CA1295767C - Coating organosol containing reactive carbamate diluent - Google Patents
Coating organosol containing reactive carbamate diluentInfo
- Publication number
- CA1295767C CA1295767C CA000515629A CA515629A CA1295767C CA 1295767 C CA1295767 C CA 1295767C CA 000515629 A CA000515629 A CA 000515629A CA 515629 A CA515629 A CA 515629A CA 1295767 C CA1295767 C CA 1295767C
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- Prior art keywords
- hydrogen
- hydroxyethyl
- propyl
- crosslinking agent
- groups
- Prior art date
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Classifications
-
- 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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C09D201/025—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing nitrogen atoms
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- Engineering & Computer Science (AREA)
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Abstract
CARBAMATE COATING COMPOSITIONS
Abstract of the Disclosure High solids coating compositions are made by blending a crosslinkable organic polymer, an organic solvent and/or diluent, at least one reactive carbamate derivative, a crosslinking agent and optionally a crosslinking catalyst. The resultant high solids coating compositions can be either solutions or dispersions depending upon the particular polymer and solvent and the reactive carbamate chosen as the reactive cosolvent or reactive diluent.
Abstract of the Disclosure High solids coating compositions are made by blending a crosslinkable organic polymer, an organic solvent and/or diluent, at least one reactive carbamate derivative, a crosslinking agent and optionally a crosslinking catalyst. The resultant high solids coating compositions can be either solutions or dispersions depending upon the particular polymer and solvent and the reactive carbamate chosen as the reactive cosolvent or reactive diluent.
Description
' ' ' ~ i7 CARBAMATE COATING COMPOSITIONS
~Field of the Invention This invention pertains to the preparation of high solids coating compositions and more parti~ularly to tbe use of nearly non-volatil~
sub~tituted carbamate~ as reacti~e diluent~ and reactlve co~ol~ent~ ~ogether w~h an org~n~c volat~le ~olvent to form the liquid vehicle ~or the application of fllm form$ng polymers. High ~olids coatings for the purpose of the present invention shall mean organic coating compositions in which the organic volatile solvents of the coating are minimized by the ~ubstitution of a reactive diluent and/or a reactive solvent for all or a part of the volatile solvent or diluent usually employed to make useful coating compo~itions from a particular film forming polymer. The coating composition may be of two types: (1) stable dispersions of an organic polymer in an organic diluent (so called NAD or o~ganosol), (2) solutions of organic polymers in organic solvents. It is the intent of this invention to disclose the preparation of high ~olids coating compositions which utilize at least one organic, non-volatile substituted, reactive carbamate which is also a solvent or dispersant for a film for~ing ~olymer to replace a part or all of the thinner required to reduce the coatings ~ormulation to the required applications vis~osity.
I~ound ol th- IAv~Ation The use of volatile organic solvents or d~luent~ to dissolve or di~perse high polymers in .. . .. ..
76,~
the formulation of organic polymer compo~ition~ and their subsequent application onto variou~ ~ubstrates requires ~he handling and disposal o~ large volumes o~ organic material~. Because of the environmental ob~ections to solvent emi~sion~ and the increa~ingly frequent discovery ~f latent health problem~ of person~ exposed to cert~in 801vent vapors, alternative method~ of coatings applicatlon be~ome a necess~ty. Con~equently there 1~ a renewed intere6t in coatings technologies which can mini~ize the emission of Vol~tile Organic Compound~ (VOC). One of the most promising ~echnologies for the reduction of solvent emissions is high solids coatings. In this technology the technioal approaches have been:
(1~ to increase the amount of polymer which can be dissolved and applied by a given amount of ~olvent by lowering the molecular weight of the polymer and (2) to prepare a stable dispersion of a high polymer in a volatile organic diluent.
In the fir~t approach ~solution), lowering the molecular weight of the polymer h~s ~erious conseq~ences on the end-use performance of the coating. These problems have been compensated for by incorporating reactive functisnality along the backbone and/or at termination of ~he polymer molecule, and after appli~ation ~onverting these relatively low molecular weight polymer~ to high polymers through coupling and/or crosslinking reactions. Even with the advent o~ highly 6pecializ~d reactive polymer systems, there is a limit a~ to how much molecular weight can be lowered go attain higher ~olid~. Beyond thi~ limit the Dol5116-1 ~'2~767 polymers are no longer Pilm forming, have poor appl~cation properties and in general do not provide acceptable coating eompositions.
The second approach ~stable dispersion), iB
not without lts adverse consequences ~180. While i~
~8 true that di~persion~ have much lower viRcosities ~t much higher solids concentrat~ons, other problem~
Arise. Because sf the physisa~l constraint~ of particula~e packinq, pigmenta1:ion becomes di~ficult and film formation becomes a ~.intering proce~s.
Most often, in these systems, there i8 the need of fugitive plasticizers to insure the continuity of the film. Even then gloss, film smoothness, hardness, adhe~ion, pigmentation and ultimate performance can be adversely affected.
To address these newer problems ~mposed by adoption of ei~her of these high solids technologies, coatings technologists have incorporated rea~tive solvents and/or reactive diluents into coatings formulations. Reactive solvents 2nd reactive diluents as used herein are nearly non-volatile organic materials which have as an integral part of ~heir ~ru~ture ~ plurality of functional groups which are co-reactive with the base film formin~ polymer and~or required crosslinking agents, and c~n r~place a part or all of the volatile organie ~olvent and/or diluent required ~o reduce the formulation to a reasonable application visco~i~y. They may be liguids or solid~ providing, ~hose whi~h ~re ~olids are fioluble; u~ible, and compatible with ~he film - . .. .
~57~;7 forming oomponents either before or after ~application and subsequent cure.
~ doption of this deinition imposes ~om~
requirements on materials which can be considered as reactive solvents and react~ve diluents. They must be:- (1) essentially non-volatile under the conditions required for cure of the ~oating, ~2) good ~olvents for the film ~orming polymers or ~n the case of the dispersions, be temporary plasticizers for the base polymer during film formation, ~3) latently co-reactive with the film forming polymer and/or the cross-linking agents under conditions required for polymer conversion, and finally ~4) be able to provide final film properties required for the intended application.
Because reactive dil~ents and reactive solvents do become a considerable part o~ the final ~ilm, the properties of the coating are related not only to the properties of the film forming polymer but also to the properties attained from the reactiYe solvent or reactive diluent upon chemical inCOrpQration into the composition. Often it is necessary to adjust the stru~ture o~ the film ~orming polymer to compliment the structure of the reactive diluent.
Such polymers are designed ~or this intended use, and are preferable to polymers u~ed in much of the prior art. However, even polymers of the prior art can be formulated, u~ing reactive diluent ~nd/or solvents, into coating compo~itions with lower emissions than the corresponding formulation of these ~dent~cal polymers using only volatile non-reac~ive ~ ents ~nd/or diluen~s.
D 1~116-1 7~7 The advantage~ o~ high solid~ coatings can be illustrated by the use of compositional phase diagrams. Since the teachings of the pre~ent invention may be applicable to coatings of either the disperslon type or solution type, two compositlonal phase diagram~ will be required to under~tand the phase relatlonships. ~igure 1 i~
simplifled phase diagram of a hypothetic~l dispersion high solids coat~ngs 8y5tem, representing the volatile diluent a~ ~, the reactive diluent a~
C, and the film forming polyrner including the cross-linking agent as B. T}le area of a single phase, 2, is separated from the area of two phases, 4, by the curved line A-A'-~. The point E
represents the application ~omposition of the high solids dispersion coating. The ~trai~ht line E-D
represen~ the changing comp~sitions during film formation; the dashed line E-B i~ the film forming pathway that ~he high solids coating of the prior art would take. In ~he later case the diluent C' is the fugitive plasticizer required for par~icle coalescence and ~ust be removed from the film by vaporization otherwi~e perfQrmance properties would be degraded. In the former the reactive diluent remains an internal part of the film ~nd is incorporated into the polymeric film by reacting ~ith the polymer through the re~ctive functionalities provided. The ~alient features of the pha~e diagram are: (i) the reactive diluent is comp~tlble wit~ (soluble in) the ba~e film forming polymer; (ii) the reacti~e diluent serves as a transi~nt plasticizer to allow film coalescen~e;
~2~i;7~
~;
(iii) the reactive diluent need not be totally ,soluble in the volatile diluent, but rather is initially distri~uted bet~een the organic liquid phase and the poly~er phase ~nd during evaporation of the volatile diluent i8 translocated to~ally to the polymer phaset liv) becau~e the reactive diluent i~ e~sent~ally non-volatile and becomes part of the ~inal coati~g, the total non-volatile~
ttotal ~ol~d~ of the coatin~ equal to the sum of the polymer including the cross-linker and the reactive diluent thus allowing lower vclatile organic emissions.
Figure 2 is a simplified compositional phase diagram of a hypothetical high solids solution coating composition representing A, as the volatile organic solvent, the reactive solvent as C~ and the film forming polymer includins any requ~red cross-linking agent as B. Because of economic constraints the volatile organic solvent, often lower cost hydrocarbons, alone is gener~lly not a good solvent for the film forming poly~er, and thus the area of a single phase, 2, is separated from the area of two phases, 4, by the curYed l~ne A-A'-B.
The point E represents the application6 composition of the high solids solution coating. The Rtrai~ht line E-D represents the changing compositions during the film forming process. The dashed line E-B
repre~ents the ~ilm forming pathway o~ a corre~ponding solution coating when C is a volatile organic olven~. The notable features of ~igure 2 are: (i) The ~eactive ~olvent is generally miscible with the v~l~tile organ~G ~olvent; the line A-C is .~.2~lt7~
in the one phase region in its ent~rety. (ii~ The coatings polymer is soluble in the reactive solvent th~ line ~-B is in the one phase reg$on in its entlrety. liii) ~he rea~tive ~DlVent ~8 essentially non-volatile and become~ a part of the final coating and cons~quently, the total ~olid~ ~non-volatiles) in the ~1m, point ~, 18 equ~ll to the ~um of the polymer in~lud~ng any requ~red ~ro~s~ ker ~nd the reactlve solvent.
In both cases the reactive diluent and/or reactive ~olvent becomes a p~rt of the final coating and as such must contribute ~:o, and not detract from the overall coating performance. The reaction product of polymer, reactive diluent and/or reactive solvent and the cross-linking agent must have suitahle properties such as toughness, adhesion, impact resi~tance, abrasion resistance, scratch resistance, resistance to solvents, chemical~, acids, and bases. It must have good color, gloss, and stability as is required according to the end use application. All of the above is well understood by those ~killed in the ~rt.
Initially the coatings technologist adapted material~ which were reaaily available for use as reactive solvents and reactive diluent6. Many of these materials have limited utility becau~e of excessive volatility, limited reactivity; poor compatibility with the ba~e ~ilm orming ~ystem, and in general degradation o~ overall coatings per~ormance. Typi~l of the early reac~ive solvents and diluents are higher boiling polyol~ e.gO, glycerol, monoglycerid~ of unsaturated fatty acids;
1,2,6-hexanetriol and its mono ester derivatives, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, 1,4-butanediol~ and the like. These mater~als have many inherent disadvantage~ including exces~lve volatility, poor ~olvency in organic medi~ marginal cc-reactivity, and ~arginal compat$bility w~th the base film forming polymer. ~!he lower molecul~r weight ~embers are especially prone to cratering and other application defects while the higher member6 of the series do not adequately reduce ~he visco6ity or provide sufficient co-reactivity with the base polymer and or cross-linking ,agent. Later polyol~
derived from alkylene oxides ~were used. Typical of these materials are polypropylene glycol~, polyethylene glycol, and copolymers in the molecular weight range of 225 to 3000; these materials have improved non-volatile character but do not provide either good solvency for a variety of film forming polymers or acceptable exterior durability in the more demanding ~pplications. Of ~pecial interest in this category are the polyether diols derived from bisphenol A and ethylene or propylene oxide. S~ill later, hydroxy ~erminated polyesters were introduced. These materials are low molecular weight polyesters of M.W. 300 to 3000 derived from caprolactonet cyclic diols, e.g., cyclohexane dime~hanol and dibasi~ ~cids such as phthalic, isophthalic, maleic, succinic and the like. Often 6mall quantitie~ of triols or tetrols were used to create polyfunctionaliey in the polyester. These ~aterial~ are in effect very low molecular weight s~
oil less ~lkyds. They ~re ~haracterized by a broad ,compatibility, good co-reactivi~y, and low volatility. These material~ represent an improvemen~ over the polyether diols, however they provide neither the viscosity reduct~on for many applications methods including spray ~nd electro~tati~ spray nor performance required for the ~ore demanding end uses.
