AU726633B2 - Transparent photochromic article including an anti-reflection surface coating - Google Patents
Transparent photochromic article including an anti-reflection surface coating Download PDFInfo
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- AU726633B2 AU726633B2 AU20785/00A AU2078500A AU726633B2 AU 726633 B2 AU726633 B2 AU 726633B2 AU 20785/00 A AU20785/00 A AU 20785/00A AU 2078500 A AU2078500 A AU 2078500A AU 726633 B2 AU726633 B2 AU 726633B2
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- photochromic article
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- 230000003287 optical effect Effects 0.000 claims description 28
- 239000011521 glass Substances 0.000 claims description 18
- 239000004033 plastic Substances 0.000 claims description 6
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
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- 229910006404 SnO 2 Inorganic materials 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
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- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical class FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
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- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims 2
- 229910052759 nickel Inorganic materials 0.000 claims 1
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- 238000000034 method Methods 0.000 description 10
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- 239000010936 titanium Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 4
- 125000003003 spiro group Chemical group 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
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- -1 silver halides Chemical class 0.000 description 3
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- JPRAEFWJEBKFCB-UHFFFAOYSA-N 2-nitro-9h-fluoren-3-amine Chemical compound C1=CC=C2C(C=C(C(=C3)[N+]([O-])=O)N)=C3CC2=C1 JPRAEFWJEBKFCB-UHFFFAOYSA-N 0.000 description 1
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 description 1
- YHWMFDLNZGIJSD-UHFFFAOYSA-N 2h-1,4-oxazine Chemical compound C1OC=CN=C1 YHWMFDLNZGIJSD-UHFFFAOYSA-N 0.000 description 1
- SDDAKNLNDQKPHE-UHFFFAOYSA-N 3',3'-dimethyl-1'-(2-methylpropyl)-6-piperidin-1-ylspiro[benzo[f][1,4]benzoxazine-3,2'-indole] Chemical compound CC(C)CN1C2=CC=CC=C2C(C)(C)C1(C=NC1=C2C=CC=CC2=2)OC1=CC=2N1CCCCC1 SDDAKNLNDQKPHE-UHFFFAOYSA-N 0.000 description 1
- XMIOCDZWGCXLIO-UHFFFAOYSA-N 3h-benzo[f][1,4]benzoxazine Chemical compound C1=CC=CC2=C(N=CCO3)C3=CC=C21 XMIOCDZWGCXLIO-UHFFFAOYSA-N 0.000 description 1
- VCMLCMCXCRBSQO-UHFFFAOYSA-N 3h-benzo[f]chromene Chemical compound C1=CC=CC2=C(C=CCO3)C3=CC=C21 VCMLCMCXCRBSQO-UHFFFAOYSA-N 0.000 description 1
- TUZVQTLSJYAYJK-UHFFFAOYSA-N 5-(2-chlorophenyl)-2,4-diphenyl-1h-imidazole Chemical compound ClC1=CC=CC=C1C1=C(C=2C=CC=CC=2)N=C(C=2C=CC=CC=2)N1 TUZVQTLSJYAYJK-UHFFFAOYSA-N 0.000 description 1
- KYNSBQPICQTCGU-UHFFFAOYSA-N Benzopyrane Chemical compound C1=CC=C2C=CCOC2=C1 KYNSBQPICQTCGU-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- IHGJSFNTBXIZGU-UHFFFAOYSA-N C1CCCCC12NC1=C(N2)C(C2=CC3=CC=CC(C3=CC2=C1)=O)=O.C1CCCCC12NC1=C(N2)C=C2C(C3=CC=CC=C3C(C2=C1)=O)=O Chemical compound C1CCCCC12NC1=C(N2)C(C2=CC3=CC=CC(C3=CC2=C1)=O)=O.C1CCCCC12NC1=C(N2)C=C2C(C3=CC=CC=C3C(C2=C1)=O)=O IHGJSFNTBXIZGU-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000675108 Citrus tangerina Species 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000006117 anti-reflective coating Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- SYFOAKAXGNMQAX-UHFFFAOYSA-N bis(prop-2-enyl) carbonate;2-(2-hydroxyethoxy)ethanol Chemical compound OCCOCCO.C=CCOC(=O)OCC=C SYFOAKAXGNMQAX-UHFFFAOYSA-N 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 150000008371 chromenes Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000005331 crown glasses (windows) Substances 0.000 description 1
- VDBXLXRWMYNMHL-UHFFFAOYSA-N decanediamide Chemical compound NC(=O)CCCCCCCCC(N)=O VDBXLXRWMYNMHL-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000013532 laser treatment Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 150000004880 oxines Chemical class 0.000 description 1
