CN1182106A - Process for preparing aqueous dispersion including polymeric latex and titanium dioxide pigment - Google Patents
Process for preparing aqueous dispersion including polymeric latex and titanium dioxide pigment Download PDFInfo
- Publication number
- CN1182106A CN1182106A CN97121279A CN97121279A CN1182106A CN 1182106 A CN1182106 A CN 1182106A CN 97121279 A CN97121279 A CN 97121279A CN 97121279 A CN97121279 A CN 97121279A CN 1182106 A CN1182106 A CN 1182106A
- Authority
- CN
- China
- Prior art keywords
- polymer latex
- latex
- acid
- titanium dioxide
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C09D17/00—Pigment pastes, e.g. for mixing in paints
- C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
- C09D17/007—Metal oxide
- C09D17/008—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
- C08J3/215—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase at least one additive being also premixed with a liquid phase
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
-
- 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
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/02—Homopolymers or copolymers of monomers containing phosphorus
-
- 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
- C09D7/80—Processes for incorporating ingredients
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Titanium dioxide pigment particles are dispersed in an aqueous medium. A selected, relatively hard, polymeric latex is added, as well as a film-forming binder to give a formulated coating composition. The selected polymeric latex can include residues of polymerized dihydrogen phosphate functional groups, or have a high level of acid functional groups or greater than one percent itaconic acid. The selected latex particles improve the opacity of the coating film. Alternatively, a single selected polymeric latex is used to both improve opacity and to serve as binder, or a mixture of a selected polymeric latex having a low effective glass transition temperature and a conventional binder latex is employed.
Description
In general, the present invention relates to the method that a kind of preparation comprises the aqueous composition of polymer latex and TiO 2 pigment; More particularly, the present invention relates to the opaque product that forms by this aqueous composition dehydration.
The water dispersion of polymer latex is used to prepare various commercially important products, and they comprise paint, coating, priming paint and printing ink.These products comprise polymer latex usually, and latex forms external phase and product is sticked together and important physical properties is provided when dehydration.Except polymer latex, most of products also comprise the particle of one or more inorganic materials.Some inorganic materials provides the important function characteristic for product, as opacity or color.
For the coating that makes plastic sheet or film and particularly formed by coating composition and paint has opacity, titanium dioxide has become elite pigment for many years.Titanium dioxide generally is the most expensive component in the prescription in paint.Should reach the ideal opaqueness in coating uses TiO 2 pigment now to become a lasting target of coatings industry simultaneously again as few as possible.
Under the situation of emulsion paint and latex coating, the common practice is the stable water dispersion that forms a kind of TiO 2 pigment and other fillers or extender earlier.This water dispersion is also referred to as " abrasive " (mill base) or " ground slurry " (grind), it may also contain and the mixable solvent of water, and for example the water-soluble polymers ionogen of glycols and glycol ester and lower molecular weight is as the grinding aid or the dispersion agent of TiO 2 pigment.The general practice is the stabilising dispersions that forms TiO 2 pigment earlier, and then add aqueous latex polymer tackiness agent and other Synergist S-421 95s to this dispersion, such as the coalescing agent or the temporary softening agent of thickening material, rheological improving agent, defoamer, tinting material, latex polymer particles and be used for base material wetting and with the tensio-active agent of colorant compatible.This method is discussed in detail, sees T.C.Patton, Paint Flow and PigmentDispersion (Wiley Interscience, 2nd edition) 290～295 (1979); Treatise onCoatings.Vol.III, Part 1 (Marcel Decker) (1975); Pigment Handbook, Vol.I (2ndedition, Wiley Interscience) (1988); Pigment Handbook, Vol.III (WileyInterscience) (1973).
People continue need to improve the effective utilization of titanium dioxide in water-based paint compositions and thereby improve opacity and other characteristics of coating composition.
The invention provides a kind of method for preparing water dispersion, this dispersion comprises elite polymer latex particle and titanium dioxide pigment particles, this dispersion is used to prepare aqueous composition, for example coating composition, paint and printing ink, and they itself produce various coatings, and these coatings are compared with the prescription of prior art and demonstrated improved opacity.
Method of the present invention plans titanium dioxide pigment particles is disperseed in the aqueous medium with a kind of pigment dispersing agent (for example polyelectrolyte pigment dispersing agent).Method of the present invention further plans to prepare a kind of selected dispersion or the suspensoid of polymer latex particle in aqueous medium.
Selected polymer latex particle can prepare with following each side method, it is believed that these methods can provide and have the monomeric insoluble polymer latex of high-load acid functional, can provide and contain the polymer latex that is higher than 1% methylene-succinic acid, dihydrogen phosphate functional monomer's copolymerization maybe can be provided.
Except selected polymer latex, can also add other components according to the different purposes of aqueous composition.For instance, such as the such binder for film formation of softer polymer latex, and for example coalescing agent, sanitas, thickening material and rheology control agent all can be involved to be used to provide other habitual component of magistral coating composition.
Best, selected polymer latex particle is by such monomer, is promptly formed by polymkeric substance that it the provided hard or the sort of monomer polymerization of inflexible under the use temperature of aqueous composition.Such monomer for example can provide envrionment temperature or room temperature (that is, about 20～23 ℃) use down have under the composition situation be at least about 20 ℃, preferably be at least about 35 ℃, more preferably be at least about the polymer materials of effective second-order transition temperature of 50 ℃.High more being suitable for more of temperature range used under comparatively high temps, for example is used to the coating of toasting.
On the other hand, selected polymer latex can have the tackiness agent that hangs down effective second-order transition temperature and be used as composition.
In comprising the aqueous composition of polymer latex and dispersed TiO 2 pigment, preparation helps the snappiness that provides bigger by the opacity of having improved provided by the invention.For example, in some cases, method of the present invention can provide a kind of being reduced to reach the opacifying property of desireing and the means of the TiO 2 pigment consumption that needs.When selected polymer latex is used for coating composition, method of the present invention can provide improved coating performance, for example opacity or opacifying power, tinting strength, mechanical property, " ICI " or " cone-plate " (high shear rate) viscosity, gloss, scrub resistance.Method of the present invention also is provided under the given TiO 2 pigment content and can makes coating have the coating composition of enhanced opacity.
Be specially adapted to improve processing property and ventilation property by the selected polymer latex particle of method of the present invention by its coating that forms and paint.On the other hand, method of the present invention can be under the low concentration of the TiO 2 pigment of costliness, and thereby can make identical with ordinary method basically coating and film with lower cost.Method of the present invention further is conceived to selected polymer latex granules preparation fully by the aqueous composition that comprises aqueous coating composition of filling a prescription, subsequently with the product that comprises coating and coated article fully by the aqueous composition formation of prescription manufacturing.
In an embodiment preferred of the present invention, method of the present invention plans to prepare a kind of two types of polymer latex particulate mixtures that are at least.Effective second-order transition temperature that first type select polymers latex particle is had preferably be at least about 20 ℃, more preferably be at least about 35 ℃, most preferably be at least about 50 ℃.Second type the polymer latex particle that is provided is used to form the tackiness agent of titanium dioxide pigment particles.This mixture can be used for preparing magistral composition, for example demonstrates the coating composition of enhanced opacity.
In another embodiment preferred, the soft polymer particle that uses two or more types is as tackiness agent, and the soft polymer particle of wherein one or more is selected polymer latexs.
Method of the present invention is provided for comprising the selected polymer latex in the aqueous composition of titanium dioxide pigment particles, and titanium dioxide pigment particles has been used a kind of pigment dispersing agent, polyelectrolyte dispersing agents for example, or a kind of stearic class stablizer carries out initial dispersion.
Method of the present invention has proposed terms of settlement for the opacity problem of water-based paint of how utilizing the polymer latex particle in practice and containing the titanium dioxide pigment particles of high density with improvement.
The polymer latex particle of selected composition and size can be effectively applied in the method for the present invention with dense dispersion form with titanium dioxide granule.
One existing by embodiment preferred in, a kind of insoluble polymer latex is by comprising high density, for example being at least that the monomer mixture of about 10% carboxylic acid functional monomers of polymer solids weight is polymerized.In another showed by embodiment preferred, polymer latex was to prepare with the monomer that comprises the methylene-succinic acid that is higher than 1% weight.In another showed by embodiment preferred, used polymer latex was to be at least a kind of undersaturated dihydrogen phosphate of polymerisable ethylene linkage by containing, and for example the monomer of the dihydrogen phosphate of methacrylic acid 2-hydroxyl ethyl ester prepares.
Method of the present invention is specially adapted to improve coating and by the opacity of its film that forms, gloss, high shear viscosity, colour developing, perviousness and mechanical property.On the other hand, the present invention can make coating and film with the essentially identical processing property of traditional method by prescription, but they have lower titanium dioxide pigment particles concentration, thereby makes production cost lower
Although in practice of the present invention, can use the whole pH value scope that can reach, but consider the solvability of oversized particles, to the two corrosion and other reasons of base material and top layer, the pH value preferably is limited in being about 2 to 12 scope, more preferably in the scope that is about 4 to 10.
Can be used in the method for the present invention through surface-treated titanium dioxide granule in advance.For example, can use in advance through the various forms surface treatment to provide aluminum oxide or silicon-dioxide or them the two the titanium dioxide of top coat of mixture, as in J.Coatings Tech.63 59～65 (1991), discussing people such as A.Brisson.
It is believed that in order to obtain optimum performance method of the present invention depends on the selected polymer latex particle under the desired big polymer latex particulate situation of high density and the relative concentration of titanium dioxide pigment particles to a certain extent.Best, use the selected polymer latex of q.s to obtain the optimal operations performance in the product by prescription fully with what prepare in use this law.
When having the formulation for coating material of the performance characteristic of desireing, preparation need not make the selected polymer latex that is used for the inventive method also play the polymer binder effect of coating or film, although this is possible or in some cases or even desire.And other polymer latex material, preferably it has the second-order transition temperature that is easy to film-forming properties under application conditions, and this effect can be provided." second-order transition temperature " is meant the phase transition temperature on second rank, and methods such as its available mechanical process such as torsion(al)braid analysis are rule of thumb determined, or calculated by monomer component with the Fox method." effectively second-order transition temperature " be meant by existing low molecular weight substance such as coalescing agent, solvent, or the like the transition temperature of the second rank phase of change.Otherwise the effect of selected polymer latex is the opacity that improves by polymer binder latex and the formed film of titanium dioxide pigment particles.In order to play this effect, may wish that selected polymer latex particle is quite hard, and under application conditions, have the higher effective second-order transition temperature, for example, be at least about 20 ℃, more preferably be at least about 35 ℃ even most preferably be at least about 50 ℃.Therefore, one of the present invention existing is provided a kind of feed to be equipped with magistral aqueous composition by embodiment preferred, for example " firmly " polymer latex particle and run-of-the-mill, film forming " soft " polymer latex particulate aqueous mixture selected, that improve opacity used of coating composition.
With regard to the polymer latex particle selected in the inventive method and the average particulate size or the diameter of titanium dioxide pigment particles, usually preferably make selected polymer latex particulate mean diameter for about 20nm to the mean diameter of about 4 times titanium dioxide pigment particles, about 20nm diameter identical extremely more preferably with the mean diameter of titanium dioxide pigment particles.One existing by embodiment preferred in, when selected " firmly " polymer latex particle situation, about 30nm to the average polymer latex diameter quilt of about 100nm preferably, and about 50nm extremely the average polymer latex diameter of about 80nm especially by preferably.
Second existing by embodiment preferred in, when selected " soft " polymer latex particle situation, the average polymer latex diameter of about 80nm to 600nm is by preferably, and the average polymer latex diameter of about 100nm to 400nm is especially by preferably.At least in the coating composition of some, when selected polymer latex particle diameter during greater than the titanium dioxide granule diameter, opacifying power is increased.
The concentration of titanium dioxide granule in formulation for coating material (and may be present in the composition any other pigment) is represented with the pigment volume concentration (PVC) of prescription.The pigment volume concentration (PVC) (hereinafter referred to as " PVC ") of prescription is to be added that by inorganic particle such in filling a prescription the overall product of polymer latex granular solids defines with the volume number that is present in the inorganic particle (comprising titanium dioxide and other granules of pigments and extender particle) in the prescription.The PVC value of composition prepared in accordance with the present invention is preferably about 5 to 60, more preferably about 10 to 50.
The total concn of granules of pigments, extender particle and emulsion polymer particle is generally represented with the solid percentage volume of prescription in prescription.Solid percentage volume is represented the dilute strength of solid in a certain liquid vehicle, for example water.
Used polymer latex can have and close relevant monomer component and the particle size of the polymeric latex binder for preparing by standard emulsion polymerization technology well known in the prior art in the present invention's practice.
One of the inventive method existing by embodiment preferred in, selected polymer latex particle itself is not for providing tackiness agent by the formed product of complete magistral aqueous composition, because do not need them to flow and the formation film, this particle can be harder than those particles that are used to provide tackiness agent.Therefore, this polymer beads can be than having the higher effective second-order transition temperature as the polymer beads of tackiness agent, and this particle is all right/or comprise the linking agent that increases hard amount.In this case, this polymer latex also can be prepared by the emulsion polymerization technology of standard, but it generally is unsuitable for as binder for film formation.
The polymer latex particle effectively selected to the inventive method can prepare with several alternative methods.In a kind of these class methods, can provide a kind of insoluble polymer latex by the variable factor in the control emulsion polymerization process, wherein the undersaturated acid functional monomer's of ethylene linkage gross weight preferably accounts for 10% of polymer latex solid weight at least.In another these class methods, polymer latex is to be prepared by the monomer that contains the methylene-succinic acid more than 1% weight.
Prepare in the selected polymer latex particulate method at another, the monomer mixture that wherein is polymerized to polymer latex comprises the dihydrogen phosphate that is at least a kind of alcohol, and alcohol wherein contains a polymerisable thiazolinyl, for example polymerisable vinyl.The example of this dihydrogen phosphate comprise the list of phosphoric acid allyl ester, phosphoric acid allyl ester cellosolve, methacrylic acid phosphoric acid hydroxyl ethyl ester, two (hydroxyethyl) fumaric acid or methylene-succinic acid or bisphosphate, or the like.The polymer latex particle that is formed by the polymerization of mixtures of the dihydrogen phosphate that comprises methacrylic acid 2-hydroxyl ethyl ester is especially by preferably.
The inventive method is not subjected to the constraint of the specific explanations of any mechanism, but it is believed that, having the acid functionality and having the selected polymer latex that is in the Pka intermediate value between strong, the weak acid all is effectively in the method for the invention, for example copolymerizable by comprising, ethylene linkage is undersaturated, have acid functional groups and be about 4-8, be more preferably those polymer latexs that the monomer polymerization of 6 Pka value forms.Must be pointed out that the Pka value of acid functional groups can change with the change of its surrounding medium.For example, when the surrounding medium that carries out copolymerization and acid functional groups when polymerisable monomer that has acid functional groups and more hydrophobic comonomer became more hydrophobicity, then the actual measurement Pka value of acid functional groups can change.Theoretically, the acid functionality's of select polymers latex Pka value must be enough high, so that make most these acid functionalities be converted to its conjugate base form under the alkaline condition of for example using always in aqueous polymers latex-based coating composition.Further theoretically, the acid functionality's of select polymers latex Pak value can not height be a kind of very weak alkali to making its conjugate base form.
So the invention provides aqueous dispersion, coating composition and comprise the selected polymer latex particle and the pigment slurry of titanium dioxide pigment particles.Selected polymer latex particle comprises, for example, and dihydrogen phosphate functional group.
These dihydrogen phosphate functional group it is believed that it is to result from the polymer latex particle, and this polymer latex particle is to form by comprising the monomer polymerization that is at least a kind of polymerisable dihydrogen phosphate functional monomer.Polymerisable dihydrogen phosphate functional monomer can be selected from the dihydrogen phosphate of a certain alcohol, and this alcohol comprises the polymerizable group that is selected from polymerisable vinyl and polymerisable nonvinylic thiazolinyl.This polymerisable dihydrogen phosphate functional monomer can be selected from the biphosphate monoesters of methacrylic acid 2-hydroxyl ethyl ester, the mixture of the phosphodiester of the biphosphate monoesters of methacrylic acid 2-hydroxyl ethyl ester and methacrylic acid 2-hydroxyl ethyl ester.
Similarly, the invention provides aqueous dispersion, coating composition, and comprise the selected polymer latex particle and the pigment slurry of titanium dioxide pigment particles.Selected polymer cavity breast particle comprises the polymeric residues of methylene-succinic acid.
Polymer latex used among the present invention can prepare with any technology commonly known in the art, for example with suspension polymerization or emulsion polymerization.The water dispersion that in technical field of polymer, prepares latex polymer particles by the undersaturated monomer of ethylene linkage with emulsion polymerization technique be for people known, and can use the emulsion method of any routine, for example one bathe and many baths method (single and multiple shot batchprocesses) and continuous processing.If necessary, can prepare monomer mixture earlier progressively is added to it in aggregation container then.Monomer component in polymerization process in the aggregation container can change, and for example can change the monomer that is added in the container and form.Both can use single-stage also can use multistage polymerization technique.Can prepare latex polymer particles with the method with the seed polymer emulsion control granule number that letex polymerization produced well known in the prior art.The particle size of latex polymer particles can be controlled by the method for adjusting initial tensio-active agent charge amount with well known in the prior art.Each method of the system of polymer latex is at D.C.Blackley, and Emulsion Polymerization discusses in (wiley, New York, 1975) widely.The preparation method of acrylic polymer latex exists, for example, Emulsion Polymerization ofAcrylic Polymers, Bulletin, Rohm andHaas Company narrates among the Philadelphia.
Polymerization starter can be used for carrying out the polymerization of polymer latex particulate.The example of the polymerization starter that can be used is included in the polymerization starter of thermolysis generation radical under the polymerization temperature.Its example comprises water-soluble and water-insoluble two classes.The example of the initiator of operable generation radical comprises persulphate, such as the persulphate of ammonium or basic metal (potassium, sodium or lithium); Azo-compound, such as 2,2 '-azo-two (isopropyl cyanides), 2,2 '-azo-two (2, the 4-methyl pentane nitrile) and the 1-tertiary butyl-azo cyanocyclohexanoic alkane; Hydroperoxide are such as tert-butyl hydroperoxide and cumene hydroperoxide; Superoxide, such as benzoyl peroxide, peroxidation decoyl, ditertiary butyl peroxide, 3,3 '-two (t-butyl peroxy) ethyl butyrate, 3,3 '-two (tert-pentyl peroxide) ethyl butyrate, tert-pentyl peroxide-2-ethylhexanoate and t-butyl peroxy pivalate; Peresters is such as t-butyl peroxy-acetate, mistake O-phthalic tert-butyl acrylate and t-butylperoxyl benzoate; And percarbonate, such as two (1-cyano group-1-first and second bases) peroxidation supercarbonate; Superphosphate, or the like.
Polymerization starter can use separately or use as the oxidation component of redox system, redox system also comprises a kind of reduction components for example xitix, oxysuccinic acid, oxyacetic acid, oxalic acid, lactic acid, thioglycolic acid, or a kind of alkali-metal sulfurous acid hydrochlorate, particularly hydrosulphite, hyposulfite or a dithionite, for example sodium bisulfite, potassium hyposulfite and two potassium sulfites or sodium formaldehyde sulphoxylate.Also the atom component usually is called as accelerator.
Initiator and accelerator are commonly called catalyzer, catalyst system or redox system, and they each can be in being used by about ratio of 0.001% to 5% of the monomer weight of copolymerization.The consumption that resembles the muriate of cobalt, iron, nickel or copper and the accelerator the vitriol can be less.The example of redox-catalyst system comprises tert-butyl hydroperoxide/sodium formaldehyde sulphoxylate/Fe (II), and ammonium persulphate/sodium bisulfite/V-Brite B/Fe (II).Polymerization temperature can be from room temperature to about 90 ℃, and polymerization temperature can carry out preferably according to catalyst system routinely.
If necessary, can use chain-transfer agent with the controlling polymers molecular weight.The example of chain-transfer agent comprises mercaptan, polythiol and polydentate compound.The example of spendable chain-transfer agent comprises alkyl sulfhydryl such as sulfur alcohol, n-propyl mercaptan, normal-butyl mercaptan, isobutyl-mercaptan, tert-butyl mercaptan, n-pentyl mercaptan, isopentyl mercaptan, tert-pentyl mercaptan, n-hexyl mercaptan, cyclohexyl mercaptan, n-octyl mercaptan, positive decyl mercaptan, n-dodecyl mercaptan; Alcohols such as Virahol, isopropylcarbinol, lauryl alcohol and uncle's octanol; Halogenated compound such as tetracol phenixin, zellon, three chloro-bromothanes, in general, its consumption can be 0 to 10% of monomer mixture weight.Polymericular weight also can for example, be selected initiator and monomeric ratio with additive method control well known in the prior art.
Catalyzer and/or chain-transfer agent can be dissolved or be dispersed in the fluid medium separately or same, and are added in the aggregation container step by step.Monomer is that pure monomer or dissolving or the monomer that is dispersed in the fluid medium all can add simultaneously with catalyzer and/or chain-transfer agent.As known in the polymerization technique, after finishing substantially, polymerization a certain amount of initiator or catalyzer can be added in the polyblend with " chasing " residual monomer.
