JP2014126761A - Laminate and manufacturing method therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate having an anti-reflection capability with a micro concavo-convex structure and offers superior scratch resistance and pencil hardness.SOLUTION: A laminate comprises at least a base material, an intermediate layer, and a micro concavo-convex structure layer laminated together. The intermediate layer and the micro concavo-convex structure layer are made of a cured active energy ray-curable composition. The micro concavo-convex structure layer has a concavo-convex structure in which a distance between each pair of adjacent protrusions is less than wavelengths of visible light. The intermediate layer is made of a hybrid of inorganic components and organic components.

Description

  The present invention relates to a laminate and a method for producing the same.

  It is known that a fine concavo-convex structure having a fine concavo-convex structure on the surface exhibits antireflection performance due to a continuous change in refractive index. In addition, the fine concavo-convex structure can also exhibit super water-repellent performance due to the lotus effect. However, on the surface of the fine concavo-convex structure, the nanoscale convex portions are easily broken, and the scratch resistance and durability are low as compared to the smooth surface formed of the same resin.

  Examples of a method for forming a fine concavo-convex structure include, for example, a method of injection molding or press molding using a stamper having an inverted structure of a fine concavo-convex structure, an active energy ray curable composition between a stamper and a transparent substrate. (Hereinafter sometimes referred to as “composition”), the composition is cured by irradiation with active energy rays, and the stamper is removed after transferring the uneven shape of the stamper. The uneven shape of the stamper in the composition A method has been proposed in which the stamper is peeled off after transferring the composition, and then the composition is cured by irradiation with active energy rays. Among these, considering the transferability of the fine concavo-convex structure and the degree of freedom of the surface composition, a method of curing the composition by irradiation with active energy rays and transferring the fine concavo-convex structure is preferable. This method is particularly suitable when a belt-shaped or roll-shaped stamper capable of continuous production is used, and is a method with excellent productivity.

  In order for the fine concavo-convex structure to exhibit good antireflection performance, the distance between adjacent convex portions or concave portions needs to be a size equal to or smaller than the wavelength of visible light.

  So far, we have proposed a fine concavo-convex structure in which a fine concavo-convex structure is formed by a method of curing the composition by irradiation of active energy rays and transferring the fine concavo-convex structure, and a composition for forming a fine concavo-convex structure. Has been.

  For example, Patent Document 1 describes that a fine concavo-convex structure having a wavelength equal to or smaller than the wavelength of visible light is prepared using a silica sol that is packed in a close packing as a template. As a composition for forming this fine concavo-convex structure, a polyfunctional monomer having an extremely high number of double bonds per molecular weight such as trimethylolpropane triacrylate is used.

  Patent Document 2 describes that the hard coat layer having fine irregularities is desirably a resin having a hardness of “H” or higher in a pencil hardness test according to JIS K5600-5-4. In the examples, polyfunctional monomers having an extremely high number of double bonds per molecular weight, such as dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and pentaerythritol tetraacrylate, are used.

  Patent Documents 2 and 3 disclose an intermediate layer that improves the adhesion and adhesion between the base film and the surface layer of the nano uneven structure. Further, Patent Document 4 discloses a laminate including a refractive index adjusting layer in the lower layer on the surface of the nano uneven structure in order to enhance the antireflection effect. Patent Document 5 discloses an antireflection film in which an intermediate layer having a function of restoring dents (self-healing function) and a hard coat layer having a different refractive index are provided thereon.

JP 2000-71290 A JP 2002-107501 A Japanese Patent No. 3627304 JP 2009-31764 A Japanese Patent No. 3676260

However, the nano uneven structures described in Patent Documents 1 to 4 do not always satisfy the scratch resistance. In particular, if the resin forming the nano uneven structure is hardened, it becomes brittle, and when the scratch test is performed with steel wool or the like, the nano uneven structure is destroyed and the antireflection performance is easily lost. Regarding the pencil hardness, it is difficult to prevent the anti-reflection performance from being lost due to the nano uneven structure being destroyed in the pencil hardness test.
Moreover, about the intermediate | middle layer of patent documents 2-4, it aims at the improvement of the adhesiveness of a layer, and antireflection performance.
The antireflection film described in Patent Document 5 has an intermediate layer having a self-repairing function against depression due to pressing, but does not necessarily have a function of improving pencil hardness.

  The present invention has been made in view of the above-mentioned background art, and the problem is that in a laminate that can exhibit a low reflectance by having a fine concavo-convex structure on the surface, both scratch resistance and pencil hardness are compatible. It is in providing the laminated body made, and its manufacturing method.

  As a result of intensive studies to solve the above problems, the present inventors have found that a laminate having a specific configuration can solve the above problems, and have reached the present invention.

That is, the present invention is a laminate formed by laminating at least a base material, an intermediate layer, and a fine uneven structure layer, and the intermediate layer and the fine uneven structure layer are a cured product of an active energy ray-curable composition. The fine concavo-convex structure layer has a concavo-convex structure in which the interval between adjacent convex portions is equal to or less than the wavelength of visible light, and the intermediate layer is a hybrid of an inorganic component and an organic component. It is.
It is preferable that the said intermediate | middle layer contains the particle | grains whose average particle diameter is below the wavelength of visible light as an inorganic component.
It is preferable that the said intermediate | middle layer contains the silica whose average particle diameter is below the wavelength of visible light as an inorganic component.
It is preferable that the inorganic component content of the intermediate layer is 50% by mass or more and 70% by mass or less.
It is preferable that the said intermediate | middle layer contains polyfunctional (meth) acrylate as an organic component.

Moreover, this invention is a manufacturing method of a laminated body characterized by including the following process (I)-(III).
Step (I): A step of forming an uncured intermediate layer by applying an active energy ray-curable composition containing a solvent onto the substrate and then drying the composition.
Step (II): A step of disposing an active energy ray-curable composition for a fine uneven structure layer between the intermediate layer and the fine uneven transfer stamper.
Step (III): A step of irradiating active energy rays from the base material side to cure the active energy ray curable composition for the intermediate layer and the fine concavo-convex structure layer, and then releasing the laminate from the stamper.

  It is preferable that the uncured intermediate layer after the step (I) has a touch-drying property.

  The present invention is also a laminate comprising at least a substrate and a hybrid layer of an organic component and an inorganic component, wherein the hybrid layer has a touch-drying property in an uncured state. It is a laminate.

ADVANTAGE OF THE INVENTION According to this invention, the laminated body excellent in the light reflection preventing performance, the light transmission performance, a mechanical characteristic, etc. can be provided. Among the mechanical properties, “steel wool resistance” reflecting scratch resistance, etc. and “pencil hardness” different from it are in a trade-off relationship, but according to the present invention, both properties are good and sufficiently practical. Can be provided. Thereby, specifically, it is possible to provide a laminate having excellent mechanical properties for applications such as antireflection for FPD, light transmission improvement, surface protection, and the like.

It is a typical sectional view showing an embodiment of a layered product of the present invention. It is typical sectional drawing which shows an example of the manufacturing process of the stamper used in order to form a fine uneven structure.

[Laminate]
The laminate of the present invention is composed of a substrate, an intermediate layer, and a fine relief structure (hereinafter also including a nano relief structure) layer. The intermediate layer and the fine concavo-convex structure layer are a cured product of an active energy ray-curable composition, and the fine concavo-convex structure layer has a concavo-convex structure in which the interval between adjacent convex portions is equal to or less than the wavelength of visible light, The intermediate layer is characterized by being a hybrid of an organic component and an inorganic component. The intermediate layer may be two or more layers, but is preferably one layer from the viewpoint of productivity and cost.

[Base material]
The base material may be any material as long as it can support the fine concavo-convex structure layer serving as the surface layer through the intermediate layer. However, as will be described later, the surface layer can be cured by irradiation with active energy rays through the base material, and a light-shielding stamper can be used. Hereinafter, it may be referred to as “light-transmitting substrate”). The light-transmitting substrate is not particularly limited as long as it is a molded body that transmits the active energy ray. Examples of the material constituting the light-transmitting substrate include methyl methacrylate (co) polymer, polycarbonate, styrene (co) polymer, methyl methacrylate-styrene copolymer, lactone ring-containing (co) polymer, and cycloolefin. Synthetic polymers such as (co) polymers; semisynthetic polymers such as cellulose diacetate, cellulose triacetate, and cellulose acetate butyrate; polyesters such as polyethylene terephthalate and polylactic acid; polyamides, polyimides, polyethersulfones, polysulfones, polyethylenes Polypropylene, polymethylpentene, polyvinyl chloride, polyvinyl acetal, polyether ketone, polyurethane, composites of these polymers (for example, composites of polymethyl methacrylate and polylactic acid, polymethyl methacrylate) Composite of polyvinyl chloride); like glass.

  The shape and manufacturing method of the substrate are not particularly limited. For example, an injection molded body, an extrusion molded body, and a cast molded body can be used. The shape may be a sheet shape, a film shape, or other three-dimensional shapes. In particular, from the viewpoint of facilitating the molding of the upper layer, the shape is preferably a flexible film. Furthermore, the surface of the substrate may be coated or corona treated for the purpose of improving properties such as adhesion, antistatic properties, scratch resistance, and weather resistance.

