JP6108095B2 - Method for manufacturing concavo-convex structure - Google Patents

Description

  The present invention relates to a method for producing a concavo-convex structure having a concavo-convex structure on the surface.

  2. Description of the Related Art Conventionally, a concavo-convex structure having a fine concavo-convex shape formed on the surface, represented by a so-called moth-eye film, is widely known. And this uneven structure body is often used as an antireflection film, an antifouling film, etc. in various display devices.

  As a prior art document disclosing such a concavo-convex structure, for example, the following Patent Document 1 can be cited.

JP 2010-082830 A

  Most of the conventional concavo-convex structures disclosed in Patent Document 1, including the concavo-convex structure, use an ionizing radiation curable resin, poured it into a predetermined mold, and then cured by irradiation with ionizing radiation. , Manufactured by peeling from the mold.

  Here, for the purpose of imparting various performances such as the purpose of improving the strength of the concavo-convex structure or the weather resistance of the concavo-convex structure, metal oxide fine particles are incorporated into the concavo-convex structure. Things have been done. And, when trying to contain metal oxide particles in the concavo-convex structure by the manufacturing method as described above, the metal oxide particles are previously contained in the ionizing radiation curable resin, and this is made into a desired mold. After pouring, it is cured by irradiating with ionizing radiation and then peeling from the mold.

  However, when the unevenness to be manufactured is very fine, for example, in the nano-order, the unevenness of the mold used is also fine. As described above, the metal oxide is not contained in the ionizing radiation curable resin. If the particles are included, the unevenness of the mold is clogged, the ionizing radiation curable resin does not flow into every corner of the unevenness, and there is a possibility that a desired fine uneven structure cannot be finally formed. is there.

The present invention has been made in such a situation, and has a concavo-convex structure on the surface, which can form a desired fine concavo-convex structure and can impart various performances such as strength and weather resistance. The present invention relates to a method for manufacturing an uneven structure.

  A method for producing a concavo-convex structure having a concavo-convex structure on a surface, wherein a mold for forming the concavo-convex structure is prepared, and the mold includes one or both of a hydrolyzable group and a hydroxyl group in total. A step of applying an ionizing radiation curable uneven structure forming material containing a metal chelate compound, and a step of obtaining a metal oxide from the metal chelate compound by heating the applied uneven structure forming material. And a step of irradiating the material for forming a concavo-convex structure after the heating with ionizing radiation, and a step of peeling a cured product cured by irradiation of the ionizing radiation from the mold.

  A method for producing a concavo-convex structure having a concavo-convex structure on a surface, the ionizing radiation-curing concavo-convex comprising a metal chelate compound having one or both of a hydrolyzable group and a hydroxyl group in total on a substrate A step of applying a structure forming material, a step of pressing a mold for forming a concavo-convex structure against the applied concavo-convex structure forming material, and formation of a concavo-convex structure in a state where the mold is pressed A step of obtaining a metal oxide from the metal chelate compound by heating the material, a step of irradiating ionizing radiation to the material for forming an uneven structure after the heating, and a cured product cured by irradiation of the ionizing radiation. And a step of peeling from the mold.

  According to the method for producing a concavo-convex structure of the present invention, the ionizing radiation curable concavo-convex structure forming material contains a predetermined metal chelate compound in advance, but at this stage, the metal chelate compound is not particulate. Therefore, even if the concavo-convex structure forming material containing this is applied to the mold, so-called clogging does not occur, and the concavo-convex structure forming material can be spread to every corner of the mold. In addition, in the manufacturing method of the present invention, since the step of obtaining a metal oxide from the metal chelate compound by heating the applied material for forming an uneven structure, the uneven structure is formed. The metal material can be contained in the concavo-convex structure, which is the object of manufacture, while maintaining the state where the material for use is spread throughout the concavo-convex portions of the mold, that is, the fine concavo-convex structure. And, by selecting the type of metal chelate compound to be used, the type of metal oxide contained inside the concavo-convex structure can be arbitrarily adjusted, so the strength, weather resistance, etc. depending on the type of metal oxide Desirable performance can be imparted to the concavo-convex structure.

