JP2013082795A - Microphase separation structure film and laminate - Google Patents

Microphase separation structure film and laminate Download PDF

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JP2013082795A
JP2013082795A JP2011222984A JP2011222984A JP2013082795A JP 2013082795 A JP2013082795 A JP 2013082795A JP 2011222984 A JP2011222984 A JP 2011222984A JP 2011222984 A JP2011222984 A JP 2011222984A JP 2013082795 A JP2013082795 A JP 2013082795A
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film
microdomain
solvent
microphase
polymer chain
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JP5736297B2 (en
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Takahiko Yamanaka
孝彦 山中
Shigeo Hara
滋郎 原
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Hamamatsu Photonics Kk
浜松ホトニクス株式会社
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Abstract

PROBLEM TO BE SOLVED: To provide a microphase separation structure film having excellent optical characteristics.SOLUTION: The microphase separation structure film 10 has a microphase separation structure 13 that contains a block copolymer having a first polymer chain and a second polymer chain, and a photocurable resin obtained by photopolymerizing a photopolymerizable monomer, and includes a microdomain 15a containing the first polymer chain and a microdomain 15b containing the second polymer chain, wherein air holes 17 are selectively formed in the microdomain 15a, not in the microdomain 15b.

Description

  The present invention relates to a microphase-separated structure film and a laminate.

  Photonic crystals and structural color bodies using a microphase-separated structure formed by self-organizing a block copolymer as a refractive index periodic structure are known (for example, Patent Documents 1 to 3). The refractive index periodic structures described in Patent Documents 1 to 3 are formed by different refractive indexes of the constituent block chains of the block copolymer forming the microphase-separated structure. It exhibits characteristics and exhibits structural color.

International Publication No. 2008/047514 Pamphlet Japanese Patent No. 3233883 Japanese Patent No. 4581377 Japanese Patent No. 3227109

Adv. Mater. 2002, 14, no. 24, December 17 "Bicontinous Cubic Block Copolymer Polymer Crystals"

  Conventional photonic crystals using a microphase-separated structure have a problem that the refractive index difference between constituent block chains is small compared to a photonic crystal using a semiconductor material or an inorganic material, and sufficient optical characteristics cannot be obtained. is there. Similarly, when the microphase-separated structure is used as the refractive index periodic structure of the structural color body, it is difficult to obtain a colorful metallic luster like a dielectric multilayer film because the difference in refractive index is small and the reflectance is low. As a method for increasing the difference in refractive index, Non-Patent Document 1 discloses a method of introducing vacancies into one component of the microphase separation structure. However, the microphase-separated structure of Non-Patent Document 1 is a photonic using a microphase-separated structure in which vacancies are introduced by vacuum dry etching, the introduction of vacancies is uneven, and optical characteristics are improved. It's hard to call it a crystal.

  In addition, in Patent Document 4 described above, when a microphase separation structure is obtained by a solution casting method, an additional component such as a polymer, an oligomer, or a monomer that is compatible with only one component of the microphase separation structure is added. A microphase-separated structure in which pores are introduced by producing a structure film and then extracting the additive component with a solvent in which the additive component can be dissolved has been disclosed. In the method described in Document 4, the microphase separation structure film is deformed when the additive component is extracted with a solvent, and thus the microphase separation structure with improved optical characteristics cannot be obtained.

  The present invention is intended to solve the above-described problems, and an object of the present invention is to provide a microphase-separated structure film having excellent optical characteristics and a laminate using the same.

  The microphase-separated structure film according to the present invention is a microphase-separated structure film having microdomains in which pores are selectively formed, and includes a block copolymer having a first polymer chain and a second polymer chain. A polymer, a photocurable resin obtained by photopolymerization of a photopolymerizable monomer, a first microdomain containing a first polymer chain, and a second polymer chain containing a second polymer chain. And a microphase separation structure including two microdomains, and pores are selectively formed in the first microdomain rather than the second microdomain.

  In the present invention, the microphase-separated structure film contains a block copolymer having a first polymer chain and a second polymer chain, and a photocurable resin obtained by photopolymerizing a photopolymerizable monomer. In addition, the microphase-separated structure includes a first microdomain containing a first polymer chain and a second microdomain containing a second polymer chain. In such a microphase-separated structure film, the three-dimensional crosslinking proceeds by photopolymerization of the photopolymerizable monomer, so that the microphase-separated structure is well maintained.

  And in the micro phase-separation structure film which concerns on this invention, the void | hole is selectively formed in the 1st micro domain rather than the 2nd micro domain. As a result, the refractive index of the first microdomain tends to be smaller than in a state where no voids are formed, and the difference in the refractive index between the first microdomain and the second microdomain is easily increased. can do. Therefore, in the microphase-separated structure film according to the present invention, excellent optical properties can be obtained. In such a microphase-separated structure film, for example, the reflectance of the film can be increased, and a metallic luster can be imparted to the film.

  The first microdomain and the second microdomain may be lamellar.

  The laminated body which concerns on this invention is equipped with the said microphase-separated structure film and the support body arrange | positioned on the at least one main surface of the said microphase-separated structure film. In the laminate according to the present invention, mechanical strength and chemical resistance can be improved as compared with the case where the microphase separation structure film is used alone, and an organic solvent or the like is added to the microphase separation structure film. It can suppress that an optical characteristic falls by contacting.

  The support is a first support disposed on one main surface of the microphase-separated structure film, a second support disposed on the other main surface of the microphase-separated structure film, And at least one of the first support and the second support may be transparent to visible light. In this case, the structural color of the microphase separation structure film can be easily recognized while the microphase separation structure film is supported by the support.

  The laminate according to the present invention may further include a protective film disposed between the support and the microphase-separated structure film. In this case, when laminating the microphase-separated structure film and the support, even if the microphase-separated structure film is likely to come into contact with an organic solvent or the like, the microphase is separated by shielding with a protective film. It can suppress that an organic solvent etc. contact a separated structure film, and the optical characteristic of a micro phase-separated structure film falls.

  ADVANTAGE OF THE INVENTION According to this invention, the micro phase-separation structure film which has the outstanding optical characteristic (for example, a reflectance, permeation | blocking block characteristic), and a laminated body using this can be provided. Such a microphase-separated structure film and laminate are useful as optical filters and structural color materials. The structural color material has a structural color in the visible light range, for example.

It is a figure which shows the micro phase-separation structure film which concerns on one Embodiment of this invention. It is a figure which shows the laminated body which concerns on 1st Embodiment of this invention. It is a figure which shows the laminated body which concerns on 2nd Embodiment of this invention. It is a figure which shows the laminated body which concerns on 3rd Embodiment of this invention. It is a figure which shows the laminated body which concerns on 4th Embodiment of this invention. It is a SEM photograph of the micro phase separation structure film of Examples 1-3. It is a SEM photograph of the micro phase separation structure film of comparative examples 2-4. It is a figure which shows the reflection spectroscopy spectrum of a micro phase-separation structure film.

  DESCRIPTION OF EXEMPLARY EMBODIMENTS Hereinafter, preferred embodiments of the invention will be described in detail with reference to the drawings.

<Micro phase separation structure film>
FIG. 1 is a diagram showing a microphase-separated structure film according to the present embodiment. Fig.1 (a) is a perspective view of a micro phase-separation structure film, FIG.1 (b) is a schematic cross section along the Ib-Ib line | wire of Fig.1 (a). A microphase-separated structure film 10 (hereinafter referred to as “film 10”) shown in FIG. 1 has a front surface (one main surface) 10a and a back surface (the other main surface) 10b facing each other substantially in parallel. Yes. The thickness of the film 10 is, for example, 10 to 300 μm. The shape of the film 10 is not particularly limited, and may be, for example, a circle (FIG. 1 (a)) or a rectangle.

  The film 10 is a structural color body formed of, for example, a polymer photonic crystal. The polymer photonic crystal contains a block copolymer (polymer block copolymer). A “block copolymer” is a copolymer in which two or more types of polymer chains (constituent block chains, segments) are bonded. For example, a first polymer chain having a monomer A as a structural unit, and a monomer B Examples thereof include a copolymer in which the second polymer chain as a structural unit is bonded at the ends of the polymer chain.

  Examples of the block copolymer include polystyrene-b-poly (methyl methacrylate), polystyrene-b-poly (ethyl methacrylate), polystyrene-b-poly (propyl methacrylate), and polystyrene-b-poly (tert-butyl methacrylate). , Polystyrene-b-poly (n-butyl methacrylate), polystyrene-b-poly (isopropyl methacrylate), polystyrene-b-poly (pentyl methacrylate), polystyrene-b-poly (hexyl methacrylate), polystyrene-b-poly (decyl) Methacrylate), polystyrene-b-poly (dodecyl methacrylate), polystyrene-b-poly (methyl acrylate), polystyrene-b-poly (tert-butyl acrylate), polystyrene-b-poly Tadiene, polystyrene-b-polyisoprene, polystyrene-b-polydimethylsiloxane, polybutadiene-b-polydimethylsiloxane, polyisoprene-b-polydimethylsiloxane, polyvinylpyridine-b-poly (methyl methacrylate), polyvinylpyridine-b- Poly (tert-butyl methacrylate), polyvinylpyridine-b-polybutadiene, polyvinylpyridine-b-isoprene, polybutadiene-b-polyvinylnaphthalene, polyvinylnaphthalene-b-poly (methyl methacrylate), polyvinylnaphthalene-b-poly (tert-butyl) 2-block copolymers such as methacrylate), polystyrene-b-polybutadiene-b-poly (methyl methacrylate), polystyrene-b-polybutadiene- -Ternary block copolymers such as poly (tert-butyl methacrylate), polystyrene-b-polyisoprene-b-poly (methyl methacrylate), polystyrene-b-polyisoprene-b-poly (tert-butyl methacrylate), etc. Can be mentioned. The block copolymer is not limited to the above as long as the refractive index is different between polymer chains. In addition, in Fig.1 (a), the form in which the film 10 contains a binary block copolymer as a block copolymer is shown as an example. The content of the block copolymer is, for example, 7 to 15% by mass based on the total mass of the film 10.

The weight average molecular weight (Mw) of the block copolymer is preferably 8.0 × 10 5 (g / mol) or more from the viewpoint of obtaining a favorable periodic structure that exhibits color developability as a structural color former. 0 × 10 5 (g / mol) or more is more preferable, and 1.0 × 10 6 (g / mol) or more is more preferable. The weight average molecular weight of the block copolymer is preferably 3.0 × 10 6 (g / mol) or less, from the viewpoint of obtaining a periodic structure that exhibits color developability as a structural color former, and preferably 2.5 × 10 6. 6 (g / mol) or less is more preferable, and 2.0 × 10 6 (g / mol) or less is more preferable. In addition, a weight average molecular weight can be obtained as a weight average molecular weight of polystyrene conversion using gel permeation chromatography (GPC).

  The film 10 has a microphase separation structure 13. “Microphase separation structure” refers to an aggregate in which a plurality of microdomains are periodically arranged. A “microdomain” is a phase formed by phase separation of different polymer chains of a block copolymer without mixing with each other.

  The microphase separation structure 13 includes lamellar microdomains 15. The microdomain 15 has a plurality of microdomains 15a and a plurality of microdomains 15b, and the microdomains 15a and the microdomains 15b are alternately stacked in layers. Each of the micro domains 15a and 15b may be oriented substantially parallel to at least one of the front surface 10a or the back surface 10b, for example. Further, each of the micro domains 15 a and 15 b may have a wave shape having an amplitude in the thickness direction of the film 10.

