CN104169745A - Coated articles having abrasion resistant, glass-like coatings - Google Patents
Coated articles having abrasion resistant, glass-like coatings Download PDFInfo
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- CN104169745A CN104169745A CN201280055402.0A CN201280055402A CN104169745A CN 104169745 A CN104169745 A CN 104169745A CN 201280055402 A CN201280055402 A CN 201280055402A CN 104169745 A CN104169745 A CN 104169745A
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Abstract
Coated articles are provided comprising: (a) a substrate; (b) a porous sol-gel layer superimposed on at least one surface of the substrate; wherein the porous sol-gel layer comprises a hydrolyzed tetraalkoxysilane; and (c) a sealant layer superimposed on at least one surface of the porous sol-gel layer; wherein the sealant layer comprises an alkyltrihalosilane. The coated articles demonstrate superior abrasion resistance due to a glass-like layer formed from the combination of the porous sol-gel layer and sealant layer.
Description
Invention field
The present invention relates to the goods of the coating of the glassy coating with wearing quality.
Background of invention
Typically conventionally there is the surface of easy frayed and chemical erosion for the manufacture of the polymer organic material of optical element, clear sheet and film.In order to prevent destroying, such material can be with protective coating coated with improving their wearing quality.
Many protective coatings with various chemical property have been developed at optical field.For example, add the coating description to some extent in the literature containing silane monomer, aluminium compound and other silane monomer of epoxy radicals.Developed such coating, it is prepared by for example aqueous colloidal dispersion of aluminium oxide in the water-alcohol solution of selectable organotrialkoxysilane of water-insoluble spreading agent.Hard coating composition, for example, containing difunctionality alkoxy silane, four functional silanes, colloid titanium dioxide or aluminium oxide and the curing catalysts system of epoxy radicals, also belong to conventional system.Although various these coating provide enough wearing qualities for plastic basis material, the wearing quality of glass is still much higher than the wearing quality of the plastics of hard coating, is therefore desirable.In harsh environment, the mobile phone, the touch-screen etc. that for example often expose, still expectation approaches the wearing quality of glass.
Expecting provides the goods with such coating, and this coating provides the wearing quality that approaches glass, simultaneously cost low, lightweight, there is resistance to impact, moisture barrier and easily remove.
Summary of the invention
The present invention relates to the goods that apply, it comprises:
(a) base material;
(b) be stacked at least one lip-deep porous sol-gel layer of described base material; The tetraalkoxysilane that wherein this porous sol-gel layer comprises hydrolysis; With
(c) be stacked at least one lip-deep sealant layer of this porous sol-gel layer; Wherein sealing agent layer comprises alkyl trihalosilane.
Detailed Description Of The Invention
Except in any operational instances or situation about being otherwise noted, the numeral of the amount of expression composition, the reaction conditions etc. using in the present specification and claims is all interpreted as under all scenario modifies by term " about ".Therefore, unless the contrary indication, below the quantity parameter that provides in instructions and claims be all approximate value, they can be according to expecting that the character that be obtained by the present invention changes.At least, and do not attempt to limit doctrine of equivalents and be applicable to the scope of claim, each numerical parameter should at least be explained according to the significant figure of being reported and by conventional rounding-off method.
Although the quantitative range providing at wide region of the present invention and parameter are all approximate values, the numerical value providing in instantiation is all as far as possible accurately reported.But any numerical value contains the error that the standard deviation of some meeting from their each self test modes certainly leads to inherently.
And, it should be understood that any numerical range of citation is all intended to comprise all subranges of wherein containing herein.For example, the scope of " 1 to 10 " intention comprise all quoted from minimum value 1 and the maximal value 10 quoted between all subranges (and comprising endpoint value), that is to say, minimum value be equal to or greater than 1 and maximal value be equal to or less than 10.
As used in this specification and the appended claims, article " ", " one " and " being somebody's turn to do " comprise multiple objects that refer to, and refer to object unless be restricted to realizingly one.
It is nonrestrictive that the of the present invention various embodiments that provide herein and example are all interpreted as for scope of the present invention.
In book and claims, use as described below, below term there is implication as follows:
" polymkeric substance " refers to and comprises homopolymer and multipolymer, and the polymkeric substance of oligomer." compound substance " refers to two or more combinations of different materials.
The term " curable " being combined with for example curable composition refers to that described composition is polymerisable or crosslinkable by functional group, for example, comprise by referring to, but be not limited to heat (comprising ambient cure), catalytic, electron beam, chemistry free radical causes, and/or light-initiated, for example, by being exposed to ultraviolet light or other actinic radiation.
The term being combined with that solidify or curable composition " solidifies ", " curing " or similarly, for example, " the curing composition " that some illustrate, refers to that any polymerisable and/or crosslinkable component of at least a portion that forms curable composition is aggregated and/or is cross-linked.In addition, composition curing is to instigate described composition to be cured condition (for example listed above those), causes the reactive functional groups reaction of said composition.It is to instigate described composition to be cured condition that term " solidifies " at least in part, and wherein at least a portion reactive group of said composition reacts.Said composition can also be cured condition, makes to obtain substantially to solidify completely, and further solidifies and can not produce physical property, the remarkable improvement of for example hardness.
