JP6686284B2 - Article containing cured product of active energy ray curable resin composition - Google Patents

Description

  The present invention relates to an active energy ray-curable resin composition suitable for forming a fine unevenness (nano unevenness) structure, a raw material for imprinting containing the active energy ray-curable resin composition, and the active energy ray-curable resin composition. The present invention relates to an article having a fine concavo-convex structure formed by using a product.

  It is known that a fine concavo-convex structure body in which nano-sized fine concavities and convexities are regularly arranged on the surface exhibits antireflection performance due to continuous change in refractive index. Such a fine concavo-convex structure is generally called a moth-eye structure. It is also known that this fine concavo-convex structure exhibits the same effect as the super water-repellent performance (lotus effect) exhibited by the lotus leaf having the fine concavo-convex structure.

As a method for producing an article having a fine uneven structure on its surface, for example, the following method has been proposed:
(I) A method of transferring a fine concavo-convex structure to the surface of a thermoplastic resin molded body by injection-molding or press-molding a thermoplastic resin using a stamper having a reverse structure of the fine concavo-convex structure on its surface;
(Ii) An active energy ray-curable resin composition is filled between a stamper having an inverted structure of a fine concavo-convex structure on the surface and a transparent substrate, and the active energy ray is irradiated to cure the resin composition, and then the stamper is peeled off. And (iii) filling the active energy ray-curable resin composition between the stamper and the transparent substrate, and then peeling off the stamper to obtain the active energy ray. A method of transferring a fine concavo-convex structure to a curable resin composition and then curing the active energy ray-curable resin composition by irradiation with active energy rays.

  Among these, the method (ii) is preferable in consideration of the transferability of the fine concavo-convex structure and the degree of freedom of the surface composition. This method is particularly suitable when using a belt-shaped or roll-shaped stamper capable of continuous production, and is a method having excellent productivity.

  The fine concavo-convex structure exhibits good antireflection performance when the adjacent convex portions or concave portions of the fine concavo-convex structure have an interval of not more than the wavelength of visible light. However, the fine concavo-convex structure having such a structure is inferior in scratch resistance as compared with a molded body having a smooth surface and subjected to abrasion resistance treatment such as a hard coat, and has a problem in durability during use. . Further, if the cured product of the resin composition used for producing the fine concavo-convex structure is not sufficiently robust, a phenomenon in which the protrusions tend to snuggle together during mold release and heat is likely to occur.

  Therefore, in order to obtain a fine concavo-convex structure having high durability and strength, a fine concavo-convex structure body in which a fine concavo-convex structure is formed by transferring a reversal fine concavo-convex structure of a stamper when the resin composition is cured by irradiation with an active energy ray, A resin composition for forming a fine concavo-convex structure has been proposed.

  For example, in Patent Document 1, the finely packed silica fine particles are used as a template to prepare a fine concavo-convex structure having convex (concave) intervals equal to or less than the wavelength of visible light, and a resin composition for forming the fine concavo-convex structure. As an example, an ultraviolet-curable resin composition containing a polyfunctional monomer having many double bonds per molecular weight such as trimethylolpropane tri (meth) acrylate is described.

  Further, Patent Document 2 discloses a film having a hard coat layer having fine irregularities, and it is preferable that the hard coat layer exhibits a hardness of “H” or more in a pencil hardness test according to JIS K5400, and As a resin forming the hard coat layer, an ultraviolet-curable resin composition containing a polyfunctional monomer having a large number of double bonds per molecular weight such as dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and pentaerythritol tetraacrylate is described. Has been done.

Further, the following resin compositions are known as preferable resin compositions for forming a fine concavo-convex structure:
(1) A photocurable resin composition containing an acrylate oligomer such as urethane acrylate and a release agent as essential components (Patent Document 3);
(2) Photocurable resin composition composed of (meth) acrylate such as ethoxylated bisphenol A di (meth) acrylate, reactive diluent such as N-vinylpyrrolidone, photopolymerization initiator and fluorine-based surfactant (Patent Document 4); and (3) a UV-curable resin composition containing a polyfunctional (meth) acrylate such as trimethylolpropane tri (meth) acrylate, a photopolymerization initiator, and a leveling agent such as a polyether-modified silicone oil ( Patent Document 1).

JP, 2000-71290, A JP, 2002-107501, A Japanese Patent No. 4156415 JP, 2007-84625, A

  However, the fine concavo-convex structures described in Patent Documents 1 and 2 are cured products having a high crosslink density and a high elastic modulus, but they do not necessarily satisfy the scratch resistance. Even in the case of a cured resin having a hardness of "H" or more in a pencil hardness test, especially in the case of a fine concavo-convex structure, fine projections may be bent or bent to impair the antireflection performance. The use is limited. Further, in these fine concavo-convex structures, the surface of the fine concavo-convex structure does not exhibit sufficient water repellency.

  On the other hand, there is known a method of using a silicone compound or a fluorine compound in order to impart water repellency to a resin molding. However, those that exhibit water repellency with a silicone compound or a fluorine compound are generally used as a general polyfunctional (meth) acrylate or urethane (meth) acrylate used in an active energy ray-curable resin composition. Its low compatibility makes it difficult to apply to hard coats that require transparency.

  The main object of the present invention is to provide an active energy ray-curable resin composition capable of forming a cured product having water repellency and high scratch resistance together with an antireflection function due to a fine concavo-convex structure, and an article formed using the same. To provide.

  As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that a fine uneven structure composed of a cured product of an active energy ray-curable resin composition containing a specific polymerizable component has high water repellency and high water repellency. They have found that they have scratch resistance and completed the present invention.

According to a preferred embodiment of the present invention, an active energy ray-curable resin composition containing a polymerizable component (P) and a photopolymerization initiator (E),
The polymerizable component (P) is based on 100% by mass of the total amount of the polymerizable component (P),
50-100% by mass of a polymerizable component (A), which is an alkanediol di (meth) acrylate prepared from an alkanediol having 6 or more carbon atoms,
A polymerizable component (B), which is at least one of silicone (meth) acrylate and alkyl (meth) acrylate, and a polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in the molecule. Including a certain polymerizable component (C) 0 to 50% by mass,
An active energy ray-curable resin composition in which the content of the photopolymerization initiator (E) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable component (P) is provided. .

According to another preferred embodiment of the present invention, an active energy ray-curable resin composition containing a polymerizable component (P) and a photopolymerization initiator (E),
The polymerizable component (P) is based on 100% by mass of the total amount of the polymerizable component (P),
1 to 100% by mass of a polymerizable component (A), which is an alkanediol di (meth) acrylate made from an alkanediol having 7 or more carbon atoms,
A polymerizable component (B), which is at least one of silicone (meth) acrylate and alkyl (meth) acrylate, and a polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in the molecule. Including a certain polymerizable component (C) 0 to 50% by mass,
An active energy ray-curable resin composition in which the content of the photopolymerization initiator (E) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable component (P) is provided. .

  According to another preferred embodiment of the present invention, there is provided a raw material for imprinting containing the above active energy ray-curable resin composition.

  According to another preferred embodiment of the present invention, an article containing a cured product of the above active energy ray-curable resin composition is provided.

  According to the embodiment of the present invention, an active energy ray-curable resin composition capable of forming a cured product having water repellency and high scratch resistance together with an antireflection function due to a fine concavo-convex structure, and an article formed using the same. Can be provided.

1 is a schematic cross-sectional view showing an article having a fine concavo-convex structure according to an embodiment of the present invention. FIG. 6 is a diagram showing a manufacturing process of a stamper used for forming a fine concavo-convex structure of an article according to the embodiment of the present invention. It is a block diagram which shows an example of the manufacturing apparatus of the article which has a fine concavo-convex structure by embodiment of this invention.

  The active energy ray-curable resin composition (X) according to the embodiment of the present invention contains a polymerizable component (P) and a photopolymerization initiator (E), and irradiation with active energy rays causes the polymerization reaction to proceed. It progresses and hardens.

  The polymerizable component (P) contains, as an essential component, the polymerizable component (A) which is an alkanediol di (meth) acrylate prepared from an alkanediol having 6 or more carbon atoms as a raw material, and further contains a silicone (meth), if necessary. A polymerizable component (B) which is an acrylate and / or an alkyl (meth) acrylate, a polymerizable component (C) which is a polyfunctional (meth) acrylate having three or more (meth) acryloyl groups in the molecule, and other The polymerizable component (D) can be included.

  Moreover, this active energy ray-curable resin composition may contain an internal mold release agent (F) and other components (G) as needed.

