KR20070017053A - Improved opaque coatings - Google Patents

Abstract

Opaque coating compositions and methods of use thereof are disclosed. An opaque coating composition can be applied to a substrate to image it. The image on the opaque coating composition allows the operator to deform the substrate. The opaque coating composition can be peeled off from the substrate.

Description

Improved opaque coatings

The present invention relates to an improved opaque coating composition. In particular, the present invention relates to an improved opaque coating composition that can be imaged and peeled off from a substrate.

Various coatings are known. Many coatings are polymer based and are applied to the surface of substrates such as metals, glass and polymers, which may or may not have been coated with one or more coating compositions. While many of these coatings are intended to be permanent, there are also coatings intended to be temporary. Such temporary coatings are for example due to adverse environmental conditions such as contact with sharp objects, contact with objects supporting transferable color bodies and contact with acid rain and other air and water pollutants. It can provide surface protection against deterioration. The time interval that the coating provides protection can be as long as months or years, and workers want the temporary coating to be removed when the level of protection provided by the worker is no longer needed.

For example, removable coatings are used during the production, storage and distribution of automobiles, aircraft, equipment, computers, furniture, sports equipment and the parts from which they are made, as well as building materials and various types of packaging. . In addition to removable coatings, industries using such coatings are preferably environmentally friendly without leaving a coating residue after coating removal.

Opaque and peelable multilayer films are commonly used in the food packaging industry. Such opaque and peelable films include core layers containing olefin polymers; A surface layer containing a mixture of another olefin polymer and a butylene polymer, or a polymer of butylene and at least one other olefin; And a coating layer on the surface layer. The opacity of these multilayer films is due to the core layer containing vacuole initiating solic particles and a small amount of light absorbing pigment.

Pore-inducing particles are particles that are not blended with the polymer matrix and appear due to the formation of a pore cavity when the film is stretched. An example of such a particle is nylon. The size, type and number of pores depends on the material, the size of the solid particles and the stretching conditions such as the stretching speed and the stretching temperature. The pores reduce density and give the film an opaque appearance due to mother-of-pearl properties, light scattering at the pore / polymer matrix interface. In general, the average particle diameter of the pore-inducing particles is 0.02 μm to 10 μm. However, it is known in the industry that such opaque films have limited compatibility because films generally have poor tear expansion and leave unwanted film residues on the substrate when they are removed from the substrate.

Current aviation industry employs amine-based coatings on the aluminum surface of an aircraft, which requires a dry film that is removed with a highly volatile organic solvent such as methylethylene ketone based solvent. However, this film has many problems. For example, the removal process is expensive because of the costs associated with using organic solvents used to remove amine based coatings. In addition, such coatings do not adequately protect the aluminum surface, thereby requiring a large amount of time for the coating removal, polishing and resurfacing or finishing processes to meet the manufacturer's specifications. Additional regrinding steps increase manufacturing costs.

In addition, typical amine coatings have serious environmental impacts due to the large amount of volatile organic compounds (VOCs) released to the atmosphere during application and gauging. For example, about 300 gallons of ami-based remover is required to remove the amine-based coating from an average sized airliner, and then about 250 gallons of methylethyl per aircraft to remove residues left by the ami-based remover. It takes ketones. In addition, amine coatings lose their ability to release, which requires large amounts of stronger solvents.

The automotive industry also has a need for coatings to protect vehicles from weathering, air pollution, chemical attack or accidental loss during manufacturing, handling, storage and transportation. In the absence of protective coatings, automotive paints are vulnerable to significant internal damage and physical damage on the assembly line. U. S. Patent No. 6,555, 615 discloses a removable coating for protecting a vehicle from attack by pollutants such as foreign objects, the harmful effects of weathering and acid rain. The coating can be removed by peeling off the motor vehicle without using volatile organic compounds.

There are coatings that can be peeled off, but there is still a need for opaque peelable coatings that can be imaged and that all coatings can be easily removed from the substrate without the need for volatile organic compounds. Such coatings can be optionally imaged so that a pattern can be formed on the coating. The patterned coating can then be coated onto the substrate, and the operator can perform one or more operations on the substrate to deform it. The coating can then be easily removed and discarded without the use of environmentally unfriendly solvents.

The composition comprises at least one opaque compound (in an amount of 5% to 80% by weight) and at least one selected from amino carboxylic acids, amphoteric imidazoline derivatives, betaines, fluorocarbons, siloxane variants thereof and macromolecular amphoteric surfactants. Amphoteric compounds.

In another embodiment, the composition comprises one or more opaque compounds (in amounts of 10% to 50% by weight) and one or more amphoteric compounds selected from α-aminocarboxylic acids, β-aminocarboxylic acids and salts thereof.

The composition is opaque and can be easily peeled off from the substrate. Thus, environmentally unfriendly solvents are not used to remove the composition from the substrate. Thus, the composition can be applied to the substrate and imaged to form a coating. The worker can then deform the substrate by performing one or more tasks on the substrate as indicated by the image.

In a further embodiment, the method of imaging comprises at least one opaque compound and at least one amphoteric compound selected from amino carboxylic acids, amphoteric imidazoline derivatives, betaines, fluorocarbons, siloxane variants thereof and macromolecular amphoteric surfactants. Providing a composition; Applying the composition to the substrate; Optionally imaging the composition to form a patterned mask; Deforming the substrate by performing one or more tasks on the substrate. The patterned mask can be removed by peeling off the substrate.

