WO2022071446A1 - Resin composition for water-repellent lens protective films, and method for protecting water-repellent lens - Google Patents

Resin composition for water-repellent lens protective films, and method for protecting water-repellent lens Download PDF

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Publication number
WO2022071446A1
WO2022071446A1 PCT/JP2021/036003 JP2021036003W WO2022071446A1 WO 2022071446 A1 WO2022071446 A1 WO 2022071446A1 JP 2021036003 W JP2021036003 W JP 2021036003W WO 2022071446 A1 WO2022071446 A1 WO 2022071446A1
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Prior art keywords
water
lens
protective film
repellent
resin composition
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PCT/JP2021/036003
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French (fr)
Japanese (ja)
Inventor
直志 高橋
淳二 權田
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日油株式会社
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Publication date
Priority claimed from JP2020165949A external-priority patent/JP2022057609A/en
Priority claimed from JP2021126788A external-priority patent/JP2023021736A/en
Application filed by 日油株式会社 filed Critical 日油株式会社
Publication of WO2022071446A1 publication Critical patent/WO2022071446A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B9/00—Machines or devices designed for grinding edges or bevels on work or for removing burrs; Accessories therefor
    • B24B9/02—Machines or devices designed for grinding edges or bevels on work or for removing burrs; Accessories therefor characterised by a special design with respect to properties of materials specific to articles to be ground
    • B24B9/06—Machines or devices designed for grinding edges or bevels on work or for removing burrs; Accessories therefor characterised by a special design with respect to properties of materials specific to articles to be ground of non-metallic inorganic material, e.g. stone, ceramics, porcelain
    • B24B9/08—Machines or devices designed for grinding edges or bevels on work or for removing burrs; Accessories therefor characterised by a special design with respect to properties of materials specific to articles to be ground of non-metallic inorganic material, e.g. stone, ceramics, porcelain of glass
    • B24B9/14—Machines or devices designed for grinding edges or bevels on work or for removing burrs; Accessories therefor characterised by a special design with respect to properties of materials specific to articles to be ground of non-metallic inorganic material, e.g. stone, ceramics, porcelain of glass of optical work, e.g. lenses, prisms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C13/00—Assembling; Repairing; Cleaning
    • G—PHYSICS
    • G02—OPTICS
    • G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
    • G02C7/00—Optical parts
    • G02C7/02—Lenses; Lens systems ; Methods of designing lenses

