Formation method of Anti-fogging and Anti-fouling layer, and formation kit of Anti-fogging and Anti-fouling layer

Abstract

To provide a formation method of an anti-fogging and anti-fouling layer and a formation kit of an anti-fogging and anti-fouling layer which can form an anti-fogging and anti-fouling layer having excellent anti-fogging property and anti-fouling property.SOLUTION: A formation method of an anti-fogging and anti-fouling layer includes the steps of: coating an active energy ray-curable resin composition containing at least one of a water-repellent monomer and a hydrophobic monomer onto an article, and forming an uncured layer; sticking a film having at least one of a water-repellent component and a hydrophobic component onto the uncured layer; and irradiating the uncured layer with active energy rays through the film and curing the uncured layer, and forming a cured layer.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a method for forming an anti-fogging and anti-fouling layer, and a kit for forming an anti-fogging and anti-fouling layer. [Background technology]

[0002] Conventionally, there is known a technique for forming an anti-fogging and anti-fouling layer having a water-repellent or hydrophobic function on the surface of an article such as an LED headlight cover, a glass window, goggles, etc. The anti-fogging and anti-fouling layer can be formed by irradiating a composition containing a resin that is cured by irradiation with active energy rays, such as UV rays. In order to form an anti-fog and anti-stain layer having the desired water repellency or hydrophobicity, it is necessary to apply the composition to an article, and then localize the water repellency or hydrophobicity on the surface of the composition, and then cure it. However, when the composition is simply irradiated with active energy rays, the oxygen in the air inhibits the polymerization reaction between monomers or oligomers in the composition, and the surface is not sufficiently cured within about several μm to about 100 μm (hereinafter, sometimes referred to as "curing inhibition"), which is a problem in that the desired anti-fog and anti-stain properties cannot be obtained.

[0003] As a method for preventing curing inhibition, for example, a method is known in which a composition is applied to the surface of an article to form an uncured layer, the air around the uncured layer is replaced with nitrogen using a dedicated device that matches the shape of the article, and then the composition is irradiated with active energy rays (see, for example, Patent Document 1).

[0004] However, some articles have complex surface shapes, and there may not be dedicated equipment that fits the shape of such articles. Furthermore, at repair sites where an anti-fogging and anti-fouling layer is to be formed again, there is a problem that forming an anti-fogging and anti-fouling layer using large-scale dedicated equipment is inefficient. For this reason, in recent years, there has been a demand for a method capable of forming an anti-fogging and anti-staining layer having excellent anti-fogging and anti-staining properties without requiring a large-scale dedicated apparatus. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2017-030347 A Summary of the Invention [Problem to be solved by the invention]

[0006] An object of one embodiment of the present invention is to provide a method for forming an anti-fogging and anti-fouling layer, which can form an anti-fogging and anti-fouling layer having excellent anti-fogging and anti-fouling properties, and a kit for forming an anti-fogging and anti-fouling layer. [Means for solving the problem]

[0007] The means for solving the above problems are as follows. <1> A step of applying an active energy ray curable resin composition containing at least one of a water repellent monomer and a hydrophobic monomer onto an article to form an uncured layer; A step of attaching a film having at least one of a water-repellent component and a hydrophobic component onto the uncured layer; a step of irradiating the uncured layer with active energy rays through the film to cure the uncured layer to form a cured layer; A method for forming an anti-fogging and anti-fouling layer, comprising: <2> The water-repellent monomer is a monomer having at least one of fluorine and silicon. <1> The method for forming an anti-fogging and anti-fouling layer according to claim 1. <3> The water-repellent component has at least one of fluorine and silicon. <1> from <2> 2. The method for forming an anti-fogging and anti-fouling layer according to claim 1 . <4> The content of the solvent contained in the active energy ray-curable resin composition is 30 mass % or less. <1> from <3> 2. The method for forming an anti-fogging and anti-fouling layer according to claim 1 . <5> The active energy ray-curable resin composition contains a filler. <1> from <4> 2. The method for forming an anti-fogging and anti-fouling layer according to claim 1 . <6> After the step of attaching the film, a step of attaching a light-shielding film onto the film; and after the step of attaching the light-shielding film, a step of peeling the light-shielding film from the film. <1> from <5> 2. The method for forming an anti-fogging and anti-fouling layer according to claim 1 . <7> an active energy ray-curable resin composition containing at least one of a water-repellent monomer or a hydrophobic monomer; A film containing at least one of a water-repellent component and a hydrophobic component; A coating member for an active energy ray-curable resin composition; A kit for forming an anti-fogging and anti-fouling layer, comprising: <8> The above-mentioned device having an active energy ray irradiation device <7> A kit for forming an anti-fogging and anti-fouling layer according to claim 1. <9> The above-mentioned having a light-shielding film <7> from <8> 2. A kit for forming an anti-fogging and anti-fouling layer according to any one of claims 1 to 11. Effect of the Invention

[0008] According to one embodiment of the present invention, there can be provided a method for forming an anti-fogging and anti-fouling layer, which can form an anti-fogging and anti-fouling layer having excellent anti-fogging and anti-fouling properties, and a kit for forming an anti-fogging and anti-fouling layer. [Brief description of the drawings]

[0009] [Figure 1A] FIG. 2 is a schematic diagram showing an example of an uncured layer forming step in the method for forming an anti-fogging and anti-fouling layer according to one embodiment of the present invention. [Figure 1B] FIG. 2 is a schematic diagram showing an example of a film attachment step in the method for forming an anti-fogging and anti-fouling layer according to one embodiment of the present invention. [Figure 1C] FIG. 2 is a schematic diagram showing an example of a hardening layer forming step in the method for forming an anti-fogging and anti-fouling layer according to one embodiment of the present invention. [Figure 1D] 1 is a schematic diagram showing an example of an anti-fogging and anti-fouling layer formed by a method for forming an anti-fogging and anti-fouling layer according to one embodiment of the present invention. [Figure 1E]1 is an enlarged view of the surface of an anti-fogging and anti-fouling layer formed by a method for forming an anti-fogging and anti-fouling layer according to one embodiment of the present invention. [Diagram 2] 1 is a schematic diagram showing an example of an anti-fogging and anti-fouling layer forming kit according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] (Method of forming anti-fogging and anti-stain layer) A method for forming an anti-fogging and anti-fouling layer according to one embodiment of the present invention includes a step of applying an active energy ray-curable resin composition containing at least one of a water-repellent monomer or a hydrophobic monomer onto an article to form an uncured layer (hereinafter, this may be referred to as an "uncured layer forming step"); a step of attaching a film containing at least one of a water-repellent component or a hydrophobic component onto the uncured layer (hereinafter, this may be referred to as a "film attaching step"); and a step of irradiating the uncured layer with active energy rays through the film to cure the uncured layer to form a cured layer (hereinafter, this may be referred to as a "cured layer forming step"); and preferably further includes a light-shielding film attaching step and a light-shielding film peeling step, as necessary, and may also include other steps. The active energy ray-curable resin composition according to one embodiment of the present invention is a composition containing a resin that is cured by irradiation with active energy rays.

[0011] 1A to 1C are schematic views showing an example of a method for forming the antifogging and antifouling layer of the first embodiment. First, as shown in FIG. 1A, in the uncured layer forming step, an active energy ray-curable resin composition is applied onto an article 10 to form an uncured layer 20A. Next, as shown in FIG. 1B, in a film attachment step, a film 30 containing a water-repellent component or a hydrophobic component is attached onto the uncured layer 20A. Next, as shown in FIG. 1C, in the cured layer forming step, the uncured layer 20A is irradiated with active energy rays 40 through the film 30 to cure the uncured layer 20A, thereby forming a cured layer 20B. Thereafter, the film 30 is removed from the cured layer 20B, so that an anti-fogging and anti-fouling layer can be formed as the cured layer 20B on the article 10, as shown in Fig. 1D. The removed film 30 can be reused to form an anti-fogging and anti-fouling layer. Fig. 1E is an enlarged view of the surface vicinity 50 of the anti-fogging and anti-fouling layer in Fig. 1D. The formed anti-fogging and anti-fouling layer (cured layer 20B in Fig. 1D) is cured after the water-repellent monomer or hydrophobic monomer contained in the active energy ray-curable resin composition is localized on the surface, and an upper layer 60 is partially formed as shown in Fig. 1E. The upper layer 60 provides the anti-fogging and anti-fouling layer with a water-repellent function or an oil-repellent function, and excellent anti-fogging and anti-fouling properties. Moreover, nano-sized water vapor can pass through the portion where the upper layer 60 is not formed. When the lower layer 70 of the anti-fogging and anti-staining layer contains a hydrophilic component, water vapor that passes through the portion where the upper layer 60 is not formed is taken in by the lower layer 70, resulting in better anti-fogging properties.

[0012] In one embodiment of the method for forming an anti-fogging and anti-fouling layer, the film 30 is attached before the uncured layer 20A is irradiated with the active energy rays 40, thereby preventing oxygen present in the air from entering the uncured layer 20A. This prevents oxygen from inhibiting the curing of the uncured layer 20A during irradiation with the active energy rays 40, and allows the surface of the anti-fogging and anti-fouling layer to be sufficiently cured. In addition, the time during which the water-repellent monomer or hydrophobic monomer in the active energy ray-curable resin composition is localized on the surface of the uncured layer 20A can be secured, so that the water-repellent monomer or hydrophobic monomer is sufficiently localized on the surface, forming an anti-fogging and anti-fouling layer having excellent anti-fogging and anti-fouling properties.

[0013] [Uncured layer formation process] The uncured layer forming step is a step of applying an active energy ray-curable resin composition containing at least one of a water-repellent monomer and a hydrophobic monomer onto an article to form an uncured layer.

[0014] The coating method in the uncured layer forming step is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include hand coating such as brush coating and potting, wire bar coating, blade coating, spin coating, reverse roll coating, die coating, spray coating, roll coating, gravure coating, microgravure coating, lip coating, air knife coating, curtain coating, comma coat method, dipping method, etc. Among these, hand coating such as brush coating and potting is preferred because it allows easy application in a short time during on-site construction.

[0015] The film thickness of the uncured layer is not particularly limited and may be appropriately selected depending on the purpose. When the active energy ray curable resin composition is applied using a precision application device, the film thickness is preferably 2 μm or more and 200 μm or less. When the active energy ray curable resin composition is applied by hand and then a film is pressed against the film in the film application step described below, the film thickness is preferably 50 μm or more and 5,000 μm or less.

[0016] -Active energy ray-curable resin composition- The active energy ray-curable resin composition contains at least one of a water-repellent monomer or a hydrophobic monomer, and preferably contains a hydrophilic monomer and a photopolymerization initiator, and further contains other components as necessary.

[0017] --Water-repellent monomer-- The water-repellent monomer has a radically polymerizable unsaturated group and a water-repellent group.

[0018] When the water-repellent monomer has a radically polymerizable unsaturated group, the water-repellent monomers are polymerized together by irradiation with active energy rays to form a polymer, and a cured film (hereinafter, may be referred to as a "cured layer").

[0019] When the water-repellent monomer has a water-repellent group, a cured layer having a water-repellent function can be formed on the surface. The water-repellent group is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include functional groups having at least one of fluorine and silicon. Among these, functional groups having fluorine are preferred because they have higher water repellency and are excellent in wiping off dirt. Examples of the functional group having at least one of fluorine and silicon include a fluoroalkyl group, a fluoroalkyl ether group, and a dimethylsiloxane group.

[0020] The water-repellent monomer may be a monofunctional monomer or a polyfunctional monomer. Specific examples of the water-repellent monomer are not particularly limited and can be appropriately selected according to the purpose, and include, for example, fluoroolefins such as tetrafluoroethylene, hexafluoropropylene, 3,3,3-trifluoropropylene, and chlorotrifluoroethylene, alkyl perfluorovinyl ethers, perfluoroalkyl vinyl ethers such as perfluoroethyl vinyl ether, perfluoropropyl vinyl ether, perfluorobutyl vinyl ether, and perfluoroisobutyl vinyl ether, perfluoroalkoxyalkyl vinyl ethers such as perfluoropropoxypropyl vinyl ether, and (meth)acrylates such as trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate, octafluoropentyl (meth)acrylate, and heptadecafluorodecyl (meth)acrylate. These may be used alone or in combination of two or more. The water-repellent monomer is preferably compatible with the hydrophilic monomer. In this specification, the term "(meth)acrylate" refers to acrylate or methacrylate. The same applies to (meth)acryloyl and (meth)acrylic.

[0021] The water-repellent monomer may be a commercially available product. Examples of commercially available water-repellent monomers containing a functional group having fluorine include the KY-1200 series manufactured by Shin-Etsu Chemical Co., Ltd., the Megafac RS series manufactured by DIC Corporation, and the Optool DAC manufactured by Daikin Industries, Ltd. Commercially available water-repellent monomers containing a silicon-containing functional group include, for example, the X-22-164 series manufactured by Shin-Etsu Chemical Co., Ltd. and the TEGO Rad series manufactured by Evonik.

[0022] The content of the water-repellent monomer is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.018% by mass or more, more preferably 0.018% by mass or more and 5.0% by mass or less, even more preferably 0.075% by mass or more and 3.0% by mass or less, and particularly preferably 0.18% by mass or more and 1.5% by mass or less, based on the total amount of the active energy ray curable resin composition. When the content is 5.0% by mass or less, the cured layer has excellent water repellency, and even if the glass transition temperature is lowered, the cured layer does not become too soft and has excellent abrasion resistance.

[0023] --Hydrophobic Monomer-- The hydrophobic monomer has a radically polymerizable unsaturated group and a hydrophobic group.

[0024] When the hydrophobic monomer has a radically polymerizable unsaturated group, the hydrophobic monomers are polymerized together by irradiation with active energy rays to form a polymer and a cured film.

[0025] When the hydrophobic monomer has a hydrophobic group, a cured layer having a hydrophobic function can be formed on the surface. The hydrophobic group is not particularly limited and can be appropriately selected depending on the purpose. Examples of the hydrophobic group include an alkyl group having 16 or more carbon atoms and a phenyl group. The hydrophobic monomer is preferably compatible with the hydrophilic monomer. The hydrophobic monomer may be a monofunctional monomer or a polyfunctional monomer.

[0026] The content of the hydrophobic monomer is not particularly limited and can be appropriately selected according to the purpose, but is preferably 0.018% by mass or more, more preferably 0.018% by mass or more and 5.0% by mass or less, even more preferably 0.075% by mass or more and 3.0% by mass or less, and particularly preferably 0.18% by mass or more and 1.5% by mass or less, based on the total amount of the active energy ray curable resin composition. When the content is 5.0% by mass or less, the cured layer has excellent hydrophobicity, and even if the glass transition temperature is lowered, the layer does not become too soft and has excellent abrasion resistance.

[0027] --Hydrophilic Monomer-- The hydrophilic monomer has a radical polymerizable unsaturated group and a hydrophilic group. The active energy ray curable resin composition contains the hydrophilic monomer, and thus the formed anti-fogging and anti-stain layer contains a hydrophilic component (water-absorbing component), so that water vapor is easily captured in the anti-fogging and anti-stain layer, thereby obtaining a more excellent anti-fogging property.

[0028] When the hydrophilic monomer has a radically polymerizable unsaturated group, the hydrophilic monomers are polymerized together by irradiation with active energy rays to form a polymer and a cured film.

[0029] The hydrophilic group is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include a polyoxyalkylene chain, a quaternary ammonium salt, a tertiary amino group, a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, a phosphonic acid group, etc. These may be used alone or in combination of two or more kinds. Examples of the polyoxyalkylene chain include a polyoxyethylene chain, a polyoxypropylene chain, etc. Among these, the polyoxyethylene chain is preferred because of its excellent hydrophilicity.

[0030] The hydrophilic monomer may be a monofunctional monomer or a polyfunctional monomer, but is preferably a polyfunctional monomer. Examples of the hydrophilic monomer include mono- or polyacrylates, or mono- or polymethacrylates obtained by reacting a polyhydric alcohol (a polyol or a polyhydroxy-containing compound) with a compound selected from the group consisting of acrylic acid, methacrylic acid, and derivatives thereof. Examples of the polyhydric alcohol include dihydric alcohol, trihydric alcohol, and tetrahydric or higher alcohol. Examples of the dihydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycols having a number average molecular weight of 300 to 1,000, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, 2,2'-thiodiethanol, and 1,4-cyclohexanedimethanol. Examples of the trihydric alcohol include trimethylolethane, trimethylolpropane, pentaglycerol, glycerol, 1,2,4-butanetriol, and 1,2,6-hexanetriol. Examples of the tetrahydric or higher alcohol include pentaerythritol, diglycerol, and dipentaerythritol.

[0031] Examples of the (meth)acrylate having a polyoxyalkylene chain include polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, ethoxylated glycerin (meth)acrylate, and ethoxylated pentaerythritol tetra(meth)acrylate. The polyethylene glycol (meth)acrylate may, for example, be methoxypolyethylene glycol (meth)acrylate. The molecular weight of the polyethylene glycol unit in the polyethylene glycol (meth)acrylate is not particularly limited and can be appropriately selected depending on the purpose. For example, the molecular weight may be 300 to 1,000. The methoxypolyethylene glycol (meth)acrylate may be a commercially available product, such as MEPM-1000 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). Among these, ethoxylated glycerin (meth)acrylate and ethoxylated pentaerythritol tetra(meth)acrylate are preferred since they can provide an anti-fogging and anti-staining layer with both appropriate hardness and hydrophilicity.

