CA2007328A1 - Adhesion and paintability improvements in pvc plastisols at low bake temperatures - Google Patents
Adhesion and paintability improvements in pvc plastisols at low bake temperaturesInfo
- Publication number
- CA2007328A1 CA2007328A1 CA002007328A CA2007328A CA2007328A1 CA 2007328 A1 CA2007328 A1 CA 2007328A1 CA 002007328 A CA002007328 A CA 002007328A CA 2007328 A CA2007328 A CA 2007328A CA 2007328 A1 CA2007328 A1 CA 2007328A1
- Authority
- CA
- Canada
- Prior art keywords
- fatty acid
- mixture
- condensation product
- composition according
- adhesion promoter
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—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 halogen; Compositions of derivatives of such polymers
- C08L27/02—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 halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—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 halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- 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
-
- 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
- C08K5/20—Carboxylic acid amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of 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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J127/00—Adhesives 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; Adhesives based on derivatives of such polymers
- C09J127/02—Adhesives 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; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J127/04—Adhesives 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; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C09J127/06—Homopolymers or copolymers of vinyl chloride
Abstract
ABSTRACT OF THE DISCLOSURE The present invention provides a new and novel vinyl chloride polymer coating material which can be top-coated with acid-catalyzed coating compositions at low curing temperatures without compromising the adhesion of the coating to the metal substrate and without inhibiting the cure of subsequently applied coating. In accordance with the present invention, a new plastisol coating composition comprises a finely-divided vinyl chloride polymer together with a plasticizer and from about 0.5 to about 5 percent by weight of a composition of an adhesion promoter which is a non-gelled condensation product of a) a polymerized fatty acid; and b) a mixture of amines being present in a concentration to produce a final amine value that ranges up to about 225, said mixture being comprised of a polyalkylene polyamine and an N-aminoalkylpiperazine. In addition, the present invention provides a new and improved adhesion promoter for use in the aforesaid vinyl chloride polymer coating composition. This adhesion promoter is comprised of the condensation product of a polymeric fatty acid and an amine mixture of a polyalkylene polyamine and an N-aminoalkylpiperazine.
Description
73~8 1 . ~DHESION AND PAINTABILITY IMPROVEMENTS IN
PVC PLASTISOLS AT LOW BAKE TEMPERATURES
The present invention relates to a process for the bonding of metallic materials and for the production of coatings on metallic materials with a polyvinyl chloride plastisol having i~proved adhesion and paintability at baking temperatures of 90C and up, which plastisol contains, as an adhesion- and paintability-improving additive, a condensation product of a polymerized fatty acid, and a polyalkylene polyamine together with an N-aminoalkylpiperazine.
Polyvinyl chloride and its copolymers have long been known to possess resistance to deterioration caused by the action of aggressive media and they are, therefore, 15 widely used to impart corrosion resistance to metallic surfaces, to bond thin sheet metal structures and to sea]
welds, especially on preprimed metal in the automotive field.
Such coatinys are applied to the surface of the material to be protected mainly in the form of a plasticized vinyl chloride polymer (plastisol) by spread coating, roller coating, spray coating or the like. In one widely used form, a plastisol coating material is prepared by combining a plasticizer or mixture of plasticizers, a polyvinyl chloride, formable into a paste and distinguished in particular by a definite swelling capacity in the plasticizer, one or more fillers, s~abilizers and, optionally, pigments and PVC
processing aids.
~)7~28 1 The formulation of plasticized polyvinyl chloride (PVC) coating materials, their preparation and methods of applying them are described in great detail in Kreke~er Wick, Kunststoff-T~andbuch ("Plastics Handbook"), 1963, Vol. II, Part l, pp. 396 et. seq.
The adhesion of the plastisol to the material to which it is applied is an important criterion for its performance. This is particularly true when the plastisol is used as a coating on preprimed metal parts. Poor adhesion of this PVC protective coating to either bare or preprimed metal reduces the efficiency of the protective coating. It also increases the likelihood of penetration by aggressive media.
Water, for example, can readily seep in between the coating and the primed metal and degrade the integrity of the system.
The poorer the adhesion o' the protective film to the metal, the greater the li~elihood that this will occur. An additional advantage of the plastisol of this invention is the inherent fle~ibility of the cured plastisol when compared to competitive systems such as acrylics.
The paintability of plastisols applied to materials such as metallic surfaces at low-bake temperatures is important in the automotive industry which applies top coatings to plastisols that are cured by acid catalysis at low-bake temperatures. The basicity of the adhesion promoter should not, therefore, interfere with such paint systems Thus, there has been a need for plastisols which make it possible to produce high-strength bonds between a wide variety of materials, especially metallic materials, and to apply acid-cured top coatings to these materials 3n especially at low-bake temperatures. ~ccording to U.S.
Patent 4,146,520, polyaminoamides having a certain XID~7~%8 imidazoline content and made from a polymerized miiture of fatty acids with a high content of trimeric and higher polymeric fatty acids and an excess of polyalkylene polyamines, are used as adhesion promoters in an amount from 0.5 to 5 weight percent, based on the plastisol mass.
According to U.S. Patent 4,717,746, heterocyclic amines of the formula HN N-R
/
wherein R is hydrogen or an aminoalkyl group, -R'-NH2, in which ~' is a saturated aliphatic chain, form adhesion promoters when condensed with polymerized fatty acids.
However, when such promoters were used at relatively low cure temperatures, for example below 140C, the adhesive properties of the plastisols were found to be below acceptab~e commercial levels as described in ~able III.
These polyaminoamides effectuate a definite improvement in adhesive strength. When used in low concentrations, however, and at low baking temperatures, they leave room for further improvement with respect to adhesion, thermal stabi~lity, elongation at rupture and paintability of the cured PVC plastisol.
The present invention provides a new and novel vinyl chloride polymer coating material which can be top-coated with acid-catalyzed coating compositions at low curing temperatures without compromising the adhesiQn of the coating to the metal substrate and without inhibiting the cure of -4~ 7~8 suhsequently applied coating. This final coating can be applied to the plastisol af~er the plastisol is cured ~wet on dry); however, the unique advantages of this invention are most clearly shown when the second coat is applied to the uncured plastisol (wet on wet).
In accordance with the present invention, a ne~
plastisol coating composition comprises a finely-~vi~od vinyl chloride polymer together with a plas~iciz~r a~d fr~
about 0.5 to about 5 percent by weight of a co~positicn ~f an adhesion promo~er which is a non-gelled conde~lsation product Of a) a polymerized fatty acid; and b) a mixture of amines being prese~t i~l a concentration to produce a final amine value tha~ r~n~es up to about 225, said mixture being comprised of ~ p~ly~lkyle~e polyamine and an N-aminoalkylpiperazine.
In addition, the present invention provides a ~e~
and improved adhesion promoter or use in the aforesaid ~inyl chloride polymer coating composition. This adhesion pr~mcter is comprised of the condensation product of a poIymeric fatty acid and an amine mixture of a polyalkylene p~lya~ine a~ a~
N-aminoalkylpiperazine, especially N-aminoethyl~ip~razine~
The present plastisol composit:ion is particu~ar~y useful as a seam sealer for the interior and exterior surfaces of automobiles which are overpainted ~ith ~ ~nal enamel, particularly a high solid coating whic~ is preferably acid-catalyzed. Such coatings are exemplifie~ ~y ~el~ine formaldehyde hydroxyacry]ics as set forth in ~.S. P~ent~
4,397,989 and 4,430,458.
