JP2008296502A - Method for manufacturing resin film having periodic structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inexpensive simple method for forming a resin film having periodic minute unevenness and to provide a manufacturing method in which a material of the resin film and a material forming the periodic structure in the resin film can be selected from among various materials in a method for forming the resin film having the periodic minute unevenness. <P>SOLUTION: The method for manufacturing the resin film with the periodic structure formed comprises a step of contracting a resin film having a periodic dot pattern. A honeycombed porous film is used as a casting mold, and its honeycombed pattern is transferred to the resin film having the periodic dot pattern. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a resin film in which a periodic structure is formed. Specifically, the present invention relates to a method of manufacturing a resin film having a periodic structure formed by shrinking a resin film having a dot pattern, to which a honeycomb pattern of a honeycomb-like porous film has been transferred.

  Members made of polymer materials such as thermoplastic polymers and photo-curable polymers, and inorganic materials such as quartz and low-melting-point glass, with fine structures of several nanometers to several hundred micrometers on the surface, are used in various fields. It is an indispensable member. These members include, for example, optical members such as diffraction gratings, brightness enhancement films, polarization reflection films, retardation films, and light guide plates; optical storage media such as CDs, DVDs, and blue-ray disks; and light such as optical waveguides and optical fibers. Communication member; used as a life science member such as a cell culture substrate or a DNA chip. In recent years, research and development have been actively conducted on microfabrication techniques for manufacturing these members.

  As the microfabrication technique, the most frequently used technique is a photolithography technique. The photolithographic technique is a technique for performing fine processing in steps of applying, exposing, developing, and etching a photoresist material. Currently, KrF and ArF excimer lasers are the mainstream of actinic rays used to expose photoresist materials in photolithography technology, but F2, extreme ultraviolet rays (EUV), and electron beams (EB) are also used as short-wavelength rays. Etc. are being researched and developed.

  Photolithographic technology requires a very expensive apparatus, requires development of a new resist material according to the wavelength of actinic rays, and requires enormous capital investment and operation costs. In addition, the variety of materials that can be processed is low, and is limited to inorganic materials such as photosensitive materials and semiconductors.

  In recent years, nanoimprint technology applying press working technology has attracted attention as a fine processing technology replacing photolithography technology. The nanoimprint technique is a technique for transferring a fine structure of a mold onto a resin by pressing a mold having a fine structure onto a resin. Once the mold is manufactured, it can be replicated in large quantities.

  However, since the nanoimprint mold is manufactured using electron beam lithography, X-ray lithography, or photolithography, a significant cost reduction cannot be expected. In addition, there are problems such that the resolution depends on the mold, the dimensional accuracy is lowered due to thermal shrinkage or photocuring shrinkage of the resin, and defects are caused by defective mold release between the mold and the resin.

On the other hand, a micropattern forming method based on a self-organization technique has attracted attention (see, for example, Non-Patent Document 1). In the micro pattern formation method by self-organization, a polymer solution is applied on a glass substrate under high humidity, then a gas is blown onto the surface to evaporate the solvent, and a honeycomb structure is formed using the condensed water droplets as a mold. It is a method of forming. Since this method uses micro water droplets that naturally condense from the air and a polymer that naturally precipitates from the solution, it does not require a complicated manufacturing apparatus and can be formed very easily and inexpensively. There is.
“Nanomaterials by Self-Organization (Ken Tanaka, etc.)”, Special Feature 3-Next Generation Technology and Nanofabrication Equipment / Systems such as Nanotech / Bio, "M &E", Industrial Research Committee, (August 2003, p.190) -195)

  The present invention is a method for forming a resin film having periodic fine irregularities, and provides an inexpensive and simple process. Furthermore, the present invention is a method of forming a resin film having periodic fine irregularities, and the material of the resin film and the material forming the periodic structure on the resin film can be selected from various materials. A manufacturing method is provided. Moreover, the manufacturing method of the resin film which can be applied to an optical film by these is provided.

  The present inventors use a "honeycomb-like porous film" that is easily and inexpensively manufactured by a self-organization technique that does not require an expensive apparatus as a mold, and transfers the honeycomb pattern to a resin film to obtain periodic A resin film having a simple dot pattern was obtained. Furthermore, it was found that by shrinking a resin film having a periodic dot pattern, a resin film having a periodic structure, which was difficult to manufacture in the past, could be manufactured, and the present invention was completed.

