CN115185021A - Anti-reflection film - Google Patents
Anti-reflection film Download PDFInfo
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- CN115185021A CN115185021A CN202210684292.XA CN202210684292A CN115185021A CN 115185021 A CN115185021 A CN 115185021A CN 202210684292 A CN202210684292 A CN 202210684292A CN 115185021 A CN115185021 A CN 115185021A
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- particles
- meth
- antireflection
- antireflection film
- nanodiamond
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- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- JSGVZVOGOQILFM-UHFFFAOYSA-N 3-methoxy-1-butanol Chemical compound COC(C)CCO JSGVZVOGOQILFM-UHFFFAOYSA-N 0.000 description 1
- QMYGFTJCQFEDST-UHFFFAOYSA-N 3-methoxybutyl acetate Chemical compound COC(C)CCOC(C)=O QMYGFTJCQFEDST-UHFFFAOYSA-N 0.000 description 1
- CCTFMNIEFHGTDU-UHFFFAOYSA-N 3-methoxypropyl acetate Chemical compound COCCCOC(C)=O CCTFMNIEFHGTDU-UHFFFAOYSA-N 0.000 description 1
- RTANHMOFHGSZQO-UHFFFAOYSA-N 4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)C#N RTANHMOFHGSZQO-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- BBPQYLQVCZPVHB-UHFFFAOYSA-N C(C)(C)(C)OOC(=O)C1=C(C(=O)C2=CC=C(C=C2)C(=O)OC)C=CC(=C1)C(=O)OC Chemical compound C(C)(C)(C)OOC(=O)C1=C(C(=O)C2=CC=C(C=C2)C(=O)OC)C=CC(=C1)C(=O)OC BBPQYLQVCZPVHB-UHFFFAOYSA-N 0.000 description 1
- NPSVLRBUTAVRHY-UHFFFAOYSA-N CCCCC(CCCC)C(C)(C(O)=O)N=NC(C)(C(CCCC)CCCC)C(O)=O Chemical compound CCCCC(CCCC)C(C)(C(O)=O)N=NC(C)(C(CCCC)CCCC)C(O)=O NPSVLRBUTAVRHY-UHFFFAOYSA-N 0.000 description 1
- 229920001747 Cellulose diacetate Polymers 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910020175 SiOH Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- BMFYCFSWWDXEPB-UHFFFAOYSA-N cyclohexyl(phenyl)methanone Chemical class C=1C=CC=CC=1C(=O)C1CCCCC1 BMFYCFSWWDXEPB-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920000636 poly(norbornene) polymer Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920006290 polyethylene naphthalate film Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- MVQLEZWPIWKLBY-UHFFFAOYSA-N tert-butyl 2-benzoylbenzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 MVQLEZWPIWKLBY-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 150000007964 xanthones Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- JLQFVGYYVXALAG-CFEVTAHFSA-N yasmin 28 Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1.C([C@]12[C@H]3C[C@H]3[C@H]3[C@H]4[C@@H]([C@]5(CCC(=O)C=C5[C@@H]5C[C@@H]54)C)CC[C@@]31C)CC(=O)O2 JLQFVGYYVXALAG-CFEVTAHFSA-N 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/11—Anti-reflection coatings
- G02B1/111—Anti-reflection coatings using layers comprising organic materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- 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
- G02B1/14—Protective coatings, e.g. hard coatings
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Surface Treatment Of Optical Elements (AREA)
- Laminated Bodies (AREA)
Abstract
The antireflection film (X) has a laminated structure comprising a substrate (11), a hard coat layer (12), and an antireflection layer (13). The antireflection layer (13) contains a curable resin, low-refractive-index particles, and nanodiamond particles. The anti-reflection layer (13) may further contain a fluorine-containing curable compound. Such an antireflection film is suitable for achieving both high antireflection property and high scratch resistance.
Description
The present application is a divisional application of an application having an application date of 2018, 8, and 6, and an application number of 201880057999.X, entitled "antireflection film".
Technical Field
The present invention relates to an antireflection film. In addition, the present application is based on Japanese patent application No. 2017-172771, japanese patent application No. 2017, 9, 8, sunward, japanese patent application No. 2018-020017, sunward, 2018, 2, 7, and Japanese patent application No. 2018-020018, sunward, 2018, 2, 7, claiming priority, and the entire contents described in these applications are cited.
Background
An antireflection film for reducing reflection of external light may be provided on the surface of a display of a tablet PC, various televisions, or the like. The antireflection film has, for example, an antireflection layer containing low refractive index particles as an outermost layer. Techniques related to such an antireflection film are described in, for example, patent documents 1 to 3 below.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2009-151270
Patent document 2: japanese unexamined patent publication No. 2014-197135
Patent document 3: japanese patent laid-open publication No. 2017-40936
Disclosure of Invention
Problems to be solved by the invention
In the antireflection layer of the antireflection film, as the content of the low refractive index particles is increased, the net refractive index of the antireflection layer tends to be decreased, and the antireflection function of the antireflection layer or the antireflection film is easily ensured. However, in the antireflection layer, the scratch resistance tends to be lower as the content of the low refractive index particles is larger. Conventionally, in order to improve the abrasion resistance of an antireflection layer or an antireflection film, a predetermined silica particle is sometimes blended in an antireflection layer as an outermost layer, but sufficient abrasion resistance may not be obtained in some cases.
The present invention has been made in view of such a background, and an object thereof is to provide an antireflection film suitable for achieving both high antireflection property and high scratch resistance.
Means for solving the problems
The antireflection film provided by the invention has a laminated structure containing a substrate, an antireflection layer and a hard coat layer arranged between the substrate and the antireflection layer. The antireflection layer contains a curable resin, low-refractive-index particles, and nanodiamond particles. In the present invention, the low refractive index particles are particles exhibiting a refractive index of 1.10 to 1.45. The refractive index can be measured based on JIS K7142. In the present invention, the nanodiamond particles may be primary particles of nanodiamond or secondary particles of nanodiamond. The primary nanodiamond particles are nanodiamond particles having a particle diameter of 10nm or less.
When the antireflection film has a laminated structure including a substrate, a hard coat layer, and an antireflection layer, the antireflection layer contains low refractive index particles as the constituent components as described above. Such a configuration is suitable for realizing high antireflection properties in the antireflection film. As described above, the antireflection film of the present invention has a hard coat layer between the substrate and the antireflection layer. Such a configuration is suitable for realizing high scratch resistance in the antireflection film. In the present antireflection film, the antireflection layer having a laminated structure together with such a hard coat layer contains the nanodiamond particles as the constituent components as described above. This constitution, in which the nano-diamond particles are contained as fine particles of diamond having extremely high mechanical strength in the anti-reflection layer forming a laminated structure together with the hard coat layer, is suitable for realizing high scratch resistance in the anti-reflection layer or the present anti-reflection film. As described above, the antireflection film of the present invention is suitable for realizing high antireflection property and high scratch resistance.
The antireflection layer preferably further contains a fluorine-containing curable compound. Such a structure is preferable from the viewpoint of stain resistance, water repellency, oil repellency, slidability, ease of wiping of fingerprints, and the like of the exposed surface of the antireflection layer.
The nanodiamond particles are preferably surface-modified nanodiamond particles with a silane coupling agent. The silane coupling agent is an organosilicon compound having both a silicon-containing reactive group capable of forming a chemical bond with an inorganic material and an organic chain bonded to the silicon. The silane coupling agent surface-modified nanodiamond particles may form covalent bonding with the surface of the nanodiamond particles through its reactive group to bond the particles together. In the present invention, the silane coupling agent is preferably bonded to the nanodiamond particles and has an organic chain containing a (meth) acryloyl group or an alkyl group. (meth) acryloyl means acryloyl and/or methacryloyl. The (meth) acryloyl group-containing organic chain of the silane coupling agent is preferably propyl acrylate and/or propyl methacrylate. The alkyl group of the organic chain as the silane coupling agent is preferably an alkyl group having 1 to 18 carbon atoms, and more preferably a methyl group. These configurations are suitable for achieving a good dispersion state of the nanodiamond particles in the antireflection layer, and therefore suitable for achieving high transparency in the antireflection layer and further in the antireflection film.
The particle diameter D50 of the nanodiamond particles (including the case of surface-modified nanodiamond particles) is preferably 100nm or less, and more preferably 30nm or less. Such a configuration is preferable in terms of achieving high transparency of the antireflection layer, and therefore is preferable in terms of achieving high transparency of the antireflection film.
