WO2022255340A1 - 反射防止フィルム、反射防止フィルムを有する積層体及び反射防止フィルムの製造方法 - Google Patents

反射防止フィルム、反射防止フィルムを有する積層体及び反射防止フィルムの製造方法 Download PDF

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Publication number
WO2022255340A1
WO2022255340A1 PCT/JP2022/022066 JP2022022066W WO2022255340A1 WO 2022255340 A1 WO2022255340 A1 WO 2022255340A1 JP 2022022066 W JP2022022066 W JP 2022022066W WO 2022255340 A1 WO2022255340 A1 WO 2022255340A1
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Prior art keywords
meth
refractive index
layer
acrylate
antireflection film
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Ceased
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PCT/JP2022/022066
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English (en)
French (fr)
Japanese (ja)
Inventor
文彰 掛谷
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Mitsubishi Gas Chemical Co Inc
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Mitsubishi Gas Chemical Co Inc
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Priority to CN202280030559.1A priority Critical patent/CN117203049A/zh
Priority to KR1020237032828A priority patent/KR20240017332A/ko
Priority to EP22816086.7A priority patent/EP4349589A4/en
Priority to US18/562,558 priority patent/US20240240046A1/en
Priority to JP2023525842A priority patent/JPWO2022255340A1/ja
Publication of WO2022255340A1 publication Critical patent/WO2022255340A1/ja
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Definitions

  • the present invention relates to an antireflection film including a base layer and a low refractive index layer having a lower refractive index than the base layer, a laminate having an antireflection film, and the like.
  • Laminated films with low surface reflectance are used, for example, for computer screens, television screens, plasma display panels, surfaces of polarizing plates used in liquid crystal display devices, sunglasses lenses, prescription spectacle lenses, viewfinder lenses for cameras, and various instruments. It is used for applications such as covers for automobiles, glass for automobiles, glass for trains, in-vehicle display panels, and housings for electronic devices.
  • an object of the present invention is to provide an antireflection film having a low surface reflectance, excellent thermoformability, and particularly good scratch resistance, a laminate having an antireflection film, and the like.
  • the inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, have a substrate layer containing a thermoplastic resin and a low refractive index layer, and the low refractive index layer is a polymer of a predetermined resin material.
  • the inventors have found that an antireflection film containing the are excellent in thermoformability and scratch resistance, and have completed the present invention.
  • the present invention includes the following: (1) a substrate layer containing a thermoplastic resin; and
  • the low refractive index layer is an aromatic diisocyanate compound (a1) and a urethane (meth)acrylate derived from one or more (meth)acryloyl compounds (a2) having a hydroxyl group and a (meth)acryloyl group in one molecule.
  • An antireflection film containing a polymer of a resin material containing (meth)acrylate.
  • the urethane (meth)acrylate is the aromatic diisocyanate compound (a1), and pentaerythritol tri(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, caprolactone (meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate. the film.
  • the (meth)acryloyl compound (a2) is pentaerythritol tri(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4 - The antireflection film according to (1) above, containing at least one selected from hydroxybutyl (meth)acrylate, caprolactone (meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate.
  • the (meth)acrylate is an optionally substituted compound having 4 to 20 carbon atoms containing at least one (meth)acryloyl group and at least one vinyl ether group ( 1) The antireflection film as described in 1).
  • the low refractive index layer further includes a low refractive index member.
  • the low refractive index member contains hollow silica.
  • the low refractive index layer contains the resin material and the low refractive index member at a weight ratio of 20:80 to 70:30.
  • the low refractive index layer further contains at least one of a photoinitiator and a fluorine-based leveling agent.
  • the antireflection film of (1) above wherein the resin material contains the urethane acrylate and the (meth)acrylate in a weight ratio of 95:5 to 70:30.
  • the antireflection film according to (1) above comprising two or more base layers.
  • the antireflection film of (1) above further comprising a hard coat layer laminated between the base layer and the low refractive index layer.
  • the base layer has a refractive index of 1.49 to 1.65, and the difference between the base layer and the hard coat layer is 0.04 or less.
  • the antireflection film as described in (14) above (16) The antireflection film of (1) above, further comprising a high refractive index layer having a higher refractive index than the base layer.
  • the base material layer has a refractive index of 1.49 to 1.65
  • the low refractive index layer has a refractive index of 1.31 to 1.40
  • the high refractive index layer has a refractive index of , 1.68 to 1.75.
  • the antireflection film as described in (16) above further comprising a hard coat layer laminated between the substrate layer and the high refractive index layer. (20) further having a hard coat layer, The base material layer has a thickness of 50 to 500 ⁇ m, the hard coat layer has a thickness of 1 to 10 ⁇ m, the high refractive index layer has a thickness of 10 to 200 nm, and the low refractive index layer has a thickness of 10 to 200 nm.
  • the antireflection film as described in (16) above which has a thickness of 10 to 200 nm.
  • the high refractive index layer contains a urethane (meth)acrylate derived from fluorene-based diol, isocyanate, and (meth)acrylate, and a polymer of a resin material containing (meth)acrylate.
  • the antireflection film described in . (22) In the sample of the antireflection film obtained by cutting to 210 mm ⁇ 297 mm ⁇ 0.3 mm (thickness), the base layer is preheated at 190 ° C. for 40 seconds, and has a deep drawing height of 1 mm or more.
  • the sample is placed so that the base material layer is in contact with a mold containing a rectangular protrusion having a vertical and horizontal size of 30 mm, and the sample is compressed using high-pressure air of 1.5 MPa.
  • the reflection according to any one of the above (1) to (21), wherein the radius R of the region where the pressurized molded body is in contact with the right-angled portion of the mold when molding is performed is 3.0 mm or less. prevention film.
  • the base layer was preheated at 190 ° C. for 40 seconds, and the deep drawing height of 1 mm or more was obtained.
  • the sample was placed in a mold including rectangular projections with a horizontal size of 30 mm so that the base material layer was in contact with the mold, and the sample was pressure-molded using high-pressure air of 1.5 MPa.
  • a substrate layer containing a thermoplastic resin containing a thermoplastic resin
  • the sample was placed in a mold including rectangular projections with a horizontal size of 30 mm so that the base material layer was in contact with the mold, and the sample was pressure-molded using high-pressure air of 1.5 MPa.
  • the antireflection film, wherein the radius R of the region where the pressure-molded body obtained is in contact with the right-angled portion of the mold is 3.0 mm or less.
  • a laminate comprising a transparent resin substrate and the antireflection film according to any one of (1) to (24) above.
  • a method for producing an antireflection film comprising a lamination step of laminating a low refractive index layer having a lower refractive index than the base layer on at least one surface of a base layer containing a thermoplastic resin, ,
  • the low refractive index layer is an aromatic diisocyanate compound (a1) and a urethane (meth)acrylate derived from one or more (meth)acryloyl compounds (a2) having a hydroxyl group and a (meth)acryloyl group in one molecule.
  • the antireflection film of the present invention comprises a substrate layer and a low refractive index layer laminated on at least one surface of the substrate layer and having a lower refractive index than that of the substrate layer. have.
  • the reflectance of the surface of the antireflection film on the low refractive index layer side is sufficiently low, and the antireflection film has excellent thermoformability and particularly excellent scratch resistance.
  • the antireflection film of the present invention is used in the display parts of computers, televisions, plasma displays, etc., the surfaces of polarizing plates used in liquid crystal display devices, sunglasses lenses, prescription spectacle lenses, and cameras. It can be suitably used in applications such as viewfinder lenses for electronic cameras, instrument covers, glass for automobiles, glass for trains, display panels for automobiles, housings for electronic devices, and the like.
  • FIG. 1 is a cross-sectional view showing a laminate structure of an antireflection film of Example 1.
  • FIG. 2 is a cross-sectional view showing a laminate structure of an antireflection film of a specific example different from Example 1.
  • FIG. FIG. 4 is a diagram showing elongation after pressure molding in an antireflection film having grid-like lines printed at predetermined intervals on its surface.
  • the antireflection film of the present invention comprises a substrate layer containing a thermoplastic resin, and a low refractive index layer laminated on at least one surface of the substrate layer and having a refractive index lower than that of the substrate layer. have.
  • a layered member included in the antireflection film, which is such a laminate, will be described below.
  • the base layer included in the antireflection film contains a thermoplastic resin.
  • the type of thermoplastic resin is not particularly limited, but polycarbonate (PC) resin, acrylic resin such as polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyethylene naphthalate (PEN), polyimide ( PI), cycloolefin copolymer (COC), norbornene-containing resin, polyether sulfone, cellophane, aromatic polyamide, and other various resins are used.
  • PC polycarbonate
  • acrylic resin such as polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), triacetyl cellulose (TAC), polyethylene naphthalate (PEN), polyimide ( PI), cycloolefin copolymer (COC), norbornene-containing resin, polyether sulfone, cellophane, aromatic polyamide, and other various resins are used.
  • Types of polycarbonate resins that can be contained in the substrate layer include -[O-R-OCO]-units (where R is an aliphatic group, an aromatic group, or an aliphatic group) containing a carbonate ester bond in the molecular main chain. It is not particularly limited as long as it contains both aromatic groups and further has a linear or branched structure, but polycarbonates having a bisphenol skeleton are preferable, and a bisphenol A skeleton or a bisphenol C skeleton is used. Particularly preferred are polycarbonates with A mixture or copolymer of bisphenol A and bisphenol C may be used as the polycarbonate resin.
  • the hardness of the substrate layer can be improved.
  • the viscosity average molecular weight of the polycarbonate resin is preferably 15,000 to 40,000, more preferably 20,000 to 35,000, still more preferably 22,500 to 25,000.
  • the acrylic resin that can be contained in the base material layer is not particularly limited, but for example, homopolymers of various (meth)acrylic acid esters represented by polymethyl methacrylate (PMMA) and methyl methacrylate (MMA), or It is a copolymer of PMMA or MMA and one or more other monomers, and a mixture of a plurality of these resins.
  • PMMA polymethyl methacrylate
  • MMA methyl methacrylate
  • MMA methyl methacrylate
  • MMA methyl methacrylate
  • MMA methyl methacrylate
  • Examples of such (meth)acrylic resins include, but are not limited to, ACRYPET (manufactured by Mitsubishi Rayon), Delpet (manufactured by Asahi Kasei Chemicals), and Parapet (manufactured by Kuraray).
  • ACRYPET manufactured by Mitsubishi Rayon
  • Delpet manufactured by Asahi Kasei Chemicals
  • Parapet manufactured by Kuraray
  • the use of a mixture containing a polycarbonate resin and the acrylic resin described above is preferable because it can improve the hardness of the substrate layer, particularly the surface layer (the layer on the side of the high refractive index layer) of the substrate layer in the laminate. .
  • the base layer may contain additives as components other than the thermoplastic resin.
  • additives as components other than the thermoplastic resin.
  • Antistatic agents, fluorescent whitening agents, antifogging agents, fluidity improvers, plasticizers, dispersants, antibacterial agents, etc. may also be added to the base layer.
  • the base material layer preferably contains 80% by mass or more of thermoplastic resin, more preferably 90% by mass or more, and particularly preferably 95% by mass or more of thermoplastic resin. Further, among the thermoplastic resins of the substrate layer, the polycarbonate resin is preferably contained in an amount of 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more.
  • the base layer preferably has a refractive index in the range of 1.49-1.65.
  • the refractive index of the substrate layer is more preferably 1.49 to 1.60, still more preferably 1.51 to 1.60, and particularly preferably about 1.53 to 1.59.
  • the thickness of the base layer is not particularly limited, it is, for example, 30 ⁇ m to 1000 ⁇ m (1 mm), preferably 50 ⁇ m to 700 ⁇ m, more preferably 50 ⁇ m to 500 ⁇ m, and particularly preferably 100 ⁇ m to 500 ⁇ m.
  • two or more base layers may be provided, and when a plurality of base layers are provided, the total thickness of the base layers is, for example, 100 ⁇ m to 1000 ⁇ m, preferably It is about 200 ⁇ m to 500 ⁇ m.
  • the substrate layer containing the multiple layers described above that is, the substrate layer serving as a multi-layer laminate
  • the substrate layer serving as a multi-layer laminate examples include the following.
  • PC polycarbonate resin
  • PC polycarbonate resin
  • PC polycarbonate resin
  • PC polycarbonate resin
  • PC polycarbonate resin
  • PC polycarbonate resin
  • PC polycarbonate resin
  • PC polycarbonate resin
  • a polycarbonate resin containing bisphenol C is used as a surface layer.
  • a material having a high hardness particularly a material having a hardness higher than that of the other base material layers.
  • the polycarbonate resin which is a thermoplastic resin used in the substrate layer as a laminate
  • the same polycarbonate resin as that forming the single-layer substrate layer, that is, the above-mentioned resin is preferably used.
  • a mixture or copolymer of bisphenol A and bisphenol C may be used.
  • a bisphenol C-based polycarbonate resin for example, a polycarbonate resin containing only bisphenol C, a mixture of bisphenol C and bisphenol A, or a polycarbonate resin containing a copolymer
  • the surface layer low refractive index layer The effect that the hardness of the side layer) can be improved is recognized.
  • a mixture of a polycarbonate resin for example, a bisphenol C-based polycarbonate resin and the acrylic resin described above may be used.
  • the antireflection film includes a low refractive index layer.
  • the low refractive index layer is laminated on at least one surface of the substrate layer.
  • the low refractive index layer has a refractive index lower than that of the substrate layer and has an antireflection function.
  • the low refractive index layer is preferably arranged on the outermost side of the antireflection film in order to suppress reflection of the antireflection film.
  • the low refractive index layer contains a polymer of a resin material containing urethane (meth)acrylate and (meth)acrylate, which will be described later in detail, and preferably a resin material containing urethane (meth)acrylate and (meth)acrylate. is formed only by the polymer of Each component of the low refractive index layer will be described below.
  • the urethane (meth)acrylate contained in the resin material includes an aromatic diisocyanate compound (a1) and one or more (meth)acryloyl groups having one hydroxyl group and at least one (meth)acryloyl group in one molecule. It is derived from the compound (a2). More specifically, the urethane (meth)acrylate is preferably formed by a reaction product of the above aromatic diisocyanate compound (a1) and (meth)acryloyl compound (a2).
  • Aromaatic diisocyanate compound (a1) An aromatic diisocyanate compound (a1) is used as a component for forming urethane (meth)acrylate.
  • aromatic diisocyanate compound (a1) aromatic compounds having two isocyanate groups (-NCO groups) are widely used, for example, those having single or multiple benzene rings, compounds having aromatic rings, etc.
  • aromatic diisocyanate compound (a1) for example, an aromatic diisocyanate compound represented by the following formula (1) can be used.
  • R is each independently a linear or branched alkyl group having 1 to 6 carbon atoms which may have a substituent or halogen, or an aromatic ring having 6 to 12 carbon atoms.
  • R is preferably an optionally substituted alkyl group having 1 to 3 carbon atoms, and examples of the substituent include an alkoxy group.
  • n is preferably an integer of 0-2, more preferably 0 or 1.
  • An aromatic diisocyanate compound in which both or one of the isocyanate groups (--NCO groups) in the above formula (1) is directly linked to a benzene ring without a methylene group may be used.
  • aromatic diisocyanate compound in which an isocyanate group (-NCO group) is directly connected to a benzene ring, such as toluene diisocyanate (2,4-toluene diisocyanate, 2,6-toluene diisocyanate).
  • aromatic diisocyanate compound (a1) examples include m- or p-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 4,4'-, 2,4'- or 2,2'- Diphenylmethane diisocyanate (MDI), toluene diisocyanate (2,4-toluene diisocyanate, 2,6-toluene diisocyanate), trimethylolpropane (TMP) adduct of toluene diisocyanate, isocyanate of toluene diisocyanate, 4,4'-toluidine diisocyanate, etc.
  • MDI Diphenylmethane diisocyanate
  • TMP trimethylolpropane
  • aromatic diisocyanate compound (a1) is xylene diisocyanate.
  • the (meth)acryloyl compound (a2) used for forming the urethane (meth)acrylate has one or more hydroxyl groups and at least one or more (meth)acryloyl groups.
  • the (meth)acryloyl compound (a2) has, for example, 1 to 3 hydroxyl groups, but the (meth)acryloyl compound (a2) having only one hydroxyl group is preferred.
  • the (meth)acryloyl compound (a2) preferably has 1 to 3 (meth)acryloyl groups, for example, a monofunctional (meth)acryloyl compound (a2- 1), a trifunctional (meth)acryloyl compound (a2-2) having three (meth)acryloyl groups, and the like are preferred.
  • the (meth)acryloyl compound (a2) any single type of compound may be used, or a mixture of a plurality of types of compounds may be used.
  • the (meth)acryloyl compound (a2) is, for example, a monofunctional compound (a2-1) having one (meth)acryloyl group in one molecule, 3 having three (meth)acryloyl groups in one molecule, Including a functional compound (a2-2) and the like, as the (meth)acryloyl compound (a2), even if only one of monofunctional and trifunctional compounds is used, monofunctional and trifunctional A mixture (mixed liquid) in which compounds are mixed may be used.
  • the monofunctional compound (a2-1) a single compound or a mixture of a plurality of types may be used, and the same applies to the trifunctional compound (a2-2).
  • the (meth)acryloyl compound (a2) a compound (a2-1) having one (meth)acryloyl group in one molecule and a trifunctional compound (a2-1) having three (meth)acryloyl groups in one molecule
  • it is preferable to use (a2-1) / (a2-2) 80/20 to 0/100 mol (molar ratio)
  • (a2-1) / (a2-2 ) 80/20 to 20/80 mol
  • (a2-1)/(a2-2) 70/30 to 30/70 mol
  • a bifunctional or tetrafunctional (meth)acryloyl compound may be used in the above ratio of the trifunctional
  • the (meth)acryloyl compound (a2) which is a hydroxyl group-containing acrylate
  • monofunctional or trifunctional (meth)acryloyl compounds such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid, 2-acryloyloxyethyl acid phosphate, caprolactone-modified 2-hydroxyethyl acrylate, 2-hydroxy-3-acryloyl
  • Specific examples of the (meth)acryloyl compound (a2) include roxypropyl acrylate, pentaerythritol triacrylate, ethoxylated pentaerythritol triacrylate, propoxylated pentaerythritol triacrylate, and caprolactone-modified
  • (meth)acryloyl compound (a2) 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2 - (meth) acryloyloxyethyl-2-hydroxyethyl-phthalic acid, 2-(meth) acryloyloxyethyl acid phosphate-caprolactone-modified 2-hydroxyethyl (meth) acrylate, 2-hydroxy-3-acryloyloxypropyl ( meth)acrylate, pentaerythritol tri(meth)acrylate, ethoxylated pentaerythritol tri(meth)acrylate, propoxylated pentaerythritol tri(meth)acrylate, caprolactone-modified 2-hydroxyethyl(meth)acrylate
  • Preferred specific examples of the (meth)acryloyl compound (a2) include pentaerythritol tri(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4 -hydroxybutyl (meth)acrylate, caprolactone (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, and the like.
  • the urethane (meth)acrylate produced as a reaction product of the above aromatic diisocyanate compound (a1) and (meth)acryloyl compound (a2) preferably has 2 to 6 (meth)acryloyl groups.
  • the urethane (meth)acrylate produced as a reaction product of the above aromatic diisocyanate compound (a1) and (meth)acryloyl compound (a2) preferably has 2 to 6 (meth)acryloyl groups.
  • a urethane (meth)acrylate having 4 or 6 (meth)acryloyl groups may be used as the resin material.
  • even in a mixture of urethane (meth)acrylates having 2 to 6 (meth)acryloyl groups such as 2, 4 or 6, only any specific ure
  • the ratio of the aromatic diisocyanate compound (a1) for forming the urethane (meth)acrylate and the total amount of the (meth)acryloyl compound (a2) is 20:80 to 75:25 (weight ratio). It is preferably 30:70 to 60:40, more preferably 35:65 to 55:45.
  • the resin material of the low refractive index layer includes a (meth)acrylate compound as well as the urethane (meth)acrylate described above. That is, the resin material of the low refractive index layer is preferably obtained as a mixture (mixed liquid) containing the above-described urethane (meth)acrylate and (meth)acrylate compound.
  • a low refractive index layer is preferably formed.
  • the (meth)acrylate compound as one component of the resin material contains at least one (meth)acryloyl group and at least one vinyl ether group, and is a compound having 4 to 20 carbon atoms which may have a substituent. Preferably.
  • the (meth)acrylate preferably has 6 to 18 carbon atoms, more preferably 8 to 16 carbon atoms. Alkyl group etc. are mentioned as a substituent of (meth)acrylate.
  • the (meth)acrylate for example, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate [2-(2-vinyloxyethoxy)ethyl acrylate: VEEA] of the following formula is used. (In the above formula, R is hydrogen or a methyl group.)
  • the (meth)acrylate compound contained in the resin material include: ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,3-propanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1 alkanediol di(meth)acrylates such as ,6-hexanediol di(meth)acrylate; alkanepolyol di(meth)acrylates such as glycerin di(meth)acrylate; Polyalkylene glycol di(meth)acrylates such as diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, etc.) ; di(meth)acrylates
  • the (meth)acrylate compound contained in the resin material include a bisphenol A di(meth)acrylate compound having an ethoxy group.