  When the substrate is a film, the thickness is preferably 500 μm or less. By using such a film substrate, a molded article having a nano uneven surface can be easily produced.

[Middle layer]
The intermediate layer of the present invention is a cured product obtained by curing a hybrid type active energy ray-curable tree species composition of an inorganic component and an organic component. As the intermediate layer composition, a composition containing an inorganic component (A), an organic component (B), an active energy ray polymerization initiator (C), and a solvent component (D) is suitably used.

(Inorganic component (A))
The inorganic component (A) is used for imparting an effect of improving pencil hardness to the intermediate layer and dryness to touch in an uncured state.

  The average particle size of the inorganic component (A) is preferably 400 nm or less, more preferably 150 nm or less, and even more preferably 50 nm or less. When the average particle size is 400 nm or less, the particle size is equal to or smaller than the visible light wavelength, and thus the intermediate layer can be made transparent. Moreover, since the adhesiveness with a base material becomes so favorable that a particle diameter is small, the one where the particle diameter of an inorganic component (A) is smaller is desirable. Specifically, an average particle diameter of about 10 to 15 nm is optimal. When the average particle size is larger than 10 nm, the viscosity of the intermediate layer composition does not become too large, and the process passability during production is good.

  Examples of the inorganic component (A) include metal oxides such as silica (silicon dioxide), alumina (aluminum oxide), zirconia (zirconium dioxide), titania (titanium dioxide), and zinc oxide. Among these, silica is preferable because the difference in refractive index between the organic component (B) and the composition for fine concavo-convex structure can be easily reduced.

  Among silicas, a solvent-dispersed colloidal silica is preferable because the average particle size is small and the solution is relatively easy to handle. Colloidal silica having a particle size of about 10 to 15 nm, 40 to 50 nm, or 70 to 100 nm is commercially available. From the viewpoint of adhesion to the above-mentioned substrate, those having a particle diameter of 10 to 15 nm are most preferable.

  The inorganic component (A) is preferably surface-modified in order to improve the dispersibility in the intermediate layer composition and to improve the adhesion at the organic / inorganic interface after the intermediate layer is cured. For example, when silica is used as the inorganic component (A), surface modification is possible by forming a chemical bond with a silanol group on the silica surface using a silane coupling agent. Examples of the functional group introduced onto the surface of the inorganic component (A) by surface modification include a (meth) acryloyl group and an alkyl group. Examples of the silane coupling agent preferably used include Shin-Etsu Chemical Co., Ltd .; KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, and the like.

As the surface modification type colloidal silica used as the inorganic component (A), for example,
Made by Nissan Chemical Industries; MEK-AC-2101, MEK-AC-2202, MEK-AC-2140Z, MEK-AC-4101, MEK-AC-5101, MIBK-SD, MIBK-SD-L, MEK-ST- 40, TOL-ST and the like.

  The ratio (inorganic component content) of the inorganic component (A) in the intermediate layer composition is the ratio of the inorganic component in the intermediate layer after coating and drying. The ratio of the inorganic component (A) is preferably in the range of 50 to 75% by mass, and more preferably in the range of 55 to 70% by mass.

  The inorganic component content referred to here is a ratio of a pure inorganic component to the inorganic component (A). For example, when the inorganic component (A) is a surface-modified colloidal silica, the ratio of the solid content of only the silica component excluding the organic group introduced by the surface modification is defined as the inorganic component content.

By making the inorganic component content within the above range, it is possible to impart touch drying properties when the intermediate layer is in an uncured state. Here, finger-drying refers to a property that does not leave a mark on the surface of the coating film when the coating film such as an uncured intermediate layer is touched. If the intermediate layer is dry to the touch, the surface of the intermediate layer is not sticky, so that the laminate can be wound or transported including a step of contacting the roll. If the inorganic component content is too low, sufficient hardness cannot be obtained and the effect of improving the pencil hardness of the intermediate layer is weakened, or the intermediate layer is coated and dried, and the surface becomes sticky in an uncured state. May not be able to wind up.
On the other hand, if the inorganic component content is too high, the surface of the intermediate layer may be whitened after coating and drying, or the adhesion with the composition for forming a fine uneven structure may be reduced. When the inorganic component content is too high, the intermediate layer is almost free from organic components in the vicinity of the surface after coating and drying.

  When the intermediate layer composition is applied to the substrate surface and dried, the organic component (B) in the intermediate layer composition preferentially permeates the substrate side at the interface between the substrate and the intermediate layer. Since the amount of the organic component penetrating the substrate side varies depending on the solvent formulation and the type of the substrate, the inorganic component content needs to be appropriately adjusted within the above range.

  When the formation of the intermediate layer and the formation of the fine concavo-convex structure layer are carried out without a winding process, the touch-drying property after coating / drying of the intermediate layer is not an important performance, so the hardness is impaired. It becomes possible to reduce the inorganic component content within a range.

(Organic component (B))
The organic component (B) has a role as a matrix that fills voids formed by the inorganic component (A), a role to penetrate the base material during coating / drying to ensure adhesion, and a composition for forming a fine concavo-convex structure layer At the same time, it cures and crosslinks to form a chemical bond at the interface with the composition for a fine concavo-convex structure layer, thereby ensuring adhesion.

  The compound that can be used as the organic component (B) preferably has a polymerizable functional group in order to impart hardness to the intermediate layer. Examples of the compound that can be used as the organic component (B) include a radical polymerizable compound, a cationic polymerizable compound, an anion polymerizable compound, etc., but the radical polymerizable compound has a wide polymerization rate and a wide range of material selection. Is preferred. As the radical polymerizable functional group, a (meth) acryloyl group having excellent active energy ray curability and abundant choice of materials is preferable.

  Since the organic component (B) plays a role of permeating into the base material during coating / drying to improve adhesion, it is preferable that the organic component (B) contains a component excellent in permeation into the base material. In order to ensure the permeability to the substrate, it is preferable that the molecular weight of the organic component (B) is small. However, it is preferable that the viscosity of the organic component (B) is high so that the intermediate layer has a touch-drying property in an uncured state after coating and drying. In general, the smaller the molecular weight, the lower the viscosity. Therefore, the organic component (B) needs to balance the properties in this trade-off relationship. Therefore, the molecular weight of the main component of the organic component (B) is preferably 100 to 10000 [g / mol], more preferably 200 to 5000 [g / mol], and still more preferably 300 to 2000 [g / mol].

  Further, the main component of the organic component (B) is required to have a high hardness after curing in order to give the intermediate layer an effect of improving pencil hardness. Specifically, the result of measuring the pencil hardness of the cured product of the main component on a glass substrate is preferably 2H or more, and more preferably 4H or more.

  The organic component (B) preferably has an intermolecular interaction with the inorganic component (A) in order to uniformly disperse the inorganic component (A) contained in the intermediate layer within the layer. For example, when the inorganic component (A) is silica, it preferably has a functional group capable of forming an intermolecular hydrogen bond. Examples of the functional group capable of forming an intermolecular hydrogen bond include a hydroxyl group and a urethane bond.

Examples of the compound that can be used as the main component of the organic component (B) include pentaerythritol (tri) tetraacrylate, dipentaerythritol (penta) hexaacrylate, tripentaerythritol polyacrylate, polypentaerythritol polyacrylate, and glycerol tris. Examples include acrylate, diglycerin tetraacrylate, polyglycerin polyacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, sorbitol hexaacrylate, and isocyanuric acid EO-modified triacrylate.
Furthermore, the alkylene oxide modified body, caprolactone modified body, etc. of said compound are mentioned.
Furthermore, urethane acrylate synthesized by reacting pentaerythritol triacrylate having a hydroxyl group or dipentaerythritol pentaacrylate with an isocyanate compound such as hexamethylene diisocyanate or isophorone diisocyanate among the above-mentioned compounds.

As a commercial item which can be used as an organic component (B), for example, Toagosei Co., Ltd. Aronix series: M-309, M-310, M-321, M-350, M-360, M-313, M -315, M-327, M-306, M-305, M-451, M-450, M-408, M-403, M-400, M-402, M-404, M-406, M-405 , Etc.
Besides, NK series manufactured by Shin-Nakamura Chemical Co., Ltd .: A-9300, A-9300-1CL, A-GLY-9E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A- Examples include TMPT, AD-TMP, A-TMMT, A-9550, A-DPH, A-PG5009E, A-PG5027E, and the like.
Others are Biscoat series manufactured by Osaka Organic Chemical Industry Co., Ltd .: V # 295, V # 300, V # 400, V # 360, V # 3PA, V # 3PMA, V # 802, V # 1000, V # 1020, STAR -501, etc.
In addition, Nippon Kayaku Co., Ltd. Kayalad series: GPO-303, TMPTA, THE-330, TPA-330, PET-30, T-1420 (T), RP-1040, DPHA, DPEA-12, DPHA-2C , D-310, DPCA-20, DPCA-60, and the like.
Other examples include Kyoeisha Chemical Co., Ltd .: UA-306H, UA-306T, UA-306I, UA-510H, and the like.
Others include Negami Kogyo Co., Ltd .: UN-906, UN-3320HA, HUN-3320HC, UN-3320HS, UN-904, UN-901T, UN-905, UN-952, and the like.

