MXPA98010885A - Additives and automotive sealants containing residue powder printers - Google Patents

Abstract

The present invention relates to compositions for use as additives in the automotive industry, which compositions contain residual powder primer and a plasticizer which is selected from the group consisting of 2-ethylhexyl diphenyl phosphate, diisoheptyl phthalate, a linear phthalate a alcohol base, a mixture of ethers containing a minimum of 55% of diesters and a maximum of 20% of dibenzoate, a mixture of esters containing a minimum of 60% of diesters and a maximum of 30% of dibenzoate and dipropylene glycol dibenzoate, and automotive sealant containing the residual powder primer, a plasticizer selected from the group consisting of 2-ethylhexyl diphenyl phosphate, diisoheptyl phthalate, a linear phthalate based on alcohols, a mixture of esters containing a minimum of 55% of diesters and a maximum of 20% dibenzoate, a mixture of esters containing a minimum of 60% of diesters and a maximum of 30% of dibenzoate and dibenzoate of dipropylene glycol, and automotive sealants: and a polymer resin

Description

ADDITIVES AND LIQUID AUTOMOTIVE OBTURANTS CONTAINING RESIDUAL DUST PRIMER FIELD OF THE INVENTION This invention relates to compositions that can be used in the automotive industry, particularly as additives in the preparation of sealing fluids for automobiles.

BACKGROUND OF THE INVENTION [0002] In automotive manufacturing, the body units and chassis thereof are coated, or printed, electrostatically with a 100% solids powder spray. The compositions of these powdered aerosols, known in the automotive industry as "powdered primers", and the methods for electrostatic application of the powdered primers are well known to those skilled in the automotive industry. It is estimated that in the order of 25 pounds per month of residual powder primer with 100% solids can be generated in each assembly plant where they are used to prime car parts, such as chassis units. The residual powder primer, this primer that does not remain fixed to the primed part of the car and that recovers after the electrostatic deposition of the powder primer in it, is currently being transported to public landfills for disposal. It would be considered a significant environmental advance and contribution if a use of the residual powder primer were discovered, so that the current practice of disposing of the residual powder primer in public landfills could be significantly reduced, or eliminated altogether. Also in automotive manufacturing, automotive seals are used to prevent the intrusion of air, water and dust into the passenger compartment of the automobile. These obturating liquids are usually prepared from plastisols, these mixtures being plasticizers and polymeric resins such as polyvinyl chloride, polyvinyl acetate or vinyl chloride and vinyl acetate copolymers. It is possible to use other polymers also in the preparation of the plastisols. The sealing liquids may also contain ingredients such as fillers, for example, calcium carbonate, talcum, calcium oxide and hollow glass spheres; rheological additives such as thixotropes, for example, silicas and clay derivatives, and pigments, for example, titanium dioxide and carbon black. Because the adhesion of a plastisol to cold rolled steel or coatings for electrodeposition (E-coat) is poor, conventional sealants may contain adhesion promoters. The most common of the adhesion promoters used in the preparation of sealing liquids is polyamidoamines. Without the adhesion promoters. These sealants or sealing liquids would present poor adhesion to substrates such as cold rolled steel and the E-coat. It has been reported that the residual paint sludge that is recovered from the "painted" car processes and that contains water, solvent and an uncured polymer, can be used in the preparation of automobile sealing fluids. However, before the residual paint sludge can be used to prepare automobile seals, the sludge from the residual paint must be subjected to extensive treatment and processing to remove all or almost all of the water or solvent from the residual sludge. The "painted" operations from which the residual sludge is recovered differ from the "electrostatic deposition" from which the residual powder primer is recovered. The powder primer never contains water or solvent, as a virgin material or as a waste material. In addition, the powder primer does not use ingredients such as thickeners, plasticizers and co-agents, which are commonly used in film-forming "paints" formulated with water and / or solvents. The present inventors, surprisingly, have discovered that the residual powder primer can be used, without further recycling or treatment, to formulate compositions that can be used in the automotive industry, specifically, the inventors have surprisingly discovered that the primer Residual powder can be used in combination with specific plasticizers to prepare compositions that can be used as additives in the automotive industry. In particular, the additives are used in the preparation of sealing fluids for automobiles. The inventors can identify at least three different advantages of their invention over the mud of prior art paints. First, the residual powder primer does not require processing to remove the unwanted solvent or water prior to its use in the preparation of automobile sealing liquids. Secondly, the residual powder primer is usually free or almost free of components such as thickeners, plasticizers and co-agents, which are commonly used in film-forming "paints" formulated with water and / or solvents. As a result, in the formulation of the compositions using residual powder primer, the formulator need not be interested in the deleterious effects that such components could have on the specific formulated compositions. Finally, the present invention provides a practical and economical solution to a significant environmental need by reducing or eliminating the amount of waste powder primer that is disposed of in public landfills, without the need for prolonged and costly recycling processes, providing unexpected improvements in car compositions that have not been reported so far. It is considered that each of the above advantages in itself constitutes a significant improvement over the prior art "paint mud" which contains water and solvent, as described above. In addition to the fact that the above three advantages can be realized at the same time, the compositions of the present invention offer other advantages which are described below.

