JP2013221992A - Article and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an article provided with a function of high abrasion resistance, and a method for easily manufacturing the articles provided with the function of high abrasion resistance.SOLUTION: In an article 10 having a fine asperity structure 14 on the surface, recessed portions 13 of the fine asperity structure 14 are filled with function-provided materials 16 with the thickness of 10 nm or more, and the height of protruding portions 12 protruding from the upper face of the filling surface is 100 nm or more. The article is provided by sticking a protective film having an adhesive layer consisting of an adhesive containing the function-provided materials, on the surface of the article having the fine asperity structure on the surface, in such a manner as bringing the surface of the article into contact with the adhesive layer, then peeling off the protective film, and shifting the adhesive into the recesses of the fine asperity structure so as to have the thickness of 10 nm or more.

Description

  The present invention relates to an article having a fine concavo-convex structure on the surface and having the surface modified to provide a function, and a method for producing the same.

  It is known that an article having a fine concavo-convex structure on the surface of which fine concavo-convex is regularly arranged exhibits antireflection properties by continuously changing the refractive index. In order for an article to exhibit better antireflection properties, it is necessary that the interval (period) between adjacent convex portions or concave portions be equal to or less than the wavelength of visible light.

In recent years, articles having functions such as water repellency by modifying the surface in addition to antireflection have been proposed.
For example, Patent Document 1 discloses a water-repellent antireflection structure having both antireflection characteristics and water repellency characteristics by coating the surface of an article having a fine uneven structure on the surface with a coating material such as fluoroalkoxysilane. It is disclosed. In Patent Document 1, the surface of the fine concavo-convex structure is coated with a coating material by a method such as chemical vapor deposition so that the concave portion of the fine concavo-convex structure is not filled with the coating material.

JP 2009-42714 A

However, as described in Patent Document 1, in the case of an article in which the surface of the fine concavo-convex structure is coated with a coating material, the coating layer made of the coating material is worn in the course of use of the article and the performance of the coating material such as water repellency May not be fully demonstrated.
In addition, the method of coating the surface of the fine concavo-convex structure with a coating material is tedious.

  This invention is made | formed in view of the said situation, and makes it a subject to provide the method which can manufacture easily the article | item provided with the function with sufficient abrasion resistance, and the article | item provided with the function with high abrasion resistance.

The present invention has the following aspects.
[1] An article having a fine concavo-convex structure on its surface, the height of the convex part that is filled with a function-imparting material with a thickness of 10 nm or more in the concave part of the fine concavo-convex structure and protrudes from the upper surface of the filling surface An article having a thickness of 100 nm or more.
[2] The article according to [1], which is an antireflective article having an average interval between convex portions of the fine concavo-convex structure having a wavelength of visible light or less.
[3] The article according to [1] or [2], wherein the function-imparting material is a silicone-based pressure-sensitive adhesive.
[4] A protective film provided with a pressure-sensitive adhesive layer made of a pressure-sensitive adhesive containing a function-imparting material was attached to the surface of an article having a fine concavo-convex structure so that the surface of the article and the pressure-sensitive adhesive layer were in contact with each other. Then, the protective film is peeled off, and the pressure-sensitive adhesive is transferred to the concave portions of the fine concavo-convex structure so as to have a thickness of 10 nm or more.

  ADVANTAGE OF THE INVENTION According to this invention, the method which can manufacture easily the article | item provided with the function with sufficient abrasion resistance and the article | item provided with the function with high abrasion resistance can be provided.

It is sectional drawing which shows an example of the articles | goods of this invention. It is sectional drawing which shows the manufacturing process of the articles | goods of this invention.

The present invention will be described in detail below.
In addition, “active energy rays” in the present specification means visible light, ultraviolet rays, electron beams, plasma, heat rays (infrared rays, etc.) and the like.
In FIGS. 1 and 2, the scale is different for each layer in order to make each layer recognizable on the drawings.
2, the same components as those in FIG. 1 are denoted by the same reference numerals, and the description thereof may be omitted.

<Article>
FIG. 1 is a cross-sectional view showing an example of the article of the present invention.
The article 10 of this example is composed of a base material 11 and a fine unevenness in which a plurality of convex parts 12 and concave parts 13 are formed of a cured product of an active energy ray-curable resin composition described later formed on the surface of the base material 11. It has the cured resin layer 15 which has the structure 14 on the surface.
In the present invention, the surface of the article 10 having the fine concavo-convex structure 14 on the surface is referred to as “the surface of the article”.

  The material of the substrate 11 may be any material that transmits light, such as methyl methacrylate (co) polymer, polycarbonate, styrene (co) polymer, methyl methacrylate-styrene copolymer, cellulose diacetate, cellulose triacetate, Examples thereof include cellulose acetate butyrate, polyester, polyamide, polyimide, polyether sulfone, polysulfone, polypropylene, polymethylpentene, polyvinyl chloride, polyvinyl acetal, polyether ketone, polyurethane, and glass.

The substrate 11 is produced by a known molding method such as an injection molding method, an extrusion molding method, or a cast molding method.
The shape of the base material 11 can be appropriately selected according to the article 10, and when the article 10 is an antireflection film or the like, a sheet shape or a film shape is preferable.

A pressure-sensitive adhesive layer (not shown) and a separate film (not shown) may be provided on the front surface (back surface) of the substrate 11 where the cured resin layer 15 is not formed. By providing the pressure-sensitive adhesive layer, it can be easily attached to other film-like or sheet-like articles (front plate, polarizing element, etc.).
The surface of the substrate 11 is subjected to various coating treatments, corona discharge treatments, and surface roughenings in order to improve adhesion to the active energy ray-curable resin composition, antistatic properties, scratch resistance, weather resistance, and the like. Processing etc. may be given.

  In the article 10, the function-imparting material 16 is filled in the recesses 13 of the fine relief structure 14. The surface of the article 10 is modified by the function-imparting material 16, and the article 10 can exhibit various functions (for example, water repellency and hydrophilicity) corresponding to the function-imparting material 16. In addition, since the function-imparting material 16 is filled in the recesses 13, the function-imparting material 16 is less likely to be worn as compared with the case where the surface of the fine concavo-convex structure is coated with a coating material as described in Patent Document 1. .

The filling amount of the function-imparting material 16 is an amount such that the thickness of the filling layer made of the function-imparting material 16 is 10 nm or more, and preferably 15 nm or more. If the function-imparting material 16 is filled in the recess 13 to a thickness of 10 nm or more, the function corresponding to the function-imparting material 16 can be exhibited without interfering with the antireflection property expressed by the fine concavo-convex structure 14. As will be described in detail later, if the average interval between the convex portions 12 of the fine concavo-convex structure 14 is equal to or smaller than the wavelength of visible light, the article 10 having both better antireflection properties and a function corresponding to the function-imparting material 16 is obtained. can get.
In order to sufficiently exhibit the function corresponding to the function-imparting material 16, the function-imparting material 16 is preferably filled in the recess 13 to a thickness of 50 nm or less.
Here, the “depth of the concave portion” is a vertical distance d ₁ from the bottom of the concave portion 13 to the top of the convex portion 12 adjacent to the concave portion 13 in FIG. It is equal to the height of the convex part 12.

  Moreover, the height of the convex part 12 of the part which protrudes from the upper surface of the filling surface of the function provision material 16 is 100 nm or more, and 120 nm or more is preferable. If the height of the convex portion 12 protruding from the upper surface of the filling surface is 100 nm or more, the antireflection property developed by the fine concavo-convex structure 14 is not hindered.

The function-imparting material 16 is not particularly limited as long as a desired function can be imparted to the article 10. For example, a hydrophobic material is used to impart water repellency to the article 10.
Examples of the hydrophobic material include a silicone compound, a fluorine-containing compound, an alkyl compound, and the like that have a water contact angle of 90 ° or more on the surface of the layer made of the hydrophobic material. Of these, silicone compounds are preferred.

Examples of the silicone compound used as the hydrophobic material include silicone adhesives such as thermoplastic silicone elastomers.
Examples of the thermoplastic silicone elastomer include a block copolymer containing polysiloxane and a polar bond. Here, the “polar bond” is, for example, a urea bond, a urethane bond, an amide bond, an ester bond, or the like.
Examples of the polysiloxane include polydimethylsiloxane, polymethylpropylsiloxane, polydipropylsiloxane, polymethyloctylsiloxane, polydioctylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane. These may be used alone or in combination of two or more.

When imparting hydrophilicity to the article 10, a hydrophilic material is used as the function-imparting material 16.
Examples of the hydrophilic material include acrylic compounds having a water contact angle of 50 ° or less on the surface of the layer made of the hydrophilic material.