  The main component of the organic component (B) is preferably 50% by mass or more, more preferably 60% by mass or more in the organic component (B).

The organic component (B) can be added with a flexibility-imparting component for the purpose of imparting toughness and bending resistance to the intermediate layer and preventing the occurrence of cracks and the like.
Examples of the compound that can be used as the flexibility-imparting component of the organic component (B) include:
Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, polybutadiene-terminated diacrylate, hydrogenated polybutadiene-terminated diacrylate, alkoxylated bisphenol Bifunctional (meth) acrylates such as A diacrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate,
Monofunctional (meth) acrylates such as methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, lauryl (meth) acrylate, (iso) stearyl (meth) acrylate, urethane (meth) acrylate, epoxy (meth) Examples thereof include acrylate and polyester (meth) acrylate.

As a commercial item which can be used as a softness | flexibility provision component of an organic component (B), for example,
NK series manufactured by Shin-Nakamura Chemical Co., Ltd .; AM-90G, AM-130G, AMP-20GY, S-1800A, A-200, A-400, A-600, A-1000, A-B1206PE, ABE-300, APG -700, A-PTMG-65, M-90G, M-230G, S, S-1800M, 4G, 9G, 14G, 23G, BPE-100, BPE-200, BPE-500, BPE-900, BPE-1300N , DOD-N, HD-N, NOD-N, and the like.
Other examples include biscort series manufactured by Osaka Organic Chemical Industry; LA, ISTA, V # 230, V # 260, and the like.
Others are manufactured by Daicel Cytec; EBECRYL 210, EBECRYL 230, EBECRYL 270, EBECRYL 9227EA, KRM 8296, EBECRYL 8402, EBECRYL 9270, EBECRYL 860L, EBECRYL 860L, EBECRYL 830L 884, EBECRYL 885, and the like.

  It is preferable that the softness | flexibility provision component of an organic component (B) is 0-50 mass% in an organic component (B), More preferably, it is 5-30 mass%.

  As the organic component (B), a polymer having a polymerizable functional group can be used. By using a polymer having a polymerizable functional group, it is easy to impart touch-drying properties in an uncured state after coating and drying the intermediate layer, and toughness and bending resistance are imparted to the intermediate layer to crack. Etc. can be prevented.

  As a compound that can be used as a polymer having a polymerizable functional group of the organic component (B), a polymer obtained by reacting a (meth) acrylate (co) polymer having a glycidyl group with acrylic acid, and a hydroxyl group (meta ) A polymer obtained by reacting an acrylate (co) polymer with an isocyanate group-containing (meth) acrylate, a polymer obtained by reacting an isocyanate group-containing (meth) acrylate (co) polymer with a hydroxyl group-containing (meth) acrylate, vinyl ether And a polymer obtained by selectively polymerizing only a vinyl ether group of a monomer having a group and a (meth) acryloyl group at the same time.

Commercially available products that can be used as the polymer having a polymerizable functional group of the organic component (B) include, for example, Taisei Fine Chemical 8KX series; 8KX-012C, 8KX-014C, 8KX-018C, 8KX-052C, 8KX -077, 8KX-078, and the like.
Other examples include Shin-Nakamura Chemical Co., Ltd .; Vanare Resin GH-1203, Nippon Shokubai Co., Ltd .; AX4-HC-M08, and the like.

  The polymer having a polymerizable functional group of the organic component (B) is preferably 0 to 90% by mass in the organic component (B).

(Active energy ray polymerization initiator (C))
The active energy ray polymerization initiator (C) is a compound that generates an active species that is cleaved by irradiation with active energy rays to initiate a polymerization reaction. As the active energy ray, ultraviolet rays are preferable from the viewpoint of apparatus cost and productivity. The active species to be generated is preferably a radical in terms of reaction rate.

  Examples of the active energy ray polymerization initiator (C) that generates radicals by ultraviolet rays include, for example, benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoylbenzoate, and 4-phenylbenzophenone. , T-butylanthraquinone, 2-ethylanthraquinone, thioxanthones (2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, etc.), acetophenones (diethoxyacetophenone, 2-hydroxy-2-methyl-1- Phenylpropan-1-one, benzyldimethyl ketal, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzene Dil-2-dimethylamino-1- (4-morpholinophenyl) -butanone), benzoin ethers (benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc.), acylphosphine oxides (2,4 , 6-trimethylbenzoyldiphenylphosphine 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.

An active energy ray polymerization initiator (C) may be used individually by 1 type, and may use 2 or more types together. 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 proportion of the active energy ray polymerization initiator (C) is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass with respect to 100% by mass of the organic component (B), and 0.2 to 3% by mass is more preferable. When the ratio of the active energy ray polymerization initiator (C) is less than 0.01% by mass, the active energy ray curable composition is not completely cured, and the intermediate layer cannot have a sufficient elastic modulus, and the pencil hardness of the laminate. May decrease. When the ratio of the active energy ray polymerization initiator (C) exceeds 10% by mass, the unreacted active energy ray polymerization initiator (C) remains in the cured product, which acts as a plasticizer, and the elastic modulus of the cured product. And the pencil hardness of the laminate may be impaired. Moreover, it may cause coloring.

(Solvent (D))
The solvent (D) is used for ensuring the coating property when the intermediate layer composition is applied and dried and the adhesion between the intermediate layer and the substrate.

  The viscosity of the intermediate layer composition that provides good coatability of the intermediate layer is preferably 3 to 200 [mPa · sec], more preferably 5 to 100 mPa [mPa · sec] at 25 ° C. For measuring the viscosity, an E-type viscometer or a B-type viscometer can be used. If the viscosity is too low, the thickness of the intermediate layer after drying cannot be increased, and the target pencil hardness may not be achieved. If the viscosity is too high, the leveling property at the time of coating may deteriorate, and streaky film thickness unevenness may occur.

  The solid content concentration of the intermediate layer composition is preferably 30% by mass or more and 80% by mass or less, and more preferably 35% by mass or more and 60% by mass or less. If the solid content concentration is too high, since the solvent (D) is small, the penetration of the organic component (B) into the substrate may be insufficient and the adhesion to the substrate may be reduced. If the solid content concentration is too low, the thickness of the intermediate layer after drying cannot be increased, and the target pencil hardness may not be achieved.

  It is preferable that a solvent (D) contains the solvent which melt | dissolves a base material in order to ensure the adhesiveness to a base material. When the solvent (D) contains a solvent that dissolves the base material, a relaxation layer in which the interface between the base material and the intermediate layer is compatible can be formed, and as a result, adhesion is improved. In such a state, since the interface reflection between the base material and the intermediate layer can be reduced, there is an effect that the generation of interference fringes and the like can be suppressed.

For example, when a triacetyl cellulose film is a base material, as a solvent for dissolving triacetyl cellulose,
Ethers having 3 to 12 carbon atoms: specifically, dibutyl ether, dimethoxymethane, dimethoxyethane, diethoxyethane, propylene oxide, 1,4-dioxane, 1
, 3-dioxolane, 1,3,5-trioxane, tetrahydrofuran, anisole and phenetole, etc.
Ketones having 3 to 12 carbon atoms: specifically, acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, methylcyclohexanone, etc.
Esters having 3 to 12 carbon atoms: specifically, ethyl formate, propyl formate, n-pentyl formate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, n-acetate
Pentyl, γ-butyrolactone, etc.
Organic solvent having two or more kinds of functional groups: Specifically, methyl 2-methoxyacetate, methyl 2-ethoxyacetate, ethyl 2-ethoxyacetate, ethyl 2-ethoxypropionate, 2-methoxyethanol, 2-propoxyethanol 2-butoxyethanol, 1,2-diacetoxyacetone, acetylacetone, diacetone alcohol, methyl acetoacetate, and ethyl acetoacetate.
Some halogen hydrocarbons dissolve triacetyl cellulose, but it is preferable not to use them in terms of the global environment and working environment.

  The solvent (D) is preferably a combination of a solvent having a high evaporation rate and a solvent having a low evaporation rate. By combining a solvent with a high evaporation rate and a slow solvent, it is possible to achieve both a short drying time and an excellent surface condition. In the case of only a solvent having a high evaporation rate, the residence time of the solvent is too short, and the time for the organic component (B) to penetrate into the base material cannot be secured, resulting in a decrease in adhesion or a rough surface and white turbidity. There is a case. On the other hand, in the case of only a solvent having a low evaporation rate, the drying time becomes long, the line speed becomes slow, and productivity may be lowered.

  The composition ratio of the solvent having a high evaporation rate and the solvent having a low evaporation rate is preferably adjusted in the range of about 40:60 to 90:10. Since the drying time and the permeability to the substrate differ depending on the type of solvent to be combined, it is necessary to optimize the composition ratio for each combination.

  Further, the solvent (D) can control the amount of the organic component (B) penetrating into the base material by combining a solvent that dissolves the base material and a solvent that does not dissolve the base material.

