WO2007097454A1 - Film having fine uneven shape and method for manufacturing same - Google Patents

Film having fine uneven shape and method for manufacturing same Download PDF

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Publication number
WO2007097454A1
WO2007097454A1 PCT/JP2007/053589 JP2007053589W WO2007097454A1 WO 2007097454 A1 WO2007097454 A1 WO 2007097454A1 JP 2007053589 W JP2007053589 W JP 2007053589W WO 2007097454 A1 WO2007097454 A1 WO 2007097454A1
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WO
WIPO (PCT)
Prior art keywords
film
shape
fine
direction
surface
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PCT/JP2007/053589
Other languages
French (fr)
Japanese (ja)
Inventor
Megumi Fujita
Mitsugu Uejima
Toshihide Murakami
Kouya Kawabata
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Zeon Corporation
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Priority to JP2006-050644 priority Critical
Priority to JP2006050644 priority
Application filed by Zeon Corporation filed Critical Zeon Corporation
Publication of WO2007097454A1 publication Critical patent/WO2007097454A1/en

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Classifications

    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS, OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/02Diffusing elements; Afocal elements
    • G02B5/0273Diffusing elements; Afocal elements characterized by the use
    • G02B5/0278Diffusing elements; Afocal elements characterized by the use used in transmission
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS, OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/02Diffusing elements; Afocal elements
    • G02B5/0205Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/021Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures
    • G02B5/0221Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures the surface having an irregular structure
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS, OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/02Diffusing elements; Afocal elements
    • G02B5/0205Diffusing elements; Afocal elements characterised by the diffusing properties
    • G02B5/021Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures
    • G02B5/0231Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures the surface having microprismatic or micropyramidal shape
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS, OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/18Diffraction gratings
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS, OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/30Polarising elements

Abstract

Provided is a manufacturing method by which a large area film having fine uneven shape on the surface can be easily obtained, and furthermore, a distance between the tops of the projecting sections, aspect ratio and distribution of the projecting sections can be freely controlled. The manufacturing method includes a step of obtaining a laminated body by forming a thin film on at least one surface of a film base material, having the laminated body contract at least in one axial direction within the surface, and folding the thin film. The film having the fine uneven shape having an average distance of 50nm-50μm between the tops of the protruding sections is provided through the method.

Description

 Specification

 Film having fine irregularities and method for producing the same

 Technical field

 The present invention relates to a film having a fine uneven shape and a method for producing the same.

 Background art

 Optical films that control light characteristics are used in, for example, optoelectronic devices such as liquid crystal displays. Examples of the optical film include a light diffusion film, a polarizing film, a prism film, a reflection film, an antireflection film, and a retardation film. These optical films can be obtained by controlling the molecular orientation of the material constituting the film, adding a function-providing material to the film, or controlling the three-dimensional structure of the film surface.

 In display devices such as liquid crystal displays, studies on large areas of display screens are underway. As a result, it has become necessary to produce large-area optical films with high accuracy.

 Conventionally known methods for forming a fine three-dimensional structure on the film surface include a method based on lithography and a method of pressing a mold against the surface.

 The lithography method is not suitable for processing a large area with high-definition processing, and the cost may be high.

 On the other hand, methods such as hot embossing technology and nanoimprint technology that press molds on the surface have made it possible to form highly precise microstructures, but this method is difficult to produce high-definition large-area molds. Is expensive. The film having an uneven shape obtained by this method has a risk of scratching due to rubbing or the like, or the uneven shape being crushed as the structure becomes finer. In addition, a film having a concavo-convex shape on the surface obtained by a method of pressing a mold on the surface using ultraviolet curable resin or the like may be warped depending on usage conditions.

[0004] As another method for forming a three-dimensional structure on the film surface, Patent Document 1 proposes a method of applying a resin to a substrate and deforming the resin with the substrate curved. However In this method, the shape control of the distance between the convex vertices of the provided structure and the ratio between the height and width of the convex part (the aspect ratio) was easy.

 Patent Document 1: Japanese Patent Laid-Open No. 2003-266570

 Disclosure of the invention

 Problems to be solved by the invention

[0005] The object of the present invention is to freely control the distance between the apexes of the convex and concave portions, the ratio between the height and width of the convex portions (the aspect ratio), and the distribution thereof, thereby providing scratch resistance. It is an object of the present invention to provide a film having a fine concavo-convex shape on the surface that does not warp even under severe use conditions. It is an object of the present invention to provide a method for producing a large-area film having fine irregularities on the surface, in which the ratio of width to width (aspect ratio) and the distribution thereof can be freely controlled.

 Means for solving the problem

[0006] As a result of studies to solve the above problems, the present inventors have obtained a laminate by forming a thin film on at least one surface of the film substrate, and then the laminate is at least in-plane. By shrinking in one axial direction, it is possible to easily obtain a film having a fine uneven shape on the surface in a large area, and the force can freely change the distance between the convex vertices, the aspect ratio, and the distribution degree thereof. Based on this knowledge, we have found that it can be controlled!

 That is, the present invention includes the following aspects.

 (1) forming a thin film by forming a thin film on at least one surface of the film substrate, and

 Including shrinking the laminate in at least one axial direction in the plane to bend the thin film,

 A method for producing a film having fine irregularities on the surface.

(2) When the contraction rate AL in the main contraction direction is expressed by Equation [1] and the contraction rate ΔM in the direction perpendicular to the main contraction direction is expressed by Equation [2], ΔL and ΔM are expressed by Equation [3] and A method for producing a film satisfying the formula [4], wherein the film has fine irregularities on the surface. Formula [1]: AL = (L0—LI) ZLO X 100 (LO: length before contraction in the main contraction direction, L 1: length after contraction in the main contraction direction)

 Formula [2]: ΔΜ = (MO-MD / MOX 100 (MO: length before shrinkage in the direction perpendicular to the main shrinkage direction, Ml: length after shrinkage in the direction perpendicular to the main shrinkage direction)

 Formula [3]: AL> 0

 Formula [4]: One (ALX0.3) ≤ ΔΜ ≤ AL

 (3) A method for producing a film having fine irregularities on the surface, wherein AL and ΔΜ satisfy formula [5].

 Formula [5]: One (ALXO.2) ≤AM≤ (ALX0.2)

 (4) The method for producing a film having a fine concavo-convex shape on the surface, wherein the fine concavo-convex shape has a structure elongated in a stripe shape within the surface.

 (5) The method for producing a film having a fine concavo-convex shape on the surface, wherein the fine concavo-convex shape has a variation coefficient of the distance between the vertices of the convex portions of 40% or less.

 [0008] (6) The thickness of the thin film is Inn! A method for producing a film having fine irregularities on the surface, which is ˜50 m.

 (7) The thin film has an inorganic material force, and the thickness of the thin film is Inn! The manufacturing method of the film which has the fine uneven | corrugated shape on the said surface which is -500 (eta) m.

 (8) The thin film has organic substance power and the thickness of the thin film is ΙΟΟηπ! The manufacturing method of the film which has fine uneven | corrugated shape on the said surface which is -50micrometer.

 (9) The organic substance is made of curable resin, and the heat treatment temperature when forming a thin film made of curable resin is made 5 ° C. or more lower than the glass transition temperature of the base film. The manufacturing method of the film which has fine uneven | corrugated shape on the said surface.

 (10) The average distance between the vertices of the fine irregularities is 50ηπ! The method for producing a film having a fine concavo-convex shape on the surface, which is ˜50 m.

 (11) The method for producing a film having a fine concavo-convex shape on the surface, wherein the film substrate is a film in which molecules are oriented in at least one in-plane direction.

[0010] (12) a first layer having a fine concavo-convex shape B on its surface, and a second layer laminated on the concavo-convex shape B and bent so as to correspond to the shape of the concavo-convex shape B Containing, convex The average distance between vertices is 50nn! Film with fine irregularities Α that is ~ 50 μm.

 (13) The film having the fine uneven shape A, wherein the average thickness of the second layer is 10% to 100% of the average height of the fine uneven shape A.

 (14) A finolem having the fine concavo-convex shape A, wherein the variation coefficient of the thickness of the second layer is 20% or less.

 (15) The film having the fine concavo-convex shape A, wherein the fine concavo-convex shape A has a coefficient of variation of the distance between the vertices of the convex portions of 80% or less.

 (16) The fine concavo-convex shape A is a film having the fine concavo-convex shape A, in which the power spectrum of the spatial frequency obtained by two-dimensional Fourier transform is distributed in the negative direction.

(17) A film having the fine concavo-convex shape A, wherein the fine concavo-convex shape A has a structure elongated in a stripe shape in a plane.

 (18) The fine concavo-convex shape A is a film having the fine concavo-convex shape A, wherein the coefficient of variation of the distance between the apexes of the convex portions is 40% or less.

 (19) A finolem having the fine concavo-convex shape A, wherein the haze is 50% or more.

 (20) A film having a fine concavo-convex shape A obtained by the above production method.

 (21) An optical element comprising a film having the fine concavo-convex shape A.

 The invention's effect

 [0011] According to the production method of the present invention, a film having a fine concavo-convex shape on the surface can be easily obtained in a large area, and the force between the vertices of the convex portions of the fine concavo-convex shape, the aspect ratio, And their distribution can be freely controlled.

 The film having a fine concavo-convex shape of the present invention is suitable as an optical element having good scratch resistance and little warpage.

 Brief Description of Drawings

FIG. 1 is a diagram showing a surface scanning electron micrograph image of the concavo-convex structure obtained in Example 3.

 FIG. 2 is a diagram showing a two-dimensional Fourier transform image of the electron micrograph image of FIG.

FIG. 3 shows a surface scanning electron micrograph image of the concavo-convex structure obtained in Example 4. 4) Schematic cross-sectional view of the structure obtained by the present invention

 FIG. 5 is a schematic cross-sectional view of the structure obtained by the present invention.

 [Fig. 6] Cross-sectional schematic diagram of the structure obtained in Comparative Example 1 (prior art)

 [FIG. 7] Schematic cross section of the structure obtained in Comparative Example 2 (prior art)

 Explanation of symbols

[0013] 1, 11: First layer (film substrate)

 2, 12: Second layer (thin film)

 3, 13: Film substrate

 4: UV cured layer

 BEST MODE FOR CARRYING OUT THE INVENTION

 [Method for producing a film having fine irregularities on the surface]

 The method for producing a film having fine irregularities on the surface of the present invention comprises a step of forming a thin film by forming a thin film on at least one surface of a film substrate, and at least one axial direction of the laminate in the plane. And a step of bending the thin film.

 [0015] (film substrate)

 The film substrate used in the production method of the present invention is not particularly limited as long as it can be contracted in at least one axial direction in the plane after the thin films are laminated. For example, the film substrate itself may be shrunk by a means such as heating, or the film base material may be shrunk in a direction orthogonal to the stretching direction when uniaxially stretched.

 [0016] The average thickness of the film substrate before shrinkage is usually 5 μm to 1 mm, preferably 20 to 200 μm, from the viewpoint of handling.

 [0017] The film base is usually formed of a resin, rubber or elastomer.

As the resin, styrene resin, acrylic resin, methacrylic resin, organic acid resin ester resin, vinyl ether resin, halogen-containing resin, olefin resin, alicyclic olefin resin, Polycarbonate-based resin, polyester-based resin, polyamide-based resin, thermoplastic polyurethane resin, polysulfone-based resin (for example, polyethersulfone, polysulfone, etc.), polyphenylene ether-based resin (for example, 2, 6 —Xylenol polymers, etc.), cellulose derivatives (eg, cellulose esters, cellulose carbamate) And cellulose ethers (for example, polydimethylsiloxane, polymethylphenol siloxane, etc.).

 [0018] As the alicyclic polyolefin resin, cyclic olefin random copolymers described in JP-A No. 05-310845 and US Pat. No. 5,179,171, JP-A No. 05-9 7978 and Hydrogenated polymers described in US Pat. No. 5,202,388, and thermoplastic dicyclopentagen-based ring-opening polymers described in JP-A-11-124429 and WO99Z20676 and hydrogen thereof An additive etc. are mentioned.

 [0019] Examples of the rubber Z elastomer include gen-based rubber such as polybutadiene and polyisoprene, styrene butadiene copolymer, acrylonitrile butadiene copolymer, acrylic rubber, urethane rubber, and silicone rubber.

 Of these, a thermoplastic resin is preferred as the material for the film substrate because it is easy to produce.

 [0020] The thermoplastic resin constituting the film base material is not particularly limited, but the power from the viewpoint of ease of processing is preferably 100 to 180 ° C with a glass transition temperature of 60 to 200 ° C. More preferably. The glass transition temperature can be measured by differential scanning calorimetry (DSC).

 [0021] Further, the thermoplastic resin constituting the film base is preferably polystyrene-equivalent weight average molecular weight power <ί or 5,000 to 500,000, more preferably <ί or 8,000 to 200,000. Particularly preferred is 10,000 to 100,000. When the weight average molecular weight is in this range, the moldability becomes good and the mechanical strength can be improved. This weight average molecular weight can be measured by gel 'permeation' chromatography.

 [0022] The resin, rubber or elastomer constituting the film substrate is a colorant such as a pigment or dye, a fluorescent brightener, a dispersant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, an antistatic agent. Agents, antioxidants, chlorine scavengers, flame retardants, crystallization nucleating agents, antiblocking agents, antifogging agents, mold release agents, organic or inorganic fillers, neutralizing agents, lubricants, decomposition agents, metal inertness Agents, antifouling agents, fluorescent brighteners, antibacterial agents, diffusing particles, thermoplastic elastomers and other compounding agents may be appropriately combined.

[0023] The film substrate is not particularly limited by its production method. The film base is the front It can be obtained, for example, by forming the above-mentioned resin etc. by a known film forming method. Examples of the film forming method include a cast molding method, an extrusion molding method, and an inflation molding method.

 [0024] The film base material that shrinks itself by means of heating or the like is usually preferably molecularly oriented in the plane. Originally, molecules try to be in a low energy arrangement state according to the bond angle between atoms. The state in which the molecules are regularly arranged in the plane includes distortion in the bonded state of the molecules, and can be said to be a high energy arrangement state. When this high energy arrangement state is reached! / When the film substrate is heated, the molecules try to return to the low energy arrangement state, and the entire film substrate contracts. The state of molecular orientation can be measured by a known method, for example, by using an automatic birefringence meter KOBRA21ADH.

 [0025] The film base material that shrinks itself by means of heating or the like is formed, for example, by forming the above-mentioned resin or the like on the original film by a known molding method and stretching the original film. Obtainable. Further, instead of stretching treatment, a film base material exhibiting shrinkage can be obtained by applying a magnetic field or electric field or rubbing treatment to orient the molecules. By forming a rubber or elastomer on an elastic film by a known molding method and pulling the coasting film in an in-plane direction, a film base material exhibiting shrinkage utilizing a restoring force due to elasticity, can do. Furthermore, a film made of a curable resin can be swollen with a solvent or the like in advance, and the film base used in the present invention can be obtained by utilizing the shrinkage that occurs when the swollen film dries. Of these, a film base material exhibiting shrinkage obtained by stretching a raw film is preferred.

 [0026] The shrinkable film base material obtained by stretching the raw film is not particularly limited by its stretching method, and may be one stretched by either a uniaxial stretching method or a biaxial stretching method. Good. In the case of biaxial stretching, it usually shrinks in two directions within the film plane.

The stretching process includes a method of uniaxial stretching in the longitudinal direction using the difference in peripheral speed on the roll side; a uniaxial stretching method such as a method of uniaxial stretching in the transverse direction using a tenter stretching machine; At the same time as extending in the longitudinal direction with a gap, the spread angle of the guide rail After stretching in the longitudinal direction using the simultaneous biaxial stretching method that stretches more in the transverse direction or the difference in peripheral speed between the rolls, both ends are gripped and stretched in the transverse direction using a tenter stretching machine. Biaxial stretching method such as sequential biaxial stretching method; in the width direction of the film using a tenter stretching machine that can add feed force, pulling force or pulling force at different speeds in the horizontal or longitudinal direction And a method of continuously obliquely stretching in the direction of an arbitrary angle Θ.

 [0027] When the shrinkage rate in the main shrinkage direction is significantly increased, elongation may occur in a direction perpendicular to the main shrinkage direction, and the elongation may cause cracks in the concavo-convex shape. From the standpoint that cracking at the time of shrinkage can be suppressed, (i) the uniaxial stretching in the transverse direction is preferably performed while the longitudinal shrinkage during stretching is preferably 20% or less, more preferably 15% or less ( Horizontal uniaxial stretching method) Force (i) Biaxial stretching in the longitudinal and lateral directions (biaxial stretching method) is preferred.