Definitions

  • the present invention relates to a resin composition for a water-repellent lens protective film for protecting the lens surface during peripheral processing of the water-repellent lens. Further, the present invention relates to a method of protecting a water-repellent lens in order to hold the lens in a processing apparatus during peripheral processing of the water-repellent lens.
  • the peripheral edge of the spectacle lens is processed using a processing device to match the frame shape of the spectacle frame.
  • This processing device holds a spectacle lens on a pair of lens chuck shafts, the lens is rotated by the rotation of the lens chuck shafts, and a processing tool such as a grindstone is pressed against the lens to process the lens into a desired shape. It is a machine.
  • a jig is attached to the spectacle lens with double-sided tape, and the jig is held on the lens chuck shaft via the jig.
  • a method of temporarily providing a protective film on the lens surface is known.
  • this method by forming a double-sided tape for fixing a jig and a protective layer having good adhesiveness to the lens surface on the lens surface, it is possible to prevent axial misalignment during lens processing.
  • the protective film can be easily peeled off from the lens after processing.
  • thermosetting protective film has a problem that the water repellency is lowered because the water repellent layer is cracked due to the influence of heat during curing and the smoothness of the surface is lost. there were.
  • a photocurable protective film when a mercury lamp or metal halide lamp that emits light in a wide wavelength range is cured using a light source, there is a problem that cracks occur because the lens absorbs the irradiation light and generates heat. there were.
  • Patent Document 1 discloses a method of forming a thermosetting protective film made of an organic polymer in which an inorganic substance is dispersed in a colloidal manner on a lens having a water-repellent function.
  • Patent Document 2 discloses a method of forming a photocurable protective film containing a metal oxide on a lens having a water-repellent function.
  • Patent Document 3 an acrylic oligomer, an acrylic monomer, a thiol compound, and a photoinitiator are used as temporary fixing agents having an appropriate peeling strength necessary for peeling a cured product from an adherend and having an appropriate flexibility of the cured product.
  • a photocurable acrylic resin composition in which the agents are combined is disclosed.
  • Patent Document 4 describes a composition in which an acrylic resin is dissolved in an organic solvent as a material for temporarily forming a protective film on the surface of a plastic spectacle lens on which an antifouling film having water and oil repellency is formed. The thing is listed.
  • the present invention has been made in view of the above-mentioned prior art, and an object thereof is a resin composition for a water-repellent lens protective film that can be uniformly applied even to a superhydrophobic lens having particularly high antifouling property. Is to provide.
  • the protective film obtained from the resin composition for a water-repellent lens protective film has an appropriate adhesiveness that it does not peel off from the water-repellent lens during processing and can be easily peeled off after processing (). Adhesion) is also required. Further, regarding the thermal influence during the formation of the protective film, a UV-LED irradiation device (emission wavelength 365 or 380-405 nm) having a narrow emission wavelength range has been attracting attention in recent years.
  • a light source having a wavelength light as close to visible light as possible as a peak wavelength is preferable, and a light source having a peak wavelength of 395 nm or more can cure the protective film without heat generation of the lens, but generally, long wavelength light is used. Since it becomes difficult to cure, there is a problem that it is difficult to cure with the composition described in the above-mentioned patent document.
  • the first object of the present invention is a resin composition having adjusted coatability and adhesion to a lens treated with superhydrophobicity, which can be uniformly coated on a lens having high water repellency and has a peak wavelength. It is an object of the present invention to provide a resin composition for a water-repellent lens protective film that can be cured even with an LED light source having a wavelength of 395 nm. This makes it possible to form a protective film on the superhydrophobic lens without causing a decrease in water repellency due to heat.
  • the protective film obtained from the resin composition for a water-repellent lens protective film has an appropriate adhesiveness that it does not peel off from the water-repellent lens during processing and can be easily peeled off after processing (). Adhesion) and not affecting the water repellency of the lens after the protective film is peeled off (non-staining) are also required. Furthermore, after the protective film is formed on the lens, it may take several months before the peripheral processing is performed, so the protective film may not change its adhesion and non-staining property even if it is stored for a long period of time. Desired.
  • the second problem of the present invention is that even a superhydrophobic lens having particularly high antifouling property can be uniformly coated, and it does not peel off from the water-repellent lens during processing and is easy after processing.
  • Another object of the present invention is to provide a method for preventing axial deviation of the lens during processing by forming a protective film on the water-repellent lens and processing the lens into a desired shape.
  • the present invention is a water-repellent lens containing (A) a polyfunctional (meth) acrylate having a weight average molecular weight of 200 to 30,000, (C) a photopolymerization initiator, and (D) a nonionic surfactant. It is a resin composition for a protective film.
  • the present invention is a method of protecting a water-repellent lens by applying the resin composition for a protective film to the water-repellent lens and providing a cured film obtained by curing as a protective layer.
  • (meth) acrylate means a generic term including both acrylate and methacrylate.
  • ⁇ to XX indicating a numerical range is a concept including a lower limit value (" ⁇ ") and an upper limit value ("XX”) unless otherwise specified. That is, to be exact, it means “more than XX and less than XX”.
  • the first resin composition for a water-repellent lens protective film of the present invention for solving the first problem is the curable resin composition according to the following [1] to [3].
  • [1] (A) Polyfunctional (meth) acrylate having a weight average molecular weight of 200 to 30,000, and (C) Photopolymerization initiator and (D) A resin composition for a water-repellent lens protective film containing a nonionic surfactant.
  • D A fluorine-based nonionic surfactant containing fluorine and having a surface tension of 26.0 mN / mm or less when 0.1 part by mass is blended in propylene glycol monomethyl ether acetate.
  • the first resin composition for a water-repellent lens protective film of the present invention can be uniformly applied to the entire surface even if the water-repellent lens has high water repellency and is difficult to apply to the surface.
  • the protective film formed of the resin composition for a water lens protective film can be easily peeled off without any residue at the time of peeling. Furthermore, since the composition can be cured by an LED ultraviolet irradiation device having a peak wavelength close to the visible light region, the thermal effect on the water-repellent lens at the time of curing is suppressed, and defects such as cracks and distortion of the water-repellent layer are suppressed. It is possible to form a protective film without generating it.
  • the resin composition for a water-repellent lens protective film of the present invention not only protects from scratches and contamination during transportation and processing, but also has an appropriate adhesion to the lens, so that it also has an axial deviation during processing. It is possible to prevent it.
  • the second resin composition for a water-repellent lens protective film of the present invention for solving the second problem is the curable resin composition according to the following [4].
  • a resin composition comprising the following components (A) to (d1). With respect to 100 parts by mass of the component (A), the component (b1) is 0.5 to 30 parts by mass, the component (C) is 0.1 to 25 parts by mass, and the component (d1) is 0.1 to 25 parts by mass.
  • a resin composition for a water-repellent lens protective film which comprises.
  • Component Polyfunctional (meth) acrylate having a weight average molecular weight of 250 to 30,000
  • Component Polyfunctional thiol compound
  • Component Photopolymerization initiator
  • Component Weight average molecular weight of 25
  • the second resin composition for a water-repellent lens protective film of the present invention has particularly high antifouling properties and can be uniformly applied even to a superhydrophobic lens that is difficult to apply to the surface.
  • the cured film obtained by curing the resin composition for the water-repellent lens protective film of the present invention has an appropriate adhesion to the water-repellent lens, so that it is possible to prevent axial misalignment during processing, and the protective film. Can be easily peeled off without any residue when peeled off.
  • the polyfunctional (meth) acrylate as the component (A) is not particularly limited as long as it is a compound having a weight average molecular weight (Mw) of 200 to 30,000 and having two or more (meth) acryloyl groups in the molecule.
  • Mw weight average molecular weight
  • Known materials can be used.
  • the component (A) only one kind may be used alone, or two or more kinds may be used in combination.
  • a preferable example of the (A) polyfunctional (meth) acrylate is a compound represented by the following general formula (formula 1).
  • R 1 is a hydrocarbon group having 2 to 300 carbon atoms or a hydrocarbon group having 2 to 300 carbon atoms containing at least one selected from the group consisting of an ether oxygen (—O—) and a hydroxyl group (—OH).
  • R 2 is a hydrogen atom or a methyl group.
  • the (A) polyfunctional (meth) acrylate include polyfunctional (meth) acrylate monomers such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate, and compounds having an epoxy group (meth).
  • polyfunctional (meth) acrylate monomers such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate
  • epoxy group meth
  • Epoxy-modified (meth) acrylate obtained by the reaction of acrylic acid polyfunctional (meth) acrylate oligomer such as urethane (meth) acrylate obtained by the reaction of diisocyanate compound, diol compound and (meth) acrylate compound having a hydroxyl group, etc.
  • urethane (meth) acrylate it is preferable to use urethane (meth) acrylate.
  • a compound having a urethane bond By using a compound having a urethane bond, the toughness of the cured film is improved, and the cured film is less likely to be torn when peeled.
  • the adhesion to the water-repellent lens is improved, and the effect of suppressing axial misalignment during processing is enhanced.
  • a compound having a flexible urethane bond the adhesive force between the cured film and the water-repellent lens is improved, and the axial deviation during processing can be suppressed.
  • urethane (meth) acrylate examples include UN-352 (number of functional groups: 2, Mw: 3,000), UN-333 (number of functional groups: 2, Mw: 3,000), UN-353 (number of functional groups:: 2, Mw: 5,000), UN-1255 (number of functional groups: 2, Mw: 8,000), UN-6200 (number of functional groups: 2, Mw: 6,500), UN-6201 (number of functional groups: 2, Mw: 1,600), UN-9000PEP (number of functional groups: 2, Mw: 5,000), UN-9200A (number of functional groups: 2, Mw: 15,000), UN-3320HA (number of functional groups: 6, Mw: 1,500), UN-904 (number of functional groups: 10, Mw: 4,900), UN-953 (number of functional groups: 20, Mw: 14,000 to 40,000), UN-954 (number of functional groups: 6, Mw: 4,500), UN-6305 (number of functional groups: 2, Mw: 27,000), H-219 (number of functional groups:
  • the weight average molecular weight of the polyfunctional (meth) acrylate is 200 to 30,000, preferably 200 to 15,000.
  • the weight average molecular weight of the polyfunctional (meth) acrylate is in the range of 200 to 30,000, the cured cured film is tough and the cured film is not easily torn when peeled, and the workability at the time of peeling is good. Furthermore, if the weight average molecular weight is in the range of 200 to 15,000, in addition to the toughness of the cured film, the water resistance is improved, and the cured film is less likely to break during peripheral processing of the water-repellent lens, so that axial misalignment is further suppressed. It is preferable because it is possible to do so.
  • the weight average molecular weight of (A) polyfunctional (meth) acrylate is preferably 250 to 30,000, and more preferably 500 to 15,000.
  • (A) When the weight average molecular weight of the polyfunctional (meth) acrylate is in the range of 250 to 30,000, the adhesion between the cured film and the water-repellent lens is improved. In addition, the toughness of the cured film is increased, and breakage of the cured film is suppressed at the time of peeling, so that workability when peeling the cured film from the water-repellent lens is improved.
  • the weight average molecular weight is detected by RI using a gel permeation chromatography apparatus HLC-8220GPC manufactured by Tosoh Corporation, TSKgel HZM-M manufactured by Tosoh Corporation as a column, and THF as an eluent. It was measured with a device and determined by polystyrene conversion.
  • the number of (meth) acryloyl groups (number of functional groups) in the molecule of (A) polyfunctional (meth) acrylate is not particularly limited as long as it is 2 or more, but is, for example, 2 to 30.
  • the upper limit is preferably 20 or less, more preferably 15 or less, still more preferably 10 or less, and particularly preferably 8 or less.
  • the content of the polyfunctional (meth) acrylate is preferably 20.0 to 99.5% by mass, more preferably 40.0 to 40.0% by mass, based on the total solid content of the resin composition for the water-repellent lens protective film. It is 99.5% by mass.
  • the content of the (A) polyfunctional (meth) acrylate is preferably 70 to 97% by mass, more preferably 75 to 95% by mass, based on the total amount of the components (A) to (D). ..
  • the content of the component (A) is 70% by mass or more, the toughness of the cured film is improved and the breakage of the cured film at the time of peeling is suppressed, so that the workability when peeling the cured film from the water-repellent lens is improved. improves.
  • it is 97% by mass or less, the adhesion between the cured film and the water-repellent lens is appropriately adjusted, and the cured film can be easily peeled off.
  • a compound having a functional group capable of reacting with the (meth) acrylate compound may be added as a curing agent.
  • a (b1) polyfunctional thiol compound having good curability in the atmosphere is preferable.
  • the polyfunctional thiol compound is not particularly limited as long as it is an organic compound having two or more thiol groups (-SH groups), and known materials can be used.
  • a polyfunctional thiol compound represented by the following general formula (formula 2) can be mentioned.
  • the polyfunctional thiol compound may be used alone or in combination of two or more.
  • R 3 is a hydrocarbon group having 2 to 30 carbon atoms, ether oxygen (-O-) and 2 to 40 carbon atoms. It is either a group consisting only of a hydrocarbon group, an isocyanurate ring, or a group consisting only of an isocyanurate ring and a hydrocarbon group.
  • polyfunctional thiol compound examples include trimethylolpropanthris (3-mercaptopropionate), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, and pentaerythritol tetrakis (3-mercaptopropionate). ), Tetraethylene glycol bis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate) and the like.
  • the weight average molecular weight of the polyfunctional thiol compound is 200 to 2,000, preferably 300 to 1,800, and more preferably 350 to 1,600. Even if the molecular weight is smaller than 200, there is no problem in terms of curability, but the polyfunctional thiol compound has high volatility and tends to have a strong odor. On the other hand, if the molecular weight is larger than 2000, the solubility in (A) polyfunctional (meth) acrylate resin may be low.
  • the characteristics of the resin composition for a water-repellent lens protective film after curing are ((B) number of functional groups of the curing agent) / (number of (meth) acryloyl groups) in the unit weight of the resin composition for the water-repellent lens protective film. It is affected by the value (hereinafter, (B) / (A) functional group ratio).
  • (B) / (A) functional group ratio When the (B) / (A) functional group ratio is in the range of 0.15 to 2.0, a dense crosslink is formed and a tough cured product is obtained.
  • the effect on the water-repellent lens can be suppressed.
  • the content of the (b1) polyfunctional thiol compound is preferably 0.5 to 30 parts by mass, more preferably 1.0 to 25 parts by mass with respect to 100 parts by mass of the component (A).
  • the content of the component (b1) is 0.5 parts by mass or more with respect to 100 parts by mass of the component (A)
  • the adhesion between the cured film and the water-repellent lens becomes appropriate, and the cured film is peeled off. Becomes easier.
  • the amount is 30 parts by mass or less, the toughness of the cured film is improved and the cured film is less likely to break at the time of peeling, so that the workability when peeling the cured film from the water-repellent lens is improved.
  • the ratio of the thiol group derived from the component (b1) to the (meth) acryloxy group derived from the component (A) is preferably 0.05 to 5.0. , More preferably 0.10 to 3.0.
  • the (b1) / (A) functional group ratio is 0.05 or more, the adhesion between the cured film and the water-repellent lens becomes appropriate, and the cured film can be easily peeled off.
  • it is 5.0 or less, the toughness of the cured film is sufficient and the fracture of the cured film at the time of peeling is suppressed, so that the workability when peeling the cured film from the water-repellent lens is improved.
  • the resin composition for a water-repellent lens protective film of the present invention contains, as a component (C), a photopolymerization initiator that generates radicals by irradiation with ultraviolet rays. Since this resin composition for a water-repellent lens protective film contains the component (C), it can be cured even when exposed to an LED ultraviolet irradiation device having a wavelength close to the visible light region, and the water-repellent lens is formed by light irradiation. The heat effect of the lens can be suppressed.
  • the component (C) is not particularly limited as long as it can polymerize a photosensitive resin, and can be appropriately selected from commonly used photopolymerization initiators.
  • Examples thereof include acylphosphine oxide-based, oxime ester-based, aromatic ketone-based, quinone-based, alkylphenone-based, imidazole-based, acridine-based, and phenylglycine-based photopolymerization initiators.
  • 6-Pentylphosphinoxide bis (2,4,6-trimethylbenzoyl) -phenylphosphinoxide, 2,4,6-trimethylbenzoyldiphenylphosphinoxide ("IRGACURE-TPO" (BASF)), ethyl-2 , 4,6-trimethylbenzoylphenylphosphinate, bis (2,4,6-trimethylbenzoyl) -phenylphosphin oxide ("IRGACURE-819" (BASF)), (2,5-dihydroxyphenyl) diphenylphosphine Examples thereof include oxide, (p-hydroxyphenyl) diphenylphosphine oxide, bis (p-hydroxyphenyl) phenylphosphin oxide, tris (p-hydroxyphenyl) phosphin oxide and the like.
  • the oxime ester-based photopolymerization initiator is a photopolymerization initiator having an oxime ester bond, and is, for example, 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) ( Product Name: OXE-01, manufactured by BASF), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] Etanone 1- (O-acetyloxime) (Product name: OXE) -02, manufactured by BASF), 1-phenyl-1,2-propanedione-2- [O- (ethoxycarbonyl) oxime] (trade name: Quantacure-PDO, manufactured by Nippon Kayaku Co., Ltd.) and the like.
  • aromatic ketone-based photopolymerization initiator examples include benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michlerketone), N, N'-tetraethyl-4,4'-diaminobenzophenone, 4 -Methoxy-4'-dimethylaminobenzophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one ("IRGACURE-651” (manufactured by BASF)), 2-benzyl-2-dimethylamino-1- (4-Methoxyphenyl) -butane-1-one ("IRGACURE-369" (manufactured by BASF)), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1-one ("IRGACURE-907” (manufactured by BASF)) and the like.
  • Examples of the quinone-based photopolymerization initiator include 2-ethylanthraquinone, phenanthrenquinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, and 2 , 3-Diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, etc. Be done.
  • alkylphenone-based photopolymerization initiator examples include benzoin-based compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin phenyl ether, and 2,2-dimethoxy-1,2-diphenylethane-1-.
  • Examples of the imidazole-based photopolymerization initiator include 2,4,5-triarylimidazole dimers, and more specifically, 2- (2-chlorophenyl) -1- [2- (2-chlorophenyl). -4,5-diphenyl-1,3-diazol-2-yl] -4,5-diphenylimidazole and other 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) ) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole Examples thereof include a dimer, a 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer and the like.
  • the component (C) contains at least one selected from the group consisting of compounds represented by the following general formula (formula 3). You may.
  • R 4 represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, or an amino group
  • R 5 and R 6 each independently have a hydrogen atom and 1 to 8 carbon atoms. It represents an alkyl group, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms.
  • R 5 and R 6 may be bonded to each other to form a cyclic structure having 3 to 16 carbon atoms.
  • R 4 to R 6 may each have a substituent except for the case of a hydroxyl group and a hydrogen atom, and the amino group having a substituent has substituents bonded to each other and has 3 to 12 carbon atoms.
  • Each R 7 independently contains one or more atoms selected from a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a mercapto group, or an oxygen atom, a nitrogen atom and a sulfur atom. It indicates an organic group having 1 to 10 carbon atoms which may be used.
  • R 4 represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, or an amino group.
  • the alkoxy group represented by R 4 may be a hydroxyl group or a methoxy group from the viewpoint of curability when a UV-LED is used as a light source.
  • R 5 and R 6 each independently have a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms. show.
  • the alkyl group represented by R 5 and R 6 may be an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 or 2 carbon atoms.
  • alkyl group examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-heptyl group, an n-hexyl group, an n-octyl group and the like.
  • the alkoxy group may be an alkoxy group having 1 to 4 carbon atoms, or may be an alkoxy group having 1 or 2 carbon atoms.
  • alkoxy group examples include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a tert-butoxy group, an n-heptyloxy group, an n-hexyloxy group, an n-octyloxy and the like.
  • the aryl group may be an aryl group having 6 to 10 carbon atoms or an aryl group having 6 to 8 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group.
  • R 5 and R 6 may be bonded to each other to form a cyclic structure having 3 to 16 carbon atoms.
  • the cyclic structure may be a cyclic structure having 4 to 10 carbon atoms or a cyclic structure having 5 to 8 carbon atoms.
  • the cyclic structure may be an alicyclic structure, and examples of the alicyclic structure include a cyclopentane structure, a cyclohexane structure, a cycloheptane structure, and a cyclooctane structure. Further, these alicyclic structures may contain carbon atoms to which R 5 and R 6 are directly bonded together.
  • the content of the (C) photopolymerization initiator is 0.05 to 20% by mass, preferably 0.1 to 10% by mass, based on the total solid content of the resin composition for the water-repellent lens protective film.
  • the content of the (C) photopolymerization initiator is preferably 0.1 to 25 parts by mass, more preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the component (A).
  • the film is sufficiently cured, so that the adhesion between the cured film and the water-repellent lens is improved and the cured film is cured. It is possible to improve the toughness of the base material and prevent the water repellency of the base material from being lowered due to the residue of the uncured component when the protective film is peeled off.
  • the content of the component (C) is 25 parts by mass or less with respect to 100 parts by mass of the component (A)
  • the amount of the photopolymerization initiator becomes appropriate, and the residue of the photopolymerization initiator when the protective film is peeled off. It is possible to prevent the deterioration of the water repellency of the base material due to the above.
  • the nonionic surfactant as the component (D) may be, for example, a hydrocarbon-based surfactant, a silicone-based surfactant, a fluorine-based surfactant, or the like.
  • hydrocarbon-based surfactants examples include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene n-octylphenyl ether, and polyoxyethylene n.
  • -Polyoxyethylene alkyl phenyl ethers such as nonylphenyl ether; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; acrylic polymers and the like.
  • hydrocarbon-based surfactant containing an acrylic polymer as a main component examples include Polyflow No. 75, Polyflow No. 90, Polyflow WS-314 (all manufactured by Kyoeisha Chemical Co., Ltd., trade name) and the like can be used.
  • silicone-based surfactants include, for example, Polyflow KL-100, Polyflow KL-401, Polyflow KL-402, Polyflow KL-403 (all manufactured by Kyoeisha Chemical Co., Ltd., trade name); KP-323, KP. -341, KP-392 (above, manufactured by Shin-Etsu Chemical Co., Ltd., trade name); SZ-1642, SZ-1677, SH192, SH193 (above, manufactured by Toray Dow Corning Co., Ltd., trade name) and the like can be used. can.
  • the fluorine-based surfactant is a fluorine-based nonionic surfactant composed of a fluorine-based segment and a non-fluorine-based segment, and examples thereof include (d1) a block copolymer composed of a fluorine-based segment and a non-fluorine-based segment.
  • examples of the combination of the fluorine segment and the non-fluorine segment of the fluorine-based surfactant include an addition polymer of a fluorinated alkyl group-containing alcohol and a monomer containing an oxyalkylene group such as ethylene oxide and proprene oxide, and fluorination.
  • Examples thereof include molecular design of a copolymer of an alkyl group-containing ethylenically unsaturated compound and a polyoxyalkylene group-containing ethylenically unsaturated compound (hereinafter referred to as “fluorinated alkyl group-containing ethylenically unsaturated compound”).
  • fluorinated alkyl group-containing ethylenically unsaturated compound As the component (d1), only one type may be used alone, or two or more types may be used in combination.
  • the component (d1) is easily surface segregated when the resin composition for forming a protective film is applied to the water-repellent lens, and the water-repellent lens is formed. It is possible to improve the coatability of. Further, by increasing the surface segregation property, the component (d1) is less likely to inhibit the curing reaction between the (A) polyfunctional (meth) acrylate and the (B) curing agent inside the coating film, so that the toughness is more excellent. A cured film is obtained.
  • the fluorinated alkyl group-containing ethylenically unsaturated compound contains a (meth) acrylic ester group from the viewpoint of compatibility with the resin composition for a water-repellent lens protective film or coating uniformity based on such compatibility.
  • the monomer to be used is suitable. Specifically, it is a fluoroalkyl (meth) acrylate represented by the following general formula (formula 4).
  • R f is a perfluoroalkyl group having 4 to 8 carbon atoms
  • R 8 is a hydrogen atom or a methyl group
  • p is an integer of 1 to 6
  • the fluorinated alkyl group R f in the fluoroalkyl (meth) acrylate preferably has 4 to 6 carbon atoms. When the number of carbon atoms is 4 or more, the surface tension lowering ability is improved, and when the number of carbon atoms is 6 or less, the compatibility with other formulations is enhanced. Fluoroalkyl (meth) acrylates can be used alone or in combination of two or more.
  • the fluorine-based nonionic surfactant preferably contains a photopolymerizable group from the viewpoint of reducing residual components in the water-repellent lens after the protective film is peeled off.
  • a preferred form thereof is a polymer having a side chain having an ethylenically unsaturated group and a side chain having a fluorinated alkyl group or a group containing an oxygen atom as a part thereof.
  • the repeating unit having an unsaturated group-containing side chain is preferably a repeating unit represented by the following general formulas (formula 5) to (formula 8) from the viewpoint of photoreactivity.
  • the repeating unit having an unsaturated group-containing side chain in one molecule may be the same or different.
  • R 9 , R 10 , R 11 , and R 12 are hydrogen atoms or methyl groups.
  • nonionic surfactants it is particularly preferable to use a fluorine-based surfactant. Since the fluorine-based surfactant has a high ability to reduce the surface tension of the resin composition for a water-repellent lens protective film, it is suitable for coating a superhydrophobic lens having a low surface energy.
  • the protective film for this purpose is required to have adhesiveness to the superhydrophobic lens so that the axis does not shift during processing, and to be easily peeled off after use.
  • the water-repellent layer formed on the surface of the superhydrophobic lens is coated with a fluorine-based coating, appropriate adhesion can be achieved by blending a fluorine-based surfactant that easily interacts with this layer into the protective film. And the contradictory properties of peelability are achieved.
  • the fluorine-based surfactant when it is blended in propylene glycol monomethyl ether acetate at a concentration of 0.1 part by mass, it is preferable that the surface tension of the blended solution is reduced to 26.0 mN / m or less, which is more preferable. Is preferably one that can be reduced to 23.0 mN / m or less.
  • a surfactant that can reduce the surface tension to 23.0 mN / m or less the surface tension can be reduced efficiently, and uniform coating can be performed with a smaller amount of addition.
  • Examples of commercially available fluorine-based surfactants having the above-mentioned ability to reduce surface tension include Megafuck F-477, Megafuck F-554, Megafuck F-557, Megafuck R-41, and Megafuck RS-56. , Megafuck RS-72-K, Megafuck RS-75-A, Megafuck RS-75-NS, Megafuck RS-78 (above, DIC Corporation, trade name), Modiper F206, Modiper F246 (above, (Product name) manufactured by Nichiyu Co., Ltd. can be used.
  • the weight average molecular weight of the block copolymer composed of a fluorine-based segment and a non-fluorine-based segment is preferably 25,000 to 100,000, more preferably 30,000 to 80,000.
  • the method for measuring the weight average molecular weight is the same as the method for measuring the weight average molecular weight of (A) polyfunctional (meth) acrylate.
  • the content of the component (D) is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total solid content of the resin composition for the water-repellent lens protective film. ..
  • the content is in the range of 0.01 to 10% by mass, the resin composition for a water-repellent lens protective film is uniformly applied even to a substrate that is extremely difficult to apply, such as a superhydrophobic lens. Will be possible.
  • the content is in the range of 0.01 to 5% by mass, when the protective film is peeled off, a uniform protective film can be obtained without causing a decrease in water repellency of the water-repellent lens due to residual surfactant.
  • the content of the block copolymer composed of the fluorine-based segment and the non-fluorine-based segment is preferably 0.1 to 25 parts by mass, more preferably 0 with respect to 100 parts by mass of the component (A). .5 to 20 parts by mass, particularly preferably 1.0 to 15 parts by mass.
  • the content of the component (d1) is 0.1 part by mass or more with respect to 100 parts by mass of the component (A)
  • the coatability to the water-repellent lens is excellent, and when it is 25 parts by mass or less, the protective film is provided. It is possible to prevent the water repellency of the substrate from being lowered due to the residue of the surfactant when the lens is peeled off.
  • the resin composition for a water-repellent lens protective film of the present invention may be diluted with an organic solvent or a reactive diluent in order to make the reaction system uniform and facilitate coating.
  • organic solvent include alcohol-based solvents, aromatic hydrocarbon-based solvents, ether-based solvents, ester-based solvents, ether ester-based solvents, and ketone-based solvents.
  • the reactive diluent a monofunctional photopolymerizable monomer having a vinyl group, an acryloyl group, a methacryloyl group and the like can be used.
  • (meth) acrylate compounds having an acryloyl group or a methacryloyl group are preferable, and for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, tert.
  • alkoxyalkyl (meth) acrylates such as 2-ethoxyethoxyethyl (meth) acrylates
  • hydroxyalkyl (meth) acrylates such as glycidyl (meth) acrylates, 2-hydroxyethyl (meth) acrylates and 2-hydroxypropyl (meth) acrylates.
  • alkoxy (poly) alkylene glycol (meth) acrylate such as methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate; N, N-dimethylaminoethyl (meth) acrylate, Dialkylaminoalkyl (meth) acrylates such as N, N-diethylaminoethyl (meth) acrylates; allyl (meth) acrylates, 1,3-butanediol (meth) acrylates, 1,4-butanediol (meth) acrylates, 1, Examples thereof include monofunctional (meth) acrylate compounds such as glycol mono (meth) acrylates such as 6-hexanediol (meth) acrylates and 3-methylpentanediol (meth) acrylates.
  • the resin composition for a water-repellent lens protective film of the present invention contains colorants such as pigments and dyes, stabilizers, flame retardants, organic fillers, plasticizers, antioxidants, and defoamers as long as the characteristics of the present invention are not impaired.
  • colorants such as pigments and dyes, stabilizers, flame retardants, organic fillers, plasticizers, antioxidants, and defoamers as long as the characteristics of the present invention are not impaired.
  • An appropriate amount of additives such as a foaming agent, a coupling agent, and a rheology control agent may be blended.
  • the method for protecting a water-repellent lens of the present invention is characterized in that a protective film formed by applying the resin composition for a water-repellent lens protective film of the present invention to the water-repellent lens and curing the water-repellent lens is provided.
  • the method for forming the protective film using the resin composition for the water-repellent lens protective film of the present invention is not particularly limited, and examples thereof include methods such as dip coating, spray coating, and spin coating.
  • the thickness of the protective film formed by using the resin composition for the water-repellent lens protective film of the present invention is not particularly limited, but it is possible to prevent axial misalignment during peripheral processing of the water-repellent lens and to prevent scratches during processing and storage. From the viewpoint, it is preferably 10 ⁇ m or more. On the other hand, the thickness of the coating film is preferably 100 ⁇ m or less so that the position shift does not occur when the center of the lens is specified.
  • the composition applied on the substrate can be irradiated with active energy rays such as ultraviolet rays to obtain a protective film.
  • active energy rays such as ultraviolet rays
  • Light sources used in the active energy ray irradiation process include, for example, UV-LED (ultraviolet LED), low pressure mercury lamp, high pressure mercury lamp, ultrahigh pressure mercury lamp, metal halide lamp, carbon arc, xenon arc, gas laser, solid laser, electron beam irradiation device. And so on.
  • UV-LEDs which consume significantly less power than conventional UV lamps and generate less heat from light sources than UV lamps, are preferable, and their beak illuminance is 395 nm or more, which is close to visible light.
  • UV-LED it is possible to suppress the influence on the water-repellent lens at the time of ultraviolet irradiation and suppress the generation of cracks in the water-repellent layer.
  • the resin composition for a water-repellent lens protective film of the present invention can be uniformly applied to a water-repellent lens having a water-repellent / oil-repellent layer formed on the surface of a plastic or glass as a base material to impart antifouling properties to the surface. .. Above all, in recent years, the resin composition for a water-repellent lens protective film of the present invention can uniformly form a protective film even for a lens having a superhydrophobic layer having further improved antifouling properties.
  • the present invention can be applied to a lens having a water-repellent layer having a contact angle of 90 ° or more with water, and is particularly effective for a lens having a water-repellent layer having a contact angle of 140 ° or more.
  • a normal water-repellent lens if the contact angle with water is 90 ° or more and 110 ° or less, a high water-repellent lens if the contact angle of water is higher than 110 ° and 140 ° or less, and superhydrophobic lens if it is larger than 140 °. It is called a lens.
  • the contact angle of the water repellent lens can be evaluated by a method called the sessile drop method.
  • a droplet of 1 ⁇ L of pure water is prepared and brought into contact with the target water-repellent lens to be dropped.
  • the angle formed by the water-repellent lens and the droplet at that time is evaluated as the contact angle.
  • Hardener B-1 Dipentaerythritol Hexakis (3-mercaptopropionate) (DPMP SC Organic Chemistry Co., Ltd .: 6-functional, molecular weight 783)
  • C Ingredient: Photopolymerization Initiator C-1: 2,2-Dimethoxy-2-phenylacetophenone (OMNIRAD651, manufactured by IGM) C-2: 2-benzyl-2- (dimethylamino) -4'-morpholinobtyrophenone (OMNIRAD369 IGM) C-3: Bis (2,4,6-trimethylbenzoyl) phenylphosphin oxide (OMNIRAD819 IGM) C-4: 1-Hydroxycyclohexylphenyl ketone (OMNIRAD184 IGM)
  • Nonionic surfactant D-1 Fluorine-based nonionic surfactant (Megafuck RS-75-A manufactured by DIC Corporation, surface tension 23.8 mN / part when 0.1 part by mass is blended in PGMEA / m)
  • D-2 Fluorine-based nonionic surfactant (Megafuck RS-78, manufactured by DIC Corporation, surface tension of 22.0 mN / m when 0.1 parts by mass is mixed in PGMEA)
  • D-3 Fluorine-based nonionic surfactant (surface tension 21.4 mN / m when 0.1 parts by mass is blended in PGMEA manufactured by Megafuck F-560 DIC Corporation)
  • D-4 Fluorine-based nonionic surfactant (surface tension 25.4 mN / m when 0.1 parts by mass is blended in PGMEA manufactured by Megafuck F-477 DIC Corporation)
  • D'-1 Fluorine-based anionic surfactant (surface tension 26.5 mN / m when
  • the components (A) to (E) are charged into the mixing vessel at the blending ratios shown in Tables 1 and 2, and are stirred at room temperature (23 ° C.) under ultraviolet rays until they become uniform with a three-one motor to make them water repellent.
  • a sample of a resin composition for a lens protective film was obtained.
  • the following viscosity, coatability, photocurability, holding power, peelability, and lens contamination property were evaluated for each of the obtained resin compositions for the water-repellent lens protective film of Examples and Comparative Examples. The results are shown in Tables 1 and 2.
  • the integrated light amount at which the surface tack was eliminated by irradiation was confirmed and evaluated as follows.
  • the integrated light intensity needs to be 20000 mJ / cm 2 or less due to the thermal effect on the lens and the curing time.
  • ⁇ The integrated light amount is 1000 mJ / cm 2 or less.
  • ⁇ More than 1000 mJ / cm 2 and less than 20000 mJ / cm 2 .
  • X More than 20000 mJ / cm 2 .
  • the holding power of the protective film formed on the superhydrophobic lens was evaluated as an evaluation of the axial deviation during peripheral processing of the water-repellent lens.
  • the holding force conformed to JIS-Z0237, and the load was changed.
  • An adhesive tape (CT405AP-24 manufactured by Nichiban Co., Ltd.) having a width of 24 mm and a length of 130 mm is attached to the center of the superhydrophobic lens on which the protective film is formed (see FIG. 1). At this time, mark with an oil-based pen so that it overlaps with the adhesive tape at the center of the lens recess.
  • the holding force measurement result is 0.0 mm.
  • the holding force measurement result is larger than 0.0 mm and 2.0 mm or less.
  • X The holding force measurement result is larger than 2.0 mm.
  • any sample can be applied to a superhydrophobic lens, and can be cured even with an LED ultraviolet irradiation device having a peak wavelength of 395 nm. Further, since it has a sufficient holding force to prevent axial deviation in the peripheral processing of the water-repellent lens, even a superhydrophobic lens can be processed into a desired shape by a conventional processing method.
  • Comparative Example 1-1 which does not contain the nonionic surfactant which is the component (D)
  • Comparative Example 1-2 which contains an anionic surfactant instead of the nonionic surfactant which is the component (D)
  • it is superhydrophobic. It cannot be coated on a water lens and cannot even form a protective film.
  • the LED ultraviolet irradiation device having a peak wavelength of 395 nm has poor curability and exceeds the allowable integrated light amount.
  • the toughness of the cured film is low, it tears at the time of peeling, resulting in poor peelability.
  • Comparative Example 1-4 the photocurability is good, but the flexibility of the cured film is high, and the holding power is equal to or higher than the specified value. As a result, misalignment occurs during peripheral machining.
  • B1 Ingredient: Polyfunctional thiol compound B-1: Dipentaerythritol hexakis (3-mercaptopropionate) (DPMP SC Organic Chemistry Co., Ltd .: 6-functional, weight average molecular weight 783) B-2: Trimethylolpropanetris (3-mercaptopropionate) (TMMP SC Organic Chemistry Co., Ltd .: trifunctional, weight average molecular weight 399)
  • (D1) Component Block copolymer composed of a fluorine-based segment and a non-fluorine-based segment
  • D-5 Fluorine-based block copolymer (Modiper F206, manufactured by NOF CORPORATION, weight average molecular weight 38,000)
  • D-6 Fluorine-based block copolymer (Modiper F246 NOF Corporation, weight average molecular weight 25,000)
  • D-7 Fluorine-based block copolymer (Modiper F3636, manufactured by NOF CORPORATION, weight average molecular weight 77,000)
  • the distance to the lens was adjusted and irradiation was performed one side at a time.
  • the contact angle of the superhydrophobic lens was calculated from the angle formed by the lens and the droplet at that time when a droplet of 1 ⁇ L of pure water was brought into contact with the surface of the target lens.
  • the holding power of the protective film formed on the superhydrophobic lens was evaluated as an evaluation of the axial deviation during peripheral processing of the lens.
  • the holding force was evaluated in accordance with JIS-Z0237, and the load was changed.
  • Temperature 23 ° C
  • Relative humidity 50%
  • Adhesive tape (CT405AP-24 manufactured by Nichiban Co., Ltd.) with a width of 24 mm and a length of 130 mm is attached to the center of the superhydrophobic lens with a protective film that has been stored for 3 months in an environment (CT405AP-24 manufactured by Nichiban Co., Ltd.). See Figure 1).
  • the holding force measurement result was 2.0 mm or less.
  • ⁇ The holding force measurement result is 0.0 mm.
  • ⁇ The holding force measurement result is larger than 0.0 mm and 0.5 mm or less.
  • ⁇ The holding force measurement result is larger than 0.5 mm and 2.0 mm or less.
  • X The holding force measurement result is larger than 2.0 mm.
  • the protective film obtained by curing the resin compositions of Examples 2-1 to 2-19 has a temperature of 23 ° C. and a relative humidity of 50%, even after being stored for 3 months in an environment with respect to the superhydrophobic lens. It had an appropriate degree of adhesion, and had high levels of holding power, peelability, and toughness. Further, the decrease in water repellency of the superhydrophobic lens after peeling of the protective film was suppressed, and the non-staining property was also excellent.
  • Comparative Examples 2-1 and 2-2 since the weight average molecular weight of the component (A) was too small or too large, the holding power of the obtained protective film on the superhydrophobic lens was determined. Or it lacked toughness. In Comparative Examples 2-3 and 2-4, since the content of the component (b1) was too small or too large, the peelability or toughness of the obtained protective film from the superhydrophobic lens was insufficient. .. In Comparative Example 2-5, since the content of the component (C) was too small, the holding power, toughness and non-staining property of the obtained protective film with respect to the superhydrophobic lens were insufficient.
  • Comparative Example 2-6 the content of the component (C) was excessive, so that the non-staining property of the obtained protective film was insufficient.
  • Comparative Example 2-7 the content of the component (d1) was excessive, so that the non-staining property of the obtained protective film was insufficient.
  • Comparative Example 2-8 since the component (d1) was not contained, the applicability to the superhydrophobic lens was insufficient.

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Abstract

The present invention addresses the problem of providing a resin composition for water-repellent lens protective films, that can be uniformly applied in particular even in the case of an ultra-water-repellent lens having a high antifouling performance.　In order to solve the problem, a resin composition for water-repellent lens protective films is provided that comprises (A) a polyfunctional (meth)acrylate having a weight-average molecular weight of 200-30,000, (C) a photopolymerization initiator, and (D) a nonionic surfactant. The present invention can thereby provide a resin composition for water-repellent lens protective films, that can be uniformly applied in particular even in the case of an ultra-water-repellent lens having a high antifouling performance.

Description

撥水レンズ保護膜用樹脂組成物及び撥水レンズを保護する方法Resin composition for water-repellent lens protective film and method for protecting water-repellent lens
　本発明は撥水レンズの周縁加工時にレンズ表面を保護するための撥水レンズ保護膜用樹脂組成物に関する。また、撥水レンズの周縁加工時に、加工装置にレンズを保持するために撥水レンズを保護する方法に関する。 The present invention relates to a resin composition for a water-repellent lens protective film for protecting the lens surface during peripheral processing of the water-repellent lens. Further, the present invention relates to a method of protecting a water-repellent lens in order to hold the lens in a processing apparatus during peripheral processing of the water-repellent lens.
　眼鏡レンズは眼鏡フレームの枠形状に合うよう加工装置を用いて周縁を加工する。この加工装置は、一対のレンズチャック軸に眼鏡レンズを保持し、レンズチャック軸の回転によりレンズが回転され、砥石等の加工具がレンズに押し当てられることにより、レンズを所望の形状に加工する機械である。その際、眼鏡レンズには両面テープで冶具を貼り付け、その冶具を介してレンズチャック軸に保持される。 The peripheral edge of the spectacle lens is processed using a processing device to match the frame shape of the spectacle frame. This processing device holds a spectacle lens on a pair of lens chuck shafts, the lens is rotated by the rotation of the lens chuck shafts, and a processing tool such as a grindstone is pressed against the lens to process the lens into a desired shape. It is a machine. At that time, a jig is attached to the spectacle lens with double-sided tape, and the jig is held on the lens chuck shaft via the jig.
　近年、水や油など汚れが付着しにくい撥水・撥油物質がレンズ表面にコーティングされた撥水レンズが多く使用されている。これらの撥水レンズはその表面が滑りやすいため、撥水処理が施されていないレンズと同様の加工法では両面テープの粘着力が不足し、レンズチャック軸の回転角度に対してレンズの回転角度がずれてしまう、いわゆる軸ずれが発生するという問題があった。 In recent years, many water-repellent lenses have been used in which the surface of the lens is coated with a water-repellent / oil-repellent substance that does not easily adhere to dirt such as water and oil. Since the surface of these water-repellent lenses is slippery, the adhesive strength of the double-sided tape is insufficient by the same processing method as the lens without water-repellent treatment, and the rotation angle of the lens with respect to the rotation angle of the lens chuck shaft. There was a problem that the so-called axis misalignment occurred.
　この軸ずれを防ぐ方法として、レンズ表面に一時的に保護膜を設ける手法が知られている。この手法では、レンズ表面に冶具固定用の両面テープ及びレンズ表面と良好な接着性を有する保護層を形成することで、レンズ加工時の軸ずれを防止できる。また、加工後はレンズから保護膜を容易に剥がすことができる。 As a method of preventing this axis shift, a method of temporarily providing a protective film on the lens surface is known. In this method, by forming a double-sided tape for fixing a jig and a protective layer having good adhesiveness to the lens surface on the lens surface, it is possible to prevent axial misalignment during lens processing. In addition, the protective film can be easily peeled off from the lens after processing.
　しかし、この保護膜を形成する際、熱硬化型保護膜では硬化時の熱による影響で、撥水層にクラックが入り、表面の平滑性が失われることから撥水性が低下してしまう問題があった。また、光硬化型保護膜であっても、広い波長範囲に発光を持つ水銀ランプやメタルハライドランプを光源用いて硬化させる場合、レンズが照射光を吸収し発熱するためクラックが発生してしまう問題があった。 However, when forming this protective film, the thermosetting protective film has a problem that the water repellency is lowered because the water repellent layer is cracked due to the influence of heat during curing and the smoothness of the surface is lost. there were. In addition, even with a photocurable protective film, when a mercury lamp or metal halide lamp that emits light in a wide wavelength range is cured using a light source, there is a problem that cracks occur because the lens absorbs the irradiation light and generates heat. there were.
　特許文献１では撥水機能を有するレンズ上に無機物をコロイド状に分散させた有機物ポリマーからなる熱硬化型保護膜を形成する手法が開示されている。
　特許文献２では撥水機能を有するレンズ上に金属酸化物を含む光硬化型保護膜を形成する手法が開示されている。
　特許文献３では被着体から硬化物を剥離させるのに必要な適度な剥離強度を有するとともに、硬化物が適度な屈曲性を有する仮固定剤として、アクリルオリゴマー、アクリルモノマー、チオール化合物及び光開始剤を組み合わせた光硬化型アクリル樹脂組成物が開示されている。
　特許文献４には、撥水・撥油性能を有する防汚膜が形成されたプラスチック眼鏡レンズの表面に、一時的に保護膜を形成するための材料として、アクリル樹脂を有機溶剤に溶解した組成物が記載されている。 Patent Document 1 discloses a method of forming a thermosetting protective film made of an organic polymer in which an inorganic substance is dispersed in a colloidal manner on a lens having a water-repellent function.
Patent Document 2 discloses a method of forming a photocurable protective film containing a metal oxide on a lens having a water-repellent function.
In Patent Document 3, an acrylic oligomer, an acrylic monomer, a thiol compound, and a photoinitiator are used as temporary fixing agents having an appropriate peeling strength necessary for peeling a cured product from an adherend and having an appropriate flexibility of the cured product. A photocurable acrylic resin composition in which the agents are combined is disclosed.
Patent Document 4 describes a composition in which an acrylic resin is dissolved in an organic solvent as a material for temporarily forming a protective film on the surface of a plastic spectacle lens on which an antifouling film having water and oil repellency is formed. The thing is listed.
特開２０１０-０８５６９１号公報Japanese Unexamined Patent Publication No. 2010-085691 国際公開第２０１７／１１０４７２号International Publication No. 2017/11472 国際公開第２０１３／０７３３６４号International Publication No. 2013/0733364 特開２００９－１０９６１１号公報Japanese Unexamined Patent Publication No. 2009-109611
　しかしながら、最近はコーティング表面の水滴の接触角が１５０°以上となる、いわゆる超撥水と呼ばれる撥水処理が増えており、このような処理が施された超撥水レンズに対しては、上述した特許文献に記載の発明では、塗工性が低いという課題があった。 However, recently, the so-called superhydrophobic treatment in which the contact angle of water droplets on the coating surface is 150 ° or more is increasing, and the above-mentioned superhydrophobic lens to which such treatment is applied is described. The invention described in the patent document has a problem of low coatability.
　本発明は前記の従来技術に鑑みてなされたものであり、その目的は、特に防汚性の高い超撥水レンズであっても均一に塗工可能である撥水レンズ保護膜用樹脂組成物を提供することにある。 The present invention has been made in view of the above-mentioned prior art, and an object thereof is a resin composition for a water-repellent lens protective film that can be uniformly applied even to a superhydrophobic lens having particularly high antifouling property. Is to provide.
（第１の課題）
　また別の観点では、撥水レンズ保護膜用樹脂組成物から得られる保護膜には、加工時は撥水レンズから剥離せず、加工後は容易に剥離可能という適度な密着性を有すること（密着性）も必要とされる。
　また、保護膜形成時の熱影響について、近年発光波長範囲が狭いＵＶ－ＬＥＤ照射装置（発光波長３６５或いは３８０－４０５ｎｍ）が注目されている。その中でもなるべく可視光に近い波長光をピーク波長にもつ光源が好ましく、特にピーク波長として３９５ｎｍ以上の光源ではレンズの発熱なく保護膜を硬化させることが可能となるが、一般的に長波長光になるほど硬化しにくくなることから、前述した特許文献に記載された組成物では硬化が困難であるという問題があった。 (First issue)
From another point of view, the protective film obtained from the resin composition for a water-repellent lens protective film has an appropriate adhesiveness that it does not peel off from the water-repellent lens during processing and can be easily peeled off after processing (). Adhesion) is also required.
Further, regarding the thermal influence during the formation of the protective film, a UV-LED irradiation device (emission wavelength 365 or 380-405 nm) having a narrow emission wavelength range has been attracting attention in recent years. Among them, a light source having a wavelength light as close to visible light as possible as a peak wavelength is preferable, and a light source having a peak wavelength of 395 nm or more can cure the protective film without heat generation of the lens, but generally, long wavelength light is used. Since it becomes difficult to cure, there is a problem that it is difficult to cure with the composition described in the above-mentioned patent document.
　そこで、本発明の第１の課題は、超撥水処理されたレンズに対する塗工性及び密着性を調整した樹脂組成物であって、撥水性の高いレンズに均一に塗工でき、且つピーク波長３９５ｎｍのＬＥＤ光源でも硬化可能である撥水レンズ保護膜用樹脂組成物を提供することである。これにより、熱による撥水性の低下を引き起こすことなく超撥水レンズ上に保護膜を形成することを可能とする。そして、超撥水レンズであっても保護膜を形成することで撥水レンズの周縁加工による軸ずれがなく、超撥水レンズを所望の形状へ加工することを目的とする。 Therefore, the first object of the present invention is a resin composition having adjusted coatability and adhesion to a lens treated with superhydrophobicity, which can be uniformly coated on a lens having high water repellency and has a peak wavelength. It is an object of the present invention to provide a resin composition for a water-repellent lens protective film that can be cured even with an LED light source having a wavelength of 395 nm. This makes it possible to form a protective film on the superhydrophobic lens without causing a decrease in water repellency due to heat. Then, even if it is a superhydrophobic lens, by forming a protective film, there is no axial deviation due to peripheral processing of the water repellent lens, and it is an object of the present invention to process the superhydrophobic lens into a desired shape.
（第２の課題）
　さらに別の観点では、撥水レンズ保護膜用樹脂組成物から得られる保護膜には、加工時は撥水レンズから剥離せず、加工後は容易に剥離可能という適度な密着性を有すること（密着性）、保護膜剥離後にレンズの撥水性に影響を与えないこと（非汚染性）も必要とされる。さらに、レンズに保護膜を形成後、周縁加工を行うまでには数ヶ月の期間が空く場合もあるため、保護膜には長期間保管を行っても密着性や非汚染性が変わらないことも求められる。 (Second issue)
From another viewpoint, the protective film obtained from the resin composition for a water-repellent lens protective film has an appropriate adhesiveness that it does not peel off from the water-repellent lens during processing and can be easily peeled off after processing (). Adhesion) and not affecting the water repellency of the lens after the protective film is peeled off (non-staining) are also required. Furthermore, after the protective film is formed on the lens, it may take several months before the peripheral processing is performed, so the protective film may not change its adhesion and non-staining property even if it is stored for a long period of time. Desired.
　よって、本発明の第２の課題は、特に防汚性の高い超撥水レンズであっても均一に塗工可能であり、且つ、加工時は撥水レンズから剥離せず、加工後には容易に剥離可能な適度な密着性を有するとともに、剥離時の硬化膜の破断が生じない強靭性を有し、剥離後に基材の撥水性に影響を与えない保護膜を形成可能な樹脂組成物を提供することである。また、撥水レンズに保護膜を形成することで加工時のレンズの軸ずれを防止し、所望の形状へ加工できる方法を提供することである。 Therefore, the second problem of the present invention is that even a superhydrophobic lens having particularly high antifouling property can be uniformly coated, and it does not peel off from the water-repellent lens during processing and is easy after processing. A resin composition capable of forming a protective film that has an appropriate degree of adhesion that can be peeled off, has toughness that does not cause breakage of the cured film at the time of peeling, and does not affect the water repellency of the base material after peeling. To provide. Another object of the present invention is to provide a method for preventing axial deviation of the lens during processing by forming a protective film on the water-repellent lens and processing the lens into a desired shape.
　本発明は（Ａ）重量平均分子量が２００～３０，０００である多官能（メタ）アクリレートと、（Ｃ）光重合開始剤と、（Ｄ）ノニオン系界面活性剤と、を含有する撥水レンズ保護膜用樹脂組成物である。 The present invention is a water-repellent lens containing (A) a polyfunctional (meth) acrylate having a weight average molecular weight of 200 to 30,000, (C) a photopolymerization initiator, and (D) a nonionic surfactant. It is a resin composition for a protective film.
　また、本発明は撥水レンズに上記保護膜用樹脂組成物を塗布、硬化して得られる硬化膜を保護層として設けることにより、撥水レンズを保護する方法である。 Further, the present invention is a method of protecting a water-repellent lens by applying the resin composition for a protective film to the water-repellent lens and providing a cured film obtained by curing as a protective layer.
　本発明によれば、特に防汚性の高い超撥水レンズであっても均一に塗工可能である撥水レンズ保護膜用樹脂組成物を提供することができる。 According to the present invention, it is possible to provide a resin composition for a water-repellent lens protective film that can be uniformly applied even to a superhydrophobic lens having particularly high antifouling property.
本発明の実施例において、保護膜の保持力を評価するための試験方法を説明する概略説明図である。It is a schematic explanatory drawing explaining the test method for evaluating the holding power of a protective film in an Example of this invention. 本発明の実施例において、保護膜の保持力の評価方法を説明する概略説明図である。It is a schematic explanatory drawing explaining the evaluation method of the holding power of the protective film in the Example of this invention.
　以下に本発明について詳しく説明する。なお、本発明において「（メタ）アクリレート」とは、アクリレートとメタクリレートの双方を含む総称を意味する。また、本発明において数値範囲を示す「○○～××」とは、別途記載が無い限り、その下限値（「○○」）や上限値（「××」）を含む概念である。すなわち、正確には「○○以上××以下」を意味する。 The present invention will be described in detail below. In the present invention, "(meth) acrylate" means a generic term including both acrylate and methacrylate. Further, in the present invention, "○○ to XX" indicating a numerical range is a concept including a lower limit value ("○○") and an upper limit value ("XX") unless otherwise specified. That is, to be exact, it means "more than XX and less than XX".
　上記第１の課題を解決するための本発明の第１の撥水レンズ保護膜用樹脂組成物は、以下の〔１〕～〔３〕に記載の硬化性樹脂組成物である。
〔１〕
　（Ａ）重量平均分子量が２００～３０，０００である多官能（メタ）アクリレートと、
　（Ｃ）光重合開始剤と、
　（Ｄ）ノニオン系界面活性剤と、を含有する撥水レンズ保護膜用樹脂組成物。
〔２〕
　（Ｄ）ノニオン系界面活性剤がフッ素を含有し、プロピレングリコールモノメチルエーテルアセテート中に０．１質量部配合した際の表面張力が２６．０ｍＮ／ｍｍ以下となるフッ素系ノニオン性界面活性剤である、〔１〕記載の撥水レンズ保護膜用樹脂組成物。
〔３〕
　照度５０～３０００ｍＷ／ｃｍ２のＬＥＤ光源を用いた際、積算光量５０００ｍＪ／ｃｍ２以下で硬化可能である、〔１〕又は〔２〕に記載の撥水レンズ保護膜用樹脂組成物。 The first resin composition for a water-repellent lens protective film of the present invention for solving the first problem is the curable resin composition according to the following [1] to [3].
[1]
(A) Polyfunctional (meth) acrylate having a weight average molecular weight of 200 to 30,000, and
(C) Photopolymerization initiator and
(D) A resin composition for a water-repellent lens protective film containing a nonionic surfactant.
[2]
(D) A fluorine-based nonionic surfactant containing fluorine and having a surface tension of 26.0 mN / mm or less when 0.1 part by mass is blended in propylene glycol monomethyl ether acetate. , [1] The resin composition for a water-repellent lens protective film according to [1].
[3]
The resin composition for a water-repellent lens protective film according to [1] or [2], which can be cured with an integrated light amount of 5000 mJ / cm 2 or less when an LED light source having an illuminance of 50 to 3000 mW / cm 2 is used.
　本発明の第１の撥水レンズ保護膜用樹脂組成物は、撥水性が高く、表面への塗工が困難な撥水レンズであっても全体に均一に塗工することができ、この撥水レンズ保護膜用樹脂組成物により形成された保護膜は、剥離時は残渣なく容易に剥がすことができる。さらに、同組成物は可視光領域に近いピーク波長を有するＬＥＤ紫外線照射装置で硬化させることが可能なため、硬化時における撥水レンズに対する熱影響を抑え、撥水層のクラックや歪といった不具合を発生させることなく保護膜の形成が可能である。また、本発明の撥水レンズ保護膜用樹脂組成物は、輸送時や加工時の傷つきや汚染から保護するだけでなく、レンズに対し適度な密着力を有することから加工時の軸ずれをも防止することが可能となる。 The first resin composition for a water-repellent lens protective film of the present invention can be uniformly applied to the entire surface even if the water-repellent lens has high water repellency and is difficult to apply to the surface. The protective film formed of the resin composition for a water lens protective film can be easily peeled off without any residue at the time of peeling. Furthermore, since the composition can be cured by an LED ultraviolet irradiation device having a peak wavelength close to the visible light region, the thermal effect on the water-repellent lens at the time of curing is suppressed, and defects such as cracks and distortion of the water-repellent layer are suppressed. It is possible to form a protective film without generating it. Further, the resin composition for a water-repellent lens protective film of the present invention not only protects from scratches and contamination during transportation and processing, but also has an appropriate adhesion to the lens, so that it also has an axial deviation during processing. It is possible to prevent it.
　上記第２の課題を解決するための本発明の第２の撥水レンズ保護膜用樹脂組成物は、以下の〔４〕に記載の硬化性樹脂組成物である。
〔４〕
　以下の（Ａ）～（ｄ１）成分を含有することを特徴とする樹脂組成物であって、
　前記（Ａ）成分１００質量部に対して、（ｂ１）成分を０．５～３０質量部、（Ｃ）成分を０．１～２５質量部、（ｄ１）成分を０．１～２５質量部含むことを特徴とする、撥水レンズ保護膜用樹脂組成物。
　（Ａ）成分：重量平均分子量が２５０～３０，０００である多官能（メタ）アクリレート
　（ｂ１）成分：多官能チオール化合物
　（Ｃ）成分：光重合開始剤
　（ｄ１）成分：重量平均分子量が２５，０００～１００，０００であり、フッ素系セグメントと非フッ素系セグメントからなるブロック共重合体 The second resin composition for a water-repellent lens protective film of the present invention for solving the second problem is the curable resin composition according to the following [4].
[4]
A resin composition comprising the following components (A) to (d1).
With respect to 100 parts by mass of the component (A), the component (b1) is 0.5 to 30 parts by mass, the component (C) is 0.1 to 25 parts by mass, and the component (d1) is 0.1 to 25 parts by mass. A resin composition for a water-repellent lens protective film, which comprises.
(A) Component: Polyfunctional (meth) acrylate having a weight average molecular weight of 250 to 30,000 (b1) Component: Polyfunctional thiol compound (C) Component: Photopolymerization initiator (d1) Component: Weight average molecular weight of 25 A block copolymer consisting of a fluorine-based segment and a non-fluorine-based segment, which ranges from 000 to 100,000.
　本発明の第２の撥水レンズ保護膜用樹脂組成物は、特に防汚性が高く、表面への塗工が困難な超撥水レンズであっても均一に塗工可能である。加えて、本発明の撥水レンズ保護膜用樹脂組成物を硬化して得られる硬化膜は、撥水レンズに対して適度な密着力を有することから加工時の軸ずれを防止でき、保護膜を剥離した際に残渣なく容易に剥がすことができる。 The second resin composition for a water-repellent lens protective film of the present invention has particularly high antifouling properties and can be uniformly applied even to a superhydrophobic lens that is difficult to apply to the surface. In addition, the cured film obtained by curing the resin composition for the water-repellent lens protective film of the present invention has an appropriate adhesion to the water-repellent lens, so that it is possible to prevent axial misalignment during processing, and the protective film. Can be easily peeled off without any residue when peeled off.
［撥水レンズ保護膜用樹脂組成物］
　以下に、本発明の撥水レンズ保護膜用樹脂組成物に使用する各成分について説明する。
＜（Ａ）成分：多官能（メタ）アクリレート＞
　（Ａ）成分である多官能（メタ）アクリレートは、重量平均分子量（Ｍｗ）が２００～３０，０００であり、分子内に（メタ）アクリロイル基を２個以上有する化合物であれば特に制限されず、公知の材料を用いることができる。なお、（Ａ）成分は、１種のみを単独で使用することもできるし、２種以上を組み合わせて使用することもできる。 [Resin composition for water-repellent lens protective film]
Hereinafter, each component used in the resin composition for a water-repellent lens protective film of the present invention will be described.
<(A) component: polyfunctional (meth) acrylate>
The polyfunctional (meth) acrylate as the component (A) is not particularly limited as long as it is a compound having a weight average molecular weight (Mw) of 200 to 30,000 and having two or more (meth) acryloyl groups in the molecule. , Known materials can be used. As the component (A), only one kind may be used alone, or two or more kinds may be used in combination.
　（Ａ）多官能（メタ）アクリレートの好ましい例として以下の一般式（式１）で表される化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000001
 A preferable example of the (A) polyfunctional (meth) acrylate is a compound represented by the following general formula (formula 1).
Figure JPOXMLDOC01-appb-C000001
　式中のａは、好ましくは２～３０である。
　Ｒ１は、炭素数２～３００の炭化水素基若しくはエーテル酸素（－Ｏ－）およびヒドロキシル基（－ＯＨ）からなる群より選択される少なくとも１種を含む炭素数２～３００の炭化水素基、イソシアヌレート環若しくはイソシアヌレート環と炭化水素基若しくは炭素数２～２０の炭化水素基のみからなる基、又は、炭素数２～２５０の炭化水素基若しくはエーテル酸素（－Ｏ－）およびヒドロキシル基（－ＯＨ）からなる群より選択される少なくとも１種を含む炭素数２～２５０の炭化水素基である。Ｒ２は、水素原子またはメチル基である。 A in the formula is preferably 2 to 30.
R 1 is a hydrocarbon group having 2 to 300 carbon atoms or a hydrocarbon group having 2 to 300 carbon atoms containing at least one selected from the group consisting of an ether oxygen (—O—) and a hydroxyl group (—OH). An isocyanurate ring or a group consisting of an isocyanurate ring and a hydrocarbon group or a hydrocarbon group having 2 to 20 carbon atoms, or a hydrocarbon group having 2 to 250 carbon atoms or an ether oxygen (-O-) and a hydroxyl group (-). It is a hydrocarbon group having 2 to 250 carbon atoms and contains at least one selected from the group consisting of OH). R 2 is a hydrogen atom or a methyl group.
　（Ａ）多官能（メタ）アクリレートの具体例としては、トリメチロールプロパントリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールヘキサアクリレート等の多官能（メタ）アクリレートモノマーや、エポキシ基を有する化合物と（メタ）アクリル酸の反応によって得られるエポキシ変性（メタ）アクリレート、ジイソシアネート化合物とジオール化合物と水酸基を有する（メタ）アクリレート化合物との反応によって得られるウレタン（メタ）アクリレート等の多官能（メタ）アクリレートオリゴマー等が挙げられる。 Specific examples of the (A) polyfunctional (meth) acrylate include polyfunctional (meth) acrylate monomers such as trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate, and compounds having an epoxy group (meth). ) Epoxy-modified (meth) acrylate obtained by the reaction of acrylic acid, polyfunctional (meth) acrylate oligomer such as urethane (meth) acrylate obtained by the reaction of diisocyanate compound, diol compound and (meth) acrylate compound having a hydroxyl group, etc. Can be mentioned.
　これらの中でもウレタン（メタ）アクリレートを用いることが好ましい。
　ウレタン結合を有する化合物を用いることで、硬化膜の強靭性が向上し、剥離する際硬化膜が破れにくくなる。また、撥水レンズとの密着力も向上し、加工時の軸ずれ抑制効果が高くなる。
　また、柔軟なウレタン結合を有する化合物を用いることで、硬化膜と撥水レンズとの密着力が向上し、加工時の軸ずれを抑制することができる。 Among these, it is preferable to use urethane (meth) acrylate.
By using a compound having a urethane bond, the toughness of the cured film is improved, and the cured film is less likely to be torn when peeled. In addition, the adhesion to the water-repellent lens is improved, and the effect of suppressing axial misalignment during processing is enhanced.
Further, by using a compound having a flexible urethane bond, the adhesive force between the cured film and the water-repellent lens is improved, and the axial deviation during processing can be suppressed.
　ウレタン（メタ）アクリレートの具体例としては、ＵＮ－３５２（官能基数：２、Ｍｗ：３，０００）、ＵＮ－３３３（官能基数：２、Ｍｗ：３，０００）、ＵＮ－３５３（官能基数：２、Ｍｗ：５，０００）、ＵＮ－１２５５（官能基数：２、Ｍｗ：８，０００）、ＵＮ－６２００（官能基数：２、Ｍｗ：６，５００）、ＵＮ－６２０１（官能基数：２、Ｍｗ：１，６００）、ＵＮ－９０００ＰＥＰ（官能基数：２、Ｍｗ：５，０００）、ＵＮ－９２００Ａ（官能基数：２、Ｍｗ：１５，０００）、ＵＮ－３３２０ＨＡ（官能基数：６、Ｍｗ：１，５００）、ＵＮ－９０４（官能基数：１０、Ｍｗ：４，９００）、ＵＮ－９５３（官能基数：２０、Ｍｗ：１４，０００～４０，０００）、ＵＮ－９５４（官能基数：６、Ｍｗ：４，５００）、ＵＮ－６３０５（官能基数：２、Ｍｗ：２７，０００）、Ｈ－２１９（官能基数：９、Ｍｗ：２５，０００～５０，０００）（以上はいずれも商品名、根上工業株式会社製）、ＥＢＥＣＲＹＬ２３０（官能基数：２、Ｍｗ：５，０００）、ＥＢＥＣＲＹＬ９２６０（官能基数：３、Ｍｗ：１，５００）、ＥＢＥＣＲＹＬ４６６６（官能基数：４、Ｍｗ：１，１００）（以上はいずれも商品名、ダイセル・オルネクス株式会社製）、ＵＸ－４１０１（官能基数：２、Ｍｗ：６，５００）、ＵＸ－６１０１（官能基数：２、Ｍｗ：６，５００）（以上はいずれも商品名、日本化薬工業株式会社製）等が挙げられる。 Specific examples of the urethane (meth) acrylate include UN-352 (number of functional groups: 2, Mw: 3,000), UN-333 (number of functional groups: 2, Mw: 3,000), UN-353 (number of functional groups:: 2, Mw: 5,000), UN-1255 (number of functional groups: 2, Mw: 8,000), UN-6200 (number of functional groups: 2, Mw: 6,500), UN-6201 (number of functional groups: 2, Mw: 1,600), UN-9000PEP (number of functional groups: 2, Mw: 5,000), UN-9200A (number of functional groups: 2, Mw: 15,000), UN-3320HA (number of functional groups: 6, Mw: 1,500), UN-904 (number of functional groups: 10, Mw: 4,900), UN-953 (number of functional groups: 20, Mw: 14,000 to 40,000), UN-954 (number of functional groups: 6, Mw: 4,500), UN-6305 (number of functional groups: 2, Mw: 27,000), H-219 (number of functional groups: 9, Mw: 25,000 to 50,000) (all of the above are trade names, Negami Kogyo Co., Ltd.), EBECRYL230 (number of functional groups: 2, Mw: 5,000), EBECRYL9260 (number of functional groups: 3, Mw: 1,500), EBECRYL4666 (number of functional groups: 4, Mw: 1,100) (and above) Are all trade names, manufactured by Daicel Ornex Co., Ltd., UX-4101 (number of functional groups: 2, Mw: 6,500), UX-6101 (number of functional groups: 2, Mw: 6,500) (all of the above). Product name, manufactured by Nippon Kayaku Kogyo Co., Ltd.), etc.
　（Ａ）多官能（メタ）アクリレートの重量平均分子量は、２００～３０，０００であり、好ましくは２００～１５，０００である。（Ａ）多官能（メタ）アクリレートの重量平均分子量が２００～３０，０００の範囲であれば、硬化した硬化膜は強靭で剥離する際硬化膜が破れにくく、剥離する際の作業性が良い。更に重量平均分子量が２００～１５，０００の範囲であれば硬化膜の強靭性に加え、耐水性が向上し、撥水レンズの周縁加工時に硬化膜が破断しにくくなるため、より軸ずれを抑制することが可能となるため好ましい。
　また、（Ａ）多官能（メタ）アクリレートの重量平均分子量は、好ましくは２５０～３０，０００であり、より好ましくは５００～１５，０００である。（Ａ）多官能（メタ）アクリレートの重量平均分子量が２５０～３０，０００の範囲であれば、硬化膜と撥水レンズとの密着力が向上する。また、硬化膜の強靭性が高まり、剥離時に硬化膜の破断を抑制するため、撥水レンズから硬化膜を剥離する際の作業性が向上する。 (A) The weight average molecular weight of the polyfunctional (meth) acrylate is 200 to 30,000, preferably 200 to 15,000. (A) When the weight average molecular weight of the polyfunctional (meth) acrylate is in the range of 200 to 30,000, the cured cured film is tough and the cured film is not easily torn when peeled, and the workability at the time of peeling is good. Furthermore, if the weight average molecular weight is in the range of 200 to 15,000, in addition to the toughness of the cured film, the water resistance is improved, and the cured film is less likely to break during peripheral processing of the water-repellent lens, so that axial misalignment is further suppressed. It is preferable because it is possible to do so.
The weight average molecular weight of (A) polyfunctional (meth) acrylate is preferably 250 to 30,000, and more preferably 500 to 15,000. (A) When the weight average molecular weight of the polyfunctional (meth) acrylate is in the range of 250 to 30,000, the adhesion between the cured film and the water-repellent lens is improved. In addition, the toughness of the cured film is increased, and breakage of the cured film is suppressed at the time of peeling, so that workability when peeling the cured film from the water-repellent lens is improved.
　本明細書において、重量平均分子量は、東ソー（株）製ゲルパーミエーションクロマトグラフィー装置ＨＬＣ－８２２０ＧＰＣを用いて、カラムとして東ソー（株）製ＴＳＫｇｅｌ　ＨＺＭ－Ｍを用い、ＴＨＦを溶離液とし、ＲＩ検出器により測定してポリスチレン換算により求めた。 In the present specification, the weight average molecular weight is detected by RI using a gel permeation chromatography apparatus HLC-8220GPC manufactured by Tosoh Corporation, TSKgel HZM-M manufactured by Tosoh Corporation as a column, and THF as an eluent. It was measured with a device and determined by polystyrene conversion.
　（Ａ）多官能（メタ）アクリレートの分子内の（メタ）アクリロイル基の数（官能基数）は、２以上であれば特に制限されないが、例えば、２～３０である。上限値として、好ましくは２０以下であり、より好ましくは１５以下であり、さらに好ましくは１０以下であり、特に好ましくは８以下である。 The number of (meth) acryloyl groups (number of functional groups) in the molecule of (A) polyfunctional (meth) acrylate is not particularly limited as long as it is 2 or more, but is, for example, 2 to 30. The upper limit is preferably 20 or less, more preferably 15 or less, still more preferably 10 or less, and particularly preferably 8 or less.
　（Ａ）多官能（メタ）アクリレートの含有量は、撥水レンズ保護膜用樹脂組成物の固形分全量を基準として、好ましくは２０．０～９９．５質量％、より好ましくは４０．０～９９．５質量％である。上記含有量とすることで、強靭な保護膜が形成でき、撥水レンズの周縁加工時の軸ずれ防止と使用後の容易な剥離性を両立できる。 The content of the polyfunctional (meth) acrylate is preferably 20.0 to 99.5% by mass, more preferably 40.0 to 40.0% by mass, based on the total solid content of the resin composition for the water-repellent lens protective film. It is 99.5% by mass. By setting the content as described above, a tough protective film can be formed, and both prevention of axial misalignment during peripheral processing of the water-repellent lens and easy peeling after use can be achieved at the same time.
　また、（Ａ）多官能（メタ）アクリレートの含有量は、（Ａ）～（Ｄ）成分全量を基準として、７０～９７質量％であることが好ましく、より好ましくは７５～９５質量％である。（Ａ）成分の含有量が７０質量％以上の場合、硬化膜の強靭性が向上し、剥離時の硬化膜の破断を抑制するため、撥水レンズから硬化膜を剥離する際の作業性が向上する。９７質量％以下の場合、硬化膜と撥水レンズとの密着力が適度に調整され、硬化膜を剥離することが容易となる。 The content of the (A) polyfunctional (meth) acrylate is preferably 70 to 97% by mass, more preferably 75 to 95% by mass, based on the total amount of the components (A) to (D). .. When the content of the component (A) is 70% by mass or more, the toughness of the cured film is improved and the breakage of the cured film at the time of peeling is suppressed, so that the workability when peeling the cured film from the water-repellent lens is improved. improves. When it is 97% by mass or less, the adhesion between the cured film and the water-repellent lens is appropriately adjusted, and the cured film can be easily peeled off.
＜（Ｂ）成分：硬化剤＞
　撥水レンズ保護膜用樹脂組成物は、（メタ）アクリレート化合物と反応しうる官能基を有する化合物を硬化剤として添加しても良い。特に限定されないが、大気下での硬化性の良い（ｂ１）多官能チオール化合物が好ましい。多官能チオール化合物とは、２個以上のチオール基（－ＳＨ基）を有する有機化合物であれば特に限定されず、公知の材料を用いることができる。例えば、下記一般式（式２）で表される多官能チオール化合物を挙げることができる。なお、多官能チオール化合物は、１種のみを単独で使用することもできるし、２種以上を組み合わせて使用することもできる。 <Component (B): Hardener>
In the resin composition for a water-repellent lens protective film, a compound having a functional group capable of reacting with the (meth) acrylate compound may be added as a curing agent. Although not particularly limited, a (b1) polyfunctional thiol compound having good curability in the atmosphere is preferable. The polyfunctional thiol compound is not particularly limited as long as it is an organic compound having two or more thiol groups (-SH groups), and known materials can be used. For example, a polyfunctional thiol compound represented by the following general formula (formula 2) can be mentioned. The polyfunctional thiol compound may be used alone or in combination of two or more.
Figure JPOXMLDOC01-appb-C000002
  
（式中のｎは２～５の整数であり、ｂは２～１０の整数であり、Ｒ３は炭素数２～３０の炭化水素基、エーテル酸素（－Ｏ－）と炭素数２～４０の炭化水素基のみからなる基、イソシアヌレート環、又はイソシアヌレート環と炭化水素基のみからなる基のいずれかである。）
Figure JPOXMLDOC01-appb-C000002
(N in the formula is an integer of 2 to 5, b is an integer of 2 to 10, R 3 is a hydrocarbon group having 2 to 30 carbon atoms, ether oxygen (-O-) and 2 to 40 carbon atoms. It is either a group consisting only of a hydrocarbon group, an isocyanurate ring, or a group consisting only of an isocyanurate ring and a hydrocarbon group.)
　上記一般式（式２）においてｎ＝１の化合物でも大きな問題なく使用可能であるが、得られる多官能チオール化合物の反応性が高いことで、これを含む撥水レンズ保護膜用樹脂組成物の保存安定性が若干悪くなる傾向がある。これに対し、ｎ＝２～５の範囲の化合物であれば、保存安定性に優れ大気下でも良好な硬化性が得られる。なお、ｎの数が大きくなるにつれて得られる多官能チオール化合物の反応性が低くなり、これを含む撥水レンズ保護膜用樹脂組成物のＵＶ照射による硬化におけるＵＶ照射量が多くなる傾向がある。したがって、上記一般式（式２）で表される化合物の中では、ｎ＝２の化合物が最も好ましい。ｎ＝２であれば、多官能チオール化合物の反応性が保存安定性と熱硬化時の硬化時間短縮との両立に最も適しているからである。 Although a compound having n = 1 in the above general formula (formula 2) can be used without any major problem, the resulting polyfunctional thiol compound has high reactivity, and thus a resin composition for a water-repellent lens protective film containing the compound has high reactivity. Storage stability tends to be slightly worse. On the other hand, if the compound is in the range of n = 2 to 5, it has excellent storage stability and good curability even in the atmosphere. As the number of n increases, the reactivity of the obtained polyfunctional thiol compound decreases, and the UV irradiation amount in curing of the resin composition for a water-repellent lens protective film containing the compound by UV irradiation tends to increase. Therefore, among the compounds represented by the above general formula (formula 2), the compound having n = 2 is most preferable. This is because when n = 2, the reactivity of the polyfunctional thiol compound is most suitable for both storage stability and shortening of the curing time at the time of heat curing.
　多官能チオール化合物の具体例としては、トリメチロールプロパントリス（３－メルカプトプロピオネート）、トリス－［（３－メルカプトプロピオニルオキシ）－エチル］－イソシアヌレート、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、テトラエチレングリコールビス（３－メルカプトプロピオネート）、ジペンタエリスリトールヘキサキス（３－メルカプトプロピオネート）等が挙げられる。 Specific examples of the polyfunctional thiol compound include trimethylolpropanthris (3-mercaptopropionate), tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, and pentaerythritol tetrakis (3-mercaptopropionate). ), Tetraethylene glycol bis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate) and the like.
　多官能チオール化合物の重量平均分子量は２００～２，０００、好ましくは３００～１，８００、より好ましくは３５０～１，６００とする。分子量が２００より小さくても硬化性に関しては問題ないが、多官能チオール化合物の揮発性が高く、臭気が強くなる傾向がある。一方、分子量が２０００より大きいと、（Ａ）多官能（メタ）アクリレート樹脂に対する溶解性が低くなる可能性がある。 The weight average molecular weight of the polyfunctional thiol compound is 200 to 2,000, preferably 300 to 1,800, and more preferably 350 to 1,600. Even if the molecular weight is smaller than 200, there is no problem in terms of curability, but the polyfunctional thiol compound has high volatility and tends to have a strong odor. On the other hand, if the molecular weight is larger than 2000, the solubility in (A) polyfunctional (meth) acrylate resin may be low.
　撥水レンズ保護膜用樹脂組成物を硬化した後の特性は、厳密には撥水レンズ保護膜用樹脂組成物単位重量中の（（Ｂ）硬化剤官能基数）／（（メタ）アクリロイル基数）（以下、（Ｂ）／（Ａ）官能基比）の値に影響を受ける。（Ｂ）／（Ａ）官能基比が０．１５～２．０の範囲にあれば、密な架橋を形成し、強靭な硬化物になる。より好ましくは０．３～１．５の範囲であり、この範囲にあれば、強靭な硬化物になるとともに、ＵＶ硬化性も良くなり、より少ない積算光量で硬化が可能となるため、硬化時の撥水レンズへの影響を抑制できる。 Strictly speaking, the characteristics of the resin composition for a water-repellent lens protective film after curing are ((B) number of functional groups of the curing agent) / (number of (meth) acryloyl groups) in the unit weight of the resin composition for the water-repellent lens protective film. It is affected by the value (hereinafter, (B) / (A) functional group ratio). When the (B) / (A) functional group ratio is in the range of 0.15 to 2.0, a dense crosslink is formed and a tough cured product is obtained. It is more preferably in the range of 0.3 to 1.5, and if it is in this range, it becomes a tough cured product, UV curability is also improved, and curing is possible with a smaller integrated light amount, so that it is possible to cure at the time of curing. The effect on the water-repellent lens can be suppressed.
　（ｂ１）多官能チオール化合物の含有量は、前記（Ａ）成分１００質量部に対して０．５～３０質量部であることが好ましく、より好ましくは１．０～２５質量部である。（ｂ１）成分の含有量が前記（Ａ）成分１００質量部に対して０．５質量部以上であると、硬化膜と撥水レンズとの密着力が適切になり、硬化膜を剥離することが容易となる。また、３０質量部以下であると、硬化膜の強靭性が向上し、剥離時に硬化膜が破断しにくくなるため、撥水レンズから硬化膜を剥離する際の作業性が向上する。 The content of the (b1) polyfunctional thiol compound is preferably 0.5 to 30 parts by mass, more preferably 1.0 to 25 parts by mass with respect to 100 parts by mass of the component (A). When the content of the component (b1) is 0.5 parts by mass or more with respect to 100 parts by mass of the component (A), the adhesion between the cured film and the water-repellent lens becomes appropriate, and the cured film is peeled off. Becomes easier. Further, when the amount is 30 parts by mass or less, the toughness of the cured film is improved and the cured film is less likely to break at the time of peeling, so that the workability when peeling the cured film from the water-repellent lens is improved.
　（Ａ）成分由来の（メタ）アクリロキシ基に対する（ｂ１）成分由来のチオール基の比率（以下、（ｂ１）／（Ａ）官能基比）は、０．０５～５．０であることが好ましく、より好ましくは０．１０～３．０である。（ｂ１）／（Ａ）官能基比が０．０５以上であると、硬化膜と撥水レンズとの密着力が適切になり、硬化膜を剥離することが容易となる。５．０以下であると、硬化膜の強靭性が十分であり、剥離時の硬化膜の破断を抑制するため、撥水レンズから硬化膜を剥離する際の作業性が向上する。 The ratio of the thiol group derived from the component (b1) to the (meth) acryloxy group derived from the component (A) (hereinafter, (b1) / (A) functional group ratio) is preferably 0.05 to 5.0. , More preferably 0.10 to 3.0. When the (b1) / (A) functional group ratio is 0.05 or more, the adhesion between the cured film and the water-repellent lens becomes appropriate, and the cured film can be easily peeled off. When it is 5.0 or less, the toughness of the cured film is sufficient and the fracture of the cured film at the time of peeling is suppressed, so that the workability when peeling the cured film from the water-repellent lens is improved.
＜（Ｃ）成分：光重合開始剤＞
　本発明の撥水レンズ保護膜用樹脂組成物は、（Ｃ）成分として、紫外線照射によりラジカルを発生する光重合開始剤を含有する。
　この撥水レンズ保護膜用樹脂組成物は、（Ｃ）成分を含有することにより、可視光領域に近い波長のＬＥＤ紫外線照射装置で露光しても硬化可能であり、光照射による撥水レンズへの熱影響を抑えることが出来る。 <Component (C): Photopolymerization initiator>
The resin composition for a water-repellent lens protective film of the present invention contains, as a component (C), a photopolymerization initiator that generates radicals by irradiation with ultraviolet rays.
Since this resin composition for a water-repellent lens protective film contains the component (C), it can be cured even when exposed to an LED ultraviolet irradiation device having a wavelength close to the visible light region, and the water-repellent lens is formed by light irradiation. The heat effect of the lens can be suppressed.
　（Ｃ）成分としては、光感光性樹脂を重合させることができるものであれば、特に制限はなく、通常用いられる光重合開始剤から適宜選択することができる。例えば、アシルホスフィンオキサイド系、オキシムエステル系、芳香族ケトン系、キノン系、アルキルフェノン系、イミダゾール系、アクリジン系、フェニルグリシン系の光重合開始剤が挙げられる。これらの中でも各種光源を用いた際の硬化性の観点から、芳香族ケトン系光重合開始剤を用いることが好ましい。 The component (C) is not particularly limited as long as it can polymerize a photosensitive resin, and can be appropriately selected from commonly used photopolymerization initiators. Examples thereof include acylphosphine oxide-based, oxime ester-based, aromatic ketone-based, quinone-based, alkylphenone-based, imidazole-based, acridine-based, and phenylglycine-based photopolymerization initiators. Among these, it is preferable to use an aromatic ketone-based photopolymerization initiator from the viewpoint of curability when various light sources are used.
　アシルホスフィンオキサイド系光重合開始剤は、アシルホスフィンオキサイド基（＞Ｐ（＝Ｏ）－Ｃ（＝Ｏ）－基）を有するものであり、例えば、（２，６－ジメトキシベンゾイル）－２，４，６－ペンチルホスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）－フェニルホスフィンオキサイド、２，４，６－トリメチルベンゾイルジフェニルホスフィンオキサイド（「ＩＲＧＡＣＵＲＥ－ＴＰＯ」（ＢＡＳＦ社製））、エチル－２，４，６－トリメチルベンゾイルフェニルホスフィネイト、ビス（２，４，６－トリメチルベンゾイル）－フェニルホスフィンオキサイド（「ＩＲＧＡＣＵＲＥ－８１９」（ＢＡＳＦ社製））、（２，５－ジヒドロキシフェニル）ジフェニルホスフィンオキサイド、（ｐ－ヒドロキシフェニル）ジフェニルホスフィンオキサイド、ビス（ｐ－ヒドロキシフェニル）フェニルホスフィンオキサイド、トリス（ｐ－ヒドロキシフェニル）ホスフィンオキサイド等が挙げられる。 The acylphosphine oxide-based photopolymerization initiator has an acylphosphine oxide group (> P (= O) -C (= O) -group), and is, for example, (2,6-dimethoxybenzoyl) -2,4. , 6-Pentylphosphinoxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphinoxide, 2,4,6-trimethylbenzoyldiphenylphosphinoxide ("IRGACURE-TPO" (BASF)), ethyl-2 , 4,6-trimethylbenzoylphenylphosphinate, bis (2,4,6-trimethylbenzoyl) -phenylphosphin oxide ("IRGACURE-819" (BASF)), (2,5-dihydroxyphenyl) diphenylphosphine Examples thereof include oxide, (p-hydroxyphenyl) diphenylphosphine oxide, bis (p-hydroxyphenyl) phenylphosphin oxide, tris (p-hydroxyphenyl) phosphin oxide and the like.
　オキシムエステル系光重合開始剤は、オキシムエステル結合を有する光重合開始剤であり、例えば、１，２－オクタンジオン－１－［４－（フェニルチオ）フェニル］－２－（Ｏ－ベンゾイルオキシム）（商品名：ＯＸＥ－０１、ＢＡＳＦ社製）、１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］エタノン１－（Ｏ－アセチルオキシム）（商品名：ＯＸＥ－０２、ＢＡＳＦ社製）、１－フェニル－１，２－プロパンジオン－２－［Ｏ－（エトキシカルボニル）オキシム］（商品名：Ｑｕａｎｔａｃｕｒｅ－ＰＤＯ、日本化薬株式会社製）等が挙げられる。 The oxime ester-based photopolymerization initiator is a photopolymerization initiator having an oxime ester bond, and is, for example, 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) ( Product Name: OXE-01, manufactured by BASF), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] Etanone 1- (O-acetyloxime) (Product name: OXE) -02, manufactured by BASF), 1-phenyl-1,2-propanedione-2- [O- (ethoxycarbonyl) oxime] (trade name: Quantacure-PDO, manufactured by Nippon Kayaku Co., Ltd.) and the like.
　芳香族ケトン系光重合開始剤としては、例えば、ベンゾフェノン、Ｎ，Ｎ’－テトラメチル－４，４’－ジアミノベンゾフェノン（ミヒラーケトン）、Ｎ，Ｎ’－テトラエチル－４，４’－ジアミノベンゾフェノン、４－メトキシ－４’－ジメチルアミノベンゾフェノン、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン（「ＩＲＧＡＣＵＲＥ－６５１」（ＢＡＳＦ社製））、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタン－１－オン（「ＩＲＧＡＣＵＲＥ－３６９」（ＢＡＳＦ社製））、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルフォリノ－プロパン－１－オン（「ＩＲＧＡＣＵＲＥ－９０７」（ＢＡＳＦ社製））等が挙げられる。 Examples of the aromatic ketone-based photopolymerization initiator include benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michlerketone), N, N'-tetraethyl-4,4'-diaminobenzophenone, 4 -Methoxy-4'-dimethylaminobenzophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one ("IRGACURE-651" (manufactured by BASF)), 2-benzyl-2-dimethylamino-1- (4-Methoxyphenyl) -butane-1-one ("IRGACURE-369" (manufactured by BASF)), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1-one ("IRGACURE-907" (manufactured by BASF)) and the like.
　キノン系光重合開始剤としては、例えば、２－エチルアントラキノン、フェナントレンキノン、２－ｔ－ブチルアントラキノン、オクタメチルアントラキノン、１，２－ベンズアントラキノン、２，３－ベンズアントラキノン、２－フェニルアントラキノン、２，３－ジフェニルアントラキノン、１－クロロアントラキノン、２－メチルアントラキノン、１，４－ナフトキノン、９，１０－フェナントラキノン、２－メチル－１，４－ナフトキノン、２，３－ジメチルアントラキノン等が挙げられる。 Examples of the quinone-based photopolymerization initiator include 2-ethylanthraquinone, phenanthrenquinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, and 2 , 3-Diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, etc. Be done.
　アルキルフェノン系光重合開始剤としては、例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインフェニルエーテル等のベンゾイン系化合物、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン（「ＩＲＧＡＣＵＲＥ－６５１」（ＢＡＳＦ社製））、１－ヒドロキシ－シクロヘキシル－フェニル－ケトン（「ＩＲＧＡＣＵＲＥ－１８４」（ＢＡＳＦ社製））、２－ヒドロキシ－２－メチル－１－フェニル－プロパン－１－オン（「ＩＲＧＡＣＵＲＥ－１１７３」（ＢＡＳＦ社製））、１－［４－（２－ヒドロキシエトキシ）－フェニル］－２－ヒドロキシ－２－メチル－１－プロパン－１－オン（「ＩＲＧＡＣＵＲＥ－２９５９」（ＢＡＳＦ社製））、２－ヒロドキシ－１－｛４－［４－（２－ヒドロキシ－２－メチル－プロピオニル）－ベンジル］フェニル｝－２－メチル－プロパン－１－オン（「ＩＲＧＡＣＵＲＥ－１２７」（ＢＡＳＦ社製））等が挙げられる。 Examples of the alkylphenone-based photopolymerization initiator include benzoin-based compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin phenyl ether, and 2,2-dimethoxy-1,2-diphenylethane-1-. On ("IRGACURE-651" (manufactured by BASF)), 1-hydroxy-cyclohexyl-phenyl-ketone ("IRGACURE-184" (manufactured by BASF)), 2-hydroxy-2-methyl-1-phenyl-propane- 1-on ("IRGACURE-1173" (manufactured by BASF)), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one ("IRGACURE-" 2959 ”(BASF)), 2-Hirodoxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1-one (“IRGACURE) -127 ”(manufactured by BASF)) and the like.
　イミダゾール系光重合開始剤としては、例えば、２，４，５－トリアリールイミダゾール二量体が例示され、より詳細には、２－（２－クロロフェニル）－１－〔２－（２－クロロフェニル）－４，５－ジフェニル－１，３－ジアゾール－２－イル〕－４，５－ジフェニルイミダゾール等の２－（ｏ－クロロフェニル）－４，５－ジフェニルイミダゾール二量体、２－（ｏ－クロロフェニル）－４，５－ジ（メトキシフェニル）イミダゾール二量体、２－（ｏ－フルオロフェニル）－４，５－ジフェニルイミダゾール二量体、２－（ｏ－メトキシフェニル）－４，５－ジフェニルイミダゾール二量体、２－（ｐ－メトキシフェニル）－４，５－ジフェニルイミダゾール二量体等が挙げられる。 Examples of the imidazole-based photopolymerization initiator include 2,4,5-triarylimidazole dimers, and more specifically, 2- (2-chlorophenyl) -1- [2- (2-chlorophenyl). -4,5-diphenyl-1,3-diazol-2-yl] -4,5-diphenylimidazole and other 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) ) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole Examples thereof include a dimer, a 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer and the like.
　これらの中でも、ＵＶ－ＬＥＤ光源を用いた際の硬化性の観点から、（Ｃ）成分は、下記一般式（式３）で表される化合物からなる群から選ばれる少なくとも１種を含有していてもよい。 Among these, from the viewpoint of curability when using a UV-LED light source, the component (C) contains at least one selected from the group consisting of compounds represented by the following general formula (formula 3). You may.
Figure JPOXMLDOC01-appb-C000003
  