(Ultraviolet absorber and / or antioxidant (E))
The intermediate layer composition may further contain an ultraviolet absorber and / or an antioxidant (E).
Examples of the ultraviolet absorber include benzophenone, benzotriazole, hindered amine, benzoate, and triazine. Examples of commercially available products include UV absorbers such as “Tinuvin 400” and “Tinuvin 479” manufactured by Ciba Specialty Chemicals, and “Viosorb110” manufactured by Kyodo Pharmaceutical.
Examples of the antioxidant include hindered phenol-based, benzimidazole-based, phosphorus-based, sulfur-based and hindered amine-based antioxidants. Commercially available products include “IRGANOX” series and “TINUVIN” series manufactured by BASF.
These ultraviolet absorbers and antioxidants may be used alone or in combination of two or more.
As for the ratio of a ultraviolet absorber and / or antioxidant (E), 0.01-5 mass% in total is preferable with respect to 100 mass% of organic components (B).

(Release agent (F))
The intermediate layer composition used in the present invention may further contain a release agent (F) and the like. The mold release agent (F) is used to temporarily transfer the intermediate layer composition and the fine relief structure at the start and end of the process in the step of curing the fine relief structure layer composition and transferring the fine relief structure. Productivity can be improved by adding it when the mold comes into contact. By adding the release agent (F), it is possible to suppress the intermediate layer composition and the cured product thereof from remaining on the surface of the fine uneven structure transfer mold.

  As the release agent (F), it is preferable to use the same compound as the internal release agent to be added to the composition for a fine uneven structure layer described later.

  Examples of the release agent (F) 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 phosphate compound, and commercially available products include JP-506H manufactured by Johoku Chemical Co., Ltd., Mold Width INT-1856 manufactured by Accel Corporation, TDP-10 manufactured by Nikko Chemicals Co., Ltd., and TDP- 8, TDP-6, TDP-2, DDP-10, DDP-8, DDP-6, DDP-4, DDP-2, TLP-4, TCP-5, and DLP-10.

  The ratio of the release agent (F) is preferably 0.01 to 1% by mass and more preferably 0.1 to 0.5% by mass with respect to 100% by mass of the organic component (B).

(Other ingredients (G))
The intermediate layer composition used in the present invention comprises a surfactant, a lubricant, a plasticizer, an antistatic agent, a light stabilizer, a flame retardant, a flame retardant aid, a polymerization inhibitor, a pH adjuster, and a dispersion as necessary. Known additives such as a property aid, a leveling agent, a filler, a silane coupling agent, a coloring agent, a reinforcing agent, an impact modifier, and a conductivity imparting agent may be included. In particular, if an antistatic agent, an ultraviolet absorber, a near infrared absorber, etc. are contained in the surface layer, it may be difficult to maintain the shape of the fine concavo-convex structure. Therefore, these additives are contained in the surface layer. It is preferable that it is contained in the intermediate layer from the viewpoint of scratch resistance of the laminate and suppression of reflection.

  The antistatic agent suppresses dust and the like from adhering to the laminate. Examples of the antistatic agent include conductive polymers such as polythiol-based, polythiophene-based, and polyaniline-based materials, inorganic fine particles such as carbon nanotubes and carbon black, lithium salts as exemplified in JP-A-2007-70449, A quaternary ammonium salt is mentioned. These may be used alone or in combination. Among these, as the antistatic agent, lithium perfluoroalkyl acid salt that does not impair the transparency of the laminate, is relatively inexpensive, and exhibits stable performance is preferable.

  The addition amount of the antistatic agent is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer component or polymer in the intermediate layer raw material (that is, 100 parts by mass of the polymerizable component in the intermediate layer). 10 mass parts is more preferable. If it is 0.5 mass part or more, the surface resistance value of a laminated body can be made low and dust adhesion prevention performance is exhibited. If it is 20 mass parts or less, the improvement degree of the performance per addition amount will be favorable, and cost can be suppressed. In order to exhibit good antistatic performance, the thickness of the surface layer laminated on the intermediate layer is preferably 100 μm or less, and more preferably 50 μm or less.

  A near-infrared absorber can give a heat insulation effect to a laminated body, and can suppress malfunction of the infrared remote control of various household appliances, when a laminated body is used for a plasma display etc. Examples of near infrared absorbers include organic dyes such as diimonium dyes, phthalocyanine dyes, dithiol metal complex dyes, substituted benzenedithiol metal complex dyes, cyanine dyes, squalium dyes, and conductive antimony Examples thereof include inorganic particles such as tin oxide fine particles, conductive tin-containing indium oxide fine particles, tungsten oxide fine particles, and composite tungsten oxide fine particles. These may be used alone or in combination.

  These additives may be added to the surface layer of the laminate. However, it is preferable to add it to the intermediate layer without adding it to the surface layer, since it is possible to suppress the maintenance of the fine uneven surface shape and to suppress the occurrence of bleed out over time.

[Fine uneven structure layer]
The fine concavo-convex structure layer of the laminate of the present invention is a cured product of the active energy ray-curable composition, and has a concavo-convex structure in which the interval between adjacent convex portions is equal to or less than the wavelength of visible light.
As the composition for a fine concavo-convex structure layer, a composition containing a polymerizable organic component (XB), an active energy ray polymerization initiator (XC), and an internal release agent (XF) is preferably used.
The composition for a fine concavo-convex structure layer is preferably one that improves the scratch resistance performance of the fine concavo-convex structure layer.

  Examples of the compound that can be used as the polymerizable organic component (XB) include radically polymerizable compounds, cationically polymerizable compounds, and anionic polymerizable compounds. The radically polymerizable compound has a wide polymerization rate and a wide range of material selection. Is preferred. As the radical polymerizable functional group, a (meth) acryloyl group having excellent active energy ray curability and abundant choice of materials is preferable.

  The compound having a (meth) acryloyl group that can be used as the polymerizable organic component (XB) preferably contains a bifunctional or higher functional (meth) acrylate as a main component in order to increase the scratch resistance of the fine relief structure. More preferably, the main component is a functional (meth) acrylate or higher.

  On the other hand, if the cured product of the composition for fine concavo-convex structure layer is too hard, the elastic modulus becomes high but becomes brittle, and the fine concavo-convex structure is easily broken or scraped, so that high scratch resistance cannot be obtained. Therefore, for example, it is effective to introduce an oxyethylene group into the cross-linked structure to give flexibility and improve scratch resistance. In order to introduce an oxyethylene group into the crosslinked structure, polyethylene glycol di (meth) acrylate may be used, or tri- or higher functional ethylene oxide-modified (hereinafter referred to as EO modification) (meth) acrylate may be used. it can.

  As the composition for a fine concavo-convex structure layer, it is preferable to adjust the hardness by combining a hard component (XB1) having a small acrylic equivalent and a soft component (XB2) having a large acrylic equivalent. The acrylic equivalent is a numerical value represented by the molecular weight per (meth) acryloyl group.

When a (meth) acrylate having an acrylic equivalent of less than 150 [g / eq] is a hard component (XB1) and a (meth) acrylate having an acrylic equivalent of 150 [g / eq] or more is a soft component (XB2), XB1) includes, for example, pentaerythritol (tri) tetraacrylate, dipentaerythritol (penta) hexaacrylate, tripentaerythritol polyacrylate, polypentaerythritol polyacrylate, glycerin triacrylate, diglycerin tetraacrylate, polyglycerin polyacrylate, Examples include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, sorbitol hexaacrylate, and the like.
Furthermore, urethane acrylate synthesized by reacting pentaerythritol triacrylate or dipentaerythritol pentaacrylate having a hydroxyl group with an isocyanate compound such as hexamethylene diisocyanate or isophorone diisocyanate among the above-mentioned compounds.

As a commercial item of hard component (XB1), for example, Toagosei Co., Ltd. Aronix series: M-309, M-315, M-306, M-305, M-451, M-450, M-408, M -403, M-400, M-402, M-404, M-406, M-405, and the like.
In addition, NK series manufactured by Shin-Nakamura Chemical Co., Ltd .: A-9300, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, AD-TMP, A-TMMT, A- 9550, A-DPH, and the like.
Other examples include Kayrad series manufactured by Nippon Kayaku Co., Ltd .: TMPTA, THE-330, PET-30, RP-1040, DPHA, and the like.
Other examples include Kyoeisha Chemical Co., Ltd .: UA-306H, UA-306T, UA-306I, UA-510H, and the like.
As the hard component (XB1), one type may be used alone, or two or more types may be used in combination.

  Examples of the soft component (XB2) that imparts flexibility to the fine concavo-convex structure and improves scratch resistance include polyethylene glycol di (meth) acrylate, pentaerythritol EO-modified tetra (meth) acrylate, and dipentaerythritol EO-modified hexa. Examples include acrylate, tripentaerythritol EO-modified (meth) acrylate, (poly) glycerin EO-modified poly (meth) acrylate, sorbitol EO-modified hexaacrylate, and trimethylolpropane EO-modified triacrylate.

As a commercial item of soft component (XB2), for example, NK series manufactured by Shin-Nakamura Chemical Co., Ltd .; A-200, A-400, A-600, A-1000, 4G, 9G, 14G, 23G, A-PG5009E, A-PG5027E, A-PG-5054E, A-GLY-9E, A-GLY-20E, ATM-35E, etc. are mentioned.
Other examples include T-200EA and S-130EA manufactured by Toho Chemical Industries.
In addition, Nippon Kayaku Co., Ltd. KAYARAD series; DPEA-12 etc. are mentioned.
In addition, Daiichi Kogyo Seiyaku Co., Ltd .: DPHA-30EO, DPHA-36EO, DPHA-42EO, DPHA-48EO, DPHA-54EO, PETA-32EO, PETA-36EO, PETA-40EO, PETA-48EO, PETA-56EO , Etc.
A soft component (XB2) may be used individually by 1 type, and may use 2 or more types together.