[0032] Examples of the quaternary ammonium salt-containing (meth)acrylate include (meth)acryloyloxyethyl trimethylammonium chloride, (meth)acryloyloxyethyl dimethylbenzyl ammonium chloride, (meth)acryloyloxyethyl dimethyl glycidyl ammonium chloride, (meth)acryloyloxyethyl trimethylammonium methyl sulfate, (meth)acryloyloxydimethylethyl ammonium ethyl sulfate, (meth)acryloyloxyethyl trimethylammonium-p-toluenesulfonate, (meth)acrylamidopropyl trimethylammonium chloride, (meth)acrylamidopropyl dimethylbenzyl ammonium chloride, (meth)acrylamidopropyl dimethyl glycidyl ammonium chloride, (meth)acrylamidopropyl trimethylammonium methyl sulfate, (meth)acrylamidopropyl dimethylethyl ammonium ethyl sulfate, (meth)acrylamidopropyl trimethylammonium-p-toluenesulfonate, and the like.

[0033] Examples of the tertiary amino group-containing (meth)acrylate include N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylamide, diethylaminopropyl (meth)acrylamide, 1,2,2,6,6-pentamethylpiperidyl (meth)acrylate, and 2,2,6,6-tetramethylpiperidyl (meth)acrylate.

[0034] Examples of the sulfonic acid group-containing monomer include vinyl sulfonic acid, allyl sulfonic acid, vinyl toluene sulfonic acid, styrene sulfonic acid, and sulfonic acid group-containing (meth)acrylate. Examples of the sulfonic acid group-containing (meth)acrylate include sulfoethyl (meth)acrylate, sulfopropyl (meth)acrylate, 2-acrylamido-2-methylpropane sulfonic acid, and terminal sulfonic acid-modified polyethylene glycol mono(meth)acrylate. These may form a salt. Examples of the salt include sodium salt, potassium salt, and ammonium salt.

[0035] Examples of the carboxylic acid group-containing monomer include acrylic acid and methacrylic acid.

[0036] Examples of the phosphate group-containing monomer include (meth)acrylates having a phosphate ester.

[0037] The molecular weight of the hydrophilic monomer is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 200 or more.

[0038] The content of the hydrophilic monomer is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 60 mass% or more, more preferably 60 mass% or more and 99.9 mass% or less, even more preferably 63 mass% or more and 95 mass% or less, and particularly preferably 65 mass% or more and 90 mass% or less, based on the total amount of the active energy ray-curable resin composition.

[0039] --Photopolymerization initiator-- The photopolymerization initiator is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include photoradical polymerization initiators, photoacid generators, bisazide compounds, hexamethoxymethylmelamine, tetramethoxyglycoyuryl, etc. Among these, photoradical polymerization initiators are preferred. The photoradical polymerization initiator is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include ethoxyphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, bis(2,6-dimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,6-dichlorobenzoyl)-2,4,4-trimethylpentylphosphine oxide, 1-phenyl 2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1,2-diphenylethanedione, and methylphenyl glyoxylate.

[0040] The content of the photopolymerization initiator is not particularly limited and can be appropriately selected depending on the purpose, but is preferably from 0.1% by mass to 10% by mass, more preferably from 0.5% by mass to 8% by mass, and particularly preferably from 1% by mass to 5% by mass, based on the total amount of the active energy ray-curable resin composition.

[0041] --Other ingredients-- The other components are not particularly limited and may be appropriately selected depending on the purpose. Examples of the other components include urethane (meth)acrylate, isocyanuric acid group-containing (meth)acrylate, filler, and solvent. These may be used to adjust the elongation rate, hardness, etc. of the anti-fogging and anti-fouling layer.

[0042] The urethane (meth)acrylate is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include aliphatic urethane (meth)acrylate, aromatic urethane (meth)acrylate, etc. Among these, aliphatic urethane (meth)acrylate is preferable.

[0043] The content of the urethane (meth)acrylate is not particularly limited and can be appropriately selected depending on the purpose, but is preferably from 10% by mass to 45% by mass, more preferably from 15% by mass to 40% by mass, and particularly preferably from 20% by mass to 35% by mass.

[0044] The filler is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include silica, zirconia, titania, tin oxide, indium tin oxide, antimony-doped tin oxide, antimony pentoxide, etc. Examples of the silica include solid silica and hollow silica.

[0045] The solvent is not particularly limited and can be appropriately selected depending on the purpose. Examples of the solvent include water and organic solvents. The organic solvent is not particularly limited and can be appropriately selected depending on the purpose. Examples of the organic solvent include aromatic solvents, alcohol solvents, ester solvents, ketone solvents, glycol ether solvents, glycol ether ester solvents, chlorine solvents, ether solvents, N-methylpyrrolidone, dimethylformamide, dimethylsulfoxide, and dimethylacetamide.

[0046] The content of the solvent is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 30% by mass or less, more preferably 5% by mass or less, based on the total amount of the active energy ray curable resin composition. When the content of the solvent is 5% by mass or less, the amount of the solvent that volatilizes after the formation of the anti-fogging and anti-fouling layer is small, so that a uniform anti-fogging and anti-fouling layer can be formed.

[0047] The method for preparing the active energy ray-curable resin composition is not particularly limited and can be appropriately selected depending on the purpose. For example, the active energy ray-curable resin composition can be prepared by mixing at least one of a water-repellent monomer or a hydrophobic monomer, and further, if necessary, a hydrophilic monomer and a photopolymerization initiator, and then mixing other components.

[0048] -Goods- The article is not particularly limited and can be appropriately selected depending on the purpose, and can be used by being attached to, for example, window materials such as glass windows, refrigerated / freezer showcases, and automobile windows, mirrors in bathrooms, mirrors such as automobile side mirrors, bathroom floors and walls, solar cell panel surfaces, security surveillance cameras, etc. In addition, since the anti-fog and anti-fouling layer of the present invention is easy to mold, examples of the article that can be used include glasses, goggles, helmets, lenses, microlens arrays, automobile headlight covers, front panels, side panels, and rear panels by utilizing in-mold molding and insert molding.