That is, this invention relates to the manufacturing method of the resin film shown below.
[1] A method for producing a resin film in which a periodic structure is formed,
Preparing a resin film having a periodic dot pattern; and shrinking the resin film having a periodic dot pattern by heat, light, infrared rays, or microwaves, and the periodic dot pattern includes: A method for producing a resin film, which is a pattern formed by transferring a honeycomb pattern using a honeycomb-like porous film as a mold.
[2] The periodic structure described in [1], wherein the periodic structure has periodic dots, and each dot has wrinkle-shaped unevenness, and the unevenness is repeated in the contracting direction. Production method.
[3] The resin film having the dot pattern is a film that shrinks by heat, light, infrared rays, or microwaves, and the shrinkage of the resin film having the dot pattern is caused by irradiation with heat, light, infrared rays, or microwaves. The production method according to [1] or [2], which is performed.
[4] The step of shrinking the resin film having the dot pattern includes:
A step of bonding the film having the dot pattern to a film shrinkable by heat, light, infrared or microwave, and a step of shrinking the multilayer film by heat, light, infrared or microwave The production method according to [1] or [2].
[5] The manufacturing method according to any one of [1] to [4], wherein the transfer of the honeycomb pattern is transfer by a physical vapor deposition method using the honeycomb-shaped porous film as a mask.
[6] The manufacturing method according to any one of [1] to [4], wherein the transfer of the honeycomb pattern is transfer by a chemical vapor deposition method using the honeycomb-shaped porous film as a mask.
[7] The transfer of the honeycomb pattern is any one of [1] to [4], which is transfer by a coating method, a spin cast method, a dip method, or a plating method using the honeycomb porous film as a mask. Manufacturing method.
[8] The production method according to [3] or [4], wherein the film that contracts by heat, light, infrared rays, or microwaves contracts anisotropically.
[9] The production method according to [3] or [4], wherein the film that shrinks by heat, light, infrared rays, or microwaves shrinks isotropically.
[10] A step of preparing the honeycomb-shaped porous film,
A step of casting a hydrophobic organic solution in which a polymer material is dissolved in a high-humidity atmosphere, a step of evaporating an organic solvent contained in the casting liquid from the casting liquid, and at the same time condensing a high-humidity atmosphere component on the surface of the casting liquid And a step of forming a cast film by evaporating fine droplets generated by the dew condensation, and the manufacturing method according to any one of [1] to [9].
[11] A step of preparing the honeycomb-shaped porous film,
A step of casting a hydrophobic organic solution in which a polymer material is dissolved. A high-humidity gas is sprayed on the casting solution to evaporate an organic solvent contained in the casting solution, and at the same time, a high-humidity atmosphere component is condensed on the surface of the casting solution. The manufacturing method according to any one of [1] to [9], further including a step including a step of forming a cast film by evaporating the fine droplets generated by the condensation.
[12] The manufacturing method according to any one of [1] to [11], wherein the resin film on which the periodic structure is formed is an optical film.

The present invention is a method for producing a resin film having a periodic structure which has been difficult to produce by shrinking a resin film having a periodic dot pattern. The periodic structure is preferably a structure having periodic dots and wrinkled irregularities on the surface of each dot.
A resin film having a periodic dot pattern can be obtained by transferring the honeycomb pattern to a resin film using a honeycomb-like porous film as a mold. The honeycomb-like porous film can be produced by a self-organizing method. The resin film may be contracted by irradiation with heat, light, infrared rays, or microwaves. Therefore, all the steps included in the production method of the present invention can be performed easily and inexpensively.

  Therefore, it becomes possible to provide a resin film having a structure that could not be achieved without using an expensive apparatus in the prior art at a low cost. Furthermore, the materials that can be used are diversified as compared with conventional microfabrication techniques (such as photo photolithography techniques).

  The manufacturing method of the resin film formed with the periodic structure according to the present invention includes a step of shrinking the resin film having a periodic dot pattern.

  The film having the periodic dot pattern is preferably prepared by preparing a honeycomb-like porous film; using the honeycomb-like porous film as a mold, and transferring the honeycomb pattern to a resin film.