  The ratio of the hard component (XB1) and the soft component (XB2) in the polymerizable organic component (XB) can be appropriately adjusted depending on the compound used. In terms of the acrylic equivalent of the polymerizable organic component (XB), when the spacing between adjacent convex portions of the fine concavo-convex structure is about 100 nm, the adjacent convex portions of the fine concavo-convex structure are about 130 to 160 [g / eq]. When the interval is about 80 nm, it is preferably adjusted at about 240 to 300 [g / eq]. In the fine concavo-convex structure, the optimum hardness of the cured product varies depending on the interval between the adjacent convex portions. The smaller the spacing between adjacent convex portions, the more likely the phenomenon that a plurality of projections of fine irregularities are brought into close contact with each other. Therefore, it is necessary to reduce the acrylic equivalent and harden the cured product of the composition for fine irregular structures. There is.

  Other compounds that can be used as the polymerizable organic component (XB) include, for example, monofunctional (meth) acrylates other than those described above, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, and reactivity. Examples thereof include polymers.

(Active energy ray polymerization initiator (XC))
The active energy ray polymerization initiator (XC) is a compound that generates an active species that is cleaved by irradiating active energy rays to initiate a polymerization reaction. As the active energy ray, ultraviolet rays are preferable from the viewpoint of apparatus cost and productivity. The active species to be generated is preferably a radical in terms of reaction rate.

  Examples of the active energy ray polymerization initiator (XC) that generates radicals by ultraviolet rays include benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoylbenzoate, and 4-phenylbenzophenone. , T-butylanthraquinone, 2-ethylanthraquinone, thioxanthones (2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, etc.), acetophenones (diethoxyacetophenone, 2-hydroxy-2-methyl-1- Phenylpropan-1-one, benzyldimethyl ketal, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone), benzoin ethers (benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc.), acylphosphine oxides (2,4 , 6-trimethylbenzoyldiphenylphosphine 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.

An active energy ray polymerization initiator (XC) may be used individually by 1 type, and may use 2 or more types together. 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 proportion of the active energy ray polymerization initiator (XC) is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass with respect to 100% by mass of the polymerizable organic component (XB). 2-3 mass% is more preferable. When the ratio of the active energy ray polymerization initiator (XC) is less than 0.01% by mass, the active energy ray curable composition is not completely cured, and the intermediate layer cannot be provided with a sufficient elastic modulus, and the pencil hardness of the laminate. May decrease. When the ratio of the active energy ray polymerization initiator (XC) exceeds 10% by mass, the unreacted active energy ray polymerization initiator (XC) remains in the cured product and acts as a plasticizer, and the elastic modulus of the cured product. And the pencil hardness of the laminate may be impaired. Moreover, it may cause coloring.

(Ultraviolet absorber and / or antioxidant (XE))
The intermediate layer composition may further contain an ultraviolet absorber and / or an antioxidant (XE) and the like.
Examples of the ultraviolet absorber include benzophenone, benzotriazole, hindered amine, benzoate, and triazine. Examples of commercially available products include UV absorbers such as “Tinuvin 400” and “Tinuvin 479” manufactured by Ciba Specialty Chemicals, and “Viosorb110” manufactured by Kyodo Pharmaceutical.
Examples of the antioxidant include hindered phenol-based, benzimidazole-based, phosphorus-based, sulfur-based and hindered amine-based antioxidants. Commercially available products include “IRGANOX” series and “TINUVIN” series manufactured by BASF.
These ultraviolet absorbers and antioxidants may be used alone or in combination of two or more.
As for the ratio of a ultraviolet absorber and / or antioxidant (XE), 0.01-5 mass% in total is preferable with respect to 100 mass% of polymerizable organic components (XB).

(Release agent (XF))
The fine concavo-convex structure layer fat composition of the present invention may contain a release agent (XF). The mold release agent (XF) is added in order to maintain the releasability from the mold for a long period in the step of curing the composition for a fine uneven structure layer and transferring the fine uneven structure.

  Examples of the release agent (XF) 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 phosphate compound, and commercially available products include JP-506H manufactured by Johoku Chemical Co., Ltd., Mold Width INT-1856 manufactured by Accel Corporation, TDP-10 manufactured by Nikko Chemicals Co., Ltd., and TDP- 8, TDP-6, TDP-2, DDP-10, DDP-8, DDP-6, DDP-4, DDP-2, TLP-4, TCP-5, DLP-10, and the like.

  The ratio of the release agent (XF) is preferably 0.01 to 1% by mass and more preferably 0.1 to 0.5% by mass with respect to 100% by mass of the polymerizable organic component (XB).

(Other components (XG))
The composition for a fine concavo-convex structure layer of the present invention includes a surfactant, a lubricant, a plasticizer, an antistatic agent, a light stabilizer, a flame retardant, a flame retardant aid, a polymerization inhibitor, a pH adjuster, if necessary. Dispersibility aids, leveling agents, fillers, silane coupling agents, colorants, reinforcing agents, impact modifiers, conductivity-imparting agents, solvents, and other known additives may be included.

[Refractive index of each layer]
The laminate of the present invention includes a constituent member of a base material, an intermediate layer, and a fine relief structure layer. The laminate of the present invention mainly has an antireflection performance due to the fine concavo-convex structure on the surface. Therefore, it is not preferable that reflection occurs at the interface of each layer of the laminate. Reflection at the interface may lead to deterioration in appearance due to generation of interference fringes as well as a decrease in antireflection performance. Therefore, it is preferable that the difference in refractive index between the base material and the intermediate layer is smaller. However, as described above, a relaxation layer in which the interface between the substrate and the intermediate layer is compatible with each other can be produced by coating and drying using a solvent as the intermediate layer composition. On the other hand, as for the interface between the intermediate layer and the fine concavo-convex structure layer, when the fine concavo-convex structure layer is formed of a solvent-based composition, a relaxation layer can be similarly formed. However, when the fine concavo-convex structure layer is formed of a solventless composition, an interface tends to remain between the intermediate layer and the fine concavo-convex structure layer. In this case, it is preferable to reduce the refractive index difference between the fine relief structure layer and the intermediate layer. Specifically, the refractive index difference between the fine relief structure layer and the intermediate layer is preferably 0 to 0.1, more preferably 0 to 0.05, and still more preferably 0 to 0.01. As the antireflection performance by the fine concavo-convex structure is higher, a slight interface reflection leads to generation of interference fringes, and therefore, the control of the refractive index difference between each layer is more important.

[Manufacturing method of laminate]
Although the manufacturing method of the laminated body of this invention is not specifically limited by the following description, The process of the following process (I)-(III) is included.
Step (I): A step of forming an uncured intermediate layer by applying an active energy ray-curable composition containing a solvent onto the substrate and then drying the composition.
Step (II): A step of disposing the active energy ray-curable composition for the fine uneven structure layer between the intermediate layer and the fine uneven transfer stamper.
Step (III): a step of irradiating active energy rays from the substrate side to cure the intermediate layer and the active energy ray-curable composition for fine concavo-convex structure layer, and then releasing the laminate from the stamper.

[Step (I)]
In the step (I), the intermediate layer composition is coated on the substrate and then dried. The step (I) ends with the intermediate layer after coating and drying remaining uncured.

  You may irradiate an active energy ray to such an extent that an intermediate | middle layer is not hardened after coating or drying an intermediate | middle layer composition. In that case, adhesion with the fine concavo-convex structure layer can be ensured by utilizing the inhibition of curing by oxygen and leaving more residual double bond groups near the surface of the intermediate layer.

  A protective film can be stuck on the intermediate layer after completion of the step (I). The protective film has functions to prevent foreign matters from adhering to the intermediate layer and to prevent blocking between the back surface of the substrate and the intermediate layer once wound up. As the protective film, a known film can be appropriately selected. Examples thereof include polyethylene terephthalate (PET) and polyethylene (PE). The surface of the protective film can be subjected to various surface treatments such as a mold release treatment, an antiblocking treatment, and an antistatic treatment.

  The coating method for the intermediate layer can be appropriately selected from various coating methods in consideration of the properties of the intermediate layer composition. Examples of the coating method include a gravure coater, a bar coater, a slot die coater, a lip coater, and a comma coater.

  The thickness of the intermediate layer after coating and drying is preferably about 5 to 40 μm, more preferably about 10 to 20 μm. If the thickness of the intermediate layer is 5 μm or more, it is possible to suppress a phenomenon in which indentation occurs due to indentation deformation by the pencil to the base material in the pencil hardness test. Moreover, if the thickness of the intermediate layer is 40 μm or less, it is possible to prevent the problem of cracking during bending and warping of the laminate. The thickness accuracy of the intermediate layer is preferably within ± 2 μm, and more preferably within ± 1 μm.

  It is preferable that the intermediate layer after the step (I) is dry to the touch in an uncured state. If it has touch dryness, the process passability is good.

[Step (II)]
In step (II), an active energy ray-curable composition for fine concavo-convex structure is disposed between the intermediate layer coated and dried in step (I) and uncured and the fine concavo-convex transfer stamper. . As a method for disposing the active energy ray-curable composition for fine concavo-convex structure, various known methods can be selected.

  When the active energy ray-curable composition for fine concavo-convex structure is solvent-free, a method (II-1) of contacting a transfer stamper after applying a curable liquid on an uncured intermediate layer using various coaters There is a method (II-2) in which a bank made of a curable liquid is formed between a roll-shaped transfer stamper and an intermediate layer, and the curable liquid is supplied to the bank from a nozzle.

  In the method (II-1), the coating method of the curing liquid of the active energy ray-curable composition for fine concavo-convex structure is appropriately determined in consideration of the properties of the active energy ray-curable composition for intermediate layer from various coating methods. Selectable. Examples of the coating method include a gravure coater, a bar coater, a slot die coater, a lip coater, and a comma coater.

  The method (II-2) includes a method in which the nozzle is replaced with a slot die coater and the like, and a curtain-like curable liquid is supplied to the bank. In this method (II-2), the film thickness of the layer made of the composition for fine concavo-convex structure is controlled by the hardness and material of the nip roll with respect to the roll-shaped transfer stamper and the nip pressure, or the gap between the roll-shaped transfer stamper and the nip roll. it can.

  When the composition for fine concavo-convex structure contains a solvent, the curable liquid is applied on the intermediate layer in the same manner as in the method (II-1) and then dried.

  About 5-40 micrometers is preferable and, as for the thickness of the layer which consists of an active energy ray curable composition for fine concavo-convex structures, about 10-20 micrometers is more preferable. If the thickness of the layer made of the active energy ray-curable composition for fine concavo-convex structure is 5 μm or more, sufficient scratch resistance can be imparted to the fine concavo-convex structure. Moreover, if the thickness of the layer made of the active energy ray-curable composition for fine concavo-convex structure is 40 μm or less, it is possible to prevent the problems of cracking during bending and warping of the laminate. The thickness accuracy of the layer made of the active energy ray-curable composition for fine concavo-convex structure is preferably within ± 2 μm, and more preferably within ± 1 μm.

[Step (III)]
In the step (III), active energy rays are irradiated from the substrate side, and the intermediate layer and the active energy ray-curable composition for fine concavo-convex structure layer are simultaneously cured. As the active energy ray, it is preferable to use ultraviolet rays from the viewpoint of apparatus cost and productivity. The irradiation amount of ultraviolet rays may be appropriately determined in consideration of the amount of initiator contained in the active energy ray-curable composition for intermediate layer and the active energy ray-curable composition for fine concavo-convex structure and the transmittance of the substrate. . The light source that generates ultraviolet rays is not particularly limited, and known ones such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a halogen lamp, and various lasers are used. The standard of the integrated light quantity is 200 to 10000 mJ / cm ² .

  In addition, when the base material absorbs a part of the ultraviolet rays, the base material may absorb the ultraviolet rays during the ultraviolet irradiation and become overheated, which may cause thermal deformation or the like. In such a case, it is preferable to take measures such as installing a filter that cuts ultraviolet rays having a wavelength that is absorbed by the base material and does not reach the intermediate layer and the fine concavo-convex structure layer, and cooling the laminate.

In step (III), the intermediate layer and the fine concavo-convex structure layer are cured simultaneously, and then the desired laminate is obtained by releasing from the stamper for fine concavo-convex structure transfer. Due to the effect of the release agent (XF) added to the active energy ray-curable composition for fine concavo-convex structure described above, the mold can be released with a low peeling force and without a chip in the fine concavo-convex structure.
Further, if the temperature at the time of mold release is lower than the temperature at the time of curing, the cured product of the resin forming the fine concavo-convex structure may be shrunk by heat shrink, and the mold release may be easier.

  The total film thickness of the intermediate layer and the fine concavo-convex structure layer cured in the step (III) is preferably about 10 μm to 80 μm, and more preferably about 20 μm to 50 μm. A thinner total film thickness is preferable because the thickness of the entire laminate of the present invention is reduced. However, in order to increase the pencil hardness of the laminate to 2H or higher, a film thickness of a certain level or more is required.

[Other processes]
As a process other than the processes (I) to (III), an inspection process such as a foreign substance or a defect can be installed between the processes (I) to (III). In addition, after the step (III), post-curing is performed by irradiating active energy rays again from the side of the fine relief structure layer to complete the curing of the intermediate layer and fine relief structure layer, or to reduce the remaining unopened initiator. The method of installing the process to let it be, the process of bonding a protective film, etc. can be considered.

[Fine relief structure]
FIGS. 1A and 1B are schematic cross-sectional views showing an embodiment of a laminate of the present invention. In FIG. 1, the laminated body 10 by which the intermediate | middle layer 15 and the surface layer (fine concavo-convex structure layer) 12 are laminated | stacked in order on the base material 11 is illustrated. As shown in FIG. 1, the surface of the surface layer 12 has a fine uneven structure in which the surface of the surface layer 12 exhibits surface antireflection properties. Specifically, it is preferable that the convex portions 13 and the concave portions 14 are formed on the surface of the surface layer 12 at approximately equal intervals. The shape of the convex part 13 of Fig.1 (a) is a cone shape or a pyramid shape, and the shape of the convex part 13 of FIG.1 (b) is bell shape. However, the shape of the convex portion 13 of the fine concavo-convex structure is not limited to these, and the occupation ratio of the cross-sectional area when cut on the surface layer 12 film surface is continuously from the center point (vertex) 13 a of the convex portion to the concave portion 14. Any structure that increases is sufficient. Further, finer convex portions may be united to form a fine concavo-convex structure. That is, even in shapes other than those shown in FIGS. 1 (a) and 1 (b), the refractive index is continuously increased from the air to the surface of the material, and the antireflection performance that achieves both low reflectance and low wavelength dependence is exhibited. Any shape can be used. In particular, a shape such as a conical shape, a pyramidal shape, a bell-shaped shape, etc. in which the cross-sectional area when cut by a plane perpendicular to the height direction of the convex portion continuously increases from the top to the bottom of the convex portion is preferable. . Further, finer protrusions may be combined to form the fine concavo-convex structure.

  In order to develop good antireflection performance, the interval between adjacent convex portions 13 or concave portions 14 of the fine concavo-convex structure [in FIG. 1A, the interval w1 between the central points (vertices) 13a of adjacent convex portions] is It is desirable that the size is equal to or smaller than the wavelength of visible light. Here, “visible light” refers to light having a wavelength of 380 to 780 nm. If this interval w1 is 400 nm or less (more preferably 380 nm or less), the scattering of visible light can be suppressed. In this case, the laminate of the present invention can be suitably used for optical applications such as an antireflection film. The lower limit value of the interval w1 is not particularly limited as long as it can be manufactured. In the case of forming a fine concavo-convex shape by a transfer method using a mold, the interval w1 is preferably 20 nm or more, and more preferably 40 nm or more from the viewpoint of ease of production of the mold. In addition, the aspect ratio represented by the height / interval w1 is preferably 0.3 or more, more preferably 0.5 or more, and 0.8 or more from the viewpoint of suppressing an increase in the minimum reflectance or the reflectance at a specific wavelength. Is particularly preferred. These lower limit values of the aspect ratio are particularly significant in terms of reducing light reflection and reducing incident angle dependency. The upper limit of the aspect ratio is not particularly limited as long as it can be manufactured. In the case of forming a fine concavo-convex shape by a transfer method using a mold, it is preferable that the aspect ratio of the convex portion is 5 or less for accurate transfer. The height of the convex portion or the depth of the concave portion [in FIG. 1A, the vertical distance d1 from the central point (bottom point) 14a of the concave portion to the central point (vertex) 13a of the convex portion] is preferably 60 nm or more, 90 nm The above is more preferable. The shape and manufacturing method of the fine concavo-convex structure that exhibits good antireflection performance are described in JP 2009-31764 A and the like, and the same shape and manufacturing method can be used in the present invention.

  The size of the fine concavo-convex structure on the surface was determined by depositing a vertical cross section of the fine concavo-convex structure for 10 minutes and observing it with a field emission scanning electron microscope (SM-7400F: manufactured by JEOL Ltd.) at an acceleration voltage of 3.00 kV. It is possible to measure the interval (period) of the matching pores and the depth of the pores, measure 10 points each, and adopt the average value.

  The laminate of the present invention is optimal as a functional article having a fine concavo-convex structure on the surface layer. Examples of such functional articles include antireflection articles and water-repellent articles provided with the laminate of the present invention. In particular, a display or an automobile member provided with the laminate of the present invention is suitable as a functional article.

[Anti-reflective article]
The antireflection article provided with the laminate of the present invention comprises a laminate having a fine concavo-convex structure as a surface layer. This antireflection article exhibits high scratch resistance and good antireflection performance. For example, a laminate having a fine concavo-convex structure is pasted on the surface of an object such as a liquid crystal display device, a plasma display panel, an electroluminescence display, a cathode ray tube display device, a lens, a show window, or a spectacle lens. Use with attachment.

