CA2176556A1 - High solids coating composition - Google Patents
High solids coating compositionInfo
- Publication number
- CA2176556A1 CA2176556A1 CA002176556A CA2176556A CA2176556A1 CA 2176556 A1 CA2176556 A1 CA 2176556A1 CA 002176556 A CA002176556 A CA 002176556A CA 2176556 A CA2176556 A CA 2176556A CA 2176556 A1 CA2176556 A1 CA 2176556A1
- Authority
- CA
- Canada
- Prior art keywords
- anhydride
- composition
- coating composition
- moiety
- pendant
- 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
- C08L73/00—Compositions of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08L59/00 - C08L71/00; Compositions of derivatives of such polymers
- C08L73/02—Polyanhydrides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
- C08G67/04—Polyanhydrides
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Abstract
A coating composition based on low molecular weight anhydride resin having pendant non-cyclic anhydride moieties, epoxy resin, active catalyst and surface tension reducing agent exhibits sprayability at low VOC and excellent performance characteristics as a coating.
Description
~6~5~
~0 95/18173 ~ PCT/US94/14166 TITLE
HIGH SOLIDS COATING COMPOSITION
S BACKGROUND OF THE INVENTION
The present invention relates to a curable coating composition particularly useful as a top coat in multi-layered coating systems.
Base coat-clear coat systems have found wide acceptance in the past decade as automotive fini~hes Continlling effort has been directed 10 to such coating systems to improve the overall appearance, the clarity of the top coat, and the resi~t~nce to deterioration. Further effort has been directed to the development of coating compositions having low volatile organic content (VOC).
Previous efforts at h~ r~vil~g the etch resistance and durability 15 of coatings had suggested the use of anhydride resins having pendant non-cyclic anhydride moieties in combination with resins that react with the polyanhydride resins to cure under curing con~litions. However, a contin~ling need exists for coating formulations which can be sprayed at exceptionally low VOC and which exhibit ont~t~n~ling performance characteristics after 20 application, and particularly resi~t~nce to ellvi~olllental etching.
SUMMARY OF THE INVENTION
The present invention provides a sprayable coating composition which can be easily applied at high solids and exhibits outst~ntling appearance and durability after application and ease of maintenance.
Specifically, the instant invention provides a curable coating composition comprising organic solvent and binder comprising (a) an anhydride resin having a molecular weight of less than about 2000 that contains (1) a central moiety, and (2) on average, more than one pen~l~nt, non-cyclic anhydride moiety bonded to each central moiety;
(b) an oligomer having epoxy functionality of at least 2 and having a molecular weight of less than about 1500;
(c) a functional amount of at least one active catalyst, and WO 95/18173 PCTltJS94/14166 ~7~56 (d) about from 0.01 to 5 Yo, by weight of the binder component (a) and (b), of at least one surface tension reducing agent in an amount sufficient to wet the surface onto which it is applied, the composition having a volatile organic contact of less than about 3.0 5 pounds per gallon, and wherein the ratio of equivalents of epoxy to anhydride is about from 0.7 to 1.4.
DET~TT .F.D DESCRIP IlON OF THE INVENTION
Anhydride resins which can be used in the present invention 10 include those having a molecular weight of less than about 2000 having a central moiety and more than one pendant, non-cyclic anhydride moiety bonded to each central moiety. The anhydride is asymmetrical, and preferably contains a moiety represented by the following formula:
O O
CM~C--O--C--R1)n wherein (CM) is a central moiety, (R1) is an organic moiety, and n is a number of pendant anhydride groups that averages greater than one.
The central moiety can be a simple organic moiety, such as an 20 aliphatic, cycloaliphatic or aromatic moiety, with a plurality of anhydride groups bonded to it. Alternalively, it can contain a plurality of repeating units which are bonded to one or more pendant arlhydride groups.
Examples of suitable non-polymeric central moieties are those derived from multifilnction~l alcohols such as pentaerythritol, trimethylolplopalle and 25 neopentyl glycol. The multifunctional alcohols are reacted with cyclic, monomeric anhydride such as methyl hexahydrophthalic anhydride to give a mllltifimctional acid cont~ining moiety. The resulting product is then reacted with ketene to form the linear pendant anhydride.
The central moiety is linked to more than one non-cyclic 30 anhydride moiety, on average. It is preferably linked to at least about 2 non-cyclic anhydride groups on average and more preferably to at least about 3 non-cyclic anhydride groups on average. The anhydride equivalent weight (formula weight per anhydride group) is preferably at least about 200 and preferably no more than about 1000.
~,~7g~6 Each anhydride moiety is typically terminated by an organic group (R1). This group is preferably aliphatic and more preferably alkyl. It preferably contains no more than about 6 carbon atoms, more preferably no more than about 4 carbon atoms, and most preferably methyl.
The oligomeric anhydride can optionally cont~in a polyvalent organic moiety (A) that is linked to a plurality of anhydride groups by a plurality of pendant linking groups (LG), as illustrated in the following formula:
O O
A~LG--C--O--~--R1) n The linking group (LG) can contain, for example, ester linkages, alkylene groups, ether linkages, urethane linkages and combinations of those. The polyvalent organic group can cont~in, for example, a polyvalent alkyl or 15 aromatic group. The combination of the polyvalent organic moiety (A) and the linking groups (LG) forms the central moiety (CM) as previously described.
The central moiety can optionally contain other functional groups in addition to the pendant non-cyclic anhydride groups. For example, 20 the central moiety may cont~in pendant acid groups, so that the anhydride is represented by the formula:
O O
CM~--O--C--R1) n (CO2H)m 25 wherein m is the number of pendant acid groups and all other characters have the m-~ning previously given. The molar ratio of pendant non-cyclic anhydride groups to pendant acid groups in the oligomeric anhydride is preferably at least about 25:75, more preferably at least about 50:50, and more highly preferably at least about 75:25. Most preferably, the anhydride 30 contains subst~nti~lly no pendant acid groups. The central moiety can also contain minor quantities of cyclic anhydride moieties.
wosstlsl73 2 17 ~ ~ ~ 6 PCT/US94/14166 The molecular weight of the anhydride resin is an important feature of the present invention, and should be less than about 2000. At molecular weights of the oligomeric anhydride greater than 2000, it is difficult to attain a sprayable composition with a volatile organic content of less than about 3.0 pounds of organic solvent per gallon of curable compositions. The molecular weight of the anhydride resin is preferably about from 400 to 1,000, and the anhydride resin preferably has 3 to 4 pendant, non-cyclic anhydride moieties bonded to each central moiety.
The oligomer component cont~in~ at least two epoxy groups and should have a molecular weight of less than about 1500. Typical epoxy components are as follows: sorbitol polyglycidyl ether, m~nnitol polyglycidyl ether, pentaelylhliLol polyglycidyl ether, glycerol polyglycidyl ether, low molecular weight epoxy resins such as epoxy resins of epichlorohydrin and bisphenol-A., di- and polyglycidyl esters of polycarboxylic acids, polyglycidyl ethers of isocyanurates, such as "Denecol" EX301 from Nagase. Sorbitol polyglycidyl ether, such as DCE-35~ from Dixie Chemical, and di- and polyglycidyl esters of acids, such as Araldite CY-184~ from Ciba-Geigy, or XU-71950 from Dow Chemical are prefe,led since they form high quality fini.ches. Cycloaliphatic epoxies can also be used, such as ERL,4221 from Union Carbide.
The present compositions contain a functional amount of at least one active catalyst. By functional amount is meant a quantity which will permit a VOC of less than about 3.0 and which " ~ es cure volatiles, eg., acetic acid. While a blend of two or more catalysts can be used in the present compo~ition~ at least one catalyst in the blend should be active below the cure temperature, that is, at least about 1S~ C below the normal curing temperature. Particularly benefici~l in the present invention are tertiary amine catalysts such as triethylene (li~mine, Bis(2-dimethyl aminoethyl)ether and N,N,N1, N1-tetramethylethylenediamine.
The active catalysts can be used alone or in combination with one or more additional catalysts, such as onium compounds including quaternary phosphonium and quaternary ~mmonillm Examples of phosphonillm catalysts which can be used in catalysts blends in accordance with the present invention are benzyl tAphenyl phosphoninm chloride; ethyl triphenyl phosphonillm bromide; tetra butyl phosphonium chloride; tetra butyl phosphonium bromide; benzyl triphenyl phosphonium iodide; benzyl 21 ~6~6 triphenyl phosphonium bromide; ethyl triphenyl phosphonium iodide and the like.
The compositions of the present invention further comprise about from 0.01 to 5 wt %, by weight of the binder components (a) and (b), S of at least one surface tension redllcing agent in an amount sufficient to wetthe surface onto which it is applied. A wide variety of surf~ct~nt~ can be used, depending on the particular coating forTmll~tion and the surface onto which it is applied. However, collvenLional silicone and fluorocarbon surf~ct~nt~ have been found to be particularly s~ticf~ctory.
The coating compositions of the present invention are formulated into high solids co~ting systems dissolved in at least one solvent.
The solvent is usually organic. Preferred solvents inrl~lde aromatic hydrocarbons such as petroleum naphtha or xylenes; ketones such as methyl amyl ketone, methyl isobutyl ketone, methyl ethyl ketone or acetone; esters 15 such as butyl acetate or hexyl acetate; and glycol ether esters such as propylene glycol monomethyl ether acetate.