Production of Honeycomb Porous Film The honeycomb porous film is preferably produced by a self-organizing method. The manufacture of the honeycomb-like porous film by the self-organization method can be performed with reference to the description of Non-Patent Document 1 and JP 2001-157574 A, for example. A method for manufacturing a honeycomb-shaped porous film by a self-organization method is characterized in that a dissipative structure generated in the evaporation process of a solvent is fixed to the film.

  The first of the preferable procedures of the self-assembly method is a step of casting a hydrophobic organic solution in which a polymer material is dissolved in a high-humidity atmosphere; when the organic solvent contained in the casting solution is evaporated from the casting solution At the same time, a step of condensing a high-humidity atmosphere component on the surface of the casting liquid; a step of producing a honeycomb film by forming a cast film by evaporating fine droplets generated by the condensation are included.

  The second preferred procedure of the self-assembly method is a step of casting a hydrophobic organic solution in which a polymer material is dissolved; when high humidity gas is sprayed on the casting solution to evaporate the organic solvent contained in the casting solution. At the same time, a step of condensing a high-humidity atmosphere component on the surface of the casting liquid; a step of producing a honeycomb film by forming a cast film by evaporating fine droplets generated by the condensation are included.

  The polymer material dissolved in the hydrophobic organic solution used in the self-assembly method is not particularly limited as long as it is soluble in the hydrophobic organic solvent, but is preferably insoluble or hardly soluble in water. Examples of polymeric materials include polyethylene, polypropylene, polybutadiene, polystyrene, polyacrylate, polymethacrylate, polyacrylamide, polymethacrylamide, polyvinyl chloride, polyvinylidene chloride, polyvinyl ether, polyvinyl carbazole, polyvinyl acetate, polyvinyl alcohol, Vinyl polymerization resins such as cycloolefin copolymer resins or copolymers thereof, polycarbonate, polyethersulfone, polylactic acid, polyhydroxybutyric acid, polycaprolactone, polyether, polyester, polyamide, polyimide, and the like are included.

  The concentration of the polymer material in the hydrophobic organic solution is 0.01 to 10% by weight, preferably 0.05 to 5% by weight. If the concentration of the polymer material in the solution is lower than 0.01% by weight, the resulting honeycomb porous film may have insufficient mechanical strength. On the other hand, if the solution concentration is higher than 10% by weight, the pore distribution and pore size of the resulting honeycomb porous film may not be uniform.

The solvent of the hydrophobic organic solution is not particularly limited as long as it is a hydrophobic organic solvent that is liquid at room temperature. Examples of the solvent include halogen-based organic solvents such as chloroform, methylene chloride, and carbon tetrachloride; aromatic hydrocarbons such as benzene, toluene, and xylene; ester-based solvents such as ethyl acetate and butyl acetate; methyl isobutyl ketone, cyclohexanone Such as ketone solvents; carbon disulfide; amide solvents; ether solvents and the like. These hydrophobic organic solvents may be used alone, or a plurality of solvents may be used in combination as a mixed solvent.
Since fine water droplets can be formed on the cast liquid film formed by casting the hydrophobic organic solution, a honeycomb pattern can be obtained by evaporating the fine water droplets.

  An amphiphilic substance may coexist in the hydrophobic organic solution. There are no particular limitations on the coexisting amphiphile, and both low-molecular substances and high-molecular substances can be used. For example, low molecular weight substances such as sodium dodecylbenzenesulfone and sodium di-2-ethylhexylsulfosuccinate; polyethylene glycol / polypropylene glycol block copolymer, polyacrylamide as the main skeleton, dodecyl group and hydrophilic side chain as hydrophobic side chains As an amphiphilic polymer having both a lactose group and a carboxyl group; or an ion complex of an anionic polymer such as heparin, dextran sulfate, DNA or RNA nucleic acid, and a long-chain alkylammonium salt; An amphiphilic polymer having hydrophilic protein as a hydrophilic group can be exemplified.

