LOW ENVIRONMENTAL TOXICITY LATEX COATINGS

Abstract: Combinations of nonvolatile reactive amines, and hydroxyl bearing, unsaturated esters and/or ethers and/or ether-esters (and/or combinations of non-hydroxyl bearing, unsaturated esters and/or ethers and/or ether-esters, and saturated hydroxyl bearing etherified and/or esterified oligomeric glycols and/or oligools), as replacements for conventionally employed volatile amines and/or ammonia as neutralizers, and organic solvents as coalescents respectively, has been found to enable the production of economical, low to no VOC acrylic and vinyl copolymer latex based coatings, paints, and inks. Further enhancement may be had by substitution of hypersurfactants, in place of conventional soaps and/or dispersants and/or detergents, in combination with the aforementioned nonvolatile reactive amines, particularly as particulate dispersants in pigmented and/or reinforced coatings.

Description: LOW ENVIRONMENTAL TOXICITY LATEX COATINGS Background of The Invention: The use of ammonia and/or volatile amines as neutralizing agents and/or stabilizers, and of alcohols, glycols, and glycol onoethers and monoesters, often in combination, at levels to 40% by volume (exclusive of water) has been employed for more than fifty years to achieve the coalescence of latex solids in acrylic, polyvinyl acetate and related copolymer resins based coatings. The volatilization of these conventional neutralizers, and coalescing components, after achieving film coalescence is normally required in order to inhibit the resultant film's breakdown (reversion) in the presence of humid environments, and to provide acceptable wear and stain resistance to the dried film. Recent concerns regarding the environmental degradation (predominantly low level ozone formation) , and the health and fire hazards associated with exposure to ammonia, volatile amines and volatile organics (VOCs), has led to increasingly strict regulatory limitations on the nature, and proportions, of VOCs which may be employed in coatings . One technique that has been employed in order to comply with said limitations in latex coating applications is the development of self coalescing latex resins which require no coalescents. However, to date, such materials have had the disadvantage of being limited to low Tg film formers with poor performance properties. Subject of The Invention: This invention teaches the use of low levels of combinations of nonvolatile reactive amines, in combination with hydroxyl 1 bearing unsaturated esters and/or ethers and/or ether-esters, 2 and/or non-hydroxyl bearing unsaturated esters and/or ethers 3 and/or ether-esters and incompletely etherified and/or esterified 4 oligomeric glycols and/or oligools as partial or full replacements 5 for conventionally employed volatile amines and/or ammonia as 6 neutralizers, and organic solvents as coalescents, respectively, 7 in latex resin applications. This invention has the advantage of 8 reducing emissions and enhancing the performance of films produced 9 from conventional latex resins, and when employed in conjunction 10 with certain types of hypersurfactants (cf. Table 5) also 11 upgrades pigment and/or extender dispersion, and reduces grind 12 times in particulate containing variants; thus enhancing plant and 13 energy use efficiencies. Synergistic performance enhancement, and 14 VOC reduction in latex resins may be attained via the employment 15 of the aforementioned technologies in combination. Partial 1.6 replacement of either or of both of the aforementioned components 17 by the alternatives of this invention is shown to provide lesser, 18 but still desirable benefits. 19 Preferred Embodiment of The Invention 20 The non-volatile reactive amines useful in the practice of 21 this invention have vapor pressures below 0.1 mm Hg at 25°C, 22 contain at least one basic nitrogen, and at least one carbon to 23 carbon double bond, and/or a transition metal ligand, and contain 24 no more than twelve carbon atoms per basic nitrogen atom. Those 25 more preferable contain one or more (meth)acryl and/or N-vinyl 6 ligands, and those most preferable have a water solubility 1 exceeding 2% at 25°C. Specific examples of such useful non- 2 volatile reactive amines are given in Table (1) . These examples 3 are intended to be illustrative rather than exhaustive of the 4 scope of useful materials. 5 6 TABLE I 7 (1A) N-vinyl pyrrolidone 8 (IB) N,N,N'-tris (2-butenyl) , ethylene diamine 9 (1C) N', methyl-1, 3-propylene diamine mono 2- propenamide 10 (ID) N, 2-propenyl, bis (2-hydroxy)propyl a ine 11 (IE) N, 2-propenyl, N'- (2-hydroxy) ethyl, hexamethylene 12 triamine 13 (IF) 4- (N, 3-hydroxypropyl, N-vinyl) 2-amino ethyl 2-butenoate 14 (1G) 2- [N, - (2-oxa-cyclopentadienyl) ] amino acetic acid ethyl 15 ester 1.6 (1H) 4-(N,N bis vinyl) 1, 3-pentanediol 17 (II) tetraethylene glycol mono 3- ( N, ethyl) amino, 2- (methyl) 18 2-propenoate 19 (1J) N,N-divinyl glutamic acid 2-propenyl ester 20 (IK) 6-(N,N bis vinyl) hexanoic acid ethyl ester 21 (1L) Titanium IV tetrakis N, 2-aminoethyl ethanolato 22 The preferred types of the hydroxyl bearing, unsaturated 23 esters and/or ethers and/or ether-esters useful in the practice 24 of this invention are those having vapor pressures below 0.1 mm 25 Hg at 25°C, which are capable of air initiated, oxidative 26 oligomerization and/or polymerization derived non-reversible bonding, under normal latex application conditions, to film component (s) and/or to substrate, in order to maximize coating properties via crosslinking the resulting latex thereby minimizing its (post film formation) environmental sensitivity. Examples of such unsaturated esters and ether and ether-esters as are useful in the practice of the instant invention are provided in Table II. These examples are intended to be illustrative rather than exhaustive of the scope of useful materials. Table II (2A) trimethylol propane bis (2-methyl) -2-propenoate ester (2B) sorbitan tetrakis 2-butenoate ester (2C) bis pentaerethyritol 2-propenolato, tris 2-propenoate ester (2D) hexanoic acid 6-hydroxy, (2-propenoato) ethyl ester (2E) citric acid mono isodecenyl ester (2F) malic acid bis cinnamyl ester (2G) 3-heptanoyl furfuryl alcohol (2H) 1, 2, 3-propanetriol 1-vinyl ether, 2-phenyl carboxylate ester (2J) trimeric 2-butenediol mono (methyl) glutarate ester (2K) ethoxylated (4) bis phenol A mono 2-propenoate ester The preferred types of the non-hydroxyl bearing unsaturated esters and/or ethers and/or ether-esters useful in conjunction with the practice of this invention are those having vapor pressures below 0.1 mm Hg at 25°C, which are capable of air initiated oxidative oligomerization and/or polymerization, and non-reversible bonding, under normal latex application conditions, to film component (s) and/or to substrate, in order to maximize coating properties via crosslinking the resulting latex thereby minimizing its (post film formation) environmental sensitivity. Examples of such non- hydroxyl bearing unsaturated esters and ether and ether- esters as are useful in the practice of the instant invention are provided in Table III. These examples are intended to be illustrative rather than exhaustive of the scope of useful materials. Table III (3A) trimethylol propane bis (2-methyl) -2-propenoate ester, mono vinyl ether (3B) 1,2, 3-propane triol tris 2-butenoate ester (3C) penta erethyritol 2-propenolato, tris 2-propenoate ester (3D) hexanoic acid 6-acetoxy, (2-propenoato) ethyl ester (3E) fumaric acid bis isodecyl ester (3F) maleic acid bis cinnamyl ester (3G) furoic acid vinyl ester (3H) 1,2, 3-hexanetriol 1,2-bis vinyl ether, phenyl carboxylate ester (3J) trimeric 2-butene-l, 4-diol bis propionate ester (3K) ethoxylated (4) bisphenol A bis 2- (methyl) -2-propenoate ester The preferred types of the incompletely etherified and/or esterified oligomeric glycols and/or oligools useful in the practice of this invention are those having vapor pressures below 0.1 mm Hg at 25°C, which are oligomers of two to 4 carbon diols, and of three to six carbon triols, wherein each of the ether and/or ester ligands contains five or fewer carbon atoms per oxygen. Examples of such incompletely etherified and/or esterified oligomeric glycols and/or oligools as are useful in the practice of the instant invention are provided in Table IV. These examples are intended to be illustrative rather than exhaustive of the scope of useful materials. Table IV (4A) penta (ethylene glycol) mono methyl ether (4B) tetra (1, 4-butylene glycol) mono (2-methyl) butyrate (4C) l-hydroxy-2, 5-bis methyl-3, 6, 9, 12-tetraoxa tetradecane (4D) 4-oxaheptane-l, 2, 6, 7-tetraol mono acetate, mono 2-propyl ether (mixed isomers) (4E) ethoxylated (6) 1, 2, 4-butanetriol bispropanoate (mixed isomers) (4F) tris 1,2,5-n pentane triol tetraethyl ether (mixed isomers) (4G) tris (1, 3-propane-diol) mono isopentyl ether (4H) 1,2- bis (2- hydroxy ethoxy ethyl) 1, 2, 3-propane triol (4J) polyethylene glycol (300) mono amyl ether (4K) tris neopentyl glycol mono n-propyl ether The surfactants most useful in the practice of this invention are those having vapor pressures below 0.1 mm Hg at 25°C, which are capable of non-reversible bonding, under normal processing conditions, to film component (s) and/or substrate in order to maximize coating properties, while minimizing post film formation environmental sensitivity, and which serve to efficiently wet substrates coated, and to disperse particulates, if any, employed in the formulated latex coating. Among the surfactants found to be useful in the practice of this invention are amphoteric detergents, and certain organometalics based on tetravalent titanium or zirconium. These last have been found to contribute significantly to substrate adhesion and improved corrosion resistance on wood, metalic and ceramic substrates, and to be particularly useful in maximizing color intensities of carbon black, azo and phthalocyanine based pigments. Specific examples of the preferred types of hypersurfactants are given in Table V. These examples are intended to be illustrative rather than exhaustive of the scope of useful materials. Table V (5A) 12-N,N,N-trimethylaminododecanoato (5B) N- (pentakis oxyethylene sulfato) triethylene diamine (5C) p- [6-N (methyl) morpholino] octyl phenyl phosphonic acid (5D) N,N,N-triethyl glutamic acid (5E) titanium 4 octyl, [ (tris octyl) diphosphato (5F) titanium 4 oxoethylene, bis (dodecyl) phenylsulfonato (5G) oxy [bis titanium 4 (bis tridecyl) diphosphate] (5H) zirconium 4 tetraethylene glycol monomethyl ether, tris (tetraethylene glycol monomethyl ether) diphosphato (5J) zirconium 4, bis w-N,N- (dimethyl) amino octanoato, 1,4- cyclohexanediolato (5K) triethylene glycol diolato, bis [zirconium 4 tris (octyl) phosphate] Those skilled in the art shall no doubt be capable of subverting the teachings of this invention via the substitution of functionally equivalent materials, e.g. employment in combination of hydroxylated and non-hydroxyl bearing esters (ether-esters) optionally in combination with partially esterified and/or etherified glycols, and or polyols, in place of either component (set) alone, (as is amply demonstrated in example No. 4.), or of unsaturated analogous unsaturated amides, for a portion of the aforementioned unsaturated ethers, esters or ether-esters disclosed above, and/or fluorination of one or more of the species of components heretofore described as necessary to the successful practice of this invention; however such non-critical modifications, and/or combinations of relevant species types, must be considered as within the scope of this disclosure. Further amplification of the scope and utility of the instant invention to latex coating applications in inks, paints and stains shall be found to be illustrated by the content (s) of examples 1 through 5. Said examples are intended to be illustrative rather than exhaustive of the extraordinarily diverse applicability of the instant invention. Example #1 This example teaches the superiority of the present invention versus the prior art with respect to the productivity, VOC emissions, and performance quality in a masonry sealer application. A masonry sealer formulation was prepared by the sequential dispersion of the indicated components (pigment dispersion times and grind quality achievement was noted) . The resulting sealer was applied via roller to smooth surface, ten day old, 8" X 18" X 1" thick concrete castings, at an application rate of one gallon per 400 square foot, dry time (to touch) was measured under conditions of 72° F and 85% humidity. After 240 hours of drying @ 72° F and 85% humidity, sealer performance was measured by weighing the dry casting, then impounding a 6" depth of water, or alternatively 6% salt solution, on such a casting for twenty four hours, then draining and weighing the drained casting. The weight percent of water, and independently that of 6% salt solution, adsorbed by said castings were used to determine sealer efficacy. The results of this study are given in Table No. 1. Formulation: in parts by weight; (in order of addition) water 200.0; neutralizer 1 , as shown; surfactant 3 , as shown, biocides 2 , 18.50; hydroκy ethyl cellulose, 5.00; potassium tris polyphosphate, 2.00; defoamer 2 , 1.00; coalescent 3 , as shown; ultramarine blue pigment, 0.25; rutile titanium dioxide, 200.0, American process zinc oxide, 25; platey talc, 250; water, 49.98; AC-625 Acrylic latex resin 3 , 352.0; defoamer 2 , 0.98; surfactant 0 , coalescent b , as shown,; water, 24.99; and sodium nitrite 2.30; thixotrope 4 , as shown (required) to adjust system viscosity to 85-90 KU at 75° F. Table No. 1 Formulation 1 2 3 4 5 neutralizer amp-95/1.98 1B/2.00 1H/1.80 1G/2.20 1D/1.78 surfactant (a) Tamol 850 7 /14.85 5A/1.80 5E/1.75 5K/1.55 5H/1.50 coalescent (a) Propylene glycol none 4J/4.50 none /34.56 surfactant (b) Triton N101 3 /2.20 none 5B/1.00 none 5D/1.25 coalescent (b) Texanol 8 /9.88 2A/16.42 3A/12.60 3F/18.55 2H/11.70 Formulation 8 10 neutralizer ammonia/1.00 1B/1.00 1H/1.80 1G/1.20 1D/1.78 1L/1.00 ammonia 1.00 AMP-95/1.00 surfactant (a) Tamol 850 7 /14.85 5A/1.80 5E/0.75 5K/1.55 5H/0.75 surfactant (b) Triton N101 6 /2.20 none Triton N101 none 5D/1.25 /2.20 coalescent (a) Propylene glycol none none 4J/4.50 Propylene glyc /34.56 /17.88 coalescent (b) Texanol 8 19.98 2A/16.42 3A/12.60 3F/18.55 2H/5.85 Formulation VQC g/1 5 Dispersion Grind Water Salt water time hr. Hegman adsorption g. adsorption g. 1 124 4 46 61 2 8 6 27 32 3 3 6 21 28 4 5 5 24 27 5 4 6 25 30 6 112 3.1 4 37 48 7 10 0.7 6 32 42 8 3 2.4 5 27 38 9 6 0.7 5 24 27 10 36 1.8 6 31 39 Notes: a) As shown; 1) A combination of 3.5 parts of Nuosept 95, and 15 parts of Nuocide 404D, Huls Corp. were employed; 2) Defo 806-102; Ultra Inc. 3) AC-625, Union Carbide Corp.; 4) Rhevis CR, Rhevis Corp.5) via EPA Method 24GC; 6) Rohm and Haas Corp.; 7) Eastman Kodak Inc. The efficacy of the coalescent systems of the instant art in producing a less water and salt permeable, acrylic latex based masonry seal coating, is compared to a conventionally coalesced counterpart, Formulation No. 1, and is obvious from the preceding data. VOC emissions reduction and improvement in both productivity and dispersion level achieved are likewise self evident. Example #2 This example teaches the superiority of the present invention versus the prior art with respect to the productivity, VOC emissions, and performance quality in a direct to metal, maintenance coating application. Direct to metal coatings were prepared by the sequential dispersion of the indicated components (pigment dispersion times were noted) . The resulting coating was spray applied to sandblasted smooth surface 24" X 8" carbon steel test panels at application rate of one gallon per 250 square feet. After 120 hours of drying @ 72° F and 85% humidity, edge sealing and scribing, the coatings' corrosion resistance performance were each measured by QUV cabinet exposure [cyclic exposure to UV radiation, 4% saline solution, and varying temperature (25°-80° C) ] . Formulation: in parts by weight (in order of addition) : water, 50.0; neutralizer, as shown; Surfactant 3 , as shown, biocide 1 , 4.00; oxidized polyethylene wax, 4.00; (disperse wax) polyurethane thixotrope 2 , as shown; defoamer 3 , 2.00; coalescent 3 , as shown, ultramarine blue pigment, 0.25; rutile titanium dioxide, 125; zinc aluminate 150; Acrylic latex resin 4 , 64.0; (disperse particulates to Hegman 7.5+) . Neutralizer, is shown; acrylic latex resin 4 , 564.0; defoamer 2 , 0.98; surfactant 0 , coalescent 0 , as shown; water, 16.00; arid sodium nitrate 2.30. Thixotrope 2 , (as required) to adjust system viscosity to 80-85 KU at 75° F . The control coating required 3.7 hours to disperse to a Hegman grind gauge reading of 7+, whereas each of the instant art coatings achieved said fineness of grind in less than one half hour. The results of this study are given in Table No. 2 Table No. 2 Formulation 1 2 3 4 5 6 neutralizer DMAMP-80 12.5 1A/4.00 1C/1.80 1E/2.20 1J/1.78 DMAMP- 80 5 /6.25 1A/ 2.00 surfactant (a) Triton CFloVlO.OO 5D/1.80 5F/1.75 5C/1.55 5J/1.50 Triton ( :F 10/5.00 thixotrope 2 15.00 5.00 5.50 8.70 5.30 9.32 coalescent (a) Diproylene glycol 4B/12.00 4E/10.5 4K/8.25 none none /34.60 surfactant (b) none none 5A 1.00 Triton none 5D/1.25 CF10 6 .4.0 coalescent (b) PmPE 7 /44.60 2A/16.42 3A/12.60 3F/18.55 2H/14.70 2H/14.70 4A/7.45 thixotrope 2 21.40 3.20 1.50 0.70 2.30 1.95 Formulation 7 8 9 10 11 12 neutralizer DMAMP-80 5 /12.5 1A 4.00 1C/1.80 1E/2.20 1J/1.78 DMAMP 80 5 /6.25 surfactant (a) Triton CFloVlO.OO 5D/1.80 5F/1.75 5C/0.55 5J/1.50 Triton CFlO/5.00 surfactant (b) none none 5A/1.00 Triton none 5D/1.25 CF10 6 /2.C 1 thixotrope 2 15.00 5.00 5.50 8.70 5.30 9.32 coalescent (a) Dipropylene glycol PmPE 7 4B/12.00 4E/10.5 4K/8.25 PmPE 7 /22.3 /17.3 /22.60 coalescent (b) 2A 8.81 2A/ 6.42 PmPE 7 3F/ 18.55 1 2H/14.70 2H/14.70 4A/7.45 thixotrope 2 18.90 6.20 4.50 3.70 2.30 6.95 Formulation VQC q/l e Initial gloss 60° gloss 6 60° gloss @ 60° gloss @ @60° 200hr. QUV 500 hr. QUV. 1-000 hr. QUV 232 82 76 31 film destroyed 9 91 87 82 76 11 93 90 88 80 8 87 86 82 61 10 88 86 85 84 13 84 80 66 59 72 85 79 46 12 57 80 76 51 18 9 28 87 84 72 63 10 7 88 86 84 78 11 8 92 90 87 85 12 77 85 80 75 48 Notes: 1) Nuosept 95,-Huls Corp. 2) Acrysol RM 2020, Rohm and Haas 3) Defo 3000; Ultra Inc. 4) HG 56, Rohm and Haas Corp. 5) 80% 2-N, N-dimethylamino-2-methyl propanol aq. 6) Union Carbide Corp. 7) propylene glycol mono phenyl ether. 8) via EPA Method 24GC The efficacy of the coalescent systems of the instant art in producing a more environmentally resistant, acrylic latex based direct to metal coating, as compared to a conventionally coalesced counterpart, Formulation No. 1, is obvious from the preceding data. VOC emissions reduction, and improvement in productivity achieved are likewise self evident. Example #3 This example teaches the superiority of the present invention versus the prior art with respect to productivity, VOC emissions, and performance quality in a polyvinyl acetate based interior flat architectural paint application. Interior flat paints, were prepared by the sequential dispersion of the indicated components (pigment dispersion times, and dispersion efficacy were noted) . The resulting coating was brush applied to unprimed drywall (gypsum sheet) @ 72° F and 80% humidity, coverage, stain removal, and scrubability performance were each measured after 7 days of drying 72+\- 2°F @ 65-80% humidity. Formulation; in parts by weight; (in order of addition) water, 200.0; neutralizer 1 , as shown; surfactant 3 , as shown, biocides 2 , 1.00; hydroxy ethyl cellulose, as shown; potassium tris polyphosphate, as shown; defoamer 3 , 1.00; coalescent 3 , as shown; ultramarine blue pigment, 0.25; rutile titanium dioxide, 250.0, water washed clay 4 , 50.0; calcium carbonate 5 , as shown; diatomite 6 , 50.0; water, 49.98; PVA latex resin 7 , 352.0; defoamer 2 , 0.98; coalescent 0 , as shown ; water, 100 .0;and sodium nitrite 2.30; thixotrope 8 , as shown (required) to adjust system viscosity to 90- 100 KU at 75° F. The results of this evaluation are shown in Table No. 3. Table No. 3 Formulation 1 2 neutralizer 28% ammonia aq. 1B/2.00 1H/1.80 1G/2.20 1D/1.78 28% ammonia 6.05 6.05 HEC(QP-4400) 5.50 1.20 1.35 1.25 1.40 1.35 surfactant (a) Tamol 731/6.90 5E/1.80 5J/1.75 5C/1.55 5F/1.5 Tamol 731/6 Triton N101/3.31 Triton N101/3.31 coalescent (a) Propylene glycol 4A/6.00 4 F/7.00 4H/5.50 4E/7.00 4E/7.00 /51.95 Texanol/9.88 Calcite 50 150 125 150 140 50 coalescent (b) none 2A/26.4 3C/12.60 3F/18.50 2J/11.90 2J/11.90 thixotrope 8 3.5 3.0 3.1 2.7 2.4 3.9 Formulation 8 10 neutralizer 28% ammonia aq. 1B/2.00 1H/1.80 1H/1.80 6.05 HEC (QP-4400) 5.50 1.20 1.35 1.25 surfactant (s) Tamol 731/ 6.9 Tamol 731/ 3.9 5J/ 1.75 Tamol 731/ 6.9 Triton N101/ 3.31 5J/1.0 Triton N101/ 3. coalescent (a) Propylene glycol 4A/6.00 Propylene glycol 4H/5.50 51.95 51.95 calcite 50 100 125 150 coalescent (b) 4E/2.00 2A/ 26.4 3C/ 12.60 3F/ 18.50 thixotrope 8 3.5 3.0 3.1 2.7 Formulation VOC g/1 9 Dispersion Time Grind Min. Coalescence Scrubs 10 Stain Removal 1 hr. Hegman temp "C 1 199 2.4 4 47 410 6 2 8 0.4 5 34 1,740 9 3 3 0.6 6 32 2,025 10 4 5 0.6 6 36 1,960 9 5 4 0.5 5 30 2,230 10 6 15 2.2 4 31 785 8 7 190 2.4 4 43 850 7 8 9 0.9 5 35 1,140 8 9 188 1.1 5 45 890 7 10 8 2.4 4 37 1,310 Notes 1) As shown; 2) Nuosept 95, Huls Corp.; 3) Defo 3000; Ultra Inc.. 4) 70C Huber Corp.5) Camel Carb., Cambel Corp.; 6) Diafil 530 viscosity of 65-70 KU, and the coating was applied by curtain coating on sanded but unprimed 4' X 8* X 0.25" laminate natural oak (on pine) substrate. The coated panels were force dried by passing same through a 180° F oven for 20 minutes, then cooled at ambient temperature (ca. 80° F) for 24 hours prior to evaluation, for abrasion and solvent resistance, to determine coating performance, efficacy. The results of this study are given in Table No. 4. Table No. 4 Formulation 1 2 3 4 5 6 7 Part A: neutralizer 28% 1A 1H 1H 1H IB IB IB ammonia aq. Part B: formulation Texanol 8.00 4.00 4.00 diethylene glycol 18.20 9.10 9.10 mono butyl ether 2A 12.05 6.00 6.00 6.00 6.00 2C 4.40 10.70 3B 4.20 6.00 4G 1.90 2.90 1.05 6.20 4J Formulation VOC g/1 1 Abrasion Solvent Stain Mix pot life resistance resistance resistance' 1 hr.@ 80°F 5 165 114 lifts poor 7.5 3 31 slight softening good 42 4 29 slight softening fair 35 3 24 no change excellent 40 3 26 no change good 61 4 98 mod. Softening fair 46 83 19 slight softening fair 21 85 78 severe softening poor 11 Notes: 1) By EPA Method 24GC; (formulations 2 through 7 produced 0 to negative VOC readings by EPA Methods 24, and 24A; 2) Tabor CS-10 wheel 1000 cycles; 3) 24 hr methyl ethyl ketone covered spot test; 4) 24 hr exposure to lipstick; 5) time to 10% loss of abrasion resistance in finished coating. This example demonstrates, that the use of the combination of components cited as the basis of the instant invention, viz. That Whittaker, Clark, and Daniels Inc. 7) Rhoplex 3077, Rohm and Haas Corp.; 8) Rhevis CR, Rhevis Corp. 9) via EPA Method 24GC. 10) ASTM method; 11) ASTM method. The efficacy of the coalescent systems of the instant art in producing a more, scrub and stain resistant PVA latex based interior flat architectural coating as compared to a conventionally coalesced counterpart, Formulation No. 1, is obvious from the preceding data. VOC emissions reduction and improvement in both productivity and dispersion level achieved are likewise self evident, as is a considerable reduction in minimum coalescence temperature, without recourse to the use of low boiling, flammable solvent (s), normally employed to induce same. Example #4 This example teaches the superiority of the present invention versus the prior art with respect to the productivity, VOC emissions, and performance quality in a force dried, clear, protective, two component acrylic latex cured - waterborne epoxy, wood cabinet coating. Component A. neutralizing agent, as shown-3.5 PBW; sodium nitrite 0.15 and defoamer (Patcote 519-Patco Coatings Inc.) were admixed with 95.85 PBW of (Acrylic latex-Maincote AE 58) , and said emulsion was subsequently mixed with 50 PBW of Component B, formulated by blending various additives, as shown, into 12.5 PBW of Genepoxy 370-H55- Daubert Chemical Co., and diluting as necessary with water to produce a total part B weight of 25 parts. Thixatrope 1 , was added, as required, to provide an initial mix nonvolatile reactive amines, in combination with hydroxyl bearing unsaturated esters and/or ethers and/or ether-esters, and/or non- hydroxyl bearing unsaturated esters and/or ethers and/or ether- esters and incompletely etherified and/or esterified oligomeric glycols and/or oligools as (partial or full) replacements for conventionally employed volatile amines and/or ammonia as neutralizers, and organic solvents as coalescents, respectively may be employed to substantially enhance the processability (pot life) , mechanical and chemical resistance properties ( abrasion and stain resistance respectfully) as well as attain VOC reduction in wood coatings. A further benefit of the instant invention as applied to wood coatings is that unlike conventionally coalesced waterborne coatings, e.g. formulation D-l latex formulations based upon the teachings of this invention, e.g. formulations D-2 through D-7, do not cause significant grain rise, thereby virtually eliminating the necessity for intercoat sanding. These data also demonstrate that subsets of the preferred combination of components herein disclosed (e.g. formulations D-3,D-5, and D-6) may provide considerable benefits relative to their conventional counterparts, such as Formulation No. 1; however, omission of one or more of the components of the combination herein disclosed leads to inferior results as compared to the inclusion of the full compliment. Example #5 This example teaches the superiority of the present invention versus the prior art with respect to the productivity, VOC emissions, and performance quality in waterborne flexographic inks. A latex flexographic ink formulation, was prepared by the sequential dispersion of the indicated components (pigment dispersion times and grind quality achievement was noted) . The resulting ink was applied via a #6 wire wound rod to bond paper, and permitted to dry. Dry time (to touch) was measured under conditions, of 72° F and 85% humidity. After 6 hours of drying @, 72° F and 85% humidity, heat seal resistance performance (face to face) was measured at 25 psig. and 2 seconds contact time) the results of this study are given in Table No. 5. Formulation: in parts by weight; (in order of addition) E-2350 resin 267; neutralizer, as shown; surfactant, as shown; Defo 1020 defoamer 4.00 Ultra Inc.; coalescent 3 , as shown; calcium lithol pigment 50% presscake, 400-Sun Chemical Corp.; Michemlube wax 5- Michelman Inc., water, as required in order to produce a viscosity of 27 seconds using a #2 Zahn cup. Relative dry ink color intensities were measured by integrating thin film reflectance spectra at 300-600 urn wavelengths using a spectrophotometer after 48 hours of drying at the above conditions Table No. 5 Formulation neutralizer 28% ammonia aq, 1D/2.00 IH/1.40 2.00 surfactant Tamol 850/4.95 5A/1.80 5E/1.75 coalescent isopropanol/48 2A/10.5 2E/20.0 Texanol/24 3C/15.5 4H/5.5 Formulation neutralizer 1F/2.00 1D/1.46 28% ammonia aq/2.00 surfactant 5K/1.55 5H/1.50 Tamol 850/ 4.95 coalescent 3C/25.0 3C/18.0 3C/18.0 4H/7.0 4H/7.0 Formulation VOC g/1 5 Dry to touch time 6 hr.Heat seal Relative color hr. resistance °c " intensity. 1 144 3.4 86 1.00 2 4 0.7 154 1.42 3 3 0.6 172 1.27 4 5 0.7 104 1.08 5 4 0.6 167 1.39 6 7 0.6 122 1.03 Notes: The efficacy of the coalescent systems of the instant art in producing a faster drying, more strongly colored, and lower VOC acrylic latex based printing ink coating as compared to a conventionally coalesced counterpart are obvious from the preceding data, as are indications that incomplete application of the teachings of this disclosure may lead to inferior results. Note the deficiencies in the heat seal performance of formulation E-4 as compared to E-2, E-3, and E-5, the benefits of hyperdispersant use as indicated E-2 to E-5 vs. E-6. Example #6 This example teaches the utility of the instant invention in the production of superior waterborne anti-scuff overprint coatings for graphic arts applications. A 30% solution of water reducible styrene-acrylic copolymer resin in water was prepared by admixture of the indicated neutralizing agent-as shown, water, and Air Product Corp's Flexbond 28 resin. Thirty parts by weight (PBW) of the preceding solution, were admixed with 50 PBW of styrene- acrylic latex resin (Flexbond 285, Air Products Corp.), coalescent, and surfactant (s) -as shown, poly ethylene wax, 2 PBW, and sufficient water to dilute the system to 100 PBW. The resulting coating was applied, in line on a high speed six color lithographic cold web press, to a solid four color print pattern, followed by in line infrared drying, and folding. Measurements of VOC (by EPA Method 24), offset, and blocking limited maximum allowable impression rates (impressions/ minute [IPM]), were made. The results are given in Table 6. Table 6 Formulation 2 3 neutralizer 28% ammonia/ 6.00 AMP 95 1 / 8. 00 AMP 95/ 8.00 coalescent (s) isopropanol/ 12 isopropanol/ 12 2G/ 4.50 surfactant Tamol 850/ 2.05 Tamol 850/ 2.05 5K/ 0.75 Formulation 5 6 neutralizer 1G/ 6.00 1G/ 6.00 1G/ 6.00 coalescent (s) 2G/ 4.50 2G/ 4.50 3C/ 3.65 4C/ 0.85 surfactant Tamol 850/ 2.05 5K/ 0.75 2K/ 0.75 Performance 1 2 3 VOC -g/1. 131 146 27 max IPM (offset) 8,240 9,235 12,720 max IPM (block) 10,150 9,950 14, ( 510 Performance 5 6 VOC -g/1. 3 4 4 max IPM (offset) 16,670 18,000 2 18, 000 max IPM (block) 17,130 18,000 18, ,000

Claims: Claims : What we claim is: 1) Compositions of matter comprising: essentially nonvolatile reactive amines; hydroxyl bearing, unsaturated esters and/or ethers and/or ether-esters; and/or combinations of non-hydroxyl bearing, unsaturated esters and/or ethers and/or ether-esters, and/or saturated hydroxyl bearing etherified and/or esterified oligomeric glycols and/or oligools. 2) Compositions of matter comprising: volatile amines and/or ammonia neutralizers; hydroxyl bearing, unsaturated esters and/or ethers and/or ether-esters; and/or combinations of non-hydroxyl bearing, unsaturated esters and/or ethers and/or ether-esters, and/or saturated hydroxyl bearing etherified and/or esterified oligomeric glycols and/or oligools. 3) Compositions of matter comprising: essentially nonvolatile reactive amines; and organic solvent coalescents. 4) Compositions of matter as defined in Claims 1, 2 and 3 having as an additional component latex resin. 5) Compositions of matter as defined in Claims 1, 2, 3 and 4 having hypersurfactants as an additional component. 6) Compositions of matter as defined in Claim 5 in which the hypersurfactants are derived from titanium or zirconium based organometalics. ompositions of matter as in Claim 4 in which the latex resin is derived from poly vinyl acetate and/or acrylic and/or a copolymer thereof.

Inventors: SUGERMAN GERALD, SUGERMAN, GERALD
Applicants: SUGERMAN GERALD, SUGERMAN, GERALD
Application year: 1997
Main classification: C09D
IPC codes: C09D5