Term " reactivity " refer to can with himself and/or other functional group spontaneously or applying after heat or having the functional group of reacting under catalyzer or by other means known in the art.
The term of term " influence of light function ", " influence of light character " or similar meaning refers to described material, for example, coating, film, base material etc., can for example, change by absorbing (or filtration) incident light radiation (, visible ray, ultraviolet ray (UV) and/or infrared ray (IR) radiation on this material production impact).In alternative embodiment, influence of light function can be light polarization, for example, and by polarization body and/or dichroic dye; The change of optical absorption property, for example, is exposed to the chromophore that changes color after actinic radiation, for example photochromic material by use; Only transmission part incident light radiation, for example, by using fixing dye, for example conventional dyestuff; Or by the combination of one or more above-mentioned influence of light functions.
" be allocated as and there is at least one influence of light character " with the term that for example rigid optical base material is combined with and refer to that the object of appointment can have the influence of light character of introducing or depending on it.For example, be allocated as the plastic substrate with influence of light character and refer to that this plastic substrate has enough internal freedom volumes to hold photochromic dyes or dye in inside.The surface of this plastic substrate also can alternatively can have photochromic and/or polarization and/or the dye layer, film or the coating that invest it.
Term " ... on ", the term of " investing ", " depending on ", " being engaged in ", " adhering to " or similar meaning refers to specified object, for example, coating, film or layer, or be directly connected to body surface, or be indirectly connected to body surface, for example,, by one or more other coating, film or layer.
Term " ophthalmology " refers to the element relevant with eye and vision and device, such as but not limited to, for the lens of glasses, for example, correct and non-correcting lens, and amplifying lens.
The term " optical quality " being combined with for example polymeric material, for example, " resin of optical quality " or " organic polymer material of optical quality " refers to described material, for example, polymeric material, resin or resin combination, be or form base material, layer, film or the coating that can be used as optical goods (for example ophthalmic lens) or be combined with optical goods.
The term " rigidity " being combined with for example optical element refers to that the object of appointment is self-supporting.
Term " optical element " refers to that the light transmission value (seeing through incident light) of described base material is at least 4%, and haze value is for being less than 1%, for example, is less than 0.5%, measures by for example Haze Gard Plus Instrument in 550 nanometers.Optical element includes, but not limited to optical goods, for example lens, optical layers, for example, optical resin layer, blooming and optical coating, and there is the optical element of influence of light character.
Term " photochromic acceptance " refers to that there are enough free spaces in described object office to allow the photochromic material of introducing wherein to look for formal transformation to become its coloured form (then returning to its colorless form) from it, reaches the degree needing for business optical application.
The term " dyeing " being combined with for example ophthalmic devices and optical element refers to that described object contains fixing light absorption agent, such as but not limited to, conventional illuminating colour, on described object or in infrared and/or UV Absorption material.The visible radiation absorption spectrum of object of dyeing to actinic radiation can marked change.
The term " non-dyeing " being combined with for example ophthalmic devices and optical element refers to that described object does not conform to fixing light absorption agent substantially.The visible radiation absorption spectrum of the object of non-dyeing can be to actinic radiation marked change.
Term " actinic radiation " comprises that electromagnetic radiation wavelength scope, from ultraviolet (" UV ") optical range, runs through visible-range, and enters the light of infra-red range.Can be generally scope from 150 to 2,000 nanometers (nm) for the wavelength of the actinic radiation of the cure coating compositions that uses in the present invention, from 180 to 1,000nm, or from 200 to 500nm electromagnetic radiation.In one embodiment, can use the UV radiation of wavelength coverage from 10 to 390nm.The example of suitable ultraviolet source comprises mercury-arc lamp, carbon lamp, low, in or high-pressure sodium lamp, eddy flow plasma arc lamp and ultraviolet light-emitting diode.Suitable ultraviolet light emission lamp is middle pressure mercury vapor lamp, and in its output power fluorescent tube length, scope is at from 200 to 600 watts/inch (79-237 watts/centimetre).
The term that is combined with for example ophthalmic devices and optical element " dyeing photochromic " refers to that described object contains fixing light absorber and photochromic material.The visible radiation absorption spectrum of described object changes in response to actinic radiation, and in the time removing actinic radiation, is that heat is reversible.For example, the photochromic object of dyeing can have the first color characteristics of light absorber (for example coloration and dyeing material), and the second color characteristics of the combination of the photochromic material of light absorber and activation in the time that photochromic material is exposed to actinic radiation.
Term " dichroic material ", the term of " dichroic dye " or similar meaning refers to, material/dyestuff is better than the absorption to another for the absorption of one of two orthogonal plane polarization component of transmitted radiation.The limiting examples of dichroic material comprises indigoid, thioindigo class, cyanine class, indane tear, azo and many (azo) dyestuff, benzoquinones class, naphthoquinones class, Anthraquinones, (many) Anthraquinones, anthracene miazines, iodine and iodates.The word synonym of term " dichromatism " and " polarization " or similar meaning.
Term " photochromic dichromatism " refers to that described material or goods have dichromatism and photochromic property.In alternative non-limiting embodiment, described material can comprise photochromic dyes/compound and dichroic dye/compound, or has photochromic and single dyestuff/compound dichroic properties.
Refer to the term " transparent " that for example base material, film, material and/or coating are combined with that described base material, coating, film and/or material have transmitted light but the undue character of diffraction not, thereby the object after it is completely visible.
Term " photochromic amount " refers to that enough photochromic materials can debate other photochromic effect for produce bore hole after activation.The specified quantitative using depends on the color intensity of expecting after radiation conventionally, and depends on the method for introducing photochromic material.Typically, the photochromic material of introducing is more, and color intensity is higher, but can reach a certain limit.There is such point, after this point, add any more material and also can not there is perceptible effect, but as expected also can add more material.
The goods of coating of the present invention comprise base material.The base material that is applicable to the goods of preparing coating of the present invention can comprise metal or any optical element known in the art, comprises non-plastic basis material, for example glass.The suitable example of plastic basis material comprises polyvalent alcohol (allyl carbonate) monomer, for example, diglycol allyl carbonate, for example diglycol two (allyl carbonate), this monomer is by PPG Industries, and Inc. sells with CR-39 trade mark; Polyureas-polyurethane (polyureaurethane) polymkeric substance, it is for example by the reaction preparation of polyurethane prepolymer and diamine curing agent, and a kind of composition of this base polymer is by PPG Industries, and Inc. is with trade mark
sell; The carbonate monomer of polyvalent alcohol (methyl) acryloyl group end-blocking; Diethylene glycol dimethacrylate monomer; The methacrylic acid phenol ester monomer of ethoxylation; Diisopropenyl benzene monomer; The trimethylolpropane triacrylate monomer of ethoxylation; Glycol methacrylate monomer; PEG double methyl methacrylate monomer; Urethane acrylate monomer; Poly-(two atmosphere A dimethylacrylates of ethoxylation); Poly-(vinyl acetate); Poly-(vinyl alcohol); Poly-(vinyl chloride); Poly-(vinylidene chloride); Tygon; Polypropylene; Polyurethane; Poly-sulfo-ammonia ester; Thermoplastic poly carbonic ether, the resin that for example carbonic ester connects, it derives from two atmosphere A photoreactive gas, and a kind of this type of material is sold with trade mark LEXAN; Polyester, the material of for example selling with trade mark MYLAR; Poly-(ethylene glycol terephthalate); Polyvinyl butyral; Poly-(methyl methacrylate), the material of for example selling with trade mark PLEXIGLAS, with polyfunctional isocyanate and polythiol or many episulfide monomer (with polythiol homopolymerization or copolymerization and/or trimerization), polyisocyanates, polyisothiocyanates and optional ethylenically unsaturated monomer or the polymkeric substance of preparing containing the vinyl monomer reaction of halogenated aromatic.Also suitable is the multipolymer of this type of monomer, and the blend of described polymkeric substance and multipolymer and other polymkeric substance for example, has formed interpenetrating networks product.Base material itself can be transparent, or base material can have influence of light character, for example dye, photochromism and/or dichromatism.In addition, base material can have at least one influence of light character.
The base material the most often using comprises polyacrylic, TAC (cellulose triacetate), DAC (cellulose diacetate), poly-allyl diglycol carbonates (ADC), nylon, polyamide, polyurethaneurea polymer, PMMA, polyethylene terephthalate, polycarbonate, sulfur-containing polyurethane, and/or sulfur-containing polyurethane (urea).
Optical goods of the present invention comprise mirror, active and passive liquid crystal cell element, amplifying lens, ophthalmology goods, for example zero diopter lens (there is no luminous efficacy) and vision correcting (prescription) lens (finished product and semi-manufacture), comprise multifocal lens (bifocal, three warmers, and progressive lens); And device for eyes, for example contact lens and intraocular lens, sunglasses, fashionable dress mirror, motion face shield, mask, safety goggles and goggles.Optical goods also can be selected from windowpane, for example window and vehicle transparency, for example automotive windshield and side window, display element and device.Term used herein " demonstration " represents to represent the visible ray of word, numeral, symbol, design or pictorial information.The example of display element and device comprises screen, monitor, and safety element.The example of safety element comprises the safety label and the certification mark that are connected to base material, for example and be not limited to: and access card and the pass, for example, admission ticket, chest card, I.D. or member card, debit card etc.; Transferable and nonnegotiable bill, for example, draft, check, debt volume, banknote, DR, stock voucher etc.; Government's property file, for example, currency, license, I.D., welfare card, visa, passport, official's certificate, contract etc.; Consumer products, for example, software, small-sized laser disc (" CDs "), digital video disc (" DVD "), electrical equipment, consumption electronic product, sports products, automobile etc.; Credit card; With product tag, label and packaging.