It is process drawing for demonstrating the 1st Embodiment of this invention. It is process drawing for demonstrating the 2nd Embodiment of this invention.

  Hereinafter, embodiments for carrying out the present invention will be described in detail with reference to the drawings. In addition, this invention is not limited to the form demonstrated below, In the range which does not deviate from a technical thought, it can implement in various deformation | transformation. In the accompanying drawings, the vertical and horizontal scales may be exaggerated for the sake of explanation, and the actual scales may differ.

<First Embodiment>
FIG. 1 is a process diagram for explaining a first embodiment of a method for producing an uneven structure according to the present invention.

(Process of applying uneven structure forming material)
As shown in FIG. 1A, in the present embodiment, a mold 10 for forming an uneven structure is prepared, and one or both of a hydrolyzable group and a hydroxyl group is added to the mold 10 in total. The process of apply | coating the ionizing radiation hardening type uneven | corrugated structure forming material 12 containing the metal chelate compound 11 which has the above is performed. The metal chelate compound 11 is not in the form of particles at this stage but is in a state of being dissolved in the concavo-convex structure forming material 12, but the chelate compound 11 is schematically shown in FIG.

  In this way, by finally containing a metal that becomes a metal oxide as the chelate compound 11, so-called clogging does not occur even when the concavo-convex structure forming material 12 is applied to the mold 10. The material for forming a concavo-convex structure can be spread to every corner of the ten concavo-convex portions.

  The mold 10 prepared in the present embodiment is not particularly limited, and may be appropriately designed and prepared according to the concavo-convex structure to be manufactured. For example, when manufacturing a so-called moth-eye film used for antireflection, the average height of the protrusions should be designed to be about 10 to 1000 nm, in other words, the average depth of the recesses should be about 10 to 1000 nm. It may be designed to be about 10 to 1000 nm even in the period of unevenness.

  Further, the material of the mold 10 is not particularly limited, and may be appropriately selected from conventionally known materials.

  As the metal chelate compound 11 having one or both of a hydrolyzable group and a hydroxyl group in total contained in the concavo-convex structure forming material 12, one or both of the hydrolyzable group and the hydroxyl group is contained. It is not particularly limited as long as it has a total of 1 or more and is formed by binding a chelate compound and can produce a metal oxide by a heating step performed later.

  Here, the hydrolyzable group refers to a functional group that hydrolyzes upon contact with water, or a functional group that can form a bond via a metal atom and an oxygen atom in the presence of water. Atoms, amino groups, alkoxy groups, ester groups, carboxy groups, phosphoryl groups, isocyanate groups, cyano groups, epoxy groups and the like can be mentioned.

  In addition, as the chelating compound bonded, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate isopropyl, acetoacetate-n-butyl, acetoacetate-sec-butyl, acetoacetate-t-butyl Β-ketoesters such as acetylacetone, hexane-2,4-dione, heptane-2,4-dione, heptane-3,5-dione, octane-2,4-dione, nonane-2,4-dione, 5 Β-diketones such as methyl-hexane-2,4-dione; saturated aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid Glycols such as ethylene glycol; glycolic acids such as oxyacetic acid; ethylenediaminetetraacetic acid (EDTA) and its Nitrogen-containing compounds such as sodium salt, ethylenediamine, 1,3-propanediamine, diethylenetriamine, pentamethyldiethylenetriamine, hexamethyltriethylenetetramine, tris [2- (dimethylamino) ethyl] amine, tri (pyridinylmethyl) amine; furan carboxylic acid Thiophenecarboxylic acid, nicotinic acid, isonicotinic acid, phenanthroline, diphenanthroline, substituted phenanthroline, 2,2 ', 6', 2 "-terpyridine, pyridineimine, crosslinked aliphatic diamine, 4,4'-di (5- Nonyl) -2,2′-bipyridine, bipyridine coordinated with O, S, Se, Te, alkyliminopyridine, alkylbipyridinylamine, alkyl-substituted tripyridine, di (alkylamino) alkylpyridine, ethylenediaminedipyri , Other heterocyclic compounds; marcapto alcohols such as 2-mercaptoethanol; dithiols such as ethanedithiol; mercaptoamines such as 2-mercaptoethylamine; dithioketones such as 2,4-pentanedithione; Examples thereof include compounds.

