WO2012141238A1 - 活性エネルギー線硬化性樹脂組成物、成形品、微細凹凸構造体、撥水性物品、モールド、及び微細凹凸構造体の製造方法 - Google Patents
活性エネルギー線硬化性樹脂組成物、成形品、微細凹凸構造体、撥水性物品、モールド、及び微細凹凸構造体の製造方法 Download PDFInfo
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- WO2012141238A1 WO2012141238A1 PCT/JP2012/059989 JP2012059989W WO2012141238A1 WO 2012141238 A1 WO2012141238 A1 WO 2012141238A1 JP 2012059989 W JP2012059989 W JP 2012059989W WO 2012141238 A1 WO2012141238 A1 WO 2012141238A1
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- mold
- resin composition
- active energy
- convex structure
- fine concavo
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- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000004113 cell culture Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- MZRQZJOUYWKDNH-UHFFFAOYSA-N diphenylphosphoryl-(2,3,4-trimethylphenyl)methanone Chemical compound CC1=C(C)C(C)=CC=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MZRQZJOUYWKDNH-UHFFFAOYSA-N 0.000 description 1
- KHAYCTOSKLIHEP-UHFFFAOYSA-N docosyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCCCCCOC(=O)C=C KHAYCTOSKLIHEP-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005323 electroforming Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000609 electron-beam lithography Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- PZDUWXKXFAIFOR-UHFFFAOYSA-N hexadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C=C PZDUWXKXFAIFOR-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004001 molecular interaction Effects 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- HPAFOABSQZMTHE-UHFFFAOYSA-N phenyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)C1=CC=CC=C1 HPAFOABSQZMTHE-UHFFFAOYSA-N 0.000 description 1
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- UFUASNAHBMBJIX-UHFFFAOYSA-N propan-1-one Chemical compound CC[C]=O UFUASNAHBMBJIX-UHFFFAOYSA-N 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
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- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/16—Surface shaping of articles, e.g. embossing; Apparatus therefor by wave energy or particle radiation, e.g. infrared heating
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/118—Anti-reflection coatings having sub-optical wavelength surface structures designed to provide an enhanced transmittance, e.g. moth-eye structures
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
Definitions
- the present invention is an active energy ray-curable resin composition capable of forming a fine concavo-convex structure having both excellent water repellency such as water drop fallability and high scratch resistance, and a molded product formed using the same.
- the present invention relates to a fine uneven structure, a water-repellent article, a mold, and a method for producing a fine uneven structure.
- a fine concavo-convex structure body having a fine concavo-convex structure in which fine concavo-convex structures are regularly arranged on the surface exhibits an antireflection performance by continuously changing the refractive index.
- the distance between adjacent convex portions or concave portions needs to be a size equal to or smaller than the wavelength of visible light.
- the fine concavo-convex structure can also exhibit super water-repellent performance due to the lotus effect.
- Examples of a method for forming a fine concavo-convex structure include, for example, a method of injection molding or press molding using a mold having an inverted structure of a fine concavo-convex structure, an active energy ray-curable resin composition between a mold and a transparent substrate.
- An article hereinafter also referred to as “resin composition”
- curing the resin composition by irradiation with active energy rays curing the resin composition by irradiation with active energy rays, transferring the uneven shape of the mold, and then removing the mold;
- a method has been proposed in which the mold is peeled after transferring the concavo-convex shape, and then the resin composition is cured by irradiation with active energy rays.
- a method of transferring the fine concavo-convex structure by curing the resin composition by irradiation with active energy rays is preferable. This method is particularly suitable when a belt-shaped or roll-shaped mold capable of continuous production is used, and is a method with excellent productivity.
- Such a fine concavo-convex structure is inferior in scratch resistance to a molded article such as a hard coat having a smooth surface produced using the same resin composition, and has a problem in durability during use.
- the resin composition used for the production of the fine concavo-convex structure is not sufficiently robust, a phenomenon in which the protrusions come close to each other easily due to release from the mold or heating.
- a water repellant component such as a fluorine compound or a silicone compound
- the surface free energy can be made extremely low by using a fluorine-based compound.
- the fluorine-based compound can also exhibit oil repellency that cannot be achieved by the silicone-based compound.
- Patent Document 1 discloses a cured film excellent in scratch resistance and antifouling property using a fluorine-based monomer component having a specific structure.
- Patent Document 2 discloses a curable composition containing a fluorine-containing polymer.
- Patent Document 3 discloses a polymer containing both silicon and fluorine, which can impart antifouling properties and slip properties.
- Patent Document 1 describes that transparency is impaired when 2 parts by mass or more of a fluorine-based monomer is added.
- an organic solvent is required to uniformly dissolve the fluorine-based monomer and the polyfunctional monomer.
- the coating solution is applied and then dried and then polymerized and cured by irradiation with active energy rays, but polymerization and curing are performed by irradiation with active energy rays in the state of pouring into the mold. In the subsequent mold release process, the solvent remains in the cured product and weakens the molded product.
- Patent Document 2 describes that the fluorine-containing polymer and the polyfunctional monomer are hardly compatible with each other, and the structure of the polyfunctional monomer is specified to solve the problem. Moreover, both patent document 2 and patent document 3 are made compatible with a polyfunctional monomer using a solvent suitably. In this case, a problem remains in the polymerization / curing process without passing through the drying step. These oligomers and polymers have a polymerizable reactive group, but there is a limit to increasing the crosslinking density, and satisfactory hardness cannot be obtained particularly for use as a fine concavo-convex structure.
- the above-described invention aims to transfer the fluorine-containing antifouling component to the surface layer in the process of volatilization of the solvent. Therefore, it is impossible to achieve the same level of water repellency and oil repellency by a molding method in which active energy rays are irradiated in a state of being poured into a mold, polymerized and cured, and then released.
- Patent Document 4 discloses a post-processing treatment in which a fluorine-based compound is applied to the surface of a fine concavo-convex structure and is connected by a silane coupling reaction or the like. According to such post-processing treatment, a certain degree of scratch resistance can be imparted to the fine concavo-convex structure, but there are problems such as peeling and sliding off of the surface layer and an increase in manufacturing cost.
- the present inventors have used an active energy ray-curable resin composition capable of forming a fine concavo-convex structure having high scratch resistance and good water repellency, and the like.
- the water-repellent article provided with the fine concavo-convex structure, its manufacturing method, and the fine concavo-convex structure was proposed (patent document 7).
- the use of a water-repellent component having a specific structure that is compatible with the general-purpose polyfunctional monomer does not require a solvent, and does not require complicated processes such as post-processing, and has a fine water-repellent property. An uneven structure can be produced.
- Patent Document 7 also uses a special silicone compound. Therefore, an active energy ray-curable resin composition capable of forming a fine concavo-convex structure or the like that exhibits good water repellency using a less expensive and easily available raw material is desired.
- the object of the present invention is to provide an antireflection function due to the fine concavo-convex structure formed on the surface, to exhibit excellent water repellency without using a fluorine-containing compound or a silicone compound, and to have high scratch resistance. It is to provide an active energy ray-curable resin composition that gives a cured product, a molded article formed using the same, a fine concavo-convex structure, a water-repellent article, a mold, and a method for producing the fine concavo-convex structure. .
- the present invention is represented by 3 to 18 parts by mass of an alkyl (meth) acrylate (A) having an alkyl group having 12 or more carbon atoms based on a total of 100 parts by mass of all monomers, and Fedor's estimation method.
- the active energy ray-curable resin composition comprises 82 to 97 parts by mass of a polyfunctional monomer (B) having 3 or more radical polymerizable functional groups in the molecule having an sp value of 20 to 23.
- the present invention provides a molded article comprising a cured product of the above active energy ray-curable resin composition, a fine concavo-convex structure having a fine concavo-convex structure on the surface thereof, and a water repellency provided with the fine concavo-convex structure.
- An article and a mold provided with the fine concavo-convex structure.
- the present invention is a method for producing a fine uneven structure having a substrate and a cured product having a fine uneven structure on the surface,
- the active energy ray-curable resin composition is disposed between a mold having a fine concavo-convex inverted structure and a substrate, and the active energy ray-curable resin composition is cured by irradiation with active energy rays. Then, the mold is peeled off to form a cured product having a fine concavo-convex structure on the surface.
- the present invention is a method for producing a fine concavo-convex structure having a substrate and a thermoplastic resin layer having a fine concavo-convex structure on the surface, A thermoplastic resin is disposed on a base material, the mold is pressed while being heated, cooled, the mold is peeled off, and a reverse structure of the fine concavo-convex structure of the mold is formed on the surface of the thermoplastic resin layer. It is a manufacturing method of the fine concavo-convex structure to be formed.
- the present invention is a method for producing a fine uneven structure having a substrate and a cured product having a fine uneven structure on the surface,
- An active energy ray-curable resin composition is disposed between the mold and the base material, and the active energy ray-curable resin composition is cured by irradiating with active energy rays, and the mold is peeled off to the surface. It is the manufacturing method of the fine concavo-convex structure which forms the hardened
- the active energy ray-curable resin composition of the present invention expresses water repellency by an alkyl (meth) acrylate (A) having an alkyl group having 12 or more carbon atoms, and expresses an appropriate hardness by a polyfunctional monomer (B). And the molded object which consists of the hardened
- alkyl (meth) acrylate (A) The alkyl (meth) acrylate (A) used in the present invention has at least one (preferably one) (meth) acryloyloxy group as a radical polymerizable functional group in the molecule, and an alkyl group having 12 or more carbon atoms. It is a compound which has this.
- the alkyl group having 12 or more carbon atoms of the alkyl (meth) acrylate (A) is a part constituting the ester structure of (meth) acrylate.
- the alkyl group has 12 or more carbon atoms
- the cured product can be imparted with good water repellency, water droplets are less likely to adhere to the surface having a fine concavo-convex structure, and the attached water droplets can easily fall down. it can.
- the alkyl group may have a branch, but is preferably a straight chain from the viewpoint of water repellency.
- the alkyl group has 12 or more carbon atoms, preferably 12 to 22, more preferably 12 to 18, and particularly preferably 16 to 18.
- the carbon number is most preferably 16.
- the alkyl (meth) acrylate (A) preferably has one (meth) acryloyloxy group as a radical polymerizable functional group in the molecule.
- Alkyl (meth) acrylate (A) when combined with polyfunctional monomer (B), becomes a clear and clear curable resin composition upon heating, but when it is cooled to room temperature, it becomes cloudy, Sometimes separated. Moreover, turbidity and wrinkles may occur in the cured product. However, when the alkyl (meth) acrylate (A) and the polyfunctional monomer (B) are in a compatible combination, the water repellency is hardly exhibited. In consideration of such points, it is preferable to use a combination in which there is no inconvenience in handling the curable resin composition and the cured product exhibits water repellency.
- alkyl (meth) acrylate (A) examples include lauryl (meth) acrylate, myristyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, and behenyl (meth) acrylate. These may be used alone or in combination of two or more.
- (Meth) acrylate means methacrylate or acrylate.
- the content of the alkyl (meth) acrylate (A) is 3 to 18 parts by weight, preferably 3 to 12 parts by weight, based on the total of 100 parts by weight of the total monomers contained in the composition.
- the amount is preferably 3 to 10 parts by mass, particularly preferably 5 to 8 parts by mass.
- the polyfunctional monomer (B) used in the present invention is a main component of the resin composition, and maintains the mechanical properties of the cured product, particularly scratch resistance, and plays a role of inducing phase separation accompanying curing.
- the polyfunctional monomer (B) has three or more radical polymerizable functional groups in the molecule. Thereby, the molecular weight between the crosslinking points of hardened
- This radically polymerizable functional group is typically a (meth) acryloyl group.
- the polyfunctional monomer (B) shows a specific sp value represented by Fedor's estimation method.
- the sp value is referred to as a solubility parameter or a solubility parameter, and is a value that serves as an index when determining solubility such as whether or not a solute is soluble in a solvent and whether or not different types of liquid are mixed.
- a method for deriving the sp value there are various methods such as a method of calculating from the heat of vaporization of the liquid and a method of calculating by integrating values based on each chemical structure.
- the Spide value of Hildebrand, Hansen Sp value, Kreveren's estimation method, and Fedor's estimation method are known. These are detailed in “SP Value Basics / Applications and Calculation Methods” published by the Information Organization.
- Fedor's estimation method of integrating values according to the chemical structure is used.
- the sp value is an index of solubility between monomers.
- the sp value derived from the Fedor's estimation method for the polyfunctional monomer (B) is 20 to 23, preferably 20.5 to 23, and more preferably 20.5 to 22.5.
- polyfunctional monomer (B) for example, trifunctional or higher functional (meth) acrylates such as epoxy (meth) acrylate, polyester (meth) acrylate, and polyether (meth) acrylate can be used. Specific examples thereof include glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and these The ethoxy modified product of These may be used alone or in combination of two or more.
- NK Ester series ATM-4E manufactured by Shin-Nakamura Chemical Co., Ltd.
- KAYARAD series DPEA-12 manufactured by Nippon Kayaku
- Aronix series M manufactured by Toagosei. -305, M-450, M-400, M-405, “EBECRYL40” manufactured by Daicel-Cytec, Inc. (all are trade names).
- the value obtained by dividing the molecular weight of the polyfunctional monomer (B) by the number of radical polymerizable functional groups is preferably 200 or less, more preferably 180 or less, and particularly preferably 110 to 150. It is. Each of these ranges is significant in terms of the elastic modulus and hardness of the cured product and the scratch resistance of the cured product in which a fine uneven structure is formed.
- the content of the polyfunctional monomer (B) is 82 to 97 parts by weight, preferably 85 to 97 parts by weight, more preferably based on 100 parts by weight of the total content of all monomers contained in the composition. 90 to 95 parts by mass.
- the content is 82 to 97 parts by weight or more, good elastic modulus, hardness, and scratch resistance of the cured product can be obtained.
- the scratch resistance of the cured product is improved, it is possible to suppress brittleness, and it is possible to suppress the occurrence of cracks when peeling the mold for forming the uneven structure. .
- the active energy ray-curable resin composition may contain a monomer (C) having one or more radically polymerizable functional groups.
- This monomer (C) is a monomer that can be copolymerized with the alkyl (meth) acrylate (A) and the polyfunctional monomer (B), and it is easy to handle while maintaining good polymerization reactivity as a whole resin composition. It is preferable that the adhesiveness with the base material is further improved.
