Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/50—Multilayers
  • B05D7/52—Two layers
  • B05D7/54—No clear coat specified
  • B05D7/546—No clear coat specified each layer being cured, at least partially, separately
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D131/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
  • C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D131/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
  • C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
  • C09D131/04—Homopolymers or copolymers of vinyl acetate
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D135/06—Copolymers with vinyl aromatic monomers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2202/00—Metallic substrate
  • B05D2202/10—Metallic substrate based on Fe
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L35/06—Copolymers with vinyl aromatic monomers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31678—Of metal
  • Y10T428/31692—Next to addition polymer from unsaturated monomers
  • Y10T428/31696—Including polyene monomers [e.g., butadiene, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers
  • Y10T428/31909—Next to second addition polymer from unsaturated monomers
  • Y10T428/31924—Including polyene monomers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers
  • Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon

Definitions

• the temporary coating comprises a blend of two interpolymers: the first, an interpolymer comprising an ethylenically unsaturated monoor poly-carboxylic acid containing from 3 to 6 carbon atoms and a vinylidene ester of a saturated aliphatic acid, said saturated acid containing from 1 to 6 carbon atoms; the second, a vinylidene aromatic hydrocarbon and an alpha-beta ethylenically unsaturated dicarboxylic acid, its anhydride or half-ester and mixtures thereof.
• the first interpolymer is comprised of vinyl acetate and crotonic acid and the second interpolymer is comprised of styrene and a half-ester of maleic acid.
• the coating is removed from the finished surface by washing with an aqueous alkaline solvent.
• the present invention relates to a method of protecting a substrate coated with a permanent cured resin system with a temporary coating applied while the permanent coating is in a less than fully cured condition.
• the temporary coatings exhibit excellent toughness, hardness and moisture resistance and can be removed when no longer needed with an aqueous alkaline detergent solution.
• green enamel is meant one that is less than fully cured. Where organic solvents are present, it is necessary that the permanent enamel be fully cured before application of the temporary coating in order to preclude the possibility of undesirable side reactions between the solvents and the enamel.
• the advantage to being able to coat a green enamel is one of time-saving in the assembly process and, as a consequence of this, reduced cost. Second, the waxy coating easily picks up and retains dust and dirt.
• a method whereby surfaces coated with a permanent cured resin system are protected by the application thereto of a temporary protective coating based upon a blend of two interpolymers; said coating being hard, tough and water resistant and capable of being removed from the substrate when the need for it no longer exists, by Washing with an aqueous alkaline solution.
• the present invention relates to a method by which substrates are coated with a curable resin system, are partially cured either at room or elevated temperatures and then, before curing is complete, are further coated with a blend of: (A) 5-95 by weight of a first interpolymer comprising: (1) about 0.5 mole percent to about 20 mole percent of an ethylenically unsaturated monoor poly-carboxylic acid containing 3 to 6 carbon atoms, and correspondingly, (2) about 99.5 mole percent to about mole percent of a vinylidene ester of a saturated aliphatic acid, said saturated acid containing 1 to 6 carbon atoms; and correspondingly, (B) 5% by weight of a second interpolymer comprising a vinylidene aromatic hydrocarbon and an alpha-beta-ethylenically unsaturated dicarboxylic acid monomer, its anhydride or half-ester with a l18 carbon atom monohydric alcohol and mixtures thereof.
• A 5-95 by weight
• the interpolymers may be blended by any of the several methods well known in the art.
• the preferred method of blending the two interpolymers for low cost and ease of handling is to dissolve them with stirring in a solvent system in which both are soluble.
• the use of water containing a small amount of ammonia has been found particularly advantageous.
• the particular alcohol to be used and the quantity in which it will be present is not critical, but will be determined by the particular case and the ends sought to be achieved.