[Water repellent article]
The water-repellent article provided with the laminate of the present invention includes a laminate having the fine uneven structure of the present invention as a surface layer. This water-based article exhibits high anti-reflection performance as well as high scratch resistance and good water repellency. For example, a laminate having a fine concavo-convex structure is attached to the surfaces of window materials, roof tiles, outdoor lighting, curved mirrors, vehicle windows, and vehicle mirrors.

  When the part to which the laminate of each target article is a three-dimensional shape, use a base material of a shape corresponding to it in advance, and form a laminate by forming an intermediate layer and a surface layer on the base material, What is necessary is just to affix this laminated body to the predetermined part of a target article.

  Further, when the target article is an image display device, the laminate of the present invention may be attached to the front plate, not limited to the surface thereof, or the front plate itself is configured from the laminate of the present invention. You can also.

  Moreover, the laminated body of this invention is applicable also to uses, such as optical uses, such as an optical waveguide, a relief hologram, a lens, and a polarization separation element, and a cell culture sheet other than the use mentioned above.

[Stamper for fine relief structure transfer]
The fine concavo-convex structure transfer stamper has an inverted structure of the fine concavo-convex structure on the surface.
Examples of the material of 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.

Examples of the method for producing the stamper include the following method (I-1) and method (I-2). From the viewpoint that the area can be increased and the production is simple, the method (I-1 Is particularly preferred.
(I-1) A method of forming anodized alumina having a plurality of pores (concave portions) 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 substrate by an electron beam lithography method, a laser beam interference method, or the like.

As the method (I-1), a method having the following steps (a) to (f) is preferable.
(A) A step of forming an oxide film on the surface of an aluminum substrate by anodizing the aluminum substrate in an electrolytic solution under a constant voltage.
(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.

Step (a):
As shown in FIG. 2, when the aluminum substrate 30 is anodized, an oxide film having pores 31 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. When the purity of aluminum is low, when anodized, an uneven structure having a size to scatter visible light may be formed due to segregation of impurities, or the regularity of pores obtained by anodization may be lowered.
Examples of the electrolytic solution include sulfuric acid, oxalic acid, and phosphoric acid.

When using oxalic acid as electrolyte:
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.
When the formation voltage is 30 to 100 V, anodized alumina having highly regular pores with a period of 100 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.

When using sulfuric acid as the electrolyte:
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.
When the formation voltage is 25 to 30 V, 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 lower, and more preferably 20 ° C. or lower. 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.

Step (b):
As shown in FIG. 2, the regularity of the pores can be improved by removing the oxide film 32 once and using it as the pore generation point 33 for anodic oxidation.

  Examples of the method for removing the oxide film include a method in which aluminum is not dissolved but is dissolved in a solution that selectively dissolves the oxide film and removed. Examples of such a solution include a chromic acid / phosphoric acid mixed solution.

Step (c):
As shown in FIG. 2, when the aluminum substrate 30 from which the oxide film has been removed is anodized again, an oxide film 34 having cylindrical pores 35 is formed.
Anodization may be performed under the same conditions as in step (a). Deeper pores can be obtained as the anodic oxidation time is lengthened.

Step (d):
As shown in FIG. 2, a process of expanding the diameter of the pores 35 (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.

Step (e):
As shown in FIG. 2, when anodized again, cylindrical pores having a small diameter that extend downward from the bottom of the cylindrical pores 35 are further formed.
Anodization may be performed under the same conditions as in step (a). Deeper pores can be obtained as the anodic oxidation time is lengthened.

Step (f):
As shown in FIG. 2, when the pore diameter enlargement process in the step (d) and the anodic oxidation in the step (e) are repeated, the pores 35 have a shape in which the diameter continuously decreases in the depth direction from the opening. The oxide film 34 is formed, and the stamper 20 having anodized alumina (aluminum porous oxide film (alumite)) on the surface of the aluminum base 30 is obtained. It is preferable that the last end is step (d).

  The total number of repetitions is preferably 3 times or more, and more preferably 5 times or more. When the number of repetitions is 2 times or less, the diameter of the pores decreases discontinuously, so the effect of reducing the reflectance of the fine concavo-convex structure formed using such anodized alumina having such pores is insufficient. .

Examples of the shape of the pore 35 include a substantially conical shape, a pyramid shape, a cylindrical shape, and the like, and a cross-sectional area of the pore in a direction orthogonal to the depth direction such as a conical shape and a pyramid shape has a depth from the outermost surface. A shape that continuously decreases in the direction is preferred.
The average interval between the pores 35 is not more than the wavelength of visible light, that is, not more than 400 nm. The average interval between the pores 12 is more preferably 140 to 260 nm or less, and particularly preferably 160 to 200 nm.
The average interval between the pores 35 is determined by measuring the interval between adjacent pores 35 (distance from the center of the pore 35 to the center of the adjacent pore 35) by electron microscope observation, and averaging these values. It is a thing.

The depth of the pores 35 is preferably 120 to 250 nm, more preferably 150 to 220 nm, and particularly preferably 160 to 190 nm.
The depth of the pore 35 is a value obtained by measuring the distance between the bottom of the pore 35 and the top of the convex portion existing between the pores 35 when observed with an electron microscope at a magnification of 30000 times. It is.
The aspect ratio of the pores 35 (depth of pores / average interval between pores) is preferably 0.7 to 1.4, and more preferably 0.8 to 1.2.

The surface of the stamper on which the fine uneven structure is formed may be treated with a release agent.
Examples of the release agent include silicone resins, fluororesins, fluorine compounds, and phosphate esters, and phosphate esters are particularly preferable. As the phosphoric acid ester, a (poly) oxyalkylene alkyl phosphoric acid compound is preferable.
Johoku Chemical Co., Ltd .: JP-506H,
Accelerator: Mold with INT-1856
Nikko Chemicals: 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.

  Hereinafter, the present invention will be described in more detail with reference to examples.

(Abrasion resistance)
Using an abrasion tester (“HIDON TRIBOGEAR TYPE-30S” manufactured by Shinto Kagaku Co., Ltd.), 1 kg (250 gf) of steel wool (Nihon Steel Wool Co., Ltd., Bonstar # 0000) cut into 2 cm ² placed on the surface of the article. / Cm ² ), a reciprocating distance of 30 mm, a head speed of 10 mm at an average of 100 mm / second, and the appearance of the surface of the article was evaluated. In appearance evaluation, an article was attached to one side of a 2.0 mm thick black acrylic plate (manufactured by Mitsubishi Rayon Co., Ltd., acrylite), and it was visually evaluated by holding it over a fluorescent lamp indoors.
A: There are less than 10 scratches that can be confirmed.
B: The area where the antireflection performance is lost in the scratched part is less than 50% of the scratched part.
C: 50% or more of the antireflection performance at the scratched portion is lost.
D: Almost all the antireflection performance of the scratched part is lost.

(Pencil hardness)
The test was performed with a load of 500 gf according to JIS K5600-5-4. After the test, the appearance was visually observed, and the hardness of the pencil with no indentation was noted. When 2H was not scratched and 3H was scratched, it was indicated as “2H”.

(Adhesion)
Based on JIS K 5400, a cross-cut peel test was performed to evaluate the adhesion between the surface layer and the intermediate layer. An acrylic plate having a thickness of 2 mm was used as the base. The grid was made with 100 squares of 10 × 10, and the number where peeling did not occur in 100 squares was evaluated.
○: No peeling at all.
(Triangle | delta): There exists peeling in the range of 1-99 mass.
X: All 100 squares peeled.

(Dry touch of intermediate layer)
After the intermediate layer is applied to the substrate and dried, it is evaluated in an uncured state. It was evaluated whether the surface of the intermediate layer was marked when touched with a nitrile glove (manufactured by AS ONE, Clean Knoll) at a pressure of 250 gf / cm ² , or the intermediate layer composition adhered.
○: No trace remains Δ: Trace remains but the intermediate layer composition does not adhere to the glove.
X: The composition for intermediate | middle layers adheres to a glove.

(Manufacture of stamper A)
A φ65 mm aluminum disk having a purity of 99.99% by mass and an electropolished thickness of 2 mm was used as the aluminum substrate.

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 stabilizing device was repeatedly turned on / off, so that an electric current was intermittently applied to the aluminum base material for 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.
Subsequently, 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 manner, the anodization and the pore diameter enlargement process were alternately repeated, and the stamper A was obtained by performing a total of 5 times.

(Manufacture of stamper B)
A φ65 mm aluminum disk having a purity of 99.99% by mass and an electropolished thickness of 2 mm was used as the aluminum substrate.

A 0.3 M oxalic acid aqueous solution was adjusted to 15 ° C., an aluminum substrate was immersed, and anodization was performed at a constant voltage of DC 40 V for 30 minutes to form an oxide film having pores.
Subsequently, 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 0.3 M oxalic acid aqueous solution adjusted to 16 ° C. and anodized at 40 V for 30 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 8 minutes was performed. In this manner, the anodization and the pore diameter enlargement process were alternately repeated, and the stamper B was obtained by performing a total of 5 times.

  The obtained stamper A and stamper B were immersed in a 0.1% by mass aqueous solution of TDP-8 (manufactured by Nikko Chemicals) for 10 minutes, pulled up and air-dried overnight for release treatment.