- the monomer (C) preferably contains no fluorine atom and silicone in the molecule, but may contain a fluorine atom and / or silicone in the molecule to the extent that the water repellency is not impaired. This is because the compatibility between the alkyl (meth) acrylate (A) and the polyfunctional monomer (B) is not affected, and the scratch resistance and adhesion to the substrate are not significantly impaired. Further, as the monomer (C), Fedor's estimation method is used because it does not affect the compatibility state of the alkyl (meth) acrylate (A) and the polyfunctional monomer (B) and does not impair the water repellency. It is preferable not to use a large amount of the sp value of 20 or more.
- the monomer (C) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl ( Alkyl (meth) acrylates such as meth) acrylate; benzyl (meth) acrylate; tetrahydrofurfuryl (meth) acrylate; (meth) acrylate having an amino group such as dimethylaminoethyl (meth) acrylate and dimethylaminopropyl (meth) acrylate ; (Meth) acrylate having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; (meth) acryl such as (meth) acryloylmorpholine and N, N-dimethyl (meth)
- the content of the monomer (C) is preferably 0 to 15 parts by mass, more preferably 0 to 10 parts by mass, particularly preferably 1 based on the total of 100 parts by mass of the total monomers contained in the composition. It is ⁇ 10 parts by mass, most preferably 3 to 8 parts by mass.
- the content is preferably 10 parts by mass or less based on the total of 100 parts by mass of all monomers contained in the composition.
- the content ratio of the alkyl (meth) acrylate (A), the polyfunctional monomer (B), and the monomer (C) may be appropriately adjusted within the respective ranges described above.
- the content of the monomer (C) is preferably determined in adjustment with the content of the alkyl (meth) acrylate (A).
- the active energy ray-curable resin composition preferably contains a slip agent (D).
- the slip agent (D) is a compound that exists on the surface of the cured resin, reduces friction on the surface, and improves scratch resistance.
- Examples of commercially available slip agents (D) include “SH3746 FLUID” and “FZ-77” manufactured by Toray Dow Corning, “KF-355A” and “KF-6011” manufactured by Shin-Etsu Chemical Co., Ltd. Name). These may be used alone or in combination of two or more.
- the content of the slip agent (D) is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass in total of the contents of all monomers contained in the composition. It is. By setting the content to 0.01 parts by mass or more, the curability of the resin composition is excellent, and the mechanical properties of the cured product, in particular, the scratch resistance is improved. By setting it as 5 mass parts or less, the fall of the elasticity modulus and abrasion resistance by a slip agent which remain
- the active energy ray-curable resin composition preferably contains an active energy ray polymerization initiator.
- This active energy ray polymerization initiator is a compound that generates a radical that is cleaved by irradiation with active energy rays to initiate a polymerization reaction.
- the active energy ray means, for example, an electron beam, ultraviolet rays, visible rays, plasma, infrared rays or other heat rays. In particular, it is preferable to use ultraviolet rays from the viewpoint of apparatus cost and productivity.
- active energy ray polymerization initiator examples include benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, methylorthobenzoylbenzoate, 4-phenylbenzophenone, t-butylanthraquinone, 2- Ethylanthraquinone; thioxanthones such as 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone; diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1 -Hydroxycyclohexyl-phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butyl Acetophenone
- persulfates such as potassium persulfate and ammonium persulfate
- peroxides such as benzoyl peroxide
- thermal polymerization initiators such as azo initiators
- the content of the active energy ray polymerization initiator is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to a total of 100 parts by mass of all monomers contained in the composition. Part, particularly preferably 0.2 to 3 parts by weight.
- the content is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to a total of 100 parts by mass of all monomers contained in the composition. Part, particularly preferably 0.2 to 3 parts by weight.
- the active energy ray curable resin composition may contain an active energy ray absorbent and / or an antioxidant.
- the active energy ray absorbent is preferably one that absorbs active energy rays irradiated upon curing of the resin composition and can suppress the deterioration of the resin.
- Examples of the active energy ray absorber include benzophenone-based UV absorbers, benzotriazole-based UV absorbers, and benzoate-based UV absorbers.
- Examples of the commercially available products include 400 and 479 of “Tinubin (registered trademark)” series manufactured by Ciba Specialty Chemicals, and 110 of “Viosorb (registered trademark)” series manufactured by Kyodo Pharmaceutical.
- antioxidants examples include phenol-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and hindered amine-based antioxidants.
- commercially available products include “IRGANOX (registered trademark)” series manufactured by Ciba Specialty Chemicals. These active energy ray absorbents and antioxidants may be used alone or in combination of two or more.
- the content of the active energy ray absorbent and / or the antioxidant is preferably 0.01 to 5 parts by mass, more preferably 0 with respect to 100 parts by mass in total of the contents of all monomers contained in the composition.
- the amount is 0.01 to 1 part by mass, particularly preferably 0.01 to 0.5 part by mass.
- the active energy ray-curable resin composition can be used as a release agent, a lubricant, a plasticizer, and an antistatic agent as long as the functions of the polyfunctional monomer (A) and mono (meth) acrylate (B) are not hindered.
- the active energy ray-curable resin composition may contain a solvent, but preferably does not contain a solvent.
- the solvent is not included, for example, there is no concern that the solvent remains in the cured product in the process of polymerizing and curing by irradiation with active energy rays in a state where the resin composition is poured into a mold, and then releasing the mold.
- the capital investment for solvent removal is unnecessary and it is preferable also at the point of cost.
- the viscosity of the resin composition measured with a rotary B-type viscometer at 25 ° C. is preferably 10,000 mPa ⁇ s or less, more preferably 5000 mPa ⁇ s or less, particularly preferably 2000 mPa ⁇ s or less. Even if this viscosity exceeds 10,000 mPa ⁇ s, workability will not be impaired if a resin composition having a viscosity within the above range by heating is used.
- the viscosity of this resin composition measured with a rotary B-type viscometer at 70 ° C. is preferably 5000 mPa ⁇ s or less, more preferably 2000 mPa ⁇ s or less.
- the viscosity of the resin composition can be adjusted by adjusting the type and content of the monomer. Specifically, when a large amount of a monomer containing a functional group having a molecular interaction such as a hydrogen bond or a chemical structure is used, the viscosity of the resin composition increases. Further, when a large amount of a low molecular weight monomer having no intermolecular interaction is used, the viscosity of the resin composition becomes low.
- the active energy ray-curable resin composition described above can be polymerized and cured to form a molded product.
- a fine uneven structure having a fine uneven structure on the surface is particularly useful.
- the fine concavo-convex structure include a substrate and a cured product having a fine concavo-convex structure on the surface.
- FIG. 1 is a schematic cross-sectional view showing an embodiment of the fine concavo-convex structure of the present invention.
- the fine concavo-convex structure shown in FIG. 1A is obtained by laminating a layer (surface layer) 12 that is a cured product of the active energy ray-curable resin composition of the present invention on a substrate 11.
- the surface of the layer 12 has a fine uneven structure.
- conical convex portions 13 and concave portions 14 are formed at equal intervals W1.
- the shape of the convex part is such that the cross-sectional area in the vertical plane increases continuously from the apex side to the substrate side, the refractive index can be increased continuously, and the reflectance varies with wavelength. (Wavelength dependence) is suppressed, and it is preferable because scattering of visible light can be suppressed to achieve a low reflectance.
