JP6449856B2 - Anti-fogging member and method for producing the same - Google Patents

Description

  The present invention relates to an antifogging member and a method for manufacturing the same.

  Conventionally, transparent base materials such as inorganic glass have been used for optical members such as windows, mirrors, glasses, goggles, camera lenses, and solar battery panels for architectural, industrial, and automotive purposes. When such a substrate is exposed to a humid atmosphere, water vapor condenses on its surface to form water droplets (condensation), which refracts or reflects light, hindering its function. There was a problem that the beauty was also lost. As a means for preventing fogging due to dew condensation on the substrate surface, a method for improving the wettability of the substrate surface with water and preventing fine water droplets from being generated is known. For example, Patent Document 1 discloses that a substrate surface is made hydrophilic by forming fine protrusions having a truncated cone shape or a cone shape having a substantially circular or polygonal bottom surface on the substrate surface. Has been. Further, Patent Document 2 discloses that a hydrophilic region in which a fine concavo-convex structure is formed and a water-repellent region in which a fine concavo-convex structure is not formed are formed on a substrate. It is disclosed that fogging of the surface of the base material is prevented because water moves to this area.

JP 2008-158293 A JP 2011-53334 A

  However, as a result of intensive studies by the present inventors, the base material on which the frustum-like or conical fine protrusions having a substantially circular or polygonal bottom as described above are insufficient in antifogging properties. I understood. In addition, the base material having a structure as described in Patent Document 2 prevents clouding caused by relatively large water droplets such as raindrops, or condensation caused in the bathroom, such as condensation in the bathroom, and in situations where water droplets are likely to grow large. Even when it is possible, when it is applied to a mirror for a bathroom or an indoor glass material, there is a drawback that fogging caused by relatively small water droplets generated in the indoor dew condensation process cannot be prevented. Accordingly, an object of the present invention is to provide a novel anti-fogging member that eliminates the drawbacks of the prior art and has excellent anti-fogging properties.

  According to the first aspect of the present invention, there is provided an antifogging member in which a concavo-convex pattern comprising a plurality of convex portions and concave portions is formed on a substrate, and the surface of the convex portion has a contact angle of water on a smooth surface. Is formed of a material having an angle of 90 degrees or less, the convex part and the concave part have an elongated shape extending straight or bent, and have a width of less than 10 μm, Is provided.

  In the antifogging member of the present invention, the cross-sectional shape perpendicular to the extending direction of the convex portion may be narrowed from the bottom portion toward the top portion. Further, the extending direction and the extending length of the convex part and the concave part may be uniform. The anti-fogging member of this invention may have the marker which shows the extension direction of the said convex part and the said recessed part further on the said base material. Further, the extending direction and the extending length of the convex part and the concave part may be non-uniform.

  In the antifogging member of the present invention, the concavo-convex depth of the concavo-convex pattern may be 25 μm or less. Moreover, the convex part length of the said uneven | corrugated pattern may be 3 times or more of the distance between convex parts. Further, the width of the convex portion and the concave portion may be 400 nm or less. The surface of the convex portion of the antifogging member may be made of an inorganic material.

  According to the second aspect of the present invention, there is provided a method for producing an antifogging member according to the first aspect, wherein an application step of forming a coating film on a substrate and a mold having an uneven pattern are pressed against the coating film. By this, the manufacturing method of the anti-fogging member which has the transcription | transfer process which transcribe | transfers the said uneven | corrugated pattern to the said coating film, and forms an uneven | corrugated structure layer on the said base material is provided.

  In the said anti-fogging member manufacturing method, in the said application | coating process, the said coating film can be formed by apply | coating the material whose water contact angle in a smooth surface is 90 degrees or less. Moreover, you may apply | coat the material whose water contact angle in a smooth surface is 90 degrees or less on the said uneven structure layer.

  According to a third aspect of the present invention, there is provided a method for producing an antifogging member according to the first aspect, wherein a coating film is formed on a concavo-convex pattern surface of a mold having a concavo-convex pattern on the surface, and the coating film There is provided a method for producing an anti-fogging member, which comprises a transfer step of bringing the coated film and the base material into close contact with each other and transferring the coating film onto the base material in accordance with the concavo-convex pattern.

  In the coating step of the manufacturing method according to the third aspect, the coating film may be formed in the concave portion of the concave / convex pattern surface of the mold, or, in the coating step, the convex portion of the concave / convex pattern surface of the mold. A coating film may be formed.

  In the coating step of the manufacturing method according to the third aspect, the coating film may be formed by coating a material having a water contact angle of 90 degrees or less on a smooth surface. In the manufacturing method according to the third aspect, a material having a water contact angle of 90 degrees or less on a smooth surface may be applied onto the coating film transferred to the substrate.

  The antifogging member of the present invention has a concavo-convex pattern consisting of elongated convex portions and concave portions extending straight or bent, and the surface of the convex portions has a water contact angle of 90 degrees or less on a smooth surface. Since water vapor is condensed on the surface of the anti-fogging member of the present invention to form water droplets, the water droplets are wet and spread along the extending direction of the convex portions and the concave portions, Since a film is formed, no small water droplets remain on the surface of the antifogging member. Therefore, the antifogging member of the present invention does not cause fogging due to water droplets and has excellent antifogging properties.

FIG. 1 is a schematic perspective view of an antifogging member according to an embodiment. Drawing 2 (a)-(d) is a schematic diagram showing an example of a plane shape of a convex part of an anti-fogging member of an embodiment. Drawing 3 (a)-(f) is an outline sectional view showing the example of the section shape of the anti-fogging member of an embodiment. FIG. 4 is a schematic plan view of the anti-fogging member of the embodiment in which a plurality of uneven patterns are formed. Drawing 5 (a)-(d) is an outline sectional view showing the example of the section structure of the anti-fogging member of an embodiment. It is a conceptual diagram which shows an example of the mode of a press process and a peeling process in the manufacturing method of the anti-fogging member of embodiment. It is a table | surface which shows the shape of the uneven | corrugated pattern of the member produced by the Example and the comparative example, the used material, and an evaluation result. It is the schematic of the shape of the water film produced by the anti-fogging effect evaluation test of an Example.

  Hereinafter, the anti-fogging member of the present invention and the manufacturing method thereof will be described with reference to the drawings.

[Anti-fogging member]
As shown in FIG. 1, the antifogging member 100 of the embodiment includes a base material 40 and a concave / convex pattern 80 including a plurality of convex portions 60 and concave portions 70 formed thereon.

  As shown in FIGS. 2A to 2D, the shape of the convex portion 60 of the antifogging member 100 of the embodiment in plan view (the shape seen from the direction perpendicular to the base material 40 of the antifogging member 100) is as shown in FIGS. It is an elongated shape that extends straight or bent. As shown in FIGS. 2 (a) and 2 (b), the convex portion 60 has a linear or elongated rectangular shape having a predetermined thickness in plan view. The end in the longitudinal direction (extending direction) may be square as shown in FIG. 2A, or may be rounded as shown in FIG. Alternatively, the convex portion 60 may have a curved shape that undulates (meanders) and extends as shown in FIGS. The thickness of the convex portion 60 may be uniform or non-uniform. Further, the projection 60 may be partially or entirely branched in plan view (see FIG. 2D). The extension length of the convex part 60 may be uniform as shown in FIGS. 2A to 2C, or may be non-uniform as shown in FIG. Further, the extending direction of the convex portion 60 and the direction of waviness (bending) may be uniform as shown in FIG. 2C, or non-uniform (irregular) as shown in FIG. There may be. The concave portion 70 is partitioned by the convex portion 60, extends along the convex portion 60, and has an elongated shape that extends straight or bent like the convex portion 60.

  The cross section obtained by cutting the convex portion 60 with a plane perpendicular to the extending direction may be rectangular as shown in FIG. 3A, or upward from the surface of the base material 40 (in a direction away from the surface of the base material 40). The shape may be tapered toward the surface. That is, the cross section of the convex portion 60 may be, for example, a triangle as shown in FIGS. 3B and 3C, a trapezoid, or a polygon as shown in FIG. Moreover, you may have external shapes, such as a kamaboko shape, a semicircle, a semi-ellipse, and a parabola as shown in FIG.3 (e). Furthermore, as shown in FIG. 3 (f), finer irregularities may be formed on the surface of the convex portion 60. When the convex part 60 has a shape in which the top part is narrower than the bottom part as shown in FIGS. 3B to 3F, that is, a tapered shape, it is easy to manufacture by the nanoimprint method as described later, and will be described later. As shown in FIG. Further, as shown in FIGS. 3A to 3F, the upper portions (upper surfaces or top portions) of the convex portions 60 are arranged at a predetermined distance from each other. As long as the top part or upper surface of a convex part is arrange | positioned at predetermined distance mutually, as shown in FIG.3 (c), the bottom face of the convex part 60 may mutually contact | connect.

  In the present application, as shown in FIG. 1, the length of the convex portion in the longitudinal direction is referred to as the convex portion length L. A surface between the bottom surfaces of adjacent convex portions is referred to as a concave portion. Further, the width of the upper part of the convex part in the cross section cut by a plane perpendicular to the extending direction of the convex part is the convex part width TW, the width of the bottom part of the convex part is the convex part bottom face width BW, and the upper part of the two convex parts. Is the distance TD between the protrusions, the distance between the bottom surfaces of the two protrusions is the recess width BD, and the height of the protrusion is the unevenness depth D.

  In the antifogging member of this embodiment, the convex portion width TW and the concave portion width BD are preferably less than 10 μm, and more preferably 5 μm or less. When the antifogging member 100 of the present embodiment is exposed to an atmosphere in which fogging is likely to occur, such as a high humidity atmosphere, water droplets generated by condensation of water vapor on the surface of the antifogging member 100 are formed on the convex portion 60 and Since the water film is united along the extending direction of the concave portion 70 to prevent the occurrence of fogging, the convex portion width TW or the concave portion width BD is 10 μm or more. The water droplets that are formed remain unbound. When the convex portion width TW and the concave portion width BD are less than 10 μm, water droplets formed on the convex portion 60 or the concave portion 70 are combined (unified) along the extending direction of the convex portion 60 and the concave portion 70 to form the water film. Become. When the convex portion width TW and the concave portion width BD are 5 μm or less, water droplets are combined to form a water film more easily. The convex part width TW or the concave part width BD can be 10 nm or more. The unevenness depth D is preferably in the range of 10 nm to 25 μm. When the unevenness depth D is less than 10 nm, the effect of water droplets coalescing along the extending direction of the convex portions 60 and the concave portions 70 to form a water film is small. When the unevenness depth D is 25 μm or more, the ratio of the protrusion width TW and the recess width BD is large, and it is difficult to form and maintain such an uneven shape. The unevenness depth D is more preferably in the range of 200 nm to 5 μm. An uneven shape having such an uneven depth D can be manufactured by a nanoimprint method. The length L of the convex portion is preferably at least three times the distance TD between the convex portions from the viewpoint of urging water droplets to spread and coalesce. Moreover, it is preferable that the convex part width TW is smaller than the convex part bottom face width BW. In this case, the convex portion 60 has a shape that tapers upward from the surface of the substrate 40, and water droplets easily enter the concave portion 70 of the concave / convex pattern 80, so that the concave / convex pattern having such a convex portion 60 is provided. The antifogging member in which 80 is formed has a high antifogging effect. Further, such a concavo-convex pattern 80 can be easily manufactured by a nanoimprint method.