- 230000003711 photoprotective effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- KEBGPKSJAISGLV-UHFFFAOYSA-N spiro[benzo[f][1,4]benzoxazine-3,2'-indole] Chemical compound C1=C2C=CC=CC2=NC21C=NC1=C3C=CC=CC3=CC=C1O2 KEBGPKSJAISGLV-UHFFFAOYSA-N 0.000 description 1
- JFLHVURVKPJADI-UHFFFAOYSA-N spiro[chromene-2,9'-xanthene] Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11C=CC2=CC=CC=C2O1 JFLHVURVKPJADI-UHFFFAOYSA-N 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
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- 238000002834 transmittance Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
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- Eyeglasses (AREA)
Description
AUSTRALIA
Patents Act COMPLETE
SPECIFICATION
(ORIGINAL)
Application Number: Class Int. Class Lodged: Complete Specification Lodged: Accepted: Published: Priority Related Art: Name of Applicant: SSola International Holdings Ltd Actual Inventor(s): FABRIZIO ANDREANI, LINO BARBIERI Address for Service: PHILLIPS ORMONDE
FITZPATRICK
Patent and Trade Mark Attorneys 367 Collins Street Melbourne 3000 AUSTRALIA Invention Title: TRANSPARENT PHOTOCHROMIC ARTICLE INCLUDING AN ANTI-REFLECTION
SURFACE
COATING
Our Ref: 610941 POF Code: 257506/44727 The following statement is a full description of this invention, including the best method of performing it known to applicant(s): 1 -2- TRANSPARENT PHOTOCHROMIC ARTICLE INCLUDING
AN
ANTI-REFLECTION SURFACE
COATING
The present application is a divisional application from Australian patent application number 15368/97, the entire disclosure of which is incorporated herein by reference.
The present invention relates to transparent photochromic articles having anti-reflection surface coatings.
The transparent articles according to the present invention are preferably employed in the preparation of articles such as optical lenses, including spectacle lenses, ophthalmic or not, visors, shields, glass sheets, protective screens, and the like.
A well known difficulty of long standing in the art and in particular in the o. production of spectacle lenses, has been the dilemma of trying to achieve very good light transmission in the visible region (wavelength 400 to 700 nm), whilst adequately protecting the eye from harmful light transmission, in particular from ultraviolet (UV) rays.
o• a The prior art suggests that the characteristics of transmission of light through an article are improved by applying an anti-reflection coating, generally including a plurality of thin layers of suitable materials, respectively of a low and high index of refraction, which increase the transmission in the range of the visible radiation whilst simultaneously reducing the quantity of light reflected from the substrate.
To adequately protect the eye from solar radiation, the prior art suggests instead incorporating into the substrate, either internally or on the surface, one or more so called photochromic compounds which are able to -3- "darken" the substrate to reduce the transmission whenever they are activated from solar radiation in the UV range (350 to 400 nm approx.).
In fact, in their "activated" state such compounds pass from colourless to coloured effectively filtering light at a wavelength corresponding to visible light (approximately 400 to 700 nm).
All the attempts carried out in the prior art to obtain a photochromic substrate having an anti-reflection surface coating, have however, up to now, inevitably encountered the unavoidable effect of reflecting or absorbing light *impinging upon the article in the UV range (the photochromic activity region) and thus causing the article not to darken as much as normally required.
0 0. 00 Accordingly, it remains a deficiency of the prior art to provide a transparent article which includes an anti-reflection surface coating that 00"simultaneously provides adequate transmission of visible light and adequate 00*°o characteristics of photochromaticity when it becomes illuminated by sun light.
V*.0.
000Accordingly, it is an object of the present invention to overcome, or at least alleviate, one or more of the difficulties related to the prior art.