  • Preferred specific examples of bisphenol A di(meth)acrylate compounds having an ethoxy group include ethoxylated (3 mol) bisphenol A di(meth)acrylate, ethoxylated (4 mol) bisphenol A di(meth)acrylate, ethoxylated ( 10 mol) bisphenol A di(meth)acrylate, propoxylated (3 mol) bisphenol A diacrylate and the like, and a more preferred specific example is ethoxylated (4 mol) bisphenol A di(meth)acrylate.
  • the ratio of urethane (meth)acrylate and (meth)acrylate compound ((meth)acrylate) is preferably 95:5 to 70:30 (weight ratio), More preferably 93:7 to 80:20, still more preferably 90:10 to 85:15.
  • the ratio of urethane (meth)acrylate and (meth)acrylate compound may be 99:1 to 60:40.
  • the low refractive index layer preferably contains a low refractive index member.
  • the low refractive index member is added to lower the refractive index of the low refractive index layer. That is, by forming the low refractive index layer using a low refractive index member, the difference in refractive index between the low refractive index layer and the base layer can be increased, and the reflectance of the antireflection film can be further reduced.
  • the low refractive index member silica, metal fluoride fine particles, and the like are preferable, and silica, particularly hollow silica, is more preferable.
  • the low refractive index member is preferably a particulate member, and the particle size (diameter: average particle size) of the particulate low refractive index member is not particularly limited, but is, for example, 10 to 200 nm, preferably 30 to 200 nm. It is 100 nm, more preferably 35 to 80 nm, particularly preferably 45 to 65 nm.
  • the (average) particle size of the particulate low refractive index member is measured, for example, by a dynamic light scattering method according to JIS Z 8828:2019 (ISO 22412:2017).
  • the refractive index value of the low refractive index layer is lower than the refractive index value of the base layer.
  • the refractive index of the low refractive index layer is preferably 1.31 to 1.40, more preferably 1.32 to 1.39, still more preferably about 1.33 to 1.38.
  • the difference between the refractive index of the low refractive index layer and the refractive index of the base layer is preferably at least 0.09, more preferably at least 0.12, and even more preferably at least 0.15. , particularly preferably at least 0.17.
  • the low refractive index layer or the resin material forming the low refractive index layer preferably contains at least one of a photoinitiator (photopolymerization initiator) and a leveling agent, and particularly contains a photoinitiator. is preferred.
  • the resin material of the low refractive index layer may contain a solvent.
  • leveling agents include fluorine-based leveling agents and silicone-based leveling agents.
  • the low refractive index layer preferably contains the resin material of the low refractive index layer and the low refractive index member at a weight ratio of 20:80 to 70:30, and the ratio of the resin material to the low refractive index member is more preferable. is 30:70 to 65:35, more preferably 35:65 to 60:40.
  • the thickness of the low refractive index layer is not particularly limited, it is preferably 10 to 200 nm, more preferably 30 to 160 nm, even more preferably 50 to 120 nm, and particularly preferably 80 to 110 nm.
  • the antireflection film may contain a high refractive index layer.
  • the high refractive index layer has a higher refractive index than the base material layer, and the high refractive index layer included in the antireflection film also has an antireflection function like the low refractive index layer.
  • Such a high refractive index layer is used as an antireflection layer in a laminate.
  • the high refractive index layer is preferably laminated between the low refractive index layer and the substrate layer.
  • the high refractive index layer contains urethane (meth)acrylate derived from fluorene-based diol, isocyanate, and (meth)acrylate, and a polymer of a resin material containing (meth)acrylate. That is, the high refractive index layer is at least a mixture of urethane (meth)acrylate obtained by dehydration condensation reaction of three components of fluorene diol, isocyanate, and (meth)acrylate, and (meth)acrylate. is preferred.
  • the urethane (meth)acrylate contained in the resin material of the high refractive index layer preferably contains at least a component represented by formula (I) below.
  • A3-O(OC)HN-A2-HN(OC)-O-A1-O-(CO)NH-A2-NH-(CO)O-(A3) (I) (In formula (I), A1 is an alkylene group derived from a fluorene diol having a total carbon number of 8 to 60 which may have a substituent; A2 is each independently an alkylene group derived from an aromatic isocyanate having a total of 6 to 20 carbon atoms which may have a substituent, A3 is each independently an optionally substituted alkyl group having a total of 4 to 30 carbon atoms containing at least one (meth)acryloyloxy group and derived from (meth)acrylate.
  • the above-mentioned alkylene group for A1 is, for example, a fluorene-based diol that may have a substituent that is an aryl group such as a phenyl group, and is preferably derived from a fluorene-based diol having a total of 12 to 54 carbon atoms. , more preferably derived from a fluorene diol having a total carbon number of 16 to 48, and particularly preferably derived from a fluorene diol having a total carbon number of 20 to 40.
  • fluorene-based diol for forming the structural unit of A1, ie, the compound having a fluorene skeleton, include the following.
  • fluorene-based diol includes fluorene compounds containing three or more hydroxyl groups. That is, fluorene diols having two hydroxyl groups include, for example, 9,9-bis(hydroxyphenyl)fluorenes, 9,9-bis(hydroxy(poly)alkoxyphenyl)fluorenes, 9,9-bis( hydroxynaphthyl)fluorenes, 9,9-bis(hydroxy(poly)alkoxynaphthyl)fluorenes, and the like.
  • Fluorene-based diols having three or more hydroxyl groups include, for example, 9,9-bis(polyhydroxyphenyl)fluorenes, 9,9-bis[poly(hydroxy(poly)alkoxy)phenyl]fluorenes, 9,9-bis(polyhydroxynaphthyl)fluorenes, 9,9-bis[poly(hydroxy(poly)alkoxy)naphthyl]fluorenes and the like.
  • 9,9-bis(hydroxyphenyl)fluorenes include, for example, 9,9-bis(hydroxyphenyl)fluorene [9,9-bis(4-hydroxyphenyl)fluorene (bisphenolfluorene), etc.], having a substituent 9,9-bis(hydroxyphenyl)fluorene ⁇ for example, 9,9-bis(alkyl-hydroxyphenyl)fluorene [9,9-bis(4-hydroxy-3-methylphenyl)fluorene (biscresolfluorene), 9, 9-bis(4-hydroxy-3-ethylphenyl)fluorene, 9,9-bis(4-hydroxy-3-butylphenyl)fluorene, 9,9-bis(3-hydroxy-2-methylphenyl)fluorene, 9 ,9-bis(4-hydroxy-3,5-dimethylphenyl)fluorene, 9,9-bis(4-hydroxy-2,6-dimethylphenyl)fluorene, etc.
  • 9,9-bis(mono- or di- C5-8 cycloalkyl-hydroxyphenyl)fluorene and the like] 9,9-bis(aryl-hydroxyphenyl)fluorene [for example, 9,9-bis(4-hydroxy-3-phenylphenyl)fluorene and the like. bis(mono- or di-C6-8 aryl-hydroxyphenyl)fluorene, etc.], 9,9-bis(aralkyl-hydroxyphenyl)fluorene [e.g., 9,9-bis(4-hydroxy-3-benzylphenyl)fluorene, etc. 9,9-bis(C6-8arylC1-2alkyl-hydroxyphenyl)fluorene, etc.] and the like ⁇ .
