With β1Difference and αmWith βmDifference；Or the α in cosine alternation area1, α2..., αmMeet the lower-left half of cosine waveform String is incremented by, β1, β2..., βmThe bottom right semifocal chord for meeting cosine waveform successively decreases, and cosine optimization area is located at the both ends in cosine alternation area, And the α in cosine optimization area1, α2..., αmWith one-to-one β1, β2..., βmDifference be less than in cosine alternation area α1With β1Difference and αmWith βmDifference.In the application another kind preferred embodiment, the α in sinusoidal alternation area1, α2..., αmThe upper left semifocal chord for meeting sinusoidal waveform is incremented by, β1, β2..., βmThe upper right semifocal chord for meeting sinusoidal waveform successively decreases, sinusoidal Optimize the both ends that area is located at sinusoidal alternation area, and the α in sinusoidal optimization area1, α2..., αmWith one-to-one β1, β2..., βm Difference be less than and the α in sinusoidal alternation area1With β1Difference and αmWith βmDifference；Or the α in sinusoidal alternation area1, α2..., αmThe lower-left semifocal chord for meeting sinusoidal waveform is incremented by, β1, β2..., βmThe bottom right semifocal chord for meeting sinusoidal waveform successively decreases, sinusoidal Optimize the both ends that area is located at sinusoidal alternation area, and the α in sinusoidal optimization area1, α2..., αmWith one-to-one β1, β2..., βm Difference be less than and the α in sinusoidal alternation area1With β1Difference and αmWith βmDifference.By above-mentioned set-up mode, avoid Between the high refractive index material layer and low refractive index material layer at sinusoidal alternation area or cosine alternation area both ends too due to thickness difference The problem of bad adaptability caused by big.
In order to increase reflectivity or increase the transmissivity of non-reflective wave band, for membrane stack quantity also according to the actual situation into Row adjustment, it is preferable that the high low-index material number of unit in each membrane stack is modified by waveform compensation coefficient factor, factor Equal to α1, α2..., αmAnd βm..., β2, β1The cosine waveform respectively formed accounts for the ratio of complete a quarter waveform, and works as α1, α2..., αmAnd βm..., β2, β1Independently meet upper left semifocal chord waveform, lower-left semifocal chord waveform, upper right semifocal chord waveform and the right side Factor is 1 when the complete a quarter waveform of one of lower semifocal chord waveform, the benefit when factor is less than 1, in each membrane stack 1-factor times that high low-index material number of unit is less than or equal to the high low-index material number of unit of membrane stack is repaid, and is mended It repays in high low-index material unit, the optical thickness coefficient of high refractive index material layer and the optical thickness of low refractive index material layer Coefficient and and the deviation of the optical thickness coefficient in its cosine waveform for compensating be less than ± 20%.
In order to realize the light absorption to specific wavelength, light suction is additionally provided in preferably above-mentioned membrane stack or transparent substrate layer Receive agent.Light absorber is arranged at least partly high refractive index material layer 21 and/or at least partly low refractive index material layer 22, will Light absorber is scattered in high refractive index material layer 21 and/or low refractive index material layer 22, is not increasing reflection membrane system additionally On the basis of thickness, narrow-band absorption effect is realized.Or the membrane stack further includes one or more layers light absorption oxidant layer 24, light absorption oxidant layer 24 are disposed adjacent with part high refractive index material layer 21 and low refractive index material layer 22.Light absorber is produced on individual light to inhale It receives in oxidant layer 24, increase light absorber dosage and the flexibility of position is set.
In order to improve the application decorating film application stability, preferably above-mentioned decorating film further includes transparent levelling blanket 30, Transparent levelling blanket 30 is arranged in the gap of engraved structure and the surface of the separate transparent substrate layer 10 of membrane stack and transparent levelling blanket The surface of 30 separate transparent substrate layer 10 forms a plane.Certainly, if the transparent levelling blanket 30 is not provided with, due to film The physical thickness of heap is nanoscale, therefore the negative effect in application is also not it is obvious that being provided with transparent levelling blanket 30 Protective effect can be realized to the membrane stack of hollow out afterwards, improve the application stability and service life of decorating film.The dress of the application Decorations film can decorate out lines effect, various figures, text and other effects, thus the shape in preferably refractive material portion 20 be lines, Figure or text.