- the interval w1 between the convex portions is a distance equal to or shorter than the wavelength of visible light (380 to 780 nm). If the interval w1 between the convex portions is 380 nm or less, the scattering of visible light can be suppressed, and the antireflection film can be suitably used for optical applications.
- the height of the convex portion or the depth of the concave portion is preferably set to such a depth that it is possible to suppress the variation in reflectance depending on the wavelength. . Specifically, it is preferably 60 nm or more, more preferably 90 nm or more, particularly preferably 150 nm or more, and most preferably 180 nm or more.
- the vertical distance d1 is in the vicinity of 150 nm, the reflectance of light having a wavelength region of 550 nm that is most easily recognized by humans can be minimized.
- the difference between the maximum reflectance and the minimum reflectance in the visible light region decreases as the height of the convex portion increases. For this reason, if the height of a convex part will be 150 nm or more, the wavelength dependence of reflected light will become small, and the difference in color visually will not be recognized.
- the convex portion may have a bell shape in which the top portion 13b of the convex portion is a curved surface, and the cross-sectional area in the vertical plane is continuously from the apex side to the substrate side.
- Increasing shapes can be employed.
- the fine concavo-convex structure is not limited to the embodiment shown in FIG. 1, and can be formed on one side or the whole surface of the substrate, or the whole or a part thereof.
- the tip of the protrusion of the convex portion is thin, and it is preferable that the area occupied by the cured product on the contact surface between the fine concavo-convex structure and the water droplet is as small as possible.
- an intermediate layer for improving various physical properties such as scratch resistance and adhesiveness may be provided between the substrate 11 and the surface layer 12.
- the substrate may be any material as long as it can support a cured product having a fine relief structure.
- the fine structure when applied to a display member, it is a transparent substrate, that is, transmits light.
- a molded body is preferred.
- the material constituting the transparent substrate include synthetic polymers such as methyl methacrylate (co) polymer, polycarbonate, styrene (co) polymer, methyl methacrylate-styrene copolymer, cellulose diacetate, cellulose triacetate, and cellulose.
- Semi-synthetic polymers such as acetate butyrate, polyethylene terephthalate, polyester such as polylactic acid, polyamide, polyimide, polyether sulfone, polysulfone, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinyl acetal, polyether ketone, Examples thereof include polyurethane, composites of these polymers (composites of polymethyl methacrylate and polylactic acid, composites of polymethyl methacrylate and polyvinyl chloride, etc.), and glass.
- the shape of the substrate may be any of a sheet shape, a film shape, and the like, and the manufacturing method thereof may be any one manufactured by any manufacturing method such as injection molding, extrusion molding, or cast molding. Furthermore, the surface of the transparent substrate may be subjected to coating or corona treatment for the purpose of improving properties such as adhesion, antistatic properties, scratch resistance, and weather resistance.
- Such a fine concavo-convex structure can be applied as an antireflection film, and can provide high scratch resistance and contaminant removal effects such as excellent fingerprint removability.
- the resin composition is disposed between a mold on which an inverted structure of a fine concavo-convex structure is formed and a base material, and the resin composition is irradiated with active energy rays (2)
- the mold is peeled off after transferring the concave / convex shape of the mold to the resin composition, and then the resin is irradiated with active energy rays.
- Examples thereof include a method for curing the composition.
- the method (1) is particularly preferable from the viewpoint of the transferability of the fine concavo-convex structure and the degree of freedom of the surface composition. This method is particularly suitable when a belt-shaped or roll-shaped mold capable of continuous production is used, and is a method with excellent productivity.
- the method for forming the inverted structure of the fine concavo-convex structure on the mold is not particularly limited, and specific examples thereof include an electron beam lithography method and a laser beam interference method.
- an appropriate photoresist film is applied on an appropriate support substrate, exposed to light such as an ultraviolet laser, an electron beam, or X-ray, and developed to obtain a mold having a fine concavo-convex structure. It can also be used as it is as a mold. It is also possible to form a fine concavo-convex structure directly on the support substrate itself by selectively etching the support substrate by dry etching through the photoresist layer and removing the resist layer.
- anodized porous alumina can be used as a mold.
- a 20 to 200 nm pore structure formed by anodizing aluminum with oxalic acid, sulfuric acid, phosphoric acid or the like as an electrolyte at a predetermined voltage may be used as a mold. According to this method, after anodizing high-purity aluminum for a long time at a constant voltage, the oxide film is once removed and then anodized again, whereby extremely highly regular pores can be formed in a self-organized manner.
- the second anodic oxidation step by combining the anodic oxidation treatment and the hole diameter enlargement treatment, it is possible to form a fine concavo-convex structure whose cross section is not a rectangle but a triangle or a bell shape. Further, the angle of the innermost portion of the pore can be sharpened by appropriately adjusting the time and conditions of the anodizing treatment and the pore diameter expanding treatment.
- a replica mold may be produced from an original mold having a fine concavo-convex structure by electroforming or the like and used as a mold.
- the shape of the mold itself is not particularly limited, and may be, for example, a flat plate shape, a belt shape, or a roll shape.
- a belt shape or a roll shape is used, the fine concavo-convex structure can be transferred continuously, and the productivity can be further increased.
- the above resin composition is disposed between such a mold and the base material.
- the resin composition is injected into the molding cavity by pressing the mold and the substrate with the resin composition placed between the mold and the substrate. You can depend on how you do it.
- polymerization curing by ultraviolet irradiation is preferable.
- a high-pressure mercury lamp, a metal halide lamp, or a fusion lamp can be used as the lamp that irradiates ultraviolet rays.
- the integrated light quantity is preferably 400 ⁇ 4000mJ / cm 2, and more preferably 400 ⁇ 2000mJ / cm 2. If the integrated light quantity is 400 mJ / cm 2 or more, the resin composition can be sufficiently cured to suppress a decrease in scratch resistance due to insufficient curing. Also. If the integrated light quantity is 4000 mJ / cm 2 or less, it is significant in terms of preventing coloration of the cured product and deterioration of the substrate.
- the irradiation intensity is not particularly limited, but it is preferable to suppress the output to a level that does not cause deterioration of the substrate.
- the mold After polymerization and curing, the mold is peeled off to obtain a cured product having a fine concavo-convex structure to obtain a fine concavo-convex structure.
- the formed fine concavo-convex structure can be attached to a separately shaped three-dimensional shaped body.
- the fine concavo-convex structure obtained in this way has a fine concavo-convex structure of the mold transferred onto the surface in a relationship between a key and a keyhole, has high scratch resistance, has water repellency, and has a continuous refractive index. Excellent antireflection performance can be exhibited by the change in the thickness, and it is suitable as an antireflection film for a film or a three-dimensional molded product.
- the water-repellent article of the present invention may be an article provided with a fine concavo-convex structure having a fine concavo-convex structure formed on the surface by polymerizing and curing the resin composition of the present invention, or the resin composition of the present invention.
- An article formed by polymerization and curing may be used.
- the water repellent article of the present invention preferably has a water contact angle of 130 ° or more, more preferably 140 ° or more.
- the falling property of a water droplet is favorable.
- a water-repellent article having a fine concavo-convex structure has high scratch resistance and good water repellency, and exhibits excellent antireflection performance.
- a fine concavo-convex structure can be used by attaching to the surfaces of window materials, roof tiles, outdoor lighting, curved mirrors, vehicle windows, and vehicle mirrors.
- the fine concavo-convex structure of the present invention when used as an antireflection film, it becomes an antireflection film having not only antireflection performance but also high scratch resistance and good water repellency.
- an object such as a liquid crystal display device such as a computer, a television, a mobile phone, an image display device such as a plasma display panel, an electroluminescence display, and a cathode ray tube display device, a lens, a show window, a spectacle lens, etc.
- An uneven structure can be attached and used.
- a base material having a shape corresponding thereto is used in advance, and the cured product of the resin composition of the present invention is formed on the base material.
- a layer may be formed to obtain a fine concavo-convex structure, which may be attached to a predetermined portion of the target article.
- the target article is an image display device, it is not limited to the surface thereof, but may be attached to the front plate, or the front plate itself may be composed of a fine concavo-convex structure.
- the fine concavo-convex structure of the present invention can be applied to, for example, optical uses such as optical waveguides, relief holograms, lenses, and polarization separation elements, and uses of cell culture sheets in addition to the uses described above.
- the active energy ray-curable resin composition of the present invention can also be used as an imprinting raw material.
- the imprinting raw material is not particularly limited as long as it contains this resin composition.
- the resin composition can be used as it is, but various additives can be contained depending on the intended molded product.
- the imprinting raw material can also be used for molding a cured product by UV curing or heat curing using a mold. It is also possible to use a method in which a mold is pressed against a resin composition that has been semi-cured by heating, the shape is transferred, peeled off from the mold, and completely cured by heat or UV.
- the active energy ray-curable resin composition of the present invention can also be used as a raw material for forming a cured film on various substrates, forming a coating film as a coating material, and irradiating active energy rays.
- a cured product can also be formed.
- the mold of the present invention is a mold (molding die) that is a cured product of the resin composition of the present invention and includes a fine concavo-convex structure having a fine concavo-convex structure on the surface.
- it may be a mold composed of a fine concavo-convex structure and another member (base material or the like), or may be a mold composed only of a fine concavo-convex structure.
- the mold of the present invention exhibits good releasability.
- the shape of the mold may be a film shape or a sheet shape. A film-like mold may be wound around a roll and used.
- a method in which a replica mold is produced from a valuable mother mold by repeating a plurality of times of transfer, and a fine concavo-convex structure having the same shape as the mother mold is transferred.
- a replica mold is manufactured using anodized aluminum as a mother mold.
- fluorine treatment is essential for use as a mold. This is because good mold release cannot be achieved unless the surface free energy of the mold resin is lowered.
- the mold of the present invention expresses moderate hardness by the polyfunctional monomer (B) while exhibiting releasability by the alkyl (meth) acrylate (A) having an alkyl group having 12 or more carbon atoms, and is curable.
- the resin composition can be prevented from penetrating into the mold.
- the mold of the present invention does not require expensive post-processing such as fluorine treatment, and becomes a mold excellent in releasability.
- the mold is a film, it can be easily transferred to a rigid material such as glass. Further, if the mold is transparent, a fine concavo-convex structure can be formed on an opaque base material by photocuring.
- the mold of this invention can be used for the manufacturing method of a fine concavo-convex structure.
- a method in which a thermoplastic resin is arranged on a substrate for example, a layer is formed by applying a thermoplastic resin
- the mold is pressed while being heated, cooled, and then the mold is peeled off
- an active energy ray-curable resin composition is disposed between a mold and a substrate, the active energy ray is irradiated to cure the resin composition, and then the mold is peeled off.
- the shape of the mold is not particularly limited, and may be, for example, a flat plate shape, a belt shape, or a roll shape.
- a belt shape or a roll shape is used, the fine concavo-convex structure can be transferred continuously, and the productivity can be further increased.
- the resin composition is filled into the molding cavity (such as the fine uneven structure of the mold) by the pressing force.
- polymerization curing by ultraviolet irradiation is preferable.
- a high-pressure mercury lamp, a metal halide lamp, or a fusion lamp can be used as the lamp that irradiates ultraviolet rays.
- the integrated light quantity is preferably 400 ⁇ 4000mJ / cm 2, more preferably 400 ⁇ 2000mJ / cm 2. If the integrated light quantity is 400 mJ / cm 2 or more, the resin composition can be sufficiently cured to suppress a decrease in scratch resistance due to insufficient curing. Also. If the integrated light quantity is 4000 mJ / cm 2 or less, it is significant in terms of preventing coloration of the cured product and deterioration of the substrate.
- the irradiation intensity is not particularly limited, but it is preferable to suppress the output to a level that does not cause deterioration of the substrate.
- the mold After polymerization and curing, the mold is peeled off to obtain a cured product having a fine concavo-convex structure to obtain a fine concavo-convex structure.
- the resin composition is peeled in an uncured state. Therefore, the surface of the fine uneven structure is hardly damaged. Moreover, it does not become a defect by being cured in a state in which bubbles remain between the resin composition and the mold. Furthermore, since the ultraviolet rays can be irradiated without passing through the base film, the curing efficiency of the fine concavo-convex structure is good, and the base film and the mold are hardly deteriorated.
- the resin composition used for the method of transferring the concavo-convex shape of the mold to the active energy ray-curable resin composition and then peeling the mold, and then irradiating the active energy ray to cure the resin composition has an extremely high viscosity.
- Those having a dynamic storage elastic modulus at room temperature of 1 ⁇ 10 7 Pa or more are preferred. If the dynamic storage elastic modulus is 1 ⁇ 10 7 Pa or more, the mold can be formed well without causing pattern collapse or stringing after the mold is peeled off until the resin composition is cured.
- the formed fine concavo-convex structure can be attached to a separately shaped three-dimensional shaped body.
- the fine concavo-convex structure obtained in this way has a fine concavo-convex structure of the mold transferred to the surface in the relationship between the key and the keyhole, and can exhibit excellent antireflection performance due to a continuous change in refractive index. It is suitable as an antireflection film for a three-dimensional molded product.
- a 1 cm square canvas cloth is attached to an abrasion tester (HEIDON manufactured by Shinto Kagaku Co., Ltd.), a load of 100 g is applied, and the fineness is achieved under a reciprocating distance of 50 mm and a head speed of 60 mm / s.
- the surface of the concavo-convex structure was scratched 1000 times. Thereafter, the appearance was visually observed and evaluated according to the following evaluation criteria. “ ⁇ ”: 0 to 2 scratches are confirmed. “ ⁇ ”: 3 to 5 scratches are confirmed. “ ⁇ ”: Six or more scratches are confirmed.
- an aluminum plate 30 having a purity of 99.99% was mirror polished by feather polishing and electrolytic polishing in a perchloric acid / ethanol mixed solution (1/4 volume ratio).
- A Process The aluminum plate 30 was anodized in a 0.3 M oxalic acid aqueous solution for 30 minutes under the conditions of a direct current of 40 V and a temperature of 16 ° C., and a crack 31 was generated in the oxide film 32.
- (C) Process This aluminum plate was anodized for 30 seconds in a 0.3 M oxalic acid aqueous solution under the conditions of a direct current of 40 V and a temperature of 16 ° C. to form an oxide film 34. The oxide film was formed along the aluminum surface to have pores 35.
- (D) Process The aluminum plate in which the oxide film 34 was formed was immersed in 5 mass% phosphoric acid at 32 ° C. for 8 minutes, and the diameter of the pores 35 was increased. Step (e) Steps (c) and (d) were repeated 5 times in total to obtain anodized porous alumina having pores 35 having a substantially conical shape with a period of 100 nm and a depth of 180 nm.