0. 00 In accordance with the present invention, it has been found that these desired characteristics may be simultaneously achieved by suitably combining the optical thickness of the layers forming the anti-reflection coating.
Accordingly, in a first aspect of the present invention there is provided a transparent photochromic article including a transparent substrate including a photochromic material; and an anti-reflection surface coating produced with a plurality of overlapping layers incorporating, alternatively a first and a second material having respectively higher and lower refractive indices, the anti-reflection coating including -4a first layer including said first material having an optical thickness of to 40 nm; a second layer including said second material having an optical thickness 40 to 55 nm; a third layer including said first material having an optical thickness of to 85 nm; a fourth layer including said second material having an optical thickness to 45 nm; a fifth layer including said first material having an optical thickness of to 65 nm; and a sixth layer including said second material having an optical thickness of 110 to 135 nm.
*eo As used herein, by the term "transparent substrate", we mean any form of transparent substrate, whether it be of glass or of plastic material.
As used herein, by the term "photochromic material" we mean a material that is able to reduce the quantity of the light transmitted by the S• substrate when exposed to solar radiation.
As used herein, by the term "optical thickness" we mean the thickness obtained by multiplying the physical thickness of the layer by the refractive index of the material forming the same layer, measured at a wavelength
(X)
of 500 nm.
The discussion of documents, acts, materials, devices, articles and the like is included in this specification solely for the purpose of providing a context for the present invention. It is not suggested or represented that any or all of these matters formed part of the prior art base or were common general knowledge in the field relevant to the present invention as it existed in Australia before the priority date of each claim of this application.
After repeated tests, the Applicants have found that when the layers of the anti-reflection coating have an optical thickness which falls within the above mentioned ranges, the reflection of the incident radiation on the substrate is minimal in the wavelength range required to activate the photochromic mixtures incorporated in, or deposited on, the substrate (approximately 350 to 400 nm) and sufficiently reduced in the visible range (approximately 400 to 700 nm), so as to simultaneously provide adequate transmission and photochromaticity for the substrate.
In fact, in contradistinction to what has been taught in the prior art the Applicants have found that the mean reflectance at the external surface of the article in the UV range as a function of wavelength is not limited to greater than 4% of the incident radiation, and may be noticeably reduced and preferably is less than approximately 1% of the incident radiation.
.As a consequence, the layers described in the present invention not aonly perform an efficient photoprotection action when exposed to solar .radiation, but also present excellent characteristics of transmission of the light in S.non-activating radiation surroundings, i.e. in surroundings in which the article will tend to resume its unactivated state characteristics.
~In accordance with the present invention, it has also been found that the same type of positive results may be achieved by varying the number of layers of the anti-reflection coating (and, that is, with a different optical structure), provided that the total optical thickness is maintained in the range of approximately 10% of the four coating layers described above.
The photochromic materials according to these aspects of the present invention may be selected from one or more of the group consisting of silver halides including mixed silver halides, anthraquinones, phthalocyanines, spirooxazines, chromenes, pyrans including spiro-pyrans and fulgides. The photochromic materials may be incorporated into the monomer formulation -6used to produce a polymer substrate layer or in the glass formulation used to produce a glass substrate or in coatings applied to substrates prior to the application of abrasion resistant or anti-reflective coatings.
Examples of preferred photochromic dyes may be selected from one or more of the group consisting of 1 ,3-dihydrospiro[2H-anthra[2,3-d]imidazole-2, 1 '-cyclohexane]-5, 1 0-dione 1 ,3-dihydrospiro[2H-anthra[2,3-d]imidazole-2, 1'-cyclohexane]-6, 11 -dione 1 ,3-dihydro 4(phenylthio)spiro[2H-anthra' 1 2-diimidazole-2, 1 -cyclohexane]6, 1 -dione 1 ,3-dihydrospiro[2-H-anthra[1 ,2-d]imidazole-2, 1 '-cycloheptane]-6, 11 -dione 1 ,3,3-tri methylspi ro'i ndole-2,3'-[3 H] nap htho[2, 1 ,4-oxazine] 2-methyl-3,3'-spiro-bi-[3H-naphtho[2,1 -b]pyran] (2-Me) e 2-phenyl-3-methyl-7-methoxy-8'-nitrospiro[4H- 1 -benzopyran-4,3'-[3H] oo. 15 naphtho][2, 1 -b]pyran Spiro[2H-1 -benzopyran-2,9'-xanthene] 9 8-methoxy-1 ',3'-dimethylspiro(2H-1 -benzopyran-2,2'-(1 'H)quinoline 2,2'-Spiro-bi-[2H-1 -benzopyran] e 5'-amino-l1',3',3'-trimethylspiro[2H- 1 -benzopyran-2,2'-indoline o Ethyl-f3-methyl-1-(3',3'-dimethyl-6-nitrospiro(2H-1 -benzopyran-2,2'-indolin-1' yl)-propenoate (1 ,3-propanedlyl)bis[3',3'-dimethyl-6-nitrospiro[2H-1 -benzopyran-2,2'indoline] 3,3'-dimethyl-6-nitrospiro[2H-1 -benzopyrao-2,2'-benzoxazoline] 6'-methylthio-3,3'-dimethyl-8-methoxy-6-nitrospiro[2H-1 -benzopyran-2,2'benzothiozoline] (1 ,2-ethanediyl)bis[8-methoxy-3-methyl-6-nitrospiro[2H-1 -benzopyran-2-2'benzothiozolinej N-N'-bis(3,3'-dimethyl-6-nitrospiro[2H- 1 -benzopyran-2,2'(3'H)-benzothioazol- 6'-yl)decanediamide -aX-(2,5-dimethyl-3-furyl)thylidene(Z)-ethylidenesuccinic anhydride; dimethyl-3-furyl) -a',8-dimethylfulgide 2 ,5-diphenyl-4-(2'-chlorophenyl)imidazole *[(2',4'-dinitrophenyl)methyljl1 H-benzimidazole *N-N-diethyl-2-phenyl..2H-.phenanthro[9, 1 0-d]imidazol-2-amine 2 -nitro-3-aminofluorene *2-amino-4-(2'-furanyl)-6H-1,3-thiazine-6-thione 3 3 -di( 4 -methoxyphenyl)..6-morpholino.3H-nfaphtho[ 2 1 -bipyran (Reversacol Corn Yellow) 3 3 -di( 4 -methoxyphenyl)3H-naphtho[2,1 -bjpyran (Reversacol Tangerine) 2 2 -di( 4 -methoxyphenyl)-5,6-dimethyl.2H-naphtho[2, 1 -blpyran (Reversacol l1 Berry Red) 0 1, 3-dihyd ro-3,3-d imethyl. 1l-isob utyl-spiro[2 H-indole-2,3'-[3 H] nap hth[2, 1b][1 ,4]oxazine] (Reversacol Oxford Blue) 0 1 ,3-dihydro-3,3-trimethyl-. l-neopentyl-6'-(4-diethylaminophenyl)spiro[2H- 'ndole-2,3'-[3Hjnaphth[2, 1-bloxazine] (Reversacol Sea Green) o 1 ,3-dihydro-3,3-dimethyll1 -isobutyl-6'-(4-diethylaminophenyl)spiro[2Hindole-2,3'-[3H]naphth[2,1 -bl[1 ,4]oxazine] (Reversacol Aqua Green) 1 ,3-dihydro-3,3-dimethyl-1 isobutyl-6'-indolino spiro[2H-indole-2,3'-[3H] naphth[2, 1-b][1 ,4]oxazine] (Reversacol Flat Purple) 1 ,3-dihydro-3,3-dimethyll-(2-phenylpropyl)-6'-indolino spiro[2H-indole-2,3'- 20 [3Hlnaphth[2,1-b][1 ,4]oxazine] (Reversacol Storm Purple) 1 ,3-dihydro-3,3-dimethyl-1 isobutyl-6'-piperidino spiro[2H-indole-2,3'-[3H] naphth[2, 1-b][1 ,4]oxazine] (Reversacol Plum Red) 0 1 3 -dihydro-5-chloro-3,3-dimethyl-1 isobutyl-6'-pipe rid ino spiro[2H-indole- 2,3'-[3H]naphth[2, 1 ,4]oxazine] (Reversacol Claret) In a preferred aspect, one or both surfaces of the photochromic substrate may be subjected to a surface treatment to improve bondability and/or compatibility. The surface treatment may be selected from one or more of the group consisting of plasma discharge, corona discharge, glow discharge, ionising radiation, UV radiation, flame treatment and laser, preferably excimer laser treatment. The surface treatment, alternatively or in addition, may include incorporating another bonding layer, for example a layer including a metal or metal compound selected from the group consisting of one or more of Chromium, Nickel, Tin, Palladium, Silicon, and/or oxides thereof.
The transparent substrate according to these aspects of the present invention may include any transparent element of glass having a refractive index, measured at 500 nm of approximately 1.5 to 1.9 such as Crown glass (n=1.523), barium glass titanium glass and lanthanum glass (n=1.8 and and in general any type of commonly used glass utilised for optical application.
9Alternatively, the transparent substrate may include any transparent element of plastic material having a refractive index of approximately 1.5 and 1.7.
Preferably, said plastic material is chosen from the group; polymer and copolymer with acrylic base, polymethylmethacrylate, polycarbonate, polyol-allylcarbonate, esters of the cellulose, polyacrylate, polyvinyls, polystyrene, polyurethane and sulfur-containing materials, including thioacrylates and the like.
A diethyleneglycol-bis-allyl-carbonate commercially available under the denomination of CR 3 9TM (PPG Industries Inc.), commonly used for the production of lenses, ophthalmic or not, for spectacles has been found to be suitable.
The transparent substrate may be formed from cross-linkable polymeric casting compositions, for example as described in the Applicants United States Patent 4,912,155, United States Patent Application No. 07/781,392, Australian Patent Applications 50581/93 and 50582/93, and European Patent Specification 453159A2, the entire disclosures of which are incorporated herein by reference.
-9- For example, in Australian Patent Application 81216/87, the entire disclosure of which is incorporated herein by reference, the Applicant describes a cross-linkable casting composition including at least polyoxyalkylene glycol diacrylate or dimethacrylate and at least one poly functional unsaturated crosslinking agent.
Further, in Australian Patent Application 75160/91, the entire disclosure of which is incorporated herein by reference, the Applicants describe a polyoxyalkylene glycol diacrylate or dimethacrylate; a monomer including a recurring unit derived from at least one radical-polymerisable bisphenol S-monomer capable of forming a homopolymer having a high refractive index of more than 1.55; and a urethane monomer having 2 to 6 terminal groups selected from a group comprising acrylic and methacrylic groups.
The range of optical lenses sold under the trade designation "Spectralite" by the Applicants have been found to be suitable.
The plastic material may include a photochromic dye which may, for example, be added to the monomer formulation used to produce the polymeric material. The variation in depth of colour may be minimised by incorporating a pigment or dye into one or more layers of the optical article.
Accordingly the transparent substrate may be of the type described in Intemational Patent Application PCT/AU96/00704 and PCT/AU96/00705 "Light Transmissible Articles with Colour Enhancing Properties" and "Light Transmissible Article with Reduced Ultraviolet Transmission", respectively to the Applicants, the entire disclosures of which are incorporated herein by reference.
The front and/or rear lens surfaces may include an abrasion resistant coating. e.g. of the type described in United States Patent 4,954,591 to the Applicants, the entire disclosure of which is incorporated herein by reference.
The front and/or rear lens surfaces may further include one or more additions conventionally used in casting compositions such as inhibitors, dyes including thermochromic and photochromic dyes, e.g. as described above, polarising agents, UV stabilisers and materials capable of modifying refractive index.
As stated above, the anti-reflection coating is formed from a first and second material in alternating layers.
S Preferably, the above mentioned first material, has a refractive index of approximately 1.6 to 2.5 and even more favourably, between approximately 1.95 and 2.4.
The first material may be selected from the group which includes: TiO 2 Ti 2 03, Ti 3 0 5 Pr 6
O
11 ,+xTiO 2 CeO 2 HfO 2 Ta 2 0s, ZrO 2 SnO 2 Preferably, the above mentioned second material, has a refractive index of approximately 1.30 to 1.48 and even more favourably, between approximately 1.38 to 1.48.
