WO2013099798A1 - 積層構造体 - Google Patents
積層構造体 Download PDFInfo
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- WO2013099798A1 WO2013099798A1 PCT/JP2012/083247 JP2012083247W WO2013099798A1 WO 2013099798 A1 WO2013099798 A1 WO 2013099798A1 JP 2012083247 W JP2012083247 W JP 2012083247W WO 2013099798 A1 WO2013099798 A1 WO 2013099798A1
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- adhesive film
- article
- peeling force
- film
- meth
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- 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
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- G02F1/1333—Constructional arrangements; Manufacturing methods
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
Definitions
- the present invention relates to a laminated structure in which the surface on the fine concavo-convex structure side of an article having a fine concavo-convex structure is protected by an adhesive film.
- a film having a fine concavo-convex structure on the surface of a substrate has been attracting attention.
- a fine concavo-convex structure referred to as a so-called Moth-Eye structure in which a plurality of protrusions (convex portions) such as a substantially conical shape and a substantially pyramidal shape are arranged has a refractive index continuously from the refractive index of air to the refractive index of the material.
- Patent Document 1 As a method for forming a fine concavo-convex structure on the surface of a substrate, anodized alumina having a fine concavo-convex structure composed of a plurality of pores (concave portions) formed by anodization is used. A method of transferring to the surface of a material has attracted attention (Patent Document 1).
- the article with the adhesive film described in Patent Document 2 is not considered to be processed into a desired shape by punching, NC cutting, or the like.
- the pressure-sensitive adhesive film is peeled off during the processing step, and a new pressure-sensitive adhesive film cannot be pasted after the processing.
- an adhesive film with high adhesion may be used.
- adhesive residue the adhesive material of the adhesive film remains in the concave portion of the fine uneven structure of the article. If there is adhesive residue in the concave portions of the fine concavo-convex structure, the optical performance of the article is likely to deteriorate. In particular, when an adhesive film is attached to the surface of the Moth-Eye structure, the adhesive material tends to remain in the recesses when the adhesive film is peeled off, and the antireflection performance is impaired.
- the present invention has been made in view of the above circumstances, and the adhesive film attached to the surface of the fine concavo-convex structure side of the article is not inadvertently peeled off, and if the adhesive film is intentionally peeled off, the work is performed.
- a laminated structure that can be easily and easily peeled off and has very little adhesive residue on a fine uneven structure.
- the present inventors have found that by using an adhesive film having specific adhesive properties, the adhesive film can be attached to the surface of the fine uneven structure side of the article and is fine even after the adhesive film is peeled off. There is very little adhesive residue on the concavo-convex structure, and without sacrificing the antireflection performance. As a result, it is possible to protect the fine concavo-convex structure from scratches and dirt during the processing process and after shipment until use. As a result, the present invention has been completed.
- the laminated structure according to the first aspect of the present invention includes an article having a fine concavo-convex structure on its surface and an adhesive film in contact with the surface of the article on the fine concavo-convex structure side.
- the average interval between the convex portions is 400 nm or less
- the low-speed peel force P of the adhesive film measured by the following method according to JIS Z0237: 2009 is 0.01 N / 25 mm or more and less than 2.5 N / 25 mm.
- the ratio (high-speed peeling force Q / low-speed peeling force P) of the high-speed peeling force Q and the low-speed peeling force P of the adhesive film measured by the following method according to JIS Z0237: 2009 is less than 2.
- the low-speed peel force P of the adhesive film is preferably 1.0 N / 25 mm or less.
- the ratio of the high-speed peeling force S and the low-speed peeling force R of the adhesive film measured by the following method (high-speed peeling force S / low-speed peeling force R) ) Is preferably 2 or less.
- the fine concavo-convex structure is preferably a transfer of the fine concavo-convex structure of anodized alumina.
- the laminated structure of the present invention does not inadvertently peel off the adhesive film attached to the surface of the article on the fine concavo-convex structure side, and can be easily peeled off with good workability if the adhesive film is intentionally peeled off. In addition, there is very little adhesive residue on the fine uneven structure.
- (meth) acrylate means acrylate or methacrylate
- (meth) acrylic acid means acrylic acid or methacrylic acid
- (meth) acrylonitrile means acrylonitrile or methacrylonitrile
- (meth) acrylamide means acrylamide or methacrylamide.
- active energy rays in the present specification means visible light, ultraviolet rays, electron beams, plasma, heat rays (infrared rays, etc.) and the like.
- FIGS. 1 to 4 the scales of the layers are different from each other in order to make each layer recognizable on the drawings. 2 to 3, the same components as those in FIG. 1 are denoted by the same reference numerals, and the description thereof may be omitted.
- FIG. 1 is a cross-sectional view showing an example of the laminated structure of the present invention.
- the laminated structure 1 includes an article 10 having a fine concavo-convex structure 16 on the surface, and an adhesive film 20 in contact with the surface of the article 10 on the fine concavo-convex structure 16 side.
- the article 10 includes a base material 12 and a plurality of convex portions 14 formed of a cured product of an active energy ray-curable resin composition, which will be described later, formed on the surface of the base material 12. And a cured resin layer 18 having a fine relief structure 16 on the surface.
- the material of the substrate 12 may be any material that transmits light, such as methyl methacrylate (co) polymer, polycarbonate, styrene (co) polymer, methyl methacrylate-styrene copolymer, cellulose diacetate, cellulose triacetate, Examples thereof include cellulose acetate butyrate, polyester, polyamide, polyimide, polyether sulfone, polysulfone, polypropylene, polymethylpentene, polyvinyl chloride, polyvinyl acetal, polyether ketone, polyurethane, and glass.
- methyl methacrylate (co) polymer polycarbonate
- styrene (co) polymer methyl methacrylate-styrene copolymer
- cellulose diacetate cellulose triacetate
- examples thereof include cellulose acetate butyrate, polyester, polyamide, polyimide, polyether sulfone, polysulfone, polypropylene, polymethylpentene,
- the base material 12 is produced by a known molding method such as an injection molding method, an extrusion molding method, or a cast molding method.
- the shape of the base material 12 can be appropriately selected according to the article 10 to be manufactured.
- the article 10 is an antireflection film or the like, a sheet shape or a film shape is preferable.
- An adhesive material layer (not shown) and a separate film (not shown) may be provided on the front surface (back surface) of the substrate 12 where the cured resin layer 18 is not formed.
- the pressure-sensitive adhesive layer By providing the pressure-sensitive adhesive layer, it can be easily attached to other film-like or sheet-like articles (front plate, polarizing element, etc.).
- Various coating treatments, corona discharge treatments, and surface roughenings are performed on the surface of the substrate 12 in order to improve adhesion to the active energy ray-curable resin composition, antistatic properties, scratch resistance, weather resistance, and the like. Processing etc. may be given.
- the cured resin layer 18 has a fine relief structure 16 on the surface.
- the cured resin layer 18 may be formed on the entire surface of the article 10 or may be formed on a part of the surface of the article 10.
- the fine concavo-convex structure 16 has a plurality of convex portions 14 made of a cured product of an active energy ray-curable resin composition described later, and is formed by transferring the fine concavo-convex structure of anodized alumina.
- the fine concavo-convex structure 16 is preferably a so-called Moth-Eye structure in which a plurality of protrusions (convex portions) having a substantially conical shape or a substantially pyramid shape are arranged.
- the article 10 having excellent antifouling properties can be obtained.
- the Moth-Eye structure in which the average interval between the convex portions 14 is equal to or less than the wavelength of visible light effectively increases the refractive index from the refractive index of air to the refractive index of the material, thereby effectively preventing reflection. It becomes a means.
- the average interval between the convex portions 14 is 400 nm or less, preferably 300 nm or less, and more preferably 250 nm or less. If the average distance between the convex portions 14 is 400 nm or less, when the cured product of the active energy ray-curable resin composition is a hydrophobic material, the hydrophobicity is likely to be strongly expressed, and in the case of a hydrophilic material, The hydrophilicity becomes strong and easily expressed, and the article 10 can be provided with excellent antifouling properties. In particular, when the average interval between the convex portions 14 is equal to or less than the wavelength of visible light, that is, 400 nm or less, the article 10 having low reflectance and low reflectance wavelength dependency can be obtained.
- the average distance between the convex portions 14 is preferably 25 nm or more, and more preferably 80 nm or more from the viewpoint of ease of formation of the convex portions 14.
- the average interval between the convex portions 14 is measured by measuring the distance between adjacent convex portions 14 (distance W 1 from the center of the convex portion 14 to the center of the adjacent convex portion 14 in FIG. 2) by electron microscope observation. These values are averaged.
- the height of the convex portion 14 is preferably 100 to 400 nm, and more preferably 150 to 300 nm. If the height of the convex portion 14 is 100 nm or more, the reflectance is sufficiently low, and the wavelength dependency of the reflectance is reduced. If the height of the convex part 14 is 400 nm or less, the scratch resistance of the convex part will be good.
- the height of the convex portion 14 is determined by electron microscope observation. The vertical distance d 1 from the height of the ten convex portions 14 (in FIG. 2, from the top of the convex portion 14 to the bottom of the concave portion adjacent to the convex portion 14). ) And the average of these values.
- the aspect ratio of the convex portion 14 (height of the convex portion 14 / length of the bottom surface of the convex portion 14) is preferably 1 to 5, more preferably 1.2 to 4, and particularly preferably 1.5 to 3. If the aspect ratio of the convex portion 14 is 1 or more, the reflectance is sufficiently low. If the aspect ratio of the convex part 14 is 5 or less, the scratch resistance of the convex part 14 will be good.
- the shape of the convex portion 14 is such that the cross-sectional area of the convex portion 14 in the direction orthogonal to the height direction continuously increases from the top to the depth direction, that is, the cross-sectional shape of the convex portion 14 in the height direction is A shape such as a triangle, trapezoid, and bell shape is preferable.
- the article 10 Since the article 10 has a fine concavo-convex structure on the surface, the article 10 is suitable as an optical article, particularly an antireflection article such as an antireflection film or a three-dimensional antireflection body.
- an image display device liquid crystal display device, plasma display panel, electroluminescence display, cathode tube display device, etc.
- lens show window, instrument window, daylighting member, eyeglass lens, Affixed to the surface of an object such as a half-wave plate or low-pass filter.
- an antireflection body is manufactured in advance using a transparent substrate having a shape according to the application, and this is used as a member constituting the surface of the object. May be.
- an antireflection film may be attached to the front plate, not limited to the surface thereof, and the front plate itself may be configured from the article 10.
- optical members optical waveguides, relief holograms, polarization separation elements, crystal devices, etc.
- cell culture sheets superhydrophobic films, superhydrophilic films, and the like.
- the article in the present invention is not limited to the illustrated example as long as it has a fine uneven structure on the surface.
- the fine concavo-convex structure is formed on the surface of the cured resin layer 18 in the illustrated example, but may be directly formed on the surface of the substrate 12 without providing the cured resin layer 18.
- the fine uneven structure is preferably formed on the surface of the cured resin layer 18 from the viewpoint that the fine uneven structure can be efficiently formed using a roll-shaped mold described later.
- the surface of the article is a region (I) having a fine concavo-convex structure, a region (II) having a higher peel strength from the adhesive film than the region (I), a region adjacent to the region (II), and a region (II). You may have area
- the article is formed on the surface of the intermediate layer so that at least a part of the surface of the base material, the intermediate layer formed on the surface of the base material so that at least part of the surface of the base material is exposed, and at least part of the surface of the intermediate layer
- a cured resin layer having a fine uneven structure formed on the surface, the surface of the cured resin layer is the region (I)
- the exposed surface of the intermediate layer is the region (II)
- the exposed surface of the substrate may be the region (III).
- the region (III) is preferably located at an end of the surface of the article having the fine concavo-convex structure on the surface.
- the pressure-sensitive adhesive film 20 protects the surface of the article 10 and is attached to the surface of the article 10 on the fine concavo-convex structure 16 side as shown in FIG. Thereby, the surface of the article 10 does not come into contact with other objects, and the fine concavo-convex structure 16 is hardly scratched. Furthermore, impurities such as dust and chemicals are less likely to enter the interface between the article 10 and the adhesive film 20, and dirt and the like are less likely to adhere to the surface of the article 10.
- the adhesive film 20 includes a film base 22 and an adhesive layer 24 including an adhesive formed on the surface of the film base 22.
- Peeling force of adhesive film on acrylic resin plate In the pressure-sensitive adhesive film 20, the low-speed peeling force P measured by the above method: No. 1 is 0.01 N / 25 mm or more and less than 2.5 N / 25 mm according to JIS Z0237: 2009, and according to JIS Z0237: 2009.
- the ratio of the high speed peel force Q and the low speed peel force P (high speed peel force Q / low speed peel force P) measured by the above method is less than 2.
- the low-speed peeling force P is 0.01 N / 25 mm or more, the adhesive film affixed on the surface of the article on the fine concavo-convex structure side will not be inadvertently peeled off.
- the low speed peeling force P is preferably 0.03 N / 25 mm or more, and more preferably 0.1 N / 25 mm or more.
- the low-speed peeling force P is less than 2.5 N / 25 mm, the adhesive residue on the fine concavo-convex structure 16 of the article 10 is hardly generated, and can be easily peeled off if the adhesive film is intentionally peeled off. Workability when peeling the adhesive film is good. That is, when the low-speed peel force P is 2.5 N / 25 mm or more, the peel strength is too strong, so that the material strength of the adhesive layer 24 cannot withstand the peel force, and cohesive failure of the adhesive layer 24 occurs. A part of the adhesive layer 24 remains in the ten fine concavo-convex structures 16, and adhesive residue is generated.
- the low speed peeling force P is preferably 2.0 N / 25 mm or less, more preferably 1.50 N / 25 mm or less, and particularly preferably 1.0 N / 25 mm or less.
- the adhesive residue hardly occurs in the concave portions of the fine concavo-convex structure of the article 10.
- the high-speed peeling force Q is smaller than the low-speed peeling force P, the hard adhesive material layer 24 is less likely to exhibit the anchoring effect. In such a case, it becomes difficult for the adhesive layer 24 to follow the fine concavo-convex structure, so that the adhesive does not remain at the bottom of the recess.
- the adhesive force when peeling the adhesive film 20 from the article 10 at a high speed does not become excessive, and the workability is also improved.
- the high speed peel force Q / low speed peel force P is preferably 1.5 or less, and more preferably 1.3 or less.
- the high speed peeling force Q / low speed peeling force P is preferably 0.1 or more, and more preferably 0.3 or more from the viewpoint of handling and workability.
- a method of setting the high speed peeling force Q / low speed peeling force P to less than 2 a method of reducing the thickness of the adhesive layer 24, a composition of the acrylic polymer constituting the adhesive material, a high glass transition point (Tg And the like, and a method of increasing the crosslinking density.
- Peeling force of adhesive film on fine concavo-convex structure of article In the pressure-sensitive adhesive film 20, the ratio of the high-speed peeling force S and the low-speed peeling force R (high-speed peeling force S / low-speed peeling force R) of the pressure-sensitive adhesive film measured by the above method 2 is preferably 2 or less. .
- the high-speed peeling force S / low-speed peeling force R is 2 or less, adhesive residue hardly occurs in the concave portions of the fine concavo-convex structure of the article 10.
- the high-speed peeling force S is smaller than the low-speed peeling force R, the hard adhesive material layer 24 is less likely to exhibit the anchoring effect. In such a case, it becomes difficult for the adhesive layer 24 to follow the fine concavo-convex structure, so that the adhesive does not remain at the bottom of the recess.
- the adhesive force when peeling the adhesive film 20 from the article 10 at a high speed does not become excessive, and the workability is also improved.
- the high speed peeling force S / low speed peeling force R is preferably 1.5 or less, and more preferably 1.3 or less.
- the high-speed peeling force S / low-speed peeling force R is preferably 0.1 or more, and more preferably 0.3 or more from the viewpoint of handling and workability.
- the high-speed peeling force S / low-speed peeling force R is set to 2 or less as a method of reducing the thickness of the adhesive material layer 24, as a composition of the acrylic polymer constituting the adhesive material, and a high glass transition point (Tg). And the like, and a method of increasing the crosslinking density.
- Film base examples of the material for the film substrate 22 include a crystalline ethylene resin, a crystalline propylene homopolymer, a crystalline propylene resin (a random copolymer of propylene and ⁇ -olefin and / or ethylene, propylene and ⁇ -olefin and / or Block copolymers with ethylene), other olefin resins (poly (1-butene), poly (4-methyl-1-pentene), etc.), acrylic resins (polymethyl acrylate, polymethyl methacrylate, ethylene- Ethyl acrylate copolymer, etc.), styrene resin (butadiene-styrene copolymer, acrylonitrile-styrene copolymer, polystyrene, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styren
- the thickness of the film substrate 22 can be appropriately selected within a range that does not impair the adhesiveness and the like, and is usually 3 to 500 ⁇ m, and preferably 5 to 200 ⁇ m. If the thickness of the film substrate 22 is less than 3 ⁇ m, wrinkles and the like are likely to occur in the production process of the adhesive film 20, and it may be difficult to stick to the article 10. When the thickness of the film substrate 22 exceeds 500 ⁇ m, it may be difficult to handle the adhesive film 20.
- the film base material 22 may be subjected to antifouling treatment, acid treatment, alkali treatment, primer treatment, anchor coating treatment, corona treatment, plasma treatment, ultraviolet treatment, antistatic treatment, etc. as necessary. .
- Adhesive layer As the adhesive material of the adhesive material layer 24, ethylene-vinyl acetate copolymer, linear low density polyethylene, ethylene- ⁇ -olefin copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block
- main polymer examples include copolymers, styrene-ethylene-butylene-styrene block copolymers, styrene-butadiene random copolymers, hydrogenated styrene-butadiene random copolymers, acrylic polymers, and the like.
- an acrylic polymer is preferable from the viewpoint of obtaining a balance between adhesiveness and peelability.
- the acrylic polymer is composed of one or more monomers such as (meth) acrylate having an alkyl group having 1 to 18 carbon atoms, and one or more copolymerizable modifying monomers as necessary. Is polymerized by homopolymerization or copolymerization by a known polymerization method such as a solution polymerization method or an emulsion polymerization method. Further, narrowing the molecular weight distribution of the main polymer by a living radical polymerization method or the like is effective in reducing the adhesive residue when the adhesive film 20 is peeled off.
- Examples of the (meth) acrylate having an alkyl group having 1 to 18 carbon atoms include esters of (meth) acrylic acid having a butyl group, 2-ethylhexyl group, isooctyl group, isononyl group, ethyl group, methyl group, and the like. .
- copolymerizable modifying monomer examples include (meth) acrylonitrile, vinyl acetate, styrene, (meth) acrylic acid, maleic anhydride, vinyl pyrrolidone, glycidyl group, dimethylaminoethyl group or hydroxyl group (meth) acrylate, ( Examples include meth) acrylamide, vinylamine, allylamine, and ethyleneimine.
- the acrylic polymer can be used as it is as the main polymer of the pressure-sensitive adhesive, but is usually mixed with a crosslinking agent for the purpose of improving the cohesive strength of the pressure-sensitive adhesive.
- Crosslinking structuring of acrylic polymer can be achieved by adding polyfunctional (meth) acrylate as an internal cross-linking agent when synthesizing acrylic polymer, or polyfunctional epoxy-based compound as external cross-linking agent after synthesizing acrylic polymer It can be carried out by adding a polyfunctional isocyanate compound or the like. In addition, you may give the crosslinking process by radiation irradiation.
- a preferable method for forming a crosslinked structure is a method of blending a polyfunctional epoxy compound or a polyfunctional isocyanate compound as an external crosslinking agent.
- polyfunctionality means bifunctionality or more.
- polyfunctional epoxy compound examples include various compounds having two or more epoxy groups in the molecule (sorbitol tetraglycidyl ether, trimethylolpropane glycidyl ether, tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl-m -Xylenediamine, triglycidyl-p-aminophenol, etc.).
- Examples of the polyfunctional isocyanate compound include various compounds having two or more isocyanate groups in the molecule (diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, etc.).
- a crosslinking agent may be used individually by 1 type, and may be used in combination of 2 or more type.
- the amount of the crosslinking agent used can be appropriately selected according to the composition, molecular weight and the like of the acrylic polymer.
- the pressure-sensitive adhesive material may be blended with a crosslinking catalyst such as dibutyltin laurate which is usually used for the pressure-sensitive adhesive material.
- a crosslinking catalyst such as dibutyltin laurate which is usually used for the pressure-sensitive adhesive material.
- reducing impurities contained in additives such as a crosslinking agent is effective in reducing adhesive residue when the adhesive film 20 is peeled off.
- the thickness of the adhesive layer 24 can be appropriately selected within a range that does not impair the adhesiveness and the like, and is usually 1 to 100 ⁇ m, preferably 3 to 50 ⁇ m, and more preferably 5 to 30 ⁇ m.
- a release film (not shown) in contact with the adhesive material layer 24 may be laminated on the adhesive film 20 for the purpose of antifouling resistance.
- the material for the release film include various resins exemplified above in the description of the film substrate 22. Among these, from the viewpoint of peelability, polystyrene, saturated ester resin, and polyamide are preferable, and polyethylene terephthalate and polyamide are more preferable.
- the surface of the release film on the side in contact with the pressure-sensitive adhesive layer 24 may be subjected to a treatment with silicone or the like as necessary within a range not impairing the effects of the present invention.
- Examples of the method for producing the adhesive film 20 include known methods such as a coextrusion molding method, a laminate molding method, a casting method, and a coating method.
- the material of the film base material 22 and the adhesive material are extruded in a molten state by a known method such as a T-die molding method or an inflation molding method, laminated, and then cooled by a cooling means such as a cooling roll.
- a cooling means such as a cooling roll.
- the method of cooling by is mentioned.
- a lamination molding method a film substrate 22 is prepared in advance by an extrusion molding method, an adhesive material is extruded on the surface of the film substrate 22 in a molten state, laminated, and then a cooling means such as a cooling roll. The method of cooling by is mentioned.
- an adhesive liquid having a solid content concentration of about 10 to 40% by mass is prepared by dissolving or dispersing the main polymer or the like in an organic solvent such as toluene or ethyl acetate alone or in a mixture.
- the pressure-sensitive adhesive film in the present invention is not particularly limited as long as it contains at least one film base material and at least one pressure-sensitive adhesive layer, but is usually about 2 to 7 layers.
- Specific examples of the layer structure of the adhesive film include a film substrate / adhesive layer, a film substrate / adhesive layer / release film, a film substrate / adhesive layer / film substrate / adhesive layer, and a film substrate / Adhesive layer / film substrate / adhesive layer / release film and the like.
- FIG. 3 is a configuration diagram showing an example of a laminated structure manufacturing apparatus according to the present invention.
- the manufacturing apparatus 30 includes a roll-shaped mold 31 having a fine concavo-convex structure on the surface, a tank 32 that contains the active energy ray-curable resin composition 18 ′, a nip roll 34 that includes a pneumatic cylinder 33, and active energy ray irradiation.
- a device 35, a peeling roll 36, and a pair of nip rolls 38 provided with a pneumatic cylinder 37 are provided.
- a manufacturing apparatus 30 shown in FIG. 3 is an apparatus that continuously manufactures the laminated structure 1 after manufacturing the article 10.
- the mold 31 is a mold for transferring the fine concavo-convex structure to the active energy ray curable resin composition 18 ′, and has anodized alumina on the surface.
- a mold having an anodized alumina on the surface can increase the area, and a roll-shaped mold can be easily produced.
- Anodized alumina is a porous oxide film (alumite) of aluminum and has a plurality of pores (concave portions) on the surface.
- a mold having an anodized alumina on its surface can be produced, for example, through the following steps (a) to (e).
- D A step of enlarging the diameter of the pores.
- E A step of repeatedly performing the step (c) and the step (d).
- the purity of aluminum is preferably 99% or more, more preferably 99.5% or more, and particularly preferably 99.8% or more. When the purity of aluminum is low, when anodized, an uneven structure having a size to scatter visible light may be formed due to segregation of impurities, or the regularity of pores obtained by anodization may be lowered.
- the electrolytic solution include sulfuric acid, oxalic acid, and phosphoric acid.
- the concentration of oxalic acid is preferably 0.7 M or less. When the concentration of oxalic acid exceeds 0.7M, the current value becomes too high, and the surface of the oxide film may become rough. When the formation voltage is 30 to 60 V, anodized alumina having highly regular pores with a period of 100 nm can be obtained. Regardless of whether the formation voltage is higher or lower than this range, the regularity tends to decrease.
- the temperature of the electrolytic solution is preferably 60 ° C. or lower, and more preferably 45 ° C. or lower. When the temperature of the electrolytic solution exceeds 60 ° C., a so-called “burn” phenomenon occurs, and the pores may be broken, or the surface may melt and the regularity of the pores may be disturbed.
- the concentration of sulfuric acid is preferably 0.7M or less. If the concentration of sulfuric acid exceeds 0.7M, the current value may become too high to maintain a constant voltage. When the formation voltage is 25 to 30 V, anodized alumina having highly regular pores with a period of 63 nm can be obtained. The regularity tends to decrease whether the formation voltage is higher or lower than this range.
- the temperature of the electrolytic solution is preferably 30 ° C. or lower, and more preferably 20 ° C. or lower. When the temperature of the electrolytic solution exceeds 30 ° C., a so-called “burn” phenomenon occurs, and the pores may be broken or the surface may melt and the regularity of the pores may be disturbed.
- Examples of the method for removing the oxide film include a method in which aluminum is not dissolved but is dissolved and removed in a solution that selectively dissolves the oxide film.
- Examples of such a solution include a chromic acid / phosphoric acid mixed solution.
- the pore diameter expansion treatment is a treatment for expanding the diameter of the pores obtained by anodic oxidation by immersing in a solution dissolving the oxide film.
- An example of such a solution is an aqueous phosphoric acid solution of about 5% by mass. The longer the pore diameter expansion processing time, the larger the pore diameter.
- the mold 31 having the anodized alumina on the surface is obtained. It is preferable that the last end is step (d).
- the total number of repetitions is preferably 3 times or more, and more preferably 5 times or more. When the number of repetitions is 2 times or less, the diameter of the pores decreases discontinuously. Therefore, the effect of reducing the reflectance of the cured resin layer 18 produced using anodized alumina having such pores is insufficient. is there.
- the surface of the anodized alumina may be treated with a release agent so that separation from the cured resin layer 18 is easy.
- the treatment method include a method of coating a silicone resin or a fluorine-containing polymer, a method of depositing a fluorine-containing compound, and a method of coating a fluorine-containing silane compound.
- Examples of the shape of the pore 40 include a substantially conical shape, a pyramid shape, a cylindrical shape, and the like, and a cross-sectional area of the pore in a direction perpendicular to the depth direction, such as a conical shape and a pyramid shape, is a depth from the outermost surface.
- a shape that continuously decreases in the direction is preferred.
- the average interval between the pores 40 is 400 nm or less, preferably 300 nm or less, and more preferably 250 nm or less. If the average interval between the pores 40 is 400 nm or less, the article 10 having a low reflectance and a low wavelength dependency of the reflectance can be obtained.
- the average interval between the pores 40 is preferably 25 nm or more, and more preferably 80 nm or more, from the viewpoint of ease of formation of the pores 40.
- the average interval between the pores 40 is obtained by measuring 10 intervals between adjacent pores 40 by electron microscope observation and averaging these values.
- the depth of the pores 40 is preferably 100 to 400 nm, and more preferably 150 to 300 nm.
- the depth of the pores 40 is obtained by measuring the depths of the ten pores 40 by electron microscope observation and averaging these values.
- the aspect ratio (depth of the pore / length of the opening of the pore) of the pore 40 is preferably 0.5 to 5, more preferably 0.7 to 4, and particularly preferably 1.0 to 3.
- the length of the opening of the pore 40 is the length of the opening in the cut surface when the pore is cut in the depth direction from the deepest portion of the pore 40.
- the tank 32 contains the active energy ray curable resin composition 18 ′, and the active energy ray curable resin is interposed between the roll-shaped mold 31 and the belt-like base material 12 that moves along the surface of the mold 31.
- Supply composition 18 ' The tank 32 contains the active energy ray curable resin composition 18 ′, and the active energy ray curable resin is interposed between the roll-shaped mold 31 and the belt-like base material 12 that moves along the surface of the mold 31.
- the nip roll 34 is disposed to face the roll-shaped mold 31.
- the nip roll 34 nips the base material 12 and the active energy ray curable resin composition 18 ′ together with the mold 31.
- the nip pressure is adjusted by a pneumatic cylinder 33 provided in the nip roll 34.
- the active energy ray irradiation device 35 is installed below the roll-shaped mold 31 and irradiates active energy rays to fill the space between the base material 12 and the mold 31 with the active energy ray curable resin composition 18 ′. Is cured. By curing the active energy ray-curable resin composition 18 ′, a cured resin layer 18 in which the fine uneven structure of the mold 31 is transferred to the surface of the base 12 is formed.
- the active energy ray irradiation device 35 include a high-pressure mercury lamp and a metal halide lamp. In this case, the amount of light irradiation energy is preferably 100 to 10,000 mJ / cm 2 .
- the peeling roll 36 is disposed on the downstream side of the active energy ray irradiation device 35 and peels the base material 12 having the cured resin layer 18 formed on the surface thereof from the roll-shaped mold 31.
- the pair of nip rolls 38 is disposed on the downstream side of the peeling roll 36 and attaches the adhesive film 20 to the article 10.
- the pair of nip rolls 38 includes an elastic roll 38a whose outer peripheral surface is formed of an elastic member such as rubber, and a rigid roll 38b whose outer peripheral surface is formed of a member having high rigidity such as metal.
- the nip pressure is adjusted by a pneumatic cylinder 37 provided in the elastic roll 38a.
- the active energy ray-curable resin composition 18 ′ appropriately contains a monomer, oligomer, or reactive polymer having a radical polymerizable bond and / or a cationic polymerizable bond in the molecule, and contains a non-reactive polymer. It may be a thing.
- Examples of the monomer having a radical polymerizable bond include (meth) acrylates (methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, s-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, alkyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl ( (Meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofur
- Monofunctional monomers such as ethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate, triethylene glycol di (meth) acrylate , Diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, 1,3-butylene glycol di (Meth) acrylate, polybutylene glycol di (meth) acrylate, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane 2,2-bis (4- (3- (meth) acryloxy-2-hydroxypropoxy) phenyl) propane, 1,2-bis (3- (meth) acryloxy-2-hydroxy
- oligomers and reactive polymers having radically polymerizable bonds examples include unsaturated polyesters (condensates of unsaturated dicarboxylic acids and polyhydric alcohols, etc.), polyester (meth) acrylates, polyether (meth) acrylates, polyols (meta ) Acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, cationic polymerization type epoxy compound, homopolymer or copolymer of the above-mentioned monomer having a radical polymerizable bond in the side chain.
- unsaturated polyesters condensates of unsaturated dicarboxylic acids and polyhydric alcohols, etc.
- polyester (meth) acrylates polyester (meth) acrylates, polyether (meth) acrylates, polyols (meta ) Acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, cationic polymerization type epoxy compound, homopolymer or copo
- the monomer, oligomer, and reactive polymer having a cationic polymerizable bond may be any compound having a cationic polymerizable functional group (cation polymerizable compound), and may be any of a monomer, an oligomer, and a prepolymer.
- the cationic polymerizable functional group include cyclic ether groups (epoxy groups, oxetanyl groups, etc.), vinyl ether groups, carbonate groups (O—CO—O groups), etc., as highly practical functional groups.
- Examples of the cationic polymerizable compound include cyclic ether compounds (such as epoxy compounds and oxetane compounds), vinyl ether compounds, carbonate compounds (such as cyclic carbonate compounds and dithiocarbonate compounds), and the like.
- Examples of the monomer having a cationic polymerizable bond include monomers having an epoxy group, an oxetanyl group, an oxazolyl group, a vinyloxy group, and the like. Among these, a monomer having an epoxy group is particularly preferable.
- Examples of the oligomer and reactive polymer having a cationic polymerizable bond include a cationic polymerization type epoxy compound.
- non-reactive polymers examples include acrylic resins, styrene resins, polyurethane resins, cellulose resins, polyvinyl butyral resins, polyester resins, and thermoplastic elastomers.
- the active energy ray-curable resin composition usually contains a polymerization initiator for curing.
- a polymerization initiator for curing.
- examples of the polymerization initiator include known ones.
- examples of the photopolymerization initiator include a radical polymerization initiator and a cationic polymerization initiator.
- Any radical polymerization initiator may be used as long as it generates an acid upon irradiation with a known active energy ray.
- An acetophenone-based photopolymerization initiator, a benzoin-based photopolymerization initiator, a benzophenone-based photopolymerization initiator, or a thioxanthone-based light is used. Examples thereof include polymerization initiators and acylphosphine oxide photopolymerization initiators.
- acetophenone photopolymerization initiator As the acetophenone photopolymerization initiator, acetophenone, p- (tert-butyl) -1 ′, 1 ′, 1′-trichloroacetophenone, chloroacetophenone, 2 ′, 2′-diethoxyacetophenone, hydroxyacetophenone, 2,2 -Dimethoxy-2'-phenylacetophenone, 2-aminoacetophenone, dialkylaminoacetophenone and the like.
- Benzoin photopolymerization initiators include benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-2- Examples include methylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, and benzyldimethyl ketal.
- Benzophenone photopolymerization initiators include benzophenone, benzoylbenzoic acid, benzoylmethyl benzoate, methyl-o-benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, hydroxypropylbenzophenone, acrylic benzophenone, 4,4'-bis (dimethyl) Amino) benzophenone and the like.
- thioxanthone photopolymerization initiator examples include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, diethylthioxanthone, dimethylthioxanthone and the like.
- acylphosphine oxide photopolymerization initiator examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoyldiethoxyphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, and the like. .
- radical polymerization initiators include ⁇ -acyl oxime ester, benzyl- (o-ethoxycarbonyl) - ⁇ -monooxime, glyoxy ester, 3-ketocoumarin, 2-ethylanthraquinone, camphorquinone, tetramethylthiuram sulfide, Examples thereof include azobisisobutyronitrile, benzoyl peroxide, dialkyl peroxide, tert-butyl peroxypivalate and the like.
- a radical polymerization initiator may be used individually by 1 type, and may use 2 or more types together.
- the cationic polymerization initiator is not particularly limited as long as it generates an acid upon irradiation with a known active energy ray, and examples thereof include sulfonium salts, iodonium salts, and phosphonium salts.
- sulfonium salts include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, bis (4- (diphenylsulfonio) -phenyl) sulfide-bis (hexafluorophosphate), bis (4- (diphenylsulfonio)) -Phenyl) sulfide-bis (hexafluoroantimonate), 4-di (p-toluyl) sulfonio-4'-tert-butylphenylcarbonyl-diphenylsulfide hexafluoroantimonate, 7-di (p-toluyl) sulfonio-2 -Isopropylthioxanthone hexafluorophosphate, 7-di (p-toluyl) sulfonio-2-isopropyl
- iodonium salt examples include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, bis (dodecylphenyl) iodoniumtetrakis (pentafluorophenyl) borate, and the like.
- Examples of the phosphonium salt include tetrafluorophosphonium hexafluorophosphate, tetrafluorophosphonium hexafluoroantimonate, and the like.
- thermal polymerization initiators include organic peroxides (methyl ethyl ketone peroxide, benzoyl peroxide, dicumyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxy octoate, tert-butyl peroxy Benzoate, lauroyl peroxide, etc.), azo compounds (azobisisobutyronitrile, etc.), redox in which the organic peroxide is combined with an amine (N, N-dimethylaniline, N, N-dimethyl-p-toluidine, etc.) A polymerization initiator etc. are mentioned.
- the addition amount of the polymerization initiator is 0.1 to 10 parts by mass with respect to 100 parts by mass of the active energy ray-curable resin composition. If the addition amount of the polymerization initiator is 0.1 parts by mass or more, the polymerization is likely to proceed. If the addition amount of the polymerization initiator is 10 parts by mass or less, the obtained cured product will not be colored and the mechanical strength will not be reduced.
- additives antioxidants, mold release agents, fluorine compounds for improving antifouling properties, etc.
- fine particles fine particles, and a small amount of solvent are added to the active energy ray-curable resin composition. It may be.
- the belt-like base material 12 is conveyed along the surface of the rotating roll-shaped mold 31, and the active energy ray-curable resin composition is supplied from the tank 32 between the base material 12 and the mold 31.
- Supply object 18 ' As shown in FIG. 3, the belt-like base material 12 is conveyed along the surface of the rotating roll-shaped mold 31, and the active energy ray-curable resin composition is supplied from the tank 32 between the base material 12 and the mold 31.
- Supply object 18 ' As shown in FIG. 3, the belt-like base material 12 is conveyed along the surface of the rotating roll-shaped mold 31, and the active energy ray-curable resin composition is supplied from the tank 32 between the base material 12 and the mold 31.
- Supply object 18 ' As shown in FIG. 3, the belt-like base material 12 is conveyed along the surface of the rotating roll-shaped mold 31, and the active energy ray-curable resin composition is supplied from the tank 32 between the base material 12 and the mold 31.
- Supply object 18 ' As shown in FIG. 3, the belt-like base material
- the base material 12 and the active energy ray curable resin composition 18 ′ are nipped between the roll-shaped mold 31 and the nip roll 34 whose nip pressure is adjusted by the pneumatic cylinder 33, and the active energy ray curable resin is obtained.
- the composition 18 ′ is uniformly distributed between the base material 12 and the mold 31, and at the same time, is filled into the pores of the fine uneven structure of the mold 31.
- the active energy ray curable resin composition 18 ′ is irradiated to the active energy ray curable resin composition 18 ′ through the base material 12 from the active energy ray irradiating device 35 installed below the roll-shaped mold 31, thereby activating the active energy ray curable resin composition.
- the cured resin layer 18 to which the fine uneven structure on the surface of the mold 31 is transferred is formed by curing the object 18 ′.
- the article 10 is obtained by peeling the base material 12 having the cured resin layer 18 formed on the surface thereof from the roll-shaped mold 31 by the peeling roll 36.
- the surface of the cured resin layer 18 formed by transferring the pores 40 as shown in FIG. 4 has a so-called Moth-Eye structure.
- the article 10 is passed between the pair of nip rolls 38, and at the same time, the adhesive film 20 fed from an adhesive film feeding machine (not shown) is attached to the surface on the side where the fine uneven structure is formed. 10 and a pair of nip rolls 38. At this time, the article 10 is fed between the elastic roll 38a and the rigid roll 38b so that the back surface (the surface on which the fine uneven structure is not formed) of the article 10 is in contact with the rigid roll 38b.
- the adhesive film 20 is such that the adhesive material layer 24 comes into contact with the surface of the article 10 (the surface on the side where the fine concavo-convex structure is formed) and the film substrate 22 comes into contact with the elastic roll 38a. And the article 10 are sent.
- the article 10 and the adhesive film 20 are sandwiched between the elastic roll 38 a and the rigid roll 38 b in a state where the adhesive material layer 24 of the adhesive film 20 is in contact with the surface of the article 10, and a pair of nip rolls 38 by the pneumatic cylinder 37.
- the adhesive film 20 is attached to the article 10 while adjusting the nip pressure. In this way, the laminated structure 1 in which the adhesive film 20 is laminated on the surface of the article 10 on the fine concavo-convex structure 16 side as shown in FIG. 1 is obtained.
- the fine concavo-convex structure 16 is unlikely to be deformed or damaged.
- the adhesive film 20 as long as it has a specific adhesion strength, a film prepared separately by the method described above may be used, or a commercially available film may be used.
- the laminated structure 1 is manufactured by continuously sticking the adhesive film 20 after producing the article 10 as described above, for the purpose of sticking the adhesive film 20 (preventing the adhesion of dirt and maintaining the shape of the fine uneven structure).
- the present invention is not limited to this, and after manufacturing the article 10, the article 10 may be temporarily collected, transferred to another production line, and the adhesive film 20 may be attached.
- the adhesive film can be easily processed without being carelessly peeled off, and the adhesive film can be intentionally peeled off. It can be easily peeled off with good workability, and there is very little adhesive residue on the fine relief structure. According to such a laminated structure, the fine concavo-convex structure can be protected from scratches and dirt during processing, inspection, storage, display, etc. of an article having the fine concavo-convex structure on the surface.
- the adhesive film is cut to 25 mm x 150 mm, and a 2 kg roll is attached to an acrylic resin plate (Mitsubishi Rayon, Acrylite S) by one reciprocation, left at a constant temperature of 23 ° C. for 30 minutes, and then peeled off at a speed of 0.3 m. / Min (when measuring the low speed peel force P) or 10 m / min (when measuring the high speed peel force Q), the adhesive film is peeled 180 ° from the surface of the acrylic resin plate, and the force required for the peel ( The peel force) was measured.
- an acrylic resin plate Mitsubishi Rayon, Acrylite S
- the adhesive film is cut to 25 mm x 150 mm, a 2 kg roll is attached to the surface of the article on the fine relief structure side, and left at 23 ° C for 1 day, and then peeled off at a peeling speed of 0.3 m / min.
- the film was peeled off at 90 ° with respect to the surface of the article, and the force required for the peeling (slow peeling force T) was measured.
- the adhesive film attached to the surface of the fine concavo-convex structure was peeled off, and incident angle: 5 ° (5 ° specular reflection included) using a spectrophotometer (Shimadzu Corporation UV-2450)
- the relative reflectance of the surface of the cured resin layer was measured in the wavelength range of 380 to 780 nm, and the visibility reflectance was calculated according to JIS R3106.
- the change in the visibility reflectance (the visibility reflectance of the article after peeling the adhesive film)
- ⁇ the visibility reflectance of the article without the adhesive film attached) was evaluated according to the following evaluation criteria.
- ⁇ It was determined that the change in the visibility reflectance was 0.1% or less and there was no adhesive residue.
- X It was judged that the change in the visibility reflectance was more than 0.1% and there was adhesive residue.
- the adhesive film is cut to 25 mm ⁇ 150 mm, and a 2 kg roll is attached to the surface of the fine concavo-convex structure side of the article by one reciprocation, left at a constant temperature of 23 ° C. for 30 minutes, and then peeled off at a speed of 0.3 m / min (low speed).
- the pressure-sensitive adhesive film was peeled off at 180 ° from the surface of the article at 10 m / min (in the case of measurement of peeling force R) or 10 m / min (in the case of measurement of high-speed peeling force S), and the force (peeling force) required for the peeling was measured. .
- the mold was dipped in a 0.1% by weight solution of a mold release agent (Daikin Kogyo Co., Ltd., OPTOOL DSX) for 10 minutes, and air-dried for 24 hours to release the surface of the oxide film.
- a mold release agent Daikin Kogyo Co., Ltd., OPTOOL DSX
- Example 1 Production of adhesive film A coating in which an adhesive solution in which an acrylic polymer and a cross-linking agent are dissolved is directly attached to a corona-treated surface of a polypropylene (film base) having a thickness of 40 ⁇ m, which is formed by a T-die molding method and subjected to corona treatment on one side.
- the coating method is applied so that the thickness of the pressure-sensitive adhesive layer after drying is 5 ⁇ m, and dried, the pressure-sensitive adhesive layer is wound inside in a roll shape, subjected to an aging treatment, and a low-speed peeling force P against the acrylic resin plate P : Adhesive film A (FM-325, manufactured by Daio Paper Industries Co., Ltd.) having 0.2 N / 25 mm and high-speed peeling force Q: 0.1 N / 25 mm was prepared.
- Adhesive film A FM-325, manufactured by Daio Paper Industries Co., Ltd.
- the roll-shaped mold was installed in the manufacturing apparatus 30 shown in FIG. 3, the article 10 was produced as follows, and the laminated structure 1 was continuously manufactured.
- a roll-shaped mold 31 was fitted into a shaft made of carbon steel for mechanical structure provided with a flow path for cooling water.
- the active energy ray-curable resin composition 18 ′ (the active energy ray-curable resin composition A or B) is nipped between the nip roll 34 and the roll-shaped mold 31 through a supply nozzle from the tank 32 at room temperature.
- the substrate 12 Mitsubishi Rayon Acrylic Film, Acryprene, film width 340 mm, length 400 m
- the nip roll 34 whose nip pressure was adjusted by the pneumatic cylinder 33 was nipped, and the active energy ray-curable resin composition 18 ′ was also filled in the pores of the mold 31.
- the active energy ray-curable resin composition 18 ′ is sandwiched between the mold 31 and the base material 12 with 240 W / cm. After irradiating ultraviolet rays from the ultraviolet irradiation device 45 and curing the active energy ray-curable resin composition 18 ′ to form the cured resin layer 18, it is peeled from the mold 31 by the peeling roll 36, and as shown in FIG. An article 10 having a fine relief structure 16 on the surface was obtained.
- the cured resin layer 18 was formed with convex portions 14 having a bottom length of 100 nm and a height of 210 nm, and the fine concavo-convex structure of the roll-shaped mold 31 was satisfactorily transferred.
- the fine uneven structure 16 was formed.
- the article 10 was fed between the elastic roll 38a and the rigid roll 38b so that the back surface (the surface on which the fine uneven structure 16 is not formed) of the article 10 is in contact with the rigid roll 38b.
- an adhesive surface (adhesive material) of an adhesive film A manufactured by Daio Paper Industries Co., Ltd., FM-325 having a low-speed peeling force P of 0.2 N / 25 mm and a high-speed peeling force Q of 0.1 N / 25 mm for an acrylic resin plate
- the adhesive film 20 was fed between the elastic roll 38a and the article 10 so that the layer) was in contact with the surface of the article 10 (the surface on the side where the fine relief structure 16 was formed).
- Example 2 Except for using an adhesive film B (S-7, manufactured by Daio Paper Industries Co., Ltd.) having a low speed peel force P of 0.8 N / 25 mm and an high speed peel force Q of 0.25 N / 25 mm for an acrylic resin plate.
- an adhesive film B S-7, manufactured by Daio Paper Industries Co., Ltd.
- Example 3 Except for using an adhesive film C (FM-355 manufactured by Daio Paper Industries Co., Ltd.) having a low speed peel force P of 1.0 N / 25 mm and a high speed peel force Q of 0.3 N / 25 mm for an acrylic resin plate.
- an adhesive film C FM-355 manufactured by Daio Paper Industries Co., Ltd.
- a laminated structure was produced and evaluated. The results are shown in Table 1.
- Example 4 The material of the film substrate is low density polyethylene, the adhesive film D (manufactured by Daio Paper Industries Co., Ltd.) having a low speed peel force P of 0.8 N / 25 mm and a high speed peel force Q of 0.3 N / 25 mm for the acrylic resin plate A laminated structure was manufactured and evaluated in the same manner as in Example 1 except that FM-125) was used. The results are shown in Table 1.
- Example 5 The material of the film substrate is polyethylene terephthalate (hereinafter referred to as PET), the adhesive film P (low-speed peeling force P to the acrylic resin plate is 0.3 N / 25 mm and high-speed peeling force Q is 0.25 N / 25 mm.
- PET polyethylene terephthalate
- the adhesive film P low-speed peeling force P to the acrylic resin plate is 0.3 N / 25 mm
- high-speed peeling force Q is 0.25 N / 25 mm.
- a laminated structure was manufactured and evaluated in the same manner as in Example 1 except that SAT HC1138T (5) -J) manufactured by Sanei Kaken Co., Ltd. was used. The results are shown in Table 1.
- the film base material is PET, the adhesive film Q (San HC1138T, SAT HC1138T (manufactured by Sanei Kaken Co., Ltd.) having a low speed peel force P of 0.4 N / 25 mm for the acrylic resin plate and a high speed peel force Q of 0.4 N / 25 mm.
- a laminated structure was produced and evaluated in the same manner as in Example 1 except that 10) -J) was used. The results are shown in Table 2.
- Comparative Example 2 Except for using an adhesive film F (manufactured by Daio Paper Industries Co., Ltd., FM-315) having a low speed peel force P of 0.1 N / 25 mm and a high speed peel force Q of 0.2 N / 25 mm for an acrylic resin plate.
- an adhesive film F manufactured by Daio Paper Industries Co., Ltd., FM-315
- a laminated structure was produced and evaluated. The results are shown in Table 2.
- Example 4 Except for using an adhesive film H (FM-340 manufactured by Daio Paper Industries Co., Ltd.) having a low speed peel force P of 0.9 N / 25 mm and a high speed peel force Q of 3.8 N / 25 mm for an acrylic resin plate. In the same manner as in Example 1, a laminated structure was produced and evaluated. The results are shown in Table 2.
- an adhesive film H FM-340 manufactured by Daio Paper Industries Co., Ltd.
- Example 7 Example except that adhesive film K (manufactured by Daio Paper Industries Co., Ltd., FM-840) having a low speed peeling force P of 1.05 N / 25 mm and a high speed peeling force Q of 4.0 N / 25 mm for the acrylic resin plate was used. In the same manner as in Example 4, a laminated structure was produced and evaluated. The results are shown in Table 3.
- the film base material is PET, the adhesive film R having a low-speed peel force P of 0.15 N / 25 mm and a high-speed peel force Q of 1.5 N / 25 mm with respect to the acrylic resin plate (SAN KAKEN, SAT HC2025P)
- SAN KAKEN, SAT HC2025P acrylic resin plate
- the material of the film base material is PET, and the material of the adhesive material is acrylic based on butyl acrylate.
- the low speed peeling force P for the acrylic resin plate is 0.34 N / 25 mm and the high speed peeling force Q is 0.
- a laminated structure was produced and evaluated in the same manner as in Example 1 except that the adhesive film T of 89 N / 25 mm was used. The results are shown in Table 4.
- the laminated structure of the present invention is useful as an antireflective article such as an optical article, particularly an antireflective film, in which a fine concavo-convex structure is protected from scratches and dirt during processing steps and from shipment to use. is there.
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Abstract
Description
本願は、2011年12月27日に、日本に出願された特願2011-284679号に基づき優先権を主張し、その内容をここに援用する。
前記物品の微細凹凸構造側の表面に接する側の表面がアクリル樹脂板に接するように、前記粘着フィルムを前記アクリル樹脂板の表面に載せ、前記粘着フィルムの上から2kgロールを1往復させて前記粘着フィルムを前記アクリル樹脂板に貼り付け、23℃恒温下で30分間放置した後、引き剥がし速度0.3m/分(低速剥離力Pの測定の場合)または10m/分(高速剥離力Qの測定の場合)で前記粘着フィルムを前記アクリル樹脂板の表面に対して180°に引き剥がし、その剥離に要する剥離力を測定する。
(3)前記(1)または(2)の積層構造体において、下記の方法で測定される前記粘着フィルムの高速剥離力Sと低速剥離力Rとの比(高速剥離力S/低速剥離力R)は、2以下であることが好ましい。
前記物品の微細凹凸構造側の表面に接する側の表面が前記物品に接するように、前記粘着フィルムを前記物品の微細凹凸構造側の表面に載せ、前記粘着フィルムの上から2kgロールを1往復させて前記粘着フィルムを前記微細凹凸構造に貼り付け、23℃ 恒温下で30分間放置した後、引き剥がし速度0.3m/分(低速剥離力Rの測定の場合)または10m/分(高速剥離力Sの測定の場合)で前記粘着フィルムを前記微細凹凸構造側の表面に対して180°に引き剥がし、その剥離に要する剥離力を測定する。
また、本明細書における「活性エネルギー線」は、可視光線、紫外線、電子線、プラズマ、熱線(赤外線等)等を意味する。
図1~4においては、各層を図面上で認識可能な程度の大きさとするため、各層ごとに縮尺を異ならせてある。
また、図2~3において、図1と同じ構成要素には同一の符号を付して、その説明を省略する場合がある。
図1は、本発明の積層構造体の一例を示す断面図である。積層構造体1は、微細凹凸構造16を表面に有する物品10と、物品10の微細凹凸構造16側の表面に接する粘着フィルム20とを有する。
物品10は、図2に示すように、基材12と、基材12の表面に形成された、後述する活性エネルギー線硬化性樹脂組成物の硬化物からなる、複数の凸部14が並んだ微細凹凸構造16を表面に有する硬化樹脂層18とを有する。
基材12の材料としては、光を透過するものであればよく、メチルメタクリレート(共)重合体、ポリカーボネート、スチレン(共)重合体、メチルメタクリレート-スチレン共重合体、セルロースジアセテート、セルローストリアセテート、セルロースアセテートブチレート、ポリエステル、ポリアミド、ポリイミド、ポリエーテルスルフォン、ポリスルフォン、ポリプロピレン、ポリメチルペンテン、ポリ塩化ビニル、ポリビニルアセタール、ポリエーテルケトン、ポリウレタン、ガラス等が挙げられる。
基材12の形状は、製造する物品10に応じて適宜選択でき、物品10が反射防止フィルム等である場合には、シート状またはフィルム状が好ましい。
基材12の表面には、活性エネルギー線硬化性樹脂組成物との密着性や、帯電防止性、耐擦傷性、耐候性等の改良のために、各種コーティング処理、コロナ放電処理、粗面化処理等が施されていてもよい。
硬化樹脂層18は、微細凹凸構造16を表面に有する。硬化樹脂層18は、物品10の表面全体に形成されていてもよく、物品10の表面の一部に形成されていてもよい。
微細凹凸構造16は、後述する活性エネルギー線硬化性樹脂組成物の硬化物からなる複数の凸部14を有するものであり、陽極酸化アルミナの微細凹凸構造を転写して形成される。
凸部14間の平均間隔は、電子顕微鏡観察によって隣接する凸部14間の間隔(図2中、凸部14の中心から隣接する凸部14の中心までの距離W1)を10点測定し、これらの値を平均したものである。
凸部14の高さは、電子顕微鏡観察によって10個の凸部14の高さ(図2中、凸部14の頭頂部から、この凸部14に隣接する凹部の底部までの垂直距離d1)を測定し、これらの値を平均したものである。
凸部14の底面の長さは、図2中、高さ方向に凸部14を切断したときの断面における底部の長さd2である。
物品10は、微細凹凸構造を表面に有するため、光学物品、特に反射防止フィルム、立体形状の反射防止体等の反射防止物品として好適である。
物品10が立体形状の反射防止体である場合には、あらかじめ用途に応じた形状の透明基材を用いて反射防止体を製造しておき、これを前記対象物の表面を構成する部材として用いてもよい。
対象物が画像表示装置である場合には、その表面に限らず、その前面板に対して反射防止フィルムを貼着してよく、前面板そのものを物品10から構成してもよい。
本発明における物品は、微細凹凸構造を表面に有するものであればよく、図示例のものに限定さない。
例えば、微細凹凸構造は、図示例においては、硬化樹脂層18の表面に形成されているが、硬化樹脂層18を設けることなく基材12の表面に直接形成されていてもよい。ただし、後述するロール状のモールドを用いて効率よく微細凹凸構造を形成できる点から、硬化樹脂層18の表面に微細凹凸構造が形成されていることが好ましい。
物品が、基材と、基材の表面の少なくとも一部が露出するように基材の表面に形成された中間層と、中間層の表面の少なくとも一部が露出するように中間層の表面に形成された、微細凹凸構造を表面に有する硬化樹脂層とを有し、前記硬化樹脂層の表面が前記領域(I)であり、前記中間層の露出した表面が前記領域(II)であり、前記基材の露出した表面が前記領域(III)であってもよい。
前記領域(III)が、前記微細凹凸構造を表面に有する物品の表面の端部に位置することが好ましい。
粘着フィルム20は、物品10の表面を保護するものであり、図1に示すように、物品10の微細凹凸構造16側の表面に貼り付けられる。これにより、物品10の表面が他の物体と接触することなく、微細凹凸構造16にキズが付きにくくなる。さらに、物品10と粘着フィルム20との界面にゴミ、薬剤等の不純物が侵入しにくくなり、物品10の表面に汚れ等が付着しにくくなる。
粘着フィルム20においては、JIS Z0237:2009に準じて前記方法:その1で測定される低速剥離力Pが0.01N/25mm以上2.5N/25mm未満であり、かつJIS Z0237:2009に準じて前記方法で測定される高速剥離力Qと低速剥離力Pとの比(高速剥離力Q/低速剥離力P)が2未満である。
粘着フィルム20においては、前記方法:その2で測定される前記粘着フィルムの高速剥離力Sと低速剥離力Rとの比(高速剥離力S/低速剥離力R)が2以下であることが好ましい。
フィルム基材22の材料としては、結晶性エチレン系樹脂、結晶性プロピレン単独重合体、結晶性プロピレン系樹脂(プロピレンとα-オレフィンおよびまたはエチレンとのランダム共重合体、プロピレンとα-オレフィンおよびまたはエチレンとのブロック共重合体等)、他のオレフィン系樹脂(ポリ(1-ブテン)、ポリ(4-メチル-1-ペンテン)等)、アクリル系樹脂(ポリメチルアクリレート、ポリメチルメタクリレート、エチレン-エチルアクリレート共重合体等)、スチレン系樹脂(ブタジエン-スチレン共重合体、アクリロニトリル-スチレン共重合体、ポリスチレン、スチレン-ブタジエン-スチレンブロック共重合体、スチレン-イソプレン-スチレンブロック共重合体、スチレン-アクリル酸共重合体等)、塩化ビニル系樹脂、フッ化ビニル系樹脂(ポリフッ化ビニル、ポリフッ化ビニリデン等)、ポリアミド(ナイロン6、ナイロン66、ナイロン12等)、飽和エステル系樹脂(ポリエチレンテレフタレート、ポリブチレンテレフタレート等)、ポリカーボネ-ト、ポリフェニレンオキシド、ポリアセタール、ポリフェニレンスルフィド、シリコーン樹脂、熱可塑性ウレタン樹脂、ポリエーテルエーテルケトン、ポリエーテルイミド、各種熱可塑性エラストマー、これらの架橋物等が挙げられる。
粘着材層24の粘着材としては、エチレン-酢酸ビニル共重合体、直鎖状低密度ポリエチレン、エチレン-α-オレフィン共重合体、スチレン-ブタジエン-スチレンブロック共重合体、スチレン-イソプレン-スチレンブロック共重合体、スチレン-エチレン-ブチレン-スチレンブロック共重合体、スチレン-ブタジエンランダム共重合体、水添スチレン-ブタジエンランダム共重合体、アクリル系ポリマー等を主ポリマーとしたものが挙げられる。
共重合性改質モノマーとしては、(メタ)アクリロニトリル、酢酸ビニル、スチレン、(メタ)アクリル酸、無水マレイン酸、ビニルピロリドン、グリシジル基、ジメチルアミノエチル基またはヒドロキシル基を有する(メタ)アクリレート、(メタ)アクリルアミド、ビニルアミン、アリルアミン、エチレンイミン等が挙げられる。
多官能イソシアネート化合物としては、分子中に2個以上のイソシアネート基を有する種々の化合物(ジフェニルメタンジイソシアネート、トリレンジイソシアネート、ヘキサメチレンジイソシアネート等)が挙げられる。
架橋剤の使用量は、アクリル系ポリマーの組成、分子量等に応じて適宜選択できる。
また、粘着材には、必要に応じて、粘着性付与剤、充填剤、顔料、着色剤、酸化防止剤等の慣用の添加剤を配合してもよい。なお、架橋剤等の添加剤に含まれる不純物を低減することは、粘着フィルム20を剥離したときの糊残りの低減に有効である。
粘着フィルム20には、耐防汚を目的として、粘着材層24に接する剥離フィルム(図示略)が積層されていてもよい。
剥離フィルムの材料としては、フィルム基材22の説明において先に例示した各種樹脂等が挙げられる。これらの中でも、剥離性の観点から、ポリスチレン、飽和エステル系樹脂、ポリアミドが好ましく、ポリエチレンテレフタレート、ポリアミドがより好ましい。
剥離フィルムの剥離性を上げるため、粘着材層24に接する側の剥離フィルムの表面に、本発明の効果を損なわない範囲で、必要に応じて、シリコーン等による処理を施してもよい。
粘着フィルム20の製造方法としては、共押出成形法、ラミネ-ト成形法、流延法、塗工法等の公知の方法が挙げられる。
ラミネ-ト成形法としては、フィルム基材22をあらかじめ押出成形法によって作製しておき、フィルム基材22の表面に粘着材を溶融状態で押出し、積層した後、冷却ロ-ル等の冷却手段によって冷却する方法が挙げられる。
流延法や塗工法としては、トルエン、酢酸エチル等の有機溶媒の単独物または混合物に、主ポリマー等を溶解または分散させて固形分濃度が10~40質量%程度の粘着材液を調製し、これを流延方式、塗工方式等の適宜な展開方式によってフィルム基材22の表面に直接付設する方法、または前記に準じ剥離フィルムの表面に粘着材層24を形成し、これをフィルム基材22の表面に移着する方法が挙げられる。
本発明における粘着フィルムは、少なくとも1層のフィルム基材、および少なくとも1層の粘着材層を含んでいれば、層構成または積層数は特に限定されないが、通常2~7層程度である。
粘着フィルムの層構成の具体例としては、フィルム基材/粘着材層、フィルム基材/粘着材層/剥離フィルム、フィルム基材/粘着材層/フィルム基材/粘着材層、フィルム基材/粘着材層/フィルム基材/粘着材層/剥離フィルム等が挙げられる。
図3は、本発明の積層構造体の製造装置の一例を示す構成図である。製造装置30は、微細凹凸構造を表面に有するロール状のモールド31と、活性エネルギー線硬化性樹脂組成物18’を収容するタンク32と、空気圧シリンダ33を備えたニップロール34と、活性エネルギー線照射装置35と、剥離ロール36と、空気圧シリンダ37を備えた一対のニップロール38とを具備する。
なお、図3に示す製造装置30は、物品10を製造した後に、連続して積層構造体1を製造する装置である。
モールド31は、活性エネルギー線硬化性樹脂組成物18’に微細凹凸構造を転写させるモールドであり、陽極酸化アルミナを表面に有する。陽極酸化アルミナを表面に有するモールドは、大面積化が可能であり、ロール状のモールドの作製が簡便である。
陽極酸化アルミナは、アルミニウムの多孔質の酸化皮膜(アルマイト)であり、表面に複数の細孔(凹部)を有する。
(a)アルミニウム基材を電解液中、陽極酸化して酸化皮膜を形成する工程。
(b)酸化皮膜を除去し、陽極酸化の細孔発生点を形成する工程。
(c)アルミニウム基材を電解液中、再度陽極酸化し、細孔発生点に細孔を有する酸化皮膜を形成する工程。
(d)細孔の径を拡大させる工程。
(e)前記工程(c)と工程(d)を繰り返し行う工程。
図4に示すように、アルミニウム基材39を陽極酸化すると、細孔40を有する酸化皮膜41が形成される。
アルミニウムの純度は、99%以上が好ましく、99.5%以上がより好ましく、99.8%以上が特に好ましい。アルミニウムの純度が低いと、陽極酸化した時に、不純物の偏析により可視光を散乱する大きさの凹凸構造が形成されたり、陽極酸化で得られる細孔の規則性が低下したりすることがある。
電解液としては、硫酸、シュウ酸、リン酸等が挙げられる。
シュウ酸の濃度は、0.7M以下が好ましい。シュウ酸の濃度が0.7Mを超えると、電流値が高くなりすぎて酸化皮膜の表面が粗くなることがある。
化成電圧が30~60Vの時、周期が100nmの規則性の高い細孔を有する陽極酸化アルミナを得ることができる。化成電圧がこの範囲より高くても低くても規則性が低下する傾向にある。
電解液の温度は、60℃以下が好ましく、45℃以下がより好ましい。電解液の温度が60℃を超えると、いわゆる「ヤケ」といわれる現象がおこり、細孔が壊れたり、表面が溶けて細孔の規則性が乱れたりすることがある。
硫酸の濃度は0.7M以下が好ましい。硫酸の濃度が0.7Mを超えると、電流値が高くなりすぎて定電圧を維持できなくなることがある。
化成電圧が25~30Vの時、周期が63nmの規則性の高い細孔を有する陽極酸化アルミナを得ることができる。化成電圧がこの範囲より高くても低くても規則性が低下する傾向がある。
電解液の温度は、30℃以下が好ましく、20℃以下がよりに好ましい。電解液の温度が30℃を超えると、いわゆる「ヤケ」といわれる現象がおこり、細孔が壊れたり、表面が溶けて細孔の規則性が乱れたりすることがある。
図4に示すように、酸化皮膜41を一旦除去し、これを陽極酸化の細孔発生点42にすることで細孔の規則性を向上できる。
図4に示すように、酸化皮膜を除去したアルミニウム基材39を再度、陽極酸化すると、円柱状の細孔40を有する酸化皮膜41が形成される。
陽極酸化は、工程(a)と同様な条件で行えばよい。陽極酸化の時間を長くするほど深い細孔を得ることができる。
図4に示すように、細孔40の径を拡大させる処理(以下、細孔径拡大処理と記す。)を行う。細孔径拡大処理は、酸化皮膜を溶解する溶液に浸漬して陽極酸化で得られた細孔の径を拡大させる処理である。このような溶液としては、5質量%程度のリン酸水溶液等が挙げられる。
細孔径拡大処理の時間を長くするほど、細孔径は大きくなる。
図4に示すように、工程(c)の陽極酸化と、工程(d)の細孔径拡大処理とを繰り返すと、直径が開口部から深さ方向に連続的に減少する形状の細孔40を有する陽極酸化アルミナが形成され、陽極酸化アルミナを表面に有するモールド31が得られる。最後は工程(d)で終わることが好ましい。
繰り返し回数は、合計で3回以上が好ましく、5回以上がより好ましい。繰り返し回数が2回以下では、非連続的に細孔の直径が減少するため、このような細孔を有する陽極酸化アルミナを用いて製造された硬化樹脂層18の反射率低減効果は不十分である。
細孔40間の平均間隔は、400nm以下であり、300nm以下が好ましく、250nm以下がより好ましい。細孔40間の平均間隔が400nm以下であれば、反射率が低く、かつ反射率の波長依存性が少ない物品10が得られる。
細孔40間の平均間隔は、電子顕微鏡観察によって隣接する細孔40間の間隔を10点測定し、これらの値を平均したものである。
細孔40の深さは、電子顕微鏡観察によって10個の細孔40の深さを測定し、これらの値を平均したものである。
細孔40の開口部の長さは、細孔40の最深部から深さ方向に細孔を切断したときの切断面における開口の長さである。
タンク32は、活性エネルギー線硬化性樹脂組成物18’を収容し、ロール状のモールド31と、モールド31の表面に沿って移動する帯状の基材12との間に、活性エネルギー線硬化性樹脂組成物18’を供給する。
ニップロール34は、ロール状のモールド31に対向して配置される。ニップロール34は、モールド31とともに基材12および活性エネルギー線硬化性樹脂組成物18’をニップする。
ニップ圧は、ニップロール34に備わる空気圧シリンダ33によって調整する。
活性エネルギー線照射装置35は、ロール状のモールド31の下方に設置され、活性エネルギー線を照射して、基材12とモールド31との間に充填された活性エネルギー線硬化性樹脂組成物18’を硬化させる。活性エネルギー線硬化性樹脂組成物18’が硬化されることによって、基材12の表面にモールド31の微細凹凸構造が転写された硬化樹脂層18が形成される。
活性エネルギー線照射装置35としては、高圧水銀ランプ、メタルハライドランプ等が挙げられる。この場合の光照射エネルギー量は、100~10000mJ/cm2が好ましい。
剥離ロール36は、活性エネルギー線照射装置35よりも下流側に配置され、硬化樹脂層18が表面に形成された基材12をロール状のモールド31から剥離する。
一対のニップロール38は、剥離ロール36の下流側に配置され、物品10に粘着フィルム20を貼り付ける。
一対のニップロール38は、外周面がゴム等の弾性部材で形成された弾性ロール38aと、外周面が金属等の剛性が高い部材で形成された剛性ロール38bとからなる。
ニップ圧は、弾性ロール38aに備わる空気圧シリンダ37によって調整する。
活性エネルギー線硬化性樹脂組成物18’は、分子中にラジカル重合性結合およびまたはカチオン重合性結合を有するモノマー、オリゴマー、反応性ポリマーを適宜含有するものであり、非反応性のポリマーを含有するものでもよい。
カチオン重合性の官能基としては、実用性の高い官能基として、環状エーテル基(エポキシ基、オキセタニル基等)、ビニルエーテル基、カーボネート基(O-CO-O基)等が挙げられる。
カチオン重合性化合物としては、環状エーテル化合物(エポキシ化合物、オキセタン化合物等)、ビニルエーテル化合物、カーボネート系化合物(環状カーボネート化合物、ジチオカーボネート化合物等)等が挙げられる。
カチオン重合性結合を有するオリゴマーおよび反応性ポリマーとしては、カチオン重合型エポキシ化合物等が挙げられる。
ラジカル重合開始剤は、1種を単独で用いてもよく、2種以上を併用してもよい。
以下、上述した製造装置30を用いて積層構造体1を製造する方法の一例を説明する。
図3に示すように、回転するロール状のモールド31の表面に沿うように帯状の基材12を搬送させ、基材12とモールド31との間に、タンク32から活性エネルギー線硬化性樹脂組成物18’を供給する。
図4に示すような細孔40を転写して形成された硬化樹脂層18の表面は、いわゆるMoth-Eye構造となる。
ついで、物品10を一対のニップロール38の間に通過させると同時に、粘着フィルム繰り出し機(図示略)から繰り出される粘着フィルム20を、微細凹凸構造が形成された側の表面に貼り付けるように、物品10と一対のニップロール38の間に供給する。
このとき、物品10は、物品10の裏面(微細凹凸構造が形成されていない側の面)が剛性ロール38bに接触するように、弾性ロール38aと剛性ロール38bとの間に送り込まれる。
一方、粘着フィルム20は、粘着材層24が物品10の表面(微細凹凸構造が形成された側の面)に接触し、フィルム基材22が弾性ロール38aと接触するようにして、弾性ロール38aと物品10の間に送り込まれる。
こうして、図1に示すような、物品10の微細凹凸構造16側の表面に粘着フィルム20が積層した積層構造体1を得る。
粘着フィルム20としては、特定の密着強度を有していれば、上述したような方法で別途作製したものを用いてもよく、市販のものを用いてもよい。
以上説明した本発明の積層構造体にあっては、特定の密着特性を有する粘着フィルムを用いるため、粘着フィルムが不用意に剥がれることなく容易に加工でき、意図的に粘着フィルムを剥がそうとすれば作業性よく容易に剥離でき、かつ微細凹凸構造への糊残りが極めて少ない。このような積層構造体によれば、微細凹凸構造を表面に有する物品の加工、検査、保管、展示等の際に、微細凹凸構造をキズや汚れから保護できる。
JIS Z0237:2009に準じて、以下の方法で粘着フィルムの剥離力を測定した。
粘着フィルムを25mm×150mmに裁断し、アクリル樹脂板(三菱レイヨン製、アクリライトS)に2kgロールを1往復して貼り付け、23℃恒温下で30分間放置した後、引き剥がし速度0.3m/分(低速剥離力Pの測定の場合)または10m/分(高速剥離力Qの測定の場合)で粘着フィルムをアクリル樹脂板の表面に対して180°に引き剥がし、その剥離に要する力(剥離力)を測定した。
粘着フィルムを25mm×150mmに裁断し、物品の微細凹凸構造側の表面に2kgロールを1往復して貼り付け、23℃恒温下で1日間放置した後、引き剥がし速度0.3m/分で粘着フィルムを物品の表面に対して90°に引き剥がし、その剥離に要する力(低速剥離力T)を測定した。
積層構造体1の物品10の微細凹凸構造側の面とは反対側を、光学粘着層を介して黒色アクリル樹脂板(三菱レイヨン社製、アクリライトEX#502、50mm×60mm)に貼り付けた。7日間経過した後、微細凹凸構造側の表面に貼り付けられた粘着フィルムを剥離し、分光光度計(島津製作所社製、UV-2450)を用い、入射角:5°(5°正反射付属装置使用)、波長380~780nmの範囲で硬化樹脂層の表面(微細凹凸構造側の面)の相対反射率を測定し、JIS R3106に準拠して視感度反射率を算出した。視感度反射率の変化=(粘着フィルムを剥離した後の物品の視感度反射率)-(粘着フィルムを貼り付けなかった物品の視感度反射率)について、以下の評価基準にて評価した。
○:視感度反射率の変化が0.1%以下、糊残りなしと判断した。
×:視感度反射率の変化が0.1%超、糊残りありと判断した。
以下の方法で粘着フィルムの剥離力を測定した。高速剥離力S/低速剥離力Rについて、以下の評価基準にて評価した。
○:高速剥離力S/低速剥離力Rが2以下。
×:高速剥離力S/低速剥離力Rが2超。
粘着フィルムを25mm×150mmに裁断し、物品の微細凹凸構造側の表面に2kgロールを1往復して貼り付け、23℃恒温下で30分間放置した後、引き剥がし速度0.3m/分(低速剥離力Rの測定の場合)または10m/分(高速剥離力Sの測定の場合)で粘着フィルムを物品の表面に対して180°に引き剥がし、その剥離に要する力(剥離力)を測定した。
純度99.90%のアルミニウムインゴットに鍛造処理を施して、直径200mm、内径155mm、厚さ350mmに切断した圧延痕のない円筒状アルミニウム基材に羽布研磨処理を施した後、これを過塩素酸、エタノール混合溶液中(体積比1:4)で電解研磨し鏡面化した。
表面が鏡面化されたアルミニウム基材について、0.3Mシュウ酸水溶液中で、浴温16℃において直流40Vの条件下で30分間陽極酸化を行い、厚さ3μmの酸化皮膜を形成した。
工程(b):
形成された酸化皮膜を、6質量%のリン酸と1.8質量%のクロム酸の混合水溶液中で一旦溶解除去した。
工程(c):
再び工程(a)と同一条件下において、30秒間陽極酸化を行い、酸化皮膜を形成した。
5質量%リン酸水溶液(30℃)中に8分間浸漬して、酸化皮膜の細孔を拡径する孔径拡大処理を施した。
工程(e):
工程(c)と工程(d)を合計で5回繰り返し、最後に水洗して、細孔の開口部の長さ:100nm、深さ:230nmの略円錐形状のテーパー状細孔を有する陽極酸化アルミナが表面に形成されたロール状のモールドを得た。
無水コハク酸/トリメチロールエタン/アクリル酸の縮合エステル(モル比1:2:4):45質量部、
1,6-ヘキサンジオールジアクリレート:45質量部、
X-22-1602(信越化学工業社製、ラジカル重合性シリコーンオイル):10質量部、
イルガキュア184(チバ・スペシャリティケミカルズ社製):3.0質量部、
イルガキュア819(チバ・スペシャリティケミカルズ社製):0.2質量部。
無水コハク酸/トリメチロールエタン/アクリル酸の縮合エステル(モル比1:2:4):75質量部、
アロニックスM260(東亞合成社製):20質量部、
アクリル酸メチル:5質量部、
イルガキュア184(チバ・スペシャリティケミカルズ社製):1.0質量部、
イルガキュア819(チバ・スペシャリティケミカルズ社製):0.3質量部。
粘着フィルムの作製:
Tダイ成形法で製膜され、片面がコロナ処理された厚さ40μmのポリプロピレン(フィルム基材)のコロナ処理面に、アクリル系ポリマーおよび架橋剤を溶解させた粘着材溶液を、直接付設する塗工法によって乾燥後の粘着材層の厚さが5μmとなるように塗工し、乾燥した後、粘着材層を内側にロール状に巻き取り、エージング処理を行い、アクリル樹脂板に対する低速剥離力P:0.2N/25mm、高速剥離力Q:0.1N/25mmの粘着フィルムA(大王加工紙工業社製、FM-325)を作製した。
ロール状のモールドを、図3に示す製造装置30に設置し、以下のようにして物品10を作製し、連続して積層構造体1を製造した。
まず、図3に示すように、ロール状のモールド31を、冷却水用の流路を内部に設けた機械構造用炭素鋼製の軸芯にはめ込んだ。ついで、活性エネルギー線硬化性樹脂組成物18’(前記活性エネルギー線硬化性樹脂組成物AまたはB)をタンク32から室温で供給ノズルを介して、ニップロール34とロール状モールド31の間にニップされている基材12(三菱レイヨン社製のアクリルフィルム、アクリプレン、フィルム幅340mm、長さ400m)の表面に供給した。この際、空気圧シリンダ33によりニップ圧が調整されたニップロール34によりニップされ、モールド31の細孔内にも活性エネルギー線硬化性樹脂組成物18’が充填された。
物品10の表面をSEMで観察したところ、硬化樹脂層18には底面の長さ:100nm、高さ:210nmの凸部14が形成され、ロール状のモールド31の微細凹凸構造が良好に転写された微細凹凸構造16が形成されていた。
一方、アクリル樹脂板に対する低速剥離力Pが0.2N/25mmかつ高速剥離力Qが0.1N/25mmである粘着フィルムA(大王加工紙工業社製、FM-325)の粘着面(粘着材層)が、物品10の表面(微細凹凸構造16が形成された側の面)に接触するようにして、粘着フィルム20を弾性ロール38aと物品10の間に送り込んだ。
そして、空気圧シリンダ37によって一対のニップロール38のニップ圧を0.1MPa~0.5MPaに調整しながら、物品10の表面に粘着フィルム20を貼り付け、図1に示すような積層構造体1を得た。評価結果を表1に示す。
アクリル樹脂板に対する低速剥離力Pが0.8N/25mmかつ高速剥離力Qが0.25N/25mmである粘着フィルムB(大王加工紙工業社製、S-7)を用いた以外は、実施例1と同様にして積層構造体を製造し、評価した。結果を表1に示す。
アクリル樹脂板に対する低速剥離力Pが1.0N/25mmかつ高速剥離力Qが0.3N/25mmである粘着フィルムC(大王加工紙工業社製、FM-355)を用いた以外は、実施例1と同様にして積層構造体を製造し、評価した。結果を表1に示す。
フィルム基材の材料が低密度ポリエチレンであり、アクリル樹脂板に対する低速剥離力Pが0.8N/25mmかつ高速剥離力Qが0.3N/25mmである粘着フィルムD(大王加工紙工業社製、FM-125)を用いた以外は、実施例1と同様にして積層構造体を製造し、評価した。結果を表1に示す。
フィルム基材の材料がポリエチレンテレフタレート(以下、PETと記す。)であり、アクリル樹脂板に対する低速剥離力Pが0.3N/25mmかつ高速剥離力Qが0.25N/25mmである粘着フィルムP(サンエー化研社製、SAT HC1138T(5)-J)を用いた以外は、実施例1と同様にして積層構造体を製造し、評価した。結果を表1に示す。
フィルム基材の材料がPETであり、アクリル樹脂板に対する低速剥離力Pが0.4N/25mmかつ高速剥離力Qが0.4N/25mmである粘着フィルムQ(サンエー化研社製、SAT HC1138T(10)-J)を用いた以外は、実施例1と同様にして積層構造体を製造し、評価した。結果を表2に示す。
アクリル樹脂板に対する低速剥離力Pが2.5N/25mmかつ高速剥離力Qが1.0N/25mmである粘着フィルムE(大王加工紙工業社製、FM-358)を用いた以外は、実施例1と同様にして積層構造体を製造し、評価した。結果を表2に示す。
アクリル樹脂板に対する低速剥離力Pが0.1N/25mmかつ高速剥離力Qが0.2N/25mmである粘着フィルムF(大王加工紙工業社製、FM-315)を用いた以外は、実施例1と同様にして積層構造体を製造し、評価した。結果を表2に示す。
アクリル樹脂板に対する低速剥離力Pが0.18N/25mmかつ高速剥離力Qが0.8N/25mmである粘着フィルムG(大王加工紙工業社製、FM-330)を用いた以外は、実施例1と同様にして積層構造体を製造し、評価した。結果を表2に示す。
アクリル樹脂板に対する低速剥離力Pが0.9N/25mmかつ高速剥離力Qが3.8N/25mmである粘着フィルムH(大王加工紙工業社製、FM-340)を用いた以外は、実施例1と同様にして積層構造体を製造し、評価した。結果を表2に示す。
アクリル樹脂板に対する低速剥離力Pが0.25N/25mmかつ高速剥離力Qが0.55N/25mmである粘着フィルムI(大王加工紙工業社製、FM-115)を用いた以外は、実施例4と同様にして積層構造体を製造し、評価した。結果を表3に示す。
アクリル樹脂板に対する低速剥離力Pが0.35N/25mmかつ高速剥離力Qが1.85N/25mmである粘着フィルムJ(大王加工紙工業社製、FM-830)を用いた以外は、実施例4と同様にして積層構造体を製造し、評価した。結果を表3に示す。
アクリル樹脂板に対する低速剥離力Pが1.05N/25mmかつ高速剥離力Qが4.0N/25mmである粘着フィルムK(大王加工紙工業社製、FM-840)を用いた以外は、実施例4と同様にして積層構造体を製造し、評価した。結果を表3に示す。
アクリル樹脂板に対する低速剥離力Pが2.5N/25mmかつ高速剥離力Qが0.9N/25mmである粘着フィルムL(大王加工紙工業社製、FM-875)を用いた以外は、実施例4と同様にして積層構造体を製造し、評価した。結果を表3に示す。
フィルム基材の材料がPETであり、アクリル樹脂板に対する低速剥離力Pが0.15N/25mmかつ高速剥離力Qが1.5N/25mmである粘着フィルムR(サンエー化研社製、SAT HC2025P)を用いた以外は、実施例1と同様にして積層構造体を製造し、評価した。結果を表3に示す。
フィルム基材の材料がPETであり、かつ粘着材の材料がオレフィン系であり、アクリル樹脂板に対する低速剥離力Pが0.11N/25mmかつ高速剥離力Qが0.41N/25mmである粘着フィルムS(パナック社製、GP50T-A75)を用いた以外は、実施例1と同様にして積層構造体を製造し、評価した。結果を表4に示す。
フィルム基材の材料がPETであり、かつ粘着材の材料がブチルアクリレートを主成分とするアクリル系であり、アクリル樹脂板に対する低速剥離力Pが0.34N/25mmかつ高速剥離力Qが0.89N/25mmである粘着フィルムTを用いた以外は、実施例1と同様にして積層構造体を製造し、評価した。結果を表4に示す。
10 物品
14 凸部
16 微細凹凸構造
20 粘着フィルム
40 細孔
41 酸化皮膜
Claims (4)
- 微細凹凸構造を表面に有する物品と、
前記物品の微細凹凸構造側の表面に接する粘着フィルムと
を有し、
前記微細凹凸構造における凸部間の平均間隔が、400nm以下であり、
JIS Z0237:2009に準じて下記の方法で測定される前記粘着フィルムの低速剥離力Pが、0.01N/25mm以上2.5N/25mm未満であり、
JIS Z0237:2009に準じて下記の方法で測定される前記粘着フィルムの高速剥離力Qと低速剥離力Pとの比(高速剥離力Q/低速剥離力P)が、2未満である、積層構造体。
(剥離力の測定方法:その1)
前記物品の微細凹凸構造側の表面に接する側の表面がアクリル樹脂板に接するように、前記粘着フィルムを前記アクリル樹脂板の表面に載せ、前記粘着フィルムの上から2kgロールを1往復させて前記粘着フィルムを前記アクリル樹脂板に貼り付け、23℃恒温下で30分間放置した後、引き剥がし速度0.3m/分(低速剥離力Pの測定の場合)または10m/分(高速剥離力Qの測定の場合)で前記粘着フィルムを前記アクリル樹脂板の表面に対して180°に引き剥がし、その剥離に要する剥離力を測定する。 - 前記粘着フィルムの低速剥離力Pが、1.0N/25mm以下である、請求項1に記載の積層構造体。
- 下記の方法で測定される前記粘着フィルムの高速剥離力Sと低速剥離力Rとの比(高速剥離力S/低速剥離力R)が、2以下である、請求項1に記載の積層構造体。
(剥離力の測定方法:その2)
前記物品の微細凹凸構造側の表面に接する側の表面が前記物品に接するように、前記粘着フィルムを前記物品の微細凹凸構造側の表面に載せ、前記粘着フィルムの上から2kgロールを1往復させて前記粘着フィルムを前記微細凹凸構造に貼り付け、23℃ 恒温下で30分間放置した後、引き剥がし速度0.3m/分(低速剥離力Rの測定の場合)または10m/分(高速剥離力Sの測定の場合)で前記粘着フィルムを前記微細凹凸構造側の表面に対して180°に引き剥がし、その剥離に要する剥離力を測定する。 - 前記微細凹凸構造が、陽極酸化アルミナの微細凹凸構造を転写したものである、請求項1~3のいずれか一項に記載の積層構造体。
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CN106457786B (zh) * | 2014-05-30 | 2018-10-09 | 日本瑞翁株式会社 | 复层膜和卷绕体 |
KR101966869B1 (ko) * | 2014-10-28 | 2019-04-09 | 주식회사 엘지화학 | 이형필름 박리안정성 측정방법 및 이형필름 적층체 |
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DE102019103800A1 (de) | 2018-12-12 | 2020-06-18 | Schreiner Group Gmbh & Co. Kg | Etikettieranordnung für Tiefkühlanwendungen, System und Verfahren zum Applizieren einer Etikettieranordnung für Tiefkühlanwendungen |
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KR20140107472A (ko) | 2014-09-04 |
JPWO2013099798A1 (ja) | 2015-05-07 |
JP6052164B2 (ja) | 2016-12-27 |
US20140363628A1 (en) | 2014-12-11 |
TW201335584A (zh) | 2013-09-01 |
CN103998229A (zh) | 2014-08-20 |
EP2799224A1 (en) | 2014-11-05 |
CN103998229B (zh) | 2016-04-13 |
EP2799224A4 (en) | 2015-05-27 |
TWI521194B (zh) | 2016-02-11 |
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