  In the film 10, the block copolymer forms an ordered characteristic microdomain structure. The microdomain 15a includes one polymer chain of the block copolymer, and the microdomains 15a include the same type of polymer chain. The microdomain 15b includes other polymer chains of the block copolymer, and includes the same kind of polymer chains. The microphase separation structure 13 has a refractive index periodic structure formed by alternately laminating the microdomains 15a and the microdomains 15b because the microdomains 15a and the microdomains 15b have different refractive indexes. Yes.

  In addition, the form (morphology) of the micro domain in the film 10 is not limited to a lamellar shape. The form of the microdomain varies depending on the composition of the block copolymer, and may be a form in which one microdomain exists in a matrix composed of another microdomain. As such a form, for example, a cylindrical form in which the one microdomain is a columnar form, a form in which the one microdomain is spherical, and a guilloidal form in which the one microdomain has a network structure The form etc. are mentioned.

  In the present embodiment, in the microphase separation structure 13, pores (voids) 17 are selectively formed in the microdomain 15 a rather than the microdomain 15 b. In the present embodiment, for example, the holes 17 are formed in the microdomain 15a, whereas the holes 17 are not formed in the microdomain 15b. The holes 17 are filled with a gas such as air, for example. The average pore diameter of the pores 17 is, for example, 10 to 200 nm, and the porosity of the microdomain is, for example, 5 to 30% by volume.

  When the pores filled with a gas such as air are formed in the microdomain including the block copolymer, the refractive index of the microdomain tends to decrease. For this reason, in the present embodiment, since the holes 17 are formed in the microdomain 15a, the refractive index of the microdomain 15a tends to be smaller than in a state where the holes 17 are not formed. Thereby, the refractive index difference of the microdomain 15a and the microdomain 15b can be enlarged easily. From the viewpoint of further increasing the difference in refractive index between the microdomain 15a and the microdomain 15b, the refractive index of the microdomain 15a in which the pores 17 are formed in the state in which the pores are not formed in the microdomain is as follows. The refractive index is preferably smaller than the refractive index. Further, from the viewpoint of further increasing the difference in refractive index between the microdomain 15a and the microdomain 15b, the refractive index of the first polymer chain included in the microdomain 15a is the refractive index of the second polymer chain included in the microdomain 15b. It is preferable to be smaller than the rate.

  As shown in FIG. 1A, the microdomain 15b does not need to have holes formed therein, but may have holes formed therein. When pores are formed in the microdomain 15b, for example, the voids are formed in the microdomains 15a and 15b in a state where the porosity of the microdomain 15a is higher than the porosity of the microdomain 15b. The holes 17 are selectively formed in the microdomain 15a rather than the microdomain 15b.

  The polymer photonic crystal constituting the film 10 is prepared by using a photopolymerizable monomer soluble in a block copolymer and a photopolymerization initiator described below as a constituent component other than the block copolymer in the presence of the photopolymerization initiator. It contains a photocurable resin (polymer compound) obtained by polymerization. The photopolymerizable monomer is preferably at least one selected from the group consisting of acrylates and methacrylates.

  The photopolymerizable monomer may be either a monofunctional monomer or a polyfunctional monomer. For example, carboxyethyl acrylate, isobornyl acrylate, octyl acrylate, lauryl acrylate, stearyl acrylate, nonylphenoxy polyethylene glycol acrylate, dicyclopentenyl acrylate , Dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentanyl methacrylate, benzyl methacrylate, octyl methacrylate, 2-ethylhexyl-di Monofunctional monomers such as glycol acrylate, diethylene glycol Acrylate, 1,4-butanediol diacrylate, 1,6-hexanediol acrylate, 1,9-nonanediol diacrylate, polypropylene glycol diacrylate, EO-modified bisphenol A diacrylate, dicyclopentanyl diacrylate, dicyclo Pentenyl diacrylate, neopentyl glycol-modified trimethylolpropane diacrylate, 4,4'-diacryloyloxystilbene, diethylene glycol methacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol methacrylate, 1,9-nonanediol Dimethacrylate, dicyclopentanyl dimethacrylate, neopentyl glycol dimethacrylate, EO-modified bisphenol A dimethacrylate, tris (2- And polyfunctional monomers such as (acryloyloxyethyl) isocyanurate and caprolactone-modified dipentaerythritol hexaacrylate. As the photopolymerizable monomer, a polyfunctional monomer is preferable, and dicyclopentanyl acrylate, neopentyl glycol-modified trimethylolpropane diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol acrylate, 1,9 -Nonanediol diacrylate and caprolactone-modified dipentaerythritol hexaacrylate are more preferable. The said photopolymerizable monomer may be used individually by 1 type, and may mix and use 2 or more types. The content of the photocurable resin is, for example, 40 to 90% by mass based on the total mass of the film 10.

  Moreover, the polymer photonic crystal constituting the film 10 may contain other components in addition to the block copolymer and the photocurable resin. Examples of other components include a plasticizer and a solvent. As a plasticizer and a solvent, the plasticizer and solvent mentioned later in the manufacturing method of the film 10 are mentioned.

  The film 10 according to the present embodiment contains a block copolymer having a first polymer chain and a second polymer chain, and a photocurable resin obtained by photopolymerizing a photopolymerizable monomer, The microphase separation structure 13 includes a microdomain 15 a including a first polymer chain and a microdomain 15 b including a second polymer chain. In such a film 10, since the three-dimensional crosslinking proceeds by photopolymerization of the photopolymerizable monomer, the microphase separation structure 13 is well maintained.

  And in the film 10, the void | hole 17 is selectively formed in the micro domain 15a rather than the micro domain 15b. Thereby, the refractive index of the microdomain 15a tends to be smaller than that in the state where the holes 17 are not formed, and the difference in refractive index between the microdomain 15a and the microdomain 15b can be easily increased. Therefore, the film 10 can obtain excellent optical characteristics.

<Method for producing microphase-separated structure film>
The method for producing a microphase-separated structure film according to the present embodiment includes, for example, a preparation process, a photopolymerization process, a plasticizer elution process, and a solvent removal process in this order.

  In the preparation step, first, the block copolymer is polymerized. Examples of the polymerization method of the block copolymer include living anionic polymerization. The form (morphology) of the microdomain can be adjusted by controlling the amount of monomer charged during polymerization.

  Next, for example, after dissolving the block copolymer and the photopolymerization initiator in the photopolymerizable monomer soluble in the block copolymer and the photopolymerization initiator, the photopolymerizable monomer and the plasticizer are added. By mixing, a polymer solution containing a block copolymer, a photopolymerization initiator, a photopolymerizable monomer and a plasticizer is prepared. At the stage of preparing such a polymer solution, for example, a microphase separation structure is formed by self-assembly of a block copolymer.

  The content of the block copolymer in the polymer solution does not need to be heated in order to reduce the viscosity in the production process, and is based on the total mass of the polymer solution from the viewpoint of making the polymer solution low in viscosity at room temperature and having fluidity. Is preferably 3 to 30% by mass, more preferably 5 to 20% by mass, and even more preferably 7 to 15% by mass. When the content of the block copolymer is less than 3% by mass, the segregation force when forming the microphase separation structure tends to decrease, and the regularity of the microphase separation structure tends to decrease. When the content of the block copolymer exceeds 30% by mass, the segregation force increases, but the viscosity increases, so that the orientation control by applying the flow field tends to be difficult.

  As the photopolymerizable monomer, the above-described photopolymerizable monomer can be used. The content of the photopolymerizable monomer in the polymer solution is, for example, 40 to 90% by mass based on the total mass of the polymer solution.

  The photopolymerization initiator is a polymerization initiator that can be activated by irradiation with actinic rays. As a photopolymerization initiator, molecules are cleaved by irradiation with actinic rays to form radicals, causing a radical polymerization reaction with a photopolymerizable polymer or monomer, thereby causing the material to have a high molecular weight (crosslinking) and gelling. The radical type photoinitiator to be advanced is mentioned. Examples of the photopolymerization initiator include benzyl dimethyl ketal, α-hydroxyalkylphenone, α-aminoalkylphenone and the like, and specifically IRGACURE651 (manufactured by Ciba Specialty Chemicals) and the like. These photoinitiators may be used individually by 1 type, and may mix and use 2 or more types. The content of the photopolymerization initiator is, for example, 0.05 to 0.5% by mass based on the total mass of the photopolymerizable monomer.

  The plasticizer is not particularly limited as long as it dissolves in the solvent used in the plasticizer elution step, and may be solid or liquid at room temperature. The solvent preferably has low solubility in the photopolymerizable monomer. Examples of the plasticizer include at least one selected from the group consisting of phthalic acid esters such as dioctyl phthalate, adipic acid esters, phosphoric acid esters, trimellitic acid esters, and citric acid esters. Among these, phthalic acid esters are preferable from the viewpoint of forming a highly ordered microphase separation structure. In addition, the plasticizer may have a difference in compatibility with each polymer chain of the block copolymer. The content of the plasticizer is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and more preferably 20 to 40% by mass based on the total mass of the polymer solution, from the viewpoint of easy introduction of pores by solvent treatment. Further preferred. When the content of the plasticizer is less than 5% by mass, it tends to be difficult to introduce sufficient pores. When content of a plasticizer exceeds 60 mass%, there exists a tendency for the mechanical strength of a micro phase-separation structure film to fall.

In the photopolymerization step, after forming the polymer solution into a desired shape, the polymer solution is irradiated with actinic rays (for example, ultraviolet rays) to photopolymerize the photopolymerizable monomer in the polymer solution to obtain a resin film. In this case, the three-dimensional crosslinking reaction of the photopolymerizable monomer proceeds, and the microphase separation structure can be fixed by a simple method. The intensity of the actinic ray is, for example, 1000 to 2000 μW / cm 2 . In addition, before irradiating an actinic ray to a polymer solution, a shear flow field etc. may be applied to a polymer solution and the orientation of a micro domain may be adjusted.

  In the plasticizer elution step, the plasticizer contained in the microdomains of the resin film is dissolved in the solvent and eluted by contacting the resin film with a solvent soluble in the plasticizer and allowing the solvent to penetrate into the resin film. Examples of the method of soaking the solvent in the resin film include a method of immersing the resin film in the solvent, a method of spraying the solvent on the resin film, and a method of dropping the solvent on the main surface of the resin film. In addition, after the plasticizer elution process, a part of the plasticizer may remain in the resin film.

  As the solvent, a solvent having compatibility with at least one of the polymer chains of the block copolymer is used, and the compatibility of the block copolymer with the first polymer chain and the compatibility with the second polymer chain are as follows. Different solvents are used. That is, the solvent compatibility with the first polymer chain is higher than the solvent compatibility with the second polymer chain.

  As a solvent, an organic solvent is mentioned from a viewpoint which can dissolve a plasticizer suitably. Further, as the solvent, from the viewpoint of effectively increasing the refractive index difference between the microdomains, a solvent that is easily compatible with the polymer chain contained in the microdomain in which the pores are formed is preferable. For example, the second polymer It is preferable to use a solvent that is more compatible with the first polymer chain than the chain.

  Further, as the solvent, a solvent having a low boiling point and high volatility is preferable from the viewpoint that the solvent can be effectively removed while maintaining the size of the pores in the solvent removal step, For example, a solvent having a boiling point of 100 ° C. or lower is more preferable.

