CA2079847C - Antisettling agents for aqueous coating compositions - Google Patents
Antisettling agents for aqueous coating compositionsInfo
- Publication number
- CA2079847C CA2079847C CA002079847A CA2079847A CA2079847C CA 2079847 C CA2079847 C CA 2079847C CA 002079847 A CA002079847 A CA 002079847A CA 2079847 A CA2079847 A CA 2079847A CA 2079847 C CA2079847 C CA 2079847C
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- Prior art keywords
- alpha
- water
- antisettling
- acid
- composition according
- Prior art date
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Classifications
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/45—Anti-settling agents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
- Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
- Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
- Y10S516/02—Organic and inorganic agents containing, except water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/919—Ionomer resins, carboxylate salt-containing copolymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/91—Suspending agents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/911—Emulsifying agents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/932—Thickener or dispersant for aqueous system
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
A pourable, liquid antisettling composition comprises at least one low molecular weight copolymer of ethylene and an alpha, beta-ethylenically unsaturated carboxylic acid that has been neutralized with a neutralizing agent and water. The composition can be an additive in aqueous coating compositions and provides excellent pigment suspension and rheological properties to aqueous based coating and ink compositions.
Description
~7~
BACKGROUND AND SUMMARY OF THE INVENTION
~ he present invention relates to anti~ettling compositions in liquid pourable form that provide excellent pigment suspension and rheological properties to aqueous coating compositions.
It is known in the art to add pigment suspension or antisettling agents to coating compositlons to prevent pigments or other finely divided solid particles from settling during ~torage. Depending on the hardness o~ the settling, it is difficult, and sometimes not possible, to evenly redisper~e by stirring the solid material throughout the coating system. The art has constantly sought materials that are useful to control the rheological properties and plgment ~uspenslon properties of ~queous fluid systems contA;n~ng finely divided solid particles and, additionally, are ea y to use.
One type of material which has been ~hown to be use$ul as antisettling or pigment suspension ag~nts for organic (or non-aqueous) coating composltions are emulsif$able polyethylene waxes dispersed in organic ~olvents ~s disclosed in U.S. Patent Nos. 3,123, 488 and 3,184, 233.
Additionally, U.S. Patent No. 3,985,56B disc}oses a ~reamy paste comprising finely divided ;~articles of n emulsifiable polyethylene wax suspended ~n a sulfated/sulfonated castor oil solution which i5 ~seful for modifying the rheologlcal and suspensi~n p~opel~e3 o~ non-aqueouC fluid systems cont~ning fi~ely ~i~ided solid particles. Moreover, U.S. Patent No. 4,97~,~119 d1cclos-s - : ~ , ,, . , -- : .
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a liquid antisettling composition for organic coating compositions which comprises at least one emulsi~iable polyethylene wax, at least one salt of an alkyl hydrogen sulfate, at least one ~alt of a reaction product of a polyvalent inorganic acicl and a fatty ester compound or fatty acid derivative, an organic solvent and, optionally, water.
U.S. Patent No. 3,937,678 discloses a process for improving the rheological properties and suspension properties of non-aqueous fluid systems cont~ning finely divided solid par~icles by adding to the non-aqueous fluid system a mixture of an amide wax having a meltlng point of from about 100~C to about 160~C obtained by reacting hydrogenated castor oil fatty acid or an organic mlxture containing at least 30 molar percent of hydrogenated castor oil fatty acid with amines, and an emulsi~iable polyethylene wax having an acid number of from about 2 to about 50, a softening point of from about 95~C to about 120~C, a density of from about 0.92 to about 0.98, and a penetration hardness of from about 1 to about 20.
Emulsifiable polyethylene waxes find, however, limited use 29 pigment suspension or ~ntisettling agents in ~queous or water-borne coatings ~ystems. Japan Kokai 76 04 087 discloses the use of emulsifiable polyethylene waxes to stabilize a dispersion of pigments in water thinned coat~ng compositions where the emulslfiable wax ifi dispersed in xylene solvent wh~ch results in a paste and the thinner is a butyl cellosolve/lsopropyl alcohol/water solvent system.
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Typically, thickeners ~uch as fumed silica or clays such as montmorillonite, hectorite, or attapulgite have been used in aqueous coating systems to correct pigment settling problems. However, these materials have the disadvantage of lowering the gloss associated with the cured coating system and are difficult to use as a post-add correction at the completion of the preparation of a paint.
These materials are difficult to disperse during the manufacture of paints and require high shear mixing equipment to achieve adequate dispersion.
Other thickeners which act as stabilizing agents to deter sedimentation include the natural gums, for example, xanthan gum, alginate, gum arabic, guar gum, tragacanth gum, and locust bean gum; cellulose derivat~ves such as carboxymethyl cellulose and hydroxyethyl cellulose, and modified starches.
Furthermore, the use of polyacrylic~acrylate thickeners such as CPE-15, WS-24, and Rheoplex B-505 commercially available from the Rohm and Haas Company have been reported in U.S. Patent 4,432,797 as providing resistance to pigment settling in a water-borne wood Rtain.
Additionally, pigment wetting agents or sur~actants based on ethoxylated nonylphenols have been added ~o water reducible coatings for pigment suspension.
U.S. Patent ~o. 4,071,487 discloses antisettling agents for use 1n pigmented aqueous lacquer ~ystems wherein the agents are water dispersible (including water-soluble) amine salts of the products formed by reacting at 200~C to -; ~ , . .. "
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,: . . , ?~J' ~J 1~ rl 250~C, a C,~20 unsaturated fatty alcohol with an ethylene dicarboxylic acid to form a substantially neutral ester which is further reacted with about 1/7 to 1/35 of its weight with an ethylene dicarboxylic acid or ~nhydride compound. The amine neutralization is performed in organic solvents miscible with water which are ~table on storage and may be incorporated into the lacquer at any point in its manufacture.
V.S. Patent No. 4,435~,575 discloses aqueous varnishes ~0 which contain mineral fillers an~or pigments and ~how virtually no sedimentation of the 601id constituents.
These varnishes are prepared by allowing a hot wax emulsion in water at between 80~C and 100~C to flow with vigorous stirring lnto the aqueous varnish cont~n~ng the mlneral fillers and/or pigments. Suitable waxes have a melting point above 60~C and a cloud point in toluene between 35~C
and 45~C. Particularly suitable waxes are montan waxes, which have been bleached and modified, or ester waxes based on modified montan waxes. The waxes can also be coupled with a nonionic emulsifier system.
In a field unrelated to ~ntisettling additlves, Japanese Tokyo Xoho 81/09,522 discloses ethylene-maleic anhydride copolymers that are treated in the molten state w~th compounds having >20H and/or primary or secondary amino groups to provide a modified ~thylene-maleic anhydride copolymer with increased melt index, Young's~
modulus, and elongation.
Furthermore, U.~S. Patent 4,381,376 discloses a method : - - : :.: - . ~ ~ -: ~
~ 1~3 ~
for forming ionic copolymer salts from low molecular weight copolymer acids formed from ethylene and an alpha, beta-ethylenically unsaturated carboxylic acid having at least one carboxylic acid groupl and cations having a valence of 1 to 3. In U.S. Patent 4,603,172, the ion1c copolymer salts o~ a low molecular w~eight copolymer acid of an alpha-olefin and alpha, beta-ethylenically unsaturated carboxylic acid are disclosed to be d.i~persion aids to disperse flnely divided inert material such as pigments in a variety of non-acqueous polymer compositions including polypropylene and polyethylene. Allied-Signal, which owns said U.S.
Patent 4,381,376, sells AClyn ionomers whioh are low molecular weight ethylene-based copolymers neutralized with metal ~alts, including sodium, zinc, calcium and magnesium salts.
Other patents of interest include BASF U.S. Patent Nos. 4,406,705 and 4,417,035 which relate to water emulsifiable hand waxes consisting of ethylene-carboxylic copolymers.
Accordingly, an ongoing search has been made for new additives for modifying the rheological ~nd suspension properties of agueous and water-borne flui~ systems containing finely divided solid particles that are effiolent, easily handled and readily dispersi~le in the~
a~ueous ~luid system requiring suspension properties. :
Ihe present invention overcomes ths prob1ems and~
disadYantages oi the prl O~ art by providing a homogeneous pourable liquid additive ln water which provides excellent '- ' ' - ' --~37 ,~
pigment suspension and rheological properties to aqueous coating compositions.
It is an object of tlhe invention to provide a liquld, pourable composition that provides suspension properties to aqueous composi~ions containing finely divided solid particles, that is easy to handle, and is readily incorporated into aqueous compositions.
It i~ a further object o~ the invention to provide a l~quid, pourable composition that provides suspension properties to agueous compositions that are stable on storage and do not exhibit excessive syneresis.
An additional ob~ect of the invention is ~o provide a process for improving the rheological and suspension properties of aqueous compositions contAin~ng finely divided solid particles.
It is yet another ob~ect of the invention to provide - stable suspensions of flnely divided solid paxticles in aqueous compositions so that these particles do not exhibit excessive syneresis or hard 6ettllng during prolonged storage periods.
Additional ob~ects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the descr$ption, or may be learned by practice of the invention. The ob~ects and advantages of the invention will be realized ~nd ~t a~ned by means of the ~nstrumentality and comblnatlons, particularly pointed out in the appended claims.
To achieve the objects and in accordance with the .
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purpose of the invention, as e~bodied and broadly described herein, the invention provides a liquid antisettling composition comprising (a) at least one low molecular weight copolymer of an alpha-olefin and an alpha, beta-ethylenically unsaturatled carboxyllc acid, (b) aneutralizing agent, and ~c) water.
The liquid antisettling composition of the invention imparts suspension properties to aqueous compositions that contain finely divided sol$d partlcles and prov~des effective rheological properties to aqueous coating compositions. The liquid anti-settling composition of the present invention is highly efficient in ~u~pension properties and can be used at lower loadings than commercially available products. The composition provides easier dispersion in aqueous paint systems than prior art pigment suspension or antisettling agents. Further, the composition of the invention can be incorporated ln the coating composition at any stage of its manufacture which results in shorter processing time. Since the composition is in liquid form that is pourable and pumpable, i~ can be easily handled in a coatings manufacturing plant and thus reduces handling time and handling losses.
The invention also provides a process for improving the rheological and suspension propertles of aqueous compositions cont~n~n~ finely divided solid particles comprising adding the liguid antisettling composit1on of the lnvention to an aqueous composition.
The invention further provides for aqueous , ~
:
compositions that contain the liguid antisettling composition that are stable suspensions of finely divided solid particles in a~ueous compositions that do not exhibit excessive syneresis or hard settling durlng prolonged storage periods.
DETAILED DESCRIPTION OF PREFERRED EMBODINENTS
The liquid antisettling composition of the present - invention is useful in agueous compositions, particularly aqueous coating compositions such as water-reducible paints.
Preferably at least one low molecular weight copolymer of an alpha-olefin and alpha, beta-ethylenically unsaturated carboxylic acid herein referred to as copolymer acid is present in the antisettling composition of the present invention in an amount of from about 3 to about 70 wei~ht percent, more preferably in an amount of from about 10 to 35 weight percent, and most preferably in an amount from about 20 to about 30 weisht percent.
The alpha, ~eta-ethylenically unsaturated carboxylic acid can be a mono-carboxyllc acid, or have more than one carboxylic acid group attached to lt. The alpha, beta-ethylenically unsaturated carboxylic acid~ which can be copolymerized with the alpha-olefi~ preferably have 3 to 8 carbon atoms. Examples of such acids include acrylic ~cid, methacrylic acid, ethacrylic acid, crotonic acid, m leic acid, and fumaric acid and ~nhydrides of dica~boxylic acids such as maleic anhydride.
The molecular weight of the low molecular weight "
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copolymer acid is from about 500 to about 20,000, preferably from about 1,000 to 15,000, more preferably from about 1,000 to about 6,000 and most preferably from about 1,000 to about 3,500.
The alpha-olefin ls preferably ethylene. The concentration of the ethylene in the copolymer is at least 50 mol percent and preferably above 80 mol percent.
A preferred copolyme~e acid 1 a copolymer of ethylene and a~ alpha, beta-ethylenically unsaturated monocarboxylic acid having 3 to 6 carbon atoms. A most preferred alpha, beta-ethylenically unsaturated monocarboxylic acid is acrylic acid.
The copolymer acid has an acid value in the range from about 20 to about 300, with an acid number from about 40 to 200 being preferred, and an acid number from about 40 to 120 being most preferred. The acid number is determined by the number of milligrams of potassium hydroxide necessary to neutralize one qram of copolymer acid.
Praferably, the copolymer acid has a density of ~rom about 0.92 to about 0.98 g~cc, a penetration hardness of from about 1 to about 60 dmm (ASTM D-5 and ASTM D-13~ and a 60ftening point of from about 70~C to about 120~C (ASTM
D-3954).
Additionally, ~nc -rs which contain a polymerizsble ethylenically unsaturated group may also be employed in the copolymers of the present invention, provided that the monomers do not adversely affect the antiset lLng~
properties of the copolymer acids. Exemplary ultable~
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- - .
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, copolymerizable monomers, which contains at least one terminal CH2=C< group, are v~nyl acetate, vinyl pyrrolidinone, methyl vinyl ether, and ethyl vinyl ether.
The low moleeular weight copolymer acids used to make the liquid antlsettling compos~tion of the present invention can be prepared by any suitable process known ln the art. An exemplary preparation method and exemplary suitable waxes are described in U.S. Patent Nos. 3,658,741 and 3,909,280 which are incorporated herein by reference.
Exemplary suitable ethylene-acrylic acid copolymers for use in the present invention may include carboxyl-containin~ ethylene copolymers such ~s ethylene-acrylic acid-vinyl acetate terpolymers. Suitable carboxyl-containing ethylene copolymers are commercially available under the A-C tradename ~rom Allied-Signal, Inc.
The neutralizing agent employed in the present invention can be a group lA metal compound such as lithium, sodium, p~tassium, cesium and the like as the hydroxide, oxide, or carbonate and the like, as well as ammonia ~nd organic amines includ~ng mono-, di-, and triethanolamine, diethylam~noethanol, 2-(2-aminoethylamino)ethanol, 2-amino-2-methyl-1-propanol and trimethylamine. Preferably, the neutralizing agent is selected ~rom ammonia or amines such as mono-, di- and triethanolamine, monoethylami~s, monopropyl amine, diethylaminoethanol, ethylene diamine, and 2-amino-2-methyl-1-propanol commerclally available ~s AMP-95 from Angus ~hemical, and the l~ke. Most preferably the neutralizing agent is triethanol amine and , diethyl~mino~thanol.
Preferably, ~he amount of neutralizing agent is present in the liquid anti~settling composition in an amount from 25~ to 200~ of the amount required to neutralize the ac$d groups of the copolymer acid, more preferably from about 75% to about 125~ of the amount required to neutralize the acid groups of the copolymer acid, and most preferably ln an amount to completely neutralize the acid groups of the copolym~r acid.
The neutralization of the preferred ethylene-acrylic acid copolymers is well known in the art. For example, BASF and Allied-Signal Inc. recommend in their li~er~ture the neutralization of these types of copolymers with an amine or ammonia to make the copolymers emulsifiable in water for use as slip and mar resistance aqents and to provide adhesion and better seal properties. The present invention is based on the surprising discovery that neutralized ethylene-acrylic acid copolymess impart antisettling behavior to water-based coatings and inks.
The copolymer acid is neutralized in water. The water is preferably present in an amount of from about 3D wt. %
to about 95 wt. ~, more preferably from about 65 wt. ~ to about 90 wt. ~, and most preferably from about 70 wt. ~ to about B0 wt. ~ of the liquid antisettllng composition.
Solvents that are ~lso misc1ble with water and are compatible with speciflc aqueous compositions can a1fio replace some or all of the water as the solvent. Exemplary~
solvents may lnclude lower alcohols such as methanol .:
~'~7 ~3~
ethanol, isopr~pa~l, pr~panol, is~pr~panol butanol, sec-butanol, cyclohexan~l, glycol ether or glycol ether acetates as long as these solvents are nat detrimental to the performance of the aqueous coatiny system.
S The finely divided s~lid particles to be ~uspended by the compositions of this invention should be of a colloidal nature or a si~e that can be dispersed in the aqueous medium. The particles should be substantlally insoluble in the medium in which they are suspended. There ls no particular upper limit on particle size, but the slze should be such that the particles ~re capable of being initially suspended in the 8elected medium. ~he ~olid - particles may be pigments, iner~ fillers, fillers, reflecting agents, and the like.
The antisettling compositions of the present ~nvention can be prepared by known technigues wherein the copolymer acids are neutralized in water or neutrali2ed neat in the melt phase and then added to water or vice versa. For example, the ingredients (the copolymer acid, a neutralizing agent, and water) may be charged to a suitable reaction vessel which iB capable of withstanding autogenous pressure and equipped with a mechanical stirrer and a thermometer. The materials can be added at any time and at any temperature and simultaneously or in ~ny order durlng the heating with the requirement that the copolymer acid i8 neutralized and dispersed in water and a uni f orm liquid mass is obtained~ The mix~ure is usually hea~ed under an inert atmosphere to a temperature of 85-140~C, preferably - - .::
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2 ~ 7 100-135~C. The use of an inert atmosphere is optlonal in that the presence of an inert gas such as nitrogen inhibits a dark coloring of the product but in no way affects product performance. The resulting li~uid product can be cooled with or without agltation~ but slow agitation is preferred. In either case, a homogeneous fluid product is obtained.
The homogeneous liquid anti~ettling compositions of the present invention can ~e employed ln various aqueous compositions to prevent settling of finely divided solid particles. The liquid antisettling composltions of the present invention may be used as a rheology modi~ier and suspension agent of finely divided solid particles in a variety of water-based compositlons. The compositions of the invention are useful, for example, in imparting antisettling properties to latex (including vinyl acrylic and acrylic latex coatings) and water-reducible products, including water-reducible alkyd paint formulations, water-based ink formulations, water-based traffic paints, water-based dip coat formulatlons, and water-based foundry compounds.
The amount of antisettling composition used ln a~
specific application is determined by numerous factors including the type of copolymer acid, the type of water-~ased compositions that require an ~nti~ettling additive,and ~he level of performance (pigment suspension control and rheology control) desired. However, a general range is from about l.0 to about 30 pounds per hundred gallons ~phg) ~, ' :': ., ' ~ , . : ~ ' , of aqueous composition.
The ef~ectiveness of the antisettling compositions of the present invention was determined by use in various aqueous coating compositions and other formulations.
The invention will be further clarified by the following examples, which are intended to be purely exemplary of the invention.
~ Example 1 240.0 g of an ethylene-acrylic acid copolymer (A-C
5120, commercially available from Allied-Signal, Inc.), 72.0 g 98~ triethanolamine, and 960.0 g water were added to a 2L Parr pressure reactor equipped with a mechanical stirrer and a cooling coil. The mixture was heated to about 135~ with stirring and was heated at about 135~ for 30 minutes followed by cooling to 60~C w$th air cooling via the internal cooling coils. Upon reaching 60~C, the mixture was further cooled to room temperature with water cooling via the internal cool$ng coils. The material, after cooling, was a white, opaque, homogeneous liquid product.
2.0 to 3.0 g of the sample were taken and dried in a forced oven for 18 hours at 105~C. The percent solids of the liquid product was determined to be 24.5~.
Example 2 . 240.0 g of an ethylene-acrylic acid copolymer (A-C
5120, commercially avallable from Allied-Signal, Inc.1, 30.0 g d~ethanol amine, and 960.0 g water were added to a 2L Parr pressure reactor equipped with a mechanical stirrer .
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and a cooling coil. With stirring, the mixture was heated to 135~C and was heated at 135~C for 30 minutes followed by cooling to 60~C with air cooling via the internal cooling coils. Upon reaching 60~C, the mixture is further cooled to room temperature with water cooling via the ~nternal coolin~ coils. The material, after cooling, was a white, opaque, homogenous liquid product.
2.0 to 3.0 g of the Isample were taken and dried in a forced air oven for 16 hours at lD5~C. The percent sollds of the liquid product was determined to be 23.5%.
Example 3 240.0 g of an ethylene-acrylic ~cid copolymer (A-C
5120, commercially available rom Allied-Signal, Xnc.), 19.3g NaOH, and 960.0 g water were added ~o a 2~ Parr pressure reactor equipped with a mechanical stirrer and a heating coil. With stirring, the mixture was heated to 135~C and was heated ~t 135~C ~or 30 minutes followed by cooling to 60~C with air cooling via the internal cooling coils. Upon reaching 60~C, the m$xture was further cooled to room temperature with water cooling via the internal cooling coils. The material, after cooling, was a whlte, opa~ue, homoqeneous li~uid product.
2.0 to 3.0 g of the ~ample were taken and dried in a forced air oven for lS hours at 105~C. ~he percent colids of the liquid product was determined to be 22.8~.
Example 4 59.1 g of an ethylene-acrylic acid copDlymer (A-C
5120, commerclally available from Allied-Signal, Inc.), .
- . . . :
- - - ~ ' . ~ . -' :: , . ' .: ~ , ' . ~' ~ , 17.7 9 98~ triethanolamine, were added to a 500 mh resin flask equipped with a water condenser, thsrmometer, nitrogen gas inlet, high speed agitator and a heatin~
mantle. The reaction flask was blanketed with a nitrogen gas atmosphere during the reaction. The reaction mixture was heated to 108~C and ~was in a m~lten form. 234.6 g water was heated to 95~C separately in a 600 mL beaker and then added to the hot reaction mixture in the resin flask with agitation. The reaction mixture was then cooled to room temperature. The material, after coolinq, was a white, opaque homogeneous liguid product.
2.0 to 3.0 g of the sample were taken and dried in a forced air oven for 16 hours at 105~C. The percent solids of the liquid product was dete ~d to be 24.0~ solids.
Example 5 160.0 g of an ethylene-acrylic acid copolymer (A-C
5120, commercially available from Allied-Signal, Inc.), 48.0 g 98~ triethanolamlne, 32.0 g sulfated castor oil (Eureka 102 commercially available from Atlas Refinery, Inc. containin~ 70~ sulfated castor oil and 30% water), and 128.0 g water were ~dded to a lL resin flask e~uipped with a water condenser, the_ - -ter, nitrogen ga~ lnlet, high speed aqitator and a heating mantle. The reactlon flask was blanketed with a nitrogen gas atmosphere durlng the reaction. The reaction mixture was then hea~ed to 95~C.
512.0 g water was then added to the heated reactlon mixture and the temperature of the reaction mixture dropped to 58~C. ~he reaction mixture was heated to 1~0~C and then - . , . . . , ,. .
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~ooled to 34~C. The material, after cooling, was a cream-colored, opaque, homogeneous liquid product.
2.0 to 3.0 g of the sample were taken and dried in a forced air oven for 16 hours at 1059C. The percent solids of the li~uid product w~s determined to be 24.5~ solids.
Example 6 5~.1 g of an ethylene-acrylic acid copolymer ~A-C
5120, commercially available from Allied-Signal, Inc.), 17.7 g 98% ~olution of tri~thanolamine, 11.8 g triethanolamine lauryl ~ulfate and ~36.4 g water were sdded to a 500 mL resin flask equipped with a water condenser, thermometer, nitrogen gas inlet, mechanical a~itator, and a heating mantle. The reactlon flask was blanketed with a nitrogen ~as atmosphere during the reaction. The reaction mixture was heated to lOO~C and then cooled to 35~C. The material, after cooling, was a white, homogeneous liquid product.
2.0 to 3.0 g of the sample were taken and dried in a forced air oven for 16 hours at 105~C~ The percent solids of the liquid product was determined to be 24.6~ solids.
E~ample 7 80.0 g of an ethylene-acrylic acid copolymer (A-C
5120, commercially available from Allied-Signal, Inc.), 24.0 g 98% triethanolamine, and 16.0 g sulfated castor oiI
(Eureka 102 commercially available from Atlas Refinery, Inc. cont~in~ng 70% sulfated castor oil and 30~ water), ~nd 320.0 g n-butanol were added to a lL res~n flask equipped with a water condenser, thermometer, nitrogen gas inlet, .
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. .
.
2 ~ f mechanical stirrer, and a heating mantle. The reaction flask was blanketed with a nitrogen gas atmosphere during the reaction. The react~on mixture was then heated to 92~C
to form a slightly ha~y liguid.
5The reaction mixture was stirred with coollng to room temperature. The material, after cool~ng, was a creamy, opaque, homogenous liqu~d product.
1.0 to 2.0 g of the sample were taken and dried ln a forced air oven for 16 hours at 105~C. The percent solids 10of the liquid product was determined to be 23.0% .
Evaluation of Antisettlinq Compositions oP
Examples 1-7 The effectiveness of the ant~settling compositi~ns of Examples 1-7 w~s determined in ~arious paint snd other 15formulations. The data cét forth below demonstrate the suitabil1ty of the anti-settlin~ compositions for use in - aqueous coating compositions.
A water-reducible alkyd paint was prepared by mixing the ingredients set forth in Formulation A in the order 20listed.
A~ter the paints were prepared, the paint properties such as fineness of grind (FOG), Brookfield viscosity, Stormer viscosity, sag resistance, ~nd pigment settling were measured at selected time interval~.
25The fineness of grind was measured in Hegman unl~s using a Hegman gauge in accordance with ASTM D1210-79.
Brookfield viscosities at 10 and 100 rpm were measured with a BrooXfield Viscometer ~odel RVT in accordance with .. . . . . .
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ASTM D1296-81. From viscosity data, a Thixotropic Index (T. I . ) was obtained as follows:
Thixotropic Index (T.I.) = Viscosity at 10 rpm Viscosity at 100 rpm 5Stormer ~iscosities were measur~d in Krebs Units (~U) with a Thomas Stormer Instrument, Model #09730-G15, in accordance with AST~ D562-81.
Sag resistance was measured in mils using a Leneta sag multinotch applicator at room temperature in accordance 10with ASTM D4400-84.
The degree of pigment settling of a paint was evaluated in accordance with ASTM D869-78. On a scale of 0-10, a rating of 0 indicates the presence ~f ~ very firm cake that cannot be reincorporated with the liquid to ~orm 15a smooth paint by stirring manually, and a rating o~ 10 represents a perfect suspension with no change from the original condition of the paint.
Formulation A: Water-Reducible Alkyd Primer Inqredient Generic Name Manufacturer Pounds~
20Deionized Water Water --- 179.7 28~ Ammonium Ammonium Aldrich Chemi- 8.3 Hydroxide Hydroxide cal Co.
Butyl Cellosolve Ethylene Union Carbide43.0 glycol mono-butyl ether BYK-301 Polysiloxene ByX Chemie 0.9 flow additlve Kelsol 3902 ~ater reduc- Reichhold 144.7 BG4-75 ible alkyd Chemic~l Co.
binder Antisettling See examples Additive Mix 5 minutes at 3,000 RPN.
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Barytes No. 1 Barium sul- Whittaker, 86.1 fate Clark & Danlels msil A10 Crystalline Illinois 18.9 silica Minerals Co.
A~c,mite Calcium ECC America,86.1 carbonate Inc.
MAPICO 297RFO Red iron Columbia Carbon 86.1 oxide Zinc Phosphate, ~inc Heyco Tech 68.9 ZP-10 Phosphate Add Dragonite media, 2mm.
Grind 15 minutes at 8,000 RPM. Use a Dispermat CV
fitted with a 60 mm disk impell~r.
Letdown:
Butyl Cellosolve Ethylene Union Carbide 11.2 glycol mono-butyl ether 6% Cobalt Intercat Drier Arzo Chemie 1.7 6% Zirco Intercat Drier Arzo Chemle 0.9 Activ-8 Drier ac- R. T. Vanderbilt 0.9 celerator Eskin #2 Antisk~nn1ng Huls 0.6 agent Deionized Water Water --- 241.1 28~ Ammonium Ammonium Aldrich 6.9 Hydroxide Hydroxide Chemical Xelsol 3902 Water reduc- Reichhold 86.1 BG4-75 ible alkyd Chemical binder Total (without ant~settling composition)1072.1 *~asic Formulation; test composltion may be prepared with different amounts, but proportional to those set orth.
~he ~tability oi the paint was tested by storing each sample of paint for a selective period at room temperature (e.g., 70~F). At the end vf an ~ging period, each ~ample was eXA ~ned ~or appearance, fineness of grind, Broo~fleld viscosity, Stormer viscosity, ~ag resistance, plgment settling and other properties, lf desired.
Example B
The material prepared according to ~xample 1 was incorporated into a water-reducible air-dry alkyd primer descr~bed in Formulation A. The antisettling composition .. . . . . ..
.
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of Example 1 was added to the millbase at a 5.0 pounds per hundred gallons loading on a solids basis. ~he paint properties w~re evaluated and are set forth in Table 1.
Comparative Example A
A water-reducible air-dry alkyd primer was prepared according to the procedure~s described in Formulation A, snd M-P-A 1075 [commercially available from RHEOX, Inc.) was added to the millbase. M-P-~ 1075 i5 a trademark representing an emulsifiable poly~thylene wax antisettling composition dispersed in n-butanol in paste form. The antisettling additive loading was equivalent to 5.0 pounds per hundred gallons on a sol$ds basis. The paint properties were evaluated and are set forth in Table l.
Examples 9-ll The material prepared according to Examples 4, 5, and 6 was incorporated into a water-reducible air-dry alkyd primer described in Formulation A. The antisettling addit~ve was added to the millbase at a 5.0 pounds per hundred gallons loading on a solids basis. The paint properties were evaluated and are set forth in Table 2.
Comparative Example B
A second water-reducible alkyd primer was prepared according to the procedures described in formulat~on ~, and M-P-A 1075 was added to the millbase. The antiset~liny additive loading was equlvalent to 5.0 pounds per hundred gallons on a solids basis. The paint proper~ies were evaluat~ed and are set forth in Table 2.
Comparative Example C
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A water-reducible alkyd primer was prepared according to the procedures described in Formulation A without the addition of an antisettling additive. The paint properties were evaluated and are set forth in Table 2.
Example 12 The material prepared according to Example 5 was incorporated into a water-reducible air-dry alkyd prlmer described in Formulation A. The antisettling composition of Example 5 was added to the millbase at a 9.0 pounds per hundred gallons loading on a solids basis. The paint properties were evaluated and are set forth in Table 3.
Example 13 The material prepared according to Example 7 was incorporated into a water-reducible air-dry alkyd primer described in Formulation A. The antisettling composition of Example 7 was added to the millbase at a 9.0 pounds per hundred gallons loading on a ~olids basis. The paint properties were evaluated and are set forth ln Table 3.
Comparative Example D
A water-reducible alkyd primer was prepared according to the procedures described ln Formulation A, and M-P-A
1075 was added to the millbase. The antisettling additive loading was e~uivalent to 9.0 pounds per hundred gallons on~
a solids basis. The paint proper$ies were evaluated and are set forth in Table 3.
Comparat~ve Example E
A second water-reducible alkyd primer was prepared according to the procedures described in Formulation A
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without the addition of an antisettling additive. The paint properties were evaluated and are ~et forth in Table 3.
Examples 14-16 A second type of water-reducible alkyd primer described in Formulation ~ was used to test the antisettling performance of the compositions prepared in accordance with Examples 1-3. The ~ntisettling compositions were added to the millbase of a water-reducible alkyd primer paint accordln~ to the procedures described in Formulation B at a loading of 10.0 pounds per hundred gallons on a solids basis. The paint properties were evaluated and are set forth in Table 4.
Comparative Ex~mple F
~ water-reducible alkyd primer was prepared according to the psocedures described in Formulation B, nnd M-P-A
1075 was added to the millbase. The antisettling additive loading was equivalent to 10.0 pounds per hundred gallons on a solids basis. The paint properties were evaluated and are set forth in Table 4.
Comparative Example G
A water-reduclble alkyd primer was prepared according to ~he procedures described in Formulation B without the addition of an antisettling additive. The paint proper~ies were evaluated and are set forth in Table 4.
.
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Formulation B: Water-Reducible Alkyd Primer Inqredient Generic Name Manufacturer Pounds*
Deion$zed Water Water --- 139.9 ~utyl Cellosolve EtheleneUnion Carblde 18.0 glyco:L mono-butyl ether Secondary Butanol Sec-butanol Ashland Chemi- 20.1 cal Co.
28% Ammonium Ammon.Lum Aldrich Chemical 3.6 Hydroxide hydroxide Co.
Xel~ol 3962-B2G-70 Water reduc-Reichhold 130.2 ible alkyd C~emical Co.
blnder Antisettling ~see examples) Additive Mix 5 minutes at 2,000 RPM. Use a Dispermat CV fitted with a 50 mm heavy duty impeller blade.
70 Barytes Barium ~h~ttaker,292.5 sulfate Clark & Daniels B2093F Red iron Hareros Pig-31.8 oxide ments, Inc.
OK412 Amorphous DeGussa 10.0 silica zinc Phosphate, ZincHeyco Tech 21.5 ZP-10 phosphate Grlnd 15 minutes at 5,400 RPM, then letdown:
Deionized Water Water --- 271.1 Butyl Cellosolve Ethylene Union Carbide8.3 qlycol mono-butyl ether Secondary Butanol Sec-butanolAshland Chemi- 9.5 cal Co.
28% Ammonium Ammonlum Aldrich Chemi-5.3 Hydroxide hydroxide cal Co.
Kelsol 3962- Water reduc- Reichhold 74.7 B2G-70 ible alkyd Chemical Co.
binder Cobalt Hydrocure DrierMooney Chemi- 1~5 II cal Co.
Manganese Drier Mooney Chemi-Hydrocure II cal Co. 3.4 Delonized Water Water --- 29.4 ~or Water Viscosity Ad~ustment Total (without nntisettlin~ composition~ 1070.8 Notes: ~he deionized wate~, butyl cellosolve, secondary butanol, 28% ammonium hydroxide, and Xelsol 3962-~2G-70 are premixed. The deionized water added as a vlscoslty adjustment ls employed to attaln :
-' ' 2~ 7 a Ford Cup No. 4 viscosity of 40 seconds.
Basic Formulation; test composition may be prepared with di~ferent amounts, but proportional to those set foxth.
Examples 17-18 The antisettling compositions of Examples 5 and 7 were added to the millbase of a water-reducible alkyd primer paint according to the procedures described in Formulatlon 8 at a loading of 9.4 pounds per hundred gallons on a solids basis. The paint properties were evaluated and are set forth in Table 5. Samples of the pain~ were also heat aged at 120~F for one month and evaluated for antisettliny properties. The pi~ment settling properties at 120~F are set forth in Table 6.
Comparatlve Example H
A water-reducible alkyd primer wa~ prepared according to the procedures described in Formulation B, and M-P-A
1075 was added to the millbase. The antisettling addi~ive loadin~ was equivalent to 9.4 pounds per hundred gallons on ~0 a solids basis. The paint properties were evaluated and are set forth in Table 5. A sample of the paint was alqo heat aged at 120~F for one month and evaluated for antisettlinq propert$esl The pigment settlln~ properties at 120~~ are set forth in ~able 6.
Comparative Exam~le I
A second water-reducible alkyd primer was prepared according to the procedures de~cribed in Formulation B
withou~ ~he addition of an antisettling additive. The paint properties were evaluated and are set forth in Table ', . ~ ~ :: . :,: :
-2 ~9 7 ~
5. ~ sample of the paint was also heat aged at 120~F for one month and evaluated for antisettling properties. The pigment cettling properties at 120~F are set forth in Table 6.
Example 19 A water-based news red ink described in Formulation C
was used to test the antisettlinq performance of the antisettling composition prepared in accordance with Example 1. A water-based ink was prepared by mixing the in~redients set forth in Formulation C in the order listed.
The antisettling composition was added to the base lnk at a loading of 3.0~. The antisettling properties of the ink were evaluated according to ASTM D869-7B and are set forth in Table 7.
Comparative Example J
A water-based news red ink was prepared according to the procedures described in Formulation C without the addition of an antisettling additive. The antisettl~ng properties of the ink were evaluated according to ~S~
D869-78 and are set forth in Table 7.
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~ormulation C. Water-Based News Red Ink Parts by Inqredient Generic Name Manufacturer Weiqht Lucidene 141 Acyrlic emulsion Morton 34.0 (30~ NV) Barium Lithol Presscake Sun Chemical Presscake 38.1 (~0% Pigment) Surfynol 104E Surfactant Air Products 0.3 -Isopropyl sopropyl Aldrich Chemi- 2.5 Alcohol alcohol cal Co.
BYX 020 Defoamer BYK Chemie 0.4 Deionized Solvent --- 24.7 Water Base Ink Total 100.0 * ~ ~
Base Ink 97,0 Antisettling Ex. 1 ---Additive 3.0 Total 100.0 Three (3~ parts of Example 1 by weight was added to 97 parts of the base ink. The ink and antisettling additive were high speed dispersed for 20 minutes and the temperature increased to 108~F. After 20 minutes, the ink was transferred to a Jiffy mill containing approximately 200 grams of steel shot. The lnk i8 shaken on a Red Devil Paint Shaker for 15 minutes. Then 20 parts water was added to the ink to adjust the Shell 2 viscosity to 16 seconds.
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Table 6 Antisettling Pi~ment Example Num~er Composition Paint Aqe Settlinq Ex. 17 Ex. 5 1 Wk, 120~F 7 2 Wks, 120~F 6 1 Mon, 120~F 4 Ex. 18 Ex. 7 1 Wk, 120~F 8 2 Wks, 120~F 7 1 Mon, 120~F 5 Comp. Ex. H M-P-A 10751 Wk, 120DF 4 2 Wks, 120~F
1 Mon, 120~F 0 Comp. Ex. I No Additive1 Wk, 120~F 2 2 Wks, 120~F 0 1 Mon, 120~F 0 Table 7 Antisettling Pigment Example Number Composition Paint Aqe Se~tlln~
~x. 19 Ex. 1 1 Day, R.T. 9 1 Wk, R. T. 8 2 Wks, R.T. 8 1 Mon, R.T. 5 Comp. Ex. J No Additive1 Day, R.T. 6 1 Wk, R. T. 4 2 Wks, R.T. 3 1 Mon, R.T.
Although the invention has been described and illustrated in detail, it is to be clearly understood that the same is by way of illustration and example, and ls not to be taken by way of limitation. For example, it i8 contemplated that a 100% ~olids amine neutsalized ethylene-acrylic acid copolymer can be utili~ed as an antisettlinq additive in paint manufacture. ~he spirit and scope of the present invention are to be llmited only by ~he term~ of the appended claims.
- . . :
. .
BACKGROUND AND SUMMARY OF THE INVENTION
~ he present invention relates to anti~ettling compositions in liquid pourable form that provide excellent pigment suspension and rheological properties to aqueous coating compositions.
It is known in the art to add pigment suspension or antisettling agents to coating compositlons to prevent pigments or other finely divided solid particles from settling during ~torage. Depending on the hardness o~ the settling, it is difficult, and sometimes not possible, to evenly redisper~e by stirring the solid material throughout the coating system. The art has constantly sought materials that are useful to control the rheological properties and plgment ~uspenslon properties of ~queous fluid systems contA;n~ng finely divided solid particles and, additionally, are ea y to use.
One type of material which has been ~hown to be use$ul as antisettling or pigment suspension ag~nts for organic (or non-aqueous) coating composltions are emulsif$able polyethylene waxes dispersed in organic ~olvents ~s disclosed in U.S. Patent Nos. 3,123, 488 and 3,184, 233.
Additionally, U.S. Patent No. 3,985,56B disc}oses a ~reamy paste comprising finely divided ;~articles of n emulsifiable polyethylene wax suspended ~n a sulfated/sulfonated castor oil solution which i5 ~seful for modifying the rheologlcal and suspensi~n p~opel~e3 o~ non-aqueouC fluid systems cont~ning fi~ely ~i~ided solid particles. Moreover, U.S. Patent No. 4,97~,~119 d1cclos-s - : ~ , ,, . , -- : .
. : : :
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a liquid antisettling composition for organic coating compositions which comprises at least one emulsi~iable polyethylene wax, at least one salt of an alkyl hydrogen sulfate, at least one ~alt of a reaction product of a polyvalent inorganic acicl and a fatty ester compound or fatty acid derivative, an organic solvent and, optionally, water.
U.S. Patent No. 3,937,678 discloses a process for improving the rheological properties and suspension properties of non-aqueous fluid systems cont~ning finely divided solid par~icles by adding to the non-aqueous fluid system a mixture of an amide wax having a meltlng point of from about 100~C to about 160~C obtained by reacting hydrogenated castor oil fatty acid or an organic mlxture containing at least 30 molar percent of hydrogenated castor oil fatty acid with amines, and an emulsi~iable polyethylene wax having an acid number of from about 2 to about 50, a softening point of from about 95~C to about 120~C, a density of from about 0.92 to about 0.98, and a penetration hardness of from about 1 to about 20.
Emulsifiable polyethylene waxes find, however, limited use 29 pigment suspension or ~ntisettling agents in ~queous or water-borne coatings ~ystems. Japan Kokai 76 04 087 discloses the use of emulsifiable polyethylene waxes to stabilize a dispersion of pigments in water thinned coat~ng compositions where the emulslfiable wax ifi dispersed in xylene solvent wh~ch results in a paste and the thinner is a butyl cellosolve/lsopropyl alcohol/water solvent system.
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Typically, thickeners ~uch as fumed silica or clays such as montmorillonite, hectorite, or attapulgite have been used in aqueous coating systems to correct pigment settling problems. However, these materials have the disadvantage of lowering the gloss associated with the cured coating system and are difficult to use as a post-add correction at the completion of the preparation of a paint.
These materials are difficult to disperse during the manufacture of paints and require high shear mixing equipment to achieve adequate dispersion.
Other thickeners which act as stabilizing agents to deter sedimentation include the natural gums, for example, xanthan gum, alginate, gum arabic, guar gum, tragacanth gum, and locust bean gum; cellulose derivat~ves such as carboxymethyl cellulose and hydroxyethyl cellulose, and modified starches.
Furthermore, the use of polyacrylic~acrylate thickeners such as CPE-15, WS-24, and Rheoplex B-505 commercially available from the Rohm and Haas Company have been reported in U.S. Patent 4,432,797 as providing resistance to pigment settling in a water-borne wood Rtain.
Additionally, pigment wetting agents or sur~actants based on ethoxylated nonylphenols have been added ~o water reducible coatings for pigment suspension.
U.S. Patent ~o. 4,071,487 discloses antisettling agents for use 1n pigmented aqueous lacquer ~ystems wherein the agents are water dispersible (including water-soluble) amine salts of the products formed by reacting at 200~C to -; ~ , . .. "
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,: . . , ?~J' ~J 1~ rl 250~C, a C,~20 unsaturated fatty alcohol with an ethylene dicarboxylic acid to form a substantially neutral ester which is further reacted with about 1/7 to 1/35 of its weight with an ethylene dicarboxylic acid or ~nhydride compound. The amine neutralization is performed in organic solvents miscible with water which are ~table on storage and may be incorporated into the lacquer at any point in its manufacture.
V.S. Patent No. 4,435~,575 discloses aqueous varnishes ~0 which contain mineral fillers an~or pigments and ~how virtually no sedimentation of the 601id constituents.
These varnishes are prepared by allowing a hot wax emulsion in water at between 80~C and 100~C to flow with vigorous stirring lnto the aqueous varnish cont~n~ng the mlneral fillers and/or pigments. Suitable waxes have a melting point above 60~C and a cloud point in toluene between 35~C
and 45~C. Particularly suitable waxes are montan waxes, which have been bleached and modified, or ester waxes based on modified montan waxes. The waxes can also be coupled with a nonionic emulsifier system.
In a field unrelated to ~ntisettling additlves, Japanese Tokyo Xoho 81/09,522 discloses ethylene-maleic anhydride copolymers that are treated in the molten state w~th compounds having >20H and/or primary or secondary amino groups to provide a modified ~thylene-maleic anhydride copolymer with increased melt index, Young's~
modulus, and elongation.
Furthermore, U.~S. Patent 4,381,376 discloses a method : - - : :.: - . ~ ~ -: ~
~ 1~3 ~
for forming ionic copolymer salts from low molecular weight copolymer acids formed from ethylene and an alpha, beta-ethylenically unsaturated carboxylic acid having at least one carboxylic acid groupl and cations having a valence of 1 to 3. In U.S. Patent 4,603,172, the ion1c copolymer salts o~ a low molecular w~eight copolymer acid of an alpha-olefin and alpha, beta-ethylenically unsaturated carboxylic acid are disclosed to be d.i~persion aids to disperse flnely divided inert material such as pigments in a variety of non-acqueous polymer compositions including polypropylene and polyethylene. Allied-Signal, which owns said U.S.
Patent 4,381,376, sells AClyn ionomers whioh are low molecular weight ethylene-based copolymers neutralized with metal ~alts, including sodium, zinc, calcium and magnesium salts.
Other patents of interest include BASF U.S. Patent Nos. 4,406,705 and 4,417,035 which relate to water emulsifiable hand waxes consisting of ethylene-carboxylic copolymers.
Accordingly, an ongoing search has been made for new additives for modifying the rheological ~nd suspension properties of agueous and water-borne flui~ systems containing finely divided solid particles that are effiolent, easily handled and readily dispersi~le in the~
a~ueous ~luid system requiring suspension properties. :
Ihe present invention overcomes ths prob1ems and~
disadYantages oi the prl O~ art by providing a homogeneous pourable liquid additive ln water which provides excellent '- ' ' - ' --~37 ,~
pigment suspension and rheological properties to aqueous coating compositions.
It is an object of tlhe invention to provide a liquld, pourable composition that provides suspension properties to aqueous composi~ions containing finely divided solid particles, that is easy to handle, and is readily incorporated into aqueous compositions.
It i~ a further object o~ the invention to provide a l~quid, pourable composition that provides suspension properties to agueous compositions that are stable on storage and do not exhibit excessive syneresis.
An additional ob~ect of the invention is ~o provide a process for improving the rheological and suspension properties of aqueous compositions contAin~ng finely divided solid particles.
It is yet another ob~ect of the invention to provide - stable suspensions of flnely divided solid paxticles in aqueous compositions so that these particles do not exhibit excessive syneresis or hard 6ettllng during prolonged storage periods.
Additional ob~ects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the descr$ption, or may be learned by practice of the invention. The ob~ects and advantages of the invention will be realized ~nd ~t a~ned by means of the ~nstrumentality and comblnatlons, particularly pointed out in the appended claims.
To achieve the objects and in accordance with the .
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purpose of the invention, as e~bodied and broadly described herein, the invention provides a liquid antisettling composition comprising (a) at least one low molecular weight copolymer of an alpha-olefin and an alpha, beta-ethylenically unsaturatled carboxyllc acid, (b) aneutralizing agent, and ~c) water.
The liquid antisettling composition of the invention imparts suspension properties to aqueous compositions that contain finely divided sol$d partlcles and prov~des effective rheological properties to aqueous coating compositions. The liquid anti-settling composition of the present invention is highly efficient in ~u~pension properties and can be used at lower loadings than commercially available products. The composition provides easier dispersion in aqueous paint systems than prior art pigment suspension or antisettling agents. Further, the composition of the invention can be incorporated ln the coating composition at any stage of its manufacture which results in shorter processing time. Since the composition is in liquid form that is pourable and pumpable, i~ can be easily handled in a coatings manufacturing plant and thus reduces handling time and handling losses.
The invention also provides a process for improving the rheological and suspension propertles of aqueous compositions cont~n~n~ finely divided solid particles comprising adding the liguid antisettling composit1on of the lnvention to an aqueous composition.
The invention further provides for aqueous , ~
:
compositions that contain the liguid antisettling composition that are stable suspensions of finely divided solid particles in a~ueous compositions that do not exhibit excessive syneresis or hard settling durlng prolonged storage periods.
DETAILED DESCRIPTION OF PREFERRED EMBODINENTS
The liquid antisettling composition of the present - invention is useful in agueous compositions, particularly aqueous coating compositions such as water-reducible paints.
Preferably at least one low molecular weight copolymer of an alpha-olefin and alpha, beta-ethylenically unsaturated carboxylic acid herein referred to as copolymer acid is present in the antisettling composition of the present invention in an amount of from about 3 to about 70 wei~ht percent, more preferably in an amount of from about 10 to 35 weight percent, and most preferably in an amount from about 20 to about 30 weisht percent.
The alpha, ~eta-ethylenically unsaturated carboxylic acid can be a mono-carboxyllc acid, or have more than one carboxylic acid group attached to lt. The alpha, beta-ethylenically unsaturated carboxylic acid~ which can be copolymerized with the alpha-olefi~ preferably have 3 to 8 carbon atoms. Examples of such acids include acrylic ~cid, methacrylic acid, ethacrylic acid, crotonic acid, m leic acid, and fumaric acid and ~nhydrides of dica~boxylic acids such as maleic anhydride.
The molecular weight of the low molecular weight "
., ; . .
.
~ : - ; :. . . -.. . : . . .
copolymer acid is from about 500 to about 20,000, preferably from about 1,000 to 15,000, more preferably from about 1,000 to about 6,000 and most preferably from about 1,000 to about 3,500.
The alpha-olefin ls preferably ethylene. The concentration of the ethylene in the copolymer is at least 50 mol percent and preferably above 80 mol percent.
A preferred copolyme~e acid 1 a copolymer of ethylene and a~ alpha, beta-ethylenically unsaturated monocarboxylic acid having 3 to 6 carbon atoms. A most preferred alpha, beta-ethylenically unsaturated monocarboxylic acid is acrylic acid.
The copolymer acid has an acid value in the range from about 20 to about 300, with an acid number from about 40 to 200 being preferred, and an acid number from about 40 to 120 being most preferred. The acid number is determined by the number of milligrams of potassium hydroxide necessary to neutralize one qram of copolymer acid.
Praferably, the copolymer acid has a density of ~rom about 0.92 to about 0.98 g~cc, a penetration hardness of from about 1 to about 60 dmm (ASTM D-5 and ASTM D-13~ and a 60ftening point of from about 70~C to about 120~C (ASTM
D-3954).
Additionally, ~nc -rs which contain a polymerizsble ethylenically unsaturated group may also be employed in the copolymers of the present invention, provided that the monomers do not adversely affect the antiset lLng~
properties of the copolymer acids. Exemplary ultable~
_g_ ... . ,: . . ~ , . :
- - .
: - .. : -- .
, copolymerizable monomers, which contains at least one terminal CH2=C< group, are v~nyl acetate, vinyl pyrrolidinone, methyl vinyl ether, and ethyl vinyl ether.
The low moleeular weight copolymer acids used to make the liquid antlsettling compos~tion of the present invention can be prepared by any suitable process known ln the art. An exemplary preparation method and exemplary suitable waxes are described in U.S. Patent Nos. 3,658,741 and 3,909,280 which are incorporated herein by reference.
Exemplary suitable ethylene-acrylic acid copolymers for use in the present invention may include carboxyl-containin~ ethylene copolymers such ~s ethylene-acrylic acid-vinyl acetate terpolymers. Suitable carboxyl-containing ethylene copolymers are commercially available under the A-C tradename ~rom Allied-Signal, Inc.
The neutralizing agent employed in the present invention can be a group lA metal compound such as lithium, sodium, p~tassium, cesium and the like as the hydroxide, oxide, or carbonate and the like, as well as ammonia ~nd organic amines includ~ng mono-, di-, and triethanolamine, diethylam~noethanol, 2-(2-aminoethylamino)ethanol, 2-amino-2-methyl-1-propanol and trimethylamine. Preferably, the neutralizing agent is selected ~rom ammonia or amines such as mono-, di- and triethanolamine, monoethylami~s, monopropyl amine, diethylaminoethanol, ethylene diamine, and 2-amino-2-methyl-1-propanol commerclally available ~s AMP-95 from Angus ~hemical, and the l~ke. Most preferably the neutralizing agent is triethanol amine and , diethyl~mino~thanol.
Preferably, ~he amount of neutralizing agent is present in the liquid anti~settling composition in an amount from 25~ to 200~ of the amount required to neutralize the ac$d groups of the copolymer acid, more preferably from about 75% to about 125~ of the amount required to neutralize the acid groups of the copolymer acid, and most preferably ln an amount to completely neutralize the acid groups of the copolym~r acid.
The neutralization of the preferred ethylene-acrylic acid copolymers is well known in the art. For example, BASF and Allied-Signal Inc. recommend in their li~er~ture the neutralization of these types of copolymers with an amine or ammonia to make the copolymers emulsifiable in water for use as slip and mar resistance aqents and to provide adhesion and better seal properties. The present invention is based on the surprising discovery that neutralized ethylene-acrylic acid copolymess impart antisettling behavior to water-based coatings and inks.
The copolymer acid is neutralized in water. The water is preferably present in an amount of from about 3D wt. %
to about 95 wt. ~, more preferably from about 65 wt. ~ to about 90 wt. ~, and most preferably from about 70 wt. ~ to about B0 wt. ~ of the liquid antisettllng composition.
Solvents that are ~lso misc1ble with water and are compatible with speciflc aqueous compositions can a1fio replace some or all of the water as the solvent. Exemplary~
solvents may lnclude lower alcohols such as methanol .:
~'~7 ~3~
ethanol, isopr~pa~l, pr~panol, is~pr~panol butanol, sec-butanol, cyclohexan~l, glycol ether or glycol ether acetates as long as these solvents are nat detrimental to the performance of the aqueous coatiny system.
S The finely divided s~lid particles to be ~uspended by the compositions of this invention should be of a colloidal nature or a si~e that can be dispersed in the aqueous medium. The particles should be substantlally insoluble in the medium in which they are suspended. There ls no particular upper limit on particle size, but the slze should be such that the particles ~re capable of being initially suspended in the 8elected medium. ~he ~olid - particles may be pigments, iner~ fillers, fillers, reflecting agents, and the like.
The antisettling compositions of the present ~nvention can be prepared by known technigues wherein the copolymer acids are neutralized in water or neutrali2ed neat in the melt phase and then added to water or vice versa. For example, the ingredients (the copolymer acid, a neutralizing agent, and water) may be charged to a suitable reaction vessel which iB capable of withstanding autogenous pressure and equipped with a mechanical stirrer and a thermometer. The materials can be added at any time and at any temperature and simultaneously or in ~ny order durlng the heating with the requirement that the copolymer acid i8 neutralized and dispersed in water and a uni f orm liquid mass is obtained~ The mix~ure is usually hea~ed under an inert atmosphere to a temperature of 85-140~C, preferably - - .::
. .
2 ~ 7 100-135~C. The use of an inert atmosphere is optlonal in that the presence of an inert gas such as nitrogen inhibits a dark coloring of the product but in no way affects product performance. The resulting li~uid product can be cooled with or without agltation~ but slow agitation is preferred. In either case, a homogeneous fluid product is obtained.
The homogeneous liquid anti~ettling compositions of the present invention can ~e employed ln various aqueous compositions to prevent settling of finely divided solid particles. The liquid antisettling composltions of the present invention may be used as a rheology modi~ier and suspension agent of finely divided solid particles in a variety of water-based compositlons. The compositions of the invention are useful, for example, in imparting antisettling properties to latex (including vinyl acrylic and acrylic latex coatings) and water-reducible products, including water-reducible alkyd paint formulations, water-based ink formulations, water-based traffic paints, water-based dip coat formulatlons, and water-based foundry compounds.
The amount of antisettling composition used ln a~
specific application is determined by numerous factors including the type of copolymer acid, the type of water-~ased compositions that require an ~nti~ettling additive,and ~he level of performance (pigment suspension control and rheology control) desired. However, a general range is from about l.0 to about 30 pounds per hundred gallons ~phg) ~, ' :': ., ' ~ , . : ~ ' , of aqueous composition.
The ef~ectiveness of the antisettling compositions of the present invention was determined by use in various aqueous coating compositions and other formulations.
The invention will be further clarified by the following examples, which are intended to be purely exemplary of the invention.
~ Example 1 240.0 g of an ethylene-acrylic acid copolymer (A-C
5120, commercially available from Allied-Signal, Inc.), 72.0 g 98~ triethanolamine, and 960.0 g water were added to a 2L Parr pressure reactor equipped with a mechanical stirrer and a cooling coil. The mixture was heated to about 135~ with stirring and was heated at about 135~ for 30 minutes followed by cooling to 60~C w$th air cooling via the internal cooling coils. Upon reaching 60~C, the mixture was further cooled to room temperature with water cooling via the internal cool$ng coils. The material, after cooling, was a white, opaque, homogeneous liquid product.
2.0 to 3.0 g of the sample were taken and dried in a forced oven for 18 hours at 105~C. The percent solids of the liquid product was determined to be 24.5~.
Example 2 . 240.0 g of an ethylene-acrylic acid copolymer (A-C
5120, commercially avallable from Allied-Signal, Inc.1, 30.0 g d~ethanol amine, and 960.0 g water were added to a 2L Parr pressure reactor equipped with a mechanical stirrer .
--- . , . -, : :~ . : . :
., . . , ,,: , , - , . . .
and a cooling coil. With stirring, the mixture was heated to 135~C and was heated at 135~C for 30 minutes followed by cooling to 60~C with air cooling via the internal cooling coils. Upon reaching 60~C, the mixture is further cooled to room temperature with water cooling via the ~nternal coolin~ coils. The material, after cooling, was a white, opaque, homogenous liquid product.
2.0 to 3.0 g of the Isample were taken and dried in a forced air oven for 16 hours at lD5~C. The percent sollds of the liquid product was determined to be 23.5%.
Example 3 240.0 g of an ethylene-acrylic ~cid copolymer (A-C
5120, commercially available rom Allied-Signal, Xnc.), 19.3g NaOH, and 960.0 g water were added ~o a 2~ Parr pressure reactor equipped with a mechanical stirrer and a heating coil. With stirring, the mixture was heated to 135~C and was heated ~t 135~C ~or 30 minutes followed by cooling to 60~C with air cooling via the internal cooling coils. Upon reaching 60~C, the m$xture was further cooled to room temperature with water cooling via the internal cooling coils. The material, after cooling, was a whlte, opa~ue, homoqeneous li~uid product.
2.0 to 3.0 g of the ~ample were taken and dried in a forced air oven for lS hours at 105~C. ~he percent colids of the liquid product was determined to be 22.8~.
Example 4 59.1 g of an ethylene-acrylic acid copDlymer (A-C
5120, commerclally available from Allied-Signal, Inc.), .
- . . . :
- - - ~ ' . ~ . -' :: , . ' .: ~ , ' . ~' ~ , 17.7 9 98~ triethanolamine, were added to a 500 mh resin flask equipped with a water condenser, thsrmometer, nitrogen gas inlet, high speed agitator and a heatin~
mantle. The reaction flask was blanketed with a nitrogen gas atmosphere during the reaction. The reaction mixture was heated to 108~C and ~was in a m~lten form. 234.6 g water was heated to 95~C separately in a 600 mL beaker and then added to the hot reaction mixture in the resin flask with agitation. The reaction mixture was then cooled to room temperature. The material, after coolinq, was a white, opaque homogeneous liguid product.
2.0 to 3.0 g of the sample were taken and dried in a forced air oven for 16 hours at 105~C. The percent solids of the liquid product was dete ~d to be 24.0~ solids.
Example 5 160.0 g of an ethylene-acrylic acid copolymer (A-C
5120, commercially available from Allied-Signal, Inc.), 48.0 g 98~ triethanolamlne, 32.0 g sulfated castor oil (Eureka 102 commercially available from Atlas Refinery, Inc. containin~ 70~ sulfated castor oil and 30% water), and 128.0 g water were ~dded to a lL resin flask e~uipped with a water condenser, the_ - -ter, nitrogen ga~ lnlet, high speed aqitator and a heating mantle. The reactlon flask was blanketed with a nitrogen gas atmosphere durlng the reaction. The reaction mixture was then hea~ed to 95~C.
512.0 g water was then added to the heated reactlon mixture and the temperature of the reaction mixture dropped to 58~C. ~he reaction mixture was heated to 1~0~C and then - . , . . . , ,. .
. . . : .: . .
~ooled to 34~C. The material, after cooling, was a cream-colored, opaque, homogeneous liquid product.
2.0 to 3.0 g of the sample were taken and dried in a forced air oven for 16 hours at 1059C. The percent solids of the li~uid product w~s determined to be 24.5~ solids.
Example 6 5~.1 g of an ethylene-acrylic acid copolymer ~A-C
5120, commercially available from Allied-Signal, Inc.), 17.7 g 98% ~olution of tri~thanolamine, 11.8 g triethanolamine lauryl ~ulfate and ~36.4 g water were sdded to a 500 mL resin flask equipped with a water condenser, thermometer, nitrogen gas inlet, mechanical a~itator, and a heating mantle. The reactlon flask was blanketed with a nitrogen ~as atmosphere during the reaction. The reaction mixture was heated to lOO~C and then cooled to 35~C. The material, after cooling, was a white, homogeneous liquid product.
2.0 to 3.0 g of the sample were taken and dried in a forced air oven for 16 hours at 105~C~ The percent solids of the liquid product was determined to be 24.6~ solids.
E~ample 7 80.0 g of an ethylene-acrylic acid copolymer (A-C
5120, commercially available from Allied-Signal, Inc.), 24.0 g 98% triethanolamine, and 16.0 g sulfated castor oiI
(Eureka 102 commercially available from Atlas Refinery, Inc. cont~in~ng 70% sulfated castor oil and 30~ water), ~nd 320.0 g n-butanol were added to a lL res~n flask equipped with a water condenser, thermometer, nitrogen gas inlet, .
.
, - ' : - ;~ ' - :
. .
.
2 ~ f mechanical stirrer, and a heating mantle. The reaction flask was blanketed with a nitrogen gas atmosphere during the reaction. The react~on mixture was then heated to 92~C
to form a slightly ha~y liguid.
5The reaction mixture was stirred with coollng to room temperature. The material, after cool~ng, was a creamy, opaque, homogenous liqu~d product.
1.0 to 2.0 g of the sample were taken and dried ln a forced air oven for 16 hours at 105~C. The percent solids 10of the liquid product was determined to be 23.0% .
Evaluation of Antisettlinq Compositions oP
Examples 1-7 The effectiveness of the ant~settling compositi~ns of Examples 1-7 w~s determined in ~arious paint snd other 15formulations. The data cét forth below demonstrate the suitabil1ty of the anti-settlin~ compositions for use in - aqueous coating compositions.
A water-reducible alkyd paint was prepared by mixing the ingredients set forth in Formulation A in the order 20listed.
A~ter the paints were prepared, the paint properties such as fineness of grind (FOG), Brookfield viscosity, Stormer viscosity, sag resistance, ~nd pigment settling were measured at selected time interval~.
25The fineness of grind was measured in Hegman unl~s using a Hegman gauge in accordance with ASTM D1210-79.
Brookfield viscosities at 10 and 100 rpm were measured with a BrooXfield Viscometer ~odel RVT in accordance with .. . . . . .
- - ' ',: ,', , ': , ~
.
. .
: ~
:
2 ~ 7 ~
ASTM D1296-81. From viscosity data, a Thixotropic Index (T. I . ) was obtained as follows:
Thixotropic Index (T.I.) = Viscosity at 10 rpm Viscosity at 100 rpm 5Stormer ~iscosities were measur~d in Krebs Units (~U) with a Thomas Stormer Instrument, Model #09730-G15, in accordance with AST~ D562-81.
Sag resistance was measured in mils using a Leneta sag multinotch applicator at room temperature in accordance 10with ASTM D4400-84.
The degree of pigment settling of a paint was evaluated in accordance with ASTM D869-78. On a scale of 0-10, a rating of 0 indicates the presence ~f ~ very firm cake that cannot be reincorporated with the liquid to ~orm 15a smooth paint by stirring manually, and a rating o~ 10 represents a perfect suspension with no change from the original condition of the paint.
Formulation A: Water-Reducible Alkyd Primer Inqredient Generic Name Manufacturer Pounds~
20Deionized Water Water --- 179.7 28~ Ammonium Ammonium Aldrich Chemi- 8.3 Hydroxide Hydroxide cal Co.
Butyl Cellosolve Ethylene Union Carbide43.0 glycol mono-butyl ether BYK-301 Polysiloxene ByX Chemie 0.9 flow additlve Kelsol 3902 ~ater reduc- Reichhold 144.7 BG4-75 ible alkyd Chemic~l Co.
binder Antisettling See examples Additive Mix 5 minutes at 3,000 RPN.
-- ~ , - , - : :' : . , ~:
-~: :
~ ~ ~ $ ,~
Barytes No. 1 Barium sul- Whittaker, 86.1 fate Clark & Danlels msil A10 Crystalline Illinois 18.9 silica Minerals Co.
A~c,mite Calcium ECC America,86.1 carbonate Inc.
MAPICO 297RFO Red iron Columbia Carbon 86.1 oxide Zinc Phosphate, ~inc Heyco Tech 68.9 ZP-10 Phosphate Add Dragonite media, 2mm.
Grind 15 minutes at 8,000 RPM. Use a Dispermat CV
fitted with a 60 mm disk impell~r.
Letdown:
Butyl Cellosolve Ethylene Union Carbide 11.2 glycol mono-butyl ether 6% Cobalt Intercat Drier Arzo Chemie 1.7 6% Zirco Intercat Drier Arzo Chemle 0.9 Activ-8 Drier ac- R. T. Vanderbilt 0.9 celerator Eskin #2 Antisk~nn1ng Huls 0.6 agent Deionized Water Water --- 241.1 28~ Ammonium Ammonium Aldrich 6.9 Hydroxide Hydroxide Chemical Xelsol 3902 Water reduc- Reichhold 86.1 BG4-75 ible alkyd Chemical binder Total (without ant~settling composition)1072.1 *~asic Formulation; test composltion may be prepared with different amounts, but proportional to those set orth.
~he ~tability oi the paint was tested by storing each sample of paint for a selective period at room temperature (e.g., 70~F). At the end vf an ~ging period, each ~ample was eXA ~ned ~or appearance, fineness of grind, Broo~fleld viscosity, Stormer viscosity, ~ag resistance, plgment settling and other properties, lf desired.
Example B
The material prepared according to ~xample 1 was incorporated into a water-reducible air-dry alkyd primer descr~bed in Formulation A. The antisettling composition .. . . . . ..
.
- ~ ~
.
~ t~ J
of Example 1 was added to the millbase at a 5.0 pounds per hundred gallons loading on a solids basis. ~he paint properties w~re evaluated and are set forth in Table 1.
Comparative Example A
A water-reducible air-dry alkyd primer was prepared according to the procedure~s described in Formulation A, snd M-P-A 1075 [commercially available from RHEOX, Inc.) was added to the millbase. M-P-~ 1075 i5 a trademark representing an emulsifiable poly~thylene wax antisettling composition dispersed in n-butanol in paste form. The antisettling additive loading was equivalent to 5.0 pounds per hundred gallons on a sol$ds basis. The paint properties were evaluated and are set forth in Table l.
Examples 9-ll The material prepared according to Examples 4, 5, and 6 was incorporated into a water-reducible air-dry alkyd primer described in Formulation A. The antisettling addit~ve was added to the millbase at a 5.0 pounds per hundred gallons loading on a solids basis. The paint properties were evaluated and are set forth in Table 2.
Comparative Example B
A second water-reducible alkyd primer was prepared according to the procedures described in formulat~on ~, and M-P-A 1075 was added to the millbase. The antiset~liny additive loading was equlvalent to 5.0 pounds per hundred gallons on a solids basis. The paint proper~ies were evaluat~ed and are set forth in Table 2.
Comparative Example C
: :, :
2 ~ 7 ~ ~L~
A water-reducible alkyd primer was prepared according to the procedures described in Formulation A without the addition of an antisettling additive. The paint properties were evaluated and are set forth in Table 2.
Example 12 The material prepared according to Example 5 was incorporated into a water-reducible air-dry alkyd prlmer described in Formulation A. The antisettling composition of Example 5 was added to the millbase at a 9.0 pounds per hundred gallons loading on a solids basis. The paint properties were evaluated and are set forth in Table 3.
Example 13 The material prepared according to Example 7 was incorporated into a water-reducible air-dry alkyd primer described in Formulation A. The antisettling composition of Example 7 was added to the millbase at a 9.0 pounds per hundred gallons loading on a ~olids basis. The paint properties were evaluated and are set forth ln Table 3.
Comparative Example D
A water-reducible alkyd primer was prepared according to the procedures described ln Formulation A, and M-P-A
1075 was added to the millbase. The antisettling additive loading was e~uivalent to 9.0 pounds per hundred gallons on~
a solids basis. The paint proper$ies were evaluated and are set forth in Table 3.
Comparat~ve Example E
A second water-reducible alkyd primer was prepared according to the procedures described in Formulation A
-2~-.~ ~ ., ' ' , .
- ~
-.
r/
without the addition of an antisettling additive. The paint properties were evaluated and are ~et forth in Table 3.
Examples 14-16 A second type of water-reducible alkyd primer described in Formulation ~ was used to test the antisettling performance of the compositions prepared in accordance with Examples 1-3. The ~ntisettling compositions were added to the millbase of a water-reducible alkyd primer paint accordln~ to the procedures described in Formulation B at a loading of 10.0 pounds per hundred gallons on a solids basis. The paint properties were evaluated and are set forth in Table 4.
Comparative Ex~mple F
~ water-reducible alkyd primer was prepared according to the psocedures described in Formulation B, nnd M-P-A
1075 was added to the millbase. The antisettling additive loading was equivalent to 10.0 pounds per hundred gallons on a solids basis. The paint properties were evaluated and are set forth in Table 4.
Comparative Example G
A water-reduclble alkyd primer was prepared according to ~he procedures described in Formulation B without the addition of an antisettling additive. The paint proper~ies were evaluated and are set forth in Table 4.
.
:'' . ~ : ' ::
2 ~ 7 ~ $ ~
Formulation B: Water-Reducible Alkyd Primer Inqredient Generic Name Manufacturer Pounds*
Deion$zed Water Water --- 139.9 ~utyl Cellosolve EtheleneUnion Carblde 18.0 glyco:L mono-butyl ether Secondary Butanol Sec-butanol Ashland Chemi- 20.1 cal Co.
28% Ammonium Ammon.Lum Aldrich Chemical 3.6 Hydroxide hydroxide Co.
Xel~ol 3962-B2G-70 Water reduc-Reichhold 130.2 ible alkyd C~emical Co.
blnder Antisettling ~see examples) Additive Mix 5 minutes at 2,000 RPM. Use a Dispermat CV fitted with a 50 mm heavy duty impeller blade.
70 Barytes Barium ~h~ttaker,292.5 sulfate Clark & Daniels B2093F Red iron Hareros Pig-31.8 oxide ments, Inc.
OK412 Amorphous DeGussa 10.0 silica zinc Phosphate, ZincHeyco Tech 21.5 ZP-10 phosphate Grlnd 15 minutes at 5,400 RPM, then letdown:
Deionized Water Water --- 271.1 Butyl Cellosolve Ethylene Union Carbide8.3 qlycol mono-butyl ether Secondary Butanol Sec-butanolAshland Chemi- 9.5 cal Co.
28% Ammonium Ammonlum Aldrich Chemi-5.3 Hydroxide hydroxide cal Co.
Kelsol 3962- Water reduc- Reichhold 74.7 B2G-70 ible alkyd Chemical Co.
binder Cobalt Hydrocure DrierMooney Chemi- 1~5 II cal Co.
Manganese Drier Mooney Chemi-Hydrocure II cal Co. 3.4 Delonized Water Water --- 29.4 ~or Water Viscosity Ad~ustment Total (without nntisettlin~ composition~ 1070.8 Notes: ~he deionized wate~, butyl cellosolve, secondary butanol, 28% ammonium hydroxide, and Xelsol 3962-~2G-70 are premixed. The deionized water added as a vlscoslty adjustment ls employed to attaln :
-' ' 2~ 7 a Ford Cup No. 4 viscosity of 40 seconds.
Basic Formulation; test composition may be prepared with di~ferent amounts, but proportional to those set foxth.
Examples 17-18 The antisettling compositions of Examples 5 and 7 were added to the millbase of a water-reducible alkyd primer paint according to the procedures described in Formulatlon 8 at a loading of 9.4 pounds per hundred gallons on a solids basis. The paint properties were evaluated and are set forth in Table 5. Samples of the pain~ were also heat aged at 120~F for one month and evaluated for antisettliny properties. The pi~ment settling properties at 120~F are set forth in Table 6.
Comparatlve Example H
A water-reducible alkyd primer wa~ prepared according to the procedures described in Formulation B, and M-P-A
1075 was added to the millbase. The antisettling addi~ive loadin~ was equivalent to 9.4 pounds per hundred gallons on ~0 a solids basis. The paint properties were evaluated and are set forth in Table 5. A sample of the paint was alqo heat aged at 120~F for one month and evaluated for antisettlinq propert$esl The pigment settlln~ properties at 120~~ are set forth in ~able 6.
Comparative Exam~le I
A second water-reducible alkyd primer was prepared according to the procedures de~cribed in Formulation B
withou~ ~he addition of an antisettling additive. The paint properties were evaluated and are set forth in Table ', . ~ ~ :: . :,: :
-2 ~9 7 ~
5. ~ sample of the paint was also heat aged at 120~F for one month and evaluated for antisettling properties. The pigment cettling properties at 120~F are set forth in Table 6.
Example 19 A water-based news red ink described in Formulation C
was used to test the antisettlinq performance of the antisettling composition prepared in accordance with Example 1. A water-based ink was prepared by mixing the in~redients set forth in Formulation C in the order listed.
The antisettling composition was added to the base lnk at a loading of 3.0~. The antisettling properties of the ink were evaluated according to ASTM D869-7B and are set forth in Table 7.
Comparative Example J
A water-based news red ink was prepared according to the procedures described in Formulation C without the addition of an antisettling additive. The antisettl~ng properties of the ink were evaluated according to ~S~
D869-78 and are set forth in Table 7.
;.. , .. ,. - - - . - ~ ., -..
: , - : -: . . - , . ..... - : -., . - . . .
~7~
~ormulation C. Water-Based News Red Ink Parts by Inqredient Generic Name Manufacturer Weiqht Lucidene 141 Acyrlic emulsion Morton 34.0 (30~ NV) Barium Lithol Presscake Sun Chemical Presscake 38.1 (~0% Pigment) Surfynol 104E Surfactant Air Products 0.3 -Isopropyl sopropyl Aldrich Chemi- 2.5 Alcohol alcohol cal Co.
BYX 020 Defoamer BYK Chemie 0.4 Deionized Solvent --- 24.7 Water Base Ink Total 100.0 * ~ ~
Base Ink 97,0 Antisettling Ex. 1 ---Additive 3.0 Total 100.0 Three (3~ parts of Example 1 by weight was added to 97 parts of the base ink. The ink and antisettling additive were high speed dispersed for 20 minutes and the temperature increased to 108~F. After 20 minutes, the ink was transferred to a Jiffy mill containing approximately 200 grams of steel shot. The lnk i8 shaken on a Red Devil Paint Shaker for 15 minutes. Then 20 parts water was added to the ink to adjust the Shell 2 viscosity to 16 seconds.
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Table 6 Antisettling Pi~ment Example Num~er Composition Paint Aqe Settlinq Ex. 17 Ex. 5 1 Wk, 120~F 7 2 Wks, 120~F 6 1 Mon, 120~F 4 Ex. 18 Ex. 7 1 Wk, 120~F 8 2 Wks, 120~F 7 1 Mon, 120~F 5 Comp. Ex. H M-P-A 10751 Wk, 120DF 4 2 Wks, 120~F
1 Mon, 120~F 0 Comp. Ex. I No Additive1 Wk, 120~F 2 2 Wks, 120~F 0 1 Mon, 120~F 0 Table 7 Antisettling Pigment Example Number Composition Paint Aqe Se~tlln~
~x. 19 Ex. 1 1 Day, R.T. 9 1 Wk, R. T. 8 2 Wks, R.T. 8 1 Mon, R.T. 5 Comp. Ex. J No Additive1 Day, R.T. 6 1 Wk, R. T. 4 2 Wks, R.T. 3 1 Mon, R.T.
Although the invention has been described and illustrated in detail, it is to be clearly understood that the same is by way of illustration and example, and ls not to be taken by way of limitation. For example, it i8 contemplated that a 100% ~olids amine neutsalized ethylene-acrylic acid copolymer can be utili~ed as an antisettlinq additive in paint manufacture. ~he spirit and scope of the present invention are to be llmited only by ~he term~ of the appended claims.
- . . :
. .
Claims (13)
1. An antisettling composition for aqueous coating systems, comprising the reaction product of (a) at least one emulsifiable copolymer of an alpha-olefin and an alpha, beta-ethylenically unsaturated carboxylic acid, and (b) a neutralizing agent.
2. The antisettling composition according to Claim 1, wherein the neutralizing agent is an amine.
3. An antisettling composition according to Claim 1 wherein said at least one emulsifiable low molecular weight copolymer of an alpha-olefin and an alpha, beta-ethylenically unsaturated carboxylic acid is present in an amount of from about 3 to about 70 weight percent of the total composition.
4. The antisettling composition according to Claim 3, wherein the alpha, beta-ethylenically unsaturated carboxylic acid has 3 to 8 carbon atoms.
5. The antisettling composition according to Claim 3, wherein said least one emulsifiable copolymer of an alpha-olefin and an alpha, beta-ethylenically unsaturated carboxylic acid has a molecular weight from about 500 to 20,000.
6. The antisettling composition according to Claim 3, wherein the alpha-olefin is ethylene with a concentration in the copolymer acid of at least 50 mol percent.
7. The antisettling composition according to Claim 6, wherein the alpha, beta-ethylenically unsaturated carboxylic acid is an alpha, beta-ethylenically unsaturated monocarboxylic acid having 3 to 6 carbon atoms.
8. The antisettling composition according to Claim 7, wherein the emulsifiable copolymer acid has a density of about 0.92 to about 0.98 g/cc, a softening point of from about 70°C to about 120°C and an acid value in the range from about 20 to 300.
9. The antisettling composition according to Claim 3, wherein the neutralizing agent is present in an amount sufficient to neutralize 25 to 200% of the acid groups in said at least one emulsifiable low molecular weight copolymer of an alpha-olefin and an alpha, beta-ethylenically unsaturated carboxylic acid and the neutralization is done in a solvent selected from the group consisting of water and solvents miscible with water and compatible with an aqueous coating system in which the composition is used, and mixtures thereof.
10. The antisettling composition according to Claim 9, wherein the solvent is selected from the group consisting of water, methanol, ethanol, isopropanol, propanol, butanol, sec-butanol, cyclohexanol, glycol ether, glycol ether acetates, and mixture thereof.
11. The antisettling composition according to Claim 10 wherein the said at least one emulsifiable low molecular weight copolymer acid is neutralized in water.
12. The antisettling composition according to Claim 3 wherein the neutralizing agent is present in an amount sufficient to completely neutralize all of the acid groups in said emulsifiable low molecular weight copolymer acid in water.
13. A process for suspending finely divided solid particles in aqueous coating compositions which comprises preparing an antisettling composition comprising a reaction product of at least one emulsifiable copolymer of an alpha-olefin and an alpha, beta-ethylenically unsaturated carboxylic acid which is neutralized with a neutralizing agent and adding the antisettling composition at any point of time during the manufacture of the aqueous coating system.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US78646391A | 1991-11-04 | 1991-11-04 | |
| US07/786,463 | 1991-11-04 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2079847A1 CA2079847A1 (en) | 1993-05-05 |
| CA2079847C true CA2079847C (en) | 1998-01-06 |
Family
ID=25138669
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002079847A Expired - Fee Related CA2079847C (en) | 1991-11-04 | 1992-10-05 | Antisettling agents for aqueous coating compositions |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5374687A (en) |
| EP (1) | EP0541477B1 (en) |
| JP (1) | JPH0734016A (en) |
| KR (1) | KR100192620B1 (en) |
| AU (1) | AU666136B2 (en) |
| BR (1) | BR9203589A (en) |
| CA (1) | CA2079847C (en) |
| DE (1) | DE69231882T2 (en) |
| MX (1) | MX9206346A (en) |
| ZA (1) | ZA926584B (en) |
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| US5824732A (en) * | 1993-07-07 | 1998-10-20 | Alliedsignal Inc. | Process for producing coating compositions containing ethylene-acrylic acid copolymers with polyamide grafts as rheology modifiers |
| CA2151112A1 (en) * | 1994-06-13 | 1995-12-14 | Michael Bennett Freeman | High temperature polymerization process and products therefrom |
| NL1000118C2 (en) * | 1995-04-11 | 1996-10-14 | Adw Chem Prod Bv | Chromium-free coating composition for metal surface treatment and method using it. |
| WO1997015382A1 (en) * | 1995-10-27 | 1997-05-01 | E.I. Du Pont De Nemours And Company | Dispersants for inorganic materials in aqueous systems |
| JP3564259B2 (en) * | 1997-05-09 | 2004-09-08 | 楠本化成株式会社 | Anti-settling agent for water-based paint |
| US6159906A (en) * | 1997-10-01 | 2000-12-12 | Rheox, Inc. | Oil well drilling fluids with improved anti-settling properties and methods of providing anti-settling properties to oil well drilling fluids |
| US6156833A (en) * | 1999-02-12 | 2000-12-05 | Pci Group, Inc. | Emulsification of non-aqueous chemical additives using soy methyl ester as the carrier |
| AU4457200A (en) * | 1999-04-16 | 2000-11-02 | E.I. Du Pont De Nemours And Company | Coating composition containing a low mfi ethylene acrylic acid copolymer |
| US6224284B1 (en) | 1999-10-12 | 2001-05-01 | Dri Mark Products Incorporated | Metallic ink composition for wick type writing instruments |
| US6852792B1 (en) | 2000-04-13 | 2005-02-08 | E. I. Du Pont De Nemours And Company | Coating composition containing a low MFI ethylene acrylic acid copolymer |
| DE50109264D1 (en) * | 2001-09-19 | 2006-05-11 | Celfa Ag Seewen | Composition for increasing the porosity and liquid absorption capacity of a layer |
| DE10215813A1 (en) * | 2002-04-10 | 2003-11-06 | Basf Ag | Thixotropic agent containing polyethylene waxes |
| KR100467489B1 (en) * | 2002-07-29 | 2005-01-24 | (주)대일화성 | anti-precipitator and manufacturing method therefor |
| DE10326630A1 (en) * | 2003-06-11 | 2005-01-05 | Basf Ag | Use of aqueous dispersions containing ethylene copolymer waxes |
| US8871270B2 (en) * | 2004-07-09 | 2014-10-28 | Corn Products Development, Inc | Tablet excipient |
| US7163642B2 (en) * | 2004-10-11 | 2007-01-16 | Hagquist James Alroy E | Composition inhibiting the expansion of fire, suppressing existing fire, and methods of manufacture and use thereof |
| US8846154B2 (en) | 2005-06-07 | 2014-09-30 | S.C. Johnson & Son, Inc. | Carpet décor and setting solution compositions |
| US8061269B2 (en) | 2008-05-14 | 2011-11-22 | S.C. Johnson & Son, Inc. | Multilayer stencils for applying a design to a surface |
| US7776108B2 (en) | 2005-06-07 | 2010-08-17 | S.C. Johnson & Son, Inc. | Composition for application to a surface |
| US7727289B2 (en) | 2005-06-07 | 2010-06-01 | S.C. Johnson & Son, Inc. | Composition for application to a surface |
| CA2610774C (en) | 2005-06-07 | 2012-09-11 | S.C. Johnson & Son, Inc. | Composition for application to a surface |
| US8557758B2 (en) | 2005-06-07 | 2013-10-15 | S.C. Johnson & Son, Inc. | Devices for applying a colorant to a surface |
| KR101326522B1 (en) * | 2007-12-13 | 2013-11-07 | 기아자동차주식회사 | Coating composition for controlling surface-roughness and a surface-treating method of automobile pipe filmed zinc-aluminum complex using the same |
| EP2404952A4 (en) * | 2009-03-03 | 2012-08-22 | Mitsui Du Pont Polychemical | Aqueous dispersion, process for producing same, and layered product |
| KR101423150B1 (en) * | 2010-02-08 | 2014-07-25 | 듀폰-미츠이 폴리케미칼 가부시키가이샤 | Aqueous dispersion and process for production thereof, and laminate |
| US20120029138A1 (en) * | 2010-08-02 | 2012-02-02 | Rhodia Operations | Anti-settling composition and methods for use |
| US8907022B2 (en) | 2011-09-01 | 2014-12-09 | E I Du Pont De Nemours And Company | Method to form an aqueous dispersion of an ionomer |
| JP6166731B2 (en) * | 2011-10-26 | 2017-07-19 | ルブリゾル アドバンスド マテリアルズ， インコーポレイテッド | Dispersant composition |
| US8841379B2 (en) | 2011-11-07 | 2014-09-23 | E I Du Pont De Nemours And Company | Method to form an aqueous dispersion of an ionomer-polyolefin blend |
| US20130149930A1 (en) | 2011-12-12 | 2013-06-13 | E I Du Pont De Nemours And Company | Methods to form an ionomer coating on a substrate |
| CN104136556A (en) | 2012-02-29 | 2014-11-05 | 纳幕尔杜邦公司 | Ionomer-poly(vinylalcohol) blends and coatings |
| US9085123B2 (en) | 2012-02-29 | 2015-07-21 | E I Du Pont De Nemours And Company | Ionomer-poly(vinylalcohol) coatings |
| US20130225021A1 (en) | 2012-02-29 | 2013-08-29 | E.I. Du Pont De Nemours And Company | Highly viscous ionomer-poly(vinylalcohol) coatings |
| CN105121480B (en) | 2012-12-21 | 2018-01-09 | 罗地亚经营管理公司 | Composition with the pH response polymers containing MAEP and/or MAHP and use its method |
| CN105263974A (en) * | 2012-12-21 | 2016-01-20 | 罗地亚经营管理公司 | Anti-settling and thickening compositions and methods for using same |
| US20150203704A1 (en) | 2014-01-22 | 2015-07-23 | E I Du Pont De Nemours And Company | Alkali metal-magnesium ionomer compositions |
| US20150203615A1 (en) | 2014-01-22 | 2015-07-23 | E I Du Pont De Nemours And Company | Alkali metal-zinc ionomer compositions |
| CN104312358A (en) * | 2014-10-08 | 2015-01-28 | 安徽真信涂料有限公司 | Functional interior wall coating material |
| DE102016113554B3 (en) | 2016-07-22 | 2018-01-25 | Savema Gmbh | Powder composition, gel and method for extinguishing and preventing the spread of fire, use of the powder composition and fire protection crust |
| WO2024010038A1 (en) * | 2022-07-08 | 2024-01-11 | 住友精化株式会社 | Resin dispersion composition |
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| US3321819A (en) * | 1964-12-24 | 1967-05-30 | Union Carbide Corp | Process for sizing and desizing textile fibers |
| US3658741A (en) * | 1966-09-19 | 1972-04-25 | Allied Chem | Homogeneous copolymers from ethylene |
| GB1268418A (en) * | 1968-09-30 | 1972-03-29 | Union Carbide Corp | Copolymer salts and printing ink compositions containing them |
| US3909280A (en) * | 1971-07-09 | 1975-09-30 | Allied Chem | Ethylene-acrylic acid-vinyl acetate terpolymer telomer waxes |
| US4173669A (en) * | 1977-09-09 | 1979-11-06 | Asahi-Dow Limited | Aqueous dispersion for coating and coated articles |
| US4381376A (en) * | 1980-12-29 | 1983-04-26 | Allied Corporation | Preparation of low molecular weight copolymer salts |
| US4370171A (en) * | 1981-02-02 | 1983-01-25 | Angus Chemical Co. | Method for dispersing comminuted solids |
| DE3112659C2 (en) * | 1981-03-31 | 1985-12-05 | Basf Farben + Fasern Ag, 2000 Hamburg | Process for the production of aqueous paints |
| US4603172A (en) * | 1981-09-25 | 1986-07-29 | Allied Corporation | Low molecular weight copolymer salts as dispersion aids in plastics |
| US4975119A (en) * | 1989-04-25 | 1990-12-04 | Rheox, Inc. | Liquid antisettling agents for organic coating compositions |
| DE3924396A1 (en) * | 1989-07-24 | 1991-01-31 | Basf Ag | PRODUCTION OF WAX DISPERSIONS WITH HIGH SOLIDS |
-
1992
- 1992-08-31 ZA ZA926584A patent/ZA926584B/en unknown
- 1992-09-15 BR BR929203589A patent/BR9203589A/en active Search and Examination
- 1992-10-05 CA CA002079847A patent/CA2079847C/en not_active Expired - Fee Related
- 1992-10-23 DE DE69231882T patent/DE69231882T2/en not_active Expired - Fee Related
- 1992-10-23 EP EP92650009A patent/EP0541477B1/en not_active Expired - Lifetime
- 1992-10-28 AU AU27401/92A patent/AU666136B2/en not_active Ceased
- 1992-11-03 KR KR1019920020501A patent/KR100192620B1/en not_active IP Right Cessation
- 1992-11-04 JP JP4318001A patent/JPH0734016A/en active Pending
- 1992-11-04 MX MX9206346A patent/MX9206346A/en not_active IP Right Cessation
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1993
- 1993-12-28 US US08/174,617 patent/US5374687A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| MX9206346A (en) | 1993-11-01 |
| AU666136B2 (en) | 1996-02-01 |
| DE69231882T2 (en) | 2001-11-29 |
| EP0541477A1 (en) | 1993-05-12 |
| US5374687A (en) | 1994-12-20 |
| ZA926584B (en) | 1993-03-08 |
| KR100192620B1 (en) | 1999-06-15 |
| BR9203589A (en) | 1993-05-11 |
| DE69231882D1 (en) | 2001-07-26 |
| EP0541477B1 (en) | 2001-06-20 |
| AU2740192A (en) | 1993-05-06 |
| CA2079847A1 (en) | 1993-05-05 |
| JPH0734016A (en) | 1995-02-03 |
| KR930010137A (en) | 1993-06-22 |
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