  The hydrophobic organic solution is cast on a substrate. Examples of the substrate include inorganic materials such as glass, metal, and silicon wafer; organic materials composed of polymers such as polypropylene, polyethylene, and polyetherketone; and mineral materials such as MICA. Furthermore, liquids such as water, liquid paraffin, and liquid polyether may be used as the base material. Furthermore, it is good also considering the film (shrinkable film) which shrink | contracts with a heat | fever, light, infrared rays, or a microwave as a base material. The shrinkable film will be described later.

  The hydrophobic organic solution may be cast in a high humidity atmosphere. The high humidity atmosphere means that the relative humidity is 50 to 95%, for example.

  The casting liquid is preferably capable of evaporating the organic solvent contained therein. If the casting liquid does not contain sufficient water, the organic solvent is evaporated by blowing high humidity gas. High humidity gas means that relative humidity is 50 to 95%, for example.

  In any case, the organic solvent is gradually evaporated from the casting liquid, and at the same time, a high humidity atmosphere component is condensed on the surface of the casting liquid to form micro droplets. Usually, the high humidity atmosphere component is moisture and the droplet is a water droplet.

  Thereafter, when the microdroplets formed on the surface of the casting liquid are evaporated, a film (honeycomb-like porous film) in which a honeycomb pattern corresponding to the shape of the microdroplets is formed is obtained.

Regarding the structure of the honeycomb-like porous film The honeycomb-like porous film obtained by the self-organization technique is a honeycomb-like porous body. For example, a honeycomb pattern in which minute holes are regularly arranged in hexagonal form. The diameter of the hole is preferably 0.1 to 100 μm, more preferably 0.1 to 10 μm. The diameter of the hole can be controlled by adjusting the conditions for forming the microdroplet.

  The honeycomb-like porous film may have either a through structure in which holes penetrate the membrane or a non-through structure in which pores do not penetrate the membrane. The penetrating or non-penetrating structure can be controlled by the film thickness of the film to be formed and the size of the minute water droplets.

Transfer of honeycomb pattern of honeycomb-shaped porous film The honeycomb-shaped porous film is used as a mold, and the honeycomb pattern is transferred to a resin film. The use of the honeycomb-like porous film as a mold includes use as a “mask”. In order to use as a mask, it is preferable that the pores of the honeycomb-like porous film are penetrated (penetrating structure).

  Therefore, when the pores of the honeycomb-like porous film are penetrated (penetrating structure), the honeycomb-like porous film is bonded to the resin film to be shrunk; or the honeycomb-like porous film is to be shrunk on the resin film to be shrunk It is preferable to use a shrinkable film as the base material for casting.

On the other hand, when the pores of the honeycomb-shaped porous film are not penetrating (non-penetrating structure), it is preferable to perform a treatment for forming a penetrating structure.
With reference to FIG. 2, the example of the process for setting it as a penetration structure is demonstrated. A honeycomb-like porous film having a non-penetrating structure is prepared (step 1). The honeycomb porous film having a non-penetrating structure is oxidized by UV ozone treatment (step 2). The surface on which the pores of the honeycomb-shaped porous film are formed is bonded to a “resin film to be shrunk” to form a multilayer film, and the multilayer film is optionally dried at room temperature and normal pressure. Further, stress is applied by bringing silicon rubber into contact with the surface of the honeycomb-like porous film where no holes are formed (step 3). Thereafter, the silicon rubber is peeled off to form periodic dots (pillars) on the resin film to be contracted (step 4).

  The “resin film to be shrunk” may be a “shrinkable film (described later)” or a normal non-shrinkable film. If a shrinkable film is used, the film can be shrunk by applying heat or the like in the shrinking step described below; if a non-shrinkable film is used, the non-shrinkable film is applied to the shrinkable film. As a multilayer film, the multilayer film can be shrunk by irradiation with heat or the like.

  A shrinkable film is a film that shrinks under the action of heat, light, infrared rays, microwaves, and the like. Examples of the material for the shrinkable film include: vinyl polymer resins such as polyethylene, polypropylene, polyvinyl chloride, polystyrene, ethylene-vinyl acetate copolymer, cycloolefin copolymer, and fluorine resins such as polyurethane resin and polyvinylidene fluoride. , Thermoplastic elastomers, silicone resins, biocompatible materials such as polycaprolactone and polylactic acid. A film obtained by uniaxially or biaxially stretching a film made of these materials may be used as the shrinkable film.