The second material may be selected from the group which includes: SiO 2 MgF 2
AIF
3 BaF 2 Na 5
A
3
F
4 Na 3
AIF
6 YF3 and fluorocarbon compounds such as Teflon and the like.
Preferably, the anti-reflection coating further includes an intermediate layer of a material, between the substrate and the first layer of the coating.
Advantageously, the intermediate layer has the double function of giving to the substrate adequate characteristics of resistance to scratches and to guarantee an adequate adhesion of the subsequent thin layers that form the antireflection coating.
-11- Preferably, the intermediate layer material has a refractive index lower than that of the substrate, for example approximately 1.38 to 1.48.
Furthermore and preferably, the intermediate layer has an optical thickness of approximately 200 to 300 nm and may be substantially made from SiO 2 Alternatively, to improve the characteristics of adhesion it is possible to use a thin intermediate layer of a material chosen from metals or oxides of Cr, *Ti, Sn, Pd and Si and having an optical thickness of approximately 1 to 5 nm.
Due to the limited thickness of this intermediate layer, the materials do not substantially compromise the optical performance of the anti-reflection coating applied to the substrate even though it has a high light absorption coefficient.
555° ~In accordance with the present invention and to any type of material used, the transparent substrate of the present invention may be used for the production of lenses or visors for spectacles, sheets, protection screens, etc.
•through well known surfacing techniques.
S..i Moreover, according to the present invention, the anti-reflection coating may be applied to both sides of the uncoated substrate, optionally after surface treatment thereof.
When the transparent substrate is made of a plastic material, the antireflection coating is preferably formed on the surfaces of the substrate according to the process and the box coaters as described in the Italian Patent No. 1.244.374 the entire disclosure of which is incorporated herein by reference.
-12- In accordance with said procedure, the various layers of the anti-reflection coating may be deposited in subsequent steps utilising a vacuum evaporation technique and exposing the growing layers to a bombardment of a beam of ions of inert gas.
Moreover, in accordance with the preferred process, the deposition of the layers may be achieved at a low temperature (generally below 80'C), using an ion beam having a medium intensity (meaning the average number of ions that reach the substrate) included between approximately 30 and 100 WA/cm 2 and the energy included between approximately 50 and 100 eV.
When the transparent substrate is made of glass, the anti-reflection coating may preferably be formed on the surface(s) of the substrate by vacuum evaporation to form the various layers of the anti-reflection coating and heating 15 the substrate.
Preferably, the substrate is maintained at an elevated temperature during the deposition of the various layers of the anti-reflection coating.
S
According to the present invention it has been found that, following the procedures mentioned above, it is possible to achieve a relatively thin antireflection coating with consequent advantages in both optical and mechanical properties.
Further characteristics and advantages of the present invention will be apparent from the following description of examples of embodiments of the present invention, given as indicative but not restrictive, with reference to the attached Figures.
Figure 1 illustrates the reflectance curves as a function of the wavelength for different photochromic substrates made of glass: without -13anti-reflection coating, and with an anti-reflection coating according to the present invention.
Figure 2 illustrates the reflectance curves as a function of the wavelength for identical photochromic substrates made of glass: without antireflection coating and with an anti-reflection coating in accordance with known techniques.
EXAMPLE 1 On samples of BK7 glass panes (n=1.52 at 500 nm) and 5 samples of Corning glass lenses (n=1.525 at 500 nm) having an opaque surface for the measuring of the reflectance, an anti-reflection coating made up of six 9.9: overlapping layers, alternatively of Pr 6 eOn mixed with xTiO 2 (n=2.15) and MgF 2 (n=1.38) were applied.
l The formation of the coating layers was carried out with a Satis 1200D deposition machine (Satis Vacuum AG), commercially available and equipped with a Leybold electronic gun having a 4kW power supply and a system controlling the flow of oxygen by MKS.
9. S The deposition parameters were the following: initial vacuum <2.0- 6 mbar; temperature before deposition 3000C.
The Pr 6 Oll+xTiO 2 layers were deposited by regulating the power of the electronic gun to a value of approx. 50% of its maximum power and introducing oxygen with a flow of approx. 9 sccm.
