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WO2018230725A1 - Composition de résine durcissable, produit durci, structure résistante et procédé de production de structure résistante - Google Patents

Composition de résine durcissable, produit durci, structure résistante et procédé de production de structure résistante Download PDF

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Publication number
WO2018230725A1
WO2018230725A1 PCT/JP2018/023004 JP2018023004W WO2018230725A1 WO 2018230725 A1 WO2018230725 A1 WO 2018230725A1 JP 2018023004 W JP2018023004 W JP 2018023004W WO 2018230725 A1 WO2018230725 A1 WO 2018230725A1
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WIPO (PCT)
Prior art keywords
resin composition
curable resin
compounds
mass
concavo
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2018/023004
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English (en)
Japanese (ja)
Inventor
淳 谷口
伸 日和佐
千佳 山下
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tokyo University of Science
Autex Inc
Resonac Holdings Corp
Original Assignee
Showa Denko KK
Tokyo University of Science
Autex Inc
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Application filed by Showa Denko KK, Tokyo University of Science, Autex Inc filed Critical Showa Denko KK
Priority to JP2019525582A priority Critical patent/JP7406193B2/ja
Publication of WO2018230725A1 publication Critical patent/WO2018230725A1/fr
Anticipated expiration legal-status Critical
Priority to JP2022113446A priority patent/JP7514461B2/ja
Ceased legal-status Critical Current

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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
    • B29C33/42—Moulds or cores; Details thereof or accessories therefor characterised by the shape of the moulding surface, e.g. ribs or grooves
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups

Definitions

  • the present invention relates to a curable resin composition, a cured product, an uneven structure, and a method for producing the same.
  • a curable resin composition that cures by polymerizing a polymerizable compound by applying energy rays such as light or heat is widely known.
  • an acid is generated to polymerize a polymerizable compound.
  • a curable composition using a polymerization initiator that initiates.
  • the curing reaction of the curable composition is performed, for example, by addition polymerization using an ethylenically unsaturated double bond in the compound or ring-opening polymerization by ring opening of a glycidyl group in the compound.
  • a polymerizable compound having an acryloyl group is generally known
  • a polymerizable compound having an epoxy ring is generally known.
  • compounds having an oxirane ring such as pentaerythritol tetraglycidyl ether are disclosed (for example, see Patent Documents 1 and 2).
  • the curable composition is used not only for the production of a molded body but also for a protective material for imparting scratch resistance, a processing material for forming a pattern, and the like.
  • a curable composition that forms a hard coating layer having a high hardness that is not easily damaged by rubbing or the like, and a mold (mold) and a substrate are sandwiched between resins, and the mold (mold) nano-order pattern
  • curable compositions for nanoimprint lithography (NIL) that transfer a dye are known.
  • UV nanoimprint lithography UV nanoimprint lithography (UV-NIL) is a technique useful for mass production of a film having an antireflection structure (ARS film).
  • ARS films are widely used for electronic devices such as semiconductors, optical devices, recording media, and the like, and are used by being attached to the surfaces of smartphones, tablets, touch panels, solar cells, LEDs, and the like.
  • Patent Document 1 JP 2013-189504 A
  • Patent Document 2 JP 2013-112649 A
  • curable compositions have been provided in the past, and although improvement in performance such as curability has been attempted, in recent years, scratch resistance, shape retention, and abrasion resistance in a cured product after curing have been achieved. There is a need for further improvements in durability. In order to improve the durability, it is effective to improve the hardness after curing.
  • the present disclosure has been made in view of the above. That is, The problem to be solved by one embodiment of the present invention is to provide a curable resin composition that is excellent in reproducibility of a fine structure such as a moth-eye structure and that has higher hardness than conventional ones. . It is preferable to provide a curable resin composition for imprinting. The problem to be solved by another embodiment of the present invention is to provide a curable resin composition that is excellent in antifouling property and has significantly improved hardness as compared with a conventional composition containing an antifouling agent. is there. It is preferable to provide a curable resin composition for hard coating (that is, formation of a hard coat layer).
  • the problem to be solved by another embodiment of the present invention is to provide a cured product having a significantly improved hardness as compared with a conventional cured product.
  • the problem to be solved by another embodiment of the present invention is to provide a concavo-convex structure having significantly improved hardness and a method for producing the same, as compared with a conventional cured product.
  • the present inventors have particularly high hardness in a curable resin composition that selectively uses pentaerythritol tetraglycidyl ether, for example, hard coating
  • the curable resin composition and the cured product of the present disclosure have been obtained based on the knowledge that they are suitable for applications and imprint applications.
  • curable resin compositions containing a surfactant as an antifouling agent have conventionally been considered to have a tendency to decrease in hardness as compared with a composition that generally does not contain an antifouling agent. Even with a composition containing a surfactant, the decrease in hardness is improved, and it becomes possible to produce a cured product having a higher hardness than before.
  • a curable resin composition that contains pentaerythritol tetraglycidyl ether and a polymerization initiator and is used in the production of an uneven structure.
  • the surfactant includes at least one selected from the group consisting of a fluorine compound and a siloxane compound.
  • ⁇ 4> The curable resin composition according to ⁇ 2> or ⁇ 3>, wherein the surfactant includes at least one selected from the group consisting of a fluorine-containing acrylic compound and a fluorine-containing siloxane compound.
  • the surfactant includes at least one selected from the group consisting of a fluorine-containing acrylic compound and a fluorine-containing siloxane compound.
  • ⁇ 5> The curable resin composition according to ⁇ 1>, further including at least one selected from the group consisting of a fluorine compound and a siloxane compound.
  • ⁇ 6> The polymerization initiator according to any one of ⁇ 1> to ⁇ 5>, wherein the polymerization initiator is at least one compound selected from the group consisting of a photoacid generator, a thermal acid generator, and a photocation generator.
  • the curable resin composition is at least one compound selected from the group consisting of a photoacid generator, a thermal acid generator, and a photocation generator.
  • ⁇ 7> Further, at least one reactivity selected from the group consisting of a glycidyl ether compound, a glycidyl ester compound, a glycidyl amine compound, an aliphatic epoxy compound, an olefin oxide epoxy compound, a silicone-modified compound, a fluorine-modified epoxy compound, and an oxetane compound.
  • At least one sensitizer selected from the group consisting of anthracene compounds, anthraquinone compounds, thioxanthone compounds, naphthalene compounds, phenanthrene compounds, chrysene compounds, perylene compounds, and acridine compounds.
  • ⁇ 10> The curing according to any one of ⁇ 1> to ⁇ 9>, wherein the content of the pentaerythritol tetraglycidyl ether is 45% by mass to 97% by mass with respect to the total mass of the curable resin composition. It is an adhesive resin composition.
  • ⁇ 11> The curable resin composition according to any one of ⁇ 1> to ⁇ 10>, wherein the pentaerythritol tetraglycidyl ether has an epoxy equivalent of 90 to 150.