The low refractive index particles are preferably hollow silica particles. The average particle diameter of the low refractive index particles is preferably 50 to 70nm. These configurations are preferable in terms of achieving good antireflection properties of the antireflection layer or the antireflection film. The average particle diameter of the low refractive index particles is an average particle diameter of the fine particles obtained from a particle diameter distribution of the fine particles measured by a dynamic light scattering method.
The mass ratio of the low refractive index particles to the nanodiamond particles in the antireflection layer is preferably in a range of 99 to 84. Such a configuration is suitable for achieving a balance between the antireflection property and the scratch resistance in the antireflection film.
The curable resin in the antireflective layer is preferably a polymer of a (meth) acryloyl group-containing compound. Such a constitution is suitable for realizing high scratch resistance in the antireflection layer or the present antireflection film. In addition, in the case where the curable resin in the antireflection layer is a polymer of a compound containing a (meth) acryloyl group, and the nanodiamond particles in the antireflection layer are surface-modified nanodiamond particles having a silane coupling agent having a (meth) acryloyl group in a surface organic chain, the (meth) acryloyl group in the surface organic chain of the surface-modified nanodiamond particles and the curable resin component are likely to react in the process of polymerization of the curable resin component at the time of forming the antireflection layer, and thus a good dispersion state of the nanodiamond particles in the antireflection layer is easily achieved. The fine dispersion of the nanodiamond particles in the anti-reflection layer contributes to the realization of high transparency in the anti-reflection layer and thus in the anti-reflection film.
The haze of the antireflection film of the present invention is preferably 1.0% or less, more preferably 0.8% or less, more preferably 0.6% or less, more preferably 0.4% or less, more preferably 0.2% or less. In the present invention, the haze means a value measured according to JIS K7136. In the present antireflection film, a configuration in which the haze is suppressed to the above-described extent is preferable in terms of ensuring good transparency.
The light emission reflectance on the side of the anti-reflective layer in the anti-reflective film of the present invention is preferably in the range of 0.5 to 2.0%, more preferably in the range of 0.5 to 1.7%, and still more preferably in the range of 0.5 to 1.5%. In the present antireflection film, a configuration in which the light emission reflectance is suppressed to the above-described degree is preferable in terms of achieving high antireflection properties.
Drawings
Fig. 1 is a partial sectional view of an antireflection film according to an embodiment of the present invention.
Fig. 2 is a process diagram showing an example of a method for producing surface-modified nanodiamond particles that can be used as a constituent component of an antireflection layer of an antireflection film of the present invention.
Description of the symbols
X anti-reflection film
11. Substrate material
12. Hard coating
13. Anti-reflection layer
Detailed Description
Fig. 1 is a partial sectional view of an antireflection film X according to an embodiment of the present invention. The antireflection film X has a laminated structure including a substrate 11, a hard coat layer 12, and an antireflection layer 13. The antireflection film X may have other layers in its laminated structure. Such an antireflection film X is provided on the surface of the optical member for use, for example, to reduce reflection of external light on the surface. Examples of the optical member include: transparent substrates for flat panel displays such as liquid crystal displays, organic electroluminescence displays, and plasma displays, and transparent panels for touch panels.
The substrate 11 is a transparent substrate, and is formed of, for example, a transparent resin film that transmits light. Examples of the transparent resin film used for the substrate 11 include: cellulose acetate membranes, polyester membranes, polycarbonate membranes, and polynorbornene membranes. Examples of the cellulose acetate-based film include: cellulose triacetate, cellulose diacetate, cellulose acetate propionate, and cellulose acetate butyrate. Examples of the polyester-based film include: polyethylene terephthalate films and polyethylene naphthalate films. The substrate 11 may be formed of a single resin film or may have a laminated structure of a plurality of resin films. The thickness of the substrate 11 is preferably 400 μm or less, more preferably 200 μm or less, and still more preferably 100 μm or less, from the viewpoint of achieving sufficient transparency of the antireflection film X.
The hard coat layer 12 is located between the substrate 11 and the antireflection layer 13, and at least the pencil hardness of the surface on the side of the antireflection layer 13 has a hardness of, for example, 2H or more. The hard coat layer 12 is, for example, a polymer or a cured product of a monomer and/or oligomer of a polyfunctional (meth) acrylate having a plurality of (meth) acryloyl groups. "(meth) acryl" means acryl and/or methacryl. "(meth) acrylate" means acrylate and/or methacrylate. Examples of the polyfunctional (meth) acrylate which is a monomer or oligomer contained in the composition for forming the hard coat layer 12 include: difunctional (meth) acrylates, trifunctional (meth) acrylates, and tetrafunctional or higher polyfunctional (meth) acrylates. Examples of difunctional (meth) acrylates include: ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate, and nonanediol di (meth) acrylate. Examples of trifunctional (meth) acrylates include: trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, and dipentaerythritol tri (meth) acrylate. Examples of the tetrafunctional or higher polyfunctional (meth) acrylate include: pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and ditrimethylolpropane hexa (meth) acrylate. The composition for forming a hard coat layer may contain one kind of polyfunctional (meth) acrylate, or may contain two or more kinds of polyfunctional (meth) acrylates. The proportion of the polyfunctional (meth) acrylate in the monomer or oligomer in the hard coat layer-forming composition is preferably 50 mass% or more, and more preferably 75 mass% or more.
The composition for forming a hard coat layer may contain a monofunctional (meth) acrylate having one (meth) acryloyl group. Examples of such monofunctional (meth) acrylates include: beta-carboxyethyl (meth) acrylate, isobornyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, EO-modified phenol (meth) acrylate, EO-modified nonylphenol (meth) acrylate, and EO-modified 2-ethylhexyl (meth) acrylate. The composition for forming a hard coat layer may contain one kind of monofunctional (meth) acrylate or two or more kinds of monofunctional (meth) acrylates. The composition for forming a hard coat layer may contain an acrylic oligomer such as epoxy (meth) acrylate, polyester (meth) acrylate, or urethane (meth) acrylate.
The composition for forming a hard coat layer preferably contains a fluorine-containing curable compound from the viewpoint of ensuring the strength and smoothness of the hard coat layer 12 to be formed. Examples of such fluorine-containing curable compounds include: fluoroalkyl (meth) acrylate, fluoro (poly) oxyalkylene glycol di (meth) acrylate, fluorine-containing epoxy resin, and fluorine-containing urethane resin. Examples of fluoroalkyl (meth) acrylates include: perfluorooctylethyl (meth) acrylate, and trifluoroethyl (meth) acrylate. Examples of the fluoro (poly) oxyalkylene glycol di (meth) acrylate include: fluoroethylene glycol di (meth) acrylate, and fluoropropylene glycol di (meth) acrylate. Examples of commercially available products of such fluorine-containing curable compounds include: "Polyfox3320" by Omnova Solution, "KY-1203" by shin-Etsu chemical Co., ltd, "Megafac RS-90" by DIC, and "Optool DSX" by Daiki Industrial Co., ltd.
The hard coat layer-forming composition preferably contains a polymerization initiator. Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator. Examples of the photopolymerization initiator include: benzophenones such as peroxyesters, other peroxides, benzoins, acetophenones, cyclohexylphenones, anthraquinones, thioxanthones, ketals, benzophenones, xanthones, and titanocenes. Examples of peroxyesters include: 3,3', 4' -tetrakis (t-butylperoxycarbonyl) benzophenone, 3 '-bis (t-butylperoxycarbonyl) -4,4' -bis (methoxycarbonyl) benzophenone, and t-butyl peroxybenzoate. Examples of the peroxides include: t-butyl hydroperoxide and di-t-butyl peroxide. Examples of benzoins include benzoin, benzoin methyl ether, and benzoin ethyl ether. Examples of the acetophenone include: acetophenone, 2-dimethoxy-2-phenylacetophenone, 2-diethoxy-2-phenylacetophenone, and 1, 1-dichloroacetophenone. Examples of cyclohexyl phenyl ketones are: 1-hydroxycyclohexyl phenyl ketone. Examples of the anthraquinones include: 2-methylanthraquinone and 2-ethylanthraquinone. As thioxanthones, there may be mentioned, for example: 2, 4-dimethylthioxanthone and 2, 4-diethylthioxanthone. Examples of ketals include: acetophenone dimethyl ketal and benzoin dimethyl ether. Examples of the thermal polymerization initiator include: azo compounds, organic peroxides, and hydrogen peroxide. Examples of azo compounds include: 2,2 '-azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), 2 '-azobis (4-methoxy-2, 4-dimethylvaleronitrile), 2' -azobis (dimethyl 2-methylpropionate), 2 '-azobis (diethyl 2-methylpropionate), and 2,2' -azobis (dibutyl 2-methylpropionate). Examples of the organic peroxide include: benzoyl peroxide, lauroyl peroxide, t-butyl peroxypivalate, and 1, 1-bis (t-butylperoxy) cyclohexane.
