CN105377999A - Polymer-encapsulated pigment particle - Google Patents

Polymer-encapsulated pigment particle Download PDF

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Publication number
CN105377999A
CN105377999A CN201480040853.6A CN201480040853A CN105377999A CN 105377999 A CN105377999 A CN 105377999A CN 201480040853 A CN201480040853 A CN 201480040853A CN 105377999 A CN105377999 A CN 105377999A
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China
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polymer
dispersion
pigments
pigment
granules
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Granted
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CN201480040853.6A
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CN105377999B (en
Inventor
詹森·尼斯
李海波
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Industrial Solution Co
Xuanwei Headquarters Co
Xuanwei Investment Management Co ltd
Sherwin Williams Co
Valspar Corp
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Valspar Sourcing Inc
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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
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10—Treatment with macromolecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C09C1/3676—Treatment with macro-molecular organic compounds
    • 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
    • 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
    • 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
    • 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
    • C09D7/41—Organic pigments; Organic dyes
    • 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
    • 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
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Paints Or Removers (AREA)

Abstract

A polymer-encapsulated pigment dispersion is prepared from a mixture of (a) a carrier; (b) pigment particles; and (c) a polymeric dispersing agent having a polymer backbone, and a zwitterionic polymer side chain comprising anionic and cationic groups. The dispersing agent may provide efficient pigment wetting and dispersion using relatively low and thus economical pigment amounts, with good opacity and good hiding characteristics, especially in titanium dioxide-containing coating compositions

Description

The granules of pigments of polymer overmold
Field
The present invention relates to the dispersion of pigment wetting and dispersion agent, pigment grind dispersion, coated pigment, and relate to painted paint and other coating composition.
Background
Titanium dioxide widely uses in paint and other coating composition but day by day expensive pigment.In many paint formulations, the single raw material that titanium dioxide representative is the most expensive.Propose multiple technologies and the amount becoming to assign to reduce titanium dioxide in coating composition formula, still provide acceptable scattering of light or opaqueness simultaneously.This constituents a kind of is the EVOQUE supplied by DowChemicalCompany tMpre-composition polymer.The EVOQUE product (EVOQUE1140, EVOQUE1180, EXP-4340 and EXP-4463) of four kinds of grades can be obtained at present, it is said that they have titanium dioxide reactivity in various degree.Claim according to its supplier, the pre-composition polymer of EVOQUE is " with TiO 2merge to be formed and not only improve the wet covering efficiency of pigment but also improve the polymer-pigment mixture of locked-in-air voids efficiency ".Set pigment opacity can be reached under the TiO 2 pigment level that the paint be made up of described mixture or other coating composition reduce to a certain extent, or the pigment opacity increased in a way can be reached under set TiO 2 pigment level.But the potential saving in titanium dioxide raw material cost and the potential benefit in pigment covering efficiency are cancelled because of EVOQUE product cost.
Other polymkeric substance multiple has been proposed in pigment, such as, as pigment dispersing agent.The synthesis of some in these polymkeric substance needs expensive initial monomers or the synthetic schemes of complexity.In other cases, polymkeric substance has high viscosity, limited colo(u)rant dispersion performance or other shortcoming.
Be appreciated that in this area the coating composition containing pigment still needing the improvement that there is even lower raw materials cost, even higher pigment covering efficiency or have lower cost and greater efficiency concurrently from the above.Open herein and claimed such composition and component and their preparation method.
Summary of the invention
In one aspect, this specification sheets provides a kind of pigment grind dispersion, it comprises the mixture of carrier, granules of pigments and polymeric dispersant, and described polymeric dispersant has polymer backbone and comprises the amphoteric ion polymer side chain of anionic group and cation group.
On the other hand, this specification sheets provides a kind of polymeric dispersions of coated pigment, it comprises the mixture of carrier, granules of pigments and polymeric dispersant, wherein said particle is coated by least one polymer layer at least partly, and described polymeric dispersant has polymer backbone and comprises the amphoteric ion polymer side chain of anionic group and cation group.
In other one side, this specification sheets provides a kind of method of the grinding distribution body that makes paints.Said method comprising the steps of: carrier, granules of pigments and polymeric dispersant are mixed, described polymeric dispersant has polymer backbone and comprises the amphoteric ion polymer side chain of anionic group and cation group.
On the other hand, this specification sheets provides a kind of method manufacturing the polymeric dispersions of coated pigment.Said method comprising the steps of: the dispersion forming carrier, granules of pigments and polymeric dispersant, described polymeric dispersant has polymer backbone and comprises the amphoteric ion polymer side chain of anionic group and cation group.In one embodiment, be make in dispersion, to comprise or add in dispersion radical initiator and one or more ethylenically unsaturated monomers subsequently, and ethylenically unsaturated monomer is polymerized to make granules of pigments coated by least one polymer layer at least partly.
On the other hand, this specification sheets provides a kind of coating composition, it comprises the dispersion of carrier, granules of pigments and polymeric dispersant, wherein said granules of pigments is coated by least one polymer layer at least partly, and described polymeric dispersant has polymer backbone and comprises the amphoteric ion polymer side chain of anionic group and cation group.In addition, described composition also comprises the one or whole in following two kinds of materials: binder for film formation, and it comprises the polymkeric substance being different from coated polymer; Or one or more in standard oil paint formula additive.
Disclosed dispersion, method and coating composition can comprise described composition, substantially become to be grouped into by described or be grouped into by described one-tenth.In exemplary preferred implementation, carrier comprises water, granules of pigments comprises titanium dioxide granule, polymer backbone comprises vinyl chain growing polymer, anionic group comprises sulfonic acid group, cation group comprises quaternary ammonium group, and granules of pigments coated is at least partly at room temperature from coalescent and without the need to the existence of the binder for film formation that comprises the polymkeric substance being different from chain growth polymkeric substance.Disclosed polymeric dispersant can utilize relatively low and therefore economic material quantity (such as, the amount of pigment, polymeric dispersant and chain growth polymkeric substance) to provide effective pigment wetting and dispersion.The colo(u)rant dispersion that preferred implementation desirably provides good granules of pigments to soak and (especially in silica containing emulsion paint) improves in final desciccator diaphragm of disclosed dispersion, method and coating composition, the dispersion wherein improved causes the pigment improved to hide efficiency.
Describe in detail
Unless the context, otherwise following term will have following implication and be applicable to odd number and plural number:
The commutative use of situation of term " one ", " one ", " at least one " and " one or more " and not usage quantity word.Therefore, such as, the coating composition comprising " one " carrier or " one " