WO2012157717A1 - 特定の表面形状を有する構造体及び該構造体の製造方法 - Google Patents
特定の表面形状を有する構造体及び該構造体の製造方法 Download PDFInfo
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- WO2012157717A1 WO2012157717A1 PCT/JP2012/062694 JP2012062694W WO2012157717A1 WO 2012157717 A1 WO2012157717 A1 WO 2012157717A1 JP 2012062694 W JP2012062694 W JP 2012062694W WO 2012157717 A1 WO2012157717 A1 WO 2012157717A1
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- Prior art keywords
- meth
- acrylate
- polymerizable composition
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- compound
- Prior art date
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- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
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- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
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- C—CHEMISTRY; METALLURGY
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- G02B5/021—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures
- G02B5/0231—Diffusing elements; Afocal elements characterised by the diffusing properties the diffusion taking place at the element's surface, e.g. by means of surface roughening or microprismatic structures the surface having microprismatic or micropyramidal shape
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- G02B1/11—Anti-reflection coatings
- G02B1/118—Anti-reflection coatings having sub-optical wavelength surface structures designed to provide an enhanced transmittance, e.g. moth-eye structures
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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Definitions
- the present invention relates to a structure having a specific surface shape, and more particularly to a structure having a specific surface shape formed by polymerizing a polymerizable composition containing a specific compound. .
- the present invention relates to a structure used for preventing reflection of light and / or improving light transmission.
- the surface layer used for a display or the like is (a) what is generally referred to as a dry method, that is, a dielectric multilayer film formed by a vapor phase process and realizing low reflectivity by an optical interference effect, (b ) What has been generally referred to as a wet method, that is, a substrate film coated with a low refractive index material has been used. In addition, as a technique completely different from these, it is known that (c) a low reflectance can be expressed by imparting a fine structure to the surface (Patent Documents 1 to 14). In general, the surface layer requires not only light reflection prevention performance and light transmission improvement performance, but also a certain mechanical strength that is resistant to abrasion and scratches when used for practical purposes, and that it is difficult to get dirt. In addition, it was necessary to easily remove the dirt.
- Patent Documents 1 to 13 list materials for such an antireflection film, and some describe that a (meth) acrylate compound is used as a polymerizable compound. is there.
- the materials listed therein are usually used for forming a general structure, and the surface layer having the special surface microstructure described in (c) above is formed from the surface of the material. In particular, it was not obtained as a result of examination from the viewpoint of making the mechanical strength such as surface scratch resistance, antifouling property, antifouling property practical.
- Patent Document 14 pays attention to mechanical strength such as surface scratch resistance in the surface layer having the special surface microstructure of (c) described above and attempts to solve it from the viewpoint of material. However, in order to further improve the mechanical strength of the surface, the difficulty of being stained, and the like, there is room for further improvement from the physical properties of the surface and the material used.
- Patent Document 15 has a description of the antireflection film having the special surface microstructure of (c) above, but Patent Document 15 is a technique for improving the haze of the antireflection film, such as surface scratch resistance. It does not improve the mechanical strength or stain resistance, and is an invention characterized by a mold for obtaining a surface fine structure by transfer, and an invention characterized by the material of an antireflection film as a structure. There wasn't. Actually, the polymerizable composition described in the examples of Patent Document 15 contains less than 50% by mass of polyethylene glycol di (meth) acrylate with respect to the entire (meth) acrylate compound.
- Patent Document 16 describes a hydrophilic antireflection film having a contact angle of less than 90 °, but the purpose and effect of making the contact angle less than 90 ° is anti-fogging (anti-fogging), and surface scratch resistance. It does not improve the mechanical strength such as the property and the stain resistance, and therefore, the material is completely different.
- the examples of Patent Document 16 are general ones such as SiO 2 (sol-gel film), PMMA (polymethyl methacrylate), and polystyrene.
- the “antireflection film having a fine structure on the surface” of the above (c) has a very special fine structure on the surface so as to suitably prevent reflection. Therefore, it is used for improving the physical properties of the surface.
- the material is required to have special characteristics, and the surface of the obtained structure must have very special physical properties. However, in the first place, such required physical properties have hardly been studied.
- FPD flat panel displays
- LCD liquid crystal display
- PDP plasma display
- OLED organic light emitting diode
- OFED organic EL
- FED field emission display
- Cathode ray tubes (CRT), lenses, meter front covers, window plates, headlight covers, show windows, etc. are increasingly required to have antireflection of light and excellent light transmission.
- antireflection film having a fine structure on the surface of the above (c) it is necessary to further improve the surface properties for practical use.
- FPD flat panel displays
- LCD liquid crystal display
- PDP plasma display
- the inorganic or organic multilayer film shown in the above (a) or (b), the antireflection film by the surface fine structure of the above (c), etc. are known. It is known that the structure having the surface microstructure (c) has a particularly excellent antireflection function.
- the preferred shape (structure) of the surface has been studied considerably together with optical theories such as the theory of light reflection and transmission.
- the material forming the (structure) has not been studied so much, and therefore, in particular, the properties such as the mechanical properties of the surface, the difficulty of attaching dirt, the ease of wiping off the dirt, etc. are insufficient, and the practical application It was not reached.
- the object of the present invention is to find not only the surface shape but also the physical properties of the surface as conditions required for a structure having light reflection preventing performance, light transmission improving performance, etc., particularly surface scratch resistance, etc. It is to provide a structure imparted with properties such as mechanical strength, difficulty of being soiled, ease of wiping dirt, etc., and can form a structure having such a specific surface shape and physical properties. It is to provide a material that can be used.
- the present inventor polymerizes a structure having a specific surface shape with a polymerizable composition containing a specific component so that a specific storage elastic modulus is obtained. It was found that the above-mentioned problems can be solved by forming the film.
- the hydrophilicity of the surface of the structure is increased, and the storage elastic modulus of the structure is in a specific range.
- the structure is flexible when stress is applied, so that the surface microstructure is prevented from being broken or scratched, and the releasability from the mold is improved.
- properties such as mechanical strength such as surface scratch resistance, stain resistance, and easy wiping of the stain to the surface of the structure.
- the mold releasability from the mold is improved in a method for producing a structure in which the substrate is pressure-bonded from above, the polymerizable composition is cured, and then peeled off from the mold. Reached.
- the mechanical strength such as surface scratch resistance and the resistance to contamination are reduced.
- properties such as ease of wiping off dirt can be further synergistically imparted to the surface of the structure, and the releasability can be further improved.
- the present invention has, on the surface, a convex portion having an average height of 100 nm to 1000 nm or a concave portion having an average depth of 100 nm to 1000 nm, and the convex portion or the concave portion has an average period of 50 nm with respect to at least one direction.
- a structure present at 400 nm or less wherein the structure is obtained by polymerizing a polymerizable composition containing a (meth) acrylate compound by light irradiation, electron beam irradiation and / or heating,
- the (meth) acrylate compound contains 53% by mass or more of polyethylene glycol di (meth) acrylate with respect to the entire (meth) acrylate compound, and the structure has a storage elastic modulus at 25 ° C. of 2 GPa or less.
- this invention provides said structure whose said polyethyleneglycol di (meth) acrylate is shown by following formula (1).
- R represents a hydrogen atom or a methyl group
- n represents the number of repeating units, and represents an average value of 4 or more and 40 or less.
- the present invention provides the above structure in which the (meth) acrylate compound further contains urethane (meth) acrylate.
- the urethane (meth) acrylate contains a tetrafunctional or higher functional urethane (meth) acrylate, and the tetrafunctional or higher functional urethane (meth) acrylate is substantially composed of a polyvalent isocyanate compound.
- the present invention provides the above-described structure containing all isocyanate groups containing a compound obtained by reacting a hydroxyl group of a compound having one hydroxyl group and two or more (meth) acryl groups in the molecule.
- the present invention also provides the above structure, wherein the polymerizable composition further contains a fluorosurfactant having an alkylene oxide repeating structure and a fluoroalkyl group.
- the present invention also provides the above-described structure wherein the fluoroalkyl group has 2 to 18 carbon atoms.
- the present invention also provides the above-described structure wherein the fluoroalkyl group is a perfluoroalkyl group.
- the present invention also provides the above structure wherein the number of repeating alkylene oxide repeating structures is 4 or more and 20 or less.
- the present invention also provides the above structure, wherein the fluorosurfactant having the alkylene oxide repeating structure and the fluoroalkyl group is represented by the following formula (F).
- R 1 represents H or F
- R 2 represents H or CH 3
- R 3 represents H or CH 3
- X represents a divalent linking group
- p is 2 or more. It is an integer of 18 or less
- q is an integer of 4 or more and 20 or less.
- the present invention also provides the above structure having a surface with a water contact angle of 35 ° or less at 20 ° C.
- the present invention also provides the above-described structure for preventing light reflection and / or improving light transmission.
- the present invention is a method for producing the above structure, which has a concave portion having an average height of 100 nm to 1000 nm or a convex portion having an average depth of 100 nm to 1000 nm on the surface, wherein the concave portion or the convex portion is
- the polymerizable composition is supplied to a mold having an average period of 50 nm or more and 400 nm or less with respect to at least one direction, and a base material is pressure-bonded thereon, and the polymerizable composition is cured and then peeled off from the mold.
- the manufacturing method of the structure characterized by the above is provided.
- the present invention also provides a method for producing the above structure, wherein the polymerizable composition further contains a fluorine-based surfactant having an alkylene oxide repeating structure and a fluoroalkyl group. .
- the present invention is a polymerizable composition for forming the above structure, which contains a (meth) acrylate compound, and the (meth) acrylate compound is 53% by mass with respect to the entire (meth) acrylate compound.
- the present invention provides a polymerizable composition characterized by containing the above polyethylene glycol di (meth) acrylate.
- the present invention also provides the above-described polymerizable composition, wherein the polymerizable composition further contains a fluorine-based surfactant having an alkylene oxide repeating structure and a fluoroalkyl group.
- the present invention also comprises the above-described polymerizable composition for forming a structure, wherein the polymerizable composition contains a (meth) acrylate compound, and the (meth) acrylate compound is the (meth)
- the present invention provides an antireflective body-forming material characterized by containing 53% by mass or more of polyethylene glycol di (meth) acrylate with respect to the entire acrylate compound.
- the present invention also provides the antireflective body-forming material, wherein the polymerizable composition further contains a fluorine-based surfactant having an alkylene oxide repeating structure and a fluoroalkyl group. .
- optical performance such as light reflection prevention performance and light transmission improvement performance, but also excellent mechanical strength such as surface scratch resistance, resistance to dirt, and easy wiping of dirt (resistance to dirt)
- mechanical strength such as surface scratch resistance, resistance to dirt, and easy wiping of dirt (resistance to dirt)
- a structure excellent in properties such as (contamination) and releasability from the mold can be provided.
- the structure of the present invention has convex portions having an average height of 100 nm to 1000 nm or concave portions having an average depth of 100 nm to 1000 nm on the surface.
- the convex portion refers to a portion protruding from the reference surface
- the concave portion refers to a portion recessed from the reference surface.
- the structure of the present invention may have a convex portion or a concave portion on the surface thereof. Moreover, you may have both a convex part and a recessed part, Furthermore, you may have the structure where they connected and waved.
- the convex portion or the concave portion is provided in at least a part of the structure.
- the structure may be provided on both surfaces of the structure, but it is essential that it is provided on at least a part of at least one surface.
- the structure is in the form of a plate or a film, it is preferable that the structure has substantially the entire surface.
- the convex portion or the concave portion is preferably provided on the outermost surface in contact with the air of the structure.
- Air has a refractive index significantly different from that of the structure of the present invention, and the interface of substances having different refractive indexes has the specific structure of the present invention, so that the antireflection performance and the transmission improvement performance are exhibited well. This is because that.
- the structure of the present invention is present on the outermost surface that is easily subjected to mechanical external force, the effects of the present invention are exhibited, and surface scratch resistance, contamination resistance, and the like are improved.
- the convex portions or the concave portions are present uniformly over at least one surface of the structure in order to achieve the above effect.
- the average height from the reference surface is 100 nm or more and 1000 nm or less, and also in the case of a concave part, the average depth from the reference surface is 100 nm. It is essential that the thickness is 1000 nm or more.
- the height or depth may not be constant, and the average value may be within the above range, but it is preferable that the height or depth has a substantially constant height or a constant depth.
- the average height or average depth is preferably 120 nm or more, and particularly preferably 150 nm or more. Further, the upper limit is preferably 700 nm or less, more preferably 500 nm or less, and particularly preferably 350 nm or less. If the average height or the average depth is too small, good optical properties may not be exhibited, and if it is too large, production may be difficult.
- the surface of the structure has a waved structure connected, it is determined whether the entire surface has a convex portion or a concave portion. That is, it is determined whether the reference surface is the surface formed by the substantially highest portion or the surface formed by the substantially deepest portion.