(Measurement of stamper pores)
A vertical section of a part of a stamper made of anodized porous alumina is deposited by Pt for 1 minute, and observed with a field emission scanning electron microscope (trade name JSM-7400F, manufactured by JEOL Ltd.) at an acceleration voltage of 3.00 kV. The interval (period) of the pores and the depth of the pores were measured. Specifically, 10 points were measured for each, and the average value was taken as the measured value. The interval (period) between the pores of the stamper A used in this example was about 180 nm, and the depth of the pores was about 180 nm. The interval (period) between the pores of the stamper B was about 100 nm, and the depth of the pores was about 180 nm.

(Composition for intermediate layer)
Table 1 shows the inorganic component (A), organic component (B), and solvent (D) used in Examples and Comparative Examples.

The photopolymerization initiator (C) used in the examples and comparative examples was obtained by adding 1.0% by mass of IRGACURE 184 (BASF) and 100% by mass of IRGACURE 819 (manufactured by BASF) with respect to 100% by mass of the organic component (B). 0.5% by mass was added.
In the mold release agent (F) used in the examples and comparative examples, TDP-2 (manufactured by Nikko Chemical Co., Ltd.) was added in an amount of 0.2% by mass relative to the organic component (B).

  About the composition for intermediate | middle layers used by the Example and the comparative example, the composition (blending ratio), solid content component ratio, inorganic component content rate, solvent component ratio, solid content concentration was shown in Table 2.

(Composition for fine uneven structure)
The polymerizable organic components (XB) of the fine concavo-convex structure compositions used in Examples and Comparative Examples are as shown in Table 3 below.

  The photopolymerization initiator (XC) used in the Examples and Comparative Examples was 1.0% by mass of IRGACURE 184 (manufactured by BASF) and IRGACURE 819 (manufactured by BASF) with respect to 100% by mass of the polymerizable organic component (XB). ) Was added by 0.5 mass%.

  In the release agent (XF) used in Examples and Comparative Examples, TDP-2 (manufactured by Nikko Chemical Co., Ltd.) was added in an amount of 0.2% by mass relative to the polymerizable organic component (XB).

  About the composition for fine concavo-convex structures used in the Examples and Comparative Examples, the composition (blending ratio) and acrylic equivalent are shown in Table 4.

(Intermediate layer coating / drying)
A light-transmitting triacetylcellulose film (manufactured by Fuji Film, product name T40UZ, thickness 40 μm) was used as the substrate. The intermediate layer composition was coated on a substrate placed on a glass plate using a bar coater. Subsequently, the laminate was dried for 3 minutes with a drier adjusted to 70 ° C. to obtain a laminate in which an uncured intermediate layer was formed on the substrate.

(Formation of fine uneven structure layer)
A suitable amount of the composition for fine concavo-convex structure is dropped on the stamper, and the intermediate layer and the composition for fine concavo-convex structure are coated with a laminate in which an uncured intermediate layer is formed on the substrate, and uniform with a roller. Squeezed out. Then, the intermediate layer and the composition for fine concavo-convex structure were cured by irradiating ultraviolet rays with a cumulative light quantity of 1000 mJ / cm ² from the substrate side using a high pressure mercury lamp. Thereafter, the stamper was peeled off to obtain a laminate having a fine relief structure on the surface.

  On the surface of this laminate, the fine uneven structure of the stamper was transferred, and when the stamper A was used, a substantially conical fine uneven structure having an average period of 180 nm and an average height of 180 nm was formed. When the stamper B was used, a substantially conical fine concavo-convex structure having an average period of 100 nm and an average height of 180 nm was formed. Table 5 shows the evaluation results of the laminate having this fine concavo-convex structure. The thicknesses of the layers made of the cured product of the composition for fine concavo-convex structure of the laminate were all 10 μm.

[Example 1]
In Example 1, since the content of the inorganic component in the intermediate layer was as low as 50% by mass, the evaluation of the touch drying property was x in an uncured state after coating and drying the intermediate layer, but showed good adhesion. The pencil hardness was H.
[Example 2]
In Example 2, since the content ratio of the inorganic component in the intermediate layer was 57% by mass, which was higher than that in Example 1, the evaluation of dryness to touch after the coating and drying of the intermediate layer was good. The pencil hardness was also better than Example 1 and 2H.
[Example 3]
In Example 3, the dryness to touch after coating and drying of the intermediate layer was good, and the pencil hardness was 2H. [Example 4]
In Example 4, the touch-drying property after coating and drying of the intermediate layer was good, and the pencil hardness was 2H. [Example 5]
In Example 5, as compared with Example 4, EBECRYL8402 which is a bifunctional urethane acrylate in which the cured product is a relatively soft DPHA instead of the hardened DPHA is used for the organic component (B) of the intermediate layer. As a result, the pencil hardness was HB.
[Example 6]
In Example 6, as shown in Table 2, the organic component (B) of the intermediate layer was a mixed system of DPHA and EBECRYL8402. As a result, the pencil hardness was 2H, and a pencil hardness equivalent to that of Example 5 in which EBECRYL8402 was not added was obtained.
[Example 7]
In Example 7, the composition for fine concavo-convex structure was changed from Composition B to Composition C as compared with Example 6. As a result, the scratch resistance evaluation result improved from B to A. Other evaluation results were the same.
[Example 8]
In Example 8, compared with Example 7, the film thickness of the intermediate layer was changed from 10 μm to 15 μm. As a result, the pencil hardness evaluation result improved from 2H to 3H. Other evaluation results were the same.
[Example 9]
Example 9 was the same as Example 8 except that the stamper was changed from stamper A to stamper B, and the fine concavo-convex structure composition was changed from composition B to composition A. As a result, the result of the pencil hardness test did not change at 3H, but the test result of the scratch resistance was C, but there was obtained a practically no problem.

[Comparative Example 1]
In Comparative Example 1, composition No. in which the intermediate layer does not contain the inorganic component (A). 7 was used. As a result, the pencil hardness was reduced to 2B.
[Comparative Example 2]
In Comparative Example 2, no intermediate layer was used. As a result, the adhesion between the substrate and the composition for fine concavo-convex structure was poor, and the adhesion evaluation result was x. Even in the pencil hardness test, the interface between the fine concavo-convex structure layer and the intermediate layer was peeled off, so evaluation was impossible.
[Comparative Example 3]
In Comparative Example 3, the composition for fine concavo-convex structure was not used. After the intermediate layer was applied and dried, the intermediate layer was brought into contact with the stamper while the stamper was heated to about 60 ° C., and the air was extracted with a roller. Then, the fine concavo-convex structure was transcribe | transferred on the hardened | cured material of an intermediate | middle layer by irradiating an ultraviolet-ray and hardening the composition for intermediate | middle layers. Release from the stamper was possible without any problem, and the fine concavo-convex structure had the same shape as other comparative examples. However, the evaluation result of scratch resistance was very poor at D, and the pencil hardness evaluation was less than 6B because the antireflection performance of the part in contact with the pencil was significantly lost in the pencil hardness test.

DESCRIPTION OF SYMBOLS 10 Laminated body 11 Base material 12 Fine uneven | corrugated structure layer 13, 13b Convex part 13a Convex part 14 Concave part 14a Bottom point of concavity 15 Intermediate | middle layer W1 Space | interval of adjacent convex part d1 From bottom point of concavity to apex of convex part Vertical distance 20 Stamper 30 Work surface 31 Pore 32 First oxide film 33 Pore generation point 34 Second oxide film

Claims (8)

  A laminate comprising at least a base material, an intermediate layer, and a fine concavo-convex structure layer, wherein the intermediate layer and the fine concavo-convex structure layer are a cured product of an active energy ray-curable composition, and the fine concavo-convex structure The layer has a concavo-convex structure in which the interval between adjacent convex portions is equal to or less than the wavelength of visible light, and the intermediate layer is a hybrid of an inorganic component and an organic component.   The laminate according to claim 1, wherein the intermediate layer includes particles having an average particle diameter that is equal to or less than a wavelength of visible light as an inorganic component.   The laminate according to claim 1, wherein the intermediate layer contains silica having an average particle diameter of not more than a wavelength of visible light as an inorganic component.   4. The laminate according to claim 1, wherein the intermediate layer has an inorganic component content of 50% by mass or more and 75% by mass or less.   The laminate according to claim 1, wherein the intermediate layer contains polyfunctional (meth) acrylate as an organic component. The manufacturing method of a laminated body characterized by including the following process (I)-(III).
Step (I): A step of forming an uncured intermediate layer by applying an active energy ray-curable composition containing a solvent onto a substrate and then drying it.
Step (II): A step of disposing an active energy ray-curable composition for forming a fine uneven structure layer between the intermediate layer and the fine uneven transfer stamper.
Step (III): a step of irradiating active energy rays from the substrate side to cure the intermediate layer and the active energy ray-curable composition for fine concavo-convex structure layer, and then releasing the laminate from the stamper.   The method for producing a laminate according to claim 6, wherein the uncured intermediate layer after the step (I) has a touch-drying property.   A laminate comprising at least a substrate and a hybrid layer of an inorganic component and an organic component, wherein the hybrid layer has a touch-drying property in an uncured state.