  The shrinkable film may be an isotropically shrinkable film or an anisotropically shrinkable film. The shrinkage ratio of the shrinkable film is preferably about 1.05 to 30 times, and more preferably 1.5 to 3 times.

  Using the honeycomb-shaped porous film as a mold, the honeycomb pattern is transferred to a shrinking resin film. For the transfer, for example, a honeycomb-shaped porous film may be used as a mask to pattern a desired material on a shrinkable resin film to form dots. After patterning, the honeycomb porous film used as a mask is peeled off, whereby a dot pattern can be formed on the shrinking resin film. The dot pattern to be formed is a periodic dot pattern corresponding to the honeycomb pattern of the honeycomb-like porous film.

  The patterning is preferably performed by physical vapor deposition, chemical vapor deposition, coating, spin casting, dipping, plating, or the like. Examples of physical vapor deposition include sputtering and vapor deposition, and examples of chemical vapor deposition include thermal CVD, plasma CVD, and photo CVD.

  The dot component patterned on the shrinkable resin film is not particularly limited, and is a metal or metal alloy such as gold, silver, copper, platinum, iron, aluminum, palladium, silicon, nickel, titanium; silicon oxide, titanium oxide, etc. Metal oxides such as silicon nitride, titanium nitride, tantalum nitride, etc .; organic polymers such as polythiophene derivatives, polypyrrole derivatives, polyphenylene derivatives, polyacene derivatives, oxazole derivatives, imidazole derivatives, coumarin derivatives, perylene derivatives, Examples thereof include small organic molecules such as quinacridone derivatives, 8-quinolinol derivatives, and metal complexes of phthalocyanine derivatives.

  The honeycomb-like porous film used as a mold or a mask is removed from the resin film on which dots are patterned. The honeycomb-like porous film may be removed by peeling it from the resin film using an adhesive tape or the like. The removal of the honeycomb-like porous film may be performed either before or after the resin film is contracted.

About Shrinkage of Film By shrinking a resin film having a periodic dot pattern, a resin film having a structure that was difficult only by the self-organization method can be obtained. When the resin film having a dot pattern is a shrinkable film, the film may be shrunk by irradiation with heat, light, infrared rays, microwaves, or the like. On the other hand, when the resin film having a dot pattern is a non-shrinkable film, the multilayer film may be shrunk as a multilayer film by being attached to the shrinkable film, for example.

  The shrinkage of the shrinkable film is such that the crosslinked polymer that has been stretched and deformed by heating to near the melting point remains deformed in the cooled state but returns to its original state when heated again to near the melting point. This is a phenomenon based on a change in the orientation state.

  The resin film having a periodic dot pattern may be contracted not only once but twice or more. When shrinking two or more times, a resin film having a periodic dot pattern is pasted on a shrinkable film to form a multilayer film, and then contracted; the resin film having a dot pattern is peeled off from the contracted multilayer film Then, the peeled resin film may be bonded again to the shrinkable film to form a multilayer film and then contracted.

About the periodic structure of the film manufactured The film in which the periodic structure manufactured by the method of the present invention is formed has periodic dots, and each dot has wrinkled irregularities. The wrinkle-like irregularities are preferably repeated in a certain direction. That is, wrinkle-like unevenness is repeated in the shrinking direction of the shrinkable film.

The diameter of the dot is preferably 0.1 to 100 μm, more preferably 0.1 to 10 μm, but is not particularly limited.
The dot period is preferably 0.01 to 100 μm, more preferably 0.01 to 10 μm, but is not particularly limited.
Further, the size of the wrinkle-shaped unevenness is not particularly limited, but preferably the unevenness width is 0.001 to 10 μm, the unevenness height is 0.001 to 10 μm, and the unevenness period is 0.001 to 10 μm. More preferably, the width of the unevenness is 0.01 to 1 μm, the height of the unevenness is 0.01 to 1 μm, and the period of the unevenness is 0.01 to 1 μm.

  The film on which the periodic structure produced by the method of the present invention is formed can be applied to various optical films by changing the material and pattern size. For example, if the dot component of the dot pattern is made of a highly reflective material such as silver or aluminum and the period of wrinkle-like irregularities is controlled to 10 to 1000 nm, it can be used as a polarizing reflection film. This is because a light component having an electric field vector orthogonal to the unevenness is transmitted and a light component having an electric field vector parallel to the uneven structure is reflected.