  Examples of the metal chelate compound 11 having one or both of a hydrolyzable group and a hydroxyl group in total include diethoxybisacetylacetonate titanium, diisopropoxybisacetylacetonate titanium, dinormalpropoxybisacetylacetonate titanium. , Dinormal butoxybisacetylacetonate titanium, diethoxybisacetylacetonate zirconium, diisopropoxybisacetylacetonate zirconium, dinormalpropoxybisacetylacetonate zirconium, dinormalbutoxybisacetylacetonate zirconium, diethoxyacetylacetonate Aluminum, diisopropoxyacetylacetonate aluminum, dinormalpropoxyacetylacetonate aluminum, dinormal Specific examples include aluminum oxyacetonate, ethoxybis (acetylacetonato) aluminum, isopropoxybis (acetylacetonato) aluminum, normalpropoxybis (acetylacetonato) aluminum, and normal butoxybis (acetylacetonato) aluminum. be able to.

  Among them, for example, when imparting strength to the produced concavo-convex structure, it is preferable to use a zirconium-based chelate compound such as diethoxybisacetylacetonate zirconium, while the produced concavo-convex structure has weather resistance. Is preferably used, a titanium-based chelate compound such as diethoxybisacetylacetonate titanium is used.

  The metal chelate compound 11 having at least one or both of the hydrolyzable group and hydroxyl group as described above is, for example, a metal compound having at least one or both of the hydrolyzable group and hydroxyl group in total. In addition, a predetermined amount of a chelate compound can be added and stirred.

  The content of the metal chelate compound 11 having one or both of a hydrolyzable group and a hydroxyl group in total is not particularly limited, and the performance to be imparted to the concavo-convex structure as the final product. Although it can design suitably according to etc., for example, several to several dozen weight% can be contained with respect to the whole concavo-convex structure forming material 12.

  The concavo-convex structure forming material 12 including the metal chelate compound 11 having one or both of a hydrolyzable group and a hydroxyl group in total has an ionizing radiation curable type, that is, has a property of being cured by irradiation with ionizing radiation. As long as it is a thing, it will not specifically limit, It can select from a conventionally well-known ionizing-radiation-curable composition etc. suitably, and can use it.

  More specifically, as long as it contains a compound (sometimes referred to as a polymerizable compound) having a functional group capable of being crosslinked and cured by being excited by irradiation with ultraviolet rays or an electron beam to cause a polymerization reaction. Although there is no limitation in particular, the composition containing a monofunctional or polyfunctional monomer, urethane (meth) acrylate, epoxy (meth) acrylate, etc. can be used, and also an ionizing radiation polymerization initiator can be added.

  Examples of the monofunctional or polyfunctional monomer include compounds having one or more ethylenically unsaturated double bonds.

  Examples of the compound having one ethylenically unsaturated double bond include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, N-vinylpyrrolidone and the like.

