Technical field
[0001]
　The present invention relates to a single-layer film having a fine uneven structure on the cross-linked resin surface obtained by polymerizing a hydrophilic composition.
Background technique
[0002]
　Optical elements such as a display device and a camera lens used in a television or a mobile phone, the eyeglasses lenses typically antireflection technique in order to increase the amount of light transmitted by reducing the surface reflection is applied. Recently, the substrate to be formed by the anti-reflection technique, cloudy, there has been an increasing improvement demand for contamination.
[0003]
　As a method for solving the fogging problem, reactive surfactant, by antifogging coating containing an acrylic oligomer, a hydrophilic, a method of improving the water absorption has been proposed (e.g., see Non-Patent Document 1.). As a means for solving the contamination problem by improving the hydrophilicity of the material surface, float was a method of removing has been proposed by watering or rain stains such as outside air hydrophobic substance adhering to the outer wall or the like (e.g., see non-Patent documents 2 and 3.).
[0004]
　Further, the hydrophilic monomer by irradiating to control the amount of ultraviolet irradiation was applied a crosslinkable polymerizable monomer composition to a surface of a substrate to form a incompletely polymerized crosslinked polymer, then coating with ultraviolet again hydrophilic monomer hydrophilic material to block or graft polymerization has been proposed in the surface of the crosslinked polymer (see Patent documents 1 and 2).
[0005]
　The antireflection technology, for example, a method of providing an inorganic particle or an antireflection multilayer film formed by laminating a number of thin film formed from organic particles such as acrylic, such as silica on the surface of the substrate.
[0006]
　As another reflection preventing technique, the period of the irregularities and a method for the fine concavo-convex pattern which is controlled to less than the wavelength of visible light is formed on the substrate surface. (Non-Patent Documents 4 and 5, see Patent Documents 4-8). The method called moth eye is obtained by utilizing the principle of (Motheye, moth eye) structure, the refractive index of the incident medium to the refractive index of the substrate along a refractive index with respect to light incident on the substrate in the depth direction of the uneven thereby suppressing the reflection of the wavelength range to be antireflection by continuously changing. The concavo-cone form such as a cone or square pyramid is illustrated. (See Patent Documents 6-8).
[0007]
　However, in the method of providing an antireflection multilayer film above the surface of the substrate, it is impossible to obtain the effect of preventing fogging, and usually, to be deposited by vacuum evaporation or the like, long deposition time cost is a problem that high.
[0008]
　As the polarizing film, a wire grid polarizer metal layer of nano-sized regularly arranged is known. As the wire grid polarizing plate to form a fine concavo-convex pattern on the substrate surface, (see for example, Patent Documents 14 and 15.) Which methods are known to laminate a metal layer in the concave portion when these methods, the metal layer the adhesion purpose of improving the, recess or process to hydrophilic is being performed, the method of the process is complicated, it has a problem of high cost.
[0009]
　As a reflective wire grid polarizer, a wire grid polarizer arranged at regular intervals in parallel fine metal wires are known. Different wavelength range reflected by the array pitch, light oscillating in parallel to the thin metal wires is reflected and light vibrating perpendicular to the thin metal wire having a property of transmitting. Thickness and arrangement interval of the metal thin wire becomes the visible light range becomes nanometer size, in order to function in the visible region, the arrangement period is 1/4 of the minimum wavelength 380nm of visible light is required, the sequence of the thin metal wires cycle is 100nm or less. By nanoimprint method the visible light region reflective wire grid polarizer substrate surface is formed by a conductive metal on the convex surface to form an uneven arrangement structure evaporation method or a special printing method (e.g., Patent Documents see 16).
[0010]
　In the method of forming the fine asperity pattern on the substrate surface, glass and general acrylic material substrate used, sufficient anti-fogging effect for a fluorine coating has been applied material is used the not obtained suffers further adheres dirt fine uneven pattern, the problem will not get dirt from microscopic asperities.
[0011]
　Recently order to solve the above problem, referring to dirt (Patent Documents 9 and 10 in which the optical element has been proposed which can is removed by wiping with water such as fingerprints adhering to the surface by hydrophilic fine uneven pattern ). However, to stains such as fingerprints adhering to the surface removed by wiping with water In these methods, after forming a fine uneven pattern, further corona treatment of the surface, plasma treatment, SiO 2 surface treatment such as depositing, etc. It is a necessary film-forming process is a problem that has cost long high. When wiping the surface with a dry to further inorganic particles are attached to the outermost surface, hardly slip, after wiping have problems hydrophilicity is significantly reduced. Moreover, only a fine uneven pattern including a hydrophilic resin can not be the is insufficient stain hydrophilic obtain a high effect of removing by wiping with water.
[0012]
　Furthermore the proposed the antifogging techniques have hydrophilic resin on the outermost surface, the surface energy of the outermost surface is high because the hydrophilic metal is present, that it is difficult wiping without slipping when wiping the gauze in a state where a dry surface problems and, reduces the hydrophilic when wiped off anti-fogging properties, antifouling properties of durability is a problem that low.