 [0028] Examples of the apparatus used for stretching include a longitudinal uniaxial stretching machine, a tenter stretching machine, a bubble stretching machine, and a roller stretching machine.

 [0029] The temperature during stretching is preferably between (Tg—30 ° C) and (Tg + 60 ° C), more preferably when the glass transition temperature of the material constituting the film substrate is Tg. A temperature force between (Tg—10 ° C) and (Tg + 50 ° C) is selected.

 The draw ratio may be appropriately selected according to the tensile properties of the film to be used so as to obtain a desired uneven shape aspect ratio. The aspect ratio referred to here is the ratio between the height and width (= height Z width) of the vertical cross-sectional shape of the convex portion in the concavo-convex shape. When the shape of the vertical cross section of the convex portion is other than a rectangle or a square, the width of the convex portion when calculating the aspect ratio is the width of the convex portion at the height of 1Z2 of the height of the convex portion.

[0030] When it is desired to obtain a concavo-convex shape with a high aspect ratio, the stretch ratio is generally set high, although it depends on the film quality and thickness of the thin film. If you want to obtain an uneven shape with a low aspect ratio, set the draw ratio low. Specifically, the ratio R1 in the main stretching direction is usually 1.01 to 30 times, more preferably 1.01 to 10 times, and more preferably 1.05 to 5 times. Stretch ratio in the main direction When the ratio R1 is less than 1.01, the uneven shape does not occur, and when it is more than 30 times, the film strength may decrease. [0031] (Thin film)

 Next, a thin film is formed on at least one surface of the film substrate. The shrinkage rate of the thin film is more preferably 10% or less, preferably 20% or less of the shrinkage rate of the film substrate under the conditions for shrinking the film substrate. If the shrinkage rate of the thin film is too large, fine uneven shapes may not be formed.

[0032] It is preferable that the average thickness of the thin film before shrinking is 1 nm to 50 μm. The thickness of the thin film is obtained by photographing a vertical section of the thin film with a transmission electron microscope and obtaining an average value of the thickness from the photograph image.

 [0033] The thin film includes an inorganic thin film and an organic thin film.

 The inorganic thin film used in the present invention has an inorganic substance power. Examples of the inorganic substance constituting the thin film include metals; metal compounds such as metal oxides and metal nitrides; nonmetals; nonmetal compounds such as nonmetal oxides, and specifically, aluminum, silicon, and magnesium. Metals or non-metals such as shim, rhodium, platinum, zinc, tin, nickel, silver, copper, gold, antimony, yttrium, indium, stainless steel, chromium, titanium, tantalum, zirconium, niobium, lanthanum, cerium; Or oxides or nitrides thereof; or a mixture thereof. When the film obtained by the production method of the present invention is used as an optical element, it is preferable to select an inorganic substance that transmits visible light, and specific examples thereof include ITO, InO, SnO, SiO. , Cul, TiO, ZrO and the like. Of these, thin

 2 3 2 2 2 2

 From the viewpoint of film flexibility, SiO is preferable.

 2

 [0034] The average thickness of the inorganic thin film is preferably 1 nm to 500 nm. If the thickness is less than lnm, it is difficult to form the uneven shape. If the thickness is more than 500 nm, the inorganic thin film layer is likely to crack when contracted. When using an inorganic thin film, the average distance between the vertices is 50ηπ! Fine irregularities of up to 1000 nm can be easily obtained.

[0035] The method of forming the inorganic thin film is not particularly limited, and vapor deposition methods such as vacuum deposition, ion plating, sputtering, CVD (chemical vapor deposition); spin coating method, dating method, roll coating method, spray method, vapor And coating methods such as gravure coater and blade coater, screen printing method, ink jet method and the like; electroless plating method, electrolytic plating method and the like. [0036] The organic thin film used in the present invention is not particularly limited as long as the thin film has a curved structure by shrinkage.

 The organic thin film preferably has a shrinkage ratio under a temperature condition for shrinking the film base material that is smaller than that of the film base material.

 The average thickness of the organic thin film is preferably 100 nm to 50 m. If it is thinner than lOOnm, it will be difficult to form uneven shapes, and if it is thicker than 50 m, it will be difficult to control the aspect ratio. Using organic thin films, the average distance between the vertices is 500ηπ! A fine uneven shape of ~ can be easily obtained.

[0037] Examples of the organic thin film include those made of thermoplastic resin and those made of curable resin.

 [0038] Examples of the thermoplastic resin include those similar to those exemplified as those that can be used for the film substrate. In addition, the thin film contains a compounding agent as well as the resin used for the film base!

 [0039] The method for forming an organic thin film comprising a thermoplastic resin includes: (1) a method of co-extruding a resin constituting a film substrate and a resin constituting a thin film; (2) a thermoplastic resin (3) A method in which a solution containing a thermoplastic resin is applied to the surface of the film substrate and dried.

 [0040] In the present invention, the film base material is made of thermoplastic resin 1, the organic thin film is made of thermoplastic resin 2, and the glass transition of thermoplastic resin 2 The temperature is preferably at least 20 ° C. higher than the glass transition temperature of the thermoplastic resin 1. The glass transition temperature can be measured by differential scanning calorimetry (DSC).

 [0041] The curable resin includes a thermosetting type and an energy ray curable type. Energy rays refer to visible rays, ultraviolet rays, electron beams, and the like.

 [0042] Specific examples of thermosetting resins include phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin. Examples thereof include fat, amino alkyd resin, melamine-urea co-condensed resin, silicon resin, and polysiloxane resin.

[0043] The energy ray curable resin is not particularly limited. Unsaturated groups (for example, attaroyloxy group, methacryloyloxy group, buroxy group, styryl group, vinyl group, etc.) and / or cationic polymerizable groups (epoxy group, thioepoxy group, buroxy group, oxetal group, etc.) ), Which includes relatively low molecular weight polyester resin, polyether resin, acrylic resin, methallyl resin, epoxy resin, urethane resin, alkyd resin, Examples include spiroacetal resin, polybutadiene resin, and polythiolpolyene resin.

 [0044] When ultraviolet rays or visible rays are used as energy rays, a photopolymerization initiator, a photosensitizer and the like are included in the curable resin. Examples of the photopolymerization initiator include acetophenones, benzophenones, Michler benzoyl benzoate, a-amino oxime ester, tetramethylthiuram monosulfide, thixanthones, and the like. Examples of the photosensitizer include n-butynoleamine, triethylamine, tri-n-butylphosphine, and the like.

 [0045] The thin film made of a curable resin may contain a curing agent such as a crosslinking agent and a polymerization initiator, and a compounding agent such as a polymerization accelerator, a solvent, and a viscosity modifier.

 [0046] The method for forming an organic thin film comprising a curable resin is not particularly limited. The organic thin film made of curable resin is obtained, for example, by applying a composition of curable resin to the film substrate surface and curing it. When forming a curable resin thin film, it is desirable to heat-treat at a temperature that is at least 5 ° C lower than the glass transition temperature T1 of the film substrate. If a high temperature is applied when forming a thin film, the film substrate may be annealed and may not shrink as designed.

 As the organic thin film, it may be easy to control the aspect ratio of the fine concavo-convex shape, and therefore it is preferable to use a curable resin thin film.

[0047] (Fold-inducing structure)

In the production method of the present invention, before forming a thin film on the surface of the film substrate, a structure (curvature inducing structure) for causing the bending of the thin film is formed on the surface of the film substrate, or the surface of the film substrate Forming a structure (curvature inducing structure) for causing the thin film to bend after forming the thin film on the substrate and before shrinking the substrate. This is preferable when you want to improve the uniformity of the distance between vertices. The structure is not particularly limited as long as it causes the thin film to bend when the base material contracts. For example, the structure is scratched on the surface by rubbing or other methods, placed on an inkjet printer or printing machine, etc. Examples include unevenness imparted by ink marks, embossing force imprinting, and the like.

 It is preferable that the bending induction structure is formed at a constant interval. The distance between the fold-inducing structures is not directly related to the distance between the desired convex and concave convex vertices, so it may be narrower or wider than the desired concave and convex convex distance. It is preferable to set the spacing of the curvature inducing structure to be 0.05 to 100 times the desired distance between the vertices of the concavo-convex shape.

[0048] In the production method of the present invention, the film base material on which the thin film is formed is then contracted to bend the thin film. The method for shrinking the film substrate may be selected as appropriate according to the type of film substrate.

