CA1168780A - Self-curable resinous compositions useful in coating applications - Google Patents
Self-curable resinous compositions useful in coating applicationsInfo
- Publication number
- CA1168780A CA1168780A CA000381872A CA381872A CA1168780A CA 1168780 A CA1168780 A CA 1168780A CA 000381872 A CA000381872 A CA 000381872A CA 381872 A CA381872 A CA 381872A CA 1168780 A CA1168780 A CA 1168780A
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G85/00—General processes for preparing compounds provided for in this subclass
- C08G85/004—Modification of polymers by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/028—Polyamidoamines
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- 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
- C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4407—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained by polymerisation reactions involving only carbon-to-carbon unsaturated bonds
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4488—Cathodic paints
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S524/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S524/901—Electrodepositable compositions
Abstract
Abstract The present invention relates to N-methylol amide-containing resinous compositions and the methods of preparing them. Aqueous dispersions of the instant resinous composition containing N-methylol amides in amounts sufficient to impart self-curing at comparatively low temperatures are disclosed.
The aqueous dispersions of the instant resinous compositions are useful as coating compositions; they are particularly suited to electrodeposition.
The aqueous dispersions of the instant resinous compositions are useful as coating compositions; they are particularly suited to electrodeposition.
Description
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De~scription . ~
Self-Curable Resi OU9 Compositions Useful in Coating Applications Technical Field The present invention relates to resinou~ coating composition~s which contain N-methylol amide groups.
~ ouncl Art Resinous material.s comprising various forms of N-methylol groups such as etherified N-metllylol &roups are known as being useful in enhancing cure propertie.s of coating ~ compositions. ~lthough coating compositions containing free N-~ethylol groups are highly reactive and well suited to enhance curing properties, they are not favored because of their high reactivity and p~rticular susceptibility to conden-sation reaction with themselves and with otller sources of active hydrogens. Consequently, resinous materiats and for that rnatter coating compositions containing free N-methylol groups, in a~ounts su~ficient to effect good cure have been difficult to prepare and handle. When used in amol1nts suffi-cient to impart good cure properties, the resinous materialscomprising free N-methylol groups can gel prematurely and become~ineffective as coating compositions.
; In consideration of the foregoing, the art has stayed clear of using free N-methylol groups in amounts which will otherwise cure very well. Instead, the N-methylol groups are either used in form~s that are less reactive, e.g., in etheri-fied forms, or in amounts which are not sufficient to effec-tively enhance cure properties.
Tlle present invention, in contrast, provides stable aqueous re~sinous compositions containing free N~nethylol groups in the form of N-methylol am~ide~ in amounts sufficient to impart excellent cure properties at comparatively low temperatures.
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Disclosure of Invention The present invention encompasses an aqueous resinous composition containing a polymer characterized by the pendant group which is oE the structure:
R Rl O R2 R3 wherein X represents sulfur, or an amino group [ N ~ of which R
is hydrogen or a hydrocarbyl group, preferably an alkyl group, containing from about 1 to 6 carbon ,3toms; and wherein R, Rl, R~ and R3, each independently, is hydrogen or hydrocarbyl group, pref~rably an aLkyl group, containing from about l to 6 carbon atoms. More preferably, the alkyl groups contain from about l to 4 carbon atoms. Most preEerahly, R', R, Rl, R2 and R3, each independently, is hydrogen or methyl. The instant aqueous re~sinous compositions may also comprise water-solubilizing groups.
The term "pendant group" as used herein is intendedto include terminal groups as well as pendant groups which are not in terminal position. In the representative structure afore-described, the open valence is satisfied by connecting it to a carbon which is a member of the polymer backbone or a carbon which is a member of the polymer side chain.
In the present invention, aqueous resinous composi-tions containing cationic hase groups, particularly those having pll of 4 or greater are preEerred.
The present invention, further, éncompasses the process of preparing the aqueous resinous composition; said proce~ss comprising reacting a polymer conta~ninp, a pendant ` ~ mercapto group, and/or a pendant amino group which is a primQry andlor secondary amine, or a mixture thereof, in an aqueous medium~with an N-methylol ethylenically unsaturated amide oE
the structure:
HC - C - C - N - CHOII
R Rl O R2 R3 ~ ~ .
.
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wherein R, Rl, R2 and R3, each independently, ls a hydrogen or hydrocarbyl group, preferably an alkyl group, containing from about 1 to 6 carbon atoms. ~ore preEerably, the alkyl group contains from abo~lt 1 to 4 carbon atoms. Most preferably, R, Rl, R2 and R3, each independently, is hydrogen or methyl.
By this invention, aqueous resinous compositions containing N-methylol amide groups in amounts sufficient to provide self~curing resins can be obtained.
The instant aqueous resinous compositions containing water-solubilizing groups are stable and can be used in coating various substrates. It is noteworthy that fLlms obtained from the aqueous compositions, particularly via cathodic electro-deposition, self-cure at low temperatures.
The reslnous compositions of the present invention are prepared by reacting an N-methylol ethylenically unsaturated amide with a polymer which contains a mercapto, and/or a pendant amino group which is a primary and/or secondary amine, or the mixture of the aforesaid polymers.
Some examples of the polymers containing the pendant amino group are those selected from the group consisting of amine adducts 2Q of epoxy group-containing polymers which are preferred, polyamide-amine resins and amino group-containing acrylic polymers. The nature and preparation of these polymers are known in the art. For example, amine adducts o epoxy group-containing polymers are described in U.S. Patent 4,116,900 to Belanger, column 3, line 46, to column 4, line 32; column 5, lines 15-25, and lines 53-62, the portions of which are herein incorporated by reference. Preferred amine adducts of epoxy group-containing polymers are those of polyepoxides with ketimines of polyalkyleneamines. These are described in U.S. Patent 4,017,438 to Jerabek et al, column 3, line 49, to column 4, line 55, and column 7, line 43, to column 5, line 51. U.S. Patent 4,001,156 to Bosso et al, column 3, line 59, to column 5, line 25 discloses epoxy-containing acrylic polymers and their ketimine adduct which can be useful herein.
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Besides the amine adductsofthe epoxy-contalning polymers, examples of other polymers containing pendant amines are poly(amine-amides) including poly(amine-ester-amides) which are prepared by con-densation of dicarboxylic acids, polyamines and, if desired, polyols.
These polymers are described in U~S. Patent 3,799,854 to Jerabek, column 3, lines 19-50.
Also, amino group-containing acrylic polymers can be used.
Rxamples thereof include those described in U.S. Patent 3,953,391 to Dowbenko et al.
Polymers containing pendant: mercapto groups are also known in the art. Examples thereof include those polymers described in U.S. Patent 4,035,272 to McGinniss, see column 1, line 52, to column 2, line 26.
Mixtures of the above-described polymers can also be used.
It is to be noted that the use of the polymers containing mercapto groups provides a means of increasing the N-methylol group content of the instant aqueous resinous composition without increasing their amino group content. This is significant in coating compositions wherein the presence of excess amino groups can adversely affect the coat-out properties of the composition.
As stated hereinbefore, the polymers containing the pendant mercapto and/or amino group or the mixture thereof are reacted in an aqueous medium with the N-methylol ethylenically unsaturated amide.
To enhance the reaction of these polymers in water, they can either be used with, or they can contain solubilizing groups, for example, a cationic group such as an amine salt, which make them compatible with the aqueous medium.
Usually, the polymers contain amino groups which are partially neutralized with acids to form dispersions in aqueous medium; they are subsequently reacted with an N-methylol ethylenically unsaturated amide. The polymers are partially neutralized with organic or inorganic acids such as acetic and lactic acid or phosphoric acid. The extent of neutralization can be about 1 to 80, more usually 5 to 50 percent of the total theoretical neutralization.
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` 1 1L6~7~0 As to the amino groups, the amount contained in the polymer can be characterized as thnt which i9 sufficient to i~
render the resinous composition cationic, that i8, transportable to the cathode when acid-solubili~ed.
The N-methylol ethylenically unsaturated amides which are useful herein are of the following structure:
~IC ~ C - C - N - CH - OH b R Rl R2 R3 ;
wherein R, Rl, R2 and R3, eAch indepeTldent]y~ is a hydrogen or a hydrocarbyl group, preferably an alkyl grcup, containing from ahout I to about 6 carbon atoms More preferably, the alkyl group conta;ns from about 1 to ~ carbon atoms Most preferably, R, Rl, R2 and R3, each independently, i8 methyl or hydrogen. , L
Specific but non-limiting ex~mples of the N-methylol ethyleni-cally unsaturated amide include N-methylolacrylamide, N-methylol- ~
15 methacrylamide and N-(l-hydroxyethyl)acrylamide. Typically, t the N-methylol ethylenically unsaturated amide is in the form of an aqueous solution.
In the preparation of the instant aqueous resinous compositions, the N-methylol ethylenically unsaturated amide i8 20 added to the aqueous dispersion of the amino and/or mercapto group-containing polymer or the mixture thereof in an amount sufficient to provide N-methylol amide groups which impart ~qelf-curing characteristics to the polymer. Self-curing char-acteristics can be determined by solvent resistance of the 25 cured coating. Coatings which can withstand at least 30 acetone double rubs are considered cured. In determining solvent resistance, a cloth is saturated with acetone and the coating rubbed back and forth (douhle rub) until the coating is softened or removed from the substrate The equivalent 30 ratio of the N-methylol etllylenically unsaturated amide to the reacting polymer containing the pendant group can be in the range of 0.1-1.0 to l O, preferably 0.5-1.0 to 1.0 of the N-methylol ethylenically unsaturated amide to the polymer. The equivalent ratio i~ determined by equivalents of unsaturstion 35 in the~N~methylol ethylenically unsaturated amide to the equ;valents of the pendant amino and/or mercapto groups in the polymer.
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Preferably, tl1e N-methylol amide group is present in amounts ranging from ahout l to 20 percent, rnore preferably from ahout 5 to 2n percent by weight (calculated value) as determined by the weight of N-methylol groups (-C~120~1) in relation to the weight of the polymer containing pendant amino and/or mercapto groups.
The amount of water WhiCIl i9 present during the reaction is that which is sufficient to prevent gelation. The amount of water which is used~ of course, depends on the nature and the amount of the N-methylol ethylenically unsaturated amide. The weight ratio of the water to the N-methylol ethylenically unsaturated amide i~ at least 0.5 to l and preferably at least l:l.
The temperature of the reaction can vary over the t range of 20 to 100C. and preferably 20 to 50C. and will depend on the reactants and the desired speed of the reaction.
Too high a temperature may activate the N-methylol ~roups and result in gelation; too low a temperature may result in extremely slow reaction or non-reaction.
The resultant aqueous resinous composition obtained from the reaction is preferably diluted with water. For reasons of stability, it is preferred that the instant aqueous resinnus composition be maintained at a pl~ range of about 4 or greater.
~hile not desiring to he hound to any particular ~ theory, it is believed that the reaction mechanism involved in ; the preparation of the compositions of the present invention is ; that of a Michael addition. The polymee, through the pendant amino or mercapto group, adds to the N-methylol ethylenically unsaturated amide at the site of unsaturation, thereby form-ing the compositions of the present invention.
In general, the instant resinous compositions have molecular weighta within the range of about 500 to 50,000 and preferably about lO00 to 5000. The molecular weight is a calculated value based on stoichiometry, for example, conden-sation polymers such a~s polyglycidyl ethers of polyphenols. If the molecular weight cannot be readlly calculated, for example, acrylic polymers, then the molecular weight is a measured value by Gel Permeation Chromatography using a polystyrene standard.
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Tlle term ~dispersioll" ag used within the context of the preSl?nt inVelltiOIl i8 believe(l to be a tw~-phase, tran~9par-ent, translucellt or opaque aqueous resinous system in which the resin is the dispersed phase and water is the continuous phnse.
5 Average particle size diameter of the resinous phase i8 gen-erally less than 10 and preferably less than 5 microns. The concentration of the resinous phase in the a~ueous medium depends upon the particular end use of the dispersion and in , general is not critical. For example, thé ~l~ueou~ dispersion 10 preferably contains at least I flnd usually from about 5 to , 50 percent by weight resin solids.
For coating applications, the aqueous medium may contain besides water a coalescing solvent~ ~he use of coal-escing solvent may be, in some instances, for improved film t 15 appearance. These solvents include hydrocarbons, alcohols, esters, ethers and ketones. The preferred coalescing solvents include mono-alcohols, glycols and polyols a.s well as ketones and other alcohols. Specific coalescing solvents include isopropanol, butanol, 2-ethylhexanol, isophorone, 4-methoxy-2-20 pentanone, ethylene and propylene glycol, and the monoethyl, monobutyl and monohexyl ethers oF ethylene glycol. The amount of coalescing solvent is not unduly critical and is generally between about 0.01 and 40 percent by weight, preEerably about 0.05 to about 25 percent by weight based on total weight of 25 a~ueous medium.
In most instances, a pigment composition and, if desired, various additives such as surfactants or wetting agents are included in the dispersion. Pigment composition may be any of the conventional types comprising, for example, iron 30 oxides, lead oxides, strontium chromate, carbon black, conl dust, titanium dioxide, talc, barium sulfate, a~s well as color pigments such as cadmium yellow, cadmium red, chromium yellow and the like. Pigmeilt content of the dispersion is usually expressed as pigment-to-resin ratio. In the practice of the 35 present invention, the pigment-to-re~sin ratios are usually within the range of 0.1 to 5:1. The other additives mentioned above are pre~sent in the dispersion in amounts of 0.01 to 3 percent by weight based on total weight of resin solids.
_ . ~ .. . _ .. _ _ ~ _ .
~ :~fi~7~0 Even though films obtained from the aqueous resinous composi-tions self-cure, it may be desirable to comb:Lne them with curing agents.
When used with curing agents, it is preferred that the polymers of the instant aqueous resinous composition also contain active hydrogens which are reactive at elevated temperatures with a curing agent. E~a~lples of active hydrogens are hydroxyl, thiol, primary amine, secondary amine (including imine) and carboxyl.
The curing agents are those which are capable of reacting with the active hydrogens to form a crosslinked product. Examples of suitable curing agents are phenolic resins, aminoplasts and polyisocyanates~ The polyisocyanates should be capped or blocked so that they will not prema-turely react with the active hydrogens.
Suitable aminoplasts for use in the invention are described in U.S. Patent 3,937,679 to Boss et al in column 16, line 3, continuing to column 17, line 47. As disclosed in the aforementioned portions of the '679 patent, the aminoplast can be used in combination with methylol phenol ethers. The aminoplast curing agent usually constitutes about 1-60 and preferably 5-40 percent by weight of the resinous composition based on total weight of the acid-solubilized resinous vehicle and the ; 20 aminoplast.
With regard to the capped or blocked polyisocyanate curing agents, these are described in U.S. Patent 4,104,147, column 7, line 36, continuing to column 8~ line 37. Sufficient capped or blocked polyiso-cyanate is present in the coating system such that the equivalent ratio of latent isocyanate groups to active hydrogens is at least 0.1:1 and preferably about 0.3 to 1:1.
; When the aqueous dispersions described above are employed for use in electrodeposition, the aqueous dispersion containing cationic groups is placed in contact with an electrically conductive anode and an electrically conductive cathode with the surface to be coated being the cathode~
.
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i Eollowing cnntact with the a~1ueous c1ispersion, an adherent film of the coating composition is deposited on the cathode when a sufficient voLtage is impressed between the electrodes. The conditions under which electrodeposition i9 carried out are, in 5 general, similar to those used in electrodeposition of other types of coatings. The applied voltage may be varied and can be, for example, as low as one volt or as high as 300 volts, but typically between 50 and 200 volts. The current density i~ L
usually between 1.0 ampere and 15 amperes per sqnare foot and 10 tends to decrease durillg electrodeposition indicating the formation of an insulating film.
The curable resinous compositions of the present invention can al80 be used in other conventional coating applications such as Elow, dip, spray and roll conting appli-15 cations. It is, however, desired to point out that the process oE electrodeposition is better suited to the application of the aqueous dispersions of the instant resinous contpositions. It has been fou1ld that films obtained from the electrodeposition of the aqueous dispersions self-cure very well and at compara-20 tively low temperatures.
For electrodeposition and other conventional coating applications, the coating composition.q can be applied to a variety of electroconductive 6ubstrates especially metals such as steel, aluminum, copper, magnesium and the like, but also ; 25 including metalli~ed plastic and conductive carbon-coated materials. For other conventional coating applications, the compositions can be applied to non-metallic substrates such as glass, wood and plastic.
After the coating has been applied by electrocoating or flow coating, it is usually cured by baking at temperatures such as 90 to 180~. for about 1 to 30 mintJtes.
Further illustrating the invention are the following examples, which, however, are not to be construed as limiting the invention to their details. All parts and percentages in the examples as well as throughout this specification are by weight unless otherwise indicated.
Exam le I
P
Th;s example shows the reaction of an epoxy polymer with a ketimine of a polyamine followed by reacting the resulting . _ , . . . _ . _ , ... .
3 7 ~ 0 pro-luct in allleotls rr:e(lium with N-m~?thylol ethylel-ica11y unsatllr.ltr~ mi(le to form an aqueouF lispersion of the resinous composition having a p~l of 8.5.
The charge Eor reacting the epoxy polymer with the 5 polyamine was as follows:
- Ingredients Parts by Weight in Grams EPON~8291 2~84.5 Bisphenol A 673.0 Diketimine of diethylenetriamine (73% solids ;n methyl isohutyl ketone ~olvent) 1650.0 Methyl ethyl ketone 500.0 lPolyglycidyl ether of bisphenol A having a molecular weight oE clbout 380 and an epoxy equivalent of about 190 which is available from Shell Chemical Compnny.
The EPON 829 and bisphenol A were akled to a reaction vessel under a nitrogen atmoslhere and heated to 150C. to initiate ~n exotherm. The reaction was allowed to exotherm for about 40 minutes with the highe~st temperature reaching 200nC.
The re~ction mixture was then held at 150C. for ahout 1-1/2 hours allowed to cool to 80C. and diluted with methyl ethyl ketone. The reaction mixture was further allowed to cool to 63~C. whereupon the addition of the methyl isobutyl ketone 7 containing the diketimine of diethylenetriamine was begun and 25 completed over a period of five minutes at a~out 53 C. The t reaction mixture was heated up to 80C. and held at that temperature for an hour.
The reaction mixture had an epoxy equivalent of infinity indicating that substantially all the epoxy function-30 ality h~d leen consumed. The resulting reaction mixture had a solids content of 78 percent.
The epoxy polymer-ketimine adduct prepared as described ahove was reacted with N-methylolacrylamide using the following charge:
35 Ingredients Parts by Wei~ht in ~rams Epoxy polymer-amine adduct prepared as described above228.1 ~actic acid (88Z aqueous) 14.8 N-methylolacrylamide (48~ aq eous) 69.1 H2O (deionized) 2033.0 ~Jr~e ~
6~3780 ~;~
I I , Ihe epoxy polymer-ketillline ad(lllct was di~ested with the lactic flCid flnd 100 ml. oF the water at room temperature for about 30 minutes followed by a dropwise addition of the aqueous N-methylolacrylami(le. ~nother 300 ml. of water was added followed by stirring of the reaction mixture for about one-half hour, then the remainder of the water was added. The reaction mixture was then filtered to give a stable aqueous resinous dispersion of the present invention having a pH of ~.7 and a solids content of 10 percent. L
Ilntreated steel panels were cathodically electroconted E
in the dispersion as produced in Rxample I. Coating at 150 P
volts for 90 seconds flnd baking at 177C. for 30 minlJtes resulted in films that were hard an-l dark in appearance. About 50 double rubs with acetone were req~lired to remove the film 15 from the substrate. Film thickness WflS 0.5 mil. .
When the dispersion was left stirring overnightl no sign of precipitation was observed, and cure response was markedly enhanced. Untreated steel panels were again electro-coated. Coating at 50 volts for 15 seconds an(l baking at 177C. ~or 20 minutes resulted in a film with excellent sol-vent resistance. The film was unaffected by 100 double rubs :
with acetone. Film Lhicklless was 1.5 mils. Similarly, a film coated at 150 volts for 15 seconds and baked at 121C. fos 20 minutes was unaffected by 100 double rubs with acetone.
Example II
This example illustrates the variation of resinousmaterials useful in preparing the instant aqueous resinous compositions. The charge for preparing the epoxy polymer-ketimine adduct was as follows:
30 IngredientsParts by Weight in Grams __ . .
EPON 10011 1395.0 PCP 02002 402.6 .
Xylene 110.7 Benzyldimethylamine 5.1 35 Diketimine of diethylenetriamine 513.0 Methyl ethyl ketone473.3 lnisphenol A based epoxy resin, suppl;ed by Shell Chemical Company, having a molecular weight of 952.
2Polycaprolactonediol~ manufactured by Union Carbide Corporation.
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.. . . .... . . ....
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.. . ... ; ............. .. , ., . _.
6~3~80 Into a propcrly equippel reaction vessel was charged a melt of the ~PON 1001 anl the PCP 0200, in xylene. Under a nitrogen blanket, the mixture wa.5 heated to reflux. Water was .
removed as a xylene a7eotrope over a period of 45 minutes, with the temperature rising to 208~C. A total of 12 ml. of water was renoved; it was then apparent that no more water was present. Thereafter, the reaction mixture was ~llowed to cool to about 135C. ~-en a sample of the reaction mixture was reduced with an equal wei~llt of 2-ethoxyethanol, it had a viscos;ty of A+ ol~ the Gardner-lloldt scale. ~t 130C., benzyl-dimethylamine was ad(le(l to the reaction mixture wllich was then held at this temperature for about 90 m;nutes. At this point, the viscosity of the mixture as determined above was E+. AEter another 30 minutes, the viscosity increased to 11+. The mixture was immediately cooled to 119C., followed by the addition of tlle diketimine. Thefe was an exother-n with the temperature rising to 121C. Two hours later at 110C., methyl ethyl ketone was added dropwise to the mixture. The resultant epoxy-ketimine addllct had a solids content of 68.7 percent.
The epoxy polymer-ketimine addllct prepared as described above was reacted with aqueous N-metilylolacrylamide. The followinF char~e was used in the reaction:
_n~redientsParts by Wei~ht in ~rams Epoxy polymer-amine adduct prepared as described above 268.0 Acetic acid 5.0 H20 (deionized) 239.5 48~ aqueous N-methylolacrylamide - 50.9 Acetic acid 2.5 30 ~'2 (deioni7ed) 602.1 The epoxy-ketimine adduct and the first batch of acetic acid were charged to a suitable reaction vessel. The first batch of water was added dropwise, followed by the addition of the N-methylolacrylamide, very slowly. m e reac- r 35 tion mixture was stirred Eor about 15 minutes followed by the addition of the secon(l batcll of acetic acid. With the remainder of the water, the reaction mixture was slowly thinned into a resultant translucent dispersion which had p p~l tE 8.2.
. . . __ .. . .. . _ _ . _ . , 6 8 ~ 8 0 The ~ollowing illustrates the stability o~ the a(lueolls re~inoug composition~s o~ the instflnt invention. The stability wa9 eValUatt?(l by deterrnining whetller samples of the resinous composition prepared in the manner of Example II
5 formed any sediment after 14 days of aging.
The resinous compositions were evaluated under the following condition~s: in both open and sealed containers and at ordinary room temperature, as well as hot-room temperature of L20 F. (49 C.). In open containers, the compositions were .
10 stirred continuously over the 14 days.
Dispersions of l0 anrl 20 percent solids content were evaluated accordingly and found to form no sediments. Disper-sionfi of 30 percent solids were evaluated with the following D
results: with the exception of the sample in R sealed container stored at 120F. (49C.), no effect on the dispersions w3s observed. At 120F. (49C.), however, the dispersion became somewhat gummy after 14 days of aging.
The following illustrates the stahility and gel-free nature of the aqueous N-methylol resinous composition at 20 varying pll. The stability was evaluated by the method of determining whether the resinous composition formed any sedi-ment after 14 days of aginF, at varying pll. A 15 percent sol;ds ~sample of the resinous compositioll as prepared in Example II having a pll of 8.2 was used as a standard. The 25 sample was contained in an open beaker for 14 days, after which time the pll was 6.5 and no sediment was observed. A fresh sample of the resinous ct~mposition having the pll adjusted to 6.0 with aceeic acid was contained in a beaker for 14 days.
Again no sediment was observed and the pll was 5.9. A third 30 sample having the pll adjusted to 5 with acetic acid was evalu-ated in the same way and found to have no sediment after 14 .
days. The pll changed from 5 to about 5.5. The fourth sample having a pH of 4.1 was evaluated in the same way and found to t have no sediment after 14 days; the pll changed from 4.1 to 1 35 4.2.
; Example III
This example illustrates the agueous resinous compo-sitions obtained from poLymers containing both pendant amino r : : : ~
,............. .... ... .. . , . . , . ____ __ . _.. ..
.
O , j~, _ 14 groups and pen(l.lllt mercapto groups. The charge for the prepara- !
tion is ns follows:
_gredients Parts by Weight in Grams Equivalents ;~
~PON 10011 505 1.00 5 Diben~yl ether 91.8 -- , Diethylenetriamine diketimine 235.9 0.65 Trimethylolpropane-tris-(3-mercaptopropionate) 146.5 1.05 1Polyglycidyl ether of bisphenol ~ having a moLecular weight of about 952, supplied by Shell Chemical Company.
Melted EPON 1001 an(l the diben7yl ether were mixed together and heate(l Eor 30 minutes to 123C. The reaction mix-ture was allowed to cool to ll0C. whereul-on diethylenetriamine diketimine and trimethylolpropane-tris-(3-mercaptopropionate) were added, coolin~ the reaction mixture further to 82C.
There was then an exotherm with the temperature rising to 93C.
The reaction mixture was then heated to 110C., held at this temperature for about 10 minutes and further heated to 117~C.
over a ~eriod of one hour.
The reaction mixture was again allowed to cool to 105C. over a period of about 90 minutes. The resulting product was furtller cooled to about 30C. and poured out of the reaction vessel as a clear dark fluid.
~queous N-methylolacrylamide was reacted with the P
above product using the following charge:
Ingredients Parts by We ~~ht in Grams The above product 213 ~cetic acid (30~ total neutraliæation) 7.5 Water (deionized) 200 30 (~8~ N-methylolacrylamide taqueous) 118.8 Water (deioniæed) 1090.7 The above product was warmed to about 70C. and digested with the acetic acid and the first batch of water for 30 minutes at room temperature. The aqueous N-methylolacryl-amide was then added. The result{ng reaction mixture was heldfor an hour and a half, at room temperature, aEter which the remainder of the water was added to thin the composition to 15 percent resin sol~ds content.
' I
~ ~ 6 ~
Ulltreated sl:eel suhstrntes were cathodically electro~
coated in the dispersion of Example ITI u3inK 100 volts ~or 90 t~
seconds at room temper.3ture. Films having excellent appearance, t insulation arld substrate adhesion were obta;ned.
When haked at 121 C. for 20 minutes, very hard films were obtained which re(luired 70 acetone double rubs to be removed. When baked at 107C. for 20 minute~s, hard film.s were obtained wllich required 75 acetone double rubs to be removed.
When baked at 83C. for 20 minutes, the films required 30-40 double rubs to be removed. Film thicknesses were about 0.5-0.6 miL.
WhiLe the illu~trative embodiments of the invention have been described hereinabove witll particularity, it will be u(lderstood that various modifications will be apparent to and can he readily ma-le by those .skilLed in the art without depart-ing from the scope ~r spirit of the invention. Accordingly, it is intended that claims directed to the invention be construed as encompassing all aspects of the invention which would be treated as equivalents by those skilled in the art to which the inveneion pertain~.
.... , ,, . . ~
, !
De~scription . ~
Self-Curable Resi OU9 Compositions Useful in Coating Applications Technical Field The present invention relates to resinou~ coating composition~s which contain N-methylol amide groups.
~ ouncl Art Resinous material.s comprising various forms of N-methylol groups such as etherified N-metllylol &roups are known as being useful in enhancing cure propertie.s of coating ~ compositions. ~lthough coating compositions containing free N-~ethylol groups are highly reactive and well suited to enhance curing properties, they are not favored because of their high reactivity and p~rticular susceptibility to conden-sation reaction with themselves and with otller sources of active hydrogens. Consequently, resinous materiats and for that rnatter coating compositions containing free N-methylol groups, in a~ounts su~ficient to effect good cure have been difficult to prepare and handle. When used in amol1nts suffi-cient to impart good cure properties, the resinous materialscomprising free N-methylol groups can gel prematurely and become~ineffective as coating compositions.
; In consideration of the foregoing, the art has stayed clear of using free N-methylol groups in amounts which will otherwise cure very well. Instead, the N-methylol groups are either used in form~s that are less reactive, e.g., in etheri-fied forms, or in amounts which are not sufficient to effec-tively enhance cure properties.
Tlle present invention, in contrast, provides stable aqueous re~sinous compositions containing free N~nethylol groups in the form of N-methylol am~ide~ in amounts sufficient to impart excellent cure properties at comparatively low temperatures.
.
:
~ : ~ : ::
:' :
~ 12~ ~ 7 ~
Disclosure of Invention The present invention encompasses an aqueous resinous composition containing a polymer characterized by the pendant group which is oE the structure:
R Rl O R2 R3 wherein X represents sulfur, or an amino group [ N ~ of which R
is hydrogen or a hydrocarbyl group, preferably an alkyl group, containing from about 1 to 6 carbon ,3toms; and wherein R, Rl, R~ and R3, each independently, is hydrogen or hydrocarbyl group, pref~rably an aLkyl group, containing from about l to 6 carbon atoms. More preferably, the alkyl groups contain from about l to 4 carbon atoms. Most preEerahly, R', R, Rl, R2 and R3, each independently, is hydrogen or methyl. The instant aqueous re~sinous compositions may also comprise water-solubilizing groups.
The term "pendant group" as used herein is intendedto include terminal groups as well as pendant groups which are not in terminal position. In the representative structure afore-described, the open valence is satisfied by connecting it to a carbon which is a member of the polymer backbone or a carbon which is a member of the polymer side chain.
In the present invention, aqueous resinous composi-tions containing cationic hase groups, particularly those having pll of 4 or greater are preEerred.
The present invention, further, éncompasses the process of preparing the aqueous resinous composition; said proce~ss comprising reacting a polymer conta~ninp, a pendant ` ~ mercapto group, and/or a pendant amino group which is a primQry andlor secondary amine, or a mixture thereof, in an aqueous medium~with an N-methylol ethylenically unsaturated amide oE
the structure:
HC - C - C - N - CHOII
R Rl O R2 R3 ~ ~ .
.
' .
~ :~6~'7~
wherein R, Rl, R2 and R3, each independently, ls a hydrogen or hydrocarbyl group, preferably an alkyl group, containing from about 1 to 6 carbon atoms. ~ore preEerably, the alkyl group contains from abo~lt 1 to 4 carbon atoms. Most preferably, R, Rl, R2 and R3, each independently, is hydrogen or methyl.
By this invention, aqueous resinous compositions containing N-methylol amide groups in amounts sufficient to provide self~curing resins can be obtained.
The instant aqueous resinous compositions containing water-solubilizing groups are stable and can be used in coating various substrates. It is noteworthy that fLlms obtained from the aqueous compositions, particularly via cathodic electro-deposition, self-cure at low temperatures.
The reslnous compositions of the present invention are prepared by reacting an N-methylol ethylenically unsaturated amide with a polymer which contains a mercapto, and/or a pendant amino group which is a primary and/or secondary amine, or the mixture of the aforesaid polymers.
Some examples of the polymers containing the pendant amino group are those selected from the group consisting of amine adducts 2Q of epoxy group-containing polymers which are preferred, polyamide-amine resins and amino group-containing acrylic polymers. The nature and preparation of these polymers are known in the art. For example, amine adducts o epoxy group-containing polymers are described in U.S. Patent 4,116,900 to Belanger, column 3, line 46, to column 4, line 32; column 5, lines 15-25, and lines 53-62, the portions of which are herein incorporated by reference. Preferred amine adducts of epoxy group-containing polymers are those of polyepoxides with ketimines of polyalkyleneamines. These are described in U.S. Patent 4,017,438 to Jerabek et al, column 3, line 49, to column 4, line 55, and column 7, line 43, to column 5, line 51. U.S. Patent 4,001,156 to Bosso et al, column 3, line 59, to column 5, line 25 discloses epoxy-containing acrylic polymers and their ketimine adduct which can be useful herein.
~ ~8~
Besides the amine adductsofthe epoxy-contalning polymers, examples of other polymers containing pendant amines are poly(amine-amides) including poly(amine-ester-amides) which are prepared by con-densation of dicarboxylic acids, polyamines and, if desired, polyols.
These polymers are described in U~S. Patent 3,799,854 to Jerabek, column 3, lines 19-50.
Also, amino group-containing acrylic polymers can be used.
Rxamples thereof include those described in U.S. Patent 3,953,391 to Dowbenko et al.
Polymers containing pendant: mercapto groups are also known in the art. Examples thereof include those polymers described in U.S. Patent 4,035,272 to McGinniss, see column 1, line 52, to column 2, line 26.
Mixtures of the above-described polymers can also be used.
It is to be noted that the use of the polymers containing mercapto groups provides a means of increasing the N-methylol group content of the instant aqueous resinous composition without increasing their amino group content. This is significant in coating compositions wherein the presence of excess amino groups can adversely affect the coat-out properties of the composition.
As stated hereinbefore, the polymers containing the pendant mercapto and/or amino group or the mixture thereof are reacted in an aqueous medium with the N-methylol ethylenically unsaturated amide.
To enhance the reaction of these polymers in water, they can either be used with, or they can contain solubilizing groups, for example, a cationic group such as an amine salt, which make them compatible with the aqueous medium.
Usually, the polymers contain amino groups which are partially neutralized with acids to form dispersions in aqueous medium; they are subsequently reacted with an N-methylol ethylenically unsaturated amide. The polymers are partially neutralized with organic or inorganic acids such as acetic and lactic acid or phosphoric acid. The extent of neutralization can be about 1 to 80, more usually 5 to 50 percent of the total theoretical neutralization.
.
` 1 1L6~7~0 As to the amino groups, the amount contained in the polymer can be characterized as thnt which i9 sufficient to i~
render the resinous composition cationic, that i8, transportable to the cathode when acid-solubili~ed.
The N-methylol ethylenically unsaturated amides which are useful herein are of the following structure:
~IC ~ C - C - N - CH - OH b R Rl R2 R3 ;
wherein R, Rl, R2 and R3, eAch indepeTldent]y~ is a hydrogen or a hydrocarbyl group, preferably an alkyl grcup, containing from ahout I to about 6 carbon atoms More preferably, the alkyl group conta;ns from about 1 to ~ carbon atoms Most preferably, R, Rl, R2 and R3, each independently, i8 methyl or hydrogen. , L
Specific but non-limiting ex~mples of the N-methylol ethyleni-cally unsaturated amide include N-methylolacrylamide, N-methylol- ~
15 methacrylamide and N-(l-hydroxyethyl)acrylamide. Typically, t the N-methylol ethylenically unsaturated amide is in the form of an aqueous solution.
In the preparation of the instant aqueous resinous compositions, the N-methylol ethylenically unsaturated amide i8 20 added to the aqueous dispersion of the amino and/or mercapto group-containing polymer or the mixture thereof in an amount sufficient to provide N-methylol amide groups which impart ~qelf-curing characteristics to the polymer. Self-curing char-acteristics can be determined by solvent resistance of the 25 cured coating. Coatings which can withstand at least 30 acetone double rubs are considered cured. In determining solvent resistance, a cloth is saturated with acetone and the coating rubbed back and forth (douhle rub) until the coating is softened or removed from the substrate The equivalent 30 ratio of the N-methylol etllylenically unsaturated amide to the reacting polymer containing the pendant group can be in the range of 0.1-1.0 to l O, preferably 0.5-1.0 to 1.0 of the N-methylol ethylenically unsaturated amide to the polymer. The equivalent ratio i~ determined by equivalents of unsaturstion 35 in the~N~methylol ethylenically unsaturated amide to the equ;valents of the pendant amino and/or mercapto groups in the polymer.
:
.... . .
7 ~
Preferably, tl1e N-methylol amide group is present in amounts ranging from ahout l to 20 percent, rnore preferably from ahout 5 to 2n percent by weight (calculated value) as determined by the weight of N-methylol groups (-C~120~1) in relation to the weight of the polymer containing pendant amino and/or mercapto groups.
The amount of water WhiCIl i9 present during the reaction is that which is sufficient to prevent gelation. The amount of water which is used~ of course, depends on the nature and the amount of the N-methylol ethylenically unsaturated amide. The weight ratio of the water to the N-methylol ethylenically unsaturated amide i~ at least 0.5 to l and preferably at least l:l.
The temperature of the reaction can vary over the t range of 20 to 100C. and preferably 20 to 50C. and will depend on the reactants and the desired speed of the reaction.
Too high a temperature may activate the N-methylol ~roups and result in gelation; too low a temperature may result in extremely slow reaction or non-reaction.
The resultant aqueous resinous composition obtained from the reaction is preferably diluted with water. For reasons of stability, it is preferred that the instant aqueous resinnus composition be maintained at a pl~ range of about 4 or greater.
~hile not desiring to he hound to any particular ~ theory, it is believed that the reaction mechanism involved in ; the preparation of the compositions of the present invention is ; that of a Michael addition. The polymee, through the pendant amino or mercapto group, adds to the N-methylol ethylenically unsaturated amide at the site of unsaturation, thereby form-ing the compositions of the present invention.
In general, the instant resinous compositions have molecular weighta within the range of about 500 to 50,000 and preferably about lO00 to 5000. The molecular weight is a calculated value based on stoichiometry, for example, conden-sation polymers such a~s polyglycidyl ethers of polyphenols. If the molecular weight cannot be readlly calculated, for example, acrylic polymers, then the molecular weight is a measured value by Gel Permeation Chromatography using a polystyrene standard.
~`
lL ~ 7 8 0 ~` !
- 7 - i I
Tlle term ~dispersioll" ag used within the context of the preSl?nt inVelltiOIl i8 believe(l to be a tw~-phase, tran~9par-ent, translucellt or opaque aqueous resinous system in which the resin is the dispersed phase and water is the continuous phnse.
5 Average particle size diameter of the resinous phase i8 gen-erally less than 10 and preferably less than 5 microns. The concentration of the resinous phase in the a~ueous medium depends upon the particular end use of the dispersion and in , general is not critical. For example, thé ~l~ueou~ dispersion 10 preferably contains at least I flnd usually from about 5 to , 50 percent by weight resin solids.
For coating applications, the aqueous medium may contain besides water a coalescing solvent~ ~he use of coal-escing solvent may be, in some instances, for improved film t 15 appearance. These solvents include hydrocarbons, alcohols, esters, ethers and ketones. The preferred coalescing solvents include mono-alcohols, glycols and polyols a.s well as ketones and other alcohols. Specific coalescing solvents include isopropanol, butanol, 2-ethylhexanol, isophorone, 4-methoxy-2-20 pentanone, ethylene and propylene glycol, and the monoethyl, monobutyl and monohexyl ethers oF ethylene glycol. The amount of coalescing solvent is not unduly critical and is generally between about 0.01 and 40 percent by weight, preEerably about 0.05 to about 25 percent by weight based on total weight of 25 a~ueous medium.
In most instances, a pigment composition and, if desired, various additives such as surfactants or wetting agents are included in the dispersion. Pigment composition may be any of the conventional types comprising, for example, iron 30 oxides, lead oxides, strontium chromate, carbon black, conl dust, titanium dioxide, talc, barium sulfate, a~s well as color pigments such as cadmium yellow, cadmium red, chromium yellow and the like. Pigmeilt content of the dispersion is usually expressed as pigment-to-resin ratio. In the practice of the 35 present invention, the pigment-to-re~sin ratios are usually within the range of 0.1 to 5:1. The other additives mentioned above are pre~sent in the dispersion in amounts of 0.01 to 3 percent by weight based on total weight of resin solids.
_ . ~ .. . _ .. _ _ ~ _ .
~ :~fi~7~0 Even though films obtained from the aqueous resinous composi-tions self-cure, it may be desirable to comb:Lne them with curing agents.
When used with curing agents, it is preferred that the polymers of the instant aqueous resinous composition also contain active hydrogens which are reactive at elevated temperatures with a curing agent. E~a~lples of active hydrogens are hydroxyl, thiol, primary amine, secondary amine (including imine) and carboxyl.
The curing agents are those which are capable of reacting with the active hydrogens to form a crosslinked product. Examples of suitable curing agents are phenolic resins, aminoplasts and polyisocyanates~ The polyisocyanates should be capped or blocked so that they will not prema-turely react with the active hydrogens.
Suitable aminoplasts for use in the invention are described in U.S. Patent 3,937,679 to Boss et al in column 16, line 3, continuing to column 17, line 47. As disclosed in the aforementioned portions of the '679 patent, the aminoplast can be used in combination with methylol phenol ethers. The aminoplast curing agent usually constitutes about 1-60 and preferably 5-40 percent by weight of the resinous composition based on total weight of the acid-solubilized resinous vehicle and the ; 20 aminoplast.
With regard to the capped or blocked polyisocyanate curing agents, these are described in U.S. Patent 4,104,147, column 7, line 36, continuing to column 8~ line 37. Sufficient capped or blocked polyiso-cyanate is present in the coating system such that the equivalent ratio of latent isocyanate groups to active hydrogens is at least 0.1:1 and preferably about 0.3 to 1:1.
; When the aqueous dispersions described above are employed for use in electrodeposition, the aqueous dispersion containing cationic groups is placed in contact with an electrically conductive anode and an electrically conductive cathode with the surface to be coated being the cathode~
.
~ ~B~37~ ~
_ 9 _ ~
i Eollowing cnntact with the a~1ueous c1ispersion, an adherent film of the coating composition is deposited on the cathode when a sufficient voLtage is impressed between the electrodes. The conditions under which electrodeposition i9 carried out are, in 5 general, similar to those used in electrodeposition of other types of coatings. The applied voltage may be varied and can be, for example, as low as one volt or as high as 300 volts, but typically between 50 and 200 volts. The current density i~ L
usually between 1.0 ampere and 15 amperes per sqnare foot and 10 tends to decrease durillg electrodeposition indicating the formation of an insulating film.
The curable resinous compositions of the present invention can al80 be used in other conventional coating applications such as Elow, dip, spray and roll conting appli-15 cations. It is, however, desired to point out that the process oE electrodeposition is better suited to the application of the aqueous dispersions of the instant resinous contpositions. It has been fou1ld that films obtained from the electrodeposition of the aqueous dispersions self-cure very well and at compara-20 tively low temperatures.
For electrodeposition and other conventional coating applications, the coating composition.q can be applied to a variety of electroconductive 6ubstrates especially metals such as steel, aluminum, copper, magnesium and the like, but also ; 25 including metalli~ed plastic and conductive carbon-coated materials. For other conventional coating applications, the compositions can be applied to non-metallic substrates such as glass, wood and plastic.
After the coating has been applied by electrocoating or flow coating, it is usually cured by baking at temperatures such as 90 to 180~. for about 1 to 30 mintJtes.
Further illustrating the invention are the following examples, which, however, are not to be construed as limiting the invention to their details. All parts and percentages in the examples as well as throughout this specification are by weight unless otherwise indicated.
Exam le I
P
Th;s example shows the reaction of an epoxy polymer with a ketimine of a polyamine followed by reacting the resulting . _ , . . . _ . _ , ... .
3 7 ~ 0 pro-luct in allleotls rr:e(lium with N-m~?thylol ethylel-ica11y unsatllr.ltr~ mi(le to form an aqueouF lispersion of the resinous composition having a p~l of 8.5.
The charge Eor reacting the epoxy polymer with the 5 polyamine was as follows:
- Ingredients Parts by Weight in Grams EPON~8291 2~84.5 Bisphenol A 673.0 Diketimine of diethylenetriamine (73% solids ;n methyl isohutyl ketone ~olvent) 1650.0 Methyl ethyl ketone 500.0 lPolyglycidyl ether of bisphenol A having a molecular weight oE clbout 380 and an epoxy equivalent of about 190 which is available from Shell Chemical Compnny.
The EPON 829 and bisphenol A were akled to a reaction vessel under a nitrogen atmoslhere and heated to 150C. to initiate ~n exotherm. The reaction was allowed to exotherm for about 40 minutes with the highe~st temperature reaching 200nC.
The re~ction mixture was then held at 150C. for ahout 1-1/2 hours allowed to cool to 80C. and diluted with methyl ethyl ketone. The reaction mixture was further allowed to cool to 63~C. whereupon the addition of the methyl isobutyl ketone 7 containing the diketimine of diethylenetriamine was begun and 25 completed over a period of five minutes at a~out 53 C. The t reaction mixture was heated up to 80C. and held at that temperature for an hour.
The reaction mixture had an epoxy equivalent of infinity indicating that substantially all the epoxy function-30 ality h~d leen consumed. The resulting reaction mixture had a solids content of 78 percent.
The epoxy polymer-ketimine adduct prepared as described ahove was reacted with N-methylolacrylamide using the following charge:
35 Ingredients Parts by Wei~ht in ~rams Epoxy polymer-amine adduct prepared as described above228.1 ~actic acid (88Z aqueous) 14.8 N-methylolacrylamide (48~ aq eous) 69.1 H2O (deionized) 2033.0 ~Jr~e ~
6~3780 ~;~
I I , Ihe epoxy polymer-ketillline ad(lllct was di~ested with the lactic flCid flnd 100 ml. oF the water at room temperature for about 30 minutes followed by a dropwise addition of the aqueous N-methylolacrylami(le. ~nother 300 ml. of water was added followed by stirring of the reaction mixture for about one-half hour, then the remainder of the water was added. The reaction mixture was then filtered to give a stable aqueous resinous dispersion of the present invention having a pH of ~.7 and a solids content of 10 percent. L
Ilntreated steel panels were cathodically electroconted E
in the dispersion as produced in Rxample I. Coating at 150 P
volts for 90 seconds flnd baking at 177C. for 30 minlJtes resulted in films that were hard an-l dark in appearance. About 50 double rubs with acetone were req~lired to remove the film 15 from the substrate. Film thickness WflS 0.5 mil. .
When the dispersion was left stirring overnightl no sign of precipitation was observed, and cure response was markedly enhanced. Untreated steel panels were again electro-coated. Coating at 50 volts for 15 seconds an(l baking at 177C. ~or 20 minutes resulted in a film with excellent sol-vent resistance. The film was unaffected by 100 double rubs :
with acetone. Film Lhicklless was 1.5 mils. Similarly, a film coated at 150 volts for 15 seconds and baked at 121C. fos 20 minutes was unaffected by 100 double rubs with acetone.
Example II
This example illustrates the variation of resinousmaterials useful in preparing the instant aqueous resinous compositions. The charge for preparing the epoxy polymer-ketimine adduct was as follows:
30 IngredientsParts by Weight in Grams __ . .
EPON 10011 1395.0 PCP 02002 402.6 .
Xylene 110.7 Benzyldimethylamine 5.1 35 Diketimine of diethylenetriamine 513.0 Methyl ethyl ketone473.3 lnisphenol A based epoxy resin, suppl;ed by Shell Chemical Company, having a molecular weight of 952.
2Polycaprolactonediol~ manufactured by Union Carbide Corporation.
F
.. . . .... . . ....
~... .
.. . ... ; ............. .. , ., . _.
6~3~80 Into a propcrly equippel reaction vessel was charged a melt of the ~PON 1001 anl the PCP 0200, in xylene. Under a nitrogen blanket, the mixture wa.5 heated to reflux. Water was .
removed as a xylene a7eotrope over a period of 45 minutes, with the temperature rising to 208~C. A total of 12 ml. of water was renoved; it was then apparent that no more water was present. Thereafter, the reaction mixture was ~llowed to cool to about 135C. ~-en a sample of the reaction mixture was reduced with an equal wei~llt of 2-ethoxyethanol, it had a viscos;ty of A+ ol~ the Gardner-lloldt scale. ~t 130C., benzyl-dimethylamine was ad(le(l to the reaction mixture wllich was then held at this temperature for about 90 m;nutes. At this point, the viscosity of the mixture as determined above was E+. AEter another 30 minutes, the viscosity increased to 11+. The mixture was immediately cooled to 119C., followed by the addition of tlle diketimine. Thefe was an exother-n with the temperature rising to 121C. Two hours later at 110C., methyl ethyl ketone was added dropwise to the mixture. The resultant epoxy-ketimine addllct had a solids content of 68.7 percent.
The epoxy polymer-ketimine addllct prepared as described above was reacted with aqueous N-metilylolacrylamide. The followinF char~e was used in the reaction:
_n~redientsParts by Wei~ht in ~rams Epoxy polymer-amine adduct prepared as described above 268.0 Acetic acid 5.0 H20 (deionized) 239.5 48~ aqueous N-methylolacrylamide - 50.9 Acetic acid 2.5 30 ~'2 (deioni7ed) 602.1 The epoxy-ketimine adduct and the first batch of acetic acid were charged to a suitable reaction vessel. The first batch of water was added dropwise, followed by the addition of the N-methylolacrylamide, very slowly. m e reac- r 35 tion mixture was stirred Eor about 15 minutes followed by the addition of the secon(l batcll of acetic acid. With the remainder of the water, the reaction mixture was slowly thinned into a resultant translucent dispersion which had p p~l tE 8.2.
. . . __ .. . .. . _ _ . _ . , 6 8 ~ 8 0 The ~ollowing illustrates the stability o~ the a(lueolls re~inoug composition~s o~ the instflnt invention. The stability wa9 eValUatt?(l by deterrnining whetller samples of the resinous composition prepared in the manner of Example II
5 formed any sediment after 14 days of aging.
The resinous compositions were evaluated under the following condition~s: in both open and sealed containers and at ordinary room temperature, as well as hot-room temperature of L20 F. (49 C.). In open containers, the compositions were .
10 stirred continuously over the 14 days.
Dispersions of l0 anrl 20 percent solids content were evaluated accordingly and found to form no sediments. Disper-sionfi of 30 percent solids were evaluated with the following D
results: with the exception of the sample in R sealed container stored at 120F. (49C.), no effect on the dispersions w3s observed. At 120F. (49C.), however, the dispersion became somewhat gummy after 14 days of aging.
The following illustrates the stahility and gel-free nature of the aqueous N-methylol resinous composition at 20 varying pll. The stability was evaluated by the method of determining whether the resinous composition formed any sedi-ment after 14 days of aginF, at varying pll. A 15 percent sol;ds ~sample of the resinous compositioll as prepared in Example II having a pll of 8.2 was used as a standard. The 25 sample was contained in an open beaker for 14 days, after which time the pll was 6.5 and no sediment was observed. A fresh sample of the resinous ct~mposition having the pll adjusted to 6.0 with aceeic acid was contained in a beaker for 14 days.
Again no sediment was observed and the pll was 5.9. A third 30 sample having the pll adjusted to 5 with acetic acid was evalu-ated in the same way and found to have no sediment after 14 .
days. The pll changed from 5 to about 5.5. The fourth sample having a pH of 4.1 was evaluated in the same way and found to t have no sediment after 14 days; the pll changed from 4.1 to 1 35 4.2.
; Example III
This example illustrates the agueous resinous compo-sitions obtained from poLymers containing both pendant amino r : : : ~
,............. .... ... .. . , . . , . ____ __ . _.. ..
.
O , j~, _ 14 groups and pen(l.lllt mercapto groups. The charge for the prepara- !
tion is ns follows:
_gredients Parts by Weight in Grams Equivalents ;~
~PON 10011 505 1.00 5 Diben~yl ether 91.8 -- , Diethylenetriamine diketimine 235.9 0.65 Trimethylolpropane-tris-(3-mercaptopropionate) 146.5 1.05 1Polyglycidyl ether of bisphenol ~ having a moLecular weight of about 952, supplied by Shell Chemical Company.
Melted EPON 1001 an(l the diben7yl ether were mixed together and heate(l Eor 30 minutes to 123C. The reaction mix-ture was allowed to cool to ll0C. whereul-on diethylenetriamine diketimine and trimethylolpropane-tris-(3-mercaptopropionate) were added, coolin~ the reaction mixture further to 82C.
There was then an exotherm with the temperature rising to 93C.
The reaction mixture was then heated to 110C., held at this temperature for about 10 minutes and further heated to 117~C.
over a ~eriod of one hour.
The reaction mixture was again allowed to cool to 105C. over a period of about 90 minutes. The resulting product was furtller cooled to about 30C. and poured out of the reaction vessel as a clear dark fluid.
~queous N-methylolacrylamide was reacted with the P
above product using the following charge:
Ingredients Parts by We ~~ht in Grams The above product 213 ~cetic acid (30~ total neutraliæation) 7.5 Water (deionized) 200 30 (~8~ N-methylolacrylamide taqueous) 118.8 Water (deioniæed) 1090.7 The above product was warmed to about 70C. and digested with the acetic acid and the first batch of water for 30 minutes at room temperature. The aqueous N-methylolacryl-amide was then added. The result{ng reaction mixture was heldfor an hour and a half, at room temperature, aEter which the remainder of the water was added to thin the composition to 15 percent resin sol~ds content.
' I
~ ~ 6 ~
Ulltreated sl:eel suhstrntes were cathodically electro~
coated in the dispersion of Example ITI u3inK 100 volts ~or 90 t~
seconds at room temper.3ture. Films having excellent appearance, t insulation arld substrate adhesion were obta;ned.
When haked at 121 C. for 20 minutes, very hard films were obtained which re(luired 70 acetone double rubs to be removed. When baked at 107C. for 20 minute~s, hard film.s were obtained wllich required 75 acetone double rubs to be removed.
When baked at 83C. for 20 minutes, the films required 30-40 double rubs to be removed. Film thicknesses were about 0.5-0.6 miL.
WhiLe the illu~trative embodiments of the invention have been described hereinabove witll particularity, it will be u(lderstood that various modifications will be apparent to and can he readily ma-le by those .skilLed in the art without depart-ing from the scope ~r spirit of the invention. Accordingly, it is intended that claims directed to the invention be construed as encompassing all aspects of the invention which would be treated as equivalents by those skilled in the art to which the inveneion pertain~.
.... , ,, . . ~
Claims (17)
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An aqueous resinous composition comprising a polymer characterized by a pendant group which is of the structure:
wherein X represents sulfur or an amino group of which R1 is hydrogen or an alkyl group containing from about l to 6 carbon atoms; and wherein R, Rl, R2 and R3, each independently, is hydrogen or an alkyl group containing from about l to 6 car-bon atoms; said composition also comprises a water-solubilizing group.
wherein X represents sulfur or an amino group of which R1 is hydrogen or an alkyl group containing from about l to 6 carbon atoms; and wherein R, Rl, R2 and R3, each independently, is hydrogen or an alkyl group containing from about l to 6 car-bon atoms; said composition also comprises a water-solubilizing group.
2. An aqueous resinous composition of Claim 1 which is of a pH of about 4 or greater.
3. A composition of Claim l wherein the alkyl groups contain from about l to about 4 carbon atoms.
4. A composition of Claim 3 wherein R', R, Rl, R2 and R3, each independently, is a hydrogen or methyl.
5. A composition of Claim l wherein the polymer is derived from a polymer containing a pendant mercapto group, and/or a pendant amino group which is a primary and/or a secondary amine, or a mixture thereof.
6. A composition of Claim 5 wherein the polymer containing the pendant amino group is selected from the group consisting of poly(amide-amine) resins, amnino group-containing acrylic polymers and polyepoxide-amine adducts.
7. A composition of Claim 6 wherein the polymer is a polyepoxide-amine adduct.
8. A composition of Claim 7 wherein the amine is a ketimine of poly(alkyleneamine).
9. A composition of Claim 8 wherein the ketimine of poly(alkyleneamine) is ketimine of diethylenetriamine.
10. A process of preparing an aqueous resinous composition, comprising:
reacting a polymer containing a pendant mercapto group, and/or a pendant amino group which is a primary and/or secondary amine, or a mixture thereof, in aqueous medium with an N-methylol ethylenically unsaturated amide of the structure:
wherein R, Rl, R2 and R3, each independently, is hydrogen or an alkyl group containing from about 1 to 6 carbon atoms.
reacting a polymer containing a pendant mercapto group, and/or a pendant amino group which is a primary and/or secondary amine, or a mixture thereof, in aqueous medium with an N-methylol ethylenically unsaturated amide of the structure:
wherein R, Rl, R2 and R3, each independently, is hydrogen or an alkyl group containing from about 1 to 6 carbon atoms.
11. A process of Claim 10 wherein the alkyl groups contain from about 1 to about 4 carbon atoms.
12. A process of Claim ll wherein R, Rl, R2 and R3, each independently, is hydrogen or methyl.
13. A process of Claim 10 wherein the polymer containing the pendant amino group is selected from the group consisting of poly-(amide-amine) resins, amino group-containing acrylic polymers and polyepoxide-amine adducts.
14. A process of Claim 13 wherein the polymer is a poly-epoxide-amine adduct.
15. A process of Claim 14 wherein the amine is a ketimine of poly(alkylene-amine).
16. A process of Claim 15 wherein the ketimine of poly(alkyl-eneamine) is ketimine of diethylenetriamine.
17. A process for cathodically electrocoating an electrically conductive surface serving as a cathode which comprises passing an electric current between said cathode and anode which are immersed in an aqueous resinous dispersion of any of Claims 1, 2 or 5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US175,163 | 1980-08-04 | ||
| US06/175,163 US4341676A (en) | 1980-08-04 | 1980-08-04 | Self-curable resinous compositions containing N-methylol amide groups useful in coating applications |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1168780A true CA1168780A (en) | 1984-06-05 |
Family
ID=22639191
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000381872A Expired CA1168780A (en) | 1980-08-04 | 1981-07-16 | Self-curable resinous compositions useful in coating applications |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US4341676A (en) |
| EP (1) | EP0056808B1 (en) |
| JP (1) | JPS608262B2 (en) |
| BE (1) | BE889837A (en) |
| BR (1) | BR8108724A (en) |
| CA (1) | CA1168780A (en) |
| ES (2) | ES503703A0 (en) |
| IT (1) | IT1137638B (en) |
| MX (1) | MX158664A (en) |
| WO (1) | WO1982000471A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59155470A (en) * | 1983-02-23 | 1984-09-04 | Kansai Paint Co Ltd | Resin composition for thermosetting paint |
| AT379406B (en) * | 1984-03-02 | 1986-01-10 | Vianova Kunstharz Ag | METHOD FOR THE PRODUCTION OF CATHODICALLY DEPOSITABLE VARNISH BINDING AGENTS |
| US4786682A (en) * | 1987-06-25 | 1988-11-22 | Ppg Industries, Inc. | Coating compositions prepared from Michael adducts |
| US5180424A (en) * | 1991-10-07 | 1993-01-19 | Westvaco Corporation | Michael addition aminopolyester resins as dilution extenders for zinc-containing metal resinate inks |
| WO1997023537A1 (en) * | 1995-12-21 | 1997-07-03 | Ppg Industries, Inc. | Coating compositions containing amine group-containing resins and such resins |
| EP1806375B1 (en) * | 2006-01-05 | 2009-04-01 | Cognis IP Management GmbH | Process for obtaining aqueous compositions comprising curing epoxy agents |
Family Cites Families (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL281758A (en) | 1961-08-03 | |||
| US4059665A (en) * | 1970-05-11 | 1977-11-22 | Rohm And Haas Company | Bonded non-woven fabric and method for making it |
| US3679564A (en) * | 1970-06-19 | 1972-07-25 | Ppg Industries Inc | Process for electrodepositing acrylic compositions |
| US3799854A (en) * | 1970-06-19 | 1974-03-26 | Ppg Industries Inc | Method of electrodepositing cationic compositions |
| US3853803A (en) * | 1971-01-27 | 1974-12-10 | Ppg Industries Inc | Method of preparing a cationic acrylic electrodepositable interpolymer |
| US3758429A (en) * | 1971-11-26 | 1973-09-11 | Monsanto Co | Ethylene vinyl chloride n methhylol acrylamide |
| US3821175A (en) * | 1971-12-29 | 1974-06-28 | Gaf Corp | Stable aqueous emulsions of vinyl ether/acrylate/n-alkylol acrylamideterpolymers and treatment of textiles therewith |
| GB1421130A (en) * | 1972-11-16 | 1976-01-14 | Harlow Chemical Ltd | Surface coating compositions |
| DE2300685A1 (en) * | 1973-01-08 | 1974-07-18 | Basf Ag | BINDERS FOR ELECTRIC DIP PAINTS |
| US4001160A (en) * | 1973-09-26 | 1977-01-04 | Chas. S. Tanner Co. | Aqueous emulsion adhesives based on C2 -C8 ethers of N-methylol amides copolymerized with vinyl esters in the presence of hydroxy functional protective colloids |
| DE2509237A1 (en) * | 1974-03-25 | 1975-10-09 | Rohm & Haas | PROCESS FOR CURING POLYMERS AND CURABLE POLYMER COMPOSITIONS |
| US4057527A (en) * | 1974-06-17 | 1977-11-08 | Borden, Inc. | Aqueous acrylate contact adhesive dispersions |
| US4079029A (en) * | 1974-08-05 | 1978-03-14 | The Dow Chemical Company | Absorbent articles made from latexes of carboxylic synthetic polyelectrolyte containing n-substituted acrylamide crosslinking agent |
| US4057521A (en) * | 1974-08-05 | 1977-11-08 | The Dow Chemical Company | Absorbent articles made from carboxylic synthetic polyelectrolytes having copolymerized N-substituted acrylamide crosslinker |
| US3925181A (en) * | 1974-10-31 | 1975-12-09 | Scm Corp | Cathodic electrocoating process |
| US3976615A (en) * | 1974-11-13 | 1976-08-24 | Desoto, Inc. | Water dispersible epoxy ether-aminoacrylate polymers |
| US4017438A (en) * | 1974-12-16 | 1977-04-12 | Ppg Industries, Inc. | Ketimine-blocked primary amine group-containing cationic electrodepositable resins |
| US4021397A (en) * | 1974-12-30 | 1977-05-03 | The B. F. Goodrich Company | Stable dispersions of water soluble amide polymers |
| US4012353A (en) * | 1975-02-03 | 1977-03-15 | Ici United States Inc. | Copolymer having quaternary ammonium, n-alkoxyalkyl amido, and carboxy groups, optionally epoxy resin, and aqueous dispersions |
| US3975251A (en) * | 1975-03-19 | 1976-08-17 | Scm Corporation | Cathodic electrocoating process |
| US4037018A (en) * | 1975-05-02 | 1977-07-19 | Scm Corporation | Cationic aqueous compositions of polymer having amine groups, acid neutralized, and abis-maleimide cross-linker, coatings and process |
| DE2535660A1 (en) * | 1975-08-09 | 1977-02-17 | Cassella Farbwerke Mainkur Ag | PROCESS FOR THE PRODUCTION OF CROSS-LINKABLE POLYMERIZED AND COPOLYMERIZED |
| JPS5263225A (en) * | 1975-10-23 | 1977-05-25 | Hitachi Chem Co Ltd | Water-soluble compositions for ship bottom paints |
| CA1111598A (en) * | 1976-01-14 | 1981-10-27 | Joseph R. Marchetti | Amine acide salt-containing polymers for cationic electrodeposition |
| US4066523A (en) * | 1976-02-17 | 1978-01-03 | Scm Corporation | Dual cure cathodic electrocoating composition |
| US4035273A (en) * | 1976-05-24 | 1977-07-12 | Scm Corporation | Cathodic electrocoating process |
| US4035274A (en) * | 1976-05-24 | 1977-07-12 | Scm Corporation | Dual cure cathodic electrocoating |
| US4166017A (en) * | 1976-05-24 | 1979-08-28 | Scm Corporation | Process for cathodic electrocoating and photocuring |
| JPS5839161B2 (en) * | 1976-08-03 | 1983-08-27 | 大日本インキ化学工業株式会社 | Manufacturing method of dispersed resin composition |
| BE857754A (en) * | 1976-08-18 | 1978-02-13 | Celanese Polymer Special Co | COMPOSITION OF RESIN FOR COATINGS, ESPECIALLY BY CATHODIC ELECTRODEPOSITION |
| US4198331A (en) * | 1978-08-28 | 1980-04-15 | Ppg Industries, Inc. | Resinous coating compositions curable by Michael adduct exchange |
-
1980
- 1980-08-04 US US06/175,163 patent/US4341676A/en not_active Expired - Lifetime
-
1981
- 1981-03-12 BR BR8108724A patent/BR8108724A/en unknown
- 1981-03-12 WO PCT/US1981/000310 patent/WO1982000471A1/en active IP Right Grant
- 1981-03-12 EP EP81901419A patent/EP0056808B1/en not_active Expired
- 1981-03-12 JP JP56501919A patent/JPS608262B2/en not_active Expired
- 1981-06-30 MX MX188098A patent/MX158664A/en unknown
- 1981-07-06 ES ES503703A patent/ES503703A0/en active Granted
- 1981-07-16 CA CA000381872A patent/CA1168780A/en not_active Expired
- 1981-07-30 IT IT23263/81A patent/IT1137638B/en active
- 1981-08-03 BE BE0/205566A patent/BE889837A/en not_active IP Right Cessation
-
1982
- 1982-06-14 ES ES513065A patent/ES8304618A1/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| WO1982000471A1 (en) | 1982-02-18 |
| IT1137638B (en) | 1986-09-10 |
| ES8300831A1 (en) | 1982-11-01 |
| EP0056808A4 (en) | 1983-01-14 |
| BE889837A (en) | 1982-02-03 |
| BR8108724A (en) | 1982-06-01 |
| EP0056808B1 (en) | 1985-06-19 |
| IT8123263A0 (en) | 1981-07-30 |
| JPS57501128A (en) | 1982-07-01 |
| ES513065A0 (en) | 1983-03-01 |
| US4341676A (en) | 1982-07-27 |
| JPS608262B2 (en) | 1985-03-01 |
| MX158664A (en) | 1989-02-24 |
| ES8304618A1 (en) | 1983-03-01 |
| ES503703A0 (en) | 1982-11-01 |
| EP0056808A1 (en) | 1982-08-04 |
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