The coating composition~ of the present invention can also contain collvenLional additives such as pigments, stabilizers, rheology control agents, flow agents, to lghening agents and fillers. Such ~ lition~l additives 20 will, of course, depend on the intenrle~l use of the co~ting composition.
Fillers, pigments, and other additives that would adversely effect the clarity of the cured co~ting will not be in~hlded if the colll~osiLion is inten~ed as a clear coating.
The compo~ition~ of the present invention have a volatile 25 organic content of less than about 3.0 pounds of organic solvent per gallon of curable composition, that is, at least about 65 wt % solids. The coating composition~ are typically applied to a substrate by collvenLional techniques such as spraying, electrostatic spraying, roller co~ting~ dipping or brushing.
The present forrnulations are particularly useful as a clear coating for 30 outdoor articles, such as ~utomobile and other vehicle body parts. The substrate is generally ~lepared with a primer and or a color coat or other surface ~lel,alation prior to coating with the present compositions. The present co~ting compositions can be applied using collvenLional techniques such as wet-on-wet applications over solvent borne basecoats, or over dried 35 water borne basecoats. The ability to apply the present composition~ by spraying techniques with the llml~ lly low VOC content is surprising.
æ~7~5~
After application to a substrate, the present compositions are cured by he~tin~ to a temperature of about from 125 to 140~C for a period of about from 15 to 90 mimltes.
The performance characteristics of the final cured coating 5 composition are excellent, providing a combination of excellent gloss and durability to abrasion, slmlight and acidic rain. At the same time, the compositions provide ease of h~n~lling, resnlting from all the components being present in a single formlll~tion, good shelf life and low volatile organiccontent.
The present invention is further illustrated by the following specific examples, in which parts and percentages are by weight unless otherwise in~lic~te~
F,xAMPLE 1 A curable coating composition was prepared from an anhydride resin, co-reactant oligomeric epoxy resin, active catalyst and surface tension reducing agent.
(a) Anhydride Resin The anhydride resin was prepared from a tetra-functional half-20 acid ester. The following co,.~ ents were charged to a re~ction vessel equipped with a he~ting m~ntle, reflux condenser, thermometer, nitrogen inlet, and stirrer:
Portion 1 Parts by Weight Pentaerythritol 478.0 Methyl hexahydrophth~lic anhydride 2250.0 Triethylamine 0.5 Portion 2 Parts by Wei~ht Xylol (135-145C) 2250.0 Total 4978.5 Portion 1 was charged into the reaction vessel, heated to o ~17~5~
under a nitrogen blanket and held for 30 minutes. After the hold period, the reaction J~ lule was cooled and Portion 2 added.
The solution ~r~ared above was used to make a linear pendant anhydride. The solution was charged into a 5L flask equipped with S a stirrer and a gas inlet tube. the gas inlet tube was attached to a ketene generator similar to the one described by Williams et al. in the Journal of Organic Chemictry 5,122, 1940. Ketene is bubbled through the solution until all of the acid groups have been co~,ve~ led to anhydride groups. Reaction progress was monitored via ~ l lR. Solvent was then removed under vacuum to give a linear pendant anhydride with the following characteristics:
% weight solids: 78.0 Anhydride eq. wt: 329 + /-4 (on solution basis) Acid eq. wt: 6176 +/- 1323 (on solution basis) The resulting linear pendant anhydride was combined with active catalysts and surface tension re~ln~ing agent.
Based on 100 parts by weight of the final coating formnl~tion, 55.85 parts of the anhydride resin was first combined with active catalysts and surface tension reducing agent, along with hindered amine light stabilizer and W screener.
A blend of two catalysts was used, in~ ling a tertiary amine catalyst available from Union Carbide as NIAX A99 (1.00 parts) and 1.44 parts of a 25~o solution of tetrabutyl phosponium chloride in propylene glycol morlomethylether acetate (PM acetate).
The sllrf~ct~nt added to this formlll~tion was 6.00 parts of a 5% solution in PM acetate of a polyciloY~ne copolymer commercially available as BYK-301. Also added to this linear pendant anhydride formulation were 1.00 parts of the hindered amine light stabilizer commercially available from Ciba Giegy as Tinuvin 292 and 1.40 parts of W screener commercially available from Ciba Giegy as Tinuvin 384.
A second formulation cont~in~l the oligomer having epoxy functionality. The material used as 24.05 parts of a diglycidyl ester commercially available from DOW as XU-71950. This was combined with 3.53 parts of butyl acetate solvent and 5.73 parts of a rheology control agent.
The rheology control agent was silica dispersed in epoxy. The silica ~ 76a56 dispersion consisted of 38.5 parts of the same diglycidyl ester and 51.5 parts of PM acetate, to which was added 10 parts of a hydrophobic silica commercially available from Degussa as Aerosil R-972~. The silica dispersion was well mixed and subjected to 5 grin~ing in a sand mill.
The two form~ tions~ respectively cont~ining the linear pendant anhydride and oli~omer having epoxy function~lity were combined in the ratios shown and sprayed onto primed metal panels coated with a basecoat and cured at 285~.
The cured coating exhibited outst~n~ing appearance and durability.
~0 95/18173 ~ PCT/US94/14166 TITLE
HIGH SOLIDS COATING COMPOSITION
S BACKGROUND OF THE INVENTION
The present invention relates to a curable coating composition particularly useful as a top coat in multi-layered coating systems.
Base coat-clear coat systems have found wide acceptance in the past decade as automotive fini~hes Continlling effort has been directed 10 to such coating systems to improve the overall appearance, the clarity of the top coat, and the resi~t~nce to deterioration. Further effort has been directed to the development of coating compositions having low volatile organic content (VOC).
Previous efforts at h~ r~vil~g the etch resistance and durability 15 of coatings had suggested the use of anhydride resins having pendant non-cyclic anhydride moieties in combination with resins that react with the polyanhydride resins to cure under curing con~litions. However, a contin~ling need exists for coating formulations which can be sprayed at exceptionally low VOC and which exhibit ont~t~n~ling performance characteristics after 20 application, and particularly resi~t~nce to ellvi~olllental etching.
SUMMARY OF THE INVENTION
The present invention provides a sprayable coating composition which can be easily applied at high solids and exhibits outst~ntling appearance and durability after application and ease of maintenance.
Specifically, the instant invention provides a curable coating composition comprising organic solvent and binder comprising (a) an anhydride resin having a molecular weight of less than about 2000 that contains (1) a central moiety, and (2) on average, more than one pen~l~nt, non-cyclic anhydride moiety bonded to each central moiety;
(b) an oligomer having epoxy functionality of at least 2 and having a molecular weight of less than about 1500;
(c) a functional amount of at least one active catalyst, and WO 95/18173 PCTltJS94/14166 ~7~56 (d) about from 0.01 to 5 Yo, by weight of the binder component (a) and (b), of at least one surface tension reducing agent in an amount sufficient to wet the surface onto which it is applied, the composition having a volatile organic contact of less than about 3.0 5 pounds per gallon, and wherein the ratio of equivalents of epoxy to anhydride is about from 0.7 to 1.4.
DET~TT .F.D DESCRIP IlON OF THE INVENTION
Anhydride resins which can be used in the present invention 10 include those having a molecular weight of less than about 2000 having a central moiety and more than one pendant, non-cyclic anhydride moiety bonded to each central moiety. The anhydride is asymmetrical, and preferably contains a moiety represented by the following formula:
O O
CM~C--O--C--R1)n wherein (CM) is a central moiety, (R1) is an organic moiety, and n is a number of pendant anhydride groups that averages greater than one.
The central moiety can be a simple organic moiety, such as an 20 aliphatic, cycloaliphatic or aromatic moiety, with a plurality of anhydride groups bonded to it. Alternalively, it can contain a plurality of repeating units which are bonded to one or more pendant arlhydride groups.
Examples of suitable non-polymeric central moieties are those derived from multifilnction~l alcohols such as pentaerythritol, trimethylolplopalle and 25 neopentyl glycol. The multifunctional alcohols are reacted with cyclic, monomeric anhydride such as methyl hexahydrophthalic anhydride to give a mllltifimctional acid cont~ining moiety. The resulting product is then reacted with ketene to form the linear pendant anhydride.
The central moiety is linked to more than one non-cyclic 30 anhydride moiety, on average. It is preferably linked to at least about 2 non-cyclic anhydride groups on average and more preferably to at least about 3 non-cyclic anhydride groups on average. The anhydride equivalent weight (formula weight per anhydride group) is preferably at least about 200 and preferably no more than about 1000.
~,~7g~6 Each anhydride moiety is typically terminated by an organic group (R1). This group is preferably aliphatic and more preferably alkyl. It preferably contains no more than about 6 carbon atoms, more preferably no more than about 4 carbon atoms, and most preferably methyl.
The oligomeric anhydride can optionally cont~in a polyvalent organic moiety (A) that is linked to a plurality of anhydride groups by a plurality of pendant linking groups (LG), as illustrated in the following formula:
O O
A~LG--C--O--~--R1) n The linking group (LG) can contain, for example, ester linkages, alkylene groups, ether linkages, urethane linkages and combinations of those. The polyvalent organic group can cont~in, for example, a polyvalent alkyl or 15 aromatic group. The combination of the polyvalent organic moiety (A) and the linking groups (LG) forms the central moiety (CM) as previously described.