SUMMARY OF THE INVENTION The present invention is directed to compositions that can be used as additives in the automotive industry, whose compositions contain waste or waste powder (IPR) and a plasticizer selected from the group consisting of: phosphate 2- ethylhexyldiphenyl, diisoheptyl phthalate, a linear phthalate based on C7-C9 alcohols, a mixture of esters and dipropylene glycol dibenzoate. When used as an additive in the preparation of formulated automobile sealing liquids, which are substantially free of an adhesion promoter, or preferably free of an adhesion promoter, the additives of the invention provide sealing liquids that exhibit adhesion which is as good as or better than conventional automobile sealing fluids containing an adhesion promoter in conventional amounts used to provide adhesion to automotive sealing fluids. Also included within the scope of the present invention are automobile sealant compositions containing a polymeric resin, IPR and a plasticizer selected from the group consisting of 2-ethylhexyldiphenyl phosphate, diisoheptyl phthalate, a linear based phthalate. of C1-C9 alcohols, a mixture of esters and dipropylene glycol dibenzoate.

DETAILED DESCRIPTION OF THE INVENTION The compositions of the present invention that can be used as additives in the automotive industry consist of a dispersion of IPR in a plasticizer selected from the group consisting of 2-ethylhexyl phosphate, diisoheptyl phthalate, a linear phthalate. based on C1-C9 alcohols, a mixture of esters and dipropylene glycol dibenzoate, in a weight ratio of IPR: plasticizer from 1:10 to 10: 1. Unless otherwise specified, all percentages of the components referred to herein are percent by weight based on the total weight of the composition containing these components. The exact relationship of IPR: plasticizer will be determined by different factors. For example, the viscosity of the desired composition using the additives of the inventive will be a factor. The specific substrate to which the composition is applied is another factor that should be considered in the choice of the appropriate ratio of IPR to plasticizer. For example, the adhesion and film-forming properties of the compositions will be different when applied to a cold-rolled steel substrate, for example, as compared to a surface that has been primed or E-coated with an aerosol primer or powder primer. The person skilled in the art, once he has the benefit of this description, will be able to easily determine the desired weight ratio of IPR: plasticizer, based on these considerations. The IPR compositions are well known to those skilled in the automotive industry and rely on the specific powder primer that was used to electrostatically coat the automobile parts. Typically, the IPR will contain a polymeric resin, such as polyester, a polyester / acrylic copolymer, or a polyester / acrylic / polyurethane terpolymer. The IPR can be used directly in the preparation of the additive compositions, that is, without the need for another treatment or processing of the IPR after it has been recovered from the electrostatic powder primer process. The composition of a common IPR is set out in Table 1. As one skilled in the automotive industry will know, the exact composition of the IPR will depend on the formulation of the particular powder primer that is used to electrostatically coat the body and chassis units. As such, the composition of Table 1 should not be considered as the only IPR that finds utility in the present invention. In contrast, the residual powder primer generated from any conventional electrostatic deposition process using conventional powder primers can be used in the present invention.