  As shown in FIG. 4, a plurality of concave / convex patterns (an aggregate of concave / convex patterns) 80 including a plurality of convex portions 60 and concave portions 70 may be formed on the base material 40. It is preferable that the distance DP between the regions where the concavo-convex pattern 80 is formed is narrower than the inter-convex distance TD. As a result, a stronger capillary force is generated between the adjacent concavo-convex patterns 80 than in the concavo-convex pattern 80 (between the adjacent convex portions 60), and moisture generated on the concavo-convex pattern 80 is discharged outside the region where the concavo-convex pattern 80 is formed. Therefore, the antifogging property of the antifogging member 100 is improved. Moreover, it is more preferable that the distance DP between the regions where the concavo-convex pattern 80 is formed is less than 10 μm. When the interval is 10 μm or more, in the region where the uneven pattern 80 is not formed, water droplets remain without being combined, and these water droplets scatter light and appear visually cloudy. However, depending on the application in which the anti-fogging member of the embodiment is used, such as an application in which part of the member may be fogged, the interval between the regions where the uneven pattern 80 is formed is not particularly limited.

  When the anti-fogging member 100 of the embodiment has a concavo-convex pattern 80 composed of linear or curved convex portions 60 and concave portions 70 extending in a uniform direction, the extending direction of the convex portions 60 and concave portions 70 of the concavo-convex pattern 80. Since the water is well-dried when air-dried along the surface, and the growth of microorganisms can be suppressed, the transparency of the antifogging member can be maintained over a long period of time.

  When the convex portions 60 and the concave portions 70 on the base material 40 are arranged extending in a uniform direction as in the anti-fogging member 100 shown in FIG. 4, the moisture on the surface of the anti-fogging member is the convex portions 60 and the concave portions 70. It is easy to move along the extending direction. Therefore, such an antifogging member 100 can be easily dried by air-drying along the extending direction of the convex part 60 and the recessed part 70. FIG. Further, even if the antifogging member 100 is used so that the extending direction of the convex portions 60 and the concave portions 70 is in the direction of gravity, the water film on the surface of the antifogging member 100 easily flows down and is removed. Can be easily dried. Thereby, since the propagation of microorganisms and the like on the surface of the antifogging member 100 can be suppressed, the transparency of the antifogging member can be maintained over a long period of time. Such an antifogging member may be provided with a marker 20 indicating the extending direction of the convex portion 60 and the concave portion 70 as shown in FIG. The shape of the marker 20 is not limited to the arrow shape as shown in the figure, and any shape can be used as long as the direction can be distinguished. The installation position of the marker 20 can also be an arbitrary position with respect to the uneven pattern 80. There is no particular limitation. The presence of such a marker 20 is advantageous in that the extending direction (drying direction) of the convex part and the concave part can be visually recognized, so that it is possible to prevent a mistake in the drying direction, installation direction, etc. of the antifogging member.

  In the antifogging member 100 of the embodiment, the surface of the convex portion 60 is made of a material having a water contact angle of 90 degrees or less on a smooth surface. In the present application, the “water contact angle on a smooth surface” is an angle formed between a surface and a water droplet surface when a smooth surface without unevenness is formed with a material and water droplets are formed on the surface. The larger the contact angle of water on the smooth surface, the more hydrophobic the surface. In addition, the contact angle of water on a smooth surface can be measured using a contact angle meter (for example, model “CA-A” manufactured by Kyowa Interface Science Co., Ltd.). Specifically, a substrate made of a material to be measured having a smooth surface (or a substrate on which a smooth film of the material to be measured is formed on the surface) is placed on a horizontal platform of a contact angle meter. Next, a syringe containing ion-exchanged water is placed above the horizontal platform of the contact angle meter, water droplets with a diameter of 2 mm are produced at the tip of the syringe, and the horizontal platform is raised until the smooth surface and the water droplets contact each other. The water drop is allowed to stand for 25 seconds on a smooth surface. The contact angle of water can be calculated by obtaining an angle formed by a straight line connecting each of the left and right end points of the water droplet and the apex of the water droplet and the smooth surface and doubling this angle.

As a material having a contact angle of water of 90 degrees or less on a smooth surface used as a material constituting the surface of the convex portion 60, in particular, a Si-based material such as silica, SiN, or SiON, or Ti such as TiO ₂ is used. Examples thereof include inorganic materials such as ITO-based materials, ITO (indium-tin-oxide) -based materials, ZnO, ZnS, ZrO ₂ , Al ₂ O ₃ , BaTiO ₃ , and SrTiO ₂ .

By using the inorganic material as described above, the surface of the convex portion 60 becomes hard, so that it is possible to prevent the surface of the antifogging member from being damaged and the transparency from being impaired. Further, the inorganic material may contain a material such as TiO ₂ having a photocatalytic function. Thereby, the hydrophilicity of the convex surface can be improved, the antifogging property of the antifogging member can be improved, or the self-cleaning property can be imparted to the antifogging member. Such a material having a photocatalytic function may be reduced in crystallinity due to alkali metal ions such as Na ions, and the photocatalytic activity may be reduced. However, since the above inorganic material does not contain an alkali metal, the photocatalytic activity is high. Can be maintained.

  In addition to the inorganic material, a curable resin material may be used. Examples of such materials include polyethylene, polypropylene, polyvinyl alcohol, polyvinylidene chloride, polyethylene terephthalate, polyvinyl chloride, polystyrene, AS resin, acrylic resin, polyamide, polyacetal, polybutylene terephthalate, glass reinforced polyethylene terephthalate, polycarbonate, Modified resins such as polyphenylene ether, polyphenylene sulfide, polyether ether ketone, fluororesin, polyarate, polysulfone, polyethersulfone, polyamideimide, polyetherimide, thermoplastic polyimide, phenol resin, melamine resin, urea resin, epoxy Thermosetting resins such as resin, unsaturated polyester resin, alkyd resin, silicone resin, diallyl phthalate resin UV curable resins such as UV curable acrylic urethane resins, UV curable polyester acrylate resins, UV curable epoxy acrylate resins, UV curable polyol acrylate resins, UV curable epoxy resins, or a mixture of two or more of these. Materials can be used. Furthermore, a material obtained by compositing the inorganic material with the resin material may be used. Further, both the inorganic material and the resin material may contain known fine particles and fillers in order to obtain hard coat properties and the like.

Various substrates can be used as the base material 40. For example, a substrate made of a transparent inorganic material such as glass, polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, etc.), acrylic resin (polymethyl methacrylate, etc.), polycarbonate, polyvinyl chloride, styrene resin ( It is possible to use a translucent substrate such as a substrate made of a resin such as an ABS resin or the like, a cellulose resin (such as triacetyl cellulose), a polyimide resin (such as a polyimide resin or a polyimide amide resin), or a cycloolefin polymer. it can. As the substrate 40, a non-translucent substrate may be used. As the non-translucent substrate, a substrate made of metal, plastic, or the like can be used. The antifogging member 100 using a light-transmitting substrate may be bonded to an opaque substrate. The substrate 40 may be a hydrophilic substrate or a hydrophobic substrate. A substrate whose surface is subjected to a hydrophilic treatment by O ₃ treatment or the like may be used as the base material 40.

  In the antifogging member of the embodiment, as shown in FIG. 5A, a layer (concavo-convex structure layer) 62 constituting the convex portion 60 and the concave portion 70 may be formed on the base material 40. In this case, the concavo-convex structure layer 62 may be made of a material whose water contact angle on the smooth surface is 90 degrees or less. In the anti-fogging member of the embodiment, as shown in FIG. 5B, a structure in which the convex portion 60 is formed on the base material 40 and the surface of the base material 40 is exposed between the convex portions 60 (concave portion). 70) may be partitioned. In this case, the structure forming the convex portion 60 may be made of a material whose water contact angle on the smooth surface is 90 degrees or less. Moreover, in the anti-fogging member of the embodiment, as shown in FIG. 5C, the surface itself of the base material 40 may constitute the convex portion 60 and the concave portion 70. In this case, the base material 40 may be made of a material whose water contact angle on the smooth surface is 90 degrees or less. Furthermore, in the anti-fogging member of the embodiment, as shown in FIG. 5D, the contact angle of water on the smooth surface is 90 degrees or less on the concavo-convex pattern formed on the base material 40. A coating 50 may be formed. In this case, the water contact angle of the material constituting the surface of the convex portion 60 (inside), the surface of the base material 40 and the concave portion 70 may be 90 degrees or less, or may exceed 90 degrees. Good.

  When a conventional transparent substrate is exposed to an atmosphere in which cloudiness is likely to occur, such as a high-humidity atmosphere, water vapor is condensed on the surface to form water droplets, and these water droplets scatter light, and thus become visually cloudy. It is known that on a superhydrophilic surface, water droplets wet and spread to form a water film to prevent fogging. However, with this anti-fogging method, the material that can be applied to the surface is limited to only a part of the super-hydrophilic material, and when the surface is contaminated and the contact angle is increased (hydrophilicity is reduced), The fogging effect cannot be obtained. In addition, a surface with minute irregularities has a larger surface area than a smooth surface, so that the wettability of the material is emphasized (i.e., apparently hydrophilic material is more hydrophilic and water repellent material is more repellent). It is known to be aqueous). However, as shown in the evaluation results of the concavo-convex pattern substrate of the comparative example to be described later, when the concavo-convex shape is a hole, pillar, weight, etc., the effect of preventing fogging is not obtained, and it is sufficient only to improve the apparent hydrophilicity A good anti-fogging effect cannot be obtained.