[0049] The shrinkage rate of the film base is such that the shrinkage AL in the main shrinkage direction and the main shrinkage direction in order to prevent the thin film or the like from cracking when the thin film is bent by the shrinkage of the film base material. It is preferable that the shrinkage rate ΔM in the direction perpendicular to the equation satisfies the equations [3] and [4]. AL and ΔΜ are defined by equations [1] and [2], respectively.

[0050] Formula [1]: AL = (LO—LDZLOX100 (L0: length before contraction in the main contraction direction, L1

: Length after contraction in the main contraction direction)

 Formula [2]: ΔΜ = (MO-MD / MOX 100 (MO: length before shrinkage in the direction perpendicular to the main shrinkage direction, Ml: length after shrinkage in the direction perpendicular to the main shrinkage direction)

 Formula [3]: AL> 0

 Formula [4]: One (ALX0.3) ≤ ΔΜ≤ AL

[0051] When it is desired to increase the anisotropy of the fine concavo-convex shape, that is, when the concavo-convex shape is elongated in a stripe shape in the plane, the formula [3] and the formula [5] are satisfied. Preferred U, Equation [5]: One (ALXO. 2) ≤ AM≤ (ALX0. 2)

[0052] The production method of the present invention is suitable for producing various optical films because the distance between convex vertexes, the aspect ratio, and the like can be arbitrarily adjusted simply by changing the shrinkage conditions. In addition, a structure that is elongated in a stripe shape within a plane required by a grid polarizer or the like is also manufactured by the present invention. It can be easily manufactured by a manufacturing method.

 [0053] The fine concavo-convex shape may be arranged randomly or regularly, but it is diffracted that the variation coefficient of the distance between the vertices of the convex portions is 40% or less. It is suitable for use as an optical element having a function, a light collecting function and a polarization function. The variation coefficient is the ratio of the standard deviation to the average value of the distance between the vertices of the convex portions (= standard deviation Z average value X 100).

 It should be noted that the main shrinkage direction is the direction in which the degree of shrinkage (shrinkage rate) is the largest. For example, a film substrate obtained by stretching a film made of thermoplastic resin shrinks when heated. When the film is stretched only in a uniaxial direction, the stretching direction is usually the main shrinking direction. In addition, when stretching is performed in the biaxial direction, the direction in which the stretching ratio is large among the two stretched directions is generally the shrinking direction.

 [0055] When a film made of thermoplastic resin is uniaxially stretched, the film shrinks in the direction perpendicular to the stretching direction during stretching. In a film base material utilizing the shrinkage during stretching, the direction perpendicular to the stretching direction is the main shrinking direction. If the shrinkage ratio ΔM in the direction perpendicular to the main shrinkage direction is negative, it means that the film has been stretched during the shrinkage treatment. When the film shrinks in the main shrinking direction, if the elongation in the direction perpendicular to the main shrinking direction becomes too large, the thin film tends to crack.

 [0056] The shrinkage rate in the direction orthogonal to the main shrinkage direction is preferably 1% to 90%, more preferably 1% to 50%.

 By the production method of the present invention, a film having the following fine uneven shape can be easily obtained.

 [Film having fine irregularities]

 The film of the present invention includes a first layer having a fine concavo-convex shape B on its surface, and a second layer laminated on the concavo-convex shape B and bent so as to correspond to the shape of the concavo-convex shape B. The average distance between the vertices of the protrusion is 50ηπ! It is a film having a fine concavo-convex shape A which is ˜50 m.

[0058] The first layer is formed of a resin, rubber, or elastomer. As the resin, rubber or elastomer constituting the first layer, the material constituting the film base is used. Can be mentioned. The average thickness of the first layer is usually ~: Lmm, preferably 20-200 μm.

 [0059] The fine concavo-convex shape B on the surface of the first layer has an average distance of 50ηπ between the vertices of the convex portions! It is preferably ~ 50 m. The convex portions in the fine concavo-convex shape B are not particularly limited by the shape, and examples thereof include a bowl shape, a trapezoidal shape, and a dot shape. The convex portions in the fine concavo-convex shape B may be arranged randomly or regularly on the surface of the first layer, but the coefficient of variation in the distance between the vertices of the convex portions is 80%. The following is suitable for use as an optical element. This coefficient of variation is the ratio of the standard deviation to the average value of the distance between the vertices of the convex portions (= standard deviation Z average value X 100). In the case where the fine irregularities B are arranged in the shape of saddle-shaped convex portions and stripes, the variation coefficient of the distance between the apexes of the convex portions is preferably 40% or less, more preferably 30% or less. In the case where the stripes are arranged, a small variation coefficient of the distance between the vertices of the convex portions means that the stripe has a high periodicity.

 [0060] The second layer is formed of an organic substance or an inorganic substance. Examples of the organic substance or inorganic substance constituting the second layer may include the same substances listed as the materials constituting the thin film. The average thickness of the second layer is preferably from lnm to 50 m. The average thickness of the second layer is preferably 10% to 100% of the average height of the convex portions of the fine concavo-convex shape A. When the average thickness of the second layer is thinner than 10% of the average height of the convex portions of the fine concavo-convex shape A, the scratch resistance may be impaired. May cause warping when used in harsh conditions.

[0061] The variation coefficient of the thickness of the second layer is preferably 20% or less. If the variation coefficient of the thickness of the second layer is greater than 20%, the thickness distribution of the second layer becomes large, which may cause warpage. The thickness of the second layer can be measured as follows. The film is cut perpendicularly in the direction of strong periodicity to obtain ultrathin sections, and the ultrathin sections are photographed with a transmission electron microscope. As for the image power, the thickness of the second layer is measured at at least 15 points on the top and bottom of the convex part, and the average value, standard deviation, and coefficient of variation are calculated from these measured values. The direction in which the periodicity of the film is strong is the power spectrum distribution force of the spatial frequency obtained by two-dimensional Fourier transform of the scanning electron micrograph image on the film surface. Two points with strong strength are extracted and the direction of the straight line connected by these two points. This direction means a direction perpendicular to the longitudinal direction of the stripe when the concave-convex shape is striped in the plane.

 [0062] The second layer is laminated on the concavo-convex shape B and is bent so as to correspond to the shape of the concavo-convex shape B. 4 and 5 are schematic views showing a vertical section of the film of the present invention. Corresponding to the uneven shape B on the surface of the first layer, the second layer is bent, and the uneven shape A is formed on the surface on the second layer side of the film.

 FIG. 6 shows the uneven shape obtained by embossing the surface of the resin film. Fig. 7 shows the uneven shape obtained by pressing the mold with UV curable resin.

 [0063] The fine uneven shape A has an average distance of 50ηπ between the vertices of the convex portions! ~ 50 μm. Further, the convex portion in the fine concavo-convex shape A is not particularly limited by the shape, and examples thereof include a bowl shape, a trapezoidal shape, and a dot shape. The convex portions in the fine concavo-convex shape A may be randomly arranged in the plane or may be regularly arranged, but the variation coefficient of the distance between the vertices of the convex portions is 80% or less. It is preferable that The coefficient of variation is the ratio of the standard deviation to the average value of the distance between the vertices of the convex part (= standard deviation Z average value X 100). In the case where fine concave and convex shapes are arranged in the shape of saddle-shaped convex portions and stripes, the variation coefficient of the distance between the vertices of the convex portions is preferably 40% or less, more preferably 30% or less.

 [0064] The average distance between the vertices of the protrusions and the coefficient of variation of the distance between the vertices of the protrusions were observed with a scanning electron microscope on a vertical cross section in the direction in which the periodicity of the film having a fine concavo-convex structure was strongest Then, measure a plurality of distances between adjacent projections from the observed image, determine the average value and standard deviation of the measured values, and the coefficient of variation (%) = standard deviation σ Ζ average value Calculate X100. In addition, at least 2 locations should be selected at a distance of 10 cm or more in the width direction of the film, and at least 2 locations should be selected from a location at least 10 cm in the direction of the film flow. The above distance is measured.

[0065] The height of the convex portion of the fine concavo-convex shape A is 5ηπ depending on the purpose! When the film of the present invention is used as an optical element, it is preferably 50ηπ! The range is ~ 10 m. The width of the protrusion (width at half the height) is preferably 5ηπ! ~ 50 μm Yes, when the film of the present invention is used as an optical element, preferably 50 nn! ~ 10 m. The aspect ratio is usually from 0.1 to 10. The aspect ratio is defined by the height of the projection Z and the width of the projection. The aspect ratio can be adjusted by controlling the film quality of the thin film, the film thickness of the thin film, the shrinkage rate of the film substrate, and the like.