  When the surface of the cured product of the active energy ray-curable resin composition (X) has a fine uneven structure, it is important to adjust the composition of the polymerizable component (P) so that the cured product has an appropriate hardness. . If the cured product is too hard, the scratch resistance of the surface of the fine concavo-convex structure tends to be low. On the other hand, if the cured product is too soft, it becomes difficult to maintain the fine concavo-convex structure, and the plurality of convex portions may unite with each other.

When the polymerizable component (P) further contains the polymerizable component (B),
The content of the polymerizable component (A) is 50 to 99.5% by mass,
The content of the polymerizable component (B) is 0.5 to 50% by mass,
The content of the polymerizable component (C) is preferably 0 to 49.5 mass%.

When the polymerizable component (P) further contains the polymerizable component (C),
The content of the polymerizable component (A) is 50 to 90% by mass,
The content of the polymerizable component (B) is 0 to 40% by mass,
The content of the polymerizable component (C) is preferably 10 to 50% by mass,
The content of the polymerizable component (A) is 50 to 89.5% by mass,
The content of the polymerizable component (B) is 0.5 to 40% by mass,
The content of the polymerizable component (C) is more preferably 10 to 49.5 mass%.

  As the silicone (meth) acrylate of the polymerizable component (B), a non-oxyalkylenated silicone (meth) acrylate having no oxyalkylene skeleton is preferable.

  The silicone (meth) acrylate of the polymerizable component (B) is preferably a compound represented by the following formula (1).

  The alkyl (meth) acrylate of the polymerizable component (B) is preferably an alkyl (meth) acrylate having an alkyl group with 8 to 22 carbon atoms.

  The active energy ray-curable resin composition according to the embodiment of the present invention may include an internal release agent (F). As the internal mold release agent (F), a (poly) oxyalkylene alkyl phosphate compound is preferable.

  According to another embodiment of the present invention, it is possible to provide a raw material for imprint containing the above active energy ray-curable resin composition.

  According to another embodiment of the present invention, an article including a cured product of the above active energy ray-curable resin composition can be provided. A cured resin layer can be included as the cured product. Further, the surface of this cured product can have a fine concavo-convex structure composed of a plurality of convex portions. In this fine concavo-convex structure, it is preferable that the average interval between adjacent convex portions is 400 nm or less.

  The articles according to the embodiments of the present invention can be applied to display members, antireflection articles, and water repellent films.

  Hereinafter, preferred embodiments of the present invention will be further described.

[Polymerizable component (A)]
The polymerizable component (A) has effects of improving scratch resistance, weather resistance, and substrate adhesion with respect to the cured product of the active energy ray-curable resin composition according to the embodiment of the present invention. For example, regarding the substrate adhesion, it is effective for polycarbonate resin and acrylic resin. Further, it is possible to obtain the effects of improving the compatibility and lowering the viscosity of the active energy ray-curable resin composition.

  The polymerizable component (A) is an alkanediol di (meth) acrylate, and the raw material alkanediol has preferably 6 or more carbon atoms, more preferably 7 or more carbon atoms, further preferably 8 or more carbon atoms, and particularly preferably 9 or more carbon atoms. preferable. When the carbon number of the alkane part is too small, the cured product of the active energy ray-curable resin composition becomes too hard, and the fine uneven structure becomes brittle and easily scratched. On the other hand, when the number of carbon atoms in the alkane part is too large, the alkanediol di (meth) acrylate may have crystallinity and the handleability may be significantly reduced. Therefore, the carbon number of the alkanediol, which is the raw material of the polymerizable component (A), is preferably 12 or less, more preferably 10 or less. The alkane part may have a linear structure or a branched structure, or may be a mixture of the two. By having a branched structure, the crystallinity can be lowered, and it becomes liquid even at low temperature, and the handleability can be improved. In addition, the cycloalkane structure has the effect of raising the glass transition temperature of the cured product and making it hard.

  Specific examples of the polymerizable component (A) include, for example, 1,6-hexanediol di (meth) acrylate, 1,7-heptanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, 1,16-hexadecanediol di (meth) acrylate acrylate, batyl Alcohol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 2-ethyl-2-butyl-propanediol di ( (Meth) acrylate, dimer diol di (meth) acrylate, cyclohexyl Sanji dimethanol di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, and hydrogenated bisphenol A di (meth) acrylate. These may be used alone or in combination of two or more.

  The content ratio of the polymerizable component (A) can be set in the range of 1 to 100% by mass, and preferably in the range of 50 to 100% by mass, based on 100% by mass of the total amount of the polymerizable component (P). Can be set. From the viewpoint of obtaining a more sufficient addition effect, it is more preferably 60% by mass or more, and further preferably 70% by mass or more. From the viewpoint of obtaining the effect of the other polymerizable component while obtaining the sufficient effect of the polymerizable component (A), the content ratio of the polymerizable component (A) is preferably 90% by mass or less, and more preferably 85% by mass or less. . By containing a sufficient amount of the polymerizable component (A), it is possible to obtain excellent effects such as scratch resistance, weather resistance and substrate adhesion in the cured product, and in the resin composition, a low viscosity is obtained. And the effect of improving the compatibility with other polymerizable components such as the polymerizable component (B) can be expected.

[Polymerizable component (B)]
The polymerizable component (B) has an effect of imparting water repellency, antifouling property and improving scratch resistance to the cured product of the active energy ray-curable resin composition according to the embodiment of the present invention.

  The polymerizable component (B) is a silicone (meth) acrylate and / or an alkyl (meth) acrylate. Hereinafter, silicone (meth) acrylate and acrylic (meth) acrylate will be described separately.

(Silicone (meth) acrylate)
Silicone (meth) acrylate is a (meth) acrylate having a silicone skeleton. The silicone (meth) acrylate suitable for the present invention will be specifically described below with some examples.

  Examples of the silicone (meth) acrylate include a silicone (meth) acrylate represented by the following formula (1) and having a propyl (meth) acrylate structure at both ends and / or one end.

  When the molecular weight of the silicone (meth) acrylate represented by the formula (1) is too large, the compatibility with other polymerizable components such as the polymerizable component (A) tends to decrease. On the other hand, if the molecular weight is too small, it becomes difficult to obtain the effects of improving water repellency and scratch resistance. Therefore, the weight average molecular weight of the silicone (meth) acrylate represented by the formula (1) is preferably about 500 to 2000.

  Examples of commercially available products of the polymerizable component (B) include, for example, product names of "Silaplane" (registered trademark) series manufactured by JNC: FM-0711, FM-0721, FM-0725, FM-7711, FM-7721, FM-7725, Shin-Etsu Chemical Co., Ltd. product name: X-22-2445, X-22-174ASX, X-22-174BX, X-22-174DX, KF-2012, X-22-2426. , X-22-2475, X-22-164, X-22-164AS, X-22-164A, X-22-164B, X-22-164C, X-22-164E, Toray Dow Corning. Product name: BY16-152C and the like.

Examples of the other silicone (meth) acrylate include silicone epoxy (meth) acrylate represented by the following formula (2).

  Examples of commercially available products of the silicone (meth) acrylate represented by the formula (2) include product names of the “Tego” (registered trademark) series manufactured by Evonik Japan: Rad2011, Rad2100, and Rad2500.

  Other silicone (meth) acrylates include (meth) acrylates obtained by modifying both ends of polydimethylsiloxane with EO and / or PO. As the commercially available product, for example, product name: X-22-1602 manufactured by Shin-Etsu Chemical Co., Ltd., product name manufactured by Big Chemie Japan: BYK-UV3500, BYK-UV3530, product name manufactured by Evonik Japan: " Tego ”(registered trademark) series: Rad2200N, Rad2250, Rad2300, product name: EBECRYL 350 manufactured by Daicel-Olnex, and the like. The above "EO modified" means ethylene oxide modified and "PO modified" means propylene oxide modified.

  Other silicone (meth) acrylates are urethane (meth) acrylates and / or polyester (meth) acrylates having a silicone skeleton, for example, polyester-modified polydimethylsiloxane having a (meth) acryloyl group, polydimethylsiloxane. Urethane (meth) acrylate which has a structure is mentioned. Examples of the commercially available product include BYK-UV3570, product name manufactured by Big Chemie Japan, and product name: "Miramer" (registered trademark) series: SIU100, SIU1000, SIU2400, SIP900, manufactured by BYK-UV3570, Miwon Specialty Chemicals. To be

  Commercially available products of silicone (meth) acrylates other than the above include, for example, product names BYK-UV 3505, 3530, 3575, and 3576 manufactured by Big Chemie Japan Co., Ltd., product names manufactured by Daicel Ornex Co., Ltd .: EBECRYL 1360, and the like. .

