WO2011078265A1 - 有機系離型剤の性能評価方法、モールドの製造方法および微細凹凸構造を表面に有する透明フィルムの製造方法 - Google Patents

有機系離型剤の性能評価方法、モールドの製造方法および微細凹凸構造を表面に有する透明フィルムの製造方法 Download PDF

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WO2011078265A1
WO2011078265A1 PCT/JP2010/073218 JP2010073218W WO2011078265A1 WO 2011078265 A1 WO2011078265 A1 WO 2011078265A1 JP 2010073218 W JP2010073218 W JP 2010073218W WO 2011078265 A1 WO2011078265 A1 WO 2011078265A1
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Prior art keywords
release agent
mold
organic
producing
meth
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PCT/JP2010/073218
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English (en)
French (fr)
Japanese (ja)
Inventor
小澤　覚
祐介 中井
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三菱レイヨン株式会社
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Priority to JP2011502165A priority Critical patent/JP5768711B2/ja
Priority to CN201080058602.2A priority patent/CN102666055B/zh
Priority to KR1020127016718A priority patent/KR101389189B1/ko
Publication of WO2011078265A1 publication Critical patent/WO2011078265A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
    • B29C33/565—Consisting of shell-like structures supported by backing material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/42—Moulds or cores; Details thereof or accessories therefor characterised by the shape of the moulding surface, e.g. ribs or grooves
    • B29C33/424—Moulding surfaces provided with means for marking or patterning
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
    • B29C33/60—Releasing, lubricating or separating agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
    • B29C37/0067—Using separating agents during or after moulding; Applying separating agents on preforms or articles, e.g. to prevent sticking to each other
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • B29C59/04—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing using rollers or endless belts
    • B29C59/046—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing using rollers or endless belts for layered or coated substantially flat surfaces
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/045—Anodisation of aluminium or alloys based thereon for forming AAO templates
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/24—Chemical after-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
    • H01L21/0274—Photolithographic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B29C2035/0827—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using UV radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • B29C59/022—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing characterised by the disposition or the configuration, e.g. dimensions, of the embossments or the shaping tools therefor
    • B29C2059/023—Microembossing

Definitions

  • the present invention relates to a method for evaluating the performance of an organic release agent, a method for producing a mold, and a method for producing a transparent film having a fine concavo-convex structure on the surface.
  • an article having a fine concavo-convex structure with a period of less than or equal to the wavelength of visible light on the surface exhibits an antireflection effect, a Lotus effect, and the like.
  • a fine concavo-convex structure called a moth-eye structure is an effective antireflection means by continuously increasing the refractive index from the refractive index of air to the refractive index of the material of the article. .
  • a method for producing a transparent film having a fine concavo-convex structure on the surface a method is known in which the fine concavo-convex structure on the surface of the mold is transferred to the surface of the base film by an optical nanoimprint method, a thermal nanoimprint method, or the like.
  • Patent Document 1 A step of sandwiching an ultraviolet curable resin composition between a mold having an inverted structure of a fine concavo-convex structure on a surface and a base film serving as a main body of a transparent film; (II) irradiating the ultraviolet curable resin composition with ultraviolet rays, curing the ultraviolet curable resin composition to form a cured film having a fine concavo-convex structure, and obtaining a transparent film; and (III) the mold and Separating the transparent film.
  • Patent Document 1 A step of sandwiching an ultraviolet curable resin composition between a mold having an inverted structure of a fine concavo-convex structure on a surface and a base film serving as a main body of a transparent film; (II) irradiating the ultraviolet curable resin composition with ultraviolet rays, curing the ultraviolet curable resin composition to form a cured film having a fine concavo-convex structure, and obtaining a transparent film; and (III) the mold and Separating the transparent film.
  • the mold surface is usually treated with an organic release agent.
  • the organic mold release agent used for the surface treatment of the mold may be deteriorated by being repeatedly used for the surface treatment of the mold or left for a long time.
  • a mold surface-treated with a deteriorated organic release agent may have insufficient surface releasability, and as a result, a transparent film may not be stably produced.
  • the present invention relates to a method for evaluating the performance of an organic release agent that can easily determine whether the performance is good or not in a short time; a method capable of producing a mold having sufficient surface releasability; and a transparent film having a fine relief structure on the surface A method capable of stably producing the product is provided.
  • the method for producing a mold according to the first aspect of the present invention includes the following steps (I) to (III): (I) The process of producing the mold main body by which the fine uneven structure was formed in the surface; (II) a step of evaluating the performance of the organic mold release agent by the performance evaluation method of the organic mold release agent described below; and (III) the surface of the mold body produced in the step (I) A step of treating with an organic mold release agent determined to have good performance by (II);
  • the performance evaluation method of the organic mold release agent is obtained by mixing an organic mold release agent and a test organic solvent and determining whether the organic mold release agent has good solubility in the test organic solvent. It consists of a method for judging the quality of the agent.
  • the step (I) is preferably a step of forming a mold body by forming anodized alumina having a plurality of pores on the surface of an aluminum substrate.
  • the organic release agent is preferably a fluorine compound having a hydrolyzable silyl group or a silanol group.
  • the dielectric constant of the test organic solvent is preferably 22 to 40.
  • the test organic solvent is preferably ethanol or N, N-dimethylformamide.
  • solubility of the organic release agent in the test organic solvent is preferable to judge the solubility of the organic release agent in the test organic solvent from the light transmittance of the mixture of the organic release agent and the test organic solvent.
  • the organic mold release agent performance evaluation method comprises mixing an organic mold release agent and a test organic solvent, and whether the organic mold release agent is soluble in the test organic solvent. From this, the quality of the organic release agent is judged.
  • the organic release agent is for treating the surface of the mold main body having a fine relief structure formed on the surface.
  • the method for producing a transparent film having a fine concavo-convex structure on the surface in the third aspect of the present invention is based on the fine concavo-convex structure on the surface of the mold obtained by the mold production method according to the first aspect of the present invention. It transfers to the surface of a material film, It is characterized by the above-mentioned.
  • the quality of the organic release agent can be easily determined in a short time.
  • a mold manufacturing method in the first aspect of the present invention a mold having a sufficient surface releasability can be manufactured.
  • the transparent film can be produced stably.
  • (meth) acrylate means acrylate or methacrylate.
  • transparent means that at least light having a wavelength of 400 to 1170 nm is transmitted.
  • the active energy ray means visible light, ultraviolet ray, electron beam, plasma, heat ray (infrared ray or the like) and the like.
  • the organic mold release agent performance evaluation method comprises mixing an organic mold release agent and a test organic solvent, and whether the organic mold release agent is soluble in the test organic solvent. From this, the quality of the organic release agent is judged.
  • the organic mold release agent may be deteriorated by being repeatedly used for the surface treatment of the mold or left for a long period of time, and may not fully exhibit the release property.
  • the present inventors have found that this is because, in the case of a compound having a hydrolyzable silyl group, intermolecular condensation occurs, the reactivity with the mold body is lowered, and the adhesiveness is lowered. .
  • the deterioration of the organic release agent cannot be determined only by the appearance of the organic release agent.
  • the presence / absence of intermolecular condensation can be examined by a nuclear magnetic resonance spectrum or the like, but the measurement takes time and effort, and an expensive apparatus is required.
  • the present inventors have focused on the fact that the solubility of the organic release agent in an organic solvent decreases due to the deterioration of the organic release agent, that is, the increase in the molecular weight of the organic release agent by intermolecular condensation. As a result, the present invention has been completed.
  • the deteriorated organic mold release agent is reduced in solubility in a test organic solvent and becomes cloudy.
  • Examples of the presence or absence of white turbidity and some confirmation methods include a method of measuring light transmittance, a method of measuring light scattering, and the like, and a method of measuring light transmittance is preferred from the viewpoint that it can be easily measured in a short time.
  • the threshold value of the light transmittance as a judgment criterion is For example, it is determined as follows. (1) The light transmittance is measured using a spectrophotometer for a mixture of an organic release agent (unused product) and a test organic solvent before being used for the surface treatment of the mold body. Subsequently, the transparent film mentioned later is manufactured using the mold surface-treated with the organic mold release agent (unused product), and the mold release property is evaluated.
  • Measure light transmittance with a spectrophotometer Specifically, a solution obtained by mixing a release agent solution described later and a test organic solvent in a volume ratio of 2/8 to 8/2 is used as a measurement solution. Moreover, what mixed the dilution solvent used for the mold release agent solution with the organic solvent for a test by the said volume ratio is used for a reference. As a measurement wavelength, an ultraviolet to visible region (for example, about 200 to 900 nm) is used.
  • organic mold release agent examples include silicone resins, fluororesins, fluorine compounds, etc., and fluorine compounds having hydrolyzable silyl groups or silanol groups from the viewpoint of excellent releasability and excellent adhesion to molds. Is preferable, and a fluorine compound having a hydrolyzable silyl group is particularly preferable.
  • fluorine compounds having hydrolyzable silyl groups include fluoroalkylsilanes, KBM-7803 (manufactured by Shin-Etsu Chemical Co., Ltd.), “OPTOOL” series (manufactured by Daikin Industries, Ltd.), Novec EGC-1720 (manufactured by Sumitomo 3M). ) And the like.
  • organic solvent for testing those having a difference in solubility (light transmittance when mixed) between a normal organic release agent and a deteriorated organic release agent are used.
  • the organic solvent for testing is preferably an organic solvent having an appropriate polarity (that is, dielectric constant).
  • the dielectric constant of the test organic solvent is preferably 10 to 70, more preferably 30 to 60, and most preferably 22 to 40.
  • the dielectric constant in the present invention is a relative dielectric constant when the dielectric constant of vacuum is 1, and is a literature value [“Solvent Handbook”, Kodansha Scientific, 1976, p. 734].
  • the organic mold release agent when used for the surface treatment of the mold body, the organic mold release agent is diluted with an organic solvent for dilution so that the surface of the mold body can be uniformly treated and used as a mold release agent solution. Therefore, also in the performance evaluation method of the organic mold release agent of the present invention, the organic mold release agent is a state of the mold release agent solution diluted with an organic solvent for dilution, which is actually used for the surface treatment of the mold body.
  • the organic solvent for dilution is not particularly limited as long as the organic mold release agent dissolves, but when a fluorine compound having a hydrolyzable silyl group or silanol group is used as the organic mold release agent, the solvent has a low dielectric constant. And hexane, chloroform, diethyl ether, tetrahydrafuran, methylene chloride, acetone, acetonitrile, N, N-dimethylformamide and the like can be mentioned.
  • the “OPTOOL” series manufactured by Daikin Industries
  • it is preferable to use the fluorine-based organic solvent “Durasurf” series manufactured by Harves.
  • the organic mold release agent is a fluorine compound having a hydrolyzable silyl group [“OPTOOL” series (manufactured by Daikin Industries)] will be described in more detail.