[0066] The fine concavo-convex shape A preferably has a spatial frequency power spectrum obtained by two-dimensional Fourier transform of a scanning electron microscopic image of the film surface distributed in one direction. When the power spectrum is distributed in one direction, it can be suitably used when it is desired that the desired optical element has anisotropy in optical characteristics such as a diffusion function, a diffraction function, and light collection. FIG. 1 is a view showing a scanning micrograph of the film surface of the present invention. FIG. 2 is a diagram showing an image obtained by two-dimensional Fourier transform of the image of FIG. Figure 2 shows that the part with strong spatial frequency intensity is distributed in the vertical direction, and that the periodicity of the film becomes stronger in this direction.

 [0067] Further, it is preferable that the fine concavo-convex shape A has a structure elongated in a stripe shape in the plane as shown in FIG. In the case where the structure is elongated in the form of stripes in the plane, it can be used for a diffraction grating, a grid polarizer or the like as described later.

 [0068] The film of the present invention preferably has a haze of 50% or more in order to be applied to an optical element, particularly a light diffusing element. Haze is measured using a turbidimeter (Nippon Denshoku NDH2000) based on JIS K7361.

 [0069] The film having the fine concavo-convex shape A of the present invention can be applied to various optical elements using the fine concavo-convex shape A on the surface. A film having a light diffusing function, a condensing function, a light diffracting function, and a polarizing function can be easily and easily manufactured in a large area by changing the distance between the apexes of the convex portions, the aspect ratio, and the distribution thereof.

 [0070] When the fine concavo-convex shape A is given a light diffusing function, it can be used for an antireflection film, a light diffusing film, a lighting cover, a reflective screen, a transmissive screen, etc. When a light condensing function is added, it can be used for a light condensing sheet.

[0071] When the fine concavo-convex shape is elongated in stripes in the plane, and the distance between the convex vertices of the fine concavo-convex shape is about the same as or slightly larger than the wavelength of light, the light is diffracted. , A film having a function of condensing or scattering can be obtained. Such a film can be used as a diffraction grating.

 [0072] When the fine concavo-convex shape is elongated in stripes in the plane, and the distance between the convex vertices of the fine concavo-convex shape is smaller than the wavelength of light or electromagnetic wave, the fine concavo-convex shape By forming a light-absorbing material such as aluminum on the part, it can be applied to elements such as a grid polarizing film, an electromagnetic wave shielding film, and an electromagnetic wave absorbing film.

 Example

 [0073] The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

 [Production Example 1] Production of film substrate

 Pellets of alicyclic olefin coconut resin (manufactured by Nippon Zeon Co., Ltd., ZEONOR1420, glass transition temperature 136 ° C) were dried at 100 ° C for 4 hours using a hot air dryer in which nitrogen was circulated. Next, this pellet was extruded at a melt resin temperature of 260 ° C using a T-die type film melt extruder equipped with a 50mm φ screw, so that a film with a width of 650mm and a thickness of 188μm was obtained. Then, 25 mm on both ends were trimmed to obtain a raw film made of alicyclic polyolefin resin having a width of 600 mm.

 [0075] (Film substrate 1A)

 Hold both ends of a 600 mm wide film with a clip and introduce it into a tenter stretching machine, at a temperature of 150 ° C, 1.5 times in the film width direction and 1 times in the film flow direction. The stretched film was stretched uniaxially, and the stretched film was released from the clipping force. Both ends were continuously trimmed to obtain a film substrate 1A having a width of 800 mm.

 Film base 1 A square 40 mm square test piece was cut out and placed in the center of the cut test piece, using a birefringence measuring device (Oji Scientific Instruments, KOBRA-21ADH) as a film base. The orientation angle was measured by measuring the phase difference of the material. It was confirmed that the film substrate 1A was molecularly oriented in the width direction.

 [0076] (Film substrate 1B)

The above-mentioned raw film with a width of 600 mm is machined vertically at a temperature of 145 ° C using a longitudinal uniaxial stretching machine. Stretched 1.3 times. The stretched film was sent to a tenter stretching (lateral uniaxial stretching) apparatus and stretched 1.6 times in the transverse direction at a temperature of 150 ° C. to obtain a film substrate 1B. A 40 mm square test piece was cut out from the film substrate 1B, and the orientation angle was measured using a birefringence measuring device [Oji Scientific Instruments, KOBRA-21ADH] at the center of the cut test piece. It was confirmed that the film substrate 1B was molecularly oriented in the width direction.

 [0077] (Film substrate 1C)

 The raw film having a width of 600 mm was stretched 1.5 times in the longitudinal direction at a temperature of 145 ° C using a longitudinal uniaxial stretching apparatus to obtain a film substrate 1C. A 40 mm square test piece was cut from the film substrate 1C, and the orientation angle was measured using a birefringence measuring device [Oji Scientific Instruments, KOBRA-21ADH] at the center of the cut test piece. It was confirmed that the film substrate 1C was molecularly oriented in the flow direction.

 (Production Example 2) Production of a solution for thermoplastic rosin thin film

 A pellet of alicyclic olefin coconut resin (manufactured by Nippon Zeon Co., Ltd., ZEONOR 1600, glass transition temperature 163 ° C.) was dissolved in cyclohexane to obtain an alicyclic olefin olefin resin solution having a concentration of 2 wt%.

 This resin solution was applied to a support film with a bar coater and dried at 100 ° C. for 30 minutes to obtain a thin film. The thin film was peeled off from the supporting film, cut into 10 cm square, and left at 140 ° C. for 1 hour. After standing, the side length was measured. The shrinkage ratio of the thin film was 0.8% (= [length after cutting (10 cm) —length after standing at 140 ° C.] ZlOcm × 100).

[0079] (Production Example 3) Production of a solution for a curable resin film

 Hexafunctional urethane acrylate oligomer (trade name: NK Oligo U-6HA, manufactured by Shin-Nakamura Chemical Co., Ltd.) 30 parts by weight, butyl acrylate, 40 parts by weight, isobornyl methacrylate (trade name: NK ester 1B, Shin-Nakamura Chemical Co., Ltd.) 30 parts by weight and 10 parts by weight of 2,2 dimethoxy-1,2-diphenol-one on a homogenizer and then diluted with toluene to a concentration of 20% by weight to prepare a UV curable resin solution did.

This UV-curable resin solution is applied to a support film with a bar coater, dried at 80 ° C for 5 minutes, and then irradiated with UV light (accumulated light amount 300 mj / cm 2 ) to cure the resin and form a thin film. Obtained. When the shrinkage rate of the thin film was measured in the same manner as in Production Example 2, the shrinkage rate was 1.4%. It was.

 [0080] (Example 1)

 On the film substrate 1A, a film winding type vacuum film forming apparatus equipped with a film forming force sword was used to form a lOnm thick SiO layer by sputtering to obtain a laminated film. Next

 2

 The surface of the SiO layer was rubbed in the film flow direction. Observation with a scanning electron microscope

 2

 As a result, linear scratches along the film flow direction were uniformly attached to the SiO layer surface.

 2

[0081] Next, the laminated film was passed through a hot air dryer in which hot air at a temperature of 140 ° C was circulated, and the shrinkage rate in the main shrinkage direction Δ L = 33%, shrinkage in the direction perpendicular to the main shrinkage direction Shrinkage was performed at a rate Δ M = 0.1%.

 [0082] When the shrink film was observed with a field emission scanning electron microscope S-4700 manufactured by Hitachi, as shown in FIG. 1, a fine uneven shape elongated in a stripe shape was uniformly formed on the surface. Was formed.

 The scanning electron microscope image was subjected to two-dimensional fast Fourier transform using image analysis software (SoftlyagingSystem, AnlySIS) to obtain the spatial frequency power spectrum distribution, and the direction showing strong periodicity was read. The sample was cut in this direction using an ultramicrotome, and the cross section was photographed with a scanning electron microscope (S-4700, manufactured by Hitachi, Ltd.). This photograph was taken at three points at least 1 Ocm apart in the film width direction and flow direction. From the scanning electron micrograph image, the distance between the convex vertices was measured at 30 points. The average distance between the convex vertices was 124 nm, and the coefficient of variation of the distance between the convex vertices was 3.6%. The aspect ratio was 2.1.