• an object of the present invention to provide a method for the protection of substates having at least one finished surface.
• This permanent coating is then partially cured, curing conditions being dependent upon the particular coating chosen. In most cases, partial curing will be carried out at elevated temperatures after a short period of air drying. As is Well known in the art, the air drying permits evaporation of volatile solvents which could cause bubbles in the finished coating, and use of elevated temperatures permits a faster rate of cure.
• the coatedsubstrate is then cooled at least to a point below the boiling temperature of the solvent system of the temporary coating to -be applied. Next, and before the permanent coat has completely cured, the temporary coating is applied. This temporary coating is based upon a blend of two interpolymers.
• the first interpolymer comprises about 0.5-mole percent to about 20 mole percent of an ethylenically unsaturated monoor poly-carboxylic acid containing 3 to 6 carbon atoms, and correspondingly, about 99.5 mole percent to about 80 mole percent of a vinylidene ester of a saturated aliphatic acid, said saturated acid containing from 1 to 6 carbon atoms.
• This first interpolymer is limited to resins that are soluble in aqueous alkali. For ready solubility, it is necessary to use an interpolymer having at least 0.5 mole of unsaturated carboxylic acid for every 99.5 moles of vinylidene ester.
• the saturated organic acid forming the vinylidene ester is limited to one containing 1 to 6 carbon atoms.
• the more preferred range is from 2 to 4 carbon atoms for reasons of easy solubility and convenient polymerization rates.
• these acids are formic, acetic, propanoic, butanoic, pentanoic, hexanoic acids, their isomers and mixtures thereof.
• the unsaturated acid in this interpolymer is limited to monoor poly-carboxylic acids containing 3 to 6 carbon atoms.
• a more preferred range for ease of solution and polymerization is 3 to 4 carbon atoms.
• acids examples include acrylic, methacrylic, crotonic, isocrotonic, 3-butenoic, angelic, tiglic, senecioic, hydrosorbic, alpha-methylene butyric, maleic, fumaric,
• the most preferred interpolymer is one of vinyl acetate and crotonic acid, owing to the relative ease by which copolymerization may be carried out.
• the upper limit of the concentration of the unsaturated acid is about 20 mole percentabove this the interpolymer becomes undesirably water sensitive.
• acid concentrations ranging from 2 to 10 mole percent are more preferred.
• an acid concentration ranging from 3 to 5 mole percent is most preferred.
• the second interpolymer is one of a vinylidene aro matic hydrocarbon with an alpha, beta-ethylenically unsaturated monomer selected from the group consisting of dicarboxylic acids, their anhydrides, their half-esters with 1-18 carbon atom monohydric alcohols and mixtures thereof.
• vinylidene aromatic hydrocarbon should be interpreted to include alkyl and halogen derivatives wherein the alkyl or halogen groups are attached to the nucleus, or to the vinylidene group, or to both.
• alkyl and halogen derivatives wherein the alkyl or halogen groups are attached to the nucleus, or to the vinylidene group, or to both. Examples are styrene, vinyl naphthalene, alpha-methylstyrene, vinyl toluene, 2,4-dimethyl styrene, o-, m-, p-chlorostyrene, 2,5- dichlorostyrene, 2-methyl-4-chlorostyrene, etc.
• Monohydric alcohols containing l-18 carbon atoms includemethanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, hendecanol, dodecanol, tridecanol, tetradecanol, ,pentadecanol, hexadecanol, heptadecanol, octadecanol, their isomers and mixtures thereof.
• the ratio of one interpolymer to the other in the blend may vary over wide limits and still retain operability.
• the proportion of one interpolymer may vary from 5 to weight percent while the other interpolymer correspondingly varies from 95 to 5 weight percent.
• a one to one ratio of the preferred vinyl acetate/crotonic acid copolymer. to the preferred styrene/maleic half-ester copolymer has been found to exhibit the optimum in toughness, film forming characteristics, adhesion, hardness, water resistance, blocking resistance and ease of removal from the permanently coated substrate.
• Example I 85 parts of water, 1 part of 28% aqueous ammonia and 10.6 parts of SD-30 alcohol are introduced into a suitable vessel.
• SD-30 alcohol is ethanol which has been denatured by adding 10 gallons of methanol to gallons of ethanol).
• To the solvent system is then added, with stirring, 2.5 parts of an interpolymer of vinyl acetate and crotonic acid wherein the crotonic acid constitutes 5 mole percent of the interpolymer and 2.5 parts of an interpolymer of styrene and a maleic acid half-ester; the ester having been formed from an 80/20 mixture of secondary butyl alcohol and methanol.
• Example II T A 4 x 8 steel test panel is sprayed with a melamineacrylic enamel which is commonly used in the automotive industry for painting automobile bodies.
• the enamel is diluted to a viscosity of 18 seconds in a #4 Ford cup with a suitable solvent in order to insure ease of sprayability.
• Sufiicient paint is applied to provide, a film thickness of approximately 1 to 1 /2 mils when dry.
• the enamel is allowed to dry in the air at room temperature for 20 minutes. It is then baked for 30 minutes at 250 F. At this point it is not completely cured.
• the panel is removed from the oven and allowed to coolto a point at which it is still warm to the touch (approximately 60 C.). The cooling time is about 5-10 minutes.
• a 10% solids solution of the blend prepared in Example I is sprayed onto the warm panel, enough of the wet coating being applied to provide a /21 /2 mil thick coating when dry.
• the panel is then put back in the oven for 1 minute at 250 F.
• the panels are seen to possess an attractive deep gloss and a smooth hard surface.
• the panels are subjected to 100% relative humidity and a temperature of 100 F. in a humidity cabinet.
• the surface coating is found to be undamaged thereby.
• the top coating is easily removed by washing with an ordinary commercially available anionic household detergent dissolved in warm water.
• Example III Part A.-2.5 parts of the vinyl acetate/crotonic acid interpolymer of Example I and 7.5 parts of the styrene/ maleic half-ester interpolymer of Example I are dissolved in 90 parts of SD- alcohol. After solution has been attained, 50 parts of 2-ethoxyethanol is added.
• Part B.-Part A is repeated using 7.5 parts of the vinyl acetate/crotonic acid interpolymer and 2.5 parts of the styrene/maleic half-ester interpolymer.
• Part C.-Part A is repeated using 10 parts of the vinyl acetate/crotonic acid interpolymer and no styrene/maleic half-ester interpolymer.
• Part D.-Part A is repeated using 10 parts of the styrene/maleic acid half-ester and no vinyl acetate/crotonic acid interpolymer.
• Part E The solution of Parts A-D are applied to partially cured enamel-coated panels as in Example II.
• the panels are subjected to accelerated weathering tests in a Weather-O-Meter. After the weathering, the coatings are removed from the substrates by washing with the detergent solution of Example H. It is found that films of Part A and Part B are easily removed from the substrates but that the films of Part C and Part D are very diflicult to remove, requiring much more time and effort. This shows that the coating systems of the present application are superior with respect to removability to systems containing only one of the components. As seen above, ease of removability is economically important to the distributor.
• Example IV Examples I and II are repeated using 5 parts of a vinyl acetate/crotom'c acid interpolymer containing 3 mole percent crotonic acid and 95 parts of a styrene/maleic acid half-ester wherein the ester has been formed using 2- butoxyethanol. Results equivalent to those described in Example H are obtained.
• Example V Examples I and II are repeated using 95 parts of the vinyl acetate/crotonic acid interpolymer of Example I and 5 parts of the styrene/maleic acid methyl half-ester. The film obtained thereby is found to be somewhat softer than that of Example I, but is still hard enough to be operable.
• the process of this invention may be employed to protect the finished surfaces of such commercial products as automobiles, appliances, furniture, architectural structures, etc.
• spraying has been the only method of application recited in the examples, any conventional method of coating application may be used, e.g. brushing, dipping, etc.
• a method for the protection of finished substrates which comprises:
• an B-ethylenically unsaturated monomer selected from the group consisting of dicarboxylic acids, anhydrides of dicarboxylic acids, half-esters of dicarboxylic acids with alcohols containing 1-18 carbon atoms and mixtures thereof, and
• the second interpolymer comprises styrene and a half-ester of maleic acid.

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Wood Science & Technology (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• Paints Or Removers (AREA)

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Cited By (7)

Citations (4)

• 1967
  • 1967-12-26 US US693135A patent/US3544349A/en not_active Expired - Lifetime
• 1968
  • 1968-12-20 GB GB1257919D patent/GB1257919A/en not_active Expired
  • 1968-12-24 DE DE19681816980 patent/DE1816980A1/de active Pending
  • 1968-12-24 FR FR1600974D patent/FR1600974A/fr not_active Expired

Patent Citations (4)

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