It is preferred that engraved structure is lines, figure or text.
In order to make those skilled in the art more easily implement the application, the reflectance coating of the application will be illustrated below Manufacturing process.
Using the high-index material with high index as a target of magnetron sputtering, will have compared with low-refraction Another target as magnetron sputtering of low-index material, pet layer is placed in magnetron sputtering chamber, one on pet layer A mask plate, the mask plate are engraved structure, and aperture sections pass through for high-index material and low-index material with shape At refractive material portion.One layer of high-index material and one layer of low-index material are sputtered first on pet layer as transition zone, so Latter two target is alternately by bombardment to alternating sputtering high refractive index material layer and low refractive index material layer on transition zone, when altogether After the high refractive index material layer and low refractive index material layer of sputtering target quantity, stop sputtering.
When the lazy weight of high refractive index material layer and low refractive index material layer that the above process is formed, above-mentioned mistake is repeated Journey is stopped after the high refractive index material layer and low refractive index material layer of sputtering target quantity in another release PET base material layer It only sputters, high refractive index material layer and low refractive index material layer exposed in two PET base material layers is glued by OCA glue Knot, and release pet layer is removed, form reflectance coating.OCA glue therein can be used as adhesive layer both come using can also be used as Bright levelling blanket come using.
It is respectively provided with high low-index material film group if it is pet layer two sides, is continued in the above-mentioned reflectance coating formed Continue magnetron sputtering on another surface of pet layer, used target can be identical with abovementioned steps, can also not Together.
The embodiment of the specific process parameter of above-mentioned magnetron sputtering, those skilled in the art can be with reference to magnetic in the prior art It controls the related of sputtering method to record, details are not described herein.
Below with reference to embodiment and comparative example, the beneficial effect of the application is further illustrated.
Embodiment 1
Simulated experiment data:
Using the pet layer with a thickness of 0.05mm as transparent substrate layer.Antireflection layer is set on pet layer and reflects the film of membrane system Heap (high refractive index material layer and low refractive index material layer intersect stacked form), wherein set the shape pattern of membrane stack as scenery with hills and waters Pattern, the hollow out gap in membrane stack are filled with PET, set the central wavelength of incident light as 532nm, high refractive index material layer is folding The titanium dioxide layer that rate is 2.354 is penetrated, low refractive index material layer is the silicon dioxide layer that refractive index is 1.46, wherein antireflection layer It is made of titanium dioxide layer and silicon dioxide layer that optical thickness is λ/4, reflects the optical thickness factor design of membrane system are as follows:
The first half membrane stacks: 0.216H 1.836L 0.303H 1.691L 0.377H 1.591L 0.561H 1.501L 0.583H 1.422L 0.677H 1.358L 0.762H 1.259L 0.851H 1.192L 0.928H 1.102L 1.010H 1.020L 1.106H 0.921L 1.184H 0.886L 1.255H 0.767L 1.346H 0.714L 1.444H 0.634L 1.552H 0.564L 1.625H 0.432L 1.680H 0.416L 1.755H 0.396L 1.902H 0.233L 3.280H 0.905L, wherein the optical thickness coefficient of high refractive index material layer is incremented by according to the upper right semifocal chord of cosine waveform, low-refraction material The optical thickness coefficient of the bed of material successively decreases according to the upper left semifocal chord of cosine waveform；
The second half membrane stacks: 0.306H 2.574L 0.425H 2.369L 0.528H 2.230L 0.784H 2.101L 0.816H 1.987L 0.951H 1.899L 1.066H 1.766L 1.192H 1.667L 1.294H 1.545L 1.412H 1.428L 1.547H 1.289L 1.656H 1.245L 1.758H 1.070L 1.886H 0.996L 2.025H 0.885L 2.175H 0.791L 2.278H 0.603L 2.348H 0.581L 2.457H 0.550L 2.661H 0.326L 4.594H 1.265L, wherein the optical thickness coefficient of high refractive index material layer is incremented by according to the upper right semifocal chord of cosine waveform, low-refraction material The optical thickness coefficient of the bed of material successively decreases according to the lower-left semifocal chord of cosine waveform；
Optical film is arranged on above-mentioned pet layer, passes through the PSA progress with a thickness of 0.1mm between 0.905L and 0.306H Bonding.
Simulation can be carried out to the light reflective of above-mentioned decorating film using Essential Macleod Film Design software, Analog result is shown in Fig. 4 and table 1.
Embodiment 2
Using two and half membrane stacks of the magnetron sputtering technique production corresponding decorating film of embodiment 1, with clean pieces of cloth and second Alcohol carries out cleaning treatment to substrate.Design the mask plate that gap is " scenery with hills and waters pattern ".
After deflating in vacuum chamber, inside dust catcher cleaning bell jar, coating materials to be evaporated is loaded in molybdenum boat, is recorded each The coating materials title of a boat.And substrate is placed in substrate frame, substrate is not tilted, which is placed in the substrate after cleaning On.Bell jar is fallen, vacuum chamber is vacuumized by coating machine operating instruction.When vacuum degree reaches 7 × 10-3After Pa, successively To coating materials fritting in molybdenum boat, the gas in coating materials is removed.Attention blocks coating materials with baffle at this time, with guarantee in fritting substrate not by It plates.After vacuum degree reaches requirement, it is coated with using the method for the extremum method of λ/4 control optical thickness, control wavelength is put In 532nm.Be coated with titanium dioxide on the pet layer of substrate first, as film layer thickens, amplifier instruction photoelectric current will under Drop.When photoelectric current numerical value just bottom out, baffle is blocked immediately.Then, drop electric current changes electrode, applying silicon oxide, plating When silica, photoelectric current rises as film thickness increases, and stops plated film when reaching extreme value, repeats above step plated film.Work as plating When optical thickness processed is the wall of λ/2, thickness is doubled, should the stopping when photoelectric current rises and drops to extreme value again.After It is several layers of the same several layers of identically controlled.
After plated film, stops heating according to coating machine operating instruction and vacuumize.It, can be to coating machine vacuum after half an hour Room inflation, takes out be coated with interferometric filter.Then coating machine is vacuumized again by operating instruction, to keep cleaning, finally It shuts down.Then two and half membrane stacks are bonded using the PSA of 0.1mm.Measurement is in TU-1221 dual-beam ultraviolet light and visible light It is carried out on photometer, directly measurement T- λ curve, three major parameter λ of dielectric interference rate optical filter is found out from curve0、 Tmax、Δλ/λ0.Photometric light path system is as shown in Figure 5.The working principle of spectrophotometer is as follows: black lamp W1Or deuterium lamp D2Hair Light out passes through reflecting mirror M1, entrance slit S1With reflecting mirror M2It is irradiated to after collimation on grating G, the light of grating G diffraction is by anti- Penetrate mirror M3, exit slit S2, reflecting mirror M4With reflecting mirror M5Two-way is divided by chopper C afterwards: being reflecting mirror M all the way6, reference light ratio Color pond R and reflecting mirror M8The reference path of composition, another way are reflecting mirror M7, sample light colorimetric pool S, reflecting mirror M9And reflecting mirror M10, sample is placed in the sample light colorimetric pool of this optical path.This two-way light intensity is alternately received by photomultiplier tube, and carries out intensity ratio Compared with, it follows that the transmitance of sample.The corner for changing chopper G, can choose different wavelength and measures, to obtain Complete transmittance curve is specifically shown in Fig. 6 and table 1 after transmittance graph is converted to reflectance curve.
Embodiment 3
Simulated experiment data:
The optical thickness coefficient of the high refractive index material layer of membrane system and the optical thickness coefficient and reality of low refractive index material layer Apply that example 1 is identical, two and half membrane stacks are arranged on two opposite surfaces of pet layer.It is set using Essential Macleod membrane system Meter software can be carried out simulation to the light reflective of above-mentioned decorating film, and analog result is shown in Fig. 7 and table 1.