- the obtained anodized porous alumina is washed with deionized water, the water on the surface is removed by air blow, and the surface antifouling coating agent (trade name Optool DSX, manufactured by Daikin Co., Ltd.) has a solid content of 0.1% by mass.
- the mold 20 was immersed in a solution diluted with a diluent (trade name HD-ZV, manufactured by Harves Co., Ltd.) for 10 minutes and air-dried for 20 hours.
- Table 1 shows the physical properties and the like of each monomer used in the examples and comparative examples.
- This active energy ray-curable resin composition was adjusted to 50 ° C. and poured onto the surface of the mold, which had been adjusted to 50 ° C., on the surface on which the pores were formed.
- the product name WE97A was coated while being spread. Thereafter, the resin composition was cured by irradiating ultraviolet rays from the film side using a fusion lamp at a belt speed of 6.0 m / min and an integrated light quantity of 1000 mJ / cm 2 . Next, the film and the mold were peeled to obtain a fine concavo-convex structure.
- the fine concavo-convex structure of the mold is transferred onto the surface of the fine concavo-convex structure, and as shown in FIG. 1A, the interval w1 between the adjacent convex portions 13 is 100 nm, and the height d1 of the convex portions 13 is 180 nm.
- a substantially conical fine concavo-convex structure was formed.
- this fine concavo-convex structure was evaluated. The results are shown in Table 2.
- Examples 2 to 18, Comparative Examples 1 to 11 A fine concavo-convex structure having the same size was produced and evaluated in the same manner as in Example 1 except that the monomers were changed to those shown in Tables 2 and 3. The results are shown in Tables 2 and 3. The unit of the blending amount in each table is “part”.
- Comparative Examples 9 and 10 the amount of the alkyl (meth) acrylate (A) and the polyfunctional monomer (B) was not appropriate, so that the water repellency was poor, the degree of crosslinking was low, and the scratch resistance was poor. Similarly in Comparative Example 11, the water repellency was poor, but the degree of crosslinking was high, so the scratch resistance was good.
- Example 19 Using the fine concavo-convex structure obtained in Example 7 as a film-shaped mold, a fine concavo-convex structure was produced as follows.
- This active energy ray-curable resin composition was dropped on the fine concavo-convex structure obtained in Example 7, and a polycarbonate plate (trade name PC1151 manufactured by Teijin Kasei Co., Ltd.) having a thickness of 500 ⁇ m was laminated on the polycarbonate plate.
- a roller was pressed from above to spread the curable resin composition.
- the resin composition was cured by irradiating ultraviolet rays from the polycarbonate plate side with a fusion lamp at a belt speed of 6.0 m / min so as to obtain an integrated light quantity of 1000 mJ / cm 2 .
- the mold was peeled off to obtain a polycarbonate plate on which a fine concavo-convex structure having the same shape as that of anodized porous alumina was formed.
- the fine concavo-convex structure obtained by curing the active energy ray-curable resin composition of the present invention achieves both high scratch resistance and good water repellency while maintaining excellent optical performance as a fine concavo-convex structure. Therefore, it can be used for, for example, building materials such as walls and roofs, window materials and mirrors for houses, automobiles, trains, ships, etc., and is extremely useful industrially. It can also be used for applications such as displays that require antireflection performance.
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Abstract
Description
微細凹凸構造の反転構造が形成されたモールドと基材との間に、前記活性エネルギー線硬化性樹脂組成物を配し、活性エネルギー線を照射して前記活性エネルギー線硬化性樹脂組成物を硬化し、モールドを剥離して、表面に微細凹凸構造を有する硬化物を形成する微細凹凸構造体の製造方法である。
基材の上に熱可塑性樹脂を配し、前記モールドを加熱しながら押し当て、冷却し、該モールドを剥離して、該熱可塑性樹脂の層の表面に該モールドの微細凹凸構造の反転構造を形成する微細凹凸構造体の製造方法である。
前記モールドと基材との間に、活性エネルギー線硬化性樹脂組成物を配し、活性エネルギー線を照射して前記活性エネルギー線硬化性樹脂組成物を硬化し、モールドを剥離して、表面に該モールドの微細凹凸構造の反転構造を有する硬化物を形成する微細凹凸構造体の製造方法である。
本発明に用いるアルキル(メタ)アクリレート(A)は、分子内にラジカル重合性官能基として(メタ)アクリロイルオキシ基を1つ以上(好ましくは1つ)有し、かつ炭素数12以上のアルキル基を有する化合物である。
本発明に用いる多官能モノマー(B)は、樹脂組成物の主成分であり、硬化物の機械特性、特に耐擦傷性を良好に維持すると共に、硬化に伴う相分離を誘起させる役割を果たす。多官能モノマー(B)は、分子内に3個以上のラジカル重合性官能基を有する。これにより、硬化物の架橋点間分子量が小さくなり、架橋密度を高くして、硬化物の弾性率や硬度を高くし、耐擦傷性に優れたものとすることができる。このラジカル重合性官能基は、代表的には(メタ)アクリロイル基である。
活性エネルギー線硬化性樹脂組成物は、1個以上のラジカル重合性官能基を有するモノマー(C)を含んでいてもよい。このモノマー(C)は、アルキル(メタ)アクリレート(A)及び多官能モノマー(B)と共重合可能なモノマーであって、樹脂組成物全体としての重合反応性を良好に維持しつつ、ハンドリング性や基材との密着性を更に向上するものであることが好ましい。
活性エネルギー線硬化性樹脂組成物は、スリップ剤(D)を含むことが好ましい。スリップ剤(D)は樹脂硬化物の表面に存在し、表面における摩擦を低減し、耐擦傷性を向上させる化合物である。スリップ剤(D)の市販品としては、例えば、東レ・ダウコーニング製「SH3746FLUID」「FZ-77」、信越化学工業製「KF-355A」、「KF-6011」が挙げられる(以上、全て商品名)。これらは1種を単独で用いてもよく、2種以上を併用してもよい。
活性エネルギー線硬化性樹脂組成物は、活性エネルギー線重合開始剤を含むことが好ましい。この活性エネルギー線重合開始剤は、活性エネルギー線の照射によって開裂し、重合反応を開始させるラジカルを発生する化合物である。活性エネルギー線とは、例えば、電子線、紫外線、可視光線、プラズマ、赤外線などの熱線等を意味する。特に、装置コストや生産性の観点から、紫外線を用いることが好ましい。
活性エネルギー線硬化性樹脂組成物の粘度に関して、モールドにより微細凹凸構造を形成して硬化させる場合、この樹脂組成物の25℃における回転式B型粘度計で測定される粘度は、好ましくは10000mPa・s以下、より好ましくは5000mPa・s以下、特に好ましくは2000mPa・s以下である。また、この粘度が10000mPa・sを超える場合であっても、加温により上記範囲内の粘度にした樹脂組成物を使用すれば、作業性を損なうことはない。この樹脂組成物の70℃における回転式B型粘度計で測定される粘度は、好ましくは5000mPa・s以下、より好ましくは2000mPa・s以下である。
以上説明した活性エネルギー線硬化性樹脂組成物は、重合及び硬化させて成形品とすることができる。その成形品として、特に微細凹凸構造を表面に有する微細凹凸構造体は極めて有用である。微細凹凸構造体としては、例えば、基材と、表面に微細凹凸構造を有する硬化物とを有するものを挙げることができる。
微細凹凸構造体の製造方法としては、例えば、(1)微細凹凸構造の反転構造が形成されたモールドと基材との間に上記樹脂組成物を配し、活性エネルギー線の照射により樹脂組成物を硬化して、モールドの凹凸形状を転写し、その後モールドを剥離する方法、(2)樹脂組成物にモールドの凹凸形状を転写してからモールドを剥離し、その後活性エネルギー線を照射して樹脂組成物を硬化する方法等が挙げられる。これらの中でも、微細凹凸構造の転写性、表面組成の自由度の点から、(1)の方法が特に好ましい。この方法は、連続生産が可能なベルト状やロール状のモールドを用いる場合に特に好適であり、生産性に優れた方法である。
本発明の撥水性物品は、本発明の樹脂組成物を重合及び硬化してなる微細凹凸構造を表面に有する微細凹凸構造体を備えた物品であってもよいし、本発明の樹脂組成物を重合及び硬化させてなる物品であってもよい。本発明の撥水性物品は、水の接触角が130°以上であることが好ましく、140°以上が更に好ましい。また、水滴の転落性が良好である。特に、微細凹凸構造体を備えた撥水性物品は、高い耐擦傷性と良好な撥水性を有すると共に、優れた反射防止性能を発現する。例えば、窓材、屋根瓦、屋外照明、カーブミラー、車両用窓、車両用ミラーの表面に、微細凹凸構造体を貼り付けて使用することができる。
本発明の活性エネルギー線硬化性樹脂組成物は、インプリント用原料にも使用できる。インプリント用原料は、この樹脂組成物を含むものであれば特に制限されない。樹脂組成物をそのまま用いることができるが、目的とする成形品に応じて各種添加剤を含有させることも可能である。
本発明のモールドは、本発明の樹脂組成物の硬化物であって微細凹凸構造を表面に有する微細凹凸構造体を備えたモールド(成形用型)である。具体的には、微細凹凸構造体と他の部材(基材等)とからなるモールドであっても良いし、微細凹凸構造体のみからなるモールドであっても良い。本発明のモールドは、良好な離型性を発現する。モールドの形状はフィルム状で用いても良いし、シート状でも良い。フィルム状のモールドをロールに巻き付けて使用しても良い。
微細凹凸構造体の製造方法に、本発明のモールドを用いることが出来る。例えば、(1)基材の上に熱可塑性樹脂を配し(例えば熱可塑性樹脂を塗布して層を形成し)、モールドを加熱しながら押し当て、冷却し、その後モールドを剥離する方法、(2)モールドと基材との間に活性エネルギー線硬化性樹脂組成物を配し、活性エネルギー線を照射して樹脂組成物を硬化し、その後モールドを剥離する方法、(3)活性エネルギー線硬化性樹脂組成物にモールドの凹凸形状を転写してからモールドを剥離し、その後活性エネルギー線を照射して樹脂組成物を硬化する方法、が挙げられる。これら方法においては、熱可塑性樹脂層の表面又は活性エネルギー線硬化性樹脂組成物の硬化物の表面に、モールドの微細凹凸構造の反転構造が形成される。
陽極酸化ポーラスアルミナからなるモールドの一部の縦断面を1分間Pt蒸着し、電界放出形走査電子顕微鏡(日本電子社製、商品名JSM-7400F)により加速電圧3.00kVで観察し、隣り合う細孔の間隔(周期)及び細孔の深さを測定した。具体的にはそれぞれ10点ずつ測定し、その平均値を測定値とした。
微細凹凸構造体の縦断面を10分間Pt蒸着し、上記(1)の場合と同じ装置及び条件にて、隣り合う凸部又は凹部の間隔及び凸部の高さを測定した。具体的にはそれぞれ10点ずつ測定し、その平均値を測定値とした。
活性エネルギー線硬化性樹脂組成物を60℃に加熱した後に冷却し、25℃のときの状態を観察した。
磨耗試験機(新東科学社製HEIDON)に1cm四方のキャンバス布を装着し、100gの荷重をかけて、往復距離50mm、ヘッドスピード60mm/sの条件にて微細凹凸構造体の表面を1000回擦傷した。その後、外観について目視にて観察し、以下の評価基準により評価した。
「○」:0~2本の傷が確認される。
「△」:3~5本の傷が確認される。
「×」:6本以上の傷が確認される。
微細凹凸構造体に1μLのイオン交換水を滴下し、自動接触角測定器(KRUSS社製)を用いて、θ/2法にて接触角を算出した。
微細凹凸構造体に20μL及び50μLのイオン交換水を滴下し、20°に傾けたときの水滴の転落具合で評価した。
「○」:転がる。
「△」:衝撃を与えると転がる。
「×」:転がらない。転落後に、水滴が残る。
図2に示す工程に従い、モールド(深さ180nm)を以下の様に作製した。
(a)工程
アルミニウム板30を、0.3Mシュウ酸水溶液中で、直流40V、温度16℃の条件で30分間陽極酸化を行い、酸化皮膜32に亀裂31を生じさせた。
(b)工程
アルミニウム板30を、6質量%リン酸/1.8質量%クロム酸混合水溶液に6時間浸漬して、酸化皮膜32を除去し、細孔31に対応する周期的な窪み33を露出させた。
(c)工程
このアルミニウム板について、0.3Mシュウ酸水溶液中、直流40V、温度16℃の条件で30秒陽極酸化を行い、酸化皮膜34を形成した。酸化皮膜をアルミニウム表面に沿って形成することにより、細孔35を有していた。
(d)工程
酸化皮膜34が形成されたアルミニウム板を、32℃の5質量%リン酸に8分間浸漬して、細孔35の径拡大処理を行った。
(e)工程
前記(c)工程及び(d)工程を合計で5回繰り返し、周期100nm、深さ180nmの略円錐形状の細孔35を有する陽極酸化ポーラスアルミナを得た。得られた陽極酸化ポーラスアルミナを脱イオン水で洗浄し、表面の水分をエアーブローで除去し、表面防汚コーティング剤(ダイキン社製、商品名オプツールDSX)を固形分0.1質量%になるように希釈剤(ハーベス社製、商品名HD-ZV)で希釈した溶液に10分間浸漬し、20時間風乾してモールド20を得た。
実施例及び比較例で用いた各モノマーの物性等を表1に示す。
[樹脂組成物の調製]
アルキル(メタ)アクリレート(A)として、ラウリルアクリレート(新中村化学社製、商品名ブレンマーLA)10部、多官能モノマー(B)として、「ATM-4E」:エトキシ化ペンタエリスリトールテトラアクリレート(新中村化学工業社製、商品名NKエステルATM-4E)90部、活性エネルギー線重合開始剤として、2,4,6-トリメチルベンゾイル-ジフェニル-フォスフィンオキサイド(日本チバガイギー社製、商品名DAROCURE TPO)0.5部、内部離型剤(アクセル社製、商品名モールドウィズINT AM-121)0.1部を混合し、活性エネルギー線硬化性樹脂組成物を調製した。
この活性エネルギー線硬化性樹脂組成物を50℃に調温し、50℃に調温したモールドの細孔が形成された表面上に流し込み、その上に厚さ38μmのポリエチレンテレフタレートフィルム(三菱樹脂製、商品名WE97A)を押し広げながら被覆した。その後、フィルム側からフュージョンランプを用いてベルトスピード6.0m/分で、積算光量1000mJ/cm2となるよう紫外線を照射して、樹脂組成物を硬化させた。次いで、フィルムとモールドを剥離して、微細凹凸構造体を得た。
モノマーを、表2及び3に示すものに変更したこと以外は、実施例1と同様にして同じサイズの微細凹凸構造体を製造し、評価した。結果を表2及び3に示す。なお、各表中の配合量の単位は「部」である。
・「LA」:ラウリルアクリレート(新中村化学社製、商品名ブレンマーLA、アルキル基の炭素数12)
・「CA」:セチルアクリレート(新中村化学社製、商品名ブレンマーCA、アルキル基の炭素数16)
・「SA」:ステアリルアクリレート(新中村化学社製、商品名ブレンマーSA、アルキル基の炭素数18)
・「VA」:ベヘニルアクリレート(新中村化学社製、商品名ブレンマーVA、アルキル基の炭素数22)
・「ATM-4E」:エトキシ化ペンタエリスリトールテトラアクリレート(新中村化学工業社製、商品名NKエステルATM-4E)
・「DPHA-6EO」:エトキシ化ジペンタエリスリトールヘキサアクリレート(第一工業製薬社製、商品名ニューフロンティアDPEA-6)
・「PET-3」:ペンタエリスリトールトリアクリレート(第一工業製薬製、商品名ニューフロンティアPET-3)
・「TMPT-3EO」:エトキシ化トリメチロールプロパントリアクリレート(新中村化学社製、商品名NKエステルTMPT-3EO)
・「U-4HA」:4官能ウレタンアクリレート(新中村化学社製、商品名NKオリゴU-4HA)
・「MA」:メチルアクリレート(sp値18.3)
・「C6DA」:1,6-ヘキサンジオールジアクリレート(大阪有機化学工業社製、商品名ビスコート230)(sp値19.6)
・「X-22-1602」:変性ポリジメチルシロキサンジアクリレート(信越化学製シリコーンジアクリレートX-22-1602、sp値19.5~19.9)
・「INT AM121」:内部離型剤(アクセル社製、商品名モールドウィズINT AM-121)
・「DAR TPO」:2,4,6-トリメチルベンゾイル-ジフェニル-ホスフィンオキサイド(日本チバガイギー社製、商品名DAROCURE TPO)
表2に示す結果から明らかなように、各実施例の微細凹凸構造体は、良好な撥水性と耐擦傷性を兼ね備えていた。
実施例7で得られた微細凹凸構造体をフィルム状のモールドとして用い、以下の様にして微細凹凸構造体を製造した。
エトキシ化ジペンタエリスリトールヘキサアクリレート(第一工業製薬社製、商品名ニューフロンティアDPEA-6)50部、1,6-ヘキサンジオールジアクリレート50部、活性エネルギー線重合開始剤として2,4,6-トリメチルベンゾイル-ジフェニル-フォスフィンオキサイド(日本チバガイギー社製、商品名DAROCURE TPO)0.5部を混合し、活性エネルギー線硬化性樹脂組成物を調製した。
この活性エネルギー線硬化性樹脂組成物を実施例7で得られた微細凹凸構造体の上に滴下し、その上に厚さ500μmのポリカーボネート板(帝人化成製、商品名PC1151)を重ね、ポリカーボネート板の上からローラーを押し当て、硬化性樹脂組成物を塗り広げた。その後、ポリカーボネート板側からフュージョンランプを用いてベルトスピード6.0m/分で、積算光量1000mJ/cm2となるよう紫外線を照射して、樹脂組成物を硬化させた。次いで、モールドを剥離して、陽極酸化ポーラスアルミナと同じ形状の微細凹凸構造体が形成されたポリカーボネート板を得た。
11 基材
12 表層(硬化物)
13 凸部
13a 凸部の頂部
13b 凸部の頂部
14 凹部
14a 凹部の底点
20 モールド
30 アルミニウム板
31 亀裂
32 酸化皮膜
33 窪み
34 酸化皮膜
35 細孔
Claims (12)
- 全モノマーの含有量の合計100質量部を基準として、炭素数12以上のアルキル基を有するアルキル(メタ)アクリレート(A)3~18質量部、及び、Fedorの推算法で表されるsp値が20~23である分子内に3個以上のラジカル重合性官能基を有する多官能モノマー(B)82~97質量部を含む活性エネルギー線硬化性樹脂組成物。
- 溶剤を含まない請求項1記載の活性エネルギー線硬化性樹脂組成物。
- 全モノマーの含有量の合計100質量部を基準として、1個以上のラジカル重合性官能基を有するモノマー(C)0~15質量部を更に含む請求項1記載の活性エネルギー線硬化性樹脂組成物。
- スリップ剤(D)を更に含む請求項1記載の活性エネルギー線硬化性樹脂組成物。
- 請求項1記載の活性エネルギー線硬化性樹脂組成物の硬化物からなる成形品。
- 請求項1記載の活性エネルギー線硬化性樹脂組成物の硬化物であって、微細凹凸構造を表面に有する微細凹凸構造体。
- 請求項6記載の微細凹凸構造体を備えた撥水性物品。
- 基材と、表面に微細凹凸構造を有する硬化物とを有する微細凹凸構造体の製造方法であって、
微細凹凸構造の反転構造が形成されたモールドと基材との間に、請求項1記載の活性エネルギー線硬化性樹脂組成物を配し、活性エネルギー線を照射して前記活性エネルギー線硬化性樹脂組成物を硬化し、モールドを剥離して、表面に微細凹凸構造を有する硬化物を形成する微細凹凸構造体の製造方法。 - 請求項6記載の微細凹凸構造体を備えたモールド。
- 基材と、表面に微細凹凸構造を有する熱可塑性樹脂層とを有する微細凹凸構造体の製造方法であって、
基材の上に熱可塑性樹脂を配し、請求項9記載のモールドを加熱しながら押し当て、冷却し、該モールドを剥離して、該熱可塑性樹脂の層の表面に該モールドの微細凹凸構造の反転構造を形成する微細凹凸構造体の製造方法。 - 基材と、表面に微細凹凸構造を有する硬化物とを有する微細凹凸構造体の製造方法であって、
請求項9記載のモールドと基材との間に、活性エネルギー線硬化性樹脂組成物を配し、活性エネルギー線を照射して前記活性エネルギー線硬化性樹脂組成物を硬化し、モールドを剥離して、表面に該モールドの微細凹凸構造の反転構造を有する硬化物を形成する微細凹凸構造体の製造方法。 - 基材と、表面に微細凹凸構造を有する硬化物とを有する微細凹凸構造体の製造方法であって、
請求項9記載のモールドの微細凹凸構造を活性エネルギー線硬化性樹脂組成物に転写してからモールドを剥離し、前記活性エネルギー線硬化性樹脂組成物を硬化して表面に該モールドの微細凹凸構造の反転構造を有する硬化物を形成する微細凹凸構造体の製造方法。
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KR20130140885A (ko) | 2013-12-24 |
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TWI474111B (zh) | 2015-02-21 |
JPWO2012141238A1 (ja) | 2014-07-28 |
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