  • N N-dimethyl is used because the difference in solubility (light transmittance when mixed) between the normal “OPTOOL” series and the deteriorated “OPTOOL” series is large.
  • Formamide is particularly preferred.
  • Durasurf HD-ZV which is a fluorine-based organic solvent, is preferable from the viewpoint of the solubility of the organic release agent.
  • the mixing ratio (release agent solution / N, N-dimethylformamide) of 0.1% by weight release agent solution obtained by diluting “OPTOOL” series with Durasurf HD-ZV and N, N-dimethylformamide is The ratio is preferably 2/8 to 8/2 (volume ratio), more preferably 4/6 to 6/4 (volume ratio), and particularly preferably 5/5 (volume ratio).
  • the organic mold release agent and the test organic solvent are mixed, and the organic mold release into the test organic solvent is performed. Since the quality of the organic release agent is judged from the quality of the solubility of the agent, the quality of the organic release agent can be easily judged in a short time. Since the performance of the organic release agent can be determined in advance, it is possible to avoid the trouble of noticing the deterioration of the mold release property due to the deterioration of the organic release agent after the production of the transparent film is started. Moreover, an organic mold release agent can be used efficiently to the limit.
  • the performance evaluation method according to the second aspect of the present invention is an organic material used when a transparent film is produced using a mold having a fine concavo-convex structure in which pores with an average interval of 20 to 400 nm are formed as described later. Suitable for evaluation of release agents. It is particularly suitable for those in which pores are formed by anodic oxidation.
  • the mold production method according to the first aspect of the present invention is a method having the following steps (I) to (III): (I) The process of producing the mold main body by which the fine uneven structure was formed in the surface; (II) a step of evaluating the performance of the organic mold release agent by the organic mold release agent performance evaluation method described below; and (III) the surface of the mold body produced in the step (I) is the step ( A step of treating with an organic mold release agent determined to have good performance by II);
  • the performance evaluation method of the organic mold release agent is obtained by mixing an organic mold release agent and a test organic solvent and determining whether the organic mold release agent has good solubility in the test organic solvent. It consists of a method for judging the quality of the agent.
  • the performance evaluation method of the organic release agent in the second aspect of the present invention can be used as the performance evaluation method of the organic release agent in the first aspect of the present invention.
  • a fine concavo-convex structure is formed on the surface of the substrate to produce a mold body.
  • the material for the substrate include metals (including those having an oxide film formed on the surface), quartz, glass, resin, ceramics, and the like.
  • the shape of the substrate include a roll shape, a circular tube shape, a flat plate shape, and a sheet shape.
  • the following method (I-1) or (I-2) may be mentioned. From the viewpoint that the area can be increased and the production is simple, the method (I-1 Is particularly preferred.
  • (I-1) A method of forming anodized alumina having a plurality of pores (recesses) on the surface of an aluminum substrate.
  • (I-2) A method of forming a fine relief structure on the surface of a substrate by lithography.
  • a method having the following steps (a) to (e) is preferable.
  • B A step of removing the oxide film and forming anodic oxidation pore generation points on the surface of the aluminum substrate.
  • C A step of anodizing the aluminum substrate again in the electrolytic solution to form an oxide film having pores at the pore generation points.
  • D A step of enlarging the diameter of the pores.
  • E A step of anodizing again in the electrolytic solution after the step (d).
  • F The process of obtaining the mold main body by which the said process (d) and the process (e) are repeated, and the anodized alumina which has several pores was formed in the surface of aluminum.
  • the shape of the aluminum substrate include a roll shape, a circular tube shape, a flat plate shape, and a sheet shape.
  • the aluminum substrate is preferably polished by mechanical polishing, feather polishing, chemical polishing, electrolytic polishing (etching treatment) or the like in order to smooth the surface state.
  • etching treatment electrolytic polishing
  • the purity of aluminum is preferably 99% or more, more preferably 99.5% or more, and particularly preferably 99.8% or more.
  • the purity of aluminum is low, when anodized, an uneven structure having a size to scatter visible light may be formed due to segregation of impurities, or the regularity of pores obtained by anodization may be lowered.
  • the electrolytic solution include sulfuric acid, oxalic acid, and phosphoric acid.
  • the concentration of oxalic acid is preferably 0.7 M or less. When the concentration of oxalic acid exceeds 0.7M, the current value becomes too high, and the surface of the oxide film may become rough. When the formation voltage is 30 to 60 V, anodized alumina having highly regular pores with a period of about 100 nm can be obtained. Regardless of whether the formation voltage is higher or lower than this range, the regularity tends to decrease.
  • the temperature of the electrolytic solution is preferably 60 ° C. or lower, and more preferably 45 ° C. or lower. When the temperature of the electrolytic solution exceeds 60 ° C., a so-called “burn” phenomenon occurs, and the pores may be broken, or the surface may melt and the regularity of the pores may be disturbed.
  • the concentration of sulfuric acid is preferably 0.7M or less. If the concentration of sulfuric acid exceeds 0.7M, the current value may become too high to maintain a constant voltage. When the formation voltage is 25 to 30 V, anodized alumina having highly regular pores with a period of about 63 nm can be obtained. The regularity tends to decrease whether the formation voltage is higher or lower than this range.
  • the temperature of the electrolytic solution is preferably 30 ° C. or less, and more preferably 20 ° C. or less. When the temperature of the electrolytic solution exceeds 30 ° C., a so-called “burn” phenomenon occurs, and the pores may be broken or the surface may melt and the regularity of the pores may be disturbed.