[0013]
　The present inventors have there above, cloudy, as a means for solving the contamination problem, certain anionic hydrophilic groups are inclined from the inside of the membrane to the membrane surface (segregation), in the vicinity of the surface anionic hydrophilic group is at a high concentration single-layer film of the proposed previously (Patent Document 3). However, it is in this single-layer film obtained an antireflection effect is difficult, also does not have a surface structure composed of a polarizer. Moreover, high surface energy for hydrophilic group in the vicinity of the surface is present in high concentrations, there was also sliding property is not sufficient.
CITATION
Patent Literature
[0014]
Patent Document 1: JP 2001-098007 Patent Publication
Patent Document 2: JP 2011-229734 Patent Publication
Patent Document 3: WO 2007/064003 Patent Publication
Patent Document 4: JP-T 2001-517319 Patent Publication
Patent Document 5: JP open 2004-205990 JP
Patent Document 6: JP 2004-287238 Patent Publication
Patent Document 7: JP 2001-272505 JP
Patent Document 8: JP 2002-286906 JP
Patent Document 9: JP 2011-28229 JP
Patent Document 10: WO 2012/133946 Patent Publication
JP 11: JP 2009-217278 JP
Patent Document 12: WO 2012/014829 Patent Publication
JP 13: WO 2013/187311 Patent Publication
JP 14 : JP 2005-070456 Patent
Patent Document 15: JP 2008-107392 Patent
Patent Document 1 6: Japanese Unexamined Patent Publication No. 2014-139664
Non-Patent Document
[0015]
Non-Patent Document 1: Dong Aki Synthesis Report, TREND 1999, February, 39 to 44 tribute
Non-Patent Document 2: Polymer, 44 (5), 307 tribute
Non-Patent Document 3: material of the future, 2 (1), 36 ~ Gong 41
non-Patent Document 4: Bernhard, C. G., Endeavour , 26, 79 (1967)
non-Patent Document 5: P. B. CLAPHAM, M. C. HUTLEY, Nature, 244, 281-282 (1973)
Summary of the Invention
Problems that the Invention is to Solve
[0016]
　The present invention, antifogging properties, excellent antifouling further antifogging durability, antifouling durability, excellent sliding property, having an antireflection function, or may have a surface structure composed of a polarizer, hydrophilic single layer film, and to provide a method for conveniently producing a monolayer film and an object.
Means for Solving the Problems
[0017]
　The present invention have conducted studies to solve the above problems, polymerizable carbon with a specific hydrophilic group - a compound having a functional group having a carbon-carbon double bond, and two or more (meth) acryloyl groups polymerization containing the copolymer and the polymer having at least one group and the specific hydrophilic group selected from the polymerizable composition cured to obtain a crosslinked resin or an epoxy group and an alkoxysilyl group, which comprises a compound having a consists crosslinked resin obtained by curing the gender composition, irregular structure at specific intervals on the surface thereof is formed, a single-layer film in which the concentration of hydrophilic groups in a specific relationship, obtained from conventional hydrophilic material is higher sliding property than the single layer film, cloudy durable, it is obtained the optically functional single layer film such as an antireflection monolayer film having an antifouling function.
[0018]
　That is, a single-layer film of the present invention, a plurality of protrusions on the surface and a single layer film having an uneven structure comprising a plurality of recesses,
among the plurality of convex portions, the distance between the apexes of the convex portions adjacent to each other There is a range of 1 nm ~ 800 nm,
the single layer film, and one or more hydrophilic groups selected from anionic hydrophilic groups and cationic hydrophilic group, polymerizable carbon - one or more functional having a carbon-carbon double bond compounds having a group (I), and
polymerizable carbon - compound having two or more functional groups having a carbon-carbon double bond (II) (where the hydroxyl group may have but anionic hydrophilic groups, and cationic sex hydrophilic group having a sulfonic acid group and at least one group and an anionic hydrophilic group selected from crosslinked resins or epoxy group and alkoxysilyl group, the polymerizable composition comprising either no) (a) copolymer And it consists crosslinked resin obtained by curing a polymerizable composition containing the polymer,
one or more of the outermost surface concentration of the hydrophilic group selected from the anionic hydrophilic groups and cationic hydrophilic groups of the single layer film (Sa1 ) and single-layer film deep concentration of hydrophilic groups in the 1/2 point (Da1) and the hydrophilic group concentration gradient of (Sa1 / Da1) is less than 1.1.
[0019]
　The single layer film, the compound (I), the compound (II), and solubility parameter σ is 9.1 (cal / cm 3 ) 1/2 residual solvent from a polymerizable composition comprising the above solvent (A) it is preferably made of a crosslinked resin obtained by curing the amount of the after more than 10%.
[0020]
　Further, a single layer film of the present invention, a plurality of protrusions on the surface and a single layer film having an uneven structure comprising a plurality of recesses,
among the plurality of convex portions, the distance between the apexes of the convex portions adjacent to each other There is a range of 1 nm ~ 800 nm,
the single layer film, an anionic hydrophilic group, and one or more hydrophilic groups selected from cationic hydrophilic group, and a hydroxyl group, polymerizable carbon - one having a carbon-carbon double bond or of a compound having a functional group (I ') (provided that if the group hydrophilic group having a hydroxyl group, polymerizable carbon - functional group having a carbon double bond is one.),
polymerizable carbon - carbon compound having a functional group having two or more double bonds (II) (where the hydroxyl group may have but anionic hydrophilic groups and cationic hydrophilic groups, can neither), and
anionic hydrophilic group, cationic hydrophilic group or two or more water, Acid groups having at least hydrophilic portion and comprising an organic acid residue hydrophobic portion and a surface active agent having a (III) (where polymerizable carbon -. Having no carbon double bond) polymerizable composition comprising a (B) of made of a crosslinked resin,
of the single layer film of the anionic hydrophilic group and hydrophilic group in the single layer film 1/2 point and the outermost surface concentration (Sa2) of the at least one hydrophilic group selected from a cationic hydrophilic group and a hydroxyl group gradient hydrophilic group concentration of the deep levels (Da2) (Sa2 / Da2) is not less than 1.1.
