Self-cleaning substrates and methods for making the same
10094027 ยท 2018-10-09
Assignee
Inventors
- Jay A. Kahn (Houston, TX, US)
- Grant Nintzel (Alpharetta, GA, US)
- Yves Biehlmann (Pfaffenheim, FR)
- Craig Belnap (Johns Creek, GA, US)
- Clinton Zediak (Tarentum, PA, US)
- John Keener (Freeport, PA, US)
- James Bell (Monroeville, PA, US)
- Albert L. Askin (Lower Burrell, PA, US)
- Paula L. Kolek (Tarentum, PA, US)
- Jean Ann Skiles (Gibsonia, PA)
Cpc classification
C23C28/00
CHEMISTRY; METALLURGY
B05D1/28
PERFORMING OPERATIONS; TRANSPORTING
C23C26/00
CHEMISTRY; METALLURGY
B05D5/08
PERFORMING OPERATIONS; TRANSPORTING
International classification
C23C28/04
CHEMISTRY; METALLURGY
C23C28/00
CHEMISTRY; METALLURGY
C23C26/00
CHEMISTRY; METALLURGY
Abstract
A methods, apparatus and compositions for producing colored, self-cleaning substrates by roll coating are provided. The roll coated, colored, self-cleaning substrates retain the predetermined color and a predetermined gloss of the colored coating, thereby facilitating their use in architectural applications. The roll coated, colored, self-cleaning substrates may be iridescent-free.
Claims
1. A method comprising: (a) first roll coating an inorganic barrier coating liquid onto at least a portion of an initial colored sheet product, wherein the inorganic barrier coating liquid is in the form of an aqueous solution; (i) wherein the initial colored sheet product comprise an organic layer disposed on a base material; (ii) wherein the initial colored sheet product comprises a predetermined color and a predetermined gloss; (b) first converting the inorganic barrier coating liquid into an inorganic barrier layer, thereby producing an intermediate product, wherein, after the first converting step, the inorganic barrier layer is located on at least a portion of the organic layer, and wherein, after the first converting step, the intermediate product retains the predetermined color and retains the predetermined gloss of the initial colored sheet product; (c) second roll coating a self-cleaning coating liquid onto at least a portion of the inorganic barrier layer, wherein the self-cleaning coating liquid is an aqueous-based liquid consisting essentially of water, titanium dioxide particles, silica and optional surfactant, and wherein the second roll coating step comprises uniformly applying the self-cleaning coating liquid to the inorganic barrier layer; and (d) second converting the self-cleaning coating liquid into a self-cleaning layer, thereby producing a final sheet product, wherein, after the second converting step, the self-cleaning layer is located on at least a portion of the inorganic barrier layer, and wherein, after the second converting step, the final sheet product retains the predetermined color and retains the predetermined gloss of the initial colored sheet product, and wherein the final sheet product is iridescent free.
2. The method of claim 1, wherein the base material is steel-based.
3. The method of claim 1, wherein the base material is aluminum-based.
4. The method of claim 1, wherein the base material is titanium-based.
5. The method of claim 1, wherein the base material is non-metallic based.
6. The method of claim 5, wherein the base material comprises at least one of a plastic and a glass.
7. The method of claim 1, wherein the base material comprises a mixture of metals and non-metallic materials.
8. The method of claim 7, wherein the base material comprises metal sheets sandwiching a polymeric sheet.
9. The method of claim 7, wherein the base material comprises non-metallic materials sandwiching a metal material.
10. The method of claim 1, wherein the inorganic barrier coating liquid is in the form of an aqueous solution comprising silica.
11. The method of claim 10, comprising: agitating the aqueous-based self-cleaning coating liquid inside a coating reservoir; and applying the aqueous-based self-cleaning coating liquid to the inorganic barrier layer.
12. The method of claim 11, wherein the agitating step comprises continuous agitation.
13. The method of claim 1, wherein the organic layer is a colored layer.
14. The method of claim 1, wherein the organic layer comprises polymeric-based materials.
15. The method of claim 1, wherein, after the second converting step (d), the titanium dioxide particles are uniformly dispersed throughout the self-cleaning layer.
16. The method of claim 1, wherein the inorganic barrier layer has a thickness of from 0.1 to 1.0 microns.
17. The method of claim 1, wherein the inorganic barrier layer has a thickness of from 0.2 to 1.0 microns.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION
(20) Broadly, the present disclosure relates to substrates that realize a combination of one or more of: (i) self-cleaning properties, (ii) a visual appearance that meets consumer acceptance standards, and (iii) a cost effective production methodology. In one embodiment, a substrate achieves at least two of these criteria. In one embodiment, a substrate achieves at least three of these criteria.
(21) In one aspect, and with reference now to
(22) Visual Appearance
(23) In one embodiment, the self-cleaning coating layer 30 retains the gloss of the material underlying the self-cleaning coating layer 30, such as the gloss of the organic layer 20. For example, the gloss of the substrate may remain relatively unchanged after application of the self-cleaning coating layer 30. In one embodiment, the gloss of a substrate having the self-cleaning coating layer 30 may change by not greater than about 20 units (% gloss units) relative to the gloss of the material underlying the self-cleaning coating layer 30. In other embodiments, the gloss of a substrate having a self-cleaning coating layer 30 changes by not more than about 15 units, or by not more than about 13 units, or by not more than about 10 units, or by not more than about 9 units, or by not more than about 8 units, or by not more than about 7 units, or by not more than about 6 units, or by not more than about 5 units, or by not more than about 4 units, or by not more than about 3 units, or by not more than about 2 units, or by not more than about 1 unit relative to the gloss of the material underlying the self-cleaning coating layer 30.
(24) Gloss may be measured in accordance with ASTM D 523. One instrument for measuring gloss is a BYK-GARDNER AG-4430 micro-TRI-gloss glossmeter, which is capable of measuring gloss as 20, 60 and 85. In one embodiment, a glossmeter measures gloss at one of 20, 60 and 85, and the substrate containing the self-cleaning coating layer 30 retains the gloss of the underlying material at this one angle. In one embodiment, a glossmeter measures gloss at two of 20, 60 and 85, and the substrate containing the self-cleaning coating layer 30 retains the gloss of the underlying material at these two angles. In one embodiment, a glossmeter measures gloss at all three of 20, 60 and 85, and the substrate containing the self-cleaning coating layer 30 retains the gloss of the underlying material at all three angles.
(25) In one embodiment, the self-cleaning coating layer 30 retains the color of the material underlying the self-cleaning coating layer 30. For example, the color of the substrate may remain relatively unchanged after application of the self-cleaning coating layer 30. In one embodiment, the color of a substrate having a self-cleaning coating layer 30 may change by not greater than about 10 Delta-E relative to the color of the material underlying the self-cleaning coating layer 30. In other embodiments, the color of a substrate may change by not greater than about 9 Delta-E, or not greater than about 8 Delta-E, or not greater than about 7 Delta-E, or not greater than about 6 Delta-E, or not greater than about 5 Delta-E, or not greater than about 4 Delta-E, or not greater than about 3 Delta-E, or not greater than about 2 Delta-E, or not greater than about 1 Delta-E.
(26) As known to those skilled in the art, Delta-E is a number that represents the distance between two colors. Delta-E may be measured using LCH, LAB and other color parameters, and via a consistent illumination source (e.g., white light of a defined wavelength and wattage output) at a consistent, specified distance between the light and the substrate, and via one of the various Delta-E equations. In one embodiment, the Delta-E equation is based on dE76. In one embodiment, the Delta-E equation is based on dE94. In one embodiment, the Delta-E equation is based on dE-CMC. In one embodiment, the Delta-E equation is based on dE-CMC 2:1. In one embodiment, the Delta-E equation is based on dE2000. The parameters surrounding these Delta-E equations are known to those skilled in the art, and are described, for example, in:
(27) (1) Historical development of CIE recommended color difference equations, by A. R. Robertson, Laboratory for Basic Standards National Research Council of Canada Ottawa, Ontario, Canada K1A OR6, Paper presented at the ISCC Conference on Color Discrimination Psychophysics, Williamsburg, Va., 1989, published in Color Research & Application, Vol. 15, Issue 3, Pages 167-170, published online 2007 by Wiley Periodicals, Inc., A Wiley Company; and
(28) (2) The development of the CIE 2000 colour-difference formula: CIEDE2000, by M. R. Luo et al. of the Colour & Imaging Institute, University of Derby, UK, in Color Research and Application, Vol. 26, Issue 5, pp. 340-350, published online 2001 by Wiley Periodicals, Inc., A Wiley Company.
(29) Each of these publications are incorporated herein by reference in their entirety.
(30) Delta-E may be measured using a consistent illumination source, located at a specified distance from the substrate, and a spectrophotometer (e.g., from Hunterlab, a.k.a., Hunter Associates Laboratory, Inc., 11491 Sunset Hills Road, Reston, Va. 20190-5280). To determine the color difference at two different viewing angles, the color values may be measured by the spectrophotometer at the first angle, and a second angle, and Delta-E determined. The second angle is generally at least 15 degrees different than the second angle, but is generally not more than 165 degrees different than the first angle. In one embodiment, Delta-E is measured in accordance with ASTM 2244. In one embodiment, Delta-E is measured using a GRETAG MACBETH COLOR-EYE 2246, or equivalent instrumentation.
(31) The self-cleaning coating layer 30 may be iridescent free. In one embodiment, a substrate 1 containing a self-cleaning coating layer 30 is iridescent free, as determined via visual inspection. In one embodiment, the visual inspection is completed via the human eye, with a vision of 20/20, and at an appropriate distance to detect iridescence in the substrate.
(32) Uniformity, Thickness and Durability
(33) To facilitate one or more of these visual appearance properties, the self-cleaning coating layer 30 may be relatively uniform. In one embodiment, a substrate 1 containing a self-cleaning coating layer 30 achieves a uniformity rating of at least H, as measured in accordance with the below described wettability test. In other embodiments, a substrate 1 containing a self-cleaning coating layer 30 achieves a uniformity rating of at least G, or a uniformity rating of at least F, or a uniformity rating of at least E, or a uniformity rating of at least D, or a uniformity rating of at least C, or a uniformity rating of at least B, or a uniformity rating of A, as measured in accordance with the below described wettability test.
(34) To facilitate one or more of these visual appearance properties, the self-cleaning coating layer 30 may be relatively thin. In one embodiment, the self-cleaning coating layer 30 has a thickness of not greater than about 1 micron. In other embodiment, the self-cleaning coating layer 30 has a thickness of not greater than about 0.9, or not greater than about 0.8 micron, or not greater than about 0.7 micron, or not greater than about 0.6 micron, or not greater than about 0.5 micron, or not greater than about 0.4 micron, or not greater than about 0.3 micron, or not greater than about 0.2 micron. The thickness of the self-cleaning coating layer 30 should be sufficiently large to facilitate self-cleaning properties. In one embodiment, the thickness of the self-cleaning coating layer is at least about 0.05 microns.
(35) The self-cleaning coating layer 30 may be durable. In one embodiment, a substrate 1 containing a self-cleaning coating layer 30 is abrasion/scratch-resistant (e.g., as measured after normal densification). In one embodiment, a substrate containing a self-cleaning coating layer 30 is able to consistently pass a pencil hardness test as defined by ASTM D3363-05. In these pencil hardness tests, the substrate 1 may consistently pass/achieve a 5H or 6H rating, or higher. In one embodiment, the self-cleaning layer is adherent. Adherent to means that a surface is capable of passing the Scotch 610 tape pull test, as defined by ASTM D3359-02, Aug. 10, 2002.
(36) Self-Cleaning Properties
(37) Passive Self-Cleaning
(38) The self-cleaning coating layer 30 facilitates self-cleaning properties. In one embodiment, the self-cleaning coating layer 30 is a passive self-cleaning layer. A passive self-cleaning layer is one that does not utilize photocatalysis to facilitate cleaning of the substrate. A passive self-cleaning layer generally is moderately hydrophilic and achieves a water contact angle of not greater than about 40. In one embodiment, a passive self-cleaning coating layer achieves a water contact angle of not greater than about 37. In other embodiments, a passive self-cleaning coating layer achieves a water contact angle of not greater than about 35, or a water contact angle of not greater than about 30, or a water contact angle of not greater than about 25, or a water contact angle of not greater than about 20, or a water contact angle of not greater than about 15. Those skilled in the art can convert these contact angle measurements to a surface tension value. For example, a contact angle below about 15 degrees equates to a surface tension of about 70 dyne/cm. For a contact angle of about 20 degrees the surface tension is about 68 dyne/cm. For a contact angle of about 38 degrees the surface tension is about 59 dyne/cm.
(39) The passive self-cleaning coating layer may facilitate self-cleaning properties via reduction of surface tension, as evidenced by the above low wetting contact angles. As a result, many contaminants (e.g., organic contaminants) will not readily adhere to the surface of passive self-cleaning coating layer. Furthermore, when water is applied (e.g., via rain or washing), contaminants are readily removed via the water.
(40) A passive self-cleaning coating later generally includes materials that facilitate the above-described visual appearance, uniformity, thickness, and/or durability properties while facilitating the reduction of surface tension of the substrate. One passive self-cleaning coating layer includes silica (SiO.sub.2), such as when applied via an aqueous solution comprising silica. In one embodiment, the silica is applied via a roll coating or a spraying process, as described in further detail below. In one embodiment, a passive silica coating is achieved via application of EASY CLEAN by PPG Industries, Pittsburgh, Pa.
(41) Active Self-Cleaning
(42) In one embodiment, the self-cleaning coating layer 30 is an active self-cleaning layer. An active self-cleaning layer is one that utilizes photocatalysis to facilitate cleaning of the substrate. An active self-cleaning layer generally is very hydrophilic and achieves a water contact angle of not greater than about 25. In one embodiment, an active self-cleaning coating layer achieves a water contact angle of not greater than about 22. In other embodiments, an active self-cleaning coating layer achieves a water contact angle of not greater than about 20, or a water contact angle of not greater than about 18, or a water contact angle of not greater than about 15, or a water contact angle of not greater than about 12, or a water contact angle of not greater than about 10, or a water contact angle of not greater than about 8, or a water contact angle of not greater than about 7.
(43) Like the passive self-cleaning coating layer, an active self-cleaning coating layer may facilitate self-cleaning properties via reduction of surface tension, as evidenced by the above low wetting contact angles. As a result, many contaminants (e.g., organic contaminants) will not readily adhere to the surface of passive self-cleaning coating layer. Furthermore, when water is applied (e.g., via rain or washing), contaminants are readily removed with the water.
(44) Additionally, an active self-cleaning coating layer may facilitate cleaning via photocatalysis. In this embodiment, the self-cleaning substrates may actively break down materials that come in contact with surfaces of the substrate, such as dirt, grime, oil, dust, and/or mold, to name a few, (visual detractants) by utilizing sunlight, fluorescent light, blacklight or any other light source at wavelengths above about 300 nm, to photocatalytically break down the visual detractants. The visual detractants may then be removed from the surface via water (e.g., rain water). In other words, visual detractants may decompose to simple organic or inorganic compounds, which re-enter the atmosphere and/or wash away under the effects of ambient conditions (e.g., heat, wind and/or rain), thus making the substrates self-cleaning. Use of self-cleaning substrates provides an easier way to maintain visually appealing surfaces, and an easier way to clean substrates, and in the absence of detergents, which may be harmful to the environment, and in the absence of a dedicated water spray, which may waste water.
(45) Photocatalysis means the use of light to excite a catalyst on a surface to release energy. The catalyst is not consumed by this reaction. The energy released from the catalyst is used to start a reaction, or reaction sequence. Semiconductors can have photocatalytic properties.
(46) Semiconductors are any of various solid crystalline substances, such as germanium, titanium, indium or silicon, or the oxides of these crystalline substances, having electrical conductivity greater than insulators. Semiconductors are distinguished from insulators by a band gap energy. Band gap energy is the energy that electrons must have to move from a valence band to a conduction band. There is an arbitrary band energy assigned of 4.0 electron volts (ev) to separate semiconductors from insulators. Semiconductors have a band gap of less than or equal to 4.0 electron volts. Titanium dioxide in the anatase crystalline form has a band gap of 3.2 ev.
(47) In one embodiment, the active self-cleaning coating layer is a titanium dioxide layer. A titanium dioxide layer is a coating containing titanium dioxide particles with particle sizes in the 10-50 nm range (generally). The coating may also contain clay, mineral, alkali and/or other semiconductor(s).
(48) The photocatalytically active self-cleaning coating layer may include a plurality of a photocatalytically active semiconductor fine particles. The particles may be uniformly dispersed within the layer (sometimes referred to herein as film) or may be non-uniformly dispersed in the film. The particles are located in the film so that at least a portion of the fine particles are partially exposed to the environment through the surface of the film so as to facilitate self-cleaning functionality. In one embodiment, titanium dioxide is used as the photocatalytically active semiconductor. Suitable types of photocatalytically active TiO.sub.2 semiconductors that may be used include, but are not limited to, anatase, rutile and brookite crystalline forms of titanium dioxide and or combinations thereof. In one embodiment, the photocatalytically active film is an anatase titanium dioxide layer, where the titanium dioxide particles are in a size range of about 10 to about 50 nm. In one embodiment, the photocatalytically active film is produced from TOTO THPC090402WC-A, which is an aqueous based liquid containing about 0.5-10 wt. % silica, 85-95 wt. % water, and 0.2-5 wt. % titanium dioxide. In this embodiment, TiO2 is the active material and silica is the film former. In one embodiment, a surfactant, such as an organic liquid (e.g., poly(oxy-1,2-ethanediyl), alphamethylomega-[3-[1,3,3,3-tetramethyl-1-[(trimethylsilyl)oxy]-1-disiloxanyl]propoxy]-) is used with the aqueous based liquid.
(49) It is believed that the mechanism of the photocatalytically active semiconductor works as follows: once the photocatalytically active semiconductor, for example TiO.sub.2, is illuminated by ultraviolet light with a wavelength above about 300 nm, electrons in the valence band are excited to the conduction band. When the electrons return to their lower energy state, energy is emitted and interacts with water vapor or oxygen molecules to form hydroxyl radicals and super oxide anions, respectively. Both the hydroxyl radicals and superoxide anions are strong oxidizing species, which can react and breakdown organic pollutants into simpler, lower molecular weight, oxidized products.
(50) Barrier Layer
(51) In one embodiment, and with reference now to
(52) Coupled to means joined to another surface. For example, a photocatalytically active film or layer may be at least partially coupled to a barrier layer via the physical interaction between the materials of those two layers. In one embodiment, a first material may be coupled to a second material, and the first material may also be adherent to the second material. Adherent to means that a surface is capable of passing the Scotch 610 tape pull test, as defined by ASTM D3359-02, Aug. 10, 2002.