Generally stop the polymer latex agglomeration of particles by in polyblend, comprising surface of stability promoting agent.In general, as known in the polymerization technique, tensio-active agent such as negatively charged ion or nonionogenic tenside or their mixture by one or more in emulsion polymerization process are stablized the latex particle of growing.The all examples that are applicable to the tensio-active agent of letex polymerization be listed in the McCutcheon ' sDetergents and Emulsifiers that publishes per year (MC publishingCo., Glen Rock, NJ) in.Also can use the stablizer of other types, for example protective colloid.Yet, preferably be chosen in the type of stablizer of surface of stability promoting agent used in the polymerization process or other types and quantity like this, can not influence the improvement of the opaqueness subsequently of the inventive method with residual stable agent in the water-containing product that causes polyreaction significantly.In addition, also know the initiator chip of adding and the functional group's that carrying adds comonomer, for example the acid functional monomer of copolymerization helps the polymer latex particulate of gained stable.Importantly want the acid monomer of pays attention stably tensio-active agent, copolymerization, remaining initiator chip or the like also may influence next step the improvement of opaqueness of the inventive method.Thereby adjusting polymerizing condition perhaps is very important so that residual initiator chip content and the surface acidity desireed to be provided to the polymer latex particle that is provided in the inventive method.
Useful in the methods of the invention polymer latex can for example, comprise that monoethylenically unsaturated monomer such as the alkyl acrylate and the alkyl methacrylate of α, β-monoethylenically unsaturated monomer prepares by various polymerisable monomers." acrylic polymer latex " means by comprising acryl (COCH=CH
2) or methacryloyl (COC (CH
3)=CH
2) monomer, particularly contain the polymer latex that the polymerisable monomer basically of (methyl) Acrylic Acid Monomer that accounts for total monomer weight about 80% is polymerized.Can also use the mixture of polymer latex.
The example that can be used for the polymer latex of the inventive method comprises the polymer latex that is formed by for example ethylene linkage polymerization of unsaturated monomers of α, β-ethylene linkage unsaturated monomer.This class monomer comprises vinylbenzene, divinyl, alpha-methyl styrene, Vinyl toluene, vinyl naphthalene, ethene, vinyl-acetic ester, branched paraffin carboxylic acid's vinyl acetate, vinylchlorid, 1, the 1-Ethylene Dichloride, vinyl cyanide, methacrylonitrile, (methyl) acrylamide, various (methyl) acrylic acid C
1-C
20Alkyl ester, (methyl) methyl acrylate for example, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) 2-EHA, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid n-octyl, (methyl) vinylformic acid ester in the positive last of the ten Heavenly stems, (methyl) vinylformic acid n-dodecane ester, (methyl) vinylformic acid tetradecane ester, (methyl) vinylformic acid n-pentyl ester, (methyl) vinylformic acid peopentyl ester, (methyl) vinylformic acid ring pentyl ester, (methyl) lauryl acrylate, (methyl) vinylformic acid oleoyl ester, (methyl) vinylformic acid palm ester and (methyl) stearyl acrylate acyl ester, other (methyl) acrylate is such as (methyl) isobornyl acrylate, (methyl) benzyl acrylate, (methyl) phenyl acrylate, (methyl) vinylformic acid 2-bromine ethyl ester, (methyl) vinylformic acid 2-phenethyl ester, (methyl) vinylformic acid 1-naphthalene ester, (methyl) alkyl acrylate oxyalkyl ester is such as (methyl) vinylformic acid ethoxy ethyl ester, ethylene linkage undersaturated two and tricarboxylic list, two and trialkyl ester and acid anhydrides such as ethyl maleate, dimethyl fumarate, the equisetic acid trimethyl, and methylene-succinic acid ethyl-methyl ester." (methyl) acrylate " expression " acrylate " and " methacrylic ester " that is used for this specification sheets claims, and " (methyl) vinylformic acid " expression " vinylformic acid " and " methacrylic acid ".The ethylene linkage unsaturated monomer also can comprise be at least a kind of to improving the molecular weight and the effective polyenoid key of the degree of crosslinking unsaturated monomer of polymkeric substance.The example of the polyenoid key unsaturated monomer that can be used comprises (methyl) propyl acrylate, tripropylene glycol two (methyl) acrylate, Diethylene Glycol two (methyl) acrylate, 1,2-hexylene glycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, 1,3 butylene glycol (methyl) acrylate, polyalkylene glycol two (methyl) acrylate, Phthalic acid, diallyl ester, trimethylolpropane tris (methyl) acrylate, Vinylstyrene, divinyl toluene, trivinylbenzene and divinyl naphthalene.
Except those aspect comprising one or more polymerisable ethylene linkage unsaturated group meanings for the monomer of " functionality ", can use the monomer that also comprises one or more other functional groups to prepare the polymer latex that is used for the inventive method.Class important monomer among these functional monomers is those the polymerisable ethylene linkage unsaturated monomers with acid functional groups, these monomeric examples comprise vinylformic acid, methacrylic acid, β-acryloxy propionic, some acid is such as vinylformic acid, ethylacrylic acid, α-Mono Chloro Acetic Acid, α-vinylacrylic acid, Ba Dousuan, α-Ben Jibingxisuan, styracin, chloro-cinnamic acid, β-styrene acrylic, methylene-succinic acid, senior-the acid oligomer of toxilic acid, a kind of dihydrogen phosphate that also contains the alcohol of polymerisable vinyl or thiazolinyl, phosphoric acid allyl ester for example, phosphoric acid allyl ester cellosolve, the list or the bisphosphate of two (methylol) fumaric acid or methylene-succinic acid, the derivative of (methyl) acrylate, for example, the phosphoric acid ester that comprises (methyl) acrylic acid hydroxy alkyl ester of (methyl) vinylformic acid 2-hydroxyl ethyl ester, Kayamer for example
(Nihon Kayaku Co., the trade mark of Ltd.) PM-1, PM-2, PA-1 and PA-2 monomer, (methyl) vinylformic acid 3-hydroxypropyl acrylate, or the like.The example of the biphosphate ester derivative that can be used comprises phosphoric acid vinyl benzyl ester, and:
CH
2＝CCH
3CO
2CH
2CH
2OPO(OH)
2
CH
2＝CCH
3CO
2CH
2CH〔OPO(OH)
2〕CH
3
CH
2＝CCH
3CO
2CH
2CH
2CH
2OPO(OH)
2
CH
2＝CCH
3CO
2CH
2CHOHCH
2OPO(OH)
2。
Thereby the present invention also provides and comprises the selected polymer latex particle and water dispersion, coating composition and the pigment slurry of TiO 2 pigment.Wherein selected polymer latex particle be by comprise be at least a kind of be selected from biphosphate vinyl benzyl ester and
CH
2＝CCH
3CO
2CH
2CH
2OPO(OH)
2、
CH
2＝CCH
3CO
2CH
2CH〔OPO(OH)
2〕CH
3、
CH
2=CCH
3CO
2CH
2CH
2CH
2OPO (OH)
2With
CH
2=CCH
3CO
2CH
2CHOHCH
2OPO (OH)
2Be polymerized.