[0021]
　The single layer film is preferably made of a crosslinked resin obtained by curing the polymerizable composition (B).
[0022]
　When applying the surface relief structure film made of a polymerizable composition of uncured the single layer film (A) or (B), the surface of the film is the compound (I ') or anionic hydrophilic group , and a hydrophilic group at least one selected from cationic hydrophilic group, an amino group, a mercapto group, and it is preferably treated with a compound having a group of one or more and selected from hydroxyl groups (IV).
[0023]
　The plurality of the distance between the other vertices of the convex portions nearest to the vertex and convex portion of any protrusion of the convex portion P n , the P (in the single-layer film) n an average value of P ave and the height direction of the coordinate axis of the concavo-convex structure and the h-axis, the lowest point of the height of the recesses is h = 0, the height of the apex of the arbitrary convex portion h = H n , the H n of the average H ave when a, H ave / P ave single layer film (1) is in the range of 0.1 to 5.0, for example, the single-layer film, a single layer film having an antireflection function It preferred when used as a.
[0024]
　Single layer film above the plurality of protrusions are cone-shaped (2), for example, preferred when used as a single layer film having an antireflection function the single layer film.
[0025]
　H axis in the height direction of the coordinate axis of the concavo-convex structure, and xy plane plane perpendicular to the h axis,
h '= 0 the lowest of the low point height of the recess, the height of the highest apex of the convex portion when the h '= H, the vertices of all of the convex portion is in contact with approximately one point and the xy plane of the height of h = H, the bottom point of all of the recesses to the xy plane of the height of h = 0 almost single-layer film which is in contact at one point (3), for example, the single layer film, preferably when used as a single layer film having an antireflection function.
[0026]
　The convex portion of the concavo-convex structure is a single-layer film (4) having a stepped side surface, for example, preferred when using the single layer film, a single-layer film (1) having an antireflection function.
[0027]
　The plurality of the distance between the other vertices of the convex portions nearest to the vertex and convex portion of any protrusion of the convex portion P n , the P (in the single-layer film) n an average value of P ave and the distance P from the apex of any protrusions ave in the range of a monolayer film there are bottom point of the concave portion of the 3 to 6 range (5), for example, the single-layer film, antireflective It preferred when used as a single layer film having a function.
[0028]
　h axis in the height direction of the coordinate axis of the concavo-convex structure, and xy plane plane perpendicular to the h axis, height h = 0 of the lowest low point of the concave portion, the height of the highest apex of the convex portion h = when the H, at any height of the xy plane in the range of less than H greater than zero height, single-layer films cross-section of the protrusions is circular (6) is, for example, the single layer film the preferred when used as a single layer film having an antireflection function.
[0029]
　The convex portion of the concavo-convex structure is arrayed in a grid pattern, the period of the concavo-convex structure is at 200nm or less, a percentage of the period of the protrusions is 0.25 or more 0.76 or less, the uneven structure in the height direction h axis coordinate axes, and xy plane plane perpendicular to the h-axis, the height of the lower low point of the concave portion h = 0, the height of the convex portion is taken as h = H, H 0.05 is ~ 0.5 [mu] m monolayer film (7), for example, preferred when used as a single layer film may have a surface structure that the single-layer film becomes polarizer.
[0030]
　Method for manufacturing a single layer film of the present invention, the polymerizable composition to form a coating film from (A),
removing the solvent from the coating film,
the mold the surface of the coating film having a pattern corresponding to the uneven structure in close contact with the step of transferring the uneven structure on the surface of the coating film,
a step of curing the coating film uneven structure is formed, and
a comprising a cured step of releasing the mold from the film obtained to.
Further, the method for producing a single layer film of the present invention,
the step of forming a coating film from the polymerizable composition (B),
a mold having a pattern corresponding to the uneven structure is brought into close contact with the surface of the coating film, an uneven structure step of transferring the coating film surface,
the step of curing the coating film uneven structure is formed, and
characterized in that it comprises curing a step of releasing the mold from the resulting film.
[0031]
　In the manufacturing method of the single-layer film, the compound (I ') or anionic hydrophilic group, a hydrophilic group at least one selected from cationic hydrophilic group, an amino group, a mercapto group, and a group of one or more selected from hydroxyl group DOO compounds with (IV) is, by the mold, which is applied to the surface having a pattern corresponding to the concavo-convex structure, a step of transferring the uneven structure on the surface of the coating film is preferably performed.
[0032]
　In the manufacturing method of the single-layer film, which is one embodiment it is preferable to form a monolayer film on the substrate. The single layer film can be used as a laminate formed from the single-layer film and the substrate.