（一般式（式３）中、Ｒ４は、水酸基、炭素数１～８のアルコキシ基、又はアミノ基を示し、Ｒ５及びＲ６は、各々独立に、水素原子、炭素数１～８のアルキル基、炭素数１～８のアルコキシ基、又は炭素数６～１２のアリール基を示す。Ｒ５とＲ６は、互いに結合して、炭素数３～１６の環状構造を形成してもよい。Ｒ４～Ｒ６は、水酸基及び水素原子の場合を除き、各々置換基を有してもよく、置換基を有するアミノ基は、置換基同士が互いに結合して、炭素数３～１２の環状構造を形成してもよい。Ｒ７は、各々独立に、水素原子、ハロゲン原子、水酸基、アミノ基、メルカプト基、又は酸素原子、窒素原子及び硫黄原子から選ばれる１種以上の原子を含んでいてもよい炭素数１～１０の有機基を示す。）
Figure JPOXMLDOC01-appb-C000003
(In the general formula (formula 3), R 4 represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, or an amino group, and R 5 and R 6 each independently have a hydrogen atom and 1 to 8 carbon atoms. It represents an alkyl group, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms. R 5 and R 6 may be bonded to each other to form a cyclic structure having 3 to 16 carbon atoms. R 4 to R 6 may each have a substituent except for the case of a hydroxyl group and a hydrogen atom, and the amino group having a substituent has substituents bonded to each other and has 3 to 12 carbon atoms. A cyclic structure may be formed. Each R 7 independently contains one or more atoms selected from a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a mercapto group, or an oxygen atom, a nitrogen atom and a sulfur atom. It indicates an organic group having 1 to 10 carbon atoms which may be used.)
　一般式（式３）中、Ｒ４は、水酸基、炭素数１～８のアルコキシ基、又はアミノ基を示す。
　Ｒ４が表すアルコキシ基は、ＵＶ－ＬＥＤを光源とした際の硬化性の観点から、水酸基又はメトキシ基であってもよい。 In the general formula (formula 3), R 4 represents a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, or an amino group.
The alkoxy group represented by R 4 may be a hydroxyl group or a methoxy group from the viewpoint of curability when a UV-LED is used as a light source.
　一般式（式３）中、Ｒ５及びＲ６は、各々独立に、水素原子、炭素数１～８のアルキル基、炭素数１～８のアルコキシ基、又は炭素数６～１２のアリール基を示す。
　Ｒ５及びＲ６が表すアルキル基は、炭素数１～４のアルキル基であってもよく、炭素数１又は２のアルキル基であってもよい。アルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ヘプチル基、ｎ－ヘキシル基、ｎ－オクチル基等が挙げられる。アルコキシ基は、炭素数１～４のアルコキシ基であってもよく、炭素数１又は２のアルコキシ基であってもよい。アルコキシ基としては、例えば、メトキシ基、エトキシ基、ｎ－プロポキシ基、イソプロポキシ基、ｎ－ブトキシ基、ｔｅｒｔ－ブトキシ基、ｎ－ヘプチルオキシ基、ｎ－ヘキシルオキシ基、ｎ－オクチルオキシ等が挙げられる。アリール基は、炭素数６～１０のアリール基であってもよく、炭素数６～８のアリール基であってもよい。アリール基としては、例えば、フェニル基、ナフチル基等が挙げられる。
　Ｒ５とＲ６は、互いに結合して、炭素数３～１６の環状構造を形成していてもよい。
　前記環状構造は、炭素数４～１０の環状構造であってもよく、炭素数５～８の環状構造であってもよい。
　前記環状構造は、脂環式構造であってもよく、脂環式構造としては、シクロペンタン構造、シクロヘキサン構造、シクロヘプタン構造、シクロオクタン構造等が挙げられる。また、これらの脂環式構造は、Ｒ５及びＲ６が共に直接結合する炭素原子を含んでいてもよい。 In the general formula (formula 3), R 5 and R 6 each independently have a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms. show.
The alkyl group represented by R 5 and R 6 may be an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 or 2 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an n-heptyl group, an n-hexyl group, an n-octyl group and the like. The alkoxy group may be an alkoxy group having 1 to 4 carbon atoms, or may be an alkoxy group having 1 or 2 carbon atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a tert-butoxy group, an n-heptyloxy group, an n-hexyloxy group, an n-octyloxy and the like. Can be mentioned. The aryl group may be an aryl group having 6 to 10 carbon atoms or an aryl group having 6 to 8 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group.
R 5 and R 6 may be bonded to each other to form a cyclic structure having 3 to 16 carbon atoms.
The cyclic structure may be a cyclic structure having 4 to 10 carbon atoms or a cyclic structure having 5 to 8 carbon atoms.
The cyclic structure may be an alicyclic structure, and examples of the alicyclic structure include a cyclopentane structure, a cyclohexane structure, a cycloheptane structure, and a cyclooctane structure. Further, these alicyclic structures may contain carbon atoms to which R 5 and R 6 are directly bonded together.
　（Ｃ）光重合開始剤の含有量は、撥水レンズ保護膜用樹脂組成物の固形分全量を基準として、０．０５～２０質量％、好ましくは０．１～１０質量％である。上記含有量とすることで、撥水レンズ保護膜用樹脂組成物のＵＶ－ＬＥＤを光源として用いた際の硬化性を向上させ、より短時間、低照度で硬化物を形成できる。 The content of the (C) photopolymerization initiator is 0.05 to 20% by mass, preferably 0.1 to 10% by mass, based on the total solid content of the resin composition for the water-repellent lens protective film. By setting the content as described above, the curability when UV-LED of the resin composition for a water-repellent lens protective film is used as a light source can be improved, and a cured product can be formed in a shorter time and with low illuminance.
　（Ｃ）光重合開始剤の含有量は、前記（Ａ）成分１００質量部に対して０．１～２５質量部であることが好ましく、より好ましくは０．５～２０質量部である。（Ｃ）成分の含有量が前記（Ａ）成分１００質量部に対して０．１質量部以上であると、十分に硬化されるため、硬化膜と撥水レンズとの密着力向上や硬化膜の強靭性向上が生じるとともに、保護膜を剥離した際に未硬化成分の残渣による基材の撥水性低下を防ぐことができる。また、（Ｃ）成分の含有量が前記（Ａ）成分１００質量部に対して２５質量部以下であると、光重合開始剤が適量となり、保護膜を剥離した際に光重合開始剤の残渣による基材の撥水性低下を防ぐことかできる。 The content of the (C) photopolymerization initiator is preferably 0.1 to 25 parts by mass, more preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the component (A). When the content of the component (C) is 0.1 part by mass or more with respect to 100 parts by mass of the component (A), the film is sufficiently cured, so that the adhesion between the cured film and the water-repellent lens is improved and the cured film is cured. It is possible to improve the toughness of the base material and prevent the water repellency of the base material from being lowered due to the residue of the uncured component when the protective film is peeled off. Further, when the content of the component (C) is 25 parts by mass or less with respect to 100 parts by mass of the component (A), the amount of the photopolymerization initiator becomes appropriate, and the residue of the photopolymerization initiator when the protective film is peeled off. It is possible to prevent the deterioration of the water repellency of the base material due to the above.
＜（Ｄ）成分：ノニオン系界面活性剤＞
　（Ｄ）成分であるノニオン系界面活性剤は、例えば、炭化水素系、シリコーン系、フッ素系等であってよい。（Ｄ）成分を添加することで、撥水レンズ保護膜用樹脂組成物の配合液の表面張力を低下させ、超撥水レンズのように極めて塗工が困難な基材に対しても均一に樹脂組成物を塗工することが可能になる。（Ｄ）成分は、１種単独又は２種以上を混合して使用することができる。 <Component (D): Nonionic surfactant>
The nonionic surfactant as the component (D) may be, for example, a hydrocarbon-based surfactant, a silicone-based surfactant, a fluorine-based surfactant, or the like. By adding the component (D), the surface tension of the compounding liquid of the resin composition for a water-repellent lens protective film is reduced, and even for a substrate that is extremely difficult to apply, such as a superhydrophobic lens. It becomes possible to apply the resin composition. The component (D) can be used alone or in combination of two or more.
　炭化水素系界面活性剤の例としては、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル等のポリオキシエチレンアルキルエーテル類；ポリオキシエチレンｎ－オクチルフェニルエーテル、ポリオキシエチレンｎ－ノニルフェニルエーテル等のポリオキシエチレンアルキルフェニルエーテル類；ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート等のポリエチレングリコールジエステル類；ソルビタン脂肪酸エステル類；脂肪酸変性ポリエステル類；アクリルポリマー等が挙げられる。アクリルポリマーを主成分とする炭化水素系界面活性剤としては、例えば、ポリフローＮｏ．７５、ポリフローＮｏ．９０、ポリフローＷＳ－３１４（以上、共栄社化学株式会社製、商品名）等を用いることができる。 Examples of hydrocarbon-based surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene n-octylphenyl ether, and polyoxyethylene n. -Polyoxyethylene alkyl phenyl ethers such as nonylphenyl ether; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; acrylic polymers and the like. Examples of the hydrocarbon-based surfactant containing an acrylic polymer as a main component include Polyflow No. 75, Polyflow No. 90, Polyflow WS-314 (all manufactured by Kyoeisha Chemical Co., Ltd., trade name) and the like can be used.
　シリコーン系界面活性剤の市販品としては、例えば、ポリフローＫＬ－１００、ポリフローＫＬ－４０１、ポリフローＫＬ－４０２、ポリフローＫＬ－４０３（以上、共栄社化学株式会社製、商品名）；ＫＰ－３２３、ＫＰ－３４１、ＫＰ－３９２（以上、信越化学工業株式会社製、商品名）；ＳＺ－１６４２、ＳＺ－１６７７、ＳＨ１９２、ＳＨ１９３（以上、東レ・ダウコーニング株式会社製、商品名）等を用いることができる。 Commercially available products of silicone-based surfactants include, for example, Polyflow KL-100, Polyflow KL-401, Polyflow KL-402, Polyflow KL-403 (all manufactured by Kyoeisha Chemical Co., Ltd., trade name); KP-323, KP. -341, KP-392 (above, manufactured by Shin-Etsu Chemical Co., Ltd., trade name); SZ-1642, SZ-1677, SH192, SH193 (above, manufactured by Toray Dow Corning Co., Ltd., trade name) and the like can be used. can.
　フッ素系界面活性剤はフッ素セグメントと非フッ素セグメントからなるフッ素系ノニオン性界面活性剤であり、例えば、（ｄ１）フッ素系セグメントと非フッ素系セグメントからなるブロック共重合体等が挙げられる。フッ素系界面活性剤のフッ素セグメントと非フッ素セグメントの組合せとしては、例えば、フッ素化アルキル基含有アルコールとエチレンオキシド、プロプレンオキシド等のオキシアルキレン基を含む単量体との付加重合体や、フッ素化アルキル基含有エチレン性不飽和化合物とポリオキシアルキレン基含有エチレン性不飽和化合物との共重合体（以下、「フッ素化アルキル基含有エチレン性不飽和化合物」という。）等の分子設計が挙げられる。なお、（ｄ１）成分は、１種のみを単独で用いてもよく、２種以上を組み合わせて用いても良い。 The fluorine-based surfactant is a fluorine-based nonionic surfactant composed of a fluorine-based segment and a non-fluorine-based segment, and examples thereof include (d1) a block copolymer composed of a fluorine-based segment and a non-fluorine-based segment. Examples of the combination of the fluorine segment and the non-fluorine segment of the fluorine-based surfactant include an addition polymer of a fluorinated alkyl group-containing alcohol and a monomer containing an oxyalkylene group such as ethylene oxide and proprene oxide, and fluorination. Examples thereof include molecular design of a copolymer of an alkyl group-containing ethylenically unsaturated compound and a polyoxyalkylene group-containing ethylenically unsaturated compound (hereinafter referred to as “fluorinated alkyl group-containing ethylenically unsaturated compound”). As the component (d1), only one type may be used alone, or two or more types may be used in combination.
　フッ素系セグメントと非フッ素系セグメントからなるブロック共重合体を用いることで、撥水レンズに保護膜形成用樹脂組成物を塗布した際に（ｄ１）成分が表面偏析し易くなり、撥水レンズへの塗工性を高めることができる。また、表面偏析性が高まることにより、塗膜内部の（Ａ）多官能（メタ）アクリレートと（Ｂ）硬化剤との硬化反応を（ｄ１）成分が阻害し難くなるため、より強靭性に優れた硬化膜が得られる。 By using a block copolymer composed of a fluorine-based segment and a non-fluorine-based segment, the component (d1) is easily surface segregated when the resin composition for forming a protective film is applied to the water-repellent lens, and the water-repellent lens is formed. It is possible to improve the coatability of. Further, by increasing the surface segregation property, the component (d1) is less likely to inhibit the curing reaction between the (A) polyfunctional (meth) acrylate and the (B) curing agent inside the coating film, so that the toughness is more excellent. A cured film is obtained.
　フッ素化アルキル基含有エチレン性不飽和化合物としては、撥水レンズ保護膜用樹脂組成物に対する相溶性、またはそのような相溶性に基づく塗膜均一性の観点から、（メタ）アクリルエステル基を含有する単量体が適している。具体的には下記一般式（式４）で表されるフルオロアルキル（メタ）アクリレートである。 The fluorinated alkyl group-containing ethylenically unsaturated compound contains a (meth) acrylic ester group from the viewpoint of compatibility with the resin composition for a water-repellent lens protective film or coating uniformity based on such compatibility. The monomer to be used is suitable. Specifically, it is a fluoroalkyl (meth) acrylate represented by the following general formula (formula 4).
Figure JPOXMLDOC01-appb-C000004
  