  As the solvent, when the block copolymer is polystyrene-b-poly (tert-butyl methacrylate), an alcohol is preferable, and methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, tert-butyl alcohol, 2- Methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, and the like are more preferable, and methanol, ethanol, 1-propanol, and 2-propanol are more preferable. These solvents tend to have higher compatibility with poly (tert-butyl methacrylate) than compatibility with polystyrene. 1-4 are preferable and, as for carbon number of the said alcohol, 1-2 are more preferable. If the alcohol has more than 4 carbon atoms, the boiling point tends to be high and it becomes difficult to introduce vacancies well.

  Further, when the block copolymer is polystyrene-b-polybutadiene, an alkane compound is preferable, and n-butane, 2-methylpropane, n-pentane, 2-methylbutane, 2,2-dimethylpropane, n-hexane, n -Low boiling point alkane compounds such as octane are more preferred. These solvents tend to have higher compatibility with polybutadiene than compatibility with polystyrene. 4-8 are preferable and, as for carbon number of the said alkane compound, 5-6 are more preferable. The alkane compound has a carbon number of less than 4 and is a gas at normal temperature and pressure, which tends to be difficult to handle. If the alkane compound has more than 8 carbon atoms, the boiling point tends to be high and it becomes difficult to introduce vacancies well.

  In the present embodiment, in order to obtain good optical characteristics, there is a difference in compatibility with the polymer chain depending on the compatibility of the block copolymer with the first polymer chain and the compatibility with the second polymer chain. A selective solvent can be appropriately used. Similarly, in the case of a ternary or higher block copolymer, a solvent can be selected according to the compatibility of each polymer chain. Moreover, the said solvent may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  In the solvent removal step, the solvent remaining in the resin film is removed from the resin film. The removal method of the solvent of a resin film is not specifically limited, For example, a resin film is dried with a blower etc. and a solvent is removed from a resin film. A part of the solvent may remain in the resin film after the solvent removal step.

  In the present embodiment, a microphase-separated structure film (for example, film 10) having microdomains in which pores are formed can be obtained through the above steps. Specifically, in the plasticizer elution step, the solvent in contact with the resin film penetrates into the resin film and comes into contact with the plasticizer, so that the plasticizer is dissolved in the solvent. And the plasticizer which melt | dissolved in the solvent is eluted from a resin film by removing the outside of a film with a solvent, or diffusing the inside of a solvent and removing it outside a film. Thereby, the solvent is filled in the space occupied by the plasticizer in the resin film, and the solvent is dispersed in the resin film.

  By the way, in the resin film, (a) the plasticizer is dispersed only in the first microdomain including the first polymer chain, and the plasticizer is not dispersed in the second microdomain including the second polymer chain. The state may be sufficient, (b) The state by which the plasticizer was disperse | distributed to both the 1st micro domain and the 2nd micro domain may be sufficient. In the case of (a), the solvent remains only in the first microdomain in the plasticizer elution step, and the solvent remaining in the first microdomain is removed from the resin film in the solvent removal step. As a result, voids are formed in the space occupied by the solvent. Thereby, a void | hole is formed only in the inside of a 1st micro domain, and a void | hole is not formed in the inside of a 2nd micro domain. That is, vacancies are selectively formed in the first microdomain rather than the second microdomain.

  In the case of (b), in the plasticizer elution step, the solvent remains in both the first microdomain and the second microdomain. In this case, if a solvent having the same compatibility with each of the microdomains is used, the solvent is removed from each of the microdomains in the solvent removal step, and pores are formed in each of the microdomains to the same extent. Thus, it is difficult to sufficiently increase the refractive index difference between the microdomains.

  On the other hand, in this embodiment, the compatibility of the solvent with respect to the first polymer chain is higher than the compatibility of the solvent with respect to the second polymer chain. In this case, in the first microdomain including the first polymer chain, when the solvent soaks into the first microdomain, the space occupied by the solvent tends to expand so as to promote the contact between the polymer chain and the solvent. There is. Thereby, the size of the space occupied by the solvent tends to be larger in the first microdomain than in the second microdomain. Thereafter, by removing the solvent in the solvent removal step, the space occupied by the solvent is formed as pores. Thereby, although a void | hole is formed in each of a 1st micro domain and a 2nd micro domain, the void | hole formed in the 1st micro domain is more than the void | hole formed in the 2nd micro domain. Also grows. Therefore, a void | hole is selectively formed in a 1st micro domain rather than a 2nd micro domain.

  In the method for producing a microphase-separated structure film according to this embodiment, a photopolymerizable monomer is photopolymerized by irradiating light to a solution containing a block copolymer, a photopolymerizable monomer, a photopolymerization initiator, and a plasticizer. By making it, the resin film containing a plasticizer is obtained. In such a resin film, since the resin film contains a plasticizer, it is easy to maintain a microphase separation structure, and mechanical properties (for example, bending deformation performance) of the film can be improved. Moreover, in the said resin film, even if it is a case where the solvent which melt | dissolves a plasticizer and a resin film is made to contact by the three-dimensional bridge | crosslinking of a block copolymer progressing by photopolymerization of a photopolymerizable monomer. The deformation of the resin film is suppressed.

  And in this embodiment, as above-mentioned, the film 10 in which the void | hole 17 was selectively formed in the micro domain 15a rather than the micro domain 15b is obtained. In such a film 10, the refractive index of the microdomain 15 a tends to be smaller than that in the state where the pores 17 are not formed, and the difference in refractive index between the microdomain 15 a and the microdomain 15 b is easily increased. be able to. Therefore, in the film 10, the film 10 having excellent optical characteristics can be easily obtained.