[0049] The material of the article is not particularly limited and can be appropriately selected depending on the purpose. Examples of the material include a resin substrate and an inorganic substrate.

[0050] The resin substrate is not particularly limited and can be appropriately selected depending on the purpose. Examples of the resin substrate include triacetyl cellulose (TAC), polyester (TPEE), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI), polyamide (PA), aramid, polyethylene (PE), polyacrylate, polyethersulfone, polysulfone, polypropylene (PP), polystyrene, diacetyl cellulose, polyvinyl chloride, acrylic resin (PMMA), polycarbonate (PC), epoxy resin, urea resin, urethane resin, melamine resin, phenolic resin, acrylonitrile-butadiene-styrene copolymer, cycloolefin polymer (COP), cycloolefin copolymer (COC), PC / PMMA laminate, and rubber-added PMMA. When the resin substrate is in the form of a film, the average thickness of the resin substrate is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 5 μm to 1,000 μm, more preferably 50 μm to 500 μm.

[0051] Examples of the inorganic substrate include metal oxides (e.g., quartz, sapphire, glass, etc.), metals (e.g., iron, chromium, nickel, molybdenum, niobium, copper, titanium, aluminum, zinc, silicon, magnesium, manganese, etc.), and alloys (e.g., combinations of the above metals). When the inorganic substrate is in the form of a film, the average thickness of the inorganic substrate is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.1 mm or more and 100 mm or less.

[0052] The article preferably has transparency.

[0053] The shape of the article is not particularly limited and may be appropriately selected depending on the purpose, but is preferably in the form of a film.

[0054] The surface of the article may be printed with letters, patterns, images, etc.

[0055] [Film application process] The film attachment step is a step of attaching a film containing at least one of a water-repellent component and a hydrophobic component onto the uncured layer. In this specification, the term "film" refers to a film containing at least one of a water-repellent component and a hydrophobic component. By attaching a film before irradiating the uncured layer with active energy rays, it is possible to prevent oxygen present in the air from entering the uncured layer. This prevents oxygen from inhibiting the curing of the uncured layer during irradiation with active energy rays, and allows the surface of the anti-fogging and anti-fouling layer to be sufficiently cured. In addition, the time during which the water-repellent monomer or hydrophobic monomer in the active energy ray-curable resin composition is localized on the surface of the uncured layer can be secured, so that the water-repellent monomer or hydrophobic monomer is sufficiently localized on the surface, forming an anti-fogging and anti-fouling layer having excellent anti-fogging and anti-fouling properties. Furthermore, since the surface free energy of the uncured layer is low, a water-repellent component or a hydrophobic component can be localized on the surface of the uncured layer.

[0056] The film contains at least one of a water-repellent component and a hydrophobic component, which promotes localization of the water-repellent monomer or the hydrophobic monomer in the uncured layer on the surface of the uncured layer, thereby obtaining better anti-fogging and anti-fouling properties. The film may be a film containing only a water-repellent component or a hydrophobic component, or a film in which at least one of a water-repellent component and a hydrophobic component is coated on the surface of a resin substrate such as PET.

[0057] The water-repellent component is not particularly limited as long as it has a water-repellent functional group (hereinafter, sometimes referred to as a "water-repellent group") and can be appropriately selected depending on the purpose. For example, a water-repellent polymer can be mentioned. The water-repellent group is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include functional groups having at least one of fluorine and silicon. Among these, functional groups having fluorine are preferred because they can localize the water-repellent or hydrophobic components in the uncured layer to the surface of the uncured layer in a short time by lowering the surface free energy of the uncured layer. Examples of the functional group having at least one of fluorine and silicon include a fluoroalkyl group, a fluoroalkyl ether group, and a dimethylsiloxane group.

[0058] Specific examples of the water-repellent polymer are not particularly limited and can be appropriately selected according to the purpose, and include, for example, fluoropolyolefins such as tetrafluoropolyethylene, hexafluoropolypropylene, 3,3,3-trifluoropolypropylene, and chlorotrifluoropolyethylene, alkyl perfluorovinyl polyethers, perfluoroalkyl polyvinyl ethers such as perfluoroethyl polyvinyl ether, perfluoropropyl polyvinyl ether, perfluorobutyl polyvinyl ether, and perfluoroisobutyl polyvinyl ether, perfluoroalkoxyalkyl polyvinyl ethers such as perfluoropropoxypropyl polyvinyl ether, and poly(meth)acrylates such as trifluoroethyl poly(meth)acrylate, tetrafluoropropyl poly(meth)acrylate, octafluoropentyl poly(meth)acrylate, and heptadecafluorodecyl poly(meth)acrylate. These may be used alone or in combination of two or more.

[0059] The hydrophobic component is not particularly limited as long as it has a hydrophobic functional group (hereinafter, may be referred to as a "hydrophobic group") and can be appropriately selected depending on the purpose. For example, a hydrophobic polymer can be mentioned. The hydrophobic group is not particularly limited and can be appropriately selected depending on the purpose. Examples of the hydrophobic group include an alkyl group having 16 or more carbon atoms and a phenyl group.

[0060] The film is not particularly limited as long as it contains at least one of a water-repellent component and a hydrophobic component, and can be appropriately selected depending on the purpose. For example, a commercially available product can be used. Examples of the commercially available products include NEOFLON PFA Film AF Series (manufactured by Daikin Industries, Ltd.), NEOFLON PFA Film NF Series (manufactured by Daikin Industries, Ltd.), MSF-100 (manufactured by Chukoh Chemical Industry Co., Ltd.), MSF-200 (manufactured by Chukoh Chemical Industry Co., Ltd.), and MSE-100 (manufactured by Chukoh Chemical Industry Co., Ltd.).