The composition for forming a hard coat layer preferably contains a solvent from the viewpoint of adjusting the coating properties thereof. Examples of the solvent include: methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, xylene, ethyl acetate, butyl acetate, 3-methoxybutyl acetate, methoxypropyl acetate, ethylene glycol monomethyl ether acetate, methanol, ethanol, isopropanol, 1-butanol, 1-methoxy-2-propanol, 3-methoxybutanol, ethoxyethanol, diisopropyl ether, ethylene glycol dimethyl ether, and tetrahydrofuran.
The hard coat layer 12 or the composition for forming a hard coat layer may further contain various additives such as a defoaming agent, a photosensitizer, an ultraviolet absorber, an antioxidant, a light stabilizer, an anti-blocking agent, a leveling agent, a surfactant, an extender, a pigment, a dye, a rust inhibitor, an antistatic agent, and a plasticizer. The hard coat layer 12 or the composition for forming a hard coat layer may contain other polymerizable components than those described above.
The thickness of the hard coat layer 12 is preferably 1 to 30 μm, and more preferably 3 to 10 μm, from the viewpoint of the balance between the transparency of the antireflection film X and the hardness of the hard coat layer 12.
The antireflection layer 13 in the antireflection film X includes a curable resin, low refractive index particles, and nanodiamond particles. The net refractive index of the antireflection layer 13 is lower than that of the hard coat layer 12, and is, for example, 1.3 to 1.4. The refractive index can be measured according to JIS K7142.
In the present embodiment, the curable resin in the antireflection layer 13 is a polymer of a (meth) acryloyl group-containing compound. The component for forming such a curable resin preferably contains a monomer and/or oligomer for forming a curable acrylic resin by polymerization reaction by irradiation with light or heating. As a monomer for forming such a monomer or oligomer, a polyfunctional (meth) acrylate can be used. Examples of the polyfunctional (meth) acrylate include: difunctional (meth) acrylates, trifunctional (meth) acrylates, and tetrafunctional or higher polyfunctional (meth) acrylates. Examples of difunctional (meth) acrylates include: ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate, and nonanediol di (meth) acrylate. Examples of trifunctional (meth) acrylates include: trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, and dipentaerythritol tri (meth) acrylate. Examples of the tetrafunctional or higher polyfunctional (meth) acrylate include: pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and ditrimethylolpropane hexa (meth) acrylate. As the monomer for forming the monomer in the curable resin-forming component and the oligomer in the curable resin-forming component, one kind of polyfunctional (meth) acrylate may be used, and two or more kinds of polyfunctional (meth) acrylates may be used. The proportion of the polyfunctional (meth) acrylate in the curable resin-forming component is preferably 50% by mass or more, and more preferably 75% by mass or more.
The curable resin forming component may contain a monofunctional (meth) acrylate having one (meth) acryloyl group. Examples of such monofunctional (meth) acrylates include: beta-carboxyethyl (meth) acrylate, isobornyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, EO-modified phenol (meth) acrylate, EO-modified nonylphenol (meth) acrylate, and EO-modified 2-ethylhexyl (meth) acrylate. The curable resin-forming component may contain one kind of monofunctional (meth) acrylate, or may contain two or more kinds of monofunctional (meth) acrylates. The curable resin-forming component may contain an acrylic oligomer such as epoxy (meth) acrylate, polyester (meth) acrylate, or urethane (meth) acrylate.
From the viewpoint of ensuring the strength and surface sliding property of the antireflection layer 13, the curable resin forming component preferably contains a fluorine-containing curable compound. The high strength and surface slip of the antireflection layer 13 contribute to achieving high scratch resistance of the antireflection layer 13 or the antireflection film X. Examples of the fluorine-containing curable compound used for the antireflection layer 13 include: fluoroalkyl (meth) acrylate, fluoro (poly) oxyalkylene glycol di (meth) acrylate, fluorine-containing epoxy resin, and fluorine-containing urethane resin. Examples of fluoroalkyl (meth) acrylates include: perfluorooctylethyl (meth) acrylate, and trifluoroethyl (meth) acrylate. Examples of the fluoro (poly) oxyalkylene glycol di (meth) acrylate include: fluoroethylene glycol di (meth) acrylate, and fluoropropylene glycol di (meth) acrylate. Examples of commercially available products of such fluorine-containing curable compounds include: "Polyfox3320" by Omnova Solution, "KY-1203" by shin-Etsu chemical Co., ltd., "Megafac RS-90" by DIC Co., ltd., and "Optool DSX" by Dajin Industrial Co., ltd.).
The curable resin-forming component preferably contains a polymerization initiator. Examples of the polymerization initiator include various photopolymerization initiators and various thermal polymerization initiators, which are listed as the polymerization initiator in the hard coat layer-forming composition.
In the present embodiment, the low refractive index particles in the anti-reflection layer 13 are those exhibiting a refractive index of 1.10 to 1.45Particles of refractive index. The refractive index can be measured based on JIS K7142. Examples of the constituent material of the low refractive index particles include: mgF 2 LiF, alF, 3 NaF. AlF, and Na 3 AlF 6 . As the low refractive index particles, particles having voids inside the particles, such as hollow particles, can be used. For particles having voids inside the particle, the net refractive index is low as a result of the combination of the refractive index of the constituent material portions and the refractive index of the air of the void portions (about 1). In the antireflection layer 13, from the viewpoint of securing hardness and effectively reducing the refractive index, the low refractive index particles are preferably hollow silica particles. Examples of commercially available low refractive index particles include: "Thruya 4320" and "Thruya 5320" available from Nissan catalytic chemical Co., ltd and "SiliNax" available from Nissan industries, ltd.
From the viewpoint of achieving good antireflection properties in the antireflection layer 13 or the antireflection film X, the average particle diameter of the low refractive index particles in the antireflection layer 13 is preferably 50 to 70nm. The average particle diameter of the low refractive index particles is an average particle diameter of the fine particles obtained from a particle diameter distribution of the fine particles measured by a dynamic light scattering method.
The content ratio of the low refractive index particles in the antireflection layer 13 is, for example, 10 to 90 mass%, preferably 30 to 70 mass%.
The nanodiamond particles in the antireflection layer 13 may be primary particles of nanodiamond or secondary particles of nanodiamond. The primary nanodiamond particles are nanodiamond particles having a particle diameter of 10nm or less. Further, the nanodiamond particles are preferably nanodiamond particles produced by a detonation method (detonation method nanodiamond particles) as described later. According to the detonation method, nano-diamond particles having a primary particle diameter of 10nm or less can be suitably synthesized.
From the viewpoint of dispersion stability, the nanodiamond particles in the antireflection layer 13 are preferably surface-modified nanodiamond particles having a silane coupling agent bonded to the surface thereof. When the silane coupling agent is an organosilicon compound having both a reactive group containing silicon and an organic chain bonded to the silicon, which can form a chemical bond with an inorganic material, the silane coupling agent for surface-modifying the nanodiamond particles forms a covalent bond with the surface of the nanodiamond particles through the reactive group, and bonds the nanodiamond particles together. Examples of the reactive group of the silane coupling agent forming the silane coupling agent bonded to the nanodiamond particles include a silanol group (-SiOH) and a hydrolyzable group capable of forming a silanol group. Examples of such hydrolyzable groups include: silicon-bonded alkoxysilyl groups such as methoxy and ethoxy, silicon-bonded halogenosilyl groups such as chlorine and bromine, and silicon-bonded acetoxy groups. These hydrolyzable groups can undergo hydrolysis reaction to form silanol groups. Through a dehydration condensation reaction between silanol groups of the silane coupling agent and, for example, hydroxyl groups of the surface of the nanodiamond, chemical bonds may be formed between the silane coupling agent and the surface of the nanodiamond. The organic chain of the silane coupling agent preferably contains a (meth) acryloyl group or an alkyl group. With such a configuration, the dispersion of the surface-modified nanodiamond particles in the antireflection layer 13 can be easily stabilized. The (meth) acryloyl group containing organic chain is preferably propyl acrylate and/or propyl methacrylate. The alkyl group forming the organic chain of the silane coupling agent is preferably an alkyl group having 1 to 18 carbon atoms, and more preferably a methyl group. Examples of the silane coupling agent in the surface-modified nanodiamond particles include: 3- (trimethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) propyl methacrylate, 3- (methyldimethoxysilyl) propyl methacrylate, 3- (methyldiethoxysilyl) propyl methacrylate, 3- (triethoxysilyl) propyl methacrylate, and trimethoxy (meth) silane.
When the silane coupling agent in the surface-modified nanodiamond particles contains a (meth) acryloyl group in the organic chain thereof, the (meth) acryloyl group in the surface organic chain of the surface-modified nanodiamond particles is easily reacted with the monomer or oligomer to introduce the nanodiamond particles into the curable resin in the process of polymerizing the monomer or oligomer for forming the curable resin. Examples of such a silane coupling agent include: 3- (trimethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) propyl methacrylate, 3- (methyldimethoxysilyl) propyl methacrylate, 3- (methyldiethoxysilyl) propyl methacrylate, and 3- (triethoxysilyl) propyl methacrylate.
The particle diameter D50 of the nanodiamond particles (including the case of surface-modified nanodiamond particles) is preferably 100nm or less, and more preferably 30nm or less. Such a configuration is preferable in terms of achieving high transparency of the antireflection layer 13, and is therefore preferable in terms of achieving high transparency of the antireflection film X.
The content of the nano-diamond particles in the antireflection layer 13 is, for example, 0.1 to 15 mass%, preferably 0.5 to 10 mass%. In addition, the mass ratio of the low refractive index particles to the nanodiamond particles in the antireflection layer 13 is preferably in the range of 99. Such a configuration is suitable for achieving a balance among the antireflection property, the scratch resistance, and the transparency of the antireflection film X.
In view of adjustment of coating properties and the like, the composition for forming the antireflection layer 13 preferably contains a solvent in addition to the above-described curable resin forming component, low refractive index particles, and nanodiamond particles. The solvent may be the same as the solvent listed above as the solvent in the composition for forming a hard coat layer.
The anti-reflective layer 13 or the composition for forming an anti-reflective layer may further contain various additives such as a defoaming agent, a photosensitizer, an ultraviolet absorber, an antioxidant, a light stabilizer, an anti-blocking agent, a leveling agent, a surfactant, an extender, a pigment, a dye, a rust inhibitor, an antistatic agent, and a plasticizer.
The thickness of the anti-reflection layer 13 is, for example, 0.07 to 0.13. Mu.m, preferably 0.08 to 0.12. Mu.m.
The haze of the antireflection film X having the laminated structure described above is preferably 1.0% or less, more preferably 0.8% or less, more preferably 0.6% or less, more preferably 0.4% or less, and more preferably 0.2% or less. In the present embodiment, the haze is a value measured according to JIS K7136. In the antireflection film X, a configuration in which the haze is suppressed to the above-described extent is preferable in terms of ensuring good transparency.
The light emission reflectance of the anti-reflection film X on the anti-reflection layer 13 side is preferably in the range of 0.5 to 2.0%, more preferably in the range of 0.5 to 1.7%, and still more preferably in the range of 0.5 to 1.5%. In the present embodiment, the light emission reflectance is a value measured according to JIS Z8701. In the antireflection film X, a configuration in which the light emission reflectance is suppressed to the above-described extent is preferable in terms of achieving high antireflection properties.
In the antireflection film X having the above-described configuration, the antireflection layer 13 contains the low refractive index particles as described above in the constituent components. Such a configuration is suitable for realizing high antireflection performance in the antireflection film X. As described above, the antireflection film X has the hard coat layer 12 between the substrate 11 and the antireflection layer 13. Such a configuration is suitable for realizing high scratch resistance in the antireflection film X. In the antireflection film X, the antireflection layer 13 having a laminated structure together with the hard coat layer 12 contains the nanodiamond particles as described above as a constituent component. This configuration of the nano-diamond particles containing the fine particles of diamond having extremely high mechanical strength in the antireflection layer 13 forming a laminated structure together with the hard coat layer 12 is suitable for realizing high scratch resistance in the antireflection layer 13 or the antireflection film X. As described above, the antireflection film X is suitable for achieving both high antireflection property and high scratch resistance.
Such an antireflection film X can be produced by, for example, sequentially forming a hard coat layer 12 and an antireflection layer 13 on a substrate 11. When forming the hard coat layer 12 on the substrate 11, first, the above-described composition for forming a hard coat layer is applied to the substrate 11 to form a composition layer. Examples of the coating mechanism include: wire rod coater, spray coater, spin coater, dip coater, die coater, unfilled corner wheel coater, and gravure coater. Next, the composition layer on the substrate 11 is dried and cured. Thereby forming the hard coat layer 12. When forming the antireflection layer 13 on the hard coat layer 12, first, an antireflection layer-forming composition containing at least the curable resin-forming component, the low refractive index particles, and the nanodiamond particles is applied on the hard coat layer 12 to form a composition layer. Examples of the coating mechanism include: wire rod coater, spray coater, spin coater, dip coater, die coater, unfilled corner wheel coater, and gravure coater. Next, the composition layer on the substrate 11 is dried and cured. The antireflection layer 13 can be formed thereby. For example, the antireflection film X can be produced as described above.
Fig. 2 is a process diagram showing an example of a method for producing surface-modified nanodiamond particles that can be used as the anti-reflection layer 13 or a constituent component of the anti-reflection layer forming composition. The method includes a production step S1, a purification step S2, a drying step S3, and a surface modification step S4.
In the production step S1, the detonation method is performed to produce nanodiamonds. First, a device in which an electric detonator is attached to a molded explosive is installed inside a pressure-resistant container for detonation, and the container is sealed in a state in which atmospheric gas consisting of atmospheric air coexists with the explosive used. The container is made of iron, for example, and the volume of the container is 0.5 to 40m 3 . As explosives, mixtures of trinitrotoluene (TNT) and cyclotrimethylenetrinitramine, i.e., hexogen (RDX), may be used. The mass ratio of TNT to RDX (TNT/RDX) is, for example, in the range of 40/60 to 60/40. The amount of explosive used is, for example, 0.05 to 2.0kg.
In the generating step S1, the electric detonator is then detonated to detonate the explosive in the container. Detonation refers to the movement of the flame surface, where the reaction occurs in an explosion accompanying a chemical reaction, at a high speed in excess of the speed of sound. At the time of detonation, an explosive is used, and nanodiamonds are produced by the action of the pressure and energy of a shock wave generated during the detonation, using carbon, which is partially liberated by incomplete combustion, as a raw material. In the case of nanodiamonds, in the product obtained by the detonation method, first, adjacent primary particles or crystallites are strongly aggregated by van der waals' force action and contribution of coulomb interaction between crystal planes, and an aggregate is formed.
In the production step S1, the container and the interior thereof are then cooled by leaving them at room temperature for 24 hours, for example. After this natural cooling, the rough nanodiamond product (including the aggregate of nanodiamond and coal generated as described above) adhered to the inner wall of the container was scraped off with a spatula, and the rough nanodiamond product was recovered. By the detonation method as described above, a crude product of the nanodiamond particles can be obtained. Further, by performing the above-described production step S1 a necessary number of times, a desired amount of a rough nanodiamond product can be obtained.
The purification step S2 in the present embodiment includes an acid treatment in which a strong acid is allowed to act on the raw nanodiamond product serving as the raw material in, for example, a water solvent. When the nanodiamond raw product obtained by the detonation method easily contains a metal oxide, the metal oxide is an oxide of Fe, co, ni, or the like derived from a container or the like used in the detonation method. The metal oxide can be dissolved and removed from the nanodiamond crude product by, for example, allowing a given strong acid to act in an aqueous solvent (acid treatment). The strong acid used in the acid treatment is preferably an inorganic acid, and examples thereof include hydrochloric acid, hydrofluoric acid, sulfuric acid, nitric acid, and aqua regia. In the acid treatment, one kind of strong acid may be used, or two or more kinds of strong acids may be used. The concentration of the strong acid used in the acid treatment is, for example, 1 to 50% by mass. The acid treatment temperature is, for example, 70 to 150 ℃. The acid treatment time is, for example, 0.1 to 24 hours. Further, the acid treatment may be carried out under reduced pressure, normal pressure or under increased pressure. After the acid treatment, the solid component (including the nanodiamond aggregate) is washed with water by decantation, for example. The decanted solid is preferably washed with water repeatedly until the pH of the precipitate reaches, for example, 2 to 3.
In the present embodiment, the refining step S2 includes an oxidation treatment for removing graphite from the nanodiamond raw product (nanodiamond aggregate before finishing refining) using an oxidizing agent. When graphite is contained in the nano-diamond crude product obtained by the detonation method, the graphite is derived from carbon partially incompletely combusted by an explosive and liberated carbon in which nano-diamond crystals are not formed. For example, after the above-described acid treatment, graphite can be removed from the nanodiamond crude product by allowing a given oxidizing agent to act in, for example, an aqueous solvent (oxidation treatment). Examples of the oxidizing agent used in the oxidation treatment include: sulfuric acid, nitric acid, chromic trioxide, dichromic acid, permanganic acid, and perchloric acid. In the oxidation treatment, one kind of oxidizing agent may be used, or two or more kinds of oxidizing agents may be used. The concentration of the oxidizing agent used in the oxidation treatment is, for example, 3 to 80 mass%. The amount of the oxidizing agent used in the oxidation treatment is, for example, 300 to 500 parts by mass with respect to 100 parts by mass of the nanodiamond crude product to be subjected to the oxidation treatment. The temperature of the oxidation treatment is, for example, 100 to 200 ℃. The oxidation treatment time is, for example, 1 to 50 hours. The oxidation treatment may be carried out under reduced pressure, atmospheric pressure, or under pressure. After such oxidation treatment, the solid component (including the nanodiamond aggregate) is washed with water by, for example, decantation or centrifugal sedimentation. When the supernatant liquid at the beginning of the washing with water is colored, it is preferable to repeat the washing with water of the solid content until the supernatant liquid becomes transparent by visual observation. By repeating the water washing, an electrolyte (NaCl or the like) as an impurity can be reduced or removed. For the nanodiamond particles obtained by the method, a low electrolyte concentration is desirable in terms of achieving high dispersibility and high dispersion stability.
The nanodiamond may also be treated with an alkali solution after such oxidation treatment. By this alkali treatment, an acidic functional group (e.g., a carboxyl group) on the surface of the nanodiamond can be converted into a salt (e.g., a carboxylate salt). The alkali solution to be used may be an aqueous sodium hydroxide solution. In the alkali treatment, the concentration of the alkali solution is, for example, 1 to 50% by mass, the treatment temperature is, for example, 70 to 150 ℃ and the treatment time is, for example, 0.1 to 24 hours. Further, the nanodiamond may be treated with an acid solution after such alkali treatment. By this acid treatment, the salt of the acidic functional group on the surface of the nanodiamond can be restored to a free acidic functional group again. The acid solution to be used may be hydrochloric acid. The acid treatment may be performed at room temperature or under heating. The nanodiamond subjected to the alkali treatment after the oxidation treatment and the acid treatment thereafter is washed with water of a solid component (including a nanodiamond aggregate) by, for example, decantation or centrifugal sedimentation.
In this method, a drying step S3 may be performed next. In this step, for example, a liquid component is evaporated from the nanodiamond-containing solution obtained through the purification step S2 using an evaporator (evaporation, drying, and solidification). The residual solid component generated by such evaporation drying and solidification can be further dried by heat drying in a drying oven. By performing the drying step S3, a powder of the nanodiamond aggregate can be obtained.
In the method, the surface modification step S4 may be performed next. The surface modification step S4 is a step for performing surface modification by bonding a predetermined silane coupling agent to the nanodiamond particles contained in the nanodiamond aggregate obtained as described above, for example. In the surface modification step S4, first, a mixed solution containing, for example, the dried nanodiamond (nanodiamond aggregate) obtained as described above, a silane coupling agent, and a solvent is stirred in a reaction vessel. Next, zirconia beads as a crushing medium were added to the mixed solution in the reaction vessel. The zirconia beads have a diameter of, for example, 15 to 500. Mu.m. Next, the nanodiamond in the solution was subjected to surface modification treatment using an ultrasonic generator equipped with a transducer capable of oscillating an ultrasonic wave. Specifically, the tip of the transducer of the ultrasonic wave generator is inserted into the reaction vessel and immersed in the solution, and the ultrasonic wave is generated by the transducer. The treatment is preferably carried out while the solution to be treated is cooled, for example, in ice water. The treatment time for such surface modification treatment is, for example, 4 to 10 hours. In the solution to be subjected to the present treatment, the content ratio of the nanodiamond is, for example, 0.5 to 5% by mass, and the concentration of the silane coupling agent is, for example, 5 to 40% by mass. As the solvent, for example: tetrahydrofuran, acetone, methyl ethyl ketone, 1-methoxypropanol, methyl isobutyl ketone, isopropanol, or 2-butanol. The mass ratio of the nanodiamond to the silane coupling agent in the solution is, for example, 2 to 1. In the surface modification treatment, cavitation is generated in the solution irradiated with ultrasonic waves due to an acoustic effect, and the zirconia beads in the solution can obtain a very large kinetic energy based on the jet generated when the cavitation (fine bubbles) is broken. Further, the zirconia beads impart impact energy to the nanodiamond aggregate in the same solution, whereby the nanodiamond particles are dispersed (crushed) from the nanodiamond aggregate, and the silane coupling agent reacts with the dissociated nanodiamond particles to form bonds. The bonding is, for example, a covalent bond generated by a dehydration condensation reaction between a silanol group on the silane coupling agent side and a surface hydroxyl group on the nano-diamond particle side. When the silane coupling agent has a hydrolyzable group, a silanol group is formed from the hydrolyzable group even by a slight amount of moisture contained in the reaction system. By the surface modification step S4 described above, surface-modified nanodiamond particles or a dispersion thereof including nanodiamond particles and a silane coupling agent bonded thereto can be produced. When unreacted nanodiamond aggregate is present in the solution after the step, the solution is allowed to stand and the supernatant is collected, whereby a surface-modified nanodiamond particle dispersion having a reduced content of unreacted nanodiamond aggregate can be obtained. The obtained surface-modified nanodiamond particle dispersion liquid may be subjected to a solvent replacement operation for changing the solvent used in the surface modification step S4 to another solvent.
For example, the above-mentioned composition for forming an antireflection layer can be prepared by mixing the surface-modified nanodiamond particle dispersion prepared as described above with the above-mentioned curable resin-forming component, low refractive index particles, and the like.
Examples
[ surface-modified nanodiamond particle ND 1 Preparation of the dispersion of (4)]
A dispersion of surface-modified nanodiamond particles (ND dispersion D1) was prepared by the following procedure.
First, a process of producing nanodiamond by a detonation method is performed. In this step, first, a device for mounting an electric detonator on the molded explosive is installed inside a pressure-resistant container for detonation, and the container is sealed. The container is made of iron and has a volume of 15m 3 . As explosive, 0.50kg of a mixture of TNT and RDX was used. The mass ratio of TNT to RDX (TNT/RDX) in this explosive was 50/50. Is connected withThen, the electric detonator is detonated, and an explosive (generation of nano-diamond by the detonation method) is detonated in the container. Next, the container and the interior thereof were cooled by being left at room temperature for 24 hours. After this natural cooling, the rough nanodiamond product (including the aggregate of the nanodiamond particles generated by the detonation method and the coal) adhered to the inner wall of the container was scraped off with a spatula, and the rough nanodiamond product was recovered.
Next, the acid treatment of the refining step is performed on the nanodiamond raw product obtained by performing the above-described production step a plurality of times. Specifically, a slurry obtained by adding 6L of 10 mass% hydrochloric acid to 200g of the crude nanodiamond product was subjected to a heat treatment under a reflux condition for 1 hour under normal pressure conditions. The heating temperature in the acid treatment is 85-100 ℃. Next, after cooling, water washing of the solid component (including the nanodiamond aggregate and coal) was performed by decantation. The decantation of the solid content was repeated until the pH of the precipitate reached 2 from the lower pH side.
Next, oxidation treatment in the refining step was performed. Specifically, 6L of 98 mass% sulfuric acid and 1L of 69 mass% nitric acid were added to the decanted and acid-treated precipitate (containing nanodiamond aggregate) to prepare a slurry, and then the slurry was subjected to a heating treatment under a reflux condition under normal pressure for 48 hours. The heating temperature in the oxidation treatment is 140 to 160 ℃. Next, after cooling, the solid component (containing the nanodiamond aggregate) was washed with water by decantation. When the supernatant liquid at the beginning of the washing was colored, the washing with the solid content by decantation was repeated until the supernatant liquid became transparent by visual observation.
Next, the precipitate (including the nanodiamond aggregate) obtained by decantation after the oxidation treatment is dried to obtain a dry powder (drying step). As a method of the drying treatment, evaporation, drying and solidification using an evaporator are employed.
