JP2013164594A - Method for manufacturing fine rugged sheet - Google Patents

Method for manufacturing fine rugged sheet Download PDF

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JP2013164594A
JP2013164594A JP2013037977A JP2013037977A JP2013164594A JP 2013164594 A JP2013164594 A JP 2013164594A JP 2013037977 A JP2013037977 A JP 2013037977A JP 2013037977 A JP2013037977 A JP 2013037977A JP 2013164594 A JP2013164594 A JP 2013164594A
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sheet
heat
method
direction
fine
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JP5673706B2 (en
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Yoshiharu Nishigori
義治 錦織
Toshiki Okayasu
俊樹 岡安
Kuniaki Muto
国昭 武藤
Yukie Otsuka
ゆき恵 大塚
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Oji Holdings Corp
王子ホールディングス株式会社
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Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a nano buckling sheet having a concavo-convex pattern shape such as an antireflective body, a phase difference plate, a light diffusing plate, and super water-repellent.
A method for producing a nano buckling sheet, wherein a continuous sheet is used as the MD direction heat-shrinkable film, and at least one or more hard layers are provided on one or both sides of the MD direction heat-shrinkable film. It is a manufacturing method of the nano buckling sheet which consists of the process of manufacturing a lamination sheet, and the process of heat-shrinking the said continuous lamination sheet continuously in a heat contraction zone.
[Selection] Figure 2

Description

The present invention relates to a method for producing a sheet having an uneven pattern shape.

It is known that a concavo-convex pattern formed of fine wavy concavo-convex patterns is formed on the surface, and the concavo-convex pattern forming sheet having an average pitch of the concavo-convex pattern equal to or less than the wavelength of visible light can be used as an optical element such as an antireflection body or a retardation plate. (Non-Patent Document 1).
Moreover, it is known that the uneven | corrugated pattern formation sheet whose average pitch of the said uneven | corrugated pattern is 1-10 micrometers can be utilized as a light diffuser (patent documents 1, 2).

As a method for producing such a concavo-convex pattern forming sheet, a photolithography method using visible light using a pattern mask, an ultraviolet laser irradiation method and an electron beam lithography method capable of finer processing are known.
In these methods, a resist layer formed on a substrate is exposed to visible light, ultraviolet laser light, or electron beam and developed to form a resist pattern layer. Using this resist pattern layer as a mask, irregularities are formed by dry etching or the like. Form a shape. However, these methods have a problem that they are complicated.
Moreover, the method of using the heat shrinkable film of CD direction is disclosed as a manufacturing method of a fine uneven | corrugated sheet (patent document 3). However, since this method shrinks in the machine width direction, a special manufacturing machine equipped with clips on both edges is required in order to prevent wide wrinkling as well as a wide manufacturing apparatus, resulting in poor productivity. In addition, there is a problem that the fine uneven shape obtained can only be in the MD direction.

JP-A-10-123307 Japanese Patent Application Laid-Open No. 2006-261064 JP 2008-304651 A

Hisao Kikuta and Koichi Iwata, "Optics", published by The Optical Society of Japan, Vol. 27, No. 1, 1998, p. 12-17

The present invention has been made in view of the above circumstances, and produced a concavo-convex pattern forming sheet that exhibits excellent performance when used as an optical element such as an antireflective body, a phase difference plate, or a light diffusing plate as a continuous sheet. Provide a way to do it.

The present invention has the following configuration.
[1] A method for producing a fine uneven sheet, wherein a continuous sheet is used as the MD-direction heat-shrinkable film, and at least one hard layer is provided on one or both sides of the MD-direction heat-shrinkable film. And a step of continuously heat-shrinking the continuous laminated sheet in a heat shrinkage zone.
[2] The method for producing a fine concavo-convex sheet according to [1], wherein in the heat shrinking step, the continuous laminated sheet is shrunk mainly in the MD direction.
[3] The method for producing a fine uneven sheet according to [1] or [2], wherein the shrinkage ratio in the MD direction in the first step is in the range of 10% to 95%.
[4] The production of the fine uneven sheet according to any one of [1] to [3], wherein the ratio of the inlet line speed to the outlet line speed of the heat shrink zone in the first step is 0.1 to 0.95. Method.
[5] A fine concavo-convex sheet, wherein the fine concavo-convex produced by the production method of [1] to [4] is stretched in the CD direction.

In this invention, the sheet | seat which gave the fine uneven | corrugated pattern on the surface can be easily formed in a large area, and the uneven | corrugated pattern formation sheet which can be utilized suitably for an optical element etc. can be manufactured simply and in large quantities.

It is sectional drawing which shows the lamination sheet in one Embodiment of the manufacturing method of the fine uneven | corrugated sheet of this invention. It is an expansion perspective view which expands and shows a part of one embodiment of the fine unevenness sheet of the present invention. Fourier transform image of atomic force microscope image Y "F-ZF diagram It is sectional drawing when the fine uneven | corrugated sheet | seat of FIG. 2 is cut | disconnected in the direction (MD direction) orthogonal to the direction (CD direction) of a fine uneven | corrugated shape. It is a figure explaining an example of the manufacturing method of a fine unevenness | corrugation replica.

First, the fine concavo-convex sheet of the present invention, as shown in FIG. 1, is a laminated sheet 10a in which at least one smooth hard layer 12a is provided on one side or both sides of a heat shrinkable film 11 (in FIG. 1, the hard layer is a hard layer). It is prepared by heating and shrinking in at least one direction. The hard layer of the laminated sheet is meandered and deformed by heat shrinking, and the fine uneven shape 13 having an uneven pattern as shown in FIG. 2 is defined as the fine uneven sheet 10 formed on the surface of the heat shrinkable film 11.
When it is desired to provide a fine uneven shape on one side of the fine uneven sheet, a hard layer is provided on one side of the heat-shrinkable film, and when a fine uneven shape is provided on both sides, a hard layer is provided on both sides of the heat-shrinkable film. When providing fine uneven | corrugated shape on both surfaces, the magnitude | size of the fine unevenness | corrugation of each surface may differ. Here, the smooth hard layer 12a of the laminated sheet 10a before heat shrinkage preferably has a center line average roughness of 0.1 μm or less as described in JIS B 0601. “Meandering deformation” refers to a deformation that forms a wavy uneven pattern as shown in FIG. In order to obtain a good fine uneven sheet, in the present invention, it is necessary to prevent the hard layer from being cracked during meandering deformation.

(Manufacturing method of fine uneven sheet)
As a method for forming the smooth hard layer 12a on the heat-shrinkable film, in the case of (A) a metal or metal compound, for example, (1) a metal or metal compound is vapor-deposited on the surface of the heat-shrinkable film 11. (2) A method of applying a metal or metal compound nanoparticle dispersion on the surface of the heat-shrinkable film 11 and drying it, (3) Vapor deposition or coating on the surface of the heat-shrinkable film 11 There are a method of modifying the processed metal or metal compound by further chemical reaction and making it a hard layer, and a method of (4) laminating a smooth hard layer prepared in advance on the surface of the heat shrinkable film 11. Can be mentioned. In the case of (B) resin, for example, (5) a method of applying a resin solution or dispersion and drying the solvent, (6) a smooth surface prepared in advance on the surface of the heat-shrinkable film 11 The method etc. which use the hard layer 12a as a lamination sheet are mentioned.
As a method for depositing the hard layer, it is preferable to use a known deposition method. Known vapor deposition methods include physical vapor deposition methods and chemical vapor deposition methods. Physical vapor deposition methods include resistance heating vapor deposition, electron beam vapor deposition, high frequency induction vapor deposition, molecular beam epitaxy vapor deposition, ion plating vapor deposition, and ion beam deposition vapor deposition. Preferred examples include sputtering deposition. Preferred examples of the chemical vapor deposition method include thermal CVD, plasma CVD, photo CVD, epitaxial CVD, atomic layer CVD, metal organic chemical vapor deposition, catalytic chemical vapor deposition, and the like. Particularly preferred vapor deposition methods are resistance heating vapor deposition, electron beam vapor deposition, and sputter vapor deposition. Only a necessary portion can be provided with a hard layer by vapor deposition, and a mask such as a film or oil can be used.
As a method for coating the hard layer, a known coating method can be used. For example, air knife coating, roll coating, blade coating, Mayer bar coating, gravure coating, spray coating, cast coating, curtain coating, die slot coating, gate roll coating, size press coating, spin coating, dip coating, inkjet coating, flexographic coating Etc. can be mentioned preferably. A hard layer can be provided by coating only where necessary, and the above-described coating method can also be used, but a gravure coating, ink jet coating, and flexo coating, which also serve as a printing method, are preferable.

As a method for heat-shrinking the laminated sheet of the present invention, for example, the following method can be applied.
It is preferable to manufacture with a machine having at least three zones of unwinding zone, heat shrinkage zone, and finishing zone. Set the winding of the continuous laminated sheet in the unwinding zone, feed out, the continuous laminated sheet in the heat shrinking zone shrinks mainly in the MD direction and deforms meandering, then in the finishing zone with the winding device A fine concavo-convex sheet is manufactured in a wound form, or a continuous fine concavo-convex sheet is cut into a sheet instead of a winding device.
In the present invention, in order to control the shrinkage rate in the MD direction due to heating, it is preferable to operate at a ratio of the outlet line speed / inlet line speed of the heat shrinkage zone of 0.05 to 0.9, 0.1 to 0. 7 is more preferable, and 0.2 to 0.55 is particularly preferable. If the ratio of the outlet line speed / inlet line speed is small, there is a problem that the shrinkage rate in the MD direction is too small. If the ratio of the outlet line speed / inlet line speed is too large, it becomes difficult to control the inlet line speed and the outlet line speed. Absent. A known method can be used to change the inlet line speed and the outlet line speed. For example, a draw method, a dancer method, a method using at least two roll circumferential speed differences, a method of gripping both end faces of a continuous sheet with a plurality of clips, and narrowing the interval between the clips in the flow direction, etc. are preferably mentioned. it can. The heating shrinkage zone can be a hot air dryer, drum dryer, infrared dryer, far-infrared dryer, burner dryer, steam dryer, or a dipping method in a hot solvent containing hot water. A known method may be used for sheet conveyance, and examples thereof include roll support conveyance, floating conveyance, belt conveyance, canvas conveyance, conveyance while grasping both end faces of a continuous sheet, and a plurality of clips.

In the fine uneven sheet of the present invention, the direction of the fine uneven shape is mainly the CD direction. As shown in FIG. 2, the fine uneven sheet of the present invention has a direction in which fine uneven peaks (peak portions 13a) are connected in one direction. The valley (the valley bottom 13b) also has a direction that is continuous in one direction. In the present invention, the direction in which the peaks and valleys are connected is referred to as the direction of fine unevenness. There are variations in the direction of the fine uneven shape, and the direction of the fine uneven shape of the present invention may be mainly the CD direction.
The degree of variation in the direction of the fine concavo-convex shape can also be grasped by the orientation degree of the fine concavo-convex shape shown below.
When the degree of orientation of the fine concavo-convex shape of the present invention is too large, the directionality of the fine concavo-convex shape is lowered. Therefore, the degree of orientation of the fine concavo-convex shape of the present invention is preferably 1.0 or less, more preferably 0. 0.7 or less, particularly preferably less than 0.4. In addition, the definition of the orientation degree of the fine unevenness | corrugation shape of this invention is as follows.
A height image is observed (converted to a gray scale image) with an atomic force microscope, and the observed gray scale image is subjected to Fourier transform. This Fourier transform image includes information on the pitch and orientation of the fine concavo-convex shape. In addition, when it is not the magnitude | size of the unevenness | corrugation which can be observed with an atomic force microscope, an optical microscope image can be used.

The degree of orientation of the present invention is obtained by taking out the orientation information of the Fourier transform image. Specifically, this will be described with reference to FIG. If the maximum luminance part of the Fourier transform image is not on the XF axis of the XF-YF coordinate plane of the Fourier transform image, rotate the center of the Fourier transform image by θ to match the maximum brightness part on the XF axis. (The reason why the θ rotation is necessary is that the sample direction is shifted because the sample is set by a human hand in the atomic force microscope observation). Many Fourier transform images have two maximum luminance portions, and should have a position rotated by approximately 180 ° around the origin. Any one of the maximum luminance portions can be arbitrarily selected and matched with the XF axis. FIG. 3 is a Fourier transformed image rotated by θ. Thereafter, a Fourier transformed image rotated by θ is referred to as a Fourier transformed image unless otherwise noted. Draw an auxiliary line Y'F parallel to the YF axis passing through (XFmax, YFmax), Y'F with the auxiliary line Y'F as the horizontal axis and the luminance (ZF axis) on the auxiliary line Y'F as the vertical axis -Create a ZF diagram. A Y ″ F-ZF diagram (FIG. 4) is created by dividing the Y′F axis value of this Y′F-ZF diagram by the average pitch A. The horizontal axis of FIG. 4 includes an index indicating the orientation of the fine uneven shape. The half width W1 of the peak in the plot of FIG. 4 (the width of the peak at a height at which the frequency is half the maximum value) represents the degree of orientation of the fine concavo-convex shape of the present invention. The larger the full width at half maximum W1, the more the orientation is dispersed, and the degree of variation in the direction of the fine concavo-convex shape.

The average pitch A of the present invention is an average value of the pitches A1, A2, A3..., And is obtained using a Fourier transform image (for example, FIG. 3) in the same manner as when the degree of orientation of the fine concavo-convex shape is obtained. It is preferable. As shown in FIG. 3, the frequency is expressed by shading on the XF-YF coordinate plane of the Fourier transform image. The frequency of the ZF axis information of the Fourier transform is smoothed as necessary, and the position (XFmax, YFmax) indicating the maximum frequency of the portion excluding the center of the Fourier transform image is the average pitch A = 1 / {√ of the present invention. (XFmax2 + YFmax2)}. The average pitch A is preferably 1 nm to 100 μm, more preferably 10 nm to 20 μm. In particular, when used as an optical element that needs to avoid light diffraction such as antireflection, the average pitch A is more preferably 1000 nm or less, and particularly preferably 200 nm or less. In particular, when used as an optical element that is expected to have light diffusibility and light collecting property, the average pitch A is more preferably 500 nm or more, and particularly preferably 1 μm to 10 μm. Further, the pitches A1, A2, A3,... May be continuously changed after satisfying that the average pitch A is 1 nm to 100 μm.
The average depth B of the fine concavo-convex shape of the present invention is a reference parallel to the surface direction of the entire fine concavo-convex sheet 10 when a cross section (see FIG. 5) obtained by cutting the fine concavo-convex sheet 10 along the length direction is viewed. The average value (BAV) of the lengths B1, B2, B3... From the line L1 to the tops of the fine irregularities and the lengths b1, b2, b3. It is the difference (bAV−BAV) from the average value (bAV).
In the present invention, in order to improve the performance of the optical element or the like, the ratio B / A between the average depth B and the average pitch A is preferably 0.1 or more, more preferably 0.3 or more. 0.7 or more is particularly preferable.

The heat shrinkable film used in the present invention is preferably an MD direction heat shrinkable film. The MD direction heat-shrinkable film of the present invention is a film that shrinks mainly in the MD direction by heating. The MD direction heat-shrinkable film needs to stretch in the CD direction by heating or to shrink at a shrinkage rate smaller than that in the MD direction. If the shrinkage rate in the CD direction becomes larger than the shrinkage rate in the MD direction, the shape direction of the fine irregularities becomes difficult to become the CD direction, so the shrinkage rate in the CD direction may be less than one-fourth of the shrinkage rate in the MD direction. Preferably, it is 1/10 or less, more preferably 1/50 or less. When extending in the CD direction, the shape direction of the fine irregularities does not become difficult to become the CD direction, so there is no particular limitation. Here, the shrinkage rate is (length before shrinkage−length after shrinkage) / (length before shrinkage) × 100 (%).
The MD direction heat shrinkable film of the present invention preferably has a shrinkage rate in the MD direction by heating of 10% or more. If it is less than 10%, the shape direction of the fine irregularities becomes the CD direction, and the average depth B is insufficient. The average depth B greatly affects the shrinkage rate. A more preferable shrinkage ratio in the MD direction of the present invention is 30% or more, and a particularly preferable shrinkage ratio is 45% or more. Although there is no upper limit of the shrinkage rate, if the shrinkage rate is too large, the productivity is extremely lowered, so that it is preferably 95% or less, and more preferably 80% or less. The temperature at which the heat shrinkage of the MD heat-shrinkable film of the present invention starts is preferably 50 ° C. or higher, more preferably 90 ° C. or higher, and particularly preferably 130 ° C. or higher. If the temperature at which heat shrinkage starts is too low, the heat shrinkable film tends to shrink when the hard layer is provided, which is not preferable.

The MD direction heat-shrinkable film of the present invention is preferably stretched only in the MD direction during film production. As a method of stretching only in the MD direction, a known method can be used. For example, a method of stretching an unstretched film in the MD direction using a peripheral speed difference of a roll or a tenter that grips a nonstretched film with a clip does not change the width. The method of opening the gap of the clip of the flow direction can be mentioned. Also in the inflation method, it can be produced by increasing the draw ratio in the flow direction. There is no restriction | limiting in particular in the manufacturing method of an unstretched film, A well-known method can be used. Examples thereof include a melt extrusion method using a T die (smoothing or cooling can be performed with a casting roll after the melt extrusion), a method of dissolving and casting in a solvent, and the like. The unstretched film may be a single layer or a multilayer of two or more layers. In the case of a multilayer, the polymer composition of each layer may be different.
After stretching only in the MD direction, heat treatment such as thermal relaxation and electron beam irradiation treatment can be used without any limitation, and there are no restrictions on surface wettability improvement treatment such as corona discharge treatment or plasma treatment. Can be done without receiving. In order to prevent blocking, for example, a knurling process can be applied to both ends of the film.
As a material for the MD direction heat-shrinkable film, known polymers can be used. Preferably, polyolefins including polyesters such as polyethylene terephthalate and polyethylene naphthalate, polystyrenes, polyethylenes, polypropylenes, and cyclopolyolefins are used. Examples thereof include polyvinyl, alcohol, polycarbonate, polyvinyl chloride, nylon, and polyacetylacetate, and polyester, polyolefin, and polycarbonate are more preferable. These polymers may be homopolymers or copolymers. Two or more kinds of polymers can be mixed and used. Moreover, a well-known antiblocking agent (For example, a silica can be mentioned as an inorganic pigment type | system | group), antioxidant, a plasticizer, a lubricant, and an antistatic agent can be mix | blended as needed.

In the present invention, a commercially available MD direction polyester shrink film, MD direction polystyrene shrink film, MD direction polyolefin shrink film, MD direction polycarbonate shrink film, MD direction polyvinyl chloride shrink film is preferable as the MD direction heat shrinkable film. Can be used.
The MD direction heat-shrinkable film of the present invention is preferably a continuous sheet, and particularly preferably handled as a winding. Since the productivity can be increased by using a continuous sheet, it is advantageous in terms of industry and price. In the case of a single sheet instead of a continuous sheet, the productivity is low because batch production is performed.