Table 1 Powder primer Table 1 (Continued) The plasticizers that are used in the preparation of the additive compositions may have certain properties when combined with the IPR. When formulated in compositions that are used in the automotive industry, for example, in automotive seals, the additives must provide compositions that are stable to excessive viscosity changes over time, ie, the compositions are stable in regarding the viscosity. In order for the compositions to be stable in viscosity, the additive containing the IPR and the plasticizer must also be stable in viscosity. Preferably, a dispersion of the IPR in the plasticizer, at a 1: 1 weight ratio, will exhibit a change in viscosity of less than 190%, preferably less than 150%, and even more preferred less than 100%, after 72 hours at a temperature of 25 ° C. The plasticizer must also be non-volatile to the extent that it does not volatilize at temperatures commonly used in processes that are used within the automotive industry that could employ the additives of the present invention. In addition to being stable to excessive change in viscosity, the plasticizer must provide dispersions that do not gel, solidify or precipitate, or otherwise undergo physical changes that render the dispersions unsatisfactory for their intended use. The plasticizers that were found to be useful to provide an IPR dispersion / plasticizer with excellent stability are 2-ethylexyldiphenyl phosphate (available from Monsanto with the trade name Sanicizer 141, CAS No. 1241-94-7), with a change of 24% and diisoheptyl phthalate (available from Exxon Chemical under the trade name Jayflex 77, CAS No. 71888-89-6), with a 38% change. Accordingly, the preferred plasticizers that are used in the preparation of the additive compositions are selected from the group consisting of 2-ethylexyldiphenyl phthalate and diisoheptyl phthalate. It was found that plasticizers that provide good to regular stability include a linear phthalate based on C7-C9 alcohols (available from BASF under the tradename Palatinol 79P, a mixture of CAS No. s68515-45-7, 68515-44- 6 and 111381-89-6), with a change of 114%; a mixture of esters containing from about 50 to about 85% of 2-methyl-, 3- (benzoyloxy) -2,2,4-trimethylpentyl ester of propanoic acid (CAS No. 22527-63-5), from about 10 to 30% of 2,2,4-trimethyl-1,3-pentanediol dibenzoate (CAS No. 68052-23-3) and from about 5 to about 10% of 2-methyl-, 2,2-dimethyl-1 - (1-methylethyl) -1,3-propandiyl ester of propanic acid (CAS No. 6846-50-0) (available from Huís America under the trade names Nuoplaz 6000 and Nuoplaz 1046). The Nuoplas 6000 was tested and found to have a 137% change. Another plasticizer having regular viscosity stability is dipropylene glycol dibenzoate (available from Kalama Chemical under the tradename K-Flex DP, CAS No. 27138-31-4), with a 186 percent change. It was found that plasticizers that provide IPR / plasticizer dispersions with poor stability, eg, greater than 200% viscosity change, include chlorinated C1-C17 alkanes (too thick for the test) available from ICI Forest Products under the trade name Cereblor S45, CAS No, 85535-85-9); adipate polyester (too thick for trial) (available from C.P. Hall under the trade name Plasthall P-760, CAS No. 103-21-1); and Texanol benzyl phthalate (too thick for the test) (available from Monsanto under the trade name Santicizer 278, CAS No. 16883-83-3). Other plasticizers include diisononyl phthalate (change 268%) (Jayflex DINP, CAS No. 68518-48-0, diisodecyl phthalate (change 206%) (Jayflex DINA; CAS No. 33703-08-1); di-1-nonyl phthalate (change 238%) (Jayflex L9P, CAS No. Unknown); and di (2-ethylhexyl) adipate (286% change) (Jayflex DOA, CAS No. 103-23-1), all of which are available from Exxon Chemical under the respective trade name Jayfiex [sic]. Additional plasticizers that provide poor stability include petroleum distillates (Viplex 885, CAS No. 68477-29-2) and a tart parafinic distillate solvent extract (Viplex 530-A), both available from Cro ley Chemical under the respective trade name Viplex. and both were too thick for the test. In addition to the excessive viscosity change for 72 hours at 25 ° C, a large part of the "bad" plasticizers exhibited gelation, solidification or physical changes over time, which would make the plasticizer and IPR combinations unacceptable for the compositions of according to the invention. When used in automotive sealing fluids, in addition to being stable, the additives must provide sealing liquids with shear strength and tensile strength that are sufficient for the intended use of sealing liquids. In addition to the IPR and the selected plasticizer, the automotive sealing fluids according to the present invention will also contain a polymeric resin of the type that is used to prepare conventional automotive sealing liquids. The polymer resin is basically used in the sealing fluid as a film former. Accordingly, the polymeric resin will be present in the sealing liquid in effective amounts to provide an automotive sealing liquid with film-forming properties sufficient for the specific end use of the sealing liquid. Once having the benefit of this disclosure, a person skilled in the sealing fluid art will be able to easily determine the exact amount of the polymeric resin necessary to provide specific film-forming properties for the specific end use. Exemplary polymer resins include poly (vinyl chloride) (PVC), poly (vinyl acetate) (PVAc) or vinyl chloride copolymers and vinyl acetate copolymers. Other polymers conventionally used to prepare conventional sealant liquids for automobiles can also be used. Preferably, the polymer resin is PVC. The automotive sealing liquid will contain from about 10 to about 50% of the polymeric resin, preferably from about 15 to about 40% of the polymeric resin and more preferably from about 20 to about 25%. The automotive sealing liquid will contain from about 0.1 to about 