  The interval between the honeycomb patterns may be narrowed by shrinking the shrinkable film on which the template is formed before transferring the honeycomb pattern. Thereafter, if the honeycomb pattern is transferred, a dot pattern with a short cycle can be formed.

  The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

Production of Honeycomb Porous Film A honeycomb porous film was produced using polystyrene as the polymer material, the amphiphilic polymer shown below, and chloroform as the solvent.

Example 1
5 mL of a chloroform solution (5 g / L) in which polystyrene and the amphiphilic polymer (10: 1 by weight) were dissolved was cast into a petri dish having a diameter of 9 cm. Immediately thereafter, air with a humidity of 70% was blown to form a non-penetrating honeycomb porous film.
The petri dish on which the film was formed was immersed in ethanol, and the honeycomb-like porous film was peeled off to obtain a self-supporting honeycomb-like porous film. The obtained honeycomb porous film was observed with a scanning electron microscope (SEM) (FIG. 1). It was confirmed that the holes were regularly arranged (period: 8.0 μm).

Transfer of honeycomb pattern to shrinkable film The prepared non-penetrating honeycomb porous film 1 was prepared (step 1 in FIG. 2), oxidized by performing UV ozone treatment 2, and oxidized honeycomb porous film. 3 was obtained (step 2 in FIG. 2).
The surface of the oxidized honeycomb porous film 3 on which the pores were formed was bonded to the Apel 8008T film 5 biaxially stretched 1.5 times to obtain a multilayer film. After the multilayer film was dried at room temperature and normal pressure, stress was applied to the honeycomb porous film surface (the surface where no pores were formed) of the multilayer film through the polydimethylsiloxane elastomer 4 (Step 3 in FIG. 2). ). Thereafter, the polydimethylsiloxane elastomer 4 was peeled off to form a pillar structure 6 on the Apel 8008T film 5 biaxially stretched 1.5 times (step 4 in FIG. 2).

  Pt / Pd dots 7 were deposited by ion sputtering on the film 5 on which the pillar structure 6 was formed (Step 5 in FIG. 2). From the film 5 on which the Pt / Pd dots 7 were deposited, the pillars were peeled off with an adhesive tape to obtain a film in which dot patterns arranged in a xagonal manner were formed. The obtained film was observed with an SEM, and a dot pattern with a period of 8.0 μm was confirmed (FIG. 3).

  On the other hand, without peeling off the pillar 6 from the film 5 on which the Pt / Pd dots 7 were deposited, the film was heat-treated on a hot stage at 100 ° C. and contracted (step 6 in FIG. 2). The pillar 6 was peeled off from the film 5 after shrinkage with the adhesive tape 8 (step 7 in FIG. 2). When the film 5 (step 8 in FIG. 2) from which the pillars 6 were peeled was observed by SEM, the period of the dots 7 was narrowed to 6.5 μm, and wrinkles having a width of about 700 nm and a height of about 300 nm were formed on the surface of each dot. It was confirmed that an uneven surface was formed (FIG. 4).

(Example 2)
Honeycomb film having a period of 7.8 μm in the same manner as in Example 1 except that 4.5 mL of a chloroform solution (5 g / L) in which polystyrene and the amphiphilic polymer (10: 1 by weight) are dissolved is cast. Got. When the same operation as in Example 1 was performed except that the obtained honeycomb film and a double uniaxially stretched Appel 8008T film were used, the dot period was narrowed to 3.8 μm, and the surface of each dot In addition, it was confirmed that wrinkled irregularities of several hundred nm were formed (FIG. 5).

(Example 3)
A honeycomb film having a period of 5.0 μm was obtained in the same manner as in Example 1 except that 3 mL of a chloroform solution (5 g / L) in which polystyrene and the above amphiphilic polymer (10: 1 by weight) were dissolved was cast. It was. The same operation as in Example 1 was performed except that the obtained honeycomb film and the 2.5-fold uniaxially stretched Apel 8008T film were used. As a result, the dot period was narrowed to 2.0 μm, and each dot It was confirmed that wrinkle-like irregularities of several hundred nm were formed on the surface (FIG. 6).

