Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/41—Compounds containing sulfur bound to oxygen
  • C08K5/42—Sulfonic acids; Derivatives thereof
• • 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
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
• • 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
  • C09D127/00—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 halogen; Coating compositions based on derivatives of such polymers
  • C09D127/02—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 halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
  • C09D127/04—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 halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
  • C09D127/06—Homopolymers or copolymers of vinyl chloride

Definitions

• the plastisol composition described herein contains at least a plastisol, e.g., a polyvinyl chloride (PVC) resin and a plasticizer, an amine-containing adhesion promoter and an acid catalyst. Methods for its use as a sealant in the automotive industry are also described.
• a plastisol e.g., a polyvinyl chloride (PVC) resin and a plasticizer, an amine-containing adhesion promoter and an acid catalyst.
• Plastisols are widely used in many industrial processes as adhesives and sealers. See, e.g., U.S. Patent Nos. 4,146,520; 4,151 ,317; 4,268,548; 4,440,900; 4,533,524; 4,673,710; 4,851 ,464; 4,900,771 ; 4,988,768; 5,032,432; 5,039,768; 5,130,200; 5,143,650; 5,160,628; 5,205,963; and 5,248,562.
• adhesives are employed to bind various substrates together while sealants are employed to produce load bearing elastic joints between two or more surfaces and to prevent the passage of air, water and dirt therethrough.
• the automotive industry is a major user of both the adhesives and sealants.
• Automobiles are assembled from several structural components which are joined together in various fashions depending on particular components and the degree of stress that will have to be endured.
• an adhesive composition is applied as a liquid and subsequently hardened to provide sufficient bonding strength.
• adhesives are utilized in the assemblies of door panels, quarter panels, tailgates and roofs. These same assemblies will typically employ sealant compositions at a later stage in the assembly line.
• Still other automobile assemblies which are welded or bolted together use sealant compositions in their seams.
• the wheel house, shock tower, rocker panel, firewall, floor hem flange, floorplan, and trunk are a few examples of where sealants, but not adhesives, are employed.
• Adhesive compositions applied in the body shop area can be high strength epoxy or modified- epoxy adhesives which are capable of bonding to oily galvanized steel.
• vinyl plastisols can be employed, however, these applications are normally limited to situations that do not require high bonding performance.
• these materials are applied at room temperature and later cured through exposure to heat. In order to apply these materials, they must be of low enough viscosity to be mechanically pumped with adequate flow rates. Normally, because of their low viscosity these materials are easily displaced when exposed to liquid impingement by various cleaning solutions (washes) to which the assembly body parts are exposed. Once the assembled parts are moved from the body shop area to the paint shop area, they are subjected to sealing, topcoating (painting), and final oven curing. Sealant compositions have been found to have those needed characteristics.
• Plastisols have been employed as sealants in the paint shop area of the body assembly line.
• the plastisols adhere well to primed metal surfaces and can be painted over. They are durable enough to withstand normal weather and user exposure. Another important quality of the plastisols is that they are not expensive.
• plastisols are dispersions of polymeric resins in plasticizers. Examples of such polymeric resins include poly(vinyl chloride), poly(vinyl acetate) and copolymers of vinyl chloride and vinyl acetate. Other polymers can be employed as well in the preparation of plastisols.
• Plasticizers are high boiling liquids which attack and plasticize the polymeric resin particles.
• the plastisols are liquids which are applied at room temperature to the substrate. The liquid is converted to a solid through exposure to heat. In effect, the heat causes the dispersed resin particles to fuse together or dissolve into the plasticizer. A solid product results upon subsequent cooling.
• the automobile body is initially primed with a coating composition to prevent corrosion of the metal.
• a coating composition to prevent corrosion of the metal.
• This can be performed in a number of ways, e.g., by cationic electrodeposition using the auto body as the cathode.
• subsequent steps in the assembly are carried out. These steps include the use of plastisols as sealants over the primed automobile body.
• the sealants are subsequently topcoated with an acid catalyzed topcoat along with the remainder of the body during the final stages of the topcoating (painting) process.
• Certain areas of the body are not readily overcoated with the topcoat and instead only contain a thin film, i.e., overspray, during the topcoating process.
• Amine-containing adhesion promoters have been employed in plastisol compositions to improve the adhesion of the plastisol to the various parts of the automobile body it is applied thereto.
• Examples of such amine-containing adhesion promoters are those disclosed in U.S. Patent Nos.4,533,524; 4,824,700; 4,8511 ,464; 5,650,482; and 6,040,385.
• One problem associated with the prior art plastisol compositions employing an amine-containing adhesion promoter is that following the plastisol sealant being applied to the primed automobile body part and the subsequent topcoating with an acid catalyzed topcoat thereon and, particularly, in the areas that are not readily overcoated, i.e., areas containing only an overspray or low film build of the topcoat, the amine- containing adhesion promoter interacts and renders ineffectual the acid catalyst in the topcoat by neutralizing the acid catalyst resulting in the topcoat possessing a tacky surface. Therefore, use of a clear coat not normally used in these areas is applied over the topcoat to provide a non- tacky surface.
• the foregoing plastisol composition comprises: a) at least one plastisol; b) an amine-containing adhesion promoter; and, c) an acid catalyst other than dinonyl napthylene, disulfonic acid.
• a method for providing a topcoat possessing a non-tacky surface on a substrate comprises the steps of applying the aforestated plastisol composition to the substrate; and, applying an acid catalyzed topcoat thereon.
• the ability to overcoat the plastisol wet-on-dry or wet-on-wet with an acid catalyzed topcoat to provide a non-tacky surface is achieved and particularly in areas that have not been readily overcoated, e.g., at thicknesses ranging from about 0.0015 inches to about 0.0065 inches, while also allowing for excellent adhesion characteristics of the plastisol.
• the plastisol composition of this invention is obtained by mixing at least one plastisol, an amine-containing adhesion promoter, and an acid catalyst other than dinonyl napthylene disulfonic acid.
• the composition is based on the surprising discovery that the addition of an acid catalyst thereto will enable a topcoat to possess a non-tacky surface when applied on the plastisol composition of this invention during its application as a sealant and, in particular, areas where the topcoat was not readily applied, i.e., applied as an overspray. While not wishing not to be bound by theory, it is believed that a significant amount of the adhesion promoter migrates to the surface of the cured plastisol.
• the migration does not adversely impact the performance of the plastisol as a sealant but it does adversely affect the curability of acid catalyzed topcoats which are then applied to the wet (wet-on-wet) or dry (wet-on-dry) plastisol. It is believed that the amine adhesion promoter in the sealant reacts with the acid catalyst in the topcoat, neutralizes it, and rendering it ineffective for catalyzing the topcoat. This means that the topcoat will not be fully cured resulting in a tacky surface of the topcoat.
• the plastisols employed in the composition of the present invention comprises finely divided resin particles dispersed in a plasticizer.
• the resins are well known in the art and have been widely used in plastisol compositions.
• Suitable resins for use herein include polyvinyl chloride resins, polyvinyl acetate resins, copolymers of vinyl chloride with vinyl addition monomers such as, for example, vinyl acetate, the vinyl acetals, maleic esters, styrene, vinylidene chloride and acrylonitrile.
• Particularly preferred polyvinyl chloride resins are the polyvinyl chloride horhopolymers.
• Blends of several different polyvinyl chloride resins can also be used and will also be referred to as the polyvinyl chloride resin, even though more than one resin may actually be present. Generally, a blend of from about 50 to about 100 percent and most preferably from about 60 to about 75 percent of a homopolymer dispersion resin can be used herein.
• Plasticizers useful in the production of the plastisol include monomeric types selected to achieve desired characteristics such as proper gelation, fusion , and flow properties.
• monomeric plasticizers include monomeric esters of phthalic, benzoic, succinic, adipic, sebacic, talic, lauric, azelaic, caprylic, hexanoic, phosphoric, oleic, glutaric, trimellitic and stearic acids.
• Specific plasticizers include dioctyl phthalate, ethylene glycol dibenzoate, dioctyl succinate, dibutyl sebacate; dibenzyl azelate, didecyl glutarate and similar compounds.