  As the compound having two or more ethylenically unsaturated double bonds, a bi- or higher functional (meth) acrylate can be preferably used. Examples of the bifunctional (meth) acrylate include linear chains such as 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol di (meth) acrylate. Alkanediol di (meth) acrylate; diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polyethylene glycol # 200 di (meth) acrylate , Polyethylene glycol # 300 di (meth) acrylate, polyethylene glycol # 400 di (meth) acrylate, polyethylene glycol # 600 di (meth) acrylate, dipropylene glycol di (meth) a Relate, alkylene such as tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polypropylene glycol # 400 di (meth) acrylate, polypropylene glycol # 700 di (meth) acrylate Glycol di (meth) acrylate; bisphenol A di (meth) acrylate, EO modified bisphenol A di (meth) acrylate, PO modified bisphenol A di (meth) acrylate, hydrogenated bisphenol A di (meth) acrylate, EO modified hydrogenated bisphenol A di (meth) acrylate, PO-modified hydrogenated bisphenol A di (meth) acrylate, bisphenol F di (meth) acrylate, EO-modified bisphenol Bisphenol di (meth) acrylates such as F di (meth) acrylate, PO modified bisphenol F di (meth) acrylate, EO modified tetrabromobisphenol A di (meth) acrylate; neopentyl glycol di (meth) acrylate, neopentyl glycol PO-modified di (meth) acrylate; hydroxypivalic acid neopentyl glycol ester di (meth) acrylate, caprolactone adduct di (meth) acrylate of hydroxypivalic acid neopentyl glycol ester; 1,6-hexanediol bis (2-hydroxy- 3-acryloyloxypropyl) ether; and di (meth) acrylates such as tricyclodecane dimethylol di (meth) acrylate and isocyanuric acid EO-modified di (meth) acrylate It is.

  Examples of the trifunctional (meth) acrylate include glycerin PO-modified tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane EO-modified tri (meth) acrylate, and trimethylolpropane PO-modified tri (meth) acrylate. , Isocyanuric acid EO-modified tri (meth) acrylate, isocyanuric acid EO-modified ε-caprolactone-modified tri (meth) acrylate, 1,3,5-triacryloylhexahydro-s-triazine, pentaerythritol tri (meth) acrylate, dipenta Erythritol tri (meth) acrylate tripropionate, pentaerythritol di (meth) acrylate monostearate, pentaerythritol di (meth) acrylate monobenzoate, etc. That.

  Examples of tetra- or higher functional (meth) acrylates include pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate monopropionate, dipentaerythritol hexa (meth) acrylate, and tetramethylolethanetetra (meth). An acrylate etc. are mentioned.

  In addition, these compounds may be those in which a part of the molecular skeleton is modified, and may be modified by ethylene oxide, propylene oxide, caprolactone, isocyanuric acid, polybasic acid, alkyl, cyclic alkyl, aromatic, bisphenol, etc. What has been made can also be used.

  The urethane (meth) acrylate is not particularly limited, but is formed by reacting the hydroxyl group of a compound having one hydroxyl group and two or more (meth) acryl groups in the molecule with the isocyanate group of the polyvalent isocyanate compound. A functional or higher urethane (meth) acrylate can be preferably used, and a tetrafunctional or more than 20 functional urethane (meth) acrylate can be more preferably used. By using urethane (meth) acrylate in the above range, the lens can be made flexible and excellent in strength.

  The polyvalent isocyanate compound is not particularly limited, and examples thereof include compounds having two or more isocyanate groups in the molecule. Examples of the compound having two isocyanate groups in the molecule include 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, and 1,4-phenylene diisocyanate. , Tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate , Isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanate methyl) Hexane, methylcyclohexane diisocyanate, m- tetramethylxylylene diisocyanate, and the like. Examples of the compound having three isocyanate groups in the molecule include trimethylolpropane-added adducts, burettes, isocyanates obtained by modifying isophorone diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and the like. A nurate body etc. are mentioned. Among these, isophorone diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate and the like are particularly preferable in the present invention.

  The compound having one hydroxyl group and two or more (meth) acryl groups in the molecule is not particularly limited, but (meth) acrylic acid is added to the hydroxyl group of the compound having three or more hydroxyl groups in the molecule. The compound which reacted: The compound etc. which the ring-opening reaction of glycidyl (meth) acrylate and (meth) acrylic acid is mentioned. Further, the compound having 3 or more hydroxyl groups in the molecule is not particularly limited. For example, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, tetramethylolethane, diglycerin, ditrimethylolethane, ditrimethylol. Examples include propane, dipentaerythritol, ditetramethylolethane; these ethylene oxide-modified compounds; these propylene oxide-modified compounds; isocyanuric acid ethylene oxide-modified compounds, propylene oxide-modified compounds, and ε-caprolactone-modified compounds. More specifically, diglycerin, ditrimethylolethane, ditrimethylolpropane, dipentaerythritol, ditetramethylolethane and the like are particularly preferable.