50% of IPR, preferably from about 5 to about 40% of IPR, and most preferably from about 10 to about 30% of IPR. The automotive sealing liquid will contain from about 0.1 to about 50% of the plasticizer, preferably from about 5 to about 40% of the plasticizer, and most preferably from about 25 to about 30% of the plasticizer. Sealant fluids for automobiles according to the present invention do not require adhesion promoters to bond the primed surfaces and the E-coat. In some, the adhesion of automotive sealing fluids containing the additive of the inventive containing the IPR and the plasticizer, still not containing an adhesion promoter of the type used to prepare the automotive sealing fluids, conventional in Effective amounts used to prepare conventional sealant liquids for automobiles is greater than or equal to that of a conventional sealing fluid containing an adhesion promoter. Although the automotive seals of the present invention may contain small amounts of an adhesion promoter of the type used to prepare seals for automobiles, conventional for improving the adhesion of cold rolled steel substrates, the automotive sealing fluids of the present invention are preferably substantially free of an adhesion promoter of the type that is used to prepare conventional automotive sealing liquids, and even more preferably, the sealing liquids are free of these adhesion promoters. By substantially free of an adhesion promoter, it is understood that automobile seals do not contain an adhesion promoter in such concentrations as are conventionally used in the preparation of conventional automotive sealant liquids containing adhesion promoters. and that do not contain IPR; or concentrations that would materially affect or modify the characteristics or properties of the sealing fluids for automobiles in accordance with the present invention. When used, the system for adhesion promotion used in the formulation of the sealing liquid preferably contains an unsaturated organosilane; an acrylic monomer; and an unsaturated acid or anhydride monomer. More preferably, it will also contain an epoxy resin or modified epoxy resin and a hardening agent for the epoxy resin, such as polyamide or modified polyamide. Examples of the unsaturated organosilanes are vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris B-methoxy-ethoxysilane, 3-methacryloxypropyltrimethoxysilane. Examples of the acrylic monomers are trimethylol propane trimethacrylate, hexanediol diacrylate and butyl methacrylate. Examples of the unsaturated acid or anhydride monomers are maleic, acrylic, crotonic, methacrylic, oleic, linoleic and tetrahydrophthalic acid or anhydride. Examples of unmodified epoxy resins are those based on diphenol A and epichlorohydrin with common properties including an epoxy value of 152 to 155 equiv / 100 g and an epoxide weight of 182 to 192. Other common epoxy resins are phenolnovola, triphenylolmethane and tetrabromo bis-A. An example of a modified epoxy resin includes the preferred liquid, epoxy, elastomeric epoxy resin which is a 40% addition product of carboxylated acrylonitrile butadiene elastomer and a bis-phenol-A and epoxy type epichlorohydrin liquid. This addition product has a weight per epoxide of 325 to 375. The curing of the modified epoxy or epoxy resin is accomplished by carrying out the reaction of the resin with a suitable curing agent or hardener. Common hardening agents are polyamides, diethylenetriamine, methandiamine, m-phenylenediamine, phenol, dicyandiamide, BF3-monoethylamine and nadicmethylanhydride [sic]. Preferred is a modified polyamide curing agent such as a latent dispersion of polyamide which is an addition product of phthalic anhydride and diethylenetriamine in an unmodified liquid epoxy resin. The most common of the adhesion promoters used in the preparation of conventional automotive sealants is polyamidoamines. When used, the adhesion promoters will comprise from about 0.5"to about 5% of the sealing liquid.The sealing fluids may also contain components such as fillers, eg, calcium carbonate, talcum, calcium oxide, and hollow spheres. glass, rheological modifiers such as pixotropes, for example, silicas and clay derivatives, solvents such as odorless mineral spirits, and pigments, for example, titanium dioxide, and carbon black.Each component is used in effective amounts to perform the function Specification for which the component is used Concentrations of fillers used in automotive fill fluids may vary from approximately 5 to approximately 60% Rheological modifier concentrations used in automobile sealing fluids may vary from approximately 1 to approximately 10% .The solvent concentrations used in automobile sealing fluids may vary from 0 to about 5%. The pigment concentrations used in automobile sealing fluids can vary from 0 to about 5%. It should be noted that, although the sealing liquids will contain pigment that have been incorporated through the IPR, additional pigment may be added when formulating a specific automotive sealing fluid, although it is not necessary. In the preparation of the automotive sealing fluids of the present invention, a stable dispersion of the residual powder primer in the plasticizer is prepared by mixing the plasticizer and the IPR in a mixer., such as a Cowles mixer, at ambient temperatures and blade speeds that are effective to form a stable dispersion. The dispersion is then mixed in a mixer, such as a Cowles mixer, under ambient conditions with the polymeric resin and, where desired, other optional components as described above. The mixing procedures are very basic and are well known to those skilled in the art of preparing automobile sealing liquids. The following examples are set forth to exemplify certain embodiments of the present invention and should not be considered to limit the scope of the invention in any way. The scope of the invention is limited only by the claims appended thereto.