Embodiment 4
Simulated experiment data:
Using the pet layer with a thickness of 0.05mm as transparent substrate layer.Antireflection layer is set on pet layer and reflects the film of membrane system Heap (high refractive index material layer and low refractive index material layer intersect stacked form), wherein set the shape of membrane stack as " KDX ", film Hollow out gap in heap is filled with PET, sets the central wavelength of incident light as 520nm, high refractive index material layer is that refractive index is 2.354 titanium dioxide layer, low refractive index material layer are the silicon dioxide layer that refractive index is 1.46, wherein antireflection layer is by optics It is formed with a thickness of the titanium dioxide layer and silicon dioxide layer of λ/4, reflects the optical thickness factor design of membrane system are as follows:
COP 0.251H 1.592L 0.552H 1.487L 0.582H 1.404L 0.675H 1.344L 0.764H 1.253L 0.834H 1.186L 0.916H 1.097L 0.988H 1.026L 1.088H 0.918L 1.165H 0.892L 1.248H 0.765L 1.350H 0.714L 1.446H 0.631L 1.552H 0.565L 1.620H 0.412L 1.250H 1.405L Air,
Simulation can be carried out to the light reflective of above-mentioned decorating film using Essential Macleod Film Design software, Analog result is shown in Fig. 8 and table 1.
Embodiment 5
Simulated experiment data:
Using the pet layer with a thickness of 0.05mm as transparent substrate layer.Antireflection layer is set on pet layer and reflects the film of membrane system Heap (high refractive index material layer and low refractive index material layer intersect stacked form), wherein set the shape of membrane stack to set texture item Line, the hollow out gap in membrane stack are filled with PET, set the central wavelength of incident light as 520nm, high refractive index material layer is refraction Rate be 2.354 titanium dioxide layer, low refractive index material layer is the silicon dioxide layer that refractive index is 1.46, wherein antireflection layer by Optical thickness is the titanium dioxide layer and silicon dioxide layer composition of λ/4, reflects the optical thickness factor design of membrane system are as follows:
COP 1.667H 1.790L 1.352H 1.284L 1.298H 1.368L 1.474H 1.567L 1.736H 2.055L 1.955H 2.135L 0.554H 1.435L 0.971H 1.206L 1.276H 1.409L 1.487H 1.606L 1.712H 1.874L 1.004H 2.104L 0.947H 1.046L 1.019H 1.135L 1.300H 1.380L 1.518H 1.643L 1.808H 1.878L 1.962H 2.219L 0.800H 0.861L 1.070H 1.194L 1.291H 1.429L 1.516H 1.635L 1.768H 1.877L 2.006H 2.141L 0.792H 1.067L 1.436H 1.901L 0.678H 1.612L 1.566H 1.612L 1.675H 1.837L 1.829H 1.385L Air
Simulation can be carried out to the light reflective of above-mentioned decorating film using Essential Macleod Film Design software, Analog result is shown in Fig. 9 and table 1.
Embodiment 6
Simulated experiment data:
Using the pet layer with a thickness of 0.05mm as transparent substrate layer.Antireflection layer is set on pet layer and reflects the film of membrane system Heap (high refractive index material layer and low refractive index material layer intersect stacked form), wherein set the shape of membrane stack as petal pattern, Hollow out gap in membrane stack is filled with PET, sets the central wavelength of incident light as 532nm, high refractive index material layer is refractive index For 2.354 titanium dioxide layer, low refractive index material layer is the silicon dioxide layer that refractive index is 1.46, wherein antireflection layer is by light It learns and is formed with a thickness of the titanium dioxide layer and silicon dioxide layer of λ/4, reflect the optical thickness factor design of membrane system are as follows:
0.216H 1.836L 0.303H 1.691L 0.377H 1.591L 0.561H 1.501L 0.583H 1.422L 0.677H 1.358L 0.762H 1.259L 0.851H 1.192L 0.928H 1.102L 1.010H 1.020L 1.106H 0.921L 1.184H 0.886L 1.255H 0.767L 1.346H 0.714L 1.444H 0.634L 1.552H 0.564L 1.625H 0.432L 1.680H 0.416L 1.755H 0.396L 1.902H 0.233L 3.280H 0.905L, wherein high The optical thickness coefficient of refractive index material is incremented by according to the upper right semifocal chord of cosine waveform, the optical thickness of low refractive index material layer Coefficient successively decreases according to the upper left semifocal chord of cosine waveform.
Simulation can be carried out to the light reflective of above-mentioned decorating film using Essential Macleod Film Design software, Analog result is shown in Figure 10 and table 1.
Embodiment 7
Light absorber ABS-642 is arranged with embodiment 2 in Film Design in the high refractive index material layer of 0.377H, Uv-531 (2-hydroxy-4-n-octoxybenzophenone) UV absorbers are set in the low refractive index material layer of 1.591L, In, weight percent of the light absorber ABS-642 in the high refractive index material layer is 1% or so, uv-531 (2- hydroxyl -4- Oxy-octyl benzophenone) weight percent of the UV absorbers in the low refractive index material layer be 1% or so.Due to upper The addition for stating ultraviolet absorber, when being deviated for 0~30 °, the offset of narrowband reflection film be can control within the scope of 50nm.
The other the same as in Example 2.Obtained light reflectivity curve is shown in Figure 11.
Comparative example 1
Printing ink layer forms multiple groups " KDX " printed words on the pet layer with a thickness of 0.150mm, is arranged on above-mentioned printed words The overall thickness of PET levelling blanket, entire pet layer and PET levelling blanket is 0.250mm.
Table 1
It can be seen that the application according to the result of Fig. 4 to Figure 11 to pass through to high refractive index material layer and low-index material The variation of the optical thickness of layer is regulated and controled, and is changed it according to the rule of cosine waveform, it is anti-to realize ideal narrowband Penetrate effect, wherein the superposition of two and half membrane stacks is so that the cut-off of the repetition cutoff wavelength of two and half membrane stacks is deep in Examples 1 and 2 Degree increases, and is filled and led up without duplicate part, to realize the narrowband reflection of repeating part, and when light passes through, shows Scenery with hills and waters pattern, and while facing, has the effect of bright-colored sharp keen, when being angularly offset, the color of pattern changes Become.In addition, according to the data comparison of the comparison of Fig. 4 and Figure 11 and embodiment 1 and embodiment 7 it can be found that increasing ultraviolet Narrowband reflection is not affected after light absorber.
And it can be seen that the analogue data of embodiment 1 and the experiment real data of embodiment 2 according to the data in table 1 Consistency is preferable, and according to the comparison of embodiment 1 and embodiment 6 it can be found that by increasing high refractive index material layer and low folding The number of plies for penetrating rate material layer is conducive to increase reflectivity and reduces the bandwidth of reflection peak, so that color is more sharp keen, reflection Color effect is more prominent.
In addition, present inventor further carries out different colorimetric detections to the decorating film of embodiment 2, find in 0 ° of coloration When, jewel green is presented in reflectance coating, and color is sharp keen, and the effect of similar green quantum dot, pure color has metal-like, Without albinism, in 45 ° of colorations, the narrow peak of narrowband reflection film deviates to the left, becomes weak cyan, and infrared part light is added, Integral color becomes metallic red, illustrates that the decorating film of the application has good color shifting properties.Comparative example 1 is conventional decorating film, Do not change colour the characteristic sharp keen with coloration.
It can be seen from the above description that the above embodiments of the present invention realized the following chievements:
According to Fabry-Perot (Fabry-Perot) principle of interference, when the frequency of incident light meets its resonance condition, Its transmission spectrum will appear very high peak value, correspond to very high transmissivity.Assuming that interference strength is distributed:
I in formula0For incident intensity；R is the energy reflectivity of reflecting surface；Phase difference of the δ between adjacent two coherent light, and enters Penetrate that light inclination angle is related, R+T=1 (R is the surface reflectivity of membrane system, and T is transmissivity).The distance between adjacent high refractive index layer And the distance between adjacent low refractive index material layer that is, wall distance, and according to Fabry-Perot interference original Reason, interference reaches cosine baud that is maximum, and transmitting according to the duality principle of light when the distance of wall is the multiple of λ/4 Property, the period of cosine becomes larger, therefore by reflection membrane system setting film structure be │ (α1Hβ1Lα2Hβ2L...αmHβmL) the membrane stack of │, since the high refractive index material layer of membrane stack and the optical thickness coefficient of low refractive index material layer follow cosine waveform Regular alternation, i.e., more than the distance between adjacent high refractive index layer and the distance between adjacent low refractive index material layer are presented The regular alternation of string waveform, will make the interference effect of specific wavelength be enhanced, then corresponding respective indices of refraction formed it is dry The trend that the wavelength band related to narrows presentation, the i.e. membrane stack can make reflectivity the range of light wavelengths of sharp change occur in very great Cheng Narrow on degree, to the effect of narrowband reflection occur, and since the membrane stack of the application is engraved structure, thus it is shown that membrane stack Pierced pattern shape be based on narrowband reflection effect when facing the decorating film, which has bright-colored sharp keen ornamental Effect, when viewing angle offset, pattern color changes, and the rear pattern color changed is still more sharp keen, to realize Decorative effect more outstanding, can be applied to the decoration of building materials, household electrical appliances 3C Product, and realize identification decoration effect outstanding Fruit.Meanwhile according to the variation of membrane stack number, there is corresponding variation in narrowband reflection peak number mesh.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.

Claims (21)

1. a kind of decorating film, wherein include:
Transparent substrate layer (10) has opposite first surface and second surface；
Membrane system is reflected, is arranged on the first surface and/or second surface of the transparent substrate layer (10), the reflection membrane system packet The refractive material portion (20) of hollow out is included, the refractive material portion (20) includes n stacked high low-index material units, each institute Stating high low-index material unit includes a high refractive index material layer (21) and a paired low refractive index material layer (22), it is │ (α that the refractive material portion (20), which includes at least one film structure,1Hβ1Lα2Hβ2L...αmHβmL) the membrane stack of │, In, H indicates the high refractive index material layer (21), and L indicates the low refractive index material layer (22), and n, m are positive integer, and 3 < n ≤ 150,3 < m≤50, m≤n, the α in the same membrane stack1, α2..., αmAnd βm..., β2, β1It is full each independently Same gradation law in the same cosine waveform of foot or sinusoidal waveform；High low-index material unit α described for i-thiH βiL, 1≤i≤n, αiIndicate i-th of high refractive index material layer (21) along the direction vertical with the transparent substrate layer (10) Upper optical thickness accounts for the multiple of λ/4, βiIndicate i-th of low refractive index material layer (22) edge and the transparent substrate layer (10) Optical thickness accounts for the multiple of λ/4 on vertical direction, and λ is the supervisory wavelength of membrane stack.
2. decorating film according to claim 1, wherein in the same membrane stack, the high low-refraction described for i-th Material cell αiHβiL, the optical thickness of the high refractive index material layer (21) are αi* λ/4, the low refractive index material layer (22) Optical thickness be βi* λ/4, the refractive index of the high refractive index material layer (21) are NH, the high refractive index material layer (21) Physical thickness is DH, then there is NH*DH=αi*λ/4；The refractive index of the low refractive index material layer (22) is NL, the low refraction The physical thickness of rate material layer (22) is DL, then there is NL*DL=βi*λ/4；Wherein, α1, α2..., αmAnd βm..., β2, β1 Meet each independently selected from range in the same sinusoidal waveform of 0~2 π or upper left semifocal chord, the lower-left half of cosine waveform Same gradation law on string, upper right semifocal chord and bottom right semifocal chord.
3. decorating film according to claim 2, wherein when the decorating film is using 455nm as supervisory wavelength, αi, βiValue Range exists: 0.01≤αi≤ 3.2,0.01≤βi≤ 3.2, it is preferable that 0.05≤αi≤ 2.8,0.05≤βi≤2.8；Preferably, 0.1≤αi≤ 2.8,0.1≤βi≤2.8；It is further preferable that 0.2≤αi≤ 2.7,0.2≤βi≤2.7。
4. decorating film according to any one of claim 1 to 3, wherein the high low-index material unit of the membrane stack Quantity account for the refraction materials portion high low-index material unit total quantity 60~99%.
5. decorating film according to any one of claim 1 to 3, wherein the physics of the high refractive index material layer (21) With a thickness of 1~400nm, preferably 10~150nm, the physical thickness of the preferably described low refractive index material layer (22) is 1~ 400nm, preferably 10~150nm.
6. decorating film according to any one of claim 1 to 3, wherein the refraction of the high refractive index material layer (21) Rate is 1.5~5.0, preferably 1.65~3.0, and the refractive index of the low refractive index material layer (22) is 1.1~1.5, preferably 1.25~1.48.
7. decorating film according to any one of claim 1 to 3, wherein formed the high refractive index material layer (21) and The refraction materials of the low refractive index material layer (22) are each independently selected from MgF2、CaF2, transition metal fluorides, ZnO, TiO2、TiN、In2O3、SnO3、Cr2O3、ZrO2、Ta2O5、LaB6、NbO、Nb2O3、Nb2O5、SiO2、SiC、Si3N4、Al2O3, it is fluorine-containing Any one or more in resin, the resin containing hollow silica.
8. decorating film according to any one of claim 1 to 3, wherein the high refractive index material layer (21) and described Total number of plies of low refractive index material layer (22) is 12~60.
9. decorating film according to any one of claim 1 to 3, wherein the optics of the high low-index material unit Admittance is greater than 1.5 or 1 < A < 1.2, the decorating film can with the width range reflection wavelength of 20~50nm 380~ 1200nm range light.
10. decorating film according to any one of claim 1 to 3, wherein the reflection membrane system further includes transparent levelling blanket (30), transparent levelling blanket (30) setting makes the separate of the reflection membrane system in the gap of the refractive material portion (20) The surface of the transparent substrate layer is plane, and the shape of the preferably described refractive material portion (20) is lines, figure or text.
11. decorating film according to claim 10, wherein the reflection membrane system further includes one or more layers adhesive layer (23), the adjacent membrane stack in part is bonded by the adhesive layer (23).
12. decorating film according to claim 11, wherein the adhesive layer (23) be OCA glue-line or PSA glue-line, preferably The adhesive layer (23) with a thickness of 0.005~0.2mm.
13. decorating film according to any one of claim 1 to 3, wherein the transparent substrate layer (10) be pet layer, COP layers, COC layers, CPI layers, PMMA layers, PEN layers, PC layers or TAC layer, the preferably described transparent substrate layer (10) with a thickness of 1~ 50μm。
14. decorating film according to claim 1, wherein in the refractive material portion (20) or the transparent substrate layer In be additionally provided with light absorber, preferably light absorber setting in at least partly described high refractive index material layer (21) and/or In at least partly described low refractive index material layer (22) or the refractive material portion (20) further includes one or more layers light absorber Layer (24), the light absorption oxidant layer (24) and the part high refractive index material layer (21) and the low refractive index material layer (22) It is disposed adjacent.
15. decorating film according to claim 14, wherein the light absorber is selected from inorganic light absorber, organic light is inhaled Any one or more in agent and organo-mineral complexing light absorber is received, the preferably described inorganic light absorber is metal oxide Or metallic salt, wherein metal in the metal oxide and the metallic salt is copper, chromium, iron or cadmium, it is preferably described to have Machine light absorber is phthalocyanine, porphyrin or azo, and the organo-mineral complexing light absorber is phthalocyanine metal chelate, porphyrin metal Chelate or azo-metal chelate.
16. a kind of decorating film, wherein the representation of the decorating film are as follows: Sub │ (α1Hβ1Lα2Hβ2L...αmHβmL)N0│ Air, Wherein, Sub represents transparent substrate layer (10), │ (α1Hβ1Lα2Hβ2L...αmHβmL)N0│ indicates that membrane stack, the membrane stack are hollow out knot Structure, Air represent atmosphere, and H is high refractive index material layer (21), and L is low refractive index material layer (22)；One high refractive index material The bed of material (21) and a matching low refractive index material layer (22) form one high low-index material unit, and m is Natural number, and 3 m≤50 <；N0 indicates the quantity of membrane stack, 1≤N0 < 10；For low-index material unit α i-th highiHβiL, 1≤i≤n, αiIndicate i-th of high refractive index material layer (21) along optical thickness on the direction vertical with the transparent substrate layer Account for the multiple of λ/4, βiIndicate that i-th of low refractive index material layer (22) are thick along optics on the direction vertical with the transparent substrate layer Degree accounts for the multiple of λ/4, and λ is the supervisory wavelength of membrane stack；
α1, α2..., αmAnd βm..., β2, β1The middle part for meeting the same gradation law on same sinusoidal waveform is sine Alternation area；α1, α2..., αmAnd βm..., β2, β1In the part of same gradation law that is unsatisfactory on same sinusoidal waveform be Sinusoidal optimization area, or
α1, α2..., αmAnd βm..., β2, β1The middle part for meeting the same gradation law in same cosine waveform is cosine Alternation area；α1, α2..., αmAnd βm..., β2, β1In the part of same gradation law that is unsatisfactory in same cosine waveform be Cosine optimizes area,
Wherein, the high refractive index material layer and the low-index material in the sinusoidal alternation area or cosine alternation area The sum of the quantity of layer accounts for the 60 of the sum of quantity of high refractive index material layer described in the membrane stack and the low refractive index material layer ~99%.
