WO2016158979A1 - Composition et article de résine durcissable par rayonnement d'énergie active - Google Patents

Composition et article de résine durcissable par rayonnement d'énergie active Download PDF

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WO2016158979A1
WO2016158979A1 PCT/JP2016/060182 JP2016060182W WO2016158979A1 WO 2016158979 A1 WO2016158979 A1 WO 2016158979A1 JP 2016060182 W JP2016060182 W JP 2016060182W WO 2016158979 A1 WO2016158979 A1 WO 2016158979A1
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polymerizable component
mass
meth
acrylate
resin composition
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PCT/JP2016/060182
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English (en)
Japanese (ja)
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大谷　剛
祐介 中井
哲哉 地紙
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三菱レイヨン株式会社
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Priority to JP2016522083A priority Critical patent/JPWO2016158979A1/ja
Publication of WO2016158979A1 publication Critical patent/WO2016158979A1/fr

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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films

Definitions

  • the present invention relates to an active energy ray-curable resin composition suitable for forming a fine unevenness (nano unevenness) structure, an imprinting raw material containing the active energy ray-curable resin composition, and the active energy ray-curable resin.
  • the present invention relates to an article having a fine concavo-convex structure formed using a composition.
  • a fine concavo-convex structure in which nano-sized fine irregularities are regularly arranged on the surface exhibits antireflection performance due to a continuous change in refractive index.
  • Such a fine concavo-convex structure is generally called a moth-eye structure. It is also known that this fine concavo-convex structure exhibits the same effect as the super water-repellent performance (lotus effect) exhibited by a lotus leaf having a fine concavo-convex structure.
  • the following method has been proposed: (I) a method of transferring a fine concavo-convex structure onto the surface of a thermoplastic resin molded article by injection molding or press molding a thermoplastic resin using a stamper having an inverted structure of the fine concavo-convex structure on the surface; (Ii) An active energy ray-curable resin composition is filled between a stamper having a reverse structure of a fine concavo-convex structure on the surface and a transparent substrate, cured by irradiation with active energy rays, and then the stamper is peeled off.
  • the method (ii) is preferable in consideration of the transferability of the fine relief structure and the degree of freedom of the surface composition.
  • This method is particularly suitable when a belt-shaped or roll-shaped stamper capable of continuous production is used, and is a method with excellent productivity.
  • the fine concavo-convex structure exhibits good antireflection performance when adjacent convex portions or concave portions of the fine concavo-convex portions have an interval equal to or shorter than the wavelength of visible light.
  • the fine concavo-convex structure having such a structure is inferior in scratch resistance as compared with a molded article having a smooth surface and subjected to an abrasion resistance treatment with a hard coat or the like, and has a problem in durability during use. .
  • the cured product of the resin composition used for the production of the fine concavo-convex structure is not sufficiently robust, a phenomenon in which the protrusions tend to come close to each other when being released from the mold or due to heat.
  • a resin composition for forming a fine concavo-convex structure has been proposed.
  • Patent Document 1 discloses that a fine concavo-convex structure having a convex portion (concave portion) interval equal to or less than the wavelength of visible light is prepared using a silica particle packed in a close packing as a template, and a resin composition for forming this fine concavo-convex structure Describes an ultraviolet curable resin composition containing a polyfunctional monomer having many double bonds per molecular weight, such as trimethylolpropane tri (meth) acrylate.
  • a polyfunctional monomer having many double bonds per molecular weight such as trimethylolpropane tri (meth) acrylate.
  • Patent Document 2 discloses a film having a hard coat layer having fine irregularities, and this hard coat layer preferably exhibits a hardness of “H” or higher in a pencil hardness test according to JISK5400, and UV curable resin compositions containing polyfunctional monomers having a large number of double bonds per molecular weight, such as dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, pentaerythritol tetraacrylate, etc. are described as resins for forming the hard coat layer. ing.
  • a resin composition preferable for forming a fine relief structure (1) A photocurable resin composition comprising an acrylate oligomer such as urethane acrylate and a release agent as essential components (Patent Document 3); (2) A photocurable resin composition comprising a (meth) acrylate such as ethoxylated bisphenol A di (meth) acrylate, a reactive diluent such as N-vinylpyrrolidone, a photopolymerization initiator, and a fluorosurfactant.
  • a photocurable resin composition comprising an acrylate oligomer such as urethane acrylate and a release agent as essential components (Patent Document 3); (2) A photocurable resin composition comprising a (meth) acrylate such as ethoxylated bisphenol A di (meth) acrylate, a reactive diluent such as N-vinylpyrrolidone, a photopolymerization initiator, and a fluorosurfactant
  • Patent Document 4 and (3) UV curable resin composition comprising a polyfunctional (meth) acrylate such as trimethylolpropane tri (meth) acrylate, a photopolymerization initiator and a leveling agent such as polyether-modified silicone oil ( Patent Document 1).
  • a polyfunctional (meth) acrylate such as trimethylolpropane tri (meth) acrylate
  • a photopolymerization initiator and a leveling agent such as polyether-modified silicone oil
  • each of the fine concavo-convex structures described in Patent Documents 1 and 2 is a cured product having a high crosslink density and a high elastic modulus, but does not necessarily satisfy the scratch resistance.
  • the antireflection performance may be impaired due to breakage or bending of the fine protrusions particularly in the case of a fine concavo-convex structure. Applications will be limited. Further, in these fine concavo-convex structures, the surface of the fine concavo-convex structure does not exhibit sufficient water repellency.
  • silicone compounds and fluorine compounds that exhibit water repellency are common polyfunctional (meth) acrylates and urethane (meth) acrylates used in active energy ray-curable resin compositions.
  • the application to a hard coat where transparency is required and transparency is required is limited.
  • the main object of the present invention is to provide an article having high water repellency and scratch resistance with an antireflection function by a fine uneven structure, and a high water repellency and scratch resistance with an antireflection function by a fine uneven structure. It is in providing the active energy ray-curable resin composition which can form the hardened
  • An article having a plurality of convex portions on the surface The plurality of convex portions have an average interval between adjacent convex portions of 400 nm or less,
  • the plurality of convex portions are made of a cured product of an active energy ray-curable resin composition,
  • the water contact angle of the part having the plurality of convex portions of the article is 80 degrees or more
  • the active energy ray-curable resinous composition includes a polymerizable component (P), a photopolymerization initiator (E), and an internal release agent (F).
  • P polymerizable component
  • E photopolymerization initiator
  • F internal release agent
  • a monoalkyl phosphate and Articles comprising at least one of dialkyl phosphates are provided.
  • An active energy ray-curable resin composition for forming a fine concavo-convex structure having a plurality of convex portions on the surface having an average interval between adjacent convex portions of 400 nm or less by an imprint method
  • the active energy ray-curable resin composition contains at least a polymerizable component (P), a photopolymerization initiator (E), and an internal release agent (F), Alkanediol di (meth) which is an esterified product of an alkanediol having 6 or more carbon atoms and (meth) acrylic acid as the polymerizable component (A) with respect to 100% by mass of the total amount of the polymerizable component (P).
  • an active energy ray-curable resin composition in which the internal release agent (F) contains at least one of a monoalkyl phosphate and a dialkyl phosphate.
  • An article comprising a cured product of the above active energy ray-curable resin composition, and having a fine concavo-convex structure on the surface having a plurality of convex portions on the surface having an average interval between adjacent convex portions of 400 nm or less, An article in which the contact angle of water on the surface of the fine concavo-convex structure is 80 degrees or more is provided.
  • an article having high water repellency and scratch resistance along with an antireflection function due to a fine concavo-convex structure, and a high water repellency and scratch resistance along with an antireflection function due to a fine concavo-convex structure An active energy ray-curable resin composition capable of forming a cured product that can be easily peeled off from a stamper can be provided.
  • the active energy ray-curable resin composition (X) includes a polymerizable component (P), a photopolymerization initiator (E), and an internal release agent (F), and an active energy ray is added thereto. By irradiating, the polymerization reaction proceeds and cures.
  • This active energy ray-curable resin composition contains, as an internal release agent (F), at least one of phosphoric acid monoester and phosphoric acid diester as an essential component.
  • the polymerizable component (P) preferably contains at least one of silicone (meth) acrylate and alkyl (meth) acrylate as the polymerizable component (B).
  • the polymerizable component (P) has a SP value (solubility parameter) calculated by the Fedors method of 19.6 with respect to 100% by mass of the total amount of the polymerizable component (P) as the polymerizable component (A). It is preferable to contain the following polymerizable components in an amount of 50% by mass to 100% by mass.
  • the polymerizable component (P) preferably contains, as the polymerizable component (A), an alkanediol di (meth) acrylate that is an esterified product of an alkanediol having 6 or more carbon atoms and (meth) acrylic acid.
  • the SP value calculated by the Fedors method of alkanediol di (meth) acrylate is more preferably 19.6 or less.
  • the polymerizable component (P) preferably includes the polymerizable component (A) described above and a polymerizable component (B) that is at least one of silicone (meth) acrylate and alkyl (meth) acrylate.
  • the polymerizable component (P) preferably further contains a polymerizable component (C) which is a polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in the molecule,
  • the polymerizable component (D) can be included.
  • this active energy ray curable resin composition may contain another component (G) as needed.
  • the surface of the cured product of the active energy ray-curable resin composition (X) has a fine concavo-convex structure
  • At least one of monoalkyl phosphate and dialkyl phosphate is included as the internal mold release agent (F).
  • the content of the internal release agent (F) can be set in the range of 0.01 to 2.0 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable component (P). From the viewpoint of obtaining a sufficient release effect, 0.05 part by mass or more is preferable, and 0.1 part by mass or more is more preferable.
  • the internal release agent (F) may be separated or precipitated from the active energy ray-curable resin composition, or the active energy ray-curable resin composition.
  • the internal mold release agent (F) may bleed from the cured product.
  • the content of the internal release agent (F) is preferably 2.0 parts by mass or less, and more preferably 1.0 part by mass or less.
  • the content of the photopolymerization initiator (E) can be set in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable component (P).
  • the content of the polymerizable component (A) is 50 to 99.5% by mass
  • the content of the polymerizable component (B) is preferably 0.5 to 50% by mass.
  • the polymerizable component (P) further contains a polymerizable component (C)
  • the content of the polymerizable component (A) is 50 to 89.5% by mass
  • the content of the polymerizable component (B) is 0.5 to 40% by mass
  • the content of the polymerizable component (C) is preferably 10 to 49.5% by mass.
  • the phosphoric acid monoester of the polymerizable component (B) is preferably a non-oxyalkylenated silicone (meth) acrylate.
  • the alkyl (meth) acrylate of the polymerizable component (B) is preferably an alkyl (meth) acrylate having an alkyl group having 8 to 22 carbon atoms.
  • the content of the polymerizable component having a polyoxyalkylene skeleton is preferably less than 10% by mass, and more preferably 5% by mass or less.
  • the content of the polymerizable component having an alicyclic structure is preferably less than 17% by mass and more preferably 10% by mass or less with respect to 100% by mass of the total amount of the polymerizable component (P). .
  • an imprinting raw material containing the active energy ray-curable resin composition can be provided.
  • an article containing a cured product of the above active energy ray-curable resin composition can be provided.
  • the cured resin layer formed on the base material can be included.
  • it can have the fine concavo-convex structure which consists of a some convex part on the surface of this hardened
  • the average interval between adjacent convex portions is preferably 400 nm or less.
  • the contact angle of water on the surface of the fine concavo-convex structure is preferably 80 degrees or more, and more preferably 135 degrees or more.
  • the article according to the embodiment of the present invention can be applied to a display member, an antireflection article, and a water repellent film.
  • the internal mold release agent (F) contains at least one of phosphoric acid monoester and phosphoric acid diester.
  • an internal mold release agent to be added to the active energy ray-curable resin composition in a method of using an anodized porous alumina as a stamper and curing the active energy ray-curable resin composition to transfer the fine uneven structure to the cured product It has been known to use phosphate ester compounds. Further, among the phosphoric acid ester compounds, it has been known that a (poly) oxyalkylene alkyl phosphoric acid compound and a phosphoric acid triester compound is excellent in releasability.
  • the active energy ray-curable resin composition having a polymerizable component (A) which is alkanediol di (meth) acrylate as a main component and a small content of oxyalkylene skeleton component is used as an internal mold release agent (poly).
  • a polymerizable component (A) which is alkanediol di (meth) acrylate as a main component and a small content of oxyalkylene skeleton component is used as an internal mold release agent (poly).
  • an oxyalkylene alkyl phosphate compound and a phosphate triester compound are used, the peel strength from the stamper after curing is large, and the effect of a water repellency imparting component such as a polymerizable component (B) is also obtained.
  • the present inventors have found as a new problem that it cannot be fully exhibited.
  • the obtained article having a fine concavo-convex structure preferably has a water contact angle of the surface of the fine concavo-convex structure of 80 degrees or more, more preferably 100 degrees or more, and further preferably 130 degrees or more, 135 degrees or more is particularly preferable.
  • the phosphoric acid monoester and / or phosphoric acid diester has a hydroxyl group as compared with the phosphoric acid triester, it is considered that the adsorbing power to the stamper surface made of anodized porous alumina is excellent.
  • the surface of anodized porous alumina is considered to contain not only pure aluminum oxide but also aluminum hydroxide and aluminum oxide hydrate, and phosphoric acid monoester and / or phosphorus
  • the hydroxyl group of the acid diester is considered to have a strong interaction with aluminum hydroxide and aluminum oxide, but the detailed mechanism is not clear.
  • monoalkyl phosphates and / or dialkyl phosphates have a high hydrophobicity because they do not have an oxyalkylene skeleton, making the stamper surface more hydrophobic. it can.
  • the surface of the stamper becomes hydrophobic and the surface free energy decreasing, the surface of the fine concavo-convex structure obtained as a cured product of the active energy ray-curable resin composition (X) formed using the stamper is also hydrophobic. It is easy to become.
  • the repellent properties contained in the active energy ray-curable resin composition (X) are present.
  • the hydrophobic functional group of the aqueous imparting component is oriented on the stamper side, and the surface of the fine uneven structure obtained as a cured product of the active energy ray-curable resin composition (X) becomes hydrophobic.
  • the alkyl group has a carbon number of, for example, 1 to 20, preferably 6 to 20, more preferably 8 to 18 can be used.
  • the internal mold release agent (F) Commercially available products of the internal mold release agent (F) include, for example, trade names manufactured by Nikko Chemicals: DDP-2, DDP-4, DDP-6, DDP-8, DDP-10, and products manufactured by Johoku Chemical Industry Co., Ltd. Name: JP-512, JP-513, JAMP-8, JAMP-12, product name manufactured by Daihachi Chemical Industry: AP-8, AP-10, MP-10, product name manufactured by SC Organic Chemicals: Phoslex Series: A-8, A-10, A-12, A-13, A-18, A-18D, A-180L, and the like.
  • monoalkyl phosphate and / or dialkyl phosphate trade names manufactured by Johoku Chemical Industry Co., Ltd .: JP-512, JP-513, JAMP-8, JAMP-12, Daihachi Chemical Industry Co., Ltd.
  • the polymerizable component (A) has an effect of improving scratch resistance, weather resistance, and substrate adhesion to the cured product of the active energy ray-curable resin composition according to the embodiment of the present invention.
  • the substrate adhesion is effective for polycarbonate resins and acrylic resins.
  • the compatibility improvement of active energy ray curable resin composition and the effect of low viscosity can also be acquired.
  • the polymerizable component (A) a polymerizable component having an SP value calculated by the Fedors method of 19.6 or less is preferable.
  • the SP value exceeds 19.6
  • the compatibility between the polymerizable component (A) and the above-mentioned internal mold release agent (F) and the polymerizable component other than the polymerizable component (A) is decreased, and is obtained.
  • the cured product may become cloudy.
  • cured material can be made hydrophobic by using a component with SP value 19.6 or less.
  • alkanediol di (meth) acrylate can be used as the polymerizable component (A).
  • carbon number of alkanediol which is a raw material of alkanediol di (meth) acrylate 7 or more are more preferable, 8 or more are further more preferable, and 9 or more are especially preferable. If the carbon number of the alkane part is too small, the cured product of the active energy ray-curable resin composition becomes too hard, and the fine uneven structure becomes brittle and easily damaged. On the other hand, when the carbon number of the alkane part is too large, the alkanediol di (meth) acrylate has crystallinity and the handleability may be significantly reduced.
  • the carbon number of the alkanediol as the raw material for the polymerizable component (A) is preferably 12 or less, and more preferably 10 or less.
  • the alkane part may have a linear structure or a branched structure, or a mixture of both. By giving a branched structure, the crystallinity can be lowered, and it becomes liquid even at a low temperature, and the handleability can be improved.
  • the cycloalkane structure has an effect of increasing the glass transition temperature of the cured product and hardening it.
  • polymerizable component (A) examples include, for example, 1,6-hexanediol di (meth) acrylate, 1,7-heptanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, 1,16-hexadecanediol di (meth) acrylate acrylate, batyl Alcohol di (meth) acrylate, 3-methyl 1,5-pentanediol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 2-ethyl-2-butyl-propanediol di ( Meth) acrylate, dimer diol di (
  • the content ratio of the polymerizable component (A) can be set in the range of 50 to 100% by mass in the total amount of 100% by mass of the polymerizable component (P). 60 mass% or more is further more preferable from the point which acquires more sufficient addition effect. From the viewpoint of obtaining the effect of the other polymerizable component while obtaining the sufficient effect of the polymerizable component (A), the content of the polymerizable component (A) is preferably 90% by mass or less, and more preferably 85% by mass or less. . If the content of the polymerizable component (A) is 50% by mass or more, in the cured product, it is possible to obtain excellent effects such as scratch resistance, weather resistance, and substrate adhesion. In the resin composition, The effect of lowering the viscosity and improving the compatibility with other polymerizable components such as the polymerizable component (B) can be expected.
  • the polymerizable component (B) has an effect of imparting water repellency and antifouling properties and improving scratch resistance to the cured product of the active energy ray-curable resin composition according to the embodiment of the present invention. In addition, there is a case where it plays an auxiliary role with respect to improvement of releasability.
  • Polymerizable component (B) is silicone (meth) acrylate and / or alkyl (meth) acrylate.
  • silicone (meth) acrylate and alkyl (meth) acrylate will be described separately.
  • Silicone (meth) acrylate is (meth) acrylate having a silicone skeleton.
  • silicone (meth) acrylate suitable for the present invention will be specifically described with some examples.
  • silicone (meth) acrylate examples include silicone (meth) acrylate having a propyl (meth) acrylate structure at both terminals and / or one terminal represented by the following formula 1.
  • the weight average molecular weight of the silicone (meth) acrylate represented by the formula (1) is preferably about 500 to 2,000.
  • Examples of commercially available products of such polymerizable component (B) include, for example, product names of “Silaplane (registered trademark)” series manufactured by JNC: FM-0711, FM-0721, FM-0725, FM-7711, FM-7721, FM-7725, product names manufactured by Shin-Etsu Chemical Co., Ltd .: X-22-2445, X-22-174ASX, X-22-174BX, X-22-174DX, KF-2012, X-22-2426 X-22-2475, X-22-164, X-22-164AS, X-22-164A, X-22-164B, X-22-164C, X-22-164E, manufactured by Toray Dow Corning Product name: BY16-152C, etc.
  • silicone (meth) acrylate examples include silicone epoxy (meth) acrylate represented by the following formula (2).
  • Examples of commercially available products of silicone (meth) acrylate represented by the formula (2) include product names of “Tego (registered trademark) series” manufactured by Evonik Japan Co., Ltd .: Rad2011, Rad2100, Rad2500, and the like.
  • silicone (meth) acrylates include (meth) acrylates in which both ends of polydimethylsiloxane are modified with EO and / or PO.
  • Examples of commercially available products include product names manufactured by Shin-Etsu Chemical Co., Ltd .: X-22-1602, product names manufactured by Big Chemie Japan, Inc .: BYK-UV3500, BYK-UV3530, and product names manufactured by Evonik Japan: "Tego” (registered trademark) series: Rad2200N, Rad2250, Rad2300, product name manufactured by Daicel Ornex Co., Ltd .: EBECRYL 350, and the like.
  • the above “EO modification” means ethylene oxide modification
  • PO modification means propylene oxide modification.
  • silicone (meth) acrylate examples include urethane (meth) acrylate and / or polyester (meth) acrylate having a silicone skeleton, for example, polyester-modified polydimethylsiloxane having a (meth) acryloyl group, polydimethylsiloxane Examples thereof include urethane (meth) acrylate having a structure.
  • examples of commercially available products include BYK-UV3570, product name manufactured by Big Chemie Japan, and product names manufactured by Miwon Specialty Chemical: “Miramer (registered trademark)” series: SIU100, SIU1000, SIU2400, SIP900, and the like. It is done.
  • Examples of commercially available products of silicone (meth) acrylates other than those mentioned above include BYK-UV3505, 3530, 3575, and 3576 manufactured by BYK-Chemie Japan, and EBECRYL 1360 manufactured by Daicel Ornex. .
  • silicone (meth) acrylates used as the polymerizable component (B) mentioned above silicone (meth) acrylate represented by formula (1), silicone (meth) acrylate represented by formula (2), and BYK- Those selected from UV3570 are preferable in terms of water repellency, scratch resistance and weather resistance.
  • the silicone (meth) acrylate shown in (1) is preferably used from the viewpoint of imparting super water repellency.
  • Silicone (meth) acrylate having an oxyalkylene structure has good compatibility but may be inferior in terms of weather resistance. Therefore, from the viewpoint of weather resistance, a non-oxyalkylenated silicone (meth) acrylate having no oxyalkylene skeleton is preferable as the polymerizable component (B).
  • the alkyl (meth) acrylate used as the polymerizable component (B) preferably has a relatively long alkyl group from the viewpoint of improving the water repellency and scratch resistance of the cured product.
  • the alkyl group preferably has 8 to 22 carbon atoms, more preferably 12 to 18 carbon atoms.
  • the alkyl group may be linear or branched. If the alkyl group is too long, the crystallinity increases and handling in a liquid state becomes difficult, and if it is too short, volatility may be a problem.
  • alkyl (meth) acrylate examples include (iso) octyl (meth) acrylate, (iso) decyl (meth) acrylate, (iso) lauryl (meth) acrylate, (iso) cetyl (meth) acrylate, ( Examples include iso) stearyl (meth) acrylate and (iso) behenyl (meth) acrylate. Among these, isostearyl (meth) acrylate is particularly preferable in terms of imparting water repellency and handling.
  • the content ratio of the polymerizable component (B) can be set in the range of 0.5 to 50% by mass in 100% by mass of the total amount of the polymerizable component (P). 1 mass% or more is more preferable from the point which acquires sufficient addition effect. If the addition amount of the polymerizable component (B) is too large, the physical properties of the cured product may be lowered, and the scratch resistance may be lowered. Therefore, the content of the polymerizable component (B) is preferably 40% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less.
  • the polymerizable component (B) When the content of the polymerizable component (B) is 0.5% by mass or more, for example, the polymerizable component (A) is 50 to 99.5% by mass, the polymerizable component (B) is 0.5 to 50% by mass,
  • the polymerizable component (C) can be set to 0 to 49.5 mass%, the polymerizable component (A) is 50 to 89.5 mass%, the polymerizable component (B) is 0.5 to 40 mass%, the polymerizable component ( C) It can be set to 10 to 49.5% by mass.
  • the content of the polymerizable component (B) is 1% by mass or more, for example, the polymerizable component (A) is 50 to 99% by mass, the polymerizable component (B) is 1 to 50% by mass, the polymerizable component (C) 0
  • the polymerizable component (A) can be set to 50 to 89% by mass, the polymerizable component (B) 1 to 40% by mass, and the polymerizable component (C) 10 to 49% by mass.
  • the polymerizable component (C) is a polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups).
  • the polymerizable component (C) can impart hardness to the cured product as the number of (meth) acryloyl groups per molecular weight increases.
  • those having a smaller molecular weight and those having a methyl group in the molecule are excellent in compatibility with other polymerizable components such as the polymerizable component (B).
  • those having a polyether structure may have poor compatibility with other polymerizable components such as the polymerizable component (B) and weather resistance.
  • polymerizable component (C) examples include, for example, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, (poly) glycerin (poly) acrylate, Pentaerythritol (tri) tetraacrylate, pentaerythritol (tri) tetramethacrylate, dipentaerythritol (penta) hexaacrylate, dipentaerythritol (penta) hexamethacrylate, polypentaerythritol poly (meth) acrylate, and their EO modifications, PO-modified or caprolactone-modified (meth) acrylate, and tri- or more functional urethane (meth) acrylate, tri- or more functional epoxy (meth) acrylate, tri- or more functional polymer
  • trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol (tri) tetraacrylate, and pentaerythritol (tri) tetramethacrylate are polymerizable components. From the viewpoint of compatibility with (B) and scratch resistance. Further, EO-modified products and PO-modified products are concerned in terms of weather resistance, so caprolactone-modified products are preferable in terms of weather resistance.
  • (tri) tetra in the names of specific examples of the polymerizable component (C) means a tribody, a tetrabody or a mixture thereof
  • (penta) hexa means a pentabody, a hexabody. Or a mixture thereof.
  • pentaerythritol (tri) tetraacrylate means pentaerythritol triacrylate (tri), pentaerythritol tetraacrylate (tetra), or a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate.
  • dipentaerythritol (penta) hexaacrylate is dipentaerythritol pentaacrylate (penta), dipentaerythritol hexaacrylate (hexa), or a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate. Means.
  • the content ratio of the polymerizable component (C) can be set in a range of 0 to 50% by mass in 100% by mass of the total amount of the polymerizable component (P). From the viewpoint of obtaining a sufficient addition effect, 5% by mass or more is preferable, and 10% by mass or more is more preferable.
  • 5% by mass or more is preferable, and 10% by mass or more is more preferable.
  • cured material will be sufficient by the problem of compatibility with other polymeric components, such as polymeric component (B). It may become impossible to maintain.
  • the content of the polymerizable component (C) can be set to 49.5% by mass or less, preferably 30% by mass or less, and preferably 25% by mass or less from the viewpoint of sufficiently securing the content of other polymerizable components. Is more preferable.
  • the other polymerizable component (D) has a polymerizable functional group having copolymerizability with other polymerizable components in the polymerizable component (P), and the polymerizable components (A), (B), It does not belong to (C).
  • the polymerizable functional group of the polymerizable component (D) is preferably radically polymerizable, and examples thereof include a methacryloyl group, an acryloyl group, an acrylamide group, a vinyl ether group, and a vinyl group.
  • Examples of functions that can be imparted with the polymerizable component (D) include substrate adhesion, dilution, water repellency, hydrophilicity, antistatic properties, slipperiness, leveling properties, scratch resistance, weather resistance, and light emission. Properties, fluorescence, color developability, conductivity, refractive index adjustment, and antioxidant.
  • Examples of the monofunctional polymerizable component (D) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, Alkyl (meth) acrylates such as 2-ethylhexyl (meth) acrylate and lauryl (meth) acrylate; benzyl (meth) acrylate; isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, adamantyl (meth) acrylate, dicyclopenta (Meth) acrylate having an alicyclic structure such as nyl (meth) acrylate and dicyclopentenyl (meth) acrylate; and having an amino group such as dimethylaminoethyl (meth) acrylate and dimethylaminopropy
  • 1,2,2,6,6-pentamethyl-4-piperidyl (meth) acrylate, 2,2,6 , 6-Tetramethyl-4-piperidyl (meth) acrylate, 2-tert-butyl acrylate-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl, 2-acrylate [1- (2-hydroxy-3,5-di-tertiary pen Ruphenyl) ethyl] -4,6-di-tertiarypentylphenyl, 3- (2H-1,2,3-benzotriazol-2-yl) -4-hydroxyphenethyl methacrylate, 3,3,4,4 , 5,5,6,6,7,7,8,8,8-tridecafluorooctyl (meth) acrylate and the like.
  • the bifunctional polymerizable component (D) includes all the bifunctional polymerizable components not included in the polymerizable component (A) and the polymerizable component (B).
  • Examples of such a bifunctional polymerizable component (D) include 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,5-pentanediol di (meta).
  • neopentyl glycol di (meth) acrylate diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di ( (Meth) acrylate, tripropylene glycol di (meth) acrylate, alkoxylated alkanediol di (meth) acrylate, alkoxylated bisphenol A di (meth) acrylate, hydroxypivalate neopentyl glycol (Meth) acrylate, caprolactone-modified hydroxypivalic acid neopentyl glycol di (meth) acrylate, alkoxylated neopentyl glycol di (meth) acrylate, polycarbonate diol di (meth) acrylate, (hydrogenated) polybutadiene-terminated (meth)
  • the content of the polymerizable component (D) is not particularly limited as long as it does not inhibit the functions of the polymerizable component (A), the polymerizable component (B), and the polymerizable component (C). , 0 to 50% by mass, preferably 0 to 30% by mass, more preferably 0 to 10% by mass.
  • the content of the polymerizable component having a polyoxyalkylene skeleton is preferably less than 10% by mass relative to 100% by mass of the total amount of the polymerizable component.
  • the polymerizable component having a polyoxyalkylene skeleton is contained in an amount of 10 parts by mass or more, the cured product of the active energy ray-curable composition becomes hydrophilic, and the article having a fine uneven structure may not exhibit sufficient water repellency. In addition, the scratch resistance and weather resistance may be reduced.
  • the content of the polymerizable component having a polyoxyalkylene skeleton is preferably 8% by mass or less and more preferably 6% by mass or less with respect to 100% by mass of the total amount of the polymerizable component.
  • content of the polymerization component of the component which has an alicyclic structure is less than 17 mass% with respect to 100 mass% of polymerizable components (P).
  • the polymerizable component having an alicyclic structure is contained in an amount of 17% by mass or more, the Tg of the cured product is increased, and when a fine concavo-convex structure is formed, the convex part forming the concavo-convex becomes brittle and the scratch resistance is reduced. There is a fear.
  • the content of the polymerizable component having an alicyclic structure is preferably 10% by mass or less, more preferably 5% by mass or less, and more preferably 0% by mass with respect to 100% by mass of the total amount of the polymerizable component. More preferably it is.
  • the photopolymerization initiator (E) is a compound that generates a radical that is cleaved by irradiating active energy rays to initiate a polymerization reaction.
  • active energy ray ultraviolet rays are preferable from the viewpoint of apparatus cost and productivity.
  • Examples of the photopolymerization initiator (E) that generates radicals by ultraviolet rays include benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoylbenzoate, 4-phenylbenzophenone, t -Butylanthraquinone, 2-ethylanthraquinone, thioxanthones (2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, etc.), acetophenones (diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane) -1-one, benzyldimethyl ketal, 1-hydroxycyclohexyl-phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2- Methylamino-1- (4-
  • photopolymerization initiator (E) one type may be used alone, or two or more types may be used in combination. When using together, it is preferable to use together 2 or more types from which absorption wavelength differs. Moreover, you may use together thermal polymerization initiators, such as persulfate (potassium persulfate, ammonium persulfate, etc.), peroxides (benzoyl peroxide, etc.), an azo initiator, as needed.
  • the content of the photopolymerization initiator (E) is preferably 0.01 to 10 parts by mass with respect to a total of 100 parts by mass of the polymerizable components (P) contained in the active energy ray-curable resin composition (X). 0.1 to 5 parts by mass is more preferable, and 0.2 to 3 parts by mass is even more preferable.
  • a photoinitiator (E) hardening of active energy ray-curable resin composition (X) may not be completed, and the mechanical physical property of the article
  • the unreacted photopolymerization initiator (E) remains in the cured product, which acts as a plasticizer, lowers the elastic modulus of the cured product, and is scratch resistant. Sexuality may be impaired. Moreover, it may cause coloring.
  • the other component (G) is a component added as necessary, and is a component other than the polymerizable component (P), the photopolymerization initiator (E), and the internal release agent (F).
  • Other components (G) are flame retardant aids, plasticizers, surfactants, antistatic agents, antioxidants, light stabilizers, polymerization inhibitors, ultraviolet absorbers, fillers, adhesion promoters, colorants. , Reinforcing agents, inorganic fillers, impact modifiers and the like.
  • an oligomer or polymer that does not have a radical polymerizable functional group, a trace amount of an organic solvent, or the like may be included.
  • polymerization inhibitor examples include hydroquinone (HQ) and hydroquinone monomethyl ether (MEHQ) as hydroquinone polymerization inhibitors, and 2,2′-methylene-bis (4-methyl-6-tert) as phenol polymerization inhibitors.
  • HQ hydroquinone
  • MEHQ hydroquinone monomethyl ether
  • 2,2′-methylene-bis (4-methyl-6-tert) 2,2′-methylene-bis (4-methyl-6-tert) as phenol polymerization inhibitors.
  • HQ hydroquinone
  • MEHQ hydroquinone monomethyl ether
  • 2,2′-methylene-bis (4-methyl-6-tert) examples of the polymerization inhibitors.
  • HQ hydroquinone
  • MEHQ hydroquinone monomethyl ether
  • BHT 2,6-ditertiary butyl-p-cresol
  • 4,4'-thiobis [ethylene (oxy) (carbonyl) (ethylene)] bis [2 , 6-bis (1,1-dimethylethyl
  • phenothiazine polymerization inhibitor examples include phenothiazine, bis ( ⁇ -methylbenzyl) phenothiazine, 3,7-dioctylphenothiazine, bis ( ⁇ , ⁇ -dimethylbenzyl) phenothiazine, and the like.
  • phenol polymerization inhibitors such as BHT can also be used as antioxidants.
  • antioxidants examples include hindered phenol-based, benzimidazole-based, phosphorus-based, sulfur-based and hindered amine-based antioxidants.
  • examples of commercially available products include “IRGANOX” (registered trademark) series manufactured by BASF.
  • Examples of the light stabilizer include hindered amine antioxidants.
  • Examples of the primary antioxidant that is a hindered amine-based radical scavenger include the following. Product name: Chimassorb 2020FDL, Chimassorb 944FDL, Tinuvin 622SF, Uvinul 5050H, Tinuvin 144, Tinuvin 765, Tinuvin 770DF, Tinuvin 4050FF.
  • ultraviolet absorbers examples include benzophenone, benzotriazole, hindered amine, benzoate, and triazine.
  • examples of commercially available products include BASF Corporation brand names: Tinuvin 400 and Tinuvin 479, and Kyodo Pharmaceutical Co., Ltd. brand names: Viosorb110.
  • the resin composition (X) When the resin composition (X) according to the embodiment of the present invention is cured by forming a fine concavo-convex structure with a stamper, the resin composition (X) may have an appropriate viscosity from the viewpoint of easy flow into the fine concavo-convex structure on the surface of the stamper. preferable.
  • the viscosity of the resin composition measured with a rotary B-type viscometer at 25 ° C. is preferably 10,000 mPa ⁇ s or less, more preferably 5000 mPa ⁇ s or less, and still more preferably 2000 mPa ⁇ s or less.
  • the viscosity at 25 degreeC is 10,000 mPa * s or more
  • the resin composition can contact a stamper by making it the viscosity of the said range by heating, it can use suitably.
  • the viscosity of the resin composition at 70 ° C. with a rotary B-type viscometer is preferably 5000 mPa ⁇ s or less, and more preferably 2000 mPa ⁇ s or less.
  • the viscosity of a resin composition is 10 mPa * s or more, a contact with a stamper is possible and the hardened
  • the viscosity of the resin composition can be adjusted by selecting the type and content of the monomer to be contained or using a viscosity modifier. Specifically, when a large amount of a monomer containing a functional group having a molecular interaction such as a hydrogen bond or a chemical structure is used, the viscosity of the resin composition increases. Further, when a large amount of a low molecular weight monomer having no intermolecular interaction is used, the viscosity of the resin composition becomes low.
  • the resin composition (X) according to the embodiment of the present invention has a relatively low viscosity, the obtained cured product can have an appropriate hardness.
  • the stamper can be peeled favorably, the formed fine uneven structure is maintained, the scratch resistance is high, and a cured product exhibiting excellent water repellency can be obtained.
  • the resin composition (X) according to the embodiment of the present invention can be polymerized and cured to form a molded product.
  • a fine concavo-convex structure having a fine concavo-convex structure on the surface is extremely useful.
  • an article using such a fine concavo-convex structure for example, an article having a base material and a cured resin layer (fine concavo-convex structure) having a fine concavo-convex structure on the surface is given. Can do.
  • FIG. 1 shows a schematic cross-sectional view of an example of an article using such a fine concavo-convex structure.
  • An article 10 having a fine concavo-convex structure shown in FIG. 1 (a) is formed on an active energy ray-curable resin composition according to an embodiment of the present invention on a base material 11 (a coating layer 15 formed on the base material 11).
  • a cured resin layer (surface layer) 12 obtained by curing X) is laminated.
  • the surface of the cured resin layer 12 has a fine uneven structure.
  • conical convex portions 13 are formed at substantially equal intervals w1.
  • the shape of the convex portion 13 is preferably a shape in which a cross-sectional area in a cross section perpendicular to the height direction (a surface parallel to the base material plane) continuously increases from the apex side of the convex portion to the base material side.
  • the refractive index can be increased continuously, the fluctuation of the reflectance due to wavelength (wavelength dependence) is suppressed, the scattering of visible light is suppressed, and a fine concavo-convex structure with low reflectance is formed. it can.
  • the contact angle of water in the part which has a several convex part is 80 degree
  • the interval w1 between the convex portions is preferably a distance of not more than the wavelength of visible light (specifically, 400 to 780 nm). If the interval w1 between the convex portions is 400 nm or less, the scattering of visible light can be suppressed, and the antireflection film can be suitably used for optical applications.
  • w1 is more preferably from 50 to 400 nm, further preferably from 50 to 250 nm, particularly preferably from 80 to 200 nm.
  • the height of the convex portion (depth of the concave portion), that is, the vertical distance d1 between the bottom 14a of the concave portion and the top portion 13a of the convex portion (hereinafter referred to as “the height of the convex portion” or “d1” unless otherwise specified).
  • the height of the convex portion Is preferably set to such a depth that the reflectance can be prevented from varying with the wavelength. Specifically, 60 nm or more is preferable, 90 nm or more is more preferable, 150 nm or more is further preferable, and 180 nm or more is particularly preferable.
  • d1 is around 150 nm, the reflectance of light in the wavelength region of 550 nm that is most easily recognized by humans can be minimized.
  • d1 When d1 is 150 nm or more, the higher the d1 is, the higher the maximum reflectance and the lowest reflectance in the visible light region are. The difference in reflectance is reduced. For this reason, if d1 is 150 nm or more, the wavelength dependency of the reflected light is reduced, and the difference in visual color is not recognized.
  • the interval w1 and the height d1 of the convex portions are measured values obtained by measurement in an image with an acceleration voltage of 3.00 kV using a field emission scanning electron microscope (trade name: JSM-7400F, manufactured by JEOL Ltd.). Arithmetic mean values can be employed.
  • the convex portion 13 may have a bell shape as shown in FIG.
  • a truncated cone shape can be adopted as a shape in which the cross-sectional area in the vertical plane continuously increases from the apex side of the convex portion to the base material side.
  • the fine concavo-convex structure is preferably a structure in which protrusions (convex portions) such as a substantially conical shape and a pyramid shape are regularly arranged.
  • the shape of the convex part is a shape in which the cross-sectional area of the cross section perpendicular to the height direction (surface parallel to the base material plane) continuously decreases from the base material side toward the top, that is, in the height direction of the convex part.
  • the cross-sectional shape along the shape is preferably a triangle, trapezoid, bell shape or the like.
  • the fine uneven structure is not limited to the embodiment shown in FIG.
  • the fine concavo-convex structure may be formed on the surface of the cured resin layer (fine concavo-convex structure). For example, one side or both sides of the base material, or the whole surface or part (location where transparency and super water repellency are required).
  • a cured resin layer can be provided on the outer surface of the cured resin layer, and a fine uneven structure can be formed on the outer surface of the cured resin layer.
  • the average interval w1 between the convex portions is preferably not more than the wavelength of visible light, that is, not more than 400 nm, more preferably 50 to 400 nm, still more preferably 50 to 250 nm, and particularly preferably 80 to 200 nm.
  • the average interval w1 between the convex portions is measured by measuring 50 intervals between the adjacent convex portions (distance from the center of the convex portion to the center of the adjacent convex portion) in the electron microscope image, and arithmetically averaging these measured values. The value obtained in this way is adopted.
  • the height d1 of the convex portion is preferably 80 nm or more, more preferably 120 nm or more, and particularly preferably 150 nm or more, particularly when w1 is in the above range, particularly in the vicinity of 100 nm. If d1 is 80 nm or more, the reflectance is sufficiently reduced, and the variation of the reflectance due to the wavelength, that is, the wavelength dependence of the reflectance is small. In view of good scratch resistance of the fine concavo-convex structure, d1 is preferably 500 nm or less, more preferably 400 nm or less, and particularly preferably 300 nm or less.
  • the height d1 of the convex portion is the height along the direction perpendicular to the substrate plane between the topmost portion of the convex portion and the bottommost portion of the concave portion existing between the convex portions in the 30000 times image of the electron microscope. 50 points are measured, and a value obtained by arithmetically averaging these measured values is adopted.
  • the aspect ratio of the protrusions (the height d1 of the protrusions / the average interval w1 between the protrusions) is preferably 0.3 or more, more preferably 0.5 or more, and 0.7 or more from the viewpoint of sufficiently suppressing the reflectance. Is particularly preferred. In view of good scratch resistance, the aspect ratio is preferably 6 or less, more preferably 4 or less, and particularly preferably 2 or less.
  • the difference in refractive index between the cured resin layer and the substrate is preferably within 0.2, more preferably within 0.1, and particularly preferably within 0.05. If the refractive index difference is within 0.2, reflection at the interface between the cured resin layer and the substrate can be suppressed.
  • the thickness of the fine concavo-convex structure layer can be set, for example, in the range of 0.5 to 100 ⁇ m, preferably in the range of 1 to 50 ⁇ m.
  • the substrate may be any material as long as it can support a cured resin layer having a fine concavo-convex structure.
  • the fine concavo-convex structure when applied to a display member, it is transparent, that is, transmits light. Those are preferred.
  • the material constituting the transparent substrate examples include synthetic polymers such as methyl methacrylate (co) polymer, polycarbonate, styrene (co) polymer, methyl methacrylate-styrene copolymer, cellulose diacetate, cellulose triacetate, Semi-synthetic polymers such as cellulose acetate butyrate; polyesters such as polyethylene terephthalate and polylactic acid, polyamide, polyimide, polyether sulfone, polysulfone, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinyl acetal, polyether ketone, Examples thereof include polyurethane, composites of these polymers (composites of polymethyl methacrylate and polylactic acid, composites of polymethyl methacrylate and polyvinyl chloride, etc.), and transparent inorganic materials such as glass.
  • synthetic polymers such as methyl methacrylate (co) polymer, polycarbonate, styrene (co)
  • the shape of the substrate may be any of a sheet shape, a film shape, and the like.
  • the method for producing the substrate is not particularly limited, and for example, those produced by any production method such as injection molding, extrusion molding, and cast molding can be used.
  • the surface of the transparent substrate may be subjected to coating or corona treatment for the purpose of improving properties such as adhesion, antistatic properties, scratch resistance, and weather resistance.
  • Such a fine concavo-convex structure can be applied as an antireflection film and can have high scratch resistance. Further, by selecting the composition type of the resin composition (X) and controlling the composition ratio, in addition to high scratch resistance, it is possible to obtain a contaminant removal effect such as excellent fingerprint removability for the cured product. .
  • a resin composition is disposed between a stamper on which an inverted structure of a fine concavo-convex structure is formed and a substrate, and the resin composition is irradiated by active energy ray irradiation.
  • the method (1) is particularly preferable from the viewpoint of the transferability of the fine relief structure and the degree of freedom of the surface composition. This method is particularly suitable when a belt-shaped roll stamper capable of continuous production is used, and is an excellent method of productivity.
  • the stamper has an inverted structure of the fine uneven structure formed on the surface of the fine uneven structure on the surface.
  • the material of the stamper include metals (including those having an oxide film formed on the surface), quartz, glass, resin, ceramics, and the like.
  • the shape of the stamper include a roll shape, a circular tube shape, a flat plate shape, and a sheet shape.
  • the method for forming the inverted structure of the fine concavo-convex structure on the stamper is not particularly limited, and specific examples thereof include an electron beam lithography method and a laser beam interference method.
  • an appropriate photoresist film is applied on an appropriate support substrate, exposed to light such as an ultraviolet laser, an electron beam, or X-ray, and developed to obtain a mold having a reversal fine uneven structure, and this mold Can also be used as a stamper.
  • the support substrate can be selectively etched by dry etching through a photoresist film patterned by exposure and development, and the photoresist film is removed to form an inverted fine concavo-convex structure directly on the support substrate itself. Is possible.
  • anodized porous alumina can be used as a stamper.
  • a pore structure having a diameter of 20 to 200 nm formed by anodizing an aluminum substrate with oxalic acid, sulfuric acid, phosphoric acid or the like as an electrolyte at a predetermined voltage may be used as a stamper.
  • the oxide film is once removed and then anodized again, so that very highly ordered pores can be self-organized. Can be formed.
  • the second anodic oxidation step by combining the anodic oxidation treatment and the hole diameter enlargement treatment, it is possible to form a fine concavo-convex structure whose cross section is not a rectangle but a triangle or a bell shape. Further, the angle of the innermost portion of the pore can be sharpened by appropriately adjusting the time and conditions of the anodizing treatment and the pore diameter expanding treatment.
  • a replica mold may be produced from an original mold having a fine concavo-convex structure by an electroforming method or the like and used as a stamper.
  • the shape of the stamper itself is not particularly limited, and may be, for example, a flat plate shape, a belt shape, or a roll shape.
  • the fine concavo-convex structure can be transferred continuously, and the productivity can be further increased.
  • a resin composition (X) is supplied and distributed between such a stamper and a base material.
  • the resin composition is pressed into the molding cavity by pressing the stamper and the substrate in a state where the resin composition is arranged between the stamper and the substrate. Can be injected.
  • the resin composition After disposing the resin composition between the stamper and the substrate, the resin composition is irradiated with active energy rays and polymerized and cured.
  • active energy rays As a method of polymerization curing, a curing treatment by ultraviolet irradiation is preferable.
  • the lamp for irradiating ultraviolet rays for example, a high-pressure mercury lamp, a metal halide lamp, a fusion lamp that is an electrodeless lamp, or a UV-LED can be used.
  • the integrated light quantity is preferably 400 ⁇ 4000mJ / cm 2, more preferably 400 ⁇ 2000mJ / cm 2.
  • the resin composition can be sufficiently cured to suppress the scratch resistance from being insufficiently cured.
  • the irradiation intensity is not particularly limited, but it is preferable to suppress the output to a level that does not cause deterioration of the substrate.
  • the stamper After the polymerization and curing of the resin composition, the stamper is peeled off to obtain a fine concavo-convex structure which is a cured product having a fine concavo-convex structure.
  • the fine concavo-convex structure obtained in this way has a high scratch resistance because the fine concavo-convex structure of the stamper is transferred to the surface in a relationship between a key and a keyhole. Moreover, it has water repellency and can also have the effect of preventing the adhesion of contaminants.
  • Such a fine concavo-convex structure can exhibit excellent antireflection performance due to a continuous change in refractive index, and is suitable as an antireflection film or an antireflection film for a three-dimensional molded product.
  • Such a fine concavo-convex structure is suitable as a display member of an image display device such as a liquid crystal display device, a plasma display panel, an electroluminescence display, or a cathode ray tube display device such as a computer, a television set, or a mobile phone.
  • a fine concavo-convex structure can be used by being attached to the surface of a transparent member such as a lens, a show window, or a spectacle lens.
  • the present invention can also be applied to optical applications such as optical waveguides, relief holograms, lenses, and polarization separation elements, and cell culture sheet applications.
  • it can be applied to building materials such as mirrors and windows, in-vehicle applications such as door mirror films and window films, and ship bottom materials by utilizing water repellency.
  • stamper As the stamper used for producing the fine concavo-convex structure, one made of anodized porous alumina is useful as described above. Hereinafter, a method of forming a plurality of fine pores having a predetermined shape on the surface of an aluminum substrate by anodic oxidation as a stamper manufacturing method will be described with reference to the process chart of FIG.
  • Step (a) is a step of forming an oxide film on the surface of the aluminum substrate by anodizing the aluminum substrate 30 in an electrolytic solution under a constant voltage.
  • the aluminum base material preferably uses aluminum having a purity of 99% or more, more preferably has a purity of 99.5% or more, and further preferably has a purity of 99.8% or more.
  • the purity of aluminum is high, when anodized, it is difficult to form a concavo-convex structure having a size that scatters visible light due to segregation of impurities, and pores formed by anodization are regularly formed.
  • the shape of the aluminum substrate may be a desired shape such as a roll shape, a tubular shape, a flat plate shape, or a sheet shape, and is preferably a roll shape when the fine concavo-convex structure is obtained as a continuous film or sheet.
  • the aluminum base material may be attached with oil used when processing into a predetermined shape, it is preferable to degrease in advance and smooth the surface by electrolytic polishing (etching). .
  • the electrolytic solution sulfuric acid, oxalic acid, phosphoric acid or the like can be used.
  • the concentration of oxalic acid is preferably 0.7 M or less.
  • the current value can be kept low, and a dense oxide film can be formed.
  • the formation voltage is preferably 30 to 60V.
  • the formation voltage is 30 to 60 V, an anodized porous alumina layer in which pores are formed with a regularity of about 100 nm can be formed. Regardless of whether the formation voltage is higher or lower than this range, the regularity of the formed pores 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 is 60 ° C. or lower, the generation of so-called “burn” is suppressed, and the pores are broken or the surface is melted to form irregular pores.
  • the concentration of sulfuric acid is preferably 0.7 M or less.
  • the concentration of sulfuric acid is 0.7 M or less, the current value can be kept low and an oxide film having a dense structure can be formed.
  • the formation voltage is preferably 25-30V.
  • the formation voltage is 25 to 30 V, an anodized porous alumina layer in which pores are formed with regularity having a period of about 63 nm can be formed. Regardless of whether the formation voltage is higher or lower than this range, the regularity of the formed pores tends to decrease.
  • the temperature of the electrolytic solution is preferably 30 ° C. or less, and more preferably 20 ° C. or less. If the temperature of the electrolytic solution is 30 ° C. or lower, the occurrence of so-called “burn” is suppressed, and the pores are broken or the surface is melted to form irregular pores.
  • Step (b) is a step of removing the oxide film and forming anodized pore generation points on the surface of the aluminum base so as to correspond to the pores 31 formed in the oxide film in step (a). It is. That is, when the oxide film 32 formed in the step (a) is removed, a recess 33 is formed on the surface of the aluminum base material at a position corresponding to the pore 31 portion.
  • the regularly arranged pores can be generated by using the recesses 33 as the anodizing pore generation points.
  • a solution that does not dissolve aluminum but selectively dissolves the oxide film is used. Examples of such a solution include a chromic acid / phosphoric acid mixed solution.
  • Step (c) is a step of forming pores by anodizing the aluminum substrate again and forming an oxide film at the pore generation points. That is, the aluminum substrate 30 from which the oxide film has been removed in the step (b) is anodized again to form an oxide film 34 having columnar pores 35. Anodization can be performed under the same conditions as in step (a). Deeper pores can be obtained as the anodic oxidation time is lengthened.
  • Step (d) is a step of expanding the diameter of the pores. That is, the anodized aluminum substrate is dipped in a solution that dissolves the oxide film to expand the diameter of the pores 35 (hereinafter referred to as “pore diameter expansion process”).
  • the solution for dissolving the oxide film for example, an about 5% by mass phosphoric acid aqueous solution can be used. Since the pore diameter can be increased as the time for the pore diameter expansion process is lengthened, the processing time is set according to the target shape.
  • Step (e) is a step of anodizing the aluminum base material after the pore diameter expansion treatment again.
  • the depth of the pores 35 is expanded as the oxide film 34 becomes thicker.
  • Anodization can be performed under the same conditions as in step (a) (and step (c)). The longer the anodic oxidation time, the deeper the pores can be formed.
  • Step (f) is a step in which the step (d) and the step (e) are repeated, and the diameter expansion and expansion of the pores 35 are repeated.
  • an oxide film 34 having pores 35 whose diameter continuously decreases from the opening in the depth direction is formed, and as a result, anodized alumina having a plurality of fine pores is formed on the aluminum substrate.
  • the stamper 20 formed on the surface can be obtained.
  • the end of step (f) preferably ends with step (d).
  • the total number of repetitions of the step (f) is preferably 3 times or more, and more preferably 5 times or more. If the number of repetitions is 3 times or more, it is possible to form pores whose diameter changes continuously, and to form a cured product having a surface of a moth-eye structure that can reduce the reflectance by such a stamper. Can do.
  • the shape of the pore 35 is an inverted structure of a fine uneven structure formed on the surface of the article, and specifically includes a substantially conical shape, a pyramid shape, a cylindrical shape, etc., such as a conical shape, a pyramid shape, etc.
  • a shape in which the pore cross-sectional area in the direction orthogonal to the depth direction continuously decreases from the outermost surface in the depth direction is preferable.
  • the average interval between the pores 35 is preferably not more than the wavelength of visible light, that is, not more than 400 nm, and more preferably not less than 20 nm.
  • the average interval between the pores the interval between adjacent pores in the electron microscope image (distance from the center of the pore to the center of the adjacent pore) is measured at 50 points, and the average value of these values is adopted. .
  • the depth of the pores 35 is preferably from 80 to 500 nm, more preferably from 120 to 400 nm, even more preferably from 150 to 300 nm, and particularly in the range where the average interval is about 100 nm.
  • 50 points of the distance between the bottom and top of the pores in an electron microscope 30000 times image are measured, and an average value of these values is adopted.
  • the aspect ratio (depth / average interval) of the pores 35 is preferably 0.8 to 5.0, more preferably 1.2 to 4.0, and still more preferably 1.5 to 3.0.
  • the surface of the stamper on which the fine uneven structure is formed may be treated with a release agent.
  • the release agent include silicone resins, fluororesins, fluorine compounds, and phosphate esters, and phosphate esters are particularly preferable.
  • Commercially available products include AXEL brand names: Mold With INT-1856, Nikko Chemicals brand names: TDP-10, TDP-8, TDP-6, TDP-2, DDP-10, DDP-8, DDP-6, DDP-4, DDP-2, TLP-4, TCP-5, DLP-10, trade names manufactured by Johoku Chemical Industry Co., Ltd .: JP-506H, JP-512, JP-513, JAMP-8, JAMP -12, product names manufactured by Daihachi Chemical Industry Co., Ltd .: AP-8, AP-10, MP-10, product names manufactured by SC Organic Chemical Co., Ltd .: Phoslex series: A-8, A-10, A-12, A -13, A-18, A-18D, A-180L, and the
  • the article having a fine concavo-convex structure formed on the surface using the stamper produced as described above has a cured resin layer 12 formed on the surface of the substrate 11, for example, as shown in FIG.
  • the cured resin layer 12 has a fine concavo-convex structure having a plurality of convex portions 13 formed from a cured resin obtained by bringing a resin composition into contact with the above stamper and curing.
  • the imprinting raw material of the present invention is not particularly limited as long as it contains the resin composition of the present invention, and the resin composition can be used as it is, but depending on the intended molded product, It is also possible to contain various additives.
  • the raw material for imprinting can also be used for molding a cured product by UV curing or further heat curing using a stamper. It is also possible to use a method in which a stamper is pressed against a resin composition that has been semi-cured by heating, the shape is transferred, peeled off from the stamper, and completely cured by heat or UV.
  • the resin composition can also be used as a raw material for forming a cured film on various substrates, and can form a coated film as a coating material and irradiate active energy rays to form a cured product. it can.
  • An article having a fine concavo-convex structure on its surface can be continuously produced, for example, using a production apparatus shown in FIG.
  • the manufacturing apparatus shown in FIG. 3 is provided with a roll-shaped stamper 41 having a reverse structure (not shown) having a fine concavo-convex structure on the surface, and a tank 43 for storing a resin composition.
  • the resin composition is supplied from the tank 43 between the roll-shaped stamper 41 and the base material 42 of the translucent band-shaped film that moves along the surface of the roll-shaped stamper 41.
  • the base material 42 and the resin composition are sandwiched between the roll stamper 41 and the nip roll 46 whose nip pressure is adjusted by the pneumatic cylinder 45, and the resin composition is interposed between the base material 42 and the roll stamper 41.
  • the concave portion of the fine uneven structure of the roll-shaped stamper 41 is filled.
  • An active energy ray irradiation device 48 is installed below the roll-shaped stamper 41, and the resin composition is irradiated with active energy rays through the base material 42 so that the resin composition can be cured. Thereby, the cured resin layer 44 to which the fine uneven structure on the surface of the roll-shaped stamper 41 is transferred is formed. Thereafter, the continuous article (fine concavo-convex structure) 40 in which the cured resin layer 44 having a fine concavo-convex structure formed on the surface and the base material 42 is integrated is peeled from the roll stamper 41 by the peeling roll 47.
  • the active energy ray irradiation device 48 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 .
  • acrylic resin, polycarbonate, styrene resin, polyester, cellulose resin (such as triacetyl cellulose), polyolefin, alicyclic polyolefin, or the like can be used.
  • An article having a fine concavo-convex structure according to an embodiment of the present invention has high scratch resistance of the fine concavo-convex structure and excellent water repellency. Therefore, the anti-reflective article (anti-reflective film, anti-reflective film, etc.), optical waveguide, relief Development of applications as optical articles such as holograms, lenses, polarization separation elements, and water repellent films can be expected, and is particularly suitable for applications as antireflection articles and water repellent films.
  • antireflection articles include antireflection films and antireflection films provided on the surfaces of image display devices (liquid crystal display devices, plasma display panels, electroluminescence displays, cathode tube display devices, etc.), lenses, show windows, and glasses. And an antireflection sheet.
  • image display devices liquid crystal display devices, plasma display panels, electroluminescence displays, cathode tube display devices, etc.
  • lenses show windows, and glasses.
  • an antireflection sheet When used in an image display device, an antireflection film may be directly attached to the image display surface, an antireflection film may be directly formed on the surface of a member constituting the image display surface, or an antireflection film is formed on the front plate. May be formed.
  • the water repellent film it can be used as a drip-preventing film for automobile door mirrors and windows, or as a snow-preventing film. Moreover, the effect of improving the light transmittance and the effect of imparting antifouling property due to water repellency can be used simultaneously by using it for a transparent base material used outdoors such as solar cells and glass for building materials.
  • Appearance evaluation was performed by attaching an article to one side of a 2.0 mm thick black acrylic plate (product name: Acrylite, manufactured by Mitsubishi Rayon Co., Ltd.) did.
  • the above transfer operation was repeated for one stamper, and the peeling force from the stamper was measured when the number of transfers was 200.
  • the peel force is measured by taking the stamper as the adherend and the cured resin layer and the base material (PET film) as an adhesive tape when releasing the cured sample (cured resin layer on the PET film) from the stamper. Then, a 90 ° peel test according to JISZ0237 was performed, and the peel force at the time of releasing from the stamper was measured.
  • stamper pores A vertical section of a part of a stamper made of anodized porous alumina was deposited by Pt for 1 minute, and observed with a field emission scanning electron microscope (manufactured by JEOL Ltd., product name: JSM-7400F) at an acceleration voltage of 3.00 kV. The interval (period) of the matching pores and the depth of the pores were measured. Specifically, 10 points were measured for each, and the average value was taken as the measured value.
  • stamper for transfer of fine relief structure A ⁇ 65 mm aluminum disk having a purity of 99.99% by mass and an electropolished thickness of 2 mm was used as the aluminum substrate.
  • the obtained mold was immersed in a 0.1% by weight aqueous solution of a release agent (trade name: TDP-8, manufactured by Nikko Chemicals) for 10 minutes, and then pulled up and air-dried overnight to perform a release treatment.
  • a release agent trade name: TDP-8, manufactured by Nikko Chemicals
  • the polymerizable component (A), polymerizable component (B), polymerizable component (C), and other polymerizable components contained in the active energy ray-curable resin composition (X) used in Examples and Comparative Examples ( D), photopolymerization initiator (E), other components (G), and internal release agent (F) are as shown in Table 1 below.
  • Example 1 Resins having the compositions shown in Table 2 were prepared as the active energy ray-curable resin composition (X). A few drops of this active energy ray-curable resin composition were dropped on the surface of a stamper for transferring a fine concavo-convex structure and covered with a PET film (Toyobo, product name: A4300, thickness: 50 ⁇ m) while spreading. Thereafter, the resin composition is cured by irradiating ultraviolet rays from the film side using an electrodeless UV lamp (manufactured by Heraeus Co., Ltd., D bulb) so that the integrated light amount measured at a wavelength of 365 nm is 1000 mJ / cm 2. I let you.
  • an electrodeless UV lamp manufactured by Heraeus Co., Ltd., D bulb
  • the cured resin layer together with the PET film was released from the stamper to obtain an article having a fine concavo-convex structure on the surface with an average interval w1: 100 nm of protrusions and a height d1: 200 nm.
  • the evaluation results are shown in Table 2.
  • Example 2 Except for changing the active energy ray-curable resin composition (X) to that shown in Table 2, an article having a fine concavo-convex structure on the surface was prepared and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.
  • Examples 1 to 4 have a sufficiently low peeling force from the stamper due to the effect of the internal mold release agent (F), and are excellent in mold release properties.
  • the water contact angle is large and the water repellency is also high.
  • Comparative Examples 1 and 2 since the internal mold release agent (F) is not included, the peeling force from the stamper is high, and the contact angle on the surface of the obtained fine concavo-convex structure is also low.
  • Example 1 when Example 1 is compared with Comparative Example 1 and Comparative Example 2, the polymerizable component (A), the polymerizable component (B), the polymerizable component (C), and the photopolymerization initiator (E) are All have the same composition, and the difference lies in the presence or absence of the internal mold release agent (F) and other components (G).
  • Example 1 containing 0.5 w% of JP-513 as an internal release agent (F), the peeling force at the time of 200 times transfer was sufficiently low as 5 [N / m], and the water contact angle was 142 [°]. It is super water repellent.
  • Comparative Example 1 and Comparative Example 2 each containing the phosphoric acid triesters TOP and TDP-2 not only have a high peel force but also a low water contact angle.
  • Comparative Example 3 is a resin composition that does not contain a polymerizable component (A) and contains a large amount of an oxyethylene group-containing component (component (D)) as a polymerizable component. It can be seen that not only becomes higher, but also the water contact angle becomes very low. Therefore, it turns out that an internal mold release agent (F) exhibits the especially outstanding effect in combination with a polymeric component (A) and a polymeric component (B).
  • Articles having a fine concavo-convex structure on the surface according to an embodiment of the present invention include antireflection articles (antireflection films, antireflection films, etc.), super water repellent articles (super water repellent films, antifouling films, etc.), optical waveguides, reliefs Development of applications as optical articles such as holograms, lenses, polarization separation elements, and cell culture sheets can be expected, and is particularly suitable for applications as antireflection articles and super water-repellent articles.
  • antireflection articles include antireflection films and antireflection films provided on the surfaces of image display devices (liquid crystal display devices, plasma display panels, electroluminescence displays, cathode tube display devices, etc.), lenses, show windows, and glasses. And an antireflection sheet.
  • image display devices liquid crystal display devices, plasma display panels, electroluminescence displays, cathode tube display devices, etc.
  • lenses show windows, and glasses.
  • an antireflection sheet examples of antireflection articles include antireflection films and antireflection films provided on the surfaces of image display devices (liquid crystal display devices, plasma display panels, electroluminescence displays, cathode tube display devices, etc.), lenses, show windows, and glasses. And an antireflection sheet.
  • Examples of the super water-repellent article include films for mirrors (door mirrors, etc.) for transportation equipment such as automobiles, films for building materials such as water-reform films, window films, and the like.
  • Laminate article with fine uneven structure
  • Base material 12 Surface layer (cured resin layer) 13, 13b Convex part 13a Convex part apex 14 Concave part 14a Concave base point 15 Coating layer W1 Distance between adjacent convex parts d1 Vertical distance from the concavity base point to the convex part apex 20 Stamper 30 Aluminum substrate 31 Pore 32 Oxide film 33 Pore generation point 34 Oxide film 35 Pore 40 Article having fine uneven structure 41 Roll stamper 42 Base material 43 Tank 44 Cured resin layer 45 Pneumatic cylinder 46 Nip roll 47 Peeling roll 48 Active energy ray irradiation device

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Surface Treatment Of Optical Elements (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne un article présentant de multiples parties saillantes sur sa surface, la distance moyenne entre deux parties saillantes quelconques adjacentes parmi les parties saillantes étant de 400 nm ou moins, chacune des multiples parties saillantes étant formée à partir d'un produit durci d'une composition de résine durcissable par rayonnement d'énergie active, l'angle de contact avec l'eau d'une région formée de parties saillantes multiples dans l'article étant de 80 degrés ou plus, la composition de résine durcissable par rayonnement d'énergie active comprenant un composant polymérisable (P), un initiateur de photopolymérisation (E) et un agent de démoulage interne (F), et l'agent de démoulage interne (F) comprenant un monoalkylphosphate et/ou un dialkylphosphate.
PCT/JP2016/060182 2015-03-30 2016-03-29 Composition et article de résine durcissable par rayonnement d'énergie active WO2016158979A1 (fr)

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