In specific implementations of the present invention, in the time will preparing some optical goods, the refractive index that may expect base material is at least 1.55.The refractive index of for example base material can scope at 1.55-1.67, for example 1.55-1.65.In such circumstances, base material can comprise polycarbonate, sulfur-containing polyurethane and/or sulfur-containing polyurethane (urea).The suitable example of the base material that comprises sulfur-containing polyurethane and sulfur-containing polyurethane (urea) can comprise those in open No.2006/0241273A1 [0010]-[0269] of the United States Patent (USP) section that is described in submission on February 22nd, 2006, includes in by reference at this.In addition, the suitable example of the base material that comprises sulfur-containing polyurethane and sulfur-containing polyurethane (urea) can comprise those that prepared by the composition of the oligomeric polythiols that comprises thioether functional, said composition is described in the section of open No.2007/0270548A1 [0053]-[0247] of the United States Patent (USP) of submitting on May 4th, 2007, includes in by reference at this.The further suitable example of sulfur-containing polyurethane can comprise open 2007/0142604A1 [0007]-[0020] of United States Patent (USP) that is described in submission on Dec 16th, 2005; [0023]-[0032]; [0034]-[0036]; [0038]-[0272] those in section, the part of all references is included in by reference at this.Similarly, the suitable example of sulfur-containing polyurethane (urea) can comprise open No.2007/0142606A1 [0006]-[0022] of United States Patent (USP) that is described in submission on Dec 16th, 2005; [0025]-[0034]; [0036]-[0038]; [0040]-[0296] those in section, the part of all references is included in by reference at this.
Porous sol-gel layer is stacked at least one surface of base material.Sol-gel is dynamic system, and wherein solution (" colloidal sol ") develops into the gelatinous two-phase system that contains liquid phase and solid phase gradually, and the form scope of solid phase is from the discrete particle in Continuous Liquid Phase to continuous polymer network.This porous sol-gel layer comprises tetraalkoxysilane.Due to the sol-gel characteristic of described composition, alkoxy silane is hydrolyzed, and they the curing forward part of described layer condense (condensed).The tetraalkoxysilane being hydrolyzed in this porous sol-gel layer typically comprises tetramethoxy-silicane and/or tetraethoxysilane.
Porous sol-gel layer conventionally by the liquid deposition of the tetraalkoxysilane of the hydrolysis in the alcohol of 1-6 carbon atom to base material, for example 5 % by weight solution of the tetraalkoxysilane of hydrolysis in isopropyl alcohol.This porous sol-gel layer can be by one or more method paint base materials, and for example spraying, dip-coating (dipping), spin coating or stream are expected on its surface.The most often use dipping.This porous sol-gel layer is dried to remove alcohol and water solvent.The typical build of the porous sol-gel layer applying for being less than 1000nm, for example, is less than 500nm, is generally 100-300nm.
Sealant layer is stacked at least one surface of this porous sol-gel layer.Sealing agent layer comprises at least one alkyl trihalosilane, for example alkyl silicofluoroform, alkyl trichlorosilane, and alkyl tribromosilane.The suitable example of alkyl trichlorosilane comprises methyl trichlorosilane, vinyl trichlorosilane, ethyl trichlorosilane, n-propyltrichlorosilan, isopropyl trichlorosilane, γ-chloropropyl trichloro-silane, isobutyl trichlorosilane, normal-butyl trichlorosilane, amyl group trichlorosilane, hexyl trichlorosilane, heptyl trichlorosilane, n-octyl trichlorosilane, iso-octyl trichlorosilane, hexadecyl trichlorosilane, 10-undecenyl trichlorosilane, 13-tetradecene base trichlorosilane, 14-15 carbene base trichlorosilanes, 15-cetene base trichlorosilane, n-octadecane base trichlorosilane and n-hexadecyl trichlorosilane.
Sealant layer can be by alkyl trihalosilane the liquid deposition in aprotic solvent to this porous sol-gel layer, for example alkyl trihalosilane is at the ISOPAR L (potpourri of isoparaffin, can available from ExxonMobil Chem i ca l s) in or 5 % by weight solution in SOLVESSO100 (potpourri of arsol, also can available from ExxonMobil Chemicals).Encapsulant composition can be by this porous sol-gel layer of one or more method paints, for example spraying, and dip-coating (dipping), spin coating, or flow coat is to its surface.The most often use dipping.Sealant is dried to remove desolventizing.
In some embodiments of the present invention, can expect to have one or more extra plays that are arranged between this base material and this porous sol-gel layer.Layer like this can be, and for example, the goods field that any optics applies is known, and can be selected from prime coat, middle layer, and the acrylic composition of UV-curable, and adhesive phase etc.Any these extra plays can have one or more influence of light character.
In some cases, prime coat coating paint substrate surface, then applies this porous sol-gel layer.Prime coat coating is arranged between base material and sol-gel layer, and adheres to substrate surface as barrier coat and/or as adhesive phase with promotion sol-gel layer.Prime coat can pass through any known method paint base material, for example, spraying, spin coating, paving is coated with, curtain coating, roller coat or dip-coating; And for example can apply, on that clean and undressed or that warp is clean and treated (, chemical treatment or Cement Composite Treated by Plasma) substrate surface.Prime coat coating is known to those skilled in the art.The selection of suitable prime coat coating will be depended on used base material, and stratification and physical compatibility that prime coat coating must apply with substrate surface with afterwards provide the function benefit of expecting for prime coat coating simultaneously, intercept and adhesive properties.