  • the method for removing the oxide film include a method in which aluminum is not dissolved but is dissolved in a solution that selectively dissolves the oxide film and removed. Examples of such a solution include a chromic acid / phosphoric acid mixed solution.
  • the pore diameter expansion treatment is a treatment for expanding the diameter of the pores obtained by anodic oxidation by immersing in a solution dissolving the oxide film. Examples of such a solution include a phosphoric acid aqueous solution of about 5% by mass. The longer the pore diameter expansion processing time, the larger the pore diameter.
  • the mold body 18 is obtained in which the oxide film 14 is formed and anodized alumina (aluminum porous oxide film (alumite)) is formed on the surface of the aluminum substrate 10. It is preferable that the last end is step (d).
  • the total number of repetitions is preferably 3 times or more, and more preferably 5 times or more.
  • the diameter of the pores decreases discontinuously, so that the effect of reducing the reflectance of the moth-eye structure formed using anodized alumina having such pores is insufficient.
  • Examples of the shape of the pore 12 include a substantially conical shape, a pyramid shape, a cylindrical shape, and the like, and a cross-sectional area of the pore in a direction orthogonal to the depth direction such as a conical shape and a pyramid shape has a depth from the outermost surface.
  • a shape that continuously decreases in the direction is preferred.
  • the average interval between the pores 12 is not more than the wavelength of visible light, that is, not more than 400 nm.
  • the average interval between the pores 12 is preferably 20 nm or more.
  • the average interval between the pores 12 was measured by measuring the distance between adjacent pores 12 (distance from the center of the pore 12 to the center of the adjacent pore 12) by electron microscope observation, and averaging these values. It is a thing.
  • the depth of the pores 12 is preferably 80 to 500 nm, more preferably 120 to 400 nm, and particularly preferably 150 to 300 nm.
  • the depth of the pore 12 is a value obtained by measuring the distance between the bottom of the pore 12 and the top of the convex portion existing between the pores 12 when observed with an electron microscope at a magnification of 30000 times. It is.
  • the aspect ratio of the pores 12 is preferably 0.8 to 5, more preferably 1.2 to 4, and particularly preferably 1.5 to 3.
  • Examples of the method for treating the surface of the mold body with an organic release agent include the following methods (II-1) and (II-2), and the surface of the mold body on the side where the fine concavo-convex structure is formed is uneven.
  • the method (II-1) is particularly preferable because it can be treated with an organic release agent.
  • (II-1) A method of immersing the mold body in a release agent solution obtained by diluting an organic release agent with an organic solvent for dilution.
  • (II-2) A method of applying an organic release agent or a release agent solution to the surface of the mold body on the side where the fine relief structure is formed.
  • Examples of the method (II-1) include a method having the following steps (g) to (k).
  • (G) A step of washing the mold main body with water.
  • (H) A step of blowing air to the mold body to remove water droplets attached to the surface of the mold body.
  • (I) A step of immersing the mold body in a release agent solution.
  • (J) A step of slowly lifting the immersed mold body from the solution.
  • (K) A step of drying the mold.
  • the surface of the mold body is determined to have a good performance by the organic mold release agent performance evaluation method. Therefore, it is possible to manufacture a mold having a sufficient surface releasability.
  • transparent film having a fine concavo-convex structure on its surface is the mold of the present invention.
  • This is a production method by a so-called nanoimprint method in which the fine concavo-convex structure on the surface of the mold obtained by the production method is transferred to the surface of the substrate film.
  • the nanoimprint method is a micro-molding method that transfers the mold's fine irregularities by pressing a mold with nano-level fine irregularities on the surface of a resin or other base material. These are classified into photo-nanoimprinting methods based on the photocuring method, and either of them may be used in the present invention.
  • the thermal nanoimprint method is a method in which a base material (thermoplastic material) is heated to a temperature higher than the glass transition temperature (that is, the resin fluidity is increased), the mold is pressed, the base material is cooled, and then the mold is released. is there.
  • the optical nanoimprint method is a method in which an active energy ray curable resin composition is irradiated with an active energy ray such as ultraviolet rays in a state where the mold is pressed against the active energy ray curable resin composition on the substrate surface, and then the active energy ray curable resin composition is cured. Is a method of releasing the mold.
  • a method for producing the transparent film of the present invention a method having the following steps (A) to (C) is preferable.
  • A) An active energy ray-curable resin composition is placed between the surface of a base film and a mold having a reverse structure of a fine concavo-convex structure on the surface and the surface treated with an organic release agent. The process of pinching.
  • the production of the transparent film by the method having the steps (A) to (C) is performed, for example, as follows using a production apparatus shown in FIG.
  • the active energy ray-curable resin composition is transferred from the tank 22 between the roll-shaped mold 20 having a fine concavo-convex structure (not shown) on the surface and the belt-shaped base film 42 that moves along the surface of the mold 20. Supply.
  • the base film 42 and the active energy ray curable resin composition are nipped between the mold 20 and the nip roll 26 whose nip pressure is adjusted by the pneumatic cylinder 24, and the active energy ray curable resin composition is
  • the film 42 and the mold 20 are uniformly distributed, and at the same time, the concave portions of the fine concavo-convex structure of the mold 20 are filled.
  • the active energy ray curable resin composition By irradiating the active energy ray curable resin composition through the base film 42 from the active energy ray irradiating device 28 installed below the mold 20, the active energy ray curable resin composition is cured. Then, the cured film 44 to which the fine uneven structure on the surface of the mold 20 is transferred is formed. By peeling the base film 42 having the cured film 44 formed on the surface from the mold 20 by the peeling roll 30, a transparent film 40 as shown in FIG. 3 is obtained.