 In addition, a cross-sectional piece for transmission electron microscope observation was produced from the shrink film using a microsampling device of a focused ion beam processing observation device (manufactured by Hitachi, Ltd., FB-2100). The cross section was observed with a transmission electron microscope (H-7500, manufactured by Hitachi, Ltd.). From the observed image, it was confirmed that the SiO layer was bent as shown in FIG. The thickness of the SiO layer

 2 2 15 points were measured at the top of the convex and the bottom of the concave. The thickness of the SiO layer (second layer) is

 2

The average was 10.4 nm and the coefficient of variation was 4.2%. The average thickness of the second layer was 10.4% of the average height of the irregular shape. [0084] An aluminum layer having a thickness of lOOnm was formed on the uneven surface of the shrink film by vacuum deposition. Next, it was immersed in an etching solution mainly composed of phosphoric acid to obtain a grid polarizing film.

 Polarization separation performance was examined using a spectrophotometer (manufactured by JASCO, UV-Vis near-infrared spectrophotometer V-570). It showed good polarization separation performance with a p-polarized light transmittance of 83% and a s-polarized light transmittance of 0.3% at a wavelength of 550 nm.

[0085] (Example 2)

 On the film substrate 1A, the solution for the resin thin film obtained in Production Example 2 was applied using a die coater and dried in a 100 ° C hot air drying oven for 30 minutes to form a thin film to form a laminated film. Got. The average thickness of the thin film was 13.

 Next, the laminated film was passed through a hot air dryer in which hot air at a temperature of 140 ° C was circulated, and the shrinkage rate AL in the main shrinkage direction was AL = 32%, and the shrinkage rate in the direction perpendicular to the main shrinkage direction was Δ Μ = Shrink at 0.2%.

 When the surface of the shrink film was observed in the same manner as in Example 1, a fine uneven shape elongated in a stripe shape was formed, and the average distance between the convex vertices was 12.7 μτη, The coefficient of variation was 19.2%. The aspect ratio was 0.59. The average thickness of the thin film (second layer) under the irregular shape was 12.4 μηι, and the coefficient of variation was 5.4%. The average thickness of the second layer was 75.2% of the average height of the irregular shape.

 When haze was measured with a turbidimeter (Nippon Denshoku NDH2000 type), it was 85%. Collimated light with a spot diameter of 2 mm was incident on the shrink film thus obtained in the direction normal to the film, and the relationship between the emission angle of transmitted light and the luminance was measured. It was confirmed that the shrink film had scattering characteristics and diffraction characteristics.

 The shrink film was cut into 10 cm squares and left in an environment of 60 ° C. and 85% RH for 500 hours, but no warpage occurred.

[0086] (Example 3)

On the film substrate 1A, the solution obtained in Production Example 3 was continuously applied using a die coater. Next, the film was dried at 80 ° C. for 5 minutes, irradiated with ultraviolet rays (accumulated light amount 300 mjZcm 2 ) to cure the resin, and a thin film was formed to obtain a laminated film. Roll this laminated film It was wound up into a shape. The average thickness of the thin film after curing was 903 nm.

 Next, the laminated film was passed through a hot air dryer in which hot air at a temperature of 140 ° C was circulated, and the shrinkage rate in the main shrinkage direction Δ L = 31%, the shrinkage rate in the direction perpendicular to the main shrinkage direction Δ

Shrinkage was performed at M = 0. 1%.

[0087] The surface of the shrink film was observed in the same manner as in Example 1. As a result, a fine concavo-convex shape elongated in a stripe shape was formed, and the average distance between the convex vertices was 1.9. ^ πι, coefficient of variation was 12.8%. The aspect ratio was 0.38. The average thickness of the thin film (second layer) under the uneven shape was 938 nm, and the coefficient of variation was 8.3%. The average thickness of the second layer was 36.0% of the average height of the irregular shape.

 When haze was measured with a turbidimeter (Nippon Denshoku NDH2000 type), it was 69%. Collimated light having a spot diameter of 2 mm was incident on the obtained shrink film from the normal direction, and the relationship between the emission angle of the transmitted light and the luminance was measured. It was confirmed that the shrink film showed strong diffraction characteristics.

[0088] (Example 4)

 On the film substrate 1B, apply the solution obtained in Production Example 3, dry at 80 ° C for 5 minutes, and then irradiate ultraviolet rays at V to cure the resin and form a thin film to obtain a laminated film It was. The average thickness of the thin film after curing was 2. The average thickness of the second layer was 50.1% of the average height of the concavo-convex shape.

 Next, the laminated film is passed through a hot air dryer in which hot air at a temperature of 140 ° C is circulated, and the shrinkage rate AL in the main shrinkage direction is 36%, and the shrinkage rate in the direction perpendicular to the main shrinkage direction is Δ Μ = Shrink at 20%.

 [0089] When the surface of the shrink film was confirmed by the same method as in Example 1, a randomly distributed concavo-convex shape such as a folded stripe as shown in Fig. 3 was formed. The average distance between the ridge points was 4.5 / ζ πι and the coefficient of variation was 63%. The aspect ratio was 0.9. The average thickness of the thin film under the irregular shape was 2.5 ^ πι, and the coefficient of variation was 6.9%. When the haze was measured with a turbidimeter (Nippon Denshoku NDH2000 type), it was 82%. there were.

[0090] Collimated light having a spot diameter of 2 mm was incident on the obtained shrink film in a normal direction force and transmitted. The relationship between the emission angle of light and the brightness was measured. It was confirmed that the shrink film had scattering characteristics.

 Steel wool # 0000 was applied to the surface on which the irregular shape was formed, and was reciprocated 10 times with a load of 0.05 MPa. After that, the surface condition was visually observed, but no scratches were observed, which was the same as before the reciprocation.

[Example 5]

 On the film substrate 1C, apply the solution obtained in Production Example 3, dry at 80 ° C for 5 minutes, and further irradiate ultraviolet rays to cure the resin to form a thin film to obtain a laminated film. It was. The average thickness of the thin film after curing was 584 nm.

 Next, the laminated film was passed through a hot air dryer in which hot air at a temperature of 140 ° C was circulated, and the shrinkage rate in the main shrinkage direction Δ L = 30%, the shrinkage rate in the direction perpendicular to the main shrinkage direction Δ

M = -9. Shrink at 2%.

[0092] When the surface of the shrink film was confirmed by the same method as in Example 1, stripe-shaped uneven shapes were observed. Cracks were found in the unevenness. The average distance between convex vertices is 1.0

^ m, coefficient of variation was 13.4%. The aspect ratio was 0.8. The average thickness of the thin film under the irregular shape was 590 nm, and the coefficient of variation was 3.8%. The average thickness of the second layer was 98.3% of the average height of the concave and convex shapes.

 When haze was measured with a turbidimeter (Nippon Denshoku NDH2000 type), it was 54%.

[0093] Collimated light having a spot diameter of 2 mm was incident on the obtained shrink film in a normal direction force, and the relationship between the emission angle of the transmitted light and the luminance was measured. It was confirmed that the shrink film exhibited diffraction characteristics.

[Example 6]

 The rubbing process performed after the SiO layer was formed was the same as Example 1 except that the rubbing process was performed before the SiO layer was formed.

twenty two

 In this way, a film having an uneven shape was produced. It was confirmed that the formed uneven shape was the same as in Example 1.

 [0095] (Comparative Example 1)

The original film was cut into A4 size. This film is elongated in stripes, with a distance between the vertices of the protrusions of 10.0 ^ m, a height of the protrusions of 10 / ζ πι, and a cross-sectional shape of the protrusions of a triangle. Using a mold having a hollow structure, the mold was thermally implemented by holding at a mold temperature of 200 ° C for 5 minutes. A film having a triangular cross-section as shown in FIG. 6 and a fine concavo-convex shape elongated in a stripe in the plane and a coefficient of variation in the distance between the vertices of the protrusions of 0.1% was obtained. When the haze was measured with a turbidimeter (Nippon Denshoku NDH2000 type), it was 32%. Steel wool # 0000 was applied to the surface on which the irregular shape was formed, and was reciprocated 10 times with a load of 0.05 MPa. Later, when the surface condition was visually observed, many scratches that could be clearly confirmed were observed.

[0096] (Comparative Example 2)

 The original film was cut into A4 size. To this film, PAK-01 manufactured by Toyo Gosei Kogyo Co., Ltd. was applied with a bar coater to a dry film thickness of 5 m and dried at 80 ° C. for 5 minutes.

The mold used in Comparative Example 1 was pressed against the coated surface, and irradiated with ultraviolet rays (accumulated light amount: 300 miZcm 2 ) to cure the resin. The mold was removed, and a film having a fine concavo-convex structure with a cross-sectional structure as shown in FIG. 7 was obtained.

 When the haze was measured with a turbidimeter (Nippon Denshoku NDH2000 type), it was 32%. When the obtained film was cut into 10 cm square and left in an environment of 60 ° C and 85% RH for 500 hours, warpage occurred in the periphery.

[0097] (Comparative Example 3)

 According to the method described in JP-A-2003-266570, 100 parts by weight of polyester resin (Toyobo Byron 500) and melamine resin (produced by Dainippon Ink, Inc.)

A coating solution was prepared by dissolving 20 parts by weight and 0.25 parts by weight of para-toluenesulfonic acid.

 This coating solution was applied onto a polyethylene terephthalate film (thickness 100 / zm) with a bar coater to a dry thickness of 5 m, and dried at 100 ° C. for 5 minutes to form a thin film. This film was wound around a cylinder with a diameter of 0.3 m and left in an oven at 180 ° C for 1 minute.

When the obtained film was observed with a scanning electron microscope, a slightly wavy convex shape was observed. When measuring the surface shape in the same way as in Example 1, the distance between the vertices is as follows: The average was 16. and the coefficient of variation was 82.1%. The aspect ratio was 0.1. The film had a structure in which the surface of the polyethylene terephthalate film layer maintained the original flat shape, and only the curable resin layer was deformed.

 When haze was measured with a turbidimeter (Nippon Denshoku NDH2000 type), it was 25%. The obtained film was cut into 10 cm square and left in an environment of 60 ° C and 85% RH for 500 hours.

Claims

The scope of the claims
 [1] including a step of forming a thin film on at least one surface of a film substrate to obtain a laminate, and a step of curving the thin film by contracting the laminate in at least one axial direction in the plane. A method for producing a film having a fine uneven shape.
 [2] Shrinkage rate in the main shrinkage direction AL is the equation [1], shrinkage rate in the direction perpendicular to the main shrinkage direction.
 The method for producing a film having fine irregularities on the surface according to claim 1, wherein Δ L and Δ M satisfy Formula [3] and Formula [4] when ΔM is represented by Formula [2].
 Formula [1]: AL = (L0—LI) ZLO X 100 (L0: length before contraction in the main contraction direction, L 1: length after contraction in the main contraction direction)
 Formula [2]: ΔΜ = (MO-MD / MOX 100 (MO: length before shrinkage in the direction perpendicular to the main shrinkage direction, Ml: length after shrinkage in the direction perpendicular to the main shrinkage direction)
 Formula [3]: AL> 0
 Formula [4]: One (ALX0.3) ≤ ΔΜ ≤ AL
[3] The method for producing a film having fine irregularities on the surface according to claim 2, wherein AL and ΔΜ satisfy the formula [5].
 Formula [5]: One (ALXO.2) ≤AM≤ (ALX0.2)
[4] The method for producing a film having a fine concavo-convex shape on the surface according to claim 3, wherein the fine concavo-convex shape is a structure elongated in a stripe shape in a plane.
[5] The fine uneven shape has a coefficient of variation of the distance between the vertices of the protrusions of 40% or less.
The manufacturing method of the film which has fine uneven | corrugated shape on the surface in any one of -4.
[6] The method for producing a film having a fine concavo-convex shape on the surface according to any one of claims 1 to 5, wherein the thin film has a thickness of 1ηπι to 50 / ζπι.
[7] The thin film is made of inorganic material, and the thickness of the thin film is Inn! The method for producing a film having a fine uneven shape on the surface according to any one of claims 1 to 5, wherein the film has a thickness of ~ 500nm.
[8] The thin film also has organic substance power, and the thickness of the thin film is ΙΟΟηπ! The manufacturing method of the film which has fine uneven | corrugated shape on the surface in any one of Claims 1-5 which are -50m.
[9] The organic substance is a curable resin, and the heat treatment temperature when forming a thin film made of the curable resin is at least 5 ° C lower than the glass transition temperature of the film substrate. A method for producing a film having a fine uneven shape on the surface described.
[10] The average distance between the vertices of the fine irregularities is 50ηπ! 1 to 50 μm
The manufacturing method of the film which has fine uneven | corrugated shape on the surface in any one of -9.
[11] Film substrate strength The method for producing a film having a fine irregular shape on the surface according to any one of claims 1 to 10, which is a film which is molecularly oriented in at least one direction in the plane.
 [12] A first layer having a fine uneven shape B on the surface, and a second layer laminated on the uneven shape B and bent so as to correspond to the shape of the uneven shape B. The average distance between the vertices of the convex part is 50ηπ! A film having fine irregularities wrinkles of up to 50 μm.
 [13] The film having the fine uneven shape A according to [12], wherein the average thickness of the second layer is 10% to 100% of the average height of the fine uneven shape A.
 [14] The film having the fine concavo-convex shape A according to [12], wherein the variation coefficient of the thickness of the second layer is 20% or less.
 [15] The film having the fine concavo-convex shape A according to claim 12, wherein the fine concavo-convex shape A has a variation coefficient of the distance between the vertices of the convex portions of 80% or less.
[16] The fine uneven shape according to any one of claims 12 to 15, wherein the fine uneven shape A has a power spectrum having a spatial frequency obtained by two-dimensional Fourier transform distributed in one direction. A film having A.
[17] The fine concavo-convex shape A has a structure elongated in a stripe shape in a plane.
17. The film having the fine uneven shape A according to any one of 16.
[18] The fine concavo-convex shape A has a coefficient of variation of the distance between the vertices of the convex portions of 40% or less.
A film having the fine irregular shape A described in 12-17.
[19] The film having a fine concavo-convex shape A according to any one of claims 12 to 18, wherein the haze is 50% or more.
[20] A finolem having a fine concavo-convex shape A obtained by the production method according to any one of claims 1 to 11. [21] An optical element comprising the film having the fine concavo-convex shape A according to any one of claims 12 to 20.
PCT/JP2007/053589 2006-02-27 2007-02-27 Film having fine uneven shape and method for manufacturing same WO2007097454A1 (en)

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JP2006050644 2006-02-27

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JP2011503643A (en) * 2007-11-06 2011-01-27 エルエムエス・カンパニー・リミテッドLMS Co.,Ltd. Optical film and illumination device including the same
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JP2011096367A (en) * 2009-10-27 2011-05-12 Furukawa Electric Co Ltd:The Glass substrate, solar cell, organic el element, and manufacturing method of glass substrate
JP2011133569A (en) * 2009-12-22 2011-07-07 Oji Paper Co Ltd Uneven pattern forming sheet, optical sheet, luminance adjusting sheet, and method of manufacturing them
CN102155711A (en) * 2010-02-12 2011-08-17 中强光电股份有限公司 The optical sheet
JP2011222012A (en) * 2010-04-05 2011-11-04 Honeywell Internatl Inc Film structure having inorganic surface structure and corresponding manufacturing method
JP2011243308A (en) * 2010-05-14 2011-12-01 Jx Nippon Oil & Energy Corp Microlens for organic el element, and organic el element using it, and method of producing them
CN102436021A (en) * 2011-12-21 2012-05-02 北京康得新复合材料股份有限公司 Prism-structure bright enhancement film with raised structures in non-uniform distribution
EP2458412A1 (en) * 2010-11-24 2012-05-30 Université de Liège Method for manufacturing an improved optical layer of a light emitting device, and light emitting device with surface nano-micro texturation based on radiation speckle lithography.
JP2012111086A (en) * 2010-11-22 2012-06-14 Oji Paper Co Ltd Irregular pattern formation sheet, method of manufacturing the same, process sheet original plate for duplicating the irregular pattern formation sheet and optical element
JP2012163652A (en) * 2011-02-04 2012-08-30 Konica Minolta Advanced Layers Inc Optical film, manufacturing method of optical film, polarizing plate and image display device
JP2013035197A (en) * 2011-08-08 2013-02-21 Tokyo Univ Of Science Method for producing geometrically minute uneven structure and sensor
JP2013047821A (en) * 2012-10-04 2013-03-07 Nitto Denko Corp Antiglare hard coat film, and polarizing plate and image display apparatus using the same
JP2013101359A (en) * 2012-12-14 2013-05-23 Oji Holdings Corp Thin metallic wire sheet having rugged shape
JP2013164594A (en) * 2013-02-27 2013-08-22 Oji Holdings Corp Method for manufacturing fine rugged sheet
JP2013178550A (en) * 2013-04-23 2013-09-09 Oji Holdings Corp Metal thin line sheet having rugged shape
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JP2014153530A (en) * 2013-02-08 2014-08-25 National Institute Of Advanced Industrial & Technology Light diffusion variable device capable of reversibly changing light diffusion state
JP2015052808A (en) * 2013-03-18 2015-03-19 王子ホールディングス株式会社 Body having fine protrusion and recession on surface and method for manufacturing body having fine protrusion and recession on surface
JP2015059977A (en) * 2013-09-17 2015-03-30 富士フイルム株式会社 Method of manufacturing transparent micro-relief structure
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US9030664B2 (en) 2010-12-30 2015-05-12 Samsung Corning Precision Materials Co., Ltd. Apparatus for measuring transmissivity of patterned glass substrate
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US10317578B2 (en) 2014-07-01 2019-06-11 Honeywell International Inc. Self-cleaning smudge-resistant structure and related fabrication methods

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JPS63301988A (en) * 1987-06-02 1988-12-08 Fuji Seal Ind Co Ltd Manufacture of deposit label
JPH0247057A (en) * 1988-08-08 1990-02-16 Toray Ind Inc Surface roughened film composite sheet and manufacture thereof
JP2000206317A (en) * 1999-01-14 2000-07-28 Dainippon Printing Co Ltd Glare shielding film, polarizing plate, display device and manufacture of glare shielding film
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JP2008304651A (en) * 2007-06-07 2008-12-18 Oji Paper Co Ltd Method of manufacturing uneven pattern formed sheet, and uneven pattern formed sheet
JP2009096081A (en) * 2007-10-17 2009-05-07 Mitsubishi Rayon Co Ltd Periodic fine irregularity structure material
US8777474B2 (en) 2007-11-06 2014-07-15 Lms Co., Ltd. Optical film and lighting device comprising the same
JP2011503643A (en) * 2007-11-06 2011-01-27 エルエムエス・カンパニー・リミテッドLMS Co.,Ltd. Optical film and illumination device including the same
JP2009122298A (en) * 2007-11-14 2009-06-04 Oji Paper Co Ltd Polarizing plate, and method for manufacturing same
JP2011040411A (en) * 2008-04-22 2011-02-24 Nippon Zeon Co Ltd Organic electroluminescent light source device
US8502440B2 (en) 2008-04-22 2013-08-06 Zeon Corporation Organic electroluminescent light source
JP2009283264A (en) * 2008-05-22 2009-12-03 National Institute Of Advanced Industrial & Technology Micro topography switch array
JP2009288655A (en) * 2008-05-30 2009-12-10 Nitto Denko Corp Antiglare hard coat film, polarizing plate and image display apparatus using the same, method for evaluating the same and method for producing the same
JP2010085990A (en) * 2008-09-03 2010-04-15 Asahi Kasei E-Materials Corp Wire grid polarizing plate
CN101846754A (en) * 2009-03-25 2010-09-29 住友化学株式会社 Anti-dazzle film
CN101846754B (en) * 2009-03-25 2014-08-13 住友化学株式会社 Anti-dazzle film
JP2010266483A (en) * 2009-05-12 2010-11-25 Oji Paper Co Ltd Method for producing metal thin line sheet having rugged shape, and metal thin line sheet having rugged shape
JP2010266479A (en) * 2009-05-12 2010-11-25 Oji Paper Co Ltd Method for producing fine rugged sheet
JP2011096367A (en) * 2009-10-27 2011-05-12 Furukawa Electric Co Ltd:The Glass substrate, solar cell, organic el element, and manufacturing method of glass substrate
JP2011133569A (en) * 2009-12-22 2011-07-07 Oji Paper Co Ltd Uneven pattern forming sheet, optical sheet, luminance adjusting sheet, and method of manufacturing them
CN102155711A (en) * 2010-02-12 2011-08-17 中强光电股份有限公司 The optical sheet
JP2011222012A (en) * 2010-04-05 2011-11-04 Honeywell Internatl Inc Film structure having inorganic surface structure and corresponding manufacturing method
JP2011243308A (en) * 2010-05-14 2011-12-01 Jx Nippon Oil & Energy Corp Microlens for organic el element, and organic el element using it, and method of producing them
JP2010211234A (en) * 2010-05-24 2010-09-24 Asahi Kasei E-Materials Corp Method for manufacturing wire grid polarizer
JP2012111086A (en) * 2010-11-22 2012-06-14 Oji Paper Co Ltd Irregular pattern formation sheet, method of manufacturing the same, process sheet original plate for duplicating the irregular pattern formation sheet and optical element
EP2458412A1 (en) * 2010-11-24 2012-05-30 Université de Liège Method for manufacturing an improved optical layer of a light emitting device, and light emitting device with surface nano-micro texturation based on radiation speckle lithography.
US9030664B2 (en) 2010-12-30 2015-05-12 Samsung Corning Precision Materials Co., Ltd. Apparatus for measuring transmissivity of patterned glass substrate
JP2012163652A (en) * 2011-02-04 2012-08-30 Konica Minolta Advanced Layers Inc Optical film, manufacturing method of optical film, polarizing plate and image display device
JP2013035197A (en) * 2011-08-08 2013-02-21 Tokyo Univ Of Science Method for producing geometrically minute uneven structure and sensor
CN102436021A (en) * 2011-12-21 2012-05-02 北京康得新复合材料股份有限公司 Prism-structure bright enhancement film with raised structures in non-uniform distribution
CN102436021B (en) * 2011-12-21 2014-10-22 北京康得新复合材料股份有限公司 Prism-structure bright enhancement film with raised structures in non-uniform distribution
JP2013047821A (en) * 2012-10-04 2013-03-07 Nitto Denko Corp Antiglare hard coat film, and polarizing plate and image display apparatus using the same
JP2013101359A (en) * 2012-12-14 2013-05-23 Oji Holdings Corp Thin metallic wire sheet having rugged shape
JP2014153530A (en) * 2013-02-08 2014-08-25 National Institute Of Advanced Industrial & Technology Light diffusion variable device capable of reversibly changing light diffusion state
JP2013164594A (en) * 2013-02-27 2013-08-22 Oji Holdings Corp Method for manufacturing fine rugged sheet
JP2015052808A (en) * 2013-03-18 2015-03-19 王子ホールディングス株式会社 Body having fine protrusion and recession on surface and method for manufacturing body having fine protrusion and recession on surface
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JPWO2015046047A1 (en) * 2013-09-25 2017-03-09 株式会社きもと Hard coat film and display element with surface member
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JP2014139017A (en) * 2014-03-05 2014-07-31 Oji Holdings Corp Method for manufacturing fine rugged sheet
US10136638B2 (en) 2014-04-22 2018-11-27 Sharp Kabushiki Kaisha Synthetic polymer film whose surface has microbicidal activity, multilayer structure having synthetic polymer film, sterilization method with the use of surface of synthetic polymer film, method for reactivating surface of synthetic polymer film, mold for production of synthetic polymer film, and mold manufacturing method
US10278387B2 (en) 2014-04-22 2019-05-07 Sharp Kabushiki Kaisha Synthetic polymer film whose surface has microbicidal activity, multilayer structure having synthetic polymer film, sterilization method with the use of surface of synthetic polymer film, method for reactivating surface of synthetic polymer film, mold for production of synthetic polymer film, and mold manufacturing method
US10071175B2 (en) 2014-04-28 2018-09-11 Sharp Kabushiki Kaisha Filter and container having microbicidal activity
US10317578B2 (en) 2014-07-01 2019-06-11 Honeywell International Inc. Self-cleaning smudge-resistant structure and related fabrication methods
US10251393B2 (en) 2014-11-20 2019-04-09 Sharp Kabushiki Kaisha Synthetic polymer film having surface provided with bactericidal activity
WO2016080245A1 (en) * 2014-11-20 2016-05-26 シャープ株式会社 Synthetic polymer film having surface provided with bactericidal activity
WO2016175170A1 (en) * 2015-04-30 2016-11-03 シャープ株式会社 Synthetic high polymer film having surface provided with antiseptic property
JPWO2016175170A1 (en) * 2015-04-30 2018-04-12 シャープ株式会社 Synthetic polymer membrane having a surface with bactericidal action
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