In some embodiments, prime coat coating can be one or several monolayers thick, and can scope at 0.1-10 micron, for example 0.1-2 or 3 microns.The thickness of prime coat can change between aforementioned value any combination of (comprising described endpoint value).A kind of suitable prime coat coating comprises organofunctional silane (for example methacryloxypropyl trimethoxy silane, a kind of catalyst material, it produces acid in the time being exposed to actinic radiation, for example, and salt), and organic solvent, for example two sweet ether or isopropyl alcohol, as be described in United States Patent (USP) 6,150, in 430, its disclosure is included in by reference at this.
The further example of suitable prime coat coating is described in United States Patent (USP) 6,025,026, and it has described a kind of composition, and said composition does not basically contain organosiloxane, and comprises the organic acid anhydride with at least one thiazolinyl connection base and the material that contains isocyanates.The disclosure content is included in by reference at this.Apply after prime coat, base material can, with for example 2-propyl alcohol rinsing of alcohol, then be used water rinse, and be dried to not a half hour in scope from the temperature of 60 DEG C to 80 DEG C.
In some embodiments of the present invention, the goods of coating further comprise the extra play being arranged between this base material and this porous sol-gel layer, and wherein this extra play is by curable film-forming composition.This curable film-forming composition is different from this porous sol-gel layer.Itself is collosol-gelatum system and comprises alkoxy silane.This alkoxy silane has general formula R
1 msi (OR
2)
4-m, wherein each R
1can be identical or different and represent organic group; Each R
2can identical or different and expression C
1-C
4alkyl, m is 0-3.R
1can be C
1-C
6alkyl, vinyl, methoxy ethyl, phenyl ,-glycidoxy propyl group, or-methacryloxypropyl.R
2can be methyl, ethyl, propyl group or butyl.The suitable example of alkoxy silane comprises methyl triethoxysilane, 3-glycidoxypropyltrime,hoxysilane, and acryloyl-oxy base silane.
For the purposes of the present invention, alkoxy silane is typically dissolved in organic solvent, for example, in alcohol, and partly by water according to following reaction hydrolysis:
R
1 mSi(OR
2)
4-m+nH
2O→R
1 mSi(OR
2)
4-m-n(OH)
n+nR
2OH
After alkoxy silane is partly hydrolyzed, can add metal oxide and/or metallic alkoxide compound.Metal-oxide compound can comprise aluminium, titanium, zirconium, cerium, niobium, tantalum, and/or tin.This compound can comprise the metal oxide (M that one or more are different
xo
y, wherein x be 1 or 2 and y be 1-4) and/or there is the metal alkoxide of following general formula:
M(OR
3)
4
Wherein M is any metal listed above, for example, and titanium or zirconium, R
3represent low-molecular-weight monovalent alkyl, for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl or isobutyl.Metal alkoxide can be the form of dimer or higher condensation, as long as alkoxy maintenance and the partly reactivity of the silanol of the alkoxy silane of hydrolysis.
Metal alkoxide forms silicon-oxygen metallic bond network with the alkoxy silane of partly hydrolysis according to following general reaction response:
In the time of the alkoxy silane complete reaction of metal alkoxide and partly hydrolysis, can add other water with hydrolysis composition, change into hydroxyl by the residue alkoxy of alkoxy silane or metal alkoxide according to following reaction:
The suitable example of metal-oxide compound can comprise cerium oxide, titanium alcoholates, zirconium alcoholates, and/or tin-oxide.In specific implementations of the present invention, metal-oxide compound comprises cerium oxide and titanium normal butyl alcohol compound.Metal-oxide compound can scope from 0.1 to 65 % by weight, and for example the amount of 1 to 25 % by weight is used, the general assembly (TW) meter of solid in the film-forming composition based on curable.
The film forming sol-gel composite waterborne liquid typically that this is curable, its viscosity can at least be sprayed them.Said composition is moisture, and can be additionally containing one or more organic solvents that can be miscible with water at least in part, for example methyl alcohol, ethanol, n-propanol, isopropyl alcohol, normal butyl alcohol etc.
The specially suitable composition that can be used as this curable film forming sol-gel composite is those that sell with title HI GARD, can be available from PPG Industries, Inc.
The film forming sol-gel composite that this is curable and be arranged on this base material and this porous sol-gel layer between any extra play can comprise multiple optional composition and/or adjuvant, they depend on the application-specific of the goods of final coating to a certain extent.For example, said composition can be dyeing and contain colorant, and/or can show influence of light character.Other optional member comprises that rheology control agent, surfactant, initiating agent, catalyzer, curing inhibitors, reductive agent, acid, alkali, antiseptic, free radical are to body, free radical scavenger and thermal stabilizer, and these auxiliary material are well known by persons skilled in the art.