In a further embodiment, the method of imaging comprises at least one opaque compound and at least one amphoteric compound selected from amino carboxylic acids, amphoteric imidazoline derivatives, betaines, fluorocarbons, siloxane variants thereof and macromolecular amphoteric surfactants. Providing a composition; Applying the composition to the first substrate; Selectively imaging the composition to form a patterned mask; Removing the patterned mask from the first substrate; Applying a patterned mask to the second substrate; Deforming the substrate by performing one or more tasks on the second substrate as indicated by the patterning mask. The patterned mask may be peeled off from the second substrate.

The compositions can be applied onto substrates such as, but not limited to, metal, glass, ceramic, wood, and polymeric materials and can be imaged using devices such as, but not limited to, lasers, laser printers, and inkjet devices. have. The imaging pattern on the mask can be used to indicate which part of the substrate to paint and cut, or which holes are made for the fasteners.

As used throughout this specification, the following symbols have the following meanings, unless the context clearly indicates otherwise: ° C = degrees Celsius; T _g = glass transition temperature; gm = gram; mg = milligrams; L = liter; mL = milliliters; 1 mil = 0.001 inch; 2.54 cm = 1 inch; Weight percent = weight percent; nm = nanometer = 10 ^-9 meters; cm = centimeters; mm = millimeters; And μm = micron.

"Polymer" and "copolymer" are used interchangeably throughout this specification. "(Meth) acrylate" includes both methacrylate and acrylate, and "(meth) acrylic acid" includes both methacrylic acid and acrylic acid. "Diluent" means a carrier or excipient such as a solvent or a solid filler. "Opaque" means a property that is not transmitted through light rays, i.e., not transparent or translucent. "Opaque" means opaque and opaque. "Translucent" means translucent. "Transparent" means the passage of light in the visible light spectrum.

Unless indicated otherwise, all percentages are by weight and based on dry weight or weight without solvent. All numerical ranges are inclusive and combinable in any order, except when such numerical ranges are logically limited to adding up to 100%.

The composition comprises one or more opaque compounds (in an amount of 5% to 80%, or 10% to 50%, or 20% to 40% by weight), and amino carboxylic acid, amphoteric imidazoline derivatives, betaine , At least one amphoteric compound selected from fluorocarbons, siloxane variants thereof and macromolecular amphoteric surfactants.

The imaging composition may be applied to the substrate in a suitable manner, including but not limited to spraying, brushing, roller coating, dipping, and application by hand. The composition may be stripped off from the substrate. Stripping avoids the use of environmentally harmful solvents.

Suitable opaque compounds can be used that provide the desired contrast to the substrate. Such compounds provide contrast between the composition and the substrate on which the composition is applied. In addition, the contrast with the substrate allows the operator to see poor residue remaining on the substrate after removing the composition.

Opaque compounds include, but are not limited to, pigments (inorganic and organic), metal salts, silica, silicates and clays. Inorganic pigments include, but are not limited to, oxides such as titanium dioxide, zirconium oxide, cerium oxide, antimony trioxide, arsenic pentoxide, aluminum oxide, zinc oxide, cobalt oxide, cadmium oxide, chromium oxide, magnesium oxide, iron oxide and lead oxide It doesn't work. Metal salts include, but are not limited to, sulfides, sulfates, carbonates, and hydroxides. Typically, opaque compounds are inorganic pigments such as titanium dioxide, aluminum oxide, cerium oxide, antimony trioxide, arsenic pentoxide, cadmium oxide, chromium oxide, zircon oxide and silicate, and indigo, phthalocyanine, para red and red, yellow, blue, Organic pigments such as flavanoids such as orange and ivory. In addition, C.I. (color index) pigment green-yellow PY-53, C.I. Pigment Yellow PY-53 and C.I. Mixed phase titanates such as Pigment Red-Yellow PBr-24, C.I. Pigment Yellow PY-119, C.I. Peakment Brown PBr-29 and C.I. Mixed phase metal oxides such as Pigment Brown PBr-31. More typically, the opaque compound is an inorganic pigment such as titanium dioxide, aluminum oxide and zircon oxide. Most typically, the inorganic pigment is titanium dioxide. Opaque compounds have an average size of 0.01 μm to 10 μm, or 0.5 μm to 5 μm, or 1 μm to 3 μm.

One or more amphoteric surfactants are included to act as a release agent to peel the composition from the substrate. Such surfactants also stabilize particles of the polymer during and after aqueous emulsion polymerization, or other suspension polymerization. Suitable amphoteric surfactants are those which have a weak acid functionality such as carboxy functionality and have an isoelectric point of pH 3 to pH 8. Such amphoteric surfactants may be included in the second component in an amount of 0.1% to 6%, or 0.25% to 5%, or 0.5% to 4% by weight of the film forming binder polymer. Such amphoteric surfactants are selected from amino carboxylic acids, amphoteric imidazoline derivatives, betaines, fluorocarbons and siloxane variants thereof and mixtures thereof.