Examples of the acrylic compound used as the hydrophilic material include acrylic pressure-sensitive adhesives such as an acrylic copolymer obtained by copolymerizing acrylate and another monomer.
As acrylates, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, isononyl acrylate, hydroxyl ethyl acrylate, 2-hydroxylpropyl acrylate, propylene glycol acrylate, polypropylene glycol monoacrylate, polyethylene glycol monoacrylate, methoxy Examples include polyethylene glycol monoacrylate, dimethylacrylamide, acryloylmorpholine, hydroxyethyl acrylamide, acrylamide, glycidyl acrylate, and cyclohexane dimethanol monoacrylate. These may be used alone or in combination of two or more.
On the other hand, as other monomers, methyl acrylate, methyl methacrylate, styrene, acrylonitrile, vinyl acetate, acrylic acid, methacrylic acid, itaconic acid, hydroxylethyl methacrylate, methacrylamide, glycidyl methacrylate, dimethylaminoethyl methacrylate, tert-butylaminoethyl Examples include methacrylate and n-ethylhexyl methacrylate. These may be used alone or in combination of two or more.

In addition, the function-imparting material 16 is filled in the concave portions 13 of the fine concavo-convex structure 14, whereby the reflectance of the surface of the article 10 tends to change. Therefore, the function-imparting material 16 also has a function of adjusting the antireflection performance of the article 10. In particular, in order to reduce the reflectance of the surface of the article 10, a low refractive index material may be used as the function-imparting material 16.
Examples of the low refractive index material include fluorine compounds and silicone compounds in which the refractive index of the surface of the layer made of the low refractive index material is 1.45 or less.
Examples of the fluorine-based compound used as the low refractive index material include a fluorine-containing monomer, a fluorine-containing silane compound, a fluorine-containing surfactant, and a fluorine-containing polymer. On the other hand, examples of the silicone compound include a silicone monomer, a silicone resin, and a silicone surfactant.

  In the article 10, all of the concave portions 13 may be filled with the same type of function-imparting material 16, or different types of function-imparting material 16 may be filled depending on the location. For example, if the recess 13 has a region filled with a hydrophobic material and a region filled with a hydrophilic material, an article having a water-repellent part having water repellency and a hydrophilic part having hydrophilicity on the same surface 10 is obtained.

The average interval between the convex portions 12 is preferably equal to or less than the wavelength of visible light. If the average interval between the convex portions 12 is equal to or less than the wavelength of visible light, good antireflection properties can be exhibited, and the article 10 of the present invention can be suitably used for optical applications such as antireflection articles.
Here, “visible light” refers to light having a wavelength of 380 to 780 nm. The average distance between the convex portions 12 is preferably 400 nm or less, more preferably 300 nm or less, and particularly preferably 250 nm or less.

The average interval between the convex portions 12 is preferably 25 nm or more, and more preferably 80 nm or more, from the viewpoint of easy formation of the convex portions 12.
The average interval between the convex portions 12 is measured by measuring the interval between adjacent convex portions 12 (distance W ₁ from the center of the convex portion 12 to the center of the adjacent convex portion 12 in FIG. 1) by electron microscope observation. These values are averaged.

110-400 nm is preferable and, as for the height of the convex part 12 (namely, depth of the recessed part 13), 150-300 nm is more preferable. If the height of the convex portion 12 is 110 nm or more, the reflectance is sufficiently low, and the wavelength dependency of the reflectance is reduced. If the height of the convex part 12 is 400 nm or less, the scratch resistance of the convex part 12 will be good.
The height of the convex portion 12 (depth of the concave portion 13) is determined by observation with an electron microscope from the height of the ten convex portions 12 (from the bottom of the concave portion 13 in FIG. 1 to the head of the convex portion 12 adjacent to the concave portion 13. The vertical distance d ₁ ) to the top is measured and these values are averaged.

  The shape of the convex portion 12 is such that the cross-sectional area of the convex portion 12 in the direction orthogonal to the height direction continuously increases from the top to the depth direction, that is, the cross-sectional shape of the convex portion 12 in the height direction is A shape such as a triangle, trapezoid, and bell shape is preferable.

<Production method>
The article 10 in which the concave portion 13 of the fine concavo-convex structure 14 is filled with the function-imparting material 16 can be manufactured as follows, for example. The article before the concave portion is filled with the function-imparting material is referred to as “article before filling”.
As shown in FIG. 2, a protection in which an adhesive layer 22 made of an adhesive containing a function-imparting material is laminated on a base film 21 on the surface of an article having a fine concavo-convex structure (article 10 ′ before filling). After sticking the film 20 so that the surface of the article 10 ′ before filling and the pressure-sensitive adhesive layer 22 are in contact with each other (FIG. 2A), the protective film 20 is peeled off to form a pressure-sensitive adhesive that forms the pressure-sensitive adhesive layer 22. The article 10 filled with the function-imparting material 16 is obtained by shifting the recesses 13 having a fine concavo-convex structure so as to have a thickness of 10 nm or more (FIG. 2B). At this time, the pressure sensitive adhesive is transferred to the concave portion 13 so that the height of the convex portion protruding from the upper surface of the pressure-sensitive adhesive filling surface transferred (filled) to the concave portion is 100 nm or more.