<Laminated body>
Since the film 10 has a micro domain of a porous body having pores, it may be necessary to improve mechanical strength and chemical resistance. In addition, when an organic solvent (for example, a solvent-based adhesive) or the like soaks in contact with the film 10, the refractive index difference between the microdomains is reduced by filling the pores of the microdomains with the organic solvent or the like, There are cases where the optical properties are degraded, such as the loss of metallic luster. On the other hand, by arranging a support on at least one main surface (front surface 10a, back surface 10b) of the film 10, mechanical strength and chemical resistance are improved as compared with the case where the film 10 is used alone. In addition, it is possible to suppress the organic solvent or the like from coming into contact with the film 10 and deteriorating the optical characteristics.

  FIG. 2 is a view showing the multilayer body according to the first embodiment. Fig.2 (a) is a perspective view of a laminated body, FIG.2 (b) is a schematic cross section along the IIb-IIb line | wire of Fig.2 (a). The laminate 100 according to the first embodiment includes the film 10 and a support 20 that is disposed on the surface 10 a of the film 10. The support 20 has a front surface 20 a and a back surface 20 b that are substantially parallel to each other, and the back surface 20 b is in contact with the front surface 10 a of the film 10.

  FIG. 3 is a view showing a laminated body according to the second embodiment. Fig.3 (a) is a perspective view of a laminated body, FIG.3 (b) is a schematic cross section along the IIIb-IIIb line | wire of Fig.3 (a). A laminate 110 according to the second embodiment includes a film 10 and a support (first support) 20 similar to the laminate 100, and a support (second support) disposed on the back surface 10b of the film 10. 30). The support 30 has a front surface 30 a and a back surface 30 b facing each other substantially in parallel, and the front surface 30 a is in contact with the back surface 10 b of the film 10.

  The thickness of the supports 20 and 30 is, for example, 0.010 to 10.000 mm. The supports 20 and 30 may be disposed on the film 10 via an adhesive.

  The supports 20 and 30 may be opaque or colored, but in the laminate 110, at least one of the support 20 and the support 30 is visible light (for example, a wavelength of 350 to 700 nm). In contrast, it is preferably transparent. In this case, the structural color of the film 10 can be easily recognized while the film 10 is supported by the supports 20 and 30.

  The supports 20 and 30 are formed of a resin material, glass, a metal material, or the like. Examples of the resin material include polyethylene, polypropylene, polyethylene terephthalate, polycarbonate, polystyrene, acrylic resin, and the like. Examples of the metal material include aluminum, stainless steel, and gold.

  Further, as shown below, a protective film may be disposed between the film 10 and the support 20 and / or between the film 10 and the support 30. In this case, when the film 10 and the supports 20 and 30 are laminated, even if the film 10 may come into contact with an organic solvent or the like (for example, an adhesive containing an organic solvent), the film 10 is shielded by the protective film. Thereby, it can suppress that the organic solvent etc. contact the film 10 and the optical characteristic of the film 10 falls.

  FIG. 4 is a view showing a laminate according to the third embodiment. Fig.4 (a) is a perspective view of a laminated body, FIG.4 (b) is a schematic cross section along the IVb-IVb line | wire of Fig.4 (a). The laminate 120 according to the third embodiment includes the film 10 and the support 20 that are the same as the laminate 100, and the protective film 40 disposed between the film 10 and the support 20.

  FIG. 5 is a view showing a laminate according to the fourth embodiment. Fig.5 (a) is a perspective view of a laminated body, FIG.5 (b) is a schematic cross section along the Vb-Vb line | wire of Fig.5 (a). The laminated body 130 which concerns on 4th Embodiment is the film 10, the support body 20, and the support body 30 similar to the laminated body 110, the protective film 50 arrange | positioned between the film 10 and the support body 20, and the film 10 and support. A protective film 60 disposed between the bodies 30.

  The thickness of the protective films 40, 50, 60 is, for example, 0.01 to 0.200 mm. An adhesive layer may be disposed between the protective films 40, 50, 60 and the film 10 and between the protective films 40, 50, 60 and the support 20, 30.

  The protective films 40, 50, 60 may be opaque or colored, but in the laminate 130, at least one of the protective film 50 and the protective film 60 is visible light (for example, a wavelength of 350 to 700 nm). ) Is preferably transparent. In this case, the support in contact with the transparent protective film is preferably transparent to visible light as well. In these cases, it becomes easy to visually recognize the structural color of the film 10.

  Examples of the protective films 40, 50, 60 include a film obtained by applying a photopolymerizable monomer and then curing, a coating film obtained by spray coating, and a metal vapor deposition film such as aluminum or gold. The protective films 40, 50, 60 are preferably films obtained by applying a photopolymerizable monomer and curing it.

  Photopolymerizable monomers include carboxyethyl acrylate, isobornyl acrylate, octyl acrylate, lauryl acrylate, stearyl acrylate, nonylphenoxy polyethylene glycol acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, dicyclopentanyl acrylate, dicyclo Monofunctional monomers such as pentenyl acrylate, benzyl acrylate, phenoxyethyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentanyl methacrylate, benzyl methacrylate, octyl methacrylate, 2-ethylhexyl-diglycol acrylate, diethylene glycol acrylate, 1,4-butane Diol diacrylate, 1,6-he Sundiol acrylate, 1,9-nonanediol diacrylate, polypropylene glycol diacrylate, EO modified bisphenol A diacrylate, dicyclopentanyl diacrylate, dicyclopentenyl diacrylate, neopentyl glycol modified trimethylolpropane diacrylate, 4 , 4'-Diacryloyloxystilbene, diethylene glycol methacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol methacrylate, 1,9-nonanediol dimethacrylate, dicyclopentanyl dimethacrylate, neopentyl glycol dimethacrylate , EO-modified bisphenol A dimethacrylate, tris (2-acryloyloxyethyl) isocyanurate, caprolactone-modified di A polyfunctional monomer such as pentaerythritol hexaacrylate may be mentioned. The photopolymerizable monomer is preferably a polyfunctional monomer, more preferably dicyclopentanyl diacrylate, dicyclopentenyl diacrylate, neopentyl glycol-modified trimethylolpropane diacrylate, or caprolactone-modified dipentaerythritol hexaacrylate. The said photopolymerizable monomer may be used individually by 1 type, and may mix and use 2 or more types.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to this.

<Production of structural coloring film>
Example 1
As a block copolymer, polystyrene-b-poly (tert-butyl methacrylate) (PS-bP (t-BuMA), weight average molecular weight 1.8 × 10 6 [g / mol], composition PS: P (t -BuMA) = 49: 51 [vol%]) was synthesized by living anionic polymerization under vacuum. Next, 1,6-hexanediol acrylate (also known as “1,6-bis (acryloyloxy) hexane”), which is a photopolymerizable monomer, and dioctyl phthalate, which is a plasticizer, are contained at a mass ratio of 70:30. The block copolymer was dissolved in a mixed solvent so as to be 10.0% by mass based on the total mass of the mixture to obtain a mixture. Further, IRGACURE651 (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator is added to the mixture so as to be 0.3% by mass with respect to the content of 1,6-hexanediol acrylate to obtain a polymer solution. It was. A lamellar block copolymer microphase separation structure was formed in this polymer solution, and the polymer solution exhibited a structural color due to the periodic structure of the microphase separation structure.

  A ring-shaped spacer having a thickness of 0.08 mm and an opening inner diameter of 40 mm was placed on the main surface of a circular quartz glass plate (diameter 50 mm, thickness 1.0 mm), and then the polymer solution was dropped into the spacer opening. . Subsequently, a circular quartz glass plate similar to the above was placed on the spacer, and the polymer solution was sandwiched between the quartz glass plates up and down to be developed into a circular film shape.

Thereafter, the polymer solution was cured by irradiating the polymer solution with ultraviolet rays for 5 minutes (1200 μW / cm 2 ) to obtain a resin film having a microphase separation structure containing a plasticizer.

  The resin film containing the plasticizer was immersed in methanol (solvent) and allowed to stand for 15 hours to elute the plasticizer in the film. Thereafter, the film was taken out from the solvent, and the solvent was dried with a blower to obtain a structural color film.

  After drying, a strong mirror-like metallic luster was observed on the methanol-treated film. Since the film was fixed by three-dimensional cross-linking of the photopolymerizable monomer, no significant change in shape such as dissolution of the film in the solvent was confirmed. From the mass comparison before and after the immersion, a decrease in mass of the plasticizer contained in the film was observed, and plasticizer elution was confirmed. Volume shrinkage was also observed. The thickness of the structural color film was 0.075 mm.

(Example 2)
First, a resin film was obtained by the same method as in Example 1. Next, a solvent treatment (plasticizer elution treatment) was applied to the resin film by the same method as in Example 1 except that ethanol was used in place of methanol to obtain a structural color film.

  A strong mirror-like metallic luster was observed on the ethanol-treated film. A large shape change such as dissolution of the film in the solvent was not confirmed. A decrease in the mass of the plasticizer contained in the film was observed, and plasticizer elution was confirmed. Volume shrinkage was also observed. The thickness of the structural color film was 0.075 mm.

(Example 3)
First, a resin film was obtained by the same method as in Example 1. Next, a solvent treatment was applied to the resin film by the same method as in Example 1 except that tert-butyl alcohol was used instead of methanol to obtain a structural color film.

  A strong mirror-like metallic luster was observed on the film treated with tert-butyl alcohol. A large shape change such as dissolution of the film in the solvent was not confirmed. A decrease in the mass of the plasticizer contained in the film was observed, and plasticizer elution was confirmed. Volume shrinkage was also observed. The thickness of the structural color film was 0.075 mm.

(Comparative Example 1)
First, a resin film was obtained by the same method as in Example 1. The resin film was prepared as a structural color film without subjecting the resin film to solvent treatment. No strong mirror-like metallic luster was observed in the structural coloring film.

(Comparative Example 2)
First, a resin film was obtained by the same method as in Example 1. Next, a solvent treatment was applied to the resin film in the same manner as in Example 1 except that n-hexane was used in place of methanol to obtain a structural color film. No strong mirror-like metallic luster was observed in the structural coloring film.

(Comparative Example 3)
First, a resin film was obtained by the same method as in Example 1. Next, a solvent treatment was applied to the resin film by the same method as in Example 1 except that acetone was used instead of methanol to obtain a structural color film. No strong mirror-like metallic luster was observed in the structural coloring film.

(Comparative Example 4)
First, a resin film was obtained by the same method as in Example 1. Next, a solvent treatment was applied to the resin film in the same manner as in Example 1 except that tetrahydrofuran was used in place of methanol to obtain a structural color film. No strong mirror-like metallic luster was observed in the structural coloring film.

<Structural observation>
The scanning electron microscope (SEM) observation result of the cross section of the structural coloring film after the solvent treatment is shown in FIGS. 6 is an SEM photograph of the structural color films of Examples 1 to 3, and FIG. 7 is an SEM photograph of the structural color films of Comparative Examples 2 to 4.

  It was observed that a large number of pores were formed in the structural coloring film by the solvent treatment. In Examples 1 to 3 using a solvent having higher compatibility with poly (tert-butyl methacrylate) than that with polystyrene, it was selective for one side microdomain of the microphase separation structure retained by three-dimensional crosslinking. It was observed that pores were formed in (FIG. 6). In Comparative Example 2 which does not have sufficient compatibility with any polymer chain, it was not observed that pores were selectively formed in one microdomain of the microphase separation structure. Further, in Comparative Examples 3 and 4 in which the compatibility with the polymer chain is the same for each polymer chain, it was not observed that vacancies were selectively formed in one microdomain of the microphase separation structure. .