~ oday the state of the art h~s advanced to the point where the real needs are apparent and further improvement in high solids coatings systems will require more versatile reactive solvents and reactive diluents.
It is the ob~ective of the present invention to demonstrate coating compositions which employ one or more nearly non-volatile, substituted carbamates to replace all or part of the volatile organic olvent or diluent used in high solids coating compositions~ The ~ubstituted earbamates of the present inven~ion have as an integral part of their 6tructure a plurality of reactive -OH and/or -NHCO- groups which are capable, through the application of heat ~nd/or in the presence of cataly~ic agents when required, of reacting wi~h the base film forming polymers and cross-linking a~ents.
It is the further ob~ective of this invention to provide re~ctive ~olvents/reactive diluents which ~erve to proYide high 601ids coatings compositions in the form af either ~olutions or dispersions.
It i8 6till ~nother objective of this invention to provide reactive ~olvents and reactive D-~5116-1 ~;~957~7 ~ 10 --diluents which will not degr~de the ~uality or ,performance of the final finished coating.
Other objects will become apparent to tho~e ~killed in the ar~ upon a further reading of the specificat~ons.
~9_ ~ igh sol~ds coating compo~itions meeting the ob~ec~s above can be pre]pared by blending (a) at leas~ one crosslinkable organic polymer free of d~ide groups;
(b) organic solvent:
(c) at least one reactive carbamate derivative having the generic formula:
R'' O
R' -N - C-O-R''' wherein each of ~' and R'' is a monovalent radi~al selected from the group consisting of hydrogen, alkyl groups having 1 to about 10 carbon~, hydroxyalkyl groups haviny 2 to about 4 carbon atoms, hydroxyalkyleneoxy groups and hydroxypolyalkyleneoxy groups and R''' i8 the same as R' or R'' except that it cannot be hydrogen, with the provisos that:
said hydroxya~kyl, hydroxyalkyleneoxy and hydroxypolyalkyleneoxy groups contain at least 1 OH
group said R' ~nd R~' or R' ~nd R~'~ groups ~an unite to form a carbon rin~ structure; ~nd D~15116-1 ~L2~
~ aid carbamate derivative6 contain either ~t least one -NH and one -OH group or at least two O~ groups;
(d3 a cro~slinking amount of a cro~slinking agent; ~nd - (e) optionally a catalytic 3mount of a crossllnki~g çat~lyst.
In th~ above carbamate derivative~ ~xcept for hydrogen, the monovalent r~dioal~ may be substituted with ether, halogen, quaternary ammonium, ~ulfonium~ phosphonium and lik~
substituent~.
Suitable organic polymers for use in the present invention include polymers which oontain a plurality of reactive -OH and/or -NHCOO -groups.
Pref~rred crosslinkable organio polymers for use in this invention having as ~n integral part of their structure a plurality of reactive -OH
and~or -NB groups include:
Polyurethane resins Polyester alkyd resins ~ydroxyl containing epoxy fatty acid esters Hydroxyl containing polyesters ~ydroxyl sontaining alkyd resins Hydroxyl eontaining aorylic interpolymers exoept acrylamides ~ydroxyl con~ining vinyl inteepolymers~
~ uch a~ ~tyrene/~crylic copolymers.
The ratio of the ~mvunts of ~olvent and reactive diluent 3r co~olvent u~ed to prepare the coating oompo~ition~ i8 aictated by ~he type of coating desired. ~hu~ in the dispersion type~ the 9~ 7 amount of reactive diluent is usually determined by the film properties desired. Usually these can be attained by ratios of reactive diluen~Jsolvent in t~e range of abou~ 5/95 to about 30~70. On the other hand in the solution type the ratio of reactive cosQlvent to 801vent i8 ~imited ~y the ~olubility charao~eri~tlcs of the polymer. Thus a more ~oluble po~ymer would require le~ ~eact~ve co~olvent ~hile a les~ soluble polymer would require more. Generally, polymer~ of the~e type~ are ~oluble in a blend of reactive cosolvent/~olvent of about 20/80 to about 60/40. In practice the base coating may be formulated at rather high ratios of reactive cosolvent/solvent i.e., about 60~40 to about 90~10 and then let down with solvent to attain application viscositie6. One skilled in the art can easily establish the optimum ratio~ for a particular coating co~position with a minimum of experimentation. The amount of organic polymer used in these compositions i8 not narrowly critical.
However, a practical range for the solution type is about 15 to abou~ 45% by weight of polymer with the amount of reactive solvent bein~ about 10 ~o about Z0~ by weight, the amount of crosslinker being about 10 to about 30% by weight and the amount of ~olvent being about 60 to ~bout 5~ by weight.
A practical range of organic polymer used for the disper~ion type of coating oomposi~ion is about 35 to about 50~ by weight, with the amount of reactive diluent being about S to about 20% by weight, the amount of crosslinker being about 5 to ` ~ 2 about ~0~ by weight and the amount o solvent being ,about 55 to about 10% by weight.
The rea~tive ~arbamate derivatives in the coatlng composition claimed herein can be designated aE eith~r react~ve co~olventl~ or reactive d~luent~
depending on the type o coat:ings formed. In the ca~e of coating compositlon~ which are dispersion~, the carbamates function ~8 reactive a~luents. In ~he c~se of coating compositions which ~re ~olutions, the carbamates function as reactive cosolvents.
The term reactive i~; used herein to mean that the carbamate derivatives can be incorporated into the finished coating by crosslinking agents which cure through NH and/or OH groups.
The reactive carbamates used in this invention may be represented by the following:
butyl 6-hydroxyhexylcarbamate 2-ethylhexyl 4-hydroxybutylcarbamate butyl 2-hydroxyethylcarbamate 2-ethylhexyl 2,3-dihydroxy-1-propylcarbamate butyl 2,3-dihy~roxy-1-propylcarbamate hexyl bi~(2-hydroxyethyl)carbamate ~-(2-hydroxyethoxy) ethyl carbamate 4-hydroxybutyl carbamate 2-hydroxy-1-propyl carbamate l-hydroxy-2-propyl carbamate 2-hydroxyethyl carbamate 1,3dihyd~oxy-2-propyl carbamate ` 2,3-di~ydroxy-1-propyl carbamate 2-hydroxydecyl carbamate l-(hydroxymethyl)nonyl carbamate 5~6~
2-hydroxyethyl ~2-hydroxyethyl)-.~ethyl)carbamate 1,3-dihydroxy~2~propyl dimethylcarbamate 2,3-dihydroxy-~-propyl dime~hylcarba~ate 2,3-dlhydroxy-1-pro~pyl tetramethyl~n~-carbam~te 2-hydroxy~thyl bi8-(2 hydroxyethyl)carbamate 3-(2,~-dlhydroxy-1-lpropyl) oxa~olidone 2-hydroxyethyl dimethyl carbamate 3-~2-hydroxyethyl)-!5-(hydroxymethylene)-oxazolidone 3-(2-hydroxyethyl) oxa~olidone 2-hydroxyethyl l-butylcarbamate l-hydroxy 2-propyl l-propylcarbamate 2-hydroxy-1-propyl l-propylcarbamate l-hydroxy-2-propyl l-butylcarbamate 2-hydroxy-1-propyl l-butylcar~ama~e 2-methyl-1-propyl 2-hydr~xyethylcarbamate 2-propyl bis(2-hydroxyethyl)carbamate 2-hydroxyethyl methylcarbamate 2-hydroxyethyl 2-hydroxyethylcarbamate 2,3-dihydroxy-1-propyl ethylcarbamate 1~3-dihydroxy-2-propyl 1 butylcarbamate 5-~hydroxyme~hylene) oxazolidone 4-(hydroxymethylene) oxazolidone 1,3-dihydroxy-2-propyl ethylcarbamate 2-hydroxyethyl ethylcarbamate 2-hydroxyethyl 2-methylpropylcarbam~te 2-hydroxy-1-propyl 2-ethylhexylcarbamate 2,3-dihydroxy l-propyl l-butylcarbamate l-hydr~xy-2-propyl ~-e~hylhexylcarbamate 5-(hydroxymethylen~)oxazolid~ne 1,3-dihydroxy-2 propyl tetramethylene carbamate 5-hydroxypyrazolidone 2-hydrcxyethyl (propyl)(2-hydroxyethyl~carbamate - 2-hydroxy-1-propyl 2-hydroxye~hylcarbamate 2-hydroxyethyl 3-hydroxy 2,2-dimethyl-1-propylcarbamate.
Illus~r~tive of su~table crossllnking agents for the high solids coating compos~tions described here~n ~re me~hylol phenol5, ~uch as 2,4,6-trimethylolphenol, polyepoxide~, such as the glycidyl epoxides or cycloaliphatic epoxides (Araldite~ 297, epOn* 582, etc.) and ~he aminoplasts ~uch as the reaction product of an aldehyde (e.g.
formaldehyde, acetaldehyde, paraPormaldehyde, trioxane, e~c.) with urea, ~hiourea, melamine, benzsguanamine, ace~oguanamine, dicyandiamine and the like. The aminoplasts may be etherified with a lower alcohol such a~ me~hyl, ethyl, butyl, isobutyl, propyl or i~opropyl al~ohol~ Aminoplasts which are of particular value in high olids coating compositions are the methylate~ urea~formaldehyde resins, the alkyl~ted benzoguanamines and methylated melamine-formaldehyde resins with the latter being the most desir~ble.
~ owever ~he crosslinking agent is not an aminoplast unles~ ~here are two or more or no ~
group~ on the R' " moiety or unle~ R' and R'' are each hydrogen or neither R' nor R'' is hydrogen.
The choice of c~talyst6 ~uitable ~or the pr~ct~ce of t~i~ inven~ion i~ dictated by the choice .. . . .
3~;2~7~i~
-- 1~
of cros~linking reaction. Thu~ if aminoplasts are employed to crosslink the organic polymer and reacti~e carba~ate, an acidic catalyst ~
preferred. Illu~trative of the acidlc cat~lyst of the invention are one or more of the following:
~lkyl~ulfonic acids ~uch as methane ~ulfonic ~cid, ethane sulfonic acld and the like, aryl~ul~onlc acids such as p-toluene ~ulfonic ac~d, alkylaryl ~ulfonic acids ~uch ~5 ~ ~10 1 ~18 ~1 y sulfonic acidr dialkyl hydrog~n phosphates ~uch as diamyl hydrogen phosph~te, aryl hydroyen phosphates ~uch as diphenyl hydrogen phosphate and phosphoric acid itself.
The diisocyana~es and blocked diisocyanates are often employed to crosslink these polymers. The polymer i~ocyanates have been extensively reviewed by Wicks (Prog. Org. Chem. 3, 73 ~1975~). A blocked isocyanate is an i~ooyanate adduc~ which is ~table at ~mbient conditions but dissociate~ to regenerate isocyanate functionality unde~ the influence of hea~. Temperatures of 120 to about 250DC are neces ary to release the blocking groups which are usually volatilized from the coating. The dissociation temperature of blo~ked isocyanates ba~ed on commercially u~ili2ed blocking agents decrease in the order: epsilon-caprolactam, phenols~
methyl ethyl ketoxime, and a~ti~e methylene compound6. Blo~ked isocyan~tes which are ~table have been described by Rosth~user ~nd ~illiams (Proc~eding6 Polymeric ~terials Science and Engineer~ng: ~ol. 509 pg. 344 (1984)~o Ca~alysts whlch promote the ure~hane r2~ction are well known . ~29~7~7 to the art and are illu~trated by tertiary amines ~uch as triethyl amine, bis(dimethylaminoethyl) ether and the li~e, organometallic ~alt~ of tin, mercury, zinc, bismuth and ~he like such as dibutyl ~in diacetat~ zinc octoate, phenyl mercuric acetate and bismuth octoate.
The amount ~f cataly~t requlred to promote the react~on ~ dependent upon the curing conditions requ~red in the coa~ing process. ~hose skilled in the art may readily determine the cataly t level with a minimum of experimentation. In practlce if a catalyst is desired it is usually in the level of .02 to about 1~ based on the weight of the organic polymer.