  Examples of the material for the base film 21 include polyolefin, polycycloolefin, polyester, polyamide, polyvinyl alcohol, and ethylene-polyvinyl alcohol. Polyolefin is preferable in terms of cost and moldability.

The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer 22 of the protective film 20 is preferably made of a function-imparting material. For example, in the case of imparting water repellency to the article 10, the silicone-based pressure-sensitive adhesive used as the above-described hydrophobic material is particularly preferable. In the case of imparting hydrophilicity, the acrylic pressure-sensitive adhesive used as the hydrophilic material described above is particularly preferable.
If the pressure-sensitive adhesive layer 22 is formed of a pressure-sensitive adhesive made of a function-imparting material, all of the pressure-sensitive adhesive that moves to the recess 13 when the protective film 20 is attached to the article 10 ′ before filling and peeled off is the function-imparting material. Therefore, the desired function can be sufficiently imparted to the article 10 even if the amount of transfer of the adhesive is 10 nm. Moreover, the trouble of adding a function-imparting material to the pressure-sensitive adhesive can be saved.

  The transfer of the adhesive to the concave portion 13 is influenced by the sticking time of the protective film 20 to the article 10 ′ before filling, but mainly depends on the type of the adhesive and the thickness of the adhesive layer 22. That is, the amount of transfer increases as the adhesive easily remains. Therefore, it is important to use a pressure-sensitive adhesive that leaves a moderate amount of adhesive so that the transfer amount is 10 nm or more.

The adhesive residue of the adhesive can be controlled by adjusting the molecular weight of the adhesive, the amount of the crosslinking agent of the adhesive, and the thickness of the adhesive layer 22, for example.
Specifically, since the adhesiveness increases as the molecular weight of the pressure-sensitive adhesive decreases, it tends to easily shift to the recess 13. Further, since the adhesiveness increases as the amount of the crosslinking agent decreases, the adhesive residue tends to remain. Moreover, since adhesiveness increases as the thickness of the pressure-sensitive adhesive layer 22 increases, the adhesive residue tends to remain easily.

In the present invention, a commercial product may be used as the protective film. As a commercially available protective film having a pressure-sensitive adhesive layer made of a pressure-sensitive adhesive that is made of a function-imparting material and has a thickness of 10 nm or more, the amount of transfer to the recesses is moderately unadhesive. Can be mentioned.
In the case of imparting water repellency to the article, for example, “PX50T01” manufactured by Panac Co., Ltd .; “DP-1020” manufactured by Hitachi Chemical Co., Ltd., and the like are suitable.
In order to increase the reflectance of the surface of the article, for example, “PX50T01” manufactured by Panac Corporation; “SAT HC2025P” manufactured by Sanei Kaken Co., Ltd. is suitable.

  The method for forming the fine concavo-convex structure on the surface of the article is not particularly limited. For example, a method of performing injection molding or press molding using a mold having a reverse structure of the fine concavo-convex structure on the surface (Method 1), a roll-like structure Using a mold, the active energy ray-curable resin composition is disposed between the mold and the base material, and the active energy ray-curable resin composition is cured by irradiation with the active energy ray to form a fine uneven structure of the mold. The method of transferring and then peeling the mold (Method 2), transferring the fine concavo-convex structure of the mold to the active energy ray-curable resin composition, peeling the mold, and then irradiating the active energy ray to activate the energy ray Examples thereof include a method (method 3) of curing the curable resin composition. Among these, the methods 2 and 3 are preferable and the method 2 is particularly preferable from the viewpoint of the transferability of the fine concavo-convex structure and the degree of freedom of the surface composition.

  Examples of the method for forming the inverted structure of the fine concavo-convex structure on the mold include an electron beam lithography method and a laser beam interference method. For example, a mold having a fine concavo-convex structure can be obtained by applying an appropriate photoresist film on the surface of an appropriate support substrate, exposing to light such as ultraviolet laser, electron beam, and X-ray, and developing. In addition, the support substrate can be selectively etched by dry etching through the photoresist layer, and the resist layer can be removed to directly form a fine concavo-convex structure on the support substrate itself.

It is also possible to use anodized porous alumina as a mold. For example, a pore structure of 20 to 200 nm formed by anodizing aluminum with oxalic acid, sulfuric acid, phosphoric acid or the like as an electrolyte at a predetermined voltage may be used as a mold. According to this method, after anodizing high-purity aluminum for a long time at a constant voltage, the oxide film is once removed and then anodized again, whereby extremely highly regular pores can be formed in a self-organized manner. Further, by combining the anodizing treatment and the pore diameter expanding treatment in the second anodizing step, it is possible to form pores having a triangular or bell-shaped cross section instead of a rectangular cross section. Further, the angle of the innermost portion of the pore can be sharpened by appropriately adjusting the time and conditions of the anodizing treatment and the pore diameter expanding treatment.
Furthermore, you may produce a replication mold by the electroforming method etc. from the mother mold which has a fine uneven structure.

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

  As a method of arranging the active energy ray curable resin composition between the mold and the base material, the mold and the base material are arranged with the active energy ray curable resin composition being arranged between the mold and the base material. Examples of the method include a method of injecting an active energy ray-curable resin composition into the fine uneven structure of the mold by pressing.

The active energy ray-curable resin composition is a resin composition that cures by irradiating active energy rays so that a polymerization reaction proceeds.
This active energy ray-curable resin composition contains a polymerization-reactive monomer component, an active energy ray polymerization initiator, and other components as necessary.

Known components can be applied to the polymerization reactive monomer component and the active energy ray polymerization initiator suitable for forming the fine uneven structure. For example, examples of the polymerization reactive monomer component include monomers, oligomers, and reactive polymers having a radical polymerizable bond and / or a cationic polymerizable bond in the molecule.
Examples of the monomer having a radical polymerizable bond include monofunctional monomers and polyfunctional monomers, and specific examples include various (meth) acrylates and derivatives thereof.
Examples of the monomer having a cationic polymerizable bond include monomers having an epoxy group, an oxetanyl group, an oxazolyl group, a vinyloxy group, and the like.
As a polymerization reactive monomer component and an active energy ray polymerization initiator suitable for forming a fine concavo-convex structure, for example, various compounds described in JP 2009-31764 A can be used.

  The active energy ray-curable resin composition is composed of an ultraviolet absorber, an antioxidant, a mold release agent, a lubricant, a plasticizer, an antistatic agent, a light stabilizer, a flame retardant, a flame retardant aid, and a polymerization inhibitor as necessary. , Fillers, silane coupling agents, colorants, reinforcing agents, inorganic fillers, impact modifiers and other additives may be included.

<Effect>
In the article of the present invention described above, the concave portion of the fine concavo-convex structure on the surface is filled with the function-imparting material. The surface of the article is modified by this function-imparting material, and the article exhibits various functions (for example, water repellency and hydrophilicity) corresponding to the function-imparting material. Further, since the function-imparting material is filled in the recesses, as described in Patent Document 1, the function-imparting material is less likely to be worn compared to the case where the surface of the fine concavo-convex structure is coated with the coating material.
Further, the filling amount of the function-imparting material is such that the thickness of the filling layer made of the function-imparting material is 10 nm or more, and the height of the convex portion protruding from the upper surface of the filling surface is 100 nm or more, The function corresponding to the function-imparting material can be exerted without interfering with the antireflection property developed by the fine concavo-convex structure of the article. In particular, when the average interval between the convex portions of the fine concavo-convex structure is equal to or less than the wavelength of visible light, the article has both better antireflection properties and a function corresponding to the function-imparting material.

  By the way, when imparting water repellency to an article, for example, a fine uneven structure itself is formed with a hydrophobic material (that is, the cured resin layer 15 shown in FIG. 1 using a hydrophobic material as the active energy ray-curable resin composition). In this case, the adhesion between the substrate 11 and the cured resin layer 15 may be reduced. Therefore, it is necessary to design the composition of the hydrophobic material (active energy ray-curable resin composition) so that the adhesion to the substrate 11 is good. Moreover, it was necessary to change an active energy ray curable resin composition each time according to the function to give.

  However, according to the present invention, functions such as water repellency are imparted to the article 10 by the function-imparting material 16 filled in the concave portions 13 of the fine concavo-convex structure 14, so that it is not necessary to use a hydrophobic material for the cured resin layer 15. . Therefore, the adhesion between the base material 11 and the cured resin layer 15 is also good. Moreover, it is not necessary to design the composition of the active energy ray curable resin composition or to change the active energy ray curable resin composition depending on the function to be imparted.

  In addition, according to the above-described method for manufacturing an article, the surface modification can be easily performed by filling the concave portion of the fine concavo-convex structure with the function-imparting material by a simple operation of sticking and peeling the protective film on the article before filling. Articles can be manufactured. Moreover, if the type of the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer of the protective film is changed, an article with different types of functions such as water repellency and hydrophilicity can be used in one mold or the same type of active energy ray-curable resin composition. It can be manufactured from things.