Term used herein " colorant " refers to any material of giving composition color and/or other opacity and/or other visual effect.Colorant can add coating with any suitable form, as the particle disperseing, dispersion, solution and/or thin slice.Single colorant, or the potpourri of two or more colorants can be in composition of the present invention.
Exemplary colorant comprises pigment, dyestuff and dye, for example, for listing in those of Dry Color Manufacturers Association (DCMA), and special effect compositions.But colorant can comprise for example insoluble meticulous pressed powder separating that can soak under the condition using.Colorant can be organic or inorganic, and can be that assemble or non-gathering.Colorant can be by grinding or simply mixing and be mixed in coating.
The example of pigment and/or color compositions comprises, but be not limited to, the thick pigment of carbazole dioxazine, azo, monoazo, bisdiazo, naphthols AS, salt type (color lake), benzimidazole, condensation product, metal complex, iso-dihydro-indole, isoindoline quinoline and many ring phthalocyanines, quinacridone, perylene, perylene, diketopyrrolo-pyrrole, thioindigo, anthraquinone, indanthrone, anthracene pyrimidine, flavanthrene, pyranthrone, anthanthrone, dioxazine, triaryl carbon, quinophthalone pigment, diketopyrrolo-pyrrole red (" DPPBO is red "), titania, carbon black, carbon fiber, graphite, other conducting pigment and/or filler and their potpourri.Term " pigment " and " painted filler " can exchange use.
The suitable example of dyestuff can comprise, but be not limited to, based on solvent and/or based on those of water, for example acid dyes, azo dyes, basic-dyeable fibre, direct dyes, disperse dyes, chemically-reactive dyes, solvent dye, sulphur dyestuff, mordant dye, for example pucherite, anthrone, perylene, aluminium, quinoline a word used for translation diketone, thiazole, thiazine, azo-compound, indigo, nitro compound, nitroso compound, oxazine, phthalocyanine, quinoline, stilbene and triphenyl methane.
Photochromic dyes is applicable in the various layer of goods of coating of the present invention, both can be independent, also can with other colorant combination.Photochromic material can comprise the material of following classification: chromene, for example, aphthopyrans, chromene, indenonaphthopyrans and phenanthro-pyrans; Spiro-pyrans, for example, spiral shell (benzo indoline) aphthopyrans, spiral shell (indoline) chromene, spiral shell (indoline) aphthopyrans, spiral shell (indoline) quino pyrans and spiral shell (indoline) pyrans; Oxazine class, for example, spiral shell (indoline) Nai Bing oxazine, spiral shell (indoline) pyrido-benzoxazine, spiral shell (benzo indoline) pyrido-benzoxazine, spiral shell (benzo indoline) Nai Bing oxazine and spiral shell (indoline) benzoxazine; Mercury dithizonate (mercury dithizonates), prisoner's o, fulgenimide, and the potpourri of these photochromic compounds.This type of photochromic compound and supplementary photochromic compound are described in United States Patent (USP) 4,931, and 220 the 8th hurdles the 52nd walk to the 22nd hurdle the 40th row; 5,645,767 the 1st hurdles the 10th walk to the 12nd hurdle the 57th row; 5,658,501 the 1st hurdles the 64th walk to the 13rd hurdle the 17th row; 6,153,126 the 2nd hurdles the 18th walk to the 8th hurdle the 60th row; 6,296,785 the 2nd hurdles the 47th walk to the 31st hurdle the 5th row; 6,348,604 the 3rd hurdles the 26th walk to the 17th hurdle the 15th row; With 6,353,102 the 1st hurdles the 62nd walk to the 11st hurdle the 64th row.Spiral shell (indoline) pyrans is also described in textbook, Techniques in Chemistry, III volume, " Photochromism ", the 3rd chapter, Glenn H.Brown, Editor, John Wi ley and Sons, Inc., New York, 1971.
Operable other photochromic material comprises the two sulphur track salt (dithiozonates) of organic-metallic, i.e. (arylazo)-formyl sulfide aryl hydrazide salt (thioformic arylhydrazidates), for example, mercury dithizonate, it is described in for example U.S. 3,361,706 the 2nd hurdles the 27th walk to the 8th hurdle the 43rd row; With prisoner's o and fulgenimide, for example 3-furyl and 3-thienyl prisoner's o and fulgenimide, they are described in the U.S. 4,931, and 220 the 1st hurdles the 39th walk to the 22nd hurdle the 41st row.Similarly, the composition of the curable film of formation of the present invention can also comprise photochromic-dichroic dye and/or conventional dichroic dye, as known in the art.
Curable film forming sol-gel composite can be by one or more method paint base materials, for example spraying, and dip-coating (dipping), spin coating, or flow coat is to its surface.The most often use dipping.This curable film-forming composition is dried to remove alcohol and water solvent.Next applying after this porous sol-gel layer, be heated the temperature 3 hours at the most of 120 ° to 135 DEG C, thereby promoting the continuous condensed of composition.The build that this curable film forming sol-gel composite shows is 2-6 micron, is generally 2-4 micron.After heating steps, apply sealing agent layer.