Background of the curing relations of hexamethoxymethylmelamine may be found in an article by R. Saxon et al. in J. Appl. Poly, Sci. 8, 475 (1964).
The invention is further described in the examples which follow. All parts and percentages are by weight unless other~ise ~pecifiedO
Example 1 PREPARATIO~ OF 2-HYDROXYET~YL D~METHYLC~RB~MATE
When ethylene carbonate i~ treated ~s in U.S. 4,520,167 with an equimolar ~mount of dimethylamine, a mixture containing 2-hydroxyethyl dimethylcarbamate i~ obtained.
Ex~mple 2 PREPARATION O~ 3-(2-HYDROXYET~YL) OX~ZOLIDON~
When dimethyl carbonate is treated with an equimolar ~ount o~ diethanolamine, a mixture ~ont~ining 3-~2-hy~roxye~hyl~oxazolidone is obtained.
~2~;7~'~
~ 18 Example 3 (2-HYDROXYETHYL) (ETHYL) CARBAMATE
,, , , ~
When ethylene carbonate ~ treated 88 in E~ample 1 with an e~ui~olar amount of N-ethyl ethanolamine, a mixture containing 2-hydroxyethyl (2-hydroxyethyl) 5ethyl) carba~at~ 1~ obtained~
Ex~mple 4 3~~2-HYDROXYETHYL) O~AZOLIDONE/CARGILL-7451 , When 3-(2-hydroxyethyl)oxazolidone i8 combined with CELLOSOLVE* Acetate ~olYent, Cargill~-7451 resin, C~ME~*-303 crosslinker (in ~n amount toichiometrically equivalen~ to the sum of resin and oxazolidone~ and p-toluenesulfonic acid catalyst~ a mixture is obtained which can be thermally cured into a hard, tough, glo~sy coating.
2-HYDROXYETHYL l2-HYDROXYETHYL) (ETHYL~
CARBA~.ATE/SARGILL~-7451 RESIN
CROSSLINKED BY CYMEL~ 303 When Example 4 is repeated with the exception that 2-hydroxyethyl~2-hydroxyethyl) (e~hyl) carbamate is substituted for 3-(2-hydroxyethyl) oxazolidone, a mixture i~
obtained which can be thermally cured into a tough, hard, glossy coating.
D-1~116-1 . .
S~7 PREPARATION OF
1,3-DIHYDROXY-2-PRoPYL CAR~AMATE AND
2~3-DIHYDROXY-l-PROPYL CARBAMAT~
__.__ When glycerine i8 treated with dimethylcarbonate, a ~ixture ~8 obtained wh~ch con~aln~ cyclic carbonates of glycerine ~4-hy~r~xymethyl-1,3-dioxol-2-one and 5-hydroxy-1,3-aioxan-2-one). When the mixture containing the~e cyclic carbonate~ i~ treated wi~h ammonia, another mixture is obtained which contains 1,3-dibydroxy-2-propyl carbamate and 2,3-dihydroxy-1-propyl carbamate.
PREPARATION OF
1~3-DlHyDRoxy-2-pRopyL ~ETRAMETHYLENE GARBAMAT~
AND 2 3-DIHYDROXY-l-PROPYL TETRAMETHYLENE CARBAMATE
~ hen Example 5 is followed except th~t the ammonia is replaced by pyrrolidine, a mixture is obtained which contains 1,3-dihydroxy-2-propyl tetramethylene carbamate and 2,3-dihydroxy-1-propyl tetramethylenecarbamate.
1,~ DIHYDROXY-2-PROPYL ~E~RAMETHYLENE CAR~AMATE AND
2,3 DIHYDROXY-l-PROPYL TETRAMETHYLENE CARBAMATE AND
CARGILL~ 745I RESIN CROSSLINKED BY CYMEL~ 303 A mixture containing 1,3-dihydroxy-2-propyl tetramet~ylenecarbamate, 7,3-dihydroxy l-propyl tetrame~hylenecarba~a~e, CELLOSOLVE ~cetate Solvent, CARGILL-~451 ~esin9 CYMEL-303 ~rosslinker and p-toluenesulfonic a~id catalyst is thermally cured to give ~ hard, tough glossy so~ting.
- 20 _ 3L~9~;~æ~
. PREPARATION OF HYDROXYETHYL BUT'YLCARBAMATE
274.8 Grams of ethylene carbonate ~3.12 moles~ were placed ln ~ round bottom flask equ~pped with ~tirrer, thermometer, addition funnel and reflux ~ondenser. 228.2 Grams ~3.12 ~ole) of butylamine ~ere charged to the ~dd$tion funnel and added to the ~tirred contentl3 of the fl~sk ~t a rAte ~ufficient to maintain them ~3~ 50-80C~ Crude product p~rity by gas chromatography was 90.6 area %
after the mixture had been a:Llowed to ~tand overnight. Stripping ~n a rotary evaporator gave 449.9 9. of product of 92.3 area % purity. The yield, corrected for purity, was 83.1~. A portion of the material was di~tilled at 2 mm Hg boiling from 124 to 126C and having area ~ purity 95.1%.
Hydroxyethyl butylcarbamate is a good solvent for a polyester re~in SCargill ~7451).
Example 10 PREPARATION O~ 2=HYDROXYETHYL METHYLCARBAMA~E
44 Grams (.5 m~le) of ethylene carbonate were placed in a 250-ml round bottom flask equipped with stirrer, addition funnel~ and thermometer.
38.75 Grams of 40~ aqueou~ methylamine (15.5 g., .5 mole contained methylamine) were charged to the addition funnel and added to the fl~k with stirring over 1025 hr. and with the fla~k contents at 38 to $2C. The resulting mixture was subjected to vacuum di~tillation giving 42.54 9. (3S.7%) of clear, c410rless liquid product boiling ~t 140C at 8 mm ~9~ The infrared ~pectrum of thi~ material was consistent with the proposed ~tructure. Purity by D~1$116-1 7~
gas chromatography was 97.8 area ~ The product had a melting point of approximately -36C and was ~iscible with water.
Example 11 PREPARATIO~ 0~ HYDROXYPRO~PYL BUTYLCARBAMATES
290.96 grams ~2.85 ~oles) of propyl~ne carbonate were ~harged to ~ 2~ round bottom fl2sk equipp~d w~th stirr~r, heater, thermometer, addition funnel and reflux condenser. 211.3 Grams ~2.85 moles) of butylamine were charged ~o the addition funnel and 610wly added to th~e ~lask contents. The maximum temperature of the reaction was 98C. The material was allowed to stand and a sample ~ubmitted for infrared analysis. The infrared spectrum was consistent with the proposed structures (i.e. an isomeric mixture of 2-hydroxy-1 and l-hydroxy -2-propyl l-butylcarbamates~. The proposed structures given above were confirmed by Proton NMR
analysis.
ExamPle 12 HYDROXYETHYL BUTYLCARBAMATE/CARGILL~-7451 RESIN
CROSSLINKED ~Y A BLOCKED AROMATIC ISOCYANATE
PREPOLYMER BASED ON TOLUENE DIISOCYANATE
A mixture of hydroxyethyl butylcarbamate, Cargill -7451 Resin, CELLOSOI,VE Ace~a~e and a blocked aromatic icocyanate prepolymer based on toluene diisocyanate (as taught in U.S. 4,518,522 ~ssigned to Mobay) is ~hermally ~ured to a hard, tough glos~y coating.
7g~7 HYDROXYETHYLBUTYL CARBAMATE AND CARGILL~ 7451 RESIN CROSSLIN~ED BY LPON't828 A mixture of ~ydroxyethyl bu~ylcarbamate, Cargill -7451 resin, CELLOSOLVE Acetate, EPON -B2~ and an amine ~atalyst ~ thermally cured to afford ~ hard, tough, 91088y coating.
Example l4 PREP~RATION OF HYDROXYPROPYL PROPYL~ARBAMATES
. .
722 Grams (7.0 moles ~ 99% purity3 of propylene carbonate was charged to a 2 1 round-bottom flask ~quipped with ~tirrer, heating mantle thermometer, feed tank and distillation head. The flask and contents wer~ hea~ed with stirring under nitrogen to 50C. At this point addition of 436 grams 17 moles ~ 98~ purity) of n-propylamine was begun and continued for a total of 3.25 hrs. during which time the temperature was maintained between 50 ~nd 62C without external heat. The temperature was then raised to 72C and held at this value for an additional 3 hrsO then the flask and contents were allowed to cool and stand overnight. ~ights were removed by heating to a maximum temperature oP 105C under 2 mm Hg pressure during l hr. with ~tirring.
~ as chromatographic analysis of this material showed 96.8 ~rea % product.
D-15116-l 23 ~Z~7&7 Example 15 When Example 9 is followed except that a chemically equivalen~ amount of 2-e~hylhexyl amine i8 ~ubstituted for n-butylamine, a m~xture containing 2-hydroxyethyl 2-ethylhexylcarbamate i~
obtained.
i ~xample _ SYNTHESI~ OF HYDROXYPROPYL 2-ETHYLHEXYLCARBA~ATES
When Example 14 is followed except that a chemically equivalent amount of 2-ethylhexylamine is substituted for n-propylamine, an isomeric mixture of 2-hydroxy-1-propyl ~-ethylhexylcarbamate and l-hydroxy-2~propyl 2-ethylhexylcarbamate i8 obtained.
Example 17 PREPARATION O~ 2-METHYL-l-PROPYL
(2-HYDROXYETHYL)CARBAMATE
An equimolar mixture of di(2~me~hyl-1-propyl~carbonate and ethanolamine is allowed to react resulting in formation of a mixture containing 2-methyl-1-propyl (2-hydroxyethyl)carbamate.
Example 18 (2-HYDROXYETHYL)CARBAMATE
When example 9 i~ followed except that a chemically equivalent amount of e~hanolamine is ubstituted for n-butylamine, a mixture containin~
2-hydroxyethyl ~2-hydroxyethyl)carbamate is obtained.
- 24 - ~ 2 Example 19 SYNTHESIS OF BUTYL
2,3-DIHYDROXYPROPYLCAR~AMATE
, An ~uimolar mixture 9f dibu~ylcarbonate and 3-amino-1~2-propanediol is allowed to react resulting in formatlon of ~ mixture containing butyl 2,3 dihydroxypropylcarbamate.
~ y~__2~
1-~YDROXY-2-PROPYL 1- BU~YL CARBAMATE
2-HYDROXY-l- iRoPYL l-~UTYL CARBAMA~2 CARGILL~ 7451 RESIN C~OS5LINKED BY A
BLOCKED AROMATIC ISOCYANAIE P~EPOLYMrR
When example 12 is followed excepting that a chemically equivalent amount of an isomeric mixture of l-hydroxy-2-propyl l-butylcarbamate and ~-hydroxy-l-propyl l-butyl carbamate i~ substitu~ed ~or hydroxyethyl butylcarbamate, a mixture is obtained which can be thermally cured to a hard, tough, glossy coating.
Exam~ 21 l-HYDROXY-2-PROPYL l-PROPYLCARBAMATE, ? HYDROXY 1-PROPYL l-PROPYLCARBAMATE~ CARGILL* 7451 RESIN CROSSLINXED BY A BLOCKED AROMATIC ISOCYANAT~
PREPOLYMER BASED ON TOLUENE DIISOCYA ~TE.
When Example 12 i8 followed except that a chemically equivalent amou~t of an i~omeric mixture of l-hydroxy-2-propyl l-propylcarbamate and 2-hydroxyl-1-propyl l-propylcarbamate ~s substituted for 2-hydroxyethyl l-butylcarbamate, a hard, glossy, tough coating is obtained.
D~15116-1 ,~ , . . .
- 25 ~
Example 22 PREPARATION OF 5-(HYDROXYMETHYLENE30XAZOL~DONE
AND 5-HYDROXPYRAZOLI~O~E
An equimolar mixture of dimethyl carbonate and 3-amino-1,2-propanediol i~ allowed to react re6ultlng ~n a mixt~re containing 5-(hydroxymethylenel oxazol~done and 5-hydroxypyrazolidone .
Example 23 PREPARATION OF 2-HYDROXYET~YL 3-HYDROX~-2 ~ ?-DIMETHYL-l-PRO~PYLCARBAMATE ~
An equimolar mixture of ethylene carbonate and 3-amino-2,2-dimethyl-1-propanol i9 allowed to react resulting in ~ mixture containing 2-hydroxyethyl 3-hydroxy-2,2-dimethyl-1 pr~pylcarbamate.