  The urethane (meth) acrylate may contain a trifunctional or lower urethane (meth) acrylate in addition to the tetrafunctional or higher functional urethane (meth) acrylate. There is no particular limitation on the chemical structure of such a trifunctional or lower urethane (meth) acrylate, and known ones can be used. The weight average molecular weight of the urethane (meth) acrylate is preferably 1000 or more and 30000 or less, and particularly preferably 1000 or more and 10,000 or less. If the molecular weight is too small, the flexibility of the lens may decrease, and if the molecular weight is too large, the strength of the lens may decrease. From the viewpoint of obtaining excellent surface properties, the double bond equivalent of the urethane acrylate oligomer is 100 to 800, preferably 150 to 500. Here, the double bond equivalent means a molecular weight per functional group capable of being crosslinked and cured by being excited by irradiation with ultraviolet rays or an electron beam to cause a polymerization reaction.

  Epoxy (meth) acrylate refers to a (meth) acrylate compound obtained by reacting a compound having an epoxy group with (meth) acrylic acid, and can make the lens layer rigid. The epoxy (meth) acrylate is not particularly limited. Specifically, for example, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, Diglycidyl ethers of alkylene glycols such as tripropylene glycol diglycidyl ether; glycerin glycidyl ethers such as glycerin diglycidyl ether; bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, PO-modified diglycidyl of bisphenol A Diglycidyl ethers of bisphenol compounds such as ether and bisphenol F diglycidyl ether, Data) and the like having a structure obtained by adding acrylic acid. Moreover, what has the structure which added (meth) acrylic acid to the polycondensation epoxy resin is mentioned. Furthermore, those having a structure in which (meth) acrylic acid is added to an epoxy resin having a structure obtained by reacting, for example, epichlorohydrin or the like with a condensation polymer such as phenol novolak or cresol novolak Is mentioned.

  In addition to the above compounds, a resin that is curable to ionizing radiation and a resin that is non-curable to ionizing radiation can be added as long as the object of the present invention can be achieved. For example, a relatively low molecular weight polyester resin having an unsaturated double bond, polyether resin, acrylic resin, epoxy resin, urethane resin, alkyd resin, spiroacetal resin, polybutadiene resin, polythiol polyene resin, etc. can be used. .

  The blending ratio of the ionizing radiation curable composition to the entire concavo-convex structure forming material 12 is not particularly limited. For example, when a urethane acrylate oligomer is used as the ionizing radiation curable composition and this is mixed with a polymerizable monomer to form the concavo-convex structure forming material 12, the urethane acrylate oligomer and the polymerizable monomer The blending ratio is preferably 8: 2 to 2: 8. If the ratio of urethane acrylate oligomer is higher than this range, the viscosity will increase, and molding may be difficult due to the generation of bubbles, while if the ratio of polymerizable monomer is higher than this range, the viscosity will decrease. This is because the ink flow may make molding difficult.