  Among the silicone (meth) acrylates used as the polymerizable component (B) mentioned above, the silicone (meth) acrylate represented by the formula (1), the silicone (meth) acrylate represented by the formula (2), and BYK-. The one selected from UV3570 is preferable in terms of water repellency, scratch resistance and weather resistance. Particularly, from the viewpoint of imparting super water repellency, it is preferable to use the silicone (meth) acrylate represented by the formula (1).

  While the silicone (meth) acrylate having an oxyalkylene structure has good compatibility, it may result in poor weather resistance. Therefore, from the viewpoint of weather resistance, as the polymerizable component (B), a non-oxyalkylenated silicone (meth) acrylate having no oxyalkylene skeleton is preferable.

(Alkyl (meth) acrylate)
The alkyl (meth) acrylate used as the polymerizable component (B) preferably has a relatively long alkyl group from the viewpoint of improving water repellency and scratch resistance of the cured product. Specifically, the alkyl group preferably has 8 to 22 carbon atoms, and more preferably 12 to 18 carbon atoms. The alkyl group may be linear or branched. If the alkyl group is too long, the crystallinity will be high, making it difficult to handle in a liquid state, and if it is too short, the volatility may be a problem. Specific examples of the alkyl (meth) acrylate include (iso) octyl (meth) acrylate, (iso) decyl (meth) acrylate, (iso) lauryl (meth) acrylate, (iso) cetyl (meth) acrylate, ( Examples thereof include iso) stearyl (meth) acrylate and (iso) behenyl (meth) acrylate. Among these, isostearyl (meth) acrylate is particularly preferable from the viewpoint of imparting water repellency and handling.

The content ratio of the polymerizable component (B) can be set in the range of 0 to 50% by mass based on 100% by mass of the total amount of the polymerizable component (P). From the viewpoint of obtaining a sufficient addition effect, 0.5% by mass or more is preferable, and 1% by mass or more is more preferable. If the amount of the polymerizable component (B) added is too large, the physical properties of the cured product may deteriorate and the scratch resistance may decrease. Therefore, the content of the polymerizable component (B) is preferably 40% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less.
When the content ratio of the polymerizable component (B) is 0.5% by mass or more, for example, the polymerizable component (A) 50 to 99.5% by mass, the polymerizable component (B) 0.5 to 50% by mass, the polymerization The amount of the polymerizable component (C) can be set to 0 to 49.5% by mass, the polymerizable component (A) is 50 to 89.5% by mass, the polymerizable component (B) is 0.5 to 40% by mass, and the polymerizable component ( C) It can be set to 10 to 49.5 mass%.
When the content ratio of the polymerizable component (B) is 1% by mass or more, for example, 50 to 99% by mass of the polymerizable component (A), 1 to 50% by mass of the polymerizable component (B), and 0 of the polymerizable component (C). Can be set to 50 to 89% by mass, the polymerizable component (A) to 50 to 89% by mass, the polymerizable component (B) to 1 to 40% by mass, and the polymerizable component (C) to 10 to 49% by mass.

[Polymerizable component (C)]
The polymerizable component (C) is a polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups. By the polymerizable component (C), the hardness of the cured product of the active energy ray-curable resin composition can be adjusted and the scratch resistance can be improved. The polymerizable component (C) can impart hardness to the cured product as the number of (meth) acryloyl groups per molecular weight increases. Further, those having a smaller molecular weight and those having a methyl group in the molecule have excellent compatibility with other polymerizable components such as the polymerizable component (B). Conversely, those having a polyether structure may be inferior in compatibility with other polymerizable components such as the polymerizable component (B) and weather resistance.

  Specific examples of the polymerizable component (C) include, for example, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, (poly) glycerin (poly) acrylate, Pentaerythritol tri (tetra) acrylate, pentaerythritol tri (tetra) methacrylate, dipentaerythritol (penta) hexaacrylate, dipentaerythritol (penta) hexamethacrylate, polypentaerythritol poly (meth) acrylate, isocyanuric acid triacrylate, and these EO-modified, PO-modified or caprolactone-modified (meth) acrylate, and trifunctional or higher functional urethane (meth) acrylate, trifunctional or higher functional epoxy (meth) Acrylate, trifunctional or more polyester (meth) acrylate, and the like. Among these, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (tetra) acrylate, pentaerythritol tri (tetra) methacrylate are polymerizable components. It is preferable in terms of compatibility with (B) and scratch resistance. Further, since the EO-modified product and the PO-modified product are concerned in terms of weather resistance, the caprolactone-modified product is preferable in terms of weather resistance.

  The content ratio of the polymerizable component (C) can be set in the range of 0 to 50% by mass or the range of 0 to 49.5% by mass in the total amount of 100% by mass of the polymerizable component (P). . From the viewpoint of obtaining a sufficient addition effect, it is preferably 5% by mass or more, and more preferably 10% by mass or more. If the addition amount of the polymerizable component (C) is too large, the transparency of the active energy ray-curable resin composition and the cured product thereof may be deteriorated due to the problem of compatibility with other polymerizable components such as the polymerizable component (B). It may not be maintained. Further, from the viewpoint of sufficiently ensuring the content of the other polymerizable component, the content ratio of the polymerizable component (C) is preferably 30% by mass or less, and more preferably 25% by mass or less.

[Polymerizable component (D)]
The other polymerizable component (D) has a polymerizable functional group having copolymerizability with the other polymerizable component in the polymerizable component (P), and the polymerizable components (A), (B), It does not belong to (C). The polymerizable functional group contained in the polymerizable component (D) is preferably a radically polymerizable group, and examples thereof include a methacryloyl group, an acryloyl group, an acrylamide group, a vinyl ether group, and a vinyl group. Functions that can be imparted by the polymerizable component (D) include, for example, substrate adhesion, dilutability, water repellency, hydrophilicity, antistatic properties, slipperiness, leveling properties, scratch resistance, weather resistance, and light emission. Properties, fluorescent properties, color development properties, conductivity properties, refractive index adjustment properties, antioxidation properties, and the like.

  Examples of the monofunctional polymerizable component (D) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, Alkyl (meth) acrylates such as 2-ethylhexyl (meth) acrylate and lauryl (meth) acrylate; benzyl (meth) acrylate; isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, adamantyl (meth) acrylate, dicyclopenta (Meth) acrylate having an alicyclic structure such as nyl (meth) acrylate and dicyclopentenyl (meth) acrylate; having an amino group such as dimethylaminoethyl (meth) acrylate and dimethylaminopropyl (meth) acrylate ) Acrylate; (meth) acrylate having a hydroxyl group such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; (meth) acrylamide derivative such as (meth) acryloylmorpholine and N, N-dimethyl (meth) acrylamide; 2) -Vinylpyridine, 4-vinylpyridine, N-vinylpyrrolidone, N-vinylformamide, vinyl acetate, etc., 1,2,2,6,6-pentamethyl-4-piperidyl = (meth) acrylate, 2,2,6, 6-Tetramethyl-4-piperidyl (meth) acrylate, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [acrylic acid] 1- (2-hydroxy-3,5-di-tertiary pliers Phenyl) ethyl] -4,6-di-tert-pentylphenyl, 3- (2H-1,2,3-benzotriazol-2-yl) -4-hydroxyphenethyl methacrylate, 3,3,4,4 , 5,5,6,6,7,7,8,8,8-tridecafluorooctyl (meth) acrylate and other fluorine-containing (meth) acrylates.

  The bifunctional polymerizable component (D) includes all the bifunctional polymerizable components that are not included in the polymerizable component (A) and the polymerizable component (B). Examples of such a bifunctional polymerizable component (D) include 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,5-pentanediol di (meth). ) Acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dioxane glycol di (meth) ) Acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, alkoxylated alkanediol di (meth) acrylate, alkoxylated bisphenol A di (meth) acrylate Hydroxipivalic acid neopentyl glycol di (meth) acrylate, caprolactone modified hydroxypivalic acid neopentyl glycol di (meth) acrylate, alkoxylated neopentyl glycol di (meth) acrylate, polycarbonate diol di (meth) acrylate, (hydrogenated) polybutadiene Examples thereof include terminal (meth) acrylate, bifunctional urethane (meth) acrylate, bifunctional epoxy (meth) acrylate, bifunctional polyester (meth) acrylate, and fluorine-containing bifunctional (meth) acrylate.

  The content ratio of the polymerizable component (D) is not particularly limited as long as it does not hinder the functions of the polymerizable component (A), the polymerizable component (B) and the polymerizable component (C). , 0 to 50 mass% can be set, 0 to 30 mass% is preferable, and 0 to 10 mass% is more preferable.

[Photopolymerization initiator (E)]
The photopolymerization initiator (E) is a compound that is cleaved by irradiation with an active energy ray to generate a radical that initiates a polymerization reaction. As the active energy ray, ultraviolet rays are preferable from the viewpoints of apparatus cost and productivity.

  Examples of the photopolymerization initiator (E) that generates radicals by ultraviolet rays include benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, methylorthobenzoylbenzoate, 4-phenylbenzophenone, and t. -Butylanthraquinone, 2-ethylanthraquinone, thioxanthones (2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, etc.), acetophenones (diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane) -1-one, benzyl dimethyl ketal, 1-hydroxycyclohexyl-phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-di Tylamino-1- (4-morpholinophenyl) -butanone, etc., benzoin ethers (benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc.), acylphosphine oxides (2,4,6-trimethylbenzoyl) Diphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, etc.), methylbenzoyl formate, 1, 7-bisacridinyl heptane, 9-phenylacridine and the like can be mentioned.

  As the photopolymerization initiator (E), one type may be used alone, or two or more types may be used in combination. When used in combination, it is preferable to use two or more kinds having different absorption wavelengths together. If necessary, a thermal polymerization initiator such as a persulfate (potassium persulfate, ammonium persulfate, etc.), a peroxide (benzoyl peroxide, etc.), an azo-based initiator or the like may be used in combination.

  The content of the photopolymerization initiator (E) is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the total of the polymerizable component (P) contained in the active energy ray-curable resin composition (X), 0.1 to 5 parts by mass is more preferable, and 0.2 to 3 parts by mass is further preferable. If the content of the photopolymerization initiator (E) is too small, the curing of the active energy ray-curable resin composition (X) may not be completed, and the mechanical properties of an article having a fine uneven structure on the surface may be impaired. If the content of the photopolymerization initiator (E) is too large, the unreacted photopolymerization initiator (E) remains in the cured product and acts as a plasticizer, decreasing the elastic modulus of the cured product and causing scratch resistance. In some cases, it may impair sex. It may also cause coloring.

[Internal release agent (F)]
Examples of the internal release agent (F) 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 (Registered trademark) and the like. 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.
The content of the internal release agent (F) can be set in the range of 0.01 to 2.0 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable component (P). From the viewpoint of obtaining a sufficient releasing effect, it is preferably 0.05 part by mass or more, and more preferably 0.1 part by mass or more. When the content of the internal release agent (F) is too large, the internal release agent (F) may separate or precipitate from the active energy ray-curable resin composition, or the active energy ray-curable resin composition. The internal release agent (F) may bleed out from the cured product. The content of the internal release agent (F) is preferably 2.0 parts by mass or less, and more preferably 1.0 part by mass or less.

As the (poly) oxyalkylene alkylphosphate compound, a compound represented by the following formula (3) is preferable from the viewpoint of releasability:
_{(HO) 3-n (O} =) P [-O- (R 2 O) m -R 1] n (3)
(R ¹ is an alkyl group, R ² is an alkylene group, m is an integer of 1 to 20, and n is an integer of 1 to ^3. )

In the formula, 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. As R ² , an alkylene group having 1 to 4 carbon atoms is preferable, and an alkylene group having 2 to 3 carbon atoms is more preferable. m is preferably an integer of 1 to 10. The (poly) oxyalkylene alkyl phosphate compound represented by the formula (3) may be any of a monoester body (n = 1), a diester body (n = 2) and a triester body (n = 3). . In the case of diester or triester, a plurality of (poly) oxyalkylenealkyl groups in one molecule may be different from each other.

  Examples of commercially available (poly) oxyalkylene alkyl phosphate compounds include the following. Product made by Johoku Chemical Co., Ltd., product name: JP-506H, product made by Axel, product name: Moldwith INT-1856, product made by Nikko Chemicals, product 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 internal release agent (F) listed here may also exhibit the functions of a surfactant, a leveling agent, and a lubricant.

[Other ingredients (G)]
The other component (G) is a component added as necessary, and is a component other than the polymerizable component (P), the photopolymerization initiator (E), and the internal release agent (F). The other component (G) is a flame retardant aid, a plasticizer, a surfactant, an antistatic agent, an antioxidant, a light stabilizer, a polymerization inhibitor, an ultraviolet absorber, a filler, an adhesion imparting agent, a colorant. , Reinforcing agents, inorganic fillers, impact modifiers and the like. In addition, it may contain an oligomer or polymer having no radically polymerizable functional group, a trace amount of an organic solvent and the like.

  Examples of the polymerization inhibitor include hydroquinone (HQ) and hydroquinone monomethyl ether (MEHQ) as hydroquinone-based polymerization inhibitors, and 2,2′-methylene-bis (4-methyl-6-tert) as phenol-based polymerization inhibitors. -Butylphenol), catechol, picric acid, tert-butylcatechol, 2,6-ditertiarybutyl-p-cresol (BHT), 4,4'-thiobis [ethylene (oxy) (carbonyl) (ethylene)] bis [2 , 6-bis (1,1-dimethylethyl) phenol], and the like. Examples of the phenothiazine-based polymerization inhibitor include phenothiazine, bis (α-methylbenzyl) phenothiazine, 3,7-dioctylphenothiazine, and bis (α, α-dimethylbenzyl) phenothiazine. Among the polymerization inhibitors listed here, a phenolic polymerization inhibitor such as BHT can also be used as an antioxidant.

  Examples of the antioxidant include hindered phenol-based antioxidants, benzimidazole-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, hindered amine-based antioxidants, and the like. Examples of commercially available products include "IRGANOX" (registered trademark) series manufactured by BASF.

  Examples of the light stabilizer include hindered amine-based antioxidants. Examples of the primary antioxidant that is a hindered amine-based radical scavenger include the following. BASF make, brand name: Chimassorb 2020FDL, Chimassorb 944FDL, Tinuvin 622SF, Uvinul 5050H, Tinuvin 144, Tinuvin 765, Tinuvin 770DF, Tinuvin 4050FF.

  Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, hindered amine-based, benzoate-based, triazine-based and the like. Examples of commercially available products include BASF's product names: TINUVIN 400, TINUVIN 479, and Kyodo Pharmaceutical Co., Ltd.'s product name: Viosorb110.

[Viscosity of resin composition]
The resin composition (X) according to the embodiment of the present invention may have an appropriate viscosity in terms of easiness of flowing into the fine uneven structure on the surface of the stamper when the fine uneven structure is formed and cured by the stamper. preferable. The viscosity of the resin composition measured with a rotary B-type viscometer at 25 ° C. is preferably 10,000 mPa · s or less, more preferably 5000 mPa · s or less, and further preferably 2000 mPa · s or less. Even if the viscosity of the resin composition at 25 ° C. is 10,000 mPa · s or more, the resin composition can be suitably used as long as it can be brought into contact with the stamper by adjusting the viscosity in the above range by heating. In this case, the viscosity of the resin composition measured by a rotary B-type viscometer at 70 ° C. is preferably 5000 mPa · s or less, and more preferably 2000 mPa · s or less. Further, when the viscosity of the resin composition is 10 mPa · s or more, contact with the stamper is possible, and a cured product having a fine uneven structure on the surface can be formed.

  The viscosity of the resin composition can be adjusted by selecting the type and content of the monomer to be contained, or by using a viscosity modifier. Specifically, when a large amount of a monomer having a functional group or a chemical structure having an intermolecular interaction such as hydrogen bond is used, the viscosity of the resin composition increases. In addition, when a large amount of low molecular weight monomer having no intermolecular interaction is used, the viscosity of the resin composition becomes low.

  The resin composition (X) according to the embodiment of the present invention has a relatively low viscosity, but the obtained cured product can have an appropriate hardness. As a result, the stamper can be peeled off favorably, the formed fine concavo-convex structure is maintained, the scratch resistance is high, and a cured product exhibiting excellent water repellency can be obtained.

[Molded product (fine concavo-convex structure) / article having a fine concavo-convex structure]
The resin composition (X) according to the embodiment of the present invention can be polymerized and cured to give a molded article. As such a molded product, a fine concavo-convex structure having a fine concavo-convex structure on its surface is extremely useful. As an article using such a fine concavo-convex structure (article having a fine concavo-convex structure), for example, one having a base material and a cured resin layer (fine concavo-convex structure) having a fine concavo-convex structure on its surface can be mentioned. You can

  A schematic cross-sectional view of an example of an article using such a fine concavo-convex structure is shown in FIG.