  • the active energy ray irradiation device 28 a high-pressure mercury lamp, a metal halide lamp or the like is preferable.
  • the amount of light irradiation energy is preferably 100 to 10,000 mJ / cm 2 .
  • Base film As the base film 42, a film having high transparency is preferable in that the active energy ray is irradiated through the base film 42.
  • the film material include acrylic resin, polyethylene terephthalate, polycarbonate, and triacetyl cellulose.
  • the cured film 44 is a film made of a cured product of an active energy ray-curable resin composition described later, and has a fine uneven structure on the surface.
  • the fine concavo-convex structure on the surface of the transparent film 40 in the case of using the anodized alumina mold is formed by transferring the fine concavo-convex structure on the surface of the anodized alumina, and is an active energy ray-curable resin composition. It has the some convex part 46 which consists of hardened
  • the fine concavo-convex structure is preferably a so-called moth-eye structure in which a plurality of protrusions (convex portions) having a substantially conical shape or a pyramid shape are arranged. It is known that the moth-eye structure in which the distance between the protrusions is less than or equal to the wavelength of visible light is an effective anti-reflection measure by continuously increasing the refractive index from the refractive index of air to the refractive index of the material. It has been.
  • the average interval between the convex portions is preferably not more than the wavelength of visible light, that is, not more than 400 nm.
  • the average distance between the convex portions is about 100 nm, so that it is more preferably 200 nm or less, and particularly preferably 150 nm or less.
  • the average interval between the convex portions is preferably 20 nm or more from the viewpoint of easy formation of the convex portions.
  • the average interval between the convex portions is obtained by measuring 50 intervals between adjacent convex portions (distance from the center of the convex portion to the center of the adjacent convex portion) by electron microscope observation, and averaging these values. .
  • the height of the protrusions is preferably 80 to 500 nm, more preferably 120 to 400 nm, and particularly preferably 150 to 300 nm when the average interval is 100 nm. If the height of the convex portion is 80 nm or more, the reflectance is sufficiently low and the wavelength dependency of the reflectance is small. If the height of a convex part is 500 nm or less, the scratch resistance of a convex part will become favorable.
  • the height of the convex portion is a value obtained by measuring the distance between the top of the convex portion and the lowest portion of the concave portion existing between the convex portions when observed with an electron microscope at a magnification of 30000 times.
  • the aspect ratio of the convex part (height of convex part / average interval between convex parts) is preferably 0.8 to 5.0, more preferably 1.2 to 4.0, and 1.5 to 3.0. Particularly preferred. If the aspect ratio of the convex portion is 1.0 or more, the reflectance is sufficiently low. If the aspect ratio of the convex portion is 5.0 or less, the scratch resistance of the convex portion is good.
  • the shape of the convex part is a shape in which the convex sectional area in the direction perpendicular to the height direction continuously increases in the depth direction from the outermost surface, that is, the sectional shape in the height direction of the convex part is a triangle, trapezoid, A shape such as a bell shape is preferred.
  • the difference between the refractive index of the cured film 44 and the refractive index of the base film 42 is preferably 0.2 or less, more preferably 0.1 or less, and particularly preferably 0.05 or less. If the refractive index difference is 0.2 or less, reflection at the interface between the cured film 44 and the base film 42 is suppressed.
  • the water contact angle on the surface of the fine concavo-convex structure is preferably 90 ° or more, more preferably 110 ° or more, and particularly preferably 120 ° or more. If the water contact angle is 90 ° or more, water stains are less likely to adhere, so that sufficient antifouling properties are exhibited. Moreover, since water does not adhere easily, anti-icing can be expected.
  • the water contact angle on the surface of the fine concavo-convex structure is preferably 25 ° or less, more preferably 23 ° or less, and particularly preferably 21 ° or less. If the water contact angle is 25 ° or less, the dirt attached to the surface is washed away with water, and oil dirt is less likely to adhere, so that sufficient antifouling properties are exhibited.
  • the water contact angle is preferably 3 ° or more from the viewpoint of suppressing the deformation of the fine concavo-convex structure due to water absorption of the cured film 44 and the accompanying increase in reflectance.
  • the active energy ray-curable resin composition contains a polymerizable compound and a polymerization initiator.
  • the polymerizable compound include monomers, oligomers, and reactive polymers having a radical polymerizable bond and / or a cationic polymerizable bond in the molecule.
  • the active energy ray-curable resin composition may contain a non-reactive polymer and an active energy ray sol-gel reactive composition.
  • Examples of the monomer having a radical polymerizable bond include a monofunctional monomer and a polyfunctional monomer.
  • Monofunctional monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, s-butyl (meth) acrylate, t- Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, alkyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, Phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth
  • Polyfunctional monomers include ethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate, triethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate , Neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, polybutylene glycol di (Meth) acrylate, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2,2-bis (4- (3- (Meth) acryloxy-2-hydroxypropoxy) phenyl) propane, 1,2-bis (3- (meth) acryloxy-2-hydroxypropoxy
  • Examples of the monomer having a cationic polymerizable bond include monomers having an epoxy group, an oxetanyl group, an oxazolyl group, a vinyloxy group, and the like, and a monomer having an epoxy group is particularly preferable.
  • oligomer or reactive polymer examples include unsaturated polyesters such as a condensate of unsaturated dicarboxylic acid and polyhydric alcohol; polyester (meth) acrylate, polyether (meth) acrylate, polyol (meth) acrylate, epoxy (meth) Examples thereof include acrylates, urethane (meth) acrylates, cationic polymerization type epoxy compounds, homopolymers of the above-described monomers having a radical polymerizable bond in the side chain, and copolymerized polymers.
  • unsaturated polyesters such as a condensate of unsaturated dicarboxylic acid and polyhydric alcohol
  • non-reactive polymers examples include acrylic resins, styrene resins, polyurethanes, cellulose resins, polyvinyl butyral, polyesters, thermoplastic elastomers, and the like.
  • active energy ray sol-gel reactive composition examples include alkoxysilane compounds and alkyl silicate compounds.
  • R 11 x Si (OR 12 ) y (1) As an alkoxysilane compound, the compound of following formula (1) is mentioned.
  • alkoxysilane compound examples include tetramethoxysilane, tetra-i-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-t-butoxysilane, methyltriethoxysilane, Examples include methyltripropoxysilane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, trimethylpropoxysilane, and trimethylbutoxysilane.
  • alkyl silicate compound examples include a compound of the following formula (2).
  • R 21 to R 24 each represents an alkyl group having 1 to 5 carbon atoms, and z represents an integer of 3 to 20.
  • alkyl silicate compound examples include methyl silicate, ethyl silicate, isopropyl silicate, n-propyl silicate, n-butyl silicate, n-pentyl silicate, acetyl silicate and the like.
  • examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl, benzophenone, p-methoxybenzophenone, 2,2-diethoxy.
  • examples of the polymerization initiator include benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoylbenzoate, 4-phenylbenzophenone, t- Thioxanthones such as butylanthraquinone, 2-ethylanthraquinone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone; diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl Dimethyl ketal, 1-hydroxycyclohexyl-phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpho Benzophene ether such as benzoin methyl ether, benzo
  • thermal polymerization initiator examples include methyl ethyl ketone peroxide, benzoyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxy octoate, organic peroxides such as t-butylperoxybenzoate and lauroyl peroxide; azo compounds such as azobisisobutyronitrile; N, N-dimethylaniline, N, N-dimethyl-p- Examples thereof include a redox polymerization initiator combined with an amine such as toluidine.
  • the amount of the polymerization initiator is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymerizable compound. When the amount of the polymerization initiator is less than 0.1 parts by mass, the polymerization is difficult to proceed. When the amount of the polymerization initiator exceeds 10 parts by mass, the cured film may be colored or the mechanical strength may be lowered.
  • the active energy ray-curable resin composition may contain an antistatic agent, a release agent, an additive such as a fluorine compound for improving antifouling properties; fine particles, and a small amount of a solvent, if necessary.
  • the active energy ray-curable resin composition capable of forming a hydrophobic material includes a fluorine-containing compound or a silicone compound. It is preferable to use a composition.
  • Fluorine-containing compounds As the fluorine-containing compound, a compound having a fluoroalkyl group represented by the following formula (3) is preferable. -(CF 2 ) n -X (3).
  • X represents a fluorine atom or a hydrogen atom
  • n represents an integer of 1 or more, preferably 1 to 20, more preferably 3 to 10, and particularly preferably 4 to 8.
  • fluorine-containing compound examples include a fluorine-containing monomer, a fluorine-containing silane coupling agent, a fluorine-containing surfactant, and a fluorine-containing polymer.
  • fluorine-containing monomer examples include a fluoroalkyl group-substituted vinyl monomer and a fluoroalkyl group-substituted ring-opening polymerizable monomer.
  • fluoroalkyl group-substituted vinyl monomer examples include fluoroalkyl group-substituted (meth) acrylates, fluoroalkyl group-substituted (meth) acrylamides, fluoroalkyl group-substituted vinyl ethers, and fluoroalkyl group-substituted styrenes.
  • fluoroalkyl group-substituted ring-opening polymerizable monomer examples include fluoroalkyl group-substituted epoxy compounds, fluoroalkyl group-substituted oxetane compounds, and fluoroalkyl group-substituted oxazoline compounds.
  • a fluoroalkyl group-substituted (meth) acrylate is preferable, and a compound of the following formula (4) is particularly preferable.
  • CH 2 C (R 41 ) C (O) O— (CH 2 ) m — (CF 2 ) n —X (4).
  • R 41 represents a hydrogen atom or a methyl group
  • X represents a hydrogen atom or a fluorine atom
  • m represents an integer of 1 to 6, preferably 1 to 3, more preferably 1 or 2
  • n represents an integer of 1 to 20, preferably 3 to 10, and more preferably 4 to 8.
  • fluorine-containing silane coupling agent a fluoroalkyl group-substituted silane coupling agent is preferable, and a compound of the following formula (5) is particularly preferable.
  • R f represents a fluorine-substituted alkyl group having 1 to 20 carbon atoms which may contain one or more ether bonds or ester bonds. Examples of R f include 3,3,3-trifluoropropyl group, tridecafluoro-1,1,2,2-tetrahydrooctyl group, 3-trifluoromethoxypropyl group, and 3-trifluoroacetoxypropyl group. It is done.
  • R 51 represents an alkyl group having 1 to 10 carbon atoms. Examples of R 51 include a methyl group, an ethyl group, and a cyclohexyl group.
  • Y represents a hydroxyl group or a hydrolyzable group.
  • the hydrolyzable group include an alkoxy group, a halogen atom, and R 52 C (O) O (wherein R 52 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms).