An automotive sealing fluid according to the present invention was prepared and identified as sealing liquid 2 in table 2. A comparative automobile sealing liquid was also prepared and identified as sealing liquid 1 in table 2.

Table 2 The sealing liquids 1 and 2 were evaluated according to the following test protocol. The results of the evaluation are established in table 3.

Test protocol Viscosity-Stability: The viscosity-stability of the IPR dispersion in the plasticizer was determined as follows. The viscosity of the dispersion was measured in a Brookfield RVT viscometer, at 20 rpm, with a needle selection dependent on the viscosity range of the dispersion being measured. The dispersion is then allowed to stand for 72 hours at 25 ° C. The viscosity of the dispersion at rest is then measured again and the change in viscosity is calculated in percent.

Physical properties The following standard ASTM methods were performed to generate the data contained in Table 3.

All methods are standard methods used in the field of automobiles to characterize the respective physical properties of automobile sealing fluids.

Shear Strength: ASTM D1002-94, modified so that the joint line in the test procedure is 0.03 inch with one inch overlap, compared to the standard ASTM procedure that has a 0.001-inch joint line and an overlap of 0.5 inches The exact bonding line and the selected overlay may depend on factors such as the sealing fluid formulation, the substrate and custom specifications.

Tensile strength: ASTM D638-94b, unmodified. Elongation: ASTM D638-94b, unmodified.

Table 3 As the data indicates, the sealing liquid 2 surprisingly has strength and elongation properties which are as good as, if not better than, the automotive sealing liquid, comparative, containing an adhesion promoter. In addition, other properties of the sealing liquid 2, for example, high stability and paintability, are equivalent to the comparative obturating liquid 1. As a result of the use of the IPR in the automotive sealing fluid formulation, the adhesion promoter can be removed and the concentrations of the polymeric resin and the filter [sic] can be significantly reduced and replaced with IPR. Accordingly, not only the invention is environmentally advantageous and as good as or better than conventional sealing liquids with respect to adhesion and the like, but the present invention can provide a significant reduction in costs in automotive filling fluids formulated with the same, in that virgin raw materials, such as resins, fillers and adhesion promoters, can be substituted with IPR.

Claims (9)

1. A composition containing: residual powder primer; a plasticizer selected from the group consisting of 2-ethylhexyldiphenyl phosphate, diisoheptyl phthalate, linear phthalate based on C7-C9 alcohols, a mixture of esters containing from about 50 to about 85% 2-methyl-, 3 - (benzoyloxy) -2,2,4-trimethylpentyl ester of propanic acid (CAS No. 22527-63-5), from about 10 to 30% of 2,2,4-trimethyl-1,3-pentanediol dibenzoate (CAS No. 68052-23-3) and from about 5 to about 10% of 2-methyl-2,2-dimethyl-1- (1-methylethyl) -1,3-propandiyl ester and dipropylene glycol dibenzoate, wherein the primer Residual powder and plasticizer are present in effective amounts to provide a stable dispersion of residual powder primer viscosity in the plasticizer.

The composition of claim 1, wherein the residual powder primer and the plasticizer are present in a weight ratio of about 1:10 to about 10: 1.

The composition of claim 1, wherein the plasticizer is selected from the group consisting of 2-ethylhexyl diphenyl phosphate, diisoheptyl phthalate, a linear phthalate based on C7-C9 alcohols and dipropylene glycol dibenzoate.

The composition of claim 1, wherein the plasticizer is selected from the group consisting of 2-ethylhexyl diphenyl phosphate, and diisoheptyl phthalate.

5. The composition of claim 1 further comprising a polymeric resin of the type used to prepare conventional automotive sealant liquids in effective amounts to provide automotive sealing film-forming properties.

6. The composition of claim 5 contains from about 0.1 to about 50% residual powder primer, from about 0.1 to about 50% plasticizer and from about 10 to about 50% polymer resin.

The composition of claim 6, wherein the polymeric resin is selected from the group consisting of: poly (vinyl chloride), poly (vinyl acetate), vinyl chloride copolymers and vinyl acetate copolymers.

8. The composition of claim 1 further contains a component that is selected from the group consisting of: an adhesion promoter, a filler, a solvent and a rheology modifier, in effective amounts to perform the specific function for which the component is used.

9. The composition of claim 1, wherein the composition is free of adhesion promoters.