WO2014157718A1 - 物品 - Google Patents
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- WO2014157718A1 WO2014157718A1 PCT/JP2014/059450 JP2014059450W WO2014157718A1 WO 2014157718 A1 WO2014157718 A1 WO 2014157718A1 JP 2014059450 W JP2014059450 W JP 2014059450W WO 2014157718 A1 WO2014157718 A1 WO 2014157718A1
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- acrylate
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- 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
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- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
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- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- 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
- G02B1/111—Anti-reflection coatings using layers comprising organic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B17/00—Methods preventing fouling
- B08B17/02—Preventing deposition of fouling or of dust
- B08B17/06—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement
- B08B17/065—Preventing deposition of fouling or of dust by giving articles subject to fouling a special shape or arrangement the surface having a microscopic surface pattern to achieve the same effect as a lotus flower
Definitions
- the present invention relates to an article.
- the following method has been proposed as a method for manufacturing an article having a fine concavo-convex structure on its surface.
- thermoplastic resin A method of transferring a fine concavo-convex structure to a thermoplastic resin when a thermoplastic resin is injection-molded or press-molded using a stamper having an inverted structure of the fine concavo-convex structure on the surface.
- the active energy ray-curable resin composition is filled between a stamper having a reverse structure of a fine concavo-convex structure on the surface and a transparent substrate, and cured by irradiation with active energy rays, and the fine concavo-convex structure is transferred.
- a method of releasing the stamper, or an active energy ray curable resin composition is filled between the stamper and the transparent substrate, and the active energy ray curable resin composition is filled into the active energy ray curable resin composition.
- the transferability of the fine concavo-convex structure is good, the degree of freedom of composition of the surface of the article is high, and continuous production is possible when the stamper is a belt or roll, and the above ( The method ii) is attracting attention.
- the active energy ray-curable resin composition used in this method for example, the following compositions have been proposed.
- a photocurable resin composition containing an acrylate oligomer such as urethane acrylate, an acrylic resin having a radical polymerizable functional group, a release agent, and a photopolymerization initiator (Patent Document 1).
- An ultraviolet curable resin composition containing a polyfunctional (meth) acrylate such as trimethylolpropane tri (meth) acrylate, a photopolymerization initiator, and a leveling agent such as polyether-modified silicone oil (Patent Document 2) .
- a photocurable resin comprising (meth) acrylate such as ethoxylated bisphenol A di (meth) acrylate, a reactive diluent such as N-vinylpyrrolidone, a photopolymerization initiator, and a fluorosurfactant.
- (meth) acrylate such as ethoxylated bisphenol A di (meth) acrylate
- a reactive diluent such as N-vinylpyrrolidone
- a photopolymerization initiator a photopolymerization initiator
- fluorosurfactant Composition (patent document 3).
- compositions (1) and (2) have the following problems.
- the photocurable resin composition (1) Since the photocurable resin composition (1) has a large amount of silicone added as a release agent, the optical performance of the cured product changes due to bleeding out. Specifically, in the examples, the layer made of the cured product of the photocurable resin composition is formed to be 5 g / m 2 , but 0.5% by mass of silicone is added as a release agent. For this reason, the silicone content per unit area is 25 mg / m 2 , and the change in the surface shape cannot be sufficiently suppressed when the silicone bleeds out.
- the ultraviolet curable resin composition (2) has the following problems. Since the amount of silicone oil added is large and the hardened layer is thick, the reflection spectrum changes due to bleed out. In the UV curable resin compositions of the examples, 0.1% by mass of silicone oil was added to the main agent, and the acrylate monomer (manufactured by Toagosei Co., Ltd., trade name: M309) used as the main agent was polymerized. 100 ppm of an inhibitor (hydroquinone monomethyl ether: MEHQ) is added. Since the cured layer made of this resin composition has a thickness of about 5 ⁇ m, the total content per unit area is about 5.5 ⁇ L / m 2 , and the surface shape of the bleed-out occurs. It is difficult to prevent changes in optical performance due to changes.
- MEHQ hydroquinone monomethyl ether
- compositions (1) to (3) have the following problems.
- the photo-curable resin composition (1) is easily damaged by rubbing. Moreover, since the hydrophilicity of the cured product is insufficient, even if an attempt is made to wipe off dirt such as fingerprints adhering to the cured product (fine concavo-convex structure), the dirt does not float with water, and it is difficult to wipe off the dirt.
- the cured product has a sufficiently high hydrophobicity, so that dirt such as fingerprints hardly adheres, but has the following problems. Since the polymerizable component of the composition has a low molecular weight, the cured product becomes hard and brittle, and is easily damaged by rubbing.
- the photocurable resin composition (3) has the following problems. Since the hydrophilicity of the cured product is insufficient, even if an attempt is made to wipe off dirt such as fingerprints adhering to the cured product (fine concavo-convex structure), the dirt does not float with water, and it is difficult to wipe off the dirt.
- the cured product of the polymerizable composition (4) and the cured product (5) have the following problems.
- Polyethylene glycol skeleton derived from polyethylene glycol di (meth) acrylate will cause oxidative degradation reaction relatively easily when heated in the presence of air, so the fine uneven structure cannot be maintained and optical performance deteriorates. May end up.
- the polyethylene glycol skeleton is hydrophilic, it is easy to absorb moisture, and there is a concern that decomposition is further promoted when heated in a hygroscopic state.
- the main object of the present invention is to provide an article with good optical performance. Another object of the present invention is to provide an article having high scratch resistance and good dirt wiping property. Another object of the present invention is to provide an article having excellent durability.
- an article is provided with a fine concavo-convex structure layer containing a cured product of an active energy ray-curable resin composition on at least one surface of a substrate,
- the active energy ray-curable resin composition includes a polymerizable component (Z1), a photopolymerization initiator (D), and an additive (E),
- the additive (E) is non-polymerizable, and an article in which the content of the additive (E) in the fine concavo-convex structure layer is 5 mg / m 2 or less is provided.
- an article comprising a fine concavo-convex structure layer containing a cured product of an active energy ray-curable resin composition on at least one surface of a substrate
- the active energy ray-curable resin composition has a linear or branched alkyl or alkenyl group having 6 to 22 carbon atoms, an oxyalkylene group having 2 to 4 carbon atoms, and a (meth) acryloyl group (meta)
- a polymerizable component (Z2) comprising acrylate (A) and a photoinitiator (D).
- an article is provided with a fine concavo-convex structure layer containing a cured product of an active energy ray-curable resin composition on at least one surface of a substrate,
- the active energy ray-curable resin composition includes a polymerizable component (Z3) and a photopolymerization initiator (D)
- An article is provided in which the polymerizable component (Z3) includes an antioxidant (F) having a polymerizable functional group.
- an antireflection article comprising any one of the above articles is provided.
- an article with good optical performance can be provided. According to another embodiment of the present invention, it is possible to provide an article having high scratch resistance and good dirt wiping property. According to another embodiment of the present invention, an article having excellent durability can be provided.
- An article according to an embodiment of the present invention includes a light-transmitting substrate such as a transparent substrate and a fine concavo-convex structure layer provided on at least one surface thereof.
- This fine concavo-convex structure layer is made of a cured product of the active energy ray-curable resin composition.
- This active energy ray-curable resin composition contains a polymerizable component (Z1), a photopolymerization initiator (D), and an additive (E).
- the content of the additive (E) in the fine concavo-convex structure layer is 5 mg / m 2 or less, and preferably 5 ⁇ L / m 2 or less.
- This content is more preferably 0.2 mg / m 2 or more or 0.2 ⁇ L / m 2 or more from the viewpoint of sufficiently obtaining the additive effect of the additive (E).
- the additive (E) is preferably non-polymerizable, and the mass average molecular weight of the additive (E) is preferably in the range of 100 to 2,000.
- the change in the reflection spectrum of the minimum reflectance in the visible light region is less than 20 nm.
- the polymerizable component (Z1) is a (meth) acrylate having a linear or branched alkyl or alkenyl group having 6 to 22 carbon atoms, an oxyalkylene group having 2 to 4 carbon atoms, and a (meth) acryloyl group.
- (A) can be included.
- This (meth) acrylate (A) will be described in a second embodiment described later.
- the polymerizable component (Z1) can contain an antioxidant (F) having a polymerizable functional group. This antioxidant (F) will be described in a third embodiment described later.
- the thickness of the fine concavo-convex structure layer is preferably 0.5 to 50 ⁇ m. This thickness is preferably 0.5 ⁇ m or more and more preferably 1 ⁇ m or more from the viewpoint of forming a desired fine uneven structure on the surface. From the viewpoint of suppressing bleed out, this thickness is preferably 50 ⁇ m or less, preferably 20 ⁇ m or less, more preferably 13 ⁇ m or less, and particularly preferably 10 ⁇ m or less. Moreover, it is preferable that the average space
- the additive (E) is preferably a non-copolymerizable compound that is not copolymerizable with the polymerizable component (Z1). Moreover, it is preferable that an additive (E) is a non-volatile compound. Moreover, it is preferable that an additive (E) contains at least one of a polymerization inhibitor and a mold release agent.
- the mass average molecular weight of the additive (E) is preferably 100 or more from the viewpoint of suppressing volatilization from the article. Such an additive (E) is distinguished from a general solvent having a molecular weight of less than 100. The mass average molecular weight of the additive (E) is preferably 2000 or less from the viewpoint of compatibility with the components constituting the composition and the raw material components. Such an additive (E) is distinguished from a general binder polymer having a mass average molecular weight exceeding 2000.
- the article according to the embodiment of the present invention can be suitably used as an antireflection article.
- the (meth) acryloyl group means an acryloyl group and / or a methacryloyl group.
- (Meth) acrylate means acrylate and / or methacrylate.
- the active energy ray means visible light, ultraviolet ray, electron beam, plasma, heat ray (infrared ray) and the like. The same applies to second and third embodiments described later.
- the resin composition A method of adding a release agent to is generally used.
- the shape to be transferred is a fine concavo-convex structure
- the transferred fine concavo-convex structure may be filled with the bleed-out product or the fine concavo-convex structure may be changed by bleed-out from the cured product.
- the antireflection performance is lost or reflected even if the fine concavo-convex structure slightly changes due to bleed-out. There may be a problem that the spectrum changes.
- the present inventors have found that in an article having a fine concavo-convex structure layer made of a cured product of the active energy ray-curable resin composition on the surface, the fine concavo-convex structure layer contains an additive (per unit area) It has been found that by suppressing the amount of E) to 5 mg / m 2 or less or 5 ⁇ L / m 2 or less, a change in optical performance due to bleed-out is suppressed, and the first embodiment of the present invention has been completed.
- the amount of the additive (E) added to the active energy ray-curable resin composition is reduced in order to suppress the change in optical performance due to bleed-out, and the active energy ray-curable resin composition is further reduced. It is preferable to control the thickness of the fine uneven structure layer made of a cured product.
- By reducing the amount of additive (E) added it is possible to reduce the absolute amount of the compound that may bleed out from the fine concavo-convex structure layer, thereby effectively suppressing a decrease in optical performance due to bleed out. It becomes possible. However, if the amount added is too small, the desired performance of the additive (E) may not be obtained.
- the amount of additive (E) contained per unit area is suppressed when a fine concavo-convex structure layer is formed. It becomes important. In particular, when the period of the fine concavo-convex structure is nano-order, even if the bleed-out amount is small, the optical performance is greatly affected. Therefore, the amount of the additive (E) contained per unit area must be kept lower. Furthermore, it was found that when the nano-order fine concavo-convex structure is a structure in which nano-order minute protrusions are laid without gaps, which is called a moth-eye structure, the optical performance degradation due to bleed-out becomes more remarkable. Therefore, it is necessary to keep the amount of additive (E) contained per unit area lower.
- a polymerizable component having a polyoxyalkylene structure such as polyethylene oxide or polypropylene oxide.
- the article according to the present embodiment includes a base material and a fine concavo-convex structure layer provided on at least one surface thereof.
- This fine concavo-convex structure layer is made of a cured product of the active energy ray-curable resin composition.
- This active energy ray-curable resin composition has a linear or branched alkyl or alkenyl group having 6 to 22 carbon atoms, an oxyalkylene group having 2 to 4 carbon atoms, and a (meth) acryloyl group (meta).
- the (meth) acrylate (A) preferably has a structure in which the alkyl group or alkenyl group and the oxyalkylene group are bonded.
- the content of the (meth) acrylate (A) in the polymerizable component (Z2) can be set in the range of 0.1 to 10% by mass.
- the cured product of the active energy ray-curable resin composition preferably has an indentation elastic modulus in the range of 50 to 4000 MPa.
- the water contact angle of the surface of the fine concavo-convex structure layer is 25 ° or less.
- the polymerizable component (Z2) preferably further contains a (meth) acrylate (B) having an oxyethylene group and two or more (meth) acryloyl groups.
- an average interval between adjacent convex portions is not more than a visible light wavelength.
- the article according to the present embodiment can be suitably used as an antireflection article.
- oxyalkylene such as an oxyethylene group (—CH 2 CH 2 O—) as a polymerizable component of the active energy ray-curable resin composition. It has been found effective to use a monomer having a group in the molecule. Examples of such a monomer include polyethylene glycol di (meth) acrylate and ethylene oxide-modified polyfunctional (meth) acrylate.
- the present inventors have developed a (meth) acrylate having a linear or branched alkyl or alkenyl group having 6 to 22 carbon atoms, an oxyalkylene group having 2 to 4 carbon atoms, and a (meth) acryloyl group ( By using A), the present invention succeeded in obtaining a fine concavo-convex structure with further improved scratch resistance while having sufficient dirt removal property by wiping with water, and completed the second embodiment of the present invention.
- this (meth) acrylate (A) has an effect of improving the releasability from the stamper in the formation of a fine uneven structure by transfer using a stamper. That is, (meth) acrylate (A) also has an effect as a reactive release agent. Due to this effect, the active energy ray-curable resin composition can be composed of only the polymerizable component (Z2) and the photopolymerization initiator (D) without adding an additive for imparting releasability. It is. Thereby, it is possible to prevent the surface shape of the fine concavo-convex structure made of the cured product of the active energy ray-curable resin composition from being changed by the additive component that has bleeded out from the cured product.
- the additive for imparting releasability can be added as long as the amount is within a range where the surface shape of the fine concavo-convex structure is not changed by bleeding out of the additive.
- An article according to the present embodiment includes a light-transmitting substrate such as a transparent substrate and a fine concavo-convex structure layer provided on at least one surface thereof.
- This fine concavo-convex structure layer is made of a cured product of the active energy ray-curable resin composition.
- This active energy ray-curable resin composition includes a polymerizable component (Z3) and a photopolymerization initiator (D), and includes an antioxidant (F) having a polymerizable functional group as the polymerizable component (Z3).
- This antioxidant (F) preferably has a (meth) acryloyl group as a polymerizable functional group. Moreover, it is preferable that this antioxidant (F) has radical scavenging ability. Moreover, it is preferable that this antioxidant (F) contains at least one of a phenolic antioxidant and a hindered amine antioxidant.
- the antioxidant (F) is a compound having a (meth) acryloyl group in the same molecule, and the compound is preferably a hindered amine compound or a compound having a hydroxyl group as a substituent on an aromatic ring.
- the polymerizable component (Z3) preferably further contains a (meth) acrylate having a polyoxyalkylene structure.
- This polyoxyalkylene structure includes a repeating unit represented by a polyoxyethylene structure: — (CH 2 CH 2 O) n —, a polyoxypropylene structure: — (CH 2 CHCH 3 O) —, and / or — (CHCH 3 CH 2 O) — a chain structure composed of repeating units, a polyoxytrimethylene structure: — (CH 2 CH 2 CH 2 O) n —, a polyoxybutylene structure: — (CH 2 CHC 2 H 5 O) — A chain structure composed of a repeating unit shown and / or a repeating unit shown by — (CHC 2 H 5 CH 2 O) —, a polyoxytetramethylene structure: — (CH 2 CH 2 CH 2 CH 2 O) n —, poly oxy pentamethylene structure :-( CH 2 CH 2 CH 2 CH 2 O)
- an average interval between adjacent convex portions of the fine concavo-convex structure layer is not more than a visible light wavelength.
- the content of the non-polymerizable additive (E) having no copolymerizability with the polymerizable component (Z3) is 0 mg / m 2 or more and 5 mg / m 2. or less, or is preferably 0 ⁇ L / m 2 or more 5 [mu] L / m 2 or less.
- the article according to the present embodiment can be suitably used as an antireflection article.
- the present inventors have found that a fine concavo-convex structure excellent in scratch resistance can be obtained by using a monomer having many oxyethylene groups (—CH 2 CH 2 O—) in the molecule.
- a monomer having many oxyethylene groups —CH 2 CH 2 O—
- polyethylene glycol It has been found that it is preferable in terms of scratch resistance to use di (meth) acrylate having an average molecular weight of polyethylene glycol in the molecule of about 300 to 1000 (the number of moles of ethylene oxide is about 7 to 23). It was.
- the polyethylene glycol chain having a structure in which oxyethylene groups are linked has a problem of heat resistance because it has a property of easily causing an oxidative degradation reaction, and also has a low hygroscopic property because of its hygroscopic property. I understand that.
- the present inventors have used an antioxidant having a functional group having copolymerizability with the polymerizable component of the active energy ray-curable resin composition, so that a fine concavo-convex structure can be obtained in various durability tests.
- the third embodiment of the present invention has been completed.
- the following effects can be obtained by using an antioxidant having a functional group copolymerizable with the polymerizable component of the active energy ray-curable resin composition.
- the antioxidant since the antioxidant has a functional group having copolymerizability with the polymerizable component of the active energy ray-curable resin composition, it is excellent in compatibility in the state of the uncured resin composition.
- the antioxidant is fixed in the cured product by a chemical bond, so that the movement in the cured product is limited, and the ability to detoxify active radicals generated in the decomposition process of the cured product.
- the durability is greatly improved by using an antioxidant having a functional group having copolymerizability with the polymerizable component of the active energy ray-curable resin composition. It has also been found that the antifouling performance due to scratch resistance and hydrophilicity of the uneven surface of the fine uneven structure layer is hardly affected by the antioxidant.
- an antioxidant having a polymerizable functional group in terms of weather resistance.
- an ultraviolet absorber In order to improve the weather resistance of the cured product of the active energy ray-curable resin composition, it is common to use an ultraviolet absorber.
- the ultraviolet absorber can prevent ultraviolet rays from reaching the deep part of the cured product and improve the weather resistance.
- the surface of the fine concavo-convex structure which is the outermost surface, is directly exposed to ultraviolet light that is not attenuated and cannot be damaged.
- the polymerizable component (Z1, Z2, Z3) contains 30 to 70% by mass of oxyethylene groups with respect to the entire polymerizable component. preferable.
- the softness of the cured product can be adjusted.
- the cured product tends to be flexible, and breakage and destruction of the projections (convex portions) of the fine concavo-convex structure can be prevented.
- the smaller the oxyethylene group content the easier it is to suppress the phenomenon in which the protrusions of the fine relief structure are united.
- the adjustment of the hardness of the cured product is preferably set optimally according to the aspect ratio of the concavo-convex structure (height of convex portions / average interval between convex portions).
- the aspect ratio is about 1.5 to 2.5
- the oxyethylene group content is preferably in the range of about 30 to 50%, and the aspect ratio is about 0.5 to 1.5.
- the oxyethylene group content is preferably in the range of 50 to 70%.
- the active energy ray-curable resin composition in the embodiment of the present invention is a resin composition that undergoes polymerization reaction and cures when irradiated with active energy rays.
- This active energy ray-curable resin composition includes a polymerizable component (Z1), a photopolymerization initiator (D), and an additive (E).
- Polymerizable component (Z1) examples include monomers, oligomers, and reactive polymers having a radical polymerizable bond and / or a cationic polymerizable bond in the molecule.
- the content ratio of the polymerizable component (Z1) is preferably 80% by mass or more, more preferably 90% by mass or more from the viewpoint of obtaining a desired resin cured layer (fine uneven structure layer).
- 95 mass% or more is more preferable.
- Examples of the monomer having a radical polymerizable bond include a monofunctional monomer, a bifunctional monomer, and a trifunctional or higher polyfunctional monomer.
- Examples of the monofunctional monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, alkyl (meth) acrylate, tridecyl (meth) acrylate, (iso) stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (Meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate,
- Styrene derivatives such as (meth) acrylamide, N-dimethyl (meth) acrylamide, N-diethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide and the like. These may be used alone or in combination of two or more.
- bifunctional monomer examples include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol # 200 di (meth) acrylate, and polyethylene glycol # 300 di (meth).
- trifunctional or higher polyfunctional monomer examples include pentaerythritol tri-tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide modified tri (meth) acrylate, trimethylolpropane propylene oxide modified triacrylate, Trifunctional monomers such as isocyanuric acid ethylene oxide modified tri (meth) acrylate; condensation reaction mixture of succinic acid / trimethylolethane / acrylic acid, dipentaerystol penta-hexa (meth) acrylate, ditrimethylolpropane tetraacrylate, poly Pentaerythritol poly (meth) acrylate, trifunctional or higher urethane (meth) acrylate, trifunctional or higher epoxy (meth) acrylate, trifunctional or higher polymer Ether (meth) acrylate, trifunctional or more silicone acrylate. These may be used alone or in combination of two or more.
- Examples of the monomer having a cationic polymerizable bond include monomers having an epoxy group, an oxetanyl group, an oxazolyl group, a vinyloxy group, and the like, and a monomer having an epoxy group is particularly preferable.
- oligomer or reactive polymer examples include unsaturated polyesters such as a condensate of unsaturated dicarboxylic acid and polyhydric alcohol; polyester (meth) acrylate, polyether (meth) acrylate, polyol (meth) acrylate, epoxy (meth) Examples thereof include (meth) acrylates such as acrylate and urethane (meth) acrylate; cationic polymerization type epoxy compounds; homopolymers of the above-described monomers having a radical polymerizable bond in the side chain, and copolymerized polymers.
- unsaturated polyesters such as a condensate of unsaturated dicarboxylic acid and polyhydric alcohol
- epoxy examples thereof include (meth) acrylates such as acrylate and urethane (meth) acrylate; cationic polymerization type epoxy compounds;
- the photopolymerization initiator (D) in the first embodiment and the second and third embodiments described later is a compound that generates a radical that is cleaved by irradiating active energy rays and initiates a polymerization reaction.
- active energy ray ultraviolet rays are preferable from the viewpoint of apparatus cost and productivity.
- Examples of the photopolymerization initiator (D) that generates radicals by ultraviolet rays include benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoylbenzoate, 4-phenylbenzophenone, t -Butylanthraquinone, 2-ethylanthraquinone, thioxanthones (2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, etc.), acetophenones (diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane) -1-one, benzyldimethyl ketal, 1-hydroxycyclohexyl-phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2- Methylamino-1- (4-
- photopolymerization initiator (D) one type may be used alone, or two or more types may be used in combination. When using together, it is preferable to use together 2 or more types from which absorption wavelength differs. Moreover, you may use together thermal polymerization initiators, such as persulfate (potassium persulfate, ammonium persulfate, etc.), peroxides (benzoyl peroxide, etc.), an azo initiator, as needed.
- the content of the photopolymerization initiator (D) is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the polymerizable components (Z1, Z2, Z3). 0.2 to 3 parts by mass is more preferable.
- a photoinitiator (D) hardening of an active energy ray curable resin composition may not be completed, and the mechanical physical property of the article
- the unreacted photopolymerization initiator (D) remains in the cured product, which acts as a plasticizer, lowers the elastic modulus of the cured product, and is scratch resistant. Sexuality may be impaired. Moreover, it may cause coloring.
- the fine concavo-convex structure layer of the article according to the embodiment of the present invention contains 5 mg / m 2 or less, or 5 ⁇ L / m 2 or less of the additive (E).
- the active energy ray-curable resin composition constituting the fine concavo-convex structure layer contains 5 mg / m 2 or less or 5 ⁇ L / m 2 or less of the additive (E).
- the additive (E) is preferably a non-polymerizable compound that does not have a polymerizable functional group and does not have copolymerizability with the polymerizable component (Z1).
- the specific gravity synthetic compound is a non-volatile compound. Preferably there is.
- additive (E) does not contain the volatile component which volatilizes easily and disappears, such as a solvent.
- Additives (E) include polymerization inhibitors, surfactants, mold release agents, leveling agents, lubricants, plasticizers, antistatic agents, light stabilizers, radical scavengers, antioxidants, flame retardants, and flame retardant aids.
- additives such as an agent, a filler, an ultraviolet absorber, a silane coupling agent, a colorant, a reinforcing agent, an inorganic filler, an impact modifier, an antifoaming agent, a fluorescent agent, and a luminescent agent.
- antioxidants from antioxidants, polymerization inhibitors, ultraviolet absorbers, light stabilizers, antifoaming agents, mold release agents, lubricants, leveling agents, surfactants, colorants, fluorescent agents, luminescent agents, and antistatic agents At least one selected is preferable.
- a polymerization inhibitor and a release agent are preferable because they are components that are highly required to be added to the active energy ray-curable resin composition.
- the polymerization inhibitor at least one of a hydroquinone polymerization inhibitor and a phenol polymerization inhibitor is preferable.
- polymerization inhibitors examples include hydroquinone (HQ) and hydroquinone monomethyl ether (MEHQ) as hydroquinone polymerization inhibitors, and 2,2′-methylene-bis (4-methyl-6) as phenol polymerization inhibitors.
- HQ hydroquinone
- MEHQ hydroquinone monomethyl ether
- 2,2′-methylene-bis (4-methyl-6) examples include 2,2′-methylene-bis (4-methyl-6) as phenol polymerization inhibitors.
- HQ hydroquinone
- MEHQ hydroquinone monomethyl ether
- phenothiazine polymerization inhibitor examples include phenothiazine, bis ( ⁇ -methylbenzyl) phenothiazine, 3,7-dioctylphenothiazine, bis ( ⁇ , ⁇ -dimethylbenzyl) phenothiazine, and the like.
- phenol polymerization inhibitors such as BHT can also be used as antioxidants.
- release agent examples include (poly) oxyalkylene alkyl phosphate compounds, fluorine-containing compounds, silicone compounds, compounds having a long-chain alkyl group, polyalkylene wax, amide wax, Teflon powder (Teflon is a registered trademark), etc. Is mentioned. These may be used alone or in combination of two or more. Among these, those containing a (poly) oxyalkylene alkyl phosphate compound as a main component are preferable.
- R 1 is an alkyl group
- R 2 is an alkylene group
- m is an integer of 1 to 20
- n is an integer of 1 to 3.
- R 1 is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 3 to 18 carbon atoms.
- R 2 is preferably an alkylene group having 1 to 4 carbon atoms, more preferably an alkylene group having 2 to 3 carbon atoms.
- a plurality of (poly) oxyalkylene alkyl groups in one molecule may be different from each other.
- Examples of commercially available (poly) oxyalkylene alkyl phosphate compounds include the following. Johoku Chemical Co., Ltd., trade name: JP-506H, Axel, trade name: Mold with INT-1856, Nikko Chemicals, trade name: TDP-10, TDP-8, TDP-6, TDP-2, DDP -10, DDP-8, DDP-6, DDP-4, DDP-2, TLP-4, TCP-5, DLP-10.
- These (poly) oxyalkylene alkyl phosphate compounds may be used alone or in combination of two or more.
- the mold release agent mentioned here may also exhibit functions as a surfactant, a leveling agent, and a lubricant.
- Examples of the light stabilizer include hindered amine antioxidants.
- Examples of the primary antioxidant that is a hindered amine-based radical scavenger include the following. Product name: Chimassorb 2020FDL, Chimassorb 944FDL, Tinuvin 622SF, Uvinul 5050H, Tinuvin 144, Tinuvin 765, Tinuvin 770DF, Tinuvin 4050FF, manufactured by BASF.
- ultraviolet absorber examples include benzophenone series, benzotriazole series, benzoate series, and triazine series.
- Commercially available products include trade names: Tinuvin 400 and Tinuvin 479 manufactured by Ciba Specialty Chemicals, Inc., and trade names: Biosorb 110 manufactured by Kyodo Pharmaceutical.
- antioxidants examples include hindered phenol-based, benzimidazole-based, phosphorus-based, and sulfur-based antioxidants in addition to the above-mentioned ones.
- the brand name made by Ciba Specialty Chemicals: "IRGANOX” series etc. are mentioned.
- the addition amount of the additive (E) can be defined by the content per unit area in the fine concavo-convex structure layer containing the cured product of the active energy ray-curable resin composition. By controlling this content, the change in the optical performance of the article due to the bleedout of the additive (E) can be suppressed. In particular, when the average interval between the convex portions adjacent to each other with the fine concavo-convex structure is equal to or less than the visible light wavelength, it is important to reduce the bleed out amount.
- the content of the additive (E) is 5 mg / m 2 or less, or 5 ⁇ L / m 2 or less in the fine concavo-convex structure layer.
- This content is preferably 0.2 mg / m 2 or more or 0.2 ⁇ L / m 2 or more from the viewpoint of sufficiently obtaining the additive effect of the additive (E).
- the additive (E) preferably contains at least one of a polymerization inhibitor and a release agent.
- the polymerization inhibitor preferably includes at least one selected from the above hydroquinone polymerization inhibitors, the above phenol polymerization inhibitors, and the above phenothiazine polymerization inhibitors, and particularly preferably includes a hydroquinone polymerization inhibitor.
- this mold release agent it is preferable to include at least one of the above mold release agents, and it is particularly preferable to include a (poly) oxyalkylene alkyl phosphate compound.
- the total amount of the polymerization inhibitor and the release agent is preferably 5 mg / m 2 or less or 5 ⁇ L / m 2 or less in the fine concavo-convex structure layer, and is 0.2 mg / m 2 or more or 0.2 ⁇ L / m 2 or more. Is preferred.
- the active energy ray-curable resin composition in the present embodiment includes an oligomer or polymer having no radically polymerizable functional group, a trace amount of an organic solvent, or the like as long as it does not inhibit the effects of the present invention. You may go out.
- the content of the additive (E) is within a specific range. Changes in optical performance can be suppressed.
- the active energy ray-curable resin composition used in the present embodiment can be cured by irradiating active energy rays so that the polymerization reaction of the monomer (polymerizable component) contained in the composition proceeds. It contains a polymerizable component (Z2) and a photopolymerization initiator (D) as essential components.
- the hardness of the cured product of the active energy ray-curable resin composition is not particularly limited, but the indentation elastic modulus is preferably in the range of 50 to 4000 MPa.
- the indentation elastic modulus is preferably 4000 MPa or less, more preferably 1000 MPa or less, and further preferably 500 MPa or less.
- the indentation elastic modulus is preferably 50 MPa or more, more preferably 100 MPa or more, and further preferably 120 MPa or more.
- the water contact angle on the surface of the fine concavo-convex structure made of a cured product of the active energy ray-curable resin composition is not particularly limited, but is preferably small from the viewpoint of easy removal by wiping dirt, More preferably, it is 25 ° or less.
- the smaller the water contact angle the higher the hydrophilicity of the surface of the fine concavo-convex structure, and it becomes easier to remove the dirt by wiping with water when dirt such as fingerprints adheres.
- the polymerizable component (Z2) has the above (meth) acrylate (A) as an essential component, and other (meth) acrylate (B) and other polymerizable component (C) ((meth) acrylate) as necessary. (A) and (meth) acrylate (B) are excluded.).
- the (meth) acrylate (A) is a compound having a linear or branched alkyl or alkenyl group having 6 to 22 carbon atoms, an oxyalkylene group having 2 to 4 carbon atoms, and a (meth) acryloyl group. Two or more (meth) acryloyl groups may be contained in one molecule. From the viewpoint of ease of synthesis of (meth) acrylate (A), it is preferable that one (meth) acryloyl group is contained in one molecule.