  An ionizing radiation polymerization initiator can be further added to the concavo-convex structure forming material 12. The ionizing radiation polymerization initiator is not particularly limited and may be appropriately selected from those generally used. Specific examples include ionizing radiation polymerization initiators such as aromatic ketones, alkylphenones, acylphosphine oxides, and titanocenes. Of these, alkylphenone series and acylphosphine oxide series are preferred. Specifically, aromatic ketones such as benzophenone, 4,4′-bisdiethylaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2-ethylanthraquinone, phenanthrene, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether Benzoin ethers such as methylbenzoin and ethylbenzoin, 2- (o-chlorophenyl) -4,5-phenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxy) Phenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,5 -Triarylimidazole dimer, 2-tri Halomethylthiazole such as chloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole Compound, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-S-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl-1,3-butadienyl) Halomethyl-S-triazine compounds such as -S-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-S-triazine, 2,2-dimethoxy-1,2-diphenylethane-1-one 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1-one, 1,2-benzyl-2-dimethylamino- -(4-morpholinophenyl) -butanone-1, benzyl, benzoylbenzoic acid, methyl benzoylbenzoate, 4-benzoyl-4'-methyldiphenylsulfide, benzylmethyl ketal, dimethylaminobenzoate, isoamyl P-dimethylaminobenzoate 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4 diethylthioxanthone, 2,4 dimethylthioxanthone, isopropylthioxanthone, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyloxime), 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], 4-benzoyl- Methyl diphenyl sulfide , 1-hydroxy-cyclohexyl-phenylketone, 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2- (dimethylamino) -2-[(4 -Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, 2 -Methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1-propanone, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl)- Benzyl] -phenyl} -2-methyl-propan-1-one, 2-hydroxy-4'-hydroxyethoxy-2-methylpropio Examples include phenone, oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone], 2,4,6-trimethylbenzoyl-diphenyl-phosphinoxide. In the present invention, oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone, 2-methyl-1- [4 is particularly preferable because yellowing can be suppressed. -(Methylthio) phenyl] -2-morpholinopropanone-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2,4,6-trimethylbenzoyl-diphenyl-phosphinoxide, etc. are particularly preferred. These ionizing radiation polymerization initiators can be used alone or in combination of two or more. The content of the ionizing radiation polymerization initiator is not particularly limited as long as it can be cured at a desired curing rate, and is about 0.5% by mass to 15% by mass with respect to the solid content of the concavo-convex structure forming material 12. It is preferable to be 3% by mass to 10% by mass. Solid content means the part except the solvent part with respect to the whole concavo-convex structure forming material 12.

  Moreover, the concavo-convex structure forming material 12 may contain other components as necessary. Examples of other components include reactive fine particles, an antistatic agent, a crosslinking agent, a curing agent, a polymerization accelerator, and a viscosity modifier.

  Further, the concavo-convex structure forming material 12 may contain a solvent. Examples of the solvent in this case include water, alcohol (eg, methanol, ethanol, propanol, isopropanol, n-butanol, s-butanol, t-butanol, benzyl alcohol, propylene glycol monomethyl ether), ketone (eg, acetone, Methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, heptanone, diisobutyl ketone, diethyl ketone), ester (eg, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate, propylene glycol monomethyl ether acetate) ), Aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride), aromatic hydrocarbons (eg, benzene) , Toluene, xylene), amide (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ether (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohol (eg, 1-methoxy-2-propanol), etc. be able to. These may be used alone or in combination of two or more. The solvent is preferably 10% or less, more preferably 5% or less, and most preferably not contained, relative to the entire concavo-convex structure forming material 12. If the content of the solvent is larger than this range, the viscosity decreases, making molding difficult due to the ink flow, or when the concavo-convex structure forming material 12 is cured by irradiating with ionizing radiation, bubbles are formed inside the concavo-convex structure. May remain.

  The method for applying the concavo-convex structure forming material 12 to the mold 10 is not particularly limited, and various commonly used application methods can be appropriately selected and used. For example, it may be applied by spraying, or a dip coating method or a spin coating method may be used.

  The thickness of the concavo-convex structure forming material 12 applied to the mold 10 is not particularly limited, and can be appropriately designed according to the use of the concavo-convex structure, which is a manufacturing object. For example, it may be about 10 μm to 200 μm.

(Process of heating uneven structure forming material)
Next, as shown in FIG. 1B, a process of heating the applied concavo-convex structure forming material 12 is performed.

  The metal oxide 13 can be obtained from the metal chelate compound 11 in the uneven structure forming material 12 by heating the uneven structure forming material 12 applied in this manner. Accordingly, various performances such as strength and weather resistance can be imparted to the manufactured concavo-convex structure.

  About the heating conditions in this process, the metal oxide 13 should just be obtained from the metal chelate compound 11, and others are not specifically limited. Depending on the type of metal chelate compound 11, for example, heating at 80 ° C. to 150 ° C. may be performed for several minutes.

  Also, the heating method is not particularly limited, and may be appropriately selected from heating methods that can satisfy the above conditions. Specifically, heating may be performed in a heating zone that is exposed to hot air.

(Process of irradiating with ionizing radiation)
Next, as shown in FIG. 1C, a step of irradiating the concavo-convex structure forming material 12 after the heating with ionizing radiation is performed.

  Here, when an electron beam is used as the ionizing radiation, the intensity of the electron beam to be irradiated may be appropriately set depending on the type of the material for forming an uneven structure. For example, the intensity of the electron beam is preferably 150 kV to 200 kV. If it is lower than 150 kV, there is a possibility that the electron beam does not reach the inside of the composition and curing may be insufficient, and if it is higher than 200 kV, there is a concern that it will become an excessive specification. The irradiation dose is preferably 5 to 15 Mrad. If it is lower than 5 Mrad, the composition may be insufficiently cured. Moreover, it is preferable that it is lower than 15 Mrad from viewpoints of productivity.

  The direction in which the ionizing radiation is irradiated is not particularly limited, but it is generally irradiated from the opposite side of the mold 10, that is, from the upper side in FIG. When the mold 10 is made of a material that transmits ionizing radiation, the ionizing radiation may be irradiated from the mold 10 side, that is, from the lower side in FIG.

(Step of peeling the concavo-convex structure)
Next, as shown in FIG. 1D, a step of peeling the cured product cured by the ionizing radiation irradiation step, that is, the concavo-convex structure 20 from the mold 10 is performed.

  The process is not particularly mentioned, and may be appropriately peeled off so as not to destroy the uneven structure formed on the surface of the uneven structure 20.

  According to the manufacturing method according to the present embodiment, a desired fine uneven structure can be formed, and various properties such as strength and weather resistance are imparted by the metal oxide 13 contained in the uneven structure 20. Can do.

<Second Embodiment>
FIG. 2 is a process diagram for explaining a second embodiment of the method for producing an uneven structure according to the present invention. Note that the metal chelate compound 11, the concavo-convex structure forming material 12, the mold 10 and the like used in the second embodiment are the same as those in the first embodiment, and thus the description thereof is omitted. For the second embodiment, only the process order will be described.

(Process of applying uneven structure forming material)
As shown in FIG. 2A, in this embodiment, a substrate 50 is prepared, and the metal chelate compound 11 having one or both of a hydrolyzable group and a hydroxyl group in total on the substrate 50. The process of apply | coating the ionizing radiation hardening type uneven | corrugated structure forming material 12 containing is performed.

  The substrate 50 used here is not particularly limited, and is appropriately selected depending on the use of the concavo-convex structure and the required performance in consideration of the function as the substrate even in the finally produced concavo-convex structure. be able to. The material may be, for example, glass, various resins, or paper. Moreover, although it does not specifically limit about the thickness of the board | substrate 50, For example, it is good also as several 10 micrometers-several mm.

(Process to press the mold)
Next, as shown in FIG. 2B, a step of pressing the mold 10 for forming the concavo-convex structure is performed.

  Next, as shown in FIG. 2C, a step of heating the concavo-convex structure forming material 12 is performed.

(Process of irradiating with ionizing radiation)
Next, as shown in FIG. 2D, a step of irradiating the concavo-convex structure forming material 12 with ionizing radiation is performed.

  In this step, as in the first embodiment, it is common to irradiate ionizing radiation from the side opposite to the mold 10, that is, from the lower side in FIG. 2D, and the mold 10 emits ionizing radiation. In the case of a transparent material, the ionizing radiation may be irradiated from the mold 10 side, that is, from the upper side in FIG.

