Multilayer coating with visual effects

Abstract

Embodiments of the present invention generally relate to the field of multilayer color coatings, and more particularly to multilayer coatings comprising one or more gel coat layers and visual effect pigments.

Description

Technology Field

[0001] related Cross-applications -reference

[0002] This application claims the benefit of U.S. provisional application No. 62 / 242,894, filed on October 16, 2015.

[0003] Technology field

[0004] Embodiments of the present invention generally relate to the field of multilayer color coatings, and more particularly to multilayer coatings comprising one or more gel coat layers and visual effect pigments. Background Technology

[0005] Gel coats are widely used in numerous applications as an outer surface layer for composite molded articles. Gel coats are typically found on composite articles exposed to environments requiring resistance to moisture, cracking, and similar properties, or on articles requiring a strong, flexible, abrasion- and impact-resistant surface and / or a smooth, glossy finish. Examples of such articles include, among others, boat hulls, bathtub enclosures, swimming pools, spas, and body panels on cars and trucks.

[0006] Gel-coated articles are typically formed by spraying a gel coat composition from a high-pressure spray gun onto the inner surface of an open mold, optionally applying one or more other materials, and applying a lamination resin for a composite article onto the gel coat or intermediate material. The forming method typically involves curing the gel coat and then removing the cured gel-coated article from the mold. Gel-coated articles may also be produced by applying a composite material into a multi-part mold, injecting or applying a gel coat composition, closing the mold, curing the gel coat, and then removing the cured gel-coated article from the mold.

[0007] Gel coats for composite articles are typically formulated from thermosetting substrate resin systems, such as unsaturated polyester, acrylate, and urethane-type resins, into which fillers, pigments, and other additives are introduced. The gel coat must exhibit low viscosity at high shear to allow for easy application to the mold, but it must also be resistant to sagging or dripping after application. Other important characteristics of the gel coat are surface tackiness and curing time.

[0008] Typically, gel coat resins are mixed with reactive, polymerizable monomers, such as styrene or methyl methacrylate (MMA), which are also used to reduce the viscosity of the resin system for applying the gel coat by spraying. Conventional gel coat compositions contain 35 to 45 wt% of reactive monomers and other volatile organic compounds (VOCs). The presence of large amounts of styrene and other VOCs results in the release of styrene vapors and other hazardous air pollutants (HAPs), which are closely regulated by government regulations.

[0009] US 20010010367 A1 discusses a luminescent polymer prepared from a composition comprising a thermosetting unsaturated polyester, a filler, and a phosphorescent pigment suspended therein, and used to manufacture gel-coated articles and molded, cast, and fiberglass-reinforced plastic (FRP) articles. The luminescent polymer is described as exhibiting bright, long-lasting photoluminescent afterglow, strong thermal stimulation of the afterglow by heat, and electroluminescent properties.

[0010] US 20070249742 A1 describes a method for substantially eliminating or essentially removing visual knitlines in an article derived from a resinous composition comprising at least one thermoplastic resin and at least one special visual effect additive. Visual effect additives comprising a metallic pigment that may be in the form of mineral flakes or flakes are discussed. Metallic pigments of various metals and average particle size ranges are discussed.

[0011] US 20110123750 A1 discusses gel coat compositions, particularly marine gel coat compositions, methods for preparing the same, and the use of the same for coating the surface of articles exposed to light, water and solvents. The gel coat incorporates precipitated silica having a BET surface of 150 to 250 m² / g, a SiO2 content of 98.5 wt% or more, and a Na2O content of 0.5 wt% or less.

[0012] US 20120225190 A1 describes a method for obtaining features of a target coating layer. Specifically, a clear coat layer is provided on a target coating layer to measure color and appearance features of the target coating. The clear coat layer may comprise a material from a renewable resource. The application also relates to a system for obtaining features of a target coating layer.

[0013] US 20150166760 A1 discusses metallic effect pigments having a coating comprising a platelet-shaped substrate, wherein the coating comprises at least one hybrid inorganic / organic layer, the hybrid layer having at least one inorganic oxide component in part and at least one organic component, the organic component being at least partially covalently bonded to the inorganic network through one or more organic network forming agents (formers). The application also discusses methods for manufacturing these metallic effect pigments and uses thereof. means of solving the problem

[0014] As one aspect of the present invention, a multilayer coating having a visual effect is provided. The coating comprises (a) a high-visibility gel coat layer comprising a thixotropic agent and an unsaturated polyester having a size and surface that does not significantly impair the clarity of the gel coat layer; (b) a visual effect layer comprising a transparent gel coat and a visual effect pigment; and (c) a color layer comprising a gel coat and a simple pigment.

[0015] In another aspect, a method for manufacturing a multilayer coating having a visual effect is provided. The method comprises applying a high-visibility gel coat resin as a layer to a mold, wherein the resin is a high-visibility gel coat resin comprising a thixotropic agent having a size and surface that does not significantly impair the clarity of the gel coat layer. The method also comprises applying a visual effect resin directly or indirectly to a transparent gel coat resin layer to form a visual effect layer. The method also comprises applying a color resin directly or indirectly to the visual effect layer to form a color layer. In some embodiments of the method, the high-visibility gel coat resin is at least partially cured before the visual effect resin is applied and / or the visual effect resin is at least partially cured before the color resin is applied. One or more of the high-visibility gel coat resin, the visual effect resin, and the color resin may be applied by spraying. The method may further comprise applying a thermosetting resin or a thermoplastic resin to the color layer and / or attaching the multilayer coating to a substrate to form an article.

[0016] As another aspect of the present invention, an article coated with the multilayer coating is provided. For example, the article may comprise a composite material (e.g., a fiber-reinforced composite material) that is at least partially coated by a multilayer coating having a visual effect.

[0017] The article may be selected from the group consisting of ships, windmills, swimming pools, bathtubs, showers, sanitary ware, tanks, pipes, tanks, conduits, fume stacks, build panels, vessels, electrical components, aircraft components, and electronic components. For example, a high-clarity gel coat comprises polyester resin, and the article is a ship hull.