  The article 10 having a fine concavo-convex structure shown in FIG. 1A has a base material 11 (a coating layer 15 formed on the base material 11), and an active energy ray-curable resin composition according to an embodiment of the present invention ( The cured resin layer (surface layer) 12 obtained by curing X) is laminated. The surface of the cured resin layer 12 has a fine uneven structure. In this fine concavo-convex structure, the conical protrusions 13 (recesses 14) are formed at substantially equal intervals w1. The shape of the protrusion 13 is preferably such that the cross-sectional area in a cross section perpendicular to the height direction (plane parallel to the plane of the base material) continuously increases from the apex side of the protrusion to the base material side. . With such a shape, the refractive index can be continuously increased, variation in reflectance (wavelength dependence) depending on wavelength is suppressed, visible light scattering is suppressed, and a fine uneven structure with low reflectance is formed. it can.

  In the fine concavo-convex structure, the interval w1 between the convex portions (recesses) is preferably a distance equal to or less than the wavelength of visible light (specifically 400 to 780 nm). When the interval w1 between the convex portions is 400 nm or less, it is possible to suppress the scattering of visible light and it can be suitably used as an antireflection film for optical applications. w1 is more preferably 50 to 400 nm, further preferably 50 to 250 nm, and particularly preferably 80 to 200 nm.

  Also, the height of the convex portion (depth of the concave portion), that is, the vertical distance d1 between the bottom point 14a of the concave portion and the top portion 13a of the convex portion (hereinafter, “height of convex portion” or “d1” unless otherwise specified). Is preferably a depth that can suppress the reflectance from varying with wavelength. Specifically, it is preferably 60 nm or more, more preferably 90 nm or more, further preferably 150 nm or more, and particularly preferably 180 nm or more. When d1 is near 150 nm, the reflectance of light in the wavelength region of 550 nm, which is most easily recognized by humans, can be the lowest. When d1 is 150 nm or more, the higher d1 is, the higher the reflectance and the lowest reflectance in the visible light region are. The difference in reflectance becomes small. Therefore, when d1 is 150 nm or more, the wavelength dependence of the reflected light becomes small, and the difference in tint cannot be visually recognized.

  Here, the interval w1 and height d1 of the convex portions are measured values obtained by measurement on an image with an acceleration voltage of 3.00 kV by a field emission scanning electron microscope (trade name: JSM-7400F, manufactured by JEOL Ltd.). An arithmetic mean value can be adopted.

  Further, the convex portion 13 may have a bell shape as shown in FIG. In addition, for example, a truncated cone shape can be adopted as the shape in which the cross-sectional area in the vertical plane continuously increases from the apex side of the convex portion to the base material side.

  The fine concavo-convex structure is preferably a structure in which protrusions (projections) having a substantially conical shape, a pyramidal shape, or the like are regularly arranged. The shape of the convex part is such that the cross-sectional area of the cross section perpendicular to the height direction (plane parallel to the base material plane) continuously decreases from the base material side toward the top, that is, in the height direction of the convex part. The cross-sectional shape is preferably triangular, trapezoidal, bell-shaped or the like.

  The fine concavo-convex structure is not limited to the embodiment shown in FIG. The fine concavo-convex structure may be formed on the surface of the cured resin layer (fine concavo-convex structure). For example, one side or both sides of the base material, or the whole surface or a part (transparency, super water repellency required) It is possible to provide a cured resin layer having a fine concavo-convex structure formed on the outer surface thereof.

  As such a fine concavo-convex structure, a moth-eye structure in which the interval between the convex portions is equal to or less than the wavelength of visible light is preferable, and the moth-eye structure of the surface of the cured product is the cured product (root portion of the convex part) from the refractive index of air. By continuously increasing the refractive index to the refractive index, it becomes an effective antireflection means. As described above, the average spacing w1 between the convex portions is preferably equal to or less than the wavelength of visible light, that is, 400 nm or less, more preferably 50 to 400 nm, further preferably 50 to 250 nm, particularly preferably 80 to 200 nm.

  The average interval w1 between the convex portions is an electron microscope image in which 50 intervals (distance from the center of the convex portion to the center of the adjacent convex portion) between the adjacent convex portions are measured, and these measured values are arithmetically averaged. The value obtained by is adopted.

  The height d1 of the convex portion is preferably 80 nm or more, more preferably 120 nm or more, particularly preferably 150 nm or more, when w1 is in the above range, particularly in the vicinity of 100 nm. When d1 is 80 nm or more, the reflectance is sufficiently reduced, and the reflectance varies with wavelength, that is, the wavelength dependency of the reflectance is small. From the viewpoint that the scratch resistance of the fine concavo-convex structure is good, d1 is preferably 500 nm or less, more preferably 400 nm or less, and particularly preferably 300 nm or less.

  The height d1 of the convex portion is the height along the direction perpendicular to the substrate plane between the top of the convex portion and the bottom of the concave portion existing between the convex portions in a 30,000 × image of an electron microscope. A value obtained by measuring 50 points and arithmetically averaging these measured values is adopted.

  The aspect ratio of the convex portion (height d1 of the convex portion / average distance w1 between the convex portions) is preferably 0.3 or more, more preferably 0.5 or more, and 0.7 or more from the viewpoint of sufficiently suppressing the reflectance. Is particularly preferable. This aspect ratio is preferably 6 or less, more preferably 4 or less, and particularly preferably 2 or less, from the viewpoint of good scratch resistance.

The difference in refractive index between the cured resin layer and the substrate is preferably 0.2 or less, more preferably 0.1 or less, and particularly preferably 0.05 or less. When the difference in refractive index is within 0.2, reflection at the interface between the cured resin layer and the base material can be suppressed.
The thickness of the fine concavo-convex structure layer can be set, for example, in the range of 0.5 to 100 μm, preferably in the range of 1 to 50 μm.

  The substrate may be any as long as it can support the cured resin layer having a fine relief structure, but when the fine relief structure is applied to a display member, it is transparent, that is, it transmits light. Those are preferable. Examples of the material forming the transparent base material include synthetic polymers such as methyl methacrylate (co) polymer, polycarbonate, styrene (co) polymer, methyl methacrylate-styrene copolymer, cellulose diacetate, and cellulose triacetate. Semi-synthetic polymers such as cellulose acetate butyrate; polyester such as polyethylene terephthalate and polylactic acid, polyamide, polyimide, polyether sulfone, polysulfone, polyethylene, polypropylene, polymethylpentene, polyvinyl chloride, polyvinyl acetal, polyether ketone, Examples of the material include polyurethane, composites of these polymers (composite of polymethylmethacrylate and polylactic acid, composite of polymethylmethacrylate and polyvinyl chloride, etc.), transparent inorganic materials such as glass.

  The shape of the base material may be any of a sheet shape, a film shape and the like. The manufacturing method of the base material is not particularly limited, and for example, those manufactured by any manufacturing method such as injection molding, extrusion molding and cast molding can be used. The surface of the transparent substrate may be subjected to coating or corona treatment for the purpose of improving properties such as adhesion, antistatic property, scratch resistance and weather resistance.

  Such a fine concavo-convex structure can be applied as an antireflection film and can have high scratch resistance. Further, by selecting the composition type and controlling the composition ratio of the resin composition (X), it is possible to obtain not only high scratch resistance of the cured product but also excellent effects of removing contaminants such as fingerprint removability. .

[Method for manufacturing fine concavo-convex structure]
As the method for producing the fine concavo-convex structure, for example, (1) a resin composition is disposed between a stamper on which an inversion structure of the fine concavo-convex structure is formed and a base material, and the resin composition is irradiated with an active energy ray. A method of curing, transferring the uneven shape of the stamper, and then peeling the stamper, (2) transferring the uneven shape of the stamper to the resin composition, peeling the stamper, and then irradiating an active energy ray to the resin composition Examples include a method of curing an object. Among these, the method (1) is particularly preferable from the viewpoints of the transferability of the fine concavo-convex structure and the degree of freedom of the surface composition. This method is particularly suitable when a belt-shaped roll stamper capable of continuous production is used, and has excellent productivity.

(Stamper)
The stamper has an inverted structure of the fine concavo-convex structure formed on the surface of the fine concavo-convex structure on the surface. Examples of materials for the stamper include metals (including those having an oxide film formed on the surface), quartz, glass, resin, ceramics, and the like. Examples of the shape of the stamper include a roll shape, a circular tube shape, a flat plate shape, and a sheet shape.