  • ⁇ 12> The curable resin composition according to any one of ⁇ 1> to ⁇ 11>, wherein a content of the polymerization initiator is 3% by mass to 30% by mass with respect to the pentaerythritol tetraglycidyl ether. It is a thing.
  • the content of the polymerization initiator is any one of ⁇ 1> to ⁇ 12>, in which the content is 0.1% by mass to 10% by mass with respect to the total mass of the curable resin composition. It is a curable resin composition.
  • the curable resin composition according to ⁇ 1> which contains the pentaerythritol tetraglycidyl ether, an alicyclic epoxy resin, and a photoacid generator that is the polymerization initiator.
  • the curable resin composition according to ⁇ 2> containing the pentaerythritol tetraglycidyl ether, an alicyclic epoxy resin, a photoacid generator that is the polymerization initiator, and the surfactant. It is.
  • the content of the pentaerythritol tetraglycidyl ether is 60% by mass to 85% by mass with respect to the total mass of the curable resin composition, and the content of the alicyclic epoxy resin is the total mass of the curable resin composition.
  • the content of the photoacid generator is 1% by mass to 6% by mass with respect to the total mass of the curable resin composition.
  • the curable resin composition. ⁇ 17> A cured product of the curable resin composition according to any one of ⁇ 1> to ⁇ 16>, wherein the scratched pencil hardness of the flat film is 7H or more.
  • a cured product of the curable resin composition according to ⁇ 1> (including curable resin compositions according to ⁇ 5> to ⁇ 16> not related to ⁇ 2>), and height Is a concavo-convex structure having a concavo-convex pattern having a pitch of 20 nm to 1000 nm.
  • the height is from 50 nm to 1000 nm.
  • a curable resin composition that is excellent in reproducibility of a fine structure such as a moth-eye structure and that has higher hardness than conventional ones.
  • a curable resin composition for nanoimprinting is provided.
  • a curable resin composition for hard coating is provided.
  • cured material is provided.
  • a concavo-convex structure having significantly improved hardness and a method for producing the same are provided as compared with a conventional cured product.
  • FIG. 6 is a graph showing the reflectance of moth-eye films of sample levels 1 to 3.
  • 3 is a graph showing the transmittance of moth-eye films of sample levels 1 to 3.
  • 3 is a graph showing the hardness of moth-eye films of sample levels 1 and 2 and sample level 3.
  • It is process drawing which shows the process of producing a moth-eye film using the curable resin composition containing a thermal acid generator.
  • (A) is a SEM photograph showing a moth-eye structure of a cured film of sample level 27, and
  • (b) is a SEM photograph showing a moth-eye structure of a cured film of sample level 28. It is a graph which shows the reflectance in the cured film of the moth-eye film of sample level 27 and sample level 28.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • an upper limit value or a lower limit value described in a numerical range may be replaced with an upper limit value or a lower limit value in another numerical range.
  • the upper limit value or the lower limit value described in a certain numerical range may be replaced with the values shown in the examples.
  • the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means.
  • (meth) acryl is a concept including both acryl and methacryl
  • (meth) acrylate is a concept including both acrylate and methacrylate.
  • the curable resin composition of the first aspect of the present disclosure contains at least pentaerythritol tetraglycidyl ether and a polymerization initiator, and is used for the production of a concavo-convex structure, preferably a reactive compound (hereinafter referred to as “reactive compound”). It is also referred to as a “reactive diluent”), an antifouling agent, a sensitizer, a silane coupling agent, and a filler, and may further contain an organic solvent and other additives as necessary.
  • the curable resin composition of the second aspect of the present disclosure contains pentaerythritol tetraglycidyl ether, a polymerization initiator, and a surfactant (hereinafter also referred to as “antifouling agent”), and forms a hard coat layer. (Hard coating), preferably containing a reactive diluent, a sensitizer, a silane coupling agent, and a filler, and if necessary, an organic solvent and / or other additions An agent may be contained.
  • the curable resin composition of the first aspect and the second aspect is also simply referred to as “the curable resin composition of the present disclosure”. Further, the “curable resin composition” is sometimes referred to as a “curable composition”.
  • the curable resin composition of the present disclosure contains pentaerythritol tetraglycidyl ether (hereinafter sometimes abbreviated as “PETG”) as a polymerizable compound.
  • PETG pentaerythritol tetraglycidyl ether
  • the conventionally known polymerizable compounds particularly by containing pentaerythritol tetraglycidyl ether selectively, it is possible to obtain a cured product with improved hardness as compared with the conventional curable resin composition. .
  • PETG a commercially available product may be used.
  • Show Free (registered trademark) series manufactured by Showa Denko KK can be used.
  • Pentaerythritol tetraglycidyl ether preferably has an epoxy equivalent of 90 to 150.
  • the epoxy equivalent of PETG is preferably 120 or less, more preferably 110 or less, and particularly preferably 100 or less for the same reason as above.
  • the lower limit of the epoxy equivalent of PETG may be 91 or more, or 92 or more.
  • the content of pentaerythritol tetraglycidyl ether (PETG) in the curable resin composition is preferably 15% by mass to 97% by mass with respect to the total mass of the curable resin composition, and 45% by mass to It is more preferably 97% by mass, and more preferably 60% by mass to 85% by mass.
  • PETG content is 15% by mass or more, high hardness is easily obtained.
  • the content of PETG is preferably 97% by mass or less in consideration of the content of other components.
  • the curable resin composition of the present disclosure contains at least one kind of polymerization initiator. By containing a polymerization initiator, the curing reaction of PETG is started.
  • the polymerization initiator is preferably at least one compound selected from the group consisting of a photoacid generator, a thermal acid generator, and a photocation generator.
  • Photopolymerization initiator photoacid generator
  • the photopolymerization initiator include onium salt compounds.
  • the onium salt compounds include aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, and the like.
  • Onium salt compounds include special phosphorus compounds such as halogen metal complex anions (BF 4 ⁇ , PF 6 ⁇ , AsF 6 ⁇ , SbF 6 ⁇ , B (6F5) 4 ⁇ and the like), and (RF) n PF 6-n . May be included as a counter ion.
  • onium salt compounds include diphenyl [4- (phenylthio) phenyl] sulfonium hexafluoroantimonate, diphenyl [(4-phenylthio) phenyl] sulfonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium Hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, 4,4′-bis [diphenylsulfonium] diphenylsulfide bishexafluorophosphate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrakis ( Pentafluorophenyl) borate, bis (4-tert-butylphenol)
  • the content of the photopolymerization initiator is preferably 0.1% by mass to 10.0% by mass and more preferably 1.0% by mass to 6.0% by mass with respect to the total mass of the curable resin composition. . Moreover, you may use a photoinitiator individually by 1 type or in combination of 2 or more types.
  • thermal acid generator As the thermal acid generator, onium salts such as quaternary ammonium salts, sulfonium salts, iodonium salts, and phosphonium salts can be used.
  • onium salts such as quaternary ammonium salts, sulfonium salts, iodonium salts, and phosphonium salts can be used.
  • quaternary ammonium salts commercially available products include K-PURE (registered trademark) CXC-1612, K-PURE CXC-1614, K-PURE CXC-1733, K-PURE CXC-1742, K manufactured by King Industries.
  • sulfonium salts include San-Aid (registered trademark) SI-60, SI-60L, SI-80
  • the content of the thermal acid generator is preferably 0.1% by mass to 10.0% by mass and more preferably 0.2% by mass to 5.0% by mass with respect to the total mass of the curable resin composition. . Moreover, you may use a thermal-polymerization initiator individually by 1 type or in combination of 2 or more types.
  • the content of the polymerization initiator is preferably 3% by mass to 90% by mass, more preferably 3% by mass to 50% by mass, and more preferably 3% by mass to 30% by mass with respect to pentaerythritol tetraglycidyl ether. Is more preferable, and the range of 3% by mass to 15% by mass is particularly preferable.
  • the content of the polymerization initiator is 3% by mass or more, it is suitable for initiating the curing reaction of PETG. Further, when the content of the polymerization initiator is 90% by mass or less, it is advantageous in terms of maintaining the storage stability of the composition after preparation and the physical property stability of the cured product.
  • the content of the polymerization initiator is preferably in the range of 0.1% by mass to 10% by mass and more preferably in the range of 1.0% by mass to 8.0% by mass with respect to the total mass of the curable resin composition.
  • the range of 1.5% by mass to 6.0% by mass is particularly preferable.
  • content of the polymerization initiator is 0.1% by mass or more, it is suitable for promoting the initiation of the curing reaction of PETG.
  • content of a polymerization initiator is 10 mass% or less, it is advantageous at the point of the storage stability after liquid preparation, and the physical property maintenance after hardening.
  • the curable resin composition of the second aspect of the present disclosure contains at least one surfactant as an antifouling agent.
  • the curable resin composition of the first aspect of the present disclosure may also contain at least one surfactant similar to that of the second aspect as an antifouling agent.
  • the curable resin composition contains a surfactant, the cured product obtained by curing can be imparted with water repellency, oil repellency, hydrophilicity, lipophilicity, and the like, and can impart antifouling properties.
  • the surfactant in the present disclosure is a compound having a fluorine atom or —SiO— structure in the molecule and capable of imparting water repellency, oil repellency, hydrophilicity, or lipophilicity to the surface of the cured film after curing. Yes, for example, fluorine compounds, silicone compounds, and silicone fluorine compounds.
  • the surfactant examples include a fluorine compound or a siloxane compound (including a fluorine-containing siloxane compound), and at least one selected from the group consisting of a fluorine-containing acrylic compound and a fluorine-containing siloxane compound is preferable.
  • a commercially available product may be used as the surfactant.
  • Commercially available products include, for example, MegaFac RS-90, RS-55, RS-72-K, RS-75, RS-76-E, RS-78, RS-90 manufactured by DIC Corporation, Neos Corporation Surfactons S386 and S651 manufactured by AGC Seimi Chemical Co., Ltd., manufactured by AGC Seimi Chemical Co., Ltd. KY-164, KY-108, KY-1203, X-71-1206, ZX-058, ZX-101, ZX-104, ZX-105, ZX-106, ZX-108, ZX- manufactured by T & K, Inc.
  • the content of the surfactant is preferably 0.1% by mass to 30% by mass, more preferably 0.5% by mass to 20% by mass, and 1.0% by mass with respect to the total mass of the curable resin composition. % To 10% by mass is more preferable. Moreover, you may use surfactant individually by 1 type or in combination of 2 or more types.
  • the curable resin composition of the present disclosure preferably further contains a reactive compound (reactive diluent) in addition to the above components.
  • a reactive compound reactive diluent
  • the curability of the curable resin composition hardness of the cured film
  • adjustment or improvement of physical properties such as elongation, adjustment of viscosity, adhesion to the substrate, and additives were added Improvement of compatibility at the time can be performed.
  • the reactive diluent is at least one selected from the group consisting of glycidyl ether compounds, glycidyl ester compounds, glycidyl amine compounds, aliphatic epoxy compounds, olefin oxide epoxy compounds, silicone modified compounds, fluorine modified epoxy compounds, and oxetane compounds.
  • Preferred examples include reactive compounds.
  • cyclic ether compounds and cyclic sulfides are preferable from the viewpoint of adjusting the physical properties of pentaerythritol tetraglycidyl ether (PETG).
  • PETG pentaerythritol tetraglycidyl ether
  • an epoxy compound and a modified epoxy compound for example, a silicone (siloxane) -modified epoxy compound, a fluorine-modified epoxy compound), an oxetane compound, and an episulfide compound are preferable.
  • the cyclic ether compound may be used alone, or two or more cyclic ether compounds may be used in combination. Furthermore, it is selected from an embodiment in which two or more epoxy compounds are used in combination, or an epoxy compound, an oxetane compound, a silicone (siloxane) -modified epoxy compound, a fluorine-modified epoxy compound, an episulfide compound, and other compounds other than these. Any of the aspect which used at least 2 sort (s) together may be sufficient.
  • epoxy compound examples include glycidyl ether compounds, glycidyl ester compounds, glycidyl amine compounds, aliphatic epoxy compounds, olefin oxide epoxy compounds, and modified products of these compounds.
  • Specific examples of the epoxy compound include bisphenol A type epoxy, bisphenol F type epoxy, hydrogenated bisphenol A type epoxy, hydrogenated bisphenol F type epoxy, bisphenol S type epoxy, brominated bisphenol A type epoxy, biphenyl type epoxy, naphthalene type.
  • an epoxy compound an alicyclic epoxy compound is preferable and the compound represented by following formula 1 is more preferable.
  • X represents a single bond or a divalent linking group.
  • the divalent linking group include a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and a group in which a plurality of these are linked.
  • the divalent hydrocarbon group in X may be linear or branched, and examples thereof include an alkylene group having 1 to 18 carbon atoms and a divalent alicyclic hydrocarbon group. Examples of the alkylene group having 1 to 18 carbon atoms include methylene, methylmethylene, dimethylmethylene, ethylene, propylene, and trimethylene groups.
  • Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylidene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1, And cycloalkylene groups (including cycloalkylidene groups) such as 4-cyclohexylene and cyclohexylidene groups.
  • X is preferably a linking group having an oxygen atom, such as —CO—, —O—CO—O—, —COO—, —O—, —CONH—, or a group in which a plurality of these groups are linked. Can be mentioned.
  • commercially available products may be used as the epoxy compound, and specific examples of the commercially available products include the Celoxide series that is an alicyclic epoxy resin manufactured by Daicel Corporation (eg, Celoxide 8000, Celoxide 2021P). , Celoxide 2081, Celoxide 8200, etc.).
  • silicone (siloxane) -modified epoxy compound examples include bis [2- (3,4-epoxycyclohexyl) ethyl] -tetramethyldisiloxane.
  • silicone (siloxane) -modified epoxy commercially available products may be used. Specific examples of commercially available products include product names: X-40-2678 and X-40- manufactured by Shin-Etsu Chemical Co., Ltd. 2670, X-40-2705, X-40-2669 and the like.
