WO2018151060A1 - Film antisalissure - Google Patents

Film antisalissure Download PDF

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Publication number
WO2018151060A1
WO2018151060A1 PCT/JP2018/004764 JP2018004764W WO2018151060A1 WO 2018151060 A1 WO2018151060 A1 WO 2018151060A1 JP 2018004764 W JP2018004764 W JP 2018004764W WO 2018151060 A1 WO2018151060 A1 WO 2018151060A1
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Prior art keywords
antifouling film
polymer layer
polymerizable composition
antifouling
weight
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PCT/JP2018/004764
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English (en)
Japanese (ja)
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芝井　康博
賢 厚母
健一郎 中松
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シャープ株式会社
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Priority to JP2018568505A priority Critical patent/JP6778768B2/ja
Publication of WO2018151060A1 publication Critical patent/WO2018151060A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/282—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing two or more oxygen atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B32B3/30—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by a layer formed with recesses or projections, e.g. hollows, grooves, protuberances, ribs
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films

Definitions

  • the present invention relates to an antifouling film. More specifically, the present invention relates to an antifouling film having a nanometer-sized uneven structure.
  • JP 2012-52125 A International Publication No. 2007/040159 JP 2012-141355 A
  • the present inventors examined, in the polymer layer which comprises the uneven structure of an optical film, by devising the constituent material, in addition to antifouling property, various characteristics also improved. It was found that a conductive film can be realized. Specifically, it has been found that if a release agent is blended as a constituent material of the polymer layer, the antifouling property is enhanced, and if a polyfunctional acrylate is blended, the abrasion resistance is enhanced. Furthermore, it was found that if the crosslink density of the polymer layer is increased and the glass transition temperature is lowered, the abrasion resistance can be remarkably increased.
  • the crosslink density is increased, but at the same time, the glass transition temperature is likely to be increased, so that there is a limit in improving the abrasion resistance.
  • the crosslink density tends to increase as the number of functional groups increases, but at the same time, the molecular weight increases and the viscosity tends to increase, so the compatibility between the polyfunctional acrylate and the release agent is low, and the desired It turned out that antifouling property and abrasion resistance are hard to be obtained.
  • the adhesiveness of the polymer layer of an antifouling film and a base material is inadequate.
  • the conventional antifouling film has the problem of improving both the antifouling property, the abrasion resistance, and the adhesion.
  • no means for solving the above problem has been found.
  • both the antifouling property, the abrasion resistance and the adhesion cannot be improved, and there is room for improvement.
  • This invention is made
  • the inventors of the present invention have made various studies on antifouling films having excellent antifouling properties, abrasion resistance, and adhesion.
  • a polyfunctional compound having a predetermined number of ethylene oxide groups As a constituent material of the polymer layer, a polyfunctional compound having a predetermined number of ethylene oxide groups. It has been found that acrylate, a release agent, and 2- (2-vinyloxyethoxy) ethyl acrylate are blended in a predetermined ratio. Thus, the inventors have conceived that the above problems can be solved brilliantly and have reached the present invention.
  • a base material there is provided a base material, and a polymer layer that is provided on the surface of the base material and has a concavo-convex structure provided on the surface with a plurality of convex portions provided at a pitch equal to or less than the wavelength of visible light.
  • An antifouling film provided, wherein the polymer layer is a cured product of the polymerizable composition, and the polymerizable composition has 3 to 9 ethylene oxide groups per functional group in terms of active ingredients.
  • an antifouling film containing 25 to 55% by weight of a polyfunctional acrylate, 0.5 to 10% by weight of a release agent, and 10 to 60% by weight of 2- (2-vinyloxyethoxy) ethyl acrylate Good.
  • the release agent may contain a fluorine-containing compound as an active ingredient.
  • the fluorine-containing compound may have a perfluoropolyether group.
  • the polymerizable composition may further contain a monofunctional amide monomer.
  • the monofunctional amide monomer may contain N, N-dimethylacrylamide.
  • the contact angle of water with respect to the surface of the polymer layer may be 130 ° or more, and the contact angle of hexadecane may be 30 ° or more.
  • the polymer layer may have a thickness of 5.0 to 20.0 ⁇ m.
  • the average pitch of the plurality of convex portions may be 100 to 400 nm.
  • the average height of the plurality of convex portions may be 50 to 600 nm.
  • the average aspect ratio of the plurality of convex portions may be 0.8 to 1.5.
  • the antifouling film excellent in both antifouling property, abrasion resistance, and adhesiveness can be provided.
  • FIG. 2 is a schematic plan view showing a polymer layer in FIG. 1. It is a cross-sectional schematic diagram for demonstrating the example of the manufacturing method of the antifouling film of embodiment.
  • X to Y means “X or more and Y or less”.
  • FIG. 1 is a schematic cross-sectional view showing the antifouling film of the embodiment.
  • FIG. 2 is a schematic plan view showing the polymer layer in FIG.