• plasticizers include esters of 2,2,4-trimethyl-1 ,3-pentanediol, citric acid esters and N-ethyl toluenesulfonamide.
• a preferred plasticizer for use herein is diisodecyl phthalate.
• Polymeric plasticizing agents can be used in conjunction with the monomeric plasticizers in order to achieve special characteristics such as permanence, weathering resistance, and especially paintability.
• Polymer plasticizers useful in the present invention include the higher molecular weight polymeric acid esters (molecular weights greater than 1000).
• these polymeric plasticizers include esters of succinic, adipic, sebacic, talic, lauric, azelaic, caprylic, hexanoic, benzoic, phthalic, phosphoric, oleic, glutaric, trimellitic, and stearic acids, including mixtures or blends of these compounds.
• the polymeric plasticizers ordinarily have low diffusion rates because of their higher molecular weights and also act to retard the migration of other components from the applied compositions.
• Suitable amine-containing adhesion promoters can be any commercially available amine-containing adhesion promoters known to one skilled in the art. Representative of the amine-containing adhesion promoters include those disclosed in U.S. Patent Nos. 4,533,524;
• Useful amine- containing adhesion promoters for use herein include, for example, monoamide compounds, polyamide compounds, polyoxyalkylene polyamines, oxyalkylene ethers of mono- or polyamines, epoxy-modified products of one or more of these compounds, mixtures thereof and the like.
• Suitable monoamines include aliphatic, aromatic, araliphatic and alicyclic monoamines such as, for example, alkyl amines with the alkyl group containing from 1 to about 20 carbon atoms, e.g., methyl, ethyl, propyl, isopropyl, butyl, octyl, lauryl amines, etc., aniline, toluidine, naphthyl amines, benzyl amine, cyclohexyl amine and the like.
• Suitable polyamines include aliphatic, aromatic, araliphatic and alicyclic polyamines such as, for example, alkylene diamines, e.g., ethylene, propylene, hexamethylene diamines, etc., and the like.
• Suitable polyoxyalkylene polyamines include ones obtainable by converting the terminal hydroxyl groups of polyether polyols into amino groups by, for example, ammonolysis.
• suitable polyether polyols are polyoxyalkylene diols, triols, tetraols and the like, obtained by adding alkylene oxides such as, for example, ethylene glycol, propylene glycol, diethylene glycol, glycerol, trimethlol propane, ethylene diamine and the like, to initiators.
• alkylene oxides such as, for example, ethylene glycol, propylene glycol, diethylene glycol, glycerol, trimethlol propane, ethylene diamine and the like.
• Illustrative of polyoxyalkylene polyamines are those represented by the general formulae (1) and (2):
• A represents an alkylene group having from 2 to about 12 carbon atoms, e.g., a propylene group
• X represents the residue of triol such as trimethylol propane
• n is an integer of about 2-50
• m is an integer about 3-50.
• Useful polyoxyalkylene polyamines include polyoxypropylene polyamines (diamines or triamines) derived from polypropylene glycols or polyoxypropylene triols and the like.
• Oxyalkylene ethers of mono- or polyamines can be obtained by adding one or more of the foregoing alkylene oxides to one or more of the aforestated mono- or/and polyamines.
• suitable amines are alkanol amines such as di- and tri- ethanol amines and the like;
• polyethylene polyamines such as ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine and the like;
• polypropylene polyamines such as propylene diamine, dipropylene triamine, tripropylene tetramine and the like;
• polycycloalkylene polyamine such as 1 ,8-p-menthane diamine, isophorone diamine, cyclohexylene diamines, 4,4'-dicyclohexylmethane diamines, 1 ,3-bis(aminomethyl)cyclohexane and the like.
• Suitable epoxy-modified amines include, for example, ones obtainable by modifying one or more of these compounds such as, for example, polyoxyalkylene polyamines, oxyalkylene mono-or polyamines, ketimines of amino-compounds, etc., with one or more epoxy compounds.
