EP0495048A1 - Vitrage de protection et procede de production - Google Patents

Vitrage de protection et procede de production

Info

Publication number
EP0495048A1
EP0495048A1 EP91913979A EP91913979A EP0495048A1 EP 0495048 A1 EP0495048 A1 EP 0495048A1 EP 91913979 A EP91913979 A EP 91913979A EP 91913979 A EP91913979 A EP 91913979A EP 0495048 A1 EP0495048 A1 EP 0495048A1
Authority
EP
European Patent Office
Prior art keywords
glazing
resin
total solids
weight percent
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP91913979A
Other languages
German (de)
English (en)
Other versions
EP0495048A4 (en
Inventor
David E. Stevenson
Paul L. Tag
Bruce Laumann
Joy M. Schaefer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tru Vue Inc
Original Assignee
Tru Vue Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tru Vue Inc filed Critical Tru Vue Inc
Publication of EP0495048A1 publication Critical patent/EP0495048A1/fr
Publication of EP0495048A4 publication Critical patent/EP0495048A4/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10018—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising only one glass sheet
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10339—Specific parts of the laminated safety glass or glazing being colored or tinted
    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
    • B32B17/10899—Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin
    • B32B17/10908—Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin in liquid form
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
    • C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • 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
    • B32B2309/00—Parameters for the laminating or treatment process; Apparatus details
    • B32B2309/60—In a particular environment
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/74—UV-absorbing coatings

Definitions

  • the present invention relates generally to the prevention of damage due to ultraviolet radiation, and more particularly to a protective glazing.
  • the spectrum of visible light extends from a wavelength of about 420 nanometers (n ) to a wavelength of about 680 nm.
  • the ultraviolet light spectrum begins at wavelengths shorter than about 420 nm and the infrared light spectrum begins at wavelengths longer than about 680 nm.
  • most damage may be caused by ultraviolet light, some dyes and pigments, sucn as those found in antique watercolors, have a certain degree of sensitivity to wavelengths at the blue end or the visible spectrum.
  • Such measures 5 may include exposing the works only to light from incandescent light sources. Filters designed to remove the damaging wavelengths of light may also be used.
  • An excellent reference on the subject of art conservation is The Museum Environment. Garry Thomson, London
  • the ideal protective glazing is one in which only the ultraviolet light is rejected while all of the visible light is transmitted.
  • a glazing which selectively attenuates certain wavelengths of the
  • the above described wavelength range over which the transition from absorption to transmission occurs is often referred to as the ultraviolet absorption edge.
  • Certain plastic materials have been developed which will reject ultraviolet light and transmit visible light. Such products are sold by the Rohm and Hass Corporation, Philadelphia, PA, under the brand names UF-3 and UF-4. These products are capable of rejecting wavelengths less than about 380 nm. The problem with these materials is that they are soft compared with glass and thus easily scratched. Static charges are also easily built-up on their surfaces, and as such, they attract dust. It is also difficult to apply antiglare or antireflection coatings directly to such plastic surfaces.
  • plastic are also not amenable to etch- type treatments sometimes used to reduce reflection and glare from glass surfaces. Further, thin film type antireflection coatings on plastic are generally not as durable as the same coatings on glass. The plastic -4- aterials which block ultraviolet wavelengths as long as 380 nm also exhibit a slight yellowish transmission color.
  • an object of the present invention is to provide a glazing having a high level of transmission for visible light and a high level of rejection for ultraviolet light.
  • the present invention is directed to a glazing.
  • the glazing comprises a glass substrate having a resin on at least one surface thereof.
  • the resin includes an ultraviolet absorbing material and a dye.
  • the dye is used to correct the transmission color of the substrate.
  • the glazing may be used to form, for example, a picture framing glass, a display case panel, a vehicle window, or an architectural window or panel.
  • the resin used in the glazing may be a polysiloxane resin.
  • Polysiloxane resins may be abrasion resistant, and may have a high degree of adhesion to glass surfaces.
  • the coated glazing is essentially as smooth as the uncoated glass substrate.
  • the coating is sufficiently hard that it may be handled and cleaned as in the same manner as glass.
  • the ultraviolet absorbing material may be an organic compound which can be incorporated into the resin.
  • Such an organic compound may be from the chemical groups benzophenones or benzothiazole ⁇ . Up to about 20 percent of such materials can be incorporated into the resin without any substantial loss in hardness or adhesion.
  • a color-neutralizing dye or a mixture of dyes, is added to the resin to offset the yellow coloration that would occur as the ultraviolet rejection range is extended closer to the visible light spectrum.
  • the dye color and concentration may be chosen to provide a predetermined neutral color value in combination with the resin and substrate color.
  • a process for forming the protective glazing may comprise the following steps.
  • a dye for correcting the transmission color may be dispersed in a high boiling point solvent.
  • the solvent, containing the dye is used to dilute a base resin containing an ultraviolet absorbing material.
  • the diluted resin can be applied co a substrate using a roll coater.
  • the resin-coated substrate may then be heated to cure the resin.
  • the solvent may be a glycol having a higher boiling point than any solvent used to formulate the base resin.
  • a diluted resin stays wet longer than the base resin. This allows a very uniform coating to be applied.
  • the glycol dilution also permits thickness control over the resin layer to within one tenth of a micron. This enables the ultraviolet blocking and neutral transmission color characteristics to be reproduced precisely from sheet to sheet.
  • the dye is added to the solvent before the solvent is added to the base resin. This is more precise and easier to implement than immersing the cured resin in a dye solution.
  • the other surface may include an antireflection treatment.