  • the antifouling film 1 includes a base material 2 and a polymer layer 3 disposed on the surface of the base material 2.
  • the material of the substrate 2 examples include resins such as triacetyl cellulose (TAC), polyethylene terephthalate (PET), and methyl methacrylate (MMA).
  • the base material 2 may appropriately contain additives such as a plasticizer in addition to the above materials.
  • the surface of the base material 2 (the surface on the polymer layer 3 side) may be subjected to easy adhesion treatment (for example, primer treatment).
  • a triacetyl cellulose film subjected to easy adhesion treatment may be used. it can.
  • the surface of the substrate 2 (the surface on the polymer layer 3 side) may be subjected to saponification treatment, and for example, a triacetyl cellulose film subjected to saponification treatment can be used.
  • the antifouling film 1 is attached to a display device including a polarizing plate such as a liquid crystal display device
  • the base material 2 may constitute a part of the polarizing plate.
  • the thickness of the substrate 2 is preferably 50 to 100 ⁇ m from the viewpoint of ensuring transparency and workability.
  • the polymer layer 3 has a concavo-convex structure in which a plurality of convex portions (projections) 4 are provided with a pitch P (distance between vertices of adjacent convex portions 4) P or less of the wavelength (780 nm) of visible light, that is, a moth-eye structure ( ⁇ ⁇ Of the structure) on the surface. Therefore, the antifouling film 1 can exhibit excellent antireflection properties (low reflectivity) due to the moth-eye structure.
  • the thickness T of the polymer layer 3 is preferably thin from the viewpoint of orienting active ingredients in the release agent described later at a high concentration on the surface of the polymer layer 3 (surface opposite to the substrate 2). Specifically, the thickness T of the polymer layer 3 is preferably 5.0 to 20.0 ⁇ m, more preferably 8.0 to 12.0 ⁇ m. As shown in FIG. 1, the thickness T of the polymer layer 3 indicates the distance from the surface on the base 2 side to the apex of the convex portion 4.
  • the shape of the convex portion 4 for example, a shape (bell shape) constituted by a columnar lower portion and a hemispherical upper portion, a cone shape (cone shape, conical shape), or the like that narrows toward the tip ( Taper shape).
  • a shape constituted by a columnar lower portion and a hemispherical upper portion
  • a cone shape cone shape, conical shape
  • Taper shape the shape of the convex portion 4
  • the bottom of the gap between adjacent convex portions 4 has an inclined shape, but it may have a horizontal shape without being inclined.
  • the average pitch of the plurality of convex portions 4 is preferably 100 to 400 nm, more preferably 100 to 200 nm, from the viewpoint of sufficiently preventing the occurrence of optical phenomena such as moire and rainbow unevenness.
  • the average pitch of the plurality of convex portions 4 is the average of the pitches of all adjacent convex portions (P in FIG. 1) in a 1 ⁇ m square region of a planar photograph taken with a scanning electron microscope. Points to the value.
  • the average height of the plurality of protrusions 4 is preferably 50 to 600 nm, more preferably 100 to 300 nm, from the viewpoint of achieving a preferable average aspect ratio of the plurality of protrusions 4 described later.
  • the average height of the plurality of convex portions 4 is the average of the heights (H in FIG. 1) of ten consecutive convex portions arranged in a cross-sectional photograph taken with a scanning electron microscope. Points to the value.
  • the convex portion having a defect or a deformed portion (such as a portion deformed when preparing a measurement sample) is excluded.
  • the average aspect ratio of the plurality of convex portions 4 is preferably 0.8 to 1.5, more preferably 1.0 to 1.3.
  • the average aspect ratio of the plurality of convex portions 4 is less than 0.8, the occurrence of optical phenomena such as moire and rainbow unevenness cannot be sufficiently prevented, and excellent antireflection properties may not be obtained.
  • the average aspect ratio of the plurality of convex portions 4 is larger than 1.5, the processability of the concavo-convex structure is reduced, sticking occurs, or the transfer condition when forming the concavo-convex structure is deteriorated (described later).
  • the mold 6 may be clogged or wound.
  • the average aspect ratio of the plurality of convex portions 4 refers to the ratio (height / pitch) between the average height and the average pitch of the plurality of convex portions 4 described above.
  • the convex portions 4 may be arranged randomly or regularly (periodically).
  • the arrangement of the protrusions 4 may be periodic, but due to the advantage that unnecessary diffracted light is not generated due to the periodicity, the arrangement of the protrusions 4 is periodic as shown in FIG. It is preferable that there is no (random).
  • the polymer layer 3 is a cured product of the polymerizable composition.
  • the polymer layer 3 include a cured product of an active energy ray-curable polymerizable composition, a cured product of a thermosetting polymerizable composition, and the like.
  • the active energy ray indicates ultraviolet rays, visible rays, infrared rays, plasma, or the like.
  • the polymer layer 3 is preferably a cured product of an active energy ray-curable polymerizable composition, and more preferably a cured product of an ultraviolet curable polymerizable composition.
  • the polymerizable composition comprises 25 to 55% by weight of a polyfunctional acrylate having 3 to 9 ethylene oxide groups per functional group (hereinafter also referred to as component A) in terms of active ingredient, and a release agent (hereinafter referred to as component). 0.5-10% by weight) and 2- (2-vinyloxyethoxy) ethyl acrylate (hereinafter also referred to as Component C) 10-60% by weight.
  • the active ingredient of the polymerizable composition refers to a constituent component of the polymer layer 3 after curing, and excludes components (for example, solvents) that do not contribute to the curing reaction (polymerization reaction). .
  • the polymerizable composition may contain other components as long as it contains components A to C in the proportions described above.
  • Component A the crosslinking density of the polymer layer 3 is increased, and appropriate hardness (elasticity) is imparted, so that the abrasion resistance is increased. Furthermore, since the interaction with the base material 2 is enhanced by the high polarity of the ethylene oxide group, the adhesion is enhanced.
  • the abrasion resistance is considered to correlate with the crosslinking density and glass transition temperature of the polymer layer 3, and if the crosslinking density is increased and the glass transition temperature is lowered, the abrasion resistance can be remarkably enhanced. For example, if the polymerizable composition contains a polyfunctional acrylate having a propylene oxide group, the glass transition temperature will be higher than when a polyfunctional acrylate having an ethylene oxide group is contained.
  • the propylene oxide group (the same applies to the hydrocarbon group) has a lower polarity than the ethylene oxide group, and the interaction with the substrate 2 is reduced, so that the adhesion is reduced. Therefore, in this embodiment, an ethylene oxide group is selected from the viewpoint of abrasion resistance and adhesion.
  • the polyfunctional acrylate refers to an acrylate having two or more acryloyl groups per molecule.
  • Component A has 2 or more functional groups.
  • the preferable upper limit of the number of functional groups of Component A is 9.
  • the number of functional groups of component A refers to the number of acryloyl groups per molecule.
  • the number of ethylene oxide groups of component A is 3 to 9, preferably 3 to 7, more preferably 4 to 5, per functional group.
  • the number of ethylene oxide groups is less than 3 per functional group, the elasticity of the polymer layer 3 is insufficient (because the hardness becomes too high), so that the abrasion resistance is lowered.
  • the number of ethylene oxide groups is more than 9 per functional group, the crosslink density of the polymer layer 3 becomes too low, so that the abrasion resistance is lowered.
  • the number of ethylene oxide groups per functional group refers to (number of ethylene oxide groups per molecule) / (number of acryloyl groups per molecule).
  • the content of component A in the polymerizable composition is 25 to 55% by weight, preferably 30 to 50% by weight, more preferably 35 to 45% by weight, in terms of active ingredient.
  • the content of component A in the polymerizable composition is less than 25% by weight in terms of active ingredient, the elasticity of the polymer layer 3 is insufficient (because the hardness becomes too high), resulting in a decrease in abrasion resistance. To do.
  • the interaction with the base material 2 by an ethylene oxide group becomes inadequate, adhesiveness falls.
  • the content of component A in the polymerizable composition is higher than 55% by weight in terms of active ingredient, the crosslink density of the polymer layer 3 becomes too low, so that the abrasion resistance is lowered.
  • the sum total of the content rate of several component A should just be in the said range in conversion of an active ingredient.
  • component A examples include polyethylene glycol (300) diacrylate, polyethylene glycol (400) diacrylate, polyethylene glycol (600) diacrylate, ethoxylated pentaerythritol tetraacrylate, and ethoxylated polyglycerin polyacrylate.
  • Known examples of polyethylene glycol (300) diacrylate include “New Frontier (registered trademark) PE-300” manufactured by Daiichi Kogyo Seiyaku Co., Ltd. (number of functional groups: 2, number of ethylene oxide groups: 3 per functional group) Etc.
  • polyethylene glycol (400) diacrylate examples include “NK Ester A-400” (number of functional groups: 2, number of ethylene oxide groups: 4.5 per functional group) manufactured by Shin-Nakamura Chemical Co., Ltd. Can be mentioned.
  • polyethylene glycol (600) diacrylate examples include “NK Ester A-600” (number of functional groups: 2, number of ethylene oxide groups: 7 per functional group) manufactured by Shin-Nakamura Chemical Co., Ltd.
  • ethoxylated pentaerythritol tetraacrylate examples include “NK ester ATM-35E” (number of functional groups: 4, number of ethylene oxide groups: 8.75 per functional group) manufactured by Shin-Nakamura Chemical Co., Ltd.
  • ethoxylated polyglycerin polyacrylate examples include “NK Economer (registered trademark) A-PG5054E” (number of functional groups: 9, number of ethylene oxide groups: 6 per functional group) manufactured by Shin-Nakamura Chemical Co., Ltd. Is mentioned.
