TW201604000A - Antifogging member and manufacturing method therefor - Google Patents

Abstract

For an antifogging member (100), a relief pattern (80) obtained from multiple protrusions (60) and recesses (70) is formed on a substrate (40). The surfaces of the protrusions (6) are configured from a material for which the contact angle of water on a level surface is not more than 90 degrees. The protrusions (60) and the recesses (70) have long thin shapes that extend in a straight or bent line and the widths thereof are less than 10 [mu]m. Because water droplets wet and spread in the direction of extension to form a water film, the retention of fine water droplets is prevented. The antifogging member (100) has excellent antifogging properties.

Description

Anti-fog member and manufacturing method thereof

The present invention relates to an anti-fog member and a method of manufacturing the same.

Transparent substrates such as inorganic glass have been used for optical components such as windows, mirrors, glasses, goggles, photographic lenses, and solar cell panels for construction, industrial, and automotive applications. Such a substrate has a problem that if exposed to a high humidity environment, water vapor condenses on the surface to generate water droplets (condensation), whereby the light is refracted or reflected, thereby hindering the function of the substrate and also impairing Beautiful. As means for preventing water mist caused by condensation of the surface of the substrate, there is known a method of improving the wettability of the surface of the substrate against water so that fine water droplets are not generated. For example, Patent Document 1 discloses that a surface of a base material is made hydrophilic by forming a fine protrusion having a tapered trapezoidal shape or a tapered shape having a substantially circular or polygonal bottom surface. Further, Patent Document 2 discloses that a hydrophilic region in which a fine uneven structure is formed and a water-repellent region in which a fine uneven structure is not formed are formed on a substrate, whereby the water is moved from the water-repellent region to the hydrophilic region, thereby preventing Water mist on the surface of the substrate.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2008-158293

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2011-53334

However, the inventors of the present invention have diligently conducted research, and as a result, it has been found that the substrate having the tapered protrusions having a substantially circular or polygonal bottom surface as described above has insufficient antifogging property. Further, the substrate having the structure described in Patent Document 2 has a drawback in that it is possible to prevent water mist caused by relatively large water droplets such as raindrops, or condensation in the bathroom, which is equal to a large amount of water and easy to grow in a wide range of water droplets. In the case of a water mist generated in the case of a bathroom or a glass material in a room, it is not possible to prevent water mist caused by relatively small water droplets generated during condensation in the room. Accordingly, it is an object of the present invention to provide a novel anti-fog member which eliminates the disadvantages of the prior art and which has excellent anti-fog properties.

According to a first aspect of the present invention, an anti-fog member is provided which is formed with a concave-convex pattern composed of a plurality of convex portions and concave portions on a base material, wherein the surface of the convex portion is made of a smooth surface. The water contact angle is 90 degrees or less, and the convex portion and the concave portion have an elongated shape extending straight or curved, and the width is less than 10 μm.

In the anti-fog member of the present invention, the cross-sectional shape of the convex portion orthogonal to the extending direction may be narrowed from the bottom to the top. Further, the extending direction and the extending length of the convex portion and the concave portion may be uniform. The anti-fog member of the present invention may further include a mark indicating the extending direction of the convex portion and the concave portion on the base material. Moreover, the extending direction and the extending length of the convex portion and the concave portion may not be uniform.

In the anti-fog member of the present invention, the unevenness of the uneven pattern may be 25 μm or less. Further, the length of the convex portion of the uneven pattern may be three times or more the distance between the convex portions. 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 anti-fog member may be made of an inorganic material.

According to a second aspect of the present invention, there is provided a method for producing an anti-fog member, which is a method for producing an anti-fog member according to a first aspect, and has the following steps: a coating step of forming a coating film on a substrate And a transfer step of transferring the uneven pattern onto the coating film by pressing a mold having a concave-convex pattern against the coating film to form an uneven structure layer on the substrate.

In the method for producing an anti-fogging member, in the coating step, the coating film can be formed by applying a material having a water contact angle of 90° or less on a smooth surface. Further, a material having a smooth surface water contact angle of 90 degrees or less may be applied to the uneven structure layer.

According to a third aspect of the present invention, there is provided a method of manufacturing an anti-fog member, which is a method for producing an anti-fog member according to a first aspect, and has the following steps: a coating step of a mold having a concave-convex pattern on its surface a concave-convex pattern surface forming a coating film; and a transfer step of adhering the mold having the coating film to the substrate, and transferring the coating film to the substrate in accordance with the uneven pattern.

In the coating step according to the manufacturing method of the third aspect, the coating film may be formed in a concave portion of the concave-convex pattern surface of the mold, or in the coating step, in the concave-convex pattern surface of the mold The convex portion forms the above coating film.

In the above coating step according to the manufacturing method of the third aspect, the coating film may be formed by coating a material having a smooth surface with a water contact angle of 90 degrees or less. Again, in accordance with the In the three-dimensional manufacturing method, a material having a smooth surface with a water contact angle of 90 degrees or less may be applied onto the coating film transferred onto the substrate.

The anti-fog member of the present invention has a concave-convex pattern composed of a convex portion and a concave portion which are elongated in a straight or curved shape, and 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, and thus When water vapor condenses on the surface of the anti-fog member of the present invention to form water droplets, the water droplets are wetted and diffused along the extending direction of the convex portion and the concave portion to form a water film, so that the surface of the anti-fog member does not remain on the surface of the anti-fog member. Small drops of water. Therefore, the antifogging member of the present invention does not generate water mist caused by water droplets, and has excellent antifogging property.

20‧‧‧buffer layer

40‧‧‧Substrate

50‧‧‧Laminating

60‧‧‧ convex

62‧‧‧ concave structure layer

70‧‧‧ recess

80‧‧‧ concave pattern

100‧‧‧ anti-fog components

Fig. 1 is a schematic perspective view of an anti-fog member of an embodiment.

2(a) to 2(d) are schematic views showing an example of a planar shape of a convex portion of the anti-fog member of the embodiment.

3(a) to 3(f) are schematic cross-sectional views showing an example of a cross-sectional shape of an anti-fog member according to an embodiment.

Fig. 4 is a schematic plan view of an anti-fog member of an embodiment in which a plurality of concave-convex patterns are formed.

5(a) to 5(d) are schematic cross-sectional views showing an example of a cross-sectional structure of an anti-fog member according to an embodiment.

Fig. 6 is a conceptual view showing an example of a pressing step and a peeling step in the method for producing an anti-fogging member according to the embodiment.

Fig. 7 is a schematic view showing the shape of a water film produced by the anti-fog effect evaluation test of the examples.

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

[anti-fog member]

As shown in FIG. 1, the anti-fog member 100 of the embodiment has a base material 40 and a concave-convex pattern 80 formed of a plurality of convex portions 60 and concave portions 70 formed thereon.

As shown in Figs. 2(a) to 2(d), the shape of the convex portion 60 of the anti-fog member 100 of the embodiment (the shape viewed from the direction perpendicular to the base material 40 of the anti-fog member 100) is straight or curved. The elongated shape that extends. As shown in FIGS. 2(a) and 2(b), the convex portion 60 has a linear shape having a specific thickness or an elongated rectangular shape in plan view. The end portion in the longitudinal direction (extension direction) may have an angular shape as shown in Fig. 2(a), or may have a curvature as shown in Fig. 2(b). Alternatively, the convex portion 60 may have a curved shape in which the meandering (snake) extends as shown in Figs. 2(c) and (d). The thickness of the convex portion 60 may be uniform or uneven. Further, the convex portion 60 may be branched partially or entirely in the plan view (see FIG. 2(d)). The extension length of the convex portion 60 may be uniform as shown in Figs. 2(a) to (c), or may be uneven as shown in Fig. 2(d). Further, the extending direction of the convex portion 60 and the direction of the meandering (bending) may be uniform as shown in Fig. 2(c), or may be uneven (irregular) as shown in Fig. 2(d). The concave portion 70 is defined by the convex portion 60 and extends along the convex portion 60, and has an elongated shape extending straight or curved like the convex portion 60.

The cross section of the convex portion 60 cut along the plane perpendicular to the extending direction may be rectangular as shown in Fig. 3(a), or may be upward from the surface of the substrate 40 (the direction away from the surface of the substrate 40). ) The shape of the tip. That is, the cross section of the convex portion 60 can be, for example, as shown in FIGS. 3(b) and 3(c). It is generally triangular, and may be trapezoidal, or may be polygonal as shown in Fig. 3(d). Further, it may have an outer shape such as a semi-cylindrical shape, a semicircular shape, a semi-elliptical shape, or a parabola as shown in Fig. 3(e). Further, as shown in FIG. 3(f), fine irregularities may be formed on the surface of the convex portion 60. When the convex portion 60 has a shape in which the top portion is narrower than the bottom portion as shown in FIGS. 3(b) to 3(f), that is, a tapered shape, it is easy to manufacture by the nanoimprint method as described below, and The anti-fog effect becomes higher as described below. Further, as shown in Figs. 3(a) to (f), the upper portion (upper surface or top portion) of the convex portion 60 is disposed at a predetermined distance from each other. As long as the top or upper surface of the convex portion is disposed at a predetermined distance from each other, the bottom surfaces of the convex portions 60 may be in contact with each other as shown in FIG. 3(c).

Further, in the present application, as shown in FIG. 1, the length in the longitudinal direction of the convex portion is referred to as the convex portion length L. Further, a surface between the bottom surfaces of the adjacent convex portions is referred to as a concave portion. Further, the width of the upper portion of the convex portion in the cross section cut along the plane perpendicular to the extending direction of the convex portion is referred to as the convex portion width TW, and the width of the bottom portion of the convex portion is referred to as the convex portion bottom surface width BW, and two The distance between the upper portions of the convex portions is referred to as the distance TD between the convex portions, the distance between the bottom surfaces of the two convex portions is referred to as the concave portion width BD, and the height of the convex portion is referred to as the concave-convex depth D.