To secure adhesion of such topco~tin~s to bare or 3 primed metal surfaces, the dual objective ~f lo~ curing temperature and non-interference with the ~ci~ cure of the -5~ 8 topcoating must be achieved wi-thout compromising the ad~esion of the vinyl chloride polymer plastisol to the metal substrate. The plastisol composition of the present invention accomplishes this dual objective without comprising plastisol adhesion to the substrate.
By comparison, plastisols prepared in accordance with the a~oresaid U.S. Patents 4,146,520 and 4,717,746 fail to pro~ide th~ excellent adhesive properties demonstrated with the present plastisol. Specifically~ when the plastisol composition of U.S. Patent 4,146,520 is employed, the topcoating does not cure due to the high amine content of the plastisol. The high amine content of the plastisol composition of the '520 patent interferes with the acid catalyst of the topcoat. On the other hand, when the amine content of the plastisol of the '520 patent is reduced, the composition gells and is not useful. It is emphasized that curing at low temperatures is desired in the automobile industry, a major user of plastisol compositions.
The present plastisol compositions, as well as the adhesion promoter composition, is characterized by a lower amine value than is employed in the composition of the aforesaid U.S. Patent 4,146,520. The amine value of the present invention ranges up to about 225 with the range 150-220 being especially preferred. This reduction is accomplished by substituting part of the polyalkylene polyamine with an N-aminoalkylpiperazine. For whatever reason, the inclusion of the N-aminoalkylpiperazine prevents gellation of the polyamidoamine adhesion additive which occurs when the normal polyalkylene polyamine level is reduced to avoid interfering with the acid catalyst of topcoating compositions. The ratio of the equivalent weights -6~ 8 of aminoalkylpiperazine to the equivalent weights of the other polyamines is from about 1 to about 5 to about 1 to about 0.25. The equivalent weight of polyamines for the purposes of this invention represents the average molecular weight of the polyamine divided by the number of primary and secondary amino groups. The equivalen-t weight of polyamines is calculated by dividing 56,108 (molecular weight of KOH
multiplied by 1000) by the Total Amine Value (TAV) of the polyamine. The TAV is determined by perchloric acid potentiometric titration (ASTM D2073). The equivalent weight of the aminoalkylpiperazine is calculated by dividing the molecular weight by two.
The polyamidoamine compositions of U.S. Patent 4,146,520 usually comprise about 35 percent by weight polyalkylene polyamine. In the new plastisol compositions of the present invention, the amine mixture for forming the polyamidoamine is below 30% by weight of the polymeric fatty acid and amine mixture collectively. Preferably, the amine mixture comprises below 25~ by weight based on the total polymeric fatty acid and amine mixture weight.
The N-aminoalkylpiperaæines to be employe~ in this invention are represented by the formula HN N-Z-NH
\ ~ 2 in which Z is an alkylene chain of up to 3 carbon atoms and a total of 5 carbon atoms. Such compounds are either readily available or easily synthesized in the laboratory. Of these, 3 N-aminoethylpiperaæine of the ~ormula -7~ ~ 8 HN N-CH2CH~NH2 \ ' is preferred.
A "polymerized fatty acid" refers, in a general way, to polymerized acids obtained from fatty acids~ Fatty acids are unsaturated natural and synthetic monobasic aliphatic acids having from 8 to 22 carbon atoms, preferably 18 carbon atoms. Fatty acids can be polymerized by known processes~
Polymeric fatty acids suited-for use in accordance with the invention are commercial products having approximately -the following composition:
-Monomeric acids5 to 15 weight percent Dimeric acids55 to 80 weight percent Trimeric and higher-10 to 35 weight percent polymerized acids . ~
In addition, polymerized fatty acids having a high trimer content may also be employed. These acids may be prepared by selective reaction based on a free-radical mechanism according to published German Patent Application DOS 25 06 211 or by generally known distillation methods from typical commercially available products and have approximately the following composition:
Monomeric acids0 to 5 weight percent 3 Dimeric acids10 to 25 weight percent Trimeric and higher~0 to 75 weight percent polymerized acids . . _ _ _ _ . . _ . _ -8- 2~7~2~
Rn especially preferred polymeric fatty acid ~r use in the invention is a commercially available dimer acid, Empol 1024 (Emery Industries, Inc.) having a reported composition of 75~ dimeric acids, 25~ trimeric acids and a trace of monomeric acids. Other Empol dimer and trimer acids are also preferred.
Suitable polyalkylene polyamines to be used in accordance with the invention are, in particular, amines which are capable of imidazoline formation. These are of the general formula ll 2N ~ ( -CH 2 -CH 2 -NH- ) -CH2 -CH 2 -NH2 wherein m is 1 to 5r for example, diethylenetriamine, triethylenetetramine or tetraethylenepentamine. These polyalkylene polyamines may optionally also contain amounts of other amines (see Vllmann Enzyklopaedie der Technischen Chemie, Vol. 14, 1~63, p. 7a). Also, polyalkylene polyamines not capable of imidazoline formation and of the general formula 2 ( H2 CH2 CH2-NH)m-cH2-cH2-cH2-NH2 wherein m is 1 to 4, for example, dipropylenetriamine or tripropylenetetramine may be used. Polyalkylene polyamines having ethylene and propylene bridges as alkylene groups, obtained by the cyanoethylation o$ the amines followed by hydrogenation (for example, N3-amine and N4-amine, see pamphlet of ~ASF AG, 1976), are also suitable for use.
In accordance with the invention, other amines, ~ too, mav be used, such as amines of the general formula 9 ~7~2~3 wherein R is aliphatic hydrocarbon, optionally substituted or interrupted by hetero atoms and in particular by oxygen atoms, having from 2 to 36 carbon atoms and more particularly from 6 to 20 carbon atoms, such as 1,2~diaminoethane, 1,6-diaminohexane, l,9-diaminononane, 1,12-diaminododecane, dimeric fatty acid amine (prepared by known processes from dimeric fatty acids), the 2,2,~(4,4,2)-trimethylhe~amethylene-diamines, 1,7-diamino-4-oxa-heptane, 1,12-diamino-4,9-dioxa-dodecane, or 1,20-diamino-4,17-dioxaeicosane.
The mixture of amines and polymeri7ed Fatty acid is condensed employing known procedures. For example, the reactants are reacted simultaneously in a reactor at a temperature of about 180-225C, optionally, under vacuum.
Any remaining water of reaction can be finally removed by reducing pressure in the reactor. The reaction product may then be diluted with solvent to whatever desired solids content and be ready for use in producing the vinyl chloride polymer plastisol. The solvent is preferrably present at 10-70 percent of the condensation product:.
The baking temperature which is optimum for a give~
polyvinyl chloride formulation (and which depends also on th~
gellation temperature of the PVC formulation used) can usually be determined simply by trial and error.
Suitable substrates for coating or bonding are all materials commonly used in this field, particularly metals and glass.
PVC PLASTISOLS AT LOW BAKE TEMPERATURES
The present invention relates to a process for the bonding of metallic materials and for the production of coatings on metallic materials with a polyvinyl chloride plastisol having i~proved adhesion and paintability at baking temperatures of 90C and up, which plastisol contains, as an adhesion- and paintability-improving additive, a condensation product of a polymerized fatty acid, and a polyalkylene polyamine together with an N-aminoalkylpiperazine.
Polyvinyl chloride and its copolymers have long been known to possess resistance to deterioration caused by the action of aggressive media and they are, therefore, 15 widely used to impart corrosion resistance to metallic surfaces, to bond thin sheet metal structures and to sea]
welds, especially on preprimed metal in the automotive field.