(53) CO.sub.2 Removal
(54) In one embodiment, a self-cleaning coating layer 40 is configured to also remove carbon dioxide from surrounding gases. Methods for configuring coatings (e.g., coatings containing photocatalytically active substances) to remove carbon dioxide, and systems and compositions relating to the same, are described in commonly-owned U.S. patent application Ser. No. 11/828,305, entitled SURFACES AND COATINGS FOR THE REMOVAL OF CARBON DIOXIDE, filed Jul. 25, 2007, which is incorporated herein by reference in its entirety.
(55) Base Material
(56) The base material 10 may be any material that can have self-cleaning coatings. In one embodiment, the base material 10 is aluminum or an aluminum alloy, such as any of the aluminum association series 1xxx, 2xxx, 3xxx, 4xxx, 5xxx, 6xxx, 7xxx, 8xxx or 9xxx aluminum alloys. As described below, aluminum-containing base materials 10 having an organic layer 20 are particularly difficult to produce via high production rate systems (e.g., via roll coating) due to the thermal limitations imposed on the processing of aluminum and/or the organic material coupled thereto. The base material 10 may be a wrought aluminum product or a cast aluminum product. In one embodiment, the wrought aluminum product is a sheet, foil or plate product. In one embodiment, the rolled product has a thickness of at least about 0.1 mm. In one embodiment, the wrought aluminum product is an extrusion. In one embodiment, the wrought aluminum product is a forging. In one embodiment, the base material 10 is an aluminum alloy suited for use in any of the commercial applications noted below. In one embodiment, the base material 10 is brushed aluminum. In one embodiment, the base material 10 is a composite aluminum product, such as a laminate aluminum product, including those described in commonly-owned U.S. Pat. No. 6,455,148.
(57) Other base materials, such as other metals (e.g., steel, titanium) may be used. Non-metallic materials may also be employed as the base 10. For example, plastics, glass, composites, fibers, ceramics, cements, laminates, particulates, meshes, sieves, aerogels, papers, and combinations thereof, to name a few, may be utilized as the base 10. In one approach, the base 10 may comprise mixtures of metals and non-metallic materials. For example, the base 10 may comprise metal sheets sandwiching a polymeric sheet therebetween. Conversely, the base 10 may comprise non-metallic materials sandwiching a metal material therebetween. Various other combinations exist to produce the base 10.
(58) Organic Layer
(59) The substrate 1 may include an organic layer 20 coupled to the base 10. An organic layer means a layer comprising predominately carbon-based or polymeric-based materials. In one embodiment, the organic layer 20 is liquid (e.g., water) impermeable and may protect the underlying base 10 from communication with liquid water or other materials that may permeate and/or contact a surface of the base 10. In one embodiment, the organic layer 20 comprises materials produced from commercially available products, such as latex-based paints, oil-based paints, silicon-based coatings, polymeric coatings, and others. In one embodiment, the organic layer 20 comprises a predetermined pigment and/or sheen so as to provide the body 10 with the desired color and/or gloss features.
(60) Base-to-Self-Cleaning Layer
(61) In one embodiment, and as illustrated in
(62) Methods and Systems for Producing Self-Cleaning Substrates
(63) To produce the self-cleaning substrates at commercially viable production rates, roll coating or spraying may be employed. One embodiment of a method and system for producing self-cleaning substrates via roll coating is illustrated in
(64) Liquid coatings are applied to substrates in a variety of methods including spray, dip, roll, knife, electrodeposition, vapor deposition, slot, and curtain coating. For metallic substrates (e.g., aluminum), liquid coating is commonly transported to the applicator roll via direct contact with a bath, by contact with a second roll that has contact with a bath, by direct spraying onto the roll, and the like. The rolls can have a metal, plastic or other type surface depending on the material to be coated. The various rolls in a roll coater are usually given common names associated with their function. In the four roll configuration shown in
(65) In the area of coating metallic substrates for packaging and architectural end uses, metallic substrates are coated in one of two ways: as a continuous web or as approx. one m.sup.2 (10 ft.sup.2) sheets. A continuous web is rewound into a coil for subsequent trimming, slitting, or fabrication. Aluminum and steel are most commonly used as the substrate. Many coatings are applied on metal webs via forward or reverse roll coat with a deformable applicator roll 520.
(66) For applying the self-cleaning coatings of the present disclosure, the applicator roll 520 generally has a pliable covering about 5-50 mm thick made from urethane, EPDM rubber or similar pliable material. The covering Shore A hardness, referred to as durometer, is about 45-85 (e.g., about 65), and the surface roughness R.sub.a is about 20-80 micro inches. R.sub.a is determined by first finding a mean line parallel to the general surface direction, dividing the surface such that the sum of the areas formed above the line is equal to the sum of the areas formed below the line, and computing the surface roughness summing the absolute values of all the areas above and below the mean line and dividing by the sampling length. This allows the applicator roll 520 to transfer liquid coating to the web 1 and conform to any web surface irregularities or roll irregularities to ensure complete coverage at a uniform film thickness.
