CA2157361C - Aqueous graft copolymer pigment dispersants - Google Patents
Aqueous graft copolymer pigment dispersants Download PDFInfo
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- CA2157361C CA2157361C CA002157361A CA2157361A CA2157361C CA 2157361 C CA2157361 C CA 2157361C CA 002157361 A CA002157361 A CA 002157361A CA 2157361 A CA2157361 A CA 2157361A CA 2157361 C CA2157361 C CA 2157361C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/04—Polymers provided for in subclasses C08C or C08F
- C08F290/046—Polymers of unsaturated carboxylic acids or derivatives thereof
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/006—Preparation of organic pigments
- C09B67/0066—Aqueous dispersions of pigments containing only dispersing agents
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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
- C09D155/00—Coating compositions based on homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C09D123/00 - C09D153/00
- C09D155/005—Homopolymers or copolymers obtained by polymerisation of macromolecular compounds terminated by a carbon-to-carbon double bond
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- 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
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/001—Pigment pastes, e.g. for mixing in paints in aqueous medium
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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
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Abstract
A pigment dispersion useful for forming coating compositions containing dispersed pigment, an aqueous carrier and a graft copolymer dispersant; wherein the graft copolymer has a weight average molecular weight of about 5,000-100,000 and has a polymeric backbone and macromonomer side chains attached to the backbone wherein 1) the polymeric backbone is hydrophobic in comparison to the side chains and contains polymerized ethylenically unsaturated, hydrophobic monomers and up to 20 % by weight, based on the weight of the graft copolymer, of polymerized ethylenically unsaturated acid containing monomers;
and 2) the side chains are hydrophilic macromonomers attached to the backbone at a single terminal point and contain polymerized ethylenically unsaturated monomers and 2-100 % by weight, based on the weight of the graft copolymer, of polymerized ethylenically unsaturated acid containing monomers and have a weight average molecular weight of about 1,000-30,000 and wherein the acid groups of the graft copolymer are neutralized with an inorganic base or an amine. The graft copolymer and a process for making the graft copolymer also are disclosed.
and 2) the side chains are hydrophilic macromonomers attached to the backbone at a single terminal point and contain polymerized ethylenically unsaturated monomers and 2-100 % by weight, based on the weight of the graft copolymer, of polymerized ethylenically unsaturated acid containing monomers and have a weight average molecular weight of about 1,000-30,000 and wherein the acid groups of the graft copolymer are neutralized with an inorganic base or an amine. The graft copolymer and a process for making the graft copolymer also are disclosed.
Description
TITLE
AQUEOUS GRAFT COPOLYMER PIGMENT DISPERSANTS
BACKGROUND OF THE INVENTION
This invention is directed to pigment dispersions and in particular to pigment dispersions formulated with a graft copolymer having acid functionality.
Water dispersible polymers are well known in the art and have 1 o been used to form waterbased coating compositions, pigment dispersions, adhesives and the like. Graft copolymers containing carboxyl groups and the preparation of these polymers is shown in Japanese Laid Open Patent Application (Kokai) No. 1-182304 dated July 20, 1989. This reference shows graft copolymers that have carboxyl groups based on acrylic and methacrylic acid in their side chains that have hydrophilic properties and teaches the use tertiary alcohol-based ester units of acrylic or methacrylic acid to form a macromonomer which is used to form a graft copolymer and then is hydrolyzed to form carboxylic acid groups on the polymer. The process taught by the reference is an inefficient process which does not form pure 2 o graft copolymer but results in a mixture of graft copolymer and low molecular weight components that are detrimental to pigment dispersions formed from the graft copolymer and finishes formed from such a composition.
Typical problems with water based coating compositions are 2 5 as follows: the pigment dispersion used to form the composition often is not completely compatible with the film forming binder constituents of the composition; the polymeric dispersant does not uniformly disperse the pigments and the pigments flocculate or agglomerate; or the dispersant does not enter into the curing reaction and remains in the film as an unwanted 3 o component which later may leach out or cause deterioration of the resulting finish.
A polymeric dispersant is needed that will form an aqueous pigment dispersion that is stable and not flocculated or agglomerated, that is compatible with a variety of polymeric film forming binders conventionally used in water based coating compositions and that will cure with the film to form a finish of automotive quality that does not deteriorate on weathering because of adverse properties caused by the presence of the polymeric dispersant.
SUMMARY OF THE INVENTION
A pigment dispersion useful for forming coating compositions containing dispersed pigment, an aqueous carrier and a graft copolymer dispersant;
to wherein the graft copolymer comprises about 90-50% by weight, of a polymeric backbone and correspondingly about 10-50% by weight, of macromonomer side chains attached to the backbone and has a weight average molecular weight of about 5,000-100,000 and wherein (1) the polymeric backbone is hydrophobic in comparison to the side chains and consists essentially of polymerized ethylenically unsaturated hydrophobic monomers and up to 20% by weight, based on the weight of the graft copolymer, of polymerized ethyIenically unsaturated acid containing monomers; and (2) the side chains are hydrophilic macromonomers attached to the 2 o backbone at a single terminal point and consists essentially of polymerized ethylenically unsaturated monomers polymerized in the presence of a cobalt chain transfer agent containing Co+2 and contains 20-50% by weight, based on the weight of the macromonomer, of polymerized ethylenically unsaturated acid containing monomers and have a weight average molecular weight of about 1,000-30,000 and wherein the acid groups of the graft copolymer are neutralized with an inorganic base or an amine.
The graft copolymer and the process for making the graft 3 o c°polymer are also part of this invention.
DET~11 ED DESCR~ON OF THE INVENTION
The novel pigment dispersion is stable and in general is non-flocculated or agglomerated and is compatible with a variety of polymeric film forming binders that are conventionally used in waterborne coating compositions and in particular is compatible with acrylic polymers that are widely used in waterborne coatings. The graft copolymer dispersant upon WO 94/21701 '~ 6' ~ PCT/US93/02701 curing of the coating, generally reacts with other film forming components of the coating composition and becomes part of the film and does not cause deterioration of the film upon weathering as may occur if it was an unreacted component of the film. Also, the freeze-thaw stability of the pigment dispersion is improved. Because the graft copolymer is an excellent pigment dispersant, the ratio of copolymer to pigment is less than is used with conventional dispersants particularly with metal oxide pigments such as iron oxide, titanium dioxide, zinc oxide and the like. The use of less dispersant reduces water sensitivity of the resulting finish.
The novel graft copolymer prepared by the process set forth herein is efficiently prepared and 100% graft copolymer is formed and not a mixture of graft copolymer and low molecular weight backbone polymer and copolymerized macromonomer segments as has generally been the case with prior art process used for making graft copolymers.
s5 The graft copolymer contains about 50-90% by weight of polymeric backbone and correspondingly about 10-50% by weight of sidechains. The graft copolymer has a weight average molecular weight of about 5,000-100,000 and preferably about 10,000-40,000. The side chains of the graft copolymer are formed from hydrophilic macromonomers that have 2 o a weight average molecular weight of about 1,000-30,000 and preferably 2,000-5,000 and contain about 2-100% by weight and preferably 20-SO% by weight, based on the weight of the macromonomer, of polymerized ethylenically unsaturated acid monomers. These sidechains are hydrophilic and keep the dispersant and pigments uniformly dispersed in the pigment 2 5 dispersion and in the resulting coating composition.
The backbone of the graft copolymer is hydrophobic relative to the sidechains and may contain up to 20% by weight , preferably 1-10% by weight, based on the weight of the graft copolymer, of polymerized ethylenically unsaturated acid monomers which are listed hereinafter. The 3 o backbone contains polymerized hydrophobic monomers such as alkyl methacrylates and acrylates, cycloaliphatic methacrylates and acrylates and aryl methacrylates and acrylates as are listed hereinafter and also may contain up to 30% by weight, based on the weight of the graft copolymer, of polymerized ethylenica.lly unsaturated non-hydrophobic monomers which 3 5 may contain functional groups. Examples of such monomers are hydroxy WO 94/21701 ~ ~~ ~ ~ PCT/US93102701 t ethyl acrylate, hydroxy ethyl methacrylate, t- butylamino ethyl methacrylate, diethyl amino ethyl acrylate, diethyl amino ethyl methacrylate, acrylamide, vitro phenol acrylate, vitro phenol methacrylate, phthalimido methyl acrylate, phthalimido methacrylate, acrylic acid, acryloamidb propane sulfonic acid.
The backbone of the graft copolymer has.~zi affinity for the surface of the pigment used in the dispersion and anchors the copolymer to the pigment and keeps the pigment dispersed and prevents the graft copolymer from returning to the aqueous phase. Reactive groups on the 1o backbone can react with the pigment and form a bond with the pigment.
Molecular weights are determined by Gel Permeation Chromatography using polystyrene as a standard.
The macromonomer contains a single terminal ethylenically unsaturated group which is polymerized into the backbone of the graft copolymer and primarily contains polymerized monomers of methacrylic acid, its esters, nitrites, amides or mixtures of these monomers.
Typical alkyl methacrylates that can be used have 1-8 carbon atoms in the alkyl group and are for example methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacLylate, butyl 2 o methacrylate, pentyl methacrylate, hexyl methacrylate, 2-ethyl hexyl methacrylate and the like. Cycloaliphatic methacrylates also can be used such as trimethylcyclohexyl methacrylate, isobutylcyclohexyl methacrylate, and the like. Aryl methacrylates also can be used such as benzyl methacrylate. Other polymerizable monomers that can be used are styrene, 2 5 alpha methyl stryrene, methacrylamide and methacrylonitrile. The above monomers can also be used in the backbone of the graft copolymer.
The macromonomer can contain 2-100% by weight, preferably about 20-50% by weight, based on the weight of the macromonomer, of polymerized ethylenically unsaturated acid. Methacrylic acid is preferred 3 o particularly if it is the sole constituent. Other acids that can be used are ethylenically unsaturated carboxylic acids such as acrylic acid, itaconic acid, malefic acid and the like. Ethylenically unsaturated sulfonic, sulfinic, phosphoric or phosphoric acid and esters thereof also can be used such as styrene sulfonic acid, acrylamido methyl propane sulfonic acid, vinyl WO 94/21701 ~' PCT/US93/02701 215'7361 phosphoric acid and its esters and the like. The above acids also can be used in the backbone of the graft copolymer.
Up to 40% by weight, based on the weight of the macromonomer, of other polymerized ethylenically unsaturated monomers 5 can be present in the macromonomer. Primarily alkyl acrylates having 1-12 carbons in the alkyl group can be used such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, 2-ethyl acrylate, nonyl acrylate, lauryl acrylate and the like can be used. G~rcloaliphatic acrylates can be used such as trimethylcyclohexyl 1 o acrylate, t-butyl cyclohexyl acrylate and the like. Aryl acrylates such as benzyl acrylate also can be used. The above monomers also can be used in the backbone of the graft copolymer.
One preferred macromonomer contains about SO-80% by weight of polymerized methyl methacrylate and 20-SO% by weight of polymerized methacrylic acid and has a weight average molecular weight of about 2,~0-5,0~.
To ensure that the resulting macromonomer only has one terminal ethylenically unsaturated group which will polymerize with the backbone monomers to form the graft copolymer, the macromonomer is 2 o polymerized by using a catalytic chain transfer agent that contains a Co+2 group, i.e. a cobalt chain transfer agent. Typically, in the first step of the process for preparing the macromonomer, the monomers are blended with an inert organic solvent which is water miscible or water dispersible and a cobalt chain transfer agent and heated usually to the reffux temperature of 2 5 the reaction mixture. In subsequent steps additional monomers and cobalt catalyst and conventional azo type polymerization catalyst such as 2,2'-azobis(2-methylbutanenitrile) and 2,2'-azobis(2,4'-dimethylpentanenitrile) 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile) are added and polymerization is continued until a macromonomer is formed of the desired 3 o molecular weight.
Preferred cobalt chain transfer agents or catalysts are described in US Patent 4,680,352 to Janowicz et al and US Patent 4,722,984 to Janowicz. Most preferred are pentacyanocobaltate (II), diaquabis(borondifluorodimethyl-glyoximato) cobaltate(II) and 3 5 diaquabis(borondifluorophenylglyoximato) cobaltate (II). Typically these chain transfer agents used at concentrations of about 5-1000 ppm based on the monomers used.
After the macromonomer is formed as described above, optionally solvent is stripped off and the backbone ~,csnomers are added to the macromonomer along with additional solvent and polymerization catalyst. Any of the aforementioned azo type cat~~~yst can be used as can other suitable catalyst such as peroxides and hy~lroperoxides. Typical of such catalyst are di-tertiarybutyl peroxide, di-cumylperoxide, tertiaryamyl peroxide, cumenehydroperoxide, di(n-propyl) peroxydicarbonate, peresters 1 o such as amyl peroxyacetate and the like. Polymerization is continued usually at the reflux temperature of the reaction mixture until a graft copolymer is formed of the desired molecular weight.
Typical solvents that can be used to form the macromonomer or the graft copolymer are ketones such as methyl ethyl ketone, isobutyl ketone, ethyl amyl ketone, acetone, alcohols such as methanol, ethanol, isopropanol, esters such as ethyl acetate, glycols such as ethylene glycol, propylene glycol, ethers such as tetrahydrofuran, ethylene glycol mono butyl ether and the like.
After the graft copolymer is formed, it is neutralized with an 2 o amine or an inorganic base such as ammonium hydroxide or sodium hydroxide and then water is added to form a dispersion. Typical amines that can be used include amino methyl propanol, amino ethyl propanol, dimethyl ethanol amine, triethylamine and the like. ~ne preferred amine is amino methyl propanol and the preferred inorganic base is ammonium hydroxide.
2 5 Particularly useful graft copolymers include the following:
a graft copolymer having a backbone of polymerized methyl acrylate and butyl acrylate and side chains of a macromonomer having a weight average molecular weight of about 2,000-5,000 and containing about 50-80% by weight, based on the weight of the macromonomer, of 3 o polymerized methyl methacrylate and 20-50% by weight, based on the weight of the macromonomer, of polymerized methacrylic acid.
a graft copolymer having a backbone of polymerized methyl acrylate and butyl acrylate and acrylamido methyl propane sulfonic acid and side chains of the above macromonomer.
WO 94/21701 ~ _ 215 7 3 6 ~ PCT~S93/02701 a graft copolymer having a backbone of polymerized methyl acrylate and butyl acrylate and acrylic acid and side chains of the above macromonomer.
a graft copolymer having a backbone of polymerized ethyl acrylate and side chains of the above macromonomer.
a graft copolymer having a backbone of polymerized ethyl acrylate and acrylic acid and side chains of the above macromonomer.
a graft copolymer having a backbone of polymerized ethyl acrylate, methyl acrylate and acrylic acid and side chains of the above macromonomer.
To form a pigment dispersion or a mill base, pigments are added to the aqueous graft copolymer dispersion and then the pigments are dispersed using conventional techniques such as high speed mixing, ball milling, sand grinding, attritor grinding or two or three roll milling.
The resulting pigment dispersion has a pigment to dispersant binder weight ratio of about 0.1/100 to 1500/100.
Any of the conventional pigments used in paints in particular waterborne paints can be used to form the pigment dispersion such as metallic oxides like titanium dioxide, iron oxides of various colors, zinc 2 o oxide, carbon black, filler pigments such as talc, china clay, barytes, carbonates, silicates and a wide variety of organic pigments such as quinacridones, phthalocyanines, perylenes, azo pigments, indanthrones, carbazoles such as carbozole violet, isoindolinones, isoindolones, thioindigo reds, benzimidazolinones, metallic flakes such aluminum flake pearlescent 2 5 flakes and the like.
It may be desirable to add other optional ingredients to the pigment dispersion such as antioxidants, flow control agents, rheology control agents such as fumed silica, microgels UV stabilizers screeners, quenchers and absorbers.
3 o Pigment dispersions of this invention can be added to a variety of waterborne coating compositions such as primer, primer surfacers, topcoats which may be monocoats or basecoats of a clear coat base coat finish. These compositions preferably have an acrylic polymer as the film forming constituent and may contain crosslinking agents such as blocked 3 5 isocyanate, alkylated melamines, epoxy resins and the like. Other film forming polymers can also be used such as acrylourethanes, polyesters and polyester urethanes, polyethers and polyether urethanes that are compatible with the pigment dispersion. It is desirable to have the film forming polymer ' of the coating composition be similar to the polymer of the pigment dispersion so that on curing the polymer of the pigment dispersion will cure ' with the coating polymer and become part of the film;oi coating.
The following examples illustrate thynvention. All parts and percentages are on a weight basis unless otherwise indicated. Molecular weights are determined by Gel Permeation Chromatography using 1 o polystyrene as the standard and tetrahydrofuran as the carrier solvent.
A macromonomer was prepared by charging the following constituents into a 3 liter flask equipped with a thermometer, stirrer dropping funnels, reffux condenser and a means for maintaining a nitrogen blanket over the reactants:
farts b,~ght i nl Methyl methacrylate 91.50 2 o Methacrylic acid 91.50 Methyl ethyl ketone 180.50 Portion 2 Diaquabis(borondifluorodiphenyl-glyoximato) 0.07 cobalt(II), Co(DPG-BF2) 2,2'-azobis(2-methylbutanenitrile) 0.50 Methyl ethyl ketone 20.00 in Methyl methacrylate monomer 251.80 Methacrylic acid monomer 205.90 so ri n4 Co(DPG-BF2) 0.07 2,2'azobis(2-methylbutanenitrile) 3.00 Methyl ethyl ketone 45.00 WO 94/21701 , P ri 2,2'azobis(2,4-dimethylpentanenitrile) 1.50 Co(DPG-BF2) 0.03 Methyl ethyl ketone 75.00 ' 5 Portion 6 2,2'azobis(2,4-dimethylpentanenitrile) 1.50 Co(DPG-BF2) 0.04 Methyl ethyl ketone 75,00 Total 1042.90 to The composition was heated to its reflux temperature in about 20 minutes. Portion 2 was added and the composition was held at its reflux temperature for 5 minutes. Portion 3 and 4 were added simultaneously while the reaction mixture was held at its reffux temperature. The addition of Portion 3 took 4 hours to complete and the addition of Portion 4 took 90 15 minutes to complete. When the addition of Portion 4 was completed, the gradual addition of Portion 5 was begun and took about 75 minutes while the reaction mixture was held at its reffux temperature. Portion 6 was added over a 75 minute period while maintaining the reaction mixture at its reffux temperature. Reffux was continued for an addition 15 minutes and the 2 o composition was cooled to room temperature.
The resulting macromonomer solution had a solids content of about 53%, contained 60% methyl methacrylate and 40% methacrylic acid and had a weight average molecular weight of about 2,558 and a number average molecular weight of about 1,482.
2 5 Solvent was stripped off in a vacuum oven to give 100% solids macromonomer which is used below to form the graft copolymer.
The following constituents were charged into a two liter flask equipped as above to form a graft copolymer solution:
Parts by Weight 3 0 rti n 1 Macromonomer (prepared above) 169.6 Butyl acrylate monomer 12.9 Methyl acrylate monomer 12.9 Isopropanol 340.0 WO 94/21701 ~ ~ PCT/US93/02701 Portion 2 2,2'-azobis(2-methylbutanenitrile) 6.0 Isopropanol 60.0 ' P i n 5 Butyl acrylate monomer 202.5 ' Methyl acrylate monomer 202.5 Portion 4 2,2'-azobis(2,4-dimethylpentanenitrile)2.0 Isopropanol 180.0 1 o Total 1184.4 Portion 1 was heated to its reflux temperature over a period of about 20 minutes. Portion 2 was added and simultaneously Portions 3 and 4 were gradually added over about a 3 hour period while maintaining the resulting reaction mixture at its reflux temperature. The reaction mixture was held at its reflux temperature for about an additional 2 hours and then cooled to room temperature.
The resulting graft polymer solution had a solids content of about 49% by weight and had the following overall approximate composition 36% butyl acrylate, 36% methyl acrylate, 17% methyl methacrylate and 11%
2 o methacrylic acid and had a weight average molecular weight of about 13,000 and a number average molecular weight of about 4,000.
A neutralized graft copolymer solution was prepared. About 37.4 parts by weight of 2-amino-2-methyl-1-propanol in 200.0 parts by weight of isopropanol was added to about 600 paxts by weight of the above graft 2 5 copolymer solution over about 20 minutes with stirring at room temperature and stirring was continues for about 30 minutes.
A waterborne pigment dispersion was prepared by charging the following constituents into a 01 Attritor media mill:
Parts b,~~ Weight 3 o Neutralized graft copolymer solution 44.84 (prepared above) Deionized water 314.44 Quinacridone magenta pigment (Hostaperm 15.72 Pink E 13-7000 from Hoechst Celanese Corp) ~i~~3si WO 94/21701 ~ PCT/US93/02701 Hi-density ceramic 1.6-2.5 mm grinding 850.00 media (ER120A from Netsch) ' Total 1225.00 The above constituents were ground for 20 hours at 500 rpm.
A uniform, transparent, waterborne pigment dispersion was formed that was stable and deflocculated and had a pH of 7.9.
Another neutralized graft copolymer solution was prepared.
About 500 parts by weight of the above graft copolymer solution was added to 23 parts by weight of ammonium hydroxide over about 20 minutes with 1 o stirring at room temperature and stirring was continued for about 30 minutes.
A waterborne pigment dispersion was prepared by charging the following constituents into a O1 Attritor media mill:
Parts b,~ght Neutralized graft copolymer solution 122.92 (prepared above neutralized with ammonium hydroxide) Isopropanol 10.40 Non-ionic surfactant (octyl phenol polyether alcohol) 6.40 Deionized water 196.28 2 o Blue pigment (Palomar blue pigment EB-8592 64.00 from Mobay) Hi-density ceramic 1.6-2.5 mm grinding media 850.00 (ER120A from Netsch) Total 1250.00 2 5 The above constituents were ground for 22 hours at 500 rpm.
A uniform, waterborne pigment dispersion was formed that was stable and deffocculated and had a pH of 9.14.
The following constituents were charged into a one liter flask 3 o equipped as in Example 1 to form a graft copolymer solution:
Parts by Weight Portion 1 Macromonomer (prepared in Example 1) 60.0 Butyl acrylate monomer 19.2 3 5 Methyl acrylate monomer 19.2 2~.~'~~6~.
Acrylic acid monomer 1.6 Isopropanol 190.0 i n2 2,2'-azobis(2-methylbutanenitrile) 1.0 Isopropanol - 10.0 ' .' r ion 3 Acrylic acid monomer 14.3 Butyl acrylate monomer 76.6 Methyl acrylate monomer 76.6 to Macromonomer (prepared in Example 32.5 1) Isopropanol 35.0 i n4 2,2'-azobis(2,4-dimethylpentanenitrile)2.5 Isopropanol 50.0 Portion 5 2,2'-azobis(2,4-dimethylpentanenitrile)1.0 Isopropanol 10.0 Total 599.5 Portion 1 was heated to its reffux temperature over a period of 2 o about 20 minutes. Portion 2 was added and simultaneously Portions 3 and 4 were gradually added over about a 3 hour period while maintaining the resulting reaction mixture at its reffux temperature. The reaction mixture was held at its reffux temperature for about an additional 2 hours. Portion 5 was added and the reaction mixture was held at its reffux temperature for an 2 5 addition 2 hours and then cooled to room temperature.
The resulting graft polymer solution had a solids content of about 48% by weight and the graft copolymer had the following overall approximate composition 32% butyl acrylate, 32% methyl acrylate, 12%
methacrylic acid, 18% methyl methacrylate and 5% acrylic acid and had a s o weight average molecular weight of about 15,000 and a number average molecular weight of about 4,000.
A neutralized graft copolymer solution was prepared. About 39 parts by weight of 2-amino-2-methyl-1-propanol was added to about 380 .
parts by weight of the above graft copolymer solution over about 20 minutes WO 94/21701 ~ ~~ PCT/US93/02701 with stirring at room temperature and stirring was continues for about 30 minutes.
- A waterborne pigment dispersion was prepared by charging the following constituents into a Ol Attritor media mill:
Parts by Weight Neutralized graft copolymer solution 7.98 (prepared above) Deionized water 307.02 Transparent iron oxide pigment 35.00 (Traps-oxide red 30-1005 from Hilton Davis) Hi-density ceramic 1.6-2.5 mm grinding 850.00 media (ER120A from Netsch) Total 1200.00 The above constituents were ground for 22 hours at 500 rpm.
A uniform, transparent, waterborne pigment dispersion was formed that was stable and deflocculated and had a pH of 8.5.
The following constituents were charged into a one liter flask equipped as in Example 1 to form a graft copolymer solution:
Farts ,Weight Portion 1 Macromonomer (prepared in Example 1) 92.5 Butyl acrylate monomer 9.6 Methyl acrylate monomer 9.6 2 5 Isopropanol 190.0 2-acrylamido-2-methyl-1-propane sulfonic acid 3.2 Deionized water 3.0 Portion 2 2,2'-azobis(2,4-dimethylpentanenitrile) 1.2 3 o Isopropanol 10.0 in Butyl acrylate monomer 86.2 Methyl acrylate monomer 86.2 WO 94/21701 ~ ~ PCTlUS93/02701 ri n4 2,2'-azobis(2,4-dimethylpentanenitrile) 3.0 Isopropanol 30.0 Portion S
2-acrylamido-2-methyl-1-propanesulfonic acid12.7 Deionized water 12.0 p i ort on 6 1.0 2,2'-azobis(2,4-dimethylpentanenitrile) Isopropanol 10.0 1 o Total 560.2 Portion 1 was heated to its reflux temperature over a period of about 20 minutes. Portion 2 was added and simultaneously Portions 3, 4 and 5 were gradually added over about a 3 hour period while maintaining the resulting reaction mixture at its reflux temperature. The reaction mixture was held at its reffux temperature for about an additional 2 hours. Portion 6 was added and the reaction mixture was held at its reffux temperature for an addition 2 hours and then cooled to room temperature.
The resulting graft polymer solution had a solids content of about 53% by weight and the graft copolymer had the following overall 2 o approximate composition 32% butyl acrylate, 32% methyl acrylate, 12%
methacrylic acid, 18% methyl methacrylate and 5% 2-acrylamido-2-methyl-1-propane sulfonic acid and had a weight average molecular weight of about 14,000 and a number average molecular weight of about 4,600.
A neutralized graft copolymer solution was prepared. About 40 parts by weight of 2-amino-2-methyl-1-propanol was added to about 485 parts by weight of the above graft copolymer solution over about 20 minutes with stirring at room temperature and stirring was continues for about 30 minutes.
A waterborne black pigment dispersion was prepared by 3 o charging the following constituents into a O1 Attritor media mill:
Parts by Weight , Neutralized graft copolymer solution 46.66 (prepared above) Deionized water 257.84 WO 94/21701 ~ ~ PCT/US93/02701 Carbon black pigment 45.50 (Raven 1170 powder from Columbian) ~ Hi-density ceramic 1.6-2.5 mm grinding 850.00 media (ER120A from Netsch) 5 Total 1200.00 The above constituents were ground for 20 hours at 500 rpm.
A uniform, waterborne pigment dispersion was formed that was stable and deflocculated and had a pH of 8.2.
A waterborne blue pigment dispersion was prepared by 1 o charging the following constituents into a 01 Attritor media mill:
Parts by Weight Neutralized graft copolymer solution 53.16 (prepared above) Deionized water 261.84 15 Blue pigment (Palomar blue pigment EB-8592 35.00 from Mobay) Hi-density ceramic 1.6-2.5 mm grinding 850.00 media (ER120A from Netsch) Total 1200.00 2 o The above constituents were ground for 24 hours at 500 rpm.
A uniform, waterborne pigment dispersion was formed that was stable and deflocculated and had a pH of 8.5.
A waterborne blue pigment II dispersion was prepared by charging the following constituents into a O1 Attritor media mill:
2 5 Parts by Weight Neutralized graft copolymer solution 53.16 (prepared above) Deionized water 261.84 Blue pigment (BT-788-D blue pigment 35.00 3 o from Cookson) Hi-density ceramic 1.6-2.5 mm grinding 850.00 media (ER120A from Netsch) r Total 1200.00 WO 94/21701 ~ PCTI1JS93/02701 The above constituents were ground for 24 hours at S00 rpm.
A uniform, waterborne pigment dispersion was formed that was stable and deflocculated and had a pH of 8.4.
The following constituents were:x:~arged into a one liter flask equipped as in Example 1 to form a graft copolymer solution:
Parts b,~gh_t Portion 1 Macromonomer (prepared in Example 84.8 1) 1 o Ethyl acrylate monomer 12.9 Isopropanol 170.0 i n2 2,2'-azobis(2-methylbutanenitrile) 3.0 Isopropanol 30.0 Portiot~
Ethyl acrylate monomer 202.5 Portion 4 2,2'-azobis(2,4-dimethylpentanenitrile)1.0 Isopropanol 90.0 2 o Total 594.2 Portion 1 was heated to its reflux temperature over a period of about 20 minutes. Portion 2 was added and simultaneously Portions 3 and 4 were gradually added over about a 3 hour period while maintaining the resulting reaction mixture at its reflux temperature. The reaction mixture 2 5 was held at its reffux temperature for about an additional 2 hours and then cooled to room temperature.
The resulting graft polymer solution had a solids content of about 51 % by weight and the graft copolymer had the following overall approximate composition 72% ethyl acrylate, 11% methacrylic acid, and 3 0 17% methyl methacrylate and had a weight average molecular weight of about 12,000 and a number average molecular weight of about 4,900.
A neutralized graft copolymer solution was prepared. About 18.4 parts by weight of 2-amino-2-methyl-1-propanol in 100.0 parts by weight of isopropanol was added to about 300 parts by weight of the above graft WO 94!21701 '' PCT//1JS93/02701 copolymer solution over about 20 minutes with stirring at room temperature and stirring was continues for about 30 minutes.
A waterborne magenta pigment dispersion was prepared by charging the following constituents into a 01 Attritor media mill:
' Parts by Weight Neutralized graft copolymer solution 47.81 (prepared above) Deionized water 302.19 Quinacridone magenta pigment 17.50 (Hostaperm Pink E Trans O1 13-7014 from Hoechst Celanese) Hi-density ceramic 1.6-2.5 mm grinding 850.00 media (ER120A from Netsch) Total 1217.50 ' The above constituents were ground for 20 hours at 500 rpm.
A uniform, transparent, waterborne pigment dispersion was formed that was stable and deflocculated and had a pH of 8.5.
The following constituents were charged into a one liter flask 2 o equipped as in Example 1 to form a graft copolymer solution:
Parts ~v Weight in Macromonomer (prepared in Example 1) 85.0 Ethyl acrylate monomer 84.0 2 5 Acrylic acid monomer 6.0 Deionized water 40.0 Isopropanol 90.0 Portion 2 T-butyl perxoy pivalate (75% solids in 2.0 3 o mineral spirits) Isopropanol 20.0 in Acrylic acid monomer 24.0 Ethyl acrylate monomer 366.0 3 5 Isopropanol 60.0 WO 94121701 PCTIUS93l02701 ri n4 T-butyl perxoy pivalate (75% solids in 4.0 mineral spirits) Isopropanol 180.0 "Total 961.0 Portion 1 was heated to its retlux temperature over a period of about 20 minutes. Portion 2 was added 'and simultaneously Portions 3 and 4 were gradually added over about a 3 hour period while maintaining the resulting reaction mixture at its reflux temperature. The reaction mixture 1 o was held at its reflux temperature for about an additional hour and then cooled to room temperature.
The resulting graft polymer solution had a solids content of about 56% by weight and the graft copolymer had the following overall approximate composition 80% ethyl acrylate, 6% methacrylic acid, 9%
methyl methacrylate and 5% acrylic acid and had a weight average molecular weight of about 24,000 and a number average molecular weight of about 5,300.
A neutralized graft copolymer solution was prepared. About 15.2 parts by weight of 2-amino-2-methyl-1-propanol in 100.0 parts by weight 2 0 of isopropanol was added to about 200 parts by weight of the above graft copolymer solution over about 20 minutes with stirring at room temperature and stirring was continues for about 30 minutes.
A waterborne transparent iron oxide pigment dispersion was prepared by charging the following constituents into a 01 Attritor media 2 5 mill:
Parts by Weight Neutralized graft copolymer solution 63.60 (prepared above) Deionized water 240.90 3 o Transparent iron oxide pigment 45.50 (Sicotrans Red L 2817 from BASF) Hi-density ceramic 1.6-2.5 mm grinding 850.00 media (ER120A from Netsch) , Total 1200.00 The above constituents were groun~! for 20 hours at 500 rpm.
A uniform, transparent, waterborne pigment dispersion was formed that was stable and deflocculated and had a pH of 8.2.
< ,EXAMPLE 6 The following constituents were charged into a five liter flask equipped as in Example 1 to~form a graft copolymer solution:
darts b,~ght Portion 1 Macromonomer (prepared in Example 1) 255.0 1 o Ethyl acrylate monomer 126.0 Methyl acrylate monomer 126.0 Acrylic acid monomer 18.0 Isopropanol 1450.0 i port 4.5 on 2,2'-azobis(2,4'dimethylpentanenitrile) Isopropanol 60.0 Portion 3 Acrylic acid monomer 72.0 Butyl acrylate monomer 549.0 2 o Methyl acrylate monomer 549.0 Portion 4 2,2'-azobis(2,4-dimethylpentanenitrile) 15.0 Isopropanol 150.0 Portion S
2 5 2,2'-azobis(2,4-dimethylpentanenitrile)1.0 Isopropanol 10.0 Total 3385.5 Portion 1 was heated to its reflux temperature over a period of about 20 minutes. Portion 2 was added and simultaneously Portions 3 and 4 3 o were gradually added over about a 3 hour period while maintaining the resulting reaction mixture at its reflux temperature. The reaction mixture was held at its reflex temperature for about an additional 2 hours and Portion 5 was added over a 5 minute period and reflex was continue for about 15 minutes then the resulting polymer solution was cooled to room 3 5 temperature.
WO 94/21701 ~ ~ PCT/U~93/02701 The resulting graft polymer solution had a solids content of about 50% by weight and the graft copolymer had the following overall approximate composition 40% butyl acrylate, 40% methyl acrylate, 6%
methacrylic acid, 9% methyl methacrylate and 5% acrylic acid and had a 5 weight average molecular weight of about 10,OOO,and a number average molecular weight of about 3,200.
A neutralized graft copolymer solution was prepared. About 130.0 parts by weight of 2-amino-2-methyl-1-propanol was added to about 2000 parts by weight of the above graft copolymer solution over about 20 1 o minutes with stirring at room temperature and stirring was continues for about 30 minutes.
A waterborne white pigment dispersion was prepared by charging the following constituents into a 1-S Attritor media mill:
Parts by Weight 15 Neutralized graft copolymer solution712.80 (prepared above) Deionized water 1813.20 Titanium dioxide pigment 3462.00 2-amino-2-methyl-1-propanol 6.00 2 o Hi-density ceramic 1.6-2.5 mm grinding5600.00 media (ER120A from Netsch) Total 11594.00 The above constituents were ground for 3 hours at 500 rpm. A
uniform, opaque, waterborne pigment dispersion was formed that was stable 2 5 and loosely flocculated and had a pH of 8.6.
A white paint was prepared with the white pigment dispersion of Example 6 and was tinted with the black pigment dispersion of Example 3 0 2. The following constituents were blended together to form the white paint:
Parts by Weight Latex 1 (core shell microgel acrylic latex having a low 330.00 acid functionality) t Latex 2 (core shell microgel acrylic latex having a high 330.00 3 5 acid functionality) Deionized water 70.00 Ethylene glycol monobutyl ether 100.00 ~ Crosslinking agent (monomeric hexa methyoxy methyl 54.00 melamine formaldehyde) ' S Deionized Water 140.00 White pigment dispersion (prepared in 280.00 Example 6) UV Screener ('"Tinuvin" 1139 in water ethylene glycol 6.00 monobutyl ether and anionic surfactant) 1 o Acrysol ASE-60 Thickener (aqueous dispersion of 164.09 3.35% by weight of crosslinked acrylic emulsion polymer) Demineralized water 97.50 Acrylsol ASE-60 Thickener 188.49 2-methyl-2-amino-1-propanol 3.50 15 Total 1763.48 The resulting basecoat had a pH of 7.4 and a Brooldield viscosity at Srpm using a #3 spindle of 2100 cps and 9.46% pigment (titanium dioxide).
The following amount of black waterborne dispersion of 2 o Example 2 was added to the white basecoat and evaluated for tinting strength.
Parts b,~ght White basecoat (prepared above) 99.27 Black pigment dispersion (prepared in Ex.2) 0.73 2 5 Total 100.00 The resulting composition had a tint strength of black/white of 1/100 and had an L Flat of 60.71 which is comparable or better than conventional commercial black pigment dispersions that are used to form coatings.
AQUEOUS GRAFT COPOLYMER PIGMENT DISPERSANTS
BACKGROUND OF THE INVENTION
This invention is directed to pigment dispersions and in particular to pigment dispersions formulated with a graft copolymer having acid functionality.
Water dispersible polymers are well known in the art and have 1 o been used to form waterbased coating compositions, pigment dispersions, adhesives and the like. Graft copolymers containing carboxyl groups and the preparation of these polymers is shown in Japanese Laid Open Patent Application (Kokai) No. 1-182304 dated July 20, 1989. This reference shows graft copolymers that have carboxyl groups based on acrylic and methacrylic acid in their side chains that have hydrophilic properties and teaches the use tertiary alcohol-based ester units of acrylic or methacrylic acid to form a macromonomer which is used to form a graft copolymer and then is hydrolyzed to form carboxylic acid groups on the polymer. The process taught by the reference is an inefficient process which does not form pure 2 o graft copolymer but results in a mixture of graft copolymer and low molecular weight components that are detrimental to pigment dispersions formed from the graft copolymer and finishes formed from such a composition.
Typical problems with water based coating compositions are 2 5 as follows: the pigment dispersion used to form the composition often is not completely compatible with the film forming binder constituents of the composition; the polymeric dispersant does not uniformly disperse the pigments and the pigments flocculate or agglomerate; or the dispersant does not enter into the curing reaction and remains in the film as an unwanted 3 o component which later may leach out or cause deterioration of the resulting finish.
A polymeric dispersant is needed that will form an aqueous pigment dispersion that is stable and not flocculated or agglomerated, that is compatible with a variety of polymeric film forming binders conventionally used in water based coating compositions and that will cure with the film to form a finish of automotive quality that does not deteriorate on weathering because of adverse properties caused by the presence of the polymeric dispersant.
SUMMARY OF THE INVENTION
A pigment dispersion useful for forming coating compositions containing dispersed pigment, an aqueous carrier and a graft copolymer dispersant;
to wherein the graft copolymer comprises about 90-50% by weight, of a polymeric backbone and correspondingly about 10-50% by weight, of macromonomer side chains attached to the backbone and has a weight average molecular weight of about 5,000-100,000 and wherein (1) the polymeric backbone is hydrophobic in comparison to the side chains and consists essentially of polymerized ethylenically unsaturated hydrophobic monomers and up to 20% by weight, based on the weight of the graft copolymer, of polymerized ethyIenically unsaturated acid containing monomers; and (2) the side chains are hydrophilic macromonomers attached to the 2 o backbone at a single terminal point and consists essentially of polymerized ethylenically unsaturated monomers polymerized in the presence of a cobalt chain transfer agent containing Co+2 and contains 20-50% by weight, based on the weight of the macromonomer, of polymerized ethylenically unsaturated acid containing monomers and have a weight average molecular weight of about 1,000-30,000 and wherein the acid groups of the graft copolymer are neutralized with an inorganic base or an amine.
The graft copolymer and the process for making the graft 3 o c°polymer are also part of this invention.
DET~11 ED DESCR~ON OF THE INVENTION
The novel pigment dispersion is stable and in general is non-flocculated or agglomerated and is compatible with a variety of polymeric film forming binders that are conventionally used in waterborne coating compositions and in particular is compatible with acrylic polymers that are widely used in waterborne coatings. The graft copolymer dispersant upon WO 94/21701 '~ 6' ~ PCT/US93/02701 curing of the coating, generally reacts with other film forming components of the coating composition and becomes part of the film and does not cause deterioration of the film upon weathering as may occur if it was an unreacted component of the film. Also, the freeze-thaw stability of the pigment dispersion is improved. Because the graft copolymer is an excellent pigment dispersant, the ratio of copolymer to pigment is less than is used with conventional dispersants particularly with metal oxide pigments such as iron oxide, titanium dioxide, zinc oxide and the like. The use of less dispersant reduces water sensitivity of the resulting finish.
The novel graft copolymer prepared by the process set forth herein is efficiently prepared and 100% graft copolymer is formed and not a mixture of graft copolymer and low molecular weight backbone polymer and copolymerized macromonomer segments as has generally been the case with prior art process used for making graft copolymers.
s5 The graft copolymer contains about 50-90% by weight of polymeric backbone and correspondingly about 10-50% by weight of sidechains. The graft copolymer has a weight average molecular weight of about 5,000-100,000 and preferably about 10,000-40,000. The side chains of the graft copolymer are formed from hydrophilic macromonomers that have 2 o a weight average molecular weight of about 1,000-30,000 and preferably 2,000-5,000 and contain about 2-100% by weight and preferably 20-SO% by weight, based on the weight of the macromonomer, of polymerized ethylenically unsaturated acid monomers. These sidechains are hydrophilic and keep the dispersant and pigments uniformly dispersed in the pigment 2 5 dispersion and in the resulting coating composition.
The backbone of the graft copolymer is hydrophobic relative to the sidechains and may contain up to 20% by weight , preferably 1-10% by weight, based on the weight of the graft copolymer, of polymerized ethylenically unsaturated acid monomers which are listed hereinafter. The 3 o backbone contains polymerized hydrophobic monomers such as alkyl methacrylates and acrylates, cycloaliphatic methacrylates and acrylates and aryl methacrylates and acrylates as are listed hereinafter and also may contain up to 30% by weight, based on the weight of the graft copolymer, of polymerized ethylenica.lly unsaturated non-hydrophobic monomers which 3 5 may contain functional groups. Examples of such monomers are hydroxy WO 94/21701 ~ ~~ ~ ~ PCT/US93102701 t ethyl acrylate, hydroxy ethyl methacrylate, t- butylamino ethyl methacrylate, diethyl amino ethyl acrylate, diethyl amino ethyl methacrylate, acrylamide, vitro phenol acrylate, vitro phenol methacrylate, phthalimido methyl acrylate, phthalimido methacrylate, acrylic acid, acryloamidb propane sulfonic acid.
The backbone of the graft copolymer has.~zi affinity for the surface of the pigment used in the dispersion and anchors the copolymer to the pigment and keeps the pigment dispersed and prevents the graft copolymer from returning to the aqueous phase. Reactive groups on the 1o backbone can react with the pigment and form a bond with the pigment.
Molecular weights are determined by Gel Permeation Chromatography using polystyrene as a standard.
The macromonomer contains a single terminal ethylenically unsaturated group which is polymerized into the backbone of the graft copolymer and primarily contains polymerized monomers of methacrylic acid, its esters, nitrites, amides or mixtures of these monomers.
Typical alkyl methacrylates that can be used have 1-8 carbon atoms in the alkyl group and are for example methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacLylate, butyl 2 o methacrylate, pentyl methacrylate, hexyl methacrylate, 2-ethyl hexyl methacrylate and the like. Cycloaliphatic methacrylates also can be used such as trimethylcyclohexyl methacrylate, isobutylcyclohexyl methacrylate, and the like. Aryl methacrylates also can be used such as benzyl methacrylate. Other polymerizable monomers that can be used are styrene, 2 5 alpha methyl stryrene, methacrylamide and methacrylonitrile. The above monomers can also be used in the backbone of the graft copolymer.
The macromonomer can contain 2-100% by weight, preferably about 20-50% by weight, based on the weight of the macromonomer, of polymerized ethylenically unsaturated acid. Methacrylic acid is preferred 3 o particularly if it is the sole constituent. Other acids that can be used are ethylenically unsaturated carboxylic acids such as acrylic acid, itaconic acid, malefic acid and the like. Ethylenically unsaturated sulfonic, sulfinic, phosphoric or phosphoric acid and esters thereof also can be used such as styrene sulfonic acid, acrylamido methyl propane sulfonic acid, vinyl WO 94/21701 ~' PCT/US93/02701 215'7361 phosphoric acid and its esters and the like. The above acids also can be used in the backbone of the graft copolymer.
Up to 40% by weight, based on the weight of the macromonomer, of other polymerized ethylenically unsaturated monomers 5 can be present in the macromonomer. Primarily alkyl acrylates having 1-12 carbons in the alkyl group can be used such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, 2-ethyl acrylate, nonyl acrylate, lauryl acrylate and the like can be used. G~rcloaliphatic acrylates can be used such as trimethylcyclohexyl 1 o acrylate, t-butyl cyclohexyl acrylate and the like. Aryl acrylates such as benzyl acrylate also can be used. The above monomers also can be used in the backbone of the graft copolymer.
One preferred macromonomer contains about SO-80% by weight of polymerized methyl methacrylate and 20-SO% by weight of polymerized methacrylic acid and has a weight average molecular weight of about 2,~0-5,0~.
To ensure that the resulting macromonomer only has one terminal ethylenically unsaturated group which will polymerize with the backbone monomers to form the graft copolymer, the macromonomer is 2 o polymerized by using a catalytic chain transfer agent that contains a Co+2 group, i.e. a cobalt chain transfer agent. Typically, in the first step of the process for preparing the macromonomer, the monomers are blended with an inert organic solvent which is water miscible or water dispersible and a cobalt chain transfer agent and heated usually to the reffux temperature of 2 5 the reaction mixture. In subsequent steps additional monomers and cobalt catalyst and conventional azo type polymerization catalyst such as 2,2'-azobis(2-methylbutanenitrile) and 2,2'-azobis(2,4'-dimethylpentanenitrile) 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile) are added and polymerization is continued until a macromonomer is formed of the desired 3 o molecular weight.
Preferred cobalt chain transfer agents or catalysts are described in US Patent 4,680,352 to Janowicz et al and US Patent 4,722,984 to Janowicz. Most preferred are pentacyanocobaltate (II), diaquabis(borondifluorodimethyl-glyoximato) cobaltate(II) and 3 5 diaquabis(borondifluorophenylglyoximato) cobaltate (II). Typically these chain transfer agents used at concentrations of about 5-1000 ppm based on the monomers used.
After the macromonomer is formed as described above, optionally solvent is stripped off and the backbone ~,csnomers are added to the macromonomer along with additional solvent and polymerization catalyst. Any of the aforementioned azo type cat~~~yst can be used as can other suitable catalyst such as peroxides and hy~lroperoxides. Typical of such catalyst are di-tertiarybutyl peroxide, di-cumylperoxide, tertiaryamyl peroxide, cumenehydroperoxide, di(n-propyl) peroxydicarbonate, peresters 1 o such as amyl peroxyacetate and the like. Polymerization is continued usually at the reflux temperature of the reaction mixture until a graft copolymer is formed of the desired molecular weight.
Typical solvents that can be used to form the macromonomer or the graft copolymer are ketones such as methyl ethyl ketone, isobutyl ketone, ethyl amyl ketone, acetone, alcohols such as methanol, ethanol, isopropanol, esters such as ethyl acetate, glycols such as ethylene glycol, propylene glycol, ethers such as tetrahydrofuran, ethylene glycol mono butyl ether and the like.
After the graft copolymer is formed, it is neutralized with an 2 o amine or an inorganic base such as ammonium hydroxide or sodium hydroxide and then water is added to form a dispersion. Typical amines that can be used include amino methyl propanol, amino ethyl propanol, dimethyl ethanol amine, triethylamine and the like. ~ne preferred amine is amino methyl propanol and the preferred inorganic base is ammonium hydroxide.
2 5 Particularly useful graft copolymers include the following:
a graft copolymer having a backbone of polymerized methyl acrylate and butyl acrylate and side chains of a macromonomer having a weight average molecular weight of about 2,000-5,000 and containing about 50-80% by weight, based on the weight of the macromonomer, of 3 o polymerized methyl methacrylate and 20-50% by weight, based on the weight of the macromonomer, of polymerized methacrylic acid.
a graft copolymer having a backbone of polymerized methyl acrylate and butyl acrylate and acrylamido methyl propane sulfonic acid and side chains of the above macromonomer.
WO 94/21701 ~ _ 215 7 3 6 ~ PCT~S93/02701 a graft copolymer having a backbone of polymerized methyl acrylate and butyl acrylate and acrylic acid and side chains of the above macromonomer.
a graft copolymer having a backbone of polymerized ethyl acrylate and side chains of the above macromonomer.
a graft copolymer having a backbone of polymerized ethyl acrylate and acrylic acid and side chains of the above macromonomer.
a graft copolymer having a backbone of polymerized ethyl acrylate, methyl acrylate and acrylic acid and side chains of the above macromonomer.
To form a pigment dispersion or a mill base, pigments are added to the aqueous graft copolymer dispersion and then the pigments are dispersed using conventional techniques such as high speed mixing, ball milling, sand grinding, attritor grinding or two or three roll milling.
The resulting pigment dispersion has a pigment to dispersant binder weight ratio of about 0.1/100 to 1500/100.
Any of the conventional pigments used in paints in particular waterborne paints can be used to form the pigment dispersion such as metallic oxides like titanium dioxide, iron oxides of various colors, zinc 2 o oxide, carbon black, filler pigments such as talc, china clay, barytes, carbonates, silicates and a wide variety of organic pigments such as quinacridones, phthalocyanines, perylenes, azo pigments, indanthrones, carbazoles such as carbozole violet, isoindolinones, isoindolones, thioindigo reds, benzimidazolinones, metallic flakes such aluminum flake pearlescent 2 5 flakes and the like.
It may be desirable to add other optional ingredients to the pigment dispersion such as antioxidants, flow control agents, rheology control agents such as fumed silica, microgels UV stabilizers screeners, quenchers and absorbers.
3 o Pigment dispersions of this invention can be added to a variety of waterborne coating compositions such as primer, primer surfacers, topcoats which may be monocoats or basecoats of a clear coat base coat finish. These compositions preferably have an acrylic polymer as the film forming constituent and may contain crosslinking agents such as blocked 3 5 isocyanate, alkylated melamines, epoxy resins and the like. Other film forming polymers can also be used such as acrylourethanes, polyesters and polyester urethanes, polyethers and polyether urethanes that are compatible with the pigment dispersion. It is desirable to have the film forming polymer ' of the coating composition be similar to the polymer of the pigment dispersion so that on curing the polymer of the pigment dispersion will cure ' with the coating polymer and become part of the film;oi coating.
The following examples illustrate thynvention. All parts and percentages are on a weight basis unless otherwise indicated. Molecular weights are determined by Gel Permeation Chromatography using 1 o polystyrene as the standard and tetrahydrofuran as the carrier solvent.
A macromonomer was prepared by charging the following constituents into a 3 liter flask equipped with a thermometer, stirrer dropping funnels, reffux condenser and a means for maintaining a nitrogen blanket over the reactants:
farts b,~ght i nl Methyl methacrylate 91.50 2 o Methacrylic acid 91.50 Methyl ethyl ketone 180.50 Portion 2 Diaquabis(borondifluorodiphenyl-glyoximato) 0.07 cobalt(II), Co(DPG-BF2) 2,2'-azobis(2-methylbutanenitrile) 0.50 Methyl ethyl ketone 20.00 in Methyl methacrylate monomer 251.80 Methacrylic acid monomer 205.90 so ri n4 Co(DPG-BF2) 0.07 2,2'azobis(2-methylbutanenitrile) 3.00 Methyl ethyl ketone 45.00 WO 94/21701 , P ri 2,2'azobis(2,4-dimethylpentanenitrile) 1.50 Co(DPG-BF2) 0.03 Methyl ethyl ketone 75.00 ' 5 Portion 6 2,2'azobis(2,4-dimethylpentanenitrile) 1.50 Co(DPG-BF2) 0.04 Methyl ethyl ketone 75,00 Total 1042.90 to The composition was heated to its reflux temperature in about 20 minutes. Portion 2 was added and the composition was held at its reflux temperature for 5 minutes. Portion 3 and 4 were added simultaneously while the reaction mixture was held at its reffux temperature. The addition of Portion 3 took 4 hours to complete and the addition of Portion 4 took 90 15 minutes to complete. When the addition of Portion 4 was completed, the gradual addition of Portion 5 was begun and took about 75 minutes while the reaction mixture was held at its reffux temperature. Portion 6 was added over a 75 minute period while maintaining the reaction mixture at its reffux temperature. Reffux was continued for an addition 15 minutes and the 2 o composition was cooled to room temperature.
The resulting macromonomer solution had a solids content of about 53%, contained 60% methyl methacrylate and 40% methacrylic acid and had a weight average molecular weight of about 2,558 and a number average molecular weight of about 1,482.
2 5 Solvent was stripped off in a vacuum oven to give 100% solids macromonomer which is used below to form the graft copolymer.
The following constituents were charged into a two liter flask equipped as above to form a graft copolymer solution:
Parts by Weight 3 0 rti n 1 Macromonomer (prepared above) 169.6 Butyl acrylate monomer 12.9 Methyl acrylate monomer 12.9 Isopropanol 340.0 WO 94/21701 ~ ~ PCT/US93/02701 Portion 2 2,2'-azobis(2-methylbutanenitrile) 6.0 Isopropanol 60.0 ' P i n 5 Butyl acrylate monomer 202.5 ' Methyl acrylate monomer 202.5 Portion 4 2,2'-azobis(2,4-dimethylpentanenitrile)2.0 Isopropanol 180.0 1 o Total 1184.4 Portion 1 was heated to its reflux temperature over a period of about 20 minutes. Portion 2 was added and simultaneously Portions 3 and 4 were gradually added over about a 3 hour period while maintaining the resulting reaction mixture at its reflux temperature. The reaction mixture was held at its reflux temperature for about an additional 2 hours and then cooled to room temperature.
The resulting graft polymer solution had a solids content of about 49% by weight and had the following overall approximate composition 36% butyl acrylate, 36% methyl acrylate, 17% methyl methacrylate and 11%
2 o methacrylic acid and had a weight average molecular weight of about 13,000 and a number average molecular weight of about 4,000.
A neutralized graft copolymer solution was prepared. About 37.4 parts by weight of 2-amino-2-methyl-1-propanol in 200.0 parts by weight of isopropanol was added to about 600 paxts by weight of the above graft 2 5 copolymer solution over about 20 minutes with stirring at room temperature and stirring was continues for about 30 minutes.
A waterborne pigment dispersion was prepared by charging the following constituents into a 01 Attritor media mill:
Parts b,~~ Weight 3 o Neutralized graft copolymer solution 44.84 (prepared above) Deionized water 314.44 Quinacridone magenta pigment (Hostaperm 15.72 Pink E 13-7000 from Hoechst Celanese Corp) ~i~~3si WO 94/21701 ~ PCT/US93/02701 Hi-density ceramic 1.6-2.5 mm grinding 850.00 media (ER120A from Netsch) ' Total 1225.00 The above constituents were ground for 20 hours at 500 rpm.
A uniform, transparent, waterborne pigment dispersion was formed that was stable and deflocculated and had a pH of 7.9.
Another neutralized graft copolymer solution was prepared.
About 500 parts by weight of the above graft copolymer solution was added to 23 parts by weight of ammonium hydroxide over about 20 minutes with 1 o stirring at room temperature and stirring was continued for about 30 minutes.
A waterborne pigment dispersion was prepared by charging the following constituents into a O1 Attritor media mill:
Parts b,~ght Neutralized graft copolymer solution 122.92 (prepared above neutralized with ammonium hydroxide) Isopropanol 10.40 Non-ionic surfactant (octyl phenol polyether alcohol) 6.40 Deionized water 196.28 2 o Blue pigment (Palomar blue pigment EB-8592 64.00 from Mobay) Hi-density ceramic 1.6-2.5 mm grinding media 850.00 (ER120A from Netsch) Total 1250.00 2 5 The above constituents were ground for 22 hours at 500 rpm.
A uniform, waterborne pigment dispersion was formed that was stable and deffocculated and had a pH of 9.14.
The following constituents were charged into a one liter flask 3 o equipped as in Example 1 to form a graft copolymer solution:
Parts by Weight Portion 1 Macromonomer (prepared in Example 1) 60.0 Butyl acrylate monomer 19.2 3 5 Methyl acrylate monomer 19.2 2~.~'~~6~.
Acrylic acid monomer 1.6 Isopropanol 190.0 i n2 2,2'-azobis(2-methylbutanenitrile) 1.0 Isopropanol - 10.0 ' .' r ion 3 Acrylic acid monomer 14.3 Butyl acrylate monomer 76.6 Methyl acrylate monomer 76.6 to Macromonomer (prepared in Example 32.5 1) Isopropanol 35.0 i n4 2,2'-azobis(2,4-dimethylpentanenitrile)2.5 Isopropanol 50.0 Portion 5 2,2'-azobis(2,4-dimethylpentanenitrile)1.0 Isopropanol 10.0 Total 599.5 Portion 1 was heated to its reffux temperature over a period of 2 o about 20 minutes. Portion 2 was added and simultaneously Portions 3 and 4 were gradually added over about a 3 hour period while maintaining the resulting reaction mixture at its reffux temperature. The reaction mixture was held at its reffux temperature for about an additional 2 hours. Portion 5 was added and the reaction mixture was held at its reffux temperature for an 2 5 addition 2 hours and then cooled to room temperature.
The resulting graft polymer solution had a solids content of about 48% by weight and the graft copolymer had the following overall approximate composition 32% butyl acrylate, 32% methyl acrylate, 12%
methacrylic acid, 18% methyl methacrylate and 5% acrylic acid and had a s o weight average molecular weight of about 15,000 and a number average molecular weight of about 4,000.
A neutralized graft copolymer solution was prepared. About 39 parts by weight of 2-amino-2-methyl-1-propanol was added to about 380 .
parts by weight of the above graft copolymer solution over about 20 minutes WO 94/21701 ~ ~~ PCT/US93/02701 with stirring at room temperature and stirring was continues for about 30 minutes.
- A waterborne pigment dispersion was prepared by charging the following constituents into a Ol Attritor media mill:
Parts by Weight Neutralized graft copolymer solution 7.98 (prepared above) Deionized water 307.02 Transparent iron oxide pigment 35.00 (Traps-oxide red 30-1005 from Hilton Davis) Hi-density ceramic 1.6-2.5 mm grinding 850.00 media (ER120A from Netsch) Total 1200.00 The above constituents were ground for 22 hours at 500 rpm.
A uniform, transparent, waterborne pigment dispersion was formed that was stable and deflocculated and had a pH of 8.5.
The following constituents were charged into a one liter flask equipped as in Example 1 to form a graft copolymer solution:
Farts ,Weight Portion 1 Macromonomer (prepared in Example 1) 92.5 Butyl acrylate monomer 9.6 Methyl acrylate monomer 9.6 2 5 Isopropanol 190.0 2-acrylamido-2-methyl-1-propane sulfonic acid 3.2 Deionized water 3.0 Portion 2 2,2'-azobis(2,4-dimethylpentanenitrile) 1.2 3 o Isopropanol 10.0 in Butyl acrylate monomer 86.2 Methyl acrylate monomer 86.2 WO 94/21701 ~ ~ PCTlUS93/02701 ri n4 2,2'-azobis(2,4-dimethylpentanenitrile) 3.0 Isopropanol 30.0 Portion S
2-acrylamido-2-methyl-1-propanesulfonic acid12.7 Deionized water 12.0 p i ort on 6 1.0 2,2'-azobis(2,4-dimethylpentanenitrile) Isopropanol 10.0 1 o Total 560.2 Portion 1 was heated to its reflux temperature over a period of about 20 minutes. Portion 2 was added and simultaneously Portions 3, 4 and 5 were gradually added over about a 3 hour period while maintaining the resulting reaction mixture at its reflux temperature. The reaction mixture was held at its reffux temperature for about an additional 2 hours. Portion 6 was added and the reaction mixture was held at its reffux temperature for an addition 2 hours and then cooled to room temperature.
The resulting graft polymer solution had a solids content of about 53% by weight and the graft copolymer had the following overall 2 o approximate composition 32% butyl acrylate, 32% methyl acrylate, 12%
methacrylic acid, 18% methyl methacrylate and 5% 2-acrylamido-2-methyl-1-propane sulfonic acid and had a weight average molecular weight of about 14,000 and a number average molecular weight of about 4,600.
A neutralized graft copolymer solution was prepared. About 40 parts by weight of 2-amino-2-methyl-1-propanol was added to about 485 parts by weight of the above graft copolymer solution over about 20 minutes with stirring at room temperature and stirring was continues for about 30 minutes.
A waterborne black pigment dispersion was prepared by 3 o charging the following constituents into a O1 Attritor media mill:
Parts by Weight , Neutralized graft copolymer solution 46.66 (prepared above) Deionized water 257.84 WO 94/21701 ~ ~ PCT/US93/02701 Carbon black pigment 45.50 (Raven 1170 powder from Columbian) ~ Hi-density ceramic 1.6-2.5 mm grinding 850.00 media (ER120A from Netsch) 5 Total 1200.00 The above constituents were ground for 20 hours at 500 rpm.
A uniform, waterborne pigment dispersion was formed that was stable and deflocculated and had a pH of 8.2.
A waterborne blue pigment dispersion was prepared by 1 o charging the following constituents into a 01 Attritor media mill:
Parts by Weight Neutralized graft copolymer solution 53.16 (prepared above) Deionized water 261.84 15 Blue pigment (Palomar blue pigment EB-8592 35.00 from Mobay) Hi-density ceramic 1.6-2.5 mm grinding 850.00 media (ER120A from Netsch) Total 1200.00 2 o The above constituents were ground for 24 hours at 500 rpm.
A uniform, waterborne pigment dispersion was formed that was stable and deflocculated and had a pH of 8.5.
A waterborne blue pigment II dispersion was prepared by charging the following constituents into a O1 Attritor media mill:
2 5 Parts by Weight Neutralized graft copolymer solution 53.16 (prepared above) Deionized water 261.84 Blue pigment (BT-788-D blue pigment 35.00 3 o from Cookson) Hi-density ceramic 1.6-2.5 mm grinding 850.00 media (ER120A from Netsch) r Total 1200.00 WO 94/21701 ~ PCTI1JS93/02701 The above constituents were ground for 24 hours at S00 rpm.
A uniform, waterborne pigment dispersion was formed that was stable and deflocculated and had a pH of 8.4.
The following constituents were:x:~arged into a one liter flask equipped as in Example 1 to form a graft copolymer solution:
Parts b,~gh_t Portion 1 Macromonomer (prepared in Example 84.8 1) 1 o Ethyl acrylate monomer 12.9 Isopropanol 170.0 i n2 2,2'-azobis(2-methylbutanenitrile) 3.0 Isopropanol 30.0 Portiot~
Ethyl acrylate monomer 202.5 Portion 4 2,2'-azobis(2,4-dimethylpentanenitrile)1.0 Isopropanol 90.0 2 o Total 594.2 Portion 1 was heated to its reflux temperature over a period of about 20 minutes. Portion 2 was added and simultaneously Portions 3 and 4 were gradually added over about a 3 hour period while maintaining the resulting reaction mixture at its reflux temperature. The reaction mixture 2 5 was held at its reffux temperature for about an additional 2 hours and then cooled to room temperature.
The resulting graft polymer solution had a solids content of about 51 % by weight and the graft copolymer had the following overall approximate composition 72% ethyl acrylate, 11% methacrylic acid, and 3 0 17% methyl methacrylate and had a weight average molecular weight of about 12,000 and a number average molecular weight of about 4,900.
A neutralized graft copolymer solution was prepared. About 18.4 parts by weight of 2-amino-2-methyl-1-propanol in 100.0 parts by weight of isopropanol was added to about 300 parts by weight of the above graft WO 94!21701 '' PCT//1JS93/02701 copolymer solution over about 20 minutes with stirring at room temperature and stirring was continues for about 30 minutes.
A waterborne magenta pigment dispersion was prepared by charging the following constituents into a 01 Attritor media mill:
' Parts by Weight Neutralized graft copolymer solution 47.81 (prepared above) Deionized water 302.19 Quinacridone magenta pigment 17.50 (Hostaperm Pink E Trans O1 13-7014 from Hoechst Celanese) Hi-density ceramic 1.6-2.5 mm grinding 850.00 media (ER120A from Netsch) Total 1217.50 ' The above constituents were ground for 20 hours at 500 rpm.
A uniform, transparent, waterborne pigment dispersion was formed that was stable and deflocculated and had a pH of 8.5.
The following constituents were charged into a one liter flask 2 o equipped as in Example 1 to form a graft copolymer solution:
Parts ~v Weight in Macromonomer (prepared in Example 1) 85.0 Ethyl acrylate monomer 84.0 2 5 Acrylic acid monomer 6.0 Deionized water 40.0 Isopropanol 90.0 Portion 2 T-butyl perxoy pivalate (75% solids in 2.0 3 o mineral spirits) Isopropanol 20.0 in Acrylic acid monomer 24.0 Ethyl acrylate monomer 366.0 3 5 Isopropanol 60.0 WO 94121701 PCTIUS93l02701 ri n4 T-butyl perxoy pivalate (75% solids in 4.0 mineral spirits) Isopropanol 180.0 "Total 961.0 Portion 1 was heated to its retlux temperature over a period of about 20 minutes. Portion 2 was added 'and simultaneously Portions 3 and 4 were gradually added over about a 3 hour period while maintaining the resulting reaction mixture at its reflux temperature. The reaction mixture 1 o was held at its reflux temperature for about an additional hour and then cooled to room temperature.
The resulting graft polymer solution had a solids content of about 56% by weight and the graft copolymer had the following overall approximate composition 80% ethyl acrylate, 6% methacrylic acid, 9%
methyl methacrylate and 5% acrylic acid and had a weight average molecular weight of about 24,000 and a number average molecular weight of about 5,300.
A neutralized graft copolymer solution was prepared. About 15.2 parts by weight of 2-amino-2-methyl-1-propanol in 100.0 parts by weight 2 0 of isopropanol was added to about 200 parts by weight of the above graft copolymer solution over about 20 minutes with stirring at room temperature and stirring was continues for about 30 minutes.
A waterborne transparent iron oxide pigment dispersion was prepared by charging the following constituents into a 01 Attritor media 2 5 mill:
Parts by Weight Neutralized graft copolymer solution 63.60 (prepared above) Deionized water 240.90 3 o Transparent iron oxide pigment 45.50 (Sicotrans Red L 2817 from BASF) Hi-density ceramic 1.6-2.5 mm grinding 850.00 media (ER120A from Netsch) , Total 1200.00 The above constituents were groun~! for 20 hours at 500 rpm.
A uniform, transparent, waterborne pigment dispersion was formed that was stable and deflocculated and had a pH of 8.2.
< ,EXAMPLE 6 The following constituents were charged into a five liter flask equipped as in Example 1 to~form a graft copolymer solution:
darts b,~ght Portion 1 Macromonomer (prepared in Example 1) 255.0 1 o Ethyl acrylate monomer 126.0 Methyl acrylate monomer 126.0 Acrylic acid monomer 18.0 Isopropanol 1450.0 i port 4.5 on 2,2'-azobis(2,4'dimethylpentanenitrile) Isopropanol 60.0 Portion 3 Acrylic acid monomer 72.0 Butyl acrylate monomer 549.0 2 o Methyl acrylate monomer 549.0 Portion 4 2,2'-azobis(2,4-dimethylpentanenitrile) 15.0 Isopropanol 150.0 Portion S
2 5 2,2'-azobis(2,4-dimethylpentanenitrile)1.0 Isopropanol 10.0 Total 3385.5 Portion 1 was heated to its reflux temperature over a period of about 20 minutes. Portion 2 was added and simultaneously Portions 3 and 4 3 o were gradually added over about a 3 hour period while maintaining the resulting reaction mixture at its reflux temperature. The reaction mixture was held at its reflex temperature for about an additional 2 hours and Portion 5 was added over a 5 minute period and reflex was continue for about 15 minutes then the resulting polymer solution was cooled to room 3 5 temperature.
WO 94/21701 ~ ~ PCT/U~93/02701 The resulting graft polymer solution had a solids content of about 50% by weight and the graft copolymer had the following overall approximate composition 40% butyl acrylate, 40% methyl acrylate, 6%
methacrylic acid, 9% methyl methacrylate and 5% acrylic acid and had a 5 weight average molecular weight of about 10,OOO,and a number average molecular weight of about 3,200.
A neutralized graft copolymer solution was prepared. About 130.0 parts by weight of 2-amino-2-methyl-1-propanol was added to about 2000 parts by weight of the above graft copolymer solution over about 20 1 o minutes with stirring at room temperature and stirring was continues for about 30 minutes.
A waterborne white pigment dispersion was prepared by charging the following constituents into a 1-S Attritor media mill:
Parts by Weight 15 Neutralized graft copolymer solution712.80 (prepared above) Deionized water 1813.20 Titanium dioxide pigment 3462.00 2-amino-2-methyl-1-propanol 6.00 2 o Hi-density ceramic 1.6-2.5 mm grinding5600.00 media (ER120A from Netsch) Total 11594.00 The above constituents were ground for 3 hours at 500 rpm. A
uniform, opaque, waterborne pigment dispersion was formed that was stable 2 5 and loosely flocculated and had a pH of 8.6.
A white paint was prepared with the white pigment dispersion of Example 6 and was tinted with the black pigment dispersion of Example 3 0 2. The following constituents were blended together to form the white paint:
Parts by Weight Latex 1 (core shell microgel acrylic latex having a low 330.00 acid functionality) t Latex 2 (core shell microgel acrylic latex having a high 330.00 3 5 acid functionality) Deionized water 70.00 Ethylene glycol monobutyl ether 100.00 ~ Crosslinking agent (monomeric hexa methyoxy methyl 54.00 melamine formaldehyde) ' S Deionized Water 140.00 White pigment dispersion (prepared in 280.00 Example 6) UV Screener ('"Tinuvin" 1139 in water ethylene glycol 6.00 monobutyl ether and anionic surfactant) 1 o Acrysol ASE-60 Thickener (aqueous dispersion of 164.09 3.35% by weight of crosslinked acrylic emulsion polymer) Demineralized water 97.50 Acrylsol ASE-60 Thickener 188.49 2-methyl-2-amino-1-propanol 3.50 15 Total 1763.48 The resulting basecoat had a pH of 7.4 and a Brooldield viscosity at Srpm using a #3 spindle of 2100 cps and 9.46% pigment (titanium dioxide).
The following amount of black waterborne dispersion of 2 o Example 2 was added to the white basecoat and evaluated for tinting strength.
Parts b,~ght White basecoat (prepared above) 99.27 Black pigment dispersion (prepared in Ex.2) 0.73 2 5 Total 100.00 The resulting composition had a tint strength of black/white of 1/100 and had an L Flat of 60.71 which is comparable or better than conventional commercial black pigment dispersions that are used to form coatings.
Claims (17)
1. A pigment dispersion comprising dispersed pigment, an aqueous carrier and a graft copolymer dispersant; wherein the graft copolymer comprises about 90-50% by weight, of a polymeric backbone and correspondingly about 10-50% by weight, of macromonomer side chains attached to the backbone and has a weight average molecular weight of about 5,000-100,000 and wherein (1) the polymeric backbone is hydrophobic in comparison to the side chains and consists essentially of polymerized ethylenically unsaturated hydrophobic monomers and up to 20% by weight, based on the weight of the graft copolymer, of polymerized ethylenically unsaturated acid containing monomers; and (2) the side chains are hydrophilic macromonomers attached to the backbone at a single terminal point and consists essentially of polymerized ethylenically unsaturated monomers polymerized in the presence of a cobalt chain transfer agent containing Co+2 and contains 20-50% by weight, based on the weight of the macromonomer, of polymerized ethylenically unsaturated acid containing monomers and have a weight average molecular weight of about 1,000-30,000 and wherein the acid groups of the graft copolymer are neutralized with an inorganic base or an amine.
2. The pigment dispersion of claim 1 in which the macromonomer consists essentially of polymerized alkyl methacrylate monomers or any mixtures thereof each having 1-8 carbon atoms in the alkyl groups and 20-50% by weight, based on the weight of the macromonomer of polymerized ethylenically unsaturated carboxylic acid and has a weight average molecular weight of about 2,000-5,000.
3. The pigment dispersion of claim 2 in which the macromonomer consists of 50-80% by weight of polymerized methyl methacrylate and 20-50% by weight of polymerized methacrylic acid.
4. The pigment dispersion of claim 1 in which the macromonomer consist essentially of polymerized alkyl methacrylate, having 1-8 carbon atoms in the alkyl groups and polymerized ethylenically unsaturated sulfonic acid and has a weight average molecular weight of about 2,000-5,000.
5. The pigment dispersion of claim 1 in which the backbone of the graft copolymer consist essentially of polymerized monomers of alkyl methacrylate, an alkyl acrylate or mixtures thereof where the alkyl groups have 1-8 carbon atoms and 1-10'% by weight, based on the weight of the graft copolymer of polymerized ethylenically unsaturated carboxylic acid or ethylenically unsaturated sulfonic acid.
6. The pigment dispersion of claim 1 in which the backbone of the graft copolymer consist essentially of polymerized monomers of alkyl methacrylate, an alkyl acrylate or mixtures thereof where the alkyl groups have 1-8 carbon atoms and 1-10% by weight, based on the weight of the graft copolymer of polymerized methacrylic acid or acrylic acid.
7. The pigment dispersion of claim 2 in which the macromonomer consists of 50-80% by weight of polymerized methyl methacrylate and 20-50% by weight of polymerized methacrylic acid and has a weight average molecular weight of about 2,000-5,000 and the backbone of the graft copolymer consists of polymerized methyl acrylate and butyl acrylate and the graft copolymer is neutralized with amino methyl propanol.
8. The pigment dispersion of claim 2 in which the macromonomer consists of 50-80% by weight of polymerized methyl methacrylate and 20-50% by weight of polymerized methacrylic acid and has a weight average molecular weight of about 2,000-5,000 and the backbone of the graft copolymer consists of polymerized methyl acrylate and butyl acrylate and acrylamido methyl propane sulfonic acid and the graft copolymer is neutralized with amino methyl propanol.
9. A graft copolymer comprising about 90-50% by weight, of a polymeric backbone and correspondingly about 10-50% by weight, of macromonomer side chains attached to the backbone and has a weight average molecular weight of about 5,000-100,000 and wherein (1) the polymeric backbone is hydrophobic in comparison to the side chains and consists essentially of polymerized ethylenically unsaturated hydrophobic monomers and up to 20% by weight, based on the weight of the graft copolymer, of polymerized ethylenically unsaturated acid containing monomers; and (2) the side chains are hydrophilic macromonomers attached to the backbone at a single terminal point and consists essentially of polymerized ethylenically unsaturated monomers and 20-50% by weight, based on the weight of the macromonomer, of polymerized ethylenically unsaturated acid and are polymerized by using a catalytic chain transfer agent containing Co+2 and the macromonomers have a weight average molecular weight of about 1,000-30,000.
10. The graft copolymer of claim 9 in which the macromonomer consists essentially of polymerized alkyl methacrylate monomers or any mixtures thereof each having 1-8 carbon atoms in the alkyl groups and 20-50% by weight, based on the weight of the macromonomer, of polymerized ethylenically unsaturated carboxylic acid and has a weight average molecular weight of about 2,000-5,000.
11. The graft copolymer of claim 9 in which the macromonomer consists of 50-80% by weight of polymerized methyl methacrylate and 20-50% by weight of polymerized methacrylic acid.
12. The graft copolymer of claim 9 in which the macromonomer consist essentially of polymerized alkyl methacrylate, having 1-8 carbon atoms in the alkyl group and polymerized ethylenically unsaturated sulfonic acid and has an weight average molecular weight of about 2,000-5,000.
13. The graft copolymer of claim 10 in which the backbone of the graft copolymer consist essentially of polymerized monomers of alkyl methacrylate, an alkyl acrylate or mixtures thereof where the alkyl groups have 1-8 carbon atoms and 1-10% by weight, based on the weight of the graft copolymer of methacrylic acid or acrylic acid.
14. The graft copolymer claim 9 in which the backbone of the graft copolymer consist essentially of polymerized monomers of alkyl methacrylate, an alkyl acrylate or mixtures thereof where the alkyl groups have 1-8 carbon atoms and 1-10% by weight, based on the weight of the graft copolymer of ethylenically unsaturated sulfonic acid.
15. The graft copolymer of claim 10 in which the macromonomer consists of 50-80% by weight of polymerized methyl methacrylate and 20-50% by weight of polymerized methacrylic acid and has a weight average molecular weight of about 2,000-5,000 and the backbone of the graft copolymer consists of polymerized methyl acrylate and butyl acrylate.
16. The graft copolymer of claim 10 in which the macromonomer consists of 50-80% by weight of polymerized methyl methacrylate and 20-50% by weight of polymerized methacrylic acid and has a weight average molecular weight of about 2,000-5,000 and the backbone of the graft copolymer consists of polymerized methyl acrylate and butyl acrylate and acrylamido methyl propane sulfonic acid.
17. A process for forming a pigment dispersion comprising pigment, an aqueous carrier and a polymeric dispersant which consists essentially of a graft copolymer having a weight average molecular weight of about 5,000-100,000 and comprises about 90-50% by weight, of a polymeric backbone having about 10-50% by weight, of macromonomer side chains attached thereto, where the backbone is hydrophobic relative to the hydrophilic side chains; the process comprising (a) preparing macromonomer, in an organic solvent, by polymerizing, using a catalytic chain transfer agent containing Co+2, ethylenically unsaturated monomers and 20-50% by weight, based on weight of the resulting macromonomer, of ethylenically unsaturated acid monomers to form a macromonomer containing acid groups and a terminal ethylenically unsaturated group, and having a weight average molecular weight of about 1,000-30,000, (b) forming, in an organic solvent, the graft copolymer by polymerizing, in the presence of said macromonomers prepared in step (a) ethylenically unsaturated hydrophobic monomers and up to 20% by weight, based on the weight of the graft copolymer, of ethylenically unsaturated acid monomers whereby said terminal group of the macromonomer is polymerized into the backbone to form the graft copolymer and neutralizing the acid groups of the copolymer with an inorganic base or an amine, (c) mixing the graft copolymer solution prepared in step (b) with an aqueous medium and pigment and dispersing the pigment therein to form a pigment dispersion.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US07/813,186 US5231131A (en) | 1991-12-24 | 1991-12-24 | Aqueous graft copolymer pigment dispersants |
PCT/US1993/002701 WO1994021701A1 (en) | 1991-12-24 | 1993-03-22 | Aqueous graft copolymer pigment dispersants |
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CA2157361A1 CA2157361A1 (en) | 1994-09-29 |
CA2157361C true CA2157361C (en) | 2005-10-25 |
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CA002157361A Expired - Fee Related CA2157361C (en) | 1991-12-24 | 1993-03-22 | Aqueous graft copolymer pigment dispersants |
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US (1) | US5231131A (en) |
EP (1) | EP0690883B1 (en) |
JP (1) | JP3438893B2 (en) |
BR (1) | BR9307765A (en) |
CA (1) | CA2157361C (en) |
DE (1) | DE69305184T2 (en) |
ES (1) | ES2092821T3 (en) |
WO (1) | WO1994021701A1 (en) |
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US6503975B1 (en) | 2000-03-29 | 2003-01-07 | E. I Du Pont De Nemours And Company | Surfactant free aqueous emulsions |
US6660793B1 (en) * | 2000-06-15 | 2003-12-09 | E. I. Du Pont De Nemours And Company | Aqueous coating compositions having improved transparency |
US6548174B2 (en) * | 2000-06-30 | 2003-04-15 | Kansai Paint Co., Ltd. | Pigment dispersing resins |
CA2420870C (en) * | 2000-09-01 | 2010-06-22 | Digiglass Pty. Ltd. | Image carrying laminated material |
US6599973B1 (en) | 2000-09-27 | 2003-07-29 | E. I. Du Pont De Nemours And Company | Aqueous graft copolymer pigment dispersants |
WO2002031010A1 (en) * | 2000-10-13 | 2002-04-18 | Kansai Paint Co., Ltd. | Resin for pigment dispersion |
EP1197537A3 (en) * | 2000-10-13 | 2004-10-13 | Kansai Paint Co., Ltd. | Pigment dispersing resins |
WO2002074822A1 (en) | 2001-03-15 | 2002-09-26 | Toagosei Co., Ltd. | Process for producing copolymer |
FR2823213B1 (en) * | 2001-04-05 | 2007-06-08 | Peintures Jefco Francis | COPOLYMER GRAFT AND LIQUID CONCENTRATE OF MINERAL FILLERS CONTAINING THEM AND THEIR USE FOR THE PREPARATION OF PAINTS IN AQUEOUS AND / OR ORGANIC CONDITIONS |
EP1247821A3 (en) * | 2001-04-05 | 2003-10-15 | Kansai Paint Co., Ltd. | Pigment dispersing resin |
AU785239B2 (en) * | 2001-06-20 | 2006-11-23 | Rohm And Haas Company | Aqueous composite particle composition |
EP1433308A2 (en) | 2001-10-04 | 2004-06-30 | E.I. Du Pont De Nemours And Company | Ink jet printing |
US20040196346A1 (en) * | 2001-10-05 | 2004-10-07 | Redding Martin E. | Ink jet printing |
US7789333B2 (en) * | 2001-11-02 | 2010-09-07 | E.I. Du Pont De Nemours And Company | Media mill process |
JP2005532924A (en) | 2001-11-21 | 2005-11-04 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Inkjet printing with uniform gloss |
US7186770B2 (en) | 2002-02-25 | 2007-03-06 | E. I. Du Pont De Nemours And Company | Unfinished rutile titanium dioxide slurry for paints and paper coatings |
US6852817B2 (en) * | 2002-03-29 | 2005-02-08 | Kansai Paint Co., Ltd. | Pigment dispersing resin and water-based pigment dispersion which contains the same |
US6582510B1 (en) | 2002-04-16 | 2003-06-24 | Arco Chemical Technology, L.P. | Use of comb-branched copolymers as pigment dispersants |
US6866799B2 (en) * | 2002-05-09 | 2005-03-15 | Anuvu, Inc. | Water-soluble electrically conductive composition, modifications, and applications thereof |
EP1507667A1 (en) * | 2002-05-17 | 2005-02-23 | E.I. Du Pont De Nemours And Company | Planarizing element for thermal printing of color filter |
JP3792602B2 (en) * | 2002-05-29 | 2006-07-05 | エルピーダメモリ株式会社 | Semiconductor memory device |
US6852803B2 (en) * | 2002-06-03 | 2005-02-08 | E. I. Du Pont De Nemours And Company | Graft copolymer with a urethane/urea group as a pigment dispersant |
US20040092622A1 (en) * | 2002-07-01 | 2004-05-13 | Pearlstine Kathryn Amy | Inkjet ink with reduced bronzing |
DE10232908A1 (en) | 2002-07-19 | 2004-01-29 | Goldschmidt Ag | Use of organically modified polysiloxanes containing phenyl derivatives as dispersants and wetting agents for fillers and pigments in aqueous pigment pastes and color or coating formulations |
US20070087137A9 (en) * | 2003-06-26 | 2007-04-19 | Elwakil Hamdy A | Decorative laminated safety glass |
JP4107036B2 (en) * | 2002-09-30 | 2008-06-25 | 東亞合成株式会社 | Pigment dispersant and water-based ink |
US7045002B2 (en) * | 2002-11-15 | 2006-05-16 | E. I. Du Pont De Nemours And Company | Interactive ink set for inkjet printing |
US6984701B2 (en) * | 2002-11-26 | 2006-01-10 | Lexmark International, Inc. | Polymeric dispersants to improve smear in printing |
MX256798B (en) * | 2002-12-12 | 2008-05-02 | Oreal | Dispersions of polymers in organic medium, and compositions comprising them. |
FR2848559B1 (en) * | 2002-12-12 | 2006-12-08 | Oreal | ACRYLIC POLYMER, DISPERSION OF SAID POLYMER STABLE IN A NONAQUEOUS AND NON - SILICONE ORGANIC MEDIUM AND COMPOSITION COMPRISING SAID DISPERSION |
US20040257417A1 (en) | 2003-04-28 | 2004-12-23 | Christian Jackson | Inkjet printing method |
US20050020730A1 (en) | 2003-05-19 | 2005-01-27 | Valentini Jose E. | Inkjet ink |
US20050039631A1 (en) * | 2003-05-23 | 2005-02-24 | Best Kevin J. | Pigmented inkjet ink set |
US20050090599A1 (en) * | 2003-06-06 | 2005-04-28 | Spinelli Harry J. | Aqueous ionically stabilized dispersions |
WO2004111165A1 (en) * | 2003-06-11 | 2004-12-23 | Ciba Specialty Chemicals Water Treatments Limited | Polymeric surfactant |
WO2005004205A2 (en) * | 2003-06-26 | 2005-01-13 | E.I. Dupont De Nemours And Company | Methods for forming patterns of a filled dielectric material on substrates |
US20050032930A1 (en) * | 2003-07-02 | 2005-02-10 | Christian Jackson | Inkjet ink |
US20050070629A1 (en) * | 2003-08-06 | 2005-03-31 | Roberts C. Chad | Inkjet ink |
EP1678263B1 (en) * | 2003-09-08 | 2007-11-07 | E.I. Dupont De Nemours And Company | Inkjet ink, ink set and method of printing |
DE10348825A1 (en) | 2003-10-21 | 2005-06-02 | Goldschmidt Ag | Dispersant for the preparation of aqueous pigment pastes |
CN1875075A (en) * | 2003-10-31 | 2006-12-06 | 东亚合成株式会社 | Water base ink |
WO2005049744A1 (en) * | 2003-11-12 | 2005-06-02 | E.I. Dupont De Nemours And Company | Inkjet ink, ink set and method of printing |
JP5085935B2 (en) * | 2003-11-13 | 2012-11-28 | チバ ホールディング インコーポレーテッド | Aqueous milling method for quinacridone pigment |
US7419542B2 (en) | 2003-11-13 | 2008-09-02 | Ciba Specialty Chemicals Corporation | 2,9-dichloro-quinacridone as α-quinacridone crystal phase inhibitor |
US7122078B2 (en) * | 2003-12-22 | 2006-10-17 | E. I. Du Pont De Nemours And Company | Ink jet ink composition |
US7682012B2 (en) * | 2003-12-29 | 2010-03-23 | E. I. Du Pont De Nemours And Company | Inkjet printing method and apparatus |
JP4758652B2 (en) * | 2004-01-19 | 2011-08-31 | 大日精化工業株式会社 | Method for producing graft copolymer having excellent pigment dispersibility, method for producing emulsions using the graft copolymers, and pigment dispersions using the graft copolymers or emulsions |
TW200604223A (en) * | 2004-01-19 | 2006-02-01 | Dainichiseika Color Chem | Graft copolymers having excellent pigment-dispersing ability, production process of the graft copolymers, production method of emulsions by use of the graft copolymers, and pigment dispersions making use of the graft copolymers or emulsions |
US20050182154A1 (en) * | 2004-01-21 | 2005-08-18 | Berge Charles T. | Inkjet inks containing crosslinked polyurethanes |
US20050166794A1 (en) * | 2004-02-04 | 2005-08-04 | Bauer Richard D. | Binder additive for inkjet ink |
ATE323745T1 (en) | 2004-02-20 | 2006-05-15 | Goldschmidt Gmbh | METHOD FOR PRODUCING HOMOGENEOUS, STORAGE-STABLE PASTES, PAINTS, LACQUERS USING IONIC LIQUIDS AS DISPERSING AIDS |
JP4852031B2 (en) * | 2004-03-02 | 2012-01-11 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Decorative laminated safety glass |
US7404849B2 (en) * | 2004-04-21 | 2008-07-29 | E. I. Du Pont De Nemours And Company | Inkjet ink set for improved color reproduction |
US7905589B2 (en) * | 2004-05-13 | 2011-03-15 | E. I. Du Pont De Nemours And Company | Inkjet printing with pigmented inks |
WO2005118716A1 (en) * | 2004-05-25 | 2005-12-15 | Lexmark International, Inc. | Polymeric dispersants to improve smear in printing |
US7351278B2 (en) * | 2004-06-09 | 2008-04-01 | E.I. Du Pont De Nemours And Company | Additive for high optical density inkjet ink |
US20050282928A1 (en) * | 2004-06-21 | 2005-12-22 | Tyau-Jeen Lin | Ink jet ink |
US20050282946A1 (en) * | 2004-06-21 | 2005-12-22 | Tyau-Jeen Lin | Titanium dioxide slurries for ink applications |
US7399351B2 (en) * | 2004-06-25 | 2008-07-15 | Ei Du Pont De Nemours And Company | Pigmented inkjet ink and ink set |
US7384465B2 (en) * | 2004-06-25 | 2008-06-10 | E.I. Du Pont De Nemours & Co. | Pigmented blue inkjet ink color reproduction |
GB0415934D0 (en) * | 2004-07-16 | 2004-08-18 | Avecia Bv | Vinyl polymer compositions |
US7530683B2 (en) * | 2004-07-29 | 2009-05-12 | E.I. Du Pont De Nemours And Company | Fixing fluid and inkjet ink sets comprising same |
WO2006050536A2 (en) * | 2004-11-08 | 2006-05-11 | E.I. Dupont De Nemours And Company | Decorative laminated safety glass |
US20060100351A1 (en) * | 2004-11-08 | 2006-05-11 | Butera Robert J | Rapid drying lacquers containing impoved rheology control additive |
US20060100350A1 (en) * | 2004-11-08 | 2006-05-11 | Barsotti Robert J | Rapid drying lacquers containing graft copolymers with segmented arms |
US7402624B2 (en) * | 2004-11-08 | 2008-07-22 | E.I. Du Pont De Nemours & Company | Graft copolymers with segmented arms and their preparation and use |
GB0428262D0 (en) * | 2004-12-23 | 2005-01-26 | Eastman Kodak Co | Dispersant for reducing viscosity of particulate solids |
DE102005007763A1 (en) * | 2005-02-19 | 2006-08-24 | Lanxess Deutschland Gmbh | Aqueous pigment preparations for brilliant ink-jet printouts |
US20060216525A1 (en) * | 2005-03-24 | 2006-09-28 | Josef Huybrechts | Aqueous coating compositions |
US7470314B2 (en) * | 2005-09-12 | 2008-12-30 | E.I. Du Pont De Nemours And Company | Inkjet ink and ink set |
US7279032B2 (en) * | 2005-09-12 | 2007-10-09 | E.I. Du Pont De Nemours & Co | Inkjet ink and ink set |
EP1924658B1 (en) * | 2005-09-15 | 2010-08-25 | E.I. Du Pont De Nemours And Company | Aqueous inkjet ink |
US7749957B2 (en) | 2006-04-06 | 2010-07-06 | E.I. Du Pont De Nemours And Company | Clay-binding peptides and methods of use |
US7635504B2 (en) * | 2006-05-05 | 2009-12-22 | E. I. Du Pont De Nemours And Company | Curable white inkjet ink |
JP4958483B2 (en) * | 2006-06-19 | 2012-06-20 | キヤノン株式会社 | Recording device |
EP2032648A1 (en) * | 2006-06-23 | 2009-03-11 | DSMIP Assets B.V. | Aqueous crosslinkable vinyl graft copolymer compositions |
US8308886B2 (en) | 2006-07-17 | 2012-11-13 | E I Du Pont De Nemours And Company | Donor elements and processes for thermal transfer of nanoparticle layers |
ES2544238T5 (en) | 2006-10-11 | 2023-11-08 | Agfa Nv | Methods for preparing curable pigment inkjet ink sets |
US7989391B2 (en) * | 2006-10-26 | 2011-08-02 | E. I. Du Pont De Nemours And Company | Seed coating composition |
JP5247023B2 (en) * | 2006-12-07 | 2013-07-24 | キヤノン株式会社 | Inkjet pigment ink |
DE102006060340B4 (en) | 2006-12-13 | 2012-12-13 | Leibniz-Institut Für Polymerforschung Dresden E.V. | Use of a durable coating of metal or glass surfaces to inhibit and / or prevent icing |
AU2007341256B2 (en) * | 2006-12-28 | 2012-09-20 | Allnex Netherlands B.V. | Waterborne polymeric dispersions |
US8211970B2 (en) * | 2007-02-21 | 2012-07-03 | E I Du Pont De Nemours And Company | Aqueous pigment dispersions |
EP2222763B1 (en) * | 2007-12-20 | 2016-04-13 | Coatings Foreign IP Co. LLC | Process for producing a multilayer coating |
EP2225313B1 (en) * | 2007-12-20 | 2016-04-13 | Coatings Foreign IP Co. LLC | Process for producing a multilayer coating |
CN101977973A (en) * | 2007-12-20 | 2011-02-16 | 纳幕尔杜邦公司 | Process for producing a multilayer coating |
US20090246481A1 (en) * | 2008-03-26 | 2009-10-01 | Fujifilm Corporation | Dispersion of water-insoluble colorant, method of producing substance containing water-insoluble colorant, fine particles of water-insoluble colorant, dispersing agent for water-insoluble colorant, and recording liquid, ink set, printed article, method of forming image and image forming apparatus using the same |
US20090306285A1 (en) * | 2008-05-08 | 2009-12-10 | E.I.Du Pont De Nemours And Company | Inkjet inks containing crosslinked polyurethanes |
JP2011521085A (en) * | 2008-05-22 | 2011-07-21 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Fixing ink used with inkjet ink |
US8092874B2 (en) | 2009-02-27 | 2012-01-10 | Eastman Kodak Company | Inkjet media system with improved image quality |
US8481678B2 (en) | 2009-03-30 | 2013-07-09 | E I Du Pont De Nemours And Company | Peptide-based tooth whitening reagents |
US8419176B2 (en) | 2009-05-29 | 2013-04-16 | Eastman Kodak Company | Aqueous compositions with improved silicon corrosion characteristics |
WO2010144903A1 (en) | 2009-06-12 | 2010-12-16 | E. I. Du Pont De Nemours And Company | Process for multilayer coating |
JP2013500851A (en) | 2009-07-30 | 2013-01-10 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Method for preparing dispersion |
KR20120112481A (en) | 2009-11-23 | 2012-10-11 | 이 아이 듀폰 디 네모아 앤드 캄파니 | Method of preparing cross-linked colorant dispersions |
US8398191B2 (en) | 2009-11-24 | 2013-03-19 | Eastman Kodak Company | Continuous inkjet printer aquous ink composition |
US20110123714A1 (en) | 2009-11-24 | 2011-05-26 | Hwei-Ling Yau | Continuous inkjet printer aquous ink composition |
WO2011135039A1 (en) * | 2010-04-28 | 2011-11-03 | Basf Se | Rheology modifying and setting polymer, composition thereof and method for making it |
US8827436B2 (en) | 2010-05-27 | 2014-09-09 | E I Du Pont De Nemours And Company | Fixer inks for use with ink jet inks |
US8434857B2 (en) | 2010-08-31 | 2013-05-07 | Eastman Kodak Company | Recirculating fluid printing system and method |
US8430492B2 (en) | 2010-08-31 | 2013-04-30 | Eastman Kodak Company | Inkjet printing fluid |
CN103282593B (en) | 2010-12-03 | 2016-01-20 | 3G穆尔门公司 | Near-infrared reflection composition and be mixed with the architectural opening overburden of described composition |
WO2012082964A2 (en) | 2010-12-15 | 2012-06-21 | E. I. Du Pont De Nemours And Company | Method of preparing encapsulated pigment dispersions with monomers which have a lower critical solution temperature |
US20130214197A1 (en) | 2010-12-15 | 2013-08-22 | Ei Du Pont De Nemours And Company | Encapsulated cross-linked pigment dispersions |
US20130231439A1 (en) | 2010-12-15 | 2013-09-05 | E.I. Du Pont De Nemours And Company | Method of preparing encapsulated pigment dispersions |
WO2012082991A2 (en) | 2010-12-15 | 2012-06-21 | E. I. Du Pont De Nemours And Company | Method of preparing pigment dispersions |
US20130225739A1 (en) | 2010-12-15 | 2013-08-29 | Harry Joseph Spinelli | Ink-jet ink comprising encapsulated cross-linked pigment dispersions |
WO2012125879A1 (en) | 2011-03-15 | 2012-09-20 | E. I. Du Pont De Nemours And Company | Aqueous ink-jet inks for improved adhesion to print substrates |
US8465578B2 (en) | 2011-03-31 | 2013-06-18 | Eastman Kodak Company | Inkjet printing ink set |
WO2012148476A2 (en) | 2011-04-25 | 2012-11-01 | E. I. Du Pont De Nemours And Company | Method of preparing encapsulated pigment dispersions which include polyurethane dispersions |
US20140045975A1 (en) | 2011-04-29 | 2014-02-13 | E I Du Pont De Nemours And Company | Method of preparing cross-linked colorant dispersions |
WO2012149324A1 (en) | 2011-04-29 | 2012-11-01 | Eastman Kodak Company | Recirculating inkjet printing fluid, system and method |
US20140026784A1 (en) | 2011-05-27 | 2014-01-30 | E I Du Pont De Nemours And Company | Pigmented inkjet ink comprising hydrophilic polymer as a bleed control agent |
WO2013009343A1 (en) | 2011-07-14 | 2013-01-17 | E. I. Du Pont De Nemours And Company | Ink jet ink comprising encapsulated pigment dispersions with minimal free polymer |
US8957134B2 (en) | 2011-07-14 | 2015-02-17 | E I Du Pont De Nemours And Company | Method of preparing encapsulated pigment dispersions with minimal free polymer |
WO2013013024A2 (en) | 2011-07-20 | 2013-01-24 | E. I. Du Pont De Nemours And Company | Inkjet inks and ink sets |
US8764161B2 (en) | 2011-08-31 | 2014-07-01 | Eastman Kodak Company | Printing fluids including a humectant |
US20140249248A1 (en) | 2011-10-27 | 2014-09-04 | E I Du Pont De Nemours And Company | Inkjet ink comprising encapsulated pigment dispersions with two encapsulation steps |
WO2013062600A1 (en) | 2011-10-27 | 2013-05-02 | E. I. Du Pont De Nemours And Company | Method of preparing encapsulated pigment dispersions with two encapsulation steps |
US20140296395A1 (en) | 2011-12-15 | 2014-10-02 | Ei Du Pont De Nemours And Company | Method of preparing encapsulated pigment dispersions with continuous additon of encapsulating monomer |
US20130237661A1 (en) | 2011-12-22 | 2013-09-12 | Thomas B. Brust | Inkjet ink composition |
US9062228B2 (en) | 2011-12-30 | 2015-06-23 | E I Du Pont De Nemours And Company | Aqueous inkjet inks containing polyurethane binders with components to interact with cellulose |
EP2798017A4 (en) | 2011-12-30 | 2015-06-03 | Du Pont | Aqueous pigment dispersions with components to interact with cellulose |
WO2013177435A2 (en) * | 2012-05-24 | 2013-11-28 | Basf Se | Hydrophilic, low acid content polymers as stabilizers for water-based emulsions |
US9458321B2 (en) | 2012-06-29 | 2016-10-04 | E I Du Pont De Nemours And Company | Method of preparing a pigment press cake and uses thereof |
US9085707B2 (en) | 2012-08-31 | 2015-07-21 | E I Du Pont De Nemours And Company | Aqueous pigment dispersions and inkjet inks |
WO2014056950A1 (en) | 2012-10-09 | 2014-04-17 | Zamtec Ltd | Method of high-speed printing for improving optical density in pigment-based inks |
WO2014061750A1 (en) * | 2012-10-18 | 2014-04-24 | 大日本印刷株式会社 | Dispersant, metal particle dispersion for conductive substrate, and production method for conductive substrate |
EP2925814B1 (en) * | 2012-11-30 | 2016-12-28 | ANGUS Chemical Company | Aminoalcohol compounds as low voc free-thaw stabilizers for paints and coatings |
US20140231674A1 (en) | 2013-02-18 | 2014-08-21 | Wayne Lee Cook | Ink jet printer composition and use |
US9815994B2 (en) | 2013-08-06 | 2017-11-14 | E I Du Pont De Nemours And Company | Aqueous pigment dispersions with components to interact with cellulose |
EP3030619A2 (en) | 2013-08-06 | 2016-06-15 | E. I. du Pont de Nemours and Company | Aqueous inkjet inks containing polymeric binders with components to interact with cellulose |
ES2665813T3 (en) * | 2013-11-04 | 2018-04-27 | Lubrizol Advanced Materials, Inc. | Acrylic dispersants with fused aromatic imide anchor groups |
WO2015102868A1 (en) | 2013-12-30 | 2015-07-09 | E. I. Du Pont De Nemours And Company | Pigmented inkjet ink comprising dispersed polyurethane and olefin ionic copolymer |
US9523011B2 (en) | 2014-06-23 | 2016-12-20 | Eastman Kodak Company | Recirculating inkjet printing fluid |
JP2018503719A (en) | 2014-12-19 | 2018-02-08 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーE.I.Du Pont De Nemours And Company | Carbon black pigment for improved durability |
JP2018505257A (en) | 2014-12-19 | 2018-02-22 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーE.I.Du Pont De Nemours And Company | Inkjet ink set for printing on offset media |
EP3234040A1 (en) | 2014-12-19 | 2017-10-25 | E. I. du Pont de Nemours and Company | Aqueous inkjet ink containing polymeric binders |
US10883009B2 (en) | 2015-11-02 | 2021-01-05 | Dupont Electronics, Inc. | Aqueous ink-jet ink containing low boiling point compositions |
EP3246365A1 (en) | 2016-05-18 | 2017-11-22 | Clariant International Ltd | Graft copolymers and compositions thereof |
US11499065B2 (en) | 2016-06-24 | 2022-11-15 | Dupont Electronics, Inc. | Aqueous inkjet inks containing a water-insoluble additive |
EP3728488B1 (en) | 2017-12-18 | 2023-03-15 | DuPont Electronics, Inc. | Ink fluid set for printing on offset media |
WO2020131865A1 (en) | 2018-12-19 | 2020-06-25 | Dupont Electronics, Inc. | A textile printing fluid set containing a pretreatment and a mixture of pigment and disperse dye |
CN109722062A (en) * | 2018-12-21 | 2019-05-07 | 英德科迪颜料技术有限公司 | A kind of preparation method of core-shell structure transparent ferric oxide coated pigment |
NL2023752B1 (en) | 2019-09-03 | 2021-04-13 | Xeikon Mfg Nv | Printing method |
EP4031629A1 (en) | 2019-09-20 | 2022-07-27 | DuPont Electronics, Inc. | Ink fluid set for printing on textile |
JP2023507768A (en) | 2019-12-18 | 2023-02-27 | デュポン エレクトロニクス インコーポレイテッド | Inkjet ink and primer fluid set |
WO2021126612A1 (en) | 2019-12-18 | 2021-06-24 | Dupont Electronics, Inc. | Inkjet ink and primer fluid set |
EP4077555A1 (en) | 2019-12-18 | 2022-10-26 | DuPont Electronics, Inc. | Inkjet ink and primer fluid set |
CN111205398A (en) * | 2020-02-25 | 2020-05-29 | 传美讯电子科技(珠海)有限公司 | Random block dispersant, preparation method thereof, UV white ink-jet color paste and preparation method thereof |
WO2023114574A1 (en) | 2021-12-14 | 2023-06-22 | Dupont Electronics, Inc. | Inkjet ink and primer fluid set |
CN118251469A (en) | 2021-12-14 | 2024-06-25 | 杜邦电子公司 | Aqueous inkjet inks containing polyurethane polymers |
US20240124731A1 (en) | 2022-09-26 | 2024-04-18 | Dupont Electronics, Inc. | Aqueous inkjet inks containing silanized silica particles |
US20240209226A1 (en) | 2022-12-23 | 2024-06-27 | Dupont Electronics, Inc. | Aqueous inkjet compositions including polymeric thickener |
Family Cites Families (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2009218C3 (en) * | 1970-02-27 | 1980-07-17 | Roehm Gmbh, 6100 Darmstadt | Process for the bead polymerization of ethylenically unsaturated monomers |
US4085168A (en) * | 1971-02-22 | 1978-04-18 | Cpc International Inc. | Chemically joined, phase separated self-cured hydrophilic thermoplastic graft copolymers and their preparation |
US3862077A (en) * | 1971-02-22 | 1975-01-21 | Cpc International Inc | Stable latexes of a chemically joined, phase separated thermoplastic graft copolymer and method for preparing the same |
US3928255A (en) * | 1971-02-22 | 1975-12-23 | Cpc International Inc | Chemically joined, phase separated self-cured hydrophilic thermoplastic graft copolymers and their preparation |
US3862097A (en) * | 1971-02-22 | 1975-01-21 | Cpc International Inc | Process for preparing copolymerizable macromolecular monomers having a substantially uniform molecular weight distribution |
US3729439A (en) * | 1971-04-30 | 1973-04-24 | Du Pont | Entropically stabilized water base dispersions |
US3801524A (en) * | 1971-04-30 | 1974-04-02 | Du Pont | Entropically stabilized water base dispersions |
JPS543482B2 (en) * | 1972-10-14 | 1979-02-23 | ||
DE2364675C2 (en) * | 1972-12-29 | 1983-06-23 | Kuraray Co., Ltd., Kurashiki, Okayama | Copolymer consisting of a polymer main chain and polymer side chains and its use for the manufacture of articles for biomedical purposes |
JPS53137230A (en) * | 1977-05-09 | 1978-11-30 | Aica Kogyo Co Ltd | Acrylic emulsion composition |
US4178318A (en) * | 1978-04-26 | 1979-12-11 | Ford Motor Company | Graft polybutadiene copolymers |
EP0007731A3 (en) * | 1978-07-28 | 1980-02-20 | Imperial Chemical Industries Plc | Process for the production of dispersions of hydrophobic particulate solids (e.g. pesticides) and the particulate dispersions thus obtained |
ZA796170B (en) * | 1978-12-07 | 1981-03-25 | Ici Ltd | Macromonomers |
DE2900110A1 (en) * | 1979-01-03 | 1980-07-10 | Wolff Walsrode Ag | SOLUBLE MACROMOLECULAR SUBSTANCES WITH HIGH DISPERSION, SUSPENDING AND LIQUID RETENTION RESISTANCE, METHOD FOR THEIR PRODUCTION AND USE |
US4355122A (en) * | 1980-12-15 | 1982-10-19 | Union Carbide Corporation | Water-borne thermoplastic polyhydroxyether compositions |
DE3106357A1 (en) * | 1981-02-20 | 1982-09-09 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING POLYMER PIGMENT PREPARATIONS AND THEIR USE |
US4672089A (en) * | 1984-08-10 | 1987-06-09 | Amerace Corporation | Retroreflective sheeting |
US4564648A (en) * | 1984-09-21 | 1986-01-14 | E. I. Du Pont De Nemours And Company | Epoxy graft acrylic water-based primer surfaces |
JPH0680088B2 (en) * | 1986-05-24 | 1994-10-12 | 綜研化学株式会社 | Manufacturing method of macromonomer |
US4746714A (en) * | 1986-06-17 | 1988-05-24 | E. I. Du Pont De Nemours And Company | Stabilized acrylic resin |
JP2543503B2 (en) * | 1986-07-01 | 1996-10-16 | 綜研化学株式会社 | Emulsion Polymerization Method Using Copolymer Having Branched Structure as Dispersion Stabilizer |
EP0269187B1 (en) * | 1986-11-28 | 1992-01-29 | Nippon Paint Co., Ltd. | Amphiphatic polymerizable vinyl monomers, vinyl resin particles derived from said monomers and preparation thereof |
US4910268A (en) * | 1987-04-22 | 1990-03-20 | Shiro Kobayashi | Acryl type macromonomer having a polyethyleneimine derivative chain and process for producing the same, as well as graft polymer having a polyethyleneimine derivative chain as the graft chain and process for producing the same |
US4927875A (en) * | 1987-09-29 | 1990-05-22 | Ppg Industries, Inc. | Method for preparing acrylic/polyester resin |
JP2585042B2 (en) * | 1988-01-12 | 1997-02-26 | 日東電工株式会社 | Method for producing graft polymer |
US5053461A (en) * | 1988-08-31 | 1991-10-01 | Mitsubishi Rayon Co., Ltd. | Preparation method of comb copolymer, acrylic comb copolymer, and impact resistant resin composition |
US5010140A (en) * | 1989-05-31 | 1991-04-23 | E. I. Du Pont De Nemours And Company | Process for preparing stabilized polymer dispersion |
-
1991
- 1991-12-24 US US07/813,186 patent/US5231131A/en not_active Expired - Lifetime
-
1993
- 1993-03-22 CA CA002157361A patent/CA2157361C/en not_active Expired - Fee Related
- 1993-03-22 JP JP52097894A patent/JP3438893B2/en not_active Expired - Fee Related
- 1993-03-22 BR BR9307765A patent/BR9307765A/en not_active IP Right Cessation
- 1993-03-22 DE DE69305184T patent/DE69305184T2/en not_active Expired - Lifetime
- 1993-03-22 WO PCT/US1993/002701 patent/WO1994021701A1/en active IP Right Grant
- 1993-03-22 EP EP93908521A patent/EP0690883B1/en not_active Expired - Lifetime
- 1993-03-22 ES ES93908521T patent/ES2092821T3/en not_active Expired - Lifetime
Cited By (9)
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US7674843B2 (en) | 2005-02-04 | 2010-03-09 | Agfa Graphics Nv | Stable pigment dispersions |
US7678845B2 (en) | 2005-02-04 | 2010-03-16 | Agfa Graphics Nv | Stable pigment dispersions |
US7691937B2 (en) | 2005-02-04 | 2010-04-06 | Agfa Graphics Nv | Polymeric dispersants containing (meth)acryloyloxybenzoic acid |
US7582152B2 (en) | 2005-07-14 | 2009-09-01 | Agfa Graphics Nv | Pigment dispersions with polymeric dispersants having pending chromophore groups |
US7582151B2 (en) | 2005-07-14 | 2009-09-01 | Agfa Graphics Nv | Pigment dispersion with polymeric dispersants having pending chromophore groups |
US7582150B2 (en) | 2005-07-14 | 2009-09-01 | Agfa Graphics Nv | Pigment dispersions with polymeric dispersants having pending chromophore groups |
US7812113B2 (en) | 2005-07-14 | 2010-10-12 | Agfa Graphics Nv | Phenylazo-acetoacetanilide derivatives with a polymerizable functional group and related compounds as monomers for preparing polymeric pigment dispersants for inkjet inks |
US7846992B2 (en) | 2005-07-14 | 2010-12-07 | Agfa Graphics Nv | Pigment dispersions with polymeric dispersants having pending chromophore groups |
US8759441B2 (en) | 2005-07-14 | 2014-06-24 | Agfa Graphics Nv | Pigment dispersions with polymeric dispersants having pending chromophore groups |
Also Published As
Publication number | Publication date |
---|---|
WO1994021701A1 (en) | 1994-09-29 |
ES2092821T3 (en) | 1996-12-01 |
JP3438893B2 (en) | 2003-08-18 |
JPH10502097A (en) | 1998-02-24 |
CA2157361A1 (en) | 1994-09-29 |
EP0690883B1 (en) | 1996-10-02 |
EP0690883A1 (en) | 1996-01-10 |
BR9307765A (en) | 1995-10-24 |
DE69305184T2 (en) | 1997-03-06 |
US5231131A (en) | 1993-07-27 |
DE69305184D1 (en) | 1996-11-07 |
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