  The method for forming the inversion structure of the fine concavo-convex structure on the stamper is not particularly limited, and specific examples thereof include an electron beam lithography method and a laser light interference method. For example, a suitable photoresist film is coated on a suitable supporting substrate, exposed to light such as an ultraviolet laser, an electron beam, or an X-ray, and developed to obtain a mold having an inverted fine concavo-convex structure. Can also be used as is as a stamper. It is also possible to directly etch the supporting substrate through the photoresist film patterned by exposure and development by dry etching and remove the photoresist film to directly form the inversion fine concavo-convex structure on the supporting substrate itself. It is possible.

  Further, as another method, it is possible to use anodized porous alumina as a stamper. For example, a pore structure having a diameter of 20 to 200 nm formed by anodizing an aluminum base material using oxalic acid, sulfuric acid, phosphoric acid or the like as an electrolytic solution at a predetermined voltage may be used as a stamper. According to this method, after anodizing a high-purity aluminum base material at a constant voltage for a long time, the oxide film is once removed and then anodized again, so that very highly ordered pores are self-assembled. Can be formed. Further, by combining the anodic oxidation treatment and the pore diameter enlargement treatment in the second anodic oxidation step, it is possible to form a fine concavo-convex structure having a triangular or bell-shaped cross section instead of a rectangular shape. It is also possible to make the angle of the deepest part of the pores sharp by appropriately adjusting the time and conditions of the anodizing treatment and the pore diameter expanding treatment.

  Furthermore, as another method, a replica mold may be produced from an original mold having a fine concavo-convex structure by electroforming or the like, and this may be used as a stamper.

  The shape of the stamper itself is not particularly limited, and may be, for example, a flat plate shape, a belt shape, or a roll shape. In particular, if it is formed into a belt shape or a roll shape, the fine concavo-convex structure can be continuously transferred, and the productivity can be further improved.

(Supply and curing step of resin composition (X))
The resin composition (X) is supplied and priced between the stamper and the base material. As a method of disposing the resin composition between the stamper and the base material, for example, by pressing the stamper and the base material in a state where the resin composition is disposed between the stamper and the base material, the resin composition is placed in the molding cavity. Can be injected.

  After disposing the resin composition between the stamper and the base material, the resin composition is irradiated with active energy rays to be polymerized and cured. As a method of polymerizing and curing, curing treatment by ultraviolet irradiation is preferable. As the lamp for irradiating with ultraviolet rays, for example, a high pressure mercury lamp, a metal halide lamp, a fusion lamp which is an electrodeless lamp, or a UV-LED can be used.

The irradiation amount of ultraviolet rays may be determined according to the absorption wavelength and content of the polymerization initiator. Normally, the integrated light quantity is preferably from ^{400~4000mJ / cm 2, 400~2000mJ / cm} 2 is more preferable. When the integrated light amount is 400 mJ / cm ² or more, it is possible to sufficiently cure the resin composition and suppress a decrease in scratch resistance due to insufficient curing. Moreover, it is preferable to set the integrated light amount to 4000 mJ / cm ² or less in order to prevent coloring of the cured product and deterioration of the substrate. The irradiation intensity is not particularly limited, but it is preferable to suppress the output to such an extent as not to cause deterioration of the base material.

  After the polymerization and curing of the resin composition, the stamper is peeled off to obtain a fine relief structure which is a cured product having a fine relief structure.

[Uses of fine concavo-convex structure]
The fine concavo-convex structure body thus obtained has a high scratch resistance because the fine concavo-convex structure of the stamper is transferred to the surface in the relationship of the key and the key hole. Further, it has water repellency and can also have the effect of preventing the attachment of contaminants. Such a fine concavo-convex structure can exhibit an excellent antireflection performance due to continuous changes in refractive index, and is suitable as an antireflection film or an antireflection film for a three-dimensional molded article.

  Such a fine concavo-convex structure is suitable as a display member of an image display device such as a liquid crystal display device, a plasma display panel, an electroluminescence display, and a cathode ray tube display device for computers, televisions, mobile phones and the like. Further, a fine concavo-convex structure can be attached and used on the surface of a transparent member such as a lens, a show window, and a spectacle lens. In addition, it can be applied to optical applications such as optical waveguides, relief holograms, lenses, and polarization separation elements, and cell culture sheet applications. Further, by utilizing water repellency, it can be applied to building materials such as mirrors and windows, automotive applications such as films for door mirrors and films for windows, and ship bottom materials.

[Method of manufacturing stamper]
As the stamper used for producing the fine concavo-convex structure, as described above, those made of anodized porous alumina are useful. A method of forming a plurality of fine pores of a predetermined shape on the surface of an aluminum substrate by anodic oxidation will be described below as a method of manufacturing the stamper with reference to the process chart of FIG.

Process (a)
The step (a) is a step of forming an oxide film on the surface of the aluminum base material by anodizing the aluminum base material 30 in an electrolytic solution under a constant voltage.
The aluminum base material is preferably made of aluminum having a purity of 99% or more, more preferably 99.5% or more, and further preferably 99.8% or more. When the purity of aluminum is high, it is difficult to form a concavo-convex structure having a size that scatters visible light due to segregation of impurities when anodizing, and the pores formed by anodizing are regularly formed. The shape of the aluminum base material may be a desired shape such as a roll shape, a tubular shape, a flat plate shape, or a sheet shape, and when the fine concavo-convex structure product is obtained as a continuous film or sheet, it is preferably a roll shape.

  Since the aluminum base material may have oil adhered to it when it is processed into a predetermined shape, it is preferable to degrease it in advance and make the surface smooth by electrolytic polishing (etching). .

  When such a surface-treated aluminum base material is anodized, an oxide film 32 having pores 31 is formed.

  As the electrolytic solution, sulfuric acid, oxalic acid, phosphoric acid or the like can be used. When oxalic acid is used as the electrolytic solution, the concentration of oxalic acid is preferably 0.7 M or less. When the concentration of oxalic acid is 0.7 M or less, the current value can be suppressed to a low level and an oxide film with a dense structure can be formed. The formation voltage is preferably 30 to 60V. When the formation voltage is 30 to 60 V, it is possible to form an anodized porous alumina layer in which pores are formed with regularity of a period of about 100 nm. Regardless of whether the formation voltage is higher or lower than this range, the regularity of the pores formed tends to decrease. The temperature of the electrolytic solution is preferably 60 ° C. or lower, more preferably 45 ° C. or lower. When the temperature of the electrolytic solution is 60 ° C. or lower, the occurrence of so-called “burning” is suppressed, and pores are broken or the surface is melted and irregular pores are suppressed from being formed.

  When sulfuric acid is used as the electrolytic solution, the concentration of sulfuric acid is preferably 0.7M or less. When the concentration of sulfuric acid is 0.7 M or less, the current value can be suppressed to a low level and an oxide film having a dense structure can be formed. The formation voltage is preferably 25 to 30V. When the formation voltage is 25 to 30 V, it is possible to form the anodized porous alumina layer in which the pores are formed with a regularity of about 63 nm. Regardless of whether the formation voltage is higher or lower than this range, the regularity of the pores formed tends to decrease. The temperature of the electrolytic solution is preferably 30 ° C. or lower, more preferably 20 ° C. or lower. When the temperature of the electrolytic solution is 30 ° C. or lower, the occurrence of so-called “burn” is suppressed, and the pores are broken or the surface is melted and irregular pores are suppressed.

Process (b)
The step (b) is a step of removing the oxide film and forming anodization pore generation points on the surface of the aluminum base material so as to correspond to the pores 31 formed in the oxide film in the step (a). Is. That is, when the oxide film 32 formed in the step (a) is removed, the recess 33 is formed on the surface of the aluminum base material at the positions corresponding to the pores 31.
By using the recesses 33 as pore generation points for anodic oxidation, it is possible to generate regularly arranged pores. To remove the oxide film, a solution that does not dissolve aluminum but selectively dissolves the oxide film is used. Examples of such a solution include a chromic acid / phosphoric acid mixed solution.

Process (c)
The step (c) is a step of forming pores by anodizing the aluminum base material again and forming an oxide film at the pore generation points. That is, the aluminum base material 30 from which the oxide film has been removed in step (b) is anodized again to form an oxide film 34 having columnar pores 35. Anodization can be performed under the same conditions as in step (a). The longer the anodic oxidation time, the deeper the pores can be obtained.

Step (d)
Step (d) is a step of expanding the diameter of the pores. That is, the anodized aluminum base material is immersed again in a solution that dissolves the oxide film to expand the diameter of the pores 35 (hereinafter referred to as "pore diameter expansion treatment").
As the solution for dissolving the oxide film, for example, a phosphoric acid aqueous solution of about 5 mass% or the like can be used. Since the pore size can be expanded as the time for the pore size expansion process is lengthened, the processing time is set according to the target shape.

Process (e)
The step (e) is a step of anodizing again the aluminum base material after the pore diameter expansion treatment. When the aluminum base material is anodized again, the depth of the pores 35 is expanded as the oxide film 34 becomes thicker. The anodization can be performed under the same conditions as in step (a) (and step (c)). The longer the anodizing time is, the deeper the pores can be formed.

Process (f)
The step (f) is a step in which the step (d) and the step (e) are repeated, and the diameter expansion and extension of the pores 35 are repeated. By this step, the oxide film 34 having the pores 35 having a shape in which the diameter continuously decreases in the depth direction from the opening is formed, and as a result, the anodized alumina having a plurality of fine pores becomes the aluminum base material. The stamper 20 formed on the surface can be obtained. The end of step (f) preferably ends with step (d).

  The total number of repetitions of step (f) is preferably 3 or more, more preferably 5 or more. When the number of repetitions is 3 or more, it is possible to form pores whose diameter continuously changes, and by using such a stamper, a cured product having a moth-eye structure surface capable of reducing reflectance can be formed. You can

  The shape of the pores 35 is an inverted structure of the fine concavo-convex structure formed on the surface of the article, and specific examples thereof include a substantially conical shape, a pyramid shape, a cylindrical shape, and the like. As described above, a shape in which the pore cross-sectional area in the direction orthogonal to the depth direction continuously decreases from the outermost surface in the depth direction is preferable.

  The average spacing between the pores 35 is preferably less than or equal to the wavelength of visible light, that is, 400 nm or less, and more preferably 20 nm or more. As the average spacing between pores, the spacing between adjacent pores (distance from the center of the pore to the center of the adjacent pore) in the electron microscope image is measured at 50 points, and the average value of these values is adopted. .

  The depth of the pores 35 is preferably 80 to 500 nm, more preferably 120 to 400 nm, further preferably 150 to 300 nm, and particularly preferably in such a range when the average interval is about 100 nm. For the depth of the pores, the distance between the bottom of the pores and the top of the pores is measured at 50 points in an electron microscope 30,000 × image, and the average value of these values is adopted.

  The aspect ratio (depth / average interval) of the pores 35 is preferably 0.8 to 5.0, more preferably 1.2 to 4.0, and even more preferably 1.5 to 3.0.

  The surface of the stamper on the side where the fine concavo-convex structure is formed may be treated with a release agent. Examples of the release agent include silicone resins, fluororesins, fluorine compounds, and phosphoric acid esters, with phosphoric acid esters being particularly preferred. As the phosphoric acid ester, a (poly) oxyalkylenealkylphosphoric acid compound is preferable, and as commercial products, trade names: JP-506H manufactured by Johoku Chemical Co., Ltd., trade names: Accelerator MOLD WITH INT-1856, Nikko Chemicals Company brand 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 etc. are mentioned.

  An article having on its surface a fine concavo-convex structure formed using the stamper produced above has a cured resin layer 12 formed on the surface of a base material 11, as shown in FIG. 1A, for example. The cured resin layer 12 has a fine concavo-convex structure having a plurality of protrusions 13 formed from a cured resin product obtained by contacting and curing the resin composition with the stamper.

[Raw materials for imprint]
The raw material for imprint of the present invention is not particularly limited as long as it contains the resin composition of the present invention, and the resin composition can be used as it is, depending on the target molded article. It is also possible to contain various additives.

  The imprint raw material can also be used for molding a cured product by UV curing or heat curing using a stamper. It is also possible to use a method in which a stamper is pressed against the resin composition in a semi-cured state by heating or the like, the shape is transferred, the stamper is peeled off, and the resin composition is completely cured by heat or UV.

  The above resin composition can also be used as a raw material for forming a cured coating on various substrates, and a coating can be formed as a coating material and irradiated with active energy rays to form a cured product. it can.

[Continuous manufacturing method of article having fine concavo-convex structure]
An article having a fine concavo-convex structure on its surface can be continuously manufactured using, for example, the manufacturing apparatus shown in FIG.

  The manufacturing apparatus shown in FIG. 3 is provided with a roll stamper 41 having an inverted structure (not shown) of a fine concavo-convex structure on the surface, and a tank 43 for storing the resin composition. The resin composition is supplied from the tank 43 between the roll stamper 41 and the substrate 42 of the translucent strip film that moves along the surface of the roll stamper 41 as the roll stamper 41 rotates. The base material 42 and the resin composition are sandwiched between the roll stamper 41 and the nip roll 46 whose nip pressure is adjusted by the pneumatic cylinder 45, and the resin composition is interposed between the base material 42 and the roll stamper 41. And the inside of the roll-shaped stamper 41 is filled with the fine concave-convex structure. An active energy ray irradiation device 48 is installed below the roll-shaped stamper 41, and the resin composition is irradiated with the active energy ray through the base material 42 so that the resin composition can be cured. Thereby, the cured resin layer 44 to which the fine concavo-convex structure on the surface of the roll stamper 41 is transferred is formed. Thereafter, the peeling roll 47 peels the continuous article (fine uneven structure) 40 in which the cured resin layer 44 having the fine uneven structure formed on the surface and the base material 42 are integrated from the roll stamper 41.

As the active energy ray irradiation device 48, a high pressure mercury lamp, a metal halide lamp, or the like is preferable, and in this case, the light irradiation energy amount is preferably 100 to 10,000 mJ / cm ² . As a material of the base material 42, acrylic resin, polycarbonate, styrene resin, polyester, cellulose resin (triacetyl cellulose, etc.), polyolefin, alicyclic polyolefin, etc. can be used.

[Use of articles having a fine concavo-convex structure]
The article having the fine concavo-convex structure according to the embodiment of the present invention has high scratch resistance of the fine concavo-convex structure and excellent water repellency, and therefore, the anti-reflection article (anti-reflection film, anti-reflection film, etc.), optical waveguide, relief. It can be expected to be used as an optical article such as a hologram, a lens, a polarization separation element, and a water repellent film, and is particularly suitable for an antireflection article and a water repellent film.

  As the antireflection article, for example, an image display device (a liquid crystal display device, a plasma display panel, an electroluminescence display, a cathode ray tube display device, etc.), an antireflection film provided on the surface of a lens, a show window, eyeglasses, etc., an antireflection film. , An antireflection sheet and the like. 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 forming the image display surface, and an antireflection film may be formed on the front plate. May be formed.

  As the water-repellent film, it can be used as an anti-drop film for automobile door mirrors and windows, or as a snow-prevention film. Further, by using it for a transparent base material used outdoors such as a solar cell or a glass for building materials, the effect of improving the light transmittance and the effect of imparting antifouling property by water repellency can be utilized at the same time.

  Hereinafter, the present invention will be described in more detail with reference to Examples. First, an evaluation method and a stamper manufacturing example will be described.

[Evaluation methods]
[1. Appearance of curable liquid]
As for the appearance of the curable liquid (active energy ray curable resin composition), put 10 mL of the curable liquid in a transparent glass bottle (capacity 20 mL), and visually check for cloudiness by holding it over a fluorescent lamp at room temperature of 23 ° C. And evaluated by the following indexes.
◯: It is transparent without any turbidity.
X: There is turbidity.

[2. Scratch resistance]
Using an abrasion tester (Shinto Kagaku Co., Ltd., product name: HEiDON TRIBOGEAR TYPE-30S), steel wool cut into 2 cm squares placed on the surface of the article (manufactured by Nippon Steel Wool Co., Ltd., product name: Bonster # 0000) Was applied with a load of 100 g (25 gf / cm ² = 0.245 N / cm ² ) and reciprocated at a reciprocating distance of 30 mm and a head speed of 100 mm / sec for 10 times to evaluate the appearance of the surface of the article. At the time of appearance evaluation, an article was attached to one surface of a 2.0 mm thick black acrylic plate (Mitsubishi Rayon Co., Ltd., product name: Acrylite), visually inspected indoors by holding it over a fluorescent lamp, and evaluated by the following indicators. did.
A: Less than 10 scratches can be confirmed in the scratched portion.
B: The number of scratches that can be confirmed in the scratched portion is 10 or more and less than 50.
C: 50 or more scratches that can be confirmed in the scratched portion. Or the scratched part looks white and cloudy.

[3. Water contact angle]
Using an automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., product name: DM-501), 1 μL of ion-exchanged water was dropped on the surface of the article, and the contact angle was measured. The contact angle was measured at three points and the average value was adopted.

[4. Measurement of stamper pores]
A part of the longitudinal cross section of the stamper made of anodized porous alumina was vapor-deposited with Pt for 1 minute and observed with a field emission scanning electron microscope (JEOL Ltd., product name: JSM-7400F) at an acceleration voltage of 3.00 kV. The interval (cycle) of the matching pores and the depth of the pores were measured. Specifically, each of 10 points was measured, and the average value was used as the measured value.

[Fabrication of stamper for transfer of fine concavo-convex structure]
An electrolytically polished φ65 mm aluminum disk having a purity of 99.99 mass% and a thickness of 2 mm was used as an aluminum substrate.

Process (a):
This aluminum disk was anodized in a 0.3 M oxalic acid aqueous solution for 6 hours under the conditions of DC 40 V and temperature 16 ° C.
Step (b):
The aluminum disk on which the oxide film was formed was immersed in a 6 mass% phosphoric acid / 1.8 mass% chromic acid mixed aqueous solution for 3 hours to remove the oxide film.
Step (c):
The aluminum disk from which the oxide film was removed was anodized in a 0.3 M oxalic acid aqueous solution for 30 seconds under the conditions of DC 40 V and temperature 16 ° C.

Step (d):
The aluminum disk on which the oxide film was formed was immersed in a 5% by mass phosphoric acid aqueous solution at 32 ° C. for 8 minutes to perform a pore diameter expansion treatment.
Process (e):
The aluminum disc after this treatment was anodized in a 0.3 M oxalic acid aqueous solution for 30 seconds under the conditions of DC 40 V and temperature 16 ° C.

Process (f):
The step (d) and the step (e) were repeated 5 times in total, and anodized alumina having substantially conical pores with an average pore spacing (cycle) of 100 nm and a depth of 200 nm was formed on the surface. A mold (stamper) was obtained.

  The obtained mold was immersed in a 0.1 mass% aqueous solution of a release agent (trade name: TDP-8, manufactured by Nikko Chemicals Co., Ltd.) for 10 minutes, pulled up, and air-dried overnight for release treatment.

[Active energy ray curable resin composition (X)]
The polymerizable component (A), the polymerizable component (B), the polymerizable component (C), and the other polymerizable components contained in the active energy ray-curable resin composition (X) used in Examples and Comparative Examples ( D), the photopolymerization initiator (E), and the internal release agent (F) are as shown in Table 1 below.

[Example 1]
As the active energy ray-curable resin composition (X), a resin having the composition shown in Table 2 was prepared. A few drops of this active energy ray-curable resin composition were hung on the surface of a stamper for transferring a fine uneven structure, and a polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., product name: A4300, thickness: 50 μm) was spread and covered. Then, the resin composition is cured by irradiating ultraviolet rays from the film side so that the integrated light amount measured at a wavelength of 365 nm using an electrodeless type UV lamp (D bulb of Heraeus Co., Ltd.) is 1000 mJ / cm ^2. Let The cured resin layer was released from the stamper together with the film to obtain an article having on the surface a fine concavo-convex structure having an average spacing w of convex portions of 1: 100 nm and a height d1: 200 nm. The evaluation results are shown in Table 2.

[Examples 2 to 8]
An article having a fine concavo-convex structure on its surface was produced and evaluated in the same manner as in Example 1 except that the active energy ray-curable resin composition (X) was changed to that shown in Table 2. The evaluation results are shown in Table 2.

[Comparative Examples 1 to 5]
An article having a fine concavo-convex structure on its surface was prepared and evaluated in the same manner as in Example 1 except that the active energy ray-curable resin composition (X) was changed to that shown in Table 3. The evaluation results are shown in Table 3.

[Evaluation Result / Comparison between Example and Comparative Example]
The articles of Examples 1 to 8 exhibited excellent steel wool scratch resistance as an effect of using the polymerizable component (A). Furthermore, the articles of Examples 4 to 8 exhibited excellent water repellency as an effect of using the polymerizable component (B). In addition, the curable liquids of Examples 1 to 8 (active energy ray-curable resin composition (X)) were all transparent in appearance.

  On the other hand, in Comparative Examples 1 to 3, since the polymerizable component (A) was not used, the steel wool scratch resistance was inferior. Specifically, the scratches were white and cloudy in Comparative Example 1, 50 or more scratches were made in Comparative Example 2, and 50 or more scratches were made in Comparative Example 3 and the scratched part was cloudy white. Further, in Comparative Examples 1 and 2, since the polymerizable component (B) was not contained, the contact angle was small and the hydrophilicity was exhibited. In Comparative Examples 4 and 5, the curable liquid became white and cloudy at the stage of preparing the curable liquid (thus, the article was not evaluated).

  The article having a fine concavo-convex structure on the surface according to the embodiment of the present invention is an antireflection article (antireflection film, antireflection film, etc.), super water repellent article (super water repellent film, antifouling film, etc.), optical waveguide, relief. It can be expected to find applications as optical articles such as holograms, lenses, polarization separation elements, and cell culture sheets, and is particularly suitable for use as antireflection articles and superhydrophobic articles.

  As the antireflection article, for example, an image display device (a liquid crystal display device, a plasma display panel, an electroluminescence display, a cathode ray tube display device, etc.), an antireflection film provided on the surface of a lens, a show window, eyeglasses, etc., an antireflection film. , An antireflection sheet and the like.

  Examples of the super water-repellent article include films for mirrors (door mirrors and the like) of transportation equipment such as automobiles, reform films for water supply, and films for building materials such as window films.

10 Laminate (article having fine concavo-convex structure)
11 base material 12 surface layer (cured resin layer)
13, 13b Convex portion 13a Convex portion apex 14 Concave portion 14a Concave bottom point 15 Coating layer W1 Distance between adjacent convex portions d1 Vertical distance from bottom point of concave portion to apex of convex portion 20 Stamper 30 Aluminum base material 31 Pore 32 Oxide film 33 Pore generation point 34 Oxide film 35 Pore 40 Article having fine uneven structure 41 Roll stamper 42 Base material 43 Tank 44 Cured resin layer 45 Pneumatic cylinder 46 Nip roll 47 Peeling roll 48 Active energy ray irradiation device

Claims (9)

An article comprising a cured product of an active energy ray-curable resin composition containing a polymerizable component (P) and a photopolymerization initiator (E),
The cured product includes a cured resin layer formed on a substrate,
The surface of the cured product has a fine concavo-convex structure composed of a plurality of convex portions,
The polymerizable component (P) is based on 100% by mass of the total amount of the polymerizable component (P),
50 to 99.5% by mass of a polymerizable component (A), which is an alkanediol di (meth) acrylate made from an alkanediol having 6 or more carbon atoms,
0.5 to 50% by mass of a polymerizable component (B) which is at least one of silicone (meth) acrylate and alkyl (meth) acrylate, and a polyfunctional (meth) having three or more (meth) acryloyl groups in the molecule. Containing 0 to 49.5 mass% of a polymerizable component (C) which is an acrylate,
The content of the photopolymerization initiator (E) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable component (P),
An article in which the silicone (meth) acrylate of the polymerizable component (B) is a compound represented by the following formula (1).

An article comprising a cured product of an active energy ray-curable resin composition containing a polymerizable component (P) and a photopolymerization initiator (E),
The cured product includes a cured resin layer formed on a substrate,
The surface of the cured product has a fine concavo-convex structure composed of a plurality of convex portions,
The polymerizable component (P) is based on 100% by mass of the total amount of the polymerizable component (P),
50 to 90% by mass of a polymerizable component (A), which is an alkanediol di (meth) acrylate prepared from an alkanediol having 6 or more carbon atoms,
A polymerizable component (B), which is at least one of silicone (meth) acrylate and alkyl (meth) acrylate, and a polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in the molecule. 10 to 50% by mass of a certain polymerizable component (C),
The content of the photopolymerization initiator (E) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the polymerizable component (P),
An article in which the silicone (meth) acrylate of the polymerizable component (B) is a compound represented by the following formula (1).

The content of the polymerizable component (A) is 50 to 89.5% by mass,
The content of the polymerizable component (B) is 0.5 to 40% by mass,
The article according to claim 1, wherein the content of the polymerizable component (C) is 10 to 49.5% by mass. The article according to any one of claims 1 to 3 , wherein the active energy ray-curable resin composition contains an internal release agent (F). The article according to claim 4 , wherein the internal release agent (F) is a (poly) oxyalkylene alkyl phosphate compound. The article according to any one of claims 1 to 5 , wherein in the fine concavo-convex structure, an average interval between adjacent convex portions is 400 nm or less. The article according to any one of claims 1 to 6 , which is a display member. The article according to any one of claims 1 to 7 , which is an antireflection article. The article according to any one of claims 1 to 6 , which is a water-repellent film.

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