The central moiety can optionally contain other functional groups in addition to the pendant non-cyclic anhydride groups. For example, 20 the central moiety may cont~in pendant acid groups, so that the anhydride is represented by the formula:
O O
CM~--O--C--R1) n (CO2H)m 25 wherein m is the number of pendant acid groups and all other characters have the m-~ning previously given. The molar ratio of pendant non-cyclic anhydride groups to pendant acid groups in the oligomeric anhydride is preferably at least about 25:75, more preferably at least about 50:50, and more highly preferably at least about 75:25. Most preferably, the anhydride 30 contains subst~nti~lly no pendant acid groups. The central moiety can also contain minor quantities of cyclic anhydride moieties.
wosstlsl73 2 17 ~ ~ ~ 6 PCT/US94/14166 The molecular weight of the anhydride resin is an important feature of the present invention, and should be less than about 2000. At molecular weights of the oligomeric anhydride greater than 2000, it is difficult to attain a sprayable composition with a volatile organic content of less than about 3.0 pounds of organic solvent per gallon of curable compositions. The molecular weight of the anhydride resin is preferably about from 400 to 1,000, and the anhydride resin preferably has 3 to 4 pendant, non-cyclic anhydride moieties bonded to each central moiety.
The oligomer component cont~in~ at least two epoxy groups and should have a molecular weight of less than about 1500. Typical epoxy components are as follows: sorbitol polyglycidyl ether, m~nnitol polyglycidyl ether, pentaelylhliLol polyglycidyl ether, glycerol polyglycidyl ether, low molecular weight epoxy resins such as epoxy resins of epichlorohydrin and bisphenol-A., di- and polyglycidyl esters of polycarboxylic acids, polyglycidyl ethers of isocyanurates, such as "Denecol" EX301 from Nagase. Sorbitol polyglycidyl ether, such as DCE-35~ from Dixie Chemical, and di- and polyglycidyl esters of acids, such as Araldite CY-184~ from Ciba-Geigy, or XU-71950 from Dow Chemical are prefe,led since they form high quality fini.ches. Cycloaliphatic epoxies can also be used, such as ERL,4221 from Union Carbide.
The present compositions contain a functional amount of at least one active catalyst. By functional amount is meant a quantity which will permit a VOC of less than about 3.0 and which " ~ es cure volatiles, eg., acetic acid. While a blend of two or more catalysts can be used in the present compo~ition~ at least one catalyst in the blend should be active below the cure temperature, that is, at least about 1S~ C below the normal curing temperature. Particularly benefici~l in the present invention are tertiary amine catalysts such as triethylene (li~mine, Bis(2-dimethyl aminoethyl)ether and N,N,N1, N1-tetramethylethylenediamine.
The active catalysts can be used alone or in combination with one or more additional catalysts, such as onium compounds including quaternary phosphonium and quaternary ~mmonillm Examples of phosphonillm catalysts which can be used in catalysts blends in accordance with the present invention are benzyl tAphenyl phosphoninm chloride; ethyl triphenyl phosphonillm bromide; tetra butyl phosphonium chloride; tetra butyl phosphonium bromide; benzyl triphenyl phosphonium iodide; benzyl 21 ~6~6 triphenyl phosphonium bromide; ethyl triphenyl phosphonium iodide and the like.
The compositions of the present invention further comprise about from 0.01 to 5 wt %, by weight of the binder components (a) and (b), S of at least one surface tension redllcing agent in an amount sufficient to wetthe surface onto which it is applied. A wide variety of surf~ct~nt~ can be used, depending on the particular coating forTmll~tion and the surface onto which it is applied. However, collvenLional silicone and fluorocarbon surf~ct~nt~ have been found to be particularly s~ticf~ctory.
The coating compositions of the present invention are formulated into high solids co~ting systems dissolved in at least one solvent.
The solvent is usually organic. Preferred solvents inrl~lde aromatic hydrocarbons such as petroleum naphtha or xylenes; ketones such as methyl amyl ketone, methyl isobutyl ketone, methyl ethyl ketone or acetone; esters 15 such as butyl acetate or hexyl acetate; and glycol ether esters such as propylene glycol monomethyl ether acetate.
The coating composition~ of the present invention can also contain collvenLional additives such as pigments, stabilizers, rheology control agents, flow agents, to lghening agents and fillers. Such ~ lition~l additives 20 will, of course, depend on the intenrle~l use of the co~ting composition.
Fillers, pigments, and other additives that would adversely effect the clarity of the cured co~ting will not be in~hlded if the colll~osiLion is inten~ed as a clear coating.
The compo~ition~ of the present invention have a volatile 25 organic content of less than about 3.0 pounds of organic solvent per gallon of curable composition, that is, at least about 65 wt % solids. The coating composition~ are typically applied to a substrate by collvenLional techniques such as spraying, electrostatic spraying, roller co~ting~ dipping or brushing.