[0018] As another aspect of the present invention, a visual effect gel coat resin is provided. The visual effect gel coat resin comprises, with respect to the total weight of the composition, 70 to 90 wt% of a high clarity gel coat resin and less than 2% of at least one silica having a BET of 260-350 m² / g.

[0019] In the above aspect of the present invention, the visual effect gel coat resin may comprise at least one unsaturated polyester resin or other crosslinkable gel coat resin.

[0020] In the above aspect of the invention, the visual effect may be selected from the group consisting of sparkle, metallic effect, pearlescent effect, gloss, image identifiability, roughness, glint, glitter, texture, or a combination thereof. For example, a preferred visual effect is a sparkle effect (also referred to as sparkling). The visual effect pigment may be metal-coated glass particles and / or may have a particle size distribution of 35 to 150 microns. The high-clarity gel coat layer may contain silica (preferably fuming silica) in an amount of less than 2 weight percent. Alternatively or additionally, the high-clarity gel coat layer comprises silica having a BET surface area of ​​260 to 350 m² / g or 280 to 330 m² / g.

[0021] In some embodiments, the high-clarity gel coat layer is formed by curing an unsaturated polyester resin containing a styrene monomer and (meth)acrylic acid and / or alkyl (meth)acrylate. One or more of the high-clarity gel coat layer, the visual effect layer, or the color layer may comprise one or more phthalate-containing polyesters, vinyl-containing polyesters, or methyl methacrylate-containing polyesters.

[0022] Defined terms

[0023] It is understood that the terms used herein are intended to describe specific embodiments only and are not intended to limit them. Additionally defined terms are the technical and scientific meanings of the defined terms as commonly understood and accepted in the technical field of this teaching.

[0024] As used in specifications and claims, the indefinite article includes both singular and plural references unless the context clearly indicates otherwise. Thus, for example, "device" includes one device and multiple devices.

[0025] As used in specifications and claims, and in addition to their common meanings, the terms “substantial” or “substantially” mean within acceptable limits or degrees. For example, “substantially cancelled” means that a person skilled in the art would consider the cancellation acceptable.

[0026] As used in specifications and claims, and in addition to their common meaning, the term “approximately” means within an acceptable limit or amount to a person skilled in the art. For example, “approximately identical” means that a person skilled in the art considers comparing an item to an identical one.

[0027] Relative terms, such as “top,” “bottom,” “upper,” “lower,” “upper,” and “lower,” may be used to describe the relationship of various elements to one another, as exemplified in the attached drawings. These relative terms are intended to include different orientations of the coating and / or article in addition to the described orientation. For example, if the article is inverted, an element described as being “top” of another element will now be “bottom” of that element. Similarly, if the article is rotated 90°, an element described as being “top” or “bottom” of another element will now be “adjacent” to the other element; “adjacent” means to place another element adjacent to it, or to have one or more layers, materials, structures, etc. between the elements.

[0028] "Visual effect" means sparkle, metallic effect, pearlescent effect, gloss, image identifiability, roughness, glint, glitter, texture, or a combination thereof.

[0029] A layer or resin can be attached directly or indirectly to another surface. "Indirect" attachment of one layer to another layer means that an intermediate layer is between them. For example, a first transparent layer can be indirectly attached to a color layer when a second transparent layer is located between the first transparent layer and the color layer.

[0030] Unless otherwise specified herein, the term “viscosity” refers to the viscosity of the polymer in monomers at 25°C (77°C) measured in centipoises (cps) using a Brookfield RV model viscometer. Viscosity under high shear is measured at a shear rate of 10,000 l / s using a cone and plate (CAP) viscometer. The term “NVM” refers to a non-volatile material (e.g., monomer) dispersed in a volatile component as measured according to ASTM D1259.

[0031] In this specification, all percentages are of weight unless otherwise indicated.

[0032] details

[0033] In the following detailed description, representative embodiments describing the detailed description are mentioned without limitation for illustrative purposes to provide an overall understanding of this teaching. Descriptions of known systems, devices, materials, methods of operation, and methods of manufacture may be omitted so as not to obscure the description of the exemplary embodiments. Nevertheless, systems, devices, materials, and methods within the authority of those skilled in the art may be used in accordance with the representative embodiments.

[0034] According to an aspect of the present invention, a multilayer coating comprising one or more high-clarity gel coat layers and one or more visual effect layers is provided, wherein a transparent barrier layer is placed on top of a radiance effect pigment layer and used so that the transparent barrier layer protects the structure and appearance of the radiance effect layer.

[0035] The coating and articles are suitable for marine, transportation, and construction industries and structures. For example, the coating can be applied to kiosks, ATMs, wall panels, and other articles. They provide visual effects similar to popular automotive metallic and pearl finishes. The coating and articles comprise an intermediate layer containing one or more visual effect additives. The coating and articles comprise one or more gel coat layers, for example, three layers, and the method comprises one or more layer application steps, for example, at least three layer application steps. The method creates a deep, rich, shimmering finish that enhances appearance and provides desired visual effects for marine and transportation surfaces. In some embodiments, the coating comprises at least three layers, namely a clear layer, a visual effect layer, and a base color layer.

[0036] In some embodiments, the visual effect layer is a decorative layer containing one or more visual effect pigments and other decorative or embellishing agents provided to impart a desired visual or aesthetic appearance. The decorative or embellishing agents may include, but are not limited to, conventional pigments, particles, and chips. In some embodiments, the multilayer coating comprises three layers, each of which is 5-12 mils, alternatively 7-10 mils.

[0037] The present coating and articles comprising one or more gel coat compositions are disclosed herein. These may be used in the manufacture of gel-coated multilayer coatings. Gel coat compositions, particularly those used for the outermost layer(s) and / or visual effect layer, have high clarity, for example, a clarity of 94 or higher as measured on the white portion of a BYKO chart.

[0038] In some embodiments, one or more layers of the coating or article are a clear gel coat. High clarity gel coat resins are available from Polynt Composites USA, Inc. In some embodiments, the clear layer is a clear polyester gel coat from an unsaturated polyester resin that yields a high clarity gel coat upon curing and / or crosslinking. For example, STYPOL 040-0901, STYPOL 040-0946, and other resins from Polynt Composites USA, Inc. may be used as components for the clear gel coat. As another example, the clear polyester gel coat layer may be formed from a resin comprising one or more phthalate-containing polyesters, vinyl-containing polyesters, or (methyl) methacrylate-containing polyesters. More preferably, the transparent polyester gel coat comprises a phthalate-containing polyester, in particular a phthalate-containing polyester derived from isophthalic neopentyl glycol (iso-NPG).

[0039] The high clarity gel coat resin or layer may comprise an unsaturated polyester resin as 40 to 95%, or 65 to 85%, of the total gel coat composition. The clear coat resin or layer may comprise a reactive monomer (e.g., styrene) as 20 to 60%, or 30 to 45%, of the total gel coat composition. The clear coat resin or layer may comprise 1 to 10%, or alternatively 3 to 8%, (meth)acrylic acid, (meth)acrylate, or other ethylenically unsaturated carboxylic acids. The high clarity gel coat resin or layer is of low color, high clarity, and high weather resistance and water resistance; an example of such a resin is STYPOL Gold Series Resins available from Polynt Composite USA, Inc., Carpentersville, Illinois.

[0040] In some embodiments, the multilayer coating comprises a high-clarity gel coat layer having a clarity of at least 94 on the white portion of the BYKO chart and / or a clarity of less than 26 on the black portion of the BYKO chart. Other suitable features for the high-clarity gel coat resin include a viscosity of 3,200-4,500 cps and a thixotropic index of 4-7.5.

[0041] The unsaturated polyester used in the coating is a reaction product of a polycarboxylic acid or anhydride and one or more polyhydric alcohols dissolved in a crosslinking monomer containing an inhibitor to prevent crosslinking until the resin is used by the manufacturer. The unsaturated polyester is a condensation product of one or more unsaturated dicarboxylic acids or anhydrides, one or more aromatic dicarboxylic acids or anhydrides, and one or more polyhydric alcohols in combination with a polymerizable vinylidene monomer. One or more of the components of the polyester must be ethylenically unsaturated, preferably a polycarboxylic acid component.

[0042] Typical unsaturated acids include dicarboxylic acids and anhydrides, such as maleic anhydride, maleic acid, fumaric acid, methacrylic acid, acrylic acid, itaconic acid, and citraconic acid. Maleic anhydride is the most economical derivative, but fumaric acid can be substituted to yield resins with similar properties but some minor structural differences. The term (meth)acrylic acid refers to acrylic acid, methacrylic acid, or a combination thereof. In the most commercial formulations, the reactivity of the polyester polymer is derived primarily from the maleic anhydride component. Maleate and fumarate-based resins using maleic anhydride, fumaric acid, or maleic acid, or mixtures thereof, are preferred in the present invention. Acrylic acid and methacrylic acid modified polyester resins are also used. The degree of unsaturation varies by including saturated dibasic acids (which include aromatic acids as long as polyester is involved), such as phthalic anhydride, isophthalic acid, phthalic acid, chlorendone anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride, tetrahydrophthalic acid and anhydride, adipic acid, succinic acid, souveric acid, sebacic acid, azelaic acid, terephthalic acid, etc. Orthophthalic (derived from phthalic anhydride or phthalic acid) and isophthalic (derived from isophthalic acid) based polyester resins and their substituted and halogenated derivatives are particularly preferred in the practice of the present invention. DCPD-modified phthalic and / or isophthalic resins may also be used.Examples of polyhydric alcohols include glycols, e.g., propylene glycol, ethylene glycol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, dibromoneopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, 1,3-butanediol, 1,5-pentanediol, 1,3-propanediol, hexylene glycol, triethylene glycol, tetraethylene glycol, dicyclopentadiene hydroxyl adduct; propylene oxide; triols, e.g., trimethylol ethane, trimethylol propane, trimethylol hexane, and hexanetriol; bisphenol A ethers and bisphenol A adducts (e.g., bisphenol dipropoxy ether and adducts of bisphenol A with ethylene oxide), hydrogenated bisphenol A and brominated bisphenol; and others.

[0043] Ethylene unsaturated polyesters are typically semi-rigid or flexible polyesters, but mixtures thereof can be used with rigid polyesters. Preferred polyesters form copolymers with vinylidene monomers. A preferred vinyl monomer is styrene. When comparing styrene to other commercially available monomers, it typically provides equivalent properties at a much lower cost. Certain monomers enhance specific properties; for example, diallyl phthalate and trialyl cyanurate extend the thermal durability required for certain electrical components. Other monomers include vinyl aromatics, such as vinyl toluene, alpha-methylstyrene, divinylbenzene, pt-butylstyrene, o-chlorostyrene, and dichlorostyrene; alkyl esters of alpha, beta-ethylenically unsaturated monocarboxylic acids, such as methyl methacrylate, methyl acrylate, ethyl acrylate, and 2-ethylhexyl acrylate; and vinyl esters, such as vinyl acetate and vinyl propionate. In some applications, these are typically used in combination with styrene. Vinyl esters are generally less suitable for the practice of the present invention. Preferably, the ethylenically unsaturated polyester comprises about 30 to 80% of a polymerizable resin-forming component, and the remainder consists of 20 to 70% crosslinked vinylidene monomers. Controlling the amount of styrene is particularly useful for obtaining a high gloss surface finish.

[0044] The coating and article comprise at least one resin for each layer. The composition of the resin for the various layers will vary based on the desired appearance. Low viscosity (500-1000 cps) resins are used so that they can be easily filled and allow trapped air to escape. High-impact grades are typically preferred to prevent chipping caused by impact or thermal stress. The concentration in the complete formulation is typically 25-95 weight%.

[0045] The resin and composition for each layer may include various other components other than unsaturated polyester, such as one or more fillers. Examples of fillers, depending on the specific physical, chemical, or electrical properties desired, include calcium carbonate (including fine synthetic high-purity grades used for high-viscosity, sagging-free coats), hydrated aluminum silicate and other silicates, clay, limestone powder, mica, talc, aluminum trihydrate, barium sulfate, pyrophyllite, feldspar, carbide, oxide, metal powder, and carbon. Fillers are used to reduce resin shrinkage, lower heat generation, increase hardness, increase thermal conductivity and dimensional stability, increase fire retardancy, or change the density and opacity of the resin. The filler concentration may vary from 5 to 75 weight percent.

[0046] The coating and article, or the layer or resin comprising the coating or article, may comprise one or more thixotropic agents. For example, the thixotropic agents include colloidal silica, precipitated silica, and / or fuming silica. Other thixotropic agents include magnesium aluminum silicate clay (e.g., bentonite). The thixotropic agents are included to prevent sagging and dripping of the gel coat when applied to vertical surfaces and pore-free dense surfaces. In some embodiments, the thixotropic agent is a powder, e.g., having a Brunauer-Emmett-Teller (BET) surface area of ​​260-350 m² / g, or alternatively 280-330 m² / g. In some embodiments, the thixotropic agent is selected from silica having a BET surface area of ​​260-350 m² / g, or alternatively 280-330 m² / g. The BET surface area can be measured by ISO 9277 "Determination of the specific surface area of ​​solids by gas adsorption -- BET method" or other suitable analytical methods. The ISO 9277 procedure is used to measure the specific N2 surface area of ​​silica and silicates according to the BET procedure. The measured value is determined by the cryogenic adsorption of nitrogen at well-defined partial pressures. The analysis was achieved as a multi-point measurement, and linear behavior was observed with a total of 5 measurements in the partial pressure range of 0.05–0.2 (p / p0).

[0047] Fuming silica (CAS no. 112945-52-5) (also known as pyrogenic silica) comprises microscopic droplets of amorphous silica that fuse into branched, chain-like, and / or three-dimensional secondary particles and subsequently aggregate into tertiary particles, because it is produced in a flame. Fuming silica has an extremely low bulk density and a high surface area. Its three-dimensional structure yields viscosity-increasing, thixotropic behavior when used as a thickener or reinforcing filler. Precipitated silica is silica (SiO2) produced by precipitation from a solution containing silicate salts.

[0048] Thixotropic agents are used to minimize filler settling and increase pigment efficiency. They may be used at concentrations of 0.1 to 15 wt%, alternatively 0.25 to 5 wt%, or alternatively 0.5 to 1.75 wt%. Other known thixotropic agents include hydrogenated castor oil and aliphatic acid amides. The thixotropic characteristics of the gel coat must be precisely controlled in terms of the thickness of the deposited film and the tendency of such film to sag. The gel coat must be uniformly thixotropic so that it does not drip when applied to vertical surfaces and pore-free dense surfaces. Gel coat formulations typically contain accelerators, as an extension of gel time can impair the curing of the gel coat within the allotted time, and subsequent application of resin laminates causes expansion and contraction of the gel coat. Special attention must be paid to the gel-time shift caused by the absorption and deactivation of cobalt accelerators by thixotropic agents such as pigments and fuming silica.

[0049] The coating and articles may comprise one or more simple pigments. A simple pigment refers to a pigment that does not provide a visual effect beyond acting as a coloring agent. These are often used in gel coats at a concentration of 0 to 10 weight percent. In the coating and articles, the color layer or the substrate gel coat layer may comprise one or more simple pigments.

[0050] The resin used in the coating and articles may contain one or more solvents. A solvent, such as acetone, may be added to the formulation to dilute it and for spray consistency. A minimal amount of solvent is used (or preferably no solvent is used), because solvents may pose risks or concerns regarding execution, manufacturing, and the environment.

[0051] Other useful components in this resin include inhibitors, curing accelerators, leveling agents, and defoaming agents.

[0052] The coating and articles comprise one or more visual effect pigments. For example, the visual effect pigments provide color and one or more other visual effects, such as sparkle, metallic effect, pearlescent effect, gloss, image identifiability, roughness, glint, glitter, texture, or a combination thereof. Preferred visual effect pigments among these are sparkle effect pigments and metal-coated glass particles. Other visual effect pigments are metallic pigments that may be in the form of mineral flakes or flakes.

[0053] Plastic articles having a shiny look, a metallic or metallic-like look, a true metallic appearance, or any angular metameric appearance are desired in many instances. Plastic articles having a shiny or metallic look can be produced by introducing a special visual effect additive, such as free metal flakes, into the plastic article in a load such that individual flakes are distinguishable to the naked eye, thereby producing an article having a shiny or metallic look. Plastic articles having a true metallic look can be produced by using a much larger load of free metal flakes.

[0054] In some embodiments, the visual effect pigment is selected from the group consisting of glass flakes, metallic pigments, metal flakes, aluminum pigments, cross-linked polymer particles, cross-linked acrylic resins, and mixtures comprising at least one of these additives.

[0055] An example of a visual effect pigment is BASF Luster pigment, which is transparent and reflects light due to its smooth surface and high refractive index. Larger particle sizes can provide a luminous effect as a visual effect. Light reflected from the platelets creates a luster with varying depth and particle sizes—smaller particles impart a satin sheen, while larger particles produce a more sparkling or glitter-like effect. Some of BASF’s MEARLIN special effect pigments feature multi-color play and active color flopping, or "flopping," where the color changes depending on the viewing angle. Although these pigments are non-metallic, they can provide a metallic-looking finish. BASF’s MEARLIN pearlescent pigments are MICA platelets coated with titanium dioxide and / or iron oxide, providing both color and visual effects for various coatings, plastics, and printing ink applications.

[0056] As another example of a visual effect pigment, Eckart’s LUXAN pearlescent pigment includes synthetically manufactured glass coated in layers. As one example, LUXAN CO001 pigment is a small glass flake that provides a transparent shimmering effect as a visual effect. Other glass pearl pigments from Eckhart that can be used as visual effect pigments include LUXAN D001, LUXAN E001, LUXAN F001, LUXAN E221, LUXAN E241, LUXAN C261, LUXAN E261, LUXAN C393, LUXAN D393, LUXAN B241, LUXAN B502, LUXAN B522, LUXAN B542, LUXAN D502, LUXAN D522, LUXAN D542, LUXAN B512, LUXAN D512, and LUXAN B393.

[0057] Desirable metallic pigments are based on metals of Groups 4, 6, 8, 9, 10, 11, 13, and 14 of the periodic table. Metallic pigments can be colored. Examples of these metallic pigments include aluminum, bronze, brass, chromium, copper, gold, iron, molybdenum, nickel, tin, titanium, zinc, etc. Metallic pigments can be manufactured by shredding to yield a wide distribution of irregular particle shapes, or by die-cutting to provide more restricted particle sizes and shapes. Glitter, a specific type of aluminum pigment manufactured from foil, may also be used. Foil, typically rolled to a gauge of less than 0.025 mm, is cut into square, rectangular, or hexagonal shapes, typically ranging in size from 0.2 to about 3 mm, and is typically coated with a clear epoxy lacquer to stop the oxidative dulling of the foil. Glitter with a large particle size can produce distinct highlights of metallic luster. Gold bronze is typically an alloy of copper and zinc with a small amount of aluminum to reduce oxidation. The range of gold colors is produced by varying the proportions of the main alloy components. In various examples, green gold alloys typically contain 70% copper, and the color becomes redder as the percentage of copper increases; 90% copper yields pale gold; and dark gold is produced by the controlled oxidation of the alloy. Gold bronze is typically available in flake form, and the coarser the grade, the more lustrous it is. However, metallic flakes, such as copper, must be handled with caution because they can be sensitive to heat, humidity, and corrosion. Metallic pigments may optionally be coated with, for example, rosin or fatty acids, such as oleic or linoleic acid. Optionally, metallic pigments may be in the form of granules containing a carrier material that may initially contain at least one polymer. Suitable carrier materials include mineral oil, wax, polyethylene, oxidized polyethylene, poly(methyl methacrylate), etc.In granular form, the metallic pigment typically constitutes about 70-80% of the granules, and the remainder is a carrier. The pigment can be used to create or enhance a bright luster, as well as a hammer and leafing finish, in the multilayer coating and articles. Suitable visual effect pigments may also comprise a number of microsphere beads having a diameter in the range of about 1 to about 1300 microns, typically in the range of about 1 to about 850 microns, and more typically in the range of about 10 to about 200 microns. In a specific embodiment, the beads are composed of glass and have a diameter of about 50 microns. In another specific embodiment, the beads are composed of barium titanate.

[0058] Coatings containing visual effect pigments, such as light-absorbing pigments, light-scattering pigments, light-interfering pigments, and light-reflecting pigments, are well known. Metallic flake pigments, such as aluminum flakes, are examples of these effect pigments and have been used to decorate automotive surfaces for the reason that they impart a flake appearance effect, which includes, for example, a differential light reflection effect commonly referred to as "flops," as well as an enhancement of depth perception within the coating and the brilliance imparted by the flake size distribution and flakes. The flop effect varies depending on the angle at which the car body is viewed. The degree of the flop effect achieved is a function of the orientation of the metallic flakes relative to the outer surface of the coating. The degree of brilliance is a function of flake size, surface smoothness, orientation, and edge uniformity. Metallic coatings also typically contain light-absorbing pigments rather than light-scattering pigments. Any light-scattering agent from the pigment or the flakes themselves, for example from the flake edges, reduces both the flops and brilliance of the coating.

[0059] Visual effect pigments typically have an average particle size in the range of about 1 to about 3500 microns, preferably about 1 to about 500 microns, preferably about 10 to about 300 microns, and more preferably about 10 to about 100 microns.

[0060] The particle size distribution of visual effect pigments can affect the visual effect. For example, larger and coarser particles tend to provide more radiance and gloss, while smaller and finer particles tend to provide more structure and opacity. In some embodiments, the visual effect pigment has a coarse particle size distribution, for example, 35 to 150 microns, or 10 to 65 microns.

[0061] In some embodiments, the visual effect pigment layer is present in the visual effect layer of the coating. The visual effect layer may be a radiance effect layer. The visual effect layer may also contain one or more other pigments or reflective particles.

[0062] Useful simple pigments include, for example, inorganic pigments. Exemplary inorganic pigments include metal oxide hydroxides and metal oxides, such as zinc oxide, titanium dioxide, iron oxide, chrome oxide, europium oxide, cerium oxide, colored alumina oxide particles, etc. Inorganic pigments may also include carbonates, such as calcium and cobalt carbonates; rutile (chrome antimony titanate and nickel antimony titanate), spinel (cobalt and iron titanate), friederite, and titanates based on pseudobrookite pigment structures.Other exemplary pigments include: (i) aluminates, e.g., cobalt aluminate and cobalt chrome aluminate; (ii) chromites, e.g., copper chromite black and cobalt chromite green; (iii) ferrites, e.g., pure ferrite spinel containing magnesium and zinc, mixed chromite / ferrite spinel, and mixed chrome iron pigments identified as Pigment Green 17 or Pigment Brown 29; (iv) sulfides and sulfates, e.g., cadmium sulfide and sulfoselenide, cerium sulfide, zinc sulfide, barium sulfate, and strontium sulfate; (v) bismuth pigments, e.g., bismuth vanadate, yttrium and cerium-substituted bismuth oxide to form mixed oxides; (vi) chromates; (vii) silicates, e.g., ultramarine and zirconium silicate pigments; (viii) cyanides, e.g., Fe(II)Fe(III) cyano complexes; (ix) calcium, lanthanum, and tantalum oxide-nitrides; manganese and cobalt phosphates; (x) carbon black; (xi) luminescent pigments, e.g., sulfides and sulfoselenides, alkali-earth sulfides and sulfoselenides, oxysulfides, borates, aluminates, gallates, silicates, germanates, halophosphates and phosphates, oxides, arsenates, vanadates, e.g., yttrium vanadate, niobates and tantalates, sulfates, tungstates and molybdates, alkali-metal halides, alkali-earth halides, anti-Stokes shift pigments, oxyhalides; (xii) quantum effect pigments, e.g., nanoscale silicon having a particle size of less than 5 nanometers; Semi-conductive luminescent nanoparticles, e.g., Cd.sub.3P.sub.2, and PbS; storage phosphors, e.g., CaS:Eu,Sm.

[0063] Phosphorescent materials include ZnS:Cu and SrS:Bi. Phosphorescent materials that can be used include those based on MAl2O4 (wherein M is a metal, such as calcium, strontium, barium, or a combination comprising at least one of the metals mentioned above). The matrix may be doped with europium and dysprosium.

[0064] Useful organic pigments and dyes include acridine dyes, aminoketone dyes, anthracene derivatives, anthraquinones, and aryl- or heteroaryl-substituted poly(C 2-8) Olefin dyes, arylmethane dyes, azine dyes, azo dyes, azo lakes, azos, benzimidazolone pigments, benzothiazole, benzoxazole, bis(hydroxyflavone), bis(styryl)biphenyl dyes, bis-benzoxazolylthiophene (BBOT), carbocyanine dyes, carbostyryl dyes, chrysene, coronene, coumarin dyes, e.g., coumarin 460 (blue) and 7-amino-4-methylcoumarin, Nile Red, etc., cyanine dyes, diazonium dyes, di-azods, di(imminiums), diketopyrrolopyrrole, dioxazine, e.g., dioxazine violet, enthrone, flavantron, infrared (IR) absorbers, e.g., ColorChem International Corp.IR1000 of the company, fluorescent dyes, e.g., anti-Stokes shift dyes that absorb at near-infrared wavelengths and emit at visible wavelengths, fluorocenes, hydrocarbon and substituted hydrocarbon dyes, hydroxyflavones, imidazole derivatives, indantron dyes, indigoid dyes, isoindolinone, lactone dyes, lanthanide chelates, metal dithiol complexes, methine dyes, naphthalimide derivatives, nitro dyes, oxazine, perinone, perylene, phthalocyanine dyes, phthalocyanine, polyazindacen, polycyclic aromatic hydrocarbon dyes, porphyrin dyes, pyrazolin, pyrazolone, pyrene, pyrillium, quinacridone, quinone imine dyes, quinophthalone, Rhodamine 700, Rhodamine 800, Rhodamine and all derivatives thereof, rubrene, scintillation dyes, e.g., oxazole or oxadiazole dyes, Squaryllium, Stilbene, Tetrachloroisoindolinone, Tetrazolium dye, Thermochromic pigment, Thiazole dye, Thiapyrillium, Triarylammonium, Thiazinex, Thioindigoid dye, Thiophene, Thioxanthen, Triarylmethane, Triarylammonium, Xanthen, 1,1'-Diethyl-2,2'-Carbocyanine Iodide, 2-(1-Naphthyl)-5-Phenyloxazole, 2-(4-(4-Dimethylaminophenyl)-1,3-Butadienyl-3-Ethylbenzothiazolium Perchlorate, 2-(4-Biphenyll)-5-(4-t-Butylphenyl)-1,2,2'-Dimethyl-p-Quarterphenyl, 2,2-Dimethyl-p-Terphenyl, 2,2'-p-phenylene-bis(5-phenyloxazole), 2,5-bis-(4-biphenylyl)-oxazole, 2,5-diphenylfuran, 2,5-diphenyloxazole, 3-(2'-benzothiazolyl)-7-diethylaminocoumarin, 3,3'-diethyl-4,4',5,5'-dibenzothiatricarbonin iodide, 3,4-oxadiazole, 3,5,3',5'-tetra-t-butyl-p-quinquophenyl, 3-diethylamino-7-diethyliminofenoxazonium perchlorate, 4,4'-diphenylstilbene, 4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran, It includes 7-dimethylamino-1-methyl-4-methoxy-8-azaquinolone-2,7-dimethylamino-4-methylquinolone-2, etc.

[0065] In some embodiments, a method for manufacturing a multilayer coating having a visual effect comprises the steps of: applying a high-clarity gel coat resin as a layer to a mold, wherein the resin is a high-clarity gel coat resin comprising a thixotropic agent having a size and surface that does not significantly impair the clarity of the gel coat layer; applying a visual effect resin directly or indirectly to a transparent gel coat resin layer to form a visual effect layer; and applying a color resin directly or indirectly to the visual effect layer to form a color layer. The high-clarity gel coat resin may be at least partially cured before the visual effect resin is applied. Alternatively or additionally, the visual effect resin may be at least partially cured before the color resin is applied. The high-clarity gel coat resin, the visual effect resin, and / or the color resin may be applied by spraying.

[0066] The method may also include applying a thermosetting resin or a thermoplastic resin to a color layer and / or attaching a multilayer coating to a substrate to form an article. For example, the substrate may be a surface selected from the group consisting of a ship, a windmill, a swimming pool, a bathtub, a shower, sanitary ware, a tank, a pipe, a tank, a conduit, a fume stack, a build panel, a vessel, an electrical component, an aircraft component, and an electronic component.

[0067] In some embodiments, a multilayer coating is produced by applying a thermosetting gel coat composition as an in-mold coating to the surface of a mold; curing the gel coat composition at ambient temperature to form a partially crosslinked, viscous to tacky-free gel coat; applying a pigment layer; and applying a color layer. The method may also include the steps of applying a material to be molded onto the partially crosslinked gel coat; applying a crosslinkable lamination resin onto the material; and curing the lamination resin and the gel coat into a solid, crosslinked, thermosetting resin at ambient temperature.

[0068] The coating and the article to be coated comprise molded articles made of thermosetting, thermoplastic, or other materials. In particular, optionally fiber-reinforced, coated, or molded articles are typically manufactured by spreading a gel coat composition over the surface of a mold having a surface corresponding to the article during negative relief. In some embodiments, the high-clarity gel coat layer will be the outermost layer of the molded article and will be exposed to the environment and provide protection from the environment. The gel coat composition resin may be spread onto the mold surface by any one of a number of techniques (e.g., brushing, hand lay-up, or spraying). Visual effect resins and color resins may be applied by the same technique or different techniques.

[0069] In some embodiments, optionally fiber-reinforced, reinforced plastic support may then be applied after a partially or fully cured gel coat composition using any one of a number of techniques (e.g., by brushing, hand lay-up, or spraying for an open molding process, or by casting for a closed molding process) to cure and demold the resulting laminate structure. Curing may be facilitated by the use of a free radical polymerization initiator.

[0070] The coating and layer can be applied using standard gel coating equipment. The layer can be applied wet-on-wet, or a film gel can be placed between the layers. LED light can be used to check the coverage of the visual effect layer. Patching can be performed with a transparent patching thinner.

[0071] The average particle size can be measured according to ISO 13320-1. This test procedure describes the measurement of the particle size distribution of silica and silicates between 0.04 and 2500 microns by laser diffraction. The application of laser diffraction using the Fraunhofer model for particle size measurement is based on the phenomenon in which particles scatter light with different intensity patterns in all directions. Scattering depends on particle size. The smaller the particle, the larger the scattering angle.

[0072] The sample to be investigated is pre-sieved through a 500-micron sieve before measurement. This is effective for crushed products, each free of material exceeding 500 microns.

[0073] Also provided is a system and kit for forming a high-clarity gel coat layer and / or a visual effect layer. In an embodiment, the system comprises individual containers packed together, each comprising: a container of at least one additive component selected from the group consisting of a high-clarity gel coat resin and a filler, a pigment, and a thixotropic agent as described herein for the gel coat; a container of a visual effect pigment; a container of a base catalyst; and instructions for combining the contents of the containers to form the high-clarity gel coat layer and / or a visual effect layer as described herein.

[0074] A system for forming a multi-layer gel-coated color article is also provided. The system or kit may comprise a high-visibility gel coat resin, a visual effect resin, and a color resin. In some embodiments, the system comprises individual containers packed together, comprising a container of a high-visibility gel coat resin; a container of a visual effect pigment; a container of a base color and a container of a base catalyst; and instructions for applying and / or combining the contents of the containers to form a multi-layer coating having a visual effect. Specific details for implementing the invention

[0075] This embodiment demonstrates that while standard transparent materials cannot be used to produce the desired gloss effect in multilayer coatings, the multilayer coating described herein possesses excellent color and gloss effects. In this embodiment, four panels were fabricated: Experimental Black, Standard Black, Experimental White, and Standard White. The test was doubled. The fabrication of the panels would be the same as in the field (transparent, effect layer, solid color, laminate) for visual measurement and drawdown on the BYK Chart PA-2810 (available from BYK-Gardner) for quantitative testing. The lab panels were fabricated using a lab-scale suction gun without any special application parameters as long as the equipment passed through them. BYK-Gardner provides drawdown cards and charts for evaluating the color, opacity, and / or clarity of coating materials.

[0076] Example 1 describes a resin for preparing a clear gel coat layer according to the present invention. Table 1 shows the components and concentrations for the Experimental Clear Gel Coat Resin. Hydrophilic exothermic silica had a BET of 280-330 m² / g.

[0077] Table 1

[0078]

[0079] Stypol Gold Series Resins are characterized by low color, high clarity, and high weather and water resistance.

[0080] Example 2 describes a resin for preparing a gel coat resin for a color layer according to the present invention. Table 2 describes the components and concentrations for the Experimental Neutral Gel Coat Resin:

[0081]

[0082] Example 3 describes a resin for the preparation of a visual effect layer. Table 3 describes the components and concentrations of the Experimental Light Silver Resin, comprising the resin described in Example 1 and LUXAN C001 as a visual effect pigment:

[0083]

[0084] Example 4 describes a resin for preparing a color layer. Table 4 describes the components and concentrations for the Experimental Deep Cosmos Resin, comprising the resin described in Example 2 and various simple pigments:

[0085]

[0086] Comparative Example A describes a resin for manufacturing a clear gel coat layer. Table A describes the components and concentrations for the Standard Clear Gel Coat Resin:

[0087]

[0088] The panel was constructed by spraying 7 mils of clear coating resin, 7 mils of visual effect resin, and 7 mils of color resin. After curing and demolding the panel, the difference between the coating and the standard coating was immediately identifiable. The blurriness of Standard Clear (Comparative Example A) was prominent on the black panel. When comparing the colors of the two black panels, the panel made with Experimental Clear (Example 1) appeared jet black, whereas Standard Clear appeared gray. The blurriness of Standard Clear (Comparative Example A) reduced the appearance of the visual effect pigments, making them less general and providing an inferior visual effect coating. Conversely, the panel containing Experimental Clear (having both black and white base color layers) had excellent visual effects, along with a high degree of gloss. The panel with Standard Clear and the white base color layer had a yellowish appearance, demonstrating the excellent clarity of the coating of the present invention with the white base color layer.

[0089] These observations are also supported by color readings of Clear resin on the black and white sections of the Byko chart (#2810), where Experimental Clear and Standard Clear were drawn down on the chart and color measurements were performed.

[0090] Colors were measured using a Datacolor International Spectraflash SF600® Plus CT color computer with Chroma-calc® software. The settings for color measurement were as follows: Large area view (LAV); specular reflection excluded; 10° ramp angle; and Hunter color coordinates. Colors are measured in a three-dimensional color space with dimensions L, a, and b. 'L' indicates the degree of black and white. L values ​​range from 0 (black) to 100 (white). 'a' indicates the degree of green and red. a values ​​range from negative (green) to positive (red). 'b' indicates the degree of blue and yellow. b values ​​range from negative (blue) to positive (yellow).

[0091] The color results for the Clear resin on the byko chart are reported as Delta E (DE), which is the total color change. This value is the square root of the sum of the squares of the differences between the initial and current L, a, and b values. Experimental White is for the resin of Example 1 drawn down against the white section of the byko chart, while Experimental Black is for the resin of Example 1 drawn down against the black section. Standard White and Black are for the resin of Comparative Example A drawn down against the white and black sections of the byko chart, respectively.

[0092] Table 5: Color values ​​for the Visual Effects panel

[0093]

[0094] These color values ​​reflect the clarity of the transparent gel coat applied to the BYKO chart and can be used as a quantifier of the gel coat's clarity. Larger numbers for white indicate higher clarity; smaller numbers for black indicate lower clarity. The Experimental Clear resin (Example 1) had a clarity of at least 94 on the white portion of the BYKO chart and less than 26 on the black portion of the BYKO chart, as measured by a Datacolor International Spectraflash instrument. These results demonstrate that the high-clarity gel coat layer and resin described herein have significantly superior clarity and color delivery compared to standard transparent coats. Experimental Clear also exhibits a much lower level of yellow color (3.55 vs. 5.99) on the white portion, further demonstrating the superior clarity of the coating of the present invention with a white base color layer.

[0095] In the context of this specification, it is specified that methods and apparatus may be implemented to maintain the teachings of the present invention. Additionally, various components, materials, structures, and parameters are included solely as examples and examples and are not included as limitations in any way. In the context of this specification, the teachings may be implemented in other applications within the scope of the claims, and components, materials, structures, and apparatus for implementing such applications may be determined.

Claims

Claim 1 A multilayer coating having a visual effect comprising: a. a high-clarity gel coat layer comprising a thixotropic agent and an unsaturated polyester having a size and surface capable of maintaining the clarity of the gel coat layer, wherein the high-clarity gel coat layer has a clarity of at least 94 on the white portion of a BYKO chart and / or a clarity of less than 26 on the black portion of a BYKO chart; b. a visual effect layer comprising a transparent gel coat and a visual effect pigment; and c. a color layer comprising a gel coat and a simple pigment. Claim 2 A multilayer coating according to claim 1, wherein the visual effect is selected from the group consisting of sparkle, metallic effect, pearlescent effect, gloss, image identifiability, roughness, glint, glitter, texture, or a combination thereof. Claim 3 A multilayer coating having a visual effect of radiance in claim 1. Claim 4 In claim 1, a multilayer coating in which the visual effect pigment is a metal-coated glass particle. Claim 5 In claim 4, a multilayer coating having a visual effect pigment with a particle size distribution of 35-150 microns. Claim 6 A multilayer coating according to claim 1, wherein the high clarity gel coat layer contains silica in an amount of less than 2 weight percent. Claim 7 In claim 1, a multilayer coating comprising silica having a high clarity gel coat layer having a BET surface area of ​​260-350 m² / g. Claim 8 In claim 1, a multilayer coating comprising silica having a high clarity gel coat layer having a BET surface area of ​​280-330 m² / g. Claim 9 delete Claim 10 A multilayer coating according to claim 1, wherein a high clarity gel coat layer is formed by curing an unsaturated polyester resin containing a styrene monomer and (meth)acrylic acid and / or alkyl (meth)acrylate. Claim 11 A multilayer coating according to claim 1, wherein one or more of the high-clarity gel coat layer, visual effect layer, or color layer comprises one or more phthalate-containing polyesters, vinyl-containing polyesters, or methyl methacrylate-containing polyesters. Claim 12 A method for manufacturing a multilayer coating having a visual effect, comprising the following steps: - applying a high-clarity gel coat resin as a layer to a mold, wherein the resin is a high-clarity gel coat resin comprising a thixotropic agent having a size and surface capable of maintaining the clarity of the gel coat layer, and the high-clarity gel coat layer has a clarity of at least 94 on the white portion of a BYKO chart and / or a clarity of less than 26 on the black portion of a BYKO chart; - forming a visual effect layer by applying a visual effect resin directly or indirectly to a transparent gel coat resin layer; - forming a color layer by applying a color resin directly or indirectly to the visual effect layer. Claim 13 A manufacturing method according to claim 12, wherein a high clarity gel coat resin is at least partially cured before a visual effect resin is applied. Claim 14 A manufacturing method according to claim 12, wherein the visual effect resin is at least partially cured before the color resin is applied. Claim 15 In claim 12, a manufacturing method in which a high-clarity gel coat resin, a visual effect resin, and a color resin are applied by spraying. Claim 16 A manufacturing method according to any one of claims 12 to 15, further comprising the step of applying a thermosetting resin or a thermoplastic resin to a color layer. Claim 17 A manufacturing method according to any one of claims 12 to 15, further comprising the step of forming an article by attaching a multilayer coating to a substrate. Claim 18 A method of manufacturing wherein the substrate is the surface of a product selected from the group consisting of a ship, a windmill, a swimming pool, a bathtub, a shower, sanitary ware, a tank, a pipe, a tank, a conduit, fume stacks, build panels, a vessel, electrical components, aircraft components, and electronic components. Claim 19 Article coated with a multilayer coating according to any one of claims 1 to 8, 10, and 11. Claim 20 Article 19, additionally comprising a composite material. Claim 21 Article 20, wherein the composite material is a fiber-reinforced article. Claim 22 Articles selected from the group consisting of ships, windmills, swimming pools, bathtubs, showers, sanitary ware, tanks, pipes, tanks, conduits, fume stacks, build panels, vessels, electrical components, aircraft components, and electronic components. Claim 23 In Clause 22, the high clarity gel coat comprises polyester resin, and the article is an article that is a ship hull. Claim 24 delete Claim 25 delete

Images