  • 9,9-bis(hydroxy(poly)alkoxyphenyl)fluorenes include, for example, 9,9-bis(hydroxyalkoxyphenyl)fluorene ⁇ e.g., 9,9-bis[4-(2-hydroxyethoxy)phenyl] Fluorene, 9,9-bis[4-(2-hydroxypropoxy)phenyl]fluorene, 9,9-bis[4-(3-hydroxypropoxy)phenyl]fluorene, 9,9-bis[4-(4-hydroxy 9,9-bis(hydroxyC2-4alkoxyphenyl)fluorene such as butoxy)phenyl]fluorene ⁇ , 9,9-bis(hydroxyalkoxy-alkylphenyl)fluorene ⁇ e.g., 9,9-bis[4-(2 -hydroxyethoxy)-3-methylphenyl]fluorene [or 2,2′-dimethyl-4,4′-(9-fluorenylidene)-bisphenoxyethanol], 9,9-bis
  • 9,9-bis(hydroxynaphthyl)fluorenes include, for example, 9,9-bis(hydroxynaphthyl)fluorenes ⁇ for example, 9,9-bis[6-(2-hydroxynaphthyl)]fluorene (or 6, 6-(9-fluorenylidene)-di(2-naphthol)), 9,9-bis[1-(6-hydroxynaphthyl)]fluorene (or 5,5-(9-fluorenylidene)-di(2-naphthol) ), optionally having substituents such as 9,9-bis[1-(5-hydroxynaphthyl)]fluorene (or 5,5-(9-fluorenylidene)-di(1-naphthol)) 9, 9-bis(monohydroxynaphthyl)fluorene ⁇ and the like.
  • 9,9-bis(hydroxy(poly)alkoxynaphthyl)fluorenes include compounds corresponding to the above 9,9-bis(hydroxynaphthyl)fluorenes, such as 9,9-bis(hydroxyalkoxynaphthyl)fluorene ⁇ for example , 9,9-bis[6-(2-(2-hydroxyethoxy)naphthyl)]fluorene, 9,9-bis[1-(6-(2-hydroxyethoxy)naphthyl)]fluorene [or 5,5′ -(9-fluorenylidene)-bis(2-naphthyloxyethanol)], 9,9-bis[1-(5-(2-hydroxyethoxy)naphthyl)]fluorene optionally having a substituent such as 9 , 9-bis(hydroxy C2-4 alkoxynaphthyl)fluorene, etc. ⁇ and the like.
  • 9,9-bis(polyhydroxyphenyl)fluorenes include 9,9-bis(dihydroxyphenyl)fluorenes, 9,9-bis(trihydroxyphenyl)fluorenes and the like.
  • 9,9-bis(dihydroxyphenyl)fluorenes include 9,9-bis(dihydroxyphenyl)fluorene [9,9-bis(3,4-dihydroxyphenyl)fluorene (biscatechol fluorene), 9,9 -bis(3,5-dihydroxyphenyl)fluorene, etc.], 9,9-bis(dihydroxyphenyl)fluorene having substituents ⁇ for example, 9,9-bis(alkyl-dihydroxyphenyl)fluorene [9,9-bis( 3,4-dihydroxy-5-methylphenyl)fluorene, 9,9-bis(3,4-dihydroxy-6-methylphenyl)fluorene, 9,9-bis(2,4-dihydroxy-3,6-
  • 9,9-bis(trihydroxyphenyl)fluorenes include 9,9-bis(trihydroxyphenyl)fluorene [e.g., 9,9-bis(2,4,6-trihydroxyphenyl)fluorene, 9,9 -bis(2,4,5-trihydroxyphenyl)fluorene, 9,9-bis(3,4,5-trihydroxyphenyl)fluorene, etc.].
  • 9,9-bis[poly(hydroxy(poly)alkoxy)phenyl]fluorenes include 9,9-bis[di(hydroxy(poly)alkoxy)phenyl]fluorenes, 9,9-bis[tri(hydroxy( Poly)alkoxy)phenyl]fluorenes and the like are included.
  • 9,9-bis[di(hydroxy(poly)alkoxy)phenyl]fluorenes include 9,9-bis[di(hydroxyalkoxy)phenyl]fluorene ⁇ e.g., 9,9-bis[3,4-di( 2-hydroxyethoxy)phenyl]fluorene [or 2,2′-bishydroxyethoxy-4,4′-(9-fluorenylidene)-bisphenoxyethanol], 9,9-bis[3,5-di(2-hydroxyethoxy ) phenyl]fluorene [or 3,3′-bishydroxyethoxy-5,5′-(9-fluorenylidene)-bisphenoxyethanol], 9,9-bis[3,4-di(3-hydroxypropoxy)phenyl]fluorene , 9,9-bis[3,5-di(3-hydroxypropoxy)phenyl]fluorene, 9,9-bis[3,4-di(2-hydroxypropoxy)phenyl]fluorene, 9,9-
  • 9,9-bis[tri(hydroxy(poly)alkoxy)phenyl]fluorenes include compounds corresponding to the above 9,9-bis[di(hydroxy(poly)alkoxy)phenyl]fluorenes, such as 9,9 -bis[tri(hydroxyalkoxy)phenyl]fluorene ⁇ for example, 9,9-bis[2,3,4-tri(2-hydroxyethoxy)phenyl]fluorene [or 2,2′,6,6′-tetrahydroxy ethoxy-5,5′-(9-fluorenylidene)-bisphenoxyethanol], 9,9-bis[2,4,6-tri(2-hydroxyethoxy)phenyl]fluorene, 9,9-bis[2,4, 9,9-bis[tri(hydroxyC2-4alkoxy) such as 5-tri(2-hydroxyethoxy)phenyl]fluorene, 9,9-bis[3,4,5-tri(2-hydroxyethoxy)phenyl]fluorene )phenyl]fluorene
  • the 9,9-bis(polyhydroxynaphthyl)fluorenes include compounds corresponding to the above 9,9-bis(hydroxynaphthyl)fluorenes, such as 9,9-bis(di- or trihydroxynaphthyl)fluorene.
  • the 9,9-bis[poly(hydroxy(poly)alkoxy)naphthyl]fluorenes include compounds corresponding to the above 9,9-bis(hydroxy(poly)alkoxynaphthyl)fluorenes, such as 9,9- and 9,9-bis[di- or tri(hydroxy(poly)alkoxy)naphthyl]fluorenes such as bis[di- or tri(hydroxyC2-4alkoxy)naphthyl]fluorene.
  • fluorene-based diol 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene.
  • the alkylene group of A2 described above is, for example, an aromatic isocyanate optionally having a substituent which is an alkyl group such as a methyl group, preferably derived from an aromatic isocyanate having a total of 6 to 16 carbon atoms. , more preferably derived from aromatic isocyanates having 7 to 14 carbon atoms, particularly preferably derived from aromatic isocyanates having 8 to 12 carbon atoms.
  • the isocyanate for forming the structural unit of A2 described above is preferably an aromatic isocyanate that can easily achieve a high refractive index, but aliphatic and alicyclic isocyanates are also used.
  • diphenylmethane diisocyanate diphenylmethane diisocyanate, toluene diisocyanate, naphthalene diisocyanate, trimethylolpropane (TMP) adduct of toluene diisocyanate, isocyanurate of toluene diisocyanate, and TMP adduct of xylene diisocyanate are preferred.