(Step of peeling the concavo-convex structure)
Next, as shown in FIG. 2E, a step of peeling the cured product cured by the ionizing radiation irradiation step, that is, the concavo-convex structure 20 from the mold 10 is performed.

  Also by the manufacturing method according to the present embodiment shown in FIG. 2, a desired fine concavo-convex structure can be formed, and various strength and weather resistance can be obtained by the metal oxide 13 contained in the concavo-convex structure 20. Performance can be imparted.

Example 1
A polyethylene terephthalate film having a thickness of 100 μm was prepared as a substrate, and a concavo-convex structure forming material having the following composition was applied thereon to a thickness of 20 μm.
<Material for forming uneven structure>
・ Urethane acrylate electron beam curable resin composition (Beam set 575: Arakawa Chemical Industries, Ltd .: 100% solids) 50 parts by weight Titanium chelate compound (Orgatechs TC-750: Matsumoto Fine Chemicals, Inc .: 95% solids) 2.6 parts by weight

  Next, a metal mold for producing a moth-eye type antireflection film was prepared, and the mold was pressed against the material for forming an uneven structure using a rubber roller with a load of 10 N / cm.

  Subsequently, the titanium chelate compound was changed to titanium oxide by heating in an oven at 100 ° C. for 3 minutes.

  Next, the concavo-convex structure as the antireflection film of Example 1 is obtained by irradiating an electron beam (irradiation dose: 5 Mrad, applied voltage: 165 kV) from the substrate side to cure the concavo-convex structure forming material and peeling it from the mold. Obtained.

(Comparative Example 1)
A concavo-convex structure as an antireflection film of Comparative Example 1 was obtained under the same conditions as in Example 1 except that the titanium chelate compound was not contained in the concavo-convex structure forming material.

(Weather resistance test)
About each of Example 1 and Comparative Example 1, as a result of conducting an accelerated test test by irradiation for 250 hours using an s-UV tester manufactured by Suga Test Instruments Co., Ltd., the concavo-convex structure of Example 1 is peeled off or discolored And had excellent weather resistance. On the other hand, peeling of the concavo-convex structure of Comparative Example 1 was confirmed at the interface with the substrate.

(UV absorption test)
For each of Example 1 and Comparative Example 1, when the spectral transmittance of ultraviolet rays (330 nm) was measured, the uneven structure of Example 1 was 34%, and the uneven structure of Comparative Example 1 was 69%. . Also from this, it was found that the concavo-convex structure of Example 1 had high ultraviolet absorption ability and excellent weather resistance.

DESCRIPTION OF SYMBOLS 10 ... Type 11 ... Metal chelate compound 12 ... Material for forming uneven structure 13 ... Metal oxide 20 ... Uneven structure 50 ... Substrate

Claims (2)

A method for producing a concavo-convex structure having a concavo-convex structure on a surface,
Prepare a mold to form the uneven structure,
Applying an ionizing radiation curable concavo-convex structure forming material containing a metal chelate compound having one or both of a hydrolyzable group and a hydroxyl group in total to the mold;
A step of obtaining a metal oxide from the metal chelate compound by heating the applied material for forming an uneven structure,
Irradiating ionizing radiation to the concavo-convex structure-forming material after heating;
Peeling the cured product cured by ionizing radiation from the mold;
The manufacturing method of the uneven structure which has an uneven structure on the surface characterized by including. A method for producing a concavo-convex structure having a concavo-convex structure on a surface,
Applying an ionizing radiation curable concavo-convex structure forming material containing a metal chelate compound having one or both of a hydrolyzable group and a hydroxyl group in total on the substrate;
A step of pressing a mold for forming a concavo-convex structure against the applied material for forming a concavo-convex structure;
A step of obtaining a metal oxide from the metal chelate compound by heating the concavo-convex structure-forming material pressed against the mold; and
Irradiating ionizing radiation to the concavo-convex structure-forming material after heating;
Peeling the cured product cured by ionizing radiation from the mold;
The manufacturing method of the uneven structure which has an uneven structure on the surface characterized by including.

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