  • Component B the active component in Component B is oriented on the surface of the polymer layer 3 (the surface on the side opposite to the substrate 2), and the surface free energy of the polymer layer 3 is reduced. Will increase. Furthermore, the slipping property is increased, and as a result, the abrasion resistance is increased.
  • the content of component B in the polymerizable composition is 0.5 to 10% by weight, preferably 1 to 5% by weight, more preferably 1.5 to 3% by weight, in terms of active ingredient.
  • the content of component B in the polymerizable composition is less than 0.5% by weight in terms of active ingredient, the amount of active ingredient that is oriented on the surface of polymer layer 3 (surface opposite to substrate 2) Therefore, the antifouling property decreases. Further, the slipperiness is lowered, and as a result, the abrasion resistance is lowered.
  • component B in the polymerizable composition When the content of component B in the polymerizable composition is higher than 10% by weight in terms of active ingredient, the compatibility with components A and C becomes too low, and the active ingredient in component B is polymer layer 3 Therefore, the antifouling property and the abrasion resistance are deteriorated. Further, along with this, the active ingredient in the component B is likely to be distributed on the base material 2 side of the polymer layer 3, so that the adhesion is lowered. Furthermore, bleeding out easily occurs in a high temperature / high humidity environment, and the optical characteristics are deteriorated. When the polymerizable composition contains a plurality of types of component B, the total content of the plurality of components B may be within the above range in terms of effective components.
  • Component B preferably contains a fluorine-containing compound (a compound containing a fluorine atom in the molecule) as an active ingredient. That is, component B preferably contains a fluorine-based mold release agent.
  • Component B includes, in addition to the fluorine-based mold release agent, for example, a silicon-type mold release agent, a phosphate ester-type mold release agent, and the like. Compared with the agent, the antifouling property and abrasion resistance are further increased.
  • the fluorine-containing compound (the active ingredient in the fluorine-based mold release agent) may have a perfluoropolyether group or a perfluoroalkyl group, but may have a perfluoropolyether group. preferable.
  • a release agent having a perfluoropolyether group a release agent having no perfluoropolyether group (for example, a release agent having a perfluoroalkyl group, a silicon release agent, a phosphate ester release agent).
  • antifouling properties and abrasion resistance are further increased.
  • fluorine-based mold release agents include “Fomblin (registered trademark) MT70” and “Fomblin AD1700” manufactured by Solvay, “Optool (registered trademark) DAC” and “Optool DAC-HP” manufactured by Daikin Industries, Ltd. "Megafac (registered trademark) RS-76-NS” manufactured by DIC, “CHEMINOX (registered trademark) FAAC-4", “CHEMINOX FAAC-6” manufactured by Unimatec.
  • silicone release agents include “BYK (registered trademark) -UV3500”, “BYK-UV3570”, “BYK-UV3575”, “BYK-UV3576” manufactured by Big Chemie Japan, manufactured by Daicel Ornex Corporation. "EBECRYL (registered trademark) 350” and the like.
  • NIKKOL registered trademark
  • TDP-2 manufactured by Nikko Chemicals, Inc.
  • Component C is a heterogeneous polymerizable monomer in which a vinyl ether group and an acryloyl group coexist in the molecule, the number of functional groups is 2, and the number of ethylene oxide groups is 1 per functional group.
  • Component C has a lower molecular weight and a lower glass transition temperature than ordinary monomers (for example, polyfunctional acrylates). Therefore, by blending Component C in the polymerizable composition, the crosslinking density of the polymer layer 3 is increased. And it becomes easy to control the glass transition temperature over a wide range.
  • the glass transition temperature of the polymer layer 3 is not sufficiently lowered and the abrasion resistance is improved only by blending the usual polyfunctional acrylate and component C into the polymerizable composition. It turned out that an effect was hard to be acquired.
  • the glass transition temperature is increased while increasing the crosslinking density of the polymer layer 3 by using the component A having a relatively low glass transition temperature among the polyfunctional acrylates and the component C in combination. Since it can be lowered, the abrasion resistance is remarkably increased.
  • component C since component C has a low viscosity, it has high compatibility with components A and B (particularly component B), and also functions as a compatibilizing agent.
  • the antifouling film 1 not only having excellent abrasion resistance but also excellent antifouling properties and adhesion is realized. can do.
  • adhesion even when a triacetyl cellulose film that has not been subjected to surface treatment (for example, easy adhesion treatment) is used as the substrate 2, a remarkable effect is obtained.
  • the content of component C in the polymerizable composition is 10 to 60% by weight, preferably 15 to 55% by weight, more preferably 20 to 50% by weight, in terms of active ingredient.
  • the content of component C in the polymerizable composition is less than 10% by weight in terms of active ingredient, the compatibility with components A and B (particularly component B) becomes too low, and effective in component B Since the components are not uniformly oriented on the surface of the polymer layer 3 (the surface opposite to the substrate 2), the antifouling property and the abrasion resistance are lowered. Furthermore, since the component B is easily insolubilized and the polymer layer 3 becomes cloudy, the haze of the polymer layer 3 increases and the transparency decreases.