[0061] The thickness of the film is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 100 μm to 3,000 μm inclusive. When the thickness is 100 μm or more, the workability is excellent, and when the thickness is 3,000 μm or less, the UV transmittance is excellent and a cheaper film can be used.

[0062] The film is preferably a UV-transmitting film, which transmits UV light and thereby cures the uncured layer.

[0063] In the film attachment step, a film may be attached onto the uncured layer and then pressed against the uncured layer (i.e., the surface of the film may be pressurized). This allows the smoothness of the surface of the uncured layer and the thickness of the film to be adjusted to desired values.

[0064] [Light-shielding film application process] The light-shielding film attaching step is a step of attaching a light-shielding film onto the film after the film attaching step. At the site where the anti-fog and anti-fouling layer is formed on the surface of the article, sunlight from outdoors or light from indoor lighting may be irradiated onto the uncured layer to which the film is attached. In this case, before the water-repellent or hydrophobic component is localized on the surface of the uncured layer, the uncured layer may be unexpectedly cured by sunlight or light from lighting (especially light with a wavelength of 500 nm or less). By carrying out the light-shielding film attachment process, it is possible to prevent the above-mentioned unexpected curing. In addition, conventionally, when forming an anti-fogging and anti-fouling layer outdoors, construction may be performed by placing a tent or box, but in one embodiment of the present invention, light can be blocked more easily by using the light-shielding film.

[0065] The light-shielding film is not particularly limited as long as it has the function of blocking light from sunlight or lighting (particularly, light with a wavelength of 500 nm or less), and can be appropriately selected depending on the purpose. Note that the "light-shielding" refers to a transmittance of 70% or less for light with a wavelength of 500 nm or less. The transmittance of the light-shielding film is 70% or less, preferably 25% or less, more preferably 10% or less, and particularly preferably 5% or less (i.e., the light-shielding rate is 30% or more, preferably 75% or more, more preferably 90% or more, and particularly preferably 95% or more). The transmittance (or light blocking rate) can be measured, for example, by using a spectrophotometer.

[0066] The light-shielding film preferably contains a light-shielding component. The light-shielding component is not particularly limited and can be appropriately selected depending on the purpose. Examples of the light-shielding component include carbon black. The light-shielding film may be a film containing only a light-shielding component, or a film in which a light-shielding component is coated on the surface of a resin substrate such as PET.

[0067] The application time of the light-shielding film is not particularly limited as long as the water-repellent or hydrophobic component is localized on the surface of the uncured layer, and can be appropriately selected depending on the purpose, but is preferably 5 seconds or more, more preferably 30 seconds or more, and particularly preferably 60 seconds or more.

[0068] [Light-shielding film peeling process] The light-shielding film peeling step is a step of peeling off the light-shielding film from the film after the light-shielding film attaching step. By attaching the light-shielding film until immediately before irradiating the uncured layer with active energy rays in the cured layer forming step described later, the curing of the uncured layer due to sunlight or light from an illumination can be prevented, and the water-repellent or hydrophobic component can be localized on the surface of the uncured layer.

[0069] [Hardened layer formation process] The cured layer forming step is a step of irradiating the uncured layer with active energy rays through the film to cure the uncured layer and form a cured layer.

[0070] The active energy rays are not particularly limited and can be appropriately selected depending on the purpose. Examples of the active energy rays include electron beams, ultraviolet rays, infrared rays, laser beams, visible light, ionizing radiation (X-rays, α-rays, β-rays, γ-rays, etc.), microwaves, and high frequency waves.

[0071] The timing of irradiating the active energy rays is not particularly limited and can be appropriately selected depending on the film thickness of the uncured layer. From the viewpoint of ensuring time for the water-repellent monomer or hydrophobic monomer to localize on the surface of the uncured layer, the irradiating time is preferably 5 seconds or more, more preferably 30 seconds or more, and particularly preferably 60 seconds or more after the film is applied onto the uncured layer.

[0072] The illuminance of the light source during irradiation with the active energy rays is not particularly limited and can be appropriately selected depending on the purpose. However, from the viewpoint of increasing the crosslink density, it is preferable to use a light source having an illuminance of 100 mW / cm. 2 More than 200mW / cm is preferable. 2 More preferably, 300 mW / cm 2 The above is particularly preferred.

[0073] The distance from the irradiation surface of the light source to the surface of the uncured layer during irradiation with the active energy rays is not particularly limited and can be appropriately selected depending on the purpose. However, from the viewpoint of being able to irradiate the active energy rays without reducing the illuminance of the light source, the distance is preferably 5 cm or less, and more preferably 1 cm or less.

[0074] The irradiation time of the active energy rays is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1 second or more per light spot, more preferably 3 seconds or more, and particularly preferably 10 seconds or more.

[0075] [Other processes] The other steps are not particularly limited and can be appropriately selected depending on the purpose. For example, a heating step can be mentioned.

[0076] The heating step is a step of heating the uncured layer, and the heating step can remove unnecessary solvent contained in the uncured layer.

[0077] The heating method is not particularly limited and can be appropriately selected depending on the purpose, but infrared heating or exposure to a high-temperature atmosphere is preferable. The heating temperature is not particularly limited and can be appropriately selected depending on the purpose, but is preferably close to or equal to the glass transition temperature of the substrate. The heating time is not particularly limited and can be appropriately selected depending on the purpose.

[0078] (Anti-fog and anti-stain layer forming kit) FIG. 2 is a schematic diagram showing an example of an anti-fogging and anti-fouling layer forming kit according to one embodiment of the present invention. 2, the kit for forming an anti-fogging and anti-fouling layer according to one embodiment of the present invention includes an active energy ray-curable resin composition 100, a film 200, and an application member 300 for the active energy ray-curable resin composition, and may further include an active energy ray irradiation device 400, if necessary. In addition, the kit may further include a light-shielding film. The anti-fogging and anti-fouling layer forming kit may include a cleaning tool for cleaning the surface of an article before applying the active energy ray-curable resin composition to the article. Moreover, the anti-fogging and anti-fouling layer forming kit may be a kit containing only the active energy ray-curable resin composition 100 and the film 200 as consumables.