  • the resin itself is sufficiently hard and adheres so well to the substrate that it can also be coated with an antireflection coating.
  • the refractive index of the resin should substantially match the refractive index of the substrate so performance of the antireflection coating is not impaired.
  • the coating can be applied economically by in-line sputtering systems such as those used for architectural glass coating.
  • the antireflection coating reduces reflection from the substrate and increases its transmission. This gain in transmission is more than sufficient to offset. the transmission loss caused by the color-correcting dye. This enables a color neutral glass glazing to be made which has enhanced ultraviolet absorbing properties.
  • the resin once applied to the glass substrate and cured is durable enough to withstand the process conditions of high volume, large area, DC reactive sputtering systems. This provides economies of scale which make protective glazings affordable for the conservation of less expensive graphic works normally seen in the home or office.
  • Figure 1A is a schematic representation of a glazing in accordance with the present invention.
  • Figure IB is a schematic representation of an antireflection coating in accordance with the present invention.
  • FIG. 1 graphically illustrates the ultraviolet blocking characteristics of glazings in accordance with the present invention
  • Figure 3 shows the arrangement of a computer spreadsheet for computing the color coordinates of color correcting dye in accordance with the present invention
  • Figure 4 graphically illustrates the method predicting the color coordinates of undiluted color correcting dye
  • Figure 5 is a schematic illustration of a roll coater for applying a resin to a substrate in accordance with the present invention.
  • Figure 6 graphically illustrates the spectral transmission characteristics of a glazing at various steps in the manufacturing process.
  • protective glazing 5 includes a glass substrate or sheet 10.
  • the glass substrate may comprise a float glass about 2.5 millimeters (mm) thick.
  • Such glass is available from Libby Owens Ford (LOF) Glass
  • a resin layer 12 may be disposed on one surface of substrate 10. Alternatively, the resin layer may be formed on both substrate surfaces.
  • An antireflection coating 14 may be disposed on both resin layer 12 and substrate 10.
  • glazing 5 may be disposed between an observer 15 and, for example, a work of art 17. As noted, the glazing may also be used in vehicles and buildings.
  • Resin layer 12 may comprise a polysiloxane resin of the type described in U.S. Patent No. 4,355,135, the entire disclosure of which is hereby incorporated by reference. Polysiloxane resins are film forming resins containing siloxane bonds alone or in combination with other chemical bonds.
  • the resin layer 12 may be formed from a base formulation in the form of an aqueous alcoholic dispersion including: (A) about 5 to 75 weight percent, based on the total solids of the base formulation, of colloidal silica; (B) about 0 to 50 weight percent, based on the total solids of the base formulation, of a partial condensate of a silanol selected from the group of silanols having the formula (i) -_ .
  • (D) about 5 to 10 weight percent, based on the total solids of the base formulation, of a crosslinker, which may be a polycarboxylic acid; and (E) about 1 weight percent, based on the total solids of the base formulation, of a curing catalyst which may be an amine.
  • the components (A) , (B) , (C) , (D) , and (E) form what may be termed a base resin composition.
  • the composition may also include about 1 to 20 weight percent, based on the total solids of the base resin composition, of an ultraviolet absorbing material such as a benzophenone, a benzothiazole, or a benzotriazole.
  • the inclusion of the crosslinker and the curing catalyst in the resin composition speeds the curing of the resin at low temperatures.
  • the above described resin composition may be cured for example at a temperature between about 50°C and 250°C.
  • the curing time is shortened at higher temperatures.
  • Curing at higher temperatures and consequently shorter times is preferable.
  • the shorter curing time allows the production line to operate faster.
  • the shorter curing time also reduces the probability of quality degradation due to airborne particulates becoming trapped in the uncured resin.
  • Curing at higher temperatures may also drive a portion of the ultraviolet absorbing material out of the resin composition before the curing is complete. This results in a thicker coating being required to achieve acceptable ultraviolet blocking. It may also result in a shallower ultraviolet absorption edge and a consequently greater tendency to introduce yellow coloration. Furthermore, as a result of the rapid curing, the ultraviolet absorbing material may not be chemically bound in the cured resin. Under extreme conditions such as boiling in water, the ultraviolet 5 absorbing material may be leached out of the resin coating, reducing its effectiveness as an ultraviolet blocker.