In the antifogging member of the present embodiment, the convex portion width TW and the concave portion width BD are preferably less than 10 μm, more preferably 5 μm or less. When the anti-fog member 100 of the present embodiment is exposed to an environment in which a water mist is easily generated in a high-humidity environment, as described below, water droplets which are condensed on the surface of the anti-fog member 100 are generated along the convex portion 60 and When the extending direction of the concave portion 70 is fused to form a water film, the generation of the water mist is prevented. However, when the convex portion width TW or the concave portion width BD is 10 μm or more, the water droplets formed in the convex portion 60 or the concave portion 70 do not bond and remain. When the convex portion width TW and the concave portion width BD are less than 10 μm, the water droplets formed in the convex portion 60 or the concave portion 70 are joined (fused) along the extending direction of the convex portion 60 and the concave portion 70 to form a water film. If the width of the convex portion TW and the concave portion When the width BD is 5 μm or less, water droplets are more easily bonded to form a water film. The convex portion width TW or the concave portion width BD can be set to 10 nm or more. The uneven depth D is preferably in the range of 10 nm to 25 μm. When the unevenness depth D is less than 10 nm, the water droplets are fused together in the extending direction of the convex portion 60 and the concave portion 70 to have a small effect of forming a water film. When the unevenness depth D is 25 μm or more, the ratio of the convex portion width TW to the concave portion width BD is large, and it is difficult to form and maintain such uneven shape. The uneven depth D is more preferably in the range of 200 nm to 5 μm. The uneven shape having such a concave-convex depth D can be produced by a nanoimprint method. From the viewpoint of promoting the wetting and diffusion of the water droplets, the length L of the convex portion is preferably three times or more the distance TD between the convex portions. Further, the convex portion width TW is preferably smaller than the convex portion bottom surface width BW. In this case, the convex portion 60 has a shape that is tapered upward from the surface of the base material 40, and the water droplets easily enter the concave portion 70 of the concave-convex pattern 80 to be fused, and thus the anti-fog having the concave-convex pattern 80 having such a convex portion 60 is formed. The anti-fog effect of the component is high. Moreover, such a concavo-convex pattern 80 is easily manufactured by a nanoimprint method.

Further, as shown in FIG. 4, a plurality of concave-convex patterns (aggregates of irregularities) 80 composed of a plurality of convex portions 60 and concave portions 70 may be formed on the base material 40. The interval DP in which the region in which the concave-convex pattern 80 is formed is preferably narrower than the distance TD between the convex portions. Thereby, a capillary force stronger in the concave-convex pattern 80 (between the adjacent convex portions 60) is generated between the adjacent concave-convex patterns 80, and moisture generated in the concave-convex pattern 80 is easily discharged to the outside of the region where the concave-convex pattern 80 is formed. Therefore, the antifogging property of the anti-fog member 100 is improved. Further, the interval DP of the region in which the uneven pattern 80 is formed is more preferably less than 10 μm. When the interval is 10 μm or more, water droplets do not adhere and remain in the region where the uneven pattern 80 is not formed, and the water droplets scatter light and are visible as water mist when visually observed. However, depending on the use of the anti-fog member of the embodiment, such as the use of the water mist in one of the members, the interval in which the uneven pattern 80 is formed is not particularly limited.

In the case where the anti-fog member 100 of the embodiment has the concave-convex pattern 80 composed of the linear or curved convex portion 60 and the concave portion 70 extending in the uniform direction, the convex portion 60 and the concave portion 70 along the concave-convex pattern 80 When the direction of extension is air-dried, the drainage is good, and the growth of microorganisms can be suppressed, so that the transparency of the anti-fog member can be maintained for a long period of time.

When the convex portion 60 and the concave portion 70 on the substrate 40 of the anti-fog member 100 are arranged in a uniform direction as shown in FIG. 4, the moisture of the surface of the anti-fogging member is easily extended along the convex portion 60 and the concave portion 70. Move in direction. Therefore, such an anti-fog member 100 can be easily dried by air drying in the extending direction of the convex portion 60 and the concave portion 70. Moreover, even if the anti-fog member 100 is used so that the extending direction of the convex portion 60 and the concave portion 70 becomes the direction of gravity, the water film on the surface of the anti-fogging member 100 is easily removed and removed, so that the anti-fogging member 100 can be easily dried. Thereby, the growth of microorganisms on the surface of the anti-fogging member 100 can be suppressed, and therefore the transparency of the anti-fog member can be maintained for a long period of time. As shown in FIG. 4, such an anti-fog member may be marked with a mark 20 indicating the direction in which the convex portion 60 and the concave portion 70 extend. The shape of the mark 20 is not limited to the shape of an arrow as shown in the drawing, and may be any shape as long as it is a shape that can distinguish directions. The installation position of the mark 20 may be set to an arbitrary position with respect to the uneven pattern 80. There is no particular limitation. When such a mark 20 is provided, the direction in which the convex portion and the concave portion extend (dry direction) can be recognized. Therefore, it is advantageous to prevent the drying direction and the installation direction of the anti-fogging member from being mistaken.

In the anti-fog member 100 of the embodiment, the surface of the convex portion 60 is made of a material having a smooth surface water contact angle of 90 degrees or less. In the present application, the term "water contact angle of a smooth surface" means an angle formed by the surface and the surface of the water droplet when a smooth surface having no unevenness is formed by a certain material and a water droplet is formed on the surface. The greater the water contact angle of the smooth surface, the more hydrophobic the surface. Furthermore, the contact angle of the water contact angle of the smooth surface can be used. The measurement is performed (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 a material to be measured is formed) is placed on a water platform of a contact angle meter. Then, a syringe with ion-exchanged water is placed above the water platform of the contact angle meter, and a water droplet having a diameter of 2 mm is formed at the front end of the syringe, so that the water platform rises to a smooth surface and contacts the water droplets to lower the water platform on the smooth surface. The water droplets were allowed to stand for 25 seconds. The angle between the straight line and the smooth surface of the left and right end points of the water droplets connected to the time point and the smooth surface of the water droplets was determined, and the angle was doubled to calculate the water contact angle.

As the material used for the surface of the projecting portion 60 of the configuration such as smooth surface water contact angle of 90 degrees or less of the material, in particular include: silicon dioxide (silica), SiN, SiON and other Si-based materials, TiO ₂ and other Ti-based Materials, ITO (Indium Tin Oxide)-based materials, inorganic materials such as 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 scratches on the surface of the anti-fogging member can be prevented and the transparency can be impaired. Further, a material such as TiO ₂ having a photocatalytic function may be contained in the inorganic material. Thereby, the hydrophilicity of the surface of the convex portion can be improved, or 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 cause a decrease in crystallinity due to an alkali metal ion such as Na ion, and the photocatalytic activity may be lowered. However, since the inorganic material does not contain an alkali metal, high photocatalytic activity can be maintained.

In addition to the above inorganic materials, a curable resin material can also be used. As such a material, for example, polyethylene, polypropylene, polyvinyl alcohol, polyvinylidene chloride, polyethylene terephthalate, polyvinyl chloride, polystyrene, AS resin, acrylic resin, polyamine can be used. Condensation Aldehyde, polybutylene terephthalate, glass-reinforced polyethylene terephthalate, polycarbonate, modified polyphenylene ether, polyphenylene sulfide, polyetheretherketone, fluororesin, polyarylate, poly Thermoplastic resins such as hydrazine, polyether oxime, polyamidoximine, polyether phthalimide, thermoplastic polyimide, or phenolic resin, melamine resin, urea resin, epoxy resin, unsaturated polyester resin, alcohol Thermosetting resin such as acid resin, polyoxyn epoxide resin, diallyl phthalate resin, ultraviolet curable urethane acrylate resin, ultraviolet curable polyester acrylate resin, ultraviolet curable epoxy acrylate resin An ultraviolet curable resin such as an ultraviolet curable polyol acrylate resin or an ultraviolet curable epoxy resin, or a material obtained by blending two or more of these. Further, a material obtained by combining the above inorganic materials in the above resin material may be used. Further, in order to obtain hard coat properties and the like, a known fine particle or a filler may be contained together with the inorganic material and the resin material.

As the substrate 40, various substrates can be used. For example, a substrate made of a transparent inorganic material such as glass or a polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, etc.) can be used. , acrylic resin (polymethyl methacrylate, etc.), polycarbonate, polyvinyl chloride, styrene resin (ABS resin, etc.), cellulose resin (such as triethylene phthalate), and polyimide A substrate having a light transmissive property such as a resin (such as a polyimine resin or a polyimide amide resin) or a resin such as a cycloolefin polymer. As the substrate 40, a non-translucent substrate can also be used. As the non-transparent substrate, a substrate made of metal, plastic, or the like can be used. The anti-fog 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. As the substrate 40, a substrate which has been subjected to a hydrophilic treatment on the surface by O ₃ treatment or the like can also be used.

In the anti-fog member of the embodiment, as shown in FIG. 5(a), a layer (concave-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, concave The convex structure layer 62 may be composed of a material having a smooth surface with a water contact angle of 90 degrees or less. In the anti-fog member of the embodiment, as shown in FIG. 5(b), the structure constituting the convex portion 60 may be formed on the base material 40, and the exposed surface of the substrate 40 may be divided between the convex portions 60. (recess 70). In this case, the structure constituting the convex portion 60 may be composed of a material having a smooth surface with a water contact angle of 90 degrees or less. Further, in the anti-fog member of the embodiment, as shown in FIG. 5(c), the surface of the base material 40 itself may constitute the convex portion 60 and the concave portion 70. In this case, the substrate 40 may be composed of a material having a smooth surface water contact angle of 90 degrees or less. Further, in the anti-fog member of the embodiment, as shown in FIG. 5(d), a concavo-convex pattern formed on the base material 40 may be formed of a material having a water contact angle of 90 degrees or less from a smooth surface. The film 50. In this case, the water contact angle of the material constituting the portion (inner) which is not exposed on the surface of the convex portion 60, the surface of the base material 40 and the concave portion 70 may be 90 degrees or less, or may exceed 90 degrees.

When a transparent substrate is exposed to a water mist-prone environment such as a high-humidity environment, water vapor condenses on the surface to generate water droplets, which scatter light and thus visually become a water mist. It is known that on the surface of super-hydrophilic, water droplets are wetted and diffused to form a water film, thereby preventing water mist. However, in the anti-fogging method, the material applicable to the surface is limited to a very small portion of the super-hydrophilic material, and if the surface is contaminated and the contact angle becomes large (hydrophilicity is lowered), the anti-fog effect cannot be obtained. Further, it is known that a surface having a fine uneven surface has a larger surface area than a smooth surface, and thus the wettability of the reinforcing material is enhanced (that is, the hydrophilic material becomes more hydrophilic in appearance, and the water-repellent material becomes More water). However, as shown in the evaluation results of the uneven pattern substrate of the comparative example described below, when the uneven shape is a hole, a column, a hammer, or the like, an antifogging effect cannot be obtained, and when the apparent hydrophilicity is improved, a sufficient antifogging effect cannot be obtained.