(67) In one embodiment, a continuously fed and moving fairly thick metal substrate sheet 1 passes over a pass, which can bend to roller pressure but is considered non-deformable, in contrast to thin metal foil, paper, and the like line roll 528 to directly contact the applicator roll 520. Substrate thickness for a continuous process of this invention will generally be between about 0.1 mm to 0.8 mm, such as between about 0.100 mm to 0.500 mm. The coating rate will vary widely depending on the coating liquid viscosity and coating thickness desired, but will usually be from about 5 m/min to 500 m/min, such as from about 200 m/min to 400 m/min.
(68) A source of self-cleaning coating precursor liquid 514 is provided and is usually held in an appropriate type container 526, although the coating liquid may, in some instances, be sprayed on an applicator roll. The precursor liquid 514 is generally aqueous and contains particulate matter, such as TiO2 or SiO2. The particulate size is generally in the range of 0.01 micron to about 0.2 to 0.3 micron. The precursor liquid is generally has a viscosity of about 1 centipoise (where one-thousand centipoises (cP) equals one Pascal-second). These precursor liquids, once applied, can be air-dried, UV (ultraviolet) or EB (electron beam) cured, heat cured, or the like, to provide the desired resulting cured coating. In one embodiment, the precursor liquid may contain a suitable surfactant to facilitate wetting of the substrate 1 surface, such as when an organic layer 20 is included. Preferred surfactants include those that are non-foaming. In one embodiment, the precursor liquid results in a passive self-cleaning coating, such as EASY CLEAN produced by PPG of Pittsburgh, Pa. In one embodiment, the precursor liquid results in for an active self-cleaning coating, such as THPC090402WC-A (Waterborne Photocatalyst Clear Coating-A) by TOTO, Japan, or TPX-220 TS or TPX-85 TS by Kon Corporation, Japan.
(69) The container 526 may include an agitator (not illustrated), such as a stir rod, to facilitate even application of the precursor liquid and attainment of a suitable visual appearance. In one embodiment, the precursor liquid is continuously or near continuously agitated so as to facilitate mixing and production of iridescent-free coating surfaces. It has been found that coatings applied in the absence of agitation may not realize an iridescent-free appearance. In one embodiment, an air driven, slow speed agitator is used inside the coating reservoir in conjunction with a pumping system that uses cross coating pan flow. In other words the coating exits the pump and enters the left side of the coating pan. The coating exits the pan, and moves back to the coating reservoir on the right side of the coating pan.
(70) The applicator roll 520 may reverse roll coat (rolls opposite to substrate) the moving substrate 1, as shown in
(71) The applicator roll 520 can be located/disposed directly opposite the metering roll 530 and a backup roll 510 as shown in the embodiment of
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(73) In either instance, the distance between the applicator roll 520 and the metering roll 530 should be sufficiently short so as to facilitate a tight metering nip. A tight metering nip facilitates production of thin, uniform self-cleaning coating layers.
(74) The precursor liquid 14 is preferably contacted with/applied to a metering roll 530 to coat the metering roll 530. This metering roll 530 is the roll to which liquid coating is initially applied and can be of any type effective to carry the coating liquid to the applicator roll 520. The metering roll 530 can be porous or non-porous, but generally has a surface roughness sufficiently high to enable metering of sufficient precursor liquid to the applicator roll 520. In this regard the metering roll 530 may be nickel or chrome-steel plated, having a surface roughness (R.sub.a) of about 150. The liquid 514 is held in an appropriate container 526 as shown in
(75) The roll coating may produce material at a rate of at least about 10 feet per minute (fpm). In one embodiment, the roll coating produces material at a rate of at least about 25 fpm. In other embodiments, the roll coating produces material at a rate of at least about 50 fpm, or at least about 75 fpm, or at least about 125 fpm, or at least about fpm. In one embodiment, the roll coating may produce material at a rate of not greater than about 800 fpm. In other embodiments, the roll coating produces material at a rate of not greater than about 700 fpm, or not greater than about 600 fpm. In some instances, the pick-up roll and metering roll are the same roll. In other instances, the pick-up roll is separate from the metering roll.
(76) When roll coating multiple coatings, such as organic coating, a barrier layer, and an active self-cleaning layer in series, the roll coating system can be arranged to have a series of rolls, ovens and/or coolers for each coating to facilitate the serial production of substrates having multiple coatings.