Such coatinys are applied to the surface of the material to be protected mainly in the form of a plasticized vinyl chloride polymer (plastisol) by spread coating, roller coating, spray coating or the like. In one widely used form, a plastisol coating material is prepared by combining a plasticizer or mixture of plasticizers, a polyvinyl chloride, formable into a paste and distinguished in particular by a definite swelling capacity in the plasticizer, one or more fillers, s~abilizers and, optionally, pigments and PVC
processing aids.
~)7~28 1 The formulation of plasticized polyvinyl chloride (PVC) coating materials, their preparation and methods of applying them are described in great detail in Kreke~er Wick, Kunststoff-T~andbuch ("Plastics Handbook"), 1963, Vol. II, Part l, pp. 396 et. seq.
The adhesion of the plastisol to the material to which it is applied is an important criterion for its performance. This is particularly true when the plastisol is used as a coating on preprimed metal parts. Poor adhesion of this PVC protective coating to either bare or preprimed metal reduces the efficiency of the protective coating. It also increases the likelihood of penetration by aggressive media.
Water, for example, can readily seep in between the coating and the primed metal and degrade the integrity of the system.
The poorer the adhesion o' the protective film to the metal, the greater the li~elihood that this will occur. An additional advantage of the plastisol of this invention is the inherent fle~ibility of the cured plastisol when compared to competitive systems such as acrylics.
The paintability of plastisols applied to materials such as metallic surfaces at low-bake temperatures is important in the automotive industry which applies top coatings to plastisols that are cured by acid catalysis at low-bake temperatures. The basicity of the adhesion promoter should not, therefore, interfere with such paint systems Thus, there has been a need for plastisols which make it possible to produce high-strength bonds between a wide variety of materials, especially metallic materials, and to apply acid-cured top coatings to these materials 3n especially at low-bake temperatures. ~ccording to U.S.
Patent 4,146,520, polyaminoamides having a certain XID~7~%8 imidazoline content and made from a polymerized miiture of fatty acids with a high content of trimeric and higher polymeric fatty acids and an excess of polyalkylene polyamines, are used as adhesion promoters in an amount from 0.5 to 5 weight percent, based on the plastisol mass.
According to U.S. Patent 4,717,746, heterocyclic amines of the formula HN N-R
/
wherein R is hydrogen or an aminoalkyl group, -R'-NH2, in which ~' is a saturated aliphatic chain, form adhesion promoters when condensed with polymerized fatty acids.
However, when such promoters were used at relatively low cure temperatures, for example below 140C, the adhesive properties of the plastisols were found to be below acceptab~e commercial levels as described in ~able III.
These polyaminoamides effectuate a definite improvement in adhesive strength. When used in low concentrations, however, and at low baking temperatures, they leave room for further improvement with respect to adhesion, thermal stabi~lity, elongation at rupture and paintability of the cured PVC plastisol.
The present invention provides a new and novel vinyl chloride polymer coating material which can be top-coated with acid-catalyzed coating compositions at low curing temperatures without compromising the adhesiQn of the coating to the metal substrate and without inhibiting the cure of -4~ 7~8 suhsequently applied coating. This final coating can be applied to the plastisol af~er the plastisol is cured ~wet on dry); however, the unique advantages of this invention are most clearly shown when the second coat is applied to the uncured plastisol (wet on wet).
In accordance with the present invention, a ne~
plastisol coating composition comprises a finely-~vi~od vinyl chloride polymer together with a plas~iciz~r a~d fr~
about 0.5 to about 5 percent by weight of a co~positicn ~f an adhesion promo~er which is a non-gelled conde~lsation product Of a) a polymerized fatty acid; and b) a mixture of amines being prese~t i~l a concentration to produce a final amine value tha~ r~n~es up to about 225, said mixture being comprised of ~ p~ly~lkyle~e polyamine and an N-aminoalkylpiperazine.
In addition, the present invention provides a ~e~
and improved adhesion promoter or use in the aforesaid ~inyl chloride polymer coating composition. This adhesion pr~mcter is comprised of the condensation product of a poIymeric fatty acid and an amine mixture of a polyalkylene p~lya~ine a~ a~
N-aminoalkylpiperazine, especially N-aminoethyl~ip~razine~
The present plastisol composit:ion is particu~ar~y useful as a seam sealer for the interior and exterior surfaces of automobiles which are overpainted ~ith ~ ~nal enamel, particularly a high solid coating whic~ is preferably acid-catalyzed. Such coatings are exemplifie~ ~y ~el~ine formaldehyde hydroxyacry]ics as set forth in ~.S. P~ent~
4,397,989 and 4,430,458.
To secure adhesion of such topco~tin~s to bare or 3 primed metal surfaces, the dual objective ~f lo~ curing temperature and non-interference with the ~ci~ cure of the -5~ 8 topcoating must be achieved wi-thout compromising the ad~esion of the vinyl chloride polymer plastisol to the metal substrate. The plastisol composition of the present invention accomplishes this dual objective without comprising plastisol adhesion to the substrate.
By comparison, plastisols prepared in accordance with the a~oresaid U.S. Patents 4,146,520 and 4,717,746 fail to pro~ide th~ excellent adhesive properties demonstrated with the present plastisol. Specifically~ when the plastisol composition of U.S. Patent 4,146,520 is employed, the topcoating does not cure due to the high amine content of the plastisol. The high amine content of the plastisol composition of the '520 patent interferes with the acid catalyst of the topcoat. On the other hand, when the amine content of the plastisol of the '520 patent is reduced, the composition gells and is not useful. It is emphasized that curing at low temperatures is desired in the automobile industry, a major user of plastisol compositions.
The present plastisol compositions, as well as the adhesion promoter composition, is characterized by a lower amine value than is employed in the composition of the aforesaid U.S. Patent 4,146,520. The amine value of the present invention ranges up to about 225 with the range 150-220 being especially preferred. This reduction is accomplished by substituting part of the polyalkylene polyamine with an N-aminoalkylpiperazine. For whatever reason, the inclusion of the N-aminoalkylpiperazine prevents gellation of the polyamidoamine adhesion additive which occurs when the normal polyalkylene polyamine level is reduced to avoid interfering with the acid catalyst of topcoating compositions. The ratio of the equivalent weights -6~ 8 of aminoalkylpiperazine to the equivalent weights of the other polyamines is from about 1 to about 5 to about 1 to about 0.25. The equivalent weight of polyamines for the purposes of this invention represents the average molecular weight of the polyamine divided by the number of primary and secondary amino groups. The equivalen-t weight of polyamines is calculated by dividing 56,108 (molecular weight of KOH
multiplied by 1000) by the Total Amine Value (TAV) of the polyamine. The TAV is determined by perchloric acid potentiometric titration (ASTM D2073). The equivalent weight of the aminoalkylpiperazine is calculated by dividing the molecular weight by two.
The polyamidoamine compositions of U.S. Patent 4,146,520 usually comprise about 35 percent by weight polyalkylene polyamine. In the new plastisol compositions of the present invention, the amine mixture for forming the polyamidoamine is below 30% by weight of the polymeric fatty acid and amine mixture collectively. Preferably, the amine mixture comprises below 25~ by weight based on the total polymeric fatty acid and amine mixture weight.
The N-aminoalkylpiperaæines to be employe~ in this invention are represented by the formula HN N-Z-NH
\ ~ 2 in which Z is an alkylene chain of up to 3 carbon atoms and a total of 5 carbon atoms. Such compounds are either readily available or easily synthesized in the laboratory. Of these, 3 N-aminoethylpiperaæine of the ~ormula -7~ ~ 8 HN N-CH2CH~NH2 \ ' is preferred.
A "polymerized fatty acid" refers, in a general way, to polymerized acids obtained from fatty acids~ Fatty acids are unsaturated natural and synthetic monobasic aliphatic acids having from 8 to 22 carbon atoms, preferably 18 carbon atoms. Fatty acids can be polymerized by known processes~
Polymeric fatty acids suited-for use in accordance with the invention are commercial products having approximately -the following composition:
-Monomeric acids5 to 15 weight percent Dimeric acids55 to 80 weight percent Trimeric and higher-10 to 35 weight percent polymerized acids . ~
In addition, polymerized fatty acids having a high trimer content may also be employed. These acids may be prepared by selective reaction based on a free-radical mechanism according to published German Patent Application DOS 25 06 211 or by generally known distillation methods from typical commercially available products and have approximately the following composition:
Monomeric acids0 to 5 weight percent 3 Dimeric acids10 to 25 weight percent Trimeric and higher~0 to 75 weight percent polymerized acids . . _ _ _ _ . . _ . _ -8- 2~7~2~
Rn especially preferred polymeric fatty acid ~r use in the invention is a commercially available dimer acid, Empol 1024 (Emery Industries, Inc.) having a reported composition of 75~ dimeric acids, 25~ trimeric acids and a trace of monomeric acids. Other Empol dimer and trimer acids are also preferred.
Suitable polyalkylene polyamines to be used in accordance with the invention are, in particular, amines which are capable of imidazoline formation. These are of the general formula ll 2N ~ ( -CH 2 -CH 2 -NH- ) -CH2 -CH 2 -NH2 wherein m is 1 to 5r for example, diethylenetriamine, triethylenetetramine or tetraethylenepentamine. These polyalkylene polyamines may optionally also contain amounts of other amines (see Vllmann Enzyklopaedie der Technischen Chemie, Vol. 14, 1~63, p. 7a). Also, polyalkylene polyamines not capable of imidazoline formation and of the general formula 2 ( H2 CH2 CH2-NH)m-cH2-cH2-cH2-NH2 wherein m is 1 to 4, for example, dipropylenetriamine or tripropylenetetramine may be used. Polyalkylene polyamines having ethylene and propylene bridges as alkylene groups, obtained by the cyanoethylation o$ the amines followed by hydrogenation (for example, N3-amine and N4-amine, see pamphlet of ~ASF AG, 1976), are also suitable for use.
In accordance with the invention, other amines, ~ too, mav be used, such as amines of the general formula 9 ~7~2~3 wherein R is aliphatic hydrocarbon, optionally substituted or interrupted by hetero atoms and in particular by oxygen atoms, having from 2 to 36 carbon atoms and more particularly from 6 to 20 carbon atoms, such as 1,2~diaminoethane, 1,6-diaminohexane, l,9-diaminononane, 1,12-diaminododecane, dimeric fatty acid amine (prepared by known processes from dimeric fatty acids), the 2,2,~(4,4,2)-trimethylhe~amethylene-diamines, 1,7-diamino-4-oxa-heptane, 1,12-diamino-4,9-dioxa-dodecane, or 1,20-diamino-4,17-dioxaeicosane.
The mixture of amines and polymeri7ed Fatty acid is condensed employing known procedures. For example, the reactants are reacted simultaneously in a reactor at a temperature of about 180-225C, optionally, under vacuum.
Any remaining water of reaction can be finally removed by reducing pressure in the reactor. The reaction product may then be diluted with solvent to whatever desired solids content and be ready for use in producing the vinyl chloride polymer plastisol. The solvent is preferrably present at 10-70 percent of the condensation product:.
The baking temperature which is optimum for a give~
polyvinyl chloride formulation (and which depends also on th~
gellation temperature of the PVC formulation used) can usually be determined simply by trial and error.
Suitable substrates for coating or bonding are all materials commonly used in this field, particularly metals and glass.
3~ The following examples are given to further illustrate the present invention.
- 1 o - ~ 017~8 Pre aration of Plastisol Adhesion Promoter No. 1 P _ A closed reactor was charged with 3,890 g of ~mpol 102g dimer acid (equivalent weight 292; 13.3 equivalents) having the predominent structural formula HooccH2(c32Hx)cH~cOOH
690 g N-aminoethylpiperazine (equivalent weight 64.8; 10.7 equivalen~s); and 921 g trlethylenetetraamine (equivalent ~eight 39.5; 10.7 equivalents) under a nitrogen atmosphere.
The- reactants were stirred by an agitator provided in the reactor and heated. As soon as water of condensation appeared in the reactor, the nitrogen gas supply was stopped and the temperature increased to bring the reaction mixture to reflux. The reaction was allowed to continue at a reflux temperature of between 190C and 250C at atmospheric pressure. The acid value of the reaction mixture was monitored and upon reaching an acid value of 2, the reactor was subjected to a mild vacuum. This was continued until the - reaction pressure was reduced to 5 mm Hg. The reaction was continued at these thermodynamic conditions, 190C to 250C
and 5 mm Hg, until the reaction mixture acid value dropped below 1Ø At that time the reactor was cooled to 150C, atmospheric pressure was reinstituted, by the addition of nitrogen gas, and Hisol (Ashland Oil Co., highly aromatic solvent) was added to acceptable handling viscosity. The addition of the Hisol permitted cooling of the reaction mixture to ambient temperature. The product of this reaction was a liquid weighing 9,520 g.
Ana~ysis of the product of this reaction, the PVC
plastisol adhesion promoter, provided the following characteristics: an acid value of 0.78 (determined by the method of ASTM D16639-70), a TAV of 74.0; a Gardner color of 10 and a viscosity at 25C of 8,880 centipoise.
~0~73~8 EXAMPLE_2 Preparation of PVC Plastisol Composition Incorporating Adhesion Promoter (Plastisol Composition No. l?
A PVC plastisol con-taining the adhesion promoter formed in accordance with Example 1 was prep~red by dissolving 5 g of the adhesion promoter in 30 g ~utyl cyclohexyl phthalate, 30 g dihexyl phthalater S0 g ~ilC7~
phthalate and 5 g benzyl alcohol. The thus for~ed s~lution was added to a preblended, finely divided solid mixture of~
60 g Vestolite 7090 polyvinyl chloride copoly~er (Huls AÇ~ r 40 g Bordon VC265 polyvinyl chloride copolymerr 110 g calcium carbonate, 30 g precipitated calcium carbonate and 15 g titanium dioxide. The solid and liquid components were ~ixe~
together under high shear to provide a smooth consiste~t plastisol mixture.
The formulation of the polyvinyl chloride tP~C~
plastisol composition of this example, denoted ~s Plasltisol Composition No. 1, is summarized in Table I bel~w.
3_~
-12~ 7~2~
1 EX~MpL~ 3 Preparation of PVC Plastisol Composition Nos. 2-6 ~ dditlonal PVC plastisol eompositions were prepared by dissolving 5 g of the adhesion promoter formed in Example 1 with mixtures of benzyl alcohol and various phthalate compounds. These liquid solutions were added to preblended, finely divided solid mixtures of polyvinyl chloride, caleium earbonate and, in some cases, titanium dioxide in aecordanee with the proeedure of Example 2.
The exact constituency of these compositions is provided in Table I below which summarizes Plastisol Composition Nos. 2 to 5.
?
2~
TABLE I
PVC Plastisol Composition No. Component Wt, q 1 Vestolite 7090 PVC Copolymer 60 Bordon VC265 PVC Copolymer 40 CaCO3 110 Precipitated CaCO3 30 TiO2 15 Butyl Cyclohexyl Phthalate 30 Dihexyl Phthalate 30 di(C7-C11) Phthalate So Benzyl Alcohol 5 Adhesion Promotor No. 15 Vestolite 7090 PVC Copolymer 60 Bordon VC265 PVC Copolymer 40 CaCO3 125 Precipitated CaCO3 3Q
Nuoplaz 1046, (Huls AG)35 Phthalate Isobutyrate Ester polyol from Texanol (Eastern) di(C7-C11) Phthalate 35 Butyl Benzyl Phthalate30 Benzyl Alcohol 5 Adhesion Promoter No. 15 3 Vestolite 7090 PVC Copolymer 60 Bordon VC265 PVC Copolymer 40 CaCO3 30 Precipitated CaCO3 50 Butyl Cyclohexyl Phthalate 50 di(C7-C11) Phthalate 25 Dihexyl Phthalate 25 Benzyl Alcohol 5 Adhesion Promoter No. 15 ~7~8 -14~
TABLE 1 (con-tinued) PVC Plas~isol Composition No. Component 4 Geon 130X33 60 (B.F. Goodrich) PVC copolymer Pliovic MC-85 (Goodyear) 40 Maleic Es-ter Copolymer CaCO3 110 Precipitated CaCO3 30 TiO2 15 Butyl Cyclohexyl Phthalate 30 Dihexyl Phthalate 30 di(C7-Cll) Phthalate 50 Benzyl Alcohol 5 Adhesion Promotor No. l 5 Oxy 6493 (Occidental Chemical 60 Corp.) PVC
? Homopolymer Bordon VC265 PVC Copolymer 40 CaC03 110 Precipitated CaCO3 30 TiO2 15 Butyl Cyclohexyl Phthalate 30 Dihexyl Phthalate 30 di(C7-Cll) Phthalate 50 Benzyl Alcohol 5 Adhesion Promotor No. 1 5 2~ 28 TABI,E 1 (continued) PVC Plastisol Composition No. Component Wt, 6 Oxy 6338 PVC Copolymer60 Bordon VC265 PVC copolymer 40 CaC03 110 Precipitated CaC03 30 Tio2 15 Bu-tyl Cyclohexyl Phthalate 30 Dihexyl Phthalate 30 di(C7-Cll) Phthalate - 50 Benzyl Alcohol 5 Adhesion Promoter No. 15 -16- ~ ~0~28 EX~MPI.E 4 Adhesion Characteristics of PVC Plastisol Compositions Each of the PVC plastisol compositions tabulated in Tahle I were tested to determine their adhesion. In this test 5 g of each of the plastisol compositions of Table I
were placed on a Uni-Prime coated test panel, a standard test panel supplied by PPG, and which is primed by electro-deposition. The plastisol composition was drawn across the panel with a drawdown bar such that a 0.02 inch thick film was formed over an area of i inch by 3 inches. The plastisol film, disposed on the test panel, was cured for 20 minutes at 120C in a forced air heated oven and then cooled for 30 minutes. Two parallel slits, approximately 1/2 inch apart, were cut into the cured plastisol film with a razor blade.
One end of the strip between the cuts was lifted off the test panel with a spatula and then pulled. If the fi.lm tore, adllesion was ~reater than cohesion.
Each of the plastisol compositions of Table 1, Composition Nos. 1-6, were tested in accordance with the above procedure and were each found to possess an adhesion ~reater than cohesive. That is, the cured plastisol film tore in each ~est.
3l~
-17- ~0~28 . _ Wet-on-wet Paintabili-ty of PVC Plastisol Compositions A test was made to determlne the wet-on-wet paintability of the plastisol compositions of Table I. In these tests a Uni-Prime coated test panel was again coated with each of the plastisol compositions of Table I in accordance with the procedure of E~ample 4.
A high solids enamel paint was spray applied over the unbaked PVC plastisol compositions. The thus formed test panel, cot~ered with the plastisol film and enamel paint topcoat, was baked at 120C for 30 minutes in a forced air oven and thereafter cooled for 30 minutes. If the enamel topcoat dried with no residual tack, the plastisol was considered to have passed the test.
All si~ compositions tabulated in Table I were found to be dry, thus, establishing that the paint had cured in each case.
~0 -18- 2~ 28 Tensile and }~,lonqation Characteristics of Plastisol Compositions The tensile and elongation characteristics of the PVC plastisol compositions of Table I were tested by initially spraying a mold release agent onto aluminum foil~
Five grams of each of the plastisol compositions of Table I, Plastisol Composition Nos. 1-6, were applied to the aluminum foil treated with the mold release agent and drawn down in accordance with the procedure set forth in Example 4. In each case, the thus formed 0.02 inch fllm of the PVC
plastisol composition was cured at a temperature of 120C for 30 minutes in a forced air oven. The film was then removed from the foil surface and its tensile strength and elongation were determined in accordance with ASTM Test Method 1412-61 T.
The results of these tests, for each of the six tested PVC plastisol compositions, appear below in Table II.
..
9~ 2~7~2~
TABLE II
PVC Plastisol Com~osition Mo. Elonqation, % Tensile Strength, k ~cm2 1 103 26.4 2 105 26.1 3 167 3~.5 4 85 20.4 19.7 6 123 22.0 ?o .
-20- 2~0~3r2~
In addition to the examples showing the utility of the invention in various plastisol compositions, ~ariations in the composition of the additive were also made to determine the scope. Plastisol adhesion promotors Nos. 2-22 were prepared as described in Example 1 with the equivalent weights of the polyamines indicated in Table III and one equivalent of dimer acid. The dimer acid Empcl 1024 (Emery Industries) was used in Examples 2-lg; Empol 101~ (Emery Industries) was used in Examples ~1 and 22.
Since adhesion promotors Nos. 12-22 gelled or became -too viscous to handle during preparation, they could not be subjected to additional testing. It is noted where the condensation product sho~s high viscosity it may be made operable by those skilled in the art by addition of an appropriate amount of an organic solvent.
Adhesion promotors Nos. 2-11 were formulated into one of the plastisol compositions Nos. 1-5 of Table I and tested for adhesion according -to Example 4 and for paintability according to Example 5, respectively. The results are reported in Table TII.
?
- 2 1 - z~ 328 U
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- I ~ ~; o lG r~ ~.
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er N ~ L ~L ~ L ~ r; ,_ ~: L^ r D- 3 r~ _ -- ~
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rv I ~;i c r-~ r; ~ r; c ~ r~ ~ r- ci _ , ~ r. N N N N N N N ~ ,,, C ~ ~ r ~ o _ r'' r~ 0 C:l O O O O 1 Q; ~J- rV G. r~
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23- 2~73~
These results indicate -that replacing a portion of the polyamines with N-aminoethylpiperaz:Lne produced an adhesion promoter with the best combination of properties in the cured plastisol. Adhesion promotors, formulated solely with N-aminoethylpiperazine, imparted poor adhesion to the plastisol compositions. Adhesion promotors formulated solely with polyalkylene polyamines either gelled during preparation due to insufficient amine content or imparted poor paintability to the plastisols due to excessive amine content. Those formulations that contained N-aminoethylpiperazine in combination with an amount of polyalkylene polyamines sufficient to impart an amine value up to about 225 provided a polyvinyl chloride plastisol composition with the desired properties of good adhesion and paintability upon low temperature curing.
- 1 o - ~ 017~8 Pre aration of Plastisol Adhesion Promoter No. 1 P _ A closed reactor was charged with 3,890 g of ~mpol 102g dimer acid (equivalent weight 292; 13.3 equivalents) having the predominent structural formula HooccH2(c32Hx)cH~cOOH
690 g N-aminoethylpiperazine (equivalent weight 64.8; 10.7 equivalen~s); and 921 g trlethylenetetraamine (equivalent ~eight 39.5; 10.7 equivalents) under a nitrogen atmosphere.
The- reactants were stirred by an agitator provided in the reactor and heated. As soon as water of condensation appeared in the reactor, the nitrogen gas supply was stopped and the temperature increased to bring the reaction mixture to reflux. The reaction was allowed to continue at a reflux temperature of between 190C and 250C at atmospheric pressure. The acid value of the reaction mixture was monitored and upon reaching an acid value of 2, the reactor was subjected to a mild vacuum. This was continued until the - reaction pressure was reduced to 5 mm Hg. The reaction was continued at these thermodynamic conditions, 190C to 250C
and 5 mm Hg, until the reaction mixture acid value dropped below 1Ø At that time the reactor was cooled to 150C, atmospheric pressure was reinstituted, by the addition of nitrogen gas, and Hisol (Ashland Oil Co., highly aromatic solvent) was added to acceptable handling viscosity. The addition of the Hisol permitted cooling of the reaction mixture to ambient temperature. The product of this reaction was a liquid weighing 9,520 g.
Ana~ysis of the product of this reaction, the PVC
plastisol adhesion promoter, provided the following characteristics: an acid value of 0.78 (determined by the method of ASTM D16639-70), a TAV of 74.0; a Gardner color of 10 and a viscosity at 25C of 8,880 centipoise.
~0~73~8 EXAMPLE_2 Preparation of PVC Plastisol Composition Incorporating Adhesion Promoter (Plastisol Composition No. l?
A PVC plastisol con-taining the adhesion promoter formed in accordance with Example 1 was prep~red by dissolving 5 g of the adhesion promoter in 30 g ~utyl cyclohexyl phthalate, 30 g dihexyl phthalater S0 g ~ilC7~
phthalate and 5 g benzyl alcohol. The thus for~ed s~lution was added to a preblended, finely divided solid mixture of~
60 g Vestolite 7090 polyvinyl chloride copoly~er (Huls AÇ~ r 40 g Bordon VC265 polyvinyl chloride copolymerr 110 g calcium carbonate, 30 g precipitated calcium carbonate and 15 g titanium dioxide. The solid and liquid components were ~ixe~
together under high shear to provide a smooth consiste~t plastisol mixture.
The formulation of the polyvinyl chloride tP~C~
plastisol composition of this example, denoted ~s Plasltisol Composition No. 1, is summarized in Table I bel~w.
3_~
-12~ 7~2~
1 EX~MpL~ 3 Preparation of PVC Plastisol Composition Nos. 2-6 ~ dditlonal PVC plastisol eompositions were prepared by dissolving 5 g of the adhesion promoter formed in Example 1 with mixtures of benzyl alcohol and various phthalate compounds. These liquid solutions were added to preblended, finely divided solid mixtures of polyvinyl chloride, caleium earbonate and, in some cases, titanium dioxide in aecordanee with the proeedure of Example 2.
The exact constituency of these compositions is provided in Table I below which summarizes Plastisol Composition Nos. 2 to 5.
?
2~
TABLE I
PVC Plastisol Composition No. Component Wt, q 1 Vestolite 7090 PVC Copolymer 60 Bordon VC265 PVC Copolymer 40 CaCO3 110 Precipitated CaCO3 30 TiO2 15 Butyl Cyclohexyl Phthalate 30 Dihexyl Phthalate 30 di(C7-C11) Phthalate So Benzyl Alcohol 5 Adhesion Promotor No. 15 Vestolite 7090 PVC Copolymer 60 Bordon VC265 PVC Copolymer 40 CaCO3 125 Precipitated CaCO3 3Q
Nuoplaz 1046, (Huls AG)35 Phthalate Isobutyrate Ester polyol from Texanol (Eastern) di(C7-C11) Phthalate 35 Butyl Benzyl Phthalate30 Benzyl Alcohol 5 Adhesion Promoter No. 15 3 Vestolite 7090 PVC Copolymer 60 Bordon VC265 PVC Copolymer 40 CaCO3 30 Precipitated CaCO3 50 Butyl Cyclohexyl Phthalate 50 di(C7-C11) Phthalate 25 Dihexyl Phthalate 25 Benzyl Alcohol 5 Adhesion Promoter No. 15 ~7~8 -14~
TABLE 1 (con-tinued) PVC Plas~isol Composition No. Component 4 Geon 130X33 60 (B.F. Goodrich) PVC copolymer Pliovic MC-85 (Goodyear) 40 Maleic Es-ter Copolymer CaCO3 110 Precipitated CaCO3 30 TiO2 15 Butyl Cyclohexyl Phthalate 30 Dihexyl Phthalate 30 di(C7-Cll) Phthalate 50 Benzyl Alcohol 5 Adhesion Promotor No. l 5 Oxy 6493 (Occidental Chemical 60 Corp.) PVC
? Homopolymer Bordon VC265 PVC Copolymer 40 CaC03 110 Precipitated CaCO3 30 TiO2 15 Butyl Cyclohexyl Phthalate 30 Dihexyl Phthalate 30 di(C7-Cll) Phthalate 50 Benzyl Alcohol 5 Adhesion Promotor No. 1 5 2~ 28 TABI,E 1 (continued) PVC Plastisol Composition No. Component Wt, 6 Oxy 6338 PVC Copolymer60 Bordon VC265 PVC copolymer 40 CaC03 110 Precipitated CaC03 30 Tio2 15 Bu-tyl Cyclohexyl Phthalate 30 Dihexyl Phthalate 30 di(C7-Cll) Phthalate - 50 Benzyl Alcohol 5 Adhesion Promoter No. 15 -16- ~ ~0~28 EX~MPI.E 4 Adhesion Characteristics of PVC Plastisol Compositions Each of the PVC plastisol compositions tabulated in Tahle I were tested to determine their adhesion. In this test 5 g of each of the plastisol compositions of Table I
were placed on a Uni-Prime coated test panel, a standard test panel supplied by PPG, and which is primed by electro-deposition. The plastisol composition was drawn across the panel with a drawdown bar such that a 0.02 inch thick film was formed over an area of i inch by 3 inches. The plastisol film, disposed on the test panel, was cured for 20 minutes at 120C in a forced air heated oven and then cooled for 30 minutes. Two parallel slits, approximately 1/2 inch apart, were cut into the cured plastisol film with a razor blade.
One end of the strip between the cuts was lifted off the test panel with a spatula and then pulled. If the fi.lm tore, adllesion was ~reater than cohesion.
Each of the plastisol compositions of Table 1, Composition Nos. 1-6, were tested in accordance with the above procedure and were each found to possess an adhesion ~reater than cohesive. That is, the cured plastisol film tore in each ~est.
3l~
-17- ~0~28 . _ Wet-on-wet Paintabili-ty of PVC Plastisol Compositions A test was made to determlne the wet-on-wet paintability of the plastisol compositions of Table I. In these tests a Uni-Prime coated test panel was again coated with each of the plastisol compositions of Table I in accordance with the procedure of E~ample 4.
A high solids enamel paint was spray applied over the unbaked PVC plastisol compositions. The thus formed test panel, cot~ered with the plastisol film and enamel paint topcoat, was baked at 120C for 30 minutes in a forced air oven and thereafter cooled for 30 minutes. If the enamel topcoat dried with no residual tack, the plastisol was considered to have passed the test.