When the preparation polymer latex, generally comprise small amount of acid official energy copolymerizable monomer therein, such as methacrylic acid and/or vinylformic acid, to give its colloidal stability.As mentioned above, in one embodiment of the invention, the polymer latex particle is preferably by comprising greater than the monomer mixture preparation of the methylene-succinic acid of 1% weight.In another embodiment preferred, comprise quite a large amount of sour official's energy copolymerisable monomers in the monomer mixture, methacrylic acid for example, its consumption for example is at least about 5% of polymer solids gross weight, preferably be at least the about 10% of polymer solids gross weight, and adopt the method that the insoluble polymer latex particle can be provided.In another embodiment preferred of the present invention, as mentioned above, used polymer latex is to comprise the derivative of the phosphoric acid part that is at least a kind of (methyl) acrylate and be preferably the monomer mixture that comprises the dihydrogen phosphate monoesters and be polymerized.The predetermined end-use of the product of producing according to the inventive method, monomer mixture can also comprise the copolymerizable functional monomer of other types.For example, also can comprise a small amount of promotion adherent copolymerizable monomer.Other types functional monomer's example comprise hydroxy functional monomers as (methyl) vinylformic acid 2-hydroxyl ethyl ester, amino functional monomers as (methyl) vinylformic acid dimethylamino ethyl ester, epoxide-functional monomer such as glycidyl methacrylate or the like.The example of operable synthetic polymer latex comprises acrylic copolymer latex, for example the copolymer emulsion of butyl acrylate/methyl methacrylate/acid and ethyl propenoate/methyl methacrylate/acid; The homopolymer of vinyl-acetic ester and copolymer emulsion comprise ethylene latex; Styrene/butadiene copolymers latex; Or the like.
Has the polymer latex that is applicable to the inventive method character by selecting to have known second-order transition temperature and acid functionality's monomeric type and concentration, can preparing.
Thereby by selecting concrete polymerization process can choose the particle size of polymer latex, particle size distribution and molecular weight, for example use specific initiator and chain-transfer agent system, these all are to be known in the polymerization technique.When polymer latex was used as tackiness agent in the water composition of making by prescription fully, the average particle size particle size of polymer latex and molecular weight all were important for the improvement of opaqueness and for the character of polymer latex.
Best, selected be used to average particle size range that the polymer latex in the inventive method has for from the median size of about four times TiO 2 pigment to being low to moderate about 20nm.For example, if when the average particle size particle size that used titanium dioxide granule has is about 200 millimicrons, then the polymer latex particle average particle size particle size scope that should have from about 20 to less than about 800 millimicrons." average particle size particle size " or " median size " is meant and uses quasielastic light scattering technique, the mean value of the BI-90 type particle diameter instrument measuring that is provided by Brookhaven Instrument Corp. for example is provided.
Titanium dioxide granule can be pretreated and the top coat of inorganics is provided thereon, for example the mixture coating of silica, aluminum oxide or silica and aluminum oxide.In addition, small-molecule substance, for example silane or titanate can be attracted to the titanium dioxide granule surface and answer with surface opposite, and the surface portion of gained is subsequently by chemical modification.The example of this small-molecule substance comprises N-2-aminoethyl-3-aminopropyl trimethoxysilane, 3-aminopropyl trimethoxysilane, 3-methacrylic acid group propyl trimethoxy silicane and vinyl nitrilotriacetic base silane.On the other hand, other materials can be adsorbed on the surface of titanium dioxide pigment particles simply.The most important example of this class material is the lower molecular weight polyelectrolyte, for example Chang Gui pigment dispersing agent.
The example that is applicable to the anionic polyelectrolyte pigment dispersing agent of the inventive method comprises polyacrylic acid, polymethyl acrylic acid, comprise the copolymerization acid of the toxilic acid of copolymerization, polyphosphate for example Potassium tripolyphosphate, or the like.
When also playing tackiness agent, polymer latex does the time spent, although in order to obtain the over-all properties of coating or film, the chemical constitution of polymeric latex binder is important, but the second-order transition temperature of polymer latex and acid functionality's number may also be important for the purposes of the present disclosure.In an embodiment of the present invention, the preferred median size of hard polymer latex particle is about 50nm to 80nm.In another embodiment, the particle diameter of preferred flexible polymer latex particle is preferably about 100nm to about 400nm.
The existence of conventional polyelectrolyte dispersing agents has remarkably influenced to the improvement of opacity of the present invention.When the concentration of the water-soluble polyelectrolyte dispersion agent of routine was low, its numerical value was equivalent to about 0.2% or when lower, and what disadvantageous effect the improvement of opacity is not almost had.When with the conventional water-soluble polyelectrolyte dispersion agent of high level, then can tangible disadvantageous effect be arranged, unless selective polymer latex meticulously to opacity.
In some cases, can come the dispersed titanium dioxide granules of pigments just may put into practice method of the present invention, although generally preferably use pigment dispersing agent without pigment dispersing agent.
In one of the present invention shows by embodiment preferred, use emulsion polymerization from the polymerisable phosphoric acid derivatives of the ethylene linkage that comprises one or more, for example the monomer mixture of the part ester of one or more phosphoric acid and methacrylic acid 2-hydroxyl ethyl ester prepares polymer latex.The example of this part ester is listed in the above, and they comprise the diester of monoesters, phosphoric acid and hydroxyethyl methylacrylate of phosphoric acid and hydroxyethyl methylacrylate and their mixture.The phosphate functional polymer latex particle that is generated with by the polymer phase ratio that does not comprise the preparation of the monomeric monomer mixture of phosphate functional, have the opacity of having improved.
Compare with the scattering coefficient of the paint formula for preparing by the polymer latex that uses routine, the inventive method can improve the opacifying power (determining by the scattering coefficient of measuring lacquer) that contains PVC emulsion paint prescription titanium dioxide, identical significantly.This improved mode of another kind of expression is identical scattering coefficient or opacifying power that method permission of the present invention reaches the minimizing of the PVC in the 20%PVC titanium dioxide paint formula 20% and use conventional polymer latex to obtain.
And, by the paint formulation of the inventive method preparation, even for example be normally used for also obtaining improved processing property in the presence of the lime carbonate and silico-aluminate of this prescription at the extender of many macrobead sizes.
In addition, when the thickening material with conventional association type and non-association type prepares coating composition, can reach improved opacifying power, and selected softening agent is not depended in this improvement with the inventive method yet.This result is wonderful and opposite with the result who runs into usually with conventional polymer latex when paint preparation.In such conventional system, the opacifying power of the paint of being prepared is to have very big variation with used thickening material function difference.Therefore, method of the present invention makes paint formulation have very big selectivity when selecting the thickening material of finished product paint formulation, and it doesn't matter and with opacifying power to the paint finished product selection of thickening material of disadvantageous effect is arranged.
In addition, except improving paint formulation opacifying property, also find method of the present invention and compare with the paint formulation of conventional polymer latex preparation, help improving the anti-early stage whipability of paint formulation, anti-metal mark, gloss, shear viscosity and washing fastness, and improved the erosion resistance of paint formulation.
In the method for the invention, (its particle size is quite little except titanium dioxide granule, be about outside 200～250nm), can also use other granules of pigments, for example generally be contained in the formulation for coating material of many types volume granules of pigments with the macrobead size that reduces the novel material cost.The example of the volume granules of pigments of the macrobead size that can be used comprise lime carbonate, silico-aluminate, non-crystalline silicon, or the like.
Similarly, titanium dioxide granule also comprises the solvent that water is miscible with the water-bearing media that the polymer latex dispersion agent grinds therein, for example dibasic alcohol and glycol ether, and they all are habitual in the coating process.The example of the solvent that the water that can be used is miscible comprise propylene glycol, ethylene glycol, ethylene glycol monomethyl ether, or the like.
Aqueous coating composition is usually prepared under the alkaline pH condition so that be with anionic latex adhesive to stablize and not agglomeration and other reasons.For example, (N.I.Gaynes ed.D.Van Nostrad Co.Inc.Princeton NJ1967) in the 189th～230 page, summarizes the principle of preparation aqueous coating composition at Formulationof Organic Coatings.
The aqueous dispersion that comprises selected polymer latex particle and titanium dioxide pigment particles provided by the invention can be used to various application scenarios.In some cases, can add " soft " polymer latex of (that is, low effective glass transition temperature for example is about 0 ℃ to 10 ℃) in dispersion, it generally adds in addition with other components, and flexible polymer latex plays the tackiness agent effect of composition.The latex polymer particles that forms tackiness agent usually contains the carboxyl-functional base.Under appropriate condition, carboxyl can be ionized and produce electric charge and make the latex electrostatic stabilization stop too early agglomeration on the latex particle surface.Volatile alkali commonly used generally is the pH value that ammonia is adjusted coating composition.When coating composition is imposed on the base material that will apply, lose volatile alkali and thereby make the pH value whereabouts of coating composition, the adhesive latex particle loses stable, forms a successive adhesive films so impel agglomeration.
Except the polymer latex particle that forms tackiness agent, selected polymer latex particle and titanium dioxide pigment particles, also can comprise habitual coating material compounding agent according to the aqueous coating composition of the inventive method preparation.For example, they can comprise above-mentioned volume pigment, such as lime carbonate, amorphous silica or the like; Defoamer; Biocides such as zinc oxide, 2-N-octyl group-4-isothiazole-3-ketone and phenylmercury acetate; Coalescing agent such as diethylene glycol monoethyl ether acetic ester and ethylene glycol monomethyl ether acetate; Softening agent such as bialkyl ortho phthalate, comprise dibutyl phthalate, dioctyl phthalate (DOP), or the like; Freeze-thaw stabilizer such as ethylene glycol, propylene glycol and Diethylene Glycol; The polyethoxylated of nonionic wetting agent such as lipid acid, alkanol, alkylphenol and dibasic alcohol (Polyethylenoxylate); Poly-electrolysis pigment dispersing agent; Thickening material such as polyelectrolyte and cellulose thickener; Rheology control agent such as associative thickener or the like; Tinting material such as tinting pigment and dyestuff; Spices; Cosolvent or the like.
Following illustrative embodiment is illustrated method of the present invention with the functional mode of selected each parameter of emulsion polymer.These embodiment will help the skilled person of the industry to understand the present invention; Yet the present invention is not limited to these embodiment.In each following embodiment, except as otherwise noted, per-cent is formed all by weight.
Embodiment 1～2
Press the 20%PVC gloss paint (comparative example 1) of the routine of following formulation standard.Pigment grind:
Composition weight (gram)
Water 30
Propylene glycol 20
Colloid 643 defoamers 1
Tamol
731 dispersion agents (25% solid) 8.19
Ti-pure
R-900 titanium dioxide 204.72Tamol 730 is a kind of polycarboxylate salt dispersant (Tamol is the trade mark of Rohm and Hass company).Tamol 731 is a kind of sodium salt of polymerization of carboxylic acid.Ti-pure is the trade mark of Du Pont de Nemours company.Ti-pure R-900 is a kind of rutile titanium dioxide of coating level.These components are worn into the pigment grind slurry in the high speed disk disperser, under low speed, mix then with following component:
Composition weight (gram)
Rhoplex
AC-61 polymer latex 493.75
Colloid 643 defoamers 4
Texanol
Coalescing agent 22.96
Triton
GR-7M tensio-active agent 2
Propylene glycol 59
Nuosept
95 sanitass 6
Water and Natrosol
250 165.07
MR cellulose thickener Rhoplex is the trade mark of Rohm and Haas company.Texanol is the trade mark of Eastman Kodak company.Triton is the trade mark of Rohm and Hass company.Nuoset is Nuodex, the trade mark of Inc..Mixture is thickened to the Si Shi viscosity of 80KU by the aqueous solution that adds cellulose thickener, by adding ammonia the pH of mixture is adjusted to 9.
For embodiment 1 is provided, repeat the paint formulation method of comparative example 1, be that 65 ℃, particle diameter are that the mixture of 71nm and the polymer latex (latex A, 37.4% solid) that contains 6% methacrylic acid etherophosphoric acid replaces the 493.75 Rhoplex AC-61 that restrain wherein with the second-order transition temperatures of the Rhoplex AC-61 (46.5% solid) of 419.66 grams and 92.04 grams.The gross weight of water is adjusted to the total solids par that keeps in the finished product paint.
For embodiment 2 is provided, repeat the paint formulation method of embodiment 1, wherein the second-order transition temperatures with 94.26 grams are that 90 ℃, particle diameter are the polymer latex A that 69nm and the polymer latex that contains 4% methylene-succinic acid (latex B, 36.5% solid) replace 92.04 grams.The gross weight of water adjusted to keep always measuring par admittedly in the finished product paint.
The Kubleka-Munk scattering coefficient of all paint is all measured with follow-on ASTM D2805-70 method.The result is listed in the Table I.
Table I example dispersion agent tackiness agent scattering coefficient comparative example 1 1% Tamol 731 AC-61 7.26 embodiment 1 1% Tamol 731 AC-61/ latex A 7.77 embodiment 2 1% Tamol 731 AC-61/ latex B 7.69
Presentation of results in the Table I, when the polymkeric substance that contains methacrylic acid etherophosphoric acid (embodiment 1) or methylene-succinic acid (embodiment 2) mixes mutually with habitual latex, compare the improvement that can cause opacity with independent habitual latex, as what reflected by the Kubleka-Munk scattering coefficient.
Embodiment 3
Preparing it by the hot method using single-stage, progressively add by the monomer of the methacrylic acid phosphoric acid acetate of methacrylic acid that comprises 1.3% weight and 1% weight calculates second-order transition temperature to be about 14 ℃, particle size is the acrylic ester polymer latex emulsion (latex C) of 45% weight as 161nm and total solids level.Under high speed, the water of the propylene glycol of Colloid 643 defoamers of Tamol 731 pigment dispersing agents of the Ti pure R-900 titanium dioxide of 200 weight parts, 8 weight parts, 1 weight part, 20 weight parts and 30 weight parts ground together and prepare the pigment grind slurry.The latex C of 495.6 weight parts is mixed with the water of 7.57 weight parts and the Texanol of 22.64 weight parts under low speed.Then add the Tritonx-405 tensio-active agent of 9.70 weight parts, the water of 49.57 weight parts, Colloid 643 defoamers of water weight part, the propylene glycol of 59 weight parts and Nuosept 95 sanitass of 6 weight parts to latex C/Texanol mixture.Add slurry to this mixture.Then add 5% (weight) Natrosol 250MR SURGICEL thickener soln of 100.4 weight parts, be 20, calculate solid volume to be 32%, calculate solid weight to be 42.1% paint (embodiment 3) thereby obtain a kind of PVC value.Assess the opacifying power of this paint and gloss and compare with the contrast lacquer.Contrast lacquer is following polymer latex preparation, and this latex is with similar method system, but has omitted methacrylic acid etherophosphoric acid (comparative example 2), and the result is listed in the Table II, and this result's demonstration has improved opacifying power and gloss with the inventive method.