PREPARATION OF 2-HYDROXYETHYL ~PROPYL3 (2-HYDROXYETHYL)CARBAMATE
When Example ~ is followed except that the butylamine is replaced by an equimolar amount of N-propyl ethanolamine, a mixture is obtained which contains 2-hydroxyethyl (propyl)~2-hydroxyethyl)-carbamate.
Example 25 PREPA~ATION OF 2-HYDROXYETHYL CARBAMATE
~ hen ethylene carbonate (1~3 dioxol-2-one) i8 treated with ammonia a mixture i8 obtained which contains 2-hydroxyethyl carbamate.
.. . .
- 26 ~
Example 26 PREPARATION OF 2-(2-HYDR0%YETHOXY)ETNYL CARBAMA~E
~ hen urea iR treated with diethylene ~lycol (2-(2-hydroxyetho~y) ethanol~, a mlxture i~ obtained which contains 2-~2-hydroxyethoxy)ethyl carbamate~
~ 27 PREPARATION 0~ YDROXY~U~YL CARBAMATE
, When ure~ l~ treateld with 1,4 butanediol, a mixture is obta~ned which contains ~hydroxybutyl carbamate.
Example 28 PREPARATION OF A MIXTURE 0~ 2-HYDROXYDECYL
CAR~AMATE AND l-(HYDROXYMETHYL)I~ONYL CARBAMATE
~ .
When urea i~ treated with 1,2-decanediol, a mixture ic obtained which contains 2-hydroxydecyl : carba~ate and l-(hydroxymethyl~ nonyl carbamate.
2-HYDROXYDECYL CARBAMATE, l-(HYDROXY-METHYL~NONYL CARBAMATE AND
A mixture of 2-hydroxydecyl carbamate, l-(hydro~ymethyl)nonyl carbamat~, ~ELLOSOLVE*
Acetate, Carqill-7451 Resin, Cymel~-303 ~rosslinker and p-toluene~ul~onlc acid is thermally cured to ~ive a h~rd, tough, glossy coating.
PREPARATIO~ OF BVTYL_2-HYDROXYETHYLCARBAMATE
When dibutylcarbonate i~ treated wi~h 2-aminoethanol ~ mixture is obtained which contains butyl 2-hydroxyethy~carbamate.
5~
.PREPARATION OF 2-ETHYLHEXYL 4-HYDROXYBUTYLCARBAMATE
_ When di~2-ethylhexyl)carbonate i8 treated with 4-ami~o-1-bu~anol, a ~ixture is obtained which contalns 2-ethylhexyl 4-hydroxybutylcarba~at2 ~ ~2 -PREPARATION OF BUTYL 6-HYI)ROXYHEXYLCARBA~T~
When dibutylcarbonate i8 treated with 6-fimino-l hexanol ~ mixture i~ obtained which contai~s butyl 6-hydroxy hexy]Lcarbamate.
Example :33 CARGILL~-7451 RESIN CROSSLINKED_BY
-A mixture containing butyl 6-hydroxyhexylcarbamate, CELLOSOLVE Acetate Solvent, Cargill-7451 resin and Cymel-327 cr~sslinker is thermally cured to give a hard, tough, ~lossy coating.
~ lthough the inYention ha~ been described in its preferred forms with a certain degree of particularity, it is understood that the present disclosure has been made only by way of example and that numerous changes can ~e made wi~hout depar~ing rom the spirit and the ~cope of the invention.
~Field of the Invention This invention pertains to the preparation of high solids coating compositions and more parti~ularly to tbe use of nearly non-volatil~
sub~tituted carbamate~ as reacti~e diluent~ and reactlve co~ol~ent~ ~ogether w~h an org~n~c volat~le ~olvent to form the liquid vehicle ~or the application of fllm form$ng polymers. High ~olids coatings for the purpose of the present invention shall mean organic coating compositions in which the organic volatile solvents of the coating are minimized by the ~ubstitution of a reactive diluent and/or a reactive solvent for all or a part of the volatile solvent or diluent usually employed to make useful coating compo~itions from a particular film forming polymer. The coating composition may be of two types: (1) stable dispersions of an organic polymer in an organic diluent (so called NAD or o~ganosol), (2) solutions of organic polymers in organic solvents. It is the intent of this invention to disclose the preparation of high ~olids coating compositions which utilize at least one organic, non-volatile substituted, reactive carbamate which is also a solvent or dispersant for a film for~ing ~olymer to replace a part or all of the thinner required to reduce the coatings ~ormulation to the required applications vis~osity.
I~ound ol th- IAv~Ation The use of volatile organic solvents or d~luent~ to dissolve or di~perse high polymers in .. . .. ..
76,~
the formulation of organic polymer compo~ition~ and their subsequent application onto variou~ ~ubstrates requires ~he handling and disposal o~ large volumes o~ organic material~. Because of the environmental ob~ections to solvent emi~sion~ and the increa~ingly frequent discovery ~f latent health problem~ of person~ exposed to cert~in 801vent vapors, alternative method~ of coatings applicatlon be~ome a necess~ty. Con~equently there 1~ a renewed intere6t in coatings technologies which can mini~ize the emission of Vol~tile Organic Compound~ (VOC). One of the most promising ~echnologies for the reduction of solvent emissions is high solids coatings. In this technology the technioal approaches have been:
(1~ to increase the amount of polymer which can be dissolved and applied by a given amount of ~olvent by lowering the molecular weight of the polymer and (2) to prepare a stable dispersion of a high polymer in a volatile organic diluent.
In the fir~t approach ~solution), lowering the molecular weight of the polymer h~s ~erious conseq~ences on the end-use performance of the coating. These problems have been compensated for by incorporating reactive functisnality along the backbone and/or at termination of ~he polymer molecule, and after appli~ation ~onverting these relatively low molecular weight polymer~ to high polymers through coupling and/or crosslinking reactions. Even with the advent o~ highly 6pecializ~d reactive polymer systems, there is a limit a~ to how much molecular weight can be lowered go attain higher ~olid~. Beyond thi~ limit the Dol5116-1 ~'2~767 polymers are no longer Pilm forming, have poor appl~cation properties and in general do not provide acceptable coating eompositions.
The second approach ~stable dispersion), iB
not without lts adverse consequences ~180. While i~
~8 true that di~persion~ have much lower viRcosities ~t much higher solids concentrat~ons, other problem~
Arise. Because sf the physisa~l constraint~ of particula~e packinq, pigmenta1:ion becomes di~ficult and film formation becomes a ~.intering proce~s.
Most often, in these systems, there i8 the need of fugitive plasticizers to insure the continuity of the film. Even then gloss, film smoothness, hardness, adhe~ion, pigmentation and ultimate performance can be adversely affected.
To address these newer problems ~mposed by adoption of ei~her of these high solids technologies, coatings technologists have incorporated rea~tive solvents and/or reactive diluents into coatings formulations. Reactive solvents 2nd reactive diluents as used herein are nearly non-volatile organic materials which have as an integral part of ~heir ~ru~ture ~ plurality of functional groups which are co-reactive with the base film formin~ polymer and~or required crosslinking agents, and c~n r~place a part or all of the volatile organie ~olvent and/or diluent required ~o reduce the formulation to a reasonable application visco~i~y. They may be liguids or solid~ providing, ~hose whi~h ~re ~olids are fioluble; u~ible, and compatible with ~he film - . .. .
~57~;7 forming oomponents either before or after ~application and subsequent cure.
~ doption of this deinition imposes ~om~
requirements on materials which can be considered as reactive solvents and react~ve diluents. They must be:- (1) essentially non-volatile under the conditions required for cure of the ~oating, ~2) good ~olvents for the film ~orming polymers or ~n the case of the dispersions, be temporary plasticizers for the base polymer during film formation, ~3) latently co-reactive with the film forming polymer and/or the cross-linking agents under conditions required for polymer conversion, and finally ~4) be able to provide final film properties required for the intended application.
Because reactive dil~ents and reactive solvents do become a considerable part o~ the final ~ilm, the properties of the coating are related not only to the properties of the film forming polymer but also to the properties attained from the reactiYe solvent or reactive diluent upon chemical inCOrpQration into the composition. Often it is necessary to adjust the stru~ture o~ the film ~orming polymer to compliment the structure of the reactive diluent.
Such polymers are designed ~or this intended use, and are preferable to polymers u~ed in much of the prior art. However, even polymers of the prior art can be formulated, u~ing reactive diluent ~nd/or solvents, into coating compo~itions with lower emissions than the corresponding formulation of these ~dent~cal polymers using only volatile non-reac~ive ~ ents ~nd/or diluen~s.
D 1~116-1 7~7 The advantage~ o~ high solid~ coatings can be illustrated by the use of compositional phase diagrams. Since the teachings of the pre~ent invention may be applicable to coatings of either the disperslon type or solution type, two compositlonal phase diagram~ will be required to under~tand the phase relatlonships. ~igure 1 i~
simplifled phase diagram of a hypothetic~l dispersion high solids coat~ngs 8y5tem, representing the volatile diluent a~ ~, the reactive diluent a~
C, and the film forming polyrner including the cross-linking agent as B. T}le area of a single phase, 2, is separated from the area of two phases, 4, by the curved line A-A'-~. The point E
represents the application ~omposition of the high solids dispersion coating. The ~trai~ht line E-D
represen~ the changing comp~sitions during film formation; the dashed line E-B i~ the film forming pathway that ~he high solids coating of the prior art would take. In ~he later case the diluent C' is the fugitive plasticizer required for par~icle coalescence and ~ust be removed from the film by vaporization otherwi~e perfQrmance properties would be degraded. In the former the reactive diluent remains an internal part of the film ~nd is incorporated into the polymeric film by reacting ~ith the polymer through the re~ctive functionalities provided. The ~alient features of the pha~e diagram are: (i) the reactive diluent is comp~tlble wit~ (soluble in) the ba~e film forming polymer; (ii) the reacti~e diluent serves as a transi~nt plasticizer to allow film coalescen~e;
~2~i;7~
~;
(iii) the reactive diluent need not be totally ,soluble in the volatile diluent, but rather is initially distri~uted bet~een the organic liquid phase and the poly~er phase ~nd during evaporation of the volatile diluent i8 translocated to~ally to the polymer phaset liv) becau~e the reactive diluent i~ e~sent~ally non-volatile and becomes part of the ~inal coati~g, the total non-volatile~
ttotal ~ol~d~ of the coatin~ equal to the sum of the polymer including the cross-linker and the reactive diluent thus allowing lower vclatile organic emissions.
Figure 2 is a simplified compositional phase diagram of a hypothetical high solids solution coating composition representing A, as the volatile organic solvent, the reactive solvent as C~ and the film forming polymer includins any requ~red cross-linking agent as B. Because of economic constraints the volatile organic solvent, often lower cost hydrocarbons, alone is gener~lly not a good solvent for the film forming poly~er, and thus the area of a single phase, 2, is separated from the area of two phases, 4, by the curYed l~ne A-A'-B.
The point E represents the application6 composition of the high solids solution coating. The Rtrai~ht line E-D represents the changing compositions during the film forming process. The dashed line E-B
repre~ents the ~ilm forming pathway o~ a corre~ponding solution coating when C is a volatile organic olven~. The notable features of ~igure 2 are: (i) The ~eactive ~olvent is generally miscible with the v~l~tile organ~G ~olvent; the line A-C is .~.2~lt7~
in the one phase region in its ent~rety. (ii~ The coatings polymer is soluble in the reactive solvent th~ line ~-B is in the one phase reg$on in its entlrety. liii) ~he rea~tive ~DlVent ~8 essentially non-volatile and become~ a part of the final coating and cons~quently, the total ~olid~ ~non-volatiles) in the ~1m, point ~, 18 equ~ll to the ~um of the polymer in~lud~ng any requ~red ~ro~s~ ker ~nd the reactlve solvent.
In both cases the reactive diluent and/or reactive ~olvent becomes a p~rt of the final coating and as such must contribute ~:o, and not detract from the overall coating performance. The reaction product of polymer, reactive diluent and/or reactive solvent and the cross-linking agent must have suitahle properties such as toughness, adhesion, impact resi~tance, abrasion resistance, scratch resistance, resistance to solvents, chemical~, acids, and bases. It must have good color, gloss, and stability as is required according to the end use application. All of the above is well understood by those ~killed in the ~rt.
