CA2020629C - Shelf stable fast-cure aqueous coating - Google Patents
Shelf stable fast-cure aqueous coating Download PDFInfo
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- CA2020629C CA2020629C CA002020629A CA2020629A CA2020629C CA 2020629 C CA2020629 C CA 2020629C CA 002020629 A CA002020629 A CA 002020629A CA 2020629 A CA2020629 A CA 2020629A CA 2020629 C CA2020629 C CA 2020629C
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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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
- C09D5/02—Emulsion paints including aerosols
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/48—Macromolecular compounds
- C04B41/483—Polyacrylates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
- C04B41/61—Coating or impregnation
- C04B41/62—Coating or impregnation with organic materials
- C04B41/63—Macromolecular compounds
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/064—Copolymers with monomers not covered by C09D133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
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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
- C09D5/004—Reflecting paints; Signal paints
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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
- C09D5/02—Emulsion paints including aerosols
- C09D5/024—Emulsion paints including aerosols characterised by the additives
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/0075—Uses not provided for elsewhere in C04B2111/00 for road construction
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
Abstract
A shelf-stable fast-cure aqueous coating is disclosed. The coating contains an anionically stabilized latex, a polyfunctional amine and a volatile base in an amount sufficient to deprotonate the conjugate acid of the amine.
Description
PATENT APPLICATION
of FRANK LANDY, ANDREW MERCURIIO and ROY FLYNN
for SHELF STABLE FAST-CURE AG~UIEOUS COATING
This invention relates to aqueous coatings, particularly aqueous road-marking paint that dries quickly after application.
Various attempts to produce an aqueous road-marking paint as a substitute for solvent-based road marking paints have been disclosed in the art. A
significant problem has been that the aqueous paints do not dry quickly enough.
European Patent Application No. 200249 discloses applying an aqueous dispersion of polymer to the road and then contacting the composition with a water soluble salt to cause the coating to dry rapidly and resist washout by a rain shower five minutes after application. This disclosure would require spraying with two compositions which would require the use of extra equipment.
European Patent application 0 066 108 dicloses an aqueous road marking composition in which the binder is a mixture of a pure acrylic resin, a carboxylated styrene/dibutyl fumarate copolymer and a polymeric, polyfunctional amine such as polypropylenimine. This application states that the disclosed compositions are not storage stable beyond 48 hours after which more polyfunctional amine must be added to restore activity.
The present invention provides a coating composition that dries quickly, develops water resistance soon after application and retains reactivity after storage.
The aqueous coating composition contains anionically stabilized emulsion polymer having a Tg greater than about 0°C, an effective amount of polyfunctional amine and a volatile base in an amount effective to raise the pH of the composition to a point high enough for the polyfunctional amine to be essentially in a non-ionized state (deprotonation) thereby eliminating polyamine interaction with the anionically stabilized emulsion and anionic ingredients in the coating.
In one aspect the invention provides an aqueous road or pavement-marking paint. The aqueous road or pavement marking paint of the invention can be used to mark lines or symbols on roads, parking lots walkways, etc. of various compositions such as asphaltic, bituminous or concrete paving with or without aggregate filler or top-dressing. This aqueous road-marking paint dries quickly, to develop early resistance to washout and tire tread printing.
of FRANK LANDY, ANDREW MERCURIIO and ROY FLYNN
for SHELF STABLE FAST-CURE AG~UIEOUS COATING
This invention relates to aqueous coatings, particularly aqueous road-marking paint that dries quickly after application.
Various attempts to produce an aqueous road-marking paint as a substitute for solvent-based road marking paints have been disclosed in the art. A
significant problem has been that the aqueous paints do not dry quickly enough.
European Patent Application No. 200249 discloses applying an aqueous dispersion of polymer to the road and then contacting the composition with a water soluble salt to cause the coating to dry rapidly and resist washout by a rain shower five minutes after application. This disclosure would require spraying with two compositions which would require the use of extra equipment.
European Patent application 0 066 108 dicloses an aqueous road marking composition in which the binder is a mixture of a pure acrylic resin, a carboxylated styrene/dibutyl fumarate copolymer and a polymeric, polyfunctional amine such as polypropylenimine. This application states that the disclosed compositions are not storage stable beyond 48 hours after which more polyfunctional amine must be added to restore activity.
The present invention provides a coating composition that dries quickly, develops water resistance soon after application and retains reactivity after storage.
The aqueous coating composition contains anionically stabilized emulsion polymer having a Tg greater than about 0°C, an effective amount of polyfunctional amine and a volatile base in an amount effective to raise the pH of the composition to a point high enough for the polyfunctional amine to be essentially in a non-ionized state (deprotonation) thereby eliminating polyamine interaction with the anionically stabilized emulsion and anionic ingredients in the coating.
In one aspect the invention provides an aqueous road or pavement-marking paint. The aqueous road or pavement marking paint of the invention can be used to mark lines or symbols on roads, parking lots walkways, etc. of various compositions such as asphaltic, bituminous or concrete paving with or without aggregate filler or top-dressing. This aqueous road-marking paint dries quickly, to develop early resistance to washout and tire tread printing.
DETAILED DESCRIPTION OF TI-IE INVENTION
The aqueous coating composition is made from:
' (A) an anionically stabilized polymer latex;
(B) a soluble or dispersible, preferably a soluble, polymer produced from monomer units in which from about 20% to 100% by weight of the monomer units contain an amine group;
(C) a volatile base in an amount effective to raise the pH of the composition to a point high enough for the polyfunctional amine to be essentially in a non-ionized state (deprotonation) thereby eliminating polyamine interaction with the anionically stabilized emulsion and anionic ingredients in the coating. The volatile base must be volatile enough to be released under air dry conditions.
According to one embodiment of the invention, the amount of polyfunctional amine is from about 0.25 to about 10 parts per 100 parts emulsion solids by weight. Further, the amount of polyfunctional amine may be provided in an amount of from about 0.4 to about 5 parts per 100 parts emulsion solids by weight, and within this range for example a polyfunctional amine may be present in the composition from about 0.6 to about 2.5 parts per 100 parts emulsion solids by weight.
ANIONICALLY STABILIZED POLYMER
The anionically stabilized emulsion polymer can be prepared by known procedures, which are published in texts on the subject such as "Emulsion Polymerization: Theory and Practice" by D. C. Blackley published by Wiley in and "Emulsion Polymerization" by F. A. Bovey et al,, published by Interscience Publishers in 1965. In general, the anionically stabilized latex polymer is a polymer or copolymer prepared from monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acryate, methyl methacrylate, ethyl methacrylate, y..~a,!
The aqueous coating composition is made from:
' (A) an anionically stabilized polymer latex;
(B) a soluble or dispersible, preferably a soluble, polymer produced from monomer units in which from about 20% to 100% by weight of the monomer units contain an amine group;
(C) a volatile base in an amount effective to raise the pH of the composition to a point high enough for the polyfunctional amine to be essentially in a non-ionized state (deprotonation) thereby eliminating polyamine interaction with the anionically stabilized emulsion and anionic ingredients in the coating. The volatile base must be volatile enough to be released under air dry conditions.
According to one embodiment of the invention, the amount of polyfunctional amine is from about 0.25 to about 10 parts per 100 parts emulsion solids by weight. Further, the amount of polyfunctional amine may be provided in an amount of from about 0.4 to about 5 parts per 100 parts emulsion solids by weight, and within this range for example a polyfunctional amine may be present in the composition from about 0.6 to about 2.5 parts per 100 parts emulsion solids by weight.
ANIONICALLY STABILIZED POLYMER
The anionically stabilized emulsion polymer can be prepared by known procedures, which are published in texts on the subject such as "Emulsion Polymerization: Theory and Practice" by D. C. Blackley published by Wiley in and "Emulsion Polymerization" by F. A. Bovey et al,, published by Interscience Publishers in 1965. In general, the anionically stabilized latex polymer is a polymer or copolymer prepared from monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acryate, methyl methacrylate, ethyl methacrylate, y..~a,!
butyl methacrylate, styrene, butadiene, ethylene, vinyl acetate, vinyl ester of "Versatic"
acid (a tertiary monocarboxylic acid having C9, Coo and C~1 chain length, the vinyl ester is also known as "vinyl versatate"), vinyl chloride, vinyl pyridine, vinylidene chloride, acrylonitrile, chloroprene, acrylic acid, mei:hacrylic acid, itaconic acid, malefic acid and fumaric acid. Polymers and copolymers of alpha-beta ethylenically unsaturated monomers and their esters, especially the acrylic and methacrylic esters, are preferred and are preferably prepared by processes given in "Emulsion Polymerization of Acrylic Monomers: May, 1966" published by the Rohm and Haas Company, Philadelphia, Pa.
The negative charge on the dispersed latex particles is obtained in any of several ways, the most common being the use of anionic surfactants or dispersants as the stabilizer during the emulsion polymerization or added to the emulsion after polymerization. Nonionic surfactants may, of course, also be present in-the latex during or after polymerization of these anionically stabilized latexes. Among the useful surtactants and dispersants are the salts of fatty rosin and naphthenic acids, condensation products of napthalene sulfonic acid and formaldehyde of low molecular weight, carboxylic polymers and copolymers of the appropriate hydrophile-lipophile balance, higher alkyyl sulfates, such as sodium lauryl sulfate, alkyl aryl sulfonates, such as dodecylbenzene sulfonate, sodium or potassium isopropylbenzene sulfonates or isopropylnaphthalene sulfonates;
sulfosuccinates, A
rv- 20 20629 such as sodium dioctylsulfosuccinate alkali metal higher alkyl sulfosuccinates, e.g.
sodium octyl sulfosuccinate, sodium N-methyl-N-palmitoyltaurate, sodium oleyl isethionate, alkali metal salts of alkylarylpolyethoxyethanol sulfates or sulfonates, e.g.
sodium t-octylphenoxy-polyethoxyethyl sulfate having 1 to 5 oxyethylene units, and the various other anionic surfactants and dispersants well-known in the art.
Another type of negatively-charged latex is that which is obtained as a result of including in the polymers small amounts of acidic groups, which may be in the salt form, such as an alkali metal or ammonium salt. Examples of such acidic groups are those derived from incorporated initiator fragments, malefic acid, vinyl sulfonic acid, crotonic acid, acrylic acid, methacrylic acid, itaconic acid, and the like.
The polymer must have a glass transition temperature (Tg) above 0°C.
Polymers having a Tg below 0°C are generally not useful since they are too soft, resulting in poor scrub resistance and accelerated dirt pickup. The invention may also be practiced using polymers of more complex morp'~hology, such as core-shell particles. These complex polymer morphologies usually display multiple Tg's and may display a Tg value below 0 degreees C as one of its multiple Tg's, however the average or effective Tg of the polymer must be above about 0 degrees C.
To prepare a storage stable composition of the amine-containing polymer and the anionically stabilized emulsion polymer, the amine-functional polymer is maintained essentially in a nonionic state by adding a sufficient amount of volatile base to raise the pH of the composition at or near the point at which substantially all the amine functional groups are in a nonionic state (deprotonation) and therefore do not interact with the anionically stabilized latex. A starting point estimate of the amount of volatile base required to reach this point can be Calculated from the number of equivalents of base needed to neutralize all of the acid groups in the latex (i.e. acid groups from: copolymerized carboxylic-bearing monomer; surtactant; or initiator) and the conjugate acid of the amine base. If the amine i;s not sufficiently deprotonated, the emulsion will exhibit observeable signs of instability over time, such as viscosity increase and microscopically observeable "particle rafting", an early stage of aggregation/ gellation. One equivalent of volatile base (based on latex acids and polyamine titers) is usually enough to yield a stable system although higher levels of volatile base (~3 to 4 equivalents) may be necessary for long term stability.
Higher amounts of volatile base cmn be used without departing from the spirit of the invention although the "quick dry" properties of the coating may be reduced. If the equipment used in the process of manufacture presents opportunities for loss of the volatile base by evaporation at any stage from when the volatile base is added until after the product is packaged in a sealed container, the amount of volatile amine loaded to the production equipment should be increased to offset the loss.
After application, the volatile base evaporates thus lowering the pH of the composition. When the pH of the composition falls to a point where the protonation of the polyamine begins to occur, the polyamine becomes cationic. The quick dry is believed to be initiated by this conversion of the polyamine to a cationic polymer in the presence of the anionically stabilized emulsion polymer, although the exact mechanism that produces the quick-dry property has not been established.
The compositions of this invention contain a polyfunctional amine, preferably a polymer containing from about 20% to 100%, and preferably at least 50% by weight of amine-containing monomer. Examples of the amine containing monomers include members of the following classes:
AMINE CLASSES
1. Aminoalkyl vinyl ethers or sulfides wherein the alkyl groups may be straight-chain or branched-chain type and have from two to three carbon atoms and wherein the nitrogen atom may be a primary, secondary, or tertiary nitrogen atom (U.S. Pat. No. 2,879,178). In the latter instance, one of the remaining hydrogen atoms may be substituted by alkyl, hydroxyalkyl, or alkoxyalkyl groups, the alkyl components of which may have one to four carbon atoms, preferably one carbon atom only. Specific examples include:
beta -aminoethyl vinyl ether; beta -aminoethyl vinyl sulfide; N-monomethyl-beta-aminoethyl vinyl ether or sulfide; N-monoethyl- beta -aminoethyl vinyl ether or sulfide; N-monobutyl- beta -aminoethyl vinyl ether or sulfide; and N-monomethyl-3-aminopropyl vinyl ether or sulfide.
2. Acrylamide or acrylic esters, such as those of the formula II:
H2C = C(R)C-(X)n A-NR~R~
(II) wherein R is H or CH3;
nis0orl;
X is O or N(H);
When n is zero, A is O(CH2) x wherein x is 2 to 3, or (O-alkylene) y wherein (O-alkylene)y is a poly(oxyalkylene) group, having a molecular weight in the range from 88 to 348, in which the individual alkylene radicals are the same or different and are either ethylene or propylene; and when n is 1, A is an alkylene group having two to 4 carbon atoms;
R' is H, methyl, or ethyl; and R~ IS H, methyl, or ethyl; and Ro is H, phenyl, benzyl, methylbenzyl, cyclohexyl, or (C1-Cs) alkyl.
Examples of compounds of formula II include:
dimethylaminoethylacrylate or methacrylate; beta -aminoethyl acrylate or methacrylate; N- beta -aminoethyl acrylamide or methacrylamide;
N-(monomethylaminoethyl)-acrylamide or methacryiamide;
N-(mono-n-butyl)-4-aminobutyl acrylate or methacrylate;
methacryloxyethoxyethylamine; and acryloxypropox:ypropoxypropylamine.
3. N-acryloxyalkyl-oxazolidines and N-acryloxyalkyltetrahydro-1,3-oxazines and the corresponding components in which the "alkyl" linkage is replaced by alkoxyalkyl and poly(alkoxy-alkyl), all of which are embraced by Formula III:
I /C~r'H2m H2C= C(R)C- A=N\ /0 C
i~
R' R2 (III) wherein R is H or CH3;
m is an integer having a value of 2 to 3;
R', when not directly joined to R2 , is selected from the group consisting of hydrogen, phenyl, benzyl, and (C~-C12) alkyl groups;
R2 , when not directly joined to R', is selected from the group consisting of hydrogen and (C~-C4) alkyl groups;
R'and R2 , when directly joined together, form a 5- to 6-carbon ring with the attached carbon atom of the ring in the formula, i.e., R'and R2 , when joined together, are selected from the group consistling of pentamethylene and tetramethylene; and A'is O(CmH2m)- or (O-alkylene)~ in which (O-alkylene)~is a poly(oxyalkylene) group, having a molecular weight in the range from 88 to 348, in which the individual alkylene radicals are the same ~or different and are either ethylene or propylene.
The compounds of Formula III can hydrolyze under various conditions to secondary amines. The hydrolysis produces products having the Formula IV:
H2C= C(R)C- A=N(H)-(CmH2m )-OH IV
() The compounds of Formula III are disclosed in U.S. Pat. Nos. 3,037,006 and 3,502,627 in the hands of a common assignee, and their corresponding foreign applications and patents and any of the monomeric compounds disclosed therein may be used in making the copolymers to be used in the composition of the present invention.
_. 2020629 Examples of compounds of Formula III include:
oxazolidinylethyl methacrylate; oxazolidinylethyl acn~late; 3-(gamma-methacryl-oxypropyl)-tetrahydro-1,3-oxazine; 3-( beta -methacryloxyethyl)-2,2-penta-methylene-oxazolidine; 3-( beta -methacryloxyethyl-2-methyl-2-propyloxazolidine;
N-2-(2-acryloxyethoxy)ethyl-oxazolidine; N-2-(2-methacryloxyethoxy)ethyl-oxazolidine; N-2-(2-methacryloxyethoxy)ethyl-5-methyl-oxazolidine;
N-2-(2-acryloxyethoxy)ethyl-5-methyl-oxazolidine; 3~-[2-(2-methacryloxyethoxy) ethyl)]-2,2-yenta-methylene-oxazolidine; 3-[2-(2-methacryloxyethoxy)ethyl)]-2,2-dimethyloxazolidine; 3-[2-(methacryloxyethoxy)ethyl]-2-phenyl-oxazolidine.
4. Polymers of monomers which readily generate amines by hydrolysis are useful as the amine-containing component or to generate i:he amine-containing component polymer of this binder composition. Examples of such monomers are acryloxy-ketimines and -aldimines, such as those of Formulas V and VI
following:
H2C=(CR)-COOA"N=Q (V) H2C = C(R)-CO-(D)n°-~ - (B)n'-~ - (A°)n° -1 - N = Q
(VI) wherein R is H or CH3;
Q is selected from the group consisting of _ /
~\RS =C-(CHR6)x 3 and =C HR ;
R6 is H or it may be methyl in one CHRs unit;
R5 is selected from the group consisting of {C~-C~2)-alkyl and cyclohexyl groups;
Ra is selected from the group consisting of (C~-C12)-alkyl and cyclohexyl R3 is selected from the group consisting of phenyl, halophenyl, (C1-C~2)-alkyl, cyclohexyl, and {C1-C4) alkoxyphenyl groups;
A"is a (C1-C~2) alkylene group;
A~, B and D are the same or different oxyalkylene groups having the formula -OCH(R~ )-CH{R~ )-wherein R~ is H, CH3, or C2H5;
x is an integer having a value of 4 to 5;
na is an integer having a value of 1 to 200;
n'is an integer having a value of 1 to 200; and n"is an integer having a value of 1 to 200, the sum of n~-1, n'-1 and n"-1 having a value of 2 to 200.
Illustrative compounds of formulas V and VI are:
2-[4-(2,6-dimethylheptylidene)-amino]-ethyl methacrylate 3-[2-(4-methylpentylidine)-amino]-propyl methacryla~te beta -(benzylideneamino)-ethyl methacrylate 3-[2-(4-methylpentylidene)-amino]-ethyl methacrylai;e 2-[4-(2,6-dimethylheptylidene)-amino]-ethyl acrylate 12-(cyclopentylidene-amino)-dodecyl methacrylate N-(1,3-dimethylbutylidene)-2-(2-methacryloxyethoxy)-ethylamine N-(benzylidene)-methacryloxyethoxyethylamine N-(1,3-dimethylbutylidene)-2-(2-acryloxyethoxy)-ethylamine N-(benzylidene)-2-(2-acryloxyethoxy)ethylamine The compounds of Formulas V and VI hydrolyze in acid, neutral, or alkaline aqueous media to produce the corresponding primary amines or salts thereof in which the group -N = Q of the formulas becomes -NH2 and O = D. The compounds of Formulas V and VI are disclosed in U.S. Pat. Nos. 3,037,969 and 3,497,485, and any of the monomeric compounds therein disclosed may be used in the making of the copolymers to be used in the water-soluble polymer portion of the compositions of 20 20~ 29 the present invention.
DESCRIPTION OF POLYMER SOLUBILITY
Water-soluble amine-containing polymers include both the completely soluble and the partly soluble polymers. The term water-soluble amine-containing polymer describes polymer that is completely soluble either in free-base, neutral, or salt form.
Some polymers are soluble at all pH's, while others are soluble over a range of pH for example from about 5 to 10. Other amine-containing polymers are generally insoluble at high pH and soluble or partly soluble at acidic pHi values, particularly in the pH
range from about 5 to about 7. By partly soluble is meant both the situation in which some of the polymer is soluble in water as well as that in which the entire polymer dissolves in the form of micelles or aggregates of individual molecules, generally, highly water swollen aggregates. The latter are often called colloidal solutions. It is preferred that most of the polymer be soluble at the acidic pH values.
AMINE POLYMER PREPARATION
In general, the amine-containing polymers may be obtained by solution polymerization in aqueous media, either neutral, alkaline, or acidic, depending upon the particular polymer sought, as generally known in the art, for example as taught in U.S. Patent 4,119,600. Generally, the polymerization is carried out in an aqueous medium containing a small amount of an acid, either organic or inorganic, such as acetic acid or hydrochloric acid. The amine-containing polymers include copolymers with up to 80% by weight one or more monoethylenically unsaturated monomers , such as methyl acrylate, acrylamide and methacrylamide. Small amounts of relatively insoluble comonomers may also be used to obtain ' he water-soluble polymers.
The insoluble polymers may contain larger amounts of these comonomers. Such monomers include, as examples, acrylic acid esters with (C1 to C18) alcohols and methacrylic acid esters with alcohols having one to 18 carbon atoms, especially (C1-C4) alkanols; styrene, vinyltoluene, vinyl acetate, vinyl chloride, vinylidene chloride, substituted styrenes, butadiene, substituted butadienes, ethylene;
and the nitrites and amides of acrylic or of methacrylic acid. The particular comonomer or comonomers used in making a given amine-containing polymer depends upon the proportion of amine-containing monomer used in making the copolymer. The polymers are thus polymers or copolymers of cationic and, optionally, nonionic vinyl monomers. Examples of the cationic monomers are 'the amines and imines; the other recited monomers are nonionic. Thus, these water-soluble copolymers contain no acid groups other than trace amounts which may be present due to impurities in the monomers used or to small extent of hydrolysis during synthesis, storage or use.
VOLATILE BASE
The type and amount of volatile base used must be sufficient to raise the pH
of the composition to about the point where the polyfunctional amine is non-ionized (deprotonated), to avoid interaction with the anionically stabilized emulsion.
The volatile base of preference is ammonia, which may be used as the sole volatile base or in admixture with other volatile or nonvolatile bases. Other volatile bases which may be employed are morpholine, the lower alkyl amines, 2-dimethylaminoethanol, N-methylmorpholine, ethylenediamine, and others.
Flller, extenders, pigments and other additives known in the art may also be used in the compositions of the invention. If pigment is used in the traffic paint composition, it is typically in the range of fifty percent pigment volume content to sixty percent pigment volume content. Examples of pigments that may be employed include clays, calcium carbonate, talc, titanium dioxide, carbon black, and various colored pigments.
Care must be exercised when selecting the type and amount of additives to avoid altering the pH of the composition to an extent that interteres with storage stability or buffering the pH to an extent that after application the pH does not fall sufficiently to initiate protonation of the polyamine. For example a paint prepared using a polyamine with a relatively low pKa and too large an amount of calcium carbonate as filler, may display an unacceptably extended cure time.
Traffic paint compositions typically have a solids content in the range of from thirty five% to seventy% by volume and a viscosity of from about 70 kreb units to about 100 kreb units. Coatings provided by the invention are also useful in other exterior coatings such as maintenance coatings, house paint, etc..
The following examples illustrate some aspects of the invention and should not be construed as limiting the scope of the invention which is described in the specification and claims.
AM = Acrylamide DMAEMA = Dimethylaminoethylmethacrylate DMAPMA = Dimethylaminopropylmethacrylamide HEMA = Hydroxyethylmethacrylate MMA = Methylmethacrylate OXEMA = Oxazolidinoethylmethacrylate p-OXEMA = poly-oxazolidinoethylmethacrylate Paint Prey The test paints were prepared according to the following standard paint 20 i! 06 29 formulation by grinding together the ingredients listed as grind ingredients below and then adding the remaining ingredients in the letdown. The emulsion was an anionic copolymer of butyl acrylate, methyl methacrylate and methacrylic acid having a T9 of 20°C, and a particle size of 200 manometers.
Grind Ingredient Amo unt (Ib:~/103 qalsl Emulsion (50% solids) 457.9 Water. 28.4 Tamal 850 7.1 TritonCF-10 2.8 Drew~~L-493 1.0 Ti Pu re 8900 100. 0 Silverbond~B 156.3 Snowflake (calcium carbonate)595.9 LetDown Texanol~" 22.9 Methanol 15.0 Drew L-493 2.~p Hydroxyethyl cellulose 15.0 (2.5% solution in water) 1,404.3 Dry Time Test This test is similar to ASTM D1640 which is a standard test for drying of organic coatings at room temperature. The test films are applied on a non-porous substrate (glass plate or metal panel) by suitable means to give a wet film thickness of 0.012 +/-.001 inches. The ASTM test method is modified in tlhat only minimal thumb pressure is used. The thumb is turned through an angle of 90° while in contact with the film. The * Trademark A
drying time at which this rotation does not break the film is recorded.
Eary Washout Resistance The test films are prepared in the same manner as for the dry time test. After the films have dried for 15 minutes at a temperature of T8°F and 50%
relative humidity, the samples were held under a stream of cold running water (tap pressure of 170-gallons per hour), which contacted the surtace of the paint film at from a nearly perpendicular to an oblique angle. The samples remained under the stream of running water for a period of five (5) minutes. At the end of this period the samples were removed from the test stream and rated by visual inspection. Samples that showed no apparent effect were rated passes ; those that exhibited slight disruption of the film were rated marginal; those samples that showed a break in the film or any film removal were rated as fails.
Scrub Resistance Films of 3.5 mils dry thickness were prepared and cured for 24 hours at 77°F
+/- 2°F and 40-55% relative humidity. The films were tested according to according to ASTM D2486. The number of scrub cycles at which 'to an area of the paint film was fully removed was recorded.
20 ~~0629 One pint of the test paint was placed in a sealed can and stored in a sealed circulation oven at 120°F for one week. The can was removed from the oven and the paint was observed. If the paint is still fluid and shows no apparent signs of bodying or separation it is rated as a pass.
Paint That Is Not Storage Stable.
To a paint formulation prepared according to the formulation described above, Ibs. of polyOXEMA (28.5% solids) was added . T'he consistency of this paint changed from a fluid mixture to a solidified mass on aging 16 hours at ambient temperature.
The procedure of the Comparative Example was repeated except that 3.9 Ibs. of ammonium hydroxide (28%) was added before the polyOXEMA. The paint remained fluid when stored at room temperature and passed the heat aging test.
Test paints were prepared by adding polyamine (polyOXEMA), as in Example 1, in the amount indicated in the table as a percent by weight based on vehicle solids.
The paints were applied to substrates and tested. The standard paint without any amine-containing polymer was used as a control. The results appear in the table below:
Level of Polyamine Scrub (%solids on Early Washout Resistance vehicle solids) Resistance Properties Control fail 950 cycle 0.27% p.OXEMA marginal --0.62% p.OXEMA passes 760 cycles 1.25% p.OXEMA passes 950 cycles 2.5% p.OXEMA passes 910 cycles The above data demonstrates that the amine-functional polymer produces early washout resistance with acceptable scrub resistance properties. Also, the paint containing 1.25% polyOXEMA dried in 10 minutes in the dry time test compared to 20 minutes dry time for the Control paint that doesn't contain polyamine.
2020'629 Paints were prepared using the indicated amine-containing polymer according to the procedure of Example 1. The paint without any amine-containing polymer was used as a control. Samples were prepared by adding amine-containing polymer to the standard formulation in the amount indicated in the table measured as a percent b~ weight based on vehicle solids. The sample emulsions were applied to substrates and tested. The results appear in the table below:
Type of Polyamine in marking paint Early Washout 7 days aging Formulation ~~1. % / 1 Resistance 120°F
none fail passes pOXEMA passes passes OXEMA/HEMA 50/50 passes passes OXEMA/ MMA 70/30 passes passes DMAPMA/ AM 70/30 passes passes DMAPMA/ HEMA 70/30 (0.44% s/s) passes passes pDMAEMA passes passes The above data demonstrates that marking paints according to the invention have early washout-resistance and were storage stable even under storage at elevated temperature.
acid (a tertiary monocarboxylic acid having C9, Coo and C~1 chain length, the vinyl ester is also known as "vinyl versatate"), vinyl chloride, vinyl pyridine, vinylidene chloride, acrylonitrile, chloroprene, acrylic acid, mei:hacrylic acid, itaconic acid, malefic acid and fumaric acid. Polymers and copolymers of alpha-beta ethylenically unsaturated monomers and their esters, especially the acrylic and methacrylic esters, are preferred and are preferably prepared by processes given in "Emulsion Polymerization of Acrylic Monomers: May, 1966" published by the Rohm and Haas Company, Philadelphia, Pa.
The negative charge on the dispersed latex particles is obtained in any of several ways, the most common being the use of anionic surfactants or dispersants as the stabilizer during the emulsion polymerization or added to the emulsion after polymerization. Nonionic surfactants may, of course, also be present in-the latex during or after polymerization of these anionically stabilized latexes. Among the useful surtactants and dispersants are the salts of fatty rosin and naphthenic acids, condensation products of napthalene sulfonic acid and formaldehyde of low molecular weight, carboxylic polymers and copolymers of the appropriate hydrophile-lipophile balance, higher alkyyl sulfates, such as sodium lauryl sulfate, alkyl aryl sulfonates, such as dodecylbenzene sulfonate, sodium or potassium isopropylbenzene sulfonates or isopropylnaphthalene sulfonates;
sulfosuccinates, A
rv- 20 20629 such as sodium dioctylsulfosuccinate alkali metal higher alkyl sulfosuccinates, e.g.
sodium octyl sulfosuccinate, sodium N-methyl-N-palmitoyltaurate, sodium oleyl isethionate, alkali metal salts of alkylarylpolyethoxyethanol sulfates or sulfonates, e.g.
sodium t-octylphenoxy-polyethoxyethyl sulfate having 1 to 5 oxyethylene units, and the various other anionic surfactants and dispersants well-known in the art.
Another type of negatively-charged latex is that which is obtained as a result of including in the polymers small amounts of acidic groups, which may be in the salt form, such as an alkali metal or ammonium salt. Examples of such acidic groups are those derived from incorporated initiator fragments, malefic acid, vinyl sulfonic acid, crotonic acid, acrylic acid, methacrylic acid, itaconic acid, and the like.
The polymer must have a glass transition temperature (Tg) above 0°C.
Polymers having a Tg below 0°C are generally not useful since they are too soft, resulting in poor scrub resistance and accelerated dirt pickup. The invention may also be practiced using polymers of more complex morp'~hology, such as core-shell particles. These complex polymer morphologies usually display multiple Tg's and may display a Tg value below 0 degreees C as one of its multiple Tg's, however the average or effective Tg of the polymer must be above about 0 degrees C.
To prepare a storage stable composition of the amine-containing polymer and the anionically stabilized emulsion polymer, the amine-functional polymer is maintained essentially in a nonionic state by adding a sufficient amount of volatile base to raise the pH of the composition at or near the point at which substantially all the amine functional groups are in a nonionic state (deprotonation) and therefore do not interact with the anionically stabilized latex. A starting point estimate of the amount of volatile base required to reach this point can be Calculated from the number of equivalents of base needed to neutralize all of the acid groups in the latex (i.e. acid groups from: copolymerized carboxylic-bearing monomer; surtactant; or initiator) and the conjugate acid of the amine base. If the amine i;s not sufficiently deprotonated, the emulsion will exhibit observeable signs of instability over time, such as viscosity increase and microscopically observeable "particle rafting", an early stage of aggregation/ gellation. One equivalent of volatile base (based on latex acids and polyamine titers) is usually enough to yield a stable system although higher levels of volatile base (~3 to 4 equivalents) may be necessary for long term stability.
Higher amounts of volatile base cmn be used without departing from the spirit of the invention although the "quick dry" properties of the coating may be reduced. If the equipment used in the process of manufacture presents opportunities for loss of the volatile base by evaporation at any stage from when the volatile base is added until after the product is packaged in a sealed container, the amount of volatile amine loaded to the production equipment should be increased to offset the loss.
After application, the volatile base evaporates thus lowering the pH of the composition. When the pH of the composition falls to a point where the protonation of the polyamine begins to occur, the polyamine becomes cationic. The quick dry is believed to be initiated by this conversion of the polyamine to a cationic polymer in the presence of the anionically stabilized emulsion polymer, although the exact mechanism that produces the quick-dry property has not been established.
The compositions of this invention contain a polyfunctional amine, preferably a polymer containing from about 20% to 100%, and preferably at least 50% by weight of amine-containing monomer. Examples of the amine containing monomers include members of the following classes:
AMINE CLASSES
1. Aminoalkyl vinyl ethers or sulfides wherein the alkyl groups may be straight-chain or branched-chain type and have from two to three carbon atoms and wherein the nitrogen atom may be a primary, secondary, or tertiary nitrogen atom (U.S. Pat. No. 2,879,178). In the latter instance, one of the remaining hydrogen atoms may be substituted by alkyl, hydroxyalkyl, or alkoxyalkyl groups, the alkyl components of which may have one to four carbon atoms, preferably one carbon atom only. Specific examples include:
beta -aminoethyl vinyl ether; beta -aminoethyl vinyl sulfide; N-monomethyl-beta-aminoethyl vinyl ether or sulfide; N-monoethyl- beta -aminoethyl vinyl ether or sulfide; N-monobutyl- beta -aminoethyl vinyl ether or sulfide; and N-monomethyl-3-aminopropyl vinyl ether or sulfide.
2. Acrylamide or acrylic esters, such as those of the formula II:
H2C = C(R)C-(X)n A-NR~R~
(II) wherein R is H or CH3;
nis0orl;
X is O or N(H);
When n is zero, A is O(CH2) x wherein x is 2 to 3, or (O-alkylene) y wherein (O-alkylene)y is a poly(oxyalkylene) group, having a molecular weight in the range from 88 to 348, in which the individual alkylene radicals are the same or different and are either ethylene or propylene; and when n is 1, A is an alkylene group having two to 4 carbon atoms;
R' is H, methyl, or ethyl; and R~ IS H, methyl, or ethyl; and Ro is H, phenyl, benzyl, methylbenzyl, cyclohexyl, or (C1-Cs) alkyl.
Examples of compounds of formula II include:
dimethylaminoethylacrylate or methacrylate; beta -aminoethyl acrylate or methacrylate; N- beta -aminoethyl acrylamide or methacrylamide;
N-(monomethylaminoethyl)-acrylamide or methacryiamide;
N-(mono-n-butyl)-4-aminobutyl acrylate or methacrylate;
methacryloxyethoxyethylamine; and acryloxypropox:ypropoxypropylamine.
3. N-acryloxyalkyl-oxazolidines and N-acryloxyalkyltetrahydro-1,3-oxazines and the corresponding components in which the "alkyl" linkage is replaced by alkoxyalkyl and poly(alkoxy-alkyl), all of which are embraced by Formula III:
I /C~r'H2m H2C= C(R)C- A=N\ /0 C
i~
R' R2 (III) wherein R is H or CH3;
m is an integer having a value of 2 to 3;
R', when not directly joined to R2 , is selected from the group consisting of hydrogen, phenyl, benzyl, and (C~-C12) alkyl groups;
R2 , when not directly joined to R', is selected from the group consisting of hydrogen and (C~-C4) alkyl groups;
R'and R2 , when directly joined together, form a 5- to 6-carbon ring with the attached carbon atom of the ring in the formula, i.e., R'and R2 , when joined together, are selected from the group consistling of pentamethylene and tetramethylene; and A'is O(CmH2m)- or (O-alkylene)~ in which (O-alkylene)~is a poly(oxyalkylene) group, having a molecular weight in the range from 88 to 348, in which the individual alkylene radicals are the same ~or different and are either ethylene or propylene.
The compounds of Formula III can hydrolyze under various conditions to secondary amines. The hydrolysis produces products having the Formula IV:
H2C= C(R)C- A=N(H)-(CmH2m )-OH IV
() The compounds of Formula III are disclosed in U.S. Pat. Nos. 3,037,006 and 3,502,627 in the hands of a common assignee, and their corresponding foreign applications and patents and any of the monomeric compounds disclosed therein may be used in making the copolymers to be used in the composition of the present invention.
_. 2020629 Examples of compounds of Formula III include:
oxazolidinylethyl methacrylate; oxazolidinylethyl acn~late; 3-(gamma-methacryl-oxypropyl)-tetrahydro-1,3-oxazine; 3-( beta -methacryloxyethyl)-2,2-penta-methylene-oxazolidine; 3-( beta -methacryloxyethyl-2-methyl-2-propyloxazolidine;
N-2-(2-acryloxyethoxy)ethyl-oxazolidine; N-2-(2-methacryloxyethoxy)ethyl-oxazolidine; N-2-(2-methacryloxyethoxy)ethyl-5-methyl-oxazolidine;
N-2-(2-acryloxyethoxy)ethyl-5-methyl-oxazolidine; 3~-[2-(2-methacryloxyethoxy) ethyl)]-2,2-yenta-methylene-oxazolidine; 3-[2-(2-methacryloxyethoxy)ethyl)]-2,2-dimethyloxazolidine; 3-[2-(methacryloxyethoxy)ethyl]-2-phenyl-oxazolidine.
4. Polymers of monomers which readily generate amines by hydrolysis are useful as the amine-containing component or to generate i:he amine-containing component polymer of this binder composition. Examples of such monomers are acryloxy-ketimines and -aldimines, such as those of Formulas V and VI
following:
H2C=(CR)-COOA"N=Q (V) H2C = C(R)-CO-(D)n°-~ - (B)n'-~ - (A°)n° -1 - N = Q
(VI) wherein R is H or CH3;
Q is selected from the group consisting of _ /
~\RS =C-(CHR6)x 3 and =C HR ;
R6 is H or it may be methyl in one CHRs unit;
R5 is selected from the group consisting of {C~-C~2)-alkyl and cyclohexyl groups;
Ra is selected from the group consisting of (C~-C12)-alkyl and cyclohexyl R3 is selected from the group consisting of phenyl, halophenyl, (C1-C~2)-alkyl, cyclohexyl, and {C1-C4) alkoxyphenyl groups;
A"is a (C1-C~2) alkylene group;
A~, B and D are the same or different oxyalkylene groups having the formula -OCH(R~ )-CH{R~ )-wherein R~ is H, CH3, or C2H5;
x is an integer having a value of 4 to 5;
na is an integer having a value of 1 to 200;
n'is an integer having a value of 1 to 200; and n"is an integer having a value of 1 to 200, the sum of n~-1, n'-1 and n"-1 having a value of 2 to 200.
Illustrative compounds of formulas V and VI are:
2-[4-(2,6-dimethylheptylidene)-amino]-ethyl methacrylate 3-[2-(4-methylpentylidine)-amino]-propyl methacryla~te beta -(benzylideneamino)-ethyl methacrylate 3-[2-(4-methylpentylidene)-amino]-ethyl methacrylai;e 2-[4-(2,6-dimethylheptylidene)-amino]-ethyl acrylate 12-(cyclopentylidene-amino)-dodecyl methacrylate N-(1,3-dimethylbutylidene)-2-(2-methacryloxyethoxy)-ethylamine N-(benzylidene)-methacryloxyethoxyethylamine N-(1,3-dimethylbutylidene)-2-(2-acryloxyethoxy)-ethylamine N-(benzylidene)-2-(2-acryloxyethoxy)ethylamine The compounds of Formulas V and VI hydrolyze in acid, neutral, or alkaline aqueous media to produce the corresponding primary amines or salts thereof in which the group -N = Q of the formulas becomes -NH2 and O = D. The compounds of Formulas V and VI are disclosed in U.S. Pat. Nos. 3,037,969 and 3,497,485, and any of the monomeric compounds therein disclosed may be used in the making of the copolymers to be used in the water-soluble polymer portion of the compositions of 20 20~ 29 the present invention.
DESCRIPTION OF POLYMER SOLUBILITY
Water-soluble amine-containing polymers include both the completely soluble and the partly soluble polymers. The term water-soluble amine-containing polymer describes polymer that is completely soluble either in free-base, neutral, or salt form.
Some polymers are soluble at all pH's, while others are soluble over a range of pH for example from about 5 to 10. Other amine-containing polymers are generally insoluble at high pH and soluble or partly soluble at acidic pHi values, particularly in the pH
range from about 5 to about 7. By partly soluble is meant both the situation in which some of the polymer is soluble in water as well as that in which the entire polymer dissolves in the form of micelles or aggregates of individual molecules, generally, highly water swollen aggregates. The latter are often called colloidal solutions. It is preferred that most of the polymer be soluble at the acidic pH values.
AMINE POLYMER PREPARATION
In general, the amine-containing polymers may be obtained by solution polymerization in aqueous media, either neutral, alkaline, or acidic, depending upon the particular polymer sought, as generally known in the art, for example as taught in U.S. Patent 4,119,600. Generally, the polymerization is carried out in an aqueous medium containing a small amount of an acid, either organic or inorganic, such as acetic acid or hydrochloric acid. The amine-containing polymers include copolymers with up to 80% by weight one or more monoethylenically unsaturated monomers , such as methyl acrylate, acrylamide and methacrylamide. Small amounts of relatively insoluble comonomers may also be used to obtain ' he water-soluble polymers.
The insoluble polymers may contain larger amounts of these comonomers. Such monomers include, as examples, acrylic acid esters with (C1 to C18) alcohols and methacrylic acid esters with alcohols having one to 18 carbon atoms, especially (C1-C4) alkanols; styrene, vinyltoluene, vinyl acetate, vinyl chloride, vinylidene chloride, substituted styrenes, butadiene, substituted butadienes, ethylene;
and the nitrites and amides of acrylic or of methacrylic acid. The particular comonomer or comonomers used in making a given amine-containing polymer depends upon the proportion of amine-containing monomer used in making the copolymer. The polymers are thus polymers or copolymers of cationic and, optionally, nonionic vinyl monomers. Examples of the cationic monomers are 'the amines and imines; the other recited monomers are nonionic. Thus, these water-soluble copolymers contain no acid groups other than trace amounts which may be present due to impurities in the monomers used or to small extent of hydrolysis during synthesis, storage or use.
VOLATILE BASE
The type and amount of volatile base used must be sufficient to raise the pH
of the composition to about the point where the polyfunctional amine is non-ionized (deprotonated), to avoid interaction with the anionically stabilized emulsion.
The volatile base of preference is ammonia, which may be used as the sole volatile base or in admixture with other volatile or nonvolatile bases. Other volatile bases which may be employed are morpholine, the lower alkyl amines, 2-dimethylaminoethanol, N-methylmorpholine, ethylenediamine, and others.
Flller, extenders, pigments and other additives known in the art may also be used in the compositions of the invention. If pigment is used in the traffic paint composition, it is typically in the range of fifty percent pigment volume content to sixty percent pigment volume content. Examples of pigments that may be employed include clays, calcium carbonate, talc, titanium dioxide, carbon black, and various colored pigments.
Care must be exercised when selecting the type and amount of additives to avoid altering the pH of the composition to an extent that interteres with storage stability or buffering the pH to an extent that after application the pH does not fall sufficiently to initiate protonation of the polyamine. For example a paint prepared using a polyamine with a relatively low pKa and too large an amount of calcium carbonate as filler, may display an unacceptably extended cure time.
Traffic paint compositions typically have a solids content in the range of from thirty five% to seventy% by volume and a viscosity of from about 70 kreb units to about 100 kreb units. Coatings provided by the invention are also useful in other exterior coatings such as maintenance coatings, house paint, etc..
The following examples illustrate some aspects of the invention and should not be construed as limiting the scope of the invention which is described in the specification and claims.
AM = Acrylamide DMAEMA = Dimethylaminoethylmethacrylate DMAPMA = Dimethylaminopropylmethacrylamide HEMA = Hydroxyethylmethacrylate MMA = Methylmethacrylate OXEMA = Oxazolidinoethylmethacrylate p-OXEMA = poly-oxazolidinoethylmethacrylate Paint Prey The test paints were prepared according to the following standard paint 20 i! 06 29 formulation by grinding together the ingredients listed as grind ingredients below and then adding the remaining ingredients in the letdown. The emulsion was an anionic copolymer of butyl acrylate, methyl methacrylate and methacrylic acid having a T9 of 20°C, and a particle size of 200 manometers.
Grind Ingredient Amo unt (Ib:~/103 qalsl Emulsion (50% solids) 457.9 Water. 28.4 Tamal 850 7.1 TritonCF-10 2.8 Drew~~L-493 1.0 Ti Pu re 8900 100. 0 Silverbond~B 156.3 Snowflake (calcium carbonate)595.9 LetDown Texanol~" 22.9 Methanol 15.0 Drew L-493 2.~p Hydroxyethyl cellulose 15.0 (2.5% solution in water) 1,404.3 Dry Time Test This test is similar to ASTM D1640 which is a standard test for drying of organic coatings at room temperature. The test films are applied on a non-porous substrate (glass plate or metal panel) by suitable means to give a wet film thickness of 0.012 +/-.001 inches. The ASTM test method is modified in tlhat only minimal thumb pressure is used. The thumb is turned through an angle of 90° while in contact with the film. The * Trademark A
drying time at which this rotation does not break the film is recorded.
Eary Washout Resistance The test films are prepared in the same manner as for the dry time test. After the films have dried for 15 minutes at a temperature of T8°F and 50%
relative humidity, the samples were held under a stream of cold running water (tap pressure of 170-gallons per hour), which contacted the surtace of the paint film at from a nearly perpendicular to an oblique angle. The samples remained under the stream of running water for a period of five (5) minutes. At the end of this period the samples were removed from the test stream and rated by visual inspection. Samples that showed no apparent effect were rated passes ; those that exhibited slight disruption of the film were rated marginal; those samples that showed a break in the film or any film removal were rated as fails.
Scrub Resistance Films of 3.5 mils dry thickness were prepared and cured for 24 hours at 77°F
+/- 2°F and 40-55% relative humidity. The films were tested according to according to ASTM D2486. The number of scrub cycles at which 'to an area of the paint film was fully removed was recorded.
20 ~~0629 One pint of the test paint was placed in a sealed can and stored in a sealed circulation oven at 120°F for one week. The can was removed from the oven and the paint was observed. If the paint is still fluid and shows no apparent signs of bodying or separation it is rated as a pass.
Paint That Is Not Storage Stable.
To a paint formulation prepared according to the formulation described above, Ibs. of polyOXEMA (28.5% solids) was added . T'he consistency of this paint changed from a fluid mixture to a solidified mass on aging 16 hours at ambient temperature.
The procedure of the Comparative Example was repeated except that 3.9 Ibs. of ammonium hydroxide (28%) was added before the polyOXEMA. The paint remained fluid when stored at room temperature and passed the heat aging test.
Test paints were prepared by adding polyamine (polyOXEMA), as in Example 1, in the amount indicated in the table as a percent by weight based on vehicle solids.
The paints were applied to substrates and tested. The standard paint without any amine-containing polymer was used as a control. The results appear in the table below:
Level of Polyamine Scrub (%solids on Early Washout Resistance vehicle solids) Resistance Properties Control fail 950 cycle 0.27% p.OXEMA marginal --0.62% p.OXEMA passes 760 cycles 1.25% p.OXEMA passes 950 cycles 2.5% p.OXEMA passes 910 cycles The above data demonstrates that the amine-functional polymer produces early washout resistance with acceptable scrub resistance properties. Also, the paint containing 1.25% polyOXEMA dried in 10 minutes in the dry time test compared to 20 minutes dry time for the Control paint that doesn't contain polyamine.
2020'629 Paints were prepared using the indicated amine-containing polymer according to the procedure of Example 1. The paint without any amine-containing polymer was used as a control. Samples were prepared by adding amine-containing polymer to the standard formulation in the amount indicated in the table measured as a percent b~ weight based on vehicle solids. The sample emulsions were applied to substrates and tested. The results appear in the table below:
Type of Polyamine in marking paint Early Washout 7 days aging Formulation ~~1. % / 1 Resistance 120°F
none fail passes pOXEMA passes passes OXEMA/HEMA 50/50 passes passes OXEMA/ MMA 70/30 passes passes DMAPMA/ AM 70/30 passes passes DMAPMA/ HEMA 70/30 (0.44% s/s) passes passes pDMAEMA passes passes The above data demonstrates that marking paints according to the invention have early washout-resistance and were storage stable even under storage at elevated temperature.
Claims (9)
1. A coating composition comprising:
a) anionically stabilized emulsion polymer having a Tg greater than about O°C;
b)a polyfunctional amine having from about 20 percent to about 100 percent of the monomer units by weight containing an amine group; and c) an amount of volatile base sufficient to raise the pH of the composition to a point where essentially all of the polyfunctional amine is in a non-ionic state.
a) anionically stabilized emulsion polymer having a Tg greater than about O°C;
b)a polyfunctional amine having from about 20 percent to about 100 percent of the monomer units by weight containing an amine group; and c) an amount of volatile base sufficient to raise the pH of the composition to a point where essentially all of the polyfunctional amine is in a non-ionic state.
2. The composition of claim 1 wherein the amount of polyfunctional amine is from about 0.25 to about 10 parts per 100 parts emulsion solids by weight.
3. The composition of claim 2 wherein the amount of polyfunctional amine is from about 0.4 to about 5 parts per 100 parts emulsion solids by weight.
4. The composition of claim 3 wherein the amount of polyfunctional amine is from about 0.6 to about 2.5 parts per 100 parts emulsion solids by weight.
5. The coating composition of claim 1 wherein the polyfunctional amine is polyoxazolidinoethylmethacrylate.
6. The coating composition of claim 1 wherein the polyfunctional amine polymer contains dimethylaminopropylmethacrylamide.
7. The coating composition of claim 1 wherein the polyfunctional amine polymer contains oxazolidinoethylmethacrylate.
8. The coating composition of claim 1 wherein the polyfunctional amine polymer contains dimethylaminoethylmethacrylate.
9. A shelf stable fast-cure aqueous traffic paint comprising a) anionically stabilized emulsion polymer having a Tg greater than about O°C;
b) a polyfunctional amine; and c) an amount of volatile base sufficient to raise the pH of the composition to a point where essentially all of the polyfunctional amine is in a non-ionic state.
b) a polyfunctional amine; and c) an amount of volatile base sufficient to raise the pH of the composition to a point where essentially all of the polyfunctional amine is in a non-ionic state.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US38394489A | 1989-07-21 | 1989-07-21 | |
| US383,944 | 1989-07-21 |
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| CA2020629A1 CA2020629A1 (en) | 1991-01-22 |
| CA2020629C true CA2020629C (en) | 2000-02-01 |
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| CA002020629A Expired - Fee Related CA2020629C (en) | 1989-07-21 | 1990-07-06 | Shelf stable fast-cure aqueous coating |
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|---|---|
| US (3) | US5527853A (en) |
| EP (1) | EP0409459B2 (en) |
| JP (1) | JP3049642B2 (en) |
| KR (1) | KR0156742B1 (en) |
| CN (1) | CN1039339C (en) |
| AT (1) | ATE153365T1 (en) |
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| BR (1) | BR9003539A (en) |
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| NO (1) | NO903176L (en) |
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|---|---|---|---|---|
| EP0594321B1 (en) * | 1992-10-23 | 1997-03-05 | Rohm And Haas Company | Aqueous composition |
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- 1990-07-09 AT AT90307464T patent/ATE153365T1/en not_active IP Right Cessation
- 1990-07-09 SG SG1996003735A patent/SG74550A1/en unknown
- 1990-07-09 ES ES90307464T patent/ES2102982T5/en not_active Expired - Lifetime
- 1990-07-09 EP EP90307464A patent/EP0409459B2/en not_active Expired - Lifetime
- 1990-07-09 DE DE69030751T patent/DE69030751T3/en not_active Expired - Lifetime
- 1990-07-11 NZ NZ234461A patent/NZ234461A/en unknown
- 1990-07-13 ZA ZA905500A patent/ZA905500B/en unknown
- 1990-07-17 NO NO90903176A patent/NO903176L/en unknown
- 1990-07-19 AU AU59113/90A patent/AU636366B2/en not_active Expired
- 1990-07-20 FI FI903685A patent/FI903685A0/en not_active IP Right Cessation
- 1990-07-20 JP JP2192855A patent/JP3049642B2/en not_active Expired - Lifetime
- 1990-07-20 IE IE266090A patent/IE902660A1/en unknown
- 1990-07-20 PT PT94785A patent/PT94785A/en not_active Application Discontinuation
- 1990-07-20 KR KR1019900011020A patent/KR0156742B1/en not_active IP Right Cessation
- 1990-07-20 TR TR90/0646A patent/TR25273A/en unknown
- 1990-07-20 BR BR909003539A patent/BR9003539A/en not_active IP Right Cessation
- 1990-07-21 CN CN90104773A patent/CN1039339C/en not_active Expired - Lifetime
-
1994
- 1994-11-14 US US08/340,461 patent/US5527853A/en not_active Ceased
-
1997
- 1997-01-28 US US08/789,231 patent/US5804627A/en not_active Expired - Lifetime
- 1997-05-02 US US08/850,708 patent/USRE36042E/en not_active Expired - Lifetime
- 1997-06-26 HK HK122197A patent/HK122197A/en not_active IP Right Cessation
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| NZ234461A (en) | 1992-11-25 |
| TR25273A (en) | 1993-01-01 |
| ATE153365T1 (en) | 1997-06-15 |
| FI903685A0 (en) | 1990-07-20 |
| PT94785A (en) | 1991-03-20 |
| BR9003539A (en) | 1991-08-27 |
| AU5911390A (en) | 1991-01-24 |
| KR910003050A (en) | 1991-02-26 |
| EP0409459B2 (en) | 2000-03-22 |
| DE69030751T3 (en) | 2004-05-27 |
| EP0409459A3 (en) | 1992-01-22 |
| DE69030751T2 (en) | 1998-01-08 |
| NO903176D0 (en) | 1990-07-17 |
| KR0156742B1 (en) | 1999-02-01 |
| HK122197A (en) | 1997-09-12 |
| USRE36042E (en) | 1999-01-12 |
| IE902660A1 (en) | 1991-02-27 |
| CN1048868A (en) | 1991-01-30 |
| CN1039339C (en) | 1998-07-29 |
| SG74550A1 (en) | 2000-08-22 |
| NO903176L (en) | 1991-01-22 |
| JP3049642B2 (en) | 2000-06-05 |
| ES2102982T3 (en) | 1997-08-16 |
| AU636366B2 (en) | 1993-04-29 |
| ES2102982T5 (en) | 2000-07-16 |
| CA2020629A1 (en) | 1991-01-22 |
| EP0409459B1 (en) | 1997-05-21 |
| EP0409459A2 (en) | 1991-01-23 |
| DE69030751D1 (en) | 1997-06-26 |
| JPH03157463A (en) | 1991-07-05 |
| ZA905500B (en) | 1991-04-24 |
| US5804627A (en) | 1998-09-08 |
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