  • the resin layer 12 may be formed from a resin composition (W) including:
  • Benzophenones, benzothiazoles and benzotriazoles are organic chemical groups that exhibit ultraviolet absorbing or blocking properties.
  • the compounds 2-hydroxy-4-methoxy-benzophenone; 2,4- dihydroxybenzophenone; and 2-(2 '-hydroxy-3,5'-di-tert- amylphenyl)benzotriazole have been used successfully. Modifications of the siloxane resin formula may be possible without impairing its capacity to host the ultraviolet blocking agents.
  • the resin layer 12 may be formed from a resin composition (WO) including: (a) about 43 weight percent of colloidal silica; (b) about 17 weight percent of the silanol methyltrimethoxysilane having the formula CH 3 Si(OCH 3 ) 3 ; (c) about 25 weight percent of the silanol glycidoxypropyltrimethoxysilane having the formula
  • Figure 2 shows the transmission as a function of wavelength for samples of 2mm thick float glass coated with a layer, between about 2 (two) and 3 (three) micrometers thick, of the cured composition (W) (curve A) and a layer between about two (2) and three (3) times of the cured composition (WO) (curve B) .
  • the curing temperature for both layers was between about 190 and 210 °C and the curing time for both layers was between about 4 (four) and 5 (five) minutes. The increased steepness of the ultraviolet absorption edge for the composition without the catalyst and crosslinker is evident.
  • Figure IB illustrates an antireflection coating 14 on resin layer 12.
  • the coating 14 on substrate 10 may be identical.
  • the coating 14 may be a multilayer design, including a first film or layer 16 of silicon ' dioxide (Si0 2 ) approximately 86 nm thick, a second film 18 of titanium dioxide (Ti0 2 ) approximately 115 nm thick, a third layer 20 of Si0 2 about 32 nm thick, and a fourth layer 22 of Ti0 2 about 13 nm thick.
  • antireflection coating 14 may be applied by DC reactive, sputtering in an atmosphere including oxygen.
  • the antireflection coating may be first applied to resin layer 12 and then to substrate 10.
  • the resin formulation should be selected to closely match the refractive index of substrate 10 so that the same antireflection coating can be applied to both the substrate and the resin. This index match also ensures that there are no interference effects between resin layer 12 and substrate 10 which would impair the function of antireflection coating 14.
  • the resin layer 12 may be applied to the surface of substrate 10 using a roll coater.
  • the above-discussed base resin compositions must be modified to facilitate effective application by a roll coater.
  • These base resin compositions may be aqueous alcoholic suspensions of the resin solids. If they are used in this form for roll coating, or even further diluted with an alcohol, they will dry too quickly when spread as a thin layer. This precludes adequate control over layer - thickness and the uniformity of that thickness. This lack of control can manifest itself as color variations over a substrate and/or color variations from one substrate to another.
  • a solvent with a higher boiling point than alcohol should be added to the base resin composition to ensure that it is diluted sufficiently so it remains flowable on the substrate until it is cured. Control of the viscosity of the resin is critical in maintaining control of the thickness of the resin layer and of the uniformity of the thickness over the surface being coated.
  • the above-discussed resin formulations may be prepared for processing by the roll coater by diluting those compositions with a glycol.
  • the resin formulation may be mixed directly from the constituents in the proportions described above.
  • the resin composition including a current agent and a catalyst, may also be obtained from a commercial supplier, for example the SDC Corporation of Anaheim, California.
  • the resin may be obtained with or without the ultraviolet blocking additive.
  • the commercial resin may include up to about 25 volume percent, based on the total volume of the resin, of propylene glycol. It was found, however, that this additive was not sufficient, at any degree of dilution, to provide the control of viscosity and flowability demanded for the present invention.
  • the flowability may be improved by adding to the commercial resin, including the propylene glycol, about 5 to 35 volume percent of hexylene glycol. Superior results, however, may be obtained when the resin formulation includes only hexylene glycol in the proportion of about 5 to 50 percent of the total volume of the resin.
  • the glycol diluent is equally effective in resin compositions with and without a crosslinker and a curing catalyst.
  • the efficacy of the hexylene glycol may be attributed to its high boiling point which helps maintain viscosity during the coating operation.