[0033]
　The single layer film, typically single-layer film (1) to (6) can be used as an antireflection film.
[0034]
　The single layer film, typically single layer (7) can be used as a polarizing film by laminating a metal layer on the projections or recesses.
[0035]
　These single-layer film can be used as a transparent material with a monolayer film. Transparent material may be used for a display device. These Symbol monolayer film may be used as an optical article comprising a monolayer film.
Effect of the invention
[0036]
　According to the present invention, by controlling the uneven structure, anti-fogging, single-layer film and the antifogging having an antireflection function excellent in antifouling properties, single-layer film having a wire grid structure which is excellent in antifouling properties easily obtained. Furthermore, the resulting single-layer film, as compared with the single-layer film having an antireflection function consisting of conventional hydrophilic materials, anti-fogging durability, antifouling durability, excellent in sliding properties.
BRIEF DESCRIPTION OF THE DRAWINGS
[0037]
[1] Figure 1 is in the embodiment schematically illustrates a method of sample preparation for measuring the anion concentration gradient of (Sa / Da).
It is a [2] Photos viewed surface of the single-layer film obtained in Example 1 from directly above photo seen in (left) and inclined 30 degrees in the state (right).
A [3] Photos viewed cross section of the single-layer film obtained in Example 1 from an oblique direction (left side) and photographs viewed from the side (right side).
4 is a photograph viewed surface of the single-layer film obtained in Example 14 from directly above.
DESCRIPTION OF THE INVENTION
[0038]
　The present invention will be described in detail. In the present specification, the optical functional monolayer film has an optical function by a single layer film having an optical function (e.g. anti-reflection function), further modified the membrane (e.g., a stack of metal layers) It means obtained monolayer film. Similarly, means a film with an optical functional film may have an optical function by a film having an optical function, further modifications to the membrane (e.g., a stack of metal layers).
[0039]
　Hydrophilic single layer film of the present invention has a plurality of protrusions and irregular structure comprising a plurality of recesses in the surface, of the plurality of protrusions, 1 nm distance between apexes of the convex portions adjacent to each other in the range of ~ 800 nm,
the single layer film is made of crosslinked resin obtained by curing described later polymerizable composition (a) or the polymerizable composition (B), anionic hydrophilic groups of the single layer film and one or more of the outermost surface concentration of the hydrophilic group (Sa) and TansomakumakuAtsu hydrophilic group concentration gradient of the deep concentration of hydrophilic groups (Da) in 1/2 point selected from cationic hydrophilic group (Sa / Da) is characterized by is 1.1 or more.
[0040]
　By having this feature, consider that can surface even at high hydrophilic resin having a high surface energy, the surface is to reduce the contact area of ​​the surface compared decreases frictional resistance between the resin is a plan It is. Therefore it is possible to impart even slip properties a resin having a high surface energy. Further, the single layer film, a hydrophilic group derived from the compound on the surface (I) or (I ') is present in high concentrations, the deep of the film there crosslinked structure derived from the compound (II) is a high concentration because you are, can be the hardness of the entire monolayer is harder than the hydrophilic material comprising a resin obtained by using a compound having a conventional hydrophilic group. The relatively composition consists conventional hydrophilic resin uniform film surface is considered to exhibit high sliding property than the membrane forming a fine uneven pattern.
[0041]
　Furthermore, smooth single layer of conventional surface made of a resin is highly hydrophilic, the entirety can be a touch surface, missing hydrophilic groups on the outermost surface hydrophilic by friction or contact with the object is reduced had a problem, a single-layer film made of a highly hydrophilic resin there an uneven pattern on the surface, the recess portion of the surface, since it is difficult to touch the object, almost without hydrophilic group is missing It believed that to maintain the high hydrophilicity of the state.
[0042]
　The outermost surface concentration is high in the direction of the coordinate axis of the concavo-convex structure of the single layer film and the h-axis, the height of the apex of the arbitrary convex portion h = H n when a hydrophilic in its height Hn It means that the group concentration.
The outermost surface concentration of the hydrophilic group (Sa) and deep concentration (Da) is to cut a predetermined monolayer film samples obliquely, and the outside air into contact with not the surface of the single-layer film, the film thickness of the monolayer film 1 / in a 2 point, anionic hydrophilic groups (e.g., sulfonic acid group, a carboxyl group, a phosphoric acid group), cationic hydrophilic groups (e.g., quaternary ammonium groups), and the concentration of the group having a hydroxyl group, time of flight measured respectively as a fragment ion intensities using type secondary ion mass spectrometer to (TOF-SIMS), determined from the value (relative intensity).
[0043]
　The outermost surface concentration (Sa), the concentration ratio of the deep concentration of hydrophilic groups in TansomakumakuAtsu 1/2 point (Da), that Sa / Da is greater than 1.1, the single layer film the concentration of hydrophilic groups at the outermost surface, which means that higher than the concentration of hydrophilic groups at a depth of thickness 1/2 from the surface (Incidentally, hereinafter, the inclination of the hydrophilic groups that the Sa / Da it may be referred to). That is, the hydrophilic group, although the distribution from the substrate side of the membrane deep to the surface, in particular density difference as a monolayer film is distributed more in the outermost surface in contact with ambient air (gradient (hydrophilic group concentration ratio) and a (Sa / Da)). The distribution of such hydrophilic groups, performance based on high surface hydrophilicity in single layer film of the present invention (e.g., anti-fogging properties, antifouling properties, self-cleaning property, antistatic property, dust adhesion preventing property) It is granted. Slope degree of the hydrophilic group (Sa / Da) is preferably 1.2 or more, more preferably 1.3 or more, further preferably 1.5 or more.
[0044]
　As the plurality of convex portions of the single layer film, a triangular prism shape, a polygonal column shape such as a quadrangular prism shape, a cylindrical shape, columnar shape, such as oval columnar, conical shape, such as polygonal shape such as a quadrangular pyramid shape cone shape, a truncated cone shape, truncated cone shape such as a truncated pyramid shape such as a quadrangular pyramid shape, etc. hemispherical and the like. In the case the highest portion of the protrusion formed on the surface of the monolayer film plane of (e.g., rectangular plane in the case of a quadrangular prism shape or a truncated quadrangular pyramid shape, a circular plane in the case of a truncated cone shape), the as a vertex the center of gravity of the plane portion.
[0045]
　The single layer film has an uneven structure Naru as described above on the surface thereof, for example, when the period of irregularities wavelength (approximately 380 nm ~ about 780 nm) of visible light fine uneven pattern, which is controlled in the following are formed , antireflection monolayer film is applied. Further, the single-layer film has an uneven structure Naru as described above on the surface thereof, for example, to form a fine concavo-convex pattern period of the irregularities are roughly controlled to 200nm or less, the metal layer on the convex portion or concave portion by stacking, a polarization function is applied to the single layer film.
[0046]
　Also the single layer film by slope of a and hydrophilic groups of the uneven structure on the surface that meets the above, further antifogging durability, antifouling durability, the monolayer film excellent in slipperiness Become.
[0047]
　In uneven structure of the surface of the single-layer film, the distance between the apexes of the convex portions adjacent to each other, is in the range of 1 nm ~ 800 nm, in order to express an anti-reflection function of the monolayer film, preferably 1 nm ~ range of 600 nm, and more preferably in the range of 10 nm ~ 300 nm, more preferably in the range of 100 nm ~ 200 nm. Also, for use as a single-layer film may have a surface structure that a single layer film comprising a polarizer, the distance between the apexes of the convex portions adjacent to each other, preferably in the range of 100 ~ 200 nm.
[0048]
　When using a single layer film as a film having an antireflection function, the distance to the nearest other apex of the convex portion to the apex and the convex portion of any of the protrusions P of the plurality of convex portions n , (the of) the P in the film n an average value of P ave and,
in the height direction of the coordinate axis of the concavo-convex structure and the h-axis, the lowest point of the height of the recesses is h = 0, the vertex of the arbitrary convex portion the height h = H n , the H n an average value of the H ave when
a, H ave / P ave (hereinafter, also referred to as aspect ratio) preferably in the range of 0.1-5.0, more preferably in the range of 0.5-2.0, preferably in the range of 1.0 to 1.5. If the aspect ratio is too low, there is a tendency that the reflection characteristic and the transmission characteristics are deteriorated, the aspect ratio is too high, in the case of manufacturing the mold to be described later an uneven structure, release properties of the mold is lowered, a single layer there is a possibility that the desired concave-convex structure formed on the surface of the membrane is destroyed.
[0049]
　The single layer film, is used as a film having an antireflection function, the convex portion of the concavo-convex structure of the single-layer film has a regular pyramidal shape, preferably a conical shape.
[0050]
　The single layer film, is used as a film having an antireflection function, the h-axis in the height direction of the coordinate axis of the concavo-convex structure of the single-layer film, and xy plane plane perpendicular to the h axis, the lowest low recess the height h of the point '= 0, the height of the highest apex of the convex portion h' is taken as = H, the vertices of all of the projections in approximately one point and the xy plane of the height of h = H contact, the bottom point of all of the recesses is preferably in contact with substantially one point and the xy plane of the height of h = 0.
[0051]
　The single-layer film of the present invention, in embodiments using a film having an antireflection function, the recess is preferably disposed substantially symmetrically with the convex portion with respect to the xy plane of the h '= H / 2 .
[0052]
　In the embodiment used as a film having an antireflection function single layer film of the present invention, the convex portion in the rugged structure preferably has a stepped side surface.
[0053]
　The single-layer film of the present invention, in embodiments using a film having an antireflection function, the deepest portion of the concave portions of the concavo-convex structure is preferably a substantially point.
[0054]
　Distance The single layer film of the present invention, in embodiments using a film having an antireflection function, and other vertexes of the protrusions closest to the vertex and convex portion of any protrusion of the plurality of protrusions the P n , (above monolayer film) that P n an average value of P ave and,
　among the plurality of convex portions nearest the second convex portion to the apex and the convex portion of the first convex portion of the distance between the apex and P, the distance P from the apex of the first convex portion ave in the range of, there is preferably a bottom point of the concave portion of the 3 to 6 range.
[0055]
　In the embodiment using a single layer film of the present invention as a film may have a surface structure composed of a polarizer, it is preferable that the convex portion of the concavo-convex structure is arranged in a grid. The shape of the convex portion is preferably a shape in which the top portion such as a quadrangular prism shape or a truncated quadrangular pyramid shape is included in the plane of the rectangle.