Next, a surface modification step was performed. Specifically, first, the nanodiamond obtained through the drying step is subjected to0.30g of the stone powder was weighed into a 50ml sample bottle, and a solution prepared by mixing the nano-diamond powder, 14g of Tetrahydrofuran (THF) as a solvent, and 1.2g of 3- (trimethoxysilyl) propyl acrylate (manufactured by Tokyo chemical Co., ltd.) as a silane coupling agent was stirred for 10 minutes. Then, 34g of zirconia beads (trade name "YTZ", 30 μm in diameter, manufactured by Tosoh corporation) were added to the solution. Next, the mixed solution was subjected to a surface modification treatment using a homogenizer (trade name: ultrasonic disperser UH-600S, manufactured by SMT) as an ultrasonic generator. Specifically, the tip of the transducer of the ultrasonic wave generator was inserted into the reaction vessel, ultrasonic waves were generated by the transducer in a state immersed in the solution, and the mixed solution in the reaction vessel was subjected to ultrasonic treatment for 8 hours while cooling the reaction vessel in ice water. In this treatment, the initially grey solution gradually blackens while increasing transparency. It is considered that this is because the nanodiamond particles gradually disperse (break) from the nanodiamond aggregate, the silane coupling agent reacts with the nanodiamond particles in a dissociated state to form bonds, and the nanodiamond particles thus subjected to surface modification are stabilized in dispersion in the THF solvent. The particle diameter D50 of the nanodiamond dispersion after 8 hours of surface modification treatment was measured by a dynamic light scattering method as described later, and was 15nm. Surface-modified nanodiamond particles (surface-modified nanodiamond particles ND) were produced as described above 1 ) The dispersion of (4).
[ surface-modified nanodiamond particle ND 2 Preparation of the dispersion of (4)]
The same production steps to the drying step as described above with respect to the ND dispersion D1 were performed, and then the following surface modification step was performed to prepare a dispersion of surface-modified nanodiamond particles (ND dispersion D2).
0.30g of the nanodiamond powder obtained through the drying step was weighed into a 50ml sample bottle, and 14g of methyl isobutyl ketone (MIBK) as a solvent and 14g of a silane coupling agent were mixed with the nanodiamond powder0.6g of trimethoxy (methyl) silane (manufactured by Tokyo chemical industry Co., ltd.) and 0.6g of hexadecyl trimethoxy silane (manufactured by Tokyo chemical industry Co., ltd.) were stirred for 10 minutes. Then, 34g of zirconia beads (trade name "YTZ", 30 μm in diameter, manufactured by Tosoh corporation) were added to the solution. Next, the mixed solution was subjected to surface modification treatment using a homogenizer (trade name: ultrasonic disperser UH-600S, manufactured by SMT) as an ultrasonic generator. Specifically, the tip of the transducer of the ultrasonic wave generator was inserted into the reaction vessel, ultrasonic waves were generated by the transducer in a state immersed in the solution, and the mixed solution in the reaction vessel was subjected to ultrasonic treatment for 9 hours while cooling the reaction vessel in ice water. In this treatment, the initially grey solution gradually blackens while increasing transparency. It is considered that this is because the nanodiamond particles gradually disperse (break up) from the nanodiamond aggregate, the silane coupling agent reacts with the dissociated nanodiamond particles to form bonds, and the nanodiamond particles whose surfaces have been modified with an alkyl group are dispersed and stabilized in the MIBK solvent. As described later, the particle diameter D50 of the surface-modified nanodiamond after the surface modification treatment for 9 hours was measured by the dynamic light scattering method, and was 18nm. Surface-modified nanodiamond particles (surface-modified nanodiamond particles ND) were produced in the manner described above 2 ) The dispersion of (4).
[ example 1]
A hard coat layer and an antireflection layer were formed in this order on a substrate as described below, and an antireflection film of example 1 was produced.
[ formation of hard coat layer ]
First, 100 parts by mass of a hexafunctional acrylic UV-curable monomer (trade name "DPHA", manufactured by Daicel Ornex corporation), 33 parts by mass of a trifunctional acrylic UV-curable monomer (trade name "PETIA", manufactured by Daicel Ornex corporation), 0.4 parts by mass of cellulose acetate propionate (trade name "CAP", manufactured by EASTMAN corporation), and 0 part by mass of a fluorine-containing UV-curable compound (trade name "Polyfox3320", manufactured by omniva Solution corporation) were prepared03 parts by mass, 2.7 parts by mass of a photopolymerization initiator (trade name "Irgacure184", manufactured by BASF), 1.3 parts by mass of a photopolymerization initiator (trade name "Irgacure907", manufactured by BASF), 187 parts by mass of methyl ethyl ketone, 31 parts by mass of 1-butanol, and 93 parts by mass of 1-methoxy-2-propanol. Then, the composition for forming a hard coat layer was applied to a 60 μm thick Triacetylcellulose (TAC) FILM (manufactured by FUJI FILM co., ltd.) as a transparent substrate by using a wire bar coater #18 to form a coating FILM, and then the coating FILM was dried at 60 ℃ for 1 minute by using a dryer. Next, the film with a coating film was subjected to an ultraviolet curing treatment using an ultraviolet irradiation apparatus (a high-pressure mercury lamp as a light source, manufactured by USHIO corporation). The ultraviolet irradiation amount was set to 200mJ/cm 2 . Thereby, a hard coat layer (hard coat layer HC) was formed on the TAC film 1 ). Namely, the HC with the hard coat layer was produced 1 The TAC film of (1). Hard coating HC 1 Is about 6 μm thick.
[ formation of antireflection layer ]
Modifying the surface with nano diamond ND 1 The dispersion liquid was allowed to stand for one day and night, and then a supernatant was collected, the supernatant was added dropwise to a mixed solvent of 16ml of toluene and 4ml of hexane (total addition amount was 10 ml), the added mixed solvent was subjected to centrifugal separation treatment (centrifugal force 20000 × g, centrifugal time 10 minutes), and the precipitated solid matter (surface-modified nanodiamond particles ND) was recovered 1 ). Tetrahydrofuran (THF) was added to the solid content thus recovered to prepare surface-modified nanodiamond particles ND 1 The THF solution (solid content concentration: 6.5% by mass) was subjected to ultrasonic treatment for 10 minutes using an ultrasonic treatment apparatus (trade name: ASU-10, manufactured by AS ONE Co., ltd.). For the surface modification nano diamond ND in the THF solution after the ultrasonic treatment 1 The particle diameter D50 was measured by a dynamic light scattering method as described later, and was found to be 12nm. On the other hand, the THF solution (containing 12.73 parts by mass of the solid content of the fluorine-containing curable compound solution) after the ultrasonic treatment was added at a quantitative ratio such that the solid content of the THF solution was 1.82 parts by mass relative to 100 parts by mass of the hollow silica particles in the antireflective coating material and the solid content of the fluorine-containing curable compound solution was 12.73 parts by massNano diamond particle ND with surface modification 1 The solid content concentration was 6.5 mass%), an antireflection coating (trade name "ELCOM P-5062", the content ratio of hollow silica particles as low refractive index particles was 1.65 mass%, the content ratio of a curable resin component was 1.35 mass%, the total solid content concentration was 3 mass%, manufactured by solar chemical co., ltd.), and a fluorine-containing curable compound solution (trade name "KY-1203", a fluorine-containing acrylic compound, the solid content concentration was 20 mass%, manufactured by shin-Etsu chemical co., ltd.) were put in a light-shielding bottle and mixed for 1 hour using a shaker. Thus, the surface-modified nanodiamond ND dispersed was prepared 1 The composition for forming an antireflective layer of (1). Next, the hard coat HC was applied to the above-mentioned tape by using a wire bar coater #4 1 Of TAC film HC 1 The composition for forming an antireflection layer was applied to form a coating film, and then the coating film was dried at 80 ℃ for 1 minute using a dryer. Next, the film with the coating film was subjected to an ultraviolet curing treatment in a nitrogen atmosphere using an ultraviolet irradiation apparatus (a high pressure mercury lamp as a light source, manufactured by USHIO corporation). The ultraviolet irradiation amount was set to 200mJ/cm 2 . Thereby, the belt hard coat HC 1 Of TAC film HC 1 An anti-reflection layer (thickness about 100 nm) is formed thereon. Thus, a film having TAC and a hard coat HC was produced 1 And an antireflection layer (containing both low refractive index particles and surface-modified nanodiamond particles ND) 1 ) The antireflection film of example 1 having a laminated structure of (3).
[ example 2]
In the preparation of the composition for forming an antireflection layer, a THF solution (containing surface-modified nanodiamond particles ND) 1 The solid content of 6.5 mass%) was changed from 1.82 parts by mass to 9.09 parts by mass and the solid content of a fluorine-containing curable compound solution (trade name "KY-1203", manufactured by shin-Etsu chemical industries, ltd.) was changed from 12.73 parts by mass to 13.94 parts by mass based on 100 parts by mass of the hollow silica particles in the antireflection coating (trade name "ELCOM P-5062", manufactured by Nikki chemical industries, ltd.), and in addition thereto, the solid content was changed from 1.82 parts by mass to 9.09 parts by mass based on 100 parts by mass of the hollow silica particles in the antireflection coatingIn example 1, the antireflection film of example 2 was produced in the same manner.