Initially the coatings technologist adapted material~ which were reaaily available for use as reactive solvents and reactive diluent6. Many of these materials have limited utility becau~e of excessive volatility, limited reactivity; poor compatibility with the ba~e ~ilm orming ~ystem, and in general degradation o~ overall coatings per~ormance. Typi~l of the early reac~ive solvents and diluents are higher boiling polyol~ e.gO, glycerol, monoglycerid~ of unsaturated fatty acids;
1,2,6-hexanetriol and its mono ester derivatives, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, hexylene glycol, 1,4-butanediol~ and the like. These mater~als have many inherent disadvantage~ including exces~lve volatility, poor ~olvency in organic medi~ marginal cc-reactivity, and ~arginal compat$bility w~th the base film forming polymer. ~!he lower molecul~r weight ~embers are especially prone to cratering and other application defects while the higher member6 of the series do not adequately reduce ~he visco6ity or provide sufficient co-reactivity with the base polymer and or cross-linking ,agent. Later polyol~
derived from alkylene oxides ~were used. Typical of these materials are polypropylene glycol~, polyethylene glycol, and copolymers in the molecular weight range of 225 to 3000; these materials have improved non-volatile character but do not provide either good solvency for a variety of film forming polymers or acceptable exterior durability in the more demanding ~pplications. Of ~pecial interest in this category are the polyether diols derived from bisphenol A and ethylene or propylene oxide. S~ill later, hydroxy ~erminated polyesters were introduced. These materials are low molecular weight polyesters of M.W. 300 to 3000 derived from caprolactonet cyclic diols, e.g., cyclohexane dime~hanol and dibasi~ ~cids such as phthalic, isophthalic, maleic, succinic and the like. Often 6mall quantitie~ of triols or tetrols were used to create polyfunctionaliey in the polyester. These ~aterial~ are in effect very low molecular weight s~
oil less ~lkyds. They ~re ~haracterized by a broad ,compatibility, good co-reactivi~y, and low volatility. These material~ represent an improvemen~ over the polyether diols, however they provide neither the viscosity reduct~on for many applications methods including spray ~nd electro~tati~ spray nor performance required for the ~ore demanding end uses.
~ oday the state of the art h~s advanced to the point where the real needs are apparent and further improvement in high solids coatings systems will require more versatile reactive solvents and reactive diluents.
It is the ob~ective of the present invention to demonstrate coating compositions which employ one or more nearly non-volatile, substituted carbamates to replace all or part of the volatile organic olvent or diluent used in high solids coating compositions~ The ~ubstituted earbamates of the present inven~ion have as an integral part of their 6tructure a plurality of reactive -OH and/or -NHCO- groups which are capable, through the application of heat ~nd/or in the presence of cataly~ic agents when required, of reacting wi~h the base film forming polymers and cross-linking a~ents.
It is the further ob~ective of this invention to provide re~ctive ~olvents/reactive diluents which ~erve to proYide high 601ids coatings compositions in the form af either ~olutions or dispersions.
It i8 6till ~nother objective of this invention to provide reactive ~olvents and reactive D-~5116-1 ~;~957~7 ~ 10 --diluents which will not degr~de the ~uality or ,performance of the final finished coating.
Other objects will become apparent to tho~e ~killed in the ar~ upon a further reading of the specificat~ons.
~9_ ~ igh sol~ds coating compo~itions meeting the ob~ec~s above can be pre]pared by blending (a) at leas~ one crosslinkable organic polymer free of d~ide groups;
(b) organic solvent:
(c) at least one reactive carbamate derivative having the generic formula:
R'' O
R' -N - C-O-R''' wherein each of ~' and R'' is a monovalent radi~al selected from the group consisting of hydrogen, alkyl groups having 1 to about 10 carbon~, hydroxyalkyl groups haviny 2 to about 4 carbon atoms, hydroxyalkyleneoxy groups and hydroxypolyalkyleneoxy groups and R''' i8 the same as R' or R'' except that it cannot be hydrogen, with the provisos that:
said hydroxya~kyl, hydroxyalkyleneoxy and hydroxypolyalkyleneoxy groups contain at least 1 OH
group said R' ~nd R~' or R' ~nd R~'~ groups ~an unite to form a carbon rin~ structure; ~nd D~15116-1 ~L2~
~ aid carbamate derivative6 contain either ~t least one -NH and one -OH group or at least two O~ groups;
(d3 a cro~slinking amount of a cro~slinking agent; ~nd - (e) optionally a catalytic 3mount of a crossllnki~g çat~lyst.
In th~ above carbamate derivative~ ~xcept for hydrogen, the monovalent r~dioal~ may be substituted with ether, halogen, quaternary ammonium, ~ulfonium~ phosphonium and lik~
substituent~.
Suitable organic polymers for use in the present invention include polymers which oontain a plurality of reactive -OH and/or -NHCOO -groups.
Pref~rred crosslinkable organio polymers for use in this invention having as ~n integral part of their structure a plurality of reactive -OH
and~or -NB groups include:
Polyurethane resins Polyester alkyd resins ~ydroxyl containing epoxy fatty acid esters Hydroxyl containing polyesters ~ydroxyl sontaining alkyd resins Hydroxyl eontaining aorylic interpolymers exoept acrylamides ~ydroxyl con~ining vinyl inteepolymers~
~ uch a~ ~tyrene/~crylic copolymers.
The ratio of the ~mvunts of ~olvent and reactive diluent 3r co~olvent u~ed to prepare the coating oompo~ition~ i8 aictated by ~he type of coating desired. ~hu~ in the dispersion type~ the 9~ 7 amount of reactive diluent is usually determined by the film properties desired. Usually these can be attained by ratios of reactive diluen~Jsolvent in t~e range of abou~ 5/95 to about 30~70. On the other hand in the solution type the ratio of reactive cosQlvent to 801vent i8 ~imited ~y the ~olubility charao~eri~tlcs of the polymer. Thus a more ~oluble po~ymer would require le~ ~eact~ve co~olvent ~hile a les~ soluble polymer would require more. Generally, polymer~ of the~e type~ are ~oluble in a blend of reactive cosolvent/~olvent of about 20/80 to about 60/40. In practice the base coating may be formulated at rather high ratios of reactive cosolvent/solvent i.e., about 60~40 to about 90~10 and then let down with solvent to attain application viscositie6. One skilled in the art can easily establish the optimum ratio~ for a particular coating co~position with a minimum of experimentation. The amount of organic polymer used in these compositions i8 not narrowly critical.
However, a practical range for the solution type is about 15 to abou~ 45% by weight of polymer with the amount of reactive solvent bein~ about 10 ~o about Z0~ by weight, the amount of crosslinker being about 10 to about 30% by weight and the amount of ~olvent being about 60 to ~bout 5~ by weight.
A practical range of organic polymer used for the disper~ion type of coating oomposi~ion is about 35 to about 50~ by weight, with the amount of reactive diluent being about S to about 20% by weight, the amount of crosslinker being about 5 to ` ~ 2 about ~0~ by weight and the amount o solvent being ,about 55 to about 10% by weight.
The rea~tive ~arbamate derivatives in the coatlng composition claimed herein can be designated aE eith~r react~ve co~olventl~ or reactive d~luent~
depending on the type o coat:ings formed. In the ca~e of coating compositlon~ which are dispersion~, the carbamates function ~8 reactive a~luents. In ~he c~se of coating compositions which ~re ~olutions, the carbamates function as reactive cosolvents.
The term reactive i~; used herein to mean that the carbamate derivatives can be incorporated into the finished coating by crosslinking agents which cure through NH and/or OH groups.
The reactive carbamates used in this invention may be represented by the following:
butyl 6-hydroxyhexylcarbamate 2-ethylhexyl 4-hydroxybutylcarbamate butyl 2-hydroxyethylcarbamate 2-ethylhexyl 2,3-dihydroxy-1-propylcarbamate butyl 2,3-dihy~roxy-1-propylcarbamate hexyl bi~(2-hydroxyethyl)carbamate ~-(2-hydroxyethoxy) ethyl carbamate 4-hydroxybutyl carbamate 2-hydroxy-1-propyl carbamate l-hydroxy-2-propyl carbamate 2-hydroxyethyl carbamate 1,3dihyd~oxy-2-propyl carbamate ` 2,3-di~ydroxy-1-propyl carbamate 2-hydroxydecyl carbamate l-(hydroxymethyl)nonyl carbamate 5~6~
2-hydroxyethyl ~2-hydroxyethyl)-.~ethyl)carbamate 1,3-dihydroxy~2~propyl dimethylcarbamate 2,3-dihydroxy-~-propyl dime~hylcarba~ate 2,3-dlhydroxy-1-pro~pyl tetramethyl~n~-carbam~te 2-hydroxy~thyl bi8-(2 hydroxyethyl)carbamate 3-(2,~-dlhydroxy-1-lpropyl) oxa~olidone 2-hydroxyethyl dimethyl carbamate 3-~2-hydroxyethyl)-!5-(hydroxymethylene)-oxazolidone 3-(2-hydroxyethyl) oxa~olidone 2-hydroxyethyl l-butylcarbamate l-hydroxy 2-propyl l-propylcarbamate 2-hydroxy-1-propyl l-propylcarbamate l-hydroxy-2-propyl l-butylcarbamate 2-hydroxy-1-propyl l-butylcar~ama~e 2-methyl-1-propyl 2-hydr~xyethylcarbamate 2-propyl bis(2-hydroxyethyl)carbamate 2-hydroxyethyl methylcarbamate 2-hydroxyethyl 2-hydroxyethylcarbamate 2,3-dihydroxy-1-propyl ethylcarbamate 1~3-dihydroxy-2-propyl 1 butylcarbamate 5-~hydroxyme~hylene) oxazolidone 4-(hydroxymethylene) oxazolidone 1,3-dihydroxy-2-propyl ethylcarbamate 2-hydroxyethyl ethylcarbamate 2-hydroxyethyl 2-methylpropylcarbam~te 2-hydroxy-1-propyl 2-ethylhexylcarbamate 2,3-dihydroxy l-propyl l-butylcarbamate l-hydr~xy-2-propyl ~-e~hylhexylcarbamate 5-(hydroxymethylen~)oxazolid~ne 1,3-dihydroxy-2 propyl tetramethylene carbamate 5-hydroxypyrazolidone 2-hydrcxyethyl (propyl)(2-hydroxyethyl~carbamate - 2-hydroxy-1-propyl 2-hydroxye~hylcarbamate 2-hydroxyethyl 3-hydroxy 2,2-dimethyl-1-propylcarbamate.
Illus~r~tive of su~table crossllnking agents for the high solids coating compos~tions described here~n ~re me~hylol phenol5, ~uch as 2,4,6-trimethylolphenol, polyepoxide~, such as the glycidyl epoxides or cycloaliphatic epoxides (Araldite~ 297, epOn* 582, etc.) and ~he aminoplasts ~uch as the reaction product of an aldehyde (e.g.
formaldehyde, acetaldehyde, paraPormaldehyde, trioxane, e~c.) with urea, ~hiourea, melamine, benzsguanamine, ace~oguanamine, dicyandiamine and the like. The aminoplasts may be etherified with a lower alcohol such a~ me~hyl, ethyl, butyl, isobutyl, propyl or i~opropyl al~ohol~ Aminoplasts which are of particular value in high olids coating compositions are the methylate~ urea~formaldehyde resins, the alkyl~ted benzoguanamines and methylated melamine-formaldehyde resins with the latter being the most desir~ble.
~ owever ~he crosslinking agent is not an aminoplast unles~ ~here are two or more or no ~
group~ on the R' " moiety or unle~ R' and R'' are each hydrogen or neither R' nor R'' is hydrogen.
The choice of c~talyst6 ~uitable ~or the pr~ct~ce of t~i~ inven~ion i~ dictated by the choice .. . . .
3~;2~7~i~
-- 1~
of cros~linking reaction. Thu~ if aminoplasts are employed to crosslink the organic polymer and reacti~e carba~ate, an acidic catalyst ~
preferred. Illu~trative of the acidlc cat~lyst of the invention are one or more of the following:
~lkyl~ulfonic acids ~uch as methane ~ulfonic ~cid, ethane sulfonic acld and the like, aryl~ul~onlc acids such as p-toluene ~ulfonic ac~d, alkylaryl ~ulfonic acids ~uch ~5 ~ ~10 1 ~18 ~1 y sulfonic acidr dialkyl hydrog~n phosphates ~uch as diamyl hydrogen phosph~te, aryl hydroyen phosphates ~uch as diphenyl hydrogen phosphate and phosphoric acid itself.
The diisocyana~es and blocked diisocyanates are often employed to crosslink these polymers. The polymer i~ocyanates have been extensively reviewed by Wicks (Prog. Org. Chem. 3, 73 ~1975~). A blocked isocyanate is an i~ooyanate adduc~ which is ~table at ~mbient conditions but dissociate~ to regenerate isocyanate functionality unde~ the influence of hea~. Temperatures of 120 to about 250DC are neces ary to release the blocking groups which are usually volatilized from the coating. The dissociation temperature of blo~ked isocyanates ba~ed on commercially u~ili2ed blocking agents decrease in the order: epsilon-caprolactam, phenols~
methyl ethyl ketoxime, and a~ti~e methylene compound6. Blo~ked isocyan~tes which are ~table have been described by Rosth~user ~nd ~illiams (Proc~eding6 Polymeric ~terials Science and Engineer~ng: ~ol. 509 pg. 344 (1984)~o Ca~alysts whlch promote the ure~hane r2~ction are well known . ~29~7~7 to the art and are illu~trated by tertiary amines ~uch as triethyl amine, bis(dimethylaminoethyl) ether and the li~e, organometallic ~alt~ of tin, mercury, zinc, bismuth and ~he like such as dibutyl ~in diacetat~ zinc octoate, phenyl mercuric acetate and bismuth octoate.
The amount ~f cataly~t requlred to promote the react~on ~ dependent upon the curing conditions requ~red in the coa~ing process. ~hose skilled in the art may readily determine the cataly t level with a minimum of experimentation. In practlce if a catalyst is desired it is usually in the level of .02 to about 1~ based on the weight of the organic polymer.
Background of the curing relations of hexamethoxymethylmelamine may be found in an article by R. Saxon et al. in J. Appl. Poly, Sci. 8, 475 (1964).
The invention is further described in the examples which follow. All parts and percentages are by weight unless other~ise ~pecifiedO
Example 1 PREPARATIO~ OF 2-HYDROXYET~YL D~METHYLC~RB~MATE
When ethylene carbonate i~ treated ~s in U.S. 4,520,167 with an equimolar ~mount of dimethylamine, a mixture containing 2-hydroxyethyl dimethylcarbamate i~ obtained.
Ex~mple 2 PREPARATION O~ 3-(2-HYDROXYET~YL) OX~ZOLIDON~
When dimethyl carbonate is treated with an equimolar ~ount o~ diethanolamine, a mixture ~ont~ining 3-~2-hy~roxye~hyl~oxazolidone is obtained.
~2~;7~'~
~ 18 Example 3 (2-HYDROXYETHYL) (ETHYL) CARBAMATE
,, , , ~
When ethylene carbonate ~ treated 88 in E~ample 1 with an e~ui~olar amount of N-ethyl ethanolamine, a mixture containing 2-hydroxyethyl (2-hydroxyethyl) 5ethyl) carba~at~ 1~ obtained~
Ex~mple 4 3~~2-HYDROXYETHYL) O~AZOLIDONE/CARGILL-7451 , When 3-(2-hydroxyethyl)oxazolidone i8 combined with CELLOSOLVE* Acetate ~olYent, Cargill~-7451 resin, C~ME~*-303 crosslinker (in ~n amount toichiometrically equivalen~ to the sum of resin and oxazolidone~ and p-toluenesulfonic acid catalyst~ a mixture is obtained which can be thermally cured into a hard, tough, glo~sy coating.
2-HYDROXYETHYL l2-HYDROXYETHYL) (ETHYL~
CARBA~.ATE/SARGILL~-7451 RESIN
CROSSLINKED BY CYMEL~ 303 When Example 4 is repeated with the exception that 2-hydroxyethyl~2-hydroxyethyl) (e~hyl) carbamate is substituted for 3-(2-hydroxyethyl) oxazolidone, a mixture i~
obtained which can be thermally cured into a tough, hard, glossy coating.
D-1~116-1 . .
S~7 PREPARATION OF
1,3-DIHYDROXY-2-PRoPYL CAR~AMATE AND
2~3-DIHYDROXY-l-PROPYL CARBAMAT~
__.__ When glycerine i8 treated with dimethylcarbonate, a ~ixture ~8 obtained wh~ch con~aln~ cyclic carbonates of glycerine ~4-hy~r~xymethyl-1,3-dioxol-2-one and 5-hydroxy-1,3-aioxan-2-one). When the mixture containing the~e cyclic carbonate~ i~ treated wi~h ammonia, another mixture is obtained which contains 1,3-dibydroxy-2-propyl carbamate and 2,3-dihydroxy-1-propyl carbamate.
PREPARATION OF
1~3-DlHyDRoxy-2-pRopyL ~ETRAMETHYLENE GARBAMAT~
AND 2 3-DIHYDROXY-l-PROPYL TETRAMETHYLENE CARBAMATE
~ hen Example 5 is followed except th~t the ammonia is replaced by pyrrolidine, a mixture is obtained which contains 1,3-dihydroxy-2-propyl tetramethylene carbamate and 2,3-dihydroxy-1-propyl tetramethylenecarbamate.
1,~ DIHYDROXY-2-PROPYL ~E~RAMETHYLENE CAR~AMATE AND
2,3 DIHYDROXY-l-PROPYL TETRAMETHYLENE CARBAMATE AND
CARGILL~ 745I RESIN CROSSLINKED BY CYMEL~ 303 A mixture containing 1,3-dihydroxy-2-propyl tetramet~ylenecarbamate, 7,3-dihydroxy l-propyl tetrame~hylenecarba~a~e, CELLOSOLVE ~cetate Solvent, CARGILL-~451 ~esin9 CYMEL-303 ~rosslinker and p-toluenesulfonic a~id catalyst is thermally cured to give ~ hard, tough glossy so~ting.
- 20 _ 3L~9~;~æ~
. PREPARATION OF HYDROXYETHYL BUT'YLCARBAMATE
274.8 Grams of ethylene carbonate ~3.12 moles~ were placed ln ~ round bottom flask equ~pped with ~tirrer, thermometer, addition funnel and reflux ~ondenser. 228.2 Grams ~3.12 ~ole) of butylamine ~ere charged to the ~dd$tion funnel and added to the ~tirred contentl3 of the fl~sk ~t a rAte ~ufficient to maintain them ~3~ 50-80C~ Crude product p~rity by gas chromatography was 90.6 area %
after the mixture had been a:Llowed to ~tand overnight. Stripping ~n a rotary evaporator gave 449.9 9. of product of 92.3 area % purity. The yield, corrected for purity, was 83.1~. A portion of the material was di~tilled at 2 mm Hg boiling from 124 to 126C and having area ~ purity 95.1%.
Hydroxyethyl butylcarbamate is a good solvent for a polyester re~in SCargill ~7451).
Example 10 PREPARATION O~ 2=HYDROXYETHYL METHYLCARBAMA~E
44 Grams (.5 m~le) of ethylene carbonate were placed in a 250-ml round bottom flask equipped with stirrer, addition funnel~ and thermometer.
38.75 Grams of 40~ aqueou~ methylamine (15.5 g., .5 mole contained methylamine) were charged to the addition funnel and added to the fl~k with stirring over 1025 hr. and with the fla~k contents at 38 to $2C. The resulting mixture was subjected to vacuum di~tillation giving 42.54 9. (3S.7%) of clear, c410rless liquid product boiling ~t 140C at 8 mm ~9~ The infrared ~pectrum of thi~ material was consistent with the proposed ~tructure. Purity by D~1$116-1 7~
gas chromatography was 97.8 area ~ The product had a melting point of approximately -36C and was ~iscible with water.
Example 11 PREPARATIO~ 0~ HYDROXYPRO~PYL BUTYLCARBAMATES
290.96 grams ~2.85 ~oles) of propyl~ne carbonate were ~harged to ~ 2~ round bottom fl2sk equipp~d w~th stirr~r, heater, thermometer, addition funnel and reflux condenser. 211.3 Grams ~2.85 moles) of butylamine were charged ~o the addition funnel and 610wly added to th~e ~lask contents. The maximum temperature of the reaction was 98C. The material was allowed to stand and a sample ~ubmitted for infrared analysis. The infrared spectrum was consistent with the proposed structures (i.e. an isomeric mixture of 2-hydroxy-1 and l-hydroxy -2-propyl l-butylcarbamates~. The proposed structures given above were confirmed by Proton NMR
analysis.
ExamPle 12 HYDROXYETHYL BUTYLCARBAMATE/CARGILL~-7451 RESIN
CROSSLINKED ~Y A BLOCKED AROMATIC ISOCYANATE
PREPOLYMER BASED ON TOLUENE DIISOCYANATE
A mixture of hydroxyethyl butylcarbamate, Cargill -7451 Resin, CELLOSOI,VE Ace~a~e and a blocked aromatic icocyanate prepolymer based on toluene diisocyanate (as taught in U.S. 4,518,522 ~ssigned to Mobay) is ~hermally ~ured to a hard, tough glos~y coating.
7g~7 HYDROXYETHYLBUTYL CARBAMATE AND CARGILL~ 7451 RESIN CROSSLIN~ED BY LPON't828 A mixture of ~ydroxyethyl bu~ylcarbamate, Cargill -7451 resin, CELLOSOLVE Acetate, EPON -B2~ and an amine ~atalyst ~ thermally cured to afford ~ hard, tough, 91088y coating.
Example l4 PREP~RATION OF HYDROXYPROPYL PROPYL~ARBAMATES
. .
722 Grams (7.0 moles ~ 99% purity3 of propylene carbonate was charged to a 2 1 round-bottom flask ~quipped with ~tirrer, heating mantle thermometer, feed tank and distillation head. The flask and contents wer~ hea~ed with stirring under nitrogen to 50C. At this point addition of 436 grams 17 moles ~ 98~ purity) of n-propylamine was begun and continued for a total of 3.25 hrs. during which time the temperature was maintained between 50 ~nd 62C without external heat. The temperature was then raised to 72C and held at this value for an additional 3 hrsO then the flask and contents were allowed to cool and stand overnight. ~ights were removed by heating to a maximum temperature oP 105C under 2 mm Hg pressure during l hr. with ~tirring.
~ as chromatographic analysis of this material showed 96.8 ~rea % product.
D-15116-l 23 ~Z~7&7 Example 15 When Example 9 is followed except that a chemically equivalen~ amount of 2-e~hylhexyl amine i8 ~ubstituted for n-butylamine, a m~xture containing 2-hydroxyethyl 2-ethylhexylcarbamate i~
obtained.
i ~xample _ SYNTHESI~ OF HYDROXYPROPYL 2-ETHYLHEXYLCARBA~ATES
When Example 14 is followed except that a chemically equivalent amount of 2-ethylhexylamine is substituted for n-propylamine, an isomeric mixture of 2-hydroxy-1-propyl ~-ethylhexylcarbamate and l-hydroxy-2~propyl 2-ethylhexylcarbamate i8 obtained.
Example 17 PREPARATION O~ 2-METHYL-l-PROPYL
(2-HYDROXYETHYL)CARBAMATE
An equimolar mixture of di(2~me~hyl-1-propyl~carbonate and ethanolamine is allowed to react resulting in formation of a mixture containing 2-methyl-1-propyl (2-hydroxyethyl)carbamate.
Example 18 (2-HYDROXYETHYL)CARBAMATE
When example 9 i~ followed except that a chemically equivalent amount of e~hanolamine is ubstituted for n-butylamine, a mixture containin~
2-hydroxyethyl ~2-hydroxyethyl)carbamate is obtained.
- 24 - ~ 2 Example 19 SYNTHESIS OF BUTYL
2,3-DIHYDROXYPROPYLCAR~AMATE
, An ~uimolar mixture 9f dibu~ylcarbonate and 3-amino-1~2-propanediol is allowed to react resulting in formatlon of ~ mixture containing butyl 2,3 dihydroxypropylcarbamate.
~ y~__2~
1-~YDROXY-2-PROPYL 1- BU~YL CARBAMATE
2-HYDROXY-l- iRoPYL l-~UTYL CARBAMA~2 CARGILL~ 7451 RESIN C~OS5LINKED BY A
BLOCKED AROMATIC ISOCYANAIE P~EPOLYMrR
When example 12 is followed excepting that a chemically equivalent amount of an isomeric mixture of l-hydroxy-2-propyl l-butylcarbamate and ~-hydroxy-l-propyl l-butyl carbamate i~ substitu~ed ~or hydroxyethyl butylcarbamate, a mixture is obtained which can be thermally cured to a hard, tough, glossy coating.
Exam~ 21 l-HYDROXY-2-PROPYL l-PROPYLCARBAMATE, ? HYDROXY 1-PROPYL l-PROPYLCARBAMATE~ CARGILL* 7451 RESIN CROSSLINXED BY A BLOCKED AROMATIC ISOCYANAT~
PREPOLYMER BASED ON TOLUENE DIISOCYA ~TE.
When Example 12 i8 followed except that a chemically equivalent amou~t of an i~omeric mixture of l-hydroxy-2-propyl l-propylcarbamate and 2-hydroxyl-1-propyl l-propylcarbamate ~s substituted for 2-hydroxyethyl l-butylcarbamate, a hard, glossy, tough coating is obtained.
D~15116-1 ,~ , . . .
- 25 ~
Example 22 PREPARATION OF 5-(HYDROXYMETHYLENE30XAZOL~DONE
AND 5-HYDROXPYRAZOLI~O~E
An equimolar mixture of dimethyl carbonate and 3-amino-1,2-propanediol i~ allowed to react re6ultlng ~n a mixt~re containing 5-(hydroxymethylenel oxazol~done and 5-hydroxypyrazolidone .
Example 23 PREPARATION OF 2-HYDROXYET~YL 3-HYDROX~-2 ~ ?-DIMETHYL-l-PRO~PYLCARBAMATE ~
An equimolar mixture of ethylene carbonate and 3-amino-2,2-dimethyl-1-propanol i9 allowed to react resulting in ~ mixture containing 2-hydroxyethyl 3-hydroxy-2,2-dimethyl-1 pr~pylcarbamate.
PREPARATION OF 2-HYDROXYETHYL ~PROPYL3 (2-HYDROXYETHYL)CARBAMATE
When Example ~ is followed except that the butylamine is replaced by an equimolar amount of N-propyl ethanolamine, a mixture is obtained which contains 2-hydroxyethyl (propyl)~2-hydroxyethyl)-carbamate.
Example 25 PREPA~ATION OF 2-HYDROXYETHYL CARBAMATE
~ hen ethylene carbonate (1~3 dioxol-2-one) i8 treated with ammonia a mixture i8 obtained which contains 2-hydroxyethyl carbamate.
.. . .
- 26 ~
Example 26 PREPARATION OF 2-(2-HYDR0%YETHOXY)ETNYL CARBAMA~E
~ hen urea iR treated with diethylene ~lycol (2-(2-hydroxyetho~y) ethanol~, a mlxture i~ obtained which contains 2-~2-hydroxyethoxy)ethyl carbamate~
~ 27 PREPARATION 0~ YDROXY~U~YL CARBAMATE
, When ure~ l~ treateld with 1,4 butanediol, a mixture is obta~ned which contains ~hydroxybutyl carbamate.
Example 28 PREPARATION OF A MIXTURE 0~ 2-HYDROXYDECYL
CAR~AMATE AND l-(HYDROXYMETHYL)I~ONYL CARBAMATE
~ .
When urea i~ treated with 1,2-decanediol, a mixture ic obtained which contains 2-hydroxydecyl : carba~ate and l-(hydroxymethyl~ nonyl carbamate.
2-HYDROXYDECYL CARBAMATE, l-(HYDROXY-METHYL~NONYL CARBAMATE AND
A mixture of 2-hydroxydecyl carbamate, l-(hydro~ymethyl)nonyl carbamat~, ~ELLOSOLVE*
Acetate, Carqill-7451 Resin, Cymel~-303 ~rosslinker and p-toluene~ul~onlc acid is thermally cured to ~ive a h~rd, tough, glossy coating.
PREPARATIO~ OF BVTYL_2-HYDROXYETHYLCARBAMATE
When dibutylcarbonate i~ treated wi~h 2-aminoethanol ~ mixture is obtained which contains butyl 2-hydroxyethy~carbamate.
5~
.PREPARATION OF 2-ETHYLHEXYL 4-HYDROXYBUTYLCARBAMATE
_ When di~2-ethylhexyl)carbonate i8 treated with 4-ami~o-1-bu~anol, a ~ixture is obtained which contalns 2-ethylhexyl 4-hydroxybutylcarba~at2 ~ ~2 -PREPARATION OF BUTYL 6-HYI)ROXYHEXYLCARBA~T~
When dibutylcarbonate i8 treated with 6-fimino-l hexanol ~ mixture i~ obtained which contai~s butyl 6-hydroxy hexy]Lcarbamate.
Example :33 CARGILL~-7451 RESIN CROSSLINKED_BY
-A mixture containing butyl 6-hydroxyhexylcarbamate, CELLOSOLVE Acetate Solvent, Cargill-7451 resin and Cymel-327 cr~sslinker is thermally cured to give a hard, tough, ~lossy coating.
~ lthough the inYention ha~ been described in its preferred forms with a certain degree of particularity, it is understood that the present disclosure has been made only by way of example and that numerous changes can ~e made wi~hout depar~ing rom the spirit and the ~cope of the invention.
Claims (56)
1. Method of making solvent borne high solids coating compositions which comprises blending:
(a) at least one crosslinkable organic polymer free of amide groups;
(b) organic solvent;
(c) at least one reactive carbamate derivative having the generic formula:
wherein each of R' and R" is a monovalant radical selected from the group consisting of hydrogen, alkyl groups having 1 to 10 carbons, hydroxyalkyl groups having 2 to about 4 carbon atoms, hydroxyalkyleneoxy groups and hydroxypolalkyleneoxy groups and R''' is the same as R' and R" except that it cannot be hydrogen, with the provisos that:
said hydroxyalkyl, hydroxyalkyleneoxy and hydroxypolalkyleneoxy groups contain at least 1 OH
group;
said R' and R" or R' and R''' groups can unite to form a carbon ring structure; and said carbamate derivatives contain either at least one -NH and one -OH group or at least two OH groups;
(d) a crosslinking amount of a crosslinking agent; and (e) optionally a catalytic amount of a crosslinking catalyst.
(a) at least one crosslinkable organic polymer free of amide groups;
(b) organic solvent;
(c) at least one reactive carbamate derivative having the generic formula:
wherein each of R' and R" is a monovalant radical selected from the group consisting of hydrogen, alkyl groups having 1 to 10 carbons, hydroxyalkyl groups having 2 to about 4 carbon atoms, hydroxyalkyleneoxy groups and hydroxypolalkyleneoxy groups and R''' is the same as R' and R" except that it cannot be hydrogen, with the provisos that:
said hydroxyalkyl, hydroxyalkyleneoxy and hydroxypolalkyleneoxy groups contain at least 1 OH
group;
said R' and R" or R' and R''' groups can unite to form a carbon ring structure; and said carbamate derivatives contain either at least one -NH and one -OH group or at least two OH groups;
(d) a crosslinking amount of a crosslinking agent; and (e) optionally a catalytic amount of a crosslinking catalyst.
2. Method claimed in claim 1 wherein R' and R" are each methyl and R''' is 1,3-dihydroxy-2-propyl.
3. Method claimed in claim 1 wherein R' is ethyl and R" and R''' are each hydroxyethyl.
4. Method claimed in claim 1 wherein R' and R" are each methyl and R'''is 2,3-dihydroxy-1-propyl.
5. Method claimed in claim 1 wherein R' and R" are linked to form a carbon ring structure and R''' is 2,3-dihydroxy-1-propyl.
6. Method claimed in claim 1 wherein R' and R" are linked to form a tetramethylene chain and R''' is 2,3-dihydroxy-1-propyl.
7. Method claimed in claim 1 wherein R' is hydrogen, R" is 6-hydroxyhexyl and R''' is butyl.
8. Method claimed in claim 1 wherein R''' is 2-hydroxyethyl and R' and R" are each hydrogen.
9. Method claimed in claim 1 wherein R''' is 4-hydroxybutyl and R' and R" are each hydrogen.
10. Method claimed in claim 1 wherein R''' is 1-hydroxy-2-propyl and R' and R" are each hydrogen.
11. Method claimed in claim 1 wherein R''' is 2-hydroxy-1-propyl and R' and R" are each hydrogen.
12. Method claimed in claim 1 wherein R''' is 2-hydroxydecyl and R' and R'' are each hydrogen.
13. Method claimed in claim 1 wherein R''' is l-(hydroxymethyl)nonyl and R' and R'' are each hydrogen.
14. Method claimed in claim 1 wherein R' is hydrogen, R" is methyl and R''' is hydroxyethyl wherein the crosslinking agent is one other than an aminoplast.
15. Method claimed in claim 1 wherein R' is hydrogen, R'' is butyl and R''' is hydroxybutyl wherein the crosslinking agent is one other than an aminoplast.
16. Method claimed in claim 1 wherein R' is hydrogen, R'' is butyl and R''' is hydroxypropyl wherein the crosslinking agent is one other than an aminoplast.
17. Method claimed in claim 1 wherein R' is hydrogen, R'' is 2-ethylhexyl and R''' is hydroxyethyl wherein the crosslinking agent is one other than an aminoplast.
18. Method claimed in claim 1 wherein R' is hydrogen, R'' is isobutyl and R''' is 2-hydroxyethyl wherein the crosslinking agent is one other than an aminoplast.
19. Method claimed in claim 1 wherein R' is n-propyl and R" and R''' are each hydroxyethyl.
20. Method claimed in claim 1 wherein R' is hydrogen and R'' and R''' are each hydroxyethyl.
21. Method claimed in claim 1 wherein R' is hydrogen, R'' is hydroxyethyl and R''' is 2-hydroxy-1-propyl.
22. Method claimed in claim 1 wherein R' and R'' are each methyl and R''' is 1,3-dihydroxy-2-propyl.
23. Method claimed in claim 1 wherein the organic polymer is a hydroxyl containing polyester alkyd resin.
24. Method claimed in claim 1 wherein the organic polymer is a hydroxy containing epoxy fatty acid ester.
25. Method claimed in claim 1 wherein the organic polymer is a hydroxy containing polyester.
26. Method claimed in claim 1 wherein the organic polymer is a hydroxy containing alkyd resin.
27. Method claimed in claim 1 wherein the organic polymer is a hydroxy containing acrylic interpolymer.
28. Method claimed in claim 27 wherein the organic polymer is a homogeneously dispersed, hydroxyl containing acrylic interpolymer,
29. Coating oomposition made by the method claimed in claim 1.
30. Method of coating substrates with organic polymers which comprises:
(1) contacting said substrates with a coating composition prepared by blending:
(A) at least one crosslinkable organic polymer free of amide groups;
(B) organlc solvent;
(C) at least one reactive carbamate derivative having the generic formula:
wherein each of R' and R'' is a monovalent radical selected from the group consisting of hydrogen, alkyl groups having 1 to about 10 carbons, hydroxyalkyl groups having 2 to about 4 carbon atoms, hydroxyalkyleneoxy groups and hydroxypolyalkyleneoxy groups and R''' is the same as R' or R'' except that it cannot be hydrogen, with the provisos that:
said hydroxyalkyl, hydroxyalkyleneoxy and hydroxypolyalkyleneoxy groups contain at least 1 OH
group;
said R' and R" or R' and R''' groups can unite to form a carbon ring structure; and said carbamate derivatives contain either at least one -NH and one -OH group or at least two OH groups;
(D) a crosslinking amount of a crosslinking agent; and (E) optionally a catalytic amount of crosslinking catalyst, and (2) curing said coating composition.
(1) contacting said substrates with a coating composition prepared by blending:
(A) at least one crosslinkable organic polymer free of amide groups;
(B) organlc solvent;
(C) at least one reactive carbamate derivative having the generic formula:
wherein each of R' and R'' is a monovalent radical selected from the group consisting of hydrogen, alkyl groups having 1 to about 10 carbons, hydroxyalkyl groups having 2 to about 4 carbon atoms, hydroxyalkyleneoxy groups and hydroxypolyalkyleneoxy groups and R''' is the same as R' or R'' except that it cannot be hydrogen, with the provisos that:
said hydroxyalkyl, hydroxyalkyleneoxy and hydroxypolyalkyleneoxy groups contain at least 1 OH
group;
said R' and R" or R' and R''' groups can unite to form a carbon ring structure; and said carbamate derivatives contain either at least one -NH and one -OH group or at least two OH groups;
(D) a crosslinking amount of a crosslinking agent; and (E) optionally a catalytic amount of crosslinking catalyst, and (2) curing said coating composition.
31. Method claimed in claim 30 wherein R9 is hydrogen, R" is methyl and R''' is; hydroxyethyl wherein the crosslinking agent is one other than an aminoplast.
32. Method claimed in claim 30 wherein R' is hydrogen, R'' is butyl and R''' is hydroxyethyl wherein the crosslinking agent is one other than an aminoplast.
33. Method claimed in claim 30 wherein R' is hydrogen, R'' is butyl and R "' is hydroxypropyl wherein the crosslinking agent is one other than an aminoplast.
34. Method claimed in claim 30 wherein R' is ethyl, R'' is hydrogen and R''' is hydroxyethyl wherein the crosslinking agent is one other than an aminoplast.
35. Method claimed in claim 30 wherein R' is hydrogen, and R'' is isobutyl and R''' is hydroxyethyl wherein the crosslinking agent is one other than an aminoplast.
36. Method claimed in claim 30 wherein R' is propyl, R'' and R''' are each hydroxyethyl.
37. Method claimed in claim 30 wherein R' is hydrogen, R'' and R''' are each hydroxyethyl wherein the crosslinking agent is one other than an aminoplast.
D-l5116-1
D-l5116-1
38. Method claimed in claim 30 wherein R''' is hydroxyethyl and R' and R'' are each hydrogen.
39. Method claimed in claim 30 wherein R''' is 4-hydroxybutyl and R' and R'' are each hydrogen.
40. Method claimed in claim 30 wherein R''' is 1-hydroxy-2-propyl and R' and R'' are each hydrogen.
41. Method claimed in claim 30 wherein R''' is 2-hydroxy-1-propyl and R' and R'' are each hydrogen.
42. Method claimed in claim 30 wherein R''' is 1-(hydroxymethyl)nonyl and R' and R'' are each hydrogen.
43. Method claimed in claim 30 wherein R' and R'' are each methyl and R''' is 2,3-dihydroxy-1-propyl.
44. Method claimed in claim 30 wherein R' and R'' are linked to form a tetramethylene chain and R''' is 2,3-dihydroxy-1-propyl.
45. Method claimed in claim 30 wherein R' is hydrogen, R'' is 2-hydroxyethyl and R''' is butyl.
46. Method claimed in claim 30 wherein R' is hydrogen, R'' is 6-hydroxyhexyl and R''' is butyl.
47. Method claimed in claim 30 wherein the crosslinking agent is hexamethoxymethylmelamine.
48. Method claimed in claim 47 wherein the crosslinking catalyst is p-toluenesulfonic acid.
49. Method claimed in claim 30 wherein the organic polymer is a hydroxyl containing polyester alkyd resin.
50. Method claimed in claim 30 wherein the organic polymer is a hydroxyl containing epoxy fatty acid ester.
51. Method claimed in claim 30 wherein the organic polymer is a hydroxyl containing polyester.
52. Method claimed in claim 30 wherein the organic polymer is a hydroxyl containing acrylic interpolymer free of amide groups.
53. Method claimed in claim 52 wherein the organic polymer is a homogeneously dispersed, hydroxyl containing acrylic interpolymer free of amide groups.
54. Method claimed in claim 1 wherein the crosslinking agent is one other than an aminoplast.
55. Method claimed in claim 30 wherein the crosslinking agent is one other than an aminoplast.
56. Method claimed in claim 1 wherein the crosslinking agent is a blocked aromatic isocyanate prepolymer based on toluene diisocyanate.
Applications Claiming Priority (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US76396185A | 1985-08-09 | 1985-08-09 | |
| US763,961 | 1985-08-09 | ||
| US77386285A | 1985-09-09 | 1985-09-09 | |
| US77386185A | 1985-09-09 | 1985-09-09 | |
| US77383085A | 1985-09-09 | 1985-09-09 | |
| US773,830 | 1985-09-09 | ||
| US773,862 | 1985-09-09 | ||
| US773,861 | 1985-09-09 | ||
| US79767085A | 1985-11-13 | 1985-11-13 | |
| US797,670 | 1985-11-13 | ||
| US80773885A | 1985-12-11 | 1985-12-11 | |
| US807,738 | 1985-12-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1295767C true CA1295767C (en) | 1992-02-11 |
Family
ID=27560280
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000515629A Expired - Lifetime CA1295767C (en) | 1985-08-09 | 1986-08-08 | Coating organosol containing reactive carbamate diluent |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0233253A1 (en) |
| CA (1) | CA1295767C (en) |
| WO (1) | WO1987000851A1 (en) |
Cited By (5)
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|---|---|---|---|---|
| US6303690B1 (en) * | 1999-12-15 | 2001-10-16 | Basf Corporation | Cathodic electrocoat having a carbamate functional resin and a carbamate functional reactive additive |
| US6362285B1 (en) | 1999-12-15 | 2002-03-26 | Basf Corporation | Curable coating compositions containing carbamate functional reactive additives |
| US6380323B1 (en) | 1999-12-15 | 2002-04-30 | Basf Corporation | Electrocoat resin compositions containing carbamate functional resins having one or more quaternary ammonium groups and at least one carbamate functional reactive additive |
| US6391968B1 (en) | 1999-12-15 | 2002-05-21 | Basf Corporation | Curable coating compositions containing carbamate functional polymers and carbamate functional reactive additives |
| US6541577B2 (en) | 2000-12-06 | 2003-04-01 | Basf Corporation | Carbamate functional polymers and oligomers |
Families Citing this family (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4814382A (en) * | 1986-10-07 | 1989-03-21 | Union Carbide Corporation | Solvent borne high solids coating compositions |
| AU609494B2 (en) * | 1987-08-04 | 1991-05-02 | Union Carbide Corporation | High solids coating compositions |
| US4931157A (en) * | 1988-02-18 | 1990-06-05 | Ppg Industries, Inc. | Epoxy resin advancement using urethane polyols and method for use thereof |
| CA1335291C (en) * | 1988-08-26 | 1995-04-18 | Han Bo Yun | Rheological additive for coating compositions |
| US5356669A (en) * | 1992-10-23 | 1994-10-18 | Basf Corporation | Composite color-plus-clear coating utilizing carbamate-functional polymer composition in the clearcoat |
| TW242644B (en) * | 1992-10-30 | 1995-03-11 | Ppg Industries Inc | |
| US6103816A (en) * | 1992-10-30 | 2000-08-15 | Ppg Industries Ohio, Inc. | Aqueous aminoplast curable film-forming compositions providing films having resistance to acid etching |
| US6235858B1 (en) | 1992-10-30 | 2001-05-22 | Ppg Industries Ohio, Inc. | Aminoplast curable film-forming compositions providing films having resistance to acid etching |
| EP0666874B1 (en) | 1992-10-30 | 1997-03-05 | Ppg Industries, Inc. | Aminoplast-curable film-forming compositions providing films having resistance to acid etching |
| US5854385A (en) * | 1995-10-06 | 1998-12-29 | Basf Corporation | Coating compositions with low molecular weight carbamate or urea component |
| US5744550A (en) * | 1994-11-03 | 1998-04-28 | Basf Corporation | Curable coating compositions containing carbamate additives |
| US5827930A (en) * | 1995-10-06 | 1998-10-27 | Basf Corporation | Curable coating composition |
| US5756213A (en) * | 1995-10-06 | 1998-05-26 | Basf Corporation | Curable coating composition having carbonate-containing component |
| US5770650A (en) * | 1995-10-06 | 1998-06-23 | Basf Corporation | Curable compositions for coatings |
| US6165618A (en) * | 1994-11-03 | 2000-12-26 | Basf Corporation | Curable coating compositions containing carbamate resin and additives |
| US6423788B1 (en) * | 1995-10-06 | 2002-07-23 | Basf Corporation | Curable coating composition |
| US5792810A (en) * | 1995-10-06 | 1998-08-11 | Basf Corporation | Curable coating composition including compound having carbamate and hydroxyl functionality |
| US5976701A (en) * | 1994-04-29 | 1999-11-02 | Ppg Industries Ohio, Inc. | Flexible aminoplast-curable film-forming compositions and composite coating |
| US5709950A (en) * | 1994-04-29 | 1998-01-20 | Ppg Industries, Inc. | Color-plus-clear composite coatings that contain polymers having carbamate functionality |
| DE69508234T2 (en) * | 1994-04-29 | 1999-10-14 | Ppg Industries Inc | FLEXIBLE AMINOPLAST CURABLE, FILM-FORMING COMPOSITIONS AND PRODUCTION OF ACID-RESISTANT FILMS |
| US5559195A (en) * | 1994-12-21 | 1996-09-24 | Basf Corporation | Coating composition containing carbamate functional and acrylamide functional components |
| US6498266B1 (en) | 1995-10-06 | 2002-12-24 | Basf Corporation | Method of preparing a carbamate- or urea-functional compound |
| US5766769A (en) * | 1995-10-06 | 1998-06-16 | Basf Corporation | Curable composition for coatings |
| US6045872A (en) * | 1998-05-01 | 2000-04-04 | Basf Corporation | Method for eliminating wrinkling in composite color-plus-clear coatings, and compositions for use therein |
| US6331596B1 (en) * | 1999-06-28 | 2001-12-18 | Basf Corporation | Method of preparing carbamate-functional polymers |
| US6228953B1 (en) * | 1999-08-20 | 2001-05-08 | Ppg Industries,Ohio, Inc. | Process for the preparation of carbamate functional polymers |
| GB0101736D0 (en) | 2001-01-23 | 2001-03-07 | Unilever Plc | Cosmetic composition |
| DE10129969A1 (en) | 2001-06-21 | 2003-01-09 | Basf Coatings Ag | Mixtures containing carbamate and / or allophanate groups, curable thermally and with actinic radiation |
| US6844395B2 (en) | 2001-12-17 | 2005-01-18 | Basf Corporation | Asymmetric diisocyanate monomers in urethane polymers and oligomers to reduce crystallinity |
| AU2002364601A1 (en) | 2001-12-17 | 2003-06-30 | Basf Corporation | Urethane polymers that reduce the effect of polylactone linkages |
| DE102004018543A1 (en) | 2004-04-14 | 2005-11-10 | Basf Ag | Carbamate-containing triazine derivatives |
| DE102009003283A1 (en) | 2009-05-20 | 2010-11-25 | Basf Se | Use of a coating composition comprising carbamate group-containing 1,3,5-triazine compounds and melamine-formaldehyde resin e.g. in top coats, base coats and/or clear coats, preferably for automotive or transportation coatings |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4520167A (en) * | 1984-02-17 | 1985-05-28 | American Cyanamid Co. | Hydroxyalkyl carbamate diluent for coating compositions and compositions containing the same |
-
1986
- 1986-08-07 WO PCT/US1986/001611 patent/WO1987000851A1/en not_active Application Discontinuation
- 1986-08-07 EP EP86905081A patent/EP0233253A1/en not_active Withdrawn
- 1986-08-08 CA CA000515629A patent/CA1295767C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6303690B1 (en) * | 1999-12-15 | 2001-10-16 | Basf Corporation | Cathodic electrocoat having a carbamate functional resin and a carbamate functional reactive additive |
| US6362285B1 (en) | 1999-12-15 | 2002-03-26 | Basf Corporation | Curable coating compositions containing carbamate functional reactive additives |
| US6380323B1 (en) | 1999-12-15 | 2002-04-30 | Basf Corporation | Electrocoat resin compositions containing carbamate functional resins having one or more quaternary ammonium groups and at least one carbamate functional reactive additive |
| US6391968B1 (en) | 1999-12-15 | 2002-05-21 | Basf Corporation | Curable coating compositions containing carbamate functional polymers and carbamate functional reactive additives |
| US6471843B2 (en) | 1999-12-15 | 2002-10-29 | Basf Corporation | Cathodic electrocoat having a carbamate functional resin and a carbamate functional reactive additive |
| US6541577B2 (en) | 2000-12-06 | 2003-04-01 | Basf Corporation | Carbamate functional polymers and oligomers |
| US6710138B2 (en) | 2000-12-06 | 2004-03-23 | Basf Corporation | Carbamate functional polymers and oligomers |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1987000851A1 (en) | 1987-02-12 |
| EP0233253A1 (en) | 1987-08-26 |
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