  • the content rate of the component C in a polymeric composition is higher than 60 weight% in conversion of an active ingredient, since the content rate of the component A in a polymeric composition falls relatively, abrasion resistance falls.
  • Component C examples include “VEEA” (molecular weight: 186, glass transition temperature: 39 ° C., viscosity: 3.65 cP) manufactured by Nippon Shokubai Co., Ltd.
  • the polymerizable composition may further contain a monofunctional amide monomer.
  • the monofunctional amide monomer is preferably used as a compatibilizing agent because it has high compatibility with the components A and B as in the case of the component C.
  • the curing shrinkage of the polymerizable composition is suppressed, and the cohesive force with the substrate 2 is increased, so that the adhesion is further increased.
  • the polymerizable composition contains a monofunctional amide monomer, the crosslinking density of the polymer layer 3 becomes low and the glass transition temperature tends to be high, so that the abrasion resistance tends to be lowered.
  • the crosslink density of polymer layer 3 is increased while ensuring compatibility with components A and B, and the glass transition temperature is increased. Can be lowered. Therefore, even when the polymerizable composition contains a monofunctional amide monomer, the antifouling film 1 having excellent antifouling properties and adhesion can be realized without impairing the abrasion resistance.
  • the monofunctional amide monomer refers to a monomer having an amide group and one acryloyl group per molecule.
  • Examples of the monofunctional amide monomer include N, N-dimethylacrylamide, N-acryloylmorpholine, N, N-diethylacrylamide, N- (2-hydroxyethyl) acrylamide, diacetone acrylamide, Nn-butoxymethylacrylamide and the like. Is mentioned.
  • a known example of N, N-dimethylacrylamide is “DMAA (registered trademark)” manufactured by KJ Chemicals.
  • Known examples of N-acryloylmorpholine include “ACMO (registered trademark)” manufactured by KJ Chemicals.
  • Known examples of N, N-diethylacrylamide include “DEAA (registered trademark)” manufactured by KJ Chemicals.
  • N- (2-hydroxyethyl) acrylamide examples include “HEAA (registered trademark)” manufactured by KJ Chemicals.
  • HEAA registered trademark
  • diacetone acrylamide examples include “DAAM (registered trademark)” manufactured by Nippon Kasei Co., Ltd.
  • NBMA Nn-butoxymethylacrylamide
  • the monofunctional amide monomer preferably contains N, N-dimethylacrylamide. According to such a configuration, the viscosity of the monofunctional amide monomer is reduced, and the compatibility with components A and B is further increased.
  • the polymerizable composition may further contain a polymerization initiator.
  • a polymerization initiator thereby, the sclerosis
  • a polymerization initiator As a polymerization initiator, a photoinitiator, a thermal polymerization initiator, etc. are mentioned, for example, Among these, a photoinitiator is preferable.
  • the photopolymerization initiator is active with respect to active energy rays, and is added to initiate a polymerization reaction for polymerizing the monomer.
  • photopolymerization initiator examples include radical polymerization initiators, anionic polymerization initiators, and cationic polymerization initiators.
  • photopolymerization initiators include acetophenones such as p-tert-butyltrichloroacetophenone, 2,2′-diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one; Ketones such as benzophenone, 4,4′-bisdimethylaminobenzophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone; benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc.
  • Benzoin ethers such as benzyl dimethyl ketal and hydroxycyclohexyl phenyl ketone; 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide; Scan (2,4,6-trimethylbenzoyl) - acylphosphine oxides such as triphenylphosphine oxide; 1-hydroxy - cyclohexyl - phenyl - phenones such as ketones, and the like.
  • 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide examples include “LUCIRIN (registered trademark) TPO” and “IRGACURE (registered trademark) TPO” manufactured by IGM Resins.
  • Known examples of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide include “IRGACURE 819” manufactured by IGM Resins.
  • Known examples of 1-hydroxy-cyclohexyl-phenyl-ketone include “IRGACURE 184” manufactured by IGM Resins.
  • the polymerizable composition may further contain a solvent (component other than the active ingredient).
  • the solvent may be contained together with the active ingredient in the components A to C, or may be contained separately from the components A to C.
  • solvent examples include alcohol (carbon number: 1 to 10: for example, methanol, ethanol, n- or i-propanol, n-, sec-, or t-butanol, benzyl alcohol, octanol, etc.), ketone (carbon number).
  • alcohol carbon number: 1 to 10: for example, methanol, ethanol, n- or i-propanol, n-, sec-, or t-butanol, benzyl alcohol, octanol, etc.
  • ketone carbon number
  • 3 to 8 For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, dibutyl ketone, cyclohexanone, etc.), ester or ether ester (carbon number 4 to 10: for example, ethyl acetate, butyl acetate, ethyl lactate, etc.), ⁇ - Butyrolactone, ethylene glycol monomethyl acetate, propylene glycol monomethyl acetate, ether (4 to 10 carbon atoms: eg EG monomethyl ether (methyl cellosorb), EG monoethyl ether (ethyl cellosorb)), diethylene glycol Butyl ether (butyl cellosolob), propylene glycol monomethyl ether, etc.), aromatic hydrocarbon (carbon number 6-10: for example, benzene, toluene, xylene, etc.), amide (carbon number 3-10: for example, di
  • the contact angle of water is 130 ° or more and the contact angle of hexadecane is 30 ° or more with respect to the surface of the polymer layer 3 (surface opposite to the substrate 2). Is preferred.
  • the use of the antifouling film 1 is not particularly limited as long as the excellent antifouling property is utilized, and for example, an optical film such as an antireflection film may be used. Such an antireflection film contributes to the improvement of visibility by being attached inside or outside the display device.
  • the antifouling property of the antifouling film 1 may mean that the dirt adhering to the surface of the polymer layer 3 (the surface opposite to the substrate 2) can be easily removed. It may mean that dirt does not easily adhere to the surface 3 (surface opposite to the substrate 2). Moreover, according to the antifouling film 1, the antifouling property higher than the conventional antifouling film (for example, fluorine-containing film) which has normal surfaces, such as a flat surface, is acquired by the effect by a moth eye structure.
  • the conventional antifouling film for example, fluorine-containing film
  • the antifouling film 1 is produced, for example, by the following production method.
  • FIG. 3 is a schematic cross-sectional view for explaining an example of a method for producing the antifouling film of the embodiment.
  • the polymerizable composition 5 is applied on the surface of the substrate 2.
  • Examples of a method for applying the polymerizable composition 5 include a method in which the polymerizable composition 5 is applied by a spray method, a gravure method, a slot die method, a bar coating method, or the like.
  • a coating method of the polymerizable composition 5 a method of coating by a gravure method or a slot die method is preferable from the viewpoint of making the film thickness uniform and improving the productivity.
  • the polymerizable composition 5 contains at least the components A to C in the proportions described above.
  • a heat treatment drying treatment for removing the solvent may be performed after the application of the polymerizable composition 5.
  • the heat treatment is preferably performed at a temperature equal to or higher than the boiling point of the solvent.
  • Examples of the curing method of the polymerizable composition 5 include a method by irradiation with active energy rays, heating, and the like. Curing of the polymerizable composition 5 is preferably performed by irradiation with active energy rays, and more preferably by irradiation with ultraviolet rays. Irradiation of the active energy ray may be performed from the base material 2 side of the polymerizable composition 5 or from the mold 6 side of the polymerizable composition 5. Moreover, the frequency
  • the above processes 1 to 4 can be performed continuously and efficiently.
  • the mold 6 for example, one produced by the following method can be used. First, aluminum used as the material of the mold 6 is formed on the surface of the support substrate by sputtering. Next, a female mold (mold 6) having a moth-eye structure can be produced by alternately repeating anodic oxidation and etching on the formed aluminum layer. At this time, the concavo-convex structure of the mold 6 can be changed by adjusting the time for performing anodic oxidation and the time for performing etching.
  • the material for the supporting base examples include glass; metals such as stainless steel and nickel; polypropylene, polymethylpentene, and cyclic olefin-based polymers (typically, norbornene-based resins such as “Zeonor” manufactured by ZEON Corporation. (Registered Trademark) "," Arton (Registered Trademark) "manufactured by JSR Corporation) and the like; polycarbonate resins; polyethylene terephthalate, polyethylene naphthalate, resins such as triacetylcellulose, and the like.
  • Examples of the shape of the mold 6 include a flat plate shape and a roll shape.
  • the surface of the mold 6 is preferably subjected to a mold release treatment. Thereby, the metal mold 6 can be easily peeled from the polymer layer 3. Further, since the surface free energy of the mold 6 becomes low, when the substrate 2 is pressed against the mold 6 in the process 2, the active ingredient in the component B is changed to the surface of the polymerizable composition 5 (substrate 2). Can be uniformly oriented on the opposite surface). Furthermore, before the polymerizable composition 5 is cured, it is possible to prevent the active ingredient in the component B from leaving the surface of the polymerizable composition 5 (the surface on the side opposite to the substrate 2). As a result, in the antifouling film 1, the active ingredient in the component B can be uniformly oriented on the surface of the polymer layer 3 (the surface on the side opposite to the substrate 2).
  • Examples of the material used for the mold release treatment of the mold 6 include a fluorine-based material, a silicon-based material, and a phosphate ester-based material.
  • fluorine-based materials include “OPTOOL DSX” and “OPTOOL AES4” manufactured by Daikin Industries, Ltd.
  • the materials used for producing the antifouling film are as follows.
  • ⁇ Mold> What was produced by the following method was used. First, aluminum as a mold material was formed on a 10 cm square glass substrate by a sputtering method. The thickness of the formed aluminum layer was 1.0 ⁇ m. Next, by repeating anodization and etching alternately on the formed aluminum layer, a large number of minute holes (the distance between the bottom points of adjacent holes (recesses) is less than the wavelength of visible light) An anodized layer provided with was formed. Specifically, an anodization, etching, anodization, etching, anodization, etching, anodization, etching, anodization, etching, and anodization are sequentially performed (anodization: 5 times, etching: 4 times) to form an aluminum layer.
  • a large number of minute holes (concave portions) having a shape (tapered shape) that narrows toward the inside of the substrate were formed. As a result, a mold having an uneven structure was obtained.
  • Anodization was performed using oxalic acid (concentration: 0.03% by weight) under conditions of a liquid temperature of 5 ° C. and an applied voltage of 80V. The time for one anodic oxidation was 25 seconds.
  • Etching was performed using phosphoric acid (concentration: 1 mol / l) at a liquid temperature of 30 ° C. The time for performing one etching was set to 25 minutes. When the mold was observed with a scanning electron microscope, the depth of the recess was 290 nm.
  • the mold surface was subjected to a mold release treatment in advance by “OPTOOL AES4” manufactured by Daikin Industries, Ltd.
  • Number of functional groups 2 Number of ethylene oxide groups: 7 per functional group Active ingredient: 100% by weight ⁇ "ATM-35E” "NK ester ATM-35E” manufactured by Shin-Nakamura Chemical Co., Ltd.
  • Number of functional groups 2 Number of ethylene oxide groups: 11.5 per functional group Active ingredient: 100% by weight ⁇ "A-DPH” “NK Ester A-DPH” manufactured by Shin-Nakamura Chemical Co., Ltd.
  • Number of functional groups 6 Number of ethylene oxide groups: 0 (not included) Active ingredient: 100% by weight ⁇ "U-10” “U-10HA” manufactured by Shin-Nakamura Chemical Co., Ltd.
  • Functional group number 10 Number of ethylene oxide groups: 0 (not included) Active ingredient: 100% by weight ⁇ "U-15” “U-15HA” manufactured by Shin-Nakamura Chemical Co., Ltd.
  • Example 1 The antifouling film of Example 1 was produced by the method described in the production method example described above.
  • the polymerizable composition R1 was applied in a band shape on the surface of the substrate 2 (“TAC2”). Then, the polymerizable composition R1 was spread over the entire surface of the substrate 2 using a bar coater. Then, the thing with the polymeric composition R1 apply
  • the surface specification of the antifouling film 1 was as follows. Shape of convex portion 4: Average pitch of bell-shaped convex portion 4: 200 nm Average height of convex part 4: 200 nm Average aspect ratio of convex part 4: 1.0
  • the surface specifications of the antifouling film 1 were evaluated using a scanning electron microscope “S-4700” manufactured by Hitachi High-Technologies Corporation. At the time of evaluation, an osmium coater “Neoc-ST” manufactured by Meiwa Forsys was used, and osmium oxide VIII manufactured by Wako Pure Chemical Industries, Ltd. was formed on the surface of the polymer layer 3 (surface opposite to the substrate 2). (Thickness: 5 nm) was applied.
  • Example 2 to 18 and Comparative Examples 1 to 19 An antifouling film of each example was produced in the same manner as in Example 1 except that the materials were changed as shown in Tables 17 to 24.
  • Hexadecane was dropped onto the surface of the polymer layer of the antifouling film of each example (the surface opposite to the substrate), and the contact angle 10 seconds after the dropping was measured.
  • a contact angle As a contact angle, a portable contact angle meter “PCA-1” manufactured by Kyowa Interface Science Co., Ltd. was used.
  • the first measurement point the central portion of the antifouling film of each example is selected, and as the second and third measurement points, 20 mm or more away from the first measurement point, In addition, two points that are point-symmetric with respect to the first measurement point were selected.
  • the black acrylic board was affixed on the surface on the opposite side to the polymer layer of a base material through the optical adhesion layer with respect to the antifouling film of each example. Then, after attaching a fingerprint to the surface of the polymer layer of the antifouling film of each example (surface opposite to the base material), “Bencot (registered trademark) S-2” manufactured by Asahi Kasei Fibers Co., Ltd. Whether or not the fingerprint was removed by reciprocating rubbing was visually observed in an environment with an illuminance of 100 lx (fluorescent lamp). Judgment criteria were as follows. ⁇ : The fingerprint was completely wiped off, and the remaining wipe was not visible.
  • ⁇ Fingerprints are inconspicuous, but a slight amount of wiping residue was visible when a fluorescent lamp was reflected.
  • X The fingerprint was not wiped off at all. Here, the case where the determination was “ ⁇ ” or “ ⁇ ” was determined to be an acceptable level (excellent fingerprint wiping property).
  • Step wool resistant First, the surface of the polymer layer of the antifouling film of each example (the surface opposite to the base material) was rubbed in a state where a load of 400 g was applied to steel wool “# 0000” manufactured by Nippon Steel Wool. Then, while visually observing in an environment with an illuminance of 100 lx (fluorescent lamp), the number “N” of scratches on the surface of the polymer layer of the antifouling film of each example (surface opposite to the base material) ( Unit: book) was counted. When rubbing with steel wool, a surface property measuring machine “HEIDON-14FW” manufactured by Shinto Kagaku Co., Ltd.
  • Comparative Examples 1 to 10 since Component C was not blended in the polymerizable composition, at least one of antifouling property, abrasion resistance, and adhesion was low.
  • the polymerizable composition contains a monofunctional amide monomer instead of Component C, but has excellent antifouling properties, abrasion resistance, and adhesion. And could not.
  • Comparative Examples 11 to 15 since Component A was not blended in the polymerizable composition, at least one of abrasion resistance and adhesion was low. In Comparative Example 11, since the component B was not blended in the polymerizable composition, the antifouling property was low.
  • Comparative Example 19 since the content of Component B in the polymerizable composition was higher than 10% by weight in terms of active ingredient, the abrasion resistance and adhesion were low. Furthermore, since component B was insolubilized, the transparency was low.
  • One embodiment of the present invention includes a base material, and a polymer layer that is provided on the surface of the base material and includes a polymer layer having a concavo-convex structure on the surface, in which a plurality of convex portions are provided at a pitch equal to or less than the wavelength of visible light.
  • An antifouling film containing 25 to 55% by weight of acrylate, 0.5 to 10% by weight of a release agent, and 10 to 60% by weight of 2- (2-vinyloxyethoxy) ethyl acrylate may be used. According to this aspect, an antifouling film having excellent antifouling properties, abrasion resistance, and adhesion can be realized.
  • the release agent may contain a fluorine-containing compound as an active ingredient. According to such a structure, antifouling property and abrasion resistance are further improved.
  • the fluorine-containing compound may have a perfluoropolyether group. According to such a configuration, it is compared with a release agent having no perfluoropolyether group (for example, a release agent having a perfluoroalkyl group, a silicon release agent, a phosphate ester release agent, etc.). Thus, the antifouling property and abrasion resistance are further increased.
  • a release agent having no perfluoropolyether group for example, a release agent having a perfluoroalkyl group, a silicon release agent, a phosphate ester release agent, etc.
  • the polymerizable composition may further contain a monofunctional amide monomer. According to such a structure, compatibility with the said polyfunctional acrylate and the said mold release agent increases more. Furthermore, the curing shrinkage of the polymerizable composition is suppressed, and the cohesive force with the substrate is increased, so that the adhesion is further increased.
  • the monofunctional amide monomer may contain N, N-dimethylacrylamide. According to such a configuration, the viscosity of the monofunctional amide monomer is decreased, and the compatibility with the polyfunctional acrylate and the release agent is further increased.
  • the contact angle of water with respect to the surface of the polymer layer may be 130 ° or more, and the contact angle of hexadecane may be 30 ° or more. According to such a configuration, the antifouling property is further increased.
  • the polymer layer may have a thickness of 5.0 to 20.0 ⁇ m. According to such a structure, the active ingredient in the said mold release agent orientates with a high density
  • the average pitch of the plurality of convex portions may be 100 to 400 nm. According to such a configuration, occurrence of optical phenomena such as moire and rainbow unevenness is sufficiently prevented.
  • the average height of the plurality of convex portions may be 50 to 600 nm. According to such a configuration, it is possible to achieve both a preferable average aspect ratio of the plurality of convex portions.
  • the average aspect ratio of the plurality of convex portions may be 0.8 to 1.5. According to such a configuration, generation of optical phenomena such as moire and rainbow unevenness is sufficiently prevented, and excellent antireflection properties can be realized. Furthermore, the occurrence of sticking due to a decrease in the workability of the concavo-convex structure and the deterioration of the transfer condition when forming the concavo-convex structure are sufficiently prevented.

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  • Polymers & Plastics (AREA)
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  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
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  • Surface Treatment Of Optical Elements (AREA)
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Abstract

La présente invention concerne un film antisalissure ayant d'excellentes propriétés antisalissure, une excellente résistance à l'abrasion et une excellente adhérence. Ce film antisalissure est pourvu d'un substrat et d'une couche de polymère qui est disposée sur la surface du substrat et qui a une structure irrégulière sur sa surface dans laquelle une pluralité de parties en saillie étant disposées à un pas égal ou inférieur à la longueur d'onde de la lumière visible, la couche de polymère étant un matériau durci d'une composition polymérisable, et la composition polymérisable contenant, en termes d'ingrédients actifs, 25 à 55 % en poids d'un (méth) acrylate polyfonctionnel ayant 3 à 9 groupes d'oxyde d'éthylène pour chaque groupe fonctionnel, 0,5 à 10 % en poids d'un agent de libération, et 10 à 60 % en poids d'acrylate d'éthyle de 2- (2-vinyloxyéthoxy) éthyle.
PCT/JP2018/004764 2017-02-17 2018-02-13 Film antisalissure WO2018151060A1 (fr)

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