- the range of the present invention is that the average length from the highest part to the deepest part is essential to be 100 nm or more and 1000 nm or less for the same reason as described above, preferably 120 nm to 700 nm, preferably 150 nm to 500 nm. Is more preferable, and 150 nm to 350 nm is particularly preferable.
- the convex portion or the concave portion is present on the surface with an average period of 50 nm or more and 400 nm or less in at least one direction.
- the convex part or the concave part may be arranged at random or may be arranged with regularity. In any case, it is preferable in terms of antireflection properties and transmission improvement properties that the convex portions or concave portions are substantially uniformly disposed on the surface of the structure. Further, it is only necessary that the average period be at least 50 nm to 400 nm in one direction, and the average period does not have to be 50 nm to 400 nm in all directions.
- the average period in at least one direction is 50 nm or more and 400 nm or less as described above.
- x-axis direction the period in the short direction
- the period in the short direction is 50 nm or more and 400 nm or less. That is, it is preferable that the period is in the above range when the direction having the shortest period is taken as one direction.
- the average period (“period” when there is regularity in the arrangement positions of the convex portions or the concave portions) is preferably 70 nm or more, more preferably 100 nm or more, particularly preferably 120 nm or more, and further preferably 150 nm or more. Moreover, 300 nm or less is preferable, 250 nm or less is more preferable, and 200 nm or less is particularly preferable. If the average period is too short or too long, the antireflection effect may not be sufficiently obtained.
- the structure of the present invention has the above-mentioned structure on the surface, and further has a structure generally called a “moth eye structure” to have a good antireflection performance. Is preferable. Moreover, it is preferable from the point of the same favorable antireflection performance to have the surface structure described in any one of Patent Documents 1 to 15.
- the aspect ratio which is a value obtained by dividing the height or depth by the average period is not particularly limited, but is preferably 1 or more in terms of optical properties, more preferably 1.5 or more, and particularly preferably 2 or more. Moreover, 5 or less is preferable on a structure manufacturing process, and 3 or less is especially preferable.
- a structure having a large aspect ratio for example, 1.5 or more
- the aspect ratio is preferably as large as possible, particularly preferably 1.5 or more, and further preferably 2 or more.
- the structure of the present invention is provided with the above structure on the surface, thereby reducing the light reflectance and improving the light transmittance.
- the “light” in this case is light including at least light having a wavelength in the visible light region.
- the structure of the present invention must be obtained by polymerizing a polymerizable composition containing a (meth) acrylate compound by light irradiation, electron beam irradiation and / or heating. is there. That is, in the structure of the present invention, the carbon-carbon double bond of the (meth) acryl group of the (meth) acrylate compound in the polymerizable composition reacts with light irradiation, electron beam irradiation and / or heating. it can.
- “(meth) acryl” means “acryl” or “methacryl”.
- light irradiation, electron beam irradiation and / or heating may be performed by any one of the group consisting of light irradiation, electron beam irradiation and heating, and two processes selected therefrom. A combination may be used, or a combination of all three treatments. Especially, it is preferable to make it harden
- the structure of the present invention is formed by the reaction of the carbon-carbon double bond of the (meth) acryl group in the polymerizable composition as the material.
- the reaction rate is not particularly limited, but it is preferably 70% or more, more preferably 85% or more, and particularly preferably 90% or more with respect to the total carbon-carbon double bond.
- reaction rate refers to the (meth) acrylic polymerizable composition before and after the reaction by infrared spectroscopy (IR), specifically, Fourier transform infrared spectrophotometer Spectrum One D (manufactured by Perkin Elmer) It is determined from the ratio of the absorbance at 1720 cm ⁇ 1 attributed to the carbon-oxygen bond of the ester bond and the absorbance at 810 cm ⁇ 1 attributed to the carbon-carbon bond measured by the reflection method (ATR method). If the reaction rate is too low, the mechanical strength and chemical resistance may be lowered.
- IR infrared spectroscopy
- ATR method reflection method
- the structure of the present invention having the specific surface structure as described above is formed from the following material (polymerizable composition), the optical performance such as the antireflection performance of light and the performance of improving light transmission, etc. Excellent, in particular, mechanical strength such as surface scratch resistance; properties such as difficulty of soiling and ease of wiping off dirt by wiping with water (contamination resistance); and the like. That is, the structure of the present invention is obtained by polymerizing a polymerizable composition containing a (meth) acrylate compound, and the (meth) acrylate compound is 53 masses relative to the entire (meth) acrylate compound.
- the structure has a storage elastic modulus at 25 ° C. of 2 GPa or less and / or a storage elastic modulus at 180 ° C. of less than 0.5 GPa.
- the structure of the present invention is formed by polymerization of a “polymerizable composition containing a (meth) acrylate compound”.
- the “polymerizable composition” must contain a (meth) acrylate compound, but further preferably contains a fluorosurfactant in order to exert the above-described effects. In order to exhibit the said effect, it is especially preferable to contain the fluorine-type surfactant which has an alkyl group.
- the “polymerizable composition” includes a polymerization initiator such as a photopolymerization initiator and a thermal polymerization initiator; a binder polymer; a fine particle; an antioxidant; an ultraviolet absorber; a light stabilizer; an antifoaming agent; A lubricant, a leveling agent, and the like.
- the components of the polymerizable composition include those that are only taken into the interior by polymerization of the (meth) acrylate compound and do not directly participate in the polymerization.
- (Meth) acrylate compound The polymerizable composition in the present invention contains a (meth) acrylate compound as an essential component.
- Polyethylene glycol di (meth) acrylate contains a (meth) acrylate compound as an essential component, and the (meth) acrylate compound is 53% of the total of the (meth) acrylate compound. It is essential to contain at least mass% of polyethylene glycol di (meth) acrylate. By including 53% by mass or more of polyethylene glycol di (meth) acrylate with respect to the entire (meth) acrylate compound, the surface of the structure is less likely to be scratched, and it is difficult to get dirt or to wipe off dirt. It becomes easy.
- the degree of polymerization is sufficiently increased, 25 ° C. and / or 180 ° It becomes easy to make the storage elastic modulus in ° C into a suitable range.
- the optical performance of the resulting structure such as light reflection prevention performance and light transmission improvement performance; mechanical strength such as surface scratch resistance; difficulty in soiling and wiping off dirt by wiping with water Easiness (hereinafter sometimes abbreviated as “contamination resistance”);
- Polyethylene glycol di (meth) acrylate is essential to be contained in an amount of 53% by mass or more based on the entire (meth) acrylate compound, more preferably 55% by mass or more, and more preferably 60% by mass or more. Particularly preferred is a content of 65% by mass or more.
- the upper limit is not particularly limited, but is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less. When two or more polyethylene glycol di (meth) acrylates are used, the above range is the total amount thereof.
- the said mass% is the mass% in single with both the polyethyleneglycol di (meth) acrylate in polymeric composition, and the other (meth) acrylate compound (coexisting (meth) acrylate compound). It is.
- these compounds are often obtained and used as solutions, but even in that case, the compound is in mass% on a single substance basis, and the solvent is excluded from the calculation of mass%. The same applies to the following.
- the hydrophilicity is not imparted satisfactorily to the surface having the specific microstructure described above.
- the storage elastic modulus at 25 ° C. and / or 180 ° C. of the obtained structure may not be within a suitable range.
- mechanical strength such as surface scratch resistance; difficulty in attaching dirt, ease of wiping off dirt by wiping with water (contamination resistance), and the like may not be sufficiently achieved.
- the content ratio of polyethylene glycol di (meth) acrylate is too large, it is effective in improving hydrophilic performance and stain resistance, but may reduce mechanical strength such as surface scratch resistance. .
- the said mass% is the mass% in a single body with respect to the polyethyleneglycol di (meth) acrylate in a polymeric composition, and (meth) acrylate compounds other than polyethyleneglycol di (meth) acrylate.
- these compounds are often obtained and used as solutions, but even in that case, the compound is in mass% on a single substance basis, and the solvent is excluded from the calculation of mass%.
- the compound itself is solid, it is mass% in terms of solid content.
- the length of the ethylene glycol chain of the polyethylene glycol di (meth) acrylate is not particularly limited. On the average, 4 units to 40 units (“n” in the formula (1)) with “—CH 2 CH 2 O—” as one unit. 4 to 40), preferably 6 units to 32 units (average value of n in formula (1) 6 to 32), more preferably 8 units to 25 units (average value of n in formula (1) 8 to 25) is particularly preferable, and 12 to 20 units (average value of n in formula (1) 12 to 20) is more preferable. If the ethylene glycol chain is too short or too long, hydrophilicity may not be imparted to the surface of the structure to a good extent.
- the storage elastic modulus at 25 ° C. may become too large or hydrophilicity may not be imparted (contact angle becomes too large), while when it is too long, The curability may deteriorate, the storage elastic modulus at 25 ° C. may become too small, the low temperature stability may deteriorate, and crystallization may occur.
- mechanical strength such as surface scratch resistance; properties such as difficulty of attaching dirt and ease of wiping off dirt by wiping with water (contamination resistance); It may not be fully achieved and may not be very good.
- Polyethylene glycol di (meth) acrylates having different numbers of units may be used alone or in combination of two or more. When using 2 or more types, it is essential that the total amount is 53 mass% or more.
- any of the (meth) acrylate compound and the polyethylene glycol di (meth) acrylate contained in the (meth) acrylate compound may be an acrylate or a methacrylate.
- the acrylate is good in polymerizability and adjusts the mechanical strength of the cured film. It is preferable from the point of being easy.
- the inclusion of polypropylene glycol di (meth) acrylate is not excluded, but polyethylene glycol di (meth) acrylate is much more preferable than polypropylene glycol di (meth) acrylate.
- the above-mentioned performance is excellent.
- the present invention is characterized by containing polyethylene glycol di (meth) acrylate in an amount of 53% by mass or more based on the entire (meth) acrylate compound.
- the structure has a storage elastic modulus at 25 ° C. of 2 GPa or less and / or a storage elastic modulus at 180 ° C. of less than 0.5 GPa.
- the composition, blending ratio, etc. of the polymerizable composition are further set, including the type and amount of the polyethylene glycol di (meth) acrylate to be used, so that the storage elastic modulus becomes like this.
- the storage elastic modulus of the structure By setting the storage elastic modulus of the structure within the above range, the surface of the structure is less likely to be scratched, less likely to get dirty, easier to wipe off dirt, and improved releasability when removed from the mold. To achieve a remarkable effect. Because the structure is flexible, it prevents the surface microstructure from being broken when it is stressed, which can be used as a trigger, resulting in mechanical strength such as surface flaw resistance and contamination. Difficulty, easy wiping of dirt (for example, the property of removing dirt by wiping with water) and the like can be imparted to the surface of the structure. The storage elastic modulus will be described in detail later.
- the above-mentioned polymerizable composition further contains a fluorine-containing surfactant described later, particularly “fluorine-containing surfactant having an alkylene oxide repeating structure and a fluoroalkyl group”, thereby allowing polyethylene glycol di ( Due to the synergistic effect of the (meth) acrylate and the fluorosurfactant, the surface of the structure is particularly difficult to be scratched, and it is particularly difficult to get dirt, especially to easily wipe off dirt. Come to play.
- a fluorine-containing surfactant described later particularly “fluorine-containing surfactant having an alkylene oxide repeating structure and a fluoroalkyl group”, thereby allowing polyethylene glycol di ( Due to the synergistic effect of the (meth) acrylate and the fluorosurfactant, the surface of the structure is particularly difficult to be scratched, and it is particularly difficult to get dirt, especially to easily wipe off dirt. Come to play.
- polyethylene glycol di (meth) acrylate examples include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and polyethylene glycol # 200 di (meth).
- Acrylate polyethylene glycol # 400 di (meth) acrylate, polyethylene glycol # 600 di (meth) acrylate, polyethylene glycol # 1000 di (meth) acrylate, polyethylene glycol # 1200 di (meth) acrylate, polyethylene glycol # 1540 di (meth)
- examples thereof include ethylene glycol di (meth) acrylate such as acrylate and polyethylene glycol # 2000 di (meth) acrylate.
- “# 200”, “# 400”, “# 600”, “# 1000”, “# 1200”, and “# 1540” are not limited to polyethylene glycol di ( A specific example is (meth) acrylate.
- “# 200” or the like correlates with the number of repeating units of the polyethylene glycol chain, “—CH 2 CH 2 O—” is one unit, “# 200” is 4 units, and “# 400” is 8 units, “# 600” means 12 units, “# 1000” means 20 units, “# 1540” means 32 units, and “# 2000” means 40 units.
- Urethane (meth) acrylate The (meth) acrylate compound in the present invention preferably further contains urethane (meth) acrylate.
- “Urethane (meth) acrylate” refers to a (meth) acrylate compound having a urethane bond in the molecule.
- the urethane (meth) acrylate used in the present invention is not particularly limited.
- the position and number of urethane bonds and the position and number of (meth) acryl groups are not particularly limited.
- the (meth) acrylate compound contains urethane (meth) acrylate
- the curability and the reaction rate are increased, and the storage elastic modulus at 25 ° C. and / or 180 ° C. of the obtained structure is within a preferable range.
- the obtained structure is excellent in flexibility, and mechanical strength such as surface scratch resistance and contamination resistance can be sufficiently achieved.
- urethane (meth) acrylate a trifunctional or higher functional urethane (meth) acrylate or a bifunctional or lower functional urethane (meth) acrylate is preferably used.
- One or more urethane (meth) acrylates may be used in combination.
- the chemical structure of the urethane (meth) acrylate is not particularly limited, and the weight average molecular weight is preferably 1000 or more and 30000 or less, more preferably 1500 or more and 15000 or less, and 2000 or more and 5000 or less. Is particularly preferred. If the molecular weight is too small, flexibility may be reduced.
- urethane (meth) acrylate As the urethane (meth) acrylate, it is preferable to contain a urethane (meth) acrylate having 3 or more functional groups (particularly preferably 4 or more functional groups). That is, it is preferable to contain a compound having 3 or more (particularly preferably 4 or more) (meth) acryl groups in the molecule. In this case, the position and number of urethane bonds, whether or not the (meth) acryl group is at the molecular end, and the like are not particularly limited. A compound having 6 or more (meth) acryl groups in the molecule is particularly preferable, and a compound having 9 or more is more preferable. The upper limit of the number of (meth) acrylic groups in the molecule is not particularly limited, but 15 or less is particularly preferable.
- the crosslink density and curability of the resulting structure will be low, and the storage modulus at 25 ° C and / or 180 ° C will be too low. In some cases, the structure may be too soft, and the surface scratch resistance may be inferior, so that sufficient mechanical strength cannot be obtained.
- the number of (meth) acrylic groups in the urethane (meth) acrylate molecule is too large, the crosslink density and curability of the resulting structure increase, but the storage elastic modulus at 25 ° C. and / or 180 ° C. In some cases, sufficient mechanical strength cannot be obtained, for example, the surface becomes too high or the film quality of the structure becomes too brittle, resulting in poor surface scratch resistance.
- the synergistic effect improves curability and flexibility. Strength and stain resistance can be sufficiently achieved. Further, when a fluorinated surfactant (especially a fluorinated surfactant having an alkylene oxide repeating structure and a fluoroalkyl group) is contained, the curability and flexibility are improved particularly by their synergistic effect. As a result, mechanical strength such as surface scratch resistance and contamination resistance can be achieved extremely suitably.
- the trifunctional or higher (preferably tetrafunctional or higher) urethane (meth) acrylate is preferably contained in the (meth) acrylate compound in an amount of 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 30% by mass or more. Preferable is less than 47% by mass. Within the above range, curability and flexibility are excellent, and scratch resistance is good.
- the structure of the tri- or more functional urethane (meth) acrylate is not particularly limited, but the compound having one hydroxyl group and two or more (meth) acryl groups in the molecule on the isocyanate group of the polyvalent isocyanate compound (a) It is preferable that the hydroxyl group of (b) reacts.
- the structure of the tetrafunctional or higher urethane (meth) acrylate is the same as described above.
- the number of isocyanate groups contained in the polyvalent isocyanate compound (a) is preferably 2 to 6, and particularly preferably 2 to 3. If it is less than the above range, the flexibility may be insufficient, and if it is more than the above range, it may be too soft or the viscosity of the polymerizable composition may increase too much.
- the polyvalent isocyanate compound (a) is not particularly limited, and examples thereof include compounds having two or more isocyanate groups in the molecule.
- examples of the compound having two isocyanate groups in the molecule include 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, and 1,4-phenylene diisocyanate.
- Examples of the compound having three isocyanate groups in the molecule include, for example, “a trimethylolpropane-added adduct formed by modifying isophorone diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, etc., a burette body, And isocyanurate form trimerized to form a 6-membered ring.
- the bifunctional isocyanate used as a raw material for the isocyanurate body is not particularly limited, but in the present invention, an isocyanurate body of isophorone diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate (HDI) is more preferable, and hexamethylene diisocyanate (HDI).
- Is a trimerized isosinurate which is particularly preferred in that it has a distance between functional groups and a structure imparting flexibility.
- the compound (b) having one hydroxyl group and two or more (meth) acrylic groups in the molecule is not particularly limited, but is a compound having three or more (p) hydroxyl groups in the molecule ( Examples thereof include a compound in which (p-1) (meth) acrylic acid has reacted with the hydroxyl group of b-1); a compound in which glycidyl (meth) acrylate and (meth) acrylic acid have undergone a ring-opening reaction, and the like.
- the compound (b) having one hydroxyl group and two or more (meth) acrylic groups in the molecule is produced when the compound is partially reacted with two or more compounds.
- the case where a compound having two or more hydroxyl groups is mixed in the molecule or the case where a compound having one (meth) acryl group is mixed is included.
- a compound in which (p-1) (meth) acrylic acid has reacted with a compound (b-1) having p hydroxyl groups (p is an integer of 3 or more) in the molecule is not particularly limited, and examples thereof include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, tetramethylolethane, diglycerin, ditrile Methylolethane, ditrimethylolpropane, dipentaerythritol, ditetramethylolethane; these ethylene oxide modified compounds; these propylene oxide modified compounds; ethylene oxide modified compounds of isocyanuric acid, propylene oxide modified compounds, ⁇ -caprolactone modified compounds; oligos Such as esters .
- the number of hydroxyl groups in compound (b-1) is particularly preferably 4 or more from the viewpoint that the number of functional groups in the resulting urethane (meth) acrylate can be increased. That is, as the compound (b-1), specifically, for example, pentaerythritol, tetramethylolethane, diglycerin, ditrimethylolethane, ditrimethylolpropane, dipentaerythritol, ditetramethylolethane and the like are particularly preferable.
- (meth) acrylic acid reacts with three of the four hydroxyl groups of diglycerin, resulting in one hydroxyl group and two or more (in this case, The compound (b) having three (meth) acrylic groups is synthesized.
- the polyvalent isocyanate compound (a) is isophorone diisocyanate
- Two (b) react to synthesize “a tetrafunctional or more urethane (meth) acrylate”.
- the urethane (meth) acrylate may be a trifunctional or lower urethane (meth) acrylate.
- the chemical structure of such a trifunctional or lower urethane (meth) acrylate and known ones can be used.
- bifunctional or lower urethane (meth) acrylate examples include bifunctional urethane (meth) acrylate having one (meth) acryl group at each of both ends of the molecule. There is no particular limitation on the chemical structure of such a bifunctional urethane (meth) acrylate.
- Polyol (meth) acrylate The (meth) acrylate compound for forming the structure of the present invention can also contain polyol (meth) acrylate.
- the “polyol (meth) acrylate” in the present invention is obtained by a dehydration condensation reaction between alcohol and (meth) acrylic acid, and has neither urethane bond nor siloxane bond, and other than the above-mentioned polyethylene glycol di (meth) acrylate. Means things.
- bifunctional polyol (meth) acrylate examples include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol di (meth) acrylate.
- a bifunctional polyol (meth) acrylate is preferable in order to impart flexibility and adjust the storage elastic modulus at 25 ° C. and / or 180 ° C.
- trifunctional polyol (meth) acrylate examples include glycerin PO-modified tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane EO-modified tri (meth) acrylate, and trimethylolpropane PO-modified tri (meth).
- isocyanuric acid EO-modified tri (meth) acrylate isocyanuric acid EO-modified ⁇ -caprolactone-modified tri (meth) acrylate, 1,3,5-triacryloylhexahydro-s-triazine, pentaerythritol tri (meth) acrylate, di Examples include pentaerythritol tri (meth) acrylate tripropionate.
- tetrafunctional or higher functional polyol (meth) acrylate examples include pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate monopropionate, dipentaerythritol hexa (meth) acrylate, tetramethylolethanetetra (meth) ) Acrylate, oligoester tetra (meth) acrylate and the like. These are used alone or in combination.
- the film quality (structure) becomes too hard, or the storage elastic modulus at 25 ° C. and / or 180 ° C. becomes too high. In some cases, the surface scratch resistance and contamination resistance may deteriorate.
- Epoxy (meth) acrylate The (meth) acrylic polymerizable composition in the present invention can also contain an epoxy (meth) acrylate.
- Epoxy (meth) acrylate refers to a (meth) acrylate compound having a structure obtained by reacting (meth) acrylic acid with an epoxy group.
- Epoxy (meth) acrylate has a rigid structure, and when blended, the film quality (structure) becomes brittle, and the storage elastic modulus at 25 ° C. and / or 180 ° C. becomes too high. Care must be taken because scratch resistance and contamination resistance may deteriorate.
- the polymerization composition in the present invention preferably further contains a fluorosurfactant, and particularly preferably contains a fluorosurfactant having an alkylene oxide repeating structure and a fluoroalkyl group. .
- a fluorosurfactant By containing a fluorosurfactant, the surface of the structure is hardly damaged (surface scratch resistance is improved), and the stain resistance can be further improved.
- “Fluorine-based surfactant” refers to a compound having a fluorine atom and having surface activity, and its chemical structure is not particularly limited as long as it contains a fluorine atom.
- a compound having a fluorine atom becomes a hydrophobic group, and a hydrophilic group is bonded to the group so long as it is a compound having performance as a surfactant, which is included in the present invention.
- the fluorine-based surfactant in the present invention is an alkylene oxide. It preferably has a repeating structure and a fluoroalkyl group.
- Such “alkylene oxide” is particularly preferably ethylene oxide from the viewpoint of improving surface scratch resistance and stain resistance.
- the alkylene oxide repeating structure may have one type of alkylene oxide chain or may have two or more types of alkylene oxide chains.
- the number of repeating alkylene oxide repeating structures is preferably 4 or more and 20 or less, more preferably 4 or more and 16 or less, and particularly preferably 4 or more and 12 or less.
- the carbon number of the fluoroalkyl group is not particularly limited, but is preferably 2 or more and 18 or less, more preferably 3 or more and 14 or less, and particularly preferably 4 or more and 8 or less.
- the fluoroalkyl group is preferably a perfluoroalkyl group. That is, as the fluorosurfactant, a perfluoroalkylethylene oxide adduct is particularly preferable.
- the carbon number of the perfluoroalkyl group is not particularly limited, but is preferably 2 or more and 18 or less, more preferably 3 or more and 14 or less, and particularly preferably 4 or more and 8 or less.
- the specific structure of the fluorosurfactant is preferably a structure in which an alkylene oxide repeating structure and a fluoroalkyl group are bonded in series, and the following formula (F) in which an alkylene oxide repeating structure and a fluoroalkyl group are bonded in series:
- a particularly preferable example of the fluorosurfactant is a structure represented by When a polymerizable surfactant represented by the following formula (1) is contained in the polymerizable composition, a structure extremely excellent in mechanical strength such as surface scratch resistance and stain resistance can be obtained.
- R 1 represents H or F
- R 2 represents H or CH 3
- R 3 represents H or CH 3
- X represents a divalent linking group
- p is 2 or more. It is an integer of 18 or less
- q is an integer of 4 or more and 20 or less.
- R 1 is preferably F, and R 2 is preferably H from the viewpoints of surface scratch resistance, contamination resistance and the like.
- p is preferably an integer of 3 or more and 14 or less from the viewpoint of surface scratch resistance, contamination resistance, etc., more preferably an integer of 4 or more and 10 or less, and an integer of 6 or more and 8 or less. Is particularly preferred.
- q is preferably an integer of 4 or more and 16 or less, and is preferably an integer of 5 or more and 10 or less from the viewpoints of surface scratch resistance and contamination resistance.
- X represents a divalent linking group, more preferably a divalent linking group having 1 to 16 atoms containing a hydrogen atom, and a divalent linking group having 1 to 10 atoms containing a hydrogen atom.
- the group is particularly preferred. Further, a divalent linking group having 1 to 6 atoms excluding a hydrogen atom is more preferable, and a divalent linking group having 1 to 4 atoms excluding a hydrogen atom is particularly preferable.
- X represents, for example, “—Y—O—” (Y represents an alkylene group having 1 to 5 carbon atoms, preferably an ethylene group or a propylene group), “—O—” or “— “COO-” is more preferable from the viewpoint of surface scratch resistance, stain resistance, and the like.
- R 1 in the formula (F) is F
- the carbon number of the perfluoroalkyl group is 4 or more and 8 or less
- R 2 in the formula (F) is H.
- a perfluoroalkylethylene oxide adduct having a repeating number of the ethylene oxide repeating structure of 4 or more and 12 or less is particularly preferable.
- the amount of the fluorosurfactant is usually 0.1 to 10 parts by weight, preferably 0.3 to 5 parts by weight, particularly preferably 0.5 to 3 parts per 100 parts by weight of the (meth) acrylate compound. Used in the range of parts by mass. If the amount is less than the above range, the effect of improving the wear resistance of the structure surface may not be obtained sufficiently.
- the composition itself may become cloudy (in a liquid state), and the transparency of the resulting structure may be reduced, or the fluorosurfactant may be liberated on the surface of the structure and contaminate the surroundings.
- the structure of the present invention is formed by polymerization of a “polymerizable composition containing a (meth) acrylate compound”.
- the “Polymerizable composition” includes, in addition to (meth) acrylate compounds, polymerization initiators such as photopolymerization initiators and thermal polymerization initiators; polymerization inhibitors; supplements; chain transfer agents; binder polymers; fine particles; UV absorbers; light stabilizers; antifoaming agents; mold release agents; lubricants; leveling agents; silicone oils; These can be appropriately selected from conventionally known ones.
- the components of the polymerizable composition include those that are only taken into the interior by polymerization of the (meth) acrylate compound and do not directly participate in the polymerization.
- the polymerizable composition in the present invention preferably contains a polymerization initiator or the like.
- the polymerizable composition as a material thereof preferably contains a photopolymerization initiator.
- the photopolymerization initiator is not particularly limited, but known ones conventionally used for radical polymerization, such as acetophenones, benzophenones, alkylaminobenzophenones, benzyls, benzoins, benzoin ethers, benzyl Aryl ketone photopolymerization initiators such as dimethylacetals, benzoylbenzoates and ⁇ -acyloxime esters; sulfur-containing photopolymerization initiators such as sulfides and thioxanthones; acylphosphine oxides such as acyl diarylphosphine oxides; And anthraquinones. Moreover, a photosensitizer can also be used together.
- the structure of the present invention is formed by electron beam irradiation, it is not essential to contain a polymerization initiator in the polymerizable composition as a material, but it may be contained.
- thermal polymerization initiator When the structure of the present invention is formed by thermal polymerization, it is preferable that a thermal polymerization initiator is contained.
- the thermal polymerization initiator known ones conventionally used for radical polymerization can be used, and examples thereof include peroxides and diazo compounds.
- the blending amount of the polymerization initiator such as a photopolymerization initiator and a thermal polymerization initiator is usually 0.2 to 10 parts by weight, preferably 0.5 to 7 parts by weight, based on 100 parts by weight of the (meth) acrylate compound. Used in a range.
- the polymerizable composition in the present invention preferably contains a light stabilizer and / or an antioxidant and / or an ultraviolet absorber.
- the structural body of the present invention is stable against light when the surface microstructure of the structural body is destroyed or the antireflection performance, the mechanical strength and mechanical properties of the surface are deteriorated due to deterioration with heat or light. It can be suppressed by containing an agent, an antioxidant, and an ultraviolet absorber.
- a preferable example of the light stabilizer is a hindered amine.
- Specific examples include TINUVIN 123, TINUVIN 144, TINUVIN 292, TINUVIN 765 (all manufactured by BASF), and the like, and these are particularly preferable in view of the above-described effects.
- antioxidants examples include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like, and phenolic antioxidants are particularly preferable.
- phenolic antioxidants examples include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like, and phenolic antioxidants are particularly preferable.
- TINUVIN 1035, TINUVIN 1010, TINUVIN 1076, TINUVIN 1330 (all manufactured by BASF) and the like can be mentioned.
- a benzotriazole UV absorber is preferable.
- TINUVIN PS, TINUVIN 99-2, TINUVIN 384-2, TINUVIN 400, TINUVIN 213, TINUVIN 571 (all manufactured by BASF) Etc. are particularly preferable in that the above-described effects are more exerted.
- Light stabilizers, antioxidants, and ultraviolet absorbers are each singularly deteriorated against heat and light, that is, destruction of the surface fine structure of the structure, antireflection performance, surface mechanical strength, mechanical properties, etc. Reduction can be suppressed. And by the combined use of the light stabilizer and the antioxidant, or the combined use of the light stabilizer, the antioxidant and the ultraviolet absorber, the deterioration of the structure over time under heat and / or ultraviolet rays is caused by the synergistic effect. Since suppression can be further achieved, it is more preferable.
- a combination of a hindered amine light stabilizer and a phenolic antioxidant is preferred, and a combination of a benzotriazole ultraviolet absorber is particularly preferred.
- the structure of the present invention is required to contain 53% by mass or more of polyethylene glycol di (meth) acrylate in the polymerizable composition as a material with respect to the entire (meth) acrylate compound. It is preferable to make the surface hydrophilic by containing polyethylene glycol di (meth) acrylate.
- hydrophilicity refers to the property of a small contact angle of water at 20 ° C. (in the present invention, it may be simply abbreviated as “contact angle”).
- the contact angle refers to the contact angle of water obtained by dropping one drop of water onto a structure having a fine concavo-convex structure defined on the surface and obtained by a tangential method.
- the contact angle was measured using a contact angle measuring device Model OCAH-200 manufactured by Dataphysica (Filderstadt). And in this invention, it defines as what was measured in that way.
- the structure in the present invention is not particularly limited to those having a hydrophilic surface. However, if the surface is hydrophilic, it is surprisingly difficult to get dirt or easy to wipe off dirt with water. It is possible to provide a structure having the above properties (contamination resistance). Since the structure having a hydrophilic surface further contains a fluorine-based surfactant (particularly preferably, “fluorine-based surfactant having an alkylene oxide repeating structure and a fluoroalkyl group”), A structure having further excellent properties (contamination resistance) such as difficulty of sticking and easy wiping of dirt by wiping with water can be obtained.
- a fluorine-based surfactant particularly preferably, “fluorine-based surfactant having an alkylene oxide repeating structure and a fluoroalkyl group”
- the above-described structure having a surface where the contact angle of water at 20 ° C. is 35 ° or less is preferable. More preferably, the contact angle is 30 ° or less, particularly preferably 25 ° or less, and further preferably 18 ° or less. If the contact angle of the surface of the structure is too large (if it is not hydrophilic), the surface of the structure may not be easily soiled or the dirt may be easily wiped off by water (contamination resistance).
- the surface hydrophilic As a method for making the surface hydrophilic, it is generally considered to introduce a hydrophilic functional group such as a hydroxyl group or a carboxyl group, but the surface imparted hydrophilicity with a polyethylene glycol chain of polyethylene glycol di (meth) acrylate Specifically, it is excellent in mechanical strength such as contamination resistance and surface scratch resistance.
- the surface imparted hydrophilicity with a polyethylene glycol chain is more specific than the surface imparted hydrophilicity with a polypropylene glycol chain, such as mechanical strength such as contamination resistance and surface scratch resistance, etc. Is excellent.
- the composition of the polymerizable composition which is a material for forming the structure of the present invention for example, the type and content of the (meth) acrylate compound are adjusted.
- the type of polyethylene glycol di (meth) acrylate (the number of ethylene glycol repeats, especially those containing an average number of repeats of 8 to 25) is adjusted, or the polyethylene glycol di (di) with respect to the total amount of (meth) acrylate compounds.
- the amount of (meth) acrylate is adjusted in the range of 53% by mass or more.
- Storage elastic modulus (storage elastic modulus at 25 ° C and 180 ° C)
- the storage elastic modulus at 25 ° C. of the structure of the present invention (in the present invention, it may be simply abbreviated as “storage elastic modulus”) is not particularly limited but is preferably 2 GPa or less, preferably 0.05 to 2 GPa. More preferably, 0.08 to 1.8 GPa is particularly preferable, 0.1 to 1.5 GPa is still more preferable, and 0.2 to 1.3 GPa is most preferable.
- the storage elastic modulus at 180 ° C. of the structure of the present invention (in the present invention, it may be simply abbreviated as “180 ° C. storage elastic modulus”) is not particularly limited, but is preferably less than 0.5 GPa, 0.05 to 0.48 GPa is more preferable, 0.1 to 0.46 GPa is particularly preferable, and 0.15 to 0.45 GPa is still more preferable.
- the storage elastic modulus is a physical property that does not depend on the shape and size of the measurement object.
- the storage elastic modulus is measured by a test piece cut out from a structure to about 5 mm ⁇ about 40 mm ⁇ about 100 ⁇ m (thickness). Alternatively, it is measured with a test piece separately polymerized to have this size.
- the measuring device is a dynamic viscoelasticity tester DMS6100 manufactured by Seiko Instruments Inc., and the test piece having the above shape is sandwiched in the direction of 20 mm, scanned in the range of ⁇ 20 ° C. to 200 ° C., and 25 ° C.
- the storage modulus at 180 ° C. is measured. If there is frequency dependence, the storage modulus measured at 10 Hz is adopted.
- the “storage modulus” or “180 ° C. storage modulus” is too low or too high, the mechanical strength at the use temperature (for example, room temperature) is inferior, the surface of the structure is easily worn, It may be easy to be damaged.
- the storage elastic modulus or “180 ° C. storage elastic modulus” is too high, the structure becomes hard and brittle, so that the surface of the structure is worn in the structure having the special surface microstructure of the present invention. It is considered that the surface is easily damaged and the surface is easily scratched.
- the storage elastic modulus or “180 ° C. storage elastic modulus” is in an appropriate range, even if it is a fine structure, the external surface of the structure is worn away by flexibly releasing external force such as friction. It is thought that it is preventing that it becomes easy to be damaged. Further, when the storage elastic modulus or “180 ° C. storage elastic modulus” is too low, the structure becomes too soft, the mechanical strength against external force such as friction is too low, and the surface of the structure is easily worn. It is considered that the surface is easily scratched.
- the composition of the polymerizable composition for example, (meta ) Type and content of acrylate compound, type and content of polymerization initiator, etc., irradiation conditions of light and electron beam used for polymerization (intensity, irradiation time, wavelength, removal of oxygen, etc.), heating conditions for polymerization ( Temperature, heating time, oxygen removal, etc.).
- the number of ethylene glycol chain repeats of polyethylene glycol di (meth) acrylate is Selecting an average of 8 to 25 or using urethane (meth) acrylate together has a synergistic effect in adjusting the storage elastic modulus to an appropriate range.
- the structure of the present invention has a special surface structure that exhibits low reflectivity and high transmittance, special physical properties are required for its physical properties.
- the present invention has been made by finding structural properties excellent in mechanical strength such as surface scratch resistance and contamination resistance in the special surface microstructure described above.
- An antireflective body-forming material comprising an acrylate compound, wherein the (meth) acrylate compound contains 53% by mass or more of polyethylene glycol di (meth) acrylate with respect to the entire (meth) acrylate compound. If used, a structure excellent in surface scratch resistance, contamination resistance and releasability as described above can be obtained.
- the manufacturing method of the structure of this invention does not have limitation in particular, For example, the following method is preferable. That is, the polymerizable composition is collected on a substrate and applied using a coating machine such as a bar coater or an applicator, or a spacer. When the structure is a film, it is applied so as to have a uniform film thickness.
- the “base material” is not particularly limited, but a film of polyethylene terephthalate (hereinafter abbreviated as “PET”), triacetyl cellulose or the like is preferable.
- PET polyethylene terephthalate
- a mold having the surface structure is bonded. After bonding, the film surface is polymerized by ultraviolet irradiation or electron beam irradiation and / or heat. Thereafter, the polymerized polymerizable composition is peeled off from the mold to produce the structure of the present invention.
- the polymerizable composition is collected directly on the mold having the surface structure.
- a coating film having a uniform film thickness may be created with a coating machine or a spacer.
- the polymerized polymerizable composition is peeled off from the mold to produce the structure of the present invention.
- a particularly preferable method for producing the structure is as follows. That is, in the manufacturing method of the structure, the surface has a concave portion having an average height of 100 nm to 1000 nm or a convex portion having an average depth of 100 nm to 1000 nm, and the concave portion or the convex portion is at least one.
- a polymerizable composition is supplied to a mold having an average period of 50 nm or more and 400 nm or less with respect to the direction, and a base material is pressure-bonded from the mold, and the polymerizable composition is cured and then peeled off from the mold. It is the manufacturing method of the structure to do.
- the surface has a concave portion having an average height of 100 nm to 1000 nm or a convex portion having an average depth of 100 nm to 1000 nm, and the concave portion or the convex portion has an average period of 50 nm to 400 nm with respect to at least one direction.
- a polymerizable composition containing a (meth) acrylate compound is supplied to an existing mold, and the polymerizable composition is cured by light irradiation, electron beam irradiation and / or heating, and then peeled off from the mold
- a more preferable method for producing a structure is the method for producing the above structure in which the polymerizable composition further contains a fluorosurfactant, and a particularly preferred method for producing the structure is the polymerization described above.
- the composition according to the above is a method for producing the above structure, which further contains “a fluorosurfactant having an alkylene oxide repeating structure and a fluoroalkyl group”.
- the mold is not particularly limited, but as an example, aluminum or an aluminum alloy is subjected to repetition of “anodizing” and “etching of the anodized film obtained thereby” on the surface of aluminum (alloy). What formed the shape is mentioned as a preferable thing. It can be preferably manufactured by the methods described in Patent Document 14 and Patent Document 15.
- the manufacturing method of the structure of the present invention will be specifically described with reference to FIG. 1, but the present invention is not limited to the specific mode of FIG. That is, an appropriate amount of the polymerizable composition (1) is supplied or applied to the mold (2) (FIG. 1 (a)), and the base material (3) is bonded obliquely with the roller side as a fulcrum (FIG. 1 (b)). ).
- the mold (2), the polymerizable composition (1), and the base material (3) bonded together are moved to the roller (4) (FIG. 1 (c)), and the mold is pressed by the roller.
- the specific structure possessed by (2) is transferred to the polymerizable composition (1) and shaped (FIG. 1 (d)). After hardening this, it peels from a type
- FIG. 2 is a schematic diagram of an example of an apparatus for continuously manufacturing a structure, but the present invention is not limited to this schematic diagram. That is, the polymerizable composition (1) is attached to the mold (2), a force is applied by the roller (4), and the base material (3) is bonded to the mold from an oblique direction. The specific structure is transferred to the polymerizable composition (1). This is cured using a curing device (6), and then peeled off from the mold (2), thereby obtaining the structure (5) targeted by the present invention.
- the support roller (7) is for lifting the structure (5) upward.
- a structure (5) free from bubbles and having no defects is obtained. Further, if a roller is used, a linear pressure is applied, so that the pressure can be increased. Therefore, a structure having a large area can be manufactured, and the pressure can be easily adjusted. Further, when the structure (5) is in the form of a film, it becomes possible to produce a structure having a uniform film thickness integrated with the base material and predetermined optical properties, and can be produced continuously. Therefore, it will be excellent in productivity.
- the structure of the present invention must be polymerized by light irradiation, electron beam irradiation and / or heating, but the wavelength of light in the case of light irradiation is not particularly limited.
- the light containing visible light and / or ultraviolet light is preferable in that the carbon-carbon double bond of the (meth) acryl group is polymerized well in the presence of a photopolymerization initiator if necessary.
- Particularly preferred is light containing ultraviolet rays.
- the light source is not particularly limited, and a known light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a halogen lamp, an electrodeless lamp, various lasers can be used.
- the intensity and wavelength of the electron beam are not particularly limited, and a known method is used.
- the temperature is not particularly limited, but is preferably 80 ° C. or higher, particularly preferably 100 ° C. or higher. Moreover, 200 degrees C or less is preferable and 180 degrees C or less is especially preferable. If the polymerization temperature is too low, the polymerization may not proceed sufficiently, and if it is too high, the polymerization may become non-uniform or the substrate may deteriorate.
- the heating time is not particularly limited, but is preferably 5 seconds or longer, and particularly preferably 10 seconds or longer. Moreover, 10 minutes or less are preferable, 2 minutes or less are especially preferable, and 30 seconds or less are still more preferable.
- the difficulty of soiling and the ease of wiping off dirt by wiping with water is because the surface microstructure is hydrophilic.
- the water component spreads to the concave portion of the hydrophilic surface, and a layer of water is formed at the interface between the soil component and the structure, and the soil component is easily wiped off when wiped off.
- the structure of the present invention having a specific surface structure has the above storage elastic modulus, it gives moderate flexibility and particularly excellent mechanical strength, and is particularly resistant to scratches on the surface and excellent in stain resistance.
- the present invention is not limited to the scope of application of the following actions and principles.
- minute portions of each unevenness This is considered to be because the mechanical properties of the structure have values within a specific range, so that the surface of the structure has the performance to withstand external forces.
- each of the unevenness becomes flexible, it does not break even when stress is applied. Therefore, it is possible to prevent scratches, such as mechanical strength such as surface scratch resistance and ease of wiping off dirt. It is considered that the property could be imparted to the structure surface.
- the polymerizable composition further contains a fluorosurfactant on the surface of the structure of the present invention having a specific surface structure
- a fluorosurfactant on the surface of the structure of the present invention having a specific surface structure
- it is flexible and gives excellent mechanical strength, and the surface is hardly scratched.
- the action / principle that makes it difficult to get dirt or easy to wipe off dirt by water wiping (contamination resistance), etc.
- the present invention is within the scope of the following action / principle.
- a structure having a specific surface structure has flexibility and mechanical strength, and a fluorosurfactant acts as a lubricant on the surface, thereby making it difficult to damage the surface. It is further improved.
- the structure of the fluorosurfactant has an alkylene oxide repeating structure and a fluoroalkyl group, so the affinity with water is improved, and a synergistic effect with a structure having a specific surface structure with hydrophilicity Thus, it is considered that it has become extremely superior in terms of the difficulty of attaching dirt and the ease of wiping off dirt by wiping with water (contamination resistance).
- Example 1 [Manufacture of structure]
- 70 g of m 24 (m represents the number of repeating units of ethylene glycol)
- the following formula (a ) 30 g of urethane (meth) acrylate (a) formed by bonding two dipentaerythritol pentaacrylates to isophorone diisocyanate, and 5 g of 1-hydroxycyclohexyl phenyl ketone as a photoinitiator.
- a composition was obtained.
- X represents a dipentaerythritol (having 6 hydroxyl groups) residue.
- the reflectance (%) of the surface of the structure after wiping was measured using the above-described reflectance measurement method, and compared with the reflectance (%) of the surface of the structure before wiping. Judgment is made based on the following criteria, and the increase in reflectance is 0.2 points or less ( ⁇ , ⁇ ) is “good”, 0.2 points or more and 0.3 points or less ( ⁇ ) is “slightly good”; Those exceeding 3 points ( ⁇ ) were judged as “bad”.
- the increase (%) in reflectance (%) was defined as “point”. That is, for example, when the reflectance (%) of the surface of the structure before wiping is 0.2% and the reflectance (%) of the surface of the structure after wiping is 0.3%, The increase in reflectance (%) is “0.1 point”.
- the state when the reflectance increase value and the fingerprint smudge were visually observed were as follows.
- Contact angle refers to the contact angle of water obtained by dropping water onto a structure having a fine concavo-convex structure defined on the surface and obtained by a tangential method. The contact angle was measured using a Model OCAH-200 contact angle measuring device manufactured by Dataphysica (Filderstadt).
- ⁇ Storage modulus> Each of the structures obtained above was cut into 5 mm ⁇ 40 mm, and test pieces of 5 mm ⁇ 40 mm ⁇ 100 ⁇ m were prepared. The measurement is performed by using a dynamic viscoelasticity tester DMS6100 manufactured by Seiko Instruments Inc., sandwiching the test piece in the direction of 20 mm, applying a force of a frequency of 10 Hz, and scanning a range of ⁇ 20 ° C. to 200 ° C. Then, the storage elastic modulus at 25 ° C. was measured and designated as “storage elastic modulus”.
- Examples 2-7, Comparative Examples 1-11 An appropriate amount of the polymerizable composition having the composition shown in Table 1 was collected on a PET film and applied in the same manner as in Example 1 so as to obtain a uniform film thickness. Thereafter, the same mold as in Example 1 was bonded and polymerized in the same manner to produce each structure.
- the unit of the numbers in Table 1 is [g].
- m represents the average number of repeating units of propylene glycol.
- urethane (meth) acrylate (b) indicates a compound in which three pentaerythritol triacrylates are bonded to a nurate (trifunctional isocyanate) formed by trimerizing hexamethylene diisocyanate to form a 6-membered ring. .
- Examples 1 to 7 containing polyethylene glycol di (meth) acrylate in an amount of 53% by mass or more based on the entire (meth) acrylate compound the surface scratch resistance is all 4 or more, and the contamination resistance is all “ ⁇ ” or more. (In other words, the increase in reflectance after wiping with water was 0.3 point or less), and all were extremely excellent overall.
- the contamination resistance was “x” (that is, the increase in reflectance after wiping with water was greater than 0.3 point).
- Comparative Examples 5 to 7 using polypropylene glycol di (meth) acrylate instead of polyethylene glycol di (meth) acrylate were also generally inferior.
- the contact angles were all 35 ° or less in Examples 1 to 7, but all the comparative examples were 40 ° or more. Actually, all the angles except 40 ° of Comparative Example 4 were extremely large as 60 °. Thus, it was found that particularly excellent surface scratch resistance and contamination resistance can be achieved in a structure having a small contact angle, that is, a hydrophilic surface.
- the storage elastic modulus at 25 ° C. was all 2 GPa or less in the measured examples, but all of the measured comparative examples were larger than 2 GPa. From this, it was found that when the storage elastic modulus at 25 ° C. is smaller than a certain value, particularly excellent surface scratch resistance and stain resistance can be achieved.
- the “180 ° C. storage elastic modulus” was all less than 0.5 GPa in the measured examples, but all measured in the comparative examples were 0.7 GPa or more.
- Examples 8 and 9 As described in Table 2, in the polyethylene glycol diacrylate represented by the formula (2), the number m of repeating units is fixed to 14, and the ratio with the urethane (meth) acrylate (a) is further increased. Evaluation was made by changing the number of people. The production method of the polymerizable composition and the structure was the same as in Example 1. The amount described in Table 2 is [parts by mass]. The results are also shown in Table 2. Further, Example 3, Example 4 and Comparative Example 2 in Table 1 are also shown in Table 2 for reference.
- Examples 8, 9, 3, and 4 containing polyethylene glycol di (meth) acrylate in an amount of 53% by mass or more based on the entire (meth) acrylate compound all have a storage elastic modulus at 25 ° C. of 2 GPa or less. Yes, all the performances were also excellent overall, but in Comparative Example 2 where the content of polyethylene glycol di (meth) acrylate was small, it was as large as 3.03 GPa and the performance was not excellent.
- the 180 ° C. storage elastic modulus of Examples 8, 9, 3, and 4 was all less than 0.5 GPa (actually 0.48 GPa or less).
- Table 3 shows the components and evaluation results of the polymerizable compositions of Reference Example 1 (using the same polymerizable composition as in Example 3) and Reference Example 2 (using the same polymerizable composition as in Comparative Example 2).
- “contamination resistance (visual determination)” was determined according to the determination standard of “state when fingerprint stain was visually observed” in the above ⁇ Contamination Resistance Evaluation Method and Criteria>.
- the contact angle was 18 ° on the surface of the microstructure in the present invention and was hydrophilic (Example 3), but it was 55 ° on the flat surface and was not hydrophilic (Reference Example 1). That is, a specific material becomes a hydrophilic surface only when it has a specific surface structure.
- the contamination resistance of the polymerizable composition of Comparative Example 2 was “ ⁇ ” on the surface of the microstructure of the present invention (Comparative Example 2), but “ ⁇ ” on the flat surface (Reference Example 2). It was found that the contamination resistance was reduced because of the surface structure. On the other hand, in the reference example 2 of the flat surface, the contamination resistance was kept good.
- Example 10 [Manufacture of structure] ⁇ Manufacture of structure numbers 1, 2, and 3>
- 61 parts by mass was contained.
- m represents the average number of repeating units.
- urethane (meth) acrylate (a) formed by bonding two dipentaerythritol pentaacrylates to isophorone diisocyanate represented by the following formula (a) is 30 parts by mass in structure number 1 and in structure number 2 In 47 mass parts and structure No. 3, 36 mass parts was contained.
- X represents a dipentaerythritol (having 6 hydroxyl groups) residue.
- the structure number 3 further contained 3 parts by mass of urethane (meth) acrylate (b) represented by the following.
- 2HEA-IPDI- Polyethyleneter of adipic acid and 1,6-hexanediol having a weight average molecular weight of 3500 and hydroxyl groups at both ends
- -IPDI-2HEA 2-hydroxyethyl acrylate
- IPDI isophorone diisocyanate
- ⁇ represents a bond of an isocyanate group and a hydroxyl group by the following normal reaction.
- each of Structure Nos. 1, 2, and 3 contains 0.5 parts by mass of the following “fluorine surfactant (a) belonging to the fluorosurfactant represented by the formula (F)”. I let you.
- R 1 represents H or F
- R 2 represents H or CH 3
- R 3 represents H or CH 3
- X represents a divalent linking group
- p is 2 or more. It is an integer of 18 or less
- q is an integer of 4 or more and 20 or less.
- Each of Structure Nos. 1, 2, and 3 contained 5 parts by mass of 1-hydroxycyclohexyl phenyl ketone as a photopolymerization initiator. With regard to Structure Nos. 1, 2, and 3, the above-described components were stirred and mixed until uniform to obtain respective polymerizable compositions. Table 4 summarizes the component composition. The unit of the numbers in Table 4 is “parts by mass”.
- Structure No. 4 was produced in the same manner as Structure No. 3 except that in the production of Structure No. 3, a fluorosurfactant (b) was used instead of the fluorosurfactant (a).
- Structure No. 5 was produced in the same manner as Structure No. 3 except that in the production of Structure No. 3, a fluorosurfactant (c) was used instead of the fluorosurfactant (a).
- Structure No. 6 was produced in the same manner as Structure No. 3 except that the content of the fluorosurfactant (a) was changed from 0.5 parts by mass to 3.0 parts by mass in the production of structure No. 3. did.
- Fluorosurfactant (d) FL-100-100st (manufactured by Shin-Etsu Chemical Co., Ltd.) is a fluorinated surfactant having a polydimethylsiloxane structure having a fluoroalkyl group (—CH 2 CH 2 CF 3 ) in the side chain. It is.
- Silicon-based lubricant A (X-22-164AS (manufactured by Shin-Etsu Chemical Co., Ltd.)) is polydimethylsiloxane modified at both ends with methacrylic acid
- silicon-based lubricant B (X-24-8201 (Shin-Etsu Chemical) Is a polydimethylsiloxane having one end modified with methacrylic acid.
- Structure No. 10 was produced in the same manner as Structure No. 1 except that it did not contain a fluorosurfactant.
- Structure No. 11 was produced in the same manner as Structure No. 2 except that it did not contain a fluorosurfactant.
- Structure No. 12 was produced in the same manner as Structure No. 3 except that it did not contain a fluorosurfactant.
- the reflectance (%) of the surface of the structure after wiping was measured using the above-described reflectance measurement method, and compared with the reflectance (%) of the surface of the structure before wiping. Judgment is made according to the following criteria, and the increase in reflectance is 0.2 points or less ( ⁇ , ⁇ , ⁇ ) is “good” ( ⁇ is “very good”), greater than 0.2 points and 0.3 points or less ( ( ⁇ ) was judged as “slightly good”, and those exceeding 0.3 points ( ⁇ ) were judged as “bad”. With respect to the four-stage criteria of Examples 1 to 9, etc., “ ⁇ ” was added to the top and “xx” was added to the bottom, and the evaluation was made in six stages.
- the increase (%) in reflectance (%) was defined as “point”. That is, for example, when the reflectance (%) of the surface of the structure before wiping is 0.2% and the reflectance (%) of the surface of the structure after wiping is 0.3%, The increase in reflectance (%) is “0.1 point”.
- the state when the reflectance increase value and the fingerprint smudge were visually observed were as follows.
- ⁇ 0.1 point or less. Fingerprint stains cannot be observed from the front after 5 reciprocations, and cannot be observed from an oblique direction, but cannot be observed from the front or at all from an oblique view after 3 reciprocations of water. A: 0.1 points or less. Fingerprint stains cannot be observed from the front after 5 reciprocations or from an oblique direction. Fingerprint stains can be observed from the front or diagonal at the time of three rounds of water wiping. ⁇ : greater than 0.1 point and less than 0.2 point. Fingerprint stains cannot be observed from the front, but can be observed slightly from an oblique direction.
- ⁇ greater than 0.2 point and less than 0.3 point. Fingerprint stains cannot be observed from the front, but can be observed from an angle. X: More than 0.3 point and less than 0.5 point, fingerprint stain can be observed even from the front. XX: Greater than 0.5 points. Fingerprint stains can be observed from the front.
- Structure Nos. 1 to 7 containing a fluorosurfactant showed an improvement in surface scratch resistance compared to Structure Nos. 8 to 12 containing no fluorosurfactant.
- the structure numbers 1 to 6 containing “a fluorosurfactant having an alkylene oxide repeating structure and a fluoroalkyl group” in particular are compared with the structure numbers 7 to 12 not containing these. In particular, further improvements in both surface scratch resistance and contamination resistance were observed. All of the fluorosurfactants (a), (b), and (c) blended in the structure numbers 1 to 6 are perfluoroalkylethylene oxide adducts.
- the structure of the present invention is excellent in light reflection prevention performance, light transmission improvement performance, and the like, it can provide good visibility.
- it has excellent mechanical strength (surface scratch resistance and surface wear resistance), contamination resistance, etc., so FPD such as LCD, PDP, OLED, FED, etc .; CRT; Lens; Window plate; Show window; Meter, It is suitably used in fields where visibility and surface performance (scratches, dirt, durability, etc.) are required, such as headlights, foreheads, covers for display cases, etc.
- FPD such as LCD, PDP, OLED, FED, etc .
- CRT CRT
- Lens Window plate
- Show window; Meter It is suitably used in fields where visibility and surface performance (scratches, dirt, durability, etc.) are required, such as headlights, foreheads, covers for display cases, etc.
- it is suitably used for applications where a mechanical external force is easily applied to the surface.
- it is widely and suitably used for the purposes of antireflection, improvement of transparency, surface
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Abstract
Description
一般にかかる表面層には、光の反射防止性能や光の透過性向上性能が必要であるのみならず、実用化の際には摩耗や傷等に強い一定の機械的強度や汚れの付き難いことや、汚れの除去が容易であることが必要であった。
本発明の構造体は、表面に、平均高さ100nm以上1000nm以下の凸部又は平均深さ100nm以上1000nm以下の凹部を有していることが必須である。ここで凸部とは、基準となる面より出っ張った部分をいい、凹部とは、基準となる面より凹んだ部分をいう。本発明の構造体は、その表面に凸部を有していても、凹部を有していてもよい。また、凸部と凹部の両方を有していてもよく、更に、それらが連結して波打った構造を有していてもよい。
更に、本発明の構造体は、光照射、電子線照射及び/又は加熱によって、(メタ)アクリレート化合物を含有する重合性組成物が重合したものであることが必須である。すなわち、本発明の構造体は、重合性組成物中の(メタ)アクリレート化合物の(メタ)アクリル基の炭素-炭素間二重結合が、光照射、電子線照射及び/又は加熱によって反応してできる。本発明において、「(メタ)アクリル」とは、「アクリル」又は「メタクリル」を意味する。
中でも、照射機器のコスト、普及度、硬化に要する時間(ラインスピード)等の点から光照射の内の紫外線照射によって硬化(重合)させることが好ましい。
反応率が低すぎると、機械的強度の低下や耐薬品性の低下をまねく場合がある。
上記したような特定の表面構造を有する本発明の構造体は、下記の材料(重合性組成物)から形成したときに、光の反射防止性能、光の透過改良性能等の光学的性能等が優れ、特に、表面耐傷性等の機械的強度;汚れの付き難さや水拭きによる汚れの拭き取り易さ等の性質(耐汚染性);等に優れたものとなる。
すなわち、本発明の構造体は、(メタ)アクリレート化合物を含有する重合性組成物が重合したものであって、該(メタ)アクリレート化合物が、該(メタ)アクリレート化合物全体に対して、53質量%以上のポリエチレングリコールジ(メタ)アクリレートを含有し、かつ、該構造体が、25℃における貯蔵弾性率が2GPa以下及び/又は180℃における貯蔵弾性率が0.5GPa未満のものであることを特徴とする。以下に、本発明の構造体用の材料について詳述する。
本発明における上記重合性組成物は、(メタ)アクリレート化合物を必須成分として含有する。
本発明における上記重合性組成物は、(メタ)アクリレート化合物を必須成分として含有するが、該(メタ)アクリレート化合物は、該(メタ)アクリレート化合物全体に対して、53質量%以上のポリエチレングリコールジ(メタ)アクリレートを含有することが必須である。ポリエチレングリコールジ(メタ)アクリレートを、(メタ)アクリレート化合物全体に対して53質量%以上含有させることによって、構造体の表面に傷が付き難くなり、また、汚れが付き難くなったり、汚れが拭き取り易くなったりする。
一方、ポリエチレングリコールジ(メタ)アクリレートの含有割合が多すぎるときは、親水性能の向上や、耐汚染性の向上には効果はあるが、表面耐傷性等の機械的強度を低下させる場合がある。
その結果として、エチレングリコール鎖が短すぎても長すぎても、表面耐傷性等の機械的強度;汚れの付き難さや水拭きによる汚れの拭き取り易さ等の性質(耐汚染性);等が十分に達成できず、極めて優れたものとはならない場合がある。
構造体が柔軟であることにより、応力がかかったときに、表面微細構造が折れ、それがきっかけとなって傷が付くことを防ぎ、その結果、表面耐傷性等の機械的強度、汚れの付き難さ、汚れの拭き取り易さ(例えば、水拭きすることで汚れが取れる性質)等を、構造体表面に付与することが可能となる。貯蔵弾性率については後で詳述する。
また、上記した「#200」、「#400」、「#600」、「#1000」、「#1200」及び「#1540」に限定されず、#200-#2000の範囲のポリエチレングリコールジ(メタ)アクリレートも具体例として挙げられる。
ここで、例えば、「#200」等は、ポリエチレングリコール鎖の繰り返し単位数と相関し、「-CH2CH2O-」を1単位として、「#200」は4単位、「#400」は8単位、「#600」は12単位、「#1000」は20単位、「#1540」は32単位、「#2000」は40単位を意味する。
本発明における(メタ)アクリレート化合物は、更に、ウレタン(メタ)アクリレートを含有することが好ましい。「ウレタン(メタ)アクリレート」とは、分子中にウレタン結合を有する(メタ)アクリレート化合物をいう。
かかるウレタン(メタ)アクリレートの化学構造には特に限定はなく、その重量平均分子量は、1000以上30000以下であることが好ましく、1500以上15000以下であることがより好ましく、2000以上5000以下であることが特に好ましい。分子量が小さすぎると、柔軟性が低下する場合がある。
ウレタン(メタ)アクリレートとしては、3官能以上(特に好ましくは4官能以上)のウレタン(メタ)アクリレートを含有するものであることが好ましい。すなわち、分子中に(メタ)アクリル基を3個以上(特に好ましくは4個以上)有する化合物を含有することが好ましい。
この場合のウレタン結合の位置や個数、(メタ)アクリル基が分子末端にあるか否か等は特に限定はない。分子中に(メタ)アクリル基を6個以上有する化合物が特に好ましく、9個以上有する化合物が更に好ましい。また、分子中の(メタ)アクリル基の個数の上限は特に限定はないが、15個以下が特に好ましい。
一方、ウレタン(メタ)アクリレート分子中の(メタ)アクリル基の数が多すぎると、得られた構造体の架橋密度や硬化性は高くなるが、25℃及び/又は180℃の貯蔵弾性率が高くなりすぎたり、構造体の膜質が脆くなりすぎたりして、表面耐傷性が劣る等、十分な機械強度が得られない場合がある。
また、更に、フッ素系界面活性剤(特に、アルキレンオキサイド繰り返し構造とフルオロアルキル基とを有するフッ素系界面活性剤)を含有させると、それらの相乗効果で、特に、硬化性、柔軟性が向上することとなり、その結果、表面耐傷性等の機械的強度や耐汚染性が、極めて好適に達成できるようになる。
4官能以上のウレタン(メタ)アクリレートについても、その構造は上記と同様である。
イソシアヌレート体の原料となる2官能イソシアネートとしては特に限定はないが、本発明には、イソホロンジイソシアネート、トリレンジイソシアネート、ヘキサメチレンジイソシアネート(HDI)のイソシアヌレート体がより好ましく、ヘキサメチレンジイソシアネート(HDI)が3量体化したイソシヌレート体が、官能基間距離があり、柔軟性を付与する構造となっている点で特に好ましい。
ウレタン(メタ)アクリレートとしては、3官能以下のウレタン(メタ)アクリレートでもよい。かかる3官能以下のウレタン(メタ)アクリレートの化学構造には特に限定はなく、公知のものが使用できる。
本発明の構造体を形成させるための(メタ)アクリレート化合物は、ポリオール(メタ)アクリレートを含有することもできる。本発明における「ポリオール(メタ)アクリレート」とは、アルコールと(メタ)アクリル酸との脱水縮合反応等で得られ、ウレタン結合もシロキサン結合も有さず、上記したポリエチレングリコールジ(メタ)アクリレート以外のものをいう。
また、本発明における(メタ)アクリル系重合性組成物は、エポキシ(メタ)アクリレートを含有することもできる。「エポキシ(メタ)アクリレート」とは、エポキシ基に(メタ)アクリル酸が反応して得られる構造を有する(メタ)アクリレート化合物をいう。
「エポキシ(メタ)アクリレート」は剛直な構造を持ち、配合することによって、膜質(構造体)がもろくなったり、25℃及び/又は180℃の貯蔵弾性率が高くなりすぎて、その結果、表面耐傷性や耐汚染性が悪くなったりする場合があるので注意する必要がある。
本発明における重合組成物は、更に、フッ素系界面活性剤を含有することが好ましく、アルキレンオキサイド繰り返し構造とフルオロアルキル基とを有するフッ素系界面活性剤を含有することが特に好ましい。フッ素系界面活性剤を含有することにより、更に、構造体の表面に傷が付き難くなり(表面耐傷性が向上し)、また、耐汚染性に更に優れたものとすることができる。
かかる「アルキレンオキサイド」は、エチレンオキサイドであることが、表面耐傷性向上、耐汚染性向上の点から特に好ましい。
アルキレンオキサイド繰り返し構造は、1種のアルキレンオキサイド鎖を有するものでも、2種以上のアルキレンオキサイド鎖を有するものでもよい。
該パーフルオロアルキル基の炭素数に特に限定はないが、2以上18以下が好ましく、3以上14以下がより好ましく、4以上8以下が特に好ましい。
下記式(1)で表されるフッ素系界面活性剤を重合性組成物に含有させると、表面耐傷性等の機械的強度、耐汚染性等に極めて優れた構造体を得ることができる。
また、pは3以上14以下の整数であることが、表面耐傷性、耐汚染性等の点から好ましく、4以上10以下の整数であることがより好ましく、6以上8以下の整数であることが特に好ましい。
qは4以上16以下の整数であることが、表面耐傷性、耐汚染性等の点から好ましく、5以上10以下の整数であることが特に好ましい。
Xは、具体的には、例えば、「-Y-O-」(Yは炭素数1~5のアルキレン基を示し、好ましくはエチレン基又はプロピレン基である)、「-O-」又は「-COO-」であることが、表面耐傷性、耐汚染性等の点から更に好ましい。
上記範囲より少ないと構造体表面の耐摩耗性の向上効果が十分得られない場合があり、上記範囲より多すぎると(メタ)アクリレート化合物との相溶性が悪くなり、構造体形成用の重合性組成物自身が(液の状態で)白濁し、得られる構造体の透明性が低下したり、構造体の表面にフッ素系界面活性剤が遊離して周囲を汚染してしまう場合がある。
本発明の構造体は、「(メタ)アクリレート化合物を含有する重合性組成物」が重合することによって形成される。「重合性組成物」は、(メタ)アクリレート化合物以外に、光重合開始剤、熱重合開始剤等の重合開始剤;重合禁止剤;補足剤;連鎖移動剤;バインダーポリマー;微粒子;酸化防止剤;紫外線吸収剤;光安定剤;消泡剤;離型剤;潤滑剤;レベリング剤;シリコーンオイル;変性シリコーンオイル等を含有することができる。
これらは、従来公知のものの中から適宜選択して用いることができる。重合性組成物の成分には、(メタ)アクリレート化合物の重合によって内部に取り込まれるだけで、それ自体が重合に直接関与しないものも含まれる。
本発明における重合性組成物には、重合開始剤等を含有させることが好ましい。本発明の構造体が、光照射によって形成される場合には、その材料となる重合性組成物には、光重合開始剤が含有されることが好ましい。光重合開始剤としては特に限定はないが、ラジカル重合に対して従来用いられている公知のもの、例えば、アセトフェノン類、ベンゾフェノン類、アルキルアミノベンゾフェノン類、ベンジル類、ベンゾイン類、ベンゾインエーテル類、ベンジルジメチルアセタール類、ベンゾイルベンゾエート類、α-アシロキシムエステル類等のアリールケトン系光重合開始剤;スルフィド類、チオキサントン類等の含硫黄系光重合開始剤;アシルジアリールホスフィンオキシド等のアシルホスフィンオキシド類;アントラキノン類等が挙げられる。また、光増感剤を併用させることもできる。
本発明における重合性組成物には、光安定剤及び/又は酸化防止剤及び/又は紫外線吸収剤を含有させることが好ましい。
本発明の構造体は、熱や光による経時劣化により、構造体の表面微細構造が破壊したり、反射防止性能、表面の機械的強度や機械的物性等が低下したりすることを、光安定剤・酸化防止剤・紫外線吸収剤の含有により抑制することができる。
具体的には、例えば、TINUVIN 123、TINUVIN 144、TINUVIN 292、TINUVIN 765(何れもBASF社製)等が挙げられ、これらは前記効果をより奏する点で特に好ましい。
具体的には、例えば、TINUVIN 1035、TINUVIN 1010、TINUVIN 1076、TINUVIN 1330(何れもBASF社製)等が挙げられ、これらは前記効果をより奏する点で特に好ましい。
本発明の構造体は、その材料となる重合性組成物中のポリエチレングリコールジ(メタ)アクリレートを、(メタ)アクリレート化合物全体に対して53質量%以上含有させることが必須であるが、ポリエチレングリコールジ(メタ)アクリレートを含有させることによって、表面を親水性にすることが好ましい。ここで、「親水性」とは、20℃における水の接触角(本発明おいては、単に「接触角」と略記する場合がある)が小さい性質をいう。
表面が親水性である構造体に、更にフッ素系界面活性剤(特に好ましくは、「アルキレンオキサイド繰り返し構造とフルオロアルキル基とを有するフッ素系界面活性剤」)が含有されていることによって、汚れの付き難さや水拭きによる汚れの拭き取り易さ等の性質(耐汚染性)が更に優れた構造体が得られる。
しかしながら、前記した「反射を防止する性質を有する特殊な形状」を有する表面においては、意外にも、表面が親水性であると、該表面の耐汚染性が向上する。本発明は、上記した特殊な表面微細構造において、その表面を親水性にすることにより、耐汚染性等に優れる表面物性が実現することを見出してなされた。
特に、ポリエチレングリコールジ(メタ)アクリレートの種類(エチレングリコールの繰返し数、特に繰返し数が平均で8から25のものを含有させる)を調整したり、(メタ)アクリレート化合物の全体量に対するポリエチレングリコールジ(メタ)アクリレートの量を53質量%以上の範囲で調整したりして行なう。
本発明の構造体の25℃における貯蔵弾性率(本発明においては、単に「貯蔵弾性率」と略記する場合がある)は、特に限定はないが、2GPa以下が好ましく、0.05~2GPaがより好ましく、0.08~1.8GPaが特に好ましく、0.1~1.5GPaが更に好ましく、0.2~1.3GPaが最も好ましい。
また、本発明の構造体の180℃における貯蔵弾性率(本発明においては、単に「180℃貯蔵弾性率」と略記する場合がある)は、特に限定はないが、0.5GPa未満が好ましく、0.05~0.48GPaがより好ましく、0.1~0.46GPaが特に好ましく、0.15~0.45GPaが更に好ましい。
また、貯蔵弾性率や「180℃貯蔵弾性率」が低すぎる場合には構造体が柔らかくなりすぎて、摩擦等の外力に対する機械的な強度が低すぎ、構造体の表面が摩耗し易くなったり、表面に傷が付き易くなったりするものと考えられる。
特に、(メタ)アクリレート化合物の全体量に対するポリエチレングリコールジ(メタ)アクリレートの量を53質量%以上の範囲で含有させることに加えて、ポリエチレングリコールジ(メタ)アクリレートのエチレングリコール鎖の繰返し数が平均で8から25のものを選択したり、ウレタン(メタ)アクリレートを併用したりすることが、貯蔵弾性率を適度な範囲に調整する上で相乗的な効果がある。
すなわち、上記の構造体形成用の重合性組成物であって、(メタ)アクリレート化合物及びフッ素系界面活性剤を含有する反射防止体形成材料を用いれば、上記したような表面対傷性や耐汚染性が極めて優れた構造体を得ることができる。
本発明の構造体の製造方法は特に限定はないが、例えば下記の方法が好ましい。すなわち、上記重合性組成物を基材上に採取、バーコーター若しくはアプリケーター等の塗工機又はスペーサーを用いて塗布する。構造体が膜状の場合には、均一膜厚になるように塗布する。ここで、「基材」としては、特に限定はないが、ポリエチレンテレフタレート(以下、「PET」と略記する)、トリアセチルセルロース等のフィルムが好適である。次いで、前記表面構造をもった型を貼り合わせる。貼り合わせた後、該フィルム面から紫外線照射若しくは電子線照射及び/又は熱により重合させる。その後、重合性組成物が重合したものを、型から剥離して本発明の構造体を製造する。
また、より好ましい構造体の製造方法は、上記重合性組成物が更にフッ素系界面活性剤を含有するものである上記の構造体の製造方法であり、特に好ましい構造体の製造方法は、上記重合性組成物が、更に、「アルキレンオキサイド繰り返し構造とフルオロアルキル基とを有するフッ素系界面活性剤」を含有するものである上記の構造体の製造方法である。
特定の表面構造を有する本発明の構造体の表面において、重合性組成物中の(メタ)アクリレート化合物全体に対して53質量%以上のポリエチレングリコールジ(メタ)アクリレートが含有されると、柔軟で、優れた機械的強度を与え、表面に傷が付き難く、また、汚れの付き難さや水拭きによる汚れの拭き取り易さ(耐汚染性)等に優れるようになる作用・原理については明らかではなく、また、以下の作用・原理の当てはまる範囲に本発明は限定される訳ではないが、機械的強度の向上については、ポリエチレングリコールジ(メタ)アクリレートの官能基分子間距離が適度であることと、エチレングリコール鎖の分子構造とが相互作用して、表面の凹凸1個1個の微細構造にかかる外力を柔軟に抗する力学物性を持った構造体の表面を形成するためと考えられる。
これに対して、親水性でない場合には、付着した汚れ(油)を水拭きしても、その水が表面の凹部にまで濡れ拡がり難く、特に凹部に入り込んだ汚れ成分が拭き取り難くなってしまうものと考えられる。
[構造体の製造]
前記式(1)に含まれる「下記の式(2)で示されるポリエチレングリコールジアクリレート」において、m=24(mはエチレングリコールの繰り返し単位数を示す)のものを70g、下記の式(a)で示されるイソホロンジイソシアネートにジペンタエリスリトールペンタアクリレートが2個結合してなるウレタン(メタ)アクリレート(a)を30g、光重合開始剤として、1-ヒドロキシシクロヘキシルフェニルケトン5gを撹拌混合して重合性組成物を得た。
得られた構造体を以下の方法で評価した。結果を表1に示す。
構造体の表面上を、新東科学(株)社製の表面試験機ドライボギアTYPE-14DRを用い、25mm円柱の平滑な断面にスチールウール#0000を均一に貼り付け、荷重400gをかけながら、速度10cm/秒で10往復させたときの傷の付き具合を観察した。以下の基準で判定し、4以上を良好、3をやや良好、2以下を不良、とした。
5:数本未満の引掻き傷あり
4:数本から10本の引掻き傷あり
3:25mm円柱の半分に引掻き傷あり
2:25mm円柱の2/3に引掻き傷あり
1:25mm円柱の全面に引掻き傷あり
島津製作所製、自記分光光度計「UV-3150」を用い、裏面に黒色テープを貼り付け、構造体の表面の5°入射絶対反射率を測定した。測定波長は、380nmから780nmとした。
人差し指の油を付着させ、構造体の表面上に強く押し付け、正面からの目視で指紋汚れがはっきり分かるようにした。その後、市販のティッシュペーパー1枚を3cm角に折りたたみ、水を十分に浸み込ませ(水滴が滴り落ちない程度)、それを手に持って、構造体の表面を、上記指紋汚れを拭き取るように、腕の自荷重位の強さで、5往復させて水拭きした。そして、拭き取り部に残った過剰の水分を乾燥したティッシュペーパーで1回拭き取った。
以下の基準で判定し、反射率の上昇が、0.2ポイント以下(◎、○)を「良好」、0.2ポイントより大きく0.3ポイント以下(△)を「やや良好」、0.3ポイントを超えるもの(×)を「不良」と判断した。
反射率(%)の上昇分(%)を「ポイント」とした。すなわち、例えば、水拭き前の構造体の表面の反射率(%)が0.2%であり、水拭き後の構造体の表面の反射率(%)が0.3%の場合には、反射率(%)の上昇は「0.1ポイント」である。
なお、反射率の上昇値と指紋汚れを目視で観察したときの状態はおおむね以下の通りだった。
◎:0.1ポイント以下。指紋汚れが正面から観察できないし斜めからでも観察できない。
○:0.1ポイントより大きく0.2ポイント以下。指紋汚れが正面から観察できないが斜めからわずかに観察できる。
△:0.2ポイントより大きく0.3ポイント以下。指紋汚れが正面から観察できないが斜めからでは観察できる。
×:0.3ポイントより大きく0.5ポイント以下、指紋汚れが正面からでも観察できる。
「接触角」は、表面に規定した微細凹凸構造を持った構造体に水を滴下し、接線法により求めた水の接触角を言う。接触角の測定は、Dataphysica(Filderstadt)社製の接触角測定装置、Model OCAH-200を用いて測定を行った。
上記で得られた構造体を、それぞれ5mm×40mmに切り出して、5mm×40mm×100μmのテストピースを作成した。測定は、セイコーインスツルメント社製の動的粘弾性試験機DMS6100を用いて、上記テストピースを、20mmの方向で挟み、10Hzの周波数の力を加え、-20℃~200℃の範囲を走査し、25℃の貯蔵弾性率を測定し、「貯蔵弾性率」とした。
上記した25℃の貯蔵弾性率の測定方法と同様に、-20℃~200℃の範囲を走査し、180℃の貯蔵弾性率を測定し、「180℃貯蔵弾性率」とした。
表1に示した組成を有する重合性組成物の適量をPETフィルム上に採取して、実施例1と同様に、均一な膜厚になるように塗布した。その後、実施例1と同様の型を貼り合わせ、同様に重合させ、それぞれの構造体を製造した。なお、表1中の数字の単位は[g]である。
表2に記載したように、式(2)で表わされるポリエチレングリコールジアクリレートにおいて、繰り返し単位数mを14に固定し、ウレタン(メタ)アクリレート(a)との比を、更にポリエチレングリコールジアクリレートが多い方に変化させて評価した。重合性組成物や構造体の製造方法は実施例1と同様であった。表2に記載の量は[質量部]である。結果も合わせて表2に示す。
また、表1中の実施例3、実施例4及び比較例2については、参考のために表2にも記載した。
また、180℃貯蔵弾性率は、実施例8、9、3、4は、全て0.5GPa未満(実際には0.48GPa以下)であった。
重合性組成物を同一にして、表面の構造の違いによる差を検討した。すなわち、実施例3と比較例2のそれぞれの重合性組成物を用い、特殊な表面微細構造を有する構造体に代えて、フラットな表面を有する構造体(型を貼り合わせて型を転写しない構造体)を用いて評価を行なった。
表3中、「耐汚染性(目視判定)」は、前記した<耐汚染性の評価方法と判定基準>の中の「指紋汚れを目視したときの状態」の判定基準に従って判定した。
耐汚染性は、比較例2の重合性組成物は、本発明の微細構造の表面では「×」であったが(比較例2)、フラット面では「◎」となり(参考例2)、特定の表面構造であるが故に耐汚染性が低下していたことが分かった。それに対して、フラット面の参考例2では、耐汚染性が良好なままキープされていた。
また、貯蔵弾性率が特定のときに、表面耐傷性の優れる構造体が得られるということが分かった。
従って、本発明における微細構造の表面である場合に限り、「(メタ)アクリレート化合物全体に対して53質量%以上のポリエチレングリコールジ(メタ)アクリレートを含有する(メタ)アクリレート化合物を含有する重合性組成物が重合した構造体」の表面で、接触角は18°となり親水性となり、それに伴い耐汚染性が「◎」となった(実施例1)。
[構造体の製造]
<構造体番号1、2、3の製造>
前記式(1)に含まれる「下記の式(2)で示されるポリエチレングリコールジアクリレート」において、m=14のものを、構造体番号1では70質量部、構造体番号2では53質量部、構造体番号3では61質量部含有させた。
2HEA-IPDI-(アジピン酸と1,6-ヘキサンジオールとの重量平均分子量3500の両末端が水酸基のポリエステル)-IPDI-2HEA
上記式において、「2HEA」は2-ヒドロキシエチルアクリレートを示し、「IPDI」はイソホロンジイソシアネートを示し、「-」はイソシアネート基と水酸基の通常の下記の反応による結合を示す。
-NCO + HO- → -NHCOO-
構造体番号1、2、3について、それぞれ上記した成分を均一になるまで撹拌混合して、それぞれの重合性組成物を得た。表4に成分組成をまとめた。なお、表4中の数字の単位は「質量部」である。
表4に示した組成を有する重合性組成物を上記と同様にして得て、その適量をPETフィルム上に採取して、実施例1と同様に、均一な膜厚になるように塗布した。その後、実施例1と同様の型を貼り合わせ、同様に重合させ、それぞれの構造体を製造した。なお、表4中の数字の単位は「質量部」である。
フッ素系界面活性剤(b)は、前記式(F)において、R1はFであり、R2はHであり、R3はHであり、Xは「-CH2CH2O-」であり、p=6、q=5のものである。
フッ素系界面活性剤(c)は、前記式(F)において、R1はFであり、R2はHであり、R3はHであり、Xは「-CH2CH2O-」であり、p=6、q=10のものである。
構造体番号7~9は、構造体番号3の製造において、フッ素系界面活性剤(a)に代えて、構造体番号7ではフッ素系界面活性剤(d):FL-100-100st(信越化学社製)を、構造体番号8ではシリコン系潤滑剤A:X-22-164AS(信越化学社製)を、構造体番号9ではシリコン系潤滑剤B:X-24-8201(信越化学社製)を用いた以外は構造体番号3と同様に製造した。
また、シリコン系潤滑剤A(X-22-164AS(信越化学社製))は、メタクリル酸で両末端を変性したポリジメチルシロキサンであり、シリコン系潤滑剤B(X-24-8201(信越化学社製))は、メタクリル酸で片末端を変性したポリジメチルシロキサンである。
構造体番号10は、フッ素系界面活性剤を含有しない点以外は構造体番号1と同様に製造した。
構造体番号11は、フッ素系界面活性剤を含有しない点以外は構造体番号2と同様に製造した。
構造体番号12は、フッ素系界面活性剤を含有しない点以外は構造体番号3と同様に製造した。
得られた構造体を以下の方法で評価した。結果を表4に示す。
構造体の表面上を、新東科学(株)社製の表面試験機ドライボギアTYPE-14DRを用い、25mm円柱の平滑な断面にスチールウール#0000を均一に貼り付け、荷重400gをかけながら、速度10cm/秒で10往復させたときの傷の付き具合を観察した。
前記実施例1~9等の判定基準「1」~「5」に、更に優れる「6」を追加した以下の基準で判定し、6を極めて良好、4~5を良好、3をやや良好、2以下を不良、とした。
6:引掻き傷なし
5:数本未満の引掻き傷あり
4:数本から10本の引掻き傷あり
3:25mm円柱の半分に引掻き傷あり
2:25mm円柱の2/3に引掻き傷あり
1:25mm円柱の全面に引掻き傷あり
<耐汚染性の評価方法と判定基準>
「反射率」と「耐汚染性」の測定方法については、前記した実施例1~9等の測定方法と同様である。
以下の基準で判定し、反射率の上昇が、0.2ポイント以下(☆、◎、○)を「良好」(☆を「極めて良好」)、0.2ポイントより大きく0.3ポイント以下(△)を「やや良好」、0.3ポイントを超えるもの(×)を「不良」と判断した。
前記実施例1~9等の4段階の判定基準に対して、最上位に「☆」と最下位に「××」とを加えて6段階で評価した。また、「☆」と区別するため、「◎」の判定基準を詳しく設定した。4段階分の重複部分(◎、○、△、×)については、前記した実施例1~9等の判定基準に対して変更はない。
なお、反射率の上昇値と指紋汚れを目視で観察したときの状態はおおむね以下の通りだった。
☆ :0.1ポイント以下。指紋汚れが、5往復後、正面から観察できないし斜めからでも観察できないものの内、水拭き取り3回の往復時点で、正面から観察できないし斜めからでも全く観察できない。
◎ :0.1ポイント以下。指紋汚れが、5往復後、正面から観察できないし斜めからでも観察できない。水拭き取り3回の往復時点では、指紋汚れが正面又は斜めから観察できる。
○ :0.1ポイントより大きく0.2ポイント以下。指紋汚れが正面から観察できないが斜めからわずかに観察できる。
△ :0.2ポイントより大きく0.3ポイント以下。指紋汚れが正面から観察できないが斜めからでは観察できる。
× :0.3ポイントより大きく0.5ポイント以下、指紋汚れが正面からでも観察できる。
××:0.5ポイントより大きい。指紋汚れが正面からでも観察でき。
<貯蔵弾性率>
<180℃貯蔵弾性率>
「接触角」、「貯蔵弾性率」及び「180℃貯蔵弾性率」の測定方法・定義については、前記した実施例1~9等の測定方法・定義と同様である。
構造体番号1ないし6に配合されたフッ素系界面活性剤(a)、(b)、(c)は何れも、パーフルオロアルキルエチレンオキサイド付加物である。
2 型
3 基材
4 ローラー
5 構造体
6 硬化装置
7 支持ローラー
Claims (17)
- 表面に、平均高さ100nm以上1000nm以下の凸部又は平均深さ100nm以上1000nm以下の凹部を有し、その凸部又は凹部が、少なくともある一の方向に対し平均周期50nm以上400nm以下で存在する構造体であって、該構造体が、光照射、電子線照射及び/又は加熱によって、(メタ)アクリレート化合物を含有する重合性組成物が重合したものであって、該(メタ)アクリレート化合物が、該(メタ)アクリレート化合物全体に対して、53質量%以上のポリエチレングリコールジ(メタ)アクリレートを含有し、かつ、該構造体が、25℃における貯蔵弾性率が2GPa以下及び/又は180℃における貯蔵弾性率が0.5GPa未満のものであることを特徴とする構造体。
- 上記(メタ)アクリレート化合物が、更に、ウレタン(メタ)アクリレートを含有する請求項1又は請求項2に記載の構造体。
- 上記ウレタン(メタ)アクリレートが、4官能以上のウレタン(メタ)アクリレートを含有するものであり、該4官能以上のウレタン(メタ)アクリレートが、多価イソシアネート化合物の実質的に全てのイソシアネート基に、分子中に1個の水酸基と2個以上の(メタ)アクリル基を有する化合物の該水酸基が反応してなるものを含有する請求項3に記載の構造体。
- 上記重合性組成物が、更に、アルキレンオキサイド繰り返し構造とフルオロアルキル基とを有するフッ素系界面活性剤を含有するものである請求項1ないし請求項4の何れかの請求項に記載の構造体。
- 上記フルオロアルキル基の炭素数が2以上18以下である請求項5に記載の構造体。
- 上記フルオロアルキル基がパーフルオロアルキル基である請求項5又は請求項6に記載の構造体。
- 上記アルキレンオキサイド繰り返し構造の繰り返し数が、4以上20以下である請求項5ないし請求項7の何れかの請求項に記載の構造体。
- 20℃における水の接触角が35°以下となる表面を有する請求項1ないし請求項9の何れかの請求項に記載の構造体。
- 光の反射防止用及び/又は光の透過改良用である請求項1ないし請求項10の何れかの請求項に記載の構造体。
- 請求項1ないし請求項11の何れかの請求項に記載の構造体の製造方法であって、表面に、平均高さ100nm以上1000nm以下の凹部又は平均深さ100nm以上1000nm以下の凸部を有し、その凹部又は凸部が、少なくともある一の方向に対し平均周期50nm以上400nm以下で存在する型に、重合性組成物を供給し、その上から基材を圧着し、該重合性組成物を硬化後、型から剥離することを特徴とする構造体の製造方法。
- 上記重合性組成物が、更に、アルキレンオキサイド繰り返し構造とフルオロアルキル基とを有するフッ素系界面活性剤を含有するものである請求項12に記載の構造体の製造方法。
- 請求項1ないし請求項11の何れかの請求項に記載の構造体形成用の重合性組成物であって、(メタ)アクリレート化合物を含有し、該(メタ)アクリレート化合物が該(メタ)アクリレート化合物全体に対して53質量%以上のポリエチレングリコールジ(メタ)アクリレートを含有するものであることを特徴とする重合性組成物。
- 上記重合性組成物が、更に、アルキレンオキサイド繰り返し構造とフルオロアルキル基とを有するフッ素系界面活性剤を含有するものである請求項14に記載の重合性組成物。
- 請求項1ないし請求項11の何れかの請求項に記載の構造体形成用の重合性組成物よりなるものであって、該重合性組成物が(メタ)アクリレート化合物を含有し、該(メタ)アクリレート化合物が該(メタ)アクリレート化合物全体に対して53質量%以上のポリエチレングリコールジ(メタ)アクリレートを含有するものであることを特徴とする反射防止体形成材料。
- 上記重合性組成物が、更に、アルキレンオキサイド繰り返し構造とフルオロアルキル基とを有するフッ素系界面活性剤を含有するものである請求項16に記載の反射防止体形成材料。
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Also Published As
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US20140065367A1 (en) | 2014-03-06 |
CN103534619A (zh) | 2014-01-22 |
KR20140037092A (ko) | 2014-03-26 |
JP2012242525A (ja) | 2012-12-10 |
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