• Suitable epoxy compounds include glycidyl ethers, e.g., bisphenol A glycidyl ether, polypropyleneglycol diglycidyl ether, phenyl glycidyl ether etc.; glycidyl esters such as dimeric acid glycidyl ester and the like; glycidyl amines such as tetraglycidyl diamino diphenyl methane and the like; linear aliphatic epoxides such as epoxydized polybutadienes and the like; alicyclic epoxides such as 3,4-epoxy-6-methylcyclohexylmethylcarboxylate; and the like.
• glycidyl ethers e.g., bisphenol A glycidyl ether, polypropyleneglycol diglycidyl ether, phenyl glycidyl ether etc.
• glycidyl esters such as
• Suitable acid catalysts other than dinonyl napthylene disulfonic acid for use in the plastisol composition of this invention can include any strong acid such as, for example, a sulfonic acid other than dinonyl napthylene disulfonic acid, e.g., amine blocked sulfonic acids, that can interact with an acid catalyzed topcoat applied on the composition thereby resulting in the topcoat possessing a non-tacky surface.
• a sulfonic acid other than dinonyl napthylene disulfonic acid e.g., amine blocked sulfonic acids
• sulfonic acids include paratoluene sulfonic acid, methyl sulfonic acid, ethyl sulfonic acid, propyl sulfonic acid, isopropyl sulfonic acid, butyl sulfonic acid, pentyl sulfonic acid, hexyl sulfonic acid, heptyl sulfonic acid, octyl sulfonic acid, nonyl sulfonic acid, decyl sulfonic acid, benzene sulfonic acid and the like with paratoluene sulfonic acid being preferred.
• the plastisol composition of this invention will ordinarily range from about 10 to about 40 weight percent of the finely divided resin, from about 20 to about 50 weight percent of the plasticizer, from about 0.1 to about 2.5 weight percent of the amine-containing adhesion promoter and from about 0.1 to about 2 weight percent of the acid catalyst, preferably from about 20 to about 35 weight percent of the finely divided resin, from about 25 to about 40 weight percent of the plasticizer, from about 0.5 to about 2 weight percent of the amine-containing adhesion promoter and from about 0.5 to about 1.5 weight percent of the acid catalyst and more preferably from about 25 to about 30 weight percent of the resin, from about 30 to about 35 weight percent of the plasticizer, from about 1 to about 1.5 weight percent of the amine-containing adhesion promoter and from about 0.75 to about 1 weight percent of the acid catalyst.
• the plastisol composition of this invention can also include optional components such as other adhesion promoters, e.g., methacrylates, epoxies, phenolic resins, silanes and the like; fillers, e.g., ground calcium carbonate, calcium sulfate, calcium oxide, magnesium oxide, titanium oxide, zinc oxide, diatomaceous earth, and the like; pigments, e.g., carbon black, titanium dioxide and the like; wetting agents, e.g., polyethylene glycol derivatives and the like, oil-absorbing substances, e.g., diatomaceous earth and the like, tackifiers, e.g., nitrile rubber, styrene butadiene, resin esters, tepene resins, and the like, rheological additives, e.g., precipitated calcium carbonates, silicas, clay derivatives and the like, waxes, e.g., castor wax, amorphous wax, bees
• the plastisol composition of this invention is particularly useful as a sealant in the assembly of automotive bodies.
• the composition of this invention can be used in the paint shop area of the assembly and is applied to a substrate that is typically primed with a corrosion-inhibiting coating prior to the composition being applied thereto.
• the composition can be used for substrates such as metal assemblies of door panels, quarter panels, tailgates and roofs that leave the body shop area.
• the sealant composition can be used for other automobile assemblies which are welded or bolted together and use the sealant compositions in their seams.
• Such assemblies include substrates such as the wheel house, shock tower, rocker panel, firewall, floor hem flange, floorplan, hood and trunk.
• the sealant composition can be applied to any of the foregoing substrates at room temperature in any convenient manner, such as pumping, troweling, flowing, brushing or spraying, either manually or robotically.
• the plastisol can then be baked, e.g., raising the temperature to a range of from about 130°C to about 160°C, such that upon cooling the sealant composition hardens to a state with an initial degree of sealing which is adequate for the intended purpose, topcoated
• the plastisol can be applied followed by the topcoat wherein both coatings are cured in a single bake (wet-on- wet), e.g., at a temperature ranging from about 250°F to about 350°F.