The laminated sheet of the present invention in which at least one smooth hard layer is provided on one side or both sides of the heat-shrinkable film is preferably a continuous sheet.
The hard layer of the present invention is composed of at least one selected from a metal, a metal compound, or a resin having a glass transition temperature that is 3 ° C. higher than the heat shrinkage temperature of the heat shrinkable film. With such a configuration, when the laminated sheet is heated and shrunk, the elastic modulus of the hard layer can be made larger than that of the heat-shrinkable film. Can be easily formed.

As metals that can be used for the hard layer, the elastic modulus does not become excessively high, and fine irregularities can be formed more easily, so gold, aluminum, silver, carbon, copper, germanium, indium, magnesium, niobium, palladium, lead It is preferably at least one metal selected from the group consisting of platinum, silicon, tin, titanium, vanadium, zinc, bismuth and nickel. The metal here includes a semi-metal.

In addition, as a metal compound, for the same reason as described above, titanium oxide, aluminum oxide, zinc oxide, magnesium oxide, tin oxide, copper oxide, indium oxide, cadmium oxide, lead oxide, silicon oxide, barium fluoride, fluoride It is preferably at least one metal compound selected from the group consisting of calcium, magnesium fluoride, zinc sulfide, ITO, and gallium arsenide. Among these, titanium oxide is preferable because it is a photocatalyst that decomposes organic substances attached to the surface when exposed to light and has a self-cleaning function.

Further, the resin may be a resin having a glass transition temperature higher by 3 ° C. or more than the heat shrinkage temperature of the heat shrinkable film. For example, polyvinyl alcohol, polystyrene, acrylic resin, styrene-acryl copolymer, styrene-acrylonitrile. Copolymers, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycarbonate, polyethersulfone, polyimide, fluororesin, silicone resin and the like may be mentioned, and two or more kinds of resins may be mixed.

When the hard layer is a metal or a metal compound, the thickness is preferably 2 μm or less. When the hard layer is a resin, the thickness is preferably 10 μm or less. This is because if the thickness of the hard layer is too thick, the hard layer may break during meandering deformation. These hard layers may have pinholes. In order to obtain a single-sided fine uneven shape, the size of each pinhole is preferably 1/10 or less of the average pitch of the fine uneven sheet.
The average pitch A of the present invention increases as the elastic modulus of the hard layer increases or the thickness of the hard layer increases.
In the present invention, a primer layer may be formed between the heat-shrinkable film and the hard layer for the purpose of improving adhesion.

ADVANTAGE OF THE INVENTION According to this invention, the fine uneven sheet | seat excellent in performance as optical elements, such as an antireflection body, a phase difference plate, and a light diffusing body, can be manufactured simply and in a large area. Moreover, it can utilize also for the wire grid polarizing plate which provided the metal fine wire using this fine uneven | corrugated shape. In addition to these optical elements, packaging materials, abrasive sheets, catalyst sheets with a catalyst on the surface of fine irregularities using a large specific surface area, photocatalytic sheets, electrode sheets with electrode agents, and other uses It can also be used for cell culture sheets, fuel cell electrolyte membranes, release films, anti-blocking films, easy-adhesion films, printability improving films, and the like. Moreover, the utilization method, such as the fine flow path through which gas or a liquid flows between the slight unevenness of a fine unevenness | corrugation sheet | seat, can be mentioned. Of course, the present invention is not limited to these applications.

(Antireflection body)
The antireflection body of the present invention includes the above-described fine uneven sheet, the average pitch A is 1 μm or less, and the ratio B / A of the average depth B to the average pitch A is 0.1 or more.
In the antireflection body of the present invention, another layer may be provided on one side or both sides of the fine uneven sheet. For example, the surface on the side where the fine unevenness is formed may be provided with an antifouling layer having a thickness of about 1 to 5 nm containing a fluororesin or a silicone resin as a main component in order to prevent contamination of the surface. Good.

The antireflective body of the present invention exhibits an intermediate refractive index between the refractive index of air and the refractive index of the fine uneven sheet (refractive index of the heat shrinkable film) in the fine uneven portion, and the intermediate refractive index is It changes continuously. Moreover, the average pitch A is 1 μm or less, and the ratio B / A between the average depth B and the average pitch A is 0.1 or more. From these things, the reflectance of light can be made especially low. As described above, the average pitch A is as short as 1 μm or less, and the ratio B / A between the average depth B and the average pitch A is as deep as 0.1 or more, so that the intermediate refractive index is continuously increased. This is because the changing portion becomes longer in the thickness direction, and the effect of suppressing the reflection of light can be remarkably exhibited.

Such an antireflection body is attached to, for example, an image display device such as a liquid crystal display panel or a plasma display, a light emitting portion tip of a light emitting diode, a surface of a solar cell panel, or the like. When it is attached to the image display device, it is possible to prevent reflection of illumination, so that the visibility of the image is improved. When it is attached to the tip of the light emitting part of the light emitting diode, the light extraction efficiency is improved. When it is attached to the surface of the solar cell panel, the amount of light taken in increases, so that the power generation efficiency of the solar cell is improved.

(Phase difference plate)
In the retardation plate of the present invention, the average pitch A of the fine uneven sheet is 1 μm or less, and the ratio B / A of the average depth B to the average pitch A is 0.1 or more. Also in the retardation plate of the present invention, other layers may be provided on one side or both sides of the fine concavo-convex sheet in the same manner as the antireflector, for example, the antifouling surface on the side where the fine concavo-convex shape is formed. A layer may be provided.

In the phase difference plate of the present invention, the effect of causing the phase difference can be exhibited remarkably. As described above, the average pitch A is as short as 1 μm or less, and the ratio B / A between the average depth B and the average pitch A is as deep as 0.1 or more. This is because the portions where the shape irregularities are alternately arranged become longer in the thickness direction, and the portion showing the optical anisotropy becomes longer. Further, when the average pitch A is approximately equal to or less than the wavelength of visible light, an equivalent phase difference can be generated over a wide visible light wavelength region.

(Light diffuser)
In the light diffuser of the present invention, the average pitch A exceeds 1 μm and is 20 μm or less, and the ratio B / A of the average depth B to the average pitch A is 0.1 or more.
In the present invention, since an MD direction heat shrinkable film is used, anisotropy appears in light diffusibility.

In the light diffuser of the present invention, the heat-shrinkable film has a light diffusing agent and an organic compound made of an inorganic compound within a range that does not significantly impair optical characteristics such as light transmittance for the purpose of further enhancing the light diffusing effect. An organic light diffusing agent or fine bubbles can be contained.

(Process element plate for optical element production and fine uneven replica)
An optical element manufacturing process sheet original plate (hereinafter referred to as a process sheet original plate) of the present invention is provided with the above-described fine unevenness sheet of the present invention, and a fine unevenness uneven pattern is formed by the following method. By transferring to other materials, it is possible to create a fine concavo-convex replica in which a concavo-convex pattern having the same average pitch and average depth as the process sheet original plate is formed on the surface, an antireflection body, a retardation plate, a light diffuser, etc. The concavo-convex pattern forming sheet that can be used as an optical element or the like is used as a mold for manufacturing a large area with a large area.

Examples of a specific method for producing a fine uneven replica using a process sheet precursor include the following methods (a) to (c).
(A) The uncured ionizing radiation curable resin is applied to the surface on which the concave and convex pattern of the process sheet original plate is formed, and the cured coating film is irradiated with ionizing radiation to cure the curable resin. A method of peeling from the process sheet master. Here, the ionizing radiation is usually ultraviolet rays or electron beams, but in the present invention, it includes visible rays, X-rays, ion rays and the like.
(B) The uncured liquid thermosetting resin is applied to the surface of the process sheet original plate on which the concave / convex pattern is formed, heated to cure the liquid thermosetting resin, and then the cured coating film is processed. A method of peeling from the original sheet.
(C) A sheet-shaped thermoplastic resin is brought into contact with the surface of the process sheet original plate on which the concave and convex pattern is formed, and the thermoplastic resin is heated and softened while being pressed against the process sheet original plate, and then cooled. A method of peeling a cooled sheet-like thermoplastic resin from a process sheet precursor.

Moreover, a secondary process sheet | seat is produced using a process sheet | seat original plate, and a fine uneven | corrugated replica can also be manufactured using the secondary process sheet | seat. Specific methods using the secondary process sheet include the following methods (d) to (f).
(D) On the surface of the process sheet original plate on which the concave / convex pattern is formed, metal plating such as nickel is performed, a plating layer (material for transferring the concave / convex pattern) is laminated, and the plating layer is peeled off from the process sheet original plate. The secondary process sheet is prepared, and then the uncured ionizing radiation curable resin is applied to the surface of the secondary process sheet that has been in contact with the concavo-convex pattern, and the curable composition is irradiated with ionizing radiation. A method of peeling the cured coating film from the secondary process sheet after curing the resin.
(E) A secondary process sheet is prepared in the same manner as in (d), and an uncured liquid thermosetting resin is applied to the surface of the secondary process sheet that has been in contact with the concavo-convex pattern. A method of peeling the cured coating film from the secondary process sheet after curing the resin.
(F) A secondary process sheet is produced in the same manner as in (d), and a sheet-like thermoplastic resin is brought into contact with the surface of the secondary process sheet that has been in contact with the concavo-convex pattern. A method of heating and softening while pressing against the secondary process sheet, cooling, and peeling the cooled sheet-like thermoplastic resin from the secondary process sheet.

A specific example of the method (a) will be described. As shown in FIG. 6, first, an uncured liquid ionizing radiation curable resin 113 c is applied by a coater 120 to the surface of the web-shaped process sheet original plate 110 on which the uneven pattern 113 a is formed. Next, the process sheet 110 coated with the curable resin is pressed by passing it through a roll 130, and the curable resin is filled into the concavo-convex pattern 113 a of the process sheet original plate 110. Thereafter, ionizing radiation is irradiated by the ionizing radiation irradiation device 140 to crosslink and cure the curable resin. And the web-like optical element 150 can be manufactured by peeling the ionizing radiation curable resin after hardening from the process sheet | seat original plate 110. FIG. When performing in a web form in this way, if the fine uneven sheet of the present invention is used as a process sheet original plate, the web-like fine uneven replica created thereby has the advantage that the direction of the fine uneven shape is the CD direction, It has characteristics that could not be obtained with a CD direction heat shrinkable film.

In the method (a), for the purpose of imparting releasability to the surface on which the uneven pattern of the process sheet original plate is formed, before coating with an uncured ionizing radiation curable resin, from a silicone resin, a fluororesin or the like. The layer to be formed may be provided with a thickness of about 1 to 10 nm.
Examples of the coater for applying an uncured ionizing radiation curable resin to the surface of the process sheet original plate on which the uneven pattern is formed include a die coater, a roll coater, and a bar coater.
Uncured ionizing radiation curable resins include epoxy acrylate, epoxidized oil acrylate, urethane acrylate, unsaturated polyester, polyester acrylate, polyether acrylate, vinyl / acrylate, polyene / acrylate, silicon acrylate, polybutadiene, and polystyrylmethyl methacrylate. 1 type selected from monomers such as prepolymers such as aliphatic acrylate, alicyclic acrylate, aromatic acrylate, hydroxyl group-containing acrylate, allyl group-containing acrylate, glycidyl group-containing acrylate, carboxy group-containing acrylate, halogen-containing acrylate, etc. The thing containing the above component is mentioned. The uncured ionizing radiation curable resin is preferably diluted with a solvent or the like.
Moreover, you may add a fluororesin, a silicone resin, etc. to uncured ionizing radiation curable resin.
When the uncured ionizing radiation curable resin is cured by ultraviolet rays, it is preferable to add a photopolymerization initiator such as acetophenones and benzophenones to the uncured ionizing radiation curable resin.

After coating the uncured liquid ionizing radiation curable resin, the substrate may be irradiated with ionizing radiation after a substrate made of resin, glass or the like is bonded. Irradiation with ionizing radiation may be performed from any one of the base material and the process sheet original plate having ionizing radiation transparency.

The thickness of the ionizing radiation curable resin sheet after curing is preferably about 0.1 to 100 μm. If the thickness of the ionizing radiation curable resin sheet after curing is 0.1 μm or more, sufficient strength can be secured, and if it is 100 μm or more, sufficient flexibility can be secured.

In the method shown in FIG. 6, the process sheet original plate is a web shape, but may be a single sheet. In the case of using a single sheet, a stamp method using a single sheet as a flat plate mold, a roll imprint method using a single sheet wound around a roll as a cylindrical mold, and the like can be applied. Moreover, you may arrange | position the sheet | seat process sheet | seat original plate inside the type | mold of an injection molding machine.
However, in the method using these single sheets, in order to mass-produce optical elements, it is necessary to repeat the process of forming the concavo-convex pattern many times. When the release property between the ionizing radiation curable resin and the process sheet is low, clogging occurs in the concavo-convex pattern when repeated many times, and the transfer of the concavo-convex pattern tends to be incomplete.
On the other hand, in the method shown in FIG. 6, since the process sheet original is web-like, it is possible to continuously form a concavo-convex pattern in a large area, so even if the number of repeated use of the concavo-convex pattern forming sheet is small, A necessary amount of optical elements can be manufactured in a short time.