- the (meth) acrylate (A) has a linear or branched alkyl group or alkenyl group having 6 to 22 carbon atoms in the molecule, thereby reducing the free energy of the surface of the fine concavo-convex structure and imparting slipperiness. Scratch resistance can be improved.
- linear or branched alkyl group having 6 to 22 carbon atoms examples include n-hexyl group, isohexyl group, n-heptyl group, isoheptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group and isononyl group.
- N-decyl group isodecyl group, n-undecyl group, isoundecyl group, n-dodecyl group, isododecyl group, n-tridecyl group, isotridecyl group, n-tetradecyl group, isotetradecyl group, n-pentadecyl group, n- Examples include hexadecyl group, 2-ethyltetradecyl group, n-heptadecyl group, n-octadecyl group, 2-ethylhexadecyl group, n-nonadecyl group, n-eicosyl group and n-docosyl group.
- Examples of the linear or branched alkenyl group having 6 to 22 carbon atoms include n-hexenyl group, isohexenyl group, n-heptenyl group, isoheptenyl group, n-octenyl group, isooctenyl group, n-nonenyl group, isononenyl group, n-decenyl group, isodecenyl group, n-undecenyl group, isoundecenyl group, n-dodecenyl group, isododecenyl group, n-tridecenyl group, isotridecenyl group, n-tetradecenyl group, isotetradecenyl group, n-pentadecenyl group, iso Pentadecenyl group, n-hexadecenyl group, isohexadecenyl group,
- the slip property is high and the (meth) acrylate (A) is liquid at room temperature (about 25 ° C.).
- the straight chain or branched alkyl group or alkenyl group having 6 to 22 carbon atoms preferably has a larger number of carbon atoms.
- the crystallinity of a straight-chain or branched alkyl group or alkenyl group having 6 to 22 carbon atoms is low.
- Is preferably, for example, a straight or branched alkyl group or alkenyl group having 6 to 18 carbon atoms, a straight or branched alkyl group or alkenyl group having 6 to 16 carbon atoms, and a straight chain having 6 to 14 carbon atoms.
- Examples thereof include a chain or branched chain alkyl group or alkenyl group. Even when the chain has a large number of carbon atoms, crystallinity can be lowered by having an unsaturated bond in the middle of the chain.
- (meth) acrylate (A) has an oxyalkylene group having 2 to 4 carbon atoms in the molecule, it is easily compatible with the active energy ray-curable resin composition. Moreover, the scratch resistance of the fine concavo-convex structure can be improved, and hydrophilicity (dirt wiping property by water wiping) can be improved.
- the oxyalkylene group having 2 to 4 carbon atoms include oxyethylene group, 1,2-oxypropylene group, 1,2-oxybutylene group, 1,3-oxybutylene group, 2,3-oxybutylene group, 1, 4-oxybutylene group and the like can be mentioned. These can be combined by random addition or block addition.
- polyoxyalkylene alkyl ether which is an alkylene oxide-modified alcohol, and acrylic acid are used as raw materials, and acrylate ester is obtained by dehydration condensation.
- the method of synthesizing is mentioned.
- the polyoxyalkylene alkyl ether include nonionic surfactants manufactured by NOF Corporation: Nonionic series.
- the method for synthesizing the acrylic ester can be appropriately selected from known synthetic methods.
- an alkylene oxide-modified alcohol is used as a raw material, and a compound having an isocyanate group and a (meth) acryloyl group in the molecule is reacted to generate a urethane bond.
- a compound having both an isocyanate group and a (meth) acryloyl group in the molecule include the product names manufactured by Showa Denko KK: Karenz AOI, Karenz MOI, Karenz BEI, and the like.
- linear or branched alkyl group having 6 to 22 carbon atoms and the oxyalkylene group are directly bonded.
- This structure can be obtained by adding alkylene oxide to a linear or branched, saturated or unsaturated alcohol having 6 to 22 carbon atoms.
- the polymerizable component (Z2) contains the (meth) acrylate (B) having an oxyethylene group
- the oxyalkylene group of the (meth) acrylate (A) is also an oxyethylene group.
- an oxyethylene group having strong hydrophilicity is preferable from the viewpoint of wiping off dirt such as fingerprints with water.
- the number of moles of oxyalkylene groups added is preferably from 1 to 30, and more preferably from 2 to 14, on average. As the number of moles of oxyalkylene group added increases, the compatibility with the active energy ray-curable resin composition increases. However, when the number of moles of oxyalkylene group added is too large, the crystallinity increases and the solid is likely to become solid at room temperature. . Therefore, the added mole number of the oxyalkylene group is preferably 30 or less, more preferably 14 or less, and further preferably 10 or less. When the number of added moles is in this range, it is difficult to become a solid at room temperature, and the handleability is good.
- the content of the (meth) acrylate (A) is preferably 0.1% by mass or more out of 100% by mass of the polymerizable component (Z2) from the viewpoint of obtaining a sufficient addition effect (particularly scratch resistance). It is more preferably 0.5% by mass or more, more preferably 0.5% by mass or more, and may be appropriately set within a range of 100% by mass or less as long as desired effects such as scratch resistance and hydrophilicity of the surface of the fine uneven structure are obtained. it can.
- the content of the (meth) acrylate (A) is determined by the polymerizable component (Z2) 100 from the viewpoint that the hydrophilicity of the surface of the fine concavo-convex structure is kept high while obtaining sufficient scratch resistance, and better dirt removal is obtained. It can be set to 10% by mass or less of the mass%, can be set to 5% by mass or less, and can be further set to 2% by mass or less.
- (meth) acrylate (A) include, for example, product names manufactured by Toagosei Co., Ltd .: Aronix M-120, product names manufactured by NOF Corporation: Blemmer series 50POEP-800B, 50AOEP-800B, PLE- 200, ALE-200, ALE-800, PSE-200, PSE-400, PSE-1300, ASEP series, product names manufactured by Sartomer: CD277, CD9075, product names manufactured by Toho Chemical Industry: EH-10A, D2E -A, D2E-MA, PH-10A, and the like.
- ((Meth) acrylate (B)) (Meth) acrylate (B) is a compound having an oxyethylene group and two or more (meth) acryloyl groups.
- the (meth) acrylate (B) has an oxyethylene group, thereby improving the hydrophilicity of the surface of the fine concavo-convex structure so that dirt such as fingerprints can be removed by wiping with water, and the active energy ray-curable resin composition Flexibility can be imparted to the cured product to prevent breakage and tearing of the fine concavo-convex structure, and to improve scratch resistance.
- the number of moles of oxyethylene groups added is preferably 23 moles or less, more preferably 14 moles or less, in terms of crystallinity and handling at room temperature, as the average number of oxyethylene groups per (meth) acryloyl group. From the viewpoint of hydrophilicity and flexibility of the fine concavo-convex structure, it is preferably 1 mol or more, more preferably 2 mol or more, and further preferably 6 mol or more.
- (meth) acrylate (B) for example, Product names manufactured by Shin-Nakamura Chemical Co., Ltd .: NK series A-200, A-400, A-600, A-1000, A-TMPT-3EO, A-TMPT-9EO, AT-20E, A-GLY-3E A-GLY-9E, A-GLY-20E, ATM-4E, ATM-35E, Product names of Daiichi Kogyo Seiyaku Co., Ltd .: New Frontier Series PE-200, PE-300, PE-600, DPHA-12EO, Product names manufactured by Sartomer: SR230, SR259, SR268, SR272, SR344, SR349, SR560, SR561, SR562, SR580, SR581, SR601, SR602, SR610, CD9038, SR101, SR150, SR205, SR209, SR210, SR231, SR252 SR348, SR480, SR540,
- the content of (meth) acrylate (B) can be set in the range of 30 to 99.9% by mass in 100% by mass of the polymerizable component (Z2). 30 mass% or more is preferable from the point which acquires sufficient addition effect (especially hydrophilicity), 50 mass% or more is more preferable, and 75 mass% or more is further more preferable. 99.9% by mass or less is preferable, 90% by mass or less is more preferable, and 85% by mass or less is more preferable from the viewpoint of obtaining sufficient scratch resistance while obtaining sufficient dirt removal property by water wiping.
- Other polymerizable components (C) are: adjustment of viscosity of active energy ray curable resin composition and improvement of adhesion, adjustment of hardness and hydrophilic / hydrophobic balance of cured product of active energy ray curable resin composition, surface of fine uneven structure It can be added for the purpose of imparting antistatic performance to the material.
- polymerizable component (C) added to impart heat resistance and weather resistance to the cured product of the active energy ray-curable resin composition for example, Product names manufactured by Sumitomo Chemical Co., Ltd .: Sumilyzer GM, Sumilyzer GS, Product names made by ADEKA: LA-82, LA-87 of ADK STAB series Product name: RUVA-93 manufactured by Otsuka Chemical Co., Ltd.
- polymerizable component (C) added to impart antistatic performance to the cured product of the active energy ray-curable resin composition for example, Product names made by Osaka Organic Chemical Industries: DMAMC, GLBT, Product name of Daiichi Kogyo Seiyaku Co., Ltd .: New Frontier R-1220, Product name manufactured by Kojinsha: DMAPAA-TSMQ, etc.
- the content of these other polymerizable components (C) can be set to the remainder excluding the content of (meth) acrylate (A) in 100% by mass of the polymerizable component (Z2).
- acrylate (B) When acrylate (B) is included, it can set to the remainder except content of (meth) acrylate (A) and content of (meth) acrylate (B). For example, it can be set to 0 to 69.9% by mass, can be set to 0 to 49.8% by mass, and can be set to 0 to 24.5% by mass.
- the addition amount of the other polymerizable component (C) can be appropriately set according to the purpose of addition and the addition amounts of (meth) acrylates (A) and (B).
- Photopolymerization initiator (D) A photoinitiator (D) is a compound as already demonstrated in 1st Embodiment. As the active energy ray, ultraviolet rays are preferable from the viewpoint of apparatus cost and productivity. Examples of the photopolymerization initiator (D) that generates radicals by ultraviolet rays include the aforementioned compounds exemplified as the photopolymerization initiator (D) in the first embodiment.
- photopolymerization initiator (D) As the photopolymerization initiator (D), as in the photopolymerization initiator (D) in the first embodiment, one type may be used alone, or two or more types may be used in combination. When using together, it is preferable to use together 2 or more types from which absorption wavelength differs. Moreover, you may use together thermal polymerization initiators, such as persulfate (potassium persulfate, ammonium persulfate, etc.), peroxides (benzoyl peroxide, etc.), an azo initiator, as needed.
- persulfate potassium persulfate, ammonium persulfate, etc.
- peroxides benzoyl peroxide, etc.
- an azo initiator as needed.
- the content of the photopolymerization initiator (D) is preferably 0.01 to 10% by mass with respect to 100% by mass of the polymerizable component (Z2) as in the photopolymerization initiator (D) in the first embodiment. 0.1 to 5% by mass is more preferable, and 0.2 to 3% by mass is more preferable.
- a photoinitiator (D) hardening of an active energy ray curable resin composition may not be completed, and the mechanical physical property of the article
- the unreacted photopolymerization initiator (D) remains in the cured product, which acts as a plasticizer, lowers the elastic modulus of the cured product, and is scratch resistant. Sexuality may be impaired. Moreover, it may cause coloring.
- the active energy ray-curable resin composition may further contain an ultraviolet absorber and / or an antioxidant as the additive (E).
- ultraviolet absorbers examples include benzophenone, benzotriazole, hindered amine, benzoate, and triazine.
- examples of commercially available products include Ciba Specialty Chemicals' product names: Tinuvin 400 and Tinuvin 479, and Kyodo Pharmaceutical's product names: Biosorb110.
- antioxidants examples include hindered phenol-based, benzimidazole-based, phosphorus-based, sulfur-based and hindered amine-based antioxidants.
- product name: IRGANOX series etc. by Ciba Specialty Chemicals are mentioned.
- ultraviolet absorbers and antioxidants may be used alone or in combination of two or more.
- the proportion of the ultraviolet absorber and / or antioxidant (additive (E)) is preferably 0.01 to 5% by mass in total with respect to 100% by mass of the polymerizable component (X), specifically, It is preferable to add in the range where the surface shape of the fine concavo-convex structure is not changed by bleed-out.
- the active energy ray-curable resin composition in the present embodiment includes, as necessary, a surfactant, a release agent, a lubricant, a plasticizer, an antistatic agent, a light stabilizer, a flame retardant, as an additive (E). It may contain known additives such as flame retardant aids, polymerization inhibitors, fillers, silane coupling agents, colorants, reinforcing agents, inorganic fillers, impact modifiers, leveling agents, radical scavengers, etc. Good.
- the additive (E) is a non-polymerizable compound that does not have a polymerizable functional group (not included in the polymerizable component (Z2)) and does not have copolymerizability with the polymerizable component (Z2).
- this non-polymerizable compound is a non-volatile compound.
- additive (E) does not contain the volatile component which volatilizes easily and disappears, such as a solvent.
- the addition amount of the additive (E) can be defined by the content per unit area in the fine concavo-convex structure layer containing the cured product of the active energy ray-curable resin composition.
- the change in the optical performance of the article due to the bleedout of the additive (E) can be suppressed.
- the content of the additive (E) is preferably 5 mg / m 2 or less, or 5 ⁇ L / m 2 or less in the fine concavo-convex structure layer.
- This content is preferably 0.2 mg / m 2 or more or 0.2 ⁇ L / m 2 or more from the viewpoint of sufficiently obtaining the additive effect of the additive (E).
- the active energy ray-curable resin composition may contain an oligomer or polymer having no radical polymerizable functional group, a trace amount of an organic solvent, or the like, if necessary.
- the components mentioned here can be added within a range in which the surface shape of the fine concavo-convex structure is not changed by bleed-out.
- the active energy ray-curable resin composition according to the second embodiment described above contains a specific (meth) acrylate (A), so that it has good scratch resistance and good wipeability of dirt such as fingerprints.
- a cured product can be formed.
- the active energy ray-curable resin composition according to the present embodiment is a resin composition that can be cured by irradiating active energy rays so that a polymerization reaction of a polymerizable component contained in the composition proceeds.
- This active energy ray-curable resin composition has a polymerizable component (Z3) and a photopolymerization initiator (D) as essential components, and further contains a polymerizable functional group as the polymerizable component (Z3).
- the antioxidant (F) which has.
- Polymerizable component (Z3) examples include monomers, oligomers, and reactive polymers having a radical polymerizable bond and / or a cationic polymerizable bond in the molecule.
- the content ratio of the polymerizable component (Z3) is preferably 80% by mass or more, more preferably 90% by mass or more from the viewpoint of obtaining a desired resin cured layer (fine uneven structure layer).
- 95 mass% or more is more preferable.
- Examples of the monomer having a radical polymerizable bond include a monofunctional monomer, a bifunctional monomer, and a trifunctional or higher polyfunctional monomer.
- the polymerizable component (A) which is a component excluding the antioxidant (F) after the polymerizable component (Z3) will be described.
- Examples of the monofunctional monomer that is the polymerizable component (A) include the above-described monofunctional monomers exemplified as the polymerizable component (Z1) in the first embodiment. These may be used alone or in combination of two or more.
- bifunctional monomer that is the polymerizable component (A) examples include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene 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, polyethylene glycol # 1000 di (meth) acrylate, dipropylene glycol di (meth) acrylate, tri Propylene glycol di (meth) acrylate, polypropylene glycol # 400 di (meth) acrylate, polypropylene glycol # 700 di (meth) acrylate, Ritetramethylene glycol # 650 di (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, alkoxylated bisphenol A di (meth) acrylate, 9,9-bis [
- Examples of the trifunctional or higher polyfunctional monomer that is the polymerizable component (A) include pentaerythritol tri-tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide-modified tri (meth) acrylate, Methylolpropane propylene oxide modified triacrylate, pentaerythritol ethylene oxide modified tetra (meth) acrylate, dipentaerythritol ethylene oxide modified hexa (meth) acrylate, polypentaerythritol ethylene oxide modified poly (meth) acrylate, (meth) acrylic acid 2- Super multifunctional pendant (meth) acrylate obtained by polymerizing only vinyl ether group of (2-vinyloxyethoxy) ethyl, polyglycerin ethylene Trifunctional monomers such as xoxide modified poly (meth) acrylate, sorbitol ethylene oxide
- Examples of the polymerizable component (A) having a cationic polymerizable bond include monomers having an epoxy group, an oxetanyl group, an oxazolyl group, a vinyloxy group, and the like, and a monomer having an epoxy group is particularly preferable.