The goods of coating of the present invention show excellent wearing quality.Bayer wear testing can be for determining surface abrasion resistance.The mar proof of product is tested the mist degree of sample after wearing and tearing by measurement and this value and the value recording on control sample is relatively quantized, and control sample is the goggles for being made up of diglycol two (allyl carbonate) in the situation that of ophthalmic product for example.Conventionally, carry out the more testing sample/tester, for example, 5 pairs, thus guarantee to add up effective result.By clean to sample to be tested and the gentle suds of tester, wash with water, then dry with air.In the controlled environment of temperature and humidity (23+/-3 DEG C and 50+/-10% relative humidity), will test sample and tester and leave standstill minimum 2 hours, abrasive substance is left standstill to minimum 24 hours simultaneously.Test sample and tester adopt Haze-Gard Plus device measuring at the transmittance of 550nm.Test sample and tester are arranged on Bayer abrader and for example aluminium oxide of wear medium (Norton ZF E-327#12 granularity), are placed in the dish of abrader.In the time that lens are tested, by their convex surface down.Abrader moves 6 minutes with the speed of 100 cycles per minute, amounts to 600 circulations.To test sample and tester and clean with gentle suds, rinsing is also dry with air.Again under 550nm, measure the mist degree of test sample and tester with Haze Gard Plus equipment.Mist degree increment is calculated by the difference of light transmission value before and after denuding.Bayer mist degree delta ratio calculates (mist degree delta ratio=mist degree (contrast)/mist degree (test sample) by the mist degree that records with tester divided by the mist degree that records of test sample.
Rollover test is a kind of abrasion test, the practical study data of the normal wear of the plastic lens of this test based on glass, uncoated plastic lens and coating and producing.It is equivalent to the normal wear of approximately a year.Rollover test based on by carrying out with the many dissimilar Mediawear of natural sawdust type mixture of substances in cylinder.In the time that test sample falls repeatedly in bucket, the abrasion that has produced natural wear type.Testing length to test sample front surface is 20 minutes.Importantly ISO reference lens, it is uncoated
lens, it manufactures to reduce curing deviation in the strict condition of controlling, and is used as tester lens.In each test, use three.After test, three lens are contrasted.Eachly carry out haze meter measurement, before wearing and tearing, carry out, and carry out another time after wearing and tearing.The gained mist degree increment of test sample is divided by the gained mist degree of ISO reference lens, thereby is its ratio of several times compared with the wearing quality that obtains test lens and ISO reference lens or uncoated animi resin lens.ISO lens are as the standard of lens material and coating, taking it as benchmark comparative result.
Following examples meant for illustration various embodiments of the present invention, limit the present invention by any way but should not be construed as.
Embodiment
Test sample uses TRIVEX base material (can purchased from PPG Industries, Inc) preparation.For each embodiment, by HI-GARD1080 coating composition (can available from PPG Industries, Inc.) paint base material.In comparative example, coating composition is solidified 3 hours at 120 DEG C, do not apply extra play.In an embodiment according to the present invention, prepare the 5 % by weight solution of tetraethoxysilane in isopropyl alcohol, and the testing substrates that has been coated with HI-GARD1080 by dipping applies.Then this testing substrates is solidified 3 hours at 120 DEG C.Then prepare 5 % by weight of octadecyl trichlorosilane in ISOPAR L, and apply by the base material of immersion coating, all excessive things are wiped.Testing substrates is carried out to above-mentioned Bayer test and rollover test.Testing substrates is further carried out QUV, synthetic perspiration's test, and hot water test, and test step is described as follows, and afterwards they is carried out to Bayer wear testing.Bayer wearing and tearing ratio is reported in following table.
Synthetic perspiration's test
Operation
1. the shape that sample edging is become to need is to remove the outer coating in region (being rims of the lens)
*
2. in 1L glass beaker, mix until 100 grams of sodium chloride and 50 grams of lactic acid are dissolved in 850 grams of deionized waters completely
3. heated solution to 50 DEG C
4. sample is remained in suitable container
5. sample is flooded 5 hours at 50 DEG C under high degree of agitation
After 6.5 hours, take out sample and wash with deionized water.Dry with soft cloth is clean.
Hot water test
Operation
1. the shape that sample edging is become to need is to remove extra-regional coating (being rims of the lens)
*
2. fill 1L beaker with deionized water
3. heated solution to 90 DEG C
4. sample is remained in suitable container
5. sample is flooded 5 hours at 90 DEG C under high degree of agitation.
After 6.5 hours, take out sample and wash with deionized water.Dry with soft cloth is clean.
QUV plate-accelerated deterioration test
Operation
1. by being installed, UV Type B lamp (313nm wavelength) sets instrument
2. fetch boiling water entrance inspection apparatus bottom water liquid level
3. set timer, expose thereby there is 4 hours UV the alternate cycles that latter 4 hours water condenses.
4. test specimen and reference sample are loaded in appropriate containers, wherein convex surface Machine oriented inner side
5. open QUV plate
6. the test duration is 5 days (120 hours)
7.5 days, close instrument and take out sample
Note, condensing with UV Exposure Temperature is that scope is at 45-55 DEG C by instrument control.