(77) Below are some embodiments of metering-to-applicator roll configurations, for reverse roll coat and forward roll coat configuration, as appropriate:
(78) TABLE-US-00001 Configuration Metering Roll Applicator Roll 1 Smooth/rough Hard metering Smooth/rough soft roll (chrome, steel, ceramic (urethane/rubber/other) finish or other) coated applicator roll 2 Smooth/rough Hard metering Smooth rough hard roll (chrome, steel, ceramic applicator roll (chrome, finish or other) steel or ceramic finish, other) 3 Smooth/rough Hard metering Smooth/rough soft roll (chrome, steel, ceramic (urethane/rubber/other) finish or other) coated applicator roll
(79) Methods of producing various self-cleaning substrates are also illustrated in
(80) Commercial Applications
(81) The self-cleaning substrates disclosed herein may be used in a variety of commercial applications due to their low-cost production methodology. For example, the substrates could be used as an architectural product, including building exterior wall panels, including aluminum composite materials (ACM), foam panel, rib panels, soffit, and flashing, to name a few. Post-painted products and other factory manufactured building materials, such as roofing, vinyl siding, terracotta, and brick, may be a useful substrate for coating with a self-cleaning coating. Other substrates include materials used in metal signage, airplanes, automobiles (e.g., cars, trucks, trailers), highway sound barriers and guards, and industrial manufacturing venting systems, to name a few. Materials for interior programs may also benefit from self-cleaning layers, such as metal, laminate, hardware, plastic, paper based ceiling panels, doors, furniture, duct work for commercial buildings, and other non-wear surfaces. The substrate may also be a food container, such as an aluminum can, where, just before filling the can with a food or consumable liquid, a UV light may be used to clean the wall of pathogens, thereby extending shelf life and increasing product safety. The self-cleaning substrate may also be useful electronic devices, solar devices, wind powered devices, environmental sensors, battery technology and polymer electronics.
(82) Various ones of the unique aspects noted hereinabove may be combined to yield visually appealing, self-cleaning substrates at commercially viable production rates. These and other aspects, advantages, and novel features of the disclosure are set forth in part in the description that follows and will become apparent to those skilled in the art upon examination of the following description and figures, or may be learned by practicing the disclosure.
(83) Wettability Test
(84) I. Materials and Apparatus
(85) 1. Squeeze type polyethylene bottle for each solution.
(86) 2. Solutions:
(87) A100% Distilled Water B90% Distilled Water, 10% Denatured Ethyl Alcohol C80% Distilled Water, 20% Denatured Ethyl Alcohol D70% Distilled Water, 30% Denatured Ethyl Alcohol E60% Distilled Water, 40% Denatured Ethyl Alcohol F50% Distilled Water, 50% Denatured Ethyl Alcohol G40% Distilled Water, 60% Denatured Ethyl Alcohol H30% Distilled Water, 70% Denatured Ethyl Alcohol
(88) II. Procedure and Evaluation
(89) 1. Inclined coated substrate approximately 45 to the horizontal.
(90) 2. An A solution is applied across the entire width of the web from the polyethylene applicator using a rapid sweeping motion.
(91) 3. If the sheet is A wettable, the top edge of the stream will not depart from its straight line before 5 seconds after application.
(92) 4. If the stream pulls from its initial straight line before 5 seconds, the B solution is then tried on a fresh wrap of sheet. If a B solution fails to wet the surface, a C solution is tried and so on.
(93) 5. The solution which wets the entire web is the wettability rating.
EXAMPLES
Example 1Spray Coating
(94) An aluminum alloy substrate is spray coated with PPG EASY COAT, and cured. The coating is iridescent. Photos of the iridescent coating are illustrated in
Example 2Brush Rolled Substrates
(95) Three cream-colored painted aluminum alloy substrates are produced. A first substrate is used as a control. A second substrate is coated with PPG EASY CLEAN via a roll brush and cured (passive coating). A second substrate is coated with PPG EASY CLEAN via a roll brush and cured (passive coating), and is then coated with TOTO THPC090402WC-A THPC090402WC-B via a roll brush and cured. Color and gloss change is tested via the three substrates by exposure to a QUV A bulb for a period of 1000 hours. As illustrated in
Example 3Roll CoatingUrethane Roll
(96) Various painted aluminum alloy substrates are roll coated via a pilot coil roll coating line. The system used to roll coat is similar to that illustrated in
Conditions for Example 3 Tests
(97) Overview: The purpose of this trial is to determine if the self cleaning coating systems could be applied by a reverse roll coat coil operation. Small coils (300 linear feet) are produced for field testing. All four coatings applied well. Line trials confirmed that the rough chrome roll (150 Ra) assisted in successful roll coat application. Each coating improved the surface tension of the incoming substrate as determined by contact angle measurement. Surface energy went from around 45 dynes/cm to at least about 68 dynes/cm, as illustrated in
