WO2018061709A1 - Film - Google Patents

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Publication number
WO2018061709A1
WO2018061709A1 PCT/JP2017/032421 JP2017032421W WO2018061709A1 WO 2018061709 A1 WO2018061709 A1 WO 2018061709A1 JP 2017032421 W JP2017032421 W JP 2017032421W WO 2018061709 A1 WO2018061709 A1 WO 2018061709A1
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WO
WIPO (PCT)
Prior art keywords
film
layer
black
holes
observed
Prior art date
Application number
PCT/JP2017/032421
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English (en)
Japanese (ja)
Inventor
朋一 梅澤
小松　寛
Original Assignee
富士フイルム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to JP2018542335A priority Critical patent/JP6904967B2/ja
Publication of WO2018061709A1 publication Critical patent/WO2018061709A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • 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
    • G02B1/11—Anti-reflection coatings
    • G02B1/118—Anti-reflection coatings having sub-optical wavelength surface structures designed to provide an enhanced transmittance, e.g. moth-eye structures

Definitions

  • the present invention relates to a film.
  • Patent Document 1 describes a film as a black laminate including a fine uneven layer and a metal nanoparticle layer.
  • the fine concavo-convex layer has a microprojection structure on the surface and is made of a cured product of the resin composition.
  • a plurality of projections are closely arranged, and the average distance between adjacent projections is 500 nm.
  • the metal nanoparticles of the metal nanoparticle layer are supported so as to cover the surface of the fine uneven layer.
  • Patent Document 2 describes a functional light-shielding film having a louver layer in which light transmission bands and light-shielding bands are alternately and repeatedly arranged, and a transparent protective layer.
  • the shading band is made of black or colored resin.
  • Patent Document 3 describes a method of forming a hole penetrating in the thickness direction in an aluminum plate, and this aluminum plate is used for various functional materials such as a current collector, a heat-resistant particulate filter, and a sound absorbing material. It is done.
  • the above-mentioned decorative film in which a pattern is printed on a film substrate, has a limit in expressiveness or variety of expression. Therefore, if an image such as a character can be observed only for the purpose, it is considered that design properties such as expressive power and diversity of expression are enhanced.
  • the films described in Patent Document 1 and Patent Document 2 do not have a function of observing an image only when it is intended.
  • An object of the present invention is to provide a film in which an image can be observed only when the object is intended.
  • the film of the present invention includes a metal layer, a film substrate, and a colored layer, and the metal layer is provided on the film substrate.
  • a plurality of holes are formed in the metal layer.
  • the film substrate is transparent and supports the metal layer.
  • the colored layer is provided on the metal layer. The plurality of holes are 100 ⁇ m even if the average value of the equivalent circle diameter on the film surface on the colored layer side is large.
  • the plurality of holes are randomly arranged in the direction along the film surface.
  • the aperture ratio of the holes on the film surface is preferably 30% at most.
  • the standard deviation of the equivalent circle diameter is preferably in the range of 0.5 ⁇ m to 40 ⁇ m.
  • the colored layer is preferably black.
  • the colored layer preferably has a plurality of convex portions arranged at a pitch equal to or smaller than the wavelength of incident light.
  • 10% of the plurality of holes are preferably closed by the colored layer.
  • the deviation of the aperture ratio of the holes on the film surface is preferably in the range of 0% to 20%.
  • a dashboard material 10 is a material that is attached as a part of a dashboard that is an interior part of an automobile.
  • the dashboard material 10 includes an interior molded body 11 and an LCD (liquid crystal display) 12.
  • the dashboard material 10 is arranged in a state in which the interior molded body 11 faces the observer and the LCD 12 is on the back side of the interior molded body 11 when viewed from the observer side.
  • the LCD 12 includes a liquid crystal panel (not shown) and a backlight (not shown) that is a light source unit that emits light from behind.
  • the display surface 12a on which the image of the liquid crystal panel is displayed is opposed to the interior molded body 11, and the light source unit constitutes the lower surface side of the LCD 12 in FIG.
  • the interior molded body 11 is a three-dimensional modeled object that is molded in three dimensions (three dimensions) so as to form part of the dashboard, and an image displayed on the display surface 12 a is observed through the interior molded body 11. Is done.
  • the interior molded body 11 includes a film 15 embodying the present invention and an interior molded body body (hereinafter referred to as a molded body body) 16 that overlaps one film surface (hereinafter referred to as a first film surface) 15 a of the film 15. With.
  • the LCD 12 is arranged in close contact with a partial region of the other film surface (hereinafter referred to as a second film surface) 15b of the film 15.
  • the LCD 12 is combined with the interior molded body 11, but the combination is not limited to the LCD 12.
  • a mask (not shown) provided with an opening having a desired shape may be combined. The mask is disposed between the light source and the interior molded body 11, and the light from the light source is molded into a target shape and irradiated to the interior molded body 11.
  • the molded body 16 is a three-dimensional modeled body for forming a dashboard, and has impact resistance, rigidity, heat resistance, etc. for functioning as a dashboard, and is formed of a transparent thermoplastic resin. .
  • the molded body 16 also has a function of forming the film 15 into a three-dimensional shape and maintaining the three-dimensional shape as described later.
  • the molded body 16 further functions as a protective material for protecting the first film surface 15a of the film 15.
  • the thermoplastic resin (thermoplastic polymer) constituting the molded body 16 is transparent to such an extent that the design properties such as color, brightness and texture obtained by the first film surface 15a of the film 15 are not impaired, and Any thermoplastic resin that can be molded by heating may be used.
  • PC polycarbonate
  • COP Cyclic Olefin Polymer
  • COC cycloolefin copolymer
  • the thickness T16 of the molded body 16 is not particularly limited, and is 4 mm in the present embodiment.
  • the boundary between the film 15 of the interior molded body 11 and the molded body 16 is drawn flat for convenience in FIG. 1 but is uneven as shown in FIG. Details of the unevenness will be described later.
  • the film 15 includes a film base 21, an adhesive layer 22, an aluminum layer (hereinafter referred to as an Al layer) 26 as a metal layer, and a black layer 27 colored black as a colored layer.
  • the film substrate 21 supports the Al layer 26.
  • the adhesive layer 22 is for improving the adhesive force between the film substrate 21 and the Al layer 26, and is not provided when the film substrate 21 and the Al layer 26 are adhered with sufficient adhesive force. Also good.
  • the film base material 21 and the adhesive layer 22 are formed of a transparent material in the same manner as the molded body 16.
  • the film substrate 21 is formed of polyethylene terephthalate (hereinafter referred to as PET), but is not limited thereto, and may be formed of a resin such as PC or cycloolefin polymer (COP). Good.
  • the adhesive layer 22 is formed of a urethane-based adhesive, but is not limited thereto, and may be formed of, for example, an epoxy-based adhesive or a polyester-based adhesive.
  • the Al layer 26 and the black layer 27 serve as an observation surface on which an image is observed in a state where an image is displayed on the display surface 12a (hereinafter referred to as a display state), and a state where the image is not displayed (hereinafter referred to as a display state). , Referred to as a non-display state) for carrying a design as a part of the dashboard.
  • the dashboard is black, and in order to have a sense of unity of color with the surrounding dashboard material (shown) when the dashboard material 10 is incorporated,
  • the black layer 27 is for observing black.
  • the Al layer 26 is for light shielding, and the black color of the black layer 27 is given depth by this light shielding function.
  • the black layer 27 is not transparent.
  • the Al layer 26 is a metal layer made of aluminum (Al).
  • the metal layer is not limited to the Al layer 26, and the metal layer may be formed of other materials. Moreover, the metal layer may be formed from a mixture of two or more different materials. For example, when the mass of the metal layer is 100, the mass of aluminum may be in the range of 98.3 to 99.9, and the mass of other materials may be in the range of 0.1 to 1.7. .
  • the material of the metal layer may be transparent or opaque, but is preferably as low as possible in incident light. Preferred metals include copper (Cu), tin (Sn), SUS (stainless steel) and the like.
  • the black layer 27 is provided on the Al layer 26, and thus is also provided on the inner wall of the hole 23 formed in the Al layer 26 (see FIG. 3).
  • the black layer 27 includes a portion provided on the inner wall of the hole 23 in a state where the hole 23 is not closed, that is, a non-closed state, and a portion provided on the inner wall of the hole 23 in a state where the hole 23 is closed. There is.
  • the non-blocking hole 23 that is not blocked by the black layer 27 is in a state in which the molded body 16 is intruded, so that the boundary between the molded body 16 and the film 15 is uneven as described above. ing.
  • the non-occluded hole 23 transmits light
  • the light emitted from the display surface 12a passes through the non-occluded hole 23 after passing through the film base 21 and the adhesive layer 22, and then the molded body. 16 is transmitted. Therefore, the image of the display surface 12 a in the display state is observed through the interior molded body 11. For example, a region displayed in black in the image on the display surface 12a is observed as black, and in a region displayed in a color other than black (including white) on the display surface 12a, the displayed color is observed as that color. Is done. In the non-display state, black color due to the Al layer 26 and the black layer 27 is observed.
  • the plurality of holes 23 that are not blocked by the black layer 27 are opened in the first film surface 15a, which is the film surface on the black layer 27 side, to form an opening 23a.
  • the size of the opening 23a is preferably non-uniform.
  • the shape of the opening 23a is preferably indefinite as shown in FIG.
  • the average value of the equivalent circle diameter D of the holes 23 on the first film surface 15a is at most 100 ⁇ m, that is, 100 ⁇ m or less. Even if the average value of the equivalent circle diameter D is large, it is 100 ⁇ m, so that the hole 23 is not visually recognized in the non-display state. However, since there are a plurality of holes 23, the first film surface 15a is uneven. Therefore, in the non-display state, the dashboard material 10 is observed as a deep black (jet black). When there is a black display area on the display surface 12a in the display state, the black display area is also observed as deep black.
  • the average value of the equivalent circle diameter D is preferably in the range of 0.1 ⁇ m to 100 ⁇ m, more preferably in the range of 0.4 ⁇ m to 50 ⁇ m, and in the range of 0.4 ⁇ m to 10 ⁇ m. More preferably it is.
  • the circle equivalent diameter is the diameter of the circle C23 when the circle C23 having the same area as the opening 23a is drawn.
  • the average value of equivalent circle diameters is an average value of equivalent circle diameters of all the openings 23a in a 600 ⁇ m ⁇ 400 ⁇ m range observed with an optical microscope.
  • FIG. 5 is a photograph of the interior molded body 11 when white light is used as a light source and the light is irradiated to the back side of the interior molded body 11 with respect to the interior molded body 11.
  • the distribution of the equivalent circle diameter D may be asymmetric with respect to the frequency peak of the equivalent circle diameter D.
  • the distribution of the equivalent circle diameter D is asymmetric as shown in FIG. 6A, an opening having a larger equivalent circle diameter D can be provided compared to the case shown in FIG. There is a merit that light is transmitted more effectively.
  • occluded by the black layer 27 has the hollow 27a, as shown in FIG. Due to the depression 27a, the dashboard material 10 is observed in black that can feel a deeper depth in the non-display state.
  • the colored layer is a color different from black, the color is observed with a deeper depth.
  • the occlusion rate is more preferably in the range of 10% to 30%, and still more preferably in the range of 15% to 25%.
  • the standard deviation of the equivalent circle diameter D is preferably in the range of 0.5 ⁇ m to 40 ⁇ m.
  • the standard deviation of the equivalent circle diameter D is 0.5 ⁇ m or more, moire (interference fringes) is hardly observed as compared with the case where the equivalent circle diameter D is less than 0.5 ⁇ m.
  • the standard deviation of the equivalent circle diameter D is 40 ⁇ m or less, it becomes difficult to feel a rough feeling as compared with the case where it is larger than 40 ⁇ m.
  • the rough feeling means that when the light transmitted through the film 15 is viewed as in the display state, the transmitted light is felt to be uneven.
  • the standard deviation of the equivalent circle diameter D refers to the standard deviation of the equivalent circle diameter D of all the openings 23a in the 600 ⁇ m ⁇ 400 ⁇ m range observed with an optical microscope.
  • the holes 23 are preferably randomly or irregularly arranged in the direction along the first film surface 15a, and this is also the case in this embodiment.
  • the “number of people” column in Table 2 indicates the number of evaluators who evaluated that moire was not observed.
  • the random degree is obtained as follows. First, attention is paid to one opening 23a on the first film surface 15a. Among the plurality of openings 23a adjacent to the one opening 23a, the three openings 23a are identified in order from the one having the smallest center distance, and the distance between the centers with the one opening 23a first focused on is specified. Then, an average value dav of the obtained three center distances is obtained. Moreover, the maximum value dmax and the minimum value dmin are specified among the obtained three center distances. The percentage obtained by ⁇ (dmax ⁇ dmin) / dav ⁇ ⁇ 100 is defined as the random degree. In the present embodiment, a range of 600 ⁇ m ⁇ 400 ⁇ m is observed with an optical microscope, and 10 random degrees are arbitrarily measured therein, and the average value is used as a representative value.
  • the center of the opening 23a for obtaining the distance between the centers is the center of gravity of the opening 23a.
  • the center of gravity may be obtained by a known method, and is described in, for example, http://ms-laboratory.jp/zai/base6/base6.htm (Internet, search on September 15, 2016).
  • the opening ratio of the holes 23 in the first film surface 15a is preferably 30% at most.
  • opening ratio is more reliably and brightly observed in the display state than when the aperture ratio is greater than 30%.
  • the aperture ratio is more preferably 10% at most, and further preferably 5% at most. Note that the lower limit value of the aperture ratio is appropriately set depending on the application.
  • the dashboard material 10 using the plurality of films 15 having different opening ratios by 10 evaluators whether or not the depth of the black color was felt was evaluated, the results shown in Table 3 were obtained. Has been obtained.
  • the “number of people” column in Table 3 indicates the number of evaluators who evaluated that the depth of black was felt, and an area where 80% of the evaluators evaluated that the depth of black was felt was a suitable range. It is said.
  • the aperture ratio (unit:%) is obtained by the following method.
  • the area of the opening 23a is S23
  • the area of the first film surface 15a is S15a.
  • the area S23 of the opening 23a is the area of the portion indicated by cross hatching in FIG. 6C
  • the area S15a of the first film surface 15a is the area of the hatched portion indicated by hatching.
  • Said opening ratio is calculated
  • the deviation of the aperture ratio on the first film surface 15a is preferably in the range of 0% to 20%. As the deviation of the aperture ratio is smaller, color unevenness is less likely to be observed on the dashboard material 10. For example, when 10 evaluators performed sensitive evaluation on whether or not color irregularities were confirmed in the dashboard material 10 using the plurality of films 15 having different aperture ratio deviations, the results shown in Table 4 were obtained. Has been obtained. The “number of people” column in Table 4 indicates the number of evaluators who evaluated that color unevenness was not confirmed, and an area where it was evaluated that color unevenness was difficult to be observed in 50% of the evaluators was in a suitable range. It is said.
  • the surface of the black layer 27 is drawn flat for convenience in FIG. 2, but the black layer 27 has a plurality of convex portions 28 on the surface as shown in FIG. Thereby, the surface of the black layer 27 is made into the fine uneven structure (moth eye structure) formed by these convex parts 28 being densely arranged.
  • the convex portion 28 has a tapered so-called cone shape, and may be a cone shape or a pyramid shape. Further, the tip of the convex portion 28 does not need to be sharp and may be rounded.
  • the first film surface 15a has a moderate refractive index with respect to the incident light that has passed through the molded body 16, and therefore, the incident light of the incident light is reduced. Absorption rate increases. Thereby, in the non-display state, the dashboard material 10 is observed in a black color where the depth can be more reliably felt.
  • the pitch (hereinafter referred to as the convex pitch) PS of the convex portions 28 is set to be equal to or less than the wavelength of the incident light.
  • the convex pitch PS is a distance between the apexes of the adjacent convex portions 28.
  • below the wavelength of incident light means that it is below the shortest wavelength among the wavelength bands of incident light.For example, when the wavelength band of incident light is in the visible light region and the shortest wavelength is 400 nm, The convex part pitch PS is 400 nm or less.
  • the convex pitch PS need not be constant, and is not constant in the present embodiment. Thus, when the convex part pitch PS is non-uniform
  • the convex part pitch PS in this embodiment is 300 nm.
  • the convex pitch PS is more preferably shorter than the shortest wavelength of the incident light, and more preferably shorter than 1 ⁇ 2 of the shortest wavelength.
  • the black layer 27 is a black colored layer containing nickel (Ni). By making it black, incident light is absorbed more and the light shielding performance is more reliably improved. Nickel is preferably included in a mass of at least 80 when the mass of the black layer 27 is 100.
  • the colored layer is not limited to the black layer 27 and may be a layer of another color.
  • the surface of the Al layer 26 on the black layer 27 side may be a smooth surface or a rough surface with irregularities. In FIG. 2 and FIG. 7, it is drawn as a smooth surface for the sake of convenience, but in this embodiment it is a rough surface.
  • the pitch of the convex portions (not shown) constituting the rough surface is larger than the convex portion pitch PS described above.
  • the pitches of the protrusions on the black layer 27 side of the Al layer 26 are not constant as with the protrusion pitch PS, so the pitch of the protrusions is adjacent to the protrusions PS as well. 11 are extracted and set as an average value of pitches between them. The pitch between each may be obtained by observing with an SEM, as in the case of obtaining the convex portion pitch PS.
  • the pitch of the protrusions on the black layer 27 side of the Al layer 26 is preferably longer than the longest wavelength in the wavelength band of incident light. For example, when the wavelength band of incident light is in the visible light region, it is visible. If the longest wavelength of light is 800 nm, it is longer than 800 nm. More specifically, the pitch of the protrusions on the black layer 27 side of the Al layer 26 is preferably set to a micro order of 1 ⁇ m (1000 nm) or more.
  • the height of the convex portion on the black layer 27 side of the Al layer 26 is preferably made larger than the height of the convex portion 28, and this is the case in this embodiment.
  • the concavo-convex structure on the surface of the Al layer 26 on the black layer 27 side scatters light that could not be absorbed by the concavo-convex structure on the surface of the black layer 27, thereby enhancing the antireflection effect and / or dashboard material, for example. 10 enhances the effect of being observed in deeper black.
  • the manufacturing method of the film 15 includes a film forming process, a hole forming process after the film forming process, a film removing process after the hole forming process, and a black layer forming process after the film removing process.
  • the film forming step an aluminum hydroxide film is formed on the surface of the Al foil of the first laminate in which the aluminum foil (hereinafter referred to as Al foil) and the film substrate 21 are bonded by the adhesive layer 22.
  • the hole forming step the hole 23 is formed by performing a local aluminum dissolution treatment.
  • the film removal step the aluminum hydroxide film is removed.
  • the black layer forming step the black layer 27 is formed.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • the above-described first laminated body denoted by reference numeral 31 in FIG. 9A is a laminated body including a film base material 21, an adhesive layer 22, and an Al foil 32.
  • the first laminate 31 may be a commercially available product, and a commercially available product (Alpet (registered trademark) manufactured by Panac Co., Ltd.) is also used in this embodiment.
  • the surface of Al foil 32 is made into the rough surface.
  • a film forming process is performed on the surface of the Al foil 32 of the first laminate 31 to form a first aluminum hydroxide film 33 (see FIG. 9B).
  • the formed second laminated body 36 has a laminated structure in which an Al foil 32 and a first aluminum hydroxide film 33 are laminated on the adhesive layer 22 in this order.
  • the film formation treatment is not particularly limited, and for example, the same treatment as a known aluminum hydroxide film formation treatment can be performed.
  • As the film forming treatment for example, conditions and apparatuses described in paragraphs [0013] to [0026] of JP 2011-201123 A can be appropriately employed.
  • the conditions for the film formation treatment are variously determined depending on the electrolyte used, and are not generally determined. However, in general, the electrolyte concentration is 1 to 80% by mass, the solution temperature is 5 to 70 ° C., and the current density is 0.5 to 60 A. / Dm 2 , voltage 1 to 100 V, and electrolysis time 1 second to 20 minutes are suitable.
  • the electrolytic treatment is preferably performed using nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid or oxalic acid, or a mixed acid of two or more of these acids.
  • electrochemical treatment is performed in an electrolytic solution containing nitric acid or hydrochloric acid, direct current may be applied between the Al foil 32 and the counter electrode, or alternating current may be applied.
  • direct current is applied to the Al foil 32, the current density is preferably 1 to 60 A / dm 2 and more preferably 5 to 50 A / dm 2 .
  • the electrochemical treatment is continuously performed, it is preferably performed by a liquid feeding method in which the Al foil 32 is fed through an electrolytic solution.
  • the amount of the first aluminum hydroxide film 33 formed by the film forming process is preferably from 0.05 ⁇ 50g / m 2, more preferably 0.1 ⁇ 10g / m 2.
  • the second laminated body 36 is subjected to an electrolytic dissolution process as a local aluminum dissolution process to form holes 23 (see FIG. 9C) in the Al foil 32, thereby generating the Al layer 26.
  • the holes 23 are also formed in the first aluminum hydroxide film 33, whereby the first aluminum hydroxide film 33 becomes the second aluminum hydroxide film 37 having the holes 23.
  • the third laminate 38 formed by this hole forming step is a laminate in which the film base 21, the adhesive layer 22, the Al layer 26, and the second aluminum hydroxide film 37 are laminated in this order. It has a structure.
  • Electrolytic dissolution treatment is not particularly limited, and direct current or alternating current can be used, and an acidic solution can be used as the electrolytic solution. Among them, it is preferable to perform electrochemical treatment using at least one acid of nitric acid and hydrochloric acid, and electrochemical treatment using a mixed acid obtained by adding at least one acid of sulfuric acid, phosphoric acid and oxalic acid to these acids. It is more preferable to carry out.
  • the acidic solution that is an electrolytic solution includes U.S. Pat. Nos. 4,671,859, 4,661,219, 4,618,405, and 4,600,482. No. 4,566,960, No. 4,566,958, No. 4,566,959, No. 4,416,972, No. 4,374,710, No. 4 , 336, 113 and 4,184, 932, etc., can also be used.
  • the concentration of the acidic solution is preferably from 0.1 to 2.5% by mass, particularly preferably from 0.2 to 2.0% by mass. Further, the liquid temperature of the acidic solution is preferably 20 to 80 ° C., more preferably 30 to 60 ° C.
  • the aqueous solution mainly composed of the above acid is an acid aqueous solution having a concentration of 1 to 100 g / L, a nitrate compound having nitrate ions such as aluminum nitrate, sodium nitrate, ammonium nitrate, or aluminum chloride, sodium chloride, ammonium chloride, etc.
  • a hydrochloric acid compound having a hydrochloric acid ion and a sulfuric acid compound having a sulfuric acid ion such as aluminum sulfate, sodium sulfate, and ammonium sulfate can be added and used in a range from 1 g / L to saturation.
  • mainly means that the main component in the aqueous solution is contained in an amount of 30% by mass or more, preferably 50% by mass or more based on the total components added to the aqueous solution.
  • the metal contained in aluminum alloys such as iron, copper, manganese, nickel, titanium, magnesium, a silica, may melt
  • a direct current is mainly used, but when an alternating current is used, the alternating current power wave is not particularly limited, and a sine wave, a rectangular wave, a trapezoidal wave, a triangular wave, etc. are used. Among these, a rectangular wave or a trapezoidal wave is preferable, and a trapezoidal wave is particularly preferable.
  • nitric acid dissolution process By means of an electrochemical dissolution process (hereinafter also referred to as “nitric acid dissolution process”) using an electrolytic solution mainly composed of nitric acid, a plurality of holes 23 having an average equivalent circle diameter D of 100 ⁇ m at most are formed. It can be formed easily.
  • the nitric acid dissolution treatment uses direct current, the average current density is 5 A / dm 2 or more, and the amount of electricity is 50 C / dm 2 or more because it is easy to control the melting point of pore formation.
  • the electrolytic treatment is preferably performed.
  • the average current density is preferably 100 A / dm 2 or less, and the amount of electricity is preferably 10,000 C / dm 2 or less.
  • the concentration and temperature of the electrolytic solution in nitric acid electrolysis are not particularly limited, and electrolysis is performed at a high concentration, for example, 30 to 60 ° C. using a nitric acid electrolytic solution having a nitric acid concentration of 15 to 35% by mass, or a nitric acid concentration of 0. Electrolysis can be performed at a high temperature, for example, at 80 ° C. or higher, using a 7-2 mass% nitric acid electrolyte. Further, electrolysis can be performed using an electrolytic solution obtained by mixing at least one of sulfuric acid, oxalic acid, and phosphoric acid having a concentration of 0.1 to 50% by mass with the nitric acid electrolytic solution.
  • the hydrochloric acid dissolution treatment uses direct current, the average current density is 5 A / dm 2 or more, and the amount of electricity is 50 C / dm 2 or more because it is easy to control the dissolution point of through-hole formation.
  • the electrolytic treatment is performed in step (b).
  • the average current density is preferably 100 A / dm 2 or less, and the amount of electricity is preferably 10,000 C / dm 2 or less.
  • the concentration and temperature of the electrolytic solution in hydrochloric acid electrolysis are not particularly limited, and electrolysis is performed at 30 to 60 ° C. using a hydrochloric acid electrolytic solution having a high concentration, for example, a hydrochloric acid concentration of 10 to 35% by mass, or a hydrochloric acid concentration of 0. Electrolysis can be performed at a high temperature, for example, at 80 ° C. or higher, using a 7-2 mass% hydrochloric acid electrolyte. Further, electrolysis can be performed using an electrolytic solution obtained by mixing at least one of sulfuric acid, oxalic acid, and phosphoric acid having a concentration of 0.1 to 50% by mass with the hydrochloric acid electrolytic solution.
  • the film removal step is a step of removing the second aluminum hydroxide film 37 by performing a chemical dissolution treatment on the third laminate 38.
  • the 4th laminated body 39 formed by this film removal process has the laminated structure on which the film base material 21, the adhesive layer 22, and the Al layer 26 were laminated
  • the dissolution treatment include the following acid etching treatment and alkali etching treatment.
  • the dissolution treatment is a treatment for dissolving the second aluminum hydroxide film 37 using a solution that preferentially dissolves aluminum hydroxide over aluminum (hereinafter referred to as “aluminum hydroxide solution”).
  • the aluminum hydroxide solution for example, nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid, chromium compound, zirconium compound, titanium compound, lithium salt, cerium salt, magnesium salt, sodium silicofluoride, fluoride
  • An aqueous solution containing at least one selected from the group consisting of zinc, manganese compounds, molybdenum compounds, magnesium compounds, barium compounds and halogens is preferred.
  • examples of the chromium compound include chromium (III) oxide and anhydrous chromium (VI) acid.
  • examples of the zirconium-based compound include zircon ammonium fluoride, zirconium fluoride, and zirconium chloride.
  • examples of the titanium compound include titanium oxide and titanium sulfide.
  • examples of the lithium salt include lithium fluoride and lithium chloride.
  • examples of the cerium salt include cerium fluoride and cerium chloride.
  • examples of the magnesium salt include magnesium sulfide.
  • Examples of the manganese compound include sodium permanganate and calcium permanganate.
  • Examples of the molybdenum compound include sodium molybdate.
  • magnesium compounds include magnesium fluoride pentahydrate.
  • barium compounds include barium oxide, barium acetate, barium carbonate, barium chlorate, barium chloride, barium fluoride, barium iodide, barium lactate, barium oxalate, barium perchlorate, barium selenate, selenite.
  • Examples thereof include barium, barium stearate, barium sulfite, barium titanate, barium hydroxide, barium nitrate, and hydrates thereof.
  • barium oxide, barium acetate, and barium carbonate are preferable, and barium oxide is particularly preferable.
  • halogen alone include chlorine, fluorine, and bromine.
  • the aluminum hydroxide solution is preferably an aqueous solution containing an acid.
  • the acid include nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid, and the like. Good. Among these, it is preferable to use nitric acid as the acid.
  • the acid concentration is preferably 0.01 mol / L or more, more preferably 0.05 mol / L or more, and still more preferably 0.1 mol / L or more. There is no particular upper limit, but generally it is preferably 10 mol / L or less, more preferably 5 mol / L or less.
  • the dissolution treatment is performed by bringing the second aluminum hydroxide film 37 into contact with the above-described solution.
  • the method of making it contact is not specifically limited, For example, the immersion method and the spray method are mentioned. Of these, the dipping method is preferred.
  • the soaking method is a process of immersing the third laminate 38 in the above-described solution. Stirring during the dipping process is preferable because a uniform process is performed.
  • the immersion treatment time is preferably 10 minutes or more, more preferably 1 hour or more, and further preferably 3 hours or more and 5 hours or more.
  • the alkali etching treatment is a treatment for dissolving the second aluminum hydroxide film 37 by bringing it into contact with an alkaline solution.
  • Examples of the alkali used in the alkaline solution include caustic alkali and alkali metal salts.
  • examples of the caustic alkali include sodium hydroxide (caustic soda) and caustic potash.
  • Examples of the alkali metal salt include alkali metal silicates such as sodium metasilicate, sodium silicate, potassium metasilicate, and potassium silicate; alkali metal carbonates such as sodium carbonate and potassium carbonate; sodium aluminate and alumina.
  • Alkali metal aluminates such as potassium acid; alkali metal aldones such as sodium gluconate and potassium gluconate; dibasic sodium phosphate, dibasic potassium phosphate, tribasic sodium phosphate, tertiary potassium phosphate, etc.
  • An alkali metal hydrogen phosphate is mentioned.
  • a caustic alkali solution and a solution containing both a caustic alkali and an alkali metal aluminate are preferable from the viewpoint of high etching rate and low cost.
  • an aqueous solution of sodium hydroxide is preferred.
  • the concentration of the alkali solution is preferably 0.1 to 50% by mass, more preferably 0.2 to 10% by mass.
  • concentration of aluminum ions is preferably 0.01 to 10% by mass, and more preferably 0.1 to 3% by mass.
  • the temperature of the alkaline solution is preferably 10 to 90 ° C.
  • the treatment time is preferably 1 to 120 seconds.
  • a method for bringing the second aluminum hydroxide film 37 into contact with the alkaline solution for example, a method in which the third laminated body 38 is passed through a tank in which the alkaline solution is accommodated, and the third laminated body 38 is charged with the alkaline solution.
  • Examples include a method of immersing in a tank and a method of spraying an alkaline solution onto the second aluminum hydroxide film 37.
  • Black layer forming step In the black layer forming step, the surface of the Al layer 26 of the fourth stacked body 39 is subjected to plating treatment, thereby forming the black layer 27.
  • the film 15 (see FIG. 2) is obtained by the plating process. Examples of the plating treatment include electrolytic plating and electroless plating.
  • An apparatus used for electroplating includes a plating apparatus 61 shown in FIG.
  • the plating apparatus 61 includes an electrolytic cell 62, an electrode 63, and a DC power source 64, and an electrolytic solution 65 is accommodated in the electrolytic cell 62.
  • the electrolytic solution 65 contains nickel.
  • the electrode 63 is disposed in the electrolytic solution 65.
  • the fourth laminate 39 is also disposed in the electrolytic solution 65 in the same manner as the electrode 63, and the fourth laminate 39 is immersed in a state facing the electrode 63.
  • the fourth laminate 39 is connected to the cathode of the DC power supply 64, and the electrode 63 is connected to the anode.
  • a plating process is performed on the surface of the Al layer 26 of the fourth stacked body 39 by a direct current flowing from the direct current power source 64 to form a black layer 27 (see FIGS. 2 and 7).
  • Examples of the electroless plating treatment include Ni—P (nickel-phosphorus) plating using phosphinate as a reducing agent. More specifically, a plating bath made of nickel sulfate, sodium phosphinate, and sodium acetate is used, and the fourth laminate 39 is immersed in the plating bath, and the surface is made of Ni—P (nickel and phosphorus). A covering film is formed.
  • the hydrogen ion exponent pH of the plating bath is preferably in the range of 4 to 6, and the temperature of the plating bath is preferably 90 ° C.
  • the coating film may be used as the black layer 27.
  • the target uneven structure is surfaced by etching the coating film in sulfuric acid or acetic acid.
  • the black layer 27 is formed.
  • a base treatment with a chemical solution may be performed from the viewpoint of preventing the black layer 27 from peeling off from the Al layer 26.
  • the obtained film 15 is formed into a three-dimensional shape by, for example, insert molding, and is integrated with the molded body 16 (see FIGS. 1 and 2), whereby the dashboard material 10 (see FIG. 1). It is said.
  • the film 15 can be used by being incorporated as a part of various molded products.
  • the black layer 27 has the fine concavo-convex structure on the surface as described above, for example, when the resin forming the molded body 16 is supplied in a molten state in the insert molding, the molten resin becomes a black layer. 27 enters the concave portion of the concave-convex structure. Therefore, by using the film 15 on which the black layer 27 having the surface of such a concavo-convex structure is formed, the dashboard material 10 having an excellent adhesive force between the molded body 16 and the film 15 can be obtained.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Laminated Bodies (AREA)
  • Optical Elements Other Than Lenses (AREA)
  • Surface Treatment Of Optical Elements (AREA)

Abstract

La présente invention concerne un film dont l'image peut être observée uniquement lorsque cela est nécessaire. Un film (15) comprend une couche d'Al (26) en tant que couche métallique, un matériau de base pour film (21) et une couche de couleur noire (27). Une pluralité de trous (23) sont formés dans la couche d'Al (26). Le diamètre de cercle équivalent moyen de la pluralité de trous (23) sur une première surface du film (15a) du côté de la couche de couleur noire (27) est inférieur ou égal à 100 µm. Le matériau de base pour film (21) est transparent et supporte la couche d'Al (26). La couche de couleur noire (27) est disposée sur la couche d'Al (26).
PCT/JP2017/032421 2016-09-28 2017-09-08 Film WO2018061709A1 (fr)

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JP2016-190421 2016-09-28

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018235488A1 (fr) * 2017-06-21 2018-12-27 富士フイルム株式会社 Corps composite
JPWO2020044900A1 (ja) * 2018-08-29 2021-09-09 富士フイルム株式会社 カバーフイルムおよび画像表示装置

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61107533U (fr) * 1984-12-18 1986-07-08
JP2005234096A (ja) * 2004-02-18 2005-09-02 Fuji Photo Film Co Ltd 表示装置
WO2012014774A1 (fr) * 2010-07-26 2012-02-02 三菱レイヨン株式会社 Dispositif de fabrication pour moule de nano-impression et procédé de fabrication pour moule de nano-impression

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL7412622A (nl) * 1974-09-24 1976-03-26 Stork Brabant Bv Rasterfilm en een werkwijze voor het vervaardi- gen van een zeefsjabloon onder toepassing van deze rasterfilm, alsmede aldus vervaardigde zeefsjabloon.
JPS582821A (ja) * 1981-06-29 1983-01-08 Seiko Epson Corp 液晶表示体装置

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61107533U (fr) * 1984-12-18 1986-07-08
JP2005234096A (ja) * 2004-02-18 2005-09-02 Fuji Photo Film Co Ltd 表示装置
WO2012014774A1 (fr) * 2010-07-26 2012-02-02 三菱レイヨン株式会社 Dispositif de fabrication pour moule de nano-impression et procédé de fabrication pour moule de nano-impression

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018235488A1 (fr) * 2017-06-21 2018-12-27 富士フイルム株式会社 Corps composite
JPWO2018235488A1 (ja) * 2017-06-21 2020-04-02 富士フイルム株式会社 複合体
JPWO2020044900A1 (ja) * 2018-08-29 2021-09-09 富士フイルム株式会社 カバーフイルムおよび画像表示装置

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JPWO2018061709A1 (ja) 2019-06-24

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