All si~ compositions tabulated in Table I were found to be dry, thus, establishing that the paint had cured in each case.
~0 -18- 2~ 28 Tensile and }~,lonqation Characteristics of Plastisol Compositions The tensile and elongation characteristics of the PVC plastisol compositions of Table I were tested by initially spraying a mold release agent onto aluminum foil~
Five grams of each of the plastisol compositions of Table I, Plastisol Composition Nos. 1-6, were applied to the aluminum foil treated with the mold release agent and drawn down in accordance with the procedure set forth in Example 4. In each case, the thus formed 0.02 inch fllm of the PVC
plastisol composition was cured at a temperature of 120C for 30 minutes in a forced air oven. The film was then removed from the foil surface and its tensile strength and elongation were determined in accordance with ASTM Test Method 1412-61 T.
The results of these tests, for each of the six tested PVC plastisol compositions, appear below in Table II.
..
9~ 2~7~2~
TABLE II
PVC Plastisol Com~osition Mo. Elonqation, % Tensile Strength, k ~cm2 1 103 26.4 2 105 26.1 3 167 3~.5 4 85 20.4 19.7 6 123 22.0 ?o .
-20- 2~0~3r2~
In addition to the examples showing the utility of the invention in various plastisol compositions, ~ariations in the composition of the additive were also made to determine the scope. Plastisol adhesion promotors Nos. 2-22 were prepared as described in Example 1 with the equivalent weights of the polyamines indicated in Table III and one equivalent of dimer acid. The dimer acid Empcl 1024 (Emery Industries) was used in Examples 2-lg; Empol 101~ (Emery Industries) was used in Examples ~1 and 22.
Since adhesion promotors Nos. 12-22 gelled or became -too viscous to handle during preparation, they could not be subjected to additional testing. It is noted where the condensation product sho~s high viscosity it may be made operable by those skilled in the art by addition of an appropriate amount of an organic solvent.
Adhesion promotors Nos. 2-11 were formulated into one of the plastisol compositions Nos. 1-5 of Table I and tested for adhesion according -to Example 4 and for paintability according to Example 5, respectively. The results are reported in Table TII.
?
- 2 1 - z~ 328 U
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er N ~ L ~L ~ L ~ r; ,_ ~: L^ r D- 3 r~ _ -- ~
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23- 2~73~
These results indicate -that replacing a portion of the polyamines with N-aminoethylpiperaz:Lne produced an adhesion promoter with the best combination of properties in the cured plastisol. Adhesion promotors, formulated solely with N-aminoethylpiperazine, imparted poor adhesion to the plastisol compositions. Adhesion promotors formulated solely with polyalkylene polyamines either gelled during preparation due to insufficient amine content or imparted poor paintability to the plastisols due to excessive amine content. Those formulations that contained N-aminoethylpiperazine in combination with an amount of polyalkylene polyamines sufficient to impart an amine value up to about 225 provided a polyvinyl chloride plastisol composition with the desired properties of good adhesion and paintability upon low temperature curing.
Claims (31)
1. An adhesion-improved plastisol composition comprising a finely-divided vinyl chloride polymer together with a plasticizer and from about 0.5 to about 5 percent by weight of the composition of an adhesion promoter which is a non-gelled condensation product of a) polymerized fatty acid; and b) a mixture of amines being present in a concentration to produce a final amine value that ranges up to about 225 in the condensation product, said mixture being comprised of polyalkylene polyamine and an N-aminoalkylpiperazine.
2. A composition according to Claim 1 where said polymerized fatty acid is a dimer fatty acid.
3. A composition according to Claim 1 wherein the mixture of amines comprises about 20-30% by weight or the condensation product.
4. A composition according to Claim 1 wherein the polyalkylene polyamine is triethylenetetramine or tetraethylenepentamine, or mixtures thereof.
5. A composition according to Claim 1 wherein 0.5 to 1.5 equivalents of the N-aminoalkylpiperzine is present per equivalent of the polymerized fatty acid.
6. A composition according to Claim 1 wherein said N-aminoalkylpiperazine is N-aminoethylpiperazine.
7. A composition according to Claim 1 further comprising an organic solvent.
8. A composition according to Claim 1 wherein the concentration of the adhesion promoter is from about 1 to 2 percent by weight of the plastisol composition.
9. An adhesion-improved plastisol composition comprising a finely-divided vinyl chloride polymer together with a plasticizer and from about 0.5 to 5 percent by weight of the composition of an adhesion promoter which is a non-gelled condensation product of a) polymerized fatty acid; and b) h mixture of amines being present in a concentration to provide at least 1.5 equivalents thereof per equivalent of polymerized fatty acid and to produce a final amine value that ranges up to about 225 in the condensation product, said mixture being comprised of triethylenetetramine, tetraethylenepentamine or mixtures thereof, and N-aminoethylpiperazine.
10. A composition according to Claim 9 wherein the polymerized fatty acid is a dimer fatty acid.
11. A composition according to Claim 9 wherein the mixture of amines comprises about 20 to about 30 percent by weight of the condensation product.
12. A composition according to Claim 9 wherein about 0.5 to about 1.5 equivalents of N-aminoethylpiperazine is present per equivalent of the polymerized fatty acid:
13. A composition according to Claim 9 further comprising an organic solvent.
14. A composition accorcling to Claim 9 wherein the concentration of the adhesion promoter is from about 1 to about 2 percent by weight of the plastisol composition.
15. An adhesion-improved plastisol composition comprising a finely-divided vinyl chloride polymer together with a plasticizer and from about 1 to 2 percent by weight of the composition of an adhesion promoter which is 2 non-gelled condensation product of a) dimer acid; and b) a mixture of amines being present in a concentration of about 22 to about 25 precent by weight of the condensation product and producing therein a final amine value that ranges up to about 225, said mixture being comprised of triethylenetetramine, tetraethylenepentamine or mixtures thereof, and N-aminoethylpiperazine, said N-aminoethylpiperazine being present in a concentration to provide from about 0.5 to about 1.5 equivalents thereof per equivalent of dimer acid.
16. A composition according to Claim 15 further comprising an organic solvent.
17. An adhesion promoter for vinyl chloride plastisols comprising the non-gelled condensation product of a) a polymerized fatty acid, and b) a mixture of amines being present in a concentration to produce a final amine value that ranges up to about 225 in the condensation product, and said mixture being comprised of a polyalkylene polyamine and an N-aminoalkylpiperazine.
18. An adhesion promoter according to Claim 17 wherein said polymerized fatty acid is a dimer fatty acid.
19. An adhesion promoter according to Claim 17 wherein the mixture of amines comprises about 20 to about 30%
by weight of the condensation product.
by weight of the condensation product.
20. A adhesion promoter according to Claim 17 wherein the polyalkylene polyamine is triethylenetetramine or tetraethylenepentamine, or mixtures thereof.
21. A composition according to Claim 17 wherein 0.5 to 1.5 equivalent of the polymerized fatty acid.
22. An adhesion promoter according to Claim 17 wherein said N-aminoalkylpiperazine is N-aminoethyl-piperazine.
23. An adhesion promoter according to Claim 17 further comprising an organic solvent.
24. An adhesion promoter for vinyl chloride plastisols which is a non-gelled condensation product of a) polymerized fatty acid; and in a concentration to provide at least 1.5 equivalents thereof per equivalent of polymerized fatty acid and to produce a final amine value that ranges up to about 225 in the condensation product, said mixture being comprised of triethylenetetramine, tetraethylenepentamine or mixtures thereof, and N-aminoethylpiperazine.