  • Epoxy compounds having fluorine atoms include 3- (2,2,3,3-tetrafluoropropoxy) -1,2-epoxypropane, 3- (1H, 1H, 5H-octafluoropenti Loxy) -1,2-epoxypropane, 3-perfluorobutyl-1,2-epoxypropane, 3-perfluorohexyl-1,2-epoxypropane, 1.4 bis (2,3-epoxypropyl)- Examples include perfluoro-n-butane, 1.6 bis (2,3-epoxypropyl) -perfluoro-n-hexane.
  • the commercial item currently marketed may be used for a fluorine-modified epoxy compound, and the product name: 1.3CHEP etc. by Daikin Industries Ltd. is mentioned as a specific example of a commercial item.
  • oxetane compounds include 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyloxetane, 3-ethyl-3 ⁇ [((3-ethyloxetane-3-yl) methoxy] methyl ⁇ oxetane, xylylenebisoxetane.
  • ETERNACOLL registered trademark
  • ETERNACOLL OXBP ETERNACOLL OXMA, etc.
  • OXT-101, OXT-212, OXT-121, and OXT-221 product name
  • OX-SQ TX OX-SQ TX manufactured by Toagosei Co., Ltd.
  • OX-SQ SI-20 product name (oxetanylsilsesquioxane or oxetanyl silicate) and the like.
  • the reactive diluent content is 5 mass with respect to the pentaerythritol tetraglycidyl ether (PETG) content.
  • PETG pentaerythritol tetraglycidyl ether
  • a curable resin composition of the present disclosure a composition containing PETG, a reactive diluent, and a polymerization initiator is one preferred embodiment, and PETG, a reactive diluent, and a polymerization initiator are included.
  • the preferable aspect in the case of containing (1) contains PETG, an alicyclic epoxy resin (preferably, the compound represented by the said Formula 1), and the photo-acid generator which is a photoinitiator.
  • an alicyclic epoxy resin preferably, a compound represented by the above formula 1
  • a photoacid generator that is a photopolymerization initiator and a surfactant
  • the curable resin composition of the present disclosure may further contain a sensitizer.
  • the sensitizer is at least one sensitizer selected from the group consisting of anthracene compounds, anthraquinone compounds, thioxanthone compounds, naphthalene compounds, phenanthrene compounds, chrysene compounds, perylene compounds, and acridine compounds. It is preferable to contain.
  • the sensitizer include anthracene, 1,2-benzoanthracene, 9-cyanoanthracene, 9,10-dicyanoanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-dibutoxyanthracene, 9 , 10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-diglycidyloxyanthracene, 9,10-bis (phenylethyl) anthracene, anthraquinone, 2-methylanthraquinone, 2 -Ethyl anthraquinone, 2-chloroanthraquinone, hydroxyanthraquinone, aminoanthraquinone, anthraquinone sulfonic acid, 1-nitroanthraquinone, 1,2-benzanthraquinone, acetophenone
  • preferred sensitizers are preferably dialkoxyanthracenes, and 2-ethyl-9,10-dimethoxyanthracene and 9,10-dibutoxyanthracene are particularly preferred from the viewpoint of excellent curability improvement effect.
  • a known sensitizer such as a coumarin-based, thiazine-based, azine-based, acridine-based, xanthene-based or titanocene-based dye-sensitized substance is used. It may be used.
  • the content of the sensitizer is preferably 0.1% by mass to 10% by mass and more preferably 0.3% by mass to 5% by mass with respect to the total mass of the curable resin composition. Moreover, you may use a sensitizer individually by 1 type or in combination of 2 or more types.
  • the curable resin composition of the present disclosure may include a coupling agent.
  • a coupling agent By containing a coupling agent, the adhesiveness between curable resin composition and a base material can be improved more.
  • the coupling agent examples include various coupling agents such as silane, titanate, and aluminate.
  • a silane coupling agent represented by “X 3 —Si (CH 2 ) n —Y” is suitable.
  • X represents a chlorine atom, a methoxy group, an ethoxy group, a methoxyethoxy, or an acetoxy group, and may contain a methyl group.
  • n is 0-3.
  • Examples of Y include a vinyl group, an epoxy group, a methacryloyloxy group, an acrylic group, an amino group, a sulfide group, a ureido group, an isocyanate group, an isocyanurate group, a styryl group, and a mercapto group.
  • silane coupling agent examples include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropyl.
  • the content of the coupling agent is preferably 0.1% by mass to 10.0% by mass and more preferably 0.5% by mass to 5.0% by mass with respect to the total mass of the curable resin composition. Moreover, you may use a coupling agent individually by 1 type or in combination of 2 or more types.
  • the curable resin composition of the present disclosure may further contain a filler such as nano-order nanoparticles depending on the application.
  • Nanoparticles refer to organic or inorganic material particles having an average primary particle size of 1 nm to 1000 nm. The average primary particle diameter is a value determined by a laser analysis type particle size distribution analyzer.
  • the nanoparticles may be any particles as long as they do not inhibit the polymerization reaction of the curable resin composition.
  • the nanoparticles include carbon, or organic material fillers such as diamond, graphene, graphene oxide, fullerene, polyethylene, polypropylene, and polystyrene.
  • the inorganic filler include gold, silver, silicon, indium tin oxide, silica, zirconia, alumina, silicon nitride, carbon nitride, aluminum nitride, boron nitride, zinc oxide, titanium oxide, and silicon carbide.
  • grains by which the coating of the nanoparticle and the chemical modification of the reactive group were given are also preferable.
  • a commercially available product may be used as the nanoparticle.
  • Examples of commercially available products include silica particles having an average primary particle size of 10 nm to 100 nm, Admanano (registered trademark) YA010C manufactured by Admatechs Co., Ltd. YA050C, YC100C, YA010-SM1, YA010-SV1, YA050-SM1, YA050-SV6, YA050C-SV2, YA010-SP3, YA050C-SP3, YC100C-SP3, and the like.
  • zirconia particles examples include Zircostar AX-ZP-153-A manufactured by Nippon Shokubai Co., Ltd., PCS, PCS-90, PCS-60 manufactured by Nippon Electric Works Co., Ltd., and the like.
  • the content of the filler is preferably 0.1% by mass to 80% by mass and more preferably 10% by mass to 50% by mass with respect to the total mass of the curable resin composition. Moreover, you may use a filler individually by 1 type or in combination of 2 or more types.
  • the curable resin composition of the present disclosure may be prepared in a diluted form containing an organic solvent.
  • organic solvent include a solvent selected from aromatic hydrocarbons, aliphatic hydrocarbons, alcohols, ether acetal esters, ketones, and nitrogen compounds.