（式中、Ｒｆは炭素数４～８のパーフルオロアルキル基であり、Ｒ８は水素原子またはメチル基であり、ｐは１～６の整数である。）
　フルオロアルキル（メタ）アクリレートにおけるフッ素化アルキル基Ｒｆの炭素数は４～６が好ましい。炭素数が４以上の場合、表面張力低下能力が向上し、炭素数が６以下の場合、他の配合物への相溶性が高まる。フルオロアルキル（メタ）アクリレートは１種を単独でまたは２種以上を組み合わせて用いることができる。
Figure JPOXMLDOC01-appb-C000004
(In the formula, R f is a perfluoroalkyl group having 4 to 8 carbon atoms, R 8 is a hydrogen atom or a methyl group, and p is an integer of 1 to 6).
The fluorinated alkyl group R f in the fluoroalkyl (meth) acrylate preferably has 4 to 6 carbon atoms. When the number of carbon atoms is 4 or more, the surface tension lowering ability is improved, and when the number of carbon atoms is 6 or less, the compatibility with other formulations is enhanced. Fluoroalkyl (meth) acrylates can be used alone or in combination of two or more.
　さらにフッ素系ノニオン性界面活性剤は、保護膜剥離後の撥水レンズに対する残留成分低減の観点から、光重合性基を含有することが好ましい。その好ましい形態は、エチレン性不飽和基を有する側鎖と、フッ素化アルキル基又はその一部に酸素原子を含む基を有する側鎖とを有する重合体である。 Further, the fluorine-based nonionic surfactant preferably contains a photopolymerizable group from the viewpoint of reducing residual components in the water-repellent lens after the protective film is peeled off. A preferred form thereof is a polymer having a side chain having an ethylenically unsaturated group and a side chain having a fluorinated alkyl group or a group containing an oxygen atom as a part thereof.
　不飽和基含有側鎖を持つ繰り返し単位は、光反応性の点から、下記一般式（式５）～（式８）で表される繰り返し単位であることが好ましい。なお、１分子中の、不飽和基含有側鎖を有する繰り返し単位は、それぞれ同じであっても異なっていてもよい。 The repeating unit having an unsaturated group-containing side chain is preferably a repeating unit represented by the following general formulas (formula 5) to (formula 8) from the viewpoint of photoreactivity. The repeating unit having an unsaturated group-containing side chain in one molecule may be the same or different.
Figure JPOXMLDOC01-appb-C000005
  