25. A composition according to Claim 24 wherein the polymerized fatty acid is a dimer fatty acid.
26. A composition according to Claim 24 wherein the mixture of amines comprises about 20 to about 30 percent by weight of the condensation product.
27. A composition according to Claim 24 wherein about 0.5 to about 1.5 equivalents of N-aminoethylpiperazine is present per equivalent of the polymerized fatty acid.
28. A composition according to Claim 24 further comprising an organic solvent.
29. An adhesion promoter for vinyl chloride plastisols which is a non-gelled condensation product of a) dimer acid; and b) a mixture of amines being present in a concentration of about 22 to about 25 percent by weight of the condensation product and producing therein, a final amine value that ranges up to about 225, said mixture being comprised of triethylenetetramine, tetraethylenepentamine or mixtures thereof, and N-aminoethylpiperazine, said N-aminoethylpiperazine being present in a concentration to provide from about 0.5 to about 1.5 equivalents thereof per equivalent of dimer acid.
30. A composition according to Claim 29 further comprising an organic solvent.
31. A method of making a coating, an adhesive bond or a seam seal which comprises applying to a substrate surface or seam, a plastisol composition according to Claim 1, 9 or 15 and baking the plastisol composition on the substrate at a temperature of at least about 90°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US29556489A | 1989-01-10 | 1989-01-10 | |
| US295,564 | 1989-01-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2007328A1 true CA2007328A1 (en) | 1990-07-10 |
Family
ID=23138233
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002007328A Abandoned CA2007328A1 (en) | 1989-01-10 | 1990-01-08 | Adhesion and paintability improvements in pvc plastisols at low bake temperatures |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5021482A (en) |
| EP (1) | EP0378205B1 (en) |
| JP (1) | JPH02258858A (en) |
| KR (1) | KR900011824A (en) |
| AT (1) | ATE98981T1 (en) |
| AU (1) | AU628122B2 (en) |
| CA (1) | CA2007328A1 (en) |
| DE (1) | DE69005315T2 (en) |
| ES (1) | ES2047159T3 (en) |
| MX (1) | MX170657B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5475056A (en) * | 1991-04-19 | 1995-12-12 | Teroson Gmbh | Plastisols which prevent the yellowing of top coats, process for their preparation and use |
| US5741383A (en) * | 1992-08-18 | 1998-04-21 | Essex Specialty Products, Inc. | Process for bonding a vehicle window |
| DE69402959T2 (en) * | 1993-02-10 | 1997-08-14 | Air Prod & Chem | ADMINISTRATOR |
| DE4342672A1 (en) * | 1993-12-15 | 1995-06-22 | Akzo Nobel Nv | Adhesion improver |
| US5777014A (en) * | 1996-12-03 | 1998-07-07 | The C.P. Hall Company | PVC sheet material having improved water-based coating receptivity |
| WO1999024508A1 (en) * | 1997-11-07 | 1999-05-20 | Henkel Corporation | Crystallization resistant amidoamine compositions |
| US6008313A (en) * | 1997-11-19 | 1999-12-28 | Air Products And Chemicals, Inc. | Polyamide curing agents based on mixtures of polyethyleneamines and piperazine derivatives |
| US5948881A (en) * | 1997-12-04 | 1999-09-07 | Air Products And Chemicals, Inc. | Polyamide curing agents based on mixtures of polyethylene-amines, piperazines and deaminated bis-(p-aminocyclohexyl) methane |
| GB2332202A (en) * | 1997-12-09 | 1999-06-16 | Courtaulds Coatings | Curable epoxy resin compositions |
| BRPI0720528A2 (en) * | 2006-12-19 | 2014-03-25 | Basf Se | USE OF POLYCARBOXYLIC ACID ESTER ESTERS AND PRE-COATING PROCESS |
| BR112014000748B1 (en) * | 2011-07-28 | 2020-03-31 | Dow Global Technologies Llc | POLYMERIC MIXTURE FORMULATION, MULTILAYER STRUCTURE AND METHOD FOR CONFIGURING A MULTILAYER STRUCTURE |
| CN108441281A (en) * | 2018-04-26 | 2018-08-24 | 北京鑫翔源长顺润滑油有限责任公司 | A kind of dimer fatty amine acid salt is as water base flame retardant hydraulic fluid extreme-pressure anti-friction additive |
| FR3085602B1 (en) | 2018-09-07 | 2023-02-24 | Psa Automobiles Sa | METHOD FOR APPLYING A MULTI-LAYER COATING TO ONE OR MORE BODY ELEMENTS OF A MOTOR VEHICLE AND INSTALLATION FOR IMPLEMENTING SUCH A METHOD |
| CN112048206B (en) * | 2020-09-15 | 2021-11-16 | 王俊宇 | Michael addition curing coating system containing adhesion promoter |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2654871C3 (en) * | 1976-12-03 | 1984-10-04 | Schering AG, 1000 Berlin und 4709 Bergkamen | Polyvinyl chloride plastisols with improved adhesion |
| DE3201265A1 (en) * | 1982-01-16 | 1983-07-28 | Schering Ag, 1000 Berlin Und 4619 Bergkamen | METHOD FOR PRODUCING COVERS AND ADHESIVE JOINT WITH POLYVINYL CHLORIDE PLASTISOLS WITH IMPROVED ADHESION AND PLASTISOLS FOR THE METHOD |
| IT1180214B (en) * | 1984-08-02 | 1987-09-23 | Chem Plast Spa | ADHESION PROMOTERS FOR PLASTISOLS ABLE TO KEEP THE COLOR OF PLASTISOLS STABLE TO THE EFFECT OF THE THERMAL APPLICATION TREATMENT |
| US4652327A (en) * | 1985-03-22 | 1987-03-24 | Union Camp Corporation | Bonding poly(vinylidene chloride) |
-
1990
- 1990-01-08 CA CA002007328A patent/CA2007328A1/en not_active Abandoned
- 1990-01-09 AU AU47799/90A patent/AU628122B2/en not_active Ceased
- 1990-01-10 AT AT90100466T patent/ATE98981T1/en not_active IP Right Cessation
- 1990-01-10 DE DE69005315T patent/DE69005315T2/en not_active Expired - Fee Related
- 1990-01-10 MX MX019062A patent/MX170657B/en unknown
- 1990-01-10 ES ES90100466T patent/ES2047159T3/en not_active Expired - Lifetime
- 1990-01-10 KR KR1019900000215A patent/KR900011824A/en active IP Right Grant
- 1990-01-10 EP EP90100466A patent/EP0378205B1/en not_active Expired - Lifetime
- 1990-01-10 JP JP2003302A patent/JPH02258858A/en active Pending
- 1990-08-21 US US07/570,966 patent/US5021482A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| AU628122B2 (en) | 1992-09-10 |
| EP0378205B1 (en) | 1993-12-22 |
| ATE98981T1 (en) | 1994-01-15 |
| MX170657B (en) | 1993-09-03 |
| AU4779990A (en) | 1990-07-19 |
| JPH02258858A (en) | 1990-10-19 |
| KR900011824A (en) | 1990-08-02 |
| EP0378205A1 (en) | 1990-07-18 |
| ES2047159T3 (en) | 1994-02-16 |
| US5021482A (en) | 1991-06-04 |
| DE69005315D1 (en) | 1994-02-03 |
| DE69005315T2 (en) | 1994-06-23 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued | ||
| FZDE | Discontinued |
Effective date: 19960708 |