As described above, the anti-fog member 100 of the present embodiment has a straight or curved shape a concave-convex pattern formed by a plurality of convex portions and concave portions extending in an elongated shape, and the surface of the convex portion is made of a material having a water contact angle of 90° or less on the smooth surface, whereby even if water droplets are generated on the surface of the member, The water droplets are fused to form a water film, thereby preventing the generation of water mist. First, the water droplets generated in the concave portion 70 are quickly and uniformly wetted and diffused in the direction in which the concave portion 70 extends by the concavo-convex pattern as a guide by the capillary phenomenon to form a water film. The water droplets generated on the surface of the convex portion 60 are also wet-diffused and fused with the water film of the concave portion 70. In this manner, the water film is formed to fill the recess 70. Further, when the condensation of the water vapor is performed, 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 is fused to each other over the unevenness, thereby also being convex and convex. The extending direction of the portion 60 and the recess 70 is gradually diffused to form a larger area water film. The water film cannot be visually recognized as a water droplet, thus preventing the generation of water mist. The concavo-convex pattern as in the present embodiment can promote the wetting and diffusion of water droplets and water film by capillary action, and thus is most suitable for anti-fog. However, the concavo-convex pattern of a shape such as a hole, a column, or a hammer cannot obtain an effect as a guide for promoting diffusion of water droplets and a water film, and a water film cannot be formed. Therefore, the anti-fog member 100 of the present embodiment has an antifogging property superior to that of the conventional anti-fog member.

The anti-fog member of the embodiment can be used for various purposes, for example, for a mirror for a vehicle, a mirror for a bathroom, a mirror for a bathroom, a mirror for a dental mirror, or a mirror for a road mirror; for example, an eyeglass lens, an optical lens, a camera lens, an internal view Mirror lens, illumination lens, semiconductor lens, lens for photocopier lens; 稜鏡; window glass for buildings and other glass for building materials; window glass for vehicles such as automobiles, rail vehicles, airplanes, ships, etc.; Windproof glass; goggles such as protective goggles, sports goggles; protective masks, sports masks, helmets, etc.; glass for display cases such as frozen food; measuring glass for measuring machines; A film or the like attached to the surface of the articles.

[Manufacturing method of anti-fog member]

The anti-fog member 100 of the embodiment can be manufactured by a nanoimprint method as described below. In the following description, a method of manufacturing the anti-fog member 100 will be described as an example. The anti-fog member 100 is formed on the base material 40 as a layer constituting the convex portion 60 and the concave portion 70 as shown in FIG. 5(a). The uneven structure layer 62 is formed of a sol-gel material. The manufacturing method of the anti-fog member 100 mainly has the following steps: a solution preparation step of preparing a sol-gel material; a coating step of applying the prepared sol-gel material to the substrate; and a drying step, the system Drying the coating film of the sol-gel material coated on the substrate; pressing step, which is pressed against the mold on which the transfer pattern is formed; and pre-baking step, pre-baking the coating film pressed against the mold; a peeling step of peeling the mold from the coating film; and a hardening step of hardening the coating film. Further, the pressing step, the pre-baking step, and the peeling step are also collectively referred to as a transfer step. The steps are described in order below.

<Solution preparation step>

In order to form the textured layer by the sol-gel method, a solution of the sol-gel material is first prepared. The uneven structure layer is preferably formed of an inorganic material in terms of being hard and not easily scratched, and as the uneven structure layer material, a sol-gel material having a water contact angle of 90 degrees or less as described above can be used. For example, in the case where a convex portion composed of cerium oxide is formed on a substrate by a sol-gel method, a metal alkoxide (cerium oxide precursor) is prepared as a sol-gel material. As the precursor of cerium oxide, tetramethoxy decane (TMOS), tetraethoxy decane (TEOS), tetraisopropoxy decane, tetra-n-propoxy decane, tetraisobutoxy decane, a tetraalkoxy decane such as tetra-n-butoxy decane, tetra-butoxy decane or tetra-butoxy decane is a tetraalkoxide monomer; or methyltrimethoxynonane or ethyltrimethyl Oxydecane, propyl trimethyl Oxy decane, isopropyl trimethoxy decane, phenyl trimethoxy decane, methyl triethoxy decane (MTES), ethyl triethoxy decane, propyl triethoxy decane, isopropyl three Ethoxy decane, phenyl triethoxy decane, methyl tripropoxy decane, ethyl tripropoxy decane, propyl tripropoxy decane, isopropyl tripropoxy decane, phenyl tripropyl Oxy decane, methyl triisopropoxy decane, ethyl triisopropoxy decane, propyl triisopropoxy decane, isopropyl triisopropoxy decane, phenyl triisopropoxy decane, a trialkoxide monomer represented by a trialkoxysilane such as tolyltriethoxydecane; dimethyldimethoxydecane, dimethyldiethoxydecane, dimethyldipropoxydecane , dimethyl diisopropoxy decane, dimethyl di-n-butoxy decane, dimethyl diisobutoxy decane, dimethyl di-second butoxy decane, dimethyl di-butoxide Base decane, diethyl dimethoxy decane, diethyl diethoxy decane, diethyl dipropoxy decane, diethyl diisopropoxy decane, diethyl di-n-butoxy Decane, diethyl diisobutoxy decane, diethyl di-butoxy decane, diethyl di-t-butoxy decane, dipropyl dimethoxy decane, dipropyl diethoxy Decane, dipropyldipropoxydecane, dipropyldiisopropoxydecane, dipropyldi-n-butoxydecane, dipropyldiisobutoxydecane,dipropyldi-butoxy Decane, dipropyldi-tert-butoxydecane, diisopropyldimethoxydecane, diisopropyldiethoxydecane, diisopropyldipropoxydecane,diisopropyldiisopropyl Oxydecane, diisopropyldi-n-butoxydecane, diisopropyldiisobutoxydecane, diisopropyldi-2-butoxydecane, diisopropyldibutoxybutane, Diphenyldimethoxydecane, diphenyldiethoxydecane, diphenyldipropoxydecane, diphenyldiisopropoxydecane, diphenyldi-n-butoxydecane, diphenyl A dialkoxymonomer represented by dioxoxydecane such as diisobutoxydecane, diphenyldi-2-butoxydecane or diphenylditributoxydecane. Further, an alkyltrialkoxide or a dialkyldialkoxydecane having an alkyl group having a C4 to C18 carbon number may also be used. Vinyl trimethoxy can also be used a monomer having a vinyl group such as a decane or a vinyl triethoxy decane; 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-glycidoxypropylmethyl dimethyl Oxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyltriethoxydecane, etc. Monomer having an epoxy group; a monomer having a styryl group such as p-styryltrimethoxydecane; 3-methylpropenyloxypropylmethyldimethoxydecane, 3-methylpropenyloxyl Monomethyl methacrylate, such as propyltrimethoxydecane, 3-methacryloxypropylmethyldiethoxydecane, 3-methylpropenyloxypropyltriethoxydecane, etc. a monomer having an acrylonitrile group such as 3-propenyloxypropyltrimethoxydecane; N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane, N- 2-(Aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-triethoxyanthracene base-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxy a monomer having an amine group such as decane; a monomer having a urea group such as 3-ureidopropyltriethoxydecane; 3-mercaptopropylmethyldimethoxydecane, 3-mercaptopropyltrimethoxydecane a monomer having a mercapto group; a monomer having a sulfur group such as bis(triethoxymethylpropyl)tetrasulfide; a monomer having an isocyanate group such as 3-isocyanatepropyltriethoxydecane; A polymer obtained by polymerizing such monomers; a metal alkoxide such as a composite material characterized by introducing a functional group or a polymer into one of the above materials. Further, some or all of the alkyl group or the phenyl group of the compounds may be substituted by fluorine. Further, examples thereof include, but are not limited to, an acetyl phthalate metal salt, a carboxylic acid metal salt, a oxychloride, a chloride, or the like. Examples of the metal species include, but are not limited to, Si, such as Ti, Sn, Al, Zn, Zr, In, or the like, and the like. It is also possible to use a precursor that is appropriately mixed with the above-mentioned oxidized metal. Further, the mesoporous structure layer may be formed by adding a surfactant to the materials. Further, as a precursor of cerium oxide, it can be used in a molecule containing an affinity with cerium oxide, A hydrolyzable group and a decane coupling agent having a water-repellent organic functional group. For example, a decane monomer such as n-octyltriethoxydecane, methyltriethoxydecane or methyltrimethoxydecane; vinyltriethoxydecane, vinyltrimethoxydecane, vinyl Vinyl decane such as tris(2-methoxyethoxy)decane or vinylmethyldimethoxydecane; 3-methylpropenyloxypropyltriethoxydecane, 3-methylpropene oxime Methyl propylene decyl decane such as propyl trimethoxy decane; 2-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, 3-glycidoxypropyltrimethoxy decane, 3- Ethylene oxide, such as glycidoxypropyltriethoxydecane, 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, etc.; 3-octylthio-1-ene Thiodecane such as triethoxy decane; 3-aminopropyltriethoxydecane, 3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropyl Amino decane such as trimethoxy decane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-(N-phenyl)aminopropyltrimethoxydecane a polymer obtained by polymerizing the monomers.

In the case where a mixture of TEOS and MTES is used as a solution of the sol-gel material, the mixing ratio can be set to 1:1, for example, in a molar ratio. The sol-gel material forms amorphous cerium oxide by performing hydrolysis and polycondensation reaction. As a synthesis condition, in order to adjust the pH of the solution, an acid such as hydrochloric acid or a base such as ammonia is added. The pH is preferably 4 or less or 10 or more. Further, water may be added for the purpose of hydrolysis. The amount of water added may be set to 1.5 times or more in terms of a molar ratio with respect to the metal alkoxide species.

Examples of the solvent of the sol-gel material solution include alcohols such as methanol, ethanol, isopropanol (IPA), and butanol; and aliphatic hydrocarbons such as hexane, heptane, octane, decane, and cyclohexane. ; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene; diethyl ether, tetrahydrofuran, Ethers such as alkane; ketones such as acetone, methyl ethyl ketone, isophorone, cyclohexanone; butoxyethyl ether, hexyloxyethyl alcohol, methoxy-2-propanol, benzyloxyethanol Ether ethers; glycols such as ethylene glycol and propylene glycol; glycol ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate; ethyl acetate, ethyl lactate And esters such as γ-butyrolactone; phenols such as phenol and chlorophenol; and guanamine such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone a halogen-based solvent such as chloroform, dichloromethane, tetrachloroethane, monochlorobenzene or dichlorobenzene; a compound containing a hetero atom such as carbon disulfide; water; and a mixed solvent thereof. In particular, ethanol and isopropyl alcohol are preferred, and it is also preferred to mix water in the same.