[0079] In an article on which an anti-fogging and anti-fouling layer is formed, peeling of the anti-fogging and anti-fouling layer occurs due to aging during use, and the anti-fogging and anti-fouling function is reduced. It is desirable to form an anti-fogging and anti-fouling layer again on such an article (hereinafter, sometimes referred to as "repair"). However, simply applying an active energy ray curable resin composition onto an article and irradiating it with active energy rays causes curing inhibition due to the influence of oxygen in the air, so that an anti-fogging and anti-fouling layer having the desired anti-fogging and anti-fouling function cannot be formed. In addition, using a dedicated device for repair is inefficient and cannot be applied to articles with complex shapes. Therefore, by using the anti-fogging and anti-fouling layer forming kit as one embodiment of the present invention, an anti-fogging and anti-fouling layer can be formed on an article more easily without the need for a dedicated device during on-site repair.

[0080] As the active energy ray-curable resin composition 100, the above-mentioned active energy ray-curable resin composition can be used.

[0081] As the film 200, the films described above can be used.

[0082] The application member 300 for the active energy ray-curable resin composition is not particularly limited and can be appropriately selected depending on the purpose. Examples of the application member 300 include a blade and a brush.

[0083] The active energy ray irradiating device 400 is not particularly limited and can be appropriately selected depending on the purpose, but a handy light is preferable because it can be easily used at the site of repairing an item.

[0084] As the light-shielding film, the above-mentioned light-shielding films can be used.

[0085] (Anti-fog and anti-stain layer) The anti-fogging and anti-fouling layer formed by the method for forming an anti-fogging and anti-fouling layer according to one embodiment of the present invention has a sufficiently hardened surface and has excellent anti-fogging and anti-fouling properties.

[0086] The pure water contact angle of the surface of the anti-fogging and anti-fouling layer is 90° or more, preferably 100° or more, more preferably 110° or more, and particularly preferably 115° or more. The pure water contact angle can be measured, for example, by an ellipse fitting method using DM-701 (manufactured by Kyowa Interface Science Co., Ltd.) under the following conditions. Put distilled water into a plastic syringe, attach a stainless steel needle to the tip, and drip the water onto the evaluation surface. Amount of water dispensed: 2μL ·Measurement temperature: 25℃ Water is dropped and the contact angle is measured 4 seconds later at 10 arbitrary points on the surface of the anti-fogging and anti-fouling coating, and the average value is regarded as the pure water contact angle.

[0087] The hexadecane contact angle of the surface of the antifogging and antifouling layer is preferably 30° or more, more preferably 60° or more, even more preferably 70° or more, and particularly preferably 80° or more. The upper limit of the hexadecane contact angle is not particularly limited and can be appropriately selected depending on the purpose, and is, for example, 150°. When the hexadecane contact angle is within the preferred range, even if fingerprints, sebum, sweat, tears, cosmetics, etc. adhere to the surface, they can be easily wiped off, which is advantageous in that excellent anti-fogging properties can be maintained. The hexadecane contact angle can be measured, for example, by an ellipse fitting method using DM-701 (manufactured by Kyowa Interface Science Co., Ltd.) under the following conditions. Put hexadecane into a plastic syringe, attach a Teflon (registered trademark) coated stainless steel needle to the tip, and drip the liquid onto the evaluation surface. Hexadecane drop volume: 2μL ·Measurement temperature: 25℃ Hexadecane is dropped, and the contact angle is measured 4 seconds later at any 10 points on the surface of the anti-fogging and anti-fouling layer, and the average value is regarded as the hexadecane contact angle.

[0088] When the pure water contact angle is within the above range and the hexadecane contact angle is within the above range, even if water-based and / or oily stains such as marker ink, fingerprints, sweat, cosmetics (foundation, UV protector, etc.) are attached, the stains are prevented from penetrating into the lower layer of the bulk. Therefore, the stains can be easily wiped off with a tissue or the like, and the anti-fogging properties return to the state before the stains were attached. EXAMPLES

[0089] Examples of the present invention will be described below, but the present invention is not limited to these examples.

[0090] Example 1 <Preparation of Anti-Fog and Anti-Stain Layer> An active energy ray-curable resin composition having the following composition was applied onto the resin substrate (FE-2000, PC substrate, average thickness 180 μm, manufactured by Mitsubishi Gas Chemical Company, Inc.) to a coating thickness of 4 μm to form an uncured layer. -Active energy ray curable resin composition (total 100% by mass)- Water-repellent monomer (KY-1203, fluorine-containing monomer) 0.962% by mass Hydrophilic monomer (NK ester A-GLY-20E) 67.307% by mass Other monomers (PETIA) 28.846% by mass Polymerization initiator (Irgacure 184D) 2.885% by mass

[0091] Next, a UV-transmitting film (Neoflon PFA AF-0500, manufactured by Daikin Industries, Ltd., fluorine-containing resin film, film thickness: 500 μm) was attached onto the formed layer of the active energy ray-curable resin composition. Next, a handy UV light (JAXMAN UV light U1 (3 W), central wavelength: 365 nm) was used to irradiate the UV-transmitting film with a dose of 1,800 mJ / cm. 2 The uncured layer was cured by irradiating it with ultraviolet light at a temperature of 150° C. to obtain a cured layer, that is, an anti-fogging and anti-fouling layer 1.

[0092] Example 2 An anti-fogging and anti-soiling layer 2 was obtained in the same manner as in Example 1, except that KY-1203 (fluorine-containing monomer) used as the water-repellent monomer was changed to X-22-164 (silicon-containing monomer).

[0093] Comparative Example 1 An anti-fogging and anti-soiling layer 3 was obtained in the same manner as in Example 1, except that in Example 1, a UV-transmitting film was not applied onto the uncured layer, and the uncured layer was cured by irradiating with active energy rays.

[0094] [Table 1] The blend amounts in Table 1 are in mass %.

[0095] The various materials in Table 1 are as follows: [Hydrophilic Monomer] NK Ester A-GLY-20E: Shin-Nakamura Chemical Co., Ltd. Ethoxylated glycerin triacrylate (Total number of repeating polyethylene oxide chain units contained in the structure: 20)

[0096] [Water-repellent monomer] KY-1203: Shin-Etsu Chemical Co., Ltd. (Meth)acrylic-terminated perfluoropolyether additives X-22-164: Shin-Etsu Chemical Co., Ltd. Silicone (meth)acrylate

[0097] [Other Monomers] PETIA: Manufactured by Daicel Allnex Corporation Mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (Polyethylene oxide chains contained in the structure: None)

[0098] [Polymerization initiator] Irgacure 184D: BASF

[0099] The obtained anti-fogging and anti-staining coatings 1 to 3 were evaluated for the following "breath anti-fogging property," "stain adhesion," "stain wiping ability," and "scratch resistance." The evaluation results are shown in Table 2.

[0100] (Anti-fog breathability) In an environment of 25°C and 37% RH, a person exhaled deeply once onto the outermost surface of the anti-fog and anti-fouling layer from a distance of 5 cm in the normal direction from the surface, and then the surface was immediately observed visually and evaluated according to the following criteria. [Evaluation Criteria] ⊚: There was no change in appearance at all on the outermost surface. ◯: Changes in appearance such as white cloudiness and water film formation were observed in part of the outermost surface. ×: Changes in appearance such as white cloudiness and water film formation were observed over the entire outermost surface.

[0101] (Stain adhesion) The outermost surface of the anti-fog and anti-stain layer was soiled with Sharpie PROFESSIONAL (a black oil-based marker, product name, manufactured by Newell Rubbermaid Co.), and the surface was visually observed and evaluated according to the following criteria. [Evaluation Criteria] ◯: The marker was repelled in droplets or lines. ×: The marker was not repelled and stuck to the surface.

[0102] (Easy to wipe off dirt) The top surface of the anti-fog and anti-fouling layer was soiled with Sharpie PROFESSIONAL (a black oil-based marker, product name, manufactured by Newell Rubbermaid), and then wiped in a circular motion 10 times with tissue (Elmore, manufactured by Kami Shoji Co., Ltd.). The surface was then visually observed and evaluated according to the following criteria. [Evaluation Criteria] ◎: The dirt was gone. ○: A small amount of dirt remained, but was within the range of usable range. ×: Stains remained.

[0103] (Scratch resistance) Steel wool (product name: Bonstar, count: #0000) was placed on the top surface of the anti-fog and anti-fouling layer and slid back and forth 10 times with a load of 400 gf / 13 mmφ (sliding stroke: 3 cm, sliding speed: 6 cm / s), and then evaluated according to the following criteria. [Evaluation Criteria] ○: No change in appearance or breath anti-fogging properties. ×: The appearance was changed, such as scratched or cloudy, and / or the anti-fogging properties were deteriorated.

[0104] [Table 2] [Industrial Applicability]

[0105] The antifogging and antifouling layer according to one embodiment of the present invention can be attached to window materials such as glass windows, refrigerated and frozen showcases, and automobile windows, mirrors in bathrooms, mirrors such as automobile side mirrors, bathroom floors and walls, the surfaces of solar cell panels, security surveillance cameras, etc. Furthermore, since the antifogging and antifouling layer of the present invention can be easily molded, it can be used by utilizing in-mold molding and insert molding for glasses, goggles, helmets, lenses, microlens arrays, automobile headlight covers, front panels, side panels, rear panels, etc. [Explanation of symbols]

[0106] 10 Goods 20A uncured layer 20B hardened layer 30 Film 40 Active energy rays 50 Near the surface of the anti-fog and anti-fouling layer 60 upper layer 70 Lower layer 100 Active energy ray-curable resin composition 200 Film 300 Coating member for active energy ray-curable resin composition 400 Active energy ray irradiation equipment

Claims

1. A step of applying an active energy ray curable resin composition containing at least one of a water repellent monomer and a hydrophobic monomer onto an article to form an uncured layer; A step of attaching a film having at least one of a water-repellent component and a hydrophobic component onto the uncured layer; a step of irradiating the uncured layer with active energy rays through the film to cure the uncured layer to form a cured layer; A method for forming an anti-fogging and anti-fouling layer, comprising:

2. The method for forming an anti-fogging and anti-soiling layer according to claim 1 , wherein the water-repellent monomer is a monomer having at least one of fluorine and silicon.

3. The method for forming an anti-fogging and anti-fouling layer according to claim 1 , wherein the water-repellent component contains at least one of fluorine and silicon.

4. The method for forming an anti-fogging and anti-fouling layer according to claim 1 , wherein the content of the solvent in the active energy ray-curable resin composition is 30 mass % or less.

5. The method for forming an anti-fogging and anti-fouling layer according to claim 1 , wherein the active energy ray-curable resin composition contains a filler.

6. After the step of attaching the film, a step of attaching a light-shielding film onto the film; The method for forming an anti-fogging and anti-fouling layer according to claim 1 , further comprising the step of peeling off the light-shielding film from the film after the step of attaching the light-shielding film.

7. an active energy ray-curable resin composition containing at least one of a water-repellent monomer or a hydrophobic monomer; A film containing at least one of a water-repellent component and a hydrophobic component; A coating member for an active energy ray-curable resin composition; A kit for forming an anti-fogging and anti-fouling layer, comprising:

8. The kit for forming an anti-fogging and anti-fouling layer according to claim 7, further comprising an active energy ray irradiation instrument.

9. The kit for forming an anti-fogging and anti-fouling layer according to any one of claims 7 to 8, further comprising a light-shielding film.

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