(98) Line Conditions/Run Details Line Speed of 150 FPM (11.2 second oven dwell time) i. Applicator roll at 50% over line speed ii. Pick-up roll at 40% under line speed Both oven zones set 250 F. i. High velocity temperature: VariedSee
(99) Product Observations: LRB 767 sample: i. PPG EZ-CLEAN, UC108219 (Trials 1-11) 1. Good coating flow (slight crows feet appearance) 2. Coating viscosity was stable in the pan 3. Coating was easy to clean up with water followed by a MEK wipe 4. Uniform gloss 5. Appearance better over matte finish 6. Wipes off directly after curing (allow longer time to cure) LRB 768 sample: i. Toto THPC090402WC-A (Trials 1-6) 1. Good coating flow (slight crows feet appearance) 2. Coating viscosity was stable in the pan 3. Coating was easy to clean up with water followed by a MEK wipe 4. Uniform gloss 5. Two component mixture 6. Severe foaming in pump bucket 7. Appearance better over matte finish 8. Wipes off directly after curing LRB 769 sample: i. KON TPX-220TS (Trials 1-4) 1. Good coating flow (slight crows feet appearance) 2. Coating viscosity was stable in the pan 3. Coating was easy to clean up with water followed by a MEK wipe 4. Uniform gloss 5. Appearance better over matte finish 6. Wipes off directly after curing LRB 770 sample: i. TOTO TPCA001 (Trials 1-7) 1. Good coating flow 2. Coating viscosity was stable in the pan 3. Coating was easy to clean up with MEK 4. Uniform gloss 5. Appearance better over matte finish 6. Wipes off directly after curing
Example 4Roll Coating
(100) Various painted aluminum alloy substrates are roll coated via a pilot coil roll coating line. The system used to roll coat is similar to that illustrated in
Conditions for Example 4 Test
(101) Overview: The purpose of this trial is to: Determine whether self cleaning coatings could be applied by a reverse roll coat coil operation containing two hard rolls; determine whether the surfactant portion of the self-cleaning coating (TOTO part B) of the two component system (TOTO HYDROTECT) was necessary to wet the pre-coated substrate. The substrate was previously coated with PPG's UC108219 coating; and Modify the pumping equipment to minimize foam build while using this two component coating system.
Line trials utilizing the two hard rolls has mixed results. The coating are successfully applied, but there is no control of coating film thickness. This application method produces sheet with areas of non-uniform layers. Roll roundness appears to be the issue; without a deformable roll the unevenness is difficult to remove. While in the two hard roll configuration, the rough pick-up roll is worn smooth after several hours of operation. Adding the surfactant to the self-cleaning coating did not appear to correct the uneven thickness issue. This suggested that surfactant is not necessary when applying it to a barrier layer made from PPG's UC108219 EZ-CLEAN barrier coating. Extension of the pumping system return pipe reduced foam build when using the TOTO self-cleaning coating with surfactant. The return pipe was extended below the coating surface inside the pump reservoir. A small coil was produced, identified as LRB776-8, using part A of the TOTO coating only (i.e., no surfactant). A urethane applicator roll was used to coat this coil.
(102) Line Conditions/Run Details Line Speed of 150 FPM (11.2 second oven dwell time) i. Applicator roll at 50% over line speed ii. Pick-up roll at 40% under line speed iii. Oven Temperature: 250 F. (high and low) iv. Coating: Toto THPC090402WC v. Reducing Solvent: None vi. Application Viscosity: No adjustment required; run as received, water thin at about 71 F. vii. Roll Types: 1. Top side applicator, ceramic, 11.0 inch diameter 2. Top side applicator, urethane 65 durometer, 11.0 inch diameter 3. Top side pickup roll, chrome plated, 150 Ra, 6.0 inch diameter 4. Roll Direction Reverse roll coated against sheet tension viii. Roll Speeds: VariousSee
(103) Product Observations LRB 776No. 1: i. Toto THPC090402WC-A, part A-only, two hard rolls (Trials 1-2) 1. Good coating flow (slight crows feet appearance) 2. Coating viscosity was stable in the pan 3. Coating was easy to clean up with water followed by a MEK wipe 4. Uniform gloss 5. No foaming in the pump reservoir 6. Uneven coating thickness 7. No ability to squeeze out roll imperfections LRB 776No. 2: i. Toto THPC090402WC-A, two hard rolls (Trials 3-5); 1. Added various amounts of TOTO part B to 4 gallons of TOTO part A 2. No coating uniformity improvement was observed. LRB 776No. 3: i. Toto THPC090402WC-A, part A only, urethane applicator roll (Trials 6-8) 1. Even coating thickness 2. Good coating flow (slight crows feet appearance) 3. Coating easily wet the pre-coated sheet 4. Uniform gloss 5. No foaming in the pump reservoir
(104) While various embodiments of the present disclosure have been described in detail, it is apparent that modifications and adaptations of those embodiments will occur to those skilled in the art. However, it is to be expressly understood that such modifications and adaptations are within the spirit and scope of the present disclosure.