The speed of deposition of the layers was set at a value of approx. 0.3 nm/s.
-14- The MgF 2 layers were deposited by regulating the power of the electronic gun to a value of approx. 15% of its maximum power.
The speed of deposition of the layers was set at a value of approx. 1 nm/s.
At the end of the deposition we achieved on each of the samples an anti-reflection coating having the composition as illustrated in the following Table 1.
.T
These samples then underwent the standard test to determine the reflectance curve as function of the wavelength in the range between 350 and 700 nm using a HITACHI Mod. 3501 spectrophotometer.
s* S The results of the measurement carried out are shown in Figure 1 (uninterrupted line).
*0o* Moreover, in the above mentioned Figure 1 the interrupted line curve illustrates the trend of the reflectance of photochromic BK7 class and Corning glass samples, devoid of any anti-reflection coating.
EXAMPLE 2 (Comparative) With the aim of comparing the anti-reflection coating of this invention to that of a standard type of coating, on 5 samples of photochromic glass lenses (to which PHOTOGREY EXTRA GRIS
T
M (Corning France has previously been added) an anti-reflection coating, according to the commercially known process known as SOLACOAT SUPER, was applied.
Said coating is made up of a layer of adhesion of Cr and four overlapping layers, applied alternatively of Ti 3 0 5 (refractive index 2.39) and SiO 2 (refractive index 1.477).
The formation of the layers of coating was carried out with a Satis 1200D deposition machine (Satis Vacuum AG), commercially available and equipped with a Leybold electronic gun having a 4kW power supply and a system controlling the flow of oxygen by MKS.
The deposition parameters were the following: initial vacuum 2.0.6 mbar; before deposition 1 0 The SiO 2 layers were deposited by regulating the power of the electronic gun to a value of approx. 20% of its maximum power and introducing •oxygen with a flow of approx. 10 sccm.
The speed of deposition of the layers was set at a value of approx. 1 nm/s.
The Ti 3 0 5 layers were deposited by regulating the power of the electronic gun to a value of approx. 50% of its maximum power and introducing oxygen with a flow of approx. 50 sccm.
The speed of deposition of the layers was set at a value of approx. 0.3 nm/s.
At the end of the deposition we achieved on each of the samples an antireflection coating, according to standard techniques, having the composition illustrated in Table 2.
These samples then underwent the standard test to determine the reflectance curve as function of the wavelength in the range between 350 and 700 nm using a HITACHI Mod. 3501 spectrophotometer.
-16- The results of the measurements carried out are shown in the graph in Figure 2 curve dotted line).
After having examined the curves shown in the attached Figures 1 and 2, it is immediately evident how the layers of the present invention result in a reduced reflection factor of radiation both in the visible light range (400 to 700 nm), and in the range activating the photochromic composite material (350 to 400 nm).
10 As a clear contrast, the layers according to the known techniques show a marked increase of the reflection factor especially in this last range, with a marked reduction both in speed and darkening intensity of the lenses after •exposure.
15 After examining the curves, it is evident that the substrate of the present eeoc invention shows a prompt photochromic response superior even to those offered by the same substrate devoid of any anti-reflection coating thanks to the "•.°increased transmittance in the range of photochromic activation (350 to 400 nm).
TABLE 1 -17- TABLE 2
S
S
S
S.
S
S
S. 5.
S
S
*555 *555 S S *5 5 55*5 S
Claims (15)
1. A transparent photochromic article including a transparent substrate including a photochromic material; and an anti-reflection surface coating thereon, produced with a plurality of overlapping layers incorporating, alternatively a first and a second material having respectively higher and lower refractive indices, the anti-reflection coating including 10 a first layer including said first material having an optical thickness of to 40 nm; a second layer including said second material having an optical thickness 40 to 55 nm; a third layer including said first material having an optical thickness of 65 to 85 nm; a fourth layer including said second material having an optical thickness 30 to 45 nm; a fifth layer including said first material having an optical thickness of to 65 nm; and 20 a sixth layer including said second material having an optical thickness of 110 to 135 nm.