  • alkoxy group examples include methoxy group, ethoxy group, propyloxy group, i-propyloxy group, butoxy group, i-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, Examples include octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group and the like.
  • halogen atom examples include Cl, Br, I and the like.
  • R 52 C (O) O examples include CH 3 C (O) O, C 2 H 5 C (O) O, and the like.
  • Fluorine-containing silane coupling agents include 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriacetoxysilane, dimethyl-3,3,3-trifluoropropylmethoxysilane, Examples include decafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane.
  • fluorine-containing surfactant examples include a fluoroalkyl group-containing anionic surfactant and a fluoroalkyl group-containing cationic surfactant.
  • fluoroalkyl group-containing anionic surfactant examples include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [omega-fluoroalkyl (C 6 -C 11 ) oxy.
  • fluoroalkyl group-containing cationic surfactant examples include aliphatic quaternary compounds such as fluoroalkyl group-containing aliphatic primary, secondary or tertiary amine acids, and perfluoroalkyl (C 6 -C 10 ) sulfonamidopropyltrimethylammonium salts. Examples thereof include ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like.
  • Fluorine-containing polymers include polymers of fluoroalkyl group-containing monomers, copolymers of fluoroalkyl group-containing monomers and poly (oxyalkylene) group-containing monomers, and copolymers of fluoroalkyl group-containing monomers and crosslinking reactive group-containing monomers. A polymer etc. are mentioned.
  • the fluorine-containing polymer may be a copolymer with another copolymerizable monomer.
  • fluorine-containing polymer a copolymer of a fluoroalkyl group-containing monomer and a poly (oxyalkylene) group-containing monomer is preferable.
  • poly (oxyalkylene) group a group represented by the following formula (6) is preferable.
  • -(OR 61 ) p- (6) R 61 represents an alkylene group having 2 to 4 carbon atoms, and p represents an integer of 2 or more. Examples of R 61 include —CH 2 CH 2 —, —CH 2 CH 2 CH 2 —, —CH (CH 3 ) CH 2 —, —CH (CH 3 ) CH (CH 3 ) —, and the like.
  • the poly (oxyalkylene) group may be composed of the same oxyalkylene unit (OR 61 ) or may be composed of two or more oxyalkylene units (OR 61 ).
  • the arrangement of two or more oxyalkylene units (OR 61 ) may be a block or random.
  • Silicone compounds examples include (meth) acrylic acid-modified silicone, silicone resin, silicone silane coupling agent and the like.
  • examples of the (meth) acrylic acid-modified silicone include silicone (di) (meth) acrylate.
  • an active energy ray-curable resin composition capable of forming a hydrophilic material is a composition containing at least a hydrophilic monomer. It is preferable to use it. From the viewpoint of scratch resistance and imparting water resistance, those containing a cross-linkable polyfunctional monomer are more preferable. In addition, the same (namely, hydrophilic polyfunctional monomer) may be sufficient as the polyfunctional monomer which can be bridge
  • the active energy ray-curable resin composition capable of forming a hydrophilic material it is more preferable to use a composition containing structural units derived from the following polymerizable compounds.
  • a constitutional unit derived from a polyfunctional (meth) acrylate having 4 or more functional groups is 10 to 50% by mass with respect to a total of 100 masses of the constituting units constituting the polymerizable compound, and is composed of a bifunctional or more hydrophilic (meth) acrylate.
  • a composition containing a structural unit derived from a polymerizable compound comprising 30 to 80% by mass of units and 0 to 20% by mass of a structural unit derived from a monofunctional monomer.
  • tetrafunctional or higher polyfunctional (meth) acrylates examples include ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, dipentaerythritol hydroxypenta (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, succinic acid / trimethylolethane / acrylic acid molar mixture 1: 2: 4 condensation reaction mixture, urethane acrylates (manufactured by Daicel-Cytec: EBECRYL220, EBECRYL1290K, EBECRYL1290K, EBECRYL5129, EBECRYL8210, EBECRYL 8301, KRM 8200), polyether acrylates (manufactured by Daicel-Cytec:
  • the proportion of the structural unit derived from a polyfunctional (meth) acrylate having 4 or more functional groups is preferably 10 to 50% by mass, more preferably 20 to 50% by mass from the viewpoint of water resistance and chemical resistance, and 30 to 50% by mass. Is particularly preferred. If the ratio of the tetrafunctional or higher polyfunctional (meth) acrylate-derived constitutional unit is 10% by mass or more, the elastic modulus is increased and the scratch resistance is improved. If the ratio of the tetrafunctional or higher polyfunctional (meth) acrylate-derived constitutional unit is 50% by mass or less, small cracks are unlikely to occur on the surface, and the appearance is unlikely to be poor.
  • Long-chain polyethylene such as Aronix M-240, Aronix M260 (manufactured by Toagosei Co., Ltd.), NK ester AT-20E, NK ester ATM-35E (manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • Examples thereof include polyfunctional acrylates having glycol and polyethylene glycol dimethacrylate. These may be used alone or in combination of two or more.
  • the total of the average repeating units of the polyethylene glycol chain present in one molecule is preferably 6 to 40, more preferably 9 to 30, and particularly preferably 12 to 20. If the average repeating unit of the polyethylene glycol chain is 6 or more, the hydrophilicity is sufficient and the antifouling property is improved. When the average repeating unit of the polyethylene glycol chain is 40 or less, the compatibility with a polyfunctional (meth) acrylate having 4 or more functionalities is improved, and the active energy ray-curable resin composition is hardly separated.