  The anti-fogging member 100 of the present embodiment has a concavo-convex pattern composed of a plurality of elongated convex portions and concave portions extending straight or bent as described above, and the surface of the convex portion is a smooth surface. Because it is made of a material with a water contact angle of 90 degrees or less, even if water droplets occur on the surface of the member, the water droplets coalesce to form a water film as follows, preventing the occurrence of cloudiness Is done. First, water droplets generated in the recesses 70 are quickly and uniformly spread in the extending direction of the recesses 70 by using a concavo-convex pattern as a guide due to capillary action, thereby forming a water film. Water droplets generated on the surface of the convex portion 60 also spread out and coalesce with the water film of the concave portion 70. In this way, a water film is formed so as to fill the recess 70. When the water vapor further condenses, not only the water film extends in the extending direction of the convex portion 60 and the concave portion 70, but also the elongated water film formed in the adjacent concave portion 70 merges with each other over the concave and convex portions. It gradually spreads in the direction orthogonal to the extending direction of the convex part 60 and the concave part 70, and a water film having a larger area is formed. Since the water film is not visually recognized as water droplets, occurrence of cloudiness is prevented. The concavo-convex pattern as in this embodiment is optimal for preventing fogging because it can promote the wetting and spreading of water droplets and water film by capillary action. However, an uneven pattern having a hole shape, pillar shape, weight shape, or the like cannot provide an effect as a guide for promoting the spread of water droplets and a water film, and a water film is not formed. Therefore, the antifogging member 100 of this embodiment has antifogging properties superior to those of conventional antifogging members.

  The antifogging member of the embodiment can be used for various applications, for example, a mirror such as a vehicle mirror, bathroom mirror, toilet mirror, dental mirror, road mirror; spectacle lens, optical lens, photograph. Lenses such as machine lenses, endoscope lenses, illumination lenses, semiconductor lenses, and copier lenses; prisms; glass windows for buildings and other building materials; vehicles such as automobiles, railway vehicles, aircraft, and ships Windshield glass for vehicles; Goggles such as protective goggles and sports goggles; shields for protective masks, sports masks and helmets; glass for display cases of frozen foods; cover glasses for measuring instruments; It can be used for a film or the like for application to the surface of an article.

[Manufacturing method of anti-fogging member]
The antifogging member 100 of the embodiment can be manufactured by a nanoimprint method as described below. In the following description, as shown in FIG. 5 (a), a layer (concavo-convex structure layer) 62 constituting the convex portion 60 and the concave portion 70 is formed on the base material 40, and the concavo-convex structure layer 62 is a sol-gel material. The manufacturing method of the anti-fogging member 100 comprised by this will be described as an example. The manufacturing method of such an antifogging member 100 mainly includes a solution preparation step for preparing a sol-gel material, an application step for applying the prepared sol-gel material to a substrate, and a coating film of the sol-gel material applied to the substrate. A drying process, a pressing process for pressing the mold on which the transfer pattern is formed, a temporary baking process for temporarily baking the coating film on which the mold is pressed, a peeling process for peeling the mold from the coating film, and a curing process for curing the coating film. . Note that the pressing step, the temporary baking step, and the peeling step are collectively referred to as a transfer step. Hereinafter, each process is demonstrated in order.

<Solution adjustment process>
In order to form the concavo-convex structure layer by the sol-gel method, first, a solution of the sol-gel material is prepared. The concavo-convex structure layer is preferably formed of an inorganic material because it is hard and hardly scratched. As the concavo-convex structure layer material, a sol-gel material having a water contact angle of 90 degrees or less on the smooth surface as described above Can be used. For example, when forming the convex part which consists of silica on a base material with a sol-gel method, a metal alkoxide (silica precursor) is prepared as a sol-gel material. As precursors of silica, tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), tetra-i-propoxysilane, tetra-n-propoxysilane, tetra-i-butoxysilane, tetra-n-butoxysilane, tetra- Tetraalkoxide monomers typified by tetraalkoxysilane such as sec-butoxysilane, tetra-t-butoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, phenyltrimethoxysilane, Methyltriethoxysilane (MTES), ethyltriethoxysilane, propyltriethoxysilane, isopropyltriethoxysilane, phenyltriethoxysilane, methyltripropoxysilane, ethyltripro Xysilane, propyltripropoxysilane, isopropyltripropoxysilane, phenyltripropoxysilane, methyltriisopropoxysilane, ethyltriisopropoxysilane, propyltriisopropoxysilane, isopropyltriisopropoxysilane, phenyltriisopropoxysilane, tolyltriethoxy Trialkoxide monomers represented by trialkoxysilanes such as silane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldiisopropoxysilane, dimethyldi-n-butoxysilane, dimethyldi-i-butoxysilane, dimethyldi- sec-Butoxysilane, Dimethyldi-t-butoxysilane, Diethyldimethoxysilane, Diethyldiethoxysilane, Diethyl Dipropoxysilane, Diethyldiisopropoxysilane, Diethyldi-n-butoxysilane, Diethyldi-i-butoxysilane, Diethyldi-sec-butoxysilane, Diethyldi-t-butoxysilane, Dipropyldimethoxysilane, Dipropyldiethoxysilane, Di Propyl dipropoxysilane, dipropyldiisopropoxysilane, dipropyldi-n-butoxysilane, dipropyldi-i-butoxysilane, dipropyldi-sec-butoxysilane, dipropyldi-t-butoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, diisopropyl Dipropoxysilane, diisopropyldiisopropoxysilane, diisopropyldi-n-butoxysilane, diisopropyldi-i-butoxysilane, diisopro Pildi-sec-butoxysilane, diisopropyldi-t-butoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldipropoxysilane, diphenyldiisopropoxysilane, diphenyldi-n-butoxysilane, diphenyldi-i-butoxysilane Dialkoxide monomers typified by dialkoxysilanes such as diphenyldi-sec-butoxysilane and diphenyldi-t-butoxysilane can be used. Furthermore, alkyltrialkoxysilane or dialkyl dialkoxysilane whose alkyl group has C4-C18 carbon atoms can also be used. Monomers having a vinyl group such as vinyltrimethoxysilane and vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxy Monomers having an epoxy group such as silane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, monomers having a styryl group such as p-styryltrimethoxysilane, 3-methacryloxypropylmethyl Monomers having a methacrylic group such as dimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropiyl Monomers having an acrylic group such as trimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltri Monomers having amino groups, such as methoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, Monomers having a ureido group such as 3-ureidopropyltriethoxysilane, monomers having a mercapto group such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, sulfs such as bis (triethoxysilylpropyl) tetrasulfide A monomer having an alkyl group, a monomer having an isocyanate group such as 3-isocyanatopropyltriethoxysilane, a polymer obtained by polymerizing a small amount of these monomers, a composite material characterized by introducing a functional group or a polymer into a part of the material, etc. The metal alkoxides may be used. In addition, some or all of the alkyl group and phenyl group of these compounds may be substituted with fluorine. Furthermore, metal acetylacetonate, metal carboxylate, oxychloride, chloride, a mixture thereof and the like can be mentioned, but not limited thereto. Examples of the metal species include, but are not limited to, Ti, Sn, Al, Zn, Zr, In, and a mixture thereof in addition to Si. What mixed suitably the precursor of the said metal oxide can also be used. Further, a mesoporous concavo-convex structure layer may be formed by adding a surfactant to these materials. Furthermore, a silane coupling agent having a hydrolyzable group having affinity and reactivity with silica and an organic functional group having water repellency can be used as a precursor of silica. For example, silane monomers such as n-octyltriethoxysilane, methyltriethoxysilane, methyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane, vinylsilane such as vinylmethyldimethoxysilane, Methacrylic silane such as 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycyl Epoxy silanes such as Sidoxypropyltriethoxysilane, 3-Mercaptopropyltrimethoxysilane, Mercaptosilanes such as 3-Mercaptopropyltriethoxysilane, 3-Octanoylthio-1-pro Sulfur silane such as rutriethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl)- Examples include aminosilanes such as 3-aminopropylmethyldimethoxysilane and 3- (N-phenyl) aminopropyltrimethoxysilane, and polymers obtained by polymerizing these monomers.

  When a mixture of TEOS and MTES is used as the sol-gel material solution, the mixing ratio thereof can be 1: 1, for example, in a molar ratio. This sol-gel material produces amorphous silica by performing hydrolysis and polycondensation reactions. In order to adjust the pH of the solution as a synthesis condition, an acid such as hydrochloric acid or an alkali such as ammonia is added. The pH is preferably 4 or less or 10 or more. Moreover, you may add water in order to perform a hydrolysis. The amount of water to be added can be 1.5 times or more in molar ratio with respect to the metal alkoxide species.

  Solvents for the sol-gel material solution include, for example, alcohols such as methanol, ethanol, isopropyl alcohol (IPA) and butanol, aliphatic hydrocarbons such as hexane, heptane, octane, decane and cyclohexane, benzene, toluene, xylene, mesitylene and the like Aromatic hydrocarbons, diethyl ether, tetrahydrofuran, dioxane and other ethers, acetone, methyl ethyl ketone, isophorone, cyclohexanone and other ketones, butoxyethyl ether, hexyloxyethyl alcohol, methoxy-2-propanol, benzyloxyethanol, etc. Ether alcohols, glycols such as ethylene glycol and propylene glycol, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, Glycol ethers such as lenglycol monomethyl ether acetate, esters such as ethyl acetate, ethyl lactate and γ-butyrolactone, phenols such as phenol and chlorophenol, N, N-dimethylformamide, N, N-dimethylacetamide, N- Amides such as methylpyrrolidone, halogen-based solvents such as chloroform, methylene chloride, tetrachloroethane, monochlorobenzene, and dichlorobenzene, hetero-containing compounds such as carbon disulfide, water, and mixed solvents thereof can be mentioned. In particular, ethanol and isopropyl alcohol are preferable, and those in which water is mixed are also preferable.

  As an additive of the sol-gel material solution, polyethylene glycol, polyethylene oxide, hydroxypropyl cellulose, polyvinyl alcohol for viscosity adjustment, alkanolamine such as triethanolamine which is a solution stabilizer, β diketone such as acetylacetone, β ketoester, Formamide, dimethylformamide, dioxane and the like can be used. Further, as an additive of the sol-gel material solution, a material that generates acid or alkali by irradiating light such as energy rays typified by ultraviolet rays such as excimer UV light can be used. By adding such a material, the sol-gel material solution can be cured by irradiation with light.

<Application process>
A solution of the sol-gel material prepared as described above is applied onto a substrate. In order to improve adhesion, a surface treatment or an easy adhesion layer may be provided on the substrate. Any coating method such as a bar coating method, a spin coating method, a spray coating method, a dip coating method, a die coating method, and an ink jet method can be used as a sol-gel material coating method. The bar coating method, the die coating method, and the spin coating method are preferable because the sol-gel material can be applied uniformly and the application can be completed quickly before the sol-gel material gels.

<Drying process>
After application of the sol-gel material, the substrate may be held in the air or under reduced pressure in order to evaporate the solvent in the coating film. If this holding time is short, the viscosity of the coating film becomes too low to transfer the uneven pattern to the coating film, and if the holding time is too long, the polymerization reaction of the precursor proceeds and the viscosity of the coating film becomes too high. The uneven pattern cannot be transferred to the film. Further, after the application of the sol-gel material, the polymerization reaction of the precursor proceeds with the progress of the evaporation of the solvent, and the physical properties such as the viscosity of the sol-gel material change in a short time. From the viewpoint of the stability of the concave / convex pattern formation, it is desirable that the drying time range in which the pattern transfer can be satisfactorily wide is sufficiently wide. It can be adjusted by the amount of solvent used at the time of material preparation (concentration of sol-gel material) or the like. In the drying process, since the solvent in the sol-gel material solution evaporates simply by holding the substrate as it is, it is not always necessary to perform an aggressive drying operation such as heating or air blowing. It may be left as it is for a predetermined time or may be transported for a predetermined time in order to perform a subsequent process. That is, the drying step is not essential in the method for manufacturing an antifogging member of the embodiment.

<Pressing process>
Next, the concavo-convex structure layer is formed by transferring the concavo-convex pattern of the mold to the coating film of the sol-gel material using the mold for concavo-convex pattern transfer. As the mold, a film mold or a metal mold that can be manufactured by a method as described later can be used, but it is desirable to use a film mold having flexibility or flexibility. At this time, the mold may be pressed against the coating film of the sol-gel material using a pressing roll. In the roll process using a pressure roll, the time for contact between the mold and the coating film is short compared to the press type. It can be prevented, gas bubbles can be prevented from being generated in the pattern due to bumping of the solvent in the sol-gel material solution, and gas traces can be prevented from remaining, in order to make a line contact with the substrate (coating film) The transfer pressure and the peeling force can be reduced, and it is easy to cope with an increase in area, and there is an advantage that bubbles are not caught during pressing. Moreover, you may heat a base material, pressing a mold. As an example of pressing a mold against a coating film of a sol-gel material using a pressing roll, a film is formed by feeding a film-shaped mold 140 between a pressing roll 122 and a substrate 40 conveyed immediately below as shown in FIG. The uneven pattern of the mold 140 can be transferred to the coating film 64 on the substrate 40. That is, when the film mold 140 is pressed against the coating film 64 by the pressing roll 122, the film mold 140 and the substrate 40 are synchronously conveyed, and the surface of the coating film 64 on the substrate 40 is transferred to the film mold 140. Cover with. At this time, the film-shaped mold 140 and the substrate 40 are brought into close contact with each other by rotating while pressing the pressing roll 122 against the back surface of the film-shaped mold 140 (the surface opposite to the surface on which the concavo-convex pattern is formed). In order to feed the long film-shaped mold 140 toward the pressing roll 122, it is convenient to use the film-shaped mold 140 as it is from the film roll around which the long film-shaped mold 140 is wound.

<Temporary firing process>
After pressing the mold against the coating film of the sol-gel material, the coating film may be calcined. Pre-baking promotes gelation of the coating film, solidifies the pattern, and makes it difficult to collapse during peeling. When pre-baking is performed, it is preferable to heat in the atmosphere at a temperature of 40 to 150 ° C. Note that the preliminary firing is not necessarily performed. In addition, when a material that generates acid or alkali by adding light such as ultraviolet rays to the sol-gel material solution is added, energy represented by ultraviolet rays such as excimer UV light is used instead of pre-baking the coating film. A line may be irradiated.

<Peeling process>
After pressing the mold or pre-baking the coating film of the sol-gel material, the mold is peeled off from the coating film. A known peeling method can be employed as a mold peeling method. Since the convex and concave portions of the concave / convex pattern of the mold used in the manufacturing method of the embodiment have an elongated shape extending straight or bent, the mold release property is good. Further, in the case where the concave / convex pattern of the mold is a pattern in which convex portions and concave portions extend in a uniform direction, the mold peeling direction may be parallel to the extending direction of the convex portions and concave portions. . Thereby, the mold releasability can be further improved. The mold may be peeled off while heating, thereby releasing the gas generated from the coating film and preventing bubbles from being generated in the film. When the roll process is used, the peeling force may be smaller than that of a plate-shaped mold used in a press method, and the mold can be easily peeled off from the coating film without remaining in the mold. In particular, since the coating is pressed while being heated, the reaction easily proceeds, and the mold is easily peeled off from the coating immediately after pressing. Furthermore, you may use a peeling roll for the improvement of the peelability of a mold. As shown in FIG. 6, the peeling roll 123 is provided on the downstream side of the pressing roll 122, and the film-like mold 140 is rotated by supporting the film-like mold 140 against the coating film 64 by the peeling roll 123. It is possible to maintain the state of being attached to the surface only by the distance between the pressing roll 122 and the peeling roll 123 (a fixed time). Then, by changing the course of the film mold 140 so that the film mold 140 is pulled up above the peeling roll 123 on the downstream side of the peeling roll 123, the film mold 140 has a coating film (uneven structure layer). ) 62 is peeled off. In addition, you may perform temporary baking and the heating of the above-mentioned coating film 64 in the period when the film-form mold 140 is adhered to the coating film 64. FIG. In addition, when using the peeling roll 123, peeling of the mold 140 can be made still easier by peeling, for example, heating at 40-150 degreeC.

<Curing process>
After removing the mold from the coating film (uneven structure layer), the uneven structure layer may be cured. In the present embodiment, the concavo-convex structure layer made of the sol-gel material can be cured by the main baking. By this firing, the hydroxyl group and the like contained in the silica (amorphous silica) constituting the concavo-convex structure layer is eliminated, and the coating film becomes stronger. The main baking is preferably performed at a temperature of 200 to 1200 ° C. for about 5 minutes to 6 hours. At this time, when the concavo-convex structure layer is made of silica, it becomes amorphous or crystalline, or a mixed state of amorphous and crystalline depending on the firing temperature and firing time. Note that the curing step is not necessarily performed. In addition, when a material that generates acid or alkali by adding light such as ultraviolet rays to the sol-gel material solution is added, energy represented by ultraviolet rays such as excimer UV light is used instead of firing the concavo-convex structure layer. By irradiating the line, the concavo-convex structure layer can be cured.

  As described above, the antifogging member having the concavo-convex pattern 80 in which the layer (concavo-convex structure layer) 62 constituting the convex portion 60 and the concave portion 70 is formed on the base material 40 as shown in FIG. 100 can be manufactured.

In addition, as a solution of the sol-gel material to be applied in the above application step, a precursor such as TiO ₂ , ZnO, ZnS, ZrO ₂ , Al ₂ O ₃ , BaTiO ₃ , SrTiO ₂ , ITO, etc., in addition to a silica precursor. A solution of

  In addition to the sol-gel method, the uneven structure layer may be formed using a method using a dispersion of fine particles of an inorganic material, a liquid phase deposition (LPD) method, or the like.

Moreover, you may form an uneven | corrugated structure layer using polysilazane. In this case, the concavo-convex structure layer formed by applying and transferring this may be converted into ceramics (silica modification) in the curing step to form the concavo-convex structure layer made of silica, SiN or SiON. “Polysilazane” is a polymer having a silicon-nitrogen bond, such as SiO ₂ , Si ₃ N _{4 made of} Si—N, Si—H, N—H, etc., and ceramics such as both intermediate solid solutions SiO _X N _Y. It is a precursor inorganic polymer. A compound which is converted to ceramic at a relatively low temperature and modified to silica or the like as represented by the following general formula (1) described in JP-A-8-112879 is more preferable.

General formula (1):
-Si (R1) (R2) -N (R3)-
In the formula, R1, R2, and R3 each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group, or an alkoxy group.

  Among the compounds represented by the general formula (1), perhydropolysilazane (also referred to as PHPS) in which all of R 1, R 2 and R 3 are hydrogen atoms, and the hydrogen part bonded to Si is partially an alkyl group or the like. Substituted organopolysilazanes are particularly preferred.

  As another example of polysilazane which is ceramicized at low temperature, silicon alkoxide-added polysilazane obtained by reacting polysilazane with silicon alkoxide (for example, JP-A No. 5-23827), glycidol-added polysilazane obtained by reacting glycidol ( For example, JP-A-6-122852), alcohol-added polysilazane obtained by reacting alcohol (for example, JP-A-6-240208), metal carboxylate-added polysilazane obtained by reacting metal carboxylate ( For example, JP-A-6-299118), an acetylacetonate complex-added polysilazane obtained by reacting a metal-containing acetylacetonate complex (for example, JP-A-6-306329), and metal fine particles are added. Metal fine particle Polysilazane (e.g., JP-A-7-196986) and the like can also be used.

  As the solvent for the polysilazane solution, hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, ethers such as halogenated hydrocarbon solvents, aliphatic ethers, and alicyclic ethers can be used. In order to promote the modification to a silicon oxide compound, an amine or metal catalyst may be added.

Moreover, in the manufacturing method of the said embodiment, although the uneven | corrugated structure layer was formed using sol-gel material, you may use curable resin material other than the above-mentioned inorganic material. When forming a concavo-convex structure layer using a curable resin, for example, after applying a curable resin to a substrate, by curing a coating film while pressing a mold having a concavo-convex pattern on the applied curable resin layer, The concave / convex pattern of the mold can be transferred to the curable resin layer. The curable resin may be applied after being diluted with an organic solvent. As the organic solvent used in this case, a solvent capable of dissolving the uncured resin can be selected and used. For example, it can be selected from known solvents such as alcohol solvents such as methanol, ethanol and isopropyl alcohol (IPA), and ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone (MIBK). Examples of the method for applying the curable resin include spin coating, spray coating, dip coating, dropping, gravure printing, screen printing, letterpress printing, die coating, curtain coating, ink jet, and sputtering. Various coating methods such as a method can be employed. As a mold having a concavo-convex pattern, for example, a desired mold such as a film mold or a metal mold can be used. Furthermore, the conditions for curing the curable resin vary depending on the type of resin used. For example, the curing temperature is in the range of room temperature to 250 ° C., and the curing time is in the range of 0.5 minutes to 3 hours. Preferably there is. It is also possible by a method of curing by irradiation of energy rays such as ultraviolet rays or electron beams, in that case, it is preferable dose is in the range of ^{20mJ / cm 2 ~5J / cm 2} .