<Optical characteristic evaluation>
Using a multi-channel spectrophotometric PMA-12 (manufactured by Hamamatsu Photonics), the reflection spectral spectrum of the structural color film was measured. FIG. 8 is a diagram showing a reflection spectrum of the structural color film. The film was slightly shrunk by the solvent treatment, and a shift of the reflection wavelength toward the lower wavelength side was observed. It was confirmed that the reflectance was significantly increased in Examples 1 to 3. In Examples 1 to 3, since pores are selectively formed only in one side component of the micro domain in the micro phase separation structure, the refractive index difference of the refractive index periodic structure is increased, and the reflectance is increased. It is guessed. On the other hand, in Comparative Examples 1 to 4, the reflectance was small, and no significant change was observed in the reflectance even when the solvent treatment was performed.

<Production and evaluation of laminates>
(Adhesion to transparent support)
Using a photo-curable resin (dicyclopentenyloxyethyl acrylate), the structural coloring film of Example 1 was bonded between two transparent polyethylene terephthalate (PET) films (thickness 0.5 mm). A multilayer film body (laminated body) having the structure of PET film-structural coloring film-PET film was obtained. The multilayer film body was a structural color body that was more resistant to deformation such as bending than the structural color film alone.

  The chemical resistance was evaluated by wiping the multilayer film several tens of times with a waste soaked with toluene. In the case of the structural color film alone, phenomena such as deformation, discoloration, and whitening were observed, but when the same treatment was performed on the multilayer film body, no deformation, discoloration, whitening, etc. were observed. It was confirmed that chemical resistance was improved by sandwiching between PET films.

(Protective coating)
A protective film having a thickness of 0.03 mm is obtained by applying dicyclopentenyl diacrylate (containing 0.3% of photopolymerization initiator IRGACURE 651) to the surface of the structural color developing film of Example 1 having a thickness of 0.075 mm and then irradiating with ultraviolet rays And a protective film-covered colored film was obtained.

  When a solvent-based adhesive was applied to the protective film and the protective film-covered structured color-developing film was adhered to the PET plate, there was no deformation, discoloration, etc., and it was possible to adhere while maintaining the metallic luster. Similarly, when a solvent-based adhesive was applied to a structural coloring film that was not covered with a protective film and adhered to a PET board, the organic coloring material contained in the adhesive filled the pores in the structural coloring film, resulting in a metallic luster. Was observed to disappear, and deformation such as deflection was observed.

  DESCRIPTION OF SYMBOLS 10 ... Micro phase-separation structure film, 10a ... Front surface (one main surface), 10b ... Back surface (the other main surface), 13 ... Micro phase-separation structure, 15, 15a, 15b ... Micro domain, 17 ... Pore, 20, 30 ... support, 40, 50, 60 ... protective film, 100, 110, 120, 130 ... laminate.

Claims (5)

  1. A microphase-separated structure film having microdomains in which pores are selectively formed,
    A block copolymer having a first polymer chain and a second polymer chain, and a photocurable resin obtained by photopolymerizing a photopolymerizable monomer, and containing the first polymer chain A microphase separation structure comprising a first microdomain and a second microdomain containing the second polymer chain,
    A microphase-separated structure film, wherein the pores are selectively formed in the first microdomain rather than the second microdomain.
  2.   The microphase-separated structure film according to claim 1, wherein the first microdomain and the second microdomain are lamellar.
  3.   A laminate comprising the microphase-separated structure film according to claim 1 or 2, and a support disposed on at least one main surface of the microphase-separated structure film.
  4. The support is a first support disposed on one main surface of the microphase separation structure film, and a second support disposed on the other main surface of the microphase separation structure film. And having a body,
    The laminate according to claim 3, wherein at least one of the first support and the second support is transparent to visible light.
  5.   The laminated body of Claim 3 or 4 further provided with the protective film arrange | positioned between the said support body and the said micro phase-separation structure film.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09131964A (en) * 1995-11-10 1997-05-20 Daicel Chem Ind Ltd Recording sheet
JPH10330492A (en) * 1997-05-29 1998-12-15 Katsunori Funaki Metal/organic polymer complex and porous body
JPH1180379A (en) * 1997-08-29 1999-03-26 Katsunori Funaki Color-developing polymer structure and its production
JP2000191819A (en) * 1998-12-24 2000-07-11 Daicel Chem Ind Ltd Micro-cell impregnated composite material and its production
JP2007269912A (en) * 2006-03-30 2007-10-18 Nitto Denko Corp Method for producing porous material, porous material, reflection-preventing membrane, method for producing reflection-preventing sheet and reflection-preventing sheet
WO2008047514A1 (en) * 2006-10-20 2008-04-24 Nagoya Institute Of Technology Microphase-separation structure, immobilized microphase-separation structure and wavelength-variable laser oscillator, temperature sensor and light filter using the structure
JP2008297467A (en) * 2007-05-31 2008-12-11 Canon Inc Method for producing polymer porous film and patterning substrate

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09131964A (en) * 1995-11-10 1997-05-20 Daicel Chem Ind Ltd Recording sheet
JPH10330492A (en) * 1997-05-29 1998-12-15 Katsunori Funaki Metal/organic polymer complex and porous body
JPH1180379A (en) * 1997-08-29 1999-03-26 Katsunori Funaki Color-developing polymer structure and its production
JP2000191819A (en) * 1998-12-24 2000-07-11 Daicel Chem Ind Ltd Micro-cell impregnated composite material and its production
JP2007269912A (en) * 2006-03-30 2007-10-18 Nitto Denko Corp Method for producing porous material, porous material, reflection-preventing membrane, method for producing reflection-preventing sheet and reflection-preventing sheet
WO2008047514A1 (en) * 2006-10-20 2008-04-24 Nagoya Institute Of Technology Microphase-separation structure, immobilized microphase-separation structure and wavelength-variable laser oscillator, temperature sensor and light filter using the structure
JP2008297467A (en) * 2007-05-31 2008-12-11 Canon Inc Method for producing polymer porous film and patterning substrate

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