Bayer abrasion resistance index (BARI) listed in table calculates divided by the % mist degree of the test sample applying by the % mist degree with the uncoated test comparison sample of TRIVEX system.Institute's value is that the wearing quality of the test sample of coating compared with uncoated test square increases how many instructions.Mist degree before and after wear testing and transmittance result are measured with Hunter Lab DP25P type colorimeter.
Table
| Embodiment | Rolling ratio | BARI | QUV | Synthetic perspiration's test | Hot water |
| Comparative example | N/A | 8 | 1 | 1 | ＜1 |
| 1 | 9.3 | ＞30 | ＞30 | ＞30 | 1.5 |
Result in upper table shows, the base material applying according to the present invention is more wear-resisting than comparative sample (be made up of TRIVEX, and be coated with HI-GARD1080), and shows better aging and water tolerance.
Although shown for illustrative purposes specific implementations of the present invention, determine for a person skilled in the art, can in the situation that not deviating from the scope of the invention defined in the appended claims, make various variations to details of the present invention.
Claims (16)
1. goods for coating, comprise:
(a) base material;
(b) be stacked at least one lip-deep porous sol-gel layer of described base material; The tetraalkoxysilane that wherein this porous sol-gel layer comprises hydrolysis; With
(c) be stacked at least one lip-deep sealant layer of this porous sol-gel layer; Wherein sealing agent layer comprises alkyl trihalosilane.
2. the goods of coating according to claim 1, wherein said base material comprises plastics, glass or metal.
3. the goods of coating according to claim 1, further comprise the one or more extra plays that are arranged between this base material and this porous sol-gel layer, it is selected from prime coat, middle layer, the acrylic composition of UV-curable, be different from the sol-gel paint composition of this porous sol-gel layer, and/or adhesive phase.
4. the goods of coating according to claim 1, wherein the build of this porous sol-gel layer is for being less than 1000nm.
5. the goods of coating according to claim 1, wherein the tetraalkoxysilane of the hydrolysis in this porous sol-gel layer comprises tetramethoxy-silicane and/or tetraethoxysilane.
6. the goods of coating according to claim 1, wherein the alkyl trihalosilane in sealing agent layer comprises octadecyl trichlorosilane.
7. the goods of coating according to claim 1, further comprise the extra play being arranged between this base material and this porous sol-gel layer, described extra play is different from this porous sol-gel layer (b), is deposited by the curable film forming sol-gel composite of the alkoxy silane that comprises hydrolysis.
8. the goods of coating according to claim 7, wherein this curable film forming sol-gel composite further comprises and the metal alkoxide of the responding property of alkoxy silane of this hydrolysis.
9. the goods of coating according to claim 7, wherein the alkoxy silane in this curable film forming sol-gel composite comprises 3-glycidoxypropyltrime,hoxysilane.
10. the goods of coating according to claim 7, wherein this curable film forming sol-gel composite further comprises the metal-oxide compound that contains aluminium, titanium, zirconium, cerium, niobium, tantalum and/or tin.
The goods of 11. coatings according to claim 7, wherein said base material comprises polyacrylic, TAC (cellulose triacetate), DAC (cellulose diacetate), poly-allyl diglycol carbonates (ADC), nylon, polyamide, polyurethaneurea polymer, PMMA, polyethylene terephthalate, polycarbonate, sulfur-containing polyurethane, and/or sulfur-containing polyurethane (urea).
The goods of 12. coatings according to claim 7, the goods of wherein said coating are optical goods.
13. optical goods according to claim 12, wherein said optical goods comprise ophthalmic devices, display element, forms, mirror, and/or active and passive liquid crystal cell element and device.
14. optical goods according to claim 13, wherein these optical goods are ophthalmic devices, it comprises correcting lens, non-correcting lens, contact lens, intraocular lens, amplifying lens, protection lens, or safety goggles.
15. optical goods according to claim 13, wherein these optical goods are display elements, comprise screen, monitor, and safety element.
16. optical goods according to claim 13, wherein the refractive index of this base material is at least 1.55.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13/672,033 | 2012-11-08 | ||
| US13/672,033 US10185057B2 (en) | 2011-11-11 | 2012-11-08 | Coated articles having abrasion resistant, glass-like coatings |
| PCT/US2012/064277 WO2013071000A2 (en) | 2011-11-11 | 2012-11-09 | Coated articles having abrasion resistant, glass-like coatings |
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| CN104169745A true CN104169745A (en) | 2014-11-26 |
| CN104169745B CN104169745B (en) | 2018-08-17 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109776833A (en) * | 2017-11-14 | 2019-05-21 | 杜邦公司 | Transparent polymer film or sheet material with resistance to scraping coating |
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| JP2001138434A (en) * | 1998-09-16 | 2001-05-22 | Matsushita Electric Ind Co Ltd | Functional film and method of manufacturing the same, and liquid crystal display element using functional film and method of manufacturing the same |
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| CN109776833B (en) * | 2017-11-14 | 2021-09-24 | 杜邦公司 | Transparent polymer film or sheet with scratch-resistant coating |
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