  According to the present invention, a resin film formed with a structure that could not be achieved without using an expensive apparatus conventionally is provided simply and inexpensively. For example, a resin film having periodic dots and formed with a structure having wrinkled irregularities on the surface of each dot is provided. The resin film provided by the production method of the present invention can be applied to a polarizing film, a polarizing reflection film, a diffraction grating, a brightness enhancement film, a light diffusion film, a cell culture substrate and the like.

It is a SEM image of the honeycomb-like porous film produced by the self-organization method. A transfer process when a non-penetrating honeycomb porous film is used as a mold is shown. An SEM image of a dot pattern obtained by dot patterning Pt / Pd on a biaxially stretched Appel 8008T film using a honeycomb porous film as a mold is shown. The SEM image of the dot pattern obtained by shrinking the film shown in FIG. 3 is shown. An SEM image of a dot pattern obtained by shrinking a film in which a dot pattern obtained by dot patterning of Pt / Pd is formed on a biaxially stretched Apel 8008T film using a honeycomb porous film as a mold is shown. . An SEM image of a dot pattern obtained by shrinking a film in which a dot pattern obtained by dot patterning of Pt / Pd is formed on a biaxially stretched Apel 8008T film using a honeycomb porous film as a mold is shown. .

Claims (12)

A method for producing a resin film having a periodic structure,
Preparing a resin film having a periodic dot pattern; and shrinking the resin film having a periodic dot pattern by heat, light, infrared rays, or microwaves, and the periodic dot pattern includes: A method for producing a resin film, which is a pattern formed by transferring a honeycomb pattern using a honeycomb-like porous film as a mold.   The manufacturing method according to claim 1, wherein the periodic structure includes periodic dots, and each dot has wrinkle-like irregularities, and the irregularities are repeated in the shrinking direction. The resin film having the dot pattern is a film that shrinks by heat, light, infrared rays, or microwaves, and the shrinkage of the resin film having the dot pattern is performed by irradiation with heat, light, infrared rays, or microwaves, The manufacturing method of Claim 1 or 2. Shrinking the resin film having the dot pattern,
A step of bonding the film having the dot pattern to a film shrinkable by heat, light, infrared rays or microwaves to obtain a multilayer film, and a step of shrinking the multilayer film by heat, light, infrared rays or microwaves The manufacturing method of Claim 1 or 2 containing this.   The transfer method according to any one of claims 1 to 4, wherein the transfer of the honeycomb pattern is transfer by a physical vapor deposition method using the honeycomb-like porous film as a mask.   The manufacturing method according to any one of claims 1 to 4, wherein the transfer of the honeycomb pattern is transfer by a chemical vapor deposition method using the honeycomb-shaped porous film as a mask.   The manufacturing method according to any one of claims 1 to 4, wherein the transfer of the honeycomb pattern is a transfer by a coating method, a spin cast method, a dip method, or a plating method using the honeycomb porous film as a mask. .   The manufacturing method of Claim 3 or 4 with which the film shrink | contracted by the said heat | fever, light, infrared rays, or a microwave shrinks anisotropically.   The manufacturing method according to claim 3 or 4, wherein the film that shrinks by heat, light, infrared rays, or microwaves shrinks isotropically. Preparing the honeycomb-shaped porous film,
A step of casting a hydrophobic organic solution in which a polymer material is dissolved in a high humidity atmosphere;
A step of evaporating an organic solvent contained in the casting liquid from the casting liquid and dewing a high-humidity atmosphere component on the surface of the casting liquid; and a process of evaporating fine droplets generated by the condensation to form a cast film ,
The manufacturing method as described in any one of Claims 1-9 which further includes the step which has these. Preparing the honeycomb-shaped porous film,
A step of casting a hydrophobic organic solution in which a polymer material is dissolved,
High humidity gas is sprayed on the casting liquid to evaporate the organic solvent contained in the casting liquid, and at the same time, the high humidity atmosphere component is condensed on the casting liquid surface, and the fine droplets generated by the condensation are evaporated. Forming a cast film;
The manufacturing method as described in any one of Claims 1-9 which further includes the step which has these.   The manufacturing method according to any one of claims 1 to 11, wherein the resin film on which the periodic structure is formed is an optical film.