  The material of the uneven structure layer may be an inorganic material or a curable resin material containing an ultraviolet absorbing material. The ultraviolet absorbing material has an action of suppressing deterioration of the film by absorbing ultraviolet rays and converting light energy into a harmless form such as heat. As the ultraviolet absorber, conventionally known ones can be used. For example, a benzotriazole-based absorbent, a triazine-based absorbent, a salicylic acid derivative-based absorbent, a benzophenone-based absorbent, or the like can be used. As described above, various materials can be used as the material constituting the concavo-convex structure layer, in particular, the surface of the convex portion, and all of them are materials in which the contact angle of water on the smooth surface is 90 degrees or less. .

  In addition, the structure which makes the convex part 60 as shown in FIG.5 (b) is formed on the base material 40, and the area | region (concave part 70) which the surface of the base material 40 exposed between the convex parts 60 is divided. The anti-fogging member 100 can be manufactured as follows, for example. In the above application step, instead of applying the sol-gel material on the substrate, the sol-gel material is applied only to the concave portions or only the convex portions of the concave / convex pattern transfer mold. In the pressing step, the sol-gel material applied to the mold is brought into close contact. Thereby, a convex portion made of a sol-gel material having a shape corresponding to the shape of the concave portion or convex portion of the mold is formed on the substrate. A region (concave portion) where the surface of the base material is exposed is defined between the convex portions thus formed.

  As shown in FIG. 5C, the antifogging member 100 in which the surface of the substrate 40 itself forms the convex portion 60 and the concave portion 70 can be manufactured as follows, for example. A resist layer having a concavo-convex pattern is formed on a substrate by a known technique such as nanoimprinting or photolithography. After the recess of the resist layer is etched to expose the substrate surface, the substrate is etched using the remaining resist layer as a mask. After etching, the remaining mask (resist) is removed with a chemical solution. By the above operation, irregularities can be formed on the surface of the substrate itself.

You may form a film further on the uneven | corrugated pattern surface of the member manufactured by the above methods. Thereby, an antifogging member as shown in FIG. As a material for the film formed on the uneven pattern surface, a material having a water contact angle of 90 degrees or less on a smooth surface is used. In the member manufactured by such a method for manufacturing an antifogging member, since the surface of the convex portion of the concavo-convex pattern is covered with a film, the base material and the material of the concavo-convex structure layer or the structure forming the convex portion are used. Any light-transmitting material can be used, and the base material and the material of the concavo-convex structure layer or the structure forming the convex part may be a material having a water contact angle of 90 degrees or less on a smooth surface, or 90 degrees More than the material may be used. A film made of a material having a water contact angle of 90 degrees or less on a smooth surface is composed of SiO _x , TiO ₂ ZnO, ZrO ₂ , Al ₂ O ₃ , ZnS, BaTiO ₃ , SrTiO ₂ , ITO (indium) as exemplified above. Sol-gel materials such as tin oxide); fine particle dispersions such as SiO ₂ , TiO ₂ , ZnO, ZnS, ZrO, BaTiO ₃ , SrTiO ₂ ; polysilazane; curing of plastic resin, thermosetting resin, ultraviolet curable resin, etc. The resin material can be formed using a material obtained by compositing the above-mentioned inorganic material with the above-mentioned resin material; a material containing these fine particles, a filler, an ultraviolet absorber, or the like.

<Mold for uneven pattern transfer>
As a mold for concavo-convex pattern transfer used in a manufacturing method of an antifogging member of the above-mentioned embodiment, a metal mold manufactured by a method mentioned below, a film-like resin mold, etc. are contained, for example. The resin constituting the resin mold includes rubber such as natural rubber or synthetic rubber. The mold has an uneven pattern on the surface.

The example of the manufacturing method of the mold for uneven | corrugated pattern transfer is demonstrated. First, a matrix pattern for forming the concave / convex pattern of the mold is prepared. For example, in the case of producing an antifogging member having a concavo-convex pattern composed of curved convex portions and concave portions extending in a non-uniform direction, a block copolymer described in WO2012 / 096368 by the present applicants. In a solvent atmosphere of a block copolymer described in WO2013 / 161454 or a method using self-assembly (microphase separation) by heating (hereinafter referred to as “BCP (Block Polymer) thermal annealing method”). Forming irregularities due to wrinkles on the polymer surface by heating / cooling the vapor deposition film on the polymer film disclosed in WO2011 / 007878A1 as appropriate (hereinafter referred to as “BCP solvent annealing method”). (Hereinafter referred to as “BKL (Buckling) method”) to form a matrix. Are preferred. When a pattern is formed by the BCP thermal annealing method or the BCP solvent annealing method, any material can be used as a material for forming the pattern, but a styrenic polymer such as polystyrene, a polyalkyl methacrylate such as polymethyl methacrylate, and the like. A block copolymer consisting of two combinations selected from the group consisting of polyethylene oxide, polybutadiene, polyisoprene, polyvinyl pyridine, and polylactic acid is preferred. The pattern formed by self-assembly of these materials is described in a horizontal cylinder structure (structure in which the cylinder is horizontally oriented with respect to the base material) as described in WO2013 / 161454, or in Macromolecules 2014, 47, 2. A vertical lamella structure (a structure in which the lamella is oriented perpendicular to the substrate) is preferable. When forming deeper irregularities, a vertical lamella structure is more preferable. Moreover, etching by irradiating energy rays typified by ultraviolet rays such as excimer UV light, and dry etching such as RIE (reactive ion etching) and ICP etching on the uneven pattern obtained by the solvent annealing treatment Etching by a method may be performed. Moreover, you may heat-process with respect to the uneven | corrugated pattern which performed such an etching. Furthermore, Adv. Mater. An unevenness having a larger unevenness depth based on an uneven pattern formed by a BCP thermal annealing method or a BCP solvent annealing method by a method as described in 2012, 24, 5688-5694, Science 322, 429 (2008), etc. A pattern can be formed. That is, a block copolymer is applied on a base layer made of SiO ₂ , Si or the like, and a self-organized structure of the block copolymer is formed by a BCP thermal annealing method or a BCP solvent annealing method. Next, one segment of the block copolymer is selectively etched away. The underlying layer is etched using the remaining segment as a mask to form a desired depth groove (concave) in the underlying layer.

  Instead of the BCP thermal annealing method, the BKL method, and the BCP solvent annealing method as described above, a concavo-convex pattern may be formed by a photolithography method. In addition, for example, by using a micromachining method such as a cutting method, an electron beam direct drawing method, a particle beam beam machining method, and an operation probe machining method, and a micromachining method using self-organization of fine particles, Can be produced. When manufacturing an anti-fogging member having a concavo-convex pattern composed of linear or curved convex portions and concave portions extending in a uniform direction, these methods are used to form a linear or curved line extending in a uniform direction. A mother mold having a concavo-convex pattern composed of a convex portion and a concave portion may be formed.

  After the concave / convex pattern matrix is formed by a BCP thermal annealing method, a BKL method, a BCP solvent annealing method, or the like, a mold in which the pattern is further transferred can be formed by an electroforming method or the like as follows. First, a seed layer that becomes a conductive layer for electroforming can be formed on a matrix having a pattern by electroless plating, sputtering, vapor deposition, or the like. The seed layer is preferably 10 nm or more in order to make the current density uniform in the subsequent electroforming process and to make the thickness of the metal layer deposited by the subsequent electroforming process constant. Examples of seed layer materials include nickel, copper, gold, silver, platinum, titanium, cobalt, tin, zinc, chromium, gold / cobalt alloy, gold / nickel alloy, boron / nickel alloy, solder, copper / nickel / chromium An alloy, a tin-nickel alloy, a nickel-palladium alloy, a nickel-cobalt-phosphorus alloy, or an alloy thereof can be used. Next, a metal layer is deposited on the seed layer by electroforming (electroplating). The thickness of the metal layer can be, for example, 10 to 30000 μm in total including the thickness of the seed layer. Any of the above metal species that can be used as a seed layer can be used as a material for the metal layer deposited by electroforming. The formed metal layer desirably has an appropriate hardness and thickness from the viewpoint of ease of processing such as pressing, peeling and cleaning of the resin layer for forming a subsequent mold.

  The metal layer including the seed layer obtained as described above is peeled off from the matrix having the concavo-convex structure to obtain a metal substrate. The peeling method may be physically peeled off, or the material forming the pattern may be removed by dissolving it using an organic solvent that dissolves them, for example, toluene, tetrahydrofuran (THF), chloroform or the like. When the metal substrate is peeled from the mother die, the remaining material components can be removed by washing. As a cleaning method, wet cleaning using a surfactant or the like, or dry cleaning using ultraviolet rays or plasma can be used. Further, for example, remaining material components may be adhered and removed using an adhesive or an adhesive. The metal substrate (metal mold) having the pattern transferred from the mother die thus obtained can be used as the mold for transferring the concavo-convex pattern of the present embodiment.

  Furthermore, by using the obtained metal substrate, the concavo-convex structure (pattern) of the metal substrate is transferred to a film-like support substrate, whereby a flexible mold like a film-like mold can be produced. For example, after the curable resin is applied to the support substrate, the resin layer is cured while pressing the uneven structure of the metal substrate against the resin layer. As a support substrate, for example, a base material made of an inorganic material such as glass, quartz, silicon, etc .; silicone resin, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), cycloolefin polymer (COP), polymethyl Examples thereof include base materials made of organic materials such as methacrylate (PMMA), polystyrene (PS), polyimide (PI), and polyarylate, and metal materials such as nickel, copper, and aluminum. The thickness of the support substrate can be in the range of 1 to 500 μm.

  Examples of the curable resin include epoxy, acrylic, methacrylic, vinyl ether, oxetane, urethane, melamine, urea, polyester, polyolefin, phenol, cross-linked liquid crystal, fluorine, and silicone. And various resins such as monomers, oligomers, polymers, and the like. The thickness of the curable resin is preferably in the range of 0.5 to 500 μm. If the thickness is less than the lower limit, the height of the irregularities formed on the surface of the cured resin layer tends to be insufficient, and if the thickness exceeds the upper limit, the influence of the volume change of the resin that occurs during curing increases and the irregular shape is well formed. It may not be possible.

Examples of the method for applying the curable resin include spin coating, spray coating, dip coating, dropping, gravure printing, screen printing, letterpress printing, die coating, curtain coating, ink jet, and sputtering. Various coating methods such as a method can be employed. Furthermore, the conditions for curing the curable resin vary depending on the type of resin used. For example, the curing temperature is in the range of room temperature to 250 ° C., and the curing time is in the range of 0.5 minutes to 3 hours. Preferably there is. It is also possible by a method of curing by irradiation of energy rays such as ultraviolet rays or electron beams, in that case, it is preferable dose is in the range of ^{20mJ / cm 2 ~5J / cm 2} .

  Next, the metal substrate is removed from the cured resin layer after curing. The method for removing the metal substrate is not limited to the mechanical peeling method, and a known method can be adopted. The film-like resin mold having a cured resin layer having irregularities formed on a support substrate that can be obtained in this manner can be used as a mold for transferring an irregular pattern of this embodiment.

  In addition, by applying a rubber-based resin material on the concavo-convex structure (pattern) of the metal substrate obtained by the above-described method, curing the applied resin material, and peeling from the metal substrate, the concavo-convex pattern of the metal substrate can be obtained. A transferred rubber mold can be produced. The obtained rubber mold can be used as a mold for transferring an uneven pattern according to this embodiment. The rubber-based resin material is particularly preferably silicone rubber, or a mixture or copolymer of silicone rubber and other materials. Examples of the silicone rubber include polyorganosiloxane, cross-linked polyorganosiloxane, polyorganosiloxane / polycarbonate copolymer, polyorganosiloxane / polyphenylene copolymer, polyorganosiloxane / polystyrene copolymer, polytrimethylsilylpropyne, poly 4-methylpentene or the like is used. Silicone rubber is cheaper than other resin materials, has excellent heat resistance, high thermal conductivity, elasticity, and is not easily deformed even under high temperature conditions. Is suitable. Furthermore, since the silicone rubber-based material has high gas and water vapor permeability, the solvent and water vapor of the transfer material can be easily transmitted. Therefore, when a rubber mold is used for the purpose of transferring a concavo-convex pattern to a sol-gel material, a silicone rubber-based material is suitable. The surface free energy of the rubber material is preferably 25 mN / m or less. Thereby, the releasability when transferring the concave / convex pattern of the rubber mold to the coating film on the substrate becomes good, and transfer defects can be prevented. For example, the rubber mold can have a length of 50 to 1000 mm, a width of 50 to 3000 mm, and a thickness of 1 to 50 mm. If the thickness of the rubber mold is smaller than the lower limit, the strength of the rubber mold is reduced, and there is a risk of damage during handling of the rubber mold. When the thickness is larger than the above upper limit, it is difficult to peel off from the master mold when the rubber mold is manufactured. Moreover, you may perform a mold release process on the uneven | corrugated pattern surface of a rubber mold as needed.

  Alternatively, a mold (liquid crystal mold) having a concavo-convex surface containing a liquid crystal substance and having a relief structure formed by alignment of the liquid crystal substance may be used as the mold for transferring the concavo-convex pattern.

  Since such a mold has a relief structure formed on the surface based on the self-organizing property of the liquid crystal substance, the area of the uneven surface is not limited as in the lithography technique. Therefore, such a mold can be easily manufactured without providing a joint even when the area of the uneven surface for transfer is large.

  In order to form a relief structure efficiently and stably, the liquid crystal material preferably has a weight average molecular weight of 1000 or more. From the same viewpoint, the liquid crystal material is preferably aligned so that a helical structure is formed. More preferably, the chiral smectic C phase or the chiral smectic CA phase formed by the orientation of the liquid crystal substance is fixed.

  The pitch of the relief structure constituting the uneven surface of the liquid crystal mold (the length of one cycle of the unevenness) can vary depending on the helical structure formed by the liquid crystal substance, but is about 3000 nm or less. Moreover, the depth of the unevenness constituting the relief structure is 3 to 500 nm. The liquid crystal mold can be easily manufactured even when it has such a fine pattern.

  The liquid crystal layer remaining after the liquid crystal layer or the substrate surface under the resist layer is exposed by etching the concave portion of the uneven surface of the liquid crystal layer or the concave portion of the uneven surface of the resist layer to which the unevenness of the liquid crystal layer is transferred. The unevenness of the liquid crystal layer or the resist can be deepened by etching the base material using the layer or the resist layer as a mask. As an etching method, etching by irradiating energy rays typified by ultraviolet rays such as excimer UV light, dry etching methods such as RIE and ICP etching, and the like can be applied.

  In the liquid crystal mold, it is preferable that the liquid crystal phase having the helical structure as described above formed by the alignment of the liquid crystal substance is fixed in a state having substantially no fluidity. As a result of fixing the orientation of the liquid crystal substance, the relief structure on the mold surface is fixed. From the viewpoints of stability of the helical structure, ease of changing the helical pitch, ease of synthesis of the liquid crystal substance constituting the helical structure, and ease of orientation due to low viscosity in the liquid crystal state, chiral smectic C It is preferred that the phase or chiral smectic CA phase is fixed.

  A liquid crystal mold is a molded product formed of a liquid crystal material that is a composition containing one or more liquid crystal substances. Since it is easy to obtain a long molded product having a large area, the liquid crystal mold is preferably a film (liquid crystal film).

  The liquid crystal mold has a step of forming a film containing a liquid crystal substance, and aligns the liquid crystal substance so that a spiral structure is formed, and fixes the alignment of the liquid crystal substance to form a relief structure on the surface of the film. And it can manufacture by the process of obtaining the film | membrane which has an uneven surface as a mold.

  A metal molded product having a concavo-convex surface transferred from the relief structure of the liquid crystal mold may be used as the concavo-convex pattern transfer mold of this embodiment. Such a metal molded product has a step of forming a film containing a liquid crystal substance, and aligns the liquid crystal substance so that a helical structure is formed, and fixes the orientation of the liquid crystal substance, thereby relieving the surface of the film. Forming a structure to obtain a film having an uneven surface, and forming a metal molded product on the uneven surface of the film to obtain a metal molded product having an uneven surface formed by transfer from a relief structure as a mold It can be manufactured by a process.

  According to these methods, even a mold having a large uneven surface for transfer can be easily manufactured without providing a joint.

  Hereinafter, although the anti-fogging member of this invention is demonstrated concretely by an Example and a comparative example, this invention is not limited to those Examples. In the following Examples 1-13 and Comparative Examples 1-14, the board | substrate which has an uneven | corrugated pattern (irregular pattern substrate) was produced, respectively, and the anti-fogging property of each uneven | corrugated pattern board | substrate was evaluated.

Example 1
First, DTM-1-2 manufactured by Kyodo International Co., Ltd. was prepared as a matrix for the uneven pattern. In this matrix, convex portions (lines) extending in a straight line having a width of 1,000 nm, a length of 4,000 μm, and a height of 5,000 nm are formed at intervals of 1,000 nm. That is, in this matrix, a line and space pattern (L & S pattern) having a convex portion (line) width of 1,000 nm, a concave portion (space) width of 1,000 nm, a concave and convex depth of 5,000 nm, and a line length of 4,000 μm is formed. ing. In this L & S pattern, the cross section of the convex portion cut perpendicularly to the length direction of the convex portion (line) is a rectangle having a width of 1,000 nm and a height of 5,000 nm. In Example 1, this L & S pattern was used as an uneven pattern.

Next, a fluorine-based UV curable resin is applied onto a PET substrate (Toyobo Cosmo Shine A-4100) and irradiated with ultraviolet rays at 600 mJ / cm ² while pressing the matrix, the fluorine-based UV curable resin. Was cured. After the resin was cured, the matrix was peeled from the cured resin. Thus, a film mold made of a PET substrate with a resin film onto which the surface shape of the matrix was transferred was obtained.

  While stirring 1 g of water, 19 g of IPA and 0.1 mL of acetic acid, 1 g of a silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-5103) was added dropwise, and further stirred for 1 hr to prepare a silane coupling agent solution. A 30 mm x 30 mm x 0.7 (thickness) mm non-alkali glass substrate (manufactured by Nippon Denki Glass) was prepared, and this substrate was thoroughly rubbed with a detergent (manufactured by Junsei Kagaku, RBS-25) and a sponge. . Thereafter, water on the substrate surface was removed by spin drying, and a silane coupling agent solution was spin-coated thereon. Spin coating was performed at 1000 rpm for 30 seconds. Thereafter, the base material was baked in an oven at 130 ° C. for 15 minutes to obtain a base material subjected to easy adhesion treatment. PAK-02 (manufactured by Toyo Gosei Co., Ltd., water contact angle during smooth film: 70 °) as a UV curable resin was dropped onto the easy adhesion treated surface of the easy adhesion treated substrate. The surface on which the uneven pattern of the film mold was formed was superimposed on the dropped UV curable resin, and the hand roller was rotated from one end to the other end of the substrate to press the mold against the coating film on the substrate. After the pressing of the mold, the mold was peeled manually from the one end to the other end so that the peeling angle (the angle of the mold with respect to the base material) was about 30 °. Thereby, the uneven | corrugated pattern board | substrate with which the uneven | corrugated pattern of the mold was transcribe | transferred was produced.

Example 2
DTM-1-2 manufactured by Kyodo International Co., Ltd. was prepared as a matrix for the uneven pattern. In this matrix, an L & S pattern having a convex portion (line) width of 5,000 nm, a concave portion (space) width of 5,000 nm, an unevenness depth of 5,000 nm, and a line length of 4,000 μm is formed. A film mold was prepared in the same manner as in Example 1 except that this L & S pattern was used as the uneven pattern, and an uneven pattern substrate was prepared in the same manner as in Example 1 using this film mold.

Comparative Example 1
In order to compare with Examples 1 and 2, DTM-1-2 manufactured by Kyodo International Co., Ltd. was prepared as a matrix for the concavo-convex pattern. In this matrix, an L & S pattern having a convex portion (line) width of 10,000 nm, a concave portion (space) width of 10,000 nm, an unevenness depth of 5,000 nm, and a line length of 4,000 μm is formed. A film mold was prepared in the same manner as in Example 1 except that this L & S pattern was used as the uneven pattern, and an uneven pattern substrate was prepared in the same manner as in Example 1 using this film mold.

Comparative Example 2
In order to compare with Examples 1 and 2, DTM-1-2 manufactured by Kyodo International Co., Ltd. was prepared as a matrix for the concavo-convex pattern. In this matrix, an L & S pattern having a convex portion (line) width of 50,000 nm, a concave portion (space) width of 50,000 nm, an unevenness depth of 5,000 nm, and a line length of 4,000 μm is formed. A film mold was prepared in the same manner as in Example 1 except that this L & S pattern was used as the uneven pattern, and an uneven pattern substrate was prepared in the same manner as in Example 1 using this film mold.

Example 3
A custom mold A (Si mold) manufactured by NTT-AT was prepared as a matrix for the concave-convex pattern. In this matrix, an L & S pattern having a convex portion (line) width of 200 nm, a concave portion (space) width of 200 nm, an unevenness depth of 200 nm, and a line length of 10,000 μm is formed. A film mold was produced in the same manner as in Example 1 except that this matrix was used, and an uneven pattern substrate was produced in the same manner as in Example 1 using this film mold.

Example 4
1 mol of dimethyldiethoxysilane (DMDES) is added dropwise to a mixture of 22 mol of ethanol, 5 mol of water, 0.004 mol of concentrated hydrochloric acid and 4 mol of acetylacetone, and surfactant S-386 (manufactured by Seimi Chemical) is added as an additive. 0.5 wt% was added, and the mixture was stirred at 23 ° C. and humidity 45% for 2 hours to obtain a sol-gel material solution. A solution of sol-gel material was spin-coated on an alkali-free glass substrate. The spin coater used was ACT-300DII (manufactured by ACTIVE), and the spin was first performed at 500 rpm for 8 seconds and then at 1000 rpm for 3 seconds. After spin coating, the coating film was dried at room temperature for 20 to 1200 seconds. The surface on which the uneven pattern of the film mold prepared in the same manner as in Example 3 was formed on the sol-gel material coating film, and the 23 ° C. press roll was rotated from one end of the substrate toward the other end. The mold was pressed against the coating on the substrate. Immediately after the pressing, the substrate was moved onto a hot plate and heated at 100 ° C. (temporary firing). After heating was continued for 30 seconds or 5 minutes, the substrate was removed from the hot plate, and the mold was manually peeled from the one end to the other end so that the peel angle was about 30 °. Thereby, the uneven | corrugated pattern board | substrate with which the uneven | corrugated pattern of the mold was transcribe | transferred was produced. In addition, the contact angle of water during the smooth film of silica formed from DMDES was 84 °.

Example 5
A concavo-convex pattern substrate was produced in the same manner as in Example 4 except that tetraethoxysilane (TEOS) was used instead of DMDES. In addition, the contact angle of water at the time of the smooth film of the silica formed from TEOS was 10 °.

Example 6
In the same manner as in Example 3, except that UVHC8558 (manufactured by Momentive Performance Materials Japan G.K., water contact angle during smooth film: 87 °) was used instead of PAK-02 as the UV curable resin. A pattern substrate was produced.

Comparative Example 3
For comparison with Examples 3 to 6, as in Example 3 except that a fluorine-based UV curable resin (contact angle of water during smooth film: 95 °) was used instead of PAK-02 as the UV curable resin. Thus, a concavo-convex pattern substrate was produced.

Example 7
A custom pattern B (Si mold) manufactured by NTT-AT was prepared as a matrix for the concave-convex pattern. In this matrix, an L & S pattern having a convex portion (line) upper portion width of 400 nm, a convex portion (line portion) lower portion width of 400 nm, a concave portion (space) width of 400 nm, an unevenness depth of 200 nm, and a line length of 10,000 μm is formed. A film mold was produced in the same manner as in Example 1 except that this matrix was used, and an uneven pattern substrate was produced in the same manner as in Example 1 using this film mold. In the matrix of the concave / convex pattern used in this example, the cross section of the convex portion cut perpendicularly to the length direction of the convex portion is a rectangle having a width of 400 nm and a height of 200 nm.

Example 8
A concavo-convex pattern substrate was produced in the same manner as in Example 4 except that the film mold produced in the same manner as in Example 7 was used.

Example 9
A concavo-convex pattern substrate was produced in the same manner as in Example 5 except that the film mold produced in the same manner as in Example 7 was used.

Example 10
A concavo-convex pattern substrate was produced in the same manner as in Example 6 except that the film mold produced in the same manner as in Example 7 was used.

Comparative Example 4
In order to compare with Examples 7 to 10, a film mold produced in the same manner as in Example 7 was used, and other than that, a concavo-convex pattern substrate was produced in the same manner as in Comparative Example 3.

Example 11
A custom-made pattern C manufactured by NTT-AT was prepared as a matrix for the concavo-convex pattern. In this matrix, an L & S pattern having a convex portion (line) upper width of 100 nm, a convex portion (line) lower portion width of 200 nm, a concave portion (space) width of 50 nm, an unevenness depth of 400 nm, and a line length of 15,000 μm is formed. A film mold was produced in the same manner as in Example 1 except that this matrix was used, and an uneven pattern substrate was produced in the same manner as in Example 1 using this film mold. Note that, in the matrix of the concavo-convex pattern used in this example, the cross section of the convex portion cut perpendicular to the length direction of the convex portion is an isosceles trapezoid having an upper base of 100 nm, a lower base of 200 nm, and a height of 400 nm.

Example 12
A concavo-convex pattern substrate was produced in the same manner as in Example 4 except that the film mold produced in the same manner as in Example 11 was used.

Example 13
A concavo-convex pattern substrate was produced in the same manner as in Example 6 except that the film mold produced in the same manner as in Example 11 was used.

Comparative Example 5
In order to compare with Examples 11-13, the film mold produced like Example 11 was used, and the uneven | corrugated pattern board | substrate was produced similarly to Comparative Example 3 except it.

Comparative Example 6
For comparison with Example 2, DTM-1-2 manufactured by Kyodo International Co., Ltd. was prepared as a matrix for the concave-convex pattern. In this matrix, a hole pattern in which cylindrical holes having a diameter of 5,000 nm and a depth of 5,000 nm are arranged at intervals of 5,000 nm (that is, a convex part width (inter-hole distance) 5,000 nm, a concave part width (hole diameter) ), A 5,000 nm hole pattern with a concavo-convex depth (hole depth) of 5,000 nm. A film mold was produced in the same manner as in Example 1 except that this hole pattern was used as an uneven pattern, and an uneven pattern substrate was produced in the same manner as in Example 1 using this film mold.

Comparative Example 7
For comparison with Example 3, FLH230 / 200-120 manufactured by SCIVAX was prepared as a matrix for the concave-convex pattern. In this matrix, a hole pattern in which cylindrical holes having a diameter of 230 nm and a depth of 200 nm are arranged at intervals of 230 nm (that is, a protrusion width (inter-hole distance) of 230 nm, a recess width (hole diameter) of 230 nm, an unevenness depth (hole) Depth) 200 nm hole pattern) is formed. A film mold was produced in the same manner as in Example 1 except that this matrix was used, and an uneven pattern substrate was produced in the same manner as in Example 1 using this film mold.

Comparative Example 8
In order to compare with Comparative Examples 3 and 7, a film mold produced in the same manner as in Comparative Example 7 was used, and other than that, a concavo-convex pattern substrate was produced in the same manner as in Comparative Example 3.

Comparative Example 9
For comparison with Example 2, DTM-1-2 manufactured by Kyodo International Co., Ltd. was prepared as a matrix for the concave-convex pattern. In this matrix, a pillar pattern in which cylindrical pillars having a diameter of 5,000 nm and a height of 5,000 nm are arranged at intervals of 5,000 nm (that is, a convex part width (pillar diameter) 5,000 nm, a concave part width (distance between pillars). ), A 5,000 nm pillar pattern with a concavo-convex depth (pillar height) of 5,000 nm. A film mold was produced in the same manner as in Example 1 except that this pillar pattern was used as an uneven pattern, and an uneven pattern substrate was produced in the same manner as in Example 1 using this film mold.

Comparative Example 10
For comparison with Example 3, FLV230 / 200-120 manufactured by SCIVAX was prepared as a matrix for the concave-convex pattern. In this matrix, a pillar pattern in which cylindrical pillars having a diameter of 230 nm and a height of 200 nm are arranged at intervals of 230 nm (that is, convex part width (pillar diameter) 230 nm, concave part width (distance between pillars) 230 nm, concave and convex depth (pillar) Height) 200 nm pillar pattern) is formed. A film mold was produced in the same manner as in Example 1 except that this matrix was used, and an uneven pattern substrate was produced in the same manner as in Example 1 using this film mold.

Comparative Example 11
In order to compare with Comparative Examples 3 and 10, a film mold produced in the same manner as in Comparative Example 10 was used, and other than that, a concavo-convex pattern substrate was produced in the same manner as in Comparative Example 3.

Comparative Example 12
For comparison with Example 3, an anti-reflective stamp manufactured by NIL Technology was prepared as a matrix for the concavo-convex pattern. In this matrix, a moth-eye pattern in which cones with a diameter of 250 nm and a height of 250 nm are arranged at intervals of 50 nm (that is, convex base width (cone diameter) 250 nm, concave width (inter-cone distance) 50 nm, uneven depth (conical height) ) A moth-eye pattern of 250 nm) is formed. A film mold was produced in the same manner as in Example 1 except that this matrix was used, and an uneven pattern substrate was produced in the same manner as in Example 1 using this film mold.

Comparative Example 13
In order to compare with Example 4 and Comparative Example 12, a concavo-convex pattern substrate was produced in the same manner as in Example 4 except that a film mold produced in the same manner as in Comparative Example 12 was used.

Comparative Example 14
In order to compare with Comparative Examples 3, 12, and 13, a concavo-convex pattern substrate was produced in the same manner as in Comparative Example 3, except that a film mold produced in the same manner as in Comparative Example 12 was used.

<Evaluation of anti-fogging effect>
The anti-fogging effect of the concavo-convex pattern substrates produced in Examples 1 to 13 and Comparative Examples 1 to 14 was evaluated as follows. The concavo-convex pattern substrate was left for 30 minutes in a temperature-controlled room at a temperature of 25 ± 2 ° C. and a humidity of 25%. Subsequently, the uneven | corrugated pattern board | substrate was left still for 1 minute on a -10 +/- 2 degreeC plate. Thereafter, the occurrence of fogging on the surface of the concavo-convex pattern substrate was visually confirmed, and those in which the clouding was not observed on the substrate surface were accepted and those in which the fogging was seen were rejected. The evaluation results are shown in the table of FIG.

<Measurement of water contact angle in smooth film>
In addition, the contact angle of water at the time of the smooth film of PAK-02, DMDES, TEOS, UVHC8558, and fluorine-type UV curable resin used in Examples 1-13 and Comparative Examples 1-14 was measured as follows.

Each of PAK-02, UVHC8558, and fluorine-based UV curable resin was spin-coated on a glass plate (made by Nippon Electric Glass Co., Ltd., OA10G) cut to 5 × 5 × 0.07 cm. Using ACT-300DII (manufactured by ACTIVE) as a spin coater, the coating was performed by spinning at 1000 rpm for 30 seconds. Subsequently, the coating film was hardened by irradiating ultraviolet rays at 600 mJ / cm ² in a nitrogen atmosphere (oxygen concentration of 0.5% or less).

  Each solution of DMDES and TEOS was spin-coated on a glass plate (OA 10G, manufactured by Nippon Electric Glass Co., Ltd.) cut to 5 × 5 × 0.07 cm to form a coating film. Using ACT-300DII (manufactured by ACTIVE) as a spin coater, the coating was first carried out at 500 rpm for 8 seconds and then spun at 1000 rpm for 3 seconds for coating. Next, the coating film was dried at room temperature for 90 seconds, and calcined at 100 ° C. for 5 minutes using a hot plate. The obtained substrate was heated at 300 ° C. for 1 hour, and the coating film was baked.

  For the smooth film made of PAK-02, UVHC8558, fluorine-based UV curable resin, silica formed from DMDES, and silica formed from TEOS, the contact angle meter (Kyowa Interface Science Co., Ltd., CA- Using A), the contact angle of water was measured. As a result, as shown in the table of FIG. 7, the water contact angle of the PAK-02 film is 70 °, the water contact angle of the UVHC8558 film is 87 °, and the water contact angle of the fluorine-based UV curable resin film is The water contact angle of the silica film formed from 95 °, DMDES was 84 °, and the water contact angle of the silica film formed from TEOS was 10 °.

  As shown in the table of FIG. 7, from the evaluation results of the anti-fogging effect of the concavo-convex pattern substrates of Examples 1 and 2 and Comparative Examples 1 and 2, the convex part width (line width) and concave part width (space width) were 10 μm. The concavo-convex pattern substrate having the L & S pattern which is less than the above has a sufficient anti-fogging effect, but the concavo-convex pattern substrate having the L & S pattern having the convex portion width (line width) and the concave portion width (space width) of 10 μm or more is anti-fogging effect. Was found to be insufficient. When the surface of the concavo-convex pattern substrate having a convex portion width (line width) and a concave portion width (space width) of less than 10 μm after the anti-fogging effect evaluation test was observed with a microscope, as shown conceptually in FIG. A water film having a shape spreading wet along the extending direction of the concave and convex portions was formed. From this, in the concavo-convex pattern substrate in which the convex portion width (line width) and the concave portion width (space width) are less than 10 μm, water droplets generated on the substrate surface are caused in the length direction of the line and space (convex portion and concave portion) ( It is thought that they were united along the extending direction. Therefore, in a concavo-convex pattern substrate having a convex portion width (line width) and a concave portion width (space width) of less than 10 μm, water droplets coalesce along the length direction of the line and space, and a water film (does not scatter light). It is thought that cloudiness did not occur. On the other hand, in a concavo-convex pattern substrate having a convex portion width (line width) or a concave portion width (space width) of 10 μm or more, relatively small water droplets that scatter light remain on the convex portion surface or the concave portion surface, and thus remain. It is thought that cloudiness occurred.

  As shown in the table of FIG. 7, from the evaluation results of the antifogging effect of the uneven pattern substrates of Examples 3 to 10 and Comparative Examples 3 and 4, the uneven pattern substrate using PAK-02, DMDES, TEOS, and UVHC8558 is Although it has a sufficient anti-fogging effect, it has been found that an uneven pattern substrate using a fluorine-based UV curable resin has an insufficient anti-fogging effect. PAK-02, DMDES, TEOS, UVHC8558 has a water contact angle of 90 degrees or less, and the fluorine UV curable resin has a water contact angle of more than 90 degrees. It has been found that the material for forming the concavo-convex pattern needs to have hydrophilicity so that the water contact angle is 90 degrees or less. When the contact angle with respect to the water of the material forming the concave / convex pattern is 90 ° or less, the water droplets are wet and spread along the length direction of the line and space as described above, and a water film (a large film that does not scatter light) It is thought that cloudiness did not occur due to water droplets. On the other hand, when the hydrophilicity of the material forming the concave-convex pattern is insufficient, the water droplets did not spread along the length direction of the line and space, and the coalescence of the water droplets as described above did not occur sufficiently. It is considered that small water droplets that scatter light remain on the substrate surface, resulting in cloudiness.

  As shown in the table of FIG. 7, from the evaluation results of the anti-fogging effect of the concavo-convex pattern substrates of Examples 11 to 13 and Comparative Example 5, the convex portion of the line and space pattern is directed from the bottom to the top on the base material side. It has been found that the antifogging effect can be obtained even when the cross section has a narrow width (that is, when the convex portion has a tapered shape) as in the case where the convex portion has a rectangular cross section.

  As shown in the table of FIG. 7, comparison of the evaluation results of the anti-fogging effect of the uneven pattern substrates of Example 2 and Comparative Examples 6 and 9 and prevention of the uneven pattern substrates of Example 3 and Comparative Examples 7, 10 and 12 From the comparison of the evaluation results of the fogging effect and the comparison of the evaluation results of the antifogging effect of the concavo-convex pattern substrates of Example 4 and Comparative Example 13, when the concavo-convex pattern is a hole pattern, a pillar pattern, or a moth-eye pattern, the concavo-convex pattern is Unlike the case of the L & S pattern, it was found that the anti-fogging effect of the uneven pattern substrate was insufficient. L & S shaped irregularities can serve as a guide for water droplets to coalesce, but holes, pillars or moth-eye irregularities do not function well as a guide for water droplet coalescence and hence holes In the concavo-convex pattern substrate having a pattern, a pillar pattern, or a moth-eye pattern, it is considered that small water droplets that scatter light remain on the substrate surface without being united and cloudy. Moreover, from the evaluation results of Comparative Examples 3, 8, 11, and 14, when the material for forming the uneven pattern is a fluorine-based UV curable resin, that is, the water contact angle of the material for forming the uneven pattern exceeds 90 degrees. In the case, the concavo-convex pattern substrate having the hole pattern, the pillar pattern, or the moth-eye pattern as well as the concavo-convex pattern substrate having the L & S pattern was found to have an insufficient antifogging effect.

  Although the present invention has been described with reference to the examples and comparative examples, the anti-fogging member of the present invention is not limited to the above-described examples, and may be appropriately modified within the scope of the technical idea described in the claims. it can.

  Since the antifogging member of the present invention has excellent antifogging properties, for example, mirrors for vehicles, bathroom mirrors, toilet mirrors, dental mirrors, road mirrors, spectacle lenses, optical lenses, and camera lenses Lenses such as endoscope lenses, illumination lenses, semiconductor lenses, and copier lenses; prisms; glass windows for buildings and other building materials; window glass for vehicles such as automobiles, railway vehicles, aircraft, and ships Windshields for vehicles; goggles such as protective goggles and sports goggles; shields for protective masks, sports masks, helmets, etc .; glass for display cases of frozen foods; cover glasses for measuring instruments; It can be used for various applications such as a film for attaching to a film.

20 buffer layer, 40 base material, 50 coating 60 convex portion, 62 concave / convex structure layer, 70 concave portion 80 concave / convex pattern, 100 anti-fogging member

Claims (13)

An anti-fogging member in which a concavo-convex pattern comprising a plurality of convex portions and concave portions is formed on a substrate,
The extending direction and the extending length of the convex part and the concave part are non-uniform,
The surface of the convex portion is made of a material having a water contact angle of 90 degrees or less on a smooth surface,
The anti-fogging member, wherein the convex part and the concave part have an elongated shape extending straight or bent and have a width of less than 10 μm.   The anti-fogging member according to claim 1, wherein a cross-sectional shape perpendicular to the extending direction of the convex portion becomes narrower from the bottom toward the top. Furthermore, the anti-fogging member of Claim 1 which has a marker which shows the extension direction of the said convex part and the said recessed part on the said base material. The anti-fogging member according to any one of claims 1 to 3, wherein an uneven depth of the uneven pattern is 25 µm or less. The antifogging member according to any one of claims 1 to 4, wherein the convex portion length of the concave-convex pattern is three times or more the distance between the convex portions. The anti-fogging member according to any one of claims 1 to 5, wherein the width of the convex portion and the concave portion is 400 nm or less. The surface of the said convex part is comprised with the inorganic material, The anti-fogging member as described in any one of Claims 1-6 characterized by the above-mentioned. A concavo-convex pattern consisting of a plurality of convex portions and concave portions is formed on a substrate, and the surface of the convex portions is made of a material having a contact angle of water of 90 degrees or less on a smooth surface, and the convex portions and the concave portions are A method for producing an antifogging member having an elongated shape extending straight or bent and having a width of less than 10 μm,
  An application step of forming a coating film on the substrate;
  A transfer step of transferring the concavo-convex pattern to the coating film by pressing a mold having a concavo-convex pattern on the coating film, and forming a concavo-convex structure layer on the substrate;
And a step of applying a material having a contact angle of water of 90 degrees or less on the smooth surface to the uneven structure layer. 9. The method for producing an antifogging member according to claim 8, wherein in the coating step, the coating film is formed by coating a material having a contact angle of water of 90 degrees or less on a smooth surface. A concavo-convex pattern consisting of a plurality of convex portions and concave portions is formed on a base material, and the surface of the convex portions is made of a material having a contact angle of water of 90 degrees or less on a smooth surface. A method for producing an antifogging member having an elongated shape extending straight or bent and having a width of less than 10 μm,
  An application step of forming a coating film on the concave / convex pattern surface of the mold having a concave / convex pattern on the surface;
  A transfer step in which the mold on which the coating film is formed and a substrate are brought into close contact with each other and the coating film is transferred to the substrate according to the uneven pattern;
  Applying a material having a water contact angle of 90 degrees or less on a smooth surface onto the coating film transferred to the substrate. The method for producing an antifogging member according to claim 10, wherein in the coating step, the coating film is formed in a concave portion of the concave / convex pattern surface of the mold. The method for producing an antifogging member according to claim 10, wherein in the coating step, the coating film is formed on a convex portion of the concave / convex pattern surface of the mold. In the said application | coating process, the said coating film is formed by apply | coating the material whose water contact angle in a smooth surface is 90 degrees or less, Anti-fog as described in any one of Claims 10-12 characterized by the above-mentioned. Manufacturing method of member.

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