The aminocarboxylic acids may have carboxy moieties present in quantized form or in carboxylate form. If one or more carboxy groups are present on the molecule, these carboxy groups can all exist in quantized form, in carboxylate form, or they can exist as some mixture of quantized and carboxylate forms. In addition, the ratio of quantized to unquantized carboxy moieties can vary from one molecule to another (or otherwise identical) molecules in a given system. Cations present as counterions for the carboxylate moiety include cations of lithium, sodium, potassium, amines (ie ammonium cations derived from quantization or other quaternary substitution of amines), zinc, zircon, calcium, magnesium, and aluminum. Include. The aminocarboxylic acid may have an amino moiety present in protonated (ammonium) or free amine form (ie, as deprotonated primary, secondary, or tertiary amine). If more than one amino group is present on the molecule, these amino groups may all be in quantized form, in free amine form, or they may be present in some mixture of quantized and free amine forms. In addition, the ratio of quantized to unprotonated amine moieties may vary from one molecule to another (or otherwise identical) molecules in a given system. Anions present as counterions for the ammonium moiety include chloride, bromide, sulfate, carbonate, hydroxide, formate, acetate, propionate and other carboxylate anions.

Suitable amino carboxylic acids are α- amino acid having the formula R ₁₂ -NH-CH ₂ COOH (wherein, R ₁₂ = C ₄ -C ₂₀ linear or branched, alkyl, alkenyl, or a silicon or fluoro-functional hydrophobic group); R ₁₂ -NH-CH ₂ CH ₂ COOH and R ₁₂ N (CH ₂ CH ₂ COOH) ₂ , wherein R ₁₂ = C ₄ -C ₂₀ straight or branched chain, alkyl, alkenyl, or fluoro or silicone functional hydrophobic group Β-aminocarboxylic acids with), but not limited to these, β-aminocarboxylic acids can be used from Henkel Corporation, King of Prussia, Pa, under the trade name DERIPHAT ^™ . Unless stated otherwise, DERIPHAT ^™ Ampholite has the formula R ₁₃ -NHCH ₂ CH ₂ COOH, wherein R ₁₃ = residue of coconut fatty acid, residue of tallow fatty acid, lauric acid, myristic acid, oleic acid, pallic acid Mitic acid, stearic acid, linoleic acid, other C ₄ -C ₂₀ straight or branched chains, alkyl, alkenyl, and mixtures thereof. DERIPHAT ^™ AMPolites useful in the present invention include sodium-N-coco-β-aminopropionate (DERIPHAT ^™ 151, flake 97% activity); N-coco-β-aminopropionic acid (DERIPHAT ^™ 151C, 42% aqueous solution); N-lauryl / myristyl-β-aminopropionic acid (DERIPHAT ^™ 17 ° C., 50% in water); Disodium-N-tallow-β-iminodipropionate, R ₁₄ N (CH ₂ CH ₂ COONa) ₂ , (DERIPHAT ^™ 154, flake 97% activity); Disodium-N-lauryl-β-iminodipropionate (DERIPHAT ^™ 160, flake 97% activity); And partial sodium salt of N-lauryl-β-iminodipropionic acid, R ₁₄ N (CH ₂ CH ₂ COOH) (CH ₂ CH ₂ COONa), (DERIPHAT ^™ 16 ° C., 30% in water). Useful polyaminocarboxylic acids include R ₁₄ C (═O) NHC ₂ H ₄ (NHC ₂ H ₄ ) _y NHCH ₂ COOH and R ₁₄ -substituted ethylenediaminetetraacetic acid (EDTA), wherein R ₁₄ = C ₄ − C ₂₀ straight or branched chain, alkyl or alkenyl, y = 0-3.

Amphoteric imidazoline derivatives useful in the present invention include a variety of substituted 2-alkyl-2-imidazolines and 2-alkenyl- having a nitrogen atom at the 1 and 3 positions of the 5-membered ring and a double bond at the 2,3 position. And those derived from 2-imidazoline. Alkyl or alkenyl groups may be C ₄ -C ₂₀ linear or branched. Amphoteric imidazoline derivatives may hydrolyze the imidazoline ring under conditions that allow further reaction with alkylating agents such as sodium chloroacetate, methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylic acid. It is prepared by the reaction of opening to the pirate. Useful amphoteric surfactants are derived from the reaction of 1- (2-hydroxyethyl) -2- (R ₁₅ ) -2-imidazoline with acrylic acid or acrylic acid esters, where R ₁₅ is a coconut fatty acid residue to be:

Coco ampopropionate,

R ₁₅ -C (══O) NCH ₂ CH ₂ N (CH ₂ CH ₂ OH) (CH ₂ CH ₂ COONa);

Coco Ampocarboxypropionic Acid,

R ₁₅ -C (══O) NHCH ₂ CH ₂ N (CH ₂ CH ₂ COOH) (CH ₂ CH ₂ CH ₂ CH ₂ COOH);

Coco ampoxycarboxypropionate,

R ₁₅ -C (══O) NHCH ₂ CH ₂ N (CH ₂ CH ₂ COONa) (CH ₂ CH ₂ CH ₂ CH ₂ COONa);

Coco ampoglycinate,

R ₁₅ -C (══O) NHCH ₂ CH ₂ N (CH ₂ CH ₂ H) (CH ₂ COONa); And

Coco ampoxycarboxyglycinate,

_{[R 15 -C (== O)} NHCH 2 CH 2 N + (CH 2 CH 2 OH) (CH 2 COONa) 2] OH -.