[0056]
　In the embodiment used as a film of single-layer film may have a surface structure composed of a polarizer of the present invention, it is preferable that the period of the concavo-convex structure is 200nm or less, and more preferably 100nm or less.
[0057]
　In the embodiment used as a film of single-layer film may have a surface structure composed of a polarizer of the present invention, the xy plane plane perpendicular to the height direction of the coordinate axis of the concavo-convex structure h axis, relative to the h-axis, the recess h = 0 low low point heights, the height of the convex portion is taken as h = H, preferably H is 0.05 ~ 0.5 [mu] m, is 0.05 ~ 0.3 [mu] m it is more preferable.
[0058]
　Single layer film of hydrophilic obtained in the present invention preferably has the higher hydrophilicity, water contact angle is usually than 50 °, preferably not more than 30 °, more preferably 20 ° or less, more preferably 10 ° is less than or equal to.
[0059]
　Water contact angle above figures following single layer film has high hydrophilicity and excellent as a water and conformability (wetting) tends hydrophilic material. Therefore, for example, anti-fogging properties, antifouling properties, self-cleaning property, antistatic property, which is useful for dust antiadhesive applications requiring. For example, the following single-layer membrane water contact angle above figures, excellent antifogging effect since it is possible to form water droplets spread water film on the membrane surface, while the water even when the dirt with dirt and the coated surface is excellent in antifouling effect it is possible to remove by floating dirt enters the. Further hydrophilic monolayer film evaporation area by the water spread expanded, dry faster evaporation rate is improved.
[0060]
　Further, a single layer film of the present invention because it has is segregated (centralized) on the surface of the hydrophilic groups at a high concentration, excellent antistatic properties as compared with conventional hydrophilic coating that has not been segregated.
[0061]
　The water contact angle is 30 ° or less, preferably 20 ° or less, more preferably 10 ° or less. In such a case, hydrophilic single layer film of the present invention, antifogging properties, antifouling properties, excellent quick-drying, antistatic properties, is particularly preferably used. Incidentally, the water contact angle is usually 0 ° or more.
[0062]
　Further, a single layer film of the present invention, when applied from the viewpoint of enhancing the hydrophilicity, the uneven structure on the surface of the film made of the polymerizable composition of the uncured (A) or (B), the membrane it is preferable that the surface of being treated by a compound described below has both reactive to hydrophilic and polymerizable composition (I ') or compound (IV). Note that the uncured in the present invention, the polymerizable composition (A) or polymerizable carbon contained in (B) - means a state in which the carbon-carbon double bond is not almost completely reacted, preferably the polymerization polymerizable contained in the sexual composition carbon - carbon double bond of the reaction rate, preferably less 60 mol%, more preferably not more than 40 mol% state. Such specific method for processing will be described in detail part of the method for manufacturing a single layer film to be described later.
[0063]
　[Polymerizable Composition]
　The above single-layer film of the present invention, the polymerizable composition, for example, obtained from the polymerizable composition (A) or the polymerizable composition (B). By making such the polymerizable composition monolayer film using, antifogging property, excellent antifouling properties, anti-reflection function has an optical function such as polarization function, or has obtained, a conventional antireflection function consisting of a hydrophilic material, having optical functions such as polarizing function, or even compared to may have a single-layer film, antifogging durability, antifouling durability, the single-layer film excellent in slipperiness can get.
[0064]
　The polymerizable composition (A), one or more hydrophilic groups selected from anionic hydrophilic groups and cationic hydrophilic group, polymerizable carbon - compounds having one or more functional groups having a carbon-carbon double bond ( I), and polymerizable carbon - compound having two or more functional groups having a carbon-carbon double bond (II) (where the hydroxyl group may have, but any anionic hydrophilic groups and cationic hydrophilic groups, the characterized in that it comprises not) have,
polymerizable composition (B) is an anionic hydrophilic group, and one or more hydrophilic groups selected from cationic hydrophilic group, and a hydroxyl group, polymerizable carbon - carbon double one or more compounds having a functional group (I ') having a bond -, (in the case provided that the hydrophilic group is a group having a hydroxyl group, polymerizable carbon functional groups having a carbon-carbon double bond is one.)
polymerizable carbon - 2 functional groups having a carbon-carbon double bond One or more compound having (II) (where the hydroxyl group may have but anionic hydrophilic groups and cationic hydrophilic groups, can neither), and
anionic hydrophilic group, a cationic hydrophilic group or 2, One or more hydroxyl groups a surfactant having a hydrophobic portion consisting of hydrophilic portion and an organic residue having at least (III) (where polymerizable carbon - no carbon double bond.) characterized in that it comprises a .
[0065]
　The composition (A) to the compound contained (I) has one or more hydrophilic groups selected from anionic hydrophilic groups and cationic hydrophilic group, polymerizable carbon - one or more functional having a carbon-carbon double bond and having a proximal. Such hydrophilic group and a carbon - compound having a functional group having a carbon-carbon double bond by curing a composition that contains, hydrophilicity may be imparted to the cured product obtained.
[0066]
　Examples of the anionic hydrophilic group include a sulfonic acid group, a carboxyl group, a phosphoric acid group, O- sulfate groups (-O-SO 3 -), and N- sulfate group (-NH-SO 3 -) and the like It is. Among these anionic hydrophilic groups, a sulfonic acid group, a carboxyl group, and a phosphoric acid group are preferable, in that the hydrophilicity of the surface increases, sulfonic acid group is more preferable.
[0067]
　The anionic hydrophilic group may be contained in the compound in the form of a salt (I).
[0068]
　Thus, typically, a sulfonic acid group is of the formula (alpha), a carboxyl group is represented by the following formula (beta), phosphoric acid group, contained in the compound in the form of the following formula (.gamma.1) or (γ2) (I) it is sufficient that.
-SO 3 Z (alpha) -COOZ (beta) -OP = O (OZ) 2 (.gamma.1) (-O) 2 P = O (OZ) 1 (.gamma.2)
　in the above formula (α) ~ (γ2), Z , a hydrogen ion, an ammonium ion is at least one monovalent cation alkali metal ions, and selected ½ atom alkaline earth metal.
[0069]
　Note that the ammonium ions in the present invention, ammonia, a primary amine, secondary amine or tertiary cation hydrogen ion to the amine is Deki bound. As the ammonium ion, from the viewpoint of hydrophilicity, cations preferably ammonia and small amine number of carbon atoms of hydrogen ions bound ammonium ions ammonia into hydrogen ions are formed by bonding, and more preferably a methyl ammonium .
[0070]
　Examples of the alkali metals, e.g., lithium, sodium, potassium, rubidium and the like.
[0071]
　Examples of the alkaline earth metals, for example, beryllium, magnesium, calcium, strontium, and barium.
[0072]
　Alkali metal ions are preferable among the above-mentioned Z, sodium ions, potassium ions, and rubidium ions are more preferable.
[0073]
　As the cationic hydrophilic group, for example, quaternary ammonium groups, betaine groups, and the like amine oxide groups. Among these cationic hydrophilic groups, preferably quaternary ammonium groups and betaine groups.
[0074]
　　As the hydrophilic group which the compound (I) has an anionic hydrophilic group.
[0075]
　Polymerizable carbon - The functional group having a carbon-carbon double bond, but the functional group is not particularly limited as long as it is radically polymerizable or ionic polymerization, for example, an acryloyl group, a methacryloyl group, acryloyloxy group, methacryloyloxy group, acryloylthio group, methacryloyl group, a heteroarylthio group, an acrylamide group, a methacrylamide group, an allyl group, a vinyl group, isopropenyl group, maleyl group (-CO-CH = CH-CO-), itaconyl radical (-CO-CH = CH-CO -), and styryl groups. In the present specification, they are collectively acryloyl and methacryloyl (meth) acryloyl, acryloyloxy and methacryloyloxy and collectively (meth) acryloyloxy, acrylate are generically and Roy Lucio and methacryloyl thio (meth) acryloyl thio, it may be referred to collectively as acrylamide and methacrylamide and (meth) acrylamide.

The scope of the claims
[Claim 1]
　Surface is a single layer film having a plurality of protrusions and irregular structure comprising a plurality of recesses,
one of the plurality of protrusions in the range distance between the apexes of the convex portions of 1 nm ~ 800 nm adjacent to each other,
the monolayer film has one or more hydrophilic groups selected from anionic hydrophilic groups and cationic hydrophilic group, polymerizable carbon - compounds having one or more functional groups having a carbon-carbon double bond (I), and polymerizable carbon - compound having two or more functional groups having a carbon-carbon double bond (II) (where the hydroxyl group may have but anionic hydrophilic groups and cationic hydrophilic groups, can neither) consists crosslinked resin of the polymerizable composition (a) containing,
monolayer films anionic hydrophilic groups and cationic monolayer film and the outermost surface concentration (Sa1) of one or more hydrophilic groups selected from hydrophilic groups deep concentration of the hydrophilic group in the 1/2 point Da1) and hydrophilic group concentration gradient of (Sa1 / da1) is not less than 1.1 monolayer.
[Claim 2]
　Surface is a single layer film having a plurality of protrusions and irregular structure comprising a plurality of recesses,
one of the plurality of protrusions in the range distance between the apexes of the convex portions of 1 nm ~ 800 nm adjacent to each other,
the monolayer film is an anionic hydrophilic group, a cationic hydrophilic group, and one or more hydrophilic groups selected from hydroxyl group, polymerizable carbon - compounds having one or more functional groups having a carbon-carbon double bond (I ') (provided that when the group hydrophilic group having a hydroxyl group, polymerizable carbon - functional group having a carbon double bond is one).
polymerizable carbon - two functional groups having a carbon-carbon double bond compounds having more than (II) (where the hydroxyl group may have but anionic hydrophilic groups and cationic hydrophilic groups, can neither), and
anionic hydrophilic group, a cationic hydrophilic group or two, parent it is having at least a more hydroxyl groups Surfactant having a hydrophobic portion comprising water portion and an organic residue (III) (where polymerizable carbon -. Having no carbon double bond) a crosslinked resin of the polymerizable composition (B) containing ,
deep concentration of the anionic hydrophilic group and hydrophilic group in the single layer film 1/2 point and the outermost surface concentration (Sa2) of the at least one hydrophilic group selected from a cationic hydrophilic group and a hydroxyl group of the single layer film (Da2) single layer hydrophilic group concentration gradient (Sa2 / Da2) is 1.1 or more and.