  • TMP trimethylolpropane
  • the alkyl group for A3 described above may have a substituent such as an alkoxy group or an aryloxy group, and is preferably an alkyl group having a total carbon number of 6 to 24, and the total carbon number is preferably 8-20.
  • the number of (meth)acryloyloxy groups in the alkyl group of A3 is preferably 1-3.
  • Preferred specific examples of the component for forming the above alkyl group of A3 include monofunctional (meth)acrylic compounds having a hydroxyl group.
  • Monofunctional (meth)acrylic compounds having a hydroxyl group include, for example, hydroxyl group-containing mono(meth)acrylates ⁇ e.g., hydroxyalkyl (meth)acrylates [e.g., 2-hydroxyethyl (meth)acrylate, 3-hydroxy Hydroxy C2-20 alkyl-(meth)acrylates such as propyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, preferably hydroxy C2-12 alkyl-(meth)acrylates, more preferably hydroxy C2-6 alkyl-( meth)acrylate], polyalkylene glycol mono(meth)acrylate [e.g.
  • poly C2-4 alkylene glycol mono(meth)acrylate such as diethylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate], 3 or more hydroxyl groups
  • N-hydroxyalkyl(meth)acrylamide e.g., N-hydroxy C1- such as N-methylol(meth)acrylamide, N-(2-hydroxyethyl)(meth)acrylamide, etc.) 4 alkyl (meth)acrylamide, etc.
  • adducts in which a lactone (e.g., C4-10 lactone such as ⁇ -caprolactone) is added to the hydroxyl group of these compounds (e.g., hydroxyalkyl (meth)acrylate) (e.g., lactone is 1 to 5 mol of adduct), and the like.
  • a lactone e.g., C4-10 lactone such as
  • (meth)acrylic compounds may be used alone or in combination of two or more.
  • a preferred specific example of the compound for forming the (meth)acryloyloxy group-containing alkyl group (A3) is 2-hydroxy-3-phenoxypropyl acrylate.
  • urethane (meth)acrylate contained in the above-mentioned resin material include compounds represented by formulas (II) to (V) below.
  • the (meth)acrylate contained in the resin material of the high refractive index layer may be the same type of compound as the (meth)acrylate contained in the resin material described above, that is, the resin material of the low refractive index layer.
  • the (meth)acrylate forming the high refractive index layer contains at least one (meth)acryloyloxy group and at least one vinyl ether group, and may have a substituent. is used.
  • the (meth)acrylate preferably has 6 to 18 carbon atoms, more preferably 8 to 16 carbon atoms. Alkyl group etc. are mentioned as a substituent of (meth)acrylate.
  • the (meth)acrylate for example, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate (VEEA) is used.
  • the high refractive index layer preferably contains a high refractive index member.
  • the high refractive index member is added to increase the refractive index value of the high refractive index layer. That is, by forming the high refractive index layer using a high refractive index member, the difference in refractive index between the high refractive index layer and the substrate layer can be increased, and the reflectance of the antireflection film can be further increased. .
  • high refractive index members include titanium oxide, zirconium oxide (ZrO 2 ), zinc oxide, alumina, colloidal alumina, lead titanate, red lead, yellow lead, zinc yellow, chromium oxide, ferric oxide, iron black, copper oxide, magnesium oxide, magnesium hydroxide, strontium titanate, yttrium oxide, hafnium oxide, niobium oxide, tantalum oxide ( Ta2O5 ), barium oxide, indium oxide, europium oxide, lanthanum oxide, zircon, tin oxide, and , lead oxide, and their composite oxides such as lithium niobate, potassium niobate, lithium tantalate, and aluminum-magnesium oxide (MgAl 2 O 4 ).
  • rare earth oxides can be used as the high refractive index member.
  • holmium oxide, erbium oxide, thulium oxide, ytterbium oxide, lutetium oxide, and the like can be used.
  • zirconia zirconium oxide is preferred as the high refractive index member.
  • the high refractive index member is preferably a particulate member.
  • the particle size (diameter: average particle size) of the particulate high refractive index member is not particularly limited, but is, for example, 1 to 100 nm, preferably 5 to 50 nm, more preferably 7.5 to 30 nm, Especially preferred is 10 to 20 nm.
  • the (average) particle diameter of the particulate high refractive index member is measured, for example, by the dynamic light scattering method according to JIS Z 8828:2019 (ISO 22412:2017), as described above.
  • the high refractive index member which is in the form of particles, for example, preferably includes a coating of an organic layer as a surface treatment layer covering the outer surface, such as a metal oxide.
  • a coating of an organic layer as a surface treatment layer covering the outer surface, such as a metal oxide.
  • the surface treatment layer is preferably a coating of an organic layer having an ultraviolet-reactive (curing) functional group introduced on the surface.
  • the high refractive index layer preferably contains the above resin material and the high refractive index member at a weight ratio of 10:90 to 40:60, and the ratio of the resin material to the high refractive index member is more preferably 15: 85 to 35:65, more preferably 20:80 to 30:70.
  • the refractive index value of the high refractive index layer is higher than the refractive index value of the substrate layer, and the refractive index of the high refractive index layer is preferably 1.68 to 1.75, more preferably 1.69. 1.74, preferably about 1.70 to 1.73. Also, the difference between the refractive index of the high refractive index layer and the refractive index of the base layer is preferably at least 0.09, more preferably at least 0.12, and still more preferably at least 0.15. , particularly preferably at least 0.17.
  • the range of the difference between the refractive index of the high refractive index layer and the refractive index of the substrate layer is, for example, 0.03 to 0.70, preferably 0.10 to 0.50, more preferably 0 0.15 to 0.26.
  • the reflectance of the surface of the antireflection film on the high refractive index layer side can be increased. can be done.
  • the high refractive index layer or the resin material forming the high refractive index layer preferably contains at least one of a photoinitiator (photopolymerization initiator) and a leveling agent, particularly a photoinitiator. is preferred.
  • the resin material may contain a solvent.
  • leveling agents include fluorine leveling agents, acrylic leveling agents, and silicone leveling agents.
  • the thickness of the high refractive index layer is not particularly limited, it is preferably 10 to 300 nm, more preferably 50 to 250 nm, even more preferably 100 to 200 nm, particularly preferably 130 to 170 nm.
  • the high refractive index layer is preferably laminated between the substrate layer and the low refractive index layer which will be detailed later. In an antireflection film having such a laminate structure, the reflectance of the entire film can be reliably reduced.
  • a layer (additional layer) other than the base layer and the antireflection layer may be laminated.
  • a layer between the base layer and the high refractive index layer, between the base layer and the low refractive index layer, or between the high refractive index layer and the low refractive index layer may be provided.
  • the thickness of the other layer (additional layer) is not particularly limited, it is preferably 0.1 to 10 ⁇ m, more preferably 0.5 to 5 ⁇ m.
  • the antireflection film may further have a hard coat layer as another layer (additional layer) described above. By providing the hard coat layer, the surface hardness of the antireflection film is improved.
  • the hard coat layer is preferably laminated between the substrate layer and the low refractive index layer or between the substrate layer and the high refractive index layer.
  • the hard coat layer is laminated between the substrate layer and the high refractive index layer.