As an additive of the sol-gel material solution, an alcohol alkanolamine such as polyethylene glycol, polyethylene oxide, hydroxypropyl cellulose, polyvinyl alcohol, or triethanolamine as a solution stabilizer may be used for viscosity adjustment. , beta ketone such as acetamidine, beta ketoester, formamide, dimethylformamide, two Alkane, etc. Further, as an additive to the sol-gel material solution, a material which generates an acid or a base by irradiation with light such as an energy ray represented by ultraviolet light such as excimer UV light can be used. By adding such a material, the sol-gel material solution can be hardened by irradiation of light.

<Coating step>

A solution of the sol-gel material prepared in the above manner is applied onto a substrate. In order to improve the adhesion, it is also possible to provide a surface treatment or an easy adhesion layer or the like on the substrate. As a coating method of the sol-gel material, 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, or an inkjet method can be used. The sol-gel material can be uniformly coated on a relatively large-area substrate, and can be quickly applied before gelation of the sol-gel material, preferably by bar coating method or die coating method. And spin coating method.

<drying step>

After the sol-gel material is applied, the substrate may be held in the atmosphere or under reduced pressure in order to evaporate the solvent in the coating film. If the holding time is short, the viscosity of the coating film becomes too low to enter When the uneven pattern is transferred to the coating film, if the holding time is too long, the polymerization reaction of the precursor proceeds, and the viscosity of the coating film becomes too high, and the transfer of the uneven pattern to the coating film cannot be performed. Further, after the sol-gel material is applied, as the evaporation of the solvent progresses, the polymerization reaction of the precursor proceeds, and the physical properties such as the viscosity of the sol-gel material also change in a short time. From the viewpoint of the stability of the formation of the concavo-convex pattern, it is preferable that the drying time range in which the pattern transfer can be performed well is sufficiently large, which can be carried out by drying temperature (holding temperature), drying pressure, sol-gel material type, sol. The mixing ratio of the types of the gel materials, the amount of the solvent used in the preparation of the sol-gel material (the concentration of the sol-gel material), and the like are adjusted. Further, in the drying step, since the substrate is directly held only, the solvent in the sol-gel material solution evaporates, so that it is not necessary to perform an active drying operation such as heating or blowing, or the substrate on which the coating film is formed can be directly The specific time is placed, or it is carried out during a specific time for the subsequent steps. That is, in the method of manufacturing the anti-fog member of the embodiment, it is not necessary to perform the drying step.

<Extrusion step>

Then, the uneven structure layer is formed by using the mold for transfer of the uneven pattern and transferring the uneven pattern of the mold to the coating film of the sol-gel material. As the mold, a film mold or a metal mold which can be produced by the method described below can be used, and it is preferable to use a film mold having flexibility or flexibility. At this time, the press roll can also be used to press the mold against the coating film of the sol-gel material. Compared with the pressing type, the roll process using the squeezing roller has the following advantages: since the contact time between the mold and the coating film is short, the difference in thermal expansion coefficient between the mold or the substrate and the platform on which the substrate is placed can be prevented. The pattern is deformed to prevent gas bubbles or residual gas traces from being generated in the pattern due to the boiling of the solvent in the sol-gel material solution, and the transfer pressure can be caused by the line contact with the substrate (coating film). The peeling force is small, and it is easy to cope with large area. No bubbles or the like are caught. Further, the substrate may be heated while pressing against the mold. As an example of pressing a mold against a coating film of a sol-gel material using a squeezing roller, as shown in FIG. 6, a film can be fed between the squeezing roller 122 and the substrate 40 directly conveyed thereunder. The uneven mold pattern of the film mold 140 is transferred to the coating film 64 on the substrate 40. In other words, when the film-shaped mold 140 is pressed against the coating film 64 by the pressing roller 122, the film-like mold 140 and the substrate 40 are simultaneously conveyed, and the coating film 64 on the substrate 40 is coated with the film-shaped mold 140. The surface. At this time, the pressing roller 122 is pressed against the back surface of the film-shaped mold 140 (the surface opposite to the surface on which the uneven pattern is formed), and the film-shaped mold 140 and the substrate 40 are adhered to each other while being in close contact with each other. . Further, when the long film-shaped mold 140 is fed toward the pressing roller 122, it is convenient to directly wind the film-shaped mold 140 from the film roll on which the long film-shaped mold 140 is wound and used.

<Pre-baking step>

After the mold is pressed against the coating film of the sol-gel material, the coating film may be pre-baked. The gelation of the coating film is promoted by pre-baking, and the pattern is cured to be less likely to be deformed at the time of peeling. In the case of pre-baking, it is preferred to heat at a temperature of 40 to 50 ° C in the atmosphere. Furthermore, pre-baking is not necessary. Further, when a material which generates an acid or an alkali by irradiating light such as ultraviolet rays to the sol-gel material solution is added, an energy line represented by ultraviolet rays such as excimer UV light may be irradiated instead of pre-coating the coating film. Roasting.

<Peeling step>

After the extrusion of the mold or the pre-baking of the coating film of the sol-gel material, the mold is peeled off from the coating film. As the peeling method of the mold, a known peeling method can be employed. Since the convex portion and the concave portion of the concave-convex pattern of the mold used in the manufacturing method of the embodiment are elongated and curved in a straight or curved manner, the mold release property is good. Moreover, the concave and convex pattern on the mold is such that the convex portion and the concave portion extend in the same direction. When the pattern is arranged, the peeling direction of the mold can be made parallel to the extending direction of the convex portion and the concave portion. Thereby, the mold release property of the mold can be further improved. It is also possible to peel off the mold while heating, thereby allowing the gas generated from the coating film to escape and preventing bubbles from being generated in the film. In the case of using a roll process, the peeling force can be made smaller than that of the plate-shaped mold used in the press type, and the mold can be easily peeled off from the coating film without leaving the film on the mold. In particular, since the coating film is heated while being heated, the reaction is easy, and the mold is easily peeled off from the coating film immediately after extrusion. Further, in order to improve the peelability of the mold, a peeling roll can also be used. As shown in Fig. 6, the peeling roller 123 is disposed on the downstream side of the pressing roller 122, and the film-shaped mold 140 is rotatably supported by the coating film 64 while being pressed by the peeling roller 123, whereby only the pressing roller 122 is used. The distance between the peeling rolls 123 (a certain period of time) can maintain the state in which the film mold 140 adheres to the coating film 64. Then, on the downstream side of the peeling roller 123, the traveling path of the film-shaped mold 140 is changed so that the film-shaped mold 140 is pulled over the peeling roll 123, whereby the film-shaped mold 140 is formed from the uneven film (bump) The structural layer) 62 is peeled off. Further, the coating film 64 may be pre-baked or heated while the film mold 140 is attached to the coating film 64. Further, when the peeling roller 123 is used, for example, peeling of the mold 140 can be more easily performed by peeling off while heating to 40 to 150 °C.

<hardening step>

After the mold is peeled off from the coating film (concave structure layer), the uneven structure layer may be cured. In the present embodiment, the uneven structure layer made of the sol-gel material can be cured by the main baking. The urethane or the like contained in the cerium oxide (amorphous cerium oxide) constituting the uneven structure layer is detached by the main firing, and the coating film is made stronger. The main calcination is preferably carried out at a temperature of 200 to 1200 ° C for about 5 minutes to 6 hours. In this case, when the uneven structure layer is made of ruthenium dioxide, it is amorphous or crystalline, or amorphous and crystalline, depending on the baking temperature and the baking time. Furthermore, the hardening step is not necessary. Further, when a material which generates an acid or a base by irradiating light such as ultraviolet rays to the sol-gel material solution is added, the uneven structure layer can be replaced by irradiation with an energy line represented by ultraviolet rays such as excimer UV light. The baking is performed to harden the uneven structure layer.

In the above manner, the anti-fog member 100 having the unevenness pattern 80 formed on the base material 40 and having the layer (concave-convex structure layer) 62 constituting the convex portion 60 and the concave portion 70 as shown in FIG. 5(a) can be manufactured.

Further, as a solution of the sol-gel material coated in the coating step, in addition to the cerium oxide precursor, TiO ₂ , ZnO, ZnS, ZrO ₂ , Al ₂ O ₃ , BaTiO ₃ , SrTiO may also be used. ₂ , a solution of precursors such as ITO.

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

Further, the polypyrazine may be used to form the uneven structure layer. In this case, the uneven structure layer formed by coating and transferring the polyazide may be ceramized (cerium oxide modified) in the curing step to form a layer composed of cerium oxide, SiN or SiON. Concave structure layer. In addition, "polyazide" means a polymer having a ruthenium-nitrogen bond, and is composed of Si-N, Si-H, NH, or the like, SiO ₂ , Si ₃ N _{4 ,} and an intermediate solid between the two. Solvent SiO _X N _Y and other ceramic precursor inorganic polymers. More preferably, it is a compound which is ceramized at a relatively low temperature and which is modified by cerium oxide or the like as represented by the following general formula (1), as described in JP-A-H08-112879.

General formula (1): -Si(R1)(R2)-N(R3)-

In the formula, R1, R2 and R3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkyl fluorenyl group, an alkylamino group or an alkoxy group.

In the compound represented by the above formula (1), it is particularly preferred that the R1, R2 and R3 are hydrogen atoms of a perhydropolyazane (also known as PHPS), or the hydrogen bonded to the Si moiety is partially alkyl. An organopolyazane substituted.

As another example of the polyazane which is ceramized at a low temperature, a decane oxide addition polyazide obtained by reacting a decane oxide with a polyazane can also be used (for example, Japanese Patent Laid-Open No. 5-238827 No. g), a dehydroglycerin-added polyazide obtained by reacting dehydroglycerol and polyazane (for example, JP-A-6-122852), and reacting an alcohol with polyazane to obtain A carboxylic acid metal salt addition polyazide obtained by reacting a carboxylic acid metal salt with polyazide (for example, JP-A-6-240208) US Pat. No. 6-299118, the addition of a ruthenium pyruvate complex obtained by reacting a metal-containing acetoacetate complex with polyazane to a polyazide (for example, JP-A-6- Japanese Patent No. 306329), a polyazoxide to which metal fine particles are added, which is obtained by adding metal fine particles to polyazane (for example, JP-A-7-196986).