The present forrnulations are particularly useful as a clear coating for 30 outdoor articles, such as ~utomobile and other vehicle body parts. The substrate is generally ~lepared with a primer and or a color coat or other surface ~lel,alation prior to coating with the present compositions. The present co~ting compositions can be applied using collvenLional techniques such as wet-on-wet applications over solvent borne basecoats, or over dried 35 water borne basecoats. The ability to apply the present composition~ by spraying techniques with the llml~ lly low VOC content is surprising.
æ~7~5~
After application to a substrate, the present compositions are cured by he~tin~ to a temperature of about from 125 to 140~C for a period of about from 15 to 90 mimltes.
The performance characteristics of the final cured coating 5 composition are excellent, providing a combination of excellent gloss and durability to abrasion, slmlight and acidic rain. At the same time, the compositions provide ease of h~n~lling, resnlting from all the components being present in a single formlll~tion, good shelf life and low volatile organiccontent.
The present invention is further illustrated by the following specific examples, in which parts and percentages are by weight unless otherwise in~lic~te~
F,xAMPLE 1 A curable coating composition was prepared from an anhydride resin, co-reactant oligomeric epoxy resin, active catalyst and surface tension reducing agent.
(a) Anhydride Resin The anhydride resin was prepared from a tetra-functional half-20 acid ester. The following co,.~ ents were charged to a re~ction vessel equipped with a he~ting m~ntle, reflux condenser, thermometer, nitrogen inlet, and stirrer:
Portion 1 Parts by Weight Pentaerythritol 478.0 Methyl hexahydrophth~lic anhydride 2250.0 Triethylamine 0.5 Portion 2 Parts by Wei~ht Xylol (135-145C) 2250.0 Total 4978.5 Portion 1 was charged into the reaction vessel, heated to o ~17~5~
under a nitrogen blanket and held for 30 minutes. After the hold period, the reaction J~ lule was cooled and Portion 2 added.
The solution ~r~ared above was used to make a linear pendant anhydride. The solution was charged into a 5L flask equipped with S a stirrer and a gas inlet tube. the gas inlet tube was attached to a ketene generator similar to the one described by Williams et al. in the Journal of Organic Chemictry 5,122, 1940. Ketene is bubbled through the solution until all of the acid groups have been co~,ve~ led to anhydride groups. Reaction progress was monitored via ~ l lR. Solvent was then removed under vacuum to give a linear pendant anhydride with the following characteristics:
% weight solids: 78.0 Anhydride eq. wt: 329 + /-4 (on solution basis) Acid eq. wt: 6176 +/- 1323 (on solution basis) The resulting linear pendant anhydride was combined with active catalysts and surface tension re~ln~ing agent.
Based on 100 parts by weight of the final coating formnl~tion, 55.85 parts of the anhydride resin was first combined with active catalysts and surface tension reducing agent, along with hindered amine light stabilizer and W screener.
A blend of two catalysts was used, in~ ling a tertiary amine catalyst available from Union Carbide as NIAX A99 (1.00 parts) and 1.44 parts of a 25~o solution of tetrabutyl phosponium chloride in propylene glycol morlomethylether acetate (PM acetate).
The sllrf~ct~nt added to this formlll~tion was 6.00 parts of a 5% solution in PM acetate of a polyciloY~ne copolymer commercially available as BYK-301. Also added to this linear pendant anhydride formulation were 1.00 parts of the hindered amine light stabilizer commercially available from Ciba Giegy as Tinuvin 292 and 1.40 parts of W screener commercially available from Ciba Giegy as Tinuvin 384.
A second formulation cont~in~l the oligomer having epoxy functionality. The material used as 24.05 parts of a diglycidyl ester commercially available from DOW as XU-71950. This was combined with 3.53 parts of butyl acetate solvent and 5.73 parts of a rheology control agent.
The rheology control agent was silica dispersed in epoxy. The silica ~ 76a56 dispersion consisted of 38.5 parts of the same diglycidyl ester and 51.5 parts of PM acetate, to which was added 10 parts of a hydrophobic silica commercially available from Degussa as Aerosil R-972~. The silica dispersion was well mixed and subjected to 5 grin~ing in a sand mill.
The two form~ tions~ respectively cont~ining the linear pendant anhydride and oli~omer having epoxy function~lity were combined in the ratios shown and sprayed onto primed metal panels coated with a basecoat and cured at 285~.
The cured coating exhibited outst~n~ing appearance and durability.
Claims (9)
1. A curable coating composition comprising organic solvent and binder comprising (a) an anhydride resin having a weight average molecular weight of less than about 2000 that contains (1) a central moiety, and (2) on average, more than one pendant, non-cyclic anhydride moiety bonded to each central moiety;
(b) an oligomer having epoxy functionality of at least 2 and having a weight average molecular weight of less than about 1500;
(c) a functional amount of at least one active catalyst, and (d) 0.01 to 5%, by weight of the binder components (a) and (b), of at least one surface tension reducing agent in an amount sufficient to allow the coating composition to wet the surface onto which it is applied, the composition having a volatile organic content of less than about 3.0 pounds per gallon, and wherein the ratio of equivalents of epoxy to anhydride is about from 0.7 to 1.4.