  • Other solvents than hexylene glycol may provide satisfactory control of viscosity. It is believed, however, that any such solvent should have a boiling point greater than about 189°C, that is, greater than the boiling point of propylene glycol.
  • the color-correcting or neutralizing dye is dissolved in the hexylene glycol before it is used to dilute the resin.
  • the dye may be a mixture of two or more solvent soluble dyes, for example a cobalt complex dye having the color index number Solvent Red 125 and a copper phthalocyanine dye having the color index number Solvent Blue 67.
  • Solvent Red 125 and Solvent Blue 67 may be obtained from the Ciba Geigy Corporation of Hawthorne, New York under the trade names Orasol Red G and Orasol Blue GN, respectively.
  • the ultraviolet blocking material is 2,2' ,4,4 ' tetrahydroxybenzophenone in the proportion of about 13.0 weight percent
  • the dye mixture may consist of 2.5 parts Orasol Blue GN and 1.0 parts Orasol Red G in the proportion of about 0.0047 weight percent of the total solids of the base resin composition.
  • the dye is chosen such that it absorbs green and red wavelengths of light perceptibly equal to the amount of blue light absorbed by the ultraviolet-absorbing agent.
  • the total absorption includes perceptibly — 13 — equal amounts of all primary colors.
  • the transmission color through the substrate is substantially neutral.
  • the transmitted light becomes more yellow. If such is the case, more dye must be added to neutralize the yellow color.
  • Quantity of dye required to effect color correction may be between about 0.001 and 0.1 weight percent, based on the total solids of the resin composition. Adding the dye to the glycol additive provides more precise control over the dying operation, as an immersion method would not be suitable for introducing such small quantities of dye.
  • the specific quantity of dye added may vary widely depending on the type and origin of the dye and its degree of dilution as purchased. A method of determining a suitable dye color and dilution independent of the concentrated dye dilutions will now be described.
  • a worksheet may be set up as shown in Figure 3.
  • wavelength values from 380 to 780 nm are entered at 10 nm intervals.
  • transmission values, for the appropriate wavelengths, of a glazing coated with a resin without a correcting dye are entered.
  • values of radiated intensity of a CIE standard illuminant such as illuminant "C" are entered.
  • the X, Y, and Z integral values are summed and entered in cell C7/R46.
  • the CIE color coordinates (x, y, and z) represent the integral values X, Y, and Z as a decimal fraction of the sum of X, Y, and Z. They may be calculated and displayed in column Cl rows Rl to R3 (shaded) .
  • the x, y, and z values for the standard illuminant (the neutral point) may be displayed in the shaded cells C2/R1, C2/R2, and C2/R3 to permit a rapid comparison with the coordinates of the glazing.
  • one or more of the tabulated wavelengths between about 500 nanometers and 700 nanometers may be selected. For example some wavelength value representing green, for example 520 nm, and some value representing red, for example 630 nm, may be selected.
  • the transmission values at the selected wavelengths are reduced until the coordinates of the glazing in the shaded cells of column * Cl match the coordinates of the illuminant in column C2. If a match can not be obtained when transmission is reduced to zero at the selected wavelength or wavelengths, additional red or green wavelengths may be selected until a match is obtained.
  • color coordinates for the correcting dye may be determined by from the reduced transmission values at the selected wavelengths. For example, the transmission values in the blue region of the spectrum, that is at _ ⁇ 7 _
  • wavelengths less than about 500 nm may be set to equal to the highest values of transmission in the spectrum of the glazing.
  • the transmission values at wavelengths less 500 nm are strongly influenced by absorption in the ultraviolet absorbing material in the resin. Setting such transmission values equal to the highest values in the spectrum thus produces the effect of removing the ultraviolet absorbing material from the resin. That which remains is equivalent to the glazing coated with a resin containing only a correcting dye.
  • the coordinates in column Cl now represent the "dye" that has been created by the selected reduction of red and green wavelengths. Any real dye which has the computed color coordinates can be used to make the color correction with that particular resin.
  • the transmission spectrum of that dye may be different from the transmission versus wavelength values represented on the spreadsheet.
  • Dye color coordinates calculated according to the above procedure will be very close to the neutral point.
  • the actual hue represented by the coordinates would, in practice, be very difficult to judge by eye. This is because of its proximity to the neutral point.
  • a procedure for determining a practical dye mixture is as follows.
  • the dye color coordinates calculated according to the above procedure are plotted on a CIE coordinate diagram along with the coordinates of the illuminant or neutral point. This is illustrated in Figure 4.
  • the point CN represents the coordinates of the standard illuminant ("C") or the neutral point and the point CU represents the coordinates of the correcting dye.
  • a straight line LC is drawn between neutral point CN and dye point CU. Any set of coordinates lying on line LD will represent to an adequate approximation a dye having the same hue but different color saturations.
  • a concentrated dye of the correct hue may be prepared by mixing a red dye and a blue dye in a container and matching the color against a sample known to have coordinates lying on line LD.
  • a more accurate technique is to employ a colorimeter such as the "Hunterlab Ultrascan Colorimeter", available from Hunter Associates Laboratory of Reston Virginia.
  • the concentrated dyes may be mixed in a sample cell, and proportions of red and blue adjusted until the color coordinates of the dye in the cell, measured on the colorimeter fall on line LD.
  • the concentrated dye mixture may then be diluted with a neutral colored solvent until the measured coordinates match the actual dye point CU.
  • the dye mixture proportions and the dilution level required to effect a proper color correction may be established.
  • the glass substrate 10 to be coated is first washed using a flat glass washer available from Bilco Inc. of New Haven, Connecticut. Such washers are typically used in the glass processing industry and can be purchased as a complete system.
  • the washing system comprises two washers and a rinse unit.
  • the glass sheet or substrate passes through the washers where it is washed with hot demineralized water, and then rinsed with deionized (DI) water. It then may be dried with a multiple air knife system and transferred by conveyor to a roll coater.
  • DI deionized
  • the roll coater may a Model 300 supplied by Black Brothers of Mendota, Illinois.
  • the roll coater is configured for forward roll application to the top surface of the substrate as the substrate travels horizontally through the coater.
  • the principle of the coater operation is illustrated by Figure 5.
  • the roll coater includes a fluid reservoir (not shown) , containing 45 gallons of the diluted resin, i..e. diluted with the glycol containing the color-correcting dye.
  • This resin formulation is metered from the fluid reservoir into space 30 between rollers 32 and 34.
  • Roller 32 is the coating roller
  • roller 34 is the doctor roller.
  • a pool 36 is formed between and extends along the length of the rollers.
  • a guard 31 covers space 30 between the rollers to prevent foreign objects or particles from entering or being caught in that space.
  • the substrate 10 is supported by rollers 40 and driven in the direction of Arrow A by roller 42. Roller 42 rotates in the direction of Arrow B and coating roller 32 rotates in the direction of Arrow C.
  • Rollers 32 and 42 may rotate at an angular velocity of about 30 revolutions per minute (rpm) .
  • the rollers 32 and 40 may each have a diameter of about 9 inches.
  • the diameters and angular velocities of the rollers translate to a line speed for substrate 10 of about 75 feet per minute.
  • the roller 34 is rotated in the direction of Arrow D. Its peripheral speed is about one-twentieth of the peripheral speed of roller 32.
  • the shear force set up by this speed differential ensures that coating 44 is transferred primarily to the surface of roller 32 and from there to substrate 10. All the rollers may be surfaced with a 40
  • Durometer EPDM rubber The above-described roll coater will accept glass sheets up to 50 inches in width.
  • the thickness control for layer 44 is effected by varying the peripheral speed of roller 34 and the pressure of roller 34 on roller 32.
  • the diluted resin may be rolled onto glass sheet 10 at a temperature of about 20°C.
  • the thickness of layer 44 may be about 7.5 micrometers.
  • the thickness of the resin layer is chosen to provide optimum ultraviolet blocking consistent with maintaining the smoothness of the finished glass. It has been- determined that the smoothness of the original glass surface may be maintained if the cured resin thickness is less than about 8 micrometers. It is difficult to maintain thickness control and uniformity if the thickness of the cured resin exceeds about 8 micrometers.
  • substrate 10 is transferred by conveyor to a curing oven.
  • the curing temperature may be between about 50°C and 250°C.
  • the curing times are adjusted according to the curing temperature.
  • the resin-coated substrate is baked for abo.ut 4 minutes at a temperature of about 200°C.
  • the resin is fully hardened.
  • the thickness of the resin layer after hardening may be about 2.5 micrometers.