  • These layers are preferably laminated in order of the refractive index layers.
  • the antireflection film having such a laminate structure a high antireflection effect is realized, and the surface hardness, that is, the hardness of the surface opposite to the substrate layer is improved.
  • the hard coat layer is preferably formed by a hard coat treatment applied to the surface of the substrate layer or the like. That is, it is preferable to laminate a hard coat layer by applying a hard coat material that can be cured by heat or by active energy rays and then curing the material.
  • a hard coat material that can be cured by heat or by active energy rays and then curing the material.
  • paints to be cured using active energy rays include resin compositions composed of one or more monofunctional or polyfunctional acrylate monomers or oligomers, more preferably resin compositions containing urethane acrylate oligomers. be done.
  • a photopolymerization initiator is preferably added as a curing catalyst to these resin compositions.
  • examples of the thermosetting resin coating include polyorganosiloxane-based and crosslinked acrylic-based coatings.
  • these resin compositions are commercially available as hard coating agents for acrylic resins or polycarbonate resins.
  • these paints may contain various stabilizers such as UV absorbers, light stabilizers, antioxidants, leveling agents, antifoaming agents, thickeners, antistatic agents, and antifogging agents.
  • a surfactant such as a surfactant may be added as appropriate.
  • An example of a hard coat paint that is cured using an active energy ray includes 40 to 95% by weight of a hexafunctional urethane acrylate oligomer and, for example, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate [acrylic acid 2 - (2-vinyloxyethoxy) ethyl: VEEA] with respect to 100 parts by weight of a photopolymerizable resin composition in which a (meth)acrylate such as VEEA is mixed at a ratio of about 5 to 60% by weight, and a photopolymerization initiator of 1 to 10 parts by weight may be added.
  • a photopolymerizable resin composition in which a (meth)acrylate such as VEEA is mixed at a ratio of about 5 to 60% by weight, and a photopolymerization initiator of 1 to 10 parts by weight may be added.
  • photopolymerization initiator generally known ones can be used. Specifically, benzoin, benzophenone, benzoin ethyl ether, benzoin isopropyl ether, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1- on, azobisisobutyronitrile, benzoyl peroxide and the like.
  • the refractive index value of the hard coat layer is preferably approximately the same as the refractive index of the base material layer (a value within the same range).
  • the hard coat layer preferably has a refractive index in the range of 1.49 to 1.65.
  • the hard coat layer preferably has a refractive index of 1.49 to 1.60, more preferably 1.51 to 1.60, and particularly preferably about 1.53 to 1.59.
  • the difference between the refractive index of the base material layer and the hard coat layer is preferably 0.04 or less, more preferably 0.03 or less, and still more preferably 0.02 or less.
  • the thickness of the hard coat layer is not particularly limited, it is preferably about 1 to 10 ⁇ m, more preferably about 2 to 8 ⁇ m, still more preferably about 3 to 7 ⁇ m.
  • ⁇ Refractive index> The refractive index of light with a wavelength of 589 nm in the resin materials of the following examples and comparative examples was measured using a spectroscopic ellipsometer Auto SE (manufactured by Horiba, Ltd.), which is an automatic thin film measuring device.
  • ⁇ Reflectance> The reflectance of the outer surface of the antireflection film, that is, the surface of the low refractive index layer opposite to the base layer, is preferably 2.0% or less as measured under the conditions of JIS Z 8722 2009. , is more preferably 1.8% or less, and even more preferably 1.5% or less.
  • the surface of the antireflection film on the side of the antireflection layer has high hardness.
  • the pencil hardness defined by JIS K-5400 is preferably 3B or more, more preferably 2B or more, and still more preferably F 2H or more, particularly preferably 2H or more.
  • the surface of the antireflection film on the low refractive index layer side preferably has excellent scratch resistance. Specifically, a load of 250 g/cm 2 was applied to medical nonwoven fabric RP cloth gauze No. 4 (manufactured by Osaki Medical Co., Ltd.), and the surface of the film of each example on the low refractive index layer side was covered 10 times. It is preferred that no visible scratches occur when reciprocated.
  • the surface particularly the surface on the low refractive index layer side, is in good condition. Specifically, cracks, whitening, foaming, and unevenness (mainly color It is preferable that no unevenness is observed and that the appearance of the obtained antireflection film surface is good.
  • the antireflection film also has excellent elongation during molding.
  • the polycarbonate resin side of the sample cut to 210 mm ⁇ 297 mm ⁇ 0.3 mm (thickness) was preheated at 190 ° C. for 40 seconds in the same manner as when evaluating thermoformability, and the deep drawing height of 1 mm or more
  • the sample is placed so that the base material layer is in contact with a mold having a right-angled protrusion with a vertical and horizontal length of 30 mm, and the sample is pressed with high-pressure air of 1.5 MPa.
  • the obtained air pressure molded body has a high elongation value calculated as follows in the region where the air pressure molded body is in contact with the rectangular protrusion of the mold. Specifically, the value of elongation is obtained by printing grid lines at a predetermined interval of, for example, 1 mm on the surface of a sample of the antireflection film, and measuring the distance between the predetermined grid lines after pressure forming compared to before pressure forming. It is calculated by the following formula (A) based on how much it has increased.
  • the antireflection film is preferably moldable so that the elongation value calculated based on the above formula (A) is sufficiently large.
  • the base layer is preheated at 190 ° C. for 40 seconds, and a deep drawing height of 1 mm or more and 5 mm or less is performed.
  • the sample is placed in a mold having a right-angled protrusion with a vertical and horizontal length of 30 mm so that the substrate layer is in contact with the mold, and 1.5 MPa high pressure air is used to blow the sample.
  • the elongation rate (%) value calculated by the formula (A) in the region where the obtained air pressure formed body contacts the right angle portion of the mold is the deep drawing of the mold It is preferably 10 times the value (%) of the height (mm) or more, and more preferably 14 times the value (%) or more. More specifically, according to the antireflection film of this example, after being placed so as to cover the right-angled part of the mold with a deep drawing height of 1 mm, in pressure molding, 10 (%) or more, and further can achieve an elongation rate of 14 (%) or more.
  • the antireflection film of this example is arranged so as to cover the right-angled shape part (projection part) of the mold with a deep drawing height of 3 mm and pressure molding is performed, 30 (%) or more, further 42 (%) ) or more elongation rate can be realized.
  • a deep draw height of 7 mm for the right-angled portion of the mold an elongation of at least 70%, or even about 100% (98%) can be achieved.
  • the laminate of the present invention for example, a laminate film, has an antireflection film, and preferably has the antireflection film described above and a transparent resin substrate.
  • a transparent resin substrate for example, a substrate obtained by laminating a methacrylic resin layer on a bisphenol A polycarbonate layer, a substrate obtained by laminating a bisphenol C polycarbonate layer on a bisphenol A polycarbonate layer, and the like are used.
  • the thickness of the resin substrate is not particularly limited, but is preferably 30 ⁇ m to 1000 ⁇ m (1 mm), more preferably 50 ⁇ m to 700 ⁇ m, still more preferably 100 ⁇ m to 500 ⁇ m.