Table II
60 ° of gloss of 20 ° of gloss of example opacifying power
Comparative example 2 6.9 14 54
Embodiment 3 7.8 24 63
Embodiment 4
Be added on the seed latex that 4 in the 24 gram deionized waters restrain ammonium persulphates and 60 grams at the deionized water to 1300 stirrings that restrain under 85 ℃ the nitrogen atmosphere.Prepare a kind of monomer emulsion by 600 gram deionized waters, 28 gram Siponate DS-4,900 gram propylene butyl esters, 876.6 gram methyl methacrylates and 23.4 gram methacrylic acids, in 200 minutes, this monomer is added with 2 gram ammonium persulphates in 100 gram deionized waters and keep 85 ℃.After reaction is finished, with dispersion cooling and filtration.This product (latex D) has that 45.6% solid, pH are 3, median size is 196nm.
Repeat to prepare the method for latex D, just replace the methyl methacrylate of 18 grams with the Kayamer PM-1 of equal weight.Kayamer is the trade mark of NihonKayamer Co.Ltd., and PM-1 contains the monoesters of have an appointment 52% hydroxyethyl methylacrylate and phosphoric acid and the monomer mixture of 33% diester.This product (latex E) contains that 46.1% solid, pH are 2.6, average particle size particle size is 185nm.
Prepare a kind of painted titanium dioxide dispersion by the deionized water of 180 grams, Tamol 731 dispersion agents (25% solid) of 7.2 grams, the Nopco NXZ defoamer of 3.0 grams, the Ti-Pure R-902 of 600 grams and the dim dispersion of Colortrend of 30 grams.The sample of latex D and latex E is adjusted pH to 9 with 28% ammoniacal liquor, and is used for being formulated in the paint that has the Ti-pure R-902 of 14% volumetric concentration in the exsiccant lacquer: to the R-902 dispersions of 29.5 grams add the water of 7.8 grams, the pH of 83.9 grams are 9 latex D, the Texanol coalescing agent of 2.6 grams, the propylene glycol of 7.2 grams and 2.5% moisture Natrosol 250MR Natvosol thickening materials of 24.0 grams.With similar method preparation glue E lacquer, but only with the latex E of 82.8 grams and the water of 8.9 grams.Allow two kinds of lacquer balances 7 days, (Colorguard GardnerInstruments) measures their Y-reflection coefficient to use 45 °/0 ° reflexometer then.According to light scattering theory, the ratio of scattering coefficient S and adsorption index K can be drawn by following formula:
S/K=2R/ (1-R)
2Wherein R is the reflection coefficient of the infinitely thick layer of dry paint.Under the condition of given titanium dioxide PVC, the difference of the Y-reflection coefficient of identical painted paint film only is that the difference owing to the titanium dioxide scattering coefficient causes.Titanium dioxide is controlled scattering and tinting material control absorption (but absorption can be considered to constant).Draw the percent difference of two kinds of identical scattering coefficients that painted paint film presented then by following formula:
((S2-S1)/S1)×100
＝((R2(1-R1)
2/R1(1-R2)
2)-1)×100
The result is listed in the Table III.
Table III
Example latex Y-reflection coefficient
Comparative example 3 D 0.504
Embodiment 4 E 0.540
These results show that the tackiness agent (latex E) that contains phosphoric acid ester is compared the raising that causes the Y-reflection coefficient with the tackiness agent (latex D) of standard, and correspondingly with the scattering coefficient raising 25% of the titanium dioxide in the dry paint.
Can improve the details of each embodiment of method of the present invention and combination, as long as these all improvement all are in the determined spirit and scope of the appended claims of the present invention.
Claims (1)
1. coating composition of forming by the water dispersion that comprises polymer latex and TiO 2 pigment, said polymer latex comprises the dihydrogen phosphate functional group, said polymer latex is the monomer-polymer that is at least a kind of polymerisable dihydrogen phosphate functional monomer by comprising, and polymerisable dihydrogen phosphate functional monomer is selected from the material with lower class:
The phosphate monoester of methacrylic acid 2-hydroxyl ethyl ester,
The phosphodiester of methacrylic acid 2-hydroxyl ethyl ester,
The phosphate monoester of methacrylic acid 3-hydroxypropyl acrylate,
The phosphodiester of methacrylic acid 3-hydroxypropyl acrylate,
The vinyl benzyl dihydrogen phosphate
CH
2＝CCH
3CO
2CH
2CH
2OPO(OH)
2，
CH
2＝CCH
3CO
2CH
2CH〔OPO(OH)
2〕CH
3，
CH
2=CCH
3CO
2CH
2CH
2CH
2OPO (OH)
2And
CH
2＝CCH
3CO
2CH
2CHOHCH
2OPO(OH)
2。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US80197691A | 1991-12-03 | 1991-12-03 | |
| US801,976 | 1991-12-03 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92115196A Division CN1073957A (en) | 1991-12-03 | 1992-12-03 | Preparation comprises the method for the water dispersion of polymer latex and TiO 2 pigment |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1182106A true CN1182106A (en) | 1998-05-20 |
Family
ID=25182507
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92115196A Pending CN1073957A (en) | 1991-12-03 | 1992-12-03 | Preparation comprises the method for the water dispersion of polymer latex and TiO 2 pigment |
| CN97121279A Pending CN1182106A (en) | 1991-12-03 | 1997-10-30 | Process for preparing aqueous dispersion including polymeric latex and titanium dioxide pigment |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92115196A Pending CN1073957A (en) | 1991-12-03 | 1992-12-03 | Preparation comprises the method for the water dispersion of polymer latex and TiO 2 pigment |
Country Status (10)
| Country | Link |
|---|---|
| KR (1) | KR930013025A (en) |
| CN (2) | CN1073957A (en) |
| AU (1) | AU3062592A (en) |
| CA (1) | CA2083366A1 (en) |
| IL (1) | IL103860A0 (en) |
| MX (1) | MX9206805A (en) |
| MY (1) | MY109300A (en) |
| NZ (1) | NZ245248A (en) |
| WO (1) | WO1993011181A1 (en) |
| ZA (1) | ZA929302B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100442086C (en) * | 2002-01-29 | 2008-12-10 | 东洋油墨制造株式会社 | Coloring composition for color filter and color filter |
| CN101195980B (en) * | 2006-11-20 | 2012-01-11 | 罗门哈斯公司 | Coated paper and paperboard |
| CN104302709A (en) * | 2012-05-11 | 2015-01-21 | 涂料外国Ip有限公司 | Aqueous coating composition having stabilized color pigments |
Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5385960A (en) * | 1991-12-03 | 1995-01-31 | Rohm And Haas Company | Process for controlling adsorption of polymeric latex on titanium dioxide |
| EP0705890A1 (en) * | 1994-10-04 | 1996-04-10 | Videojet Systems International, Inc. | White ink for marking candy substrates |
| DE19811314A1 (en) | 1998-03-16 | 1999-09-23 | Basf Ag | Aqueous, pigment containing composition useful for production of dispersion dyes |
| US6214467B1 (en) | 1998-07-24 | 2001-04-10 | Rohm And Haas Company | Polymer-pigment composites |
| US6433117B1 (en) * | 1999-08-04 | 2002-08-13 | E. I. Du Pont De Nemours & Company | Phosphorylated polymer dispersants for inks |
| AU782594B2 (en) * | 2000-11-21 | 2005-08-11 | Rohm And Haas Company | Polymer-pigment composites |
| US7812079B2 (en) | 2001-02-22 | 2010-10-12 | Valspar Sourcing, Inc. | Coating compositions containing low VOC compounds |
| US6638998B2 (en) | 2001-04-18 | 2003-10-28 | Basf Ag | Use of surfactants for improving the compatibility of inorganic pigments in aqueous coating compositions |
| DE10126717A1 (en) | 2001-05-31 | 2002-12-05 | Basf Ag | Pigment-containing, solvent-free preparation |
| BR0300551A (en) * | 2002-03-13 | 2004-08-10 | Rohm & Haas | Polymer composition, process for forming a polymer composition, monomer composition, and method for applying a polymer composition |
| EP1496091A1 (en) | 2003-07-08 | 2005-01-12 | Rohm And Haas Company | Aqueous polymer composition |
| EP1582567B2 (en) * | 2004-04-01 | 2011-11-16 | Rohm And Haas Company | Aqueous coating composition |
| EP1746137B1 (en) | 2005-07-19 | 2008-08-13 | Rohm and Haas Company | Anti-flocculant aqueous coating composition |
| NZ553410A (en) | 2006-03-02 | 2008-06-30 | Rohm & Haas | Scrub and stain-resistant copolymer coating composition |
| EP1923505B1 (en) | 2006-11-20 | 2011-02-23 | Rohm and Haas Company | Coated paper and paperboard |
| WO2013159090A2 (en) | 2012-04-20 | 2013-10-24 | Valspar Sourcing, Inc. | Titanium dioxide pigment grind dispersion and paint |
| WO2013159098A1 (en) | 2012-04-20 | 2013-10-24 | Valspar Sourcing, Inc. | Method for making titanium dioxide pigment grind dispersion and paint |
| EP2847284B1 (en) * | 2012-05-06 | 2019-05-01 | Ethox Chemicals, LLC | Method for improving the effectiveness of titanium dioxide containing coatings |
| US9816002B2 (en) | 2012-10-12 | 2017-11-14 | Dow Global Technologies Llc | Aqueous coating composition with improved viscosity stability |
| JP6041170B2 (en) * | 2013-06-04 | 2016-12-07 | パナソニックＩｐマネジメント株式会社 | Room temperature curable photocatalyst paint, room temperature curable coating composition and interior material |
| CA2873207C (en) * | 2013-12-20 | 2022-04-05 | Rohm And Haas Company | Pigmented coating composition with a phosphorus acid functionalized binder |
| EP3194515B1 (en) * | 2014-07-28 | 2019-01-09 | Dow Global Technologies LLC | Poly(vinyl acetate) dispersion, and paint formulation comprising thereof |
| AU2015343385B2 (en) * | 2014-11-03 | 2017-06-08 | Benjamin Moore & Co. | Additives for improved hiding and paint compositions containing same |
| CN108026400B (en) * | 2015-09-15 | 2021-12-31 | 惠普发展公司，有限责任合伙企业 | White ink |
| WO2018065574A1 (en) * | 2016-10-07 | 2018-04-12 | Basf Se | Latex paint containing titanium dioxide pigment |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL161769C (en) * | 1975-09-25 | 1980-03-17 | Synres Internationaal Nv | PROCESS FOR PREPARING STABLE AQUEOUS EMULSIONS OF ADDITION POLYMERS AND COPOLYMERS. |
| US4102843A (en) * | 1977-01-07 | 1978-07-25 | Rohm And Haas Company | Dispersing paint pigments |
| US4421660A (en) * | 1980-12-15 | 1983-12-20 | The Dow Chemical Company | Colloidal size hydrophobic polymers particulate having discrete particles of an inorganic material dispersed therein |
| GB2090602B (en) * | 1981-01-06 | 1984-08-15 | Mitsubishi Rayon Co | Polymer composition |
| US4506057A (en) * | 1983-12-19 | 1985-03-19 | The Dow Chemical Company | Stable latexes containing phosphorus surface groups |
-
1992
- 1992-11-04 AU AU30625/92A patent/AU3062592A/en not_active Abandoned
- 1992-11-04 WO PCT/US1992/009434 patent/WO1993011181A1/en active Application Filing
- 1992-11-19 CA CA002083366A patent/CA2083366A1/en not_active Abandoned
- 1992-11-24 NZ NZ245248A patent/NZ245248A/en unknown
- 1992-11-24 IL IL103860A patent/IL103860A0/en unknown
- 1992-11-25 MY MYPI92002148A patent/MY109300A/en unknown
- 1992-11-26 MX MX9206805A patent/MX9206805A/en unknown
- 1992-12-01 ZA ZA929302A patent/ZA929302B/en unknown
- 1992-12-03 KR KR1019920023202A patent/KR930013025A/en not_active Application Discontinuation
- 1992-12-03 CN CN92115196A patent/CN1073957A/en active Pending
-
1997
- 1997-10-30 CN CN97121279A patent/CN1182106A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100442086C (en) * | 2002-01-29 | 2008-12-10 | 东洋油墨制造株式会社 | Coloring composition for color filter and color filter |
| CN101195980B (en) * | 2006-11-20 | 2012-01-11 | 罗门哈斯公司 | Coated paper and paperboard |
| CN104302709A (en) * | 2012-05-11 | 2015-01-21 | 涂料外国Ip有限公司 | Aqueous coating composition having stabilized color pigments |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2083366A1 (en) | 1993-06-04 |
| NZ245248A (en) | 1995-09-26 |
| AU3062592A (en) | 1993-06-28 |
| MY109300A (en) | 1996-12-31 |
| IL103860A0 (en) | 1993-04-04 |
| CN1073957A (en) | 1993-07-07 |
| MX9206805A (en) | 1993-07-01 |
| ZA929302B (en) | 1993-06-21 |
| WO1993011181A1 (en) | 1993-06-10 |
| KR930013025A (en) | 1993-07-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1182106A (en) | Process for preparing aqueous dispersion including polymeric latex and titanium dioxide pigment | |
| AU782871B2 (en) | Polymer-pigment composites | |
| AU664967B2 (en) | Process for controlling adsorption of polymeric latex on titanium dioxide | |
| JP4437105B2 (en) | Opacifying particles | |
| AU671963B2 (en) | Aqueous dispersion of composite particles including polymeric latex | |
| CN1252157C (en) | Polymer-pigment composite material | |
| US9441102B2 (en) | Opacifying pigment particle | |
| US8283404B2 (en) | Opacifying pigment particle | |
| CN1041314C (en) | Process for preparing an aqueous dispersion | |
| JP5827629B2 (en) | Opaque pigment particles | |
| CN100341936C (en) | Clouring polymer composition | |
| CN1121462C (en) | Method for providing waterborne coating composition with improved color acceptance | |
| CN1278285A (en) | Fluoropolymer dispersion coatings from modified thermoplastic vinylidene fluoride based resins | |
| CN1243533A (en) | Stabilized non-polymeric acetoacetate esters that promote adhesion to metallic and oxidized substrates | |
| EP3215577B1 (en) | Additives for improved hiding and paint compositions containing same | |
| JP2001254020A (en) | Non-aqueous dispersible resin composition and its use | |
| JPH11228875A (en) | Coating material composition for outdoor use |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |