WO2019093164A1 - 積層体、反射防止構造体及びカメラモジュール搭載装置 - Google Patents

積層体、反射防止構造体及びカメラモジュール搭載装置 Download PDF

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Publication number
WO2019093164A1
WO2019093164A1 PCT/JP2018/039990 JP2018039990W WO2019093164A1 WO 2019093164 A1 WO2019093164 A1 WO 2019093164A1 JP 2018039990 W JP2018039990 W JP 2018039990W WO 2019093164 A1 WO2019093164 A1 WO 2019093164A1
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WIPO (PCT)
Prior art keywords
light shielding
shielding film
light
reflection
laminate
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Ceased
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PCT/JP2018/039990
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English (en)
French (fr)
Japanese (ja)
Inventor
宏士 須賀田
俊一 梶谷
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Dexerials Corp
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Dexerials Corp
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Publication date
Application filed by Dexerials Corp filed Critical Dexerials Corp
Priority to PL18877179.4T priority Critical patent/PL3708358T3/pl
Priority to EP18877179.4A priority patent/EP3708358B1/en
Priority to CN201880071894.XA priority patent/CN111316136B/zh
Priority to KR1020207012562A priority patent/KR102694084B1/ko
Priority to US16/760,907 priority patent/US11614568B2/en
Publication of WO2019093164A1 publication Critical patent/WO2019093164A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • 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
    • B32B7/023—Optical properties
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133502—Antiglare, refractive index matching layers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133512—Light shielding layers, e.g. black matrix

Definitions

  • the present invention relates to a laminate, an antireflective structure, and a camera module mounting apparatus, which are thin-filmed, are excellent in antireflective performance, and can keep the reflection chromaticity neutral.
  • a display device such as a liquid crystal display or an optical device such as a camera is a base material such as a display plate or a lens in order to avoid deterioration of visibility and image quality (occurrence of color unevenness, ghost etc.) due to reflection of light from the outside.
  • anti-reflection processing such as formation of an anti-reflection film is performed on the light incident surface of the lens.
  • Patent Document 1 is a solid-state imaging device that forms an image by photoelectrically converting light incident on a semiconductor substrate, and forms a fine concavo-convex structure on the light incident surface of the semiconductor substrate. It is disclosed that the film formation of the anti-reflection film can suppress the occurrence of the reflection of light on the light incident surface.
  • thinning for example, 15 ⁇ m or less
  • the total thickness of the outermost layer and the intermediate layer needs to be 25 ⁇ m or more in order to form the fine uneven structure without problems, and there is room for improvement from the viewpoint of thinning.
  • the present invention has been made in view of the above circumstances, and a laminate and an antireflective structure that can be made thin, have excellent antireflection performance, and can keep the reflection chromaticity neutral. Intended to be provided.
  • another object of the present invention is to provide a camera module mounting apparatus which can obtain a captured image in which thin film formation is achieved and color unevenness is suppressed by using such a laminate.
  • the present inventors have formed an antireflection structure having a fine concavo-convex structure on the surface via an adhesive layer, and also made visible the concavo-convex cycle of the fine concavo-convex structure.
  • the wavelength equal to or less than the wavelength of light
  • the color difference between the reflected light of the light shielding film and the reflected light of the antireflective structure is small (specifically, 1.5) It has been found that the reflection chromaticity can be kept neutral between the surface on which the anti-reflection processing technology is applied and the surface around it by setting the following conditions.
  • a laminate comprising a display plate, a light shielding film provided on the display plate, and an antireflection structure having a fine uneven structure on the surface
  • the light shielding film has a non-light shielding portion without a light shielding film in a part thereof
  • the anti-reflection structure is formed on the non-light-shielding portion through an adhesive layer, and the fine asperity structure has an asperity cycle equal to or less than the wavelength of visible light
  • ⁇ E a color difference between the reflected light of the light shielding film and the reflected light of the anti-reflection structure represented by the following formula is 1.5 or less.
  • a 1 and b 1 represent the a * and b * values in the CIE 1976 (L * a * b * ) color system of the reflected light of the light shielding film
  • a 2 and b 2 are And a * value and b * value in the CIE 1976 (L * a * b * ) color system of reflected light of the anti-reflection structure.
  • the film can be made thinner, the antireflection performance is excellent, and the reflection chromaticity can be kept neutral.
  • a laminate comprising: the laminate according to any one of (1) to (5); and a camera module provided at a position facing the anti-reflection structure in the laminate. Camera module mounting device.
  • the present invention it is possible to provide a laminate and an anti-reflection structure that are excellent in anti-reflection performance and capable of maintaining the reflection chromaticity in neutral, while achieving a thin film. Further, according to the present invention, it is possible to provide a camera module mounting device that can be thinned using the above-described laminate and obtain a captured image in which color unevenness is suppressed.
  • FIG. 5 is an enlarged, schematic cross-sectional view of another embodiment of the structure and the adhesive layer. It is a schematic diagram showing an example of a manufacturing process for manufacturing an antireflection structure of a layered product concerning one embodiment of the present invention.
  • FIG. 2 is a cross-sectional view schematically illustrating a camera module and a laminate in an embodiment of the camera module mounting device of the present invention.
  • FIGS. 1 to 3 may be schematically shown at a scale or shape different from the actual one for the convenience of description.
  • the laminate of the present invention is a laminate comprising a display panel 10, a light shielding film 20 provided on the display panel 10, and an antireflective structure 30 having a fine uneven structure on the surface. It is body 1. And, in the laminate 1 of the present invention, the light shielding film 20 has a non-light shielding portion 21 without the light shielding film 20 in a part thereof, and the anti-reflection structure 30 has an adhesive layer on the non light shielding portion 21. Formed through 40, The fine concavo-convex structure 30 has a concavo-convex period P (see FIG.
  • a color difference ( ⁇ E) between the reflected light of the light shielding film and the reflected light of the anti-reflection structure represented by the following equation is 1.5 or less.
  • a 1 and b 1 represent the a * and b * values in the CIE 1976 (L * a * b * ) color system of the reflected light of the light shielding film
  • a 2 and b 2 are And a * value and b * value in the CIE 1976 (L * a * b * ) color system of reflected light of the anti-reflection structure.
  • the antireflective structure 30 While forming the antireflective structure 30 having a fine concavo-convex structure on the surface through the adhesive layer 40 and making the concavo-convex period P of the fine concavo-convex structure 30 equal to or less than the wavelength of visible light, it achieves high film thickness Antireflection performance can be realized. Furthermore, by reducing the color difference ⁇ E between the reflected light of the light shielding film 20 and the reflected light of the anti-reflection structure 30 to 1.5 or less, the surface on which the anti-reflection processing technology is applied (in FIG. The reflected chromaticity can be kept neutral between the surface) and the peripheral surface (the surface of the light shielding film 20 in FIG. 1).
  • the laminated body 1 of this invention is equipped with the display board 10, as shown in FIG.
  • the display plate 10 is a member serving as a substrate or a support plate of the laminate 1 of the present invention.
  • the material constituting the display plate 10 is not particularly limited, and can be appropriately selected according to the purpose of use of the laminate.
  • the material of the display plate glass, poly (methyl methacrylate) (PMMA), and those coated with any organic material (polyimide etc.) may be mentioned.
  • the said display board is transparent. Since it is used as a liquid crystal display, a touch panel, etc., it is for transmitting light.
  • transparent means that the transmittance of light having a wavelength belonging to the visible light band (approximately 360 nm to 830 nm) is high, and for example, the transmittance of the light is 70% or more.
  • the shape of the display plate is not particularly limited except that it is plate-like, and can be appropriately selected according to the purpose of use of the laminate.
  • the surface on which the light shielding film and the anti-reflection structure are laminated (the lower surface of the display panel 10 in FIG. 1) can be, for example, a flat surface in order to facilitate the formation thereof.
  • the laminate 1 of the present invention further includes a light shielding film 20 on the display plate 10, as shown in FIG.
  • the light shielding film 20 enhances the light shielding property, and blocks the light reaching the solid-state imaging device even when the thin-film display panel 10 transmits light (in particular, light having a wavelength of 800 nm or more). It is a member of
  • the material constituting the light shielding film is not particularly limited, and a known light shielding film can be appropriately used depending on the use.
  • a material which comprises the said light shielding film the composition for light shielding films which contained light shielding particles, a filler, other additives, etc. in binder resin can be used, for example.
  • binder resin examples include (meth) acrylic resins, urethane resins, polyvinyl alcohol, polyvinyl butyral, polyvinyl formals, polyamides, polyesters, etc. (meth) acrylic resins or urethane resins Etc. These resins may also have carboxylic acid groups, sulfonic acid groups, phosphonic acid groups, phosphoric acid groups, sulfonamide groups and the like as acid groups.
  • the light shielding particles for example, carbon black, titanium black, tungsten compound, zinc white, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, red lead, iron oxide Red, yellow lead, zinc yellow (one zinc yellow, two zinc yellows), ultramarine blue, Prussia blue (potassium ferrocyanide), zircon gray, praseodymium yellow, chromium titanium yellow, chromium green, peacock, Victoria green And inorganic pigments such as bitumen (irrespective of Prussian blue), vanadium zirconium blue, chromium tin pink, porcelain enamel, salmon pink and the like.
  • light shielding dyes such as cyanine dyes, phthalocyanine dyes, naphthalocyanine dyes, immonium dyes, aminoum dyes, quinolium dyes, pyrilium dyes, or metal complex dyes such as Ni complex dyes, etc. It can also be included.
  • the content of the light shielding particles in the light shielding film composition is not particularly limited, but is preferably 30 to 70% by mass, and more preferably 40 to 60% by mass with respect to the total solid content. Is more preferable, and 45 to 55% by mass is more preferable.
  • the composition for a light shielding film can contain a filler and other additives, as needed.
  • the filler is not particularly limited as long as it enhances the reflectance, and, for example, an organic filler, an inorganic filler, and an inorganic-organic composite filler can be used.
  • the organic filler include synthetic resin particles and natural polymer particles, preferably acrylic resin, polyethylene, polypropylene, polyethylene oxide, polypropylene oxide, polyethylene oxide, polyethylene imine, polystyrene, polyurethane, polyurea, polyester, polyamide, polyimide And resin particles such as carboxymethyl cellulose, gelatin, starch, chitin, chitosan and the like.
  • metals and metal compounds such as silica, mica compounds, glass, zinc oxide, alumina, zircon oxide, tin oxide, potassium titanate, strontium titanate, aluminum borate, magnesium oxide, magnesium borate, hydroxide hydroxide
  • Aluminum, magnesium hydroxide, calcium hydroxide, titanium hydroxide, basic magnesium sulfate, calcium carbonate, magnesium carbonate, calcium carbonate, calcium sulfate, magnesium sulfate, calcium silicate, magnesium silicate, calcium silicate, calcium phosphate, silicon nitride, titanium nitride, aluminum nitride, Silicon carbide, titanium carbide, zinc sulfide and composites of at least two or more of these, and the like can be mentioned.
  • well-known additives such as a polymeric compound, a polymerization initiator, a dispersing agent, a sensitizer, a crosslinking agent effect accelerator, surfactant, etc. are mentioned, for example.
  • the average thickness of the light shielding film 20 is not particularly limited, but is preferably 30 ⁇ m or less and more preferably 10 ⁇ m or less from the viewpoint of thinning of the laminate 1. Furthermore, in order to maintain a high light shielding effect, the thickness of the light shielding film 20 is preferably 3 ⁇ m or more.
  • the average thickness of the light shielding film 20 is a thickness calculated by taking the average of the portions on which the light shielding film 20 is formed excluding the thickness of the non-light shielding portion 21 described later. For example, it can be obtained by measuring and averaging the thickness of any five places of the light shielding film 20.
  • the said light shielding film 20 has the non-light-shielding part 21 in which the light shielding film 20 is not formed in the part.
  • the non-light shielding portion 21 is a portion of the light shielding film 20 where the light shielding film is not formed.
  • the non-light shielding portion 21 may be a through hole as shown in FIG. 1 or may be partially filled with a transparent material.
  • the size of the non-light shielding portion 21 is not particularly limited, and can be appropriately changed according to the size of the anti-reflection structure 30. However, it is preferable to make the portion where the anti-reflection structure 30 is not formed as small as possible. This is to reliably block the light reaching the solid-state imaging device. Specifically, when the light shielding film and the non-light shielding portion 21 are viewed from the front, preferably 50% of the area of the non-light shielding portion 21 (that is, the opening area of the light shielding film 20), more preferably 100 It is preferable that the antireflective structure 30 be formed in the range of%.
  • the method of forming the light shielding film 20 is not particularly limited, and it is possible to appropriately use a known forming method according to the thickness of the light shielding film 20, conditions of manufacturing facilities and the like.
  • a spin coating method a spray coating method, a slit coating method, an ink jet method, a spin coating method, a cast coating method, a roll coating method, a screen printing method, etc.
  • the light shielding film 20 can be formed by performing hardening treatment such as light irradiation treatment and heat treatment.
  • the laminated body 1 of this invention equips the said non-light-shielding part 21 with the anti-reflection structure 30 which has a fine concavo-convex structure in the surface, as shown in FIG.
  • the said reflection preventing structure 30 can improve the reflection preventing performance of the laminated body 1 by the fine concavo-convex structure of the surface formed in the surface.
  • FIG. 2A shows one embodiment of the antireflective structure 30 and the adhesive layer 40.
  • the projections and depressions of the fine concavo-convex structure of the anti-reflection structure 30 may be arranged periodically (for example, in a zigzag grid, a rectangular grid), as shown in FIG. It is also possible to arrange at random.
  • the shapes of the convex portion and the concave portion are not particularly limited, and may be shell type, cone type, column shape, needle shape or the like.
  • the shape of a recessed part means the shape formed of the inner wall of a recessed part.
  • the fine concavo-convex structure of the anti-reflection structure 30 has a concavo-convex cycle (concave-convex pitch) P which is equal to or less than the wavelength of visible light (for example, 830 nm or less).
  • the upper limit of the unevenness cycle P is more preferably 350 nm or less, further preferably 280 nm or less, and the lower limit of the unevenness cycle P is more preferably 100 nm or more, still more preferably 150 nm or more.
  • corrugated period P of the said uneven structure is an arithmetic mean value of the distance between adjacent convex parts and between recessed parts.
  • the uneven period P can be observed by, for example, a scanning electron microscope (SEM) or a cross-sectional transmission electron microscope (cross-sectional TEM).
  • SEM scanning electron microscope
  • cross-sectional TEM cross-sectional transmission electron microscope
  • a method of deriving the arithmetic mean value of the distances between adjacent convex portions and concave portions for example, a plurality of combinations of adjacent convex portions and / or plural combinations of adjacent concave portions are picked up, and each combination
  • the method of measuring the distance between the convex part which comprises these, and the distance between recessed parts, and averaging a measured value is mentioned.
  • corrugated height (depth of a recessed part) H of the said fine concavo-convex structure is 190 nm or more. This is because the reflected chromaticity can be kept neutral more reliably.
  • the average asperity height P of the fine asperity structure is preferably 320 nm or less from the viewpoint of thinning of the laminate.
  • corrugated height H of the said fine concavo-convex structure as shown to Fig.2 (a), it is the distance from the bottom of a recessed part to the vertex of a convex part. For example, it can obtain by measuring the unevenness height H of five places) and calculating the average.
  • the thickness of the support portion under the fine concavo-convex structure where the fine concavo-convex structure of the antireflective structure 30 is not formed (hereinafter, referred to as “base part” of the antireflective structure 30) is not particularly limited. It can be about 9000 9000 nm.
  • the fine concavo-convex structure of the anti-reflection structure 30 needs to be at least on the surface not in contact with the adhesive layer 40 as shown in FIG. As shown in 2 (b), it is also possible to provide a fine uneven structure on both sides.
  • a resin composition that cures by a curing reaction such as active energy ray curable resin composition (photocurable resin composition, electron beam curable resin composition), thermosetting resin composition, etc.
  • Resin compositions containing a reactive compound and a polymerization initiator are not carried out.
  • polymerizable compound for example, (i) an esterified product obtained by reacting (meth) acrylic acid or a derivative thereof in a ratio of 2 mol or more with 1 mol of polyhydric alcohol, (ii) polyhydric alcohol Esterified products obtained from polyvalent carboxylic acid or its anhydride and (meth) acrylic acid or its derivative can be used.
  • polyhydric alcohols such as trimethylol ethane, trimethylol propane, glycerin and pentaerythritol and malonic acid, succinic acid, adipic acid, glutaric acid, sebacic acid, fumaric acid, itaconic acid and maleic anhydride
  • esterified material etc. which are obtained by making the polyvalent carboxylic acid or its anhydride selected from etc., and (meth) acrylic acid or its derivative (s) react are mentioned.
  • These polymerizable compounds may be used alone or in combination of two or more.
  • examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl, benzophenone, p-methoxybenzophenone , 2,2-diethoxyacetophenone, ⁇ , ⁇ -dimethoxy- ⁇ -phenylacetophenone, methylphenylglyoxylate, ethylphenylglyoxylate, 4,4'-bis (dimethylamino) benzophenone, 1-hydroxycyclohexyl Carbonyl compounds such as phenyl-ketone and 2-hydroxy-2-methyl-1-phenylpropan-1-one; Sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; 2, , 6-trimethyl benzoyl over diphenyl chromatography phosphine oxide
  • examples of the electron beam polymerization initiator include benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoyl benzoate, 4-phenylbenzophenone, Thioxanthones such as t-butyl anthraquinone, 2-ethyl anthraquinone, 2,4-diethylthioxanthone, isopropyl thioxanthone, 2,4-dichlorothioxanthone, etc .; diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one , Benzyldimethyl ketal, 1-hydroxycyclohexyl-phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholine) Acetophenones such as
  • thermal polymerization initiator examples include methyl ethyl ketone peroxide, benzoyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxy octoate, t Organic peroxides such as -butylperoxybenzoate and lauroyl peroxide; azo compounds such as azobisisobutyronitrile; N, N-dimethylaniline and N, N-dimethyl-p-toluidine as the organic peroxides And a redox polymerization initiator in which an amine such as E. coli is combined.
  • photopolymerization initiators electron beam polymerization initiators and thermal polymerization initiators may be used alone or in combination as desired.
  • the amount of the polymerization initiator is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the polymerizable compound. Within such a range, curing proceeds sufficiently, and the molecular weight of the cured product is adequate to obtain sufficient strength, and the cured product becomes colored due to the residue of the polymerization initiator, etc. Problem does not occur.
  • the resin composition may contain, if necessary, a non-reactive polymer and an active energy ray sol-gel reactive component, and a thickener, a leveling agent, an ultraviolet light absorber, a light stabilizer, and a heat stable.
  • a non-reactive polymer and an active energy ray sol-gel reactive component may contain, if necessary, a thickener, a leveling agent, an ultraviolet light absorber, a light stabilizer, and a heat stable.
  • Various additives such as additives, solvents, and inorganic fillers can also be included.
  • the anti-reflection structure 30 having a fine concavo-convex structure on the surface can be obtained by passing through a sandwiching pressure bonding process, a curing process and a peeling process.
  • the resin composition for an antireflective structure is sandwiched and pressure-bonded by a holding film having a fine uneven structure on the surface and a holding film having a flat surface. It is a process. Specifically, first, a holding film (first holding film 201a) having a fine uneven structure on the surface and a holding film (second holding film 201b) having a flat surface are prepared. Subsequently, as shown to Fig.3 (a), the resin composition 151 for anti-reflective structures is clamped so as to face each other by the above-mentioned 1st holding
  • the holding film 201a having a fine uneven structure on the surface is, for example, a fine film having a predetermined uneven pattern on a base material made of a transparent and hard to break material (for example, polyethylene terephthalate, triacetyl cellulose etc.). It can produce by forming an uneven
  • the thickness of the antireflection structure 30 finally obtained can be adjusted by adjusting the pressure at the time of pressure bonding.
  • the sandwiched resin composition 151 for an antireflective structure is cured by irradiation with an active energy ray such as UV light, and the antireflective structure having a fine uneven structure on both sides
  • an active energy ray such as UV light
  • the sandwiching resin composition 151 for an antireflective structure is irradiated with active energy rays to cure the resin composition 151 for an antireflective structure.
  • a holding film laminate 250 including the antireflective structure 30 having a fine concavo-convex structure on the surface is obtained.
  • the said peeling process is a process of peeling holding film 201a, 201b from the holding film laminated body 250, and obtaining the reflection preventing structure 30, as shown in FIG.3 (c).
  • the obtained anti-reflection structure 30 is subjected to a process such as washing as required.
  • the method of manufacturing the anti-reflection structure 30 is not limited to the above-described method (FIGS. 3A to 3C) through the sandwiching pressure bonding step, the curing step, and the peeling step, for example, After curing the resin composition for antireflective structure, it is possible to produce the antireflective structure 30 by forming a fine concavo-convex structure by sputtering or the like.
  • the laminate 1 further includes an adhesive layer 40 for bonding the anti-reflection structure 30 to the non-light shielding portion 21.
  • the adhesive layer 40 is made of an adhesive in order to bond the antireflective structure 30 to the non-light shielding portion 21, the antireflective performance of the antireflective structure 30 is not reduced. It is necessary to use the material.
  • the specific material is not particularly limited, and a resin composition that cures by a curing reaction can be appropriately used.
  • the adhesive layer 40 is preferably made of an ultraviolet curable adhesive. It is because high bondability can be realized.
  • ultraviolet curable resin ultraviolet curable acrylic resin, an ultraviolet curable epoxy resin, etc. are mentioned, for example.
  • the method of forming the adhesive layer 40 is not particularly limited.
  • the adhesive layer 40 is a layer made of an ultraviolet curable adhesive
  • ultraviolet light is applied in the non-light shielding portion 21 in a state where the ultraviolet curable adhesive is pressure bonded to the antireflective structure 30.
  • the adhesive layer 40 can be formed.
  • the adhesive layer 40 is preferably made thin within a range in which high bondability can be maintained. Specifically, as shown in FIGS. 2A and 2B, the total thickness T of the antireflective structure 30 and the adhesive layer 40 is preferably 30 ⁇ m or less, and 10 ⁇ m or less. Is more preferred.
  • the color difference ( ⁇ E) between the reflected light of the light shielding film 20 and the reflected light of the anti-reflection structure 30 represented by the following equation is 1.5 or less. I assume. By setting the color difference ⁇ E between the reflected light of the light shielding film 20 and the reflected light of the anti-reflection structure 30 to 1.5 or less, the surface of the anti-reflection structure 30 and the peripheral surface (in FIG. It is possible to keep the reflection chromaticity neutral with the surface of the film 20, and when the laminate of the present invention is used for a camera module mounting apparatus, it is possible to obtain a captured image in which color unevenness is suppressed.
  • a 1 and b 1 in the above formulas represent the a * value and the b * value in the CIE 1976 (L * a * b * ) color system of the reflected light of the light shielding film 20.
  • a 2 and b 2 is a representation of the a * and b * values in the CIE1976 (L * a * b *) color system of the reflected light of the anti-reflection structure 30.
  • the CIE 1976 (L * a * b * ) color system is one of the uniform color spaces defined by the CIE in 1976, and is three-dimensional orthogonal to the lightness index L and the chromaticness index a * and b *.
  • a color space using coordinates is called an L * a * b * color space, and is a color system using this color space.
  • the ⁇ E needs to be 1.5 or less, but is preferably 1.0 or less from the viewpoint of making the reflection chromaticity of the surface of the anti-reflection structure 30 and the peripheral surface more neutral. More preferably, it is 0.7 or less.
  • the a * value and the b * value in the color system can be obtained by using a commercially available measuring device.
  • the material, the shape, the thickness, and the reflection prevention of the light shielding film 20 It is possible to carry out by changing the material of the structure 30, the uneven period P of the uneven structure, the uneven height H of the uneven structure, and the like.
  • the difference ( ⁇ Y) between the luminous reflectance (Y value) of the light shielding film 20 and the luminous reflectance (Y value) of the anti-reflection structure 30 is 0.5 or less. Is preferred. This is because the lightness on the chromaticity diagram can be made almost the same condition, so that the reflection chromaticity of the surface of the anti-reflection structure 30 and the surface around it can be maintained more neutral.
  • the luminous reflectance (Y value) is a reflectance that takes into consideration that the brightness felt by the eye changes depending on the visibility, and the color of the specularly reflected light in the CIE 1931 XYZ color space (X, Y, Z) when expressed or (x, y, Y) when expressed in CIE xy Y color space, and a commercially available spectrophotometer (for example, V650 manufactured by JASCO Corporation) It can be measured by
  • the luminous reflectance and the reflectance difference of each of the light shielding film and the reflection preventing structure 30 can be adjusted, for example, by changing the density of the fine uneven structure and the uneven height.
  • the camera module mounting apparatus 300 of the present invention comprises the laminate 1 of the present invention, and a camera module 310 provided at a position facing the anti-reflection structure 30 in the laminate. It is characterized by According to the camera module mounting apparatus of the present invention, a still image or a moving image can be photographed through the laminate of the present invention by the image pickup element of the camera module, so that the reflection of light is suppressed and the obtained pickup image is obtained. It is possible to suppress the occurrence of color unevenness and the like.
  • Example 1-1 As shown in FIG. 1, as shown in FIG. 1, the display plate 10, the light shielding film 20 provided on the display plate 10, and the anti-reflection structure 30 having a micro uneven structure on the surface are provided. A model of laminate 1 was produced. Then, the chromaticity (irradiation angle: 5 °) of the reflected light was calculated for each of the light shielding film 20 and the anti-reflection structure 30.
  • the display plate 10 is a glass substrate
  • the light shielding film 20 contains carbon black
  • a spray paint containing butyl acetate, ethyl acetate, nitrocellulose, diisobutyl ketone, isopropyl alcohol, isobutanol, etc. is applied to the surface of the glass substrate.
  • the antireflective structure 30 is made of “UVX-6366” (1,6-hexanediol diacrylate, tetrahydrofurfuryl acrylate, and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide manufactured by Toagosei Co., Ltd.
  • the micro-relief structure has an asperity period of 150 to 250 nm, an asperity height of 220 nm, a thickness of the base portion having no asperity structure is 1000 nm, and a refractive index n of 1.520.
  • an ultraviolet curable resin was used, and the thickness was 3000 nm.
  • the total thickness of the antireflective structure 30 and the adhesive layer 40 is 4220 nm (about 4.2 ⁇ m).
  • Table 1 shows the structure of the antireflective structure, the total thickness ( ⁇ m) of the antireflective structure and the adhesive layer, and the a * value in the CIE 1976 (L * a * b * ) color system of the reflected light of the antireflective structure.
  • b * values (a 2 and b 2 ), the calculation results of the color difference ⁇ E between the reflected light of the light shielding film and the reflected light of the anti-reflection structure are shown.
  • Comparative Example 1-1 In Comparative Example 1-1, as a reflection preventing technology, a reflection preventing film (Dry-AR direct) obtained by alternately laminating NbO X and SiO 2 in total of four layers instead of the reflection preventing structure 30 having a fine concavo-convex structure A laminate was produced under the same conditions as in Example 1-1 except that the formation (formation) was performed.
  • Table 1 shows the structure of the antireflective structure, the total thickness ( ⁇ m) of the antireflective film and the adhesive layer, and a * value and b in the CIE 1976 (L * a * b * ) color system of the reflected light of the antireflective film. The calculation results of the value * and the color difference ⁇ E between the reflected light of the light shielding film and the reflected light of the antireflective film are shown.
  • Table 1 shows the structure of the antireflective structure, the total thickness ( ⁇ m) of the antireflective film and the adhesive layer, and a * value and b in the CIE 1976 (L * a * b * ) color system of the reflected light of the antireflective film. The calculation results of the value * and the color difference ⁇ E between the reflected light of the light shielding film and the reflected light of the antireflective film are shown.
  • Table 1 shows the structure of the antireflective structure, the total thickness ( ⁇ m) of the antireflective film and the adhesive layer, and a * value and b in the CIE 1976 (L * a * b * ) color system of the reflected light of the antireflective film. The calculation results of the value * and the color difference ⁇ E between the reflected light of the light shielding film and the reflected light of the antireflective film are shown.
  • Example 1-2 to 1-7 comparative examples 1-4 to 1--7
  • the height of the unevenness was changed in the micro-relief structure of the anti-reflection structure 30 (the specific height of the unevenness is The laminate was produced under the same conditions as in Example 1-1 except for the following Table 2).
  • Table 3 shows the unevenness height (nm) of the antireflective structure, the a * value and the b * value in the CIE 1976 (L * a * b * ) color system of the reflected light of the antireflective structure, the reflected light of the light shielding film
  • DELTA color difference
  • Example 2 As shown in FIG. 1, as shown in FIG. 1, the display plate 10, the light shielding film 20 provided on the display plate 10, and the anti-reflection structure 30 having a micro uneven structure on the surface are provided. The laminate 1 was actually produced. And about the light shielding film 20 and the anti-reflection structure 30, the chromaticity (irradiation angle: 5 degrees) of reflected light was measured, respectively.
  • the display plate 10 is a glass substrate, and the light shielding film 20 contains carbon black, and a spray paint containing butyl acetate, ethyl acetate, nitrocellulose, diisobutyl ketone, isopropyl alcohol, isobutanol, etc. is applied to the surface of the glass substrate.
  • the antireflective structure 30 is made of “UVX-6366” (1,6-hexanediol diacrylate, tetrahydrofurfuryl acrylate, and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide manufactured by Toagosei Co., Ltd.
  • the micro-convex-concave structure has an asperity cycle of 150 to 250 nm, a convex-concave height of 220 nm, and a thickness of the base without the micro-concave-convex structure is 1000 nm. Furthermore, the thickness of the adhesive layer 40 was set to 3780 nm using an ultraviolet curable resin.
  • the total thickness of the antireflective structure 30 and the adhesive layer 40 is 5000 nm (5 ⁇ m).
  • Table 2 shows the structure of the antireflective structure, the total thickness ( ⁇ m) of the antireflective structure and the adhesive layer, and the a * value in the CIE 1976 (L * a * b * ) color system of the reflected light of the antireflective structure.
  • b * values the calculation results of the color difference ⁇ E between the reflected light of the light shielding film and the reflected light of the anti-reflection structure are shown.
  • Example 2 About the sample of Example 2 A spectral spectrum is acquired using an ultraviolet visible near infrared spectrophotometer "V-650" manufactured by JASCO Corporation, and CIE 1976 (L * a * of the antireflective structure is obtained therefrom . b * ) The a * value and the b * value in the color system, and the color difference ⁇ E between the reflected light of the light shielding film and the reflected light of the antireflective structure were calculated. The measurement results are shown in Table 2. From the results of Table 2, it was found that ⁇ E of Example 2 was suppressed to be small as in Example 1-1, and the reflection chromaticity was kept neutral.
  • the present invention it is possible to provide a laminate and an anti-reflection structure that are excellent in anti-reflection performance and capable of maintaining the reflection chromaticity in neutral, while achieving a thin film. Further, according to the present invention, it is possible to provide a camera module mounting apparatus capable of obtaining a captured image in which thin film formation is achieved and color unevenness is suppressed by using the laminate of the present invention.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Optical Elements (AREA)
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  • Transforming Light Signals Into Electric Signals (AREA)
PCT/JP2018/039990 2017-11-07 2018-10-26 積層体、反射防止構造体及びカメラモジュール搭載装置 Ceased WO2019093164A1 (ja)

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PL18877179.4T PL3708358T3 (pl) 2017-11-07 2018-10-26 Laminowany korpus, struktura przeciwodblaskowa i uchwyt do mocowania modułu kamery
EP18877179.4A EP3708358B1 (en) 2017-11-07 2018-10-26 Laminated body, antireflection structure, and camera module mounting device
CN201880071894.XA CN111316136B (zh) 2017-11-07 2018-10-26 层叠体、防反射结构体及照相机模块搭载装置
KR1020207012562A KR102694084B1 (ko) 2017-11-07 2018-10-26 적층체, 반사 방지 구조체 및 카메라 모듈 탑재 장치
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KR20200085750A (ko) 2020-07-15
TWI795456B (zh) 2023-03-11
EP3708358B1 (en) 2022-11-16
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