  • substrates may be coated using resin formulations from which the crosslinker and curing catalyst are omitted. This may be possible because of the high curing temperature of about 200°C. Steps .are taken in the process described above to minimize particulate contamination of the resin coating.
  • the process may be carried out inside a Class 100 clean room enclosure. This includes the transfer of the substrates from the washers to the coater and from the coater to the curing oven.
  • the oven itself is operated with a flowing filtered air supply and a positive pressure designed to maintain the interior in a Class 100 condition.
  • a resin management system should include a filtering system to extract particulates from the diluted resin.
  • This system may comprise a 1 micron prefilter and a 0.4 micron absolute filter. Excess resin which results from the thickness control process described above is pumped, using a two stage diaphragm pump, through the filtering system and then returned to the fluid reservoir. This aspect of the process reduces waste as well as manufacturing costs.
  • Figure 6 shows the spectral performance of a glass glazing at different stages of the fabrication process.
  • Curve C represents a transmission versus wavelength plot for an untreated glass sheet or- substrate.
  • Curve D is a transmission versus wavelength plot for the sheet plus a resin coating applied using the above-described process.
  • Curve E shows the transmission of the finished glazing according to the construction of Figure 1A.
  • the visible spectral range is the range V extending from the blue limit of visibility VB (at about 420 nm) to the red limit of visibility VR (at about 680 nm) .
  • the effectiveness of the color-neutralizing or correcting dye is evident from the slight drop in transmission in the yellow-green region G and the red region R. As can be seen, the dye causes a perceptibly equal loss of transmission of the red and green wavelengths to match the loss of transmission of the blue wavelengths between VB and a wavelength of about 450 nm.
  • the color-neutralizing dye plus the ultraviolet absorbing material remove perceptibly equal proportions of the three primary colors from the light transmitted through the substrate.
  • the transmission color is, therefore, color neutral as opposed to yellow had the dye not been used.
  • the total loss in visible light transmission resulting from the blue absorption and the dye color correction is approximately 4 percent. This can be seen by the transmission differences between Curves C and D ( Figure 6) .
  • the finished product See Curve E
  • the amount and composition of dye is determined by the transmission loss of blue light caused by the ultraviolet absorbing material. If the ultraviolet absorption were at sufficiently short wavelengths, the dye may not be needed.
  • Another embodiment of the present invention includes providing the ultraviolet blocking property of the resin by using inorganic materials, such as cerium oxide, titanium oxide, neodymium cxide, and zinc oxide.
  • the oxide materials may be introduced into the polysiloxane resins in the form of a collodial suspension. Up to 15 percent weight of cerium dioxide may be introduced into the resin in this way. When colloidal suspensions of ultraviolet blocking oxides are used, the amount of colloidal silica used may be correspondingly reduced.
  • Organic ultraviolet blocking materials may be omitted from the resin if inorganic ultraviolet blocking materials are used.
  • a resin-coated glazing about 7.7 micrometers thick and containing 6 weight percent, based on the total solids of the base formulation, of cerium oxide -24- provides complete blocking of ultraviolet wavelengths shorter than about 365 nm.
  • the resin composition having the inorganic blocking material may be formulated without a crosslinker and a curing catalyst if the curing temperature is about 200°C.
  • polysiloxane resins may be formulated to include ultraviolet blocking materials and color correcting dye.
  • resins may include, for example, acrylics, methacrylates and melamines.
  • polysiloxane resins are preferred because they have excellent adhesion to glass and may have hardness comparable to glass.
  • antireflection coatings could be used.
  • the coatings could have more layers or fewer layers, and be made from various materials.
  • Such coatings could be applied by thermal evaporation techniques provided the temperature of the resin-coated glass was not allowed to rise above about 260°C during the deposition process.
  • an antireflection coating by chemical treatments as, for example, described in U.S. Patent No. 2,490,662.
  • a film having a lower refractive index than the glass is formed on the glass by selective chemical removal of certain components of the glass.
  • the glass substrate may also be chemically etched to form a light diffusing surface. This procedure, however, while reducing surface reflection, does not provide an increase in transmission.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Wood Science & Technology (AREA)
  • Surface Treatment Of Glass (AREA)
  • Paints Or Removers (AREA)