In the methods (b) and (e), examples of the liquid thermosetting resin include uncured melamine resin, urethane resin, and epoxy resin.
The curing temperature in the method (b) is preferably lower than the glass transition temperature of the process sheet original plate. This is because if the curing temperature is equal to or higher than the glass transition temperature of the process sheet precursor, the uneven pattern of the process sheet precursor may be deformed during curing.

In the methods (c) and (f), examples of the thermoplastic resin include acrylic resin, polyolefin, polyester, and the like.
The pressure when pressing the sheet-like thermoplastic resin against the secondary process sheet is preferably 1 to 100 MPa. If the pressure at the time of pressing is 1 MPa or more, the concavo-convex pattern can be transferred with high accuracy, and if it is 100 MPa or less, excessive pressurization can be prevented.
Moreover, it is preferable that the heating temperature of the thermoplastic resin in the method (c) is lower than the glass transition temperature of the process sheet original plate. This is because if the heating temperature is equal to or higher than the glass transition temperature of the process sheet precursor, the uneven pattern of the process sheet precursor may be deformed during heating.
The cooling temperature after heating is preferably less than the glass transition temperature of the thermoplastic resin because the uneven pattern can be transferred with high accuracy.

Among the methods (a) to (c), the method (a) using an ionizing radiation curable resin is preferable in that heating can be omitted and deformation of the concavo-convex pattern of the process sheet original plate can be prevented.

In the methods (d) to (f), the thickness of the secondary process sheet is preferably about 50 to 500 μm. If the thickness of the secondary process sheet is 50 μm or more, the secondary process sheet has sufficient strength, and if it is 500 μm or less, sufficient flexibility can be secured.
In the methods (d) to (f), since a secondary process sheet with small deformation due to heat is used as a process sheet, an ionizing radiation curable resin, a thermosetting resin, or a thermoplastic resin is used as a material for the uneven pattern forming sheet. Either of these can be used.

In addition, in (d)-(f), the uneven | corrugated pattern of the process sheet | seat original plate was transcribe | transferred to the metal, and the secondary process sheet | seat was obtained, but you may transcribe | transfer to resin and obtain a secondary process sheet | seat. Examples of the resin that can be used in this case include polycarbonate, polyacetal, polysulfone, acrylic resin, and ionizing radiation curable resin used in the method (a). When using an ionizing radiation curable resin, the ionizing radiation curable resin is sequentially applied, cured, and peeled in the same manner as in the method (a) to obtain a secondary process sheet.

The fine uneven sheet or secondary process sheet used as the process sheet original plate may be used as a protective layer without peeling, and the protective layer may be peeled immediately before use of the fine uneven replica.
The fine concavo-convex sheet and fine concavo-convex replica obtained as described above may be provided with an adhesive layer on the surface opposite to the surface on which the concavo-convex pattern is formed.

Hereinafter, the present invention will be described by way of examples.

<Example 1>
The polyethylene terephthalate polymer is directly polymerized so that the polymer composition is terephthalic acid: sebacic acid / ethylene glycol: diethylene glycol: neopentyl glycol: 1,4-butanediol = 97: 3/53: 2: 20: 25 And polymerized. This was mixed with 0.05% by mass of silica having an average particle size of 2.5 μm, dried at 150 ° C. for 6 hours, and melt-extruded with a T-die at 280 ° C. to obtain an unstretched film having a thickness of 200 μm. After this non-stretched film is preheated at 100 ° C. for 10 seconds, it is longitudinally stretched at 80 ° C. at a stretch ratio of 5 times, and after longitudinal stretching, heat treatment is performed at 70 ° C. for 10 seconds to form a continuous sheet of MD direction heat-shrinkable film A. A winding was obtained.
Silicon dioxide was vapor-deposited on one side of the obtained MD direction heat shrinkable film A so as to have a thickness of 1.5 nm, and the laminated sheet 1 was obtained by winding.
Winding of the obtained laminated sheet was placed in the unwinding zone, and a floating hot air dryer set at 150 ° C. was conveyed as a heat shrinkage zone to be contracted and wound. The line speed was adjusted to stay in the heat shrink zone for 10 seconds, and the outlet line speed / inlet line speed ratio in the heat shrink zone was set to 0.4. Thereby, the shrinkage | contraction sheet 1 without a big wrinkle of 60% of shrinkage ratio was obtained.
When the surface of the surface of the obtained shrinkable sheet 1 provided with the hard layer was observed with an atomic force microscope (Nanoscope III manufactured by Nihon Beco), a fine uneven shape was observed, and the direction of the fine uneven shape was the CD direction. I confirmed that there was. Moreover, the average pitch A, the average depth B, and the orientation degree W1 were calculated | required with the following method. After converting the atomic force microscope image to a grayscale image, two-dimensional Fourier transform is performed. The frequency (ZF) of the Fourier transform image is smoothed, and the average pitch A = 1 / {√ (XFmax2 + YFmax2)} is calculated from the position (XFmax, YFmax) indicating the maximum frequency of the portion excluding the center of the Fourier transform image. Asked. Subsequently, using this Fourier transform image, the degree of orientation is obtained by the method shown in “Best Mode for Carrying Out the Invention”. That is, the Fourier transform image is created by rotating the maximum luminance part of the Fourier transform image by θ on the XF axis of the XF-YF coordinate plane by θ and rotating the θ so that the maximum luminance part coincides on the XF axis, (XFmax, Y'F-ZF diagram with an auxiliary line Y'F passing through the YF axis passing through YFmax), the auxiliary line Y'F as the horizontal axis, and the luminance (ZF axis) on the auxiliary line Y'F as the vertical axis Create The Y´F-ZF diagram is created by dividing the Y´F-axis value of this Y´F-ZF diagram by the average pitch A. From the Y´-ZF diagram, the peak half-value width W1 (frequency is the maximum value) The peak width at half the height) was determined, and the degree of orientation W1 was determined. In the cross-sectional image obtained from the atomic force microscope measurement, the average depth B was obtained from 10 peaks and valleys. The results are shown in Table 1.

<Example 2>
A polyethylene terephthalate polymer was polymerized by a direct polymerization method so that the polymer composition was terephthalic acid / ethylene glycol = 1/1. This was mixed with 0.05% by mass of silica having an average particle size of 2.5 μm, dried at 150 ° C. for 6 hours, and melt-extruded with a T-die at 285 ° C. to obtain an unstretched film having a thickness of 200 μm. This non-stretched film was preheated at 100 ° C. for 10 seconds, and then longitudinally stretched at 100 ° C. at a stretch ratio of 5 to obtain a continuous sheet of MD direction heat-shrinkable film B.
Aluminum oxide was vapor-deposited on one side of the obtained MD-direction heat-shrinkable film B so as to have a thickness of 2 nm, and the laminated sheet 2 was obtained by winding.
Winding of the obtained laminated sheet was placed in the unwinding zone, and a floating hot air dryer set at 130 ° C. was conveyed as a heat shrinkage zone and contracted and wound. The line speed was adjusted so as to stay in the heat shrink zone for 20 seconds, and the outlet line speed / inlet line speed ratio of the heat shrink zone was set to 0.8. Thereby, the shrinkage | contraction sheet 2 without a big wrinkle of shrinkage rate 20% was obtained. When the surface shape was observed in the same manner as in Example 1, a fine uneven shape was observed, and it was confirmed that the direction of the fine uneven shape was the CD direction. Table 1 shows the average pitch A, the average depth B, and the degree of orientation W1.

<Example 3>
92.5% by mass of the polyethylene terephthalate polymer of Example 2 was mixed with 7.5% by mass of polybutylene terephthalate, and 0.05% by mass of silica having an average particle size of 2.5 μm was blended therewith, and at 150 ° C. for 6 hours. After drying, it was melt-extruded with a T-die at 285 ° C. to obtain an unstretched film having a thickness of 200 μm. This unstretched film was preheated at 100 ° C. for 10 seconds, and then longitudinally stretched at 100 ° C. at a stretch ratio of 3.5 times to obtain a continuous sheet of the MD direction heat-shrinkable film C.
Aluminum was vapor-deposited on one side of the obtained MD direction heat-shrinkable film C so as to have a thickness of 0.7 nm, and the laminated sheet 3 was obtained by winding.
Winding of the obtained laminated sheet was placed in the unwinding zone, and a floating hot air dryer set at 130 ° C. was conveyed as a heat shrinkage zone and contracted and wound. The line speed was adjusted so as to stay in the heat shrink zone for 30 seconds, and the outlet line speed / inlet line speed ratio of the heat shrink zone was set to 0.7. Thereby, the shrinkage | contraction sheet 3 without a big wrinkle with a shrinkage | contraction rate of 30% was obtained. When the surface shape was observed in the same manner as in Example 1, a fine uneven shape was observed, and it was confirmed that the direction of the fine uneven shape was the CD direction. Table 1 shows the average pitch A, the average depth B, and the degree of orientation W1.

<Example 4>
Polyethylene terephthalate polymer A so that the polymer composition is terephthalic acid: isophthalic acid / ethylene glycol = 83: 17/100, and polyethylene terephthalate so that terephthalic acid: isophthalic acid / tetramethylene glycol = 70: 30/100 Polyethylene terephthalate polymer C was polymerized by direct polymerization method so that polymer B was terephthalic acid: isophthalic acid / ethylene glycol = 87: 13/100. Polyethylene terephthalate polymer A and polyethylene terephthalate polymer B were mixed at a mass ratio of 4: 1, and 0.05% by mass of silica having an average particle size of 2.5 μm was blended to obtain a surface layer resin. Polyethylene terephthalate polymer C was used as the core layer resin. Each was dried at 150 ° C. for 6 hours, then supplied to two extruder hoppers for the surface layer and core layer, extruded at 290 ° C. onto a cooling drum having a surface temperature of 20 ° C. with a multi-manifold die, and rapidly cooled. A two-layer, three-layer unstretched film having a layer thickness of 180 μm and a surface layer thickness of 15 μm / core layer thickness of 150 μm / surface layer thickness of 15 μm was obtained. This non-stretched film was preheated at 100 ° C. for 10 seconds, then longitudinally stretched at 76 ° C. at a stretch ratio of 3.7 times, and after longitudinal stretching, heat treatment was performed at 77 ° C. for 10 seconds to continuously heat-shrink the MD direction film D. Sheet winding was obtained.
On one side of the obtained MD direction heat-shrinkable film D, polystyrene was coated and dried by gravure coating so as to have a thickness of 10 nm after drying as a hard layer, and a laminated sheet 4 was obtained by winding.
Winding of the obtained laminated sheet was installed in the unwinding zone, and a floating hot air dryer set at 90 ° C. was conveyed as a heat shrinkage zone to be contracted and wound. The line speed was adjusted so as to stay in the heat shrinkage zone for 60 seconds, and the outlet line speed / inlet line speed ratio of the heat shrinkage zone was set to 0.5. Thereby, the shrinkage | contraction sheet 4 without a big wrinkle of shrinkage | contraction rate 50% was obtained. When the surface shape was observed in the same manner as in Example 1, a fine uneven shape was observed, and it was confirmed that the direction of the fine uneven shape was the CD direction. Table 1 shows the average pitch A, the average depth B, and the degree of orientation W1.

<Example 5>
As the heat-shrinkable film, a polycarbonate-based MD direction heat-shrinkable film (brand T-1080 [Teijin Kasei Co., Ltd.]) is used, and silicon dioxide is deposited on one side so as to have a thickness of 2 nm, and the laminated sheet 5 is wound. I got it.
Winding of the obtained laminated sheet was placed in the unwinding zone, and a floating hot air dryer set at 200 ° C. was conveyed as a heat shrinkage zone, contracted and wound up. The line speed was adjusted so as to stay in the heat shrink zone for 30 seconds, and the outlet line speed / inlet line speed ratio of the heat shrink zone was set to 0.7. As a result, a shrinkable sheet 5 having a large shrinkage rate of 30% was obtained. When the surface shape was observed in the same manner as in Example 1, a fine uneven shape was observed, and it was confirmed that the direction of the fine uneven shape was the CD direction. Table 1 shows the average pitch A, the average depth B, and the degree of orientation W1.

<Example 6>
When the same procedure as in Example 2 was performed except that the thickness of the aluminum oxide was 25 nm, a contracted sheet 6 without large wrinkles was obtained, and a micro uneven shape was observed on the hard layer surface of the contracted sheet. Was confirmed to be the CD direction. Table 1 shows the average pitch A, the average depth B, and the degree of orientation W1.

<Example 7>
A laminated sheet 7 was obtained in the same manner as in Example 4 except that the thickness of the polystyrene hard layer was 1 μm. Winding of the obtained laminated sheet was installed in the unwinding zone, and a floating hot air dryer set at 90 ° C. was conveyed as a heat shrinkage zone to be contracted and wound. The line speed was adjusted so as to stay in the heat shrinkage zone for 20 seconds, and the outlet line speed / inlet line speed ratio of the heat shrinkage zone was set to 0.7. Thereby, the shrinkage | contraction sheet 7 without a big wrinkle with a shrinkage | contraction rate of 30% was obtained. A fine uneven shape was observed on the hard layer surface of the shrinkable sheet, and it was confirmed that the direction of the fine uneven shape was the CD direction. Table 1 shows the average pitch A, the average depth B, and the degree of orientation W1.

<Comparative Example 1>
As the heat-shrinkable film, except that a CD-direction heat-shrinkable film (HISHIPET LX-14S [manufactured by Mitsubishi Plastics Co., Ltd.] is used, the same process as in Example 1 was performed. As a result, a usable sheet could not be obtained.

<Comparative example 2>
As the heat-shrinkable film, except that a CD-direction heat-shrinkable film (Hispet LX-14S [manufactured by Mitsubishi Plastics Co., Ltd.) is used, the same process as in Example 7 was performed. As a result, a usable sheet could not be obtained.

<Comparative Example 3>
The both ends of the laminated sheet provided with a hard layer on a heat-shrinkable film are gripped with clips and heated at 100 ° C. for 1 minute while applying tension, so that the shrinkage is 60% in the CD direction. Otherwise, the same procedure as in Comparative Example 1 was performed to obtain a shrink sheet 13 having no large wrinkles. At this time, the outlet line speed / inlet line speed ratio of the heat shrinkage zone was 1. A fine uneven shape was observed on the surface of the obtained shrinkable sheet on the hard layer side, and it was confirmed that the direction of the fine uneven shape was the MD direction. Table 1 shows the average pitch A, the average depth B, and the degree of orientation W1.

<Comparative example 4>
The both ends of the laminated sheet provided with a hard layer on a heat-shrinkable film are gripped by clips and heated at 90 ° C. for 30 minutes while applying tension, thereby shrinking to a shrinkage rate of 30% in the CD direction. Otherwise, the same procedure as in Comparative Example 2 was performed to obtain a shrink sheet 14 having no large wrinkles. At this time, the outlet line speed / inlet line speed ratio of the heat shrinkage zone was 1. A fine uneven shape was observed on the surface of the obtained shrinkable sheet on the hard layer side, and it was confirmed that the direction of the fine uneven shape was the MD direction. Table 1 shows the average pitch A, the average depth B, and the degree of orientation W1.

The fine concavo-convex sheet of the present invention is an optical element such as an antireflective body, a phase difference plate, a light diffuser, a wire grid polarizing plate provided with metal fine wires using this fine concavo-convex shape, in addition to these optical elements, Packaging materials, polishing sheets, catalyst sheets with a catalyst on the surface of fine irregularities using a large specific surface area, photocatalytic sheets, electrode sheets with electrode agents, cell culture sheets, electrolytes for fuel cells It can also be used for films, release films, anti-blocking films, easy-adhesion films, printability improving films, and the like. Also, a plurality of the above applications can be used.

DESCRIPTION OF SYMBOLS 10 Fine uneven | corrugated sheet 10a Laminated sheet 11 Heat-shrinkable film 12 Hard layer 12a Smooth hard layer 13 Fine uneven | corrugated shape 13a Mountain top part 13b Valley bottom part

[1] A laminated sheet provided with at least one smooth hard layer on one or both sides of a heat-shrinkable film is conveyed and heated in the heat-shrink zone to cause the hard layer of the laminated sheet to have wavy irregularities. A method for producing a fine concavo-convex sheet in which a fine concavo-convex shape is formed mainly in the CD direction on the surface of a heat-shrinkable film by being deformed so as to form a pattern.
[2] The method for producing a fine uneven sheet according to [1], wherein the degree of orientation of the fine uneven shape is 1.0 or less.
[3] A method for producing a fine uneven replica, wherein the fine uneven sheet produced by the method of [1] or [2] is transferred to another material.

Claims (5)

  1. A method for producing a fine concavo-convex sheet, wherein a continuous sheet is used as the MD-direction heat-shrinkable film, and a continuous laminated sheet having at least one hard layer provided on one or both sides of the MD-direction heat-shrinkable film is produced. The manufacturing method of the fine uneven | corrugated sheet which consists of a process and the process of heat-shrinking the said continuous laminated sheet continuously in a heat-shrink zone.
  2. The method for producing a fine uneven sheet according to claim 1, wherein in the heat shrinking step, the continuous laminated sheet is shrunk mainly in the MD direction.
  3. The manufacturing method of the fine uneven | corrugated sheet | seat of Claim 1 or 2 whose shrinkage | contraction rate of MD direction of a 1st process is the range of 10%-95%.
  4. The method for producing a fine uneven sheet according to any one of claims 1 to 3, wherein the ratio of the inlet line speed to the outlet line speed of the heat shrinkage zone in the first step is 0.1 to 0.95.
  5. The fine unevenness | corrugation manufactured by the manufacturing method of Claims 1-4 is extended | stretched to CD direction, The fine unevenness | corrugation sheet characterized by the above-mentioned.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002311240A (en) * 2001-04-16 2002-10-23 Konica Corp Retardation film, method for manufacturing the same and elliptical polarization plate
JP2003247155A (en) * 2002-02-25 2003-09-05 Kao Corp Three-dimensional sheet material
WO2007097454A1 (en) * 2006-02-27 2007-08-30 Zeon Corporation Film having fine uneven shape and method for manufacturing same
JP2008304701A (en) * 2007-06-07 2008-12-18 Oji Paper Co Ltd Uneven pattern formed sheet, its manufacturing method, process sheet original plate for manufacturing light diffusion body, and method for manufacturing light diffusion body
JP2009086577A (en) * 2007-10-03 2009-04-23 Oji Paper Co Ltd Light diffuser, method of manufacturing light diffuser, plane light emitting device, display device, and lighting device

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002311240A (en) * 2001-04-16 2002-10-23 Konica Corp Retardation film, method for manufacturing the same and elliptical polarization plate
JP2003247155A (en) * 2002-02-25 2003-09-05 Kao Corp Three-dimensional sheet material
WO2007097454A1 (en) * 2006-02-27 2007-08-30 Zeon Corporation Film having fine uneven shape and method for manufacturing same
JP2008304701A (en) * 2007-06-07 2008-12-18 Oji Paper Co Ltd Uneven pattern formed sheet, its manufacturing method, process sheet original plate for manufacturing light diffusion body, and method for manufacturing light diffusion body
JP2009086577A (en) * 2007-10-03 2009-04-23 Oji Paper Co Ltd Light diffuser, method of manufacturing light diffuser, plane light emitting device, display device, and lighting device

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