[ example 3]
In the preparation of the composition for forming an antireflection layer, a THF solution (containing surface-modified nanodiamond particles ND) 1 An antireflection film of example 3 was produced in the same manner as in example 1 except that the solid content of the solid content concentration was changed from 1.82 parts by mass to 18.18 parts by mass with respect to 100 parts by mass of the hollow silica particles in the antireflection coating (trade name "ELCOM P-5062", manufactured by hitachi catalytic chemical co., ltd.) and the solid content of the fluorine-containing curable compound solution (trade name "KY-1203", manufactured by shin-Etsu chemical Co., ltd.) was changed from 12.73 parts by mass to 15.15 parts by mass).
[ example 4]
The surface-modified nanodiamond ND was mixed at a ratio of the solid content of the dispersion to 100 parts by mass of the hollow silica particles in the antireflection coating, 9.09 parts by mass, and the solid content of the fluorine-containing curable compound solution, 13.94 parts by mass 2 The dispersion (solid content concentration: 6.5 mass%), an antireflection coating (trade name "ELCOM P-5062", content of hollow silica particles as low refractive index particles: 1.65 mass%, content of curable resin component: 1.35 mass%, total solid content concentration: 3 mass%, manufactured by solar chemical corporation), and a fluorine-containing curable compound solution (trade name "KY-1203", fluorine-containing acrylic compound, solid content concentration: 20 mass%, manufactured by shin-Etsu chemical Co., ltd.) were put in a light-shielding bottle and mixed for 1 hour using a shaker. Thus, the surface-modified nanodiamond ND dispersed therein was prepared 2 The composition for forming an antireflection layer of (1). Next, the hard coat HC was applied to the above-mentioned coated film using a wire bar coater #4 1 Of TAC film HC 1 The composition for forming an antireflection layer was applied to form a coating film, and the coating film was dried at 80 ℃ for 1 minute using a dryer. Next, the film with the coating film was subjected to a nitrogen atmosphere using an ultraviolet irradiation apparatus (high pressure mercury lamp as a light source, manufactured by USHIO Co., ltd.)Ultraviolet curing treatment in (1). The ultraviolet irradiation amount was set to 200mJ/cm 2 . Thereby, the belt hard coat HC 1 Of TAC film HC 1 On which an anti-reflection layer (thickness of about 100 nm) is formed. Thus, a film having TAC and a hard coat HC was produced 1 And an antireflection layer (containing both low refractive index particles and surface-modified nanodiamond particles ND) 2 ) The antireflection film of example 4 having a laminated structure of (3).
[ example 5]
A hard coat layer and an antireflection layer were formed in this order on a substrate as described below, and an antireflection film of example 5 was produced.
[ formation of hard coat layer ]
First, a hard coat layer-forming composition containing 100 parts by mass of an acrylic UV curable monomer (trade name "NSX-401M", manufactured by kyoho chemical corporation, containing a photopolymerization initiator) in which zirconia was dispersed, 117 parts by mass of methyl ethyl ketone, 23 parts by mass of 1-butanol, and 82 parts by mass of 1-methoxy-2-propanol was prepared. Then, the composition for forming a hard coat layer was applied to a 60 μm thick Triacetylcellulose (TAC) FILM (manufactured by FUJI FILM co., ltd.) as a transparent substrate by using a wire bar coater #18 to form a coating FILM, and then the coating FILM was dried at 60 ℃ for 1 minute by using a dryer. Next, the film with a coating film was subjected to an ultraviolet curing treatment using an ultraviolet irradiation apparatus (a high-pressure mercury lamp as a light source, manufactured by USHIO corporation). The ultraviolet irradiation amount was set to 200mJ/cm 2 . Thereby, a hard coat layer (hard coat layer HC) was formed on the TAC film 2 ). Namely, the HC with the hard coat layer was produced 2 The TAC film of (1). Hard coating HC 2 Is about 6 μm thick.
[ formation of antireflection layer ]
The antireflective coating (trade name "ELCOM P-5062", the content of hollow silica particles as low refractive index particles is 1.65 mass%, the content of curable resin component is 1.35 mass%, and the total solid content concentration is 3 parts by mass, in such a quantity ratio that the solid content of Thrulya 4320 is 27.80 parts by mass and IPA is 798 parts by mass with respect to 100 parts by mass of hollow silica particles in the antireflective coatingAmount%, manufactured by solar volatile catalytic chemical corporation), a dispersion of hollow silica particles as low refractive index particles (trade name "thruya 4320", the content ratio or solid content concentration of the hollow silica particles is 20% by mass, manufactured by solar volatile catalytic chemical corporation), and isopropyl alcohol (IPA) were mixed. The content of the hollow silica particles in the mixed solution was 1.83 mass%, the content of the curable resin component was 1.17 mass%, and the total solid content concentration was 3 mass%. Then, the mixed solution and the nanodiamond-containing THF solution (containing surface-modified nanodiamond particles ND) after the ultrasonic treatment in example 1 were mixed at a ratio of 4.92 parts by mass of the solid content of the THF solution to 127.8 parts by mass of the hollow silica particles in the mixed solution described below and 10.38 parts by mass of the solid content of the fluorine-containing curable compound solution 1 The solid content concentration was 6.5 mass%), and a fluorine-containing curable compound solution (trade name "KY-1203", a fluorine-containing acrylic compound, a solid content concentration of 20 mass%, manufactured by shin-Etsu chemical Co., ltd.) were put into a light-shielding bottle and mixed for 1 hour using a shaker. Thus, the surface-modified nanodiamond ND dispersed therein was prepared 1 The composition for forming an antireflection layer of (1). Next, the hard coat HC was applied to the above-mentioned tape by using a wire bar coater #4 2 Of TAC film HC 2 The composition for forming an antireflection layer was applied to form a coating film, and the coating film was dried at 80 ℃ for 1 minute using a dryer. Next, the film with the coating film was subjected to an ultraviolet curing treatment in a nitrogen atmosphere using an ultraviolet irradiation apparatus (a high pressure mercury lamp as a light source, manufactured by USHIO corporation). The ultraviolet irradiation amount was set to 200mJ/cm 2 . Thereby, the belt hard coat HC 2 Of TAC film HC 2 On which an anti-reflection layer (thickness of about 100 nm) is formed. Thus, a film having TAC and a hard coat HC was produced 2 And an antireflection layer (containing both low refractive index particles and surface-modified nanodiamond particles ND) 1 ) The antireflection film of example 5 having a laminated structure of (3).
Comparative example 1
An antireflection film of comparative example 1 was produced in the same manner as in example 1, except that a nanodiamond-containing THF solution was not used, and the amount of solid content of the fluorine-containing curable compound solution (trade name "KY-1203", manufactured by shin-Etsu chemical Co., ltd.) was changed from 12.73 parts by mass to 12.12 parts by mass with respect to 100 parts by mass of the hollow silica particles in the antireflection coating (trade name "ELCOM P-5062", manufactured by Nissan chemical Co., ltd.).
Measurement of particle diameter D50
The particle diameter D50 of the surface-modified nanodiamond particles contained in the surface-modified nanodiamond particle dispersion was a particle diameter at a cumulative value of 50% obtained from a particle size distribution measured by a dynamic light scattering method (non-contact back scattering method) using a device manufactured by Malvern corporation (trade name "Zetasizer Nano ZS").
Total light transmittance
The antireflection films of examples 1 to 5 and comparative example 1 were measured for total light transmittance (%) using a total light transmittance measuring apparatus (trade name "NDH-5000W", manufactured by Nippon Denshoku industries Co., ltd.). This measurement was performed in accordance with JIS K7105. The results are shown in table 1.
Haze
The anti-reflection films of examples 1 to 5 and comparative example 1 were measured for haze (%) using a haze measuring apparatus (trade name "NDH-5000W", manufactured by Nippon Denshoku industries Co., ltd.). This measurement was carried out according to JIS K7136. The results are shown in table 1.
Luminous reflectance
In each of the anti-reflection films of examples 1 to 5 and comparative example 1, OCA (optically transparent adhesive material) was bonded to the surface opposite to the anti-reflection layer to form an adhesive surface, and a black acrylic plate was bonded to the adhesive surface to prepare a sample for measurement. Then, the light emission reflectance (%) was measured with a reflection spectrophotometer (trade name "UH-3900", manufactured by Hitachi High-Tech Co., ltd.) on the side of the antireflection layer of each of the measurement samples prepared from the antireflection films of examples 1 to 5 and comparative example 1. This measurement was performed according to JIS Z8701. The results are shown in table 1.
"scratch resistance
The anti-scratch property of the anti-reflection films of examples 1 to 5 and comparative example 1 was examined using an anti-scratch property tester and steel wool #0000 (manufactured by japan steel wool corporation) as a friction material reciprocating on a test object surface. In this test, the test environment was 23 ℃ and 50% RH, the moving length of the friction material on the surface to be tested was 10cm, and the load of the friction material on the surface to be tested was 200g/cm 2 The number of times of reciprocating motion of the friction material with respect to the test object surface was 1000. In this test, the entire back surface of each film subjected to the rubbing operation under the above-described conditions was coated with a black marker, and then the degree of scratching of the rubbed portion on the side surface of the anti-reflection layer was visually observed by reflected light. Then, the abrasion resistance of the surface on the side of the anti-reflection layer of each of the anti-reflection films of examples 1 to 5 and comparative example 1 was evaluated based on the following evaluation criteria: a case where no scratch was found even when carefully observed was evaluated as excellent (. Circleincircle.); the case where 5 or less scratches were observed when carefully observed was evaluated as good (. Smallcircle.); and, a case where a scar was clearly observed was evaluated as poor (x). The results are shown in table 1.
[ evaluation ]
The anti-reflective films of examples 1 to 5 all showed a total light transmittance of 94.9% or more, a haze of 0.8% or less, and a luminous reflectance of 1.3% or less, and also showed excellent scratch resistance.
As a summary of the above, the configuration of the present invention and its modifications are described below.
[ additional notes 1]
An antireflection film having a laminated structure comprising a substrate, an antireflection layer, and a hard coat layer located between the substrate and the antireflection layer,
the antireflection layer includes a curable resin, low refractive index particles, and nanodiamond particles.
[ additional notes 2]
The antireflection film according to supplementary note 1, wherein,
the anti-reflective layer further contains a fluorine-containing curable compound.
[ additional notes 3]
The antireflection film according to supplementary note 1 or 2, wherein,
the nano-diamond particles are surface-modified nano-diamond particles with a silane coupling agent.
[ additional notes 4]
The antireflection film according to supplementary note 3, wherein,
the silane coupling agent is bonded to the nanodiamond particles, and has an organic chain containing a (meth) acryloyl group.
[ additional notes 5]
The antireflection film according to supplementary note 4, wherein,
the (meth) acryloyl group is propyl acrylate and/or propyl methacrylate.
[ additional notes 6]
The antireflection film according to supplementary note 3, wherein,
the silane coupling agent is bonded to the nanodiamond particles and has an organic chain containing an alkyl group.
[ supplement 7]
The antireflection film according to supplementary note 6, wherein,
the alkyl group has 1 to 18 carbon atoms.
[ additional notes 8]
The antireflection film according to supplementary note 7, wherein,
the alkyl group is a methyl group.
[ appendix 9]
The antireflection film according to any one of supplementary notes 1 to 8, wherein,
the particle diameter D50 of the nano-diamond particles is 100nm or less or 30nm or less.
[ appendix 10]
The antireflection film according to any one of supplementary notes 1 to 9, wherein,
the low refractive index particles are hollow silica particles.
[ appendix 11]
The antireflection film according to any one of supplementary notes 1 to 10, wherein,
the low refractive index particles have an average particle diameter of 50 to 70nm.
[ appendix 12]
The antireflection film according to any one of supplementary notes 1 to 11, wherein,
the mass ratio of the low refractive index particles to the nanodiamond particles in the antireflection layer is in a range from 99 to 84.
[ supplement note 13]
The antireflection film according to any one of supplementary notes 1 to 12, wherein,
the curable resin is a polymer of a (meth) acryloyl group-containing compound.
[ supplementary notes 14]
The antireflection film according to any one of supplementary notes 1 to 13, which has a haze of 1.0% or less, 0.8% or less, 0.6% or less, 0.4% or less, or 0.2% or less.
[ supplement character 15]
The antireflection film according to any one of supplementary notes 1 to 14, wherein,
the light emission reflectance on the side of the anti-reflection layer is in the range of 0.5 to 2.0%, 0.5 to 1.7%, or 0.5 to 1.5%.
Claims (14)
1. An antireflection film having a laminated structure comprising a substrate, an antireflection layer, and a hard coat layer located between the substrate and the antireflection layer,
the antireflection layer contains a curable resin, low-refractive-index particles, and nanodiamond particles, and the mass ratio of the low-refractive-index particles to the nanodiamond particles in the antireflection layer is in the range of 99 to 84,
the content of the nano-diamond particles is 0.1 to 15 mass%.
2. The antireflection film according to claim 1,
the antireflection layer further contains a fluorine-containing curable compound.
3. The antireflection film according to claim 1 or 2,
the nano-diamond particles are surface-modified nano-diamond particles with a silane coupling agent.
4. The antireflection film according to claim 3,
the silane coupling agent is bonded to the nanodiamond particles and has an organic chain containing a (meth) acryloyl group.
5. The antireflection film according to claim 4,
the (meth) acryloyl group is propyl acrylate and/or propyl methacrylate.
6. The antireflection film according to claim 3,
the silane coupling agent is bonded to the nanodiamond particles and has an organic chain containing an alkyl group.
7. The antireflection film according to claim 6,
the alkyl group has 1 to 18 carbon atoms.
8. The antireflection film according to claim 7,
the alkyl group is a methyl group.
9. The antireflection film according to any one of claims 1 to 8,
the particle diameter D50 of the nano-diamond particles is less than or equal to 30 nm.
10. The antireflection film according to any one of claims 1 to 9,
the low refractive index particles are hollow silica particles.
11. The antireflection film according to any one of claims 1 to 10,
the low refractive index particles have an average particle diameter of 50 to 70nm.
12. The antireflection film according to any one of claims 1 to 11,
the curable resin is a polymer of a (meth) acryloyl group-containing compound.
13. The antireflection film according to any one of claims 1 to 12, having a haze of 1.0% or less.
14. The antireflection film according to any one of claims 1 to 13,
the light emission reflectance on the anti-reflection layer side is in the range of 0.5 to 2.0%.
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| JP2017-172771 | 2017-09-08 | ||
| JP2017172771 | 2017-09-08 | ||
| JP2018020018A JP6636069B2 (en) | 2017-09-08 | 2018-02-07 | Anti-reflection film |
| JP2018-020018 | 2018-02-07 | ||
| JP2018020017A JP7224106B2 (en) | 2017-09-08 | 2018-02-07 | anti-reflection film |
| CN201880057999.XA CN111051930A (en) | 2017-09-08 | 2018-08-06 | Anti-reflection film |
| PCT/JP2018/029480 WO2019049578A1 (en) | 2017-09-08 | 2018-08-06 | Anti-reflection film |
| JP2018-020017 | 2018-09-13 |
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| CN1908700A (en) * | 2005-08-03 | 2007-02-07 | 富士胶片株式会社 | Antireflection film, polarizing plate, and image display device |
| JP2007163754A (en) * | 2005-12-13 | 2007-06-28 | Sekisui Chem Co Ltd | Coating agent for antireflection and antireflection film |
| CN101341427A (en) * | 2006-08-14 | 2009-01-07 | 大日本印刷株式会社 | Anti-dazzling optical laminate |
| CN101581801A (en) * | 2008-05-14 | 2009-11-18 | 东丽世韩有限公司 | Anti-reflection membrane with exellent scratch resistance property and surface sliding property |
| CN102736138A (en) * | 2011-03-30 | 2012-10-17 | 株式会社腾龙 | Antireflection film and optical device |
| CN103460079A (en) * | 2011-04-26 | 2013-12-18 | 大日本印刷株式会社 | Antireflection film, polarizing plate, and image display device |
| CN103765249A (en) * | 2011-05-16 | 2014-04-30 | 大日本印刷株式会社 | Method for producing antireflection film, antireflection film, polarizing plate, and image display device |
| CN103185905A (en) * | 2011-12-28 | 2013-07-03 | 株式会社腾龙 | Anti-reflection film and optical element |
| JP2015043046A (en) * | 2013-08-26 | 2015-03-05 | コニカミノルタ株式会社 | Optical reflection film and optical reflector using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2019049578A1 (en) | 2019-03-14 |
| WO2019049579A1 (en) | 2019-03-14 |
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