Moreover, if it is the manufacturing method of the articles | goods mentioned above, if the kind of adhesive is changed with the location of the adhesive layer of a protective film, ie, the area | region of the adhesive which consists of hydrophobic materials, for example, and the adhesive which consists of hydrophilic materials If a protective film provided with a pressure-sensitive adhesive layer having these areas is used, an article having a water-repellent part having water repellency and a hydrophilic part having hydrophilicity on the same surface can be produced.
Furthermore, with this manufacturing method, since the protective film can be stuck on the surface of the article until the article is used, it is possible to prevent dirt and the like from adhering to the surface, It is also possible to maintain (protect) the shape. Therefore, it is possible to simultaneously protect the surface of the article, prevent adhesion of dirt, and impart a function to the article.

<Other embodiments>
The article of the present invention is not limited to the article 10 shown in FIGS. The article 10 shown in FIGS. 1 and 2 has a fine concavo-convex structure formed on the entire surface, but a fine concavo-convex structure may be formed on a part of the surface. Moreover, the fine concavo-convex structure may be formed also on the other surface (back surface) of the article.
Further, the configuration of the article 10 is not limited to the one composed of the base material 11 and the cured resin layer 15, and may be one that does not include the base material 11, and can be appropriately set depending on the application.

  Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.

(Pores of anodized alumina)
A portion of the anodized alumina is shaved, platinum is deposited on the cross section for 1 minute, and a field emission scanning electron microscope (“JSM-7400F” manufactured by JEOL Ltd.) is used at an acceleration voltage of 3.00 kV. The cross section was observed, and the interval between the pores and the depth of the pores were measured. Each measurement was performed for 10 points, and an average value was obtained.

(Convex and concave parts of cured resin layer)
Platinum was vapor-deposited on the longitudinal section of the cured resin layer for 10 minutes, and the section was observed in the same manner as the anodized alumina, and the interval between the convex portions and the depth of the concave portions (the height of the convex portions) were measured. Each measurement was performed for 10 points, and an average value was obtained.

(Measurement of the thickness of the function-imparting material and the height of the protrusion protruding from the top surface of the filling surface)
Platinum is vapor-deposited on the longitudinal section of the cured resin layer for 10 minutes, and the cross section is observed in the same manner as in the case of anodized alumina. The height of the part was measured. The measurement was performed for 10 points, and the average value was obtained.

(Measurement of reflectance)
A black acrylic resin plate (manufactured by Mitsubishi Rayon Co., Ltd., “Acrylite EX # 502”, 50 mm × 60 mm) is pasted on the back surface of the measurement object (the surface on which the mold surface structure is not transferred) via an optical adhesive layer. It was. Using this as a sample, a spectrophotometer (manufactured by Shimadzu Corporation, “UV-2450”) is used to measure in an incident angle of 5 ° (using a 5 ° regular reflection accessory device) and a wavelength of 380 to 780 nm. The relative reflectance of the surface of the object (transfer surface onto which the surface structure of the mold was transferred) was measured, and the visibility reflectance was calculated according to JIS R3106.

(Measurement of water contact angle)
The contact angle was calculated by the θ / 2 method using an automatic contact angle measuring instrument (“DM-701” manufactured by Kyowa Interface Science Co., Ltd.). Specifically, 2 μL of ion-exchanged water was dropped on the surface of the measurement object, and the contact angle 10 seconds after dropping was measured. Furthermore, the same operation was performed 4 times by changing the position where water was dropped, and an average value of 5 times in total was obtained.

(Mold production)
A mold having a pore depth of 180 nm was produced as follows.
First, an aluminum plate having a purity of 99.99% was polished with a blanket and then electropolished in a perchloric acid / ethanol mixed solution (1/4 volume ratio) to form a mirror surface.
The aluminum plate was anodized in a 0.3 M oxalic acid aqueous solution under the conditions of a direct current of 40 V and a temperature of 16 ° C. for 30 minutes to form an oxide film having pores (step (a)).
The aluminum plate on which the oxide film was formed was immersed in a 6% by mass phosphoric acid / 1.8% by mass chromic acid mixed aqueous solution for 6 hours to remove the oxide film, exposing periodic depressions corresponding to the pores. (Step (b)).
The aluminum plate was anodized for 30 seconds in a 0.3 M oxalic acid aqueous solution under conditions of a direct current of 40 V and a temperature of 16 ° C. to form an oxide film having pores (step (c)).
The aluminum plate on which the oxide film was formed was immersed in 5% by mass phosphoric acid at 32 ° C. for 8 minutes, and the pore diameter was expanded (step (d)).
The aluminum plate was anodized in a 0.3 M oxalic acid aqueous solution at a direct current of 40 V and a temperature of 16 ° C. for 30 seconds to form small-diameter pores extending downward from the pores (step (e)).
Step (d) and step (e) are repeated four times in total, and finally step (e) is performed, and anodized alumina having substantially conical pores with an average interval of 100 nm and a depth of 180 nm is formed on the surface. A plate-shaped mold was obtained.
After the obtained mold is washed with deionized water, the surface moisture is removed by air blow, and the surface antifouling coating agent (“OPTOOL DSX”, manufactured by Daikin Industries, Ltd.) is 0.1% by mass in solid content. Thus, it was immersed in a solution diluted with a diluent (manufactured by Harves Co., Ltd., “HD-ZV”) for 10 minutes, pulled up from the solution and air-dried for 20 hours to obtain a mold treated with a release agent.

(Protective film)
As the protective film, protective films A to C shown in Table 1 were used.

[Example 1]
The active energy ray-curable resin composition A having the following composition is poured onto the surface of the mold, and coated with an acrylic film having a thickness of 100 μm (Mitsubishi Rayon Co., Ltd., “Acryprene”). Using a mercury lamp, the resin was cured by irradiating with ultraviolet rays at an energy of 1000 mJ / cm ² to form a cured resin layer.
The mold was released from the film to obtain an article (pre-filling article) having a fine concavo-convex structure on the surface with an average interval of protrusions: 100 nm and a depth of recesses (height of protrusions): 170 nm.
About the obtained article before filling, the reflectance of the surface and the water contact angle were measured. The results are shown in Table 2. In addition, Table 2 shows the depth of the concave portion (height of the convex portion) of the article before filling.

(Active energy ray-curable resin composition A)
Condensed ester of succinic anhydride / trimethylolethane / acrylic acid (molar ratio 1: 2: 4): 45 parts by mass
1,6-hexanediol diacrylate: 45 parts by mass,
X-22-1602 (manufactured by Shin-Etsu Chemical Co., Ltd., radical polymerizable silicone oil): 10 parts by mass,
Irgacure 184 (manufactured by BASF): 1.0 part by mass,
Irgacure 819 (manufactured by BASF): 0.3 parts by mass.

After the obtained pre-filling article was attached to a black acrylic plate via an adhesive, a protective film A was applied to the surface of the pre-filling article using a 2 kg rubber roller in an environment of 23 ° C. and 50% RH. It was stuck at a speed of 2 m / min so that the pressure-sensitive adhesive layer was in contact. This was allowed to stand for 7 days in an environment of 23 ° C. and 50% RH, and then the protective film A was peeled off to obtain an article (filled article) in which the concave portion of the fine concavo-convex structure was filled with an adhesive (function-imparting material). .
For the obtained filled article, the thickness of the function-imparting material filled in the concave portions, the height of the convex portions protruding from the upper surface of the filled surface, the reflectance of the surface, and the water contact angle were measured. The results are shown in Table 2.

[Example 2]
Except for using the active energy ray-curable resin composition B having the composition shown below, in the same manner as in Example 1, the average interval between the convex portions: 100 nm, the depth of the concave portions (height of the convex portions): 170 nm. An article before filling was obtained.
Except for using the obtained pre-filling article and protective film B, an article (filled article) in which a concave portion having a fine concavo-convex structure was filled with a pressure-sensitive adhesive (function-imparting material) was prepared in the same manner as in Example 1, and various measurements were performed. Went. The results are shown in Table 2.

(Active energy ray-curable resin composition B)
Condensed ester of succinic anhydride / trimethylolethane / acrylic acid (molar ratio 1: 2: 4): 75 parts by mass
Aronix M260 (Toagosei Co., Ltd.): 20 parts by mass,
Methyl acrylate: 5 parts by mass
Irgacure 184 (manufactured by BASF): 1.0 part by mass,
Irgacure 819 (manufactured by BASF): 0.3 parts by mass.

[Example 3]
Except for using the active energy ray-curable resin composition C having the composition shown below, in the same manner as in Example 1, the average interval between the convex portions: 100 nm, the depth of the concave portions (height of the convex portions): 170 nm. An article before filling was obtained.
Using the resulting pre-filled article and protective film C, the adhesive (function-imparting material) was filled into the concave portions of the fine concavo-convex structure in the same manner as in Example 1 except that the sticking time of the protective film was changed to 21 days. The manufactured article (filled article) was manufactured and subjected to various measurements. The results are shown in Table 2.

(Active energy ray-curable resin composition C)
GX-8862V (Daiichi Kogyo Seiyaku Co., Ltd.): 45 parts by mass,
DPEA-12 (manufactured by Nippon Kayaku Co., Ltd.): 25 parts by mass,
Aronix M260 (Toagosei Co., Ltd.): 25 parts by mass,
Methyl acrylate: 5 parts by mass
Irgacure 184 (manufactured by BASF): 1.0 part by mass,
Irgacure 819 (manufactured by BASF): 0.3 parts by mass.

As is clear from Table 2, in the case of Example 1 using the protective film A provided with the pressure-sensitive adhesive layer made of an acrylic pressure-sensitive adhesive, the reflectance of the surface of the article was 0 as compared to before the protective film A was attached. Increased from 11% to 0.27%.
In the case of Example 2 using the protective film B provided with a pressure-sensitive adhesive layer made of a silicone-based pressure-sensitive adhesive, the reflectance of the surface of the article is 0.05% to 0.72% compared to before the protective film B is attached. Rose to. Further, the water contact angle of the article increased from 17 ° to 137 °, and water repellency could be imparted.
In the case of Example 3 using the protective film C provided with a pressure-sensitive adhesive layer made of an acrylic pressure-sensitive adhesive, the reflectance of the surface of the article is 0.11% to 0.23% compared to before the protective film C is attached. Rose to. Further, the water contact angle of the article increased from 19 ° to 94 °, and water repellency could be imparted.
In addition, the raise of the reflectance in Examples 1-3 does not affect antireflection property.

[Example 4]
<Example 4-1>
Except for using the active energy ray-curable resin composition B, an article before filling having an average interval of protrusions of 100 nm and a depth of protrusions (height of the protrusions) of 170 nm was obtained in the same manner as in Example 1. It was.
Using the obtained pre-filling article and protective film B, the adhesive (function-imparting material) is filled in the concave portions of the fine concavo-convex structure in the same manner as in Example 1 except that the sticking time of the protective film is changed to 30 minutes. Manufactured article (filled article) was measured, and the thickness of the function-imparting material filled in the concave portion of the article, the height of the convex portion protruding from the upper surface of the filling surface, and the water contact angle of the surface of the article were measured. . The results are shown in Table 3.

<Example 4-2>
Except for using the active energy ray-curable resin composition B, an article before filling having an average interval of protrusions of 100 nm and a depth of protrusions (height of the protrusions) of 170 nm was obtained in the same manner as in Example 1. It was.
Using the resulting pre-filled article and protective film B, the adhesive (function-imparting material) was filled into the concave portions of the fine concavo-convex structure in the same manner as in Example 1 except that the sticking time of the protective film was changed to 1 day. Manufactured article (filled article) was measured, and the thickness of the function-imparting material filled in the concave portion of the article, the height of the convex portion protruding from the upper surface of the filling surface, and the water contact angle of the surface of the article were measured. . The results are shown in Table 3.

In addition, in Table 3, the result of the water contact angle (before sticking) of Example 2 is set as Reference Example 1, and the result of the water contact angle of Example 2 (after sticking) is set as Example 4-3. Described.
As is clear from Table 3, it was found that if the protective film B provided with a pressure-sensitive adhesive layer made of a silicone-based pressure-sensitive adhesive was used, water repellency could be imparted to the article regardless of the sticking time of the protective film B.

10: goods
10 ': article before filling,
11: base material,
12: convex part,
13: recess,
14: Micro uneven structure,
15: cured resin layer,
16: Function-imparting material,
20: protective film,
21: base film,
22: Adhesive layer.

Claims (4)

An article having a fine concavo-convex structure on its surface,
An article in which the concave portion of the fine concavo-convex structure is filled with a function-imparting material with a thickness of 10 nm or more, and the height of the convex portion protruding from the upper surface of the filling surface is 100 nm or more.   The article according to claim 1, wherein the article is an antireflection article having an average interval between convex portions of the fine concavo-convex structure having a wavelength of visible light or less.   The article according to claim 1 or 2, wherein the function-imparting material is a silicone-based pressure-sensitive adhesive.   After attaching a protective film provided with a pressure-sensitive adhesive layer made of a pressure-sensitive adhesive containing a function-imparting material to the surface of the article having a fine concavo-convex structure on the surface so that the surface of the article and the pressure-sensitive adhesive layer are in contact, protection A method for producing an article, in which the film is peeled off and the pressure-sensitive adhesive is transferred to the concave portion of the fine concavo-convex structure so as to have a thickness of 10 nm or more.

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