17. decorating film according to claim 16, wherein
The α in cosine alternation area1, α2..., αmThe upper left semifocal chord for meeting the cosine waveform is incremented by, β1, β2..., βmMeet The upper right semifocal chord of the cosine waveform successively decreases, and cosine optimization area is located at the both ends in cosine alternation area, and the cosine Optimize the α in area1, α2..., αmWith one-to-one β1, β2..., βmDifference be less than and the α in cosine alternation area1 With β1Difference and αmWith βmDifference；Or
The α in cosine alternation area1, α2..., αmThe lower-left semifocal chord for meeting the cosine waveform is incremented by, β1, β2..., βmMeet The bottom right semifocal chord of the cosine waveform successively decreases, and cosine optimization area is located at the both ends in cosine alternation area, and the cosine Optimize the α in area1, α2..., αmWith one-to-one β1, β2..., βmDifference be less than and the α in cosine alternation area1 With β1Difference and αmWith βmDifference.
18. decorating film according to claim 16, wherein
The α in the sine alternation area1, α2..., αmThe upper left semifocal chord for meeting institute's sine and cosine waveform is incremented by, β1, β2..., βmMeet The upper right semifocal chord of the sinusoidal waveform successively decreases, and the sinusoidal optimization area is located at the both ends in the sinusoidal alternation area, and the sine Optimize the α in area1, α2..., αmWith one-to-one β1, β2..., βmDifference be less than and the sinusoidal alternation area in α1 With β1Difference and αmWith βmDifference；Or
The α in the sine alternation area1, α2..., αmThe lower-left semifocal chord for meeting the sinusoidal waveform is incremented by, β1, β2..., βmMeet The bottom right semifocal chord of the sinusoidal waveform successively decreases, and the sinusoidal optimization area is located at the both ends in the sinusoidal alternation area, and the sine Optimize the α in area1, α2..., αmWith one-to-one β1, β2..., βmDifference be less than and the sinusoidal alternation area in α1 With β1Difference and αmWith βmDifference.
19. decorating film according to claim 16, wherein the high low-index material number of unit quilt in each membrane stack Waveform compensation coefficient factor modification, the factor are equal to α1, α2..., αmAnd βm..., β2, β1The cosine respectively formed Waveform accounts for the ratio of complete a quarter waveform, and works as α1, α2..., αmAnd βm..., β2, β1Independently meet upper left semifocal chord wave Described in when the complete a quarter waveform of one of shape, lower-left semifocal chord waveform, upper right semifocal chord waveform and bottom right semifocal chord waveform Factor is 1, when the factor is less than 1, the high low-index material number of unit of compensation in each membrane stack is less than etc. In 1-factor times of the high low-index material number of unit of the membrane stack, and the high low-index material unit of compensation In, it the optical thickness coefficient of the high refractive index material layer and the optical thickness coefficient of low refractive index material layer and is compensated with it The deviation of optical thickness coefficient in the cosine waveform is less than ± 20%.
20. decorating film according to claim 16, which is characterized in that also set in the membrane stack or the transparent substrate layer It is equipped with light absorber, preferably light absorber setting is in at least partly described high refractive index material layer (21) and/or at least portion Divide in the low refractive index material layer (22) or the membrane stack further includes one or more layers light absorption oxidant layer (24), the light is inhaled Oxidant layer (24) are received to be disposed adjacent with the part high refractive index material layer (21) and the low refractive index material layer (22).
21. decorating film according to claim 16, which is characterized in that the decorating film further includes transparent levelling blanket (30), The transparent levelling blanket (30) is arranged in the gap of the engraved structure and the separate transparent substrate layer of the membrane stack (10) surface far from the transparent substrate layer (10) on surface and the transparent levelling blanket (30) forms a plane, preferably The engraved structure is lines, figure or text.
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