Abstract

Un vitrage de protection (5) comprend un substrat de verre (10) et un revêtement en résine (12) sur au moins une surface du substrat. Le revêtement comprend une matière d'absorption des ultraviolets et un colorant pour corriger la couleur de transmission du substrat (10).
EP19910913979 1990-07-24 1991-07-19 Protective glazing and process for making the same Withdrawn EP0495048A4 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US55767690A 1990-07-24 1990-07-24
US557676 1990-07-24
US72861191A 1991-07-11 1991-07-11
US728611 1991-07-11

Publications (2)

Publication Number Publication Date
EP0495048A1 true EP0495048A1 (fr) 1992-07-22
EP0495048A4 EP0495048A4 (en) 1993-11-24

Family

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EP19910913979 Withdrawn EP0495048A4 (en) 1990-07-24 1991-07-19 Protective glazing and process for making the same

Country Status (4)

Country Link
EP (1) EP0495048A4 (fr)
JP (1) JPH05501894A (fr)
CA (1) CA2066198A1 (fr)
WO (1) WO1992001557A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0785097A1 (fr) 1995-11-30 1997-07-23 COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN-MICHELIN & CIE Bande de roulement de pneumatique prévulcanisée pour rechapage

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5371138A (en) * 1990-07-24 1994-12-06 Tru Vue, Inc. Ultraviolet blocking polysiloxane resin and process for making the same
EP0597391B1 (fr) * 1992-11-09 1998-09-09 Central Glass Company, Limited Plaque de verre avec un revêtement multicouche absorbant les rayonnements ultraviolets
US6187845B1 (en) 1999-05-03 2001-02-13 Ciba Specialty Chemicals Corporation Stabilized adhesive compositions containing highly soluble, red-shifted, photostable benzotriazole UV absorbers and laminated articles derived therefrom
US6245915B1 (en) 1999-05-03 2001-06-12 Ciba Specialty Chemicals Corporation Asymmetrical bisbenzotriazoles substituted by a perfluoroalkyl moiety
US6191199B1 (en) 1999-05-03 2001-02-20 Ciba Speciatly Chemicals Corporation Stabilized adhesive compositions containing highly soluble, high extinction photostable hydroxyphenyl-s-triazine UV absorbers and laminated articles derived therefrom
US6268415B1 (en) 1999-05-03 2001-07-31 Ciba Specialty Chemicals Corporation Stabilized adhesive compositions containing highly soluble, photostable benzotriazole UV absorbers and laminated articles derived therefrom
IT249284Y1 (it) * 2000-10-02 2003-04-08 Fiat Auto Spa Lastra di materiale trasparente.
US7663739B2 (en) 2002-10-18 2010-02-16 Board Of Regents, The University Of Texas System Customizable spectral profiles for filtering
EP1815182A4 (fr) 2004-09-22 2013-01-23 Univ Texas Sources d'eclairage et profils spectraux personnalisables
US20070184283A1 (en) * 2006-01-10 2007-08-09 Breshears Jean D Glass Structure and Method of Making the Same
US8570498B2 (en) 2009-05-15 2013-10-29 Board Of Regents, The University Of Texas System Filters, illuminants, and customized spectral profiles for reducing perceptible changes in appearance
EP3204933A4 (fr) * 2014-10-10 2018-07-18 Michael Shipman Feuille planaire luminescente

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1267607A (fr) * 1960-09-16 1961-07-21 Detag Plaque de verre absorbant les rayons ultra-violets
FR1273247A (fr) * 1960-11-08 1961-10-06 Film plastique notamment pour glaces de vitrines ou similaires ainsi que glaces et vitres pourvues de ce dispositif
US4139652A (en) * 1977-11-30 1979-02-13 Ppg Industries, Inc. Solvent system for electrostatic shade band deposition process

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4476281A (en) * 1978-11-30 1984-10-09 General Electric Company Silicone resin coating composition
JPS56109847A (en) * 1980-01-29 1981-08-31 Kanegafuchi Chem Ind Co Ltd Primer composition
US4355135A (en) * 1981-11-04 1982-10-19 Dow Corning Corporation Tintable abrasion resistant coatings
CA1293655C (fr) * 1985-04-30 1991-12-31 Takashi Taniguchi Article optique antireflechissement, et sa preparation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1267607A (fr) * 1960-09-16 1961-07-21 Detag Plaque de verre absorbant les rayons ultra-violets
FR1273247A (fr) * 1960-11-08 1961-10-06 Film plastique notamment pour glaces de vitrines ou similaires ainsi que glaces et vitres pourvues de ce dispositif
US4139652A (en) * 1977-11-30 1979-02-13 Ppg Industries, Inc. Solvent system for electrostatic shade band deposition process

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO9201557A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0785097A1 (fr) 1995-11-30 1997-07-23 COMPAGNIE GENERALE DES ETABLISSEMENTS MICHELIN-MICHELIN & CIE Bande de roulement de pneumatique prévulcanisée pour rechapage

Also Published As

Publication number Publication date
CA2066198A1 (fr) 1992-01-25
JPH05501894A (ja) 1993-04-08
WO1992001557A1 (fr) 1992-02-06
EP0495048A4 (en) 1993-11-24

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