2. A transparent photochromic article according to claim 1, wherein the number of layers of the anti-reflection surface coating is varied, provided that the total optical thickness of the anti-reflection coating is maintained in the range of
3. A transparent photochromic article according to claim 1, wherein the first material has a refractive index of 1.6 to -19-
4. A transparent photochromic article according to claim 3, wherein the first material is selected from the group consisting of TiO 2 Ti 2 03, Ti 3 0 5 11 +xTiO 2 CeO 2 HfO 2 Ta20s, ZrO2, SnO 2
5. A transparent photochromic article according to claim 1, wherein the second material has a refractive index of 1.30 to 1.48.
6. A transparent photochromic article according to claim 1, wherein the .second material is selected from the group consisting of: SiO 2 MgF 2 AIF, 10 BaF 2 Na 5 ,Al 3 F 1 4 Na 3 AIF 6 YF3 and fluorocarbon compounds.
7. A transparent photochromic article according to claim 1, wherein the transparent substrate is made of glass having a refractive index of 1.5 to 1.9. 15
8. A transparent photochromic article according to claim 1, wherein the transparent substrate is made of plastic having a refractive index of 1.3 to 1.7.
9. A transparent photochromic article according to claim 8, wherein the lastic material is selected from the group consisting of; polymers and 20 copolymers with an acrylic base, polymethylmethacrylates, polycarbonates polyol allylcarbonates, the esters of cellulose, polyacrylates, polyvinyls, polystyrenes, polyurethanes and sulfur-containing materials.
A transparent photochromic article according to claim 1, further including an intermediate layer between said substrate and said first layer.
11. A transparent photochromic article according to claim 10 wherein the intermediate layer has an optical thickness of 200 to 300 nm.
12. A transparent photochromic article according to claim 10, wherein the intermediate layer has an optical thickness of 1 and 5 nm and incorporating a material selected from the group consisting of metals or oxides of: Cr, Ni, Sn, Pd. and Si.
13. A transparent photochromic article according to claim 1, wherein the mean reflectance at the external surface is less than or equal to 1% in the UV range.
14. A transparent photochromic article according to claim 1 in the form of a lens or visor for spectacles. 10
15. A transparent photochromic article according to claim 1 in the form of glass sheets or panes or protection screens. *0* S16. A transparent photochromic article according to claim 1 substantially as hereinbefore described with reference to any of the Examples. 0 DATED: 9th March 2000 PHILLIPS ORMONDE FITZPATRICK P* Attorneys for: SOLA INTERNATIONAL HOLDINGS LTD Qc-"a-JipL^
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU20785/00A AU726633B2 (en) | 1996-01-31 | 2000-03-09 | Transparent photochromic article including an anti-reflection surface coating |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITMI96A000162 | 1996-01-31 | ||
| AU20785/00A AU726633B2 (en) | 1996-01-31 | 2000-03-09 | Transparent photochromic article including an anti-reflection surface coating |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU15368/97A Division AU719476B2 (en) | 1996-01-31 | 1997-01-31 | Transparent photochromic article including an anti-reflection surface coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU2078500A AU2078500A (en) | 2000-06-01 |
| AU726633B2 true AU726633B2 (en) | 2000-11-16 |
Family
ID=3710096
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU20785/00A Ceased AU726633B2 (en) | 1996-01-31 | 2000-03-09 | Transparent photochromic article including an anti-reflection surface coating |
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| Country | Link |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4852974A (en) * | 1985-07-19 | 1989-08-01 | Optische Werke G. Rodenstock | Anti-reflection film for an optical element consisting of an organic material |
| AU7897591A (en) * | 1989-12-01 | 1991-06-26 | Viratec Thin Films, Inc. | Antireflection layer system with integral uv blocking properties |
-
2000
- 2000-03-09 AU AU20785/00A patent/AU726633B2/en not_active Ceased
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4852974A (en) * | 1985-07-19 | 1989-08-01 | Optische Werke G. Rodenstock | Anti-reflection film for an optical element consisting of an organic material |
| AU7897591A (en) * | 1989-12-01 | 1991-06-26 | Viratec Thin Films, Inc. | Antireflection layer system with integral uv blocking properties |
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|---|---|
| AU2078500A (en) | 2000-06-01 |
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