• the substrate is topcoated with an acid catalyzed topcoat with some areas possessing only an overspray and oven baked to a totally cured state by plastisol fusion of the sealer and also the topcoat paint.
• Typical topcoats include, for example, high performance acrylic topcoats which are cured by conventional acid catalysts.
• the applied composition of this invention is also able to withstand these operations without causing cosmetic-type problems such as discoloration, cracking, etc. After the sealant composition is painted over, the final product will have a smooth finish with substantially no tackiness or transfer where the topcoat was applied.
• EXAMPLE 1 To a mixing vessel, a mixture of 10.49 grams of linear dinonyl phthalate plasticizer, 5.14 grams of diisoheptyl phthalate plasticizer, 10.52 grams of polyester adipate plasticizer, 1.51 grams vinyl chloride-vinyl acetate-maleic acid terpolymer, 4.28 grams of m,p-cresol propoxylate, 1.21 grams of precipitated silica, 0.1 1 grams glycerine, 14.29 grams ground calcium carbonate, 15.07 grams precipitated calcium carbonate, 15.52 grams PVC resin, 15.52 grams vinyl chloride-vinyl acetate copolymer, 1.61 grams polyamidoamine, 0.25 grams blocked isocyanate, 1.46 grams calcium sulfonate plasticizer, 2.02 grams of glass beads (hollow glass microspheres) and 1.00 grams of Nacure® 2547 available from King Industries (Norwalk, CT) was formed. After mixing was commenced, the mixing continued under
• EXAMPLE 2 The PVC plastisol of Example 1 was applied to electrodeposition coated metal panels as a sealant at thickness of 0.04" and baked for 30 minutes at 270° F. The baked panels were further baked for an additional 30 minutes at 270°F. The sealant was then cooled until it reached room temperature.
• the electrodeposition coated metal panels were then painted with an acid catalyzed topcoat at different thicknesses as shown below in
• the PVC plastisol of Example 1 was applied to electrodeposition coated metal panels as a sealant at a thickness of 0.04" and baked for 30 minutes at 270° F. The baked panels were further baked for an additional 30 minutes at 270°F. The sealant was then cooled until it reached room temperature.
• the electrodeposition coated metal panels were then painted with an acid catalyzed topcoat at different thicknesses as shown below in Table 1 over the area where the sealant was applied.
• the topcoat was then evaluated for paint tack and transfer by touching the painted surface with a finger and noting the paint tack or transfer of the paint. These results are summarized below in Table 2.
• the electrodeposition coated metal panels were then painted with an acid catalyzed topcoat at different thicknesses as shown below in
• COMPARATIVE EXAMPLE B The PVC plastisol of Comparative Example A was applied to electrodeposition coated metal panels as a sealant at thickness of 0.04" and baked for 30 minutes at 270°F. The baked panels were further baked for an additional 30 minutes at 270 °F. The sealant was then cooled until it reached room temperature. The electrodeposition coated metal panels were then painted with an acid catalyzed topcoat at different thicknesses as shown below in Table 4 over the area where the sealant was applied. The topcoat was then evaluated for paint tack and transfer by touching the painted surface with a finger and noting the paint tack or transfer of the paint. These results are summarized below in Table 4.
• Comparative Example B illustrates that when a topcoat is applied onto a substrate containing a sealant composition outside the scope of this invention tackiness and/or transfer occurred in the areas that contained only an overspray.

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• Chemical & Material Sciences (AREA)
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• Chemical Kinetics & Catalysis (AREA)
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• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
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• Adhesives Or Adhesive Processes (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 2001
  • 2001-05-17 WO PCT/US2001/016003 patent/WO2001094464A1/en not_active Application Discontinuation
  • 2001-05-17 AU AU2001263232A patent/AU2001263232A1/en not_active Abandoned
  • 2001-05-17 EP EP01937504A patent/EP1301568A4/de not_active Withdrawn
  • 2001-05-17 CA CA002413972A patent/CA2413972A1/en not_active Abandoned

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