  • the proportion of the structural unit derived from a bifunctional or higher functional hydrophilic (meth) acrylate is preferably 30 to 80% by mass, more preferably 40 to 70% by mass.
  • the proportion of the structural unit derived from a bifunctional or higher hydrophilic (meth) acrylate is 30% by mass or more, the hydrophilicity is sufficient and the antifouling property is improved.
  • the proportion of the structural unit derived from a bifunctional or higher hydrophilic (meth) acrylate is 80% by mass or less, the elastic modulus is increased and the scratch resistance is improved.
  • hydrophilic monofunctional monomers examples include monofunctional (meth) acrylates having a polyethylene glycol chain in the ester group such as M-20G, M-90G, and M-230G (manufactured by Shin-Nakamura Chemical Co., Ltd.), hydroxyalkyl (meth) acrylates, etc. And cationic monomers such as monofunctional (meth) acrylates having a hydroxyl group in the ester group, monofunctional acrylamides, methacrylamidopropyltrimethylammonium methyl sulfate, and methacryloyloxyethyltrimethylammonium methyl sulfate.
  • a viscosity modifier such as acryloylmorpholine or vinylpyrrolidone
  • an adhesion improver such as acryloyl isocyanate for improving the adhesion to the article body, or the like may be used.
  • the proportion of the structural unit derived from the monofunctional monomer is preferably 0 to 20% by mass, and more preferably 5 to 15% by mass.
  • the proportion of the structural unit derived from the monofunctional monomer is 20% by mass or less, the structural unit derived from tetrafunctional or higher polyfunctional (meth) acrylate or the structural unit derived from bifunctional or higher hydrophilic (meth) acrylate is insufficient. Therefore, antifouling property or scratch resistance is sufficiently developed.
  • the monofunctional monomer may be blended in an active energy ray-curable resin composition in an amount of 0 to 35 parts by mass as a low-polymerization polymer obtained by (co) polymerizing one or more types.
  • a polymer having a low degree of polymerization 40/60 of monofunctional (meth) acrylates having a polyethylene glycol chain in an ester group such as M-230G (manufactured by Shin-Nakamura Chemical Co., Ltd.) and methacrylamide propyltrimethylammonium methyl sulfate.
  • Copolymer oligomer (MRC Unitech Co., Ltd., MG polymer) and the like can be mentioned.
  • the use of the transparent film 40 includes an antireflection film, an antifogging film, an antifouling film, a water-repellent film, more specifically, an antireflection film for display, an automobile meter cover, an automobile mirror, an automobile window, organic or inorganic. Electroluminescent light extraction efficiency improving members, solar cell members and the like can be mentioned.
  • the transparent film is not limited to the transparent film 40 in the illustrated example.
  • the fine concavo-convex structure may be directly formed on the surface of the base film 42 without providing the cured film 44. However, it is preferable that the fine concavo-convex structure is formed on the surface of the cured film 44 from the viewpoint that the fine concavo-convex structure can be efficiently formed using the roll-shaped mold 20.
  • a transparent film obtained by the mold manufacturing method of the present invention having a sufficient surface releasability is used. Can be manufactured stably.
  • Example 1 (Preparation of release agent solution) Release tool solution with 0.1% by weight release agent concentration using Optool DSX (Daikin Kogyo Co., Ltd.) as the organic release agent and Durasurf HD-ZV (Harves Co., Ltd.) as the organic solvent for dilution. was prepared.
  • An anodized alumina having a substantially conical pore having an average period of about 100 nm and a depth of about 240 nm is obtained.
  • the mold main body a formed on the surface was obtained.
  • Example 2 Without exchanging the release agent solution of Example 1, the surface treatment of the mold body a with the same release agent solution was repeated 10 times in total. When the light transmittance of a 1: 1 volume ratio mixture of the release agent solution and N, N-dimethylformamide as in Example 1 was measured, the light transmittance at a wavelength of 400 nm was 80%. The fine concavo-convex structure of the mold was transferred onto the acrylic film in the same manner as in Example 1 except that the release agent solution was used. Mold release was performed smoothly.
  • Example 3 Without changing the release agent solution of Example 1, the surface treatment of the mold main body a with the same release agent solution was repeated 20 times in total. When the light transmittance of a 1: 1 volume ratio mixture of the release agent solution and N, N-dimethylformamide as in Example 1 was measured, the light transmittance at a wavelength of 400 nm was 64%. The fine concavo-convex structure of the mold was transferred onto the acrylic film in the same manner as in Example 1 except that the release agent solution was used. Mold release was performed smoothly.
  • the mold obtained by the production method of the present invention is useful for producing an optical film having a fine concavo-convex structure called a moth-eye structure on the surface.

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JP4856785B2 (ja) * 2010-04-09 2012-01-18 三菱レイヨン株式会社 微細凹凸構造を表面に有する物品の製造方法および製造装置
JP2013018214A (ja) * 2011-07-12 2013-01-31 Hitachi Industrial Equipment Systems Co Ltd パターン転写装置およびパターン転写方法
WO2017164046A1 (ja) * 2016-03-23 2017-09-28 シャープ株式会社 光学フィルムの製造方法、及び、金型
WO2021054081A1 (ja) 2019-09-18 2021-03-25 Ｐｈｃホールディングス株式会社 電極基板およびその製造方法、ならびに、そのような電極基板を用いたバイオセンサ

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CN112770885B (zh) * 2018-09-27 2022-01-21 东洋纺株式会社 陶瓷生片制造用脱模薄膜

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JP5768711B2 (ja) 2015-08-26
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