(b) an oligomer having epoxy functionality of at least 2 and having a weight average molecular weight of less than about 1500;
(c) a functional amount of at least one active catalyst, and (d) 0.01 to 5%, by weight of the binder components (a) and (b), of at least one surface tension reducing agent in an amount sufficient to allow the coating composition to wet the surface onto which it is applied, the composition having a volatile organic content of less than about 3.0 pounds per gallon, and wherein the ratio of equivalents of epoxy to anhydride is about from 0.7 to 1.4.
2. A composition of Claim 1 wherein the active catalyst is selected from at least one compound selected from the group consisting of onium compounds and tertiary amines.
3. A composition of Claim 2 wherein the onium compound consists essentially of at least one phosphoninm compound.
4. A composition of Claim 2 wherein the onium compound comprises tetrabutylphosphonium halide.
5. A composition of Claim 1 wherein the anhydride resin comprises essentially of the reaction product of pentaerythritol, a methyl hexahydrophthalic anhydride and ketene.
6. A composition of Claim 1 herein the anhydride resin has from 3 to 4 pendant, non-cyclic anhydride moieties bonded to each central moiety.
7. A curable coating composition of Claim 1 wherein the oligomer is selected from glycidyl ethers of low molecular weight polyols, polyglycidyl esters of polyacids, glycidyl methacrylate or glycidyl acrylate containing acrylic polymers or a compatible mixture of any of the above.
8. A composition of Claim 10 wherein the oligomer consists essentially diglycidyl ester of 1, 2-cyclohexane dicarboxylic acid.
9. A curable coating composition of Claim 1 applied to a substrate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US17581993A | 1993-12-29 | 1993-12-29 | |
| US08/175,819 | 1993-12-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2176556A1 true CA2176556A1 (en) | 1995-07-06 |
Family
ID=22641768
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002176556A Abandoned CA2176556A1 (en) | 1993-12-29 | 1994-12-21 | High solids coating composition |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US6146703A (en) |
| EP (1) | EP0737222B1 (en) |
| JP (1) | JP2746481B2 (en) |
| BR (1) | BR9408497A (en) |
| CA (1) | CA2176556A1 (en) |
| DE (1) | DE69413713T2 (en) |
| DK (1) | DK0737222T3 (en) |
| ES (1) | ES2123950T3 (en) |
| WO (1) | WO1995018173A1 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR950704396A (en) * | 1992-11-12 | 1995-11-20 | 스티븐 에스. 그레이스 | Curable composition containing anhydride resins |
| WO1996001864A1 (en) * | 1994-07-08 | 1996-01-25 | E.I. Du Pont De Nemours And Company | Low voc refinish coating composition |
| AU1383699A (en) | 1997-11-06 | 1999-05-31 | Edgington Company, The | Coating composition |
| WO2002068551A2 (en) | 2001-02-27 | 2002-09-06 | Akzo Nobel N.V. | Reactive non-isocyanate coating compositions |
| US20040048531A1 (en) * | 2002-09-09 | 2004-03-11 | Hector Belmares | Low formaldehyde emission panel |
| US20080021147A1 (en) * | 2006-06-14 | 2008-01-24 | Jun Lin | Process for forming a dispersion of silica nano-particles |
| JP2009539603A (en) * | 2006-06-14 | 2009-11-19 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Painted substrate with improved scratch and abrasion resistance |
| US9051473B2 (en) * | 2006-06-14 | 2015-06-09 | Axalta Coating Systems Ip Co., Llc | Clear coating compositions comprising dispersed silica nono-particles and processes for using |
| TWI506085B (en) | 2014-12-31 | 2015-11-01 | Ind Tech Res Inst | Resin composition and coating material using the same |
Family Cites Families (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1993828A (en) * | 1932-05-16 | 1935-03-12 | Du Pont | Synthetic resin |
| CH482819A (en) * | 1968-03-12 | 1969-12-15 | Henkel & Cie Gmbh | Thermosetting adhesives |
| US3631157A (en) * | 1970-02-09 | 1971-12-28 | Dow Chemical Co | Reactive mixed anhydride-containing polymers and a method for their preparation |
| US3852236A (en) * | 1970-12-21 | 1974-12-03 | Gulf Research Development Co | Homogeneous thermosettable composition of a polyanhydride and a polyepoxide |