- Examples of the oligomer or reactive polymer as the polymerizable component (A) include unsaturated polyesters such as a condensate of unsaturated dicarboxylic acid and polyhydric alcohol; polyester (meth) acrylate, polyether (meth) acrylate, polyol ( (Meth) acrylates such as (meth) acrylates, epoxy (meth) acrylates, urethane (meth) acrylates; cationic polymerization type epoxy compounds; homopolymers or copolymers of the above-mentioned monomers having radical polymerizable bonds in the side chains It is done.
- unsaturated polyesters such as a condensate of unsaturated dicarboxylic acid and polyhydric alcohol
- polyester (meth) acrylate, polyether (meth) acrylate, polyol ( (Meth) acrylates such as (meth) acrylates, epoxy (meth) acrylates, urethane (meth) acrylates
- the polymerizable component (A) preferably contains a (meth) acrylate having such a polyoxyalkylene structure and another (meth) acrylate-based polymerizable component that can be easily copolymerized therewith.
- the (meth) acrylate having a polyoxyalkylene structure and the other (meth) acrylate-based polymerizable component are preferably bifunctional or more polyfunctional (meth) acrylate-based polymerizable components.
- polyoxyalkylene structure examples include a polyoxyethylene structure, a polyoxypropylene structure, a polyoxytrimethylene structure, a polyoxybutylene structure, a polyoxytetramethylene structure, and a polyoxypentamethylene structure.
- a polyoxyethylene structure having no methyl group, a polyoxytrimethylene structure, and a polyoxytetramethylene structure are preferable because the mobility of the molecular chain can be secured, and the fine uneven structure is hardly broken.
- the polyoxyethylene structure is more preferable in that it can impart high hydrophilicity to the surface of the fine concavo-convex structure to further improve the antifouling property.
- the antioxidant (F) has a polymerizable functional group and is contained in the polymerizable component (Z3).
- examples of the antioxidant (F) include those having a radical polymerizable bond and / or a cationic polymerizable bond in the molecule as a polymerizable functional group.
- the polymerizable functional group possessed by the antioxidant (F) is preferably a (meth) acryloyl group.
- Examples of the antioxidant (F) include a primary antioxidant having a radical scavenging ability and stopping an oxidative decomposition reaction due to a radical chain, and a secondary antioxidant having a peroxide resolution.
- Examples of the primary antioxidant include phenolic antioxidants and hindered amine antioxidants.
- a hindered amine compound having a (meth) acryloyl group is exemplified as a hindered amine antioxidant
- a phenolic antioxidant is a compound having a hydroxyl group as a substituent on an aromatic ring, and (meth) in the same molecule.
- Examples include compounds having an acryloyl group.
- Examples of secondary antioxidants include phosphorus-based antioxidants and sulfur-based antioxidants.
- metal deactivators also have an antioxidant action. This is because the transition metal reacts with hydroperoxide to generate harmful peroxy radicals.
- metal deactivators There are two types of metal deactivators: one that reacts with metal ions to form an inactive chelate compound, and the other that forms a protective film by adsorbing to metal surfaces, but is used as an antioxidant (F). Is preferably the type that reacts with metal ions to form an inactive chelate compound. Examples of the type that reacts with a metal ion to form an inactive chelate include thiocarbamates and salicylic acids.
- antioxidant (F) having radical scavenging ability is preferred as the antioxidant (F).
- the addition amount of the antioxidant (F) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, and 10% by mass in the polymerizable component (Z3). % Or less is preferable, 5 mass% or less is more preferable, and 1 mass% or less is more preferable. If the amount added is too large, the scratch resistance on the surface of the fine concavo-convex structure may be impaired, or the hydrophilicity may be impaired and the antifouling property may be lost. Further, when the antioxidant (F) has radical scavenging ability and the polymerizable component (Z3) has radical polymerizability, the polymerizable component (Z3) may be added if the amount of the antioxidant (F) is excessive. Curing by radical polymerization reaction may be inhibited. If the amount added is too small, the antioxidant effect may not be sufficiently exhibited.
- a plurality of antioxidants (F) may be used simultaneously.
- a combination that exhibits a synergistic effect is preferable, and a combination that does not cause antagonism is preferable.
- hindered phenolic antioxidants may exhibit the regeneration effect of phenolic antioxidants.
- coloring occurs by a specific combination.
- Photopolymerization initiator (D) A photoinitiator (D) is a compound as already demonstrated in 1st Embodiment. As the active energy ray, ultraviolet rays are preferable from the viewpoint of apparatus cost and productivity. Examples of the photopolymerization initiator (D) that generates radicals by ultraviolet rays include the aforementioned compounds exemplified as the photopolymerization initiator (D) in the first embodiment.
- photopolymerization initiator (D) As the photopolymerization initiator (D), as in the photopolymerization initiator (D) in the first embodiment, one type may be used alone, or two or more types may be used in combination. When using together, it is preferable to use together 2 or more types from which absorption wavelength differs. Moreover, you may use together thermal polymerization initiators, such as persulfate (potassium persulfate, ammonium persulfate, etc.), peroxides (benzoyl peroxide, etc.), an azo initiator, as needed.
- persulfate potassium persulfate, ammonium persulfate, etc.
- peroxides benzoyl peroxide, etc.
- an azo initiator as needed.
- the content of the photopolymerization initiator (D) is preferably 0.01 to 10% by mass with respect to 100% by mass of the polymerizable component (Z3) as in the photopolymerization initiator (D) in the first embodiment. 0.1 to 5% by mass is more preferable, and 0.2 to 3% by mass is more preferable.
- a photoinitiator (D) hardening of an active energy ray curable resin composition may not be completed, and the mechanical physical property of the article
- the unreacted photopolymerization initiator (D) remains in the cured product, which acts as a plasticizer, lowers the elastic modulus of the cured product, and is scratch resistant. Sexuality may be impaired. Moreover, it may cause coloring.
- the active energy ray-curable resin composition according to the embodiment of the present invention may further include an additive (E).
- the additive (E) is a non-polymerizable compound that does not have a polymerizable functional group (not included in the polymerizable component (Z3)) and does not have copolymerizability with the polymerizable component (Z3).
- this non-polymerizable compound is a non-volatile compound.
- additive (E) does not contain the volatile component which volatilizes easily and disappears, such as a solvent.
- Additives (E) include polymerization inhibitors, surfactants, mold release agents, leveling agents, lubricants, plasticizers, antistatic agents, light stabilizers, radical scavengers, antioxidants, flame retardants, and flame retardant aids. Examples thereof include known additives such as an agent, a filler, an ultraviolet absorber, a silane coupling agent, a colorant, a reinforcing agent, an inorganic filler, and an impact modifier.
- a polymerization inhibitor and a release agent are components that need to be added to the active energy ray-curable resin composition.
- polymerization inhibitor examples include the above-described polymerization inhibitors exemplified as the polymerization inhibitor in the first embodiment.
- phenol-based polymerization inhibitors such as BHT can also be used as antioxidants.
- release agent examples include the above-described release agents exemplified as the release agent in the first embodiment. These may be used alone or in combination of two or more. Among these, those containing a (poly) oxyalkylene alkyl phosphate compound as a main component are preferable.
- R 1 is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 3 to 18 carbon atoms.
- R 2 is preferably an alkylene group having 1 to 4 carbon atoms, more preferably an alkylene group having 2 to 3 carbon atoms.
- m is preferably an integer of 1 to 10.
- Examples of the commercially available product of the (poly) oxyalkylene alkyl phosphate compound include the above-described commercially available products exemplified as the release agent in the first embodiment. These (poly) oxyalkylene alkyl phosphate compounds may be used alone or in combination of two or more.
- the mold release agent mentioned here may also exhibit functions as a surfactant, a leveling agent, and a lubricant.
- Examples of the light stabilizer include hindered amine antioxidants.
- Examples of the primary antioxidant that is a hindered amine-based radical scavenger include the above-described light stabilizers exemplified as the light stabilizer in the first embodiment.
- the additives (E) mentioned here include those having the same effect as the antioxidant (F), but can be added for the purpose of supplementing the function of the antioxidant (F).
- UV absorber examples include benzophenone series, benzotriazole series, benzoate series, and triazine series.
- examples of commercially available products include BASF's trade names: Tinuvin 400 and Tinuvin 479, and Kyodo Pharmaceutical's trade names: Viosorb 110.
- antioxidants examples include hindered phenol-based, benzimidazole-based, phosphorus-based, and sulfur-based antioxidants in addition to the above-mentioned ones.
- BASF BASF
- IRGANOX IRGANOX series etc.
- the additives (E) listed here include those having the same effect as the antioxidant (F), but can be added for the purpose of supplementing the function of the antioxidant (F).
- the addition amount of the additive (E) can be defined by the content per unit area in the fine concavo-convex structure layer containing the cured product of the active energy ray-curable resin composition. By controlling this content, the change in the optical performance of the article due to the bleedout of the additive (E) can be suppressed. In particular, when the average interval between the convex portions adjacent to each other in the fine concavo-convex structure is not more than the visible light wavelength, it is particularly important to reduce the bleed out amount.
- the content of the additive (E) is preferably 5 mg / m 2 or less, or 5 ⁇ L / m 2 or less in the fine concavo-convex structure layer.
- This content is preferably 0.2 mg / m 2 or more or 0.2 ⁇ L / m 2 or more from the viewpoint of sufficiently obtaining the additive effect of the additive (E).
- the additive (E) preferably contains at least one of a polymerization inhibitor and a release agent.
- the polymerization inhibitor preferably includes at least one selected from the above hydroquinone polymerization inhibitors, the above phenol polymerization inhibitors, and the above phenothiazine polymerization inhibitors, and particularly preferably includes a hydroquinone polymerization inhibitor.
- this mold release agent it is preferable to include at least one of the above mold release agents, and it is particularly preferable to include a (poly) oxyalkylene alkyl phosphate compound.
- the total amount of the polymerization inhibitor and the release agent is preferably 5 mg / m 2 or less or 5 ⁇ L / m 2 or less in the fine concavo-convex structure layer, and is 0.2 mg / m 2 or more or 0.2 ⁇ L / m 2 or more. Is preferred.
- the total content is preferably 0.2 mg / m 2 or more or 0.2 ⁇ L / m 2 or more from the viewpoint of sufficiently obtaining the additive effect of the additive (E).
- the active energy ray-curable resin composition in the present embodiment includes an oligomer or polymer having no radically polymerizable functional group, a trace amount of an organic solvent, or the like as long as it does not inhibit the effects of the present invention. You may go out.
- the article according to the embodiment of the present invention is Excellent durability.
- the active energy ray-curable resin composition can adjust the hardness of the cured product to an appropriate range by adjusting the acrylic equivalent.
- the acrylic equivalent is a numerical value represented by the molecular weight per (meth) acryloyl group.
- the smaller the acrylic equivalent the higher the concentration of (meth) acryloyl groups, and a cured product having a higher crosslink density can be obtained. Conversely, the greater the acrylic equivalent, the lower the concentration of (meth) acryloyl groups, and a cured product having a lower crosslinking density can be obtained.
- the acrylic equivalent of the active energy ray-curable resin composition is the mass ratio of each component [% by mass] W1, W2, W3,... And the molecular weight of each component [g / mol] M1, M2, M3,.
- the number of functional groups F1, F2, F3,... Of each component is used, it is represented by the following formula (2).
- the acrylic equivalent of the active energy ray-curable resin composition is preferably from 130 [g / eq] to 600 [g / eq], more preferably from 200 [g / eq] to 400 [g / eq].
- the acrylic equivalent of the active energy ray-curable resin composition that forms a fine concavo-convex structure is too small, the crosslink density is high, so that the protrusions become brittle and are easily broken or scraped, so that the scratch resistance is lowered.
- the acrylic equivalent is too large, the cured product itself becomes too soft due to the low crosslinking density, and the cured product is greatly scratched or crushed up to a portion having no fine uneven structure, and the scratch resistance is reduced.
- the protrusions come into contact with each other and become easy to unite.
- the surface may appear white and cloudy due to light scattering.
- the viscosity of the active energy ray-curable resin composition is preferably not too high from the viewpoint of easy flow into the fine uneven structure on the surface of the stamper. Therefore, the viscosity of the active energy ray-curable resin composition on a rotary B-type viscometer at 25 ° C. is preferably 10000 mPa ⁇ s or less, more preferably 5000 mPa ⁇ s or less, and further preferably 2000 mPa ⁇ s or less.
- the viscosity of the active energy ray-curable resin composition exceeds 10,000 mPa ⁇ s, there is no particular problem as long as the viscosity can be lowered by heating in advance when contacting with the stamper.
- the viscosity of the active energy ray-curable resin composition in a rotary B-type viscometer at 70 ° C. is preferably 5000 mPa ⁇ s or less, and more preferably 2000 mPa ⁇ s or less. If the viscosity is too low, it may spread out and hinder the production, and is preferably 10 mPa ⁇ s or more.
- an article having a fine concavo-convex structure can be formed.
- An article according to an embodiment of the present invention has, on the surface, a fine concavo-convex structure formed by bringing the active energy ray-curable resin composition described above into contact with a stamper having a reverse structure of the fine concavo-convex structure on the surface and curing the composition.
- FIG. 1 is a cross-sectional view showing an example of an article provided with a fine relief structure layer.
- the article 40 includes a base material 42 and a cured resin layer 44 formed on the surface of the base material 42.
- the cured resin layer 44 is a fine concavo-convex structure layer having a plurality of convex portions 46 on the surface thereof.
- the thickness of the fine concavo-convex structure layer can be set in the range of 0.5 to 100 ⁇ m. This thickness is preferably 0.5 ⁇ m or more and more preferably 1 ⁇ m or more from the viewpoint of forming a desired fine uneven structure on the surface. From the viewpoint of suppressing bleed out, this thickness can be set to 100 ⁇ m or less, preferably 50 ⁇ m or less, more preferably 20 ⁇ m or less, further preferably 13 ⁇ m or less, and particularly preferably 10 ⁇ m or less.
- the base material 42 is preferably a molded body that transmits light.
- the base material include acrylic resin (polymethyl methacrylate, etc.), polycarbonate, styrene (co) polymer, methyl methacrylate-styrene copolymer, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, polyester ( Polyethylene terephthalate, etc.), polyamide, polyimide, polyether sulfone, polysulfone, polyolefin (polyethylene, polypropylene, etc.), polymethylpentene, polyvinyl chloride, polyvinyl acetal, polyether ketone, polyurethane, glass and the like.
- the base material 42 may be an injection molded body, an extrusion molded body, or a cast molded body.
- the shape of the substrate 42 may be a sheet shape or a film shape.
- the surface of the base material 42 may be subjected to a coating treatment, a corona treatment or the like in order to improve adhesion, antistatic properties, scratch resistance, weather resistance, and the like.
- the cured resin layer 44 is a film made of a cured product of the active energy ray-curable resin composition, and has a fine uneven structure on the surface.
- the fine uneven structure on the surface of the article 40 is formed by transferring the fine uneven structure on the surface of the anodized alumina, and the active energy ray-curable resin composition And a plurality of convex portions 46 made of a cured product.
- the fine concavo-convex structure is preferably a so-called moth-eye structure in which a plurality of protrusions (convex portions) having a substantially conical shape or a pyramid shape are arranged. It is known that the moth-eye structure in which the distance between the protrusions is less than or equal to the wavelength of visible light is an effective anti-reflection measure by continuously increasing the refractive index from the refractive index of air to the refractive index of the material. It has been.
- the aspect ratio of the concavo-convex (the height of the ridge) is the balance between the average spacing between the ridges and the height of the ridges. It is important that the average distance between the convex portions is within a specific range.
- the average interval between adjacent convex portions is preferably not more than the wavelength of visible light, that is, not more than 400 nm. If the average interval is too large, visible light scattering tends to occur. From the viewpoint of suppressing the scattering of visible light and applying to optical applications such as antireflection articles, the average distance between adjacent convex portions is preferably 400 nm or less, more preferably 380 nm or less, further preferably 250 nm or less, and further 200 nm or less. preferable. Further, from the viewpoint of the effect of the desired fine concavo-convex structure and ease of molding, it is preferably 80 nm or more, more preferably 100 nm or more, and further preferably 160 nm or more.
- the average distance between adjacent convex parts is the distance between adjacent convex parts (distance from the center of the convex part to the center of the adjacent convex part) measured by electron microscope observation at 50 points, and these values are averaged. It is.
- the antireflection performance is largely determined by the height of the protrusion (convex portion).
- the height of the convex portion can be set in the range of 120 to 250 nm.
- the height of the convex portion is preferably 250 nm or less, more preferably 220 nm or less, and further preferably 190 nm or less.
- 120 nm or more is preferable, 150 nm or more is more preferable, and 160 nm or more is further more preferable.
- the height of the convex part is a value obtained by measuring the distance between the top part of the convex part and the bottom part of the concave part existing between the convex parts when observed with an electron microscope at a magnification of 30000 times.
- the aspect ratio of the concavo-convex part (height of the convex part / average interval between the convex parts) can be set in the range of 0.5 to 3.0.
- the aspect ratio is preferably 0.5 or more, and more preferably 0.8 or more.
- the aspect ratio is preferably 3.0 or less, more preferably 2.5 or less, and further preferably 1.2 or less.
- the shape of the convex part is a shape in which the convex sectional area of the cross section along the direction orthogonal to the height direction (base plane direction) continuously increases in the depth direction from the outermost surface, that is, the height of the convex part.
- the cross-sectional shape along the direction (perpendicular to the substrate plane) is preferably a triangle, trapezoid, bell shape or the like.
- the difference between the refractive index of the cured resin layer 44 and the refractive index of the substrate 42 is preferably 0.2 or less, more preferably 0.1 or less, and particularly preferably 0.05 or less. As the refractive index difference is smaller, reflection at the interface between the cured resin layer 44 and the substrate 42 can be suppressed.
- stamper has an inverted structure of a fine concavo-convex structure on the surface.
- material of the stamper include metals (including those having an oxide film formed on the surface), quartz, glass, resin, ceramics, and the like.
- shape of the stamper include a roll shape, a circular tube shape, a flat plate shape, and a sheet shape.
- Examples of the method for producing the stamper include the following method (I-1) and method (I-2), and the method (I-1) is possible because the area can be increased and the production is simple. Is particularly preferred.
- (I-1) A method of forming anodized alumina having a plurality of pores (recesses) on the surface of an aluminum substrate.
- (I-2) A method of forming an inverted structure of a fine concavo-convex structure on the surface of a stamper base material by an electron beam lithography method, a laser beam interference method or the like.
- an electrolytic aluminum plating substrate coated with aluminum by electroplating may be used as the aluminum substrate.
- a method having the following steps (a) to (f) is preferable.
- B A step of removing the oxide film and forming anodic oxidation pore generation points on the surface of the aluminum substrate.
- C After the step (b), the step of anodizing the aluminum substrate again in the electrolytic solution to form an oxide film having pores at the pore generation points.
- D A step of expanding the diameter of the pores after the step (c).
- E A step of anodizing again in the electrolytic solution after the step (d).
- F A step of repeatedly performing step (d) and step (e) to obtain a stamper in which anodized alumina having a plurality of pores is formed on the surface of an aluminum substrate.
- Process (a) can be performed as follows. As shown in FIG. 2, when the aluminum substrate 10 is anodized, an oxide film 14 having pores 12 is formed. Examples of the shape of the aluminum substrate include a roll shape, a circular tube shape, a flat plate shape, and a sheet shape. Since the oil used when processing the aluminum base material into a predetermined shape may be adhered, it is preferable to degrease the aluminum base material in advance.
- the aluminum substrate is preferably subjected to electrolytic polishing (etching) in order to smooth the surface state.
- the purity of aluminum is preferably 99% or more, more preferably 99.5% or more, and particularly preferably 99.8% or more.
- the electrolytic solution include sulfuric acid, oxalic acid, and phosphoric acid.
- the concentration of oxalic acid is preferably 0.8 M or less. When the concentration of oxalic acid exceeds 0.8M, the current value becomes too high, and the surface of the oxide film may become rough.
- the formation voltage is preferably in the range of 30 to 100V. When the formation voltage is in this range, anodized alumina having highly regular pores with a period of 100 nm to 200 nm can be obtained. Regardless of whether the formation voltage is higher or lower than this range, the regularity tends to decrease.
- the temperature of the electrolytic solution is preferably 60 ° C. or lower, and more preferably 45 ° C. or lower. When the temperature of the electrolytic solution exceeds 60 ° C., a so-called “burn” phenomenon occurs, and the pores may be broken or the surface may melt and the regularity of the pores may be disturbed.
- Anodization using sulfuric acid as the electrolyte can be performed as follows.
- the concentration of sulfuric acid is preferably 0.7M or less. If the concentration of sulfuric acid exceeds 0.7M, the current value may become too high to maintain a constant voltage.
- the formation voltage is preferably in the range of 25-30V. When the formation voltage is in this range, anodized alumina having highly regular pores with a period of 63 nm can be obtained. The regularity tends to decrease whether the formation voltage is higher or lower than this range.
- the temperature of the electrolytic solution is preferably 30 ° C. or less, and more preferably 20 ° C. or less. When the temperature of the electrolytic solution exceeds 30 ° C., a so-called “burn” phenomenon occurs, and the pores may be broken or the surface may melt and the regularity of the pores may be disturbed.
- Process (b) can be performed as follows. As shown in FIG. 2, the oxide film 14 is removed, and anodic oxidation pore generation points 16 are formed on the surface of the substrate. Thereby, the regularity of the pore of the oxide film formed later can be improved.
- Examples of the method for removing the oxide film 14 include a method in which aluminum is not dissolved but is dissolved and removed in a solution that selectively dissolves the oxide film. Examples of such a solution include a chromic acid / phosphoric acid mixed solution.
- Step (c) can be performed as follows. As shown in FIG. 2, when the aluminum substrate 10 from which the oxide film has been removed is anodized again, an oxide film 14 having cylindrical pores 12 is formed. Anodization can be performed under the same conditions as in step (a). Deeper pores can be obtained as the anodic oxidation time is lengthened.
- Process (d) can be performed as follows. As shown in FIG. 2, a process for expanding the diameter of the pores 12 (hereinafter referred to as a pore diameter expansion process) is performed.
- the pore diameter expansion treatment is a treatment for expanding the diameter of the pores obtained by anodic oxidation by immersing in a solution dissolving the oxide film. Examples of such a solution include a phosphoric acid aqueous solution of about 5% by mass. The longer the pore diameter expansion processing time, the larger the pore diameter.
- Process (e) can be performed as follows. As shown in FIG. 2, when anodized again, cylindrical pores having a small diameter extending downward from the bottom of the cylindrical pores 12 are formed. Anodization can be performed under the same conditions as in step (a). Deeper pores can be obtained as the anodic oxidation time is lengthened.
- Process (f) can be performed as follows. As shown in FIG. 2, when the pore diameter enlargement process in the step (d) and the anodization in the step (e) are repeated, the pores 12 have a shape in which the diameter continuously decreases in the depth direction from the opening. An oxide film 14 is formed, and a stamper 18 having anodized alumina (aluminum porous oxide film (alumite)) on the surface of the aluminum substrate 10 is obtained. It is preferable that the last end is step (d).
- the total number of repetitions of these steps is preferably 3 times or more, and more preferably 5 times or more.
- the diameter of the pores decreases discontinuously, so that the effect of reducing the reflectance of the moth-eye structure formed using anodized alumina having such pores is insufficient.
- the shape of the pore 12 includes a substantially conical shape, a pyramid shape, a cylindrical shape, and the like, and the cross-sectional area of the pore along the direction orthogonal to the depth direction is the largest, such as a conical shape and a pyramid shape.
- a shape that continuously decreases in the depth direction from the surface is preferable.
- the average interval between the pores 12 can be formed according to a predetermined fine uneven structure.
- the average interval between the pores is preferably not more than the wavelength of visible light, that is, not more than 400 nm, more preferably not more than 380 nm, still more preferably not more than 250 nm, and particularly preferably not more than 200 nm.
- the average distance between the pores is preferably 80 nm or more, more preferably 100 nm or more, and further preferably 160 nm or more.
- the average interval between the pores 12 is measured by measuring the distance between adjacent pores 12 (distance from the center of the pore 12 to the center of the adjacent pore 12) by electron microscope observation, and averaging these values. It is a thing.
- the depth of the pores 12 can be formed according to a predetermined fine uneven structure.
- the depth of the pores is preferably 250 nm or less, more preferably 220 nm or less, and further preferably 190 nm or less. Further, the depth of the pores is preferably 120 nm or more, more preferably 150 nm or more, and further preferably 160 nm or more.
- the depth of the pore 12 is a value obtained by measuring the distance between the bottom of the pore 12 and the top of the convex portion existing between the pores 12 when observed with an electron microscope at a magnification of 30000 times. It is.
- the aspect ratio of the pores 12 (the depth of the pores / the average interval between the pores) can be formed according to a predetermined fine concavo-convex structure, and can be set in the range of 0.5 to 3.0. A range of .8 to 1.2 is preferred.
- the surface of the stamper on which the fine uneven structure is formed may be treated with a release agent.
- the release agent include silicone resins, fluororesins, fluorine compounds, and phosphate esters, and phosphate esters are particularly preferable.
- the phosphoric acid ester is preferably a (poly) oxyalkylene alkyl phosphoric acid compound, and commercially available products are trade names manufactured by Johoku Chemical Co., Ltd .: JP-506H, commercial products manufactured by Accel Corporation: Mold With INT-1856, Nikko Chemicals Product names: TDP-10, TDP-8, TDP-6, TDP-2, DDP-10, DDP-8, DDP-6, DDP-4, DDP-2, TLP-4, TCP-5, And DLP-10.
- An article having a fine concavo-convex structure on its surface can be manufactured as follows using, for example, a manufacturing apparatus shown in FIG.
- a resin composition is supplied.
- the base material 42 and the active energy ray curable resin composition are sandwiched between the roll stamper 20 and the nip roll 26 whose nip pressure is adjusted by the pneumatic cylinder 24, and the active energy ray curable resin composition is placed on the base material. 42 and the roll stamper 20 are uniformly distributed, and at the same time, the concave portions of the fine uneven structure of the roll stamper 20 are filled.
- the active energy ray curable resin composition is irradiated from the active energy ray irradiating device 28 installed below the roll-shaped stamper 20 through the base material 42 to the active energy ray curable resin composition to cure the active energy ray curable resin composition.
- the cured resin layer 44 to which the fine uneven structure on the surface of the roll stamper 20 is transferred is formed.
- An article 40 as shown in FIG. 1 is obtained by peeling the base material 42 having the cured resin layer 44 formed on the surface from the roll stamper 20 by the peeling roll 30.
- the active energy ray irradiation device 28 a high-pressure mercury lamp, a metal halide lamp or the like is preferable.
- the amount of light irradiation energy is preferably 100 to 10,000 mJ / cm 2 .
- a light transmissive film can be used as the base material 42.
- a material of the film acrylic resin, polycarbonate, styrene resin, polyester, cellulose resin (triacetyl cellulose, etc.), polyolefin, alicyclic polyolefin, etc. Is mentioned.
- Articles having a fine concavo-convex structure on the surface according to an embodiment of the present invention are antireflection articles (antireflection films, antireflection films, etc.), optical articles such as optical waveguides, relief holograms, lenses, and polarization separation elements, and cell culture sheets. This is particularly suitable for use as an antireflection article.
- the article having the fine concavo-convex structure on the surface according to the embodiment of the present invention may be a light transmissive article.
- antireflection articles include antireflection films and antireflection films provided on the surfaces of image display devices (liquid crystal display devices, plasma display panels, electroluminescence displays, cathode tube display devices, etc.), lenses, show windows, and glasses. And an antireflection sheet.
- image display devices liquid crystal display devices, plasma display panels, electroluminescence displays, cathode tube display devices, etc.
- lenses show windows, and glasses.
- an antireflection sheet When used in an image display device, an antireflection film may be directly attached to the image display surface, an antireflection film may be directly formed on the surface of a member constituting the image display surface, or an antireflection film is formed on the front plate. May be formed.
- the fine concavo-convex structure is formed using the active energy ray-curable resin composition containing a specific (meth) acrylate, the fine concavo-convex structure has scratch resistance. High and good wipeability of dirt such as fingerprints.
- the sample having the fine concavo-convex structure transferred thereon was attached to a black acrylic plate (trade name: Acrylite, manufactured by Mitsubishi Rayon Co., Ltd.), and then stored for 7 days in an environment of room temperature 23 ° C. and humidity 50%, and then the reflection spectrum was measured.
- the reflection spectrum was measured using a spectrophotometer (manufactured by Shimadzu Corporation, product name: UV-2450) with a 5 ° specular reflectance spectrum in the range of 380 nm to 780 nm. After measuring the reflection spectrum, a part of the fine uneven surface was wiped with ethanol, and then the reflection spectrum was measured again to confirm the change of the reflection spectrum.
- the change in the reflection spectrum was measured at three points each, and when the bottom (minimum value) of the reflectance in the visible light region (380 nm to 780 nm) changed more than 20 nm on average before and after, it was judged that there was a change in the spectrum.
- the bottom of the reflectance of the portion wiped with ethanol changes by about 20 nm or more, the boundary between the wiped portion and the portion not wiped can be visually confirmed.
- the evaluation index was as follows.
- ⁇ The reflection spectrum does not change before and after wiping with ethanol.
- X There is a change in the reflection spectrum before and after wiping with ethanol.
- the thickness of the fine concavo-convex structure layer was calculated by excluding the thickness of the light transmissive substrate from the thickness of the laminate (article) after the fine concavo-convex structure was transferred.
- the thickness of the laminate and the light-transmitting substrate was measured using a Digimatic standard outer micrometer (manufactured by Mitutoyo Corporation).
- composition of additive (E) The content of the additive (E) is based on the content of the additive (E) in the active energy ray resin composition and the film thickness of the layer (cured resin layer) made of a cured product of the active energy ray curable resin composition. Calculated.
- AA Scratches can not be confirmed
- A Less than 10 scratches that can be confirmed
- B 10 or more and less than 30 scratches that can be confirmed
- C 30 or more scratches that can be confirmed
- D Antireflection performance is lost in an area of 50% or more of the scratched portion.
- ⁇ Fingerprints can be completely removed by wiping twice or less. ⁇ : Fingerprints can be completely removed by wiping 3 to 10 times. X: Fingerprint remains even after wiping 10 times.
- the durability test was conducted as follows.
- the sample to which the fine concavo-convex structure was transferred was affixed to a black acrylic plate (trade name: Acrylite, manufactured by Mitsubishi Rayon Co., Ltd.) and then held for 500 hours in an environment with an air temperature of 60 ° C. and a humidity of 90%.
- the evaluation index regarding the projection shape maintenance, the surface shape of the fine irregularities was observed with an electron microscope, and “ ⁇ ” was given when the projections were not united, and “X” was given.
- the presence / absence of bleed-out was evaluated as ⁇ when there was no change in the reflection spectrum before and after wiping with ethanol, and x when there was.
- the reflection spectrum was measured using a spectrophotometer (manufactured by Shimadzu Corporation, product name: UV-2450) with a 5 ° specular reflectance spectrum in the range of 380 nm to 780 nm. After measuring the reflection spectrum, a part of the fine uneven surface was wiped with ethanol, and then the reflection spectrum was measured again to confirm the change of the reflection spectrum. The change in the reflection spectrum was measured at three points each, and when the bottom (minimum value) of the reflectance in the visible light region (380 nm to 780 nm) changed more than 20 nm on average before and after, it was judged that there was a change in the spectrum.
- the 0.3 M oxalic acid aqueous solution was adjusted to 15 ° C., the aluminum base material was immersed, and the power source of the direct current stabilization device was repeatedly turned on and off, so that an electric current was intermittently applied to the aluminum base material to perform anodization.
- the operation of applying a constant voltage of 80 V every 30 seconds for 5 seconds was repeated 60 times to form an oxide film having pores.
- the aluminum substrate on which the oxide film was formed was immersed in a 70 ° C. aqueous solution in which 6% by mass of phosphoric acid and 1.8% by mass of chromic acid were mixed to dissolve and remove the oxide film.
- the aluminum base material from which the oxide film was dissolved and removed was immersed in a 0.05 M oxalic acid aqueous solution adjusted to 16 ° C. and anodized at 80 V for 7 seconds. Then, the pore diameter expansion process which expands the pore of an oxide film by immersing in 5 mass% phosphoric acid aqueous solution adjusted to 32 degreeC for 20 minutes was performed. In this way, the anodization and the pore size enlargement process were alternately repeated, and a total of 5 times was performed.
- stamper (mold) was immersed in a 0.1% by weight aqueous solution of a mold release agent (manufactured by Nikko Chemicals, trade name: TDP-8) for 10 minutes, pulled up and air-dried overnight for release treatment. gave.
- a mold release agent manufactured by Nikko Chemicals, trade name: TDP-8
- composition of active energy ray-curable resin composition The polymerization component (Z), photopolymerization initiator (D), and additive (E) contained in the active energy ray-curable resin compositions used in Examples and Comparative Examples are shown in Tables 1A, 1B, and 1C below. It is as follows. In the table, “PEG” means polyethylene glycol, and “EO” means ethylene oxide.
- the numerical value of the polymerizable component (Z1, Z2 or Z3) in the other tables is the mass ratio of the entire polymerizable component (Z1, Z2 or Z3) (% By mass) and the numerical values of the photopolymerization initiator (D) and additive (E) (release agent, polymerization inhibitor, antioxidant) are mass ratios relative to the polymerizable component (Z1, Z2 or Z3). (Mass%).
- Example A1 As a polymerization component (Z1), 20% by mass of NK ester A-TMM-3LM-N (manufactured by Shin-Nakamura Chemical Co., Ltd., product name) and 80% of NK ester ATM-35E (manufactured by Shin-Nakamura Chemical Co., Ltd., product name) As a photopolymerization initiator (D), 0.1% by mass of Irgacure 184 (manufactured by BASF, product name) and Irgacure 819 (manufactured by BASF, based on 100% by mass of the polymerizable component (Z1) Name) 0.5% by weight, release agent (additive (E)) as a mixture of NIKKOL TDP-2 (manufactured by Nikko Chemicals, product name) 0.1% by weight, active energy ray curable resin composition A product was prepared. MEHQ, which is a polymerization inhibitor (additive (E)), was originally contained in the polymer
- a few drops of the active energy ray-curable resin composition is dropped on the surface of the stamper and coated with a triacetyl cellulose film (product name: TD80ULM, manufactured by Fuji Film Co., Ltd.) having a thickness of 80 ⁇ m while spreading, and then a high-pressure mercury lamp from the film side.
- TD80ULM triacetyl cellulose film
- the stamper was released from the film to obtain an article having a fine concavo-convex structure on the film surface with an average interval of protrusions of 180 nm and a height of 180 nm.
- Table 2 The evaluation results are shown in Table 2.
- Examples A2 to A8, Comparative Example A1 The fine concavo-convex structure was the same as Example A1, except that the composition type, composition ratio (% by mass), and thickness of the cured layer (fine concavo-convex structure layer) of the active energy ray-curable resin composition were as shown in Table 2A. An article having a surface was obtained. The evaluation results are shown in Table 2A.
- Example A1 to A8 since the content of the additive (E) was 5 mg / m 2 or less or 5 ⁇ L / m 2 or less, the change in the reflection spectrum was suppressed, and good evaluation results were obtained. On the other hand, in Comparative Example A1, the amount of the additive (E) was too large, and the reflection spectrum changed before and after wiping with ethanol.
- Example B1 As a polymerizable component (Z2), Blemmer ALE-200 (manufactured by NOF Corporation, product name) is 0.3% by mass, and NK ester A-GLY-20E (manufactured by Shin-Nakamura Chemical Co., Ltd., product name) is 84.7% by mass.
- the high pressure mercury lamp is applied from the film side.
- the stamper was released from the film to obtain an article having a fine concavo-convex structure on the surface with an average interval of protrusions of 180 nm and a height of protrusions of 180 nm.
- Table 2B The evaluation results are shown in Table 2B.
- Examples B2 to B11, Comparative Examples B1 to B7, Reference Examples B1 to B3 An article having a fine concavo-convex structure on its surface is obtained in the same manner as in Example 1 except that the polymerizable component (Z) of the active energy ray-curable resin composition is changed to those shown in Tables 2B, 3B and 4B. It was. The evaluation results are shown in Table 2B, Table 3B, and Table 4B. Numerical values relating to the polymerizable components (A), (B), and (C) in Table 2B, Table 3B, and Table 4B indicate the content (% by mass) of each component in the polymerizable component (Z2).
- the active energy ray-curable resin composition containing (meth) acrylate (A) was used, the cured product had good steel wool scratch resistance.
- the steel wool scratch resistance test result is 100 gf / cm 2 (0.98 N / cm 2 ) and AA (no scratches), and the fingerprint wiping property is also good. It was good.
- Comparative Examples B2 and B3 a polymerizable component containing lauryl acrylate not modified with EO was used. As a result, the fingerprint wiping property of the cured product was impaired.
- Comparative Examples B4 and B5 a polymerizable component containing methoxypolyethylene glycol acrylate was used. As a result, since the alkyl group was a methyl group, slipperiness could not be imparted, resulting in poor scratch resistance of the cured product.
- Comparative Examples B6 and B7 a polymerizable component containing an acrylate having a silicone skeleton was used. As a result, although the cured product had scratch resistance, the curable liquid became cloudy and the cured product also became cloudy. In addition, the fingerprint wiping property was greatly reduced.
- Reference Example B1 and Reference Example B2 are excellent in continuous transferability because they contain a release agent, but Reference Example B3 is inferior in continuous transferability because it does not contain a release agent.
- the composition of Example B11 does not contain a release agent, it can exhibit excellent release properties due to the effect of ALE-200, which is a (meth) acrylate (A) having a (meth) acryloyl group. Was confirmed.
- Example C1 In the polymerizable component (Z3), 20% by mass of NK ester A-TMM-3LM-N (manufactured by Shin-Nakamura Chemical Co., Ltd., product name) as a polymerizable component (A), NK ester ATM-35E (Shin-Nakamura Chemical) 79% by mass (product name) manufactured by Kogyo Co., Ltd., 1% by mass of ADEKA STAB LA-82 (manufactured by ADEKA, product name) as an antioxidant (F), and Irgacure 184 (BASF) as a photopolymerization initiator (D) Nikkol TDP-2 (Nikko Chemicals Co., Ltd.) with 0.1% by mass of product name (product name), 0.5% by mass of Irgacure 819 (product name, product name of BASF), and release agent (additive (E)) Manufactured, product name) 0.1% by mass was mixed to prepare an active energy ray-curable
- the high pressure mercury lamp is applied from the film side.
- the stamper was released from the film to obtain an article having a fine concavo-convex structure on the surface with an average interval of protrusions of 180 nm and a height of 180 nm.
- Table 2C The evaluation results are shown in Table 2C.
- Examples C2 to C4 Comparative Examples C1 to C4
- An article having a fine concavo-convex structure on the surface was obtained in the same manner as in Example C1, except that the composition ratio (mass%) and composition type of the active energy ray-curable resin composition were as shown in Table 2C.
- the evaluation results are shown in Table 2C.
- Example C1 to C4 since antioxidant (F) is included, the protrusion shape after a wet heat durability test can be maintained, and the addition amount of additive (E) is 5 [mg / m 2 ] or less. Therefore, the optical performance change by the bleed-out after the wet heat durability test could be suppressed.
- Comparative Examples C1 and C2 did not contain the antioxidant (F), so the protrusion shape could not be maintained. In Comparative Examples C3 and C4, the protrusion shape could be maintained, but the change in optical performance due to bleed out could not be suppressed.
- the article according to the embodiment of the present invention can maintain excellent optical performance, it can be used for various displays such as a television, a mobile phone, and a portable game machine, and is extremely useful industrially.
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Abstract
Description
前記活性エネルギー線硬化性樹脂組成物が、重合性成分(Z1)と光重合開始剤(D)と添加剤(E)とを含み、
添加剤(E)は、非重合性であり、前記微細凹凸構造層における添加剤(E)の含有量が5mg/m2以下である物品が提供される。
前記活性エネルギー線硬化性樹脂組成物が、炭素数6~22の直鎖もしくは分岐鎖のアルキル基またはアルケニル基と、炭素数2~4のオキシアルキレン基と、(メタ)アクリロイル基を有する(メタ)アクリレート(A)を含む重合性成分(Z2)と、光重合開始剤(D)を含む、物品が提供される。
前記活性エネルギー線硬化性樹脂組成物が、重合性成分(Z3)と光重合開始剤(D)を含み、
前記重合性成分(Z3)が、重合性官能基を有する酸化防止剤(F)を含む、物品が提供される。
本発明の実施形態による物品は、透明基板等の光透過性基材と、その少なくとも一方の表面に設けられた微細凹凸構造層を含む。この微細凹凸構造層は、活性エネルギー線硬化性樹脂組成物の硬化物からなる。この活性エネルギー線硬化性樹脂組成物は、重合性成分(Z1)と光重合開始剤(D)と添加剤(E)とを含む。前記微細凹凸構造層における添加剤(E)の含有量は、5mg/m2以下であり、かつ5μL/m2以下が好ましい。添加剤(E)の添加効果を十分に得る点から、この含有量は0.2mg/m2以上または0.2μL/m2以上がより好ましい。添加剤(E)は、非重合性であることが好ましく、また、添加剤(E)の質量平均分子量が100~2000の範囲にあることが好ましい。前記微細凹凸構造層の表面をエタノールで拭く前後において、可視光領域における反射率の最小値の反射スペクトルの変化が20nm未満であることが好ましい。
本実施形態による物品は、基材と、その少なくとも一方の表面に設けられた微細凹凸構造層を含む。この微細凹凸構造層は、活性エネルギー線硬化性樹脂組成物の硬化物からなる。この活性エネルギー線硬化性樹脂組成物は、炭素数6~22の直鎖もしくは分岐鎖のアルキル基またはアルケニル基と、炭素数2~4のオキシアルキレン基と、(メタ)アクリロイル基を有する(メタ)アクリレート(A)を含む重合性成分(Z2)と、光重合開始剤(D)を含む。
本実施形態による物品は、透明基板等の光透過性基材と、その少なくとも一方の表面に設けられた微細凹凸構造層を含む。この微細凹凸構造層は、活性エネルギー線硬化性樹脂組成物の硬化物からなる。この活性エネルギー線硬化性樹脂組成物は、重合性成分(Z3)と光重合開始剤(D)を含み、重合性成分(Z3)として、重合性官能基を有する酸化防止剤(F)を含む。
(活性エネルギー線硬化性樹脂組成物)
本発明の実施形態における活性エネルギー線硬化性樹脂組成物とは、活性エネルギー線を照射することで、重合反応が進行し、硬化する樹脂組成物である。この活性エネルギー線硬化性樹脂組成物は、重合性成分(Z1)と、光重合開始剤(D)と、添加剤(E)とを含む。
重合性成分(Z1)は、分子中にラジカル重合性結合および/またはカチオン重合性結合を有するモノマー、オリゴマー、反応性ポリマー等が挙げられる。活性エネルギー線硬化性樹脂組成物において、重合性成分(Z1)の含有比率は、所望の樹脂硬化層(微細凹凸構造層)を得る点から、80質量%以上が好ましく、90質量%以上がより好ましく、95質量%以上がさらに好ましい。
第1の実施形態並びに後述の第2及び第3の実施形態における光重合開始剤(D)は、活性エネルギー線を照射することで開裂し、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しては、装置コストや生産性の点から、紫外線が好ましい。
本発明の実施形態による物品の微細凹凸構造層は、添加剤(E)を5mg/m2以下、または5μL/m2以下含む。そのためには、この微細凹凸構造層を構成する活性エネルギー線硬化性樹脂組成物が添加剤(E)を5mg/m2以下、または5μL/m2以下含むことが好ましい。添加剤(E)は、重合性官能基を有さず、重合性成分(Z1)との共重合性を有さない非重合性化合物であることが好ましく、この比重合成化合物は不揮発性化合物であることが好ましい。また、添加剤(E)には溶剤などの容易に揮発して消失する揮発性成分は含まないことが好ましい。
(HO)3-n(O=)P[-O-(R2O)m-R1]n (1)
(R1は、アルキル基であり、R2は、アルキレン基であり、mは1~20の整数であり、nは1~3の整数である。)
式中、R1としては、炭素数1~20のアルキル基が好ましく、炭素数3~18のアルキル基がより好ましい。R2としては、炭素数1~4のアルキレン基が好ましく、炭素数2~3のアルキレン基がより好ましい。mは、1~10の整数が好ましい。式(1)で示される(ポリ)オキシアルキレンアルキルリン酸化合物は、モノエステル体(n=1)、ジエステル体(n=2)、トリエステル体(n=3)のいずれであってもよい。また、ジエステル体またはトリエステル体の場合、1分子中の複数の(ポリ)オキシアルキレンアルキル基はそれぞれ異なっていてもよい。
本実施形態における活性エネルギー線硬化性樹脂組成物は、必要に応じて、本発明の効果を阻害しない範囲において、ラジカル重合性の官能基を有さないオリゴマーやポリマー、微量の有機溶媒等を含んでいてもよい。
(活性エネルギー線硬化性樹脂組成物)
本実施形態に用いられる活性エネルギー線硬化性樹脂組成物は、活性エネルギー線を照射することで、この組成物に含まれるモノマー(重合性成分)の重合反応が進行し、硬化することができるものであり、重合性成分(Z2)と、光重合開始剤(D)を必須成分として含む。
重合性成分(Z2)は、上記の(メタ)アクリレート(A)を必須成分とし、必要に応じて他の(メタ)アクリレート(B)、及び他の重合性成分(C)((メタ)アクリレート(A)、(メタ)アクリレート(B)を除く。)を含むことができる。
(メタ)アクリレート(A)は、炭素数6~22の直鎖もしくは分岐鎖のアルキル基またはアルケニル基と、炭素数2~4のオキシアルキレン基と、(メタ)アクリロイル基を有する化合物である。一分子中に(メタ)アクリロイル基を2個以上含んでいてもよい。(メタ)アクリレート(A)の合成の容易さ等の観点から、一分子中に(メタ)アクリロイル基を1個含むことが好ましい。
(メタ)アクリレート(B)は、オキシエチレン基と2個以上の(メタ)アクリロイル基を有する化合物である。
新中村化学工業社製の製品名:NKシリーズのA-200、A-400、A-600、A-1000、A-TMPT-3EO、A-TMPT-9EO、AT-20E、A-GLY-3E、A-GLY-9E、A-GLY-20E、ATM-4E、ATM-35E、
第一工業製薬社製の製品名:ニューフロンティアシリーズのPE-200、PE-300、PE-600、DPHA-12EO、
サートマー社製の製品名:SR230、SR259、SR268、SR272、SR344、SR349、SR560、SR561、SR562、SR580、SR581、SR601、SR602、SR610、CD9038、SR101、SR150、SR205、SR209、SR210、SR231、SR252、SR348、SR480、SR540、SR541、SR542、CD542、SR603、SR740、SR9036、SR415、SR454、SR499、SR502、SR9035、SR494、
日本化薬社製の製品名:KAYARADシリーズのPEG400DA、R-551、R-712、THE-330、RP-1040、DPEA-12、等が挙げられる。
その他の重合性成分(C)は、活性エネルギー線硬化性樹脂組成物の粘度調整や密着性向上、活性エネルギー線硬化性樹脂組成物の硬化物の硬さや親水疎水バランスの調整、微細凹凸構造表面への帯電防止性能付与などの目的で添加することができる。
第一工業製薬社製の製品名:ニューフロンティア PET-3、
日本化薬製の製品名:KAYARADシリーズのTMPTA、PET-30、T-1420(T)、DPHA、D-310、DCPA-20、DPCA-30、DPCA-60、
サートマー社製の製品名:SR351S、SR368、SR444、SR350、SR295、SR355、SR399、
根上工業社製の製品名:UN-904、UN-906、H-219、UN-3320HS、UN-3320HA、UN-3320HB、UN-3320HC、
共栄社化学社製の製品名:UA-306H、UA-306T、UA-306I、UA-510H、等が挙げられる。このような成分としては、ペンタエリスリトール(メタ)アクリレート、ジペンタエリスリトール(メタ)アクリレート等の多官能(メタ)アクリレートをより好適に用いることができる。
興人社製の製品名:DMAA、ACMO、NIPAM、DEAA、HEAA、VOZO、DMAPAA、DMAEA、
大阪有機化学工業社製の製品名:HEA、HPA、4-HBA、TBA、NOAA、IOAA、INAA、LA、STA、ISTA、IBXA、V#155、V#160、V#192、V#150、2-MTA、V#190、V#230、V#260、V#310P、V#335HP、V#150D、V#190D、V#230D、V#3F、V#3FM、V#4F、V#8F、V#8FM、V#13F、MEDOL-10、MEDOL-10、1-AdA、1-AdMA、GBLA、GBLMA、
東亞合成株式会社製の製品名:アロニックスシリーズのMT-1000、M-101A、M-102、M-111、M-113、M-117、M-220、M-225、M-270、M-140、M-145、等が挙げられる。
住友化学工業社製の製品名:スミライザーGM、スミライザーGS、
ADEKA社製の製品名:アデカスタブシリーズのLA-82、LA-87、
大塚化学社製の製品名:RUVA-93、等が挙げられる。
大阪有機化学工業社製の製品名:DMAMC、GLBT、
第一工業製薬社製の製品名:ニューフロンティア R-1220、
興人社製の製品名:DMAPAA-TSMQ、等が挙げられる。
ビックケミー社製の製品名:BYK-UV3530、BYK-UV3570、BYK-UV3500、
エボニック社製の製品名:TEGO Radシリーズの2010、2011、2100、2200N、2250、2300、2500、2600、2650、2700、等が挙げられる。
光重合開始剤(D)は、第1の実施形態において既に説明した通りの化合物である。活性エネルギー線としては、装置コストや生産性の点から、紫外線が好ましい。紫外線によってラジカルを発生する光重合開始剤(D)としては、第1の実施形態における光重合開始剤(D)として例示した前述の化合物が挙げられる。
活性エネルギー線硬化性樹脂組成物は、添加剤(E)として、紫外線吸収剤および/または酸化防止剤をさらに含んでもよい。
本実施形態における活性エネルギー線硬化性樹脂組成物は、必要に応じて、添加剤(E)として、界面活性剤、離型剤、滑剤、可塑剤、帯電防止剤、光安定剤、難燃剤、難燃助剤、重合禁止剤、充填剤、シランカップリング剤、着色剤、強化剤、無機フィラー、耐衝撃性改質剤、レベリング剤、ラジカル補足剤等の公知の添加剤を含んでいてもよい。添加剤(E)は、重合性官能基を有さず(重合性成分(Z2)に含まれず)、重合性成分(Z2)との共重合性を有さない非重合性化合物であることが好ましく、この非重合性化合物は不揮発性化合物であることが好ましい。また、添加剤(E)には溶剤などの容易に揮発して消失する揮発性成分は含まないことが好ましい。添加剤(E)の添加量は、活性エネルギー線硬化性樹脂組成物の硬化物を含む微細凹凸構造層における単位面積当たりの含有量で規定することができる。この含有量を制御することにより、添加剤(E)のブリードアウトによる物品の光学性能の変化を抑えることができる。特に微細凹凸構造が隣り合う凸部同士の平均間隔が可視光波長以下であるような場合、特にブリードアウト量を少なくすることが重要になる。添加剤(E)の含有量は、微細凹凸構造層において、5mg/m2以下、または5μL/m2以下であることが好ましい。この範囲より多くの添加剤(E)が含まれる場合、添加剤(E)のブリードアウトによる光学性能の変化を十分に防ぐことが困難になる。添加剤(E)の添加効果を十分に得る点から、この含有量は0.2mg/m2以上または0.2μL/m2以上が好ましい。
(活性エネルギー線硬化性樹脂組成物)
本実施形態による活性エネルギー線硬化性樹脂組成物とは、活性エネルギー線を照射することで、この組成物に含まれる重合性成分の重合反応が進行し、硬化することができる樹脂組成物である。この活性エネルギー線硬化性樹脂組成物は、重合性成分(Z3)と、光重合開始剤(D)とを必須成分とするものであり、重合性成分(Z3)として、さらに重合性官能基を有する酸化防止剤(F)を含む。
重合性成分(Z3)は、分子中にラジカル重合性結合および/またはカチオン重合性結合を有するモノマー、オリゴマー、反応性ポリマー等が挙げられる。活性エネルギー線硬化性樹脂組成物において、重合性成分(Z3)の含有比率は、所望の樹脂硬化層(微細凹凸構造層)を得る点から、80質量%以上が好ましく、90質量%以上がより好ましく、95質量%以上がさらに好ましい。
酸化防止剤(F)は重合性官能基を有し、重合性成分(Z3)に含まれる。酸化防止剤(F)は、重合性官能基として分子中にラジカル重合性結合および/またはカチオン重合性結合を有するものが挙げられる。酸化防止剤(F)が有する重合性官能基としては、(メタ)アクリロイル基が好ましい。
光重合開始剤(D)は、第1の実施形態において既に説明した通りの化合物である。活性エネルギー線としては、装置コストや生産性の点から、紫外線が好ましい。紫外線によってラジカルを発生する光重合開始剤(D)としては、第1の実施形態における光重合開始剤(D)として例示した前述の化合物が挙げられる。
本発明の実施形態による活性エネルギー線硬化性樹脂組成物は、添加剤(E)をさらに含んでも良い。添加剤(E)は、重合性官能基を有さず(重合性成分(Z3)に含まれず)、重合性成分(Z3)との共重合性を有さない非重合性化合物であることが好ましく、この非重合性化合物は不揮発性化合物であることが好ましい。また、添加剤(E)には溶剤などの容易に揮発して消失する揮発性成分は含まないことが好ましい。
本実施形態における活性エネルギー線硬化性樹脂組成物は、必要に応じて、本発明の効果を阻害しない範囲において、ラジカル重合性の官能基を有さないオリゴマーやポリマー、微量の有機溶媒等を含んでいてもよい。
活性エネルギー線硬化性樹脂組成物は、そのアクリル当量を調整することで硬化物の硬さを適切な範囲に調整できる。
活性エネルギー線硬化性樹脂組成物の粘度は、スタンパの表面の微細凹凸構造への流れ込みやすさの点から、高すぎないことが好ましい。よって、活性エネルギー線硬化性樹脂組成物の、25℃における回転式B型粘度計での粘度は、10000mPa・s以下が好ましく、5000mPa・s以下がより好ましく、2000mPa・s以下がさらに好ましい。
上述の第1、第2及び第3の実施形態における活性エネルギー線硬化性樹脂組成物を用いて、微細凹凸構造を有する物品を形成することができる。
スタンパは、微細凹凸構造の反転構造を表面に有するものである。スタンパの材料としては、金属(表面に酸化皮膜が形成されたものを含む。)、石英、ガラス、樹脂、セラミックス等が挙げられる。スタンパの形状としては、ロール状、円管状、平板状、シート状等が挙げられる。
(I-1)アルミニウム基材の表面に、複数の細孔(凹部)を有する陽極酸化アルミナを形成する方法。
(I-2)スタンパ基材の表面に、電子ビームリソグラフィ法、レーザ光干渉法等によって微細凹凸構造の反転構造を形成する方法。
(a)アルミニウム基材を電解液中、定電圧下で陽極酸化してアルミニウム基材の表面に酸化皮膜を形成する工程。
(b)酸化皮膜を除去し、アルミニウム基材の表面に陽極酸化の細孔発生点を形成する工程。
(c)工程(b)の後、アルミニウム基材を電解液中、再度陽極酸化し、細孔発生点に細孔を有する酸化皮膜を形成する工程。
(d)工程(c)の後、細孔の径を拡大させる工程。
(e)工程(d)の後、電解液中、再度陽極酸化する工程。
(f)工程(d)と工程(e)を繰り返し行い、複数の細孔を有する陽極酸化アルミナがアルミニウム基材の表面に形成されたスタンパを得る工程。
微細凹凸構造を表面に有する物品は、例えば、図3に示す製造装置を用いて、下記のようにして製造することができる。
本発明の実施形態による微細凹凸構造を表面に有する物品は、反射防止物品(反射防止フィルム、反射防止膜等)、光導波路、レリーフホログラム、レンズ、偏光分離素子等の光学物品、細胞培養シートとしての用途展開が期待でき、特に反射防止物品としての用途に適している。本発明の実施形態による微細凹凸構造を表面に有する物品は、光透過性物品であってもよい。
微細凹凸構造を転写したサンプルを黒色アクリル板(三菱レイヨン社製、商品名:アクリライト)に貼り付け後、室温23℃、湿度50%の環境下で7日間保管した後に反射スペクトルを測定した。反射スペクトルは分光光度計(島津製作所社製、製品名:UV-2450)を使用して5°正反射率のスペクトルを380nm~780nmの範囲で計測した。反射スペクトルの測定後に微細凹凸表面の一部をエタノールで拭いた後、再度反射スペクトルを測定して反射スペクトルの変化を確認した。反射スペクトルの変化は各3点ずつ測定し、可視光領域(380nm~780nm)での反射率のボトム(最小値)が前後で平均20nm以上変化した場合は、スペクトルの変化があると判断した。エタノールで拭いた部分の反射率のボトムがおよそ20nm以上変化すると、拭いた部分と拭いていない部分の境界が目視で確認できる程度となる。評価の指標は以下の通りとした。
×:エタノールで拭く前後で反射スペクトルの変化がある。
微細凹凸構造層(硬化樹脂層)の厚さは、微細凹凸構造を転写した後の積層体(物品)の厚さから光透過性基材の厚さを除くことで算出した。積層体及び光透過性基材の厚さは、デジマチック標準外側マイクロメータ(ミツトヨ社製)を使用して測定した。
添加剤(E)の含有量は、活性エネルギー線樹脂組成物中の添加剤(E)の含有量と活性エネルギー線硬化性樹脂組成物の硬化物からなる層(硬化樹脂層)の膜厚から算出した。
磨耗試験機(新東科学社製、製品名:HEiDON TRIBOGEAR TYPE-30S)を用い、物品の表面に置かれた2cm×2cmにカットしたスチールウール(日本スチールウール社製、製品名:ボンスター#0000)に400g(100gf/cm2(0.98N/cm2))および1kg(250gf/cm2(2.45N/cm2))の荷重をかけ、往復距離:30mm、ヘッドスピード:平均100mm/秒にて10回往復させ、物品の表面の外観を評価した。外観評価に際しては、2.0mm厚の黒色アクリル板(三菱レイヨン社製、製品名:アクリライト)の片面に物品を貼り付け、屋内で蛍光灯にかざして目視で評価した。以下に従って耐擦傷性を判定した。
A:確認できる傷が10本未満、
B:確認できる傷が10本以上30本未満、
C:確認できる傷が30本以上、
D:擦傷部分の50%以上の面積で反射防止性能が失われる。
水道水を1.0cc(1mL)染込ませたワイパー(大王製紙社製、製品名:エリエールプロワイプ)を用い、表面に指紋が付着した物品の表面を一方向に拭き取った後、物品の表面の外観を評価した。以下に従って指紋拭き取り性を判定した。
△:3回以上10回以下のふき取りで指紋が完全に除去できる、
×:10回ふき取り後でも、指紋が残る。
硬化性液(活性エネルギー線硬化性樹脂組成物)の外観が透明かどうかを目視で判断した。実施例および比較例に関しては、硬化性液が完全に透明な場合は硬化物も透明であった。また、硬化性液に白濁があった場合は、その硬化物にも白濁が確認された。
×:白濁有り。
耐久試験は次のようにして行った。微細凹凸構造を転写したサンプルを黒色アクリル板(三菱レイヨン社製、商品名:アクリライト)に貼り付けた後、気温60℃、湿度90%の環境下で500時間保持した。評価の指標は、突起形状維持に関しては電子顕微鏡で微細凹凸表面形状を観察し、突起の合一が無い場合に○、ある場合は×とした。また、ブリードアウトの有無については、エタノール拭き前後での反射スペクトル変化が無い場合に○、ある場合は×とした。反射スペクトルは分光光度計(島津製作所社製、製品名:UV-2450)を使用して5°正反射率のスペクトルを380nm~780nmの範囲で計測した。反射スペクトルの測定後に微細凹凸表面の一部をエタノールで拭いた後、再度反射スペクトルを測定して反射スペクトルの変化を確認した。反射スペクトルの変化は各3点ずつ測定し、可視光領域(380nm~780nm)での反射率のボトム(最小値)が前後で平均20nm以上変化した場合は、スペクトルの変化があると判断した。エタノールで拭いた部分の反射率のボトムがおよそ20nm以上変化すると、拭いた部分と拭いていない部分の境界が目視で確認できる程度となる。エタノール拭きは、エタノール約1mLをベンコット(旭化成せんい社製、商品名:M-3II)に染込ませて5往復させた。
純度99.99質量%、電解研磨した厚さ2mmのφ65mmアルミニウム円盤をアルミニウム基材として用いた。
スタンパ(モールド)から硬化後のサンプルを離型する際に、スタンパを被着体、硬化樹脂と基材を粘着テープに見立てて、JISZ0237に準拠する90°剥離試験を行い、スタンパからの離型時の剥離力を測定した。
スタンパの微細凹凸構造が形成された側に10μLの活性エネルギー線硬化性樹脂組成物を滴下し、厚さ80μmのトリアセチルセルロースフィルム(富士フイルム社製、製品名:TD80ULM)で押し広げながら被覆した後、フィルム側から高圧水銀灯を用いて1000mJ/cm2のエネルギーで紫外線を照射して硬化させた。フィルムからスタンパを離型して、微細凹凸構造をフィルム表面に有する物品を得た。
実施例および比較例で用いた活性エネルギー線硬化性樹脂組成物に含まれる重合成分(Z)、光重合開始剤(D)、添加剤(E)は、下記の表1A、表1B及び表1Cの通りである。なお、表中の「PEG」はポリエチレングリコールを意味し、「EO」はエチレンオキサイドを意味する。なお、その他の表(表2A、表2B~表4B、表2C)中の重合性成分(Z1、Z2又はZ3)の数値は、重合性成分(Z1、Z2又はZ3)の全体に占める質量比率(質量%)であり、光重合開始剤(D)、添加剤(E)(離型剤、重合禁止剤、酸化防止剤)の数値は、重合性成分(Z1、Z2又はZ3)に対する質量比率(質量%)である。
重合成分(Z1)として、NKエステル A-TMM-3LM-N(新中村化学工業社製、製品名)を20質量%、NKエステル ATM-35E(新中村化学工業社製、製品名)を80質量%、重合性成分(Z1)100質量%に対して、光重合開始剤(D)として、Irgacure 184(BASF社製、製品名)を0.1質量%、Irgacure 819(BASF社製、製品名)を0.5質量%、離型剤(添加剤(E))として、NIKKOL TDP-2(日光ケミカルズ社製、製品名)を0.1質量%混合して活性エネルギー線硬化性樹脂組成物を調製した。重合禁止剤(添加剤(E))であるMEHQは、もとから重合成分(Z)に含まれていたものとしてその含有量は0.036質量%であった。
活性エネルギー線硬化性樹脂組成物の組成種、組成比(質量%)、硬化層(微細凹凸構造層)の厚みを表2Aに示す通りとした以外は、実施例A1と同様にして微細凹凸構造を表面に有する物品を得た。評価結果を表2Aに示す。
重合性成分(Z2)として、ブレンマーALE-200(日油製、製品名)を0.3質量%、NKエステル A-GLY-20E(新中村化学工業社製、製品名)を84.7質量%、ニューフロンティア PET-3(第一工業製薬社製、製品名)を15質量%、光重合開始剤(D)として、IRGACURE184(BASF社製、製品名)を1.0質量%、IRGACURE819(BASF社製、製品名)を0.5質量%、離型剤として、NIKKOL TDP-2(日光ケミカルズ社製、製品名)を0.01質量%混合して活性エネルギー線硬化性樹脂組成物を調製した。
活性エネルギー線硬化性樹脂組成物の重合性成分(Z)を表2B、表3B及び表4Bに示すものに変更した以外は、実施例1と同様にして微細凹凸構造を表面に有する物品を得た。評価結果を表2B、表3B及び表4Bに示す。表2B、表3B及び表4B中の重合性成分(A)、(B)、(C)に係る数値は、重合性成分(Z2)における各成分の含有量(質量%)を示す。
重合性成分(Z3)中、重合性成分(A)として、NKエステル A-TMM-3LM-N(新中村化学工業社製、製品名)を20質量%、NKエステル ATM-35E(新中村化学工業社製、製品名)を79質量%、酸化防止剤(F)としてADEKA STAB LA-82(ADEKA社製、製品名)を1質量%、光重合開始剤(D)として、Irgacure 184(BASF社製、製品名)を0.1質量%、Irgacure 819(BASF社製、製品名)を0.5質量%、離型剤(添加剤(E))として、NIKKOL TDP-2(日光ケミカルズ社製、製品名)を0.1質量%混合して活性エネルギー線硬化性樹脂組成物を調製した。重合禁止剤(添加剤(E))であるMEHQは、もとから重合性成分(Z)に含まれていたものとしてその含有量は0.036質量%であった。
活性エネルギー線硬化性樹脂組成物の組成比(質量%)、組成種を表2Cに示す通りとした以外は、実施例C1と同様にして微細凹凸構造を表面に有する物品を得た。評価結果を表2Cに示す。
12 細孔(微細凹凸構造の反転構造)
14 酸化被膜
16 細孔発生点
18 スタンパ
20 ロール状スタンパ
22 タンク
24 空気圧シリンダ
26 ニップロール
28 活性エネルギー線照射装置
30 剥離ロール
40 物品
42 基材
44 硬化樹脂層
46 凸部
Claims (24)
- 基材の少なくとも一方の表面に活性エネルギー線硬化性樹脂組成物の硬化物を含む微細凹凸構造層を備えた物品であって、
前記活性エネルギー線硬化性樹脂組成物が、重合性成分(Z1)と光重合開始剤(D)と添加剤(E)とを含み、
添加剤(E)は、非重合性であり、前記微細凹凸構造層における添加剤(E)の含有量が5mg/m2以下である、物品。 - 添加剤(E)の質量平均分子量が100~2000の範囲にある、請求項1に記載の物品。
- 前記微細凹凸構造層の表面をエタノールで拭く前後において、可視光領域における反射率の最小値の反射スペクトルの変化が20nm未満である、請求項1又は2に記載の物品。
- 前記添加剤(E)は、酸化防止剤、重合禁止剤、紫外線吸収剤、光安定剤、消泡剤、離型剤、滑剤、レベリング剤、界面活性剤、着色剤、蛍光剤、発光剤、帯電防止剤からなる群から選ばれる少なくとも一種からなる、請求項1から3のいずれか一項に記載の物品。
- 前記添加剤(E)は、重合禁止剤と離型剤の少なくとも一方を含む、請求項4に記載の物品。
- 前記重合禁止剤は、ヒドロキノン系重合禁止剤とフェノール系重合禁止剤の少なくとも一方を含む、請求項4又は5に記載の物品。
- 前記離型剤は、(ポリ)オキシアルキレンアルキルリン酸化合物を含む、請求項4から6のいずれか一項に記載の物品。
- 前記重合性成分(Z1)は、炭素数6~22の直鎖もしくは分岐鎖のアルキル基またはアルケニル基と、炭素数2~4のオキシアルキレン基と、(メタ)アクリロイル基を有する(メタ)アクリレート(A)を含む、請求項1から7のいずれか一項に記載の物品。
- 前記重合性成分(Z1)は、重合性官能基を有する酸化防止剤(F)を含む、請求項1から8のいずれか一項に記載の物品。
- 基材の少なくとも一方の表面に活性エネルギー線硬化性樹脂組成物の硬化物を含む微細凹凸構造層を備える物品であって、
前記活性エネルギー線硬化性樹脂組成物が、炭素数6~22の直鎖もしくは分岐鎖のアルキル基またはアルケニル基と、炭素数2~4のオキシアルキレン基と、(メタ)アクリロイル基を有する(メタ)アクリレート(A)を含む重合性成分(Z2)と、光重合開始剤(D)を含む、物品。 - 前記(メタ)アクリレート(A)は、前記アルキル基またはアルケニル基と、前記オキシアルキレン基が結合した構造を有する、請求項10に記載の物品。
- 前記重合性成分(Z2)における前記(メタ)アクリレート(A)の含有量は0.1~10質量%の範囲にある、請求項10又は11に記載の物品。
- 基材の少なくとも一方の表面に活性エネルギー線硬化性樹脂組成物の硬化物を含む微細凹凸構造層を備えた物品であって、
前記活性エネルギー線硬化性樹脂組成物が、重合性成分(Z3)と光重合開始剤(D)を含み、
前記重合性成分(Z3)が、重合性官能基を有する酸化防止剤(F)を含む、物品。 - 前記酸化防止剤(F)は、前記重合性官能基として(メタ)アクリロイル基を有する、請求項9又は13に記載の物品。
- 前記酸化防止剤(F)は、ラジカル補足能を有する、請求項9、13又は14に記載の物品。
- 前記酸化防止剤(F)は、フェノール系酸化防止剤およびヒンダードアミン系酸化防止剤の少なくとも一方を含む、請求項9及び13から15のいずれか一項に記載の物品。
- 前記酸化防止剤(F)は、同一分子内に(メタ)アクリロイル基を有する化合物であって、該化合物は、ヒンダードアミン化合物、または芳香族環にヒドロキシル基を置換基として有する化合物である、請求項9及び13から16のいずれか一項に記載の物品。
- 前記重合性成分(Z3)との共重合性を有さない非重合性化合物を添加剤(E)として含む、請求項13から17のいずれか一項に記載の物品。
- 前記重合性成分は、重合性成分全体に対してオキシエチレン基を30~70質量%含む、請求項1から17のいずれか一項に記載の物品。
- 前記重合性成分は、オキシエチレン基と2個以上の(メタ)アクリロイル基を有する(メタ)アクリレート(B)を含む、請求項1から19のいずれか一項に記載の物品。
- 前記重合性成分は、2個以上の(メタ)アクリロイル基を有するペンタエリスリトール(メタ)アクリレート又はジペンタエリスリトール(メタ)アクリレートを含む、請求項1から20のいずれか一項に記載の物品。
- 前記微細凹凸構造層の厚みが1~50μmの範囲にある、請求項1から21のいずれか一項に記載の物品。
- 前記微細凹凸構造層の隣り合う凸部同士の平均間隔が可視光波長以下である、請求項1から22のいずれか一項に記載の物品。
- 請求項1から23のいずれか一項に記載の物品からなる反射防止物品。
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017169838A1 (ja) * | 2016-03-30 | 2017-10-05 | Dic株式会社 | 光学物品用活性エネルギー線硬化型樹脂組成物、硬化物及び光学シート |
WO2018154843A1 (ja) * | 2017-02-24 | 2018-08-30 | シャープ株式会社 | 加飾フィルム |
CN109571836A (zh) * | 2017-09-29 | 2019-04-05 | 夏普株式会社 | 防污膜的制造方法 |
JP2019109502A (ja) * | 2017-12-19 | 2019-07-04 | キヤノン株式会社 | 光学素子、その製造方法、撮像装置、および光学機器 |
WO2019168117A1 (ja) * | 2018-03-01 | 2019-09-06 | Jnc株式会社 | 親水化されたポリフッ化ビニリデン系微多孔膜 |
JPWO2018139418A1 (ja) * | 2017-01-30 | 2019-12-19 | シャープ株式会社 | 防汚性フィルム |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0542386B2 (ja) | 1984-09-07 | 1993-06-28 | Kobe Steel Ltd | |
JP2000071290A (ja) | 1998-08-28 | 2000-03-07 | Teijin Ltd | 反射防止物品の製造方法 |
JP2007084625A (ja) | 2005-09-20 | 2007-04-05 | Hitachi Chem Co Ltd | 光硬化性樹脂組成物及びこれを用いたパターン形成方法 |
JP2008088299A (ja) * | 2006-10-02 | 2008-04-17 | Mitsubishi Rayon Co Ltd | 樹脂組成物、硬化物の製造方法及び積層体。 |
JP4156415B2 (ja) | 2003-03-20 | 2008-09-24 | 大日本印刷株式会社 | 賦型方法、賦型フィルム、及び射出成形品 |
JP2010077367A (ja) * | 2008-09-29 | 2010-04-08 | Fujifilm Corp | インク組成物、及び、インクジェット記録方法 |
WO2011049186A1 (ja) * | 2009-10-20 | 2011-04-28 | 帝人化成株式会社 | 高品位な意匠面を有する湾曲部材の製造方法および該方法から製造された部材 |
JP4689718B2 (ja) | 2007-02-09 | 2011-05-25 | 三菱レイヨン株式会社 | 透明成形体およびこれを用いた反射防止物品 |
JP2011246517A (ja) * | 2010-05-24 | 2011-12-08 | Mitsubishi Rayon Co Ltd | 活性エネルギー線硬化型樹脂組成物、凹凸形状物品及び光記録媒体 |
JP2011256307A (ja) * | 2010-06-10 | 2011-12-22 | Mitsubishi Rayon Co Ltd | 注型用活性エネルギー線硬化性樹脂組成物および光学部品 |
JP5042386B2 (ja) * | 2005-10-04 | 2012-10-03 | 株式会社Dnpファインケミカル | 特定の表面形状と物性を有する構造体及びその構造体形成用の(メタ)アクリル系重合性組成物 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050148676A1 (en) * | 2002-03-18 | 2005-07-07 | Yasuhiro Doi | Resin composition and optical element |
JP2006259150A (ja) * | 2005-03-16 | 2006-09-28 | Tamura Kaken Co Ltd | 感光性樹脂組成物およびプリント配線板 |
US7258437B2 (en) * | 2005-09-07 | 2007-08-21 | Transitions Optical, Inc. | Photochromic multifocal optical article |
JP5792425B2 (ja) * | 2009-09-28 | 2015-10-14 | 大日本印刷株式会社 | 反射防止フィルム製造用組成物、反射防止フィルム、反射防止フィルムの製造方法、偏光板、および液晶表示装置 |
US20130004718A1 (en) * | 2010-03-17 | 2013-01-03 | Tsuyoshi Takihara | Active energy ray curable resin composition and article having fine concave-convex structure on surface |
CN103649142B (zh) * | 2011-07-05 | 2015-09-09 | 三菱丽阳株式会社 | 表面具有微细凹凸结构的物品和具备该物品的影像显示装置 |
TWI474917B (zh) * | 2012-06-15 | 2015-03-01 | Mitsubishi Rayon Co | 物品、活性能量線硬化性樹脂組成物、光透射性物品活性能量線硬化性樹脂組成物以及抗反射物品 |
-
2014
- 2014-03-31 JP JP2014517062A patent/JP6394389B2/ja active Active
- 2014-03-31 CN CN201480016777.5A patent/CN105377543B/zh active Active
- 2014-03-31 US US14/780,082 patent/US20160054478A1/en not_active Abandoned
- 2014-03-31 WO PCT/JP2014/059450 patent/WO2014157718A1/ja active Application Filing
- 2014-03-31 KR KR1020157025271A patent/KR101805278B1/ko active IP Right Grant
- 2014-03-31 TW TW103111932A patent/TWI623427B/zh active
- 2014-03-31 EP EP14775087.1A patent/EP2979854A4/en not_active Withdrawn
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0542386B2 (ja) | 1984-09-07 | 1993-06-28 | Kobe Steel Ltd | |
JP2000071290A (ja) | 1998-08-28 | 2000-03-07 | Teijin Ltd | 反射防止物品の製造方法 |
JP4156415B2 (ja) | 2003-03-20 | 2008-09-24 | 大日本印刷株式会社 | 賦型方法、賦型フィルム、及び射出成形品 |
JP2007084625A (ja) | 2005-09-20 | 2007-04-05 | Hitachi Chem Co Ltd | 光硬化性樹脂組成物及びこれを用いたパターン形成方法 |
JP5042386B2 (ja) * | 2005-10-04 | 2012-10-03 | 株式会社Dnpファインケミカル | 特定の表面形状と物性を有する構造体及びその構造体形成用の(メタ)アクリル系重合性組成物 |
JP2008088299A (ja) * | 2006-10-02 | 2008-04-17 | Mitsubishi Rayon Co Ltd | 樹脂組成物、硬化物の製造方法及び積層体。 |
JP4689718B2 (ja) | 2007-02-09 | 2011-05-25 | 三菱レイヨン株式会社 | 透明成形体およびこれを用いた反射防止物品 |
JP2010077367A (ja) * | 2008-09-29 | 2010-04-08 | Fujifilm Corp | インク組成物、及び、インクジェット記録方法 |
WO2011049186A1 (ja) * | 2009-10-20 | 2011-04-28 | 帝人化成株式会社 | 高品位な意匠面を有する湾曲部材の製造方法および該方法から製造された部材 |
JP2011246517A (ja) * | 2010-05-24 | 2011-12-08 | Mitsubishi Rayon Co Ltd | 活性エネルギー線硬化型樹脂組成物、凹凸形状物品及び光記録媒体 |
JP2011256307A (ja) * | 2010-06-10 | 2011-12-22 | Mitsubishi Rayon Co Ltd | 注型用活性エネルギー線硬化性樹脂組成物および光学部品 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2979854A4 |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017169838A1 (ja) * | 2016-03-30 | 2017-10-05 | Dic株式会社 | 光学物品用活性エネルギー線硬化型樹脂組成物、硬化物及び光学シート |
JPWO2017169838A1 (ja) * | 2016-03-30 | 2018-06-28 | Dic株式会社 | 光学物品用活性エネルギー線硬化型樹脂組成物、硬化物及び光学シート |
JPWO2018139418A1 (ja) * | 2017-01-30 | 2019-12-19 | シャープ株式会社 | 防汚性フィルム |
WO2018154843A1 (ja) * | 2017-02-24 | 2018-08-30 | シャープ株式会社 | 加飾フィルム |
JPWO2018154843A1 (ja) * | 2017-02-24 | 2019-12-12 | シャープ株式会社 | 加飾フィルム |
CN109571836A (zh) * | 2017-09-29 | 2019-04-05 | 夏普株式会社 | 防污膜的制造方法 |
JP2019109502A (ja) * | 2017-12-19 | 2019-07-04 | キヤノン株式会社 | 光学素子、その製造方法、撮像装置、および光学機器 |
JP7378924B2 (ja) | 2017-12-19 | 2023-11-14 | キヤノン株式会社 | 光学素子、その製造方法、撮像装置、および光学機器 |
WO2019168117A1 (ja) * | 2018-03-01 | 2019-09-06 | Jnc株式会社 | 親水化されたポリフッ化ビニリデン系微多孔膜 |
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KR101805278B1 (ko) | 2017-12-05 |
TW201446516A (zh) | 2014-12-16 |
EP2979854A4 (en) | 2016-04-06 |
US20160054478A1 (en) | 2016-02-25 |
KR20150119322A (ko) | 2015-10-23 |
TWI623427B (zh) | 2018-05-11 |
CN105377543A (zh) | 2016-03-02 |
CN105377543B (zh) | 2017-08-01 |
JP6394389B2 (ja) | 2018-09-26 |
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