As the solvent of the polyazirane solution, a hydrocarbon solvent such as an aliphatic hydrocarbon, an alicyclic hydrocarbon or an aromatic hydrocarbon, an ether such as a halogenated hydrocarbon solvent, an aliphatic ether or an alicyclic ether can be used. In order to promote the modification of the cerium oxide compound, an amine or metal catalyst may also be added.

Further, in the production method of the above embodiment, the opaque structure layer is formed using a sol-gel material, but a curable resin material may be used in addition to the above-mentioned inorganic material. When the uneven structure layer is formed using a curable resin, for example, after applying the curable resin to the substrate, the mold having the uneven pattern may be pressed against the applied curable resin layer to coat the coated resin layer. The film is hardened, and the uneven pattern of the mold is transferred to the curable resin layer. The curable resin can also be applied after being diluted with an organic solvent. As the organic solvent used in this case, those which dissolve the resin before hardening can be selected. For example, it can be selected from known solvents such as an alcohol solvent such as methanol, ethanol or isopropyl alcohol (IPA), or a ketone solvent such as acetone, methyl ethyl ketone or methyl isobutyl ketone (MIBK). As a method of applying the curable resin, for example, a spin coating method, a spray coating method, a dip coating method, a dropping method, a gravure printing method, a screen printing method, a letterpress printing method, a die coating method, or a shower can be employed. Various coating methods such as a curtain coating method, an inkjet method, and a sputtering method. As the mold having the uneven pattern, for example, a mold required for a film mold, a metal mold, or the like can be used. Further, the conditions for curing the curable resin vary depending on the type of the resin to be used. For example, the curing temperature is preferably in the range of room temperature to 250 ° C, and the curing time is in the range of 0.5 minute to 3 hours. Further, it may be a method of curing by irradiation with an energy ray such as an ultraviolet ray or an electron beam. In this case, the irradiation amount is preferably in the range of 20 mJ/cm ² to 5 J/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 effect of suppressing deterioration of the film by absorbing ultraviolet rays and converting the light energy into a form which is harmless to heat. As the ultraviolet absorber, those known from the prior art can be used, for example, a benzotriazole-based absorbent, three can be used. It is an absorbent, a salicylic acid derivative-based absorbent, a benzophenone-based absorbent, and the like. As described above, various materials can be used as the material constituting the uneven structure layer, particularly the surface constituting the convex portion, but each of them is a material having a water contact angle of 90 degrees or less as a smooth surface.

Further, as shown in FIG. 5(b), a structure constituting the convex portion 60 is formed on the base material 40, and an area (recessed portion 70) in which the surface of the base material 40 is exposed is partitioned between the convex portions 60. The mist member 100 can be manufactured, for example, in the following manner. In the above coating step, instead of the substrate The sol-gel material is coated thereon, and the sol-gel material is applied only to the concave or convex portion of the concave-convex pattern transfer mold. In the above extrusion step, the sol-gel material applied to the mold is adhered. Thereby, a convex portion made of a sol-gel material having a shape corresponding to the shape of the concave portion or the convex portion of the mold is formed on the base material. Between the convex portions formed in this manner, a region (concave portion) where the surface of the substrate is exposed is divided.

The anti-fogging member 100 which constitutes the convex portion 60 and the concave portion 70 on the surface of the substrate 40 as shown in Fig. 5(c) can be produced, for example, in the following manner. A resist layer having a concavo-convex pattern is formed on the substrate according to a known technique such as nanoimprinting or photolithography. After the concave portion of the resist layer is etched to expose the surface of the substrate, the remaining resist layer is used as a mask to etch the substrate. After the etching, the remaining mask (resist) is removed by the chemical solution. By the above operation, irregularities can be formed on the surface of the substrate itself.

A film may be formed on the concave-convex pattern surface of the member produced by the method described above. Thereby, an anti-fog member as shown in Fig. 5 (d) is obtained. As a material of the film formed on the surface of the uneven pattern, a material having a water contact angle of 90 degrees or less on a smooth surface is used. In the member manufactured by the method for producing such an anti-fogging member, the surface of the convex portion of the concave-convex pattern is covered with a coating film, so that any light-transmitting material can be used as the base material, and the uneven structure layer or the convex portion can be used. The material of the structure, the substrate, and the structure of the uneven structure layer or the structure constituting the convex portion may be a material having a water contact angle of 90 degrees or less on a smooth surface, or a material exceeding 90 degrees. The film composed of a material having a water contact angle of 90° or less on a smooth surface may be SiO _X , TiO ₂ , ZnO, ZrO ₂ , Al ₂ O ₃ , ZnS, BaTiO ₃ , SrTiO ₂ , ITO as exemplified above. Sol-gel material such as (indium tin oxide); fine particle dispersion such as SiO ₂ , TiO ₂ , ZnO, ZnS, ZrO, BaTiO ₃ , SrTiO ₂ ; polyazide; plastic resin, thermosetting resin, ultraviolet curable resin A curable resin material, a material obtained by compounding the above inorganic material in the resin material, and the like, wherein the fine particles, the filler, the ultraviolet absorbing material, and the like are contained therein.

<Concave pattern transfer printing mold>

The concave-convex pattern transfer mold used in the method for producing an anti-fog member of the above-described embodiment includes, for example, a metal mold or a film-shaped resin mold produced by the following method. The rubber constituting the resin mold also contains rubber such as natural rubber or synthetic rubber. The mold has a concave-convex pattern on the surface.

An example of a method of manufacturing a concave-convex pattern transfer mold will be described. First, the production of the master pattern for forming the concave-convex pattern of the mold is performed. For example, in the case of producing an anti-fog member having a concave-convex pattern composed of a curved convex portion and a concave portion extending in a non-uniform direction, it is preferably used in WO2012/096368, which is hereby incorporated by reference. A method of using a block copolymer by self-organization (microphase separation) by heating (hereinafter referred to as "BCP (Block Copolymer) thermal annealing method") or a block copolymer described in WO 2013/161454 The method of self-organization in a solvent environment (hereinafter referred to as "BCP solvent annealing method" as appropriate) or the method of forming a polymer surface by heating and cooling a vapor deposited film on a polymer film as disclosed in WO2011/007878A1 The method of forming the unevenness of the wrinkles (hereinafter referred to as "BKL (Buckling) method" as appropriate) forms a master mold. In the case of patterning by BCP thermal annealing or BCP solvent annealing, the material for patterning may be any material, preferably selected from styrenic polymers such as polystyrene, such as polymethacrylic acid. Block copolymerization of two combinations of methyl ester polyalkyl methacrylate, polyethylene oxide, polybutadiene, polyisoprene, polyvinyl pyridine, and polylactic acid Things. The pattern formed by the self-organization of the materials is preferably a horizontal cylindrical structure as described in WO 2013/161454 (a structure in which a cylinder is horizontally aligned with respect to a substrate), or as Macromolecules 2014, 47, 2 The vertical sheet structure described (the structure in which the sheet is vertically aligned with respect to the substrate). In the case of forming a deeper unevenness, it is more preferably a vertical sheet structure. Further, the concave-convex pattern obtained by the solvent annealing treatment may be etched by irradiation with an energy line represented by ultraviolet rays such as excimer UV light, or by RIE (Reactive Ion Etching) or ICP (Inductively Coupled Plasma). Etching by etching by dry etching. Further, the uneven pattern subjected to such etching may be subjected to heat treatment. Further, the concave-convex depth can be formed based on the concave-convex pattern formed by BCP thermal annealing or BCP solvent annealing by a method as described in Adv. Mater. 2012, 24, 5688-5694, Science 322, 429 (2008), or the like. Larger concave and convex pattern. That is, the block copolymer is coated on the underlayer composed of SiO ₂ , Si or the like, and the self-assembled structure of the block copolymer is formed by BCP thermal annealing or BCP solvent annealing. Then, one of the block copolymers is selectively etched and removed. The remaining layer is etched as a mask to form a desired depth groove (concave portion) in the substrate layer.

The concave-convex pattern may be formed by photolithography instead of the BCP thermal annealing method, the BKL method, and the BCP solvent annealing method as described above. Further, for example, the concave and convex pattern of the master mold can be produced by a micromachining method such as a cutting method, an electron beam direct drawing method, a particle beam processing method, an operation probe processing method, or a microfabrication method using self-organization of fine particles. . In the case of manufacturing an anti-fog member having a concave-convex pattern composed of a linear or curved convex portion and a concave portion extending in a uniform direction, the method may be used to form a linear shape extending in a uniform direction. Or a mother mold of a concave-convex pattern formed by a curved convex portion and a concave portion.

After the master mold of the concave-convex pattern is formed by a BCP thermal annealing method, a BKL method, or a BCP solvent annealing method, a mold in which a pattern is transferred can be formed by electroforming or the like as follows. First, it can be made into electroconductive for electroforming by electroless plating, sputtering, vapor deposition, etc. A seed layer of the layer is formed on the master mold having the pattern. In order to make the current density in the subsequent electroforming step uniform and to fix the thickness of the metal layer deposited by the subsequent electroforming step, the seed layer is preferably 10 nm or more. As the material of the seed layer, for example, nickel, copper, gold, silver, platinum, titanium, cobalt, tin, zinc, chromium, gold-cobalt alloy, gold-nickel alloy, boron-nickel alloy, solder, copper-nickel can be used. - a chromium alloy, a tin-nickel alloy, a nickel-palladium alloy, a nickel-cobalt-phosphorus alloy, or the like, and the like. Next, a metal layer is deposited on the seed layer by electroforming (electric field plating). The thickness of the metal layer may be, for example, a thickness of 10 to 30000 μm as a whole including the thickness of the seed layer. As the material of the metal layer deposited by electroforming, any of the above-mentioned metal species which can be used as the seed layer can be used. The metal layer to be formed preferably has a moderate hardness and thickness in terms of ease of handling such as pressing, peeling, and washing of the resin layer for forming the subsequent mold.

The metal layer containing the seed layer obtained in the above manner is peeled off from the master mold having the uneven structure to obtain a metal substrate. The peeling method may be physical peeling, or may be dissolved and removed by using a solvent such as toluene, tetrahydrofuran (THF), chloroform or the like to dissolve the patterned material. When the metal substrate is peeled off from the master mold, the remaining material components can be removed by washing. As the washing method, wet cleaning using a surfactant or the like or dry cleaning using ultraviolet rays or plasma can be employed. Further, for example, an adhesive or an adhesive may be used to adhere and remove the remaining material components. The metal substrate (metal mold) from which the pattern is transferred from the master mold thus obtained can be used as the mold for transfer of concave-convex pattern of the present embodiment.

Further, by using the obtained metal substrate, the uneven structure (pattern) of the metal substrate is transferred to the film-shaped support substrate, whereby a mold having flexibility like a film 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. Examples of the support substrate include glass and stone. a substrate composed of inorganic materials such as bismuth and bismuth; from polyoxyn epoxide, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), cycloolefin A substrate composed of an organic material such as a polymer (COP), a polymethyl methacrylate (PMMA), a polystyrene (PS), a polyimine (PI), or a polyarylate; a metal material such as nickel, copper or aluminum. . Further, the thickness of the support substrate can be in the range of 1 to 500 μm.

Examples of the curable resin include epoxy-based, acrylic-based, methacrylic-based, vinyl ether-based, oxetane-based, urethane-based, melamine-based, urea-based, and polyester-based polyester resins. Various resins such as monomers, oligomers, and polymers such as polyolefins, phenols, crosslinked liquid crystals, fluorine-based, polyfluorene-based, and polyamidiamines. The thickness of the curable resin is preferably in the range of 0.5 to 500 μm. When the thickness is less than the lower limit, the height of the unevenness formed on the surface of the cured resin layer tends to be insufficient. When the thickness exceeds the upper limit, the influence of the volume change of the resin generated during curing increases, and the uneven shape may not be formed satisfactorily. The possibility.

As a method of applying the curable resin, for example, a spin coating method, a spray coating method, a dip coating method, a dropping method, a gravure printing method, a screen printing method, a letterpress printing method, a die coating method, or a shower can be employed. Various coating methods such as a curtain coating method, an inkjet method, and a sputtering method. Further, the conditions for curing the curable resin vary depending on the type of the resin to be used. For example, the curing temperature is preferably in the range of room temperature to 250 ° C, and the curing time is in the range of 0.5 minute to 3 hours. Further, it may be a method of curing by irradiation with an energy ray such as an ultraviolet ray or an electron beam. In this case, the irradiation amount is preferably in the range of 20 mJ/cm ² to 5 J/cm ² .

Then, the hardened resin layer is self-hardened to remove the metal substrate. The method of removing the metal substrate is not limited to the mechanical peeling method, and a known method can be employed. The film-shaped resin mold having the hardened resin layer on which the unevenness is formed on the support substrate can be used as this embodiment A mold for transfer pattern of concave and convex patterns.

Further, a rubber-based resin material is applied onto the uneven structure (pattern) of the metal substrate obtained by the above method, and the applied resin material is cured and peeled off from the metal substrate, whereby the unevenness of the transferred metal substrate can be produced. Patterned rubber mold. The obtained rubber mold can be used as the mold for transfer pattern of the uneven pattern of the present embodiment. The rubber-based resin material is preferably a polyoxyethylene rubber, or a mixture or copolymer of a polyoxyxene rubber and other materials. As the polyoxyxene rubber, for example, polyorganosiloxane, crosslinked polyorganosiloxane, polyorganosiloxane/polycarbonate copolymer, polyorganosiloxane/polyphenylene copolymer, polyorganofluorene can be used. Oxylkane/polystyrene copolymer, polytrimethyldecylpropyne, polytetramethylpentene, and the like. Polyoxymethylene rubber is cheaper than other resin materials, has excellent heat resistance, high thermal conductivity, and elasticity, and is not easily deformed even under high temperature conditions. Therefore, it is preferable to carry out the uneven pattern transfer process under high temperature conditions. Further, since the polyoxymethylene rubber-based material has high gas or water vapor permeability, it is easy to penetrate the solvent or water vapor of the material to be transferred. Therefore, in the case where a rubber mold is used in order to transfer the uneven pattern to the sol-gel material, a polyoxymethylene rubber-based material is preferable. Further, the surface free energy of the rubber-based material is preferably 25 mN/m or less. Thereby, the mold release property at the time of transferring the uneven pattern of the rubber mold to the coating film on the substrate becomes good, and the transfer failure can be prevented. The rubber mold can be, for example, 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 less than the above lower limit, the strength of the rubber mold becomes small, and there is a possibility of breakage during the operation of the rubber mold. When the thickness is larger than the above upper limit, it is difficult to peel off from the main mold when the rubber mold is produced. Further, it is also possible to perform a mold release treatment on the concave-convex pattern surface of the rubber mold as needed.

Further, as the mold for transferring the uneven pattern, a mold containing a liquid crystal material and having an uneven surface of a relief structure formed by the alignment of the liquid crystal material (liquid crystal mold) may be used. With).

Since such a mold has a embossed structure formed on the surface based on the self-organization property of the liquid crystal material, there is no limitation in the area of the uneven surface such as lithography. Therefore, such a mold can be easily manufactured without providing a bonding wire even when the area of the uneven surface for transfer is large.

In order to form the relief structure efficiently and stably, the liquid crystal material preferably has a weight average molecular weight of 1,000 or more. From the same viewpoint, the liquid crystal material is preferably aligned in such a manner as to form a spiral structure. Further, it is more preferable to fix a chiral smectic C phase or a chiral smectic CA phase formed by alignment of a liquid crystal material.

The distance between the embossed structures constituting the uneven surface of the liquid crystal mold (the length of one period of the unevenness) can be changed to be approximately 3,000 nm or less in accordance with the spiral structure formed by the liquid crystal material or the like. Further, the depth of the concavities and convexities constituting the relief structure is 3 to 500 nm. The liquid crystal mold can be easily manufactured even in the case of having such a fine pattern.

After the concave portion of the concave-convex surface of the liquid crystal layer or the concave portion of the uneven surface of the resist layer on which the unevenness of the liquid crystal layer is transferred is etched to expose the surface of the substrate under the liquid crystal layer or the resist layer, The residual liquid crystal layer or the resist layer can be used as a mask to etch the substrate or the like to make the liquid crystal layer or the resist have a deeper unevenness. As the etching method, etching by irradiation with an energy ray represented by ultraviolet light such as excimer UV light, dry etching method such as RIE or ICP etching, or the like can be applied.

In the liquid crystal mold, the liquid crystal phase having the spiral structure as described above formed by the alignment of the liquid crystal material is preferably fixed in a state of substantially no fluidity. As a result of the alignment of the liquid crystal material being fixed, the relief structure of the surface of the mold is fixed. The stability of the helical structure, the ease of change of the helical pitch, the ease of synthesis of the liquid crystal material constituting the helical structure, and the From the viewpoint of ease of alignment caused by low viscosity in a liquid crystal state, it is preferred to immobilize a chiral smectic C phase or a chiral smectic CA phase.

The liquid crystal mold is a molded article formed of a liquid crystal material containing a composition of one or two or more liquid crystal materials. In the case of a molded article which is easy to obtain a long strip having a large area, the liquid crystal mold is preferably a film (liquid crystal film).

The liquid crystal mold can be manufactured by forming a film containing a liquid crystal material; forming a ridge structure on the surface of the film by aligning the liquid crystal material in a manner to form a spiral structure and fixing the alignment of the liquid crystal material. A film having an uneven surface is used as a mold.

A metal molded article having a concave-convex surface transferred from a relief structure of a liquid crystal mold can also be used as the concave-convex pattern transfer mold of the present embodiment. Such a metal molded article can be produced by forming a film containing a liquid crystal material; forming a ridge on the surface of the film by aligning the liquid crystal material in a manner of forming a spiral structure and fixing the alignment of the liquid crystal material The structure is such that a film having an uneven surface is obtained; a metal molded article is formed on the uneven surface of the film, and a metal molded article having an uneven surface formed by transfer from the relief structure is obtained as a mold.

According to these methods, even a mold having a large area of the uneven surface for transfer can be easily produced without providing a bonding wire.

[Examples]

Hereinafter, the anti-fog member of the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the examples. In the following Examples 1 to 13 and Comparative Examples 1 to 14, substrates (concavo-convex pattern substrates) having a concavo-convex pattern were produced, and the antifogging properties of the respective concavo-pattern substrates were evaluated.

Example 1

First, DTM-1-2 manufactured by KYODO INTERNATIONAL Co., Ltd. was prepared as a mother mold of a concave-convex pattern. In the master mold, convex portions (lines) extending linearly with a width of 1,000 nm, a length of 4,000 μm, and a height of 5,000 nm were formed at intervals of 1,000 nm. That is, in the master mold, a line and a gap pattern (L&S pattern) having a convex portion (line) width of 1,000 nm, a concave portion (gap) width of 1,000 nm, a concave-convex depth of 5,000 nm, and a line length of 4,000 μm were formed. In the L&S pattern, the cross section of the convex portion cut perpendicularly to the longitudinal 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, the L&S pattern was used as a concavo-convex pattern.

Then, a fluorine-based UV curable resin was applied to a PET substrate (manufactured by Toyobo Co., Ltd., COSMOSHINE A-4100), and the fluorine-based UV curable resin was cured by irradiating ultraviolet rays at 600 mJ/cm ^{2 while} pressing against the master mold. After the resin is hardened, the master mold is peeled off from the hardened resin. Thus, a film mold composed of a PET substrate having a resin film to which the surface shape of the master mold was transferred was obtained.

1 g of a stirred water, 19 g of IPA, and 0.1 mL of acetic acid were added dropwise with 1 g of a decane coupling agent (KBM-5103, manufactured by Shin-Etsu Chemical Co., Ltd.), followed by further stirring for 1 hr to prepare a decane coupling agent solution. An alkali-free glass substrate (manufactured by Nippon Electric Glass Co., Ltd.) of 30 mm × 30 mm × 0.7 (thickness) mm was prepared, and the substrate was sufficiently scrubbed with a cleaning agent (manufactured by Pure Chemical Co., Ltd., RBS-25) and a sponge. Thereafter, the moisture of the surface of the substrate was removed by spin drying, and the decane coupling agent solution was spin-coated thereon. The spin coating was carried out at 1000 rpm for 30 seconds. Thereafter, the substrate was baked in an oven at 130 ° C for 15 minutes to obtain a substrate which was easily treated. PAK-02 (a water contact angle: 70° when manufactured by Toyo Seiki Co., Ltd., manufactured by Toyo Seiki Co., Ltd.) as a UV curable resin was dropped on the easy-to-handle surface of the substrate which was subsequently treated. The surface of the film mold having the concave-convex pattern is superposed on the dropped UV-curable resin, and the hand pressure roller is rotationally moved from one end of the substrate toward the other end. The mold is pressed against the coating film on the substrate. After the extrusion of the mold was completed, the mold was peeled off from the one end toward the other end by a manual operation so that the peeling angle (the angle of the mold with respect to the substrate) became about 30°. Thereby, the uneven pattern substrate on which the uneven pattern of the mold was transferred was produced.

Example 2

DTM-1-2 manufactured by KYODO INTERNATIONAL Co., Ltd. was prepared as a master of the concave-convex pattern. In this master mold, an L&S pattern having a convex portion (line) width of 5,000 nm, a concave portion (gap) width of 5,000 nm, a concave-convex depth of 5,000 nm, and a line length of 4,000 μm was formed. A film mold was produced in the same manner as in Example 1 except that the L&S pattern was used as the uneven pattern, and a concave-convex pattern substrate was produced in the same manner as in Example 1 using the 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 mother mold of a concave-convex pattern. In this master mold, an L&S pattern having a convex portion (line) width of 10,000 nm, a concave portion (gap) width of 10,000 nm, a concave-convex depth of 5,000 nm, and a line length of 4,000 μm was formed. A film mold was produced in the same manner as in Example 1 except that the L&S pattern was used as the uneven pattern, and a concave-convex pattern substrate was produced in the same manner as in Example 1 using the 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 mother mold of a concave-convex pattern. In this master mold, an L&S pattern having a convex portion (line) width of 50,000 nm, a concave portion (gap) width of 50,000 nm, a concave-convex depth of 5,000 nm, and a line length of 4,000 μm was formed. A film mold was produced in the same manner as in Example 1 except that the L&S pattern was used as the uneven pattern, and bumps were produced in the same manner as in Example 1 using the film mold. Pattern substrate.

Example 3

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

Example 4

In a liquid mixed with 22 mol of ethanol, 5 mol of water, 0.004 mol of concentrated hydrochloric acid and 4 mol of acetamidineacetone, 1 mol of dimethyldiethoxydecane (DMDES) was added dropwise, and then a surfactant S-386 (SEIMI) was added. 0.5 wt% of the compound manufactured by CHEMICAL was stirred at 23 ° C and a humidity of 45% for 2 hours to obtain a solution of a sol-gel material. A solution of the sol gel material is spin coated on an alkali-free glass substrate. The spin coating system used ACT-300DII (manufactured by ACTIVE Co., Ltd.), and the spinning system 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 of the film mold produced in the same manner as in Example 3 in which the uneven pattern was formed was superposed on the coating film of the sol-gel material, and the 23° C. squeeze roll was rotated from one end of the substrate toward the other end. This presses the mold against the coating film on the substrate. Immediately after the extrusion, the substrate was moved to a hot plate and heated at 100 ° C (pre-baking). After heating for 30 seconds or 5 minutes, the substrate was removed from the hot plate, and the mold was peeled off from the one end toward the other end by a manual operation so that the peeling angle became about 30°. Thereby, the uneven pattern substrate on which the uneven pattern of the mold was transferred was produced. Further, the water contact angle of the smooth film of cerium oxide formed of DMDES was 84°.

Example 5

A concave-convex pattern substrate was produced in the same manner as in Example 4 except that tetraethoxysilane (TEOS) was used instead of DMDES. Further, the water contact angle of the smooth film of cerium oxide formed by TEOS was 10°.

Example 6

A concave-convex pattern substrate was produced in the same manner as in Example 3 except that UVHC8558 (water contact angle: 87° in a smooth film) was used instead of PAK-02.

Comparative example 3

In the same manner as in Example 3, except that a fluorine-based UV curable resin (water contact angle at a smoothing film: 95°) was used instead of PAK-02 as a UV curable resin, in the same manner as in Example 3 A concave-convex pattern substrate is produced.

Example 7

A custom pattern B (Si mold) manufactured by NTT-AT Co., Ltd. was prepared as a mother mold of the concave-convex pattern. In the master mold, an L&S pattern having a convex portion (line) upper width of 400 nm, a convex portion (line) lower portion width of 400 nm, a concave portion (gap) width of 400 nm, a concave-convex depth of 200 nm, and a line length of 10,000 μm was formed. A film mold was produced in the same manner as in Example 1 except that the master mold was used, and a concave-convex pattern substrate was produced in the same manner as in Example 1 using the film mold. In the master mold of the concave-convex pattern used in the present embodiment, the cross section of the convex portion cut perpendicularly to the longitudinal direction of the convex portion has a rectangular shape with a width of 400 nm and a height of 200 nm.

Example 8

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

Example 9

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

Comparative example 4

A concave-convex pattern substrate was produced in the same manner as in Comparative Example 3 except that the film molds produced in the same manner as in Example 7 were used in comparison with Examples 7 to 10.

Example 11

A custom pattern C manufactured by NTT-AT Co., Ltd. was prepared as a master mold of the concave-convex pattern. In the master mold, an L&S pattern having a convex portion (line) upper width of 100 nm, a convex portion (line) lower width of 200 nm, a concave portion (gap) width of 50 nm, a concave-convex depth of 400 nm, and a line length of 15,000 μm was formed. A film mold was produced in the same manner as in Example 1 except that the master mold was used, and a concave-convex pattern substrate was produced in the same manner as in Example 1 using the film mold. Further, in the master mold of the uneven pattern used in the present embodiment, the cross section of the convex portion cut perpendicularly to the longitudinal direction of the convex portion is an isosceles trapezoid having an upper bottom of 100 nm, a lower base of 200 nm, and a height of 400 nm.

Example 12

A concave-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 Example 11 was used.

Example 13

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

Comparative Example 5

A concave-convex pattern substrate was produced in the same manner as in Comparative Example 3 except that the film molds produced in the same manner as in Example 11 were used in comparison with Examples 11 to 13.

Comparative Example 6

For comparison with Example 2, DTM-1-2 manufactured by KYODO INTERNATIONAL Co., Ltd. was prepared as a master mold of the concave-convex pattern. In the master mold, 5,000 nm is arranged at intervals of 5,000 nm. A hole pattern of a cylindrical shape hole having a depth of 5,000 nm (that is, a hole pattern having a convex portion width (inter-hole distance) of 5,000 nm, a concave portion width (aperture) of 5,000 nm, and a concave-convex depth (pore depth) of 5,000 nm). A film mold was produced in the same manner as in Example 1 except that the hole pattern was used as the uneven pattern, and a concave-convex pattern substrate was produced in the same manner as in Example 1 using the film mold.

Comparative Example 7

For comparison with Example 3, FLH230/200-120 manufactured by SCIVAX Co., Ltd. was prepared as a master mold of the concave-convex pattern. In the master mold, 230 nm is arranged at intervals of 230 nm. A hole pattern of a cylindrical shape having a depth of 200 nm (that is, a hole pattern having a convex portion width (inter-hole distance) of 230 nm, a concave portion width (aperture) of 230 nm, and a concave-convex depth (pore depth) of 200 nm). A film mold was produced in the same manner as in Example 1 except that the master mold was used, and a concave-convex pattern substrate was produced in the same manner as in Example 1 using the film mold.

Comparative Example 8

For comparison with Comparative Examples 3 and 7, a film produced in the same manner as in Comparative Example 7 was used. A concave-convex pattern substrate was produced in the same manner as in Comparative Example 3 except for the mold.

Comparative Example 9

For comparison with Example 2, DTM-1-2 manufactured by KYODO INTERNATIONAL Co., Ltd. was prepared as a master mold of the concave-convex pattern. In the master mold, 5,000 nm is arranged at intervals of 5,000 nm. A column pattern of a cylindrical column having a height of 5,000 nm (that is, a column pattern having a convex portion width (column diameter) of 5,000 nm, a concave portion width (inter-column distance) of 5,000 nm, and a concave-convex depth (column height) of 5,000 nm). A film mold was produced in the same manner as in Example 1 except that the column pattern was used as the uneven pattern, and a concave-convex pattern substrate was produced in the same manner as in Example 1 using the film mold.

Comparative Example 10

For comparison with Example 3, FLP230/200-120 manufactured by SCIVAX Co., Ltd. was prepared as a master mold of the concave-convex pattern. In the master mold, 230 nm is arranged at intervals of 230 nm. A column pattern of a cylindrical column having a height of 200 nm (that is, a column pattern having a convex portion width (column diameter) of 230 nm, a concave portion width (inter-column distance) of 230 nm, and a concave-convex depth (column height) of 200 nm). A film mold was produced in the same manner as in Example 1 except that the master mold was used, and a concave-convex pattern substrate was produced in the same manner as in Example 1 using the film mold.

Comparative Example 11

A concave-convex pattern substrate was produced in the same manner as in Comparative Example 3 except that the film molds produced in the same manner as in Comparative Example 10 were used for comparison with Comparative Examples 3 and 10.

Comparative Example 12

For comparison with Example 3, an Anti-Reflective stamp manufactured by NIL Technology was prepared as a master of the concave-convex pattern. In the master mold, 250 nm is arranged at intervals of 50 nm. A moth-eye pattern of a cone having a height of 250 nm (that is, a moth-eye pattern of a base width (cone diameter) of a convex portion of 250 nm, a recess width (inter-cone distance) of 50 nm, and a concave-convex depth (cone height) of 250 nm). A film mold was produced in the same manner as in Example 1 except that the master mold was used, and a concave-convex pattern substrate was produced in the same manner as in Example 1 using the film mold.

Comparative Example 13

A concave-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 in comparison with Example 4 and Comparative Example 12.

Comparative Example 14

A concave-convex pattern substrate was produced in the same manner as in Comparative Example 3 except that the film molds produced in the same manner as in Comparative Example 12 were used for comparison with Comparative Examples 3, 12 and 13.

<Evaluation of anti-fog effect>

The antifogging effects of the uneven pattern substrates produced in Examples 1 to 13 and Comparative Examples 1 to 14 were evaluated as follows. The concave-convex pattern substrate was placed in a thermostatic chamber at a temperature of 25 ± 2 ° C and a humidity of 25% for 30 minutes. Then, the textured pattern substrate was allowed to stand on a plate of -10 ± 2 ° C for 1 minute. Thereafter, the state of occurrence of water mist on the surface of the uneven pattern substrate was visually confirmed, and those who did not see the water mist on the surface of the substrate were regarded as qualified, and those who saw the water mist were regarded as unacceptable. The evaluation results are shown in Table 1 as the eligibility as ○ and the failure as X.

<Measurement of water contact angle when smoothing film>

Further, the water contact angles of the smooth films of PAK-02, DMDES, TEOS, UVHC8558 and fluorine-based UV curable resins used in Examples 1 to 13 and Comparative Examples 1 to 14 were measured as follows.

Each of PAK-02, UVHC8558, and a fluorine-based UV-curing resin was spin-coated on a glass plate (manufactured by Nippon Electric Glass Co., Ltd., OA10G) cut into 5 × 5 × 0.07 cm. The coating was carried out by using ACT-300DII (manufactured by ACTIVE Co., Ltd.) as a spin coater and rotating at 1000 rpm for 30 seconds. Then, the coating film was cured by irradiating ultraviolet rays at 600 mJ/cm ² in a nitrogen atmosphere (oxygen concentration of 0.5% or less).

A solution of each of DMDES and TEOS was spin-coated on a glass plate (manufactured by Nippon Electric Glass Co., Ltd., OA10G) cut into 5 × 5 × 0.07 cm to form a coating film. Using ACT-300DII (manufactured by ACTIVE Co., Ltd.) as a spin coater, the film was first applied at 500 rpm for 8 seconds and then rotated at 1000 rpm for 3 seconds. Then, the coating film was dried at room temperature for 90 seconds, and prebaked 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.

A contact angle meter (Concord Interface Science) was used for a smooth film made of PAK-02, UVHC8558, a fluorine-based UV curable resin, cerium oxide formed of DMDES, and cerium oxide formed of TEOS. Manufactured by the company, CA-A) to determine the water contact angle. As a result, as shown in Table 1, the water contact angle of the PAK-02 film was 70°, the water contact angle of the UVHC8558 film was 87°, and the water contact angle of the fluorine-based UV curable resin film was 95°, by DMDES. The water contact angle of the formed cerium oxide film was 84°, and the water contact angle of the cerium oxide film formed by TEOS was 10°.

As shown in Table 1, according to the evaluation results of the antifogging effects of the concave-convex pattern substrates of Examples 1 and 2 and Comparative Examples 1 and 2, it was found that the width of the convex portion (line width) and the width of the concave portion (gap width) were less than 10 μm. The L&S pattern of the concave-convex pattern substrate has a sufficient anti-fog effect, The anti-fog effect of the concave-convex pattern substrate having the L&S pattern having a convex portion width (line width) and a concave portion width (gap width) of 10 μm or more is insufficient. The surface of the concave-convex pattern substrate having a convex portion width (line width) and a concave portion width (gap width) of less than 10 μm after the anti-fog effect evaluation test was observed with a microscope, and as a result, as shown conceptually in FIG. The water film of the shape in which the concave portion and the convex portion of the concave-convex pattern are wetted and diffused. In this case, it is considered that in the concave-convex pattern substrate in which the width of the convex portion (line width) and the width of the concave portion (gap width) are less than 10 μm, the water droplets generated on the surface of the substrate are along the longitudinal direction of the line and the gap (the convex portion and the concave portion) (the extending direction) ) Fusion. Therefore, it is considered that in the concave-convex pattern substrate in which the width of the convex portion (line width) and the width of the concave portion (gap width) are less than 10 μm, the water droplets are fused along the longitudinal direction of the line and become a water film (a large water droplet which does not scatter light) Therefore, no water mist will be produced. On the other hand, in the concave-convex pattern substrate in which the width of the convex portion (line width) or the width of the concave portion (gap width) is 10 μm or more, it is considered that the relatively small water droplets which scatter light are not fused to the surface of the convex portion or the surface of the concave portion. Therefore, water mist is generated.

As shown in Table 1, according to the evaluation results of the antifogging effects of the concave-convex pattern substrates of Examples 3 to 10 and Comparative Examples 3 and 4, it was found that the concave-convex pattern substrate using PAK-02, DMDES, TEOS, and UVHC8558 had sufficient antifogging. As a result, the anti-fog effect of the concave-convex pattern substrate using the fluorine-based UV curable resin is insufficient. The water contact angle of PAK-02, DMDES, TEOS, and UVHC8558 is 90 degrees or less, and the water contact angle of the fluorine-based UV curable resin exceeds 90 degrees. Therefore, in order to obtain a sufficient antifogging effect, it is necessary to have a concave-convex pattern. The water contact angle of the material is hydrophilic below 90 degrees. When the contact angle of the material forming the concave-convex pattern with water is 90° or less, it is considered that the water droplets are wetted and diffused along the longitudinal direction of the line as described above, and become a water film (large water droplets that do not scatter light). ), so there is no water mist. On the other hand, when the hydrophilicity of the material forming the concave-convex pattern is insufficient, it is considered that the water droplet does not flow along the length of the line and the gap. The wet diffusion does not sufficiently produce the fusion of the water droplets as described above, so that the smaller water droplets that scatter light are left on the surface of the substrate to generate a water mist.

As shown in Table 1, according to the evaluation results of the antifogging effects of the concave-convex pattern substrates of Examples 11 to 13 and Comparative Example 5, it is understood that the convex portions of the line and gap patterns have a width which narrows from the bottom of the substrate side toward the upper portion. In the case of the cross-sectional shape (that is, the case where the convex portion has a tapered shape), the anti-fog effect is also obtained in the same manner as the case where the cross section of the convex portion is rectangular.

As shown in Table 1, the comparison results of the antifogging effects of the concave-convex pattern substrates of Example 2 and Comparative Examples 6 and 9 and the antifogging effects of the concave-convex pattern substrates of Example 3 and Comparative Examples 7, 10 and 12 were The comparison between the evaluation results and the evaluation results of the antifogging effects of the concave-convex pattern substrates of Example 4 and Comparative Example 13 shows that when the concave-convex pattern is a hole pattern, a column pattern, or a moth-eye pattern, the concave-convex pattern is In the case of the L&S pattern, the anti-fog effect of the concave-convex pattern substrate is insufficient. It is considered that the unevenness of the L&S shape can function as a guide for water droplet fusion, and the unevenness of the shape of a hole, a column or a moth eye is insufficient as a guide for water droplet fusion, and therefore, has a hole pattern, a column pattern or a moth. In the concave-convex pattern substrate of the eye pattern, the smaller water droplets that scatter light are not fused to the surface of the substrate, and water mist is generated. Further, according to the evaluation results of Comparative Examples 3, 8, 11, and 14, when the material forming the uneven pattern is a fluorine-based UV curable resin, that is, when the water contact angle of the material forming the uneven pattern exceeds 90 degrees Similarly to the concave-convex pattern substrate having the L&S pattern, the anti-fog effect of the concave-convex pattern substrate having the hole pattern, the column pattern, or the moth-eye pattern is also insufficient.

Although the present invention has been described above by way of examples and comparative examples, the anti-fog member of the present invention is not limited to the above-described embodiment, and can be appropriately changed within the scope of the technical idea described in the claims.

[Industrial availability]

The anti-fog member of the present invention has excellent anti-fog property, and thus can be used, for example, for a mirror for a vehicle, a mirror for a bathroom, a mirror for a bathroom, a mirror for a dental mirror, or a mirror for a road mirror; for example, an eyeglass lens, an optical lens, a camera lens , endoscope lens, illumination lens, semiconductor lens, lens for lens for photocopier; 稜鏡; window glass for buildings and other glass for building materials; window glass for vehicles such as automobiles, rail vehicles, airplanes, ships, etc. Windshield for vehicles; goggles such as protective goggles, sports goggles; protective masks, sports masks, helmets, etc.; glass for display cases such as frozen food; cover glass for measuring machines ; for various applications such as film attached to the surface of such articles.

40‧‧‧Substrate

60‧‧‧ convex

70‧‧‧ recess

80‧‧‧ concave pattern

100‧‧‧ anti-fog components

BD‧‧‧ recess width

BW‧‧‧Bottom width

D‧‧‧bump depth

L‧‧‧protrusion length

TD‧‧‧distal distance

TW‧‧‧protrusion width

Claims (17)

An anti-fog member is formed on a substrate and has a concave-convex pattern composed of a plurality of convex portions and concave portions, wherein the surface of the convex portion is composed of a material having a smooth surface water contact angle of 90 degrees or less. The convex portion and the concave portion have an elongated shape extending straight or curved, and have a width of less than 10 μm. The anti-fog member according to claim 1, wherein the cross-sectional shape of the convex portion orthogonal to the extending direction is narrowed from the bottom to the top. The anti-fog member according to claim 1, wherein the convex portion and the concave portion have a uniform extending direction and an extended length. An anti-fog member according to claim 3, further comprising a mark indicating a direction in which the convex portion and the concave portion extend in the base material. The anti-fog member according to claim 1, wherein the convex portion and the concave portion have a non-uniform extending direction and an extending length. The anti-fog member according to the first aspect of the invention, wherein the concave-convex pattern has a concave-convex depth of 25 μm or less. The anti-fog member according to claim 1, wherein the convex portion has a length of the convex portion which is three times or more the distance between the convex portions. The anti-fog member according to claim 1, wherein the width of the convex portion and the concave portion is 400 nm or less. The anti-fog member according to claim 1, wherein the surface of the convex portion is made of an inorganic material. The invention relates to a method for producing an anti-fog member according to any one of claims 1 to 9, and has the following steps: a coating step of forming a coating film on a substrate; In the transfer step, the concave-convex pattern is transferred to the coating film by pressing a mold having a concave-convex pattern onto the coating film, thereby forming an uneven structure layer on the substrate. The method for producing an anti-fog member according to claim 10, wherein the coating film is formed by applying a material having a water contact angle of 90 degrees or less on the smooth surface. The method for producing an anti-fog member according to claim 10, wherein a material having a smooth contact surface having a water contact angle of 90 degrees or less is applied to the uneven structure layer. A method for producing an anti-fog member according to any one of claims 1 to 9 and having the following steps: a coating step of embossing a mold having a concave-convex pattern on its surface Forming a coating film on the pattern surface; and transferring the film to the substrate with the coating film formed thereon, and transferring the coating film to the substrate according to the uneven pattern. The method for producing an anti-fog member according to claim 13, wherein in the coating step, the coating film is formed on a concave portion of the concave-convex pattern surface of the mold. The method for producing an anti-fog member according to claim 13, wherein in the coating step, the coating film is formed on a convex portion of the concave-convex pattern surface of the mold. The method for producing an anti-fog member according to claim 13, wherein the coating film is formed by applying a material having a water contact angle of 90 degrees or less on the smooth surface. The method for manufacturing an anti-fog member according to claim 13, wherein the transfer to the base The coating film is coated with a smooth surface having a water contact angle of 90 degrees or less.