| US3781379A (en) * | 1971-08-16 | 1973-12-25 | Ford Motor Co | Powdered coating compositions containing glycidyl methacrylate copolymers with anhydride crosslinking agents and flow control agent |
| US4374954A (en) | 1973-09-06 | 1983-02-22 | Ford Motor Company | Powder paint with epoxy and hydroxy copolymer and anhydride |
| US3888943A (en) * | 1973-12-19 | 1975-06-10 | Ford Motor Co | Powder coating compositions comprising a blend of coreactive polymers - i |
| US3919345A (en) * | 1974-03-04 | 1975-11-11 | Ford Motor Co | Powdered coating composition containing polyanhydride, epoxy and anhydride functional copolymer and flow control agent |
| US4308363A (en) * | 1980-04-03 | 1981-12-29 | The Dow Chemical Company | Halogenation of organic polymers having anhydride groups |
| DE3173824D1 (en) * | 1980-10-27 | 1986-03-27 | Ici Plc | Process of coating using mixed solutions of an epoxy resin and of acid anhydride curing agents |
| DE3147458A1 (en) * | 1981-12-01 | 1983-07-14 | Hoechst Ag, 6230 Frankfurt | STABLE AQUEOUS EPOXY RESIN DISPERSION, METHOD FOR THE PRODUCTION AND USE THEREOF |
| JPS61233011A (en) * | 1985-04-10 | 1986-10-17 | Mitsubishi Electric Corp | Epoxy resin composition |
| US4681811A (en) * | 1985-08-19 | 1987-07-21 | Ppg Industries, Inc. | Color plus clear coatings employing polyepoxides and polyacid curing agents in the clear coat |
| US5227243A (en) * | 1986-03-14 | 1993-07-13 | The Sherwin-Williams Company | Hydroxy addition polymer, anhydride addition polymer and cycloaliphatic polyepoxide |
| JPH0623238B2 (en) * | 1986-04-08 | 1994-03-30 | 日本ゼオン株式会社 | Acrylate elastomer-vulcanizable composition |
| US4732790A (en) * | 1986-08-21 | 1988-03-22 | Ppg Industries, Inc. | Color plus clear application of thermosetting high solids coating composition of hydroxy-functional epoxies and anhydrides |
| US5043220A (en) * | 1987-11-16 | 1991-08-27 | The Sherwin-Williams Company | Substrate coated with a basecoat and/or a clearcoat of an acid-functional compound, an anhydride-functional compound, an epoxy-functional compound and a hydroxy-functional compound |
| US5411809A (en) * | 1987-11-16 | 1995-05-02 | The Sherwin-Williams Company | Reactive coatings comprising an acid-functional compound, an anhydride-functional compound and an epoxy-functional compound |
| US4906677A (en) * | 1988-06-27 | 1990-03-06 | E. I. Du Pont De Nemours & Company | Multi-component coating composition comprising an anhydride containing polymer, a glycidyl component and a phosphonium catalyst |
| JP3208448B2 (en) * | 1990-04-30 | 2001-09-10 | 冨士薬品工業株式会社 | Protective film composition for color filter formation |
| US5206295A (en) * | 1991-02-25 | 1993-04-27 | E. I. Du Pont De Nemours And Company | Coating composition comprising an anhydride-containing polymer and a structured epoxy-containing polymer |
| DE69230795T2 (en) * | 1991-11-26 | 2000-08-03 | Kansai Paint Co Ltd | CROSSLINKING AGENTS AND CROSSLINKABLE COMPOSITION |
| KR950704396A (en) * | 1992-11-12 | 1995-11-20 | 스티븐 에스. 그레이스 | Curable composition containing anhydride resins |
-
1994
- 1994-12-21 DK DK95905881T patent/DK0737222T3/en active
- 1994-12-21 DE DE69413713T patent/DE69413713T2/en not_active Expired - Fee Related
- 1994-12-21 ES ES95905881T patent/ES2123950T3/en not_active Expired - Lifetime
- 1994-12-21 CA CA002176556A patent/CA2176556A1/en not_active Abandoned
- 1994-12-21 EP EP95905881A patent/EP0737222B1/en not_active Expired - Lifetime
- 1994-12-21 WO PCT/US1994/014166 patent/WO1995018173A1/en active IP Right Grant
- 1994-12-21 JP JP7518048A patent/JP2746481B2/en not_active Expired - Lifetime
- 1994-12-21 BR BR9408497A patent/BR9408497A/en not_active IP Right Cessation
-
1997
- 1997-09-17 US US08/932,111 patent/US6146703A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09500928A (en) | 1997-01-28 |
| DE69413713D1 (en) | 1998-11-05 |
| ES2123950T3 (en) | 1999-01-16 |
| JP2746481B2 (en) | 1998-05-06 |
| DK0737222T3 (en) | 1999-06-21 |
| BR9408497A (en) | 1997-08-26 |
| EP0737222B1 (en) | 1998-09-30 |
| US6146703A (en) | 2000-11-14 |
| EP0737222A1 (en) | 1996-10-16 |
| WO1995018173A1 (en) | 1995-07-06 |
| DE69413713T2 (en) | 1999-02-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |