CA1120625A - Pigmented air drying latex paints having superior gloss - Google Patents
Pigmented air drying latex paints having superior glossInfo
- Publication number
- CA1120625A CA1120625A CA000298225A CA298225A CA1120625A CA 1120625 A CA1120625 A CA 1120625A CA 000298225 A CA000298225 A CA 000298225A CA 298225 A CA298225 A CA 298225A CA 1120625 A CA1120625 A CA 1120625A
- Authority
- CA
- Canada
- Prior art keywords
- copolymer
- solution
- water
- pigment
- latex
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229920000126 latex Polymers 0.000 title claims abstract description 24
- 239000004816 latex Substances 0.000 title claims abstract description 23
- 239000003973 paint Substances 0.000 title claims abstract description 21
- 238000007605 air drying Methods 0.000 title claims abstract description 12
- 229920001577 copolymer Polymers 0.000 claims abstract description 45
- 239000000049 pigment Substances 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 239000000839 emulsion Substances 0.000 claims abstract description 13
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 238000000227 grinding Methods 0.000 claims abstract description 8
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 239000004408 titanium dioxide Substances 0.000 claims description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 5
- 229940093475 2-ethoxyethanol Drugs 0.000 claims description 5
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical group CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229960002887 deanol Drugs 0.000 claims description 4
- 239000012972 dimethylethanolamine Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 229960005196 titanium dioxide Drugs 0.000 claims 2
- 235000010215 titanium dioxide Nutrition 0.000 claims 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims 1
- 239000007787 solid Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- -1 hydroxy amines Chemical class 0.000 description 5
- 239000004908 Emulsion polymer Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000019612 pigmentation Effects 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- PYSGFFTXMUWEOT-UHFFFAOYSA-N 3-(dimethylamino)propan-1-ol Chemical compound CN(C)CCCO PYSGFFTXMUWEOT-UHFFFAOYSA-N 0.000 description 1
- CDOUZKKFHVEKRI-UHFFFAOYSA-N 3-bromo-n-[(prop-2-enoylamino)methyl]propanamide Chemical compound BrCCC(=O)NCNC(=O)C=C CDOUZKKFHVEKRI-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 description 1
- PYSOFCRZGINJKU-UHFFFAOYSA-N OC(=O)C=C.C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 Chemical compound OC(=O)C=C.C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 PYSOFCRZGINJKU-UHFFFAOYSA-N 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940043237 diethanolamine Drugs 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical group C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 description 1
- XPNLOZNCOBKRNJ-UHFFFAOYSA-N ethyl prop-2-enoate;methyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C=C.COC(=O)C(C)=C XPNLOZNCOBKRNJ-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229940071826 hydroxyethyl cellulose Drugs 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229940086542 triethylamine Drugs 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A high gloss, water base, pigmented latex is provided by grinding a pigment into a water-free solution of a carboxyl-functional addition solution copolymerized copolymer of monoethylenically unsaturated monomers inclu-ding at least about 10%, by weight of monoethylenically unsaturated carboxylic acid in water miscible alcoholic organic solvent, the copolymer being at least partially neutralized at the time of grinding with an hydroxy amine, to render the said copolymer dispersible in water, and thereby form a nonaqueous pigment paste, and then mixing the nonaqueous pigment paste with an air drying aqueous latex of aqueous emulsion copolymerized copolymer particles.
The invention includes the latex paint so-produced.
A high gloss, water base, pigmented latex is provided by grinding a pigment into a water-free solution of a carboxyl-functional addition solution copolymerized copolymer of monoethylenically unsaturated monomers inclu-ding at least about 10%, by weight of monoethylenically unsaturated carboxylic acid in water miscible alcoholic organic solvent, the copolymer being at least partially neutralized at the time of grinding with an hydroxy amine, to render the said copolymer dispersible in water, and thereby form a nonaqueous pigment paste, and then mixing the nonaqueous pigment paste with an air drying aqueous latex of aqueous emulsion copolymerized copolymer particles.
The invention includes the latex paint so-produced.
Description
~2~6;2S
This invention relates to high gloss, water base, pigmented air drying latex house paints.
Conventional air drying latex paints develop little gloss, as is well known. These conventional latex paints include pigment which is dis-persed in the water phase by means of surfactants or wetting agents, and this leads to low gloss. The pigment is quite differently dispersed in this in-vention, leading to a very significant increase in gloss, as will be illus-trated.
According to one aspect of the present invention there is pro-vided a method of producing a high gloss, air drying water base, pigmentedlatex paint comprising, grinding 3 - 12 parts of pigment into a water-free solution containing 1 part of an at least partially neutralized carboxyl-functional addition solution copolym0rized copolymer of 10% to 40% of mono-ethylenically unsaturated carboxylic acid, the major proportion of said pig-ment being titanium dioxide and said solution containing 40% to 70% of alco-holic organic solvent based on the weight of the solution copolymer, said copolymer being at least partially neutralized with a hydroxy amine having the formula:
X
R - N - R'OH
in which R is hydrogen or an alkyl group, R' is an alkylene group, and X is either R or R'OH, to render the said copolymer dispersible in water, and thereby form a nonaqueous pigment paste, and then mixing the nonaqueous pig-ment paste with an air drying aqueous latex consisting essentially of emul-sified aqueous emulsion copolymer particles having a Tg below 20C., the co-polymer of said latex containing less than about 4% of reactive monomers.
The organic solvent is preferably an alcoholic solvent. The invention fur-ther provides the latex paint so-produced.
Referring more particularly to the solution copolymerized copoly-mer of monoethylenically unsaturated monomers containing a high level of car-boxyl functionality, any
This invention relates to high gloss, water base, pigmented air drying latex house paints.
Conventional air drying latex paints develop little gloss, as is well known. These conventional latex paints include pigment which is dis-persed in the water phase by means of surfactants or wetting agents, and this leads to low gloss. The pigment is quite differently dispersed in this in-vention, leading to a very significant increase in gloss, as will be illus-trated.
According to one aspect of the present invention there is pro-vided a method of producing a high gloss, air drying water base, pigmentedlatex paint comprising, grinding 3 - 12 parts of pigment into a water-free solution containing 1 part of an at least partially neutralized carboxyl-functional addition solution copolym0rized copolymer of 10% to 40% of mono-ethylenically unsaturated carboxylic acid, the major proportion of said pig-ment being titanium dioxide and said solution containing 40% to 70% of alco-holic organic solvent based on the weight of the solution copolymer, said copolymer being at least partially neutralized with a hydroxy amine having the formula:
X
R - N - R'OH
in which R is hydrogen or an alkyl group, R' is an alkylene group, and X is either R or R'OH, to render the said copolymer dispersible in water, and thereby form a nonaqueous pigment paste, and then mixing the nonaqueous pig-ment paste with an air drying aqueous latex consisting essentially of emul-sified aqueous emulsion copolymer particles having a Tg below 20C., the co-polymer of said latex containing less than about 4% of reactive monomers.
The organic solvent is preferably an alcoholic solvent. The invention fur-ther provides the latex paint so-produced.
Referring more particularly to the solution copolymerized copoly-mer of monoethylenically unsaturated monomers containing a high level of car-boxyl functionality, any
-2-llZ~;2Si addition copoly~er of monoethylenically unsaturated monomers may be used, the usual monomers being acrylic or vinyl acetate, including at least about 10% by weight of monoethylenically unsaturated carboxylic acid. However, in this invention, it is preferred that both the solution copolymer and also the emulsion copolymerized latex copoly-mer contain a major proportion (more than 50% by weight) of acrylic esters, more particularly constituted by a blend of methyl methacrylate with alkyl acrylate in which the alkyl group contains from 1-8 carbon atoms. Styrene, vinyl toluene, or vinyl acetate may be used in place of the methyl methacrylate, but these are less preferred. Acrylonitrile may also be present. These are nonreactive monoethylenic monomers. Hydroxy functional monomers may also be present, such as 2-hydroxyethyl acrylate, and amide groups are also permissible, such as are provided by acrylamide, meth-acrylamide, or other monoethylenic carboxylic acid amide.
The copolymers of high acidity are solution copolymers which denotes copolymerization in organic solvent solution. Water miscible organic solvents, and especially alcohols, such as butanol, 2-ethoxy ethanol and 2-butoxy ethanol, are preferably selected in this invention since the copolymer is ultimately dispersed in the aqueous medium provided by the latex.
At least 10%, up to about 40%, of the copolymer is to be constituted by monoethylenically unsaturated carboxylic acid. Many acids are appropriate, particularly acrylic acid. Other appropriate acids are methacrylic acid, crotonic acid, itaconic acid, monobutyl maleate, and the like. Preferred proportions are from 15-30% of the copolymer.
l~Z~62S
The solution copolymerization which is used is a conventional one which is carried out in solvent solution in the presence of a free radical polymerization catalyst.
Preferred water miscible organic solvents are 2-ethoxy ethanol and 2-butoxy ethanol, though numerous others are well known and useful herein, such as isopropanol, acetone, and the like.
The copolymer solution is then at least partially neutralized with an amine, hydroxy amines giving the best lQ results. Neutralization is carried out to the extend needed for subsequent dispersion in water, neutralization to at least about 50% of the acidity of the copolymer being generally contemplated.
While amines, such as triethyl amine or ammonium hydroxide (usually considered an amine in the art of solu-bilizing carboxyl copolymers) are generally useful, hydroxy amines yield significantly better gloss. Hydroxy amines have the formula:
X
R-N-R'OH, in which R is hydrogen, or an alkyl group, preferably an alkyl group containing 1-4 carbon atoms, R' is an alkylene group, preferably containing 1-4 carbon atoms, and X is either R or R'OH.
Appropriate hydroxy amines are illustrated by pro-panol amine, diethanol amine, dipropanol amine, dimethyl ethanol amine, dimethyl propanol amine, diethyl ethanol amine, methyl diethanol amine, ethyl diethanol amine, and the like. Tertiary amines containing at least one hydroxy group are particularly contemplated, and the invention will be illustrated using dimethyl ethanol amine.
~12~fi'~S
While any pigment may be included in the paints of this invention, titanium dioxide pigment, both rutile and anatase, are particularly contemplated. The hydroxy amines are especially significant in achieving the effect of dis-persion and high gloss containing results contemplated herein when titanium dioxide pigment is relied upon to pro-vide the major proportion of the pigmentation. The propor-tion of pigment should be sufficient to provide a paste in known fashion. A pigment volume concentration of at least 10% is usual.
After neutralization of at least a portion of the carboxyl functionality contained in the copolymer solution, the pigment is added and conventional grinding is carried out to produce a pigment paste. In preferred practice, from 3-12 parts by weight of pigment are dis-persed in the copolymer-solvent solution per part of copolymer, more preferab].y from 5-lO parts of pigment per part of copolymer. The aqueous latex providing the bulk of the resin solids of the paint is then added either directly or after preliminary admixture of a small amount of water, into the neutralized solvent solution.
The neutralized solution of carboxyl-functional solution copolymer preferably contains from 40% to 70% of solvent, based on the weight of the solution copolymer, to provide a viscosity appropriate for grinding in the pigment.
While any conventional air drying emulsion copolymer latex used in the paint industry may be employed herein, vinyl acetate-butyl acrylate copolymers, vinyl acetate-ethylene copolymers, and methyl methacrylate-ethyl acrylate (or butyl acrylate) copolymers illustrate the more usual paint latices, and the methyl methacrylate-acrylic ester copolymers are preferred. In general, aqueous emulsion copolymers having a Tg below 20C. are useful herein since these provide air dry paints. Tg denotes the glass transition temperature and is well recognized to define the nature of an emulsion copolymer which is not significantly cross-linked in the emulsion. A small amount of coalescing solvent, as is well known, may be present to facilitate air drying. Reactive monomers cannot be present in the large amounts needed for a baking system, for these would have to be reacted in order to provide good film properties, and baking is not available in a house paint.
Thus, up to about 1% of a carboxylic monomer may be included for emulsion stability and up to about 2% of amine-functional monomers may be present to maximize adhesion and other properties, but larger amounts of reactive materials should be avoided since these are inconsistent with an air dry latex. The total proportion of reactive monomers should be less than about 4%. The amine functional monomers are illustrated in United States patents 3,356,653; 3,356,654;
The copolymers of high acidity are solution copolymers which denotes copolymerization in organic solvent solution. Water miscible organic solvents, and especially alcohols, such as butanol, 2-ethoxy ethanol and 2-butoxy ethanol, are preferably selected in this invention since the copolymer is ultimately dispersed in the aqueous medium provided by the latex.
At least 10%, up to about 40%, of the copolymer is to be constituted by monoethylenically unsaturated carboxylic acid. Many acids are appropriate, particularly acrylic acid. Other appropriate acids are methacrylic acid, crotonic acid, itaconic acid, monobutyl maleate, and the like. Preferred proportions are from 15-30% of the copolymer.
l~Z~62S
The solution copolymerization which is used is a conventional one which is carried out in solvent solution in the presence of a free radical polymerization catalyst.
Preferred water miscible organic solvents are 2-ethoxy ethanol and 2-butoxy ethanol, though numerous others are well known and useful herein, such as isopropanol, acetone, and the like.
The copolymer solution is then at least partially neutralized with an amine, hydroxy amines giving the best lQ results. Neutralization is carried out to the extend needed for subsequent dispersion in water, neutralization to at least about 50% of the acidity of the copolymer being generally contemplated.
While amines, such as triethyl amine or ammonium hydroxide (usually considered an amine in the art of solu-bilizing carboxyl copolymers) are generally useful, hydroxy amines yield significantly better gloss. Hydroxy amines have the formula:
X
R-N-R'OH, in which R is hydrogen, or an alkyl group, preferably an alkyl group containing 1-4 carbon atoms, R' is an alkylene group, preferably containing 1-4 carbon atoms, and X is either R or R'OH.
Appropriate hydroxy amines are illustrated by pro-panol amine, diethanol amine, dipropanol amine, dimethyl ethanol amine, dimethyl propanol amine, diethyl ethanol amine, methyl diethanol amine, ethyl diethanol amine, and the like. Tertiary amines containing at least one hydroxy group are particularly contemplated, and the invention will be illustrated using dimethyl ethanol amine.
~12~fi'~S
While any pigment may be included in the paints of this invention, titanium dioxide pigment, both rutile and anatase, are particularly contemplated. The hydroxy amines are especially significant in achieving the effect of dis-persion and high gloss containing results contemplated herein when titanium dioxide pigment is relied upon to pro-vide the major proportion of the pigmentation. The propor-tion of pigment should be sufficient to provide a paste in known fashion. A pigment volume concentration of at least 10% is usual.
After neutralization of at least a portion of the carboxyl functionality contained in the copolymer solution, the pigment is added and conventional grinding is carried out to produce a pigment paste. In preferred practice, from 3-12 parts by weight of pigment are dis-persed in the copolymer-solvent solution per part of copolymer, more preferab].y from 5-lO parts of pigment per part of copolymer. The aqueous latex providing the bulk of the resin solids of the paint is then added either directly or after preliminary admixture of a small amount of water, into the neutralized solvent solution.
The neutralized solution of carboxyl-functional solution copolymer preferably contains from 40% to 70% of solvent, based on the weight of the solution copolymer, to provide a viscosity appropriate for grinding in the pigment.
While any conventional air drying emulsion copolymer latex used in the paint industry may be employed herein, vinyl acetate-butyl acrylate copolymers, vinyl acetate-ethylene copolymers, and methyl methacrylate-ethyl acrylate (or butyl acrylate) copolymers illustrate the more usual paint latices, and the methyl methacrylate-acrylic ester copolymers are preferred. In general, aqueous emulsion copolymers having a Tg below 20C. are useful herein since these provide air dry paints. Tg denotes the glass transition temperature and is well recognized to define the nature of an emulsion copolymer which is not significantly cross-linked in the emulsion. A small amount of coalescing solvent, as is well known, may be present to facilitate air drying. Reactive monomers cannot be present in the large amounts needed for a baking system, for these would have to be reacted in order to provide good film properties, and baking is not available in a house paint.
Thus, up to about 1% of a carboxylic monomer may be included for emulsion stability and up to about 2% of amine-functional monomers may be present to maximize adhesion and other properties, but larger amounts of reactive materials should be avoided since these are inconsistent with an air dry latex. The total proportion of reactive monomers should be less than about 4%. The amine functional monomers are illustrated in United States patents 3,356,653; 3,356,654;
3,356,655; and 3,509,0~5.
It is desired to call particular attention to some of the superior attributes which are obtained in pigmented paints formulated in accordance with this invention in com-parison with other commercially available semigloss paints, aside from the significant improvement in gloss which is obtained. Thus, better visual hiding is obtained at the same level of pigmentation, and the pigment dispersing properties are superior. This enables dispersion in the absence of the surfactants normally introduced to aid in 1~2~)~25 dispersing the pigment. This characteristic is particu-larly beneficial from the standpoint of processing because in the previous technique of grinding the pigment into water containing a surfactant, foaming was troublesome.
Also, and from the product standpoint, higher solids con-tent paints are enabled by this invention. The superior dispersion also enables darker colors using smaller amounts of prime pigment (the titanium dioxide), and the tendency of the pigment to flocculate is avoided.
From the standpoint of application, it has been found that wetting of the substrate is superior and the rheology of the coating is better, causing brush marks to flow out and become less discernible. The better wetting which is obtained enables the formulation of paints in which the polyester component normally introduced to provide the desired chalk penetration can be eliminated. As a result, one can wet chalky surfaces without introducing any tendency to yellow.
It is also possible in this invention to reduce the proportion of titanium dioxide pigment which is needed for hiding, and this can be done by increasing the amount of extender pigment, such as aluminum silicate. This is not possible in the corresponding conventional system where aluminum silicate introduction reduces gloss.
Throughout this specification, and particularly in the examples and claims which follow, all proportions are by weight unless otherwise specified.
llZ~Z5 Example 1 (For Comparison) Charge Composition (Pounds) 83 Water
It is desired to call particular attention to some of the superior attributes which are obtained in pigmented paints formulated in accordance with this invention in com-parison with other commercially available semigloss paints, aside from the significant improvement in gloss which is obtained. Thus, better visual hiding is obtained at the same level of pigmentation, and the pigment dispersing properties are superior. This enables dispersion in the absence of the surfactants normally introduced to aid in 1~2~)~25 dispersing the pigment. This characteristic is particu-larly beneficial from the standpoint of processing because in the previous technique of grinding the pigment into water containing a surfactant, foaming was troublesome.
Also, and from the product standpoint, higher solids con-tent paints are enabled by this invention. The superior dispersion also enables darker colors using smaller amounts of prime pigment (the titanium dioxide), and the tendency of the pigment to flocculate is avoided.
From the standpoint of application, it has been found that wetting of the substrate is superior and the rheology of the coating is better, causing brush marks to flow out and become less discernible. The better wetting which is obtained enables the formulation of paints in which the polyester component normally introduced to provide the desired chalk penetration can be eliminated. As a result, one can wet chalky surfaces without introducing any tendency to yellow.
It is also possible in this invention to reduce the proportion of titanium dioxide pigment which is needed for hiding, and this can be done by increasing the amount of extender pigment, such as aluminum silicate. This is not possible in the corresponding conventional system where aluminum silicate introduction reduces gloss.
Throughout this specification, and particularly in the examples and claims which follow, all proportions are by weight unless otherwise specified.
llZ~Z5 Example 1 (For Comparison) Charge Composition (Pounds) 83 Water
4.5 Anionic Surfactant - sodium salt of polyacrylic acid (Rohm and Haas Tamol 731*may be used) 125 Titanium dioxide rutile Disperse the pigment using a high speed mixer Add the following in order 425 Water )dissolve0 10 Hydroxy ethyl cellulose) thickener 8 Diethylene glycol monobutyl ether (coalescing agent) 319 Acrylic Emulsion Polymer (47% solids) - see note 1 4 Defoamer (Drew L-475*may be used) 1 Anionic surfactant (dioctyl sodium sulfosuccinate [60% solids in isopropanol]) Solids: 28% by weight Weight per gallon: 9.4 pounds The formulation contains:
125 pounds of titanium dioxide pigment 150 pounds of emulsion polymer solids Note 1 - The acrylic emulsion polymer utilized is made in accordance with the teachings of Example 2 of United States Patent 3,356,653 and had the following monomer composition:
53% methyl methacrylate 44% butyl acrylate 1% methacrylic acid 2% amino adduct (see Example 1 of Patent 3,356,653) ~OV/~
*Trademarks ~;25 Example 2 Example 1 was repeated, only the 4.5 pounds of the anionic surfactant dispersant and the 83 pounds of water were replaced with 27.2 pounds of water soluble acrylic copolymer solution of Example 3 at 55% solids. The propor-tion of acrylic emulsion was reduced to maintain the solids content at 150 pounds:
135 pounds - 90% - Emulsion polymer solids 15 pounds - 10% - Water soluble acrylic polymer ]0 solids Example 3 Charge Composition (grams) 1080 2-Ethoxy ethanol solvent - heat to 120C.
360 Methyl methacrylate 1700 Ethyl acrylate 520 Acrylic acid Benzoyl peroxide Add the above over a three hour period while maintaining temperature at 120C. Hold one hour and add:
12 Tertiary-butyl perbenzote Hold 1 1/2 hours. Start cooling and add:
370 2-Ethoxy ethanol solvent Cool to 70C. and add the following over a 20 minute period:
650 Dimethyl ethanol amine.
Strain to provide an acrylic copolymer solution:
~onvolatile solids: 55%
Viscosity (Gardner) Z3 Acid value (nonvolatiles) 148 _9_ ~2~6Z5 ~ queous latex paints prepared in accordance with Examples 1 and 2 were compared as follows:
Gloss Example 1 Example 2 60 ~loss meter readlng Dry 1 week at room temperature 36 78 Film Properties Scrub resistance Good Good Blocking resistance Good Good Burnishing resistance Good Good 10 Stain removal Very good Very good Hiding Good Very good As will be seen, the invention has been illust-rated by a comparison between two similar latex paints, one produced in conventional fashion (Example 1), and the other produced in accordance with the teachings of this invention (Example 2).
The generally superior properties which are produced have been described previously, and the marked increase in gloss (from 36 to 78 measured on a 60 gloss-meter) represents a large increase which stands out underthe most casual inspection.
125 pounds of titanium dioxide pigment 150 pounds of emulsion polymer solids Note 1 - The acrylic emulsion polymer utilized is made in accordance with the teachings of Example 2 of United States Patent 3,356,653 and had the following monomer composition:
53% methyl methacrylate 44% butyl acrylate 1% methacrylic acid 2% amino adduct (see Example 1 of Patent 3,356,653) ~OV/~
*Trademarks ~;25 Example 2 Example 1 was repeated, only the 4.5 pounds of the anionic surfactant dispersant and the 83 pounds of water were replaced with 27.2 pounds of water soluble acrylic copolymer solution of Example 3 at 55% solids. The propor-tion of acrylic emulsion was reduced to maintain the solids content at 150 pounds:
135 pounds - 90% - Emulsion polymer solids 15 pounds - 10% - Water soluble acrylic polymer ]0 solids Example 3 Charge Composition (grams) 1080 2-Ethoxy ethanol solvent - heat to 120C.
360 Methyl methacrylate 1700 Ethyl acrylate 520 Acrylic acid Benzoyl peroxide Add the above over a three hour period while maintaining temperature at 120C. Hold one hour and add:
12 Tertiary-butyl perbenzote Hold 1 1/2 hours. Start cooling and add:
370 2-Ethoxy ethanol solvent Cool to 70C. and add the following over a 20 minute period:
650 Dimethyl ethanol amine.
Strain to provide an acrylic copolymer solution:
~onvolatile solids: 55%
Viscosity (Gardner) Z3 Acid value (nonvolatiles) 148 _9_ ~2~6Z5 ~ queous latex paints prepared in accordance with Examples 1 and 2 were compared as follows:
Gloss Example 1 Example 2 60 ~loss meter readlng Dry 1 week at room temperature 36 78 Film Properties Scrub resistance Good Good Blocking resistance Good Good Burnishing resistance Good Good 10 Stain removal Very good Very good Hiding Good Very good As will be seen, the invention has been illust-rated by a comparison between two similar latex paints, one produced in conventional fashion (Example 1), and the other produced in accordance with the teachings of this invention (Example 2).
The generally superior properties which are produced have been described previously, and the marked increase in gloss (from 36 to 78 measured on a 60 gloss-meter) represents a large increase which stands out underthe most casual inspection.
Claims (9)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method of producing a high gloss, air drying water base, pigmented latex paint comprising, grinding 3-12 parts of pigment into a water-free solution containing 1 part of an at least partially neutralized carboxyl-functional addition solution copolymerized copolymer of 10% to 40% of monoethylenically unsaturated carboxylic acid, the major proportion of said pigment being titanium dioxide and said solution containing 40% to 70%
of alcoholic organic solvent based on the weight of the solution copolymer, said copolymer being at least partially neutralized with an hydroxy amine having the formula:
in which R is hydrogen or an alkyl group, R' is an alkylene group, and X is either R or R'OH, to render the said copoly-mer disperisble in water, and thereby form a nonaqueous pigment paste, and then mixing the nonaqueous pigment paste with an air drying aqueous latex consisting essentially of emulsified aqueous emulsion copolymer particles having a Tg below 20°C., the copolymer of said latex containing less than about 4% of reactive monomers.
of alcoholic organic solvent based on the weight of the solution copolymer, said copolymer being at least partially neutralized with an hydroxy amine having the formula:
in which R is hydrogen or an alkyl group, R' is an alkylene group, and X is either R or R'OH, to render the said copoly-mer disperisble in water, and thereby form a nonaqueous pigment paste, and then mixing the nonaqueous pigment paste with an air drying aqueous latex consisting essentially of emulsified aqueous emulsion copolymer particles having a Tg below 20°C., the copolymer of said latex containing less than about 4% of reactive monomers.
2. A method as recited in claim 1 in which said hydroxy amine is a tertiary amine and said R and R' groups contain from 1-4 carbon atoms.
3. A method as recited in claim 2 in which said hydroxy amine is dimethyl ethanol amine.
4. A method as recited in claim 1 in which said solution copolymer contains from 15% to 30% of monoethylenically unsat-urated carboxylic acid.
5. A method as recited in claim 1 in which said solution copolymer and said aqueous emulsion copolymer each include more than 50% by weight of a blend of methyl methacrylate and C1-C8 alkyl acrylate.
6. A method as recited in claim 1 in which from 5-10 parts of pigment are ground into said water free solution con-taining 1 part of said at least partially neutralized solution copolymer.
7. A method as recited in claim 6 in which said alcoholic organic solvent consists essentially of 2-ethoxy ethanol and 2-butoxy ethanol.
8. A method as recited in claim 1 in which said aqueous emulsion copolymer consists of a blend of methyl methacrylate and C2-C4 alkyl acrylate, up to about 1% of monoethylenic carboxylic acid and up to about 2% of a monoethylenic amine-functional monomer.
9. The high gloss, water base, pigmented air drying latex paint produced by grinding 3-12 parts of pigment into a water-free solution containing 1 part of an at least partially neutral-ized carboxyl-functional addition solution copolymerized copoly-mer of 10% to 40% of monoethylenically unsaturated carboxylic acid, the major proportion of said pigment being titanium diox-ide and said solution containing 40% to 70% of alcoholic organic solvent based on the weight of the solution copolymer, said copolymer being at least partially neutralized with a hydroxy amine having the formula:
in which R is hydrogen or an alkyl group, R' is an alkylene group, and X is either R or R'OH, to render the said copolymer dispersible in water, and thereby form a nonaqueous pigment paste, and then mixing the nonaqueous pigment paste with an air drying aqueous latex consisting essentially of emulsified aqueous emulsion copolymer particles having a Tg below 20°C, the copolymer of said latex containing less than about 4% of reactive monomers.
in which R is hydrogen or an alkyl group, R' is an alkylene group, and X is either R or R'OH, to render the said copolymer dispersible in water, and thereby form a nonaqueous pigment paste, and then mixing the nonaqueous pigment paste with an air drying aqueous latex consisting essentially of emulsified aqueous emulsion copolymer particles having a Tg below 20°C, the copolymer of said latex containing less than about 4% of reactive monomers.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US804,009 | 1977-06-06 | ||
US05/804,009 US4110292A (en) | 1975-06-24 | 1977-06-06 | Pigmented air drying latex paints having superior gloss |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1120625A true CA1120625A (en) | 1982-03-23 |
Family
ID=25187964
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000298225A Expired CA1120625A (en) | 1977-06-06 | 1978-03-06 | Pigmented air drying latex paints having superior gloss |
Country Status (1)
Country | Link |
---|---|
CA (1) | CA1120625A (en) |
-
1978
- 1978-03-06 CA CA000298225A patent/CA1120625A/en not_active Expired
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