  • laminate films include, for example, computers, especially computer screens, televisions, especially television screens, films attached to the surface of plasma display panels, polarizing plates used in liquid crystal display devices, sunglasses lenses, prescription spectacle lenses, Films used for the surfaces of viewfinder lenses for cameras, covers for various instruments, glass for automobiles, glass for trains, in-vehicle display panels, housings for electronic devices, and the like can be mentioned.
  • a material such as a resin composition is processed into a layer (sheet) by a conventional method.
  • a resin composition is processed into a layer (sheet) by a conventional method.
  • it is a method by extrusion molding and cast molding.
  • extrusion molding pellets, flakes or powder of the resin composition of the present invention are melted and kneaded in an extruder, extruded from a T-die or the like, and the obtained semi-molten sheet is cooled while being pressed by rolls.
  • a method of solidifying to form a sheet may be mentioned.
  • the low refractive index layer is formed by applying the above-described resin material to the outer surface of the single or multiple substrate layers and curing the material.
  • the antireflection layer can be formed by laminating a low refractive index layer having a lower refractive index than the base layer on at least one surface of the base layer containing the thermoplastic resin.
  • the high refractive index layer can be formed by the same process as the lamination process of the low refractive index layer using the resin material for the high refractive index layer.
  • techniques for curing the resin material techniques such as photocuring and heat curing can be employed.
  • a laminate film is produced by laminating a transparent resin base material, for example, by a known method on the antireflection film produced in this way.
  • a transparent transparent resin layer (refractive index: 1.491) was laminated on a polycarbonate resin layer (refractive index: 1.584) made of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A).
  • a resin sheet (DF02U manufactured by Mitsubishi Gas Chemical Company, Inc.; total thickness: 300 ⁇ m) was used as a base layer.
  • urethane (meth)acrylate resin materials (U-1) to (U-8) as reaction products obtained by reacting each compound, and the mixed solution (
  • a urethane acrylate liquid (resin content: 80% by mass: solvent (methyl ethyl ketone): 20% by mass) was prepared.
  • Urethane acrylate liquid (U-1) of Examples 1 to 6 ⁇ Polymer of meta-xylene diisocyanate and pentaerythritol triacrylate (refractive index is 1.508)
  • U-2) ⁇ Polymers of meta-xylene diisocyanate, pentaerythritol triacrylate and caprolactone acrylate
  • Urethane acrylate liquid (U-5) of Comparative Examples 1 to 4 ⁇ Polymer of isophorone diisocyanate and pentaerythritol triacrylate (refractive index is 1.495)
  • U-8) ⁇ Polymer of isophorone diisocyanate, pentaerythritol triacrylate and 2-hydroxybutyl
  • VEEA 2-(2-Vinyloxyethoxy)ethyl acrylate
  • 1-hydroxy-cyclohexyl-phenyl-ketone (OMNIRAD 184 manufactured by IGM Resins B.V.) as a photoinitiator was added at 5% by weight, and a leveling agent RS-78 (manufactured by DIC: the solid content as a leveling agent was 40% by weight and the solvent diluted with MEK) was added to and dissolved in the mixture, and a solvent (propylene glycol monomethyl ether) was added to adjust the concentration so that the solid content was 1.5% by weight.
  • the obtained material was used as a low refractive index paint for a low refractive index layer.
  • HC-1 a hard coat resin (2-acryloyl-ethyl Ethyl-2-hydroxyethyl-phthalic acid:caprolactone acrylate molar ratio is 50:50)
  • HC-2 Hard coat resin HC-1 and HC-2 consisting of xylene diisocyanate (1175 parts by weight) and 2-hydroxypropyl acrylate (1625 parts by weight) were mixed at 80:20 (weight ratio), 5% by weight of 1-hydroxy-cyclohexyl-phenyl-ketone (OMNIRAD 184 manufactured by IGM Resins BV) was added as an initiator, and a solvent (propylene glycol monomethyl ether) was added to adjust the concentration so that the solid content was 30% by weight. was adjusted (HC-3). Incidentally, the values of the respective parts by weight mentioned above are charged amounts.
  • a hard coat paint of HC-3 was applied to the methacrylic resin layer of the base material layer so as to give a dry film thickness of 3 ⁇ m, and dried at 100° C. for 1 minute. Further, ultraviolet rays were irradiated with an ultraviolet curing device so that the integrated light quantity was 250 mJ/cm 2 to form a hard coat layer (refractive index value: 1.51). Next, a low refractive index paint was applied on the hard coat layer so that the dry film thickness was 100 nm, and dried at 100° C. for 1 minute. Furthermore, a low refractive index layer was formed by irradiating ultraviolet rays with an ultraviolet curing apparatus under a nitrogen purge so that the integrated light amount was 250 mJ/cm 2 .
  • Scratch resistance A load of 500 g/cm 2 was applied to medical nonwoven fabric RP cloth gauze No. 4 (manufactured by Osaki Medical Co., Ltd.), and the surface of the film of each example on the low refractive index layer side was reciprocated 1000 times to remove scratches. The situation was judged visually.
  • Reflectance luminous reflectance: Measured according to JIS Z 8722-009 with SD6000 manufactured by Nippon Denshoku Industries Co., Ltd. In order to prevent reflection from the back surface (substrate layer side) of the film of each example, the measurement was performed by attaching a black vinyl tape to the surface opposite to the coated surface.
  • the antireflection film obtained in each example was cut into a size of 210 mm x 297 mm x (thickness) 0.3 mm, and the polycarbonate resin side of the obtained sample was preheated at 190°C for about 40 seconds.
  • pressure forming was performed with high pressure air of 1.5 MPa at a deep drawing height using a mold having right-angled protrusions.
  • the deep drawing height was set in increments of 1 mm, such as 1 mm, 2 mm, and 5 mm or more for the rectangular mold.
  • the value of the radius R of the region in contact with the right-angled portion of the mold was measured and described as "right-angled shape radius R (mm)" in Table 1 below. It can be said that the smaller this value, the better the moldability.
  • the radius R of the right-angled portion was measured using a contact contour measuring machine CONTOURECORD 2700/503 (manufactured by Tokyo Seimitsu Co., Ltd.).
  • the surface state (cracks, whitening, foaming, unevenness) of the obtained molded body was observed, and when neither cracks, whitening, foaming, or unevenness was observed, the scratch resistance was evaluated as "no damage".
  • the molded article having a deep drawing height of 1 mm or more and a right-angled portion having a radius R of 3.0 mm or less and which could be molded in a flawless state was comprehensively evaluated as "good” in thermoformability.
  • the deep drawing height of the obtained molded body that is, the height to the area molded on the mold convex part (projection part) with respect to the reference plane in the film which is the molded body It was actually measured as a value of "deep drawing height (mm)".
  • Table 1 shows the measurement results of the properties of the films of the above Examples and Comparative Examples.
  • the refractive index in the table is the value of the paint before polymerization of each layer, and the value of the refractive index after polymerization was approximately 0.02 higher than the value of the paint before polymerization in all layers.
  • the antireflection films of Examples had high interlayer adhesion, good scratch resistance, excellent thermoformability despite having high surface hardness, and low surface reflectance. rice field.
  • an antireflection film 10B with excellent properties can be obtained (see FIG. 2).

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PCT/JP2022/022066 2021-06-03 2022-05-31 反射防止フィルム、反射防止フィルムを有する積層体及び反射防止フィルムの製造方法 Ceased WO2022255340A1 (ja)

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