Surfactant internal salts containing at least one quaternary ammonium cation and at least one carboxy anion are called betaines. The nomenclature of betaine is derived from a single compound (trimethylammonio) acetate called betaine and exists as an internal salt. Betaines useful as amphoteric surfactants in the present invention have the general formula: R ₁₆ N ⁺ (CH ₃ ) ₂ CH ₂ COO ⁻ ; R ₁₆ CONHCH ₂ CH ₂ CH ₂ N ⁺ (CH ₃ ) ₂ CH ₂ COO ⁻ ; And ^{_{R 16 -O-CH 2 -N +}} (CH 3) 2 CH 2 COO - in, where, R ₁₆ = C ₄ -C ₂₀ linear or branched, alkyl, alkenyl, or fluoro or silicone functional hydrophobic group . Specific examples of betaines include N-dodecyl-N, N-dimethylglycine and cocamidopropyl betaine and MONATERIC ^™ CAB available from Mona Industries.

Typically, when fluorocarbon substituents are attached to amphoteric surfactants, these substituents are branched or unbranched perfluoroalkyl groups having 6 to 18 carbon atoms. However, these substituents may be partially fluorinated. They also have aryl functional groups. Examples of fluorocarbon amphoteric surfactants include fluorinated alkyl FLUORAD ^™ FC100 and fluorinated alkyl ZONYL ^™ FSK from 3M and Dupont, respectively.

Typical siloxane functional amphoteric surfactants have the following structure, for example:

Where

R ₁₇ represents an amphoteric moiety,

m + n is 3-50.

One example is the polyalkyl betaine polysiloxane copolymer ABIL ^™ B9950 from Goldschmidt Chemical Corporation.

Macromolecular amphoteric surfactants useful in the present invention include proteins, protein hydrolysates, protein hydrolysate derivatives, starch derivatives, and synthetic amphoteric oligomers and polymers. Macromolecular amphoteric surfactants with carboxyl functional groups are particularly useful.

In addition to the opaque agent and the amphoteric surfactant, the composition includes one or more film forming polymers that act as binders. Any film forming polymer binder having a T _g of -60 ° C to 80 ° C, or for example -60 ° C to 40 ° C, or for example 0 ° C to 35 ° C, can be used without adversely affecting the desired color or contrast. have. The film forming polymer is included in an amount of 10% to 90% by weight, or for example 15% to 70% by weight, or for example 25% to 60% by weight. Typically, the film forming polymer is derived from a mixture of acid and monomeric monomers. Suitable acid functional monomers include (meth) acrylic acid, maleic acid, fumaric acid, citraconic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-hydroxyethyl acrylol phosphonate, 2-hydroxypropyl acrylol Phosphonates and 2-hydroxy-alpha-acrylol phosphonates.

Suitable flyback monomers include (meth) acrylic acid esters, such as methyl acrylate, 2-ethyl hexyl acrylate, n-butylacrylate, n-hexyl acrylate, methyl methacrylate, hydroxy ethyl acrylate, butyl methacrylate , Octyl acrylate, 2-ethoxy ethyl methacrylate, t-butyl acrylate, 1,5-pentanediol diacrylate, N, N-diethylaminoethyl acrylate, ethylene glycol diacrylate, 1,3 Propanediol diacrylate, decamethylene glycol diacrylate, decamethylene glycol dimethacrylate, 1,4-cyclohexanediol diacrylate, 2,2-dimethylol propane diacrylate, glycerol diacrylate, tri Propylene Glycol Diacrylate, Glycerol Triacrylate, 2,2-Di (p-hydroxyphenyl) -propane Dimethacrylate, Triethylene Glycol Cold Diacrylate, Polyoxyethyl-2,2-di (p-hydroxyphenyl) -propane dimethacrylate, triethylene glycol dimethacrylate, polyoxypropyltrimethylol propane triacrylate, ethylene glycol di Methacrylate, butylene glycol dimethacrylate, 1,3-propanediol dimethacrylate, 1,2,4-butanetriol trimethacrylate, 2,2,4-trimethyl-1,3-pentane Diol dimethacrylate, pentaerythritol trimethacrylate, 1-phenyl ethylene-1,2-dimethacrylate, pentaerythritol tetramethacrylate, trimethylol propane trimethacrylate, 1,5-pentanediol dimethacrylate Acrylates; Styrene and substituted styrenes such as 2-methyl styrene and vinyl toluene and vinyl esters such as vinyl acrylate and vinyl methacrylate.

When the film forming polymer has a T _g of −60 ° C. to 0 ° C., the film forming polymer is typically from 0.1% to 6% by weight of at least one carboxy functional monomer, or such as from 0.5% to 6% by weight of the polymer total weight. Weight percent, or, for example, 1 weight percent to 5 weight percent of at least one carboxy functional monomer. If the film forming polymer has a T _g of 0 ° C. to 80 ° C. and one or more bases are included in the composition to maintain the pH at 3 to 11 or such as 8 to 11, the polymer is optionally in polymerized units of the dry film polymer. 0.1 to 6 weight percent, or such as 0.5 to 6 weight percent, or such as 0.1 to 5 weight percent of the carboxy functional monomer, based on the total weight.

Other suitable polymers include, but are not limited to, nonionic polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, hydroxy-ethylcellulose, and hydroxyethylpropyl methylcellulose. Also polymers such as polyvinyl acetate can be used.

Optionally, polyvalent metal cations that form ionic bonds with carboxylic acid groups on one or more monomers comprising a polymer may be included. Any suitable polyvalent cation that forms an ionic bond with the carboxylic acid group to form a crosslink can be used. Such cations include, but are not limited to, Mg ²⁺ , Sr ²⁺ , Ba ²⁺ , Ca ²⁺ , Zn ²⁺ , Al ³⁺ , Zr ⁴⁺ or mixtures thereof. Such polyvalent cations are included in the imaging composition in amounts of 0.001 to 0.1 mole / 100 gm of dry polymer, or for example 0.01 to 0.08 mole / 100 gm of dry polymer, or for example 0.02 to 0.05 mole / 100 gm of dry polymer.

The composition may optionally comprise one or more additives. Such additives include, but are not limited to, plasticizers, thickeners, rheology modifiers, ionic and nonionic surfactants, acid and base buffers, preservatives, flow agents and diluents.

Any suitable plasticizer can be used. The plasticizer may be included in an amount of 0.5% to 15% by weight, or for example 1% to 10% by weight of the second component. Suitable plasticizers are phthalate esters such as dibutylphthalate, diheptylphthalate, dioctylphthalate and diallyl phthalate, glycols such as polyethylene glycol and polypropylene glycol, glycol esters such as triethylene glycol diacetate, tetraethylene glycol diacetate, and Dipropylene glycol dibenzoate, phosphonate esters, such as tricresylphosphonate, triphenylphosphonate, amides such as p-toluenesulfonamide, benzenesulfonamide, Nn-butylacetonamide, aliphatic dibasic acid esters, Diisobutyl adipate, dioctyl adipate, dimethyl sebacate, dioctyl azelate, dibutyl maleate, triethyl citrate, tri-n-butylacetyl citrate, butyl laurate, dioctyl-4, 5-diepoxycyclohexane-1,2-dicarboxyle Including the agent and glycerin triacetyl ester is not limited to only one thereof.

One or more flow agents may also be included. The glidant may be included in an amount of 0.05% to 5% by weight, or for example 0.1% to 2% by weight of the second component. Suitable flow agents include, but are not limited to, alkylacrylate copolymers. One example of such an alkyl acrylate is a copolymer of ethyl acrylate and 2-ethylhexyl acrylate.

Surfactants may be included in the composition in amounts of 0.5% to 10% by weight, or for example 1% to 5% by weight. Suitable nonionic surfactants include, but are not limited to, polyethylene oxide ethers, polyethylene oxide derivatives, aromatic ethoxylates, acetylene ethylene oxide and block copolymers of ethylene oxide and propylene oxide. Suitable ionic surfactants include, but are not limited to, alkali metal, alkaline earth metal, ammonium and alkanolammonium salts of alkyl sulfates, alkyl ethoxy sulfates, and alkyl benzene sulfonates.

Any suitable thickening agent may be included in the composition. Typically, the amount of thickening agent is 0.05% to 10% by weight, or for example 1% to 5% by weight. Suitable thickening agents include, but are not limited to, low molecular weight polyurethanes such as having at least three hydrophobic groups linked by hydrophilic polyether groups. The molecular weight of such thickeners is 10,000 to 200,000. Other suitable thickening agents include hydrophobically modified alkali soluble emulsions, hydrophobically modified hydroxyethyl cellulose and hydrophobically modified polyacrylamides.

Rheology modifiers may be included in conventional amounts. Typically, rheology modifiers are used in amounts of 0.5% to 20%, or such as 5% to 15% by weight. Rheology modifiers include, but are not limited to, vinyl aromatic polymers and acrylic polymers.

Diluents may be included as excipients or carriers for the components. Diluents are added as needed. Solid diluents or fillers are typically added to bring the dry weight of the components to 100% by weight. Solid diluents include, but are not limited to, cellulose. Liquid diluents or solvents are used to make the compositions into solutions, suspensions, dispersions or emulsions. The solvent may be water or organic, or a mixture thereof. Organic solvents are alcohols such as methyl, ethyl and isopropyl alcohol, diisopropyl ether, diethylene glycol dimethyl ether, 1,4-dioxane, tetrahydrofuran or 1,2-dimethoxy propane, and esters such as butyro Lactones, ethylene glycol carbonates and propylene glycol carbonates, ether esters such as methoxyethyl acetate, ethoxyethyl acetate, 1-methoxypropyl-2-acetate, 2-methoxypropyl-1-acetate, 1-ethoxy Propyl-2-acetate and 2-ethoxypropyl-1-acetate, ketones such as acetone and methylethyl ketone, nitrile, such as acetonitrile, propionitrile and methoxypropionitrile, sulfones such as sulfolane, dimethylsulfone and Diethylsulfone, and phosphate esters such as but not limited to trimethyl phosphonate and triethyl phosphonate No. Solvents also include coalescing solvents such as ethers. Examples of such ethers include ethylene glycol phenyl ether and tripropylene glycol n-butylether.

 Opaque coating compositions can be prepared by any suitable method. One method is to dissolve or disperse the water insoluble compound in the coalescing solvent. Any solvent that dissolves or disperses the water insoluble compound can be used. Such coalescing solvents include, but are not limited to, ester alcohols and glycol ethers. The solution or dispersion is then emulsified with an aqueous base portion comprising a polymeric binder and other water-soluble compounds. Oil-in-water emulsions can be prepared using conventional emulsification methods.

The composition may be in the form of a concentrate. In such concentrates, the solids content is 80% to 98% by weight, or for example 85% to 95% by weight. The concentrate may be diluted with water, one or more organic solvents, or a mixture of water and one or more organic solvents. The concentrate may be diluted to a solids content of 5% by weight to less than 80% by weight, or such as 10% by weight to 70% by weight, or such as 20% by weight to 60% by weight.

The composition can be imaged on any suitable substrate, such as metal, wood, glass, ceramic, and polymeric materials. Typically, the composition is imaged on a polymeric material. Polymeric materials include cellulose and its derivatives, polyolefins such as polyethylene and polypropylene, vinyl chloride, polystyrene, acrylonitrile-butadiene-styrene, polyvinyl alcohol, polyacryl, acrylonitrile-styrene polymers, vinylidene chloride, acrylonitrile Acrylic styrene polymer, acrylonitrile ethylene-propylene-terpolymer styrene polymer, polyurethane, polyvinyl butyral polymer, poly-4-methylpentene-1 polymer, polybutene-1 polymer, poly (vinylidene fluoride) polymer, Polyvinyl fluoride polymers, polycarbonates, copolyester carbonates, polyamides, polyacetals, polyphenylene oxides, polyesters such as polybutylene terephthalate and polyethylene terephthalate, polyphenylene sulfides, polyimides, polysulfones, Polyether sulfone, aromatic poly It includes esters, glycol polyester, polyarylate, and mixtures thereof is not limited to only one thereof.

Such polymeric materials are typically used as support films. The film thickness can be 0.5 mil to 10 mil, or for example 2 mil to 8 mil. The composition is dried after coating on a support film. After drying it is optionally imaged. The image formed on the composition can be scored and the selected portions peeled off the polymer substrate. The remaining part is peeled off from the substrate and placed on another substrate to function as a mask. The operator can deform the workpiece depending on the color contrast between the mask and the second substrate or workpiece having the pattern. For example, the mask can act as a stencil. The mask can be applied to a metal, wood, glass ceramic or plastic substrate. The pattern on the mask selectively exposes a metal, wood or plastic substrate and paints the exposed portions to form an image or logo on the substrate to create a sign or poster, for example. In addition, the exposed portion of the substrate may be cut or scored. The cut or scored portions may be removed to leave holes for fasteners, or the shape of the substrate may be modified as in glass cutting. The part of the composition left on the substrate is stripped off. No volatile organic solvent is needed.

The composition can be imaged with an ink jet printer, a laser printer or a laser. Any suitable ink jet device can be used to selectively apply ink to the composition. For example, the imaging composition can be applied to a polymer film and dried. Thereafter, the polymer film having the dried imaging composition is passed through an ink jet device or a laser printer. An ink jet device or laser printer digitally stores information in its memory for optional mask design. An image is formed on the dried composition as the polymer film with the imaging composition passes through the device or fritter. An example of a suitable computer program is a standard computer aided design (CAD) program for generating tooling data. The operator can easily change the selective deposition of the ink on the composition by changing the program digitally stored in the ink jet device or laser printer.

 In addition, the composition can be imaged with a laser. The composition is applied to a substrate and a laser programmed to selectively image the composition is applied. Heat from the laser burns the image in the dry composition. A part is peeled off from the substrate having the remaining part serving as a mask. The operator can then deform the exposed portion of the substrate. After the operator has performed his job, the mask can be peeled off and removed from the substrate. Any residual residue is visible to the naked eye due to the color or contrast contrast between the mask residue and the substrate and may peel off.

Coating compositions can also be used to prevent dye leaching from the imaging composition. Photoimaging compositions may be used to form images on substrates such as parts of aircraft, automobiles, and other products. Such substrates are often coated with a primer before painting. The photosensitive dye of the photoimaging composition can be leached from the photoimaging composition to the primer on the substrate. This can cause unwanted discoloration and degrade the performance of the photoimaging composition. To prevent leaching, a coating composition heavily loaded with pigment may be applied to the substrate before applying the photoimaging composition. In addition, large loadings of pigments in the coating composition provide excellent color contrast between the color of the photoimaging composition and the substrate. This provides the operator with a clear image on the substrate so that they can perform work on the substrate as indicated by the color of the photoimaging composition. In addition, incorporating a pigment into the coating composition, as opposed to the photoimaging composition, increases the light velocity of the photoimaging composition to Δ = + 0.5- + 1. The operator can then peel off and discard the coating composition and photoimaging composition from the substrate. Non-environmental solvents need not be used to remove the coating composition and photoimaging composition from the substrate.

In addition to the uses described above, opaque coating compositions can be used for general masking or hiding of the substrate. For example, an opaque coating composition can be applied over the sign to provide a blank template from which new sign can be made. When an advertising campaign is conducted, the opaque coating composition with artwork may be peeled off from the substrate and an iterative process may be done. Other uses include, but are not limited to, masking for lowering room temperature or for privacy purposes.

Example 1

Opaque Coating Composition With Titanium Dioxide

The opaque coating composition has a composition as described in Table 1 below.

compound  weight% Film Forming Acrylic Polymer Binder 80 Titanium dioxide 5 Coco ampopropionate 5 Ethylene Glycol Phenyl Ether One water 9

Acrylic polymers are latex polymers that can be prepared according to methods known in the art or are commercially available from the Rohm and Haas Company of Philadelphia, PA under the trademark RHOPLEX ™ E-1801. The liquid compounds are blended together at room temperature to form an emulsion. Then, titanium oxide particles having an average size of 1 μm are blended with the emulsion at room temperature to form a suspension. The suspension is white in appearance due to the titanium dioxide pigment.

The coating composition is then sprayed onto a polycarbonate film having an area of 50 cm x 40 cm and a thickness of 1 mil. The coating is air dried at room temperature and placed in a spectra Apollo drop-on-demand inkjet device with a piezoelectric drop-on-demand inkjet head. The inkjet device is programmed to selectively apply ink to the coating composition to form the outline of the letters of the alphabet. After the coating composition on the polycarbonate film has penetrated the inkjet device, the coating composition draws a line along the outline, and portions within the outline peel off from the polycarbonate film. The patterned mask is peeled off the polycarbonate film with an image of the letters of the alphabet.

The patterned mask is then peeled off the polycarbonate film and placed on a metal plate having a rectangular shape. The mask covers the entire metal plate except the image of the letters. The metal plate together with the mask is then spray painted. The mask is then peeled off the metal plate with the lettering left on the metal plate forming the sign.

Example 2

Opaque Coating Compositions and Photoimilation Compositions

The opaque coating composition consists of the compounds described in Table 2 below.

compound  weight% Vinyl Acetate / Acrylic Copolymer Emulsion 75 Titanium dioxide 10 Ethylene Glycol Phenyl Ether One Coco Ampocarboxy Glycinate One water 13

Vinyl acetate / acrylic copolymers are known in the art. The copolymer is commercially available from the Rohm and Haas Company under the trademark ROVACE ™ 661. Cocoampoxy glycinate is mixed with ethylene glycol to form a uniform suspension and then added to the copolymer emulsion and mixed. Then the mixture is mixed with water. Titanium dioxide pigments having an average particle size of 0.5 μm are mixed with the emulsion. The resulting coating composition was white in appearance.

The following photosensitive components are prepared at room temperature under red light.

ingredient  weight% Vinyl Acetate / Acrylic Copolymer Emulsion 75 2-alkyl-2-imidazoline 2 Vinyl aromatic polymer 4 Leuco crystal violet One Tribromo methyl phenyl sulfone 5 2 ', 3', 5 ', 7'-tetraiodo-3,4,5,6-tetrachlorofluorine disodium salt One 2,2'-methylene-bis (4-methyl-6-tert-butylphenol) One Ethylene Glycol Phenyl Ether One water 10

The copolymer, vinyl aromatic polymer, and 2-alkyl-2-imidazoline are mixed in water to form an emulsion.

Imaging Components: leuco crystal violet, tribromo methyl phenyl sulfone, 2 ', 3', 5 ', 7'-tetraiodo-3,4,5,6-tetrachlorofluorine disodium salt, and micro-encapsulation 2,2'-methylene-bis (4-methyl-6-tert-butylphenol) is dissolved in ethylene glycol phenyl ether to form an organic solution. The aqueous emulsion and the organic solution are mixed to form an oil in the water emulsion photoimidation composition.

The opaque coating is roller coated on the surface of an aluminum airplane body coated with BR127 epoxy primer providing a dark green aluminum surface. The opaque coating is white and provides color contrast to the aluminum surface. The opaque coating is air dried on the aluminum surface.

The photosensitive composition is spray coated onto the opaque coating. The photosensitive composition is translucent and the opaque coating is visible under the photosensitive composition. The photosensitive composition is then dried.

The operator selectively images the outline of the company logo on the photosensitive composition using a 3D, 532 nm Nd: YAG laser at 5 mW. The outline turns purple and the white background from the opaque coating provides a sharp contrast between the purple outline and the dark green aluminum surface. The operator can easily distinguish the purple outline.

The photosensitive composition and the opaque coating beneath it are lined along the purple outline, with portions within the outline peeling away from the fuselage leaving behind an exposed aluminum surface. The exposed aluminum is then painted to form a company logo on the fuselage. After this, the residue of the opaque coating and the photosensitive composition is peeled off and removed from the body. Environmentally unfriendly organic solvents are used to remove the photosensitive composition and opaque coating from the fuselage.

No indication of pigment leaching with epoxy primer in the photosensitive composition is observed. No red feature of the leaching is observed. In addition, the inclusion of pigments in the coating composition is expected to increase the porosity of color change by a factor of Δ = + 0.5 to +1, as measured by conventional reflection densitometers.

Example 3

Opaque Coating Composition With Aluminum Oxide

The following composition is prepared at room temperature.

ingredient  weight% Copolymers of Styrene and Acrylic Acid 70 Sodium-N-coco-b-aminopropionate 2 Aluminum oxide 20 Tripropylene glycol n-butyl ether 2 water 6

 Sodium-N-coco-b-aminopropionate is mixed with styrene and acrylic copolymers to form a suspension. The suspension is then mixed with tripropylene glycol n-butyl ether to form a secondary suspension. Thereafter, water is mixed with the suspension. The mixing process is carried out at room temperature. Aluminum oxide pigments with an average particle size of 0.5 μm are added. Mixing is carried out at room temperature.

 The opaque coating composition is then roller coated in a 50 cm x 30 cm polyethylene terephthalate film with a thickness of 2 mils. The film along with the opaque coating penetrates through a conventional radar printer programmed to allow the ink to be selectively applied to the opaque coating to form the outlines of letters and numbers. The opaque coating is drawn along the outline, and this portion peels off the film, forming a mask with a pattern of letters and numbers.

After this, the mask is peeled off the film and applied to a rectangular metal plate. Paint is applied using a spray gun. The mask is peeled off the metal plate and removed. An environmentally friendly solvent is used to remove the mask from the metal plate. Lettered metal plates can be used as a sign.

Example 4

Opaque coating composition with zirconium oxide

 The opaque coating composition described in the table below is prepared.

ingredient  weight% Polyvinyl acetate 20 Zirconium oxide 60 2-alkyl-2-imidazoline 2 Diethylene glycol dimethyl ether 4 water 14

 2-alkyl-2-imidazoline is mixed with a polyvinyl acetate polymer binder to form a suspension. After this, the suspension is mixed with diethylene glycol dimethyl ether. Then water is added to the mixture. The mixing process is carried out at room temperature.

Zirconium oxide with an average particle size of 2 μm is added to the mixture to form a dispersion. Mixing is carried out at room temperature.

The dispersion is then spray coated onto a 50 cm x 50 cm polyethylene terephthalate film with a thickness of 1 mil. The coating is dried at room temperature to form an opaque coating on the film.

The coated film then passes through a drop-on-demand spectra Apollo inkjet device with a piezoelectric drop-on-demand inkjet head. Inkjet devices are programmed to selectively apply ink to outline numbers and letters on the opaque coating composition. After the film penetrates the inkjet, the outline is drawn, and portions within the outline peel off from the film. The residue of the opaque coating composition is peeled off the film and applied to the metal plate to form a patterned mask. The metal plate with the mask is spray painted. The mask then peels off the metal plate, leaving an image of numbers and letters on the metal. The worker forms a road sign with a metal plate.

Example 5

Opaque Coating Composition With Talc

An opaque coating composition is prepared having the components described in the table below.

ingredient  weight% Polyvinyl pyrrolidone 30 talc 40 Disodium-N-tallow-b-iminodipropionate 5 Diisopropyl ether 5 water 20

 Disodium-N-tallow-b-iminodipropionate is mixed with polyvinyl pyrrolidone to form a suspension. Thereafter, the suspension is mixed with diisopropyl ether. Then water is added to the mixture. Mixing is carried out at room temperature.

Talc pigment with an average particle size of 0.5 μm is added to the mixture. Mixing is carried out at room temperature.

The opaque composition is then spray coated onto the polyethylene terephthalate film as described in Example 4. An opaque coating was used to prepare the sign as in Example 4. The opaque coating is peeled off and removed from the metal plate.

Example 6

Opaque coating composition and photoimmunization composition having antimony trioxide

An opaque coating is prepared having the components listed in the table below.

ingredient  weight% Polyvinyl Alcohol / Polyvinyl Pyrrolidone 50/50 Mixture 40 Antimony trioxide 40 Coco Ampocarboxypropionate 6 Ethylene Glycol Phenyl Ether 4 water 10

Cocoampocarboxypropionate is mixed with a polyvinyl alcohol / polyvinyl pyrrolidone mixture to form a suspension. Ethylene glycol phenyl ether is mixed with water and the combination is mixed with suspension. Antimony trioxide pigment with an average particle diameter of 3 μm is added to the mixture to form a dispersion.

The opaque dispersion is spray coated on an aluminum airplane body coated with epoxy primer BR127. After the opaque coating is dried, a photoimmunizing composition having the composition of Example 2 is applied to the opaque coating. The photoimmunizing composition is then selectively imaged. The operator then performs one or more operations on the aluminum fuselage as shown by the image as in Example 2.

Inclusion of antimony trioxide in the coating composition is believed to increase the response of the photoimidation composition to the laser by a factor of Δ = + 0.5 to +1 measured by the reflective densitometer. In addition, there is no significant leaching of the dye into the epoxy primer in the photoimidation composition. Opaque coatings and photoimmunization compositions are stripped from aluminum. An environmentally unfriendly solvent is not necessary.

Claims (10)

At least one opaque compound in an amount from 5% to 80% by weight; And at least one amphoteric compound selected from amino carboxylic acids, amphoteric imidazoline derivatives, betaines, fluorocarbons, siloxane variants thereof and macromolecular amphoteric surfactants. The composition of claim 1, wherein the at least one opaque compound is selected from pigments, metal salts, silicas, silicates and clays. The composition of claim 1 wherein the amphoteric compound is from 0.1% to 6% by weight of the composition. The composition of claim 1, wherein the amphoteric compound has an isoelectric point of pH 3 to pH 8. A composition comprising at least one opaque compound in an amount of 10% to 50% by weight and at least one amphoteric compound selected from α-aminocarboxylic acids, β-aminocarboxylic acids and salts thereof. 6. The method of claim 5, wherein the at least one opaque compound is selected from titanium dioxide, aluminum oxide, zirconium oxide, antimony trioxide, cerium oxide, arsenic pentoxide, magnesium oxide, cobalt oxide, cadmium oxide, chromium oxide, iron oxide, lead oxide and zinc oxide. Composition. a) at least one opaque compound; And one or more amphoteric compounds selected from amino carboxylic acids, amphoteric imidazoline derivatives, betaines, fluorocarbons, siloxane variants thereof and macromolecular amphoteric surfactants; b) applying the composition to the first substrate; c) optionally image the composition to form a patterned mask; d) peeling off the patterned mask from the first substrate; e) applying the patterning mask to the second substrate; f) performing one or more tasks on the second substrate as indicated by the patterned mask. 8. The method of claim 7, wherein the composition is imaged with an ink jet device, a laser printer or a laser. a) at least one opaque compound; And one or more amphoteric compounds selected from amino carboxylic acids, amphoteric imidazoline derivatives, betaines, fluorocarbons, siloxane variants thereof and macromolecular amphoteric surfactants; b) applying the composition to the substrate; c) forming an image on the composition; d) performing one or more tasks on the substrate as indicated by the image. The method of claim 9 wherein the image is formed with a laser.