  • organic solvent examples include toluene, xylene, hexane, cyclohexane, styrene, octanedecane, petroleum ether, petroleum naphtha, ethyl alcohol, isopropyl alcohol, propanol, ethylene glycol, propylene glycol, ⁇ -butyrolactone, ethyl acetate, butyl acetate, Acetone, methyl ethyl ketone, acetonitrile, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate , Ethylene glycol monoethyl ether Tate, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and
  • the curable resin composition of the present disclosure may further include an anti-aging agent, an antioxidant, a coloring agent, a viscosity modifier, a flame retardant, an ultraviolet absorber, a discoloration preventing agent, an antibacterial agent, an antistatic agent, if necessary.
  • Additives such as a plasticizer, a lubricant, an antifoaming agent, a thickener, a thixotropic agent, a leveling agent, and a release agent can be contained.
  • colorant examples include dyes, carbon black, titanium oxide, zinc oxide, iron oxide, anthraquinone series, and phthalocyanine series.
  • anti-aging agents and antioxidants that are stabilizers include hindered phenol compounds, phosphorus compounds, benzophenone compounds, hydrazine compounds, and the like.
  • the -Curing method of curable resin composition- Curing of the curable resin composition can be performed by applying an active energy ray of 200 nm to 1300 nm (light such as ultraviolet rays), heat of 50 ° C. to 250 ° C., or both.
  • the curable resin composition can be cured by irradiation with an active energy ray of 200 nm to 850 nm (preferably 250 nm to 560 nm) or by heating at a temperature of 80 ° C. to 180 ° C.
  • active energy rays include ⁇ rays, ⁇ rays, X rays, ultraviolet rays, visible rays, infrared rays, and electron beams.
  • cured with light such as an ultraviolet-ray, visible light, an infrared ray, is preferable, and the photocurable composition hardened
  • the curable resin composition When the curable resin composition is cured by irradiation with active energy rays, it is preferable to use an ultraviolet irradiation device as an exposure device and irradiate the curable resin composition with active energy rays.
  • an ultraviolet irradiation apparatus for example, an exposure apparatus provided with a light source such as a metal halide lamp, a high-pressure mercury lamp, a laser exposure machine, or an LED can be used.
  • the irradiation amount of ultraviolet rays is preferably 1,000 mJ / cm 2 to 40,000 mJ / cm 2 , more preferably 3,000 mJ / cm 2 to 9,000 mJ / cm 2. It is.
  • a temperature of 80 ° C. to 180 ° C. is used with respect to the curable resin composition using an infrared heating device that heats the object with infrared rays or a heating device such as an electric furnace. It is preferable to heat in the range of 1 minute to 120 minutes.
  • the curable resin composition of the first aspect of the present disclosure is used for production (imprint) of an uneven structure.
  • a concavo-convex structure is obtained by curing the curable resin composition to form a concavo-convex structure (particularly, a moth-eye structure) on the substrate. Since the curable resin composition of the present disclosure is used, it is possible to produce a concavo-convex structure having high hardness and excellent antireflection properties.
  • the concavo-convex structure is preferably a concavo-convex structure having a nanoscale fine concavo-convex pattern.
  • the uneven pattern preferably has a height of 50 nm to 1000 nm (preferably 100 nm to 300 nm) and a pitch of 20 nm to 1000 nm (preferably 50 nm to 150 nm).
  • the height and pitch of the concavo-convex pattern of the mold are within the above range, the effect of molding using the curable resin composition of the present disclosure can be obtained satisfactorily, and a concavo-convex structure excellent in antireflection properties is produced can do.
  • the curable resin composition of the second aspect of the present disclosure is used for forming a hard coating, that is, a hard coat layer.
  • the curable resin composition of the second aspect of the present disclosure has a curing performance of selectively including PETG and curing.
  • PETG PETG
  • the antifouling component was contained, there was a problem that the curability was lowered, whereas in the curable resin composition of the second aspect of the present disclosure, high hardness was obtained even if the antifouling component was contained, And the outstanding antifouling property can also be provided. Accordingly, when a hard coat layer is provided on the surface of a member used in a field where high strength is required using the curable resin composition of the second aspect of the present disclosure, strength resistance to external force and antifouling property Can be compatible.
  • the cured product of the present disclosure is a cured product of the curable resin composition of the present disclosure described above, and has a scratch pencil hardness of 7H or more in a flat film.
  • a cured product having a further improved hardness can be obtained as compared with a conventional curable resin composition.
  • Scratch pencil hardness conforms to JIS-K5600 5-4 mechanical method, and has two wheels on one side, and has a cylindrical hole into which a pencil with an angle of 45 ° ⁇ 1 ° is inserted at the center.
  • Test machine No. It is a value measured using 553-S (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) and applying a load of 750 ⁇ 10 g.
  • a scratched pencil hardness of 7H or more in the flat film indicates higher hardness and superior durability than conventional.
  • the scratch pencil hardness is preferably as close to 9H as possible, more preferably 8H or more, and more preferably 9H or more.
  • the concavo-convex structure of the present disclosure is a cured product of the curable resin composition of the first aspect described above, and has a concavo-convex pattern having a height of 50 nm to 1000 nm and a pitch of 20 nm to 1000 nm.
  • the curable resin composition of the first aspect described above since the curable resin composition of the first aspect described above is used, the surface hardness after curing is high and a fine structure can be easily obtained. Therefore, the height: 50 nm to 1000 nm , Pitch: Suitable for producing a fine uneven pattern of 20 nm to 1000 nm.
  • the curable resin composition of the first aspect described above is suitable for the production (imprint) of a concavo-convex structure, and a fine concavo-convex structure (particularly a moth-eye structure) can be obtained with good reproducibility, and
  • a structure (cured product) such as a replica mold formed using a master mold is excellent in hardness. Since replica molds are cheaper and more suitable for mass production than master molds, replica molds are widely used, but replica molds having a moth-eye structure, for example, using the curable resin composition of the present disclosure have high hardness. Excellent wear resistance and durability.
  • the concavo-convex structure of the present disclosure may be produced using any method as long as it is a method using the curable resin composition of the first aspect described above.
  • the concavo-convex structure of the present disclosure is preferably prepared by using the curable resin composition of the first aspect described above, and forming a concavo-convex pattern having a height of 50 nm to 1000 nm and a pitch of 20 nm to 1000 nm. It is performed by a method having a step of forming and curing.
  • the concavo-convex structure a mold having a concavo-convex pattern having a height of 50 nm to 1000 nm and a pitch of 20 nm to 1000 nm and a substrate coated with a curable resin composition are prepared, and the curable structure is prepared.
  • An introduction step of bringing the concavo-convex pattern into contact with the resin composition and pressing to introduce the curable resin composition into the concavo-convex pattern, a curing step of curing the introduced curable resin composition, and a curable resin composition You may perform by the method which has the mold release process of releasing the said base material provided with the uneven structure obtained by making it harden
  • FIG. 1 is a schematic view showing a manufacturing process of the concavo-convex structure.
  • the imprint apparatus 100 includes a stage 5, a push jig 6, a feed roller 7, and a take-up roller 8.
  • the imprint apparatus 100 is an apparatus for manufacturing the concavo-convex structure 10 (base material 1 having a concavo-convex structure).
  • Stage 5 is a table for placing and fixing the mold 2. As shown to Fig.1 (a), the mold 2 is fixed to the stage 5 so that an uneven
  • the push jig 6 is for raising and lowering the stage 5, and the mold 2 is raised and lowered by fixing the mold 2 on the stage 5.
  • the base material 1 to which the curable resin composition 3 is applied and the uneven pattern of the mold 2 can be brought into contact with each other.
  • the resin composition 3 can be introduced into the concavo-convex pattern.
  • the base material 1 having a concavo-convex structure can be released from the mold 2 as described later.
  • the sheet-like substrate 1 is wound around a feed roller 7 and a take-up roller 8.
  • the feeding roller 7 is a roller for feeding the wound sheet-like base material 1 to the stage 5 side on which the mold 2 is fixed.
  • the take-up roller 8 is a roll of the wound sheet-like base material 1 on the mold 2. Is a roller for winding from the fixed stage 5 side.
  • the substrate 1 coated with the curable resin composition 3 and the mold 2 including the concavo-convex pattern are pressed by bringing the concavo-convex pattern into contact with the curable resin composition 3. Then, the curable resin composition 3 is introduced into the concavo-convex pattern. In addition, the curable resin composition is applied to the base material 1 before the introducing step.
  • the method for applying the curable resin composition is not particularly limited.
  • the stage 5 to which the mold 2 is fixed is raised at a constant speed to bring the substrate 1 coated with the curable resin composition 3 and the concave / convex pattern of the mold 2 into contact, and then the curable resin composition.
  • the base material 1 on which the object 3 is applied and the mold 2 having the concavo-convex pattern are pressed with a constant pressure.
  • the mold and the substrate are preferably pressed at a pressure of 0.005 MPa to 1 MPa, more preferably pressed at a pressure of 0.01 MPa to 0.2 MPa, and a pressure of 0.01 MPa to 0.03 MPa. It is more preferable to press, and it is particularly preferable to press at a pressure of 0.01 MPa to 0.02 MPa.
  • a sufficient amount of the curable resin composition can be introduced into the concavo-convex pattern.
  • the concavo-convex structure having an excellent function with respect to transparency and antireflection properties is obtained. can get.
  • corrugated pattern can be suitably adjusted by pressing with the pressure of 1 Mpa or less.
  • the curable resin composition 3 introduce
  • the base material 1 and the photocurable composition having light transmittance are used, and the base material 1 is irradiated with ultraviolet rays (UV) from the side opposite to the side on which the mold 2 is fixed. Since the substrate 1 has optical transparency, the ultraviolet rays irradiated to the substrate 1 are transmitted through the substrate 1 and irradiated to the curable resin composition 3. Thereby, since the curable resin composition 3 introduced into the concavo-convex pattern is cured, a cured concavo-convex structure is formed on the substrate 1.
  • UV ultraviolet rays
  • the irradiation time and irradiation amount at the time of irradiating the curable resin composition 3 with ultraviolet rays are not particularly limited as long as they are sufficient to cure the curable resin composition 3 introduced into the concavo-convex pattern.
  • the tip of the concavo-convex structure is easily broken and remains at the bottom of the mold, and the problem of shortening the mold life tends to occur.
  • the manufacturing method of the concavo-convex structure of the present disclosure the hardness of the cured product after curing is high, so that the tip of the concavo-convex structure is not easily damaged, and a mold release that reproduces a fine structure pattern is possible.
  • the concavo-convex structure obtained by the manufacturing method of the concavo-convex structure of the present disclosure is superior in antireflection and water repellency compared to the concavo-convex structure 40 obtained by conventional nanoimprint, and is a concavo-convex structure, for example.
  • the mold has a long life.
  • Example 1 Sample level 1- -Preparation of curable composition- Brown erythritol tetraglycidyl ether (PETG; trade name: Show Free (registered trademark), manufactured by Showa Denko KK) 9 in a brown glass wide mouth standard bottle (Sansho Co., Ltd., glass wide mouth standard bottle 1K, full amount: 14 ml) 0.5 g and 0.5 g of triallylsulfonium salt (photo acid generator; trade name: CPI210S, manufactured by San Apro Co., Ltd.), and a hand homogenizer (MH-1000, manufactured by ASONE Co., Ltd.) and a test tube mixer ( VXRS1 (manufactured by IKA) was mixed with stirring to prepare a curable composition.
  • PETG Brown erythritol tetraglycidyl ether
  • Show Free registered trademark
  • an ultraviolet irradiation device model
  • ECS5-015010 metal halide lamp 1.5 kW, manufactured by iGraphics Co., Ltd.
  • the test piece having the hard coat layer was left at room temperature for 1 day.
  • the test piece after standing is compliant with JIS-K5600 5-4 mechanical method, has two wheels on one side, and has a cylindrical hole into which a pencil with an angle of 45 ° ⁇ 1 ° is inserted at the center.
  • Hand pencil scratch hardness tester No. Using a 553-S (manufactured by Yasuda Seiki Seisakusho Co., Ltd.), the scratch pencil hardness of the hard coat layer was measured under a load of 750 ⁇ 10 g. The scratch pencil hardness is evaluated in the range of 6B to 9H, and the closer to 9H, the harder the property.
  • mold release treatment fluorine mold release agent; coated with OPTOOL DSX manufactured by Daikin Industries, Ltd.
  • a moth eye structure The processing conditions for GC are as follows.
  • EIG-210ER manufactured by Elionix
  • ECR electron cyclotron resonance
  • the curable composition 14 was applied to the processed surface of the prepared GC moth-eye mold 12 at a coating amount of 1.25 g / m 2 to form a coating film 14.
  • a polyester film 16 manufactured by Toyobo Co., Ltd., Cosmo Shine (registered trademark) A4300; PET film) 16 was disposed on the membrane 14.
  • the coating film 14 is irradiated with ultraviolet rays through the PET film (the irradiation amount of the sample level 1 to 3 is 10000 mJ / cm 2 , the sample level is 1 to 3) Illuminance: 50 mW / cm 2 ) was used as a cured film, and the cured film 24 was released together with the PET film 16 to produce a moth-eye film to which the moth-eye structure was transferred. That is, a moth-eye film was produced by nanoimprint lithography (NIL, UV-NIL) using a curable resin.
  • NIL nanoimprint lithography
  • sample level 2- In sample level 1, except that the composition was changed as shown in Table 2 below, a test piece having a hard coat layer and a moth-eye film were prepared in the same manner as in sample level 1, and further measured and evaluated. .
  • the results of measurement and evaluation are shown in Table 2 and FIG. 6, FIG. 8A, FIG. 8B and FIG.
  • sample level 3-7- In sample level 1, except that the composition was changed as shown in Table 2 below, a test piece having a hard coat layer and a moth-eye film were prepared in the same manner as in sample level 1, and further measured and evaluated. . The results of measurement and evaluation are shown in Table 2 and FIGS.
  • -Celoxide 8000 Alicyclic epoxy compound manufactured by Daicel Corporation-EPICLON EXA-830-CRP: Bisphenol F type epoxy resin, manufactured by DIC Corporation-CPI210S: Triallylsulfonium salt (photoacid generator; trade name: CPI210S, San Apro Co., Ltd.)
  • KY-1203 One-terminal (meth) acryl-modified perfluoropolyether compound (fluorine antifouling additive, manufactured by Shin-Etsu Chemical Co., Ltd.)
  • Example 2 Sample level 8-20-
  • a test piece having a hard coat layer was produced in the same manner as in Sample Level 1 except that the composition was changed as shown in Table 3 below at Sample Level 1.
  • the same measurement and evaluation as those of the sample level 1 were performed on some of the test pieces.
  • another part of the test piece was placed in a thermostatic chamber (SAFETY OPEN SPH-201, manufactured by Espec Co., Ltd.) having an atmospheric temperature of 85 ° C. and left for 30 minutes. Measurements and evaluations similar to those described above were performed. The results of measurement and evaluation are shown in Table 3.
  • Table 3 shows the influence of the type and concentration of reactive diluents at sample levels 8 to 20.
  • steel wool scuffing properties could be improved by containing PETG and an epoxy compound that is a reactive diluent.
  • the concentration in the case of containing the reactive diluent is preferably in the range of less than 30% by mass.
  • the surface of the cured film (Martens hardness) is high, and the reflectance and transmission by the rubbing test are high. The change in rate is also considered to be small.
  • Example 3 Sample level 21-26- A sample piece having a hard coat layer was prepared in the same manner as in the sample level 1 except that the composition was changed as shown in Table 4 below in the sample level 1, and further, measurement and evaluation were performed. Table 4 shows the results of measurement and evaluation.
  • Table 4 shows the effect of the type of polymerization initiator on sample levels 21 to 26. As shown in Table 4, the influence obtained by changing the type of the polymerization initiator was small, and the hardness obtained in combination with PETG was excellent regardless of which polymerization initiator was used. In addition, when the moth-eye film is produced, as in sample levels 1 and 2, scars are hardly generated by the rubbing test, the surface of the cured film (Martens hardness) is high, and the reflectance and transmission by the rubbing test are high. The change in rate is also considered to be small.
  • Example 4 Sample level 27-28- -Preparation of curable composition- A curable composition was prepared in the same manner as in Sample Level 1 except that the composition was changed as shown in Table 5 below.
  • Table 5 shows the influence of the type of polymerization initiator on sample levels 27 to 28. As shown in Table 5, the effect of being constituted in a thermosetting system using a thermal acid generator as a polymerization initiator is small, and the hardness obtained in combination with PETG is excellent even if a thermal acid generator is used. It was.
  • the curable composition 14 was applied at a coating amount of 1.25 g / m 2 on the processed surface of the GC moth-eye mold 12 produced in the same manner as the sample level 1.
  • a film 14 was formed, and a glass substrate 26 having a thickness of 150 ⁇ m was placed on the coating film 14.
  • the GC moth-eye mold is heated to a cured film under the heating conditions of a temperature of 130 ° C., a load of 1500 N, and a load time of 900 seconds, and the cured film 24 is released together with the glass substrate 26.
  • a moth-eye sheet having the moth-eye structure transferred thereon was produced.
  • the surface of the cured film 24 of the moth-eye sheet obtained above was observed with a scanning electron microscope (SEM; ERA-8800FE, manufactured by Elionix). As a result, it was visually confirmed that a good moth-eye structure was transferred and formed on the moth-eye sheets produced using the curable compositions of sample levels 27 to 28 as shown in FIG. Furthermore, the reflectance of the cured film surface of the moth-eye film was measured using an ultraviolet-visible-near infrared spectrophotometer (SolidSpec-3700, Shimadzu Corporation). The result is shown in FIG.
  • Example 5 Sample level 29-36- A sample piece having a hard coat layer was prepared in the same manner as in the sample level 1 except that the composition was changed as shown in Table 6 below in the sample level 1, and further measurement and evaluation were performed. Further, the antifouling property was evaluated by the following method. The results of measurement and evaluation are shown in Table 6 below.
  • the antifouling property was evaluated by the following oil-based magic wiping test.
  • the prepared curable composition was applied onto a glass slide having a size of 76 mm ⁇ 26 mm with a No22 bar coater, and using an ultraviolet irradiation device (model: ECS5-015010, metal halide lamp 1.5 kW, manufactured by Eye Graphics Co., Ltd.).
  • Ultraviolet rays were irradiated under the conditions of an irradiation amount of 6,000 mJ / cm 2 and an illuminance of 50 mW / cm 2 to cure the coating film, and left for 1 day.
  • Table 6 shows the compositions containing antifouling components in sample levels 29 to 36. As shown in Table 6, by containing an antifouling component, it was possible to impart wiping properties while maintaining high hardness and scratch resistance. On the other hand, in the sample level 36 containing an antifouling component but not containing PETG, a good result was obtained with wiping properties, but it was impossible to achieve both hardness and scratch resistance.
  • a moth-eye film was prepared using the curable compositions of sample level 32 and sample level 36, and the moth-eye structure and wiping property were evaluated.
  • the curable composition 14 is applied at a coating amount of 1.25 g / m 2 on the processed surface of the prepared GC moth-eye mold 12 to form a coating film 14.
  • a polyester film 16 manufactured by Toyobo Co., Ltd., Cosmo Shine (registered trademark) A4300; PET film
  • the coating film 14 was irradiated with UV light through a PET film (irradiation amount: 10,000 mJ / cm 2 , illuminance: 50 mW / cm 2 ) to form a cured film. Then, by releasing the cured film 24 together with the PET film 16, a moth-eye film to which the moth-eye structure was transferred was produced.
  • the rubbing test was repeated 10 times, and the following evaluation was performed for the presence or absence of scratches on the surface of the cured film.
  • I. Image Evaluation The surface of the cured film of the moth-eye film before and after the abrasion test was observed with a scanning electron microscope (SEM; ERA-8800FE, manufactured by Elionix Co., Ltd.), and the presence or absence of scratches due to abrasion was evaluated by SEM photographs.
  • Wipeability An artificial fingerprint liquid was dropped on the transfer surface of the moth-eye structure of the moth-eye film, and the operation of wiping oil-based ink with Kimwipe S-200 (manufactured by Nippon Paper Crecia Co., Ltd.) was repeated, and the number of times that the wipe could be wiped was recorded.
  • the moth-eye film of sample level 32 was subjected to a wiping test after heat-treating the moth-eye film under the following conditions.
  • ⁇ Condition> ⁇ Heating temperature: 85 °C ⁇ Heating time: 30 minutes ⁇
  • Artificial fingerprint liquid Artificial fingerprint liquid [Artificial fingerprint liquid]
  • the artificial fingerprint liquid used here is composed of rhodamine B (manufactured by Tokyo Chemical Industry Co., Ltd., CAS.NO81-88-9) with the following composition described in JIS K2246 (2007) rust prevention oil. It was prepared by adding 0.1% by mass with respect to.
  • FIG. 15 the artificial fingerprint liquid could be wiped off satisfactorily.
  • FIG. 16 the SEM photograph at the time of wiping off artificial fingerprint liquid 20 times is shown in FIG.
  • FIGS. 17A and 17B changes in reflectance and transmittance before and after wiping 20 times.
  • the reduction width was less than 1%.
  • Example 6 Example level 37-38- A test piece having a hard coat layer was prepared in the same manner as in the sample level 1 except that the composition was changed as shown in Table 7 below in the sample level 1, and further, measurement and evaluation were performed. Further, the adhesive strength was evaluated as an index of the sensitization effect by the following method. The results of measurement and evaluation are shown in Table 7 below.
  • the adhesive strength was measured using a test specimen that did not transmit the absorption wavelength of the polymerization initiator, and the adhesiveness was evaluated.
  • the evaluation results are shown in Table 7 below.
  • the coating thickness of the curable composition is made constant on the degreased surface.
  • a mending tape MP-18, manufactured by Sumitomo 3M Limited
  • the curable composition is applied to the surface of the epoxy glass plate on which the mending tape is applied, and the two epoxy glass plates are alternately bonded so that the application area of the curable composition is 26 mm ⁇ 3 mm,
  • a specimen was prepared by pressing with a bee-type clip (Kuri-44, manufactured by KOKUYO Corporation). Thereafter, using an ultraviolet irradiation device (model: ECS5-1015010, metal halide lamp 1.5 kW, manufactured by Eye Graphics Co., Ltd.), the curable composition of the test specimen was irradiated with 9,000 mJ / cm 2 and an illuminance of 100 mW / Ultraviolet rays were irradiated at cm 2 to cure the curable composition.
  • the irradiated specimen was left at room temperature (25 ° C.) for 1 day.
  • two glass plates were pulled at a pulling speed of 50 mm / min using Autograph AG-5KNXplus (manufactured by Shimadzu Corporation), and the shear adhesive strength was measured.
  • Table 7 shows the compositions containing sensitizers in sample levels 37 to 38.
  • the epoxy glass plate used does not transmit the absorption wavelength of the polymerization initiator, but the curable composition of sample levels 37 to 38 contains a sensitizer, so that the absorption wavelength of the sensitizer is 350 nm to 400 nm.
  • the ultraviolet ray in the wavelength range was irradiated, the polymerization initiator was sensitive and could be cured. That is, it can be said that a composition containing a polymerization initiator and a sensitizer is also effective as a method for curing PETG.
  • Example 7 Sample level 39-42- A test piece having a hard coat layer was prepared in the same manner as in Sample Level 1 except that the composition was changed as shown in Table 8 below. Table 8 shows the results of measurement and evaluation.
  • Table 8 shows the results of the sample levels 39 to 42 when the composition contains a filler. As shown in Table 8, even in the composition containing the filler, the hardness obtained in combination with PETG was excellent.
  • moth-eye films were prepared using the curable compositions of sample levels 39 and 42, and the moth-eye structure was evaluated.
  • the curable composition 14 is applied at a coating amount of 1.25 g / m 2 on the processed surface of the prepared GC moth-eye mold 12 to form a coating film 14.
  • a polyester film 16 manufactured by Toyobo Co., Ltd., Cosmo Shine (registered trademark) A4300; PET film) 16 was disposed on the membrane 14.
  • the coating film 14 was irradiated with ultraviolet rays through a PET film (irradiation amount: 10,000 mJ / cm 2 , illuminance: 50 mW / cm 2 ) to form a cured film, and the cured film 24 was released together with the PET film 16 to produce a moth-eye film to which the moth-eye structure was transferred.
  • Example 8 Sample level 43-44- A sample piece having a hard coat layer was prepared in the same manner as in the sample level 1 except that the composition was changed as shown in Table 9 below in the sample level 1, and further, measurement and evaluation were performed. Furthermore, adhesive strength was measured as an index for evaluating adhesiveness by the following method. The results of measurement and evaluation are shown in Table 9 below.
  • -Adhesiveness- A spacer for making the coating thickness of the curable composition constant on the surface after degreasing one surface of a slide glass (S1214, Matsunami Glass Industry Co., Ltd.) having a size of 76 mm ⁇ 26 mm with acetone.
  • a mending tape MP-18, manufactured by Sumitomo 3M Limited
  • the curable composition is applied to the surface of the slide glass plate on which the mending tape is attached, and the two epoxy glass plates are alternately laminated so that the application area of the curable composition is 26 mm ⁇ 3 mm.
  • a specimen was prepared by pressing with a mold clip (Kuri-44, manufactured by KOKUYO Co., Ltd.).
  • the curable composition of the test specimen was irradiated with 9,000 mJ / cm 2 and an illuminance of 100 mW / Ultraviolet rays were irradiated at cm 2 to cure the curable composition. Thereafter, the irradiated specimen was left at room temperature (25 ° C.) for 1 day. After leaving the test piece, two glass plates were pulled at a pulling speed of 50 mm / min using Autograph AG-5KNXplus (manufactured by Shimadzu Corporation), and the shear adhesive strength was measured. Separately from the above, the shear glass strength was measured in the same manner by replacing the slide glass plate with an acrylic plate or a polycarbonate plate (PC plate). The measurement results are shown in Table 9 below.
  • Table 9 shows the results when the compositions containing the silane coupling agent were used in sample levels 43 to 44. As shown in Table 9, even in the composition containing the silane coupling agent, the hardness obtained in combination with PETG was excellent. In addition, when the moth-eye film is produced, as in sample levels 1 and 2, scars are hardly generated by the rubbing test, the surface of the cured film (Martens hardness) is high, and the reflectance and transmission by the rubbing test are high. The change in rate is also considered to be small.
  • the curable resin composition of the present disclosure is suitable for various uses that require high hardness, and is preferably used in the fields of antireflection, diffraction grating (optical element), LSI (integrated circuit wiring), polarizing plate, and nanoimprint.
  • nanoimprint field it is suitable for forming various patterns such as a moth-eye pattern such as a cone or polygonal pyramid, a pillar structure, a hole structure, a microlens array structure, a honeycomb structure, a lattice structure, a line & space structure, and a replica mold.

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Abstract

L'invention concerne : une composition de résine durcissable qui contient un éther tétraglycidylique de pentaérythritol et un initiateur de polymérisation, et est utilisée pour produire une structure résistante ; un produit durci ; une structure résistante ; et un procédé de production de la structure résistante.
PCT/JP2018/023004 2017-06-15 2018-06-15 Composition de résine durcissable, produit durci, structure résistante et procédé de production de structure résistante Ceased WO2018230725A1 (fr)

Priority Applications (2)

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JP2019525582A JP7406193B2 (ja) 2017-06-15 2018-06-15 ナノインプリント用硬化性樹脂組成物、硬化物の製造方法、及び凹凸構造体の製造方法
JP2022113446A JP7514461B2 (ja) 2017-06-15 2022-07-14 硬化性樹脂組成物及び硬化物

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