Figure JPOXMLDOC01-appb-C000006
  
Figure JPOXMLDOC01-appb-C000007
  
Figure JPOXMLDOC01-appb-C000008
  
　Ｒ９、Ｒ１０、Ｒ１１、Ｒ１２は水素原子またはメチル基である。
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000008
R 9 , R 10 , R 11 , and R 12 are hydrogen atoms or methyl groups.
　これらノニオン系界面活性剤の中でも特にフッ素系界面活性剤を用いることが好ましい。フッ素系界面活性剤は、撥水レンズ保護膜用樹脂組成物の表面張力を低下させる能力が高いため、表面エネルギーの低い超撥水レンズの塗工に適している。また、本用途の保護膜は、加工時においては軸ずれが発生しないよう超撥水レンズに対する密着性を有し、使用後は容易に剥離するよう剥離性が求められる。超撥水レンズの表面に形成される撥水層はフッ素系のコーティング処理がされているため、この層と相互作用しやすいフッ素系界面活性剤を保護膜にも配合することで適度な密着性と剥離性という相反する特性が達成される。
　また、フッ素系界面活性剤としてはプロピレングリコールモノメチルエーテルアセテート中に０.１質量部の濃度で配合した際、その配合液の表面張力が２６．０ｍＮ／ｍ以下まで低下させるものが好ましく、より好ましくは２３．０ｍＮ／ｍ以下まで低下できるものが好ましい。２３．０ｍＮ／ｍ以下まで表面張力を低下できる界面活性剤を用いることで効率的に表面張力を低下でき、より少量の添加で均一な塗工が可能となる。 Among these nonionic surfactants, it is particularly preferable to use a fluorine-based surfactant. Since the fluorine-based surfactant has a high ability to reduce the surface tension of the resin composition for a water-repellent lens protective film, it is suitable for coating a superhydrophobic lens having a low surface energy. In addition, the protective film for this purpose is required to have adhesiveness to the superhydrophobic lens so that the axis does not shift during processing, and to be easily peeled off after use. Since the water-repellent layer formed on the surface of the superhydrophobic lens is coated with a fluorine-based coating, appropriate adhesion can be achieved by blending a fluorine-based surfactant that easily interacts with this layer into the protective film. And the contradictory properties of peelability are achieved.
Further, as the fluorine-based surfactant, when it is blended in propylene glycol monomethyl ether acetate at a concentration of 0.1 part by mass, it is preferable that the surface tension of the blended solution is reduced to 26.0 mN / m or less, which is more preferable. Is preferably one that can be reduced to 23.0 mN / m or less. By using a surfactant that can reduce the surface tension to 23.0 mN / m or less, the surface tension can be reduced efficiently, and uniform coating can be performed with a smaller amount of addition.
　前述した表面張力低下能を有するフッ素系界面活性剤の市販品としては、例えば、メガファックＦ－４７７、メガファックＦ－５５４、メガファックＦ－５５７、メガファックＲ－４１、メガファックＲＳ－５６、メガファックＲＳ－７２－Ｋ、メガファックＲＳ－７５－Ａ、メガファックＲＳ－７５－ＮＳ、メガファックＲＳ－７８（以上、ＤＩＣ株式会社製、商品名）、モディパーＦ２０６、モディパーＦ２４６（以上、日油株式会社製、商品名）等を用いることができる。 Examples of commercially available fluorine-based surfactants having the above-mentioned ability to reduce surface tension include Megafuck F-477, Megafuck F-554, Megafuck F-557, Megafuck R-41, and Megafuck RS-56. , Megafuck RS-72-K, Megafuck RS-75-A, Megafuck RS-75-NS, Megafuck RS-78 (above, DIC Corporation, trade name), Modiper F206, Modiper F246 (above, (Product name) manufactured by Nichiyu Co., Ltd. can be used.
　（ｄ１）フッ素系セグメントと非フッ素系セグメントからなるブロック共重合体の重量平均分子量は２５，０００～１００，０００が好ましく、より好ましくは３０，０００～８０，０００である。重量平均分子量が２５，０００未満であると、保護膜を剥離した際に界面活性剤の残渣により基材の撥水性が低下し、１００，０００を超えると、撥水レンズへの塗工性が低下する。なお、重量平均分子量の測定方法は、（Ａ）多官能（メタ）アクリレートの重量平均分子量の測定方法と同一である。 (D1) The weight average molecular weight of the block copolymer composed of a fluorine-based segment and a non-fluorine-based segment is preferably 25,000 to 100,000, more preferably 30,000 to 80,000. When the weight average molecular weight is less than 25,000, the water repellency of the substrate is lowered due to the residue of the surfactant when the protective film is peeled off, and when it exceeds 100,000, the coatability to the water repellent lens is improved. descend. The method for measuring the weight average molecular weight is the same as the method for measuring the weight average molecular weight of (A) polyfunctional (meth) acrylate.
　重量平均分子量が２５，０００～１００，０００である（ｄ１）フッ素系セグメントと非フッ素系セグメントからなるブロック共重合体の市販品としては、モディパーＦ２０６、モディパーＦ２４６、モディパーＦ３６３６（以上はいずれも商品名、日油株式会社製）等が挙げられる。 As commercially available block copolymers composed of (d1) fluorine-based segments and non-fluorine-based segments having a weight average molecular weight of 25,000 to 100,000, Modiper F206, Modiper F246, and Modiper F3636 (all of the above are commercial products). Name, manufactured by NOF CORPORATION), etc.
　（Ｄ）成分の含有量は、撥水レンズ保護膜用樹脂組成物の固形分全量を基準として、０．０１～１０質量％が好ましく、より好ましくは０．０１～５質量％の範囲である。含有量が０．０１～１０質量％の範囲であれば、超撥水レンズのように極めて塗工が困難な基材に対しても均一に撥水レンズ保護膜用樹脂組成物を塗工することが可能になる。さらに０．０１～５質量％の範囲であれば保護膜を剥離した際、界面活性剤の残存による撥水レンズの撥水性低下を引き起こすことなく、均一な保護膜を得ることが可能となる。 The content of the component (D) is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, based on the total solid content of the resin composition for the water-repellent lens protective film. .. When the content is in the range of 0.01 to 10% by mass, the resin composition for a water-repellent lens protective film is uniformly applied even to a substrate that is extremely difficult to apply, such as a superhydrophobic lens. Will be possible. Further, if the content is in the range of 0.01 to 5% by mass, when the protective film is peeled off, a uniform protective film can be obtained without causing a decrease in water repellency of the water-repellent lens due to residual surfactant.
　（ｄ１）フッ素系セグメントと非フッ素系セグメントからなるブロック共重合体の含有量は、前記（Ａ）成分１００質量部に対して０．１～２５質量部であることが好ましく、より好ましくは０．５～２０質量部、特に好ましくは１．０～１５質量部である。（ｄ１）成分の含有量が前記（Ａ）成分１００質量部に対して０．１質量部以上であると、撥水レンズへの塗工性が優れ、２５質量部以下であると、保護膜を剥離した際に界面活性剤の残渣による基材の撥水性低下を防ぐことができる。 (D1) The content of the block copolymer composed of the fluorine-based segment and the non-fluorine-based segment is preferably 0.1 to 25 parts by mass, more preferably 0 with respect to 100 parts by mass of the component (A). .5 to 20 parts by mass, particularly preferably 1.0 to 15 parts by mass. When the content of the component (d1) is 0.1 part by mass or more with respect to 100 parts by mass of the component (A), the coatability to the water-repellent lens is excellent, and when it is 25 parts by mass or less, the protective film is provided. It is possible to prevent the water repellency of the substrate from being lowered due to the residue of the surfactant when the lens is peeled off.
＜（Ｅ）：希釈剤＞
　本発明の撥水レンズ保護膜用樹脂組成物は、反応系を均一にし、塗工を容易にするために有機溶媒や反応性希釈剤で希釈して使用してもよい。
　そのような有機溶媒としては、アルコール系溶剤、芳香族炭化水素系溶剤、エーテル系溶剤、エステル系溶剤及びエーテルエステル系溶剤、ケトン系溶剤が挙げられる。
　反応性希釈剤としてはビニル基、アクリロイル基、メタクリロイル基等を有する、単官能性の光重合性単量体を用いることができる。これらのうち、アクリロイル基又はメタクリロイル基を有する（メタ）アクリレート化合物が好ましく、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソデシル（メタ）アクリレート、ｎ－ヘキシル（メタ）アクリレート、ステアリル（メタ）アクリレート、ラウリル（メタ）アクリレート、トリデシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート等のアルキル（メタ）アクリレート；エトキシエチル（メタ）アクリレート、メトキシエチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、２－メトキシエトキシエチル（メタ）アクリレート、２－エトキシエトキシエチル（メタ）アクリレート等のアルコキシアルキル（メタ）アクリレート；グリシジル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート；メトキシジエチレングリコール（メタ）アクリレート、エトキシジエチレングリコール（メタ）アクリレート、メトキシジプロピレングリコール（メタ）アクリレート等のアルコキシ（ポリ）アルキレングリコール（メタ）アクリレート；Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノエチル（メタ）アクリレート等のジアルキルアミノアルキル（メタ）アクリレート；アリル（メタ）アクリレート、１，３－ブタンジオール（メタ）アクリレート、１，４－ブタンジオール（メタ）アクリレート、１，６－ヘキサンジオール（メタ）アクリレート、３－メチルペンタンジオール（メタ）アクリレート等のグリコールモノ（メタ）アクリレート等の単官能性の（メタ）アクリレート化合物が挙げられる。
　なお、希釈剤の配合量は、本発明の特性を損なわない範囲において任意に調整すればよい。 <(E): Diluent>
The resin composition for a water-repellent lens protective film of the present invention may be diluted with an organic solvent or a reactive diluent in order to make the reaction system uniform and facilitate coating.
Examples of such an organic solvent include alcohol-based solvents, aromatic hydrocarbon-based solvents, ether-based solvents, ester-based solvents, ether ester-based solvents, and ketone-based solvents.
As the reactive diluent, a monofunctional photopolymerizable monomer having a vinyl group, an acryloyl group, a methacryloyl group and the like can be used. Of these, (meth) acrylate compounds having an acryloyl group or a methacryloyl group are preferable, and for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, tert. -Butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, n-hexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) ) Alkyl (meth) acrylates such as acrylates, cyclohexyl (meth) acrylates, isobornyl (meth) acrylates; ethoxyethyl (meth) acrylates, methoxyethyl (meth) acrylates, butoxyethyl (meth) acrylates, 2-methoxyethoxyethyl (meth). ) Acrylate, alkoxyalkyl (meth) acrylates such as 2-ethoxyethoxyethyl (meth) acrylates; hydroxyalkyl (meth) acrylates such as glycidyl (meth) acrylates, 2-hydroxyethyl (meth) acrylates and 2-hydroxypropyl (meth) acrylates. ) Acrylate; alkoxy (poly) alkylene glycol (meth) acrylate such as methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate; N, N-dimethylaminoethyl (meth) acrylate, Dialkylaminoalkyl (meth) acrylates such as N, N-diethylaminoethyl (meth) acrylates; allyl (meth) acrylates, 1,3-butanediol (meth) acrylates, 1,4-butanediol (meth) acrylates, 1, Examples thereof include monofunctional (meth) acrylate compounds such as glycol mono (meth) acrylates such as 6-hexanediol (meth) acrylates and 3-methylpentanediol (meth) acrylates.
The blending amount of the diluent may be arbitrarily adjusted as long as the characteristics of the present invention are not impaired.
　本発明の撥水レンズ保護膜用樹脂組成物には、本発明の特性を損なわない範囲において顔料、染料等の着色剤、安定剤、難燃剤、有機充填剤、可塑剤、酸化防止剤、消泡剤、カップリング剤、レオロジーコントロール剤等の添加剤を適量配合してもよい。 The resin composition for a water-repellent lens protective film of the present invention contains colorants such as pigments and dyes, stabilizers, flame retardants, organic fillers, plasticizers, antioxidants, and defoamers as long as the characteristics of the present invention are not impaired. An appropriate amount of additives such as a foaming agent, a coupling agent, and a rheology control agent may be blended.
［撥水レンズを保護する方法］
　本発明の撥水レンズを保護する方法は、撥水レンズに本発明の撥水レンズ保護膜用樹脂組成物を塗布、硬化してなる保護膜を設けることを特徴とするものである。 [How to protect the water repellent lens]
The method for protecting a water-repellent lens of the present invention is characterized in that a protective film formed by applying the resin composition for a water-repellent lens protective film of the present invention to the water-repellent lens and curing the water-repellent lens is provided.
＜保護膜の形成＞
　本発明の撥水レンズ保護膜用樹脂組成物を用いて保護膜を形成する方法は特に制限されないが、例えば、ディップコート、スプレーコート、スピンコート等の方法を挙げることができる。本発明の撥水レンズ保護膜用樹脂組成物を用いて形成される保護膜の厚みは、特に制限されないが、撥水レンズの周縁加工時の軸ずれ防止や、加工及び保管時の傷つき防止の観点から、１０μｍ以上である方が好ましい。一方、塗膜の厚みは、レンズ中心を特定する際位置ずれが生じないように、１００μｍ以下であることが好ましい。 <Formation of protective film>
The method for forming the protective film using the resin composition for the water-repellent lens protective film of the present invention is not particularly limited, and examples thereof include methods such as dip coating, spray coating, and spin coating. The thickness of the protective film formed by using the resin composition for the water-repellent lens protective film of the present invention is not particularly limited, but it is possible to prevent axial misalignment during peripheral processing of the water-repellent lens and to prevent scratches during processing and storage. From the viewpoint, it is preferably 10 μm or more. On the other hand, the thickness of the coating film is preferably 100 μm or less so that the position shift does not occur when the center of the lens is specified.
　本発明の撥水レンズ保護膜用樹脂組成物を塗布した後に、基材上に塗布された当該組成物を紫外線等の活性エネルギー線を照射して保護膜を得ることができる。活性エネルギー線照射工程で用いられる光源としては、例えばＵＶ－ＬＥＤ（紫外線ＬＥＤ）、低圧水銀灯、高圧水銀灯、超高圧水銀灯、メタルハライドランプ、カーボンアーク、キセノンアーク、気体レーザー、固体レーザー、電子線照射装置等が挙げられる。
　中でも従来のＵＶランプ等と比較して消費電力が大幅に少なく、光源から発生する熱量がＵＶランプと比較して特に少ないＵＶ－ＬＥＤが好ましく、さらにはそのビーク照度が可視光に近い３９５ｎｍ以上であるＵＶ－ＬＥＤを用いることで紫外線照射時の撥水レンズへの影響を抑制し、撥水層におけるクラックの発生を抑制することが出来る。 After applying the resin composition for a water-repellent lens protective film of the present invention, the composition applied on the substrate can be irradiated with active energy rays such as ultraviolet rays to obtain a protective film. Light sources used in the active energy ray irradiation process include, for example, UV-LED (ultraviolet LED), low pressure mercury lamp, high pressure mercury lamp, ultrahigh pressure mercury lamp, metal halide lamp, carbon arc, xenon arc, gas laser, solid laser, electron beam irradiation device. And so on.
Among them, UV-LEDs, which consume significantly less power than conventional UV lamps and generate less heat from light sources than UV lamps, are preferable, and their beak illuminance is 395 nm or more, which is close to visible light. By using a certain UV-LED, it is possible to suppress the influence on the water-repellent lens at the time of ultraviolet irradiation and suppress the generation of cracks in the water-repellent layer.
　本発明の撥水レンズ保護膜用樹脂組成物はプラスチック又はガラスを基材として、表面に防汚性を付与するために撥水・撥油層を形成した撥水レンズに対し、均一に塗工出来る。中でも近年更に防汚性を高めた超撥水層を形成したレンズでも本発明の撥水レンズ保護膜用樹脂組成物は均一に保護膜を形成可能である。本発明は水に対する接触角が９０°以上となる撥水層を備えたレンズに適用でき、接触角が１４０°以上の撥水層を備えたレンズに対し特に有効である。水に対する接触角９０°以上、１１０°以下であれば通常の撥水レンズ、水の接触角が１１０°より高く、１４０°以下であれば高撥水レンズ、１４０°よりも大きければ超撥水レンズと称される。 The resin composition for a water-repellent lens protective film of the present invention can be uniformly applied to a water-repellent lens having a water-repellent / oil-repellent layer formed on the surface of a plastic or glass as a base material to impart antifouling properties to the surface. .. Above all, in recent years, the resin composition for a water-repellent lens protective film of the present invention can uniformly form a protective film even for a lens having a superhydrophobic layer having further improved antifouling properties. The present invention can be applied to a lens having a water-repellent layer having a contact angle of 90 ° or more with water, and is particularly effective for a lens having a water-repellent layer having a contact angle of 140 ° or more. A normal water-repellent lens if the contact angle with water is 90 ° or more and 110 ° or less, a high water-repellent lens if the contact angle of water is higher than 110 ° and 140 ° or less, and superhydrophobic lens if it is larger than 140 °. It is called a lens.
　撥水レンズの接触角は液滴法と呼ばれる方法で評価できる。純水１μＬの液滴を作製し、対象撥水レンズへ接触させて着滴させる。その時の撥水レンズと液滴のなす角度を接触角として評価する。 The contact angle of the water repellent lens can be evaluated by a method called the sessile drop method. A droplet of 1 μL of pure water is prepared and brought into contact with the target water-repellent lens to be dropped. The angle formed by the water-repellent lens and the droplet at that time is evaluated as the contact angle.
＜第１の実施例（第１の撥水レンズ保護膜用樹脂組成物）＞
（Ａ）成分：多官能（メタ）アクリレート
Ａ－１：エチレンオキシド変性ビスフェノールＡジメタクリレート（ブレンマーＰＤＢＥ－２００Ａ　日油株式会社製：２官能、分子量５４１）
Ａ－２：ウレタンアクリレート（アートレジンＵＮ－２７００　根上工業社製：２官能、重量平均分子量２０００）
Ａ－３：ウレタンアクリレート（アートレジンＵＮ－３５２　根上工業社製：２官能、重量平均分子量３０００）
Ａ－４：ポリエーテル系ウレタンアクリレート（アートレジンＵＮ－６２００　根上工業社製：２官能、重量平均分子量８０００）
Ａ－５：ポリカーボネート系ウレタンアクリレート（アートレジンＵＮ－９２００Ａ　根上工業社製：２官能、重量平均分子量１５０００）
Ａ－６：ポリエーテル系ウレタンアクリレート（アートレジンＵＮ－６３０５　根上工業社製：２官能、重量平均分子量２７０００）
Ａ’－１：エチレングリコールジメタクリレート（ライトエステルＥＧ　共栄社化学株式会社製：２官能、分子量１９８）
Ａ’－２：ウレタンアクリレート（紫光ＵＶ－３７００Ｂ　日本合成化学工業株式会社製：２官能、量平均分子量３８０００） <First Example (First Water-Repellent Lens Protective Film Resin Composition)>
(A) Ingredient: Polyfunctional (meth) acrylate A-1: Ethylene oxide-modified bisphenol A dimethacrylate (Blemmer PDBE-200A manufactured by NOF CORPORATION: bifunctional, molecular weight 541)
A-2: Urethane acrylate (Art Resin UN-2700, manufactured by Negami Kogyo Co., Ltd .: bifunctional, weight average molecular weight 2000)
A-3: Urethane acrylate (Art Resin UN-352 Negami Kogyo Co., Ltd .: Bifunctional, weight average molecular weight 3000)
A-4: Polyether-based urethane acrylate (Art Resin UN-6200, manufactured by Negami Kogyo Co., Ltd .: bifunctional, weight average molecular weight 8000)
A-5: Polycarbonate urethane acrylate (Art Resin UN-9200A, manufactured by Negami Kogyo Co., Ltd .: bifunctional, weight average molecular weight 15000)
A-6: Polyether-based urethane acrylate (Art Resin UN-6305, manufactured by Negami Kogyo Co., Ltd .: bifunctional, weight average molecular weight 27000)
A'-1: Ethylene glycol dimethacrylate (light ester EG, manufactured by Kyoeisha Chemical Co., Ltd .: bifunctional, molecular weight 198)
A'-2: Urethane acrylate (Shikou UV-3700B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd .: bifunctional, weight average molecular weight 38000)
（Ｂ）成分：硬化剤
Ｂ－１：ジペンタエリスリトール　ヘキサキス（３－メルカプトプロピオネート）（ＤＰＭＰ　ＳＣ有機化学株式会社製：６官能、分子量７８３） (B) Ingredient: Hardener B-1: Dipentaerythritol Hexakis (3-mercaptopropionate) (DPMP SC Organic Chemistry Co., Ltd .: 6-functional, molecular weight 783)
（Ｃ）成分：光重合開始剤
Ｃ－１：２，２－ジメトキシー２－フェニルアセトフェノン（ＯＭＮＩＲＡＤ６５１　ＩＧＭ社製）
Ｃ－２：２－ベンジルー２－（ジメチルアミノ）－４’－モルフォリノブチロフェノン（ＯＭＮＩＲＡＤ３６９　ＩＧＭ社製）
Ｃ－３：ビス（２、４、６－トリメチルベンゾイル）フェニルフォスフィンオキシド（ＯＭＮＩＲＡＤ８１９　ＩＧＭ社製）
Ｃ－４：１－ヒドロキシシクロヘキシルフェニルケトン（ＯＭＮＩＲＡＤ１８４　ＩＧＭ社製） (C) Ingredient: Photopolymerization Initiator C-1: 2,2-Dimethoxy-2-phenylacetophenone (OMNIRAD651, manufactured by IGM)
C-2: 2-benzyl-2- (dimethylamino) -4'-morpholinobtyrophenone (OMNIRAD369 IGM)
C-3: Bis (2,4,6-trimethylbenzoyl) phenylphosphin oxide (OMNIRAD819 IGM)
C-4: 1-Hydroxycyclohexylphenyl ketone (OMNIRAD184 IGM)
（Ｄ）成分：ノニオン性界面活性剤
Ｄ－１：フッ素系ノニオン性界面活性剤（メガファックＲＳ－７５－Ａ　ＤＩＣ株式会社製、PGMEA中に０.１質量部配合時表面張力２３．８ｍＮ／ｍ）
Ｄ－２：フッ素系ノニオン性界面活性剤（メガファックＲＳ－７８　ＤＩＣ株式会社製、PGMEA中に０.１質量部配合時表面張力２２．０ｍＮ／ｍ）
Ｄ－３：フッ素系ノニオン性界面活性剤（メガファックＦ-５６０　ＤＩＣ株式会社製PGMEA中に０.１質量部配合時表面張力２１．４ｍＮ／ｍ）
Ｄ－４：フッ素系ノニオン性界面活性剤（メガファックＦ－４７７　ＤＩＣ株式会社製PGMEA中に０.１質量部配合時表面張力２５．４ｍＮ／ｍ）
Ｄ’－１：フッ素系アニオン性界面活性剤（メガファックＦ－１１４　ＤＩＣ株式会社製PGMEA中に０.１質量部配合時表面張力２６．５ｍＮ／ｍ） (D) Ingredient: Nonionic surfactant D-1: Fluorine-based nonionic surfactant (Megafuck RS-75-A manufactured by DIC Corporation, surface tension 23.8 mN / part when 0.1 part by mass is blended in PGMEA / m)
D-2: Fluorine-based nonionic surfactant (Megafuck RS-78, manufactured by DIC Corporation, surface tension of 22.0 mN / m when 0.1 parts by mass is mixed in PGMEA)
D-3: Fluorine-based nonionic surfactant (surface tension 21.4 mN / m when 0.1 parts by mass is blended in PGMEA manufactured by Megafuck F-560 DIC Corporation)
D-4: Fluorine-based nonionic surfactant (surface tension 25.4 mN / m when 0.1 parts by mass is blended in PGMEA manufactured by Megafuck F-477 DIC Corporation)
D'-1: Fluorine-based anionic surfactant (surface tension 26.5 mN / m when 0.1 parts by mass is blended in PGMEA manufactured by Megafuck F-114 DIC Corporation)
（Ｅ）成分：希釈剤
Ｅ－１：メチルエチルケトン
Ｅ－２：ブチルアクリレート (E) Ingredient: Diluent E-1: Methyl ethyl ketone E-2: Butyl acrylate
　表１、２に示す配合比で（Ａ）～（Ｅ）成分をそれぞれ混合容器へ投入し、室温（２３℃）、紫外線カット下でスリーワンモーターにて均一になるまで撹拌することで、撥水レンズ保護膜用樹脂組成物のサンプルを得た。得られた実施例及び比較例の各撥水レンズ保護膜用樹脂組成物に対して以下の粘度、塗工性、光硬化性、保持力、剥離性、レンズ汚染性の評価を行った。その結果を表１、２に示す。 The components (A) to (E) are charged into the mixing vessel at the blending ratios shown in Tables 1 and 2, and are stirred at room temperature (23 ° C.) under ultraviolet rays until they become uniform with a three-one motor to make them water repellent. A sample of a resin composition for a lens protective film was obtained. The following viscosity, coatability, photocurability, holding power, peelability, and lens contamination property were evaluated for each of the obtained resin compositions for the water-repellent lens protective film of Examples and Comparative Examples. The results are shown in Tables 1 and 2.
[超撥水レンズへの保護膜形成]
　評価には純水の接触角が１５０°となる超撥水層を備えたプラスチックレンズを用いた。この超撥水レンズに対し、実施例及び比較例の撥水レンズ保護膜用樹脂組成物をディップコート法によりコートした。コート後、室温（２３℃）、紫外線がカットされた空間で１０分間静置し乾燥させ、ＬＥＤ紫外線照射装置（ウシオ電機株式会社製Ｕｎｉｊｅｔ　Ｅ１１０ＩＩＨＤ―３６５）を用い、照度５００ｍＷ／ｃｍ２になるようレンズとの距離を調節して片面ずつ照射した。また、３９５ｎｍをピーク波長にもつＬＥＤ紫外線照射装置（ウシオ電機株式会社製Ｕｎｉｊｅｔ　Ｅ１１０ＩＩＨＤ―３９５）でも同様の手法で硬化させた。 [Formation of protective film on superhydrophobic lens]
For the evaluation, a plastic lens having a superhydrophobic layer having a contact angle of pure water of 150 ° was used. The superhydrophobic lens was coated with the resin compositions for the water-repellent lens protective film of Examples and Comparative Examples by the dip coating method. After coating, leave it at room temperature (23 ° C) for 10 minutes in a space where ultraviolet rays are cut, and dry it. Using an LED ultraviolet irradiation device (Unijet E110IIHD-365 manufactured by Ushio, Inc.), the illuminance is 500 mW / cm 2 . The distance to the lens was adjusted and irradiation was performed one side at a time. Further, the LED ultraviolet irradiation device (Unijet E110IIHD-395 manufactured by Ushio, Inc.) having a peak wavelength of 395 nm was also cured by the same method.
［粘度測定］
　試料を２５℃で３分間放置した後に、Ｅ型粘度計（東機産業社製ＲＥ－８５Ｌ、コーン：ＣＯＲＤ－１　１°３４’×Ｒ２４を用いて測定条件：２５℃、２０ｒｐｍで「粘度（ｍＰａ・ｓ）」を測定した。 [Viscosity measurement]
After leaving the sample at 25 ° C for 3 minutes, use an E-type viscometer (RE-85L manufactured by Toki Sangyo Co., Ltd., cone: CORD-1 1 ° 34'x R24) under measurement conditions: 25 ° C, 20 rpm for "viscosity ( mPa · s) ”was measured.
［塗工性評価］
　前述したディップコート法により超撥水レンズへ撥水レンズ保護膜用樹脂組成物をコートし、硬化させた。ハジキが見られた場合、レンズ端部からコートされていない部分の最大の幅をハジキの大きさとして計測し、以下の通り評価した。なお、塗工性はハジキの大きさが１０ｍｍ以下にする必要がある。
　　　◎：ハジキ無し。
　　　○：端部からコートできていない部分が１０ｍｍ以下である。
　　　×：端部からコートできていない部分が１０ｍｍより大きい。 [Evaluation of coatability]
The resin composition for a water-repellent lens protective film was coated on the superhydrophobic lens by the above-mentioned dip coating method and cured. When repellent was observed, the maximum width of the uncoated portion from the end of the lens was measured as the size of the repellent and evaluated as follows. The coatability needs to be 10 mm or less in the size of the repellent.
◎: No repellent.
◯: The portion not coated from the end is 10 mm or less.
X: The portion not coated from the end is larger than 10 mm.
［光硬化性評価］
　コート後の撥水レンズ保護膜用樹脂組成物をＬＥＤ紫外線照射装置にて硬化させる際、照射により表面のタックが無くなる積算光量を確認し、以下の通り評価した。なお、レンズへの熱影響及び硬化時間から積算光量は２００００ｍＪ／ｃｍ２以下にする必要がある。
　　　◎：積算光量が１０００ｍＪ／ｃｍ２以下である。
　　　○：１０００ｍＪ／ｃｍ２より多く２００００ｍＪ／ｃｍ２以下である。
　　　×：２００００ｍＪ／ｃｍ２より多い。 [Evaluation of photocurability]
When the resin composition for a water-repellent lens protective film after coating was cured by an LED ultraviolet irradiation device, the integrated light amount at which the surface tack was eliminated by irradiation was confirmed and evaluated as follows. The integrated light intensity needs to be 20000 mJ / cm 2 or less due to the thermal effect on the lens and the curing time.
⊚: The integrated light amount is 1000 mJ / cm 2 or less.
◯: More than 1000 mJ / cm 2 and less than 20000 mJ / cm 2 .
X: More than 20000 mJ / cm 2 .
［保持力評価］
　撥水レンズの周縁加工時の軸ずれ評価として、超撥水レンズへ形成した保護膜の保持力を評価した。保持力はＪＩＳ－Ｚ０２３７に準拠し、荷重を変更して行った。保護膜を形成した超撥水レンズ中心部に幅２４ｍｍ、長さ１３０ｍｍの粘着テープ（ニチバン社製ＣＴ４０５ＡＰ－２４）を張り付ける（図１参照。）。この時、粘着テープ上とレンズ凹部の中心部で重なるよう油性ペンで印をつける。粘着テープのレンズに張り付けた端部と反対側の端部に重さ１４．７Ｎの荷重をかけ、１０分間後に凸面と凹面の印にずれが生じた距離を測定した（図２参照。）。得られた測定結果について以下の通りに評価した。
　　　◎：保持力測定結果が０．０ｍｍである。
　　　○：保持力測定結果が０．０ｍｍより大きく、２．０ｍｍ以下である。
　　　×：保持力測定結果が２．０ｍｍより大きい。 [Holding power evaluation]
The holding power of the protective film formed on the superhydrophobic lens was evaluated as an evaluation of the axial deviation during peripheral processing of the water-repellent lens. The holding force conformed to JIS-Z0237, and the load was changed. An adhesive tape (CT405AP-24 manufactured by Nichiban Co., Ltd.) having a width of 24 mm and a length of 130 mm is attached to the center of the superhydrophobic lens on which the protective film is formed (see FIG. 1). At this time, mark with an oil-based pen so that it overlaps with the adhesive tape at the center of the lens recess. A load with a weight of 14.7 N was applied to the end portion opposite to the end portion attached to the lens of the adhesive tape, and the distance at which the marks on the convex and concave surfaces were displaced after 10 minutes was measured (see FIG. 2). The obtained measurement results were evaluated as follows.
⊚: The holding force measurement result is 0.0 mm.
◯: The holding force measurement result is larger than 0.0 mm and 2.0 mm or less.
X: The holding force measurement result is larger than 2.0 mm.
［剥離性］
　超撥水レンズへ形成した保護膜に対し、テープを端部に貼り保護膜を剥離した後、レンズの外観と剥離性を目視で確認して、以下の通り評価した。
　　　○：残渣なく剥離されている。
　　　×：剥離時に裂けや割れが発生または剥離できない。 [Removability]
A tape was attached to the end of the protective film formed on the superhydrophobic lens to peel off the protective film, and then the appearance and peelability of the lens were visually confirmed and evaluated as follows.
◯: Peeled without residue.
X: Tears or cracks occur or cannot be peeled off during peeling.
［レンズ汚染性］
　超撥水レンズから保護膜を剥離した後、レンズに対し油性マジック（寺西化学工業社製マジックインキ（黒））でレンズに線を引いた際のインクのハジキを観察し、以下の通り評価した。なお、保護膜を形成する前は油性マジックのインクはハジくが、レンズ表面に汚染物質が残っていると撥水性が低下し、ハジキが悪くなる。
　　　○：直線で描いたインクが点状になる。
　　　×：直線で描いたインクにハジキが見られない。 [Lens contamination]
After peeling off the protective film from the superhydrophobic lens, we observed the ink repellent when drawing a line on the lens with oil-based marker (Magic Ink (black) manufactured by Teranishi Chemical Industry Co., Ltd.) and evaluated as follows. .. Before forming the protective film, the oil-based marker ink is repellent, but if contaminants remain on the lens surface, the water repellency decreases and the repelling becomes worse.
◯: The ink drawn in a straight line becomes a dot.
×: No repelling is seen in the ink drawn in a straight line.
　表１、２に示すように実施例においてはいずれのサンプルも超撥水レンズに塗工可能で、且つピーク波長が３９５ｎｍのＬＥＤ紫外線照射装置でも硬化可能である。また、撥水レンズの周縁加工における軸ずれを防止するのに十分な保持力を有することから超撥水レンズであっても従来の加工方法で所望の形状に加工できる。 As shown in Tables 1 and 2, in the examples, any sample can be applied to a superhydrophobic lens, and can be cured even with an LED ultraviolet irradiation device having a peak wavelength of 395 nm. Further, since it has a sufficient holding force to prevent axial deviation in the peripheral processing of the water-repellent lens, even a superhydrophobic lens can be processed into a desired shape by a conventional processing method.
　一方、（Ｄ）成分であるノニオン系界面活性剤を含まない比較例１－１、（Ｄ）成分であるノニオン系界面活性剤ではなくアニオン性界面活性剤を含む比較例１－２では超撥水レンズにコートすることが出来ず、保護膜を形成すらできない。また、比較例１－３ではピーク波長３９５ｎｍのＬＥＤ紫外線照射装置で硬化性が悪く、許容できる積算光量を越えてしまう。更に硬化膜の靭性が低いため、剥離時に裂けるため剥離性が悪い。比較例１－４では、光硬化性は良好だが、硬化膜の柔軟性が高く、保持力が規定値以上となる。これより、周縁加工時の軸ずれが発生してしまう。 On the other hand, in Comparative Example 1-1 which does not contain the nonionic surfactant which is the component (D), and Comparative Example 1-2 which contains an anionic surfactant instead of the nonionic surfactant which is the component (D), it is superhydrophobic. It cannot be coated on a water lens and cannot even form a protective film. Further, in Comparative Example 1-3, the LED ultraviolet irradiation device having a peak wavelength of 395 nm has poor curability and exceeds the allowable integrated light amount. Furthermore, since the toughness of the cured film is low, it tears at the time of peeling, resulting in poor peelability. In Comparative Example 1-4, the photocurability is good, but the flexibility of the cured film is high, and the holding power is equal to or higher than the specified value. As a result, misalignment occurs during peripheral machining.
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
＜第２の実施例（第２の撥水レンズ保護膜用樹脂組成物）＞
（Ａ）成分：多官能（メタ）アクリレート
Ａ－１：エチレンオキシド変性ビスフェノールＡジメタクリレート（ブレンマーＰＤＢＥ－２００Ａ　日油株式会社製：２官能、重量平均分子量５４１）
Ａ－７： ウレタンアクリレート（アートレジンＵＮ－３３３　根上工業社製：２官能、重量平均分子量３，０００）
Ａ－８： ポリエーテル系ウレタンアクリレート（アートレジンＵＮ－１２５５　根上工業社製：２官能、重量平均分子量８，０００）
Ａ－５： ポリカーボネート系ウレタンアクリレート（アートレジンＵＮ－９２００Ａ　根上工業社製：２官能、重量平均分子量１５，０００）
Ａ－９： 脂肪族ウレタンアクリレート（ＥＢＥＣＲＹＬ４６６６　ダイセル・オルネクス社製：４官能、重量平均分子量１，１００）
Ａ’－１：エチレングリコールジメタクリレート（ライトエステルＥＧ　共栄社化学株式会社製：２官能、分子量１９８）
Ａ’－２：ウレタンアクリレート（紫光ＵＶ－３７００Ｂ　三菱ケミカル株式会社製：２官能、量平均分子量３８，０００） <Second Example (Second Water-Repellent Lens Protective Film Resin Composition)>
(A) Ingredient: Polyfunctional (meth) acrylate A-1: Ethylene oxide-modified bisphenol A dimethacrylate (Blemmer PDBE-200A manufactured by NOF CORPORATION: bifunctional, weight average molecular weight 541)
A-7: Urethane acrylate (Art Resin UN-333 Negami Kogyo Co., Ltd .: Bifunctional, weight average molecular weight 3,000)
A-8: Polyether-based urethane acrylate (Art Resin UN-1255, manufactured by Negami Kogyo Co., Ltd .: bifunctional, weight average molecular weight 8,000)
A-5: Polycarbonate urethane acrylate (Art Resin UN-9200A, manufactured by Negami Kogyo Co., Ltd .: bifunctional, weight average molecular weight 15,000)
A-9: Aliphatic urethane acrylate (EBECRYL4666, manufactured by Dycel Ornex: tetrafunctional, weight average molecular weight 1,100)
A'-1: Ethylene glycol dimethacrylate (light ester EG, manufactured by Kyoeisha Chemical Co., Ltd .: bifunctional, molecular weight 198)
A'-2: Urethane acrylate (Shikou UV-3700B manufactured by Mitsubishi Chemical Corporation: bifunctional, weight average molecular weight 38,000)
（ｂ１）成分：多官能チオール化合物
Ｂ－１：ジペンタエリスリトールヘキサキス（３－メルカプトプロピオネート）（ＤＰＭＰ　ＳＣ有機化学株式会社製：６官能、重量平均分子量７８３）
Ｂ－２：トリメチロールプロパントリス（３－メルカプトプロピオネート）（ＴＭＭＰ　ＳＣ有機化学株式会社製：３官能、重量平均分子量３９９） (B1) Ingredient: Polyfunctional thiol compound B-1: Dipentaerythritol hexakis (3-mercaptopropionate) (DPMP SC Organic Chemistry Co., Ltd .: 6-functional, weight average molecular weight 783)
B-2: Trimethylolpropanetris (3-mercaptopropionate) (TMMP SC Organic Chemistry Co., Ltd .: trifunctional, weight average molecular weight 399)
（Ｃ）成分：光重合開始剤
Ｃ－１：２，２－ジメトキシー２－フェニルアセトフェノン（ＯＭＮＩＲＡＤ６５１　ＩＧＭ社製） (C) Ingredient: Photopolymerization Initiator C-1: 2,2-Dimethoxy-2-phenylacetophenone (OMNIRAD651, manufactured by IGM)
（ｄ１）成分：フッ素系セグメントと非フッ素系セグメントからなるブロック共重合体
Ｄ－５：フッ素系ブロックコポリマー（モディパーＦ２０６　日油株式会社製、重量平均分子量３８，０００）
Ｄ－６：フッ素系ブロックコポリマー（モディパーＦ２４６　日油株式会社製、重量平均分子量２５，０００）
Ｄ－７：フッ素系ブロックコポリマー（モディパーＦ３６３６　日油株式会社製、重量平均分子量７７，０００） (D1) Component: Block copolymer composed of a fluorine-based segment and a non-fluorine-based segment D-5: Fluorine-based block copolymer (Modiper F206, manufactured by NOF CORPORATION, weight average molecular weight 38,000)
D-6: Fluorine-based block copolymer (Modiper F246 NOF Corporation, weight average molecular weight 25,000)
D-7: Fluorine-based block copolymer (Modiper F3636, manufactured by NOF CORPORATION, weight average molecular weight 77,000)
（Ｅ）成分：希釈剤
Ｅ－１：メチルエチルケトン
Ｅ－２：ブチルアクリレート
Ｅ－３：イソプロピルアセテート (E) Ingredient: Diluent E-1: Methyl ethyl ketone E-2: Butyl acrylate E-3: Isopropyl acetate
　表３～５に示す配合比で（Ａ）～（Ｄ）成分及び（Ｅ）希釈剤を混合容器へ投入し、室温（２３℃）、紫外線カット下でスリーワンモーターを用いて均一になるまで撹拌することで、撥水レンズ保護膜用樹脂組成物のサンプルを得た。得られた実施例及び比較例の各撥水レンズ保護膜用樹脂組成物に対して以下の塗工性、密着性（保持力、剥離性、強靭性）及び非汚染性の評価を行った。その結果を表３～５に示す。 Add the components (A) to (D) and the diluent (E) to the mixing vessel at the blending ratios shown in Tables 3 to 5, and stir at room temperature (23 ° C.) under UV protection using a three-one motor until uniform. By doing so, a sample of the resin composition for the water-repellent lens protective film was obtained. The following coatability, adhesion (retaining power, peelability, toughness) and non-staining property were evaluated for each of the obtained resin compositions for the water-repellent lens protective film of Examples and Comparative Examples. The results are shown in Tables 3-5.
[超撥水レンズへの保護膜形成]
　評価には純水の接触角が１５０°以上となる超撥水層を備えたプラスチックレンズ（直径７５ｍｍ）を用いた。この超撥水レンズに対し、実施例及び比較例の撥水レンズ保護膜用樹脂組成物をディップコート法により硬化後膜厚が２０μｍとなるようにコートした。コート後、室温（２３℃）、紫外線がカットされた空間で１０分間静置し乾燥させ、ＬＥＤ紫外線照射装置（ウシオ電機株式会社製Ｕｎｉｊｅｔ　Ｅ１１０ＩＩＨＤ―３９５）を用い、照度５００ｍＷ／ｃｍ２になるようレンズとの距離を調節して片面ずつ照射した。なお、超撥水レンズの接触角は、対象レンズ表面に純水１μＬの液滴を接触させ、その時のレンズと液滴のなす角度により算出した。 [Formation of protective film on superhydrophobic lens]
For the evaluation, a plastic lens (diameter 75 mm) provided with a superhydrophobic layer having a contact angle of pure water of 150 ° or more was used. The superhydrophobic lens was coated with the resin compositions for the water-repellent lens protective film of Examples and Comparative Examples so that the film thickness after curing was 20 μm by the dip coating method. After coating, leave it to stand at room temperature (23 ° C) for 10 minutes in a space where ultraviolet rays are cut, and dry it. Using an LED ultraviolet irradiation device (Unijet E110IIHD-395 manufactured by Ushio, Inc.), the illuminance is 500 mW / cm 2 . The distance to the lens was adjusted and irradiation was performed one side at a time. The contact angle of the superhydrophobic lens was calculated from the angle formed by the lens and the droplet at that time when a droplet of 1 μL of pure water was brought into contact with the surface of the target lens.
［塗工性評価］
　前述したディップコート法により超撥水レンズへ撥水レンズ保護膜用樹脂組成物をコートし、硬化させた。ハジキが見られた場合、レンズ端部からコートされていない部分の最大の幅をハジキの大きさとして計測し、以下の通り評価した。なお、塗工性はハジキの大きさが１０ｍｍ以下を合格とした。
　　　◎：ハジキ無し。
　　　○：端部からコートできていない部分が５ｍｍ以下である。
　　　△：端部からコートできていない部分が５ｍｍより大きく１０ｍｍ以下である。
　　　×：端部からコートできていない部分が１０ｍｍより大きい。 [Evaluation of coatability]
The resin composition for a water-repellent lens protective film was coated on the superhydrophobic lens by the above-mentioned dip coating method and cured. When repellent was observed, the maximum width of the uncoated portion from the end of the lens was measured as the size of the repellent and evaluated as follows. As for the coatability, it was accepted that the size of the repellent was 10 mm or less.
◎: No repellent.
◯: The portion not coated from the end is 5 mm or less.
Δ: The portion not coated from the end portion is larger than 5 mm and 10 mm or less.
X: The portion not coated from the end is larger than 10 mm.
［保持力評価］
　レンズの周縁加工時の軸ずれ評価として、超撥水レンズへ形成した保護膜の保持力を評価した。保持力評価はＪＩＳ－Ｚ０２３７に準拠し、荷重を変更して行った。温度：２３℃、相対湿度：５０％環境下で３ヶ月保管した保護膜形成済み超撥水レンズの中心部に幅２４ｍｍ、長さ１３０ｍｍの粘着テープ（ニチバン社製ＣＴ４０５ＡＰ－２４）を貼り付ける（図１参照）。この時、粘着テープ上とレンズ凹部の中心部で重なるよう油性ペンで印をつける。粘着テープのレンズに貼り付けた端部と反対側の端部に重さ１４．７Ｎの荷重をかけ、１０分間後に凸面と凹面の印にずれが生じた距離を測定した（図２参照）。得られた測定結果について以下の通り評価した。なお、保持力測定結果は２．０ｍｍ以下を合格とした。
　　　◎：保持力測定結果が０．０ｍｍである。
　　　○：保持力測定結果が０．０ｍｍより大きく、０．５ｍｍ以下である。
　　　△：保持力測定結果が０．５ｍｍより大きく２．０ｍｍ以下である。
　　　×：保持力測定結果が２．０ｍｍより大きい。 [Holding power evaluation]
The holding power of the protective film formed on the superhydrophobic lens was evaluated as an evaluation of the axial deviation during peripheral processing of the lens. The holding force was evaluated in accordance with JIS-Z0237, and the load was changed. Temperature: 23 ° C, Relative humidity: 50% Adhesive tape (CT405AP-24 manufactured by Nichiban Co., Ltd.) with a width of 24 mm and a length of 130 mm is attached to the center of the superhydrophobic lens with a protective film that has been stored for 3 months in an environment (CT405AP-24 manufactured by Nichiban Co., Ltd.). See Figure 1). At this time, mark with an oil-based pen so that it overlaps with the adhesive tape at the center of the lens recess. A load with a weight of 14.7 N was applied to the end portion opposite to the end portion attached to the lens of the adhesive tape, and the distance at which the marks on the convex and concave surfaces were displaced after 10 minutes was measured (see FIG. 2). The obtained measurement results were evaluated as follows. The holding force measurement result was 2.0 mm or less.
⊚: The holding force measurement result is 0.0 mm.
◯: The holding force measurement result is larger than 0.0 mm and 0.5 mm or less.
Δ: The holding force measurement result is larger than 0.5 mm and 2.0 mm or less.
X: The holding force measurement result is larger than 2.0 mm.
［剥離性］
　温度：２３℃、相対湿度：５０％環境下で３ヶ月保管した保護膜形成済み超撥水レンズの端部に粘着テープ（ニチバン社製ＣＴ４０５ＡＰ－２４）を貼り付けた後、手でテープを剥離した。同位置で粘着テープの貼付・剥離を繰り返し、保護膜が剥離するまでに必要なテープの剥離回数を確認し、以下の通り評価した。なお、剥離性は〇又は△を合格とした。
　　　〇：１回のテープ剥離で保護膜を剥離できる。
　　　△：２～５回のテープ剥離で保護膜を剥離できる。
　　　×：５回以上のテープ剥離を行っても保護膜を剥離できない。 [Removability]
Temperature: 23 ° C, Relative humidity: 50% Adhesive tape (CT405AP-24 manufactured by Nichiban Co., Ltd.) is attached to the end of the superhydrophobic lens with a protective film that has been stored for 3 months in an environment, and then the tape is peeled off by hand. bottom. The adhesive tape was repeatedly applied and peeled off at the same position, and the number of times the tape was peeled off before the protective film was peeled off was confirmed and evaluated as follows. As for the peelability, 〇 or Δ was regarded as acceptable.
〇: The protective film can be peeled off with one tape peeling.
Δ: The protective film can be peeled off by peeling the tape 2 to 5 times.
X: The protective film cannot be peeled off even if the tape is peeled off 5 times or more.
［強靭性］
　温度：２３℃、相対湿度：５０％環境下で３ヶ月保管した保護膜形成済み超撥水レンズの端部に粘着テープ（ニチバン社製ＣＴ４０５ＡＰ－２４）を貼り付けた後、手でテープを剥離した。剥離した保護膜の形状を確認し、以下の通り、評価した。なお、強靭性は〇又は△を合格とした。
　　　〇：保護膜に亀裂がない。
　　　△：保護膜に３０ｍｍ未満の亀裂がある。
　　　×：保護膜が破断し、１回のテープ剥離では保護膜を剥離できない。 [Toughness]
Temperature: 23 ° C, Relative humidity: 50% Adhesive tape (CT405AP-24 manufactured by Nichiban Co., Ltd.) is attached to the end of the superhydrophobic lens with a protective film that has been stored for 3 months in an environment, and then the tape is peeled off by hand. bottom. The shape of the peeled protective film was confirmed and evaluated as follows. The toughness was evaluated as 〇 or Δ.
〇: There are no cracks in the protective film.
Δ: The protective film has a crack of less than 30 mm.
X: The protective film is broken and the protective film cannot be peeled off by one tape peeling.
［非汚染性］
　温度：２３℃、相対湿度：５０％環境下で３ヶ月保管した保護膜形成済み超撥水レンズから保護膜を剥離した後、レンズに対し油性マジック（寺西化学工業社製マジックインキ（黒））でレンズに線を引いた際のインクのハジキを観察し、以下の通り評価した。なお、保護膜を形成する前のレンズ表面は油性マジックのインクをはじくが、レンズ表面に汚染物質が残っていると撥水性が低下する。なお、非汚染性は〇又は△を合格とした。
　　　〇：直線で描いたインクが点状になる。
　　　△：直線で描いたインクが細い線状になる。
　　　×：直線で描いたインクにハジキが見られない。 [Non-polluting]
Temperature: 23 ° C, Relative humidity: 50% After peeling off the protective film from the protective film-formed superhydrophobic lens stored for 3 months in an environment, oil-based marker (Magic ink (black) manufactured by Teranishi Chemical Industry Co., Ltd.) The ink repellent when a line was drawn on the lens was observed and evaluated as follows. The lens surface before forming the protective film repels oil-based marker ink, but if contaminants remain on the lens surface, the water repellency decreases. The non-contamination property was evaluated as 〇 or Δ.
〇: The ink drawn in a straight line becomes a dot.
Δ: The ink drawn in a straight line becomes a thin line.
×: No repelling is seen in the ink drawn in a straight line.
　表３、４の結果から、実施例２－１～２－１９の樹脂組成物はいずれも超撥水レンズに対する塗工性が良好であった。また、実施例２－１～２－１９の樹脂組成物を硬化させて得られた保護膜は温度：２３℃、相対湿度：５０％環境下で３ヶ月保管後においても、超撥水レンズに対する適度な密着性を有しており、保持力、剥離性及び強靭性が高いレベルで並立されていた。さらに、保護膜剥離後の超撥水レンズの撥水性低下も抑えられており、非汚染性にも優れていた。 From the results in Tables 3 and 4, all of the resin compositions of Examples 2-1 to 2-19 had good coatability on the superhydrophobic lens. Further, the protective film obtained by curing the resin compositions of Examples 2-1 to 2-19 has a temperature of 23 ° C. and a relative humidity of 50%, even after being stored for 3 months in an environment with respect to the superhydrophobic lens. It had an appropriate degree of adhesion, and had high levels of holding power, peelability, and toughness. Further, the decrease in water repellency of the superhydrophobic lens after peeling of the protective film was suppressed, and the non-staining property was also excellent.
　一方、表５の結果から、比較例２－１、２－２では、（Ａ）成分の重量平均分子量が過小、又は過大であるため、得られた保護膜の超撥水レンズに対する保持力、或いは強靭性が不足していた。比較例２－３、２－４では、（ｂ１）成分の含有量が過少、又は過多であるため、得られた保護膜の超撥水レンズからの剥離性、或いは強靭性が不足していた。比較例２－５では、（Ｃ）成分の含有量が過少であるため、得られた保護膜の超撥水レンズに対する保持力、強靭性及び非汚染性が不足していた。比較例２－６では、（Ｃ）成分の含有量が過多であるため、得られた保護膜の非汚染性が不足していた。比較例２－７では、（ｄ１）成分の含有量が過多であるため、得られた保護膜の非汚染性が不足していた。比較例２－８では、（ｄ１）成分を含有していないため、超撥水レンズへの塗布性が不足していた。 On the other hand, from the results in Table 5, in Comparative Examples 2-1 and 2-2, since the weight average molecular weight of the component (A) was too small or too large, the holding power of the obtained protective film on the superhydrophobic lens was determined. Or it lacked toughness. In Comparative Examples 2-3 and 2-4, since the content of the component (b1) was too small or too large, the peelability or toughness of the obtained protective film from the superhydrophobic lens was insufficient. .. In Comparative Example 2-5, since the content of the component (C) was too small, the holding power, toughness and non-staining property of the obtained protective film with respect to the superhydrophobic lens were insufficient. In Comparative Example 2-6, the content of the component (C) was excessive, so that the non-staining property of the obtained protective film was insufficient. In Comparative Example 2-7, the content of the component (d1) was excessive, so that the non-staining property of the obtained protective film was insufficient. In Comparative Example 2-8, since the component (d1) was not contained, the applicability to the superhydrophobic lens was insufficient.
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013

Claims (5)

  1. 　（Ａ）重量平均分子量が２００～３０，０００である多官能（メタ）アクリレートと、
    　（Ｃ）光重合開始剤と、
    　（Ｄ）ノニオン系界面活性剤と、を含有する撥水レンズ保護膜用樹脂組成物。     (A) Polyfunctional (meth) acrylate having a weight average molecular weight of 200 to 30,000, and
    (C) Photopolymerization initiator and
    (D) A resin composition for a water-repellent lens protective film containing a nonionic surfactant.
  2. 　（Ｄ）ノニオン系界面活性剤がフッ素を含有し、プロピレングリコールモノメチルエーテルアセテート中に０．１質量部配合した際の表面張力が２６．０ｍＮ／ｍｍ以下となるフッ素系ノニオン性界面活性剤である、請求項１記載の撥水レンズ保護膜用樹脂組成物。 (D) A fluorine-based nonionic surfactant containing fluorine and having a surface tension of 26.0 mN / mm or less when 0.1 part by mass is blended in propylene glycol monomethyl ether acetate. , The resin composition for a water-repellent lens protective film according to claim 1.
  3. 　照度５０～３０００ｍＷ／ｃｍ２のＬＥＤ光源を用いた際、積算光量５０００ｍＪ／ｃｍ２以下で硬化可能である、請求項１又は請求項２に記載の撥水レンズ保護膜用樹脂組成物。 The resin composition for a water-repellent lens protective film according to claim 1 or 2, which can be cured with an integrated light amount of 5000 mJ / cm 2 or less when an LED light source having an illuminance of 50 to 3000 mW / cm 2 is used.
  4. 　以下の（Ａ）～（ｄ１）成分を含有することを特徴とする樹脂組成物であって、
    　前記（Ａ）成分１００質量部に対して、（ｂ１）成分を０．５～３０質量部、（Ｃ）成分を０．１～２５質量部、（ｄ１）成分を０．１～２５質量部含むことを特徴とする、撥水レンズ保護膜用樹脂組成物。
    　（Ａ）成分：重量平均分子量が２５０～３０，０００である多官能（メタ）アクリレート
    　（ｂ１）成分：多官能チオール化合物
    　（Ｃ）成分：光重合開始剤
    　（ｄ１）成分：重量平均分子量が２５，０００～１００，０００であり、フッ素系セグメントと非フッ素系セグメントからなるブロック共重合体     A resin composition comprising the following components (A) to (d1).
    With respect to 100 parts by mass of the component (A), the component (b1) is 0.5 to 30 parts by mass, the component (C) is 0.1 to 25 parts by mass, and the component (d1) is 0.1 to 25 parts by mass. A resin composition for a water-repellent lens protective film, which comprises.
    (A) Component: Polyfunctional (meth) acrylate having a weight average molecular weight of 250 to 30,000 (b1) Component: Polyfunctional thiol compound (C) Component: Photopolymerization initiator (d1) Component: Weight average molecular weight of 25 A block copolymer consisting of a fluorine-based segment and a non-fluorine-based segment, which ranges from 000 to 100,000.
  5. 　撥水レンズに請求項１から請求項４のいずれかに記載の撥水レンズ保護膜用樹脂組成物を塗布、硬化してなる保護膜を設けることにより、撥水レンズを保護する方法。

          A method for protecting a water-repellent lens by applying the resin composition for a water-repellent lens protective film according to any one of claims 1 to 4 to the water-repellent lens and providing a cured protective film.
PCT/JP2021/036003 2020-09-30 2021-09-29 Resin composition for water-repellent lens protective films, and method for protecting water-repellent lens WO2022071446A1 (en)

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JP2021-126788 2021-08-02
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* Cited by examiner, † Cited by third party
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JP2004122238A (en) * 2002-08-05 2004-04-22 Sola Optical Japan Kk Shaft slippage preventing kit for use in shaping lens for glasses and lens shaping method for glasses using the same
KR20080013292A (en) * 2006-08-08 2008-02-13 나노크리스탈주식회사 Temporary protective coating composition for oil-repellent optical lens
US20080292787A1 (en) * 2006-03-27 2008-11-27 Essilor International (Compagnie Generale D'optique Edging Process of Lens Using Transparent Coating Layer for Protecting Lens
JP2009109611A (en) * 2007-10-29 2009-05-21 Seiko Epson Corp Plastic spectacle lens with protective coat film
WO2013073364A1 (en) * 2011-11-17 2013-05-23 株式会社スリーボンド Acrylic resin composition
JP2013228437A (en) * 2012-04-24 2013-11-07 Hoya Lense Manufacturing Philippine Inc Spectacle lens, method for manufacturing the spectacle lens, and treatment liquid
JP2015044936A (en) * 2013-08-28 2015-03-12 セメダイン株式会社 Composition for temporary fixation and temporary fixation and detachment method
JP2015223688A (en) * 2014-05-30 2015-12-14 東海光学株式会社 Displacement preventive coating agent
JP2017125178A (en) * 2016-01-07 2017-07-20 デンカ株式会社 COMPOSITION AND Temporary fixing method of member using the same

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004122238A (en) * 2002-08-05 2004-04-22 Sola Optical Japan Kk Shaft slippage preventing kit for use in shaping lens for glasses and lens shaping method for glasses using the same
US20080292787A1 (en) * 2006-03-27 2008-11-27 Essilor International (Compagnie Generale D'optique Edging Process of Lens Using Transparent Coating Layer for Protecting Lens
KR20080013292A (en) * 2006-08-08 2008-02-13 나노크리스탈주식회사 Temporary protective coating composition for oil-repellent optical lens
JP2009109611A (en) * 2007-10-29 2009-05-21 Seiko Epson Corp Plastic spectacle lens with protective coat film
WO2013073364A1 (en) * 2011-11-17 2013-05-23 株式会社スリーボンド Acrylic resin composition
JP2013228437A (en) * 2012-04-24 2013-11-07 Hoya Lense Manufacturing Philippine Inc Spectacle lens, method for manufacturing the spectacle lens, and treatment liquid
JP2015044936A (en) * 2013-08-28 2015-03-12 セメダイン株式会社 Composition for temporary fixation and temporary fixation and detachment method
JP2015223688A (en) * 2014-05-30 2015-12-14 東海光学株式会社 Displacement preventive coating agent
JP2017125178A (en) * 2016-01-07 2017-07-20 デンカ株式会社 COMPOSITION AND Temporary fixing method of member using the same

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