[Claim 3]
　When giving an uneven structure on the surface of the film made of the uncured polymerizable composition (A) or (B), the compound of the surface of the film according to claim 2 (I ') or anionic hydrophilic group, and a hydrophilic group at least one selected from cationic hydrophilic group, an amino group, a mercapto group, and compounds having a group of one or more and selected from hydroxyl single according to claim 1 or 2 being processed by (IV) layer film.
[Claim 4]
　The plurality of convex portions, a single layer film according to any one of claims 1 to 3, in the range distance between the apexes of the convex portions of 100 nm ~ 600 nm adjacent to each other.
[Claim 5]
　The plurality of the distance between the other vertices of the convex portions nearest to the vertex and convex portion of any protrusion of the convex portion P n , the P (in the single-layer film) n an average value of P ave and,
in the height direction of the coordinate axis of the concavo-convex structure and the h-axis, the lowest point of the height of the recesses is h = 0, the height of the apex of the arbitrary convex portion h = H n , the H n of the average H ave when
a, H ave / P ave single layer film according to any one of claims 1 to 4 in the range of 0.1 to 5.0.
[Claim 6]
　Single-layer film according to any one of claims 1 to 5, the plurality of convex portions are cone-shaped.
[Claim 7]
　h axis in the height direction of the coordinate axis of the concavo-convex structure, and xy plane plane perpendicular to the h axis, h '= 0 the lowest of the low point height of the recess, the height of the highest apex of the convex portion when the h '= H, the vertices of all of the convex portion is in contact with approximately one point and the xy plane of the height of h = H, the bottom point of all of the recesses to the xy plane of the height of h = 0 almost single-layer film according to any one of claims 1 to 6 in contact at one point.
[8.]
　Single-layer film according to any one of claims 1 to 7, the convex portion of the concavo-convex structure having a stepped side surface.
[Claim 9]
　The plurality of the distance between the other vertices of the convex portions nearest to the vertex and convex portion of any protrusion of the convex portion P n , the P (in the single-layer film) n an average value of P ave and,
the distance P from the apex of any protrusions ave in the range of a single layer film according to any one of claims 1 to 8, there is a bottom point of the concave portion of the 3 to 6 range.
[Claim 10]
　h axis in the height direction of the coordinate axis of the concavo-convex structure, and xy plane plane perpendicular to the h axis, height h = 0 of the lowest low point of the concave portion, the height of the highest apex of the convex portion h = when the H, at any height of the xy plane in the range of less than H greater than zero height, single-layer film according to any one of claims 1 to 9, the cross section of the convex portion has a circular shape .
[Claim 11]
　The convex portion of the concavo-convex structure is arrayed in a grid pattern, the period of the concavo-convex structure is at 200nm or less, a percentage of the period of the protrusions is 0.25 or more 0.76 or less, the uneven structure in the height direction h axis coordinate axes, and xy plane plane perpendicular to the h-axis, the height of the lower low point of the concave portion h = 0, the height of the convex portion is taken as h = H, H 0.05 single-layer film according to any one of claims 1 to 3 which is ~ 0.5 [mu] m.
[Claim 12]
　Forming a coating film from a polymerizable composition according (A) in claim 1,
removing the solvent from the coating film,
a mold having a pattern corresponding to the uneven structure is brought into close contact with the coating surface, irregular structure transferring the coating film surface step,
a step of curing the coating film uneven structure is formed, and
a mold from the cured obtained film comprising the step of releasing
the single layer film according to claim 1 a method of manufacturing.
[Claim 13]
　Forming a coating film from a polymerizable composition according (B) in claim 2,
a mold having a pattern corresponding to the uneven structure is brought into close contact with the surface of the coating film, the step of transferring the uneven structure on the surface of the coating film,
a step of curing the coating film uneven structure is formed, and
includes a mold from the cured obtained film a step of releasing
a method for producing a single-layer film of claim 2.
[Claim 14]
　A compound according to claim 2 (I ') or an anionic hydrophilic group, compounds having a hydrophilic group at least one selected from cationic hydrophilic group, an amino group, a mercapto group, and a group of one or more selected from hydroxyl group (IV) is, by the mold, which is applied to the surface having a pattern corresponding to the concavo-convex structure, the method for producing a single layer film according to claim 12 or 13 performing the process of transferring an uneven structure on the surface of the coating film.
[Claim 15]
　Method for manufacturing a single layer film according to any one of claims 12-14 to form a monolayer film on the substrate.
[Claim 16]
　Antireflection film made of a single layer film according to any one of claims 1 to 10.
[Claim 17]
　Polarizer obtained by laminating a metal film on the convex portions or concave portions of the single-layer film of claim 11.
[Claim 18]
　Transparent material comprising at least one selected from the polarizer according to claim 1 monolayer film according to ~ 11, the anti-reflection film and the claim 17 of claim 16.
[Claim 19]
　Single-layer film of claim 1 to 11, the optical article comprising a at least one selected from the polarizer according to the antireflection film and the claim 17 of claim 16.
[Claim 20]
　Display device comprising a transparent material according to claim 18.
[Claim 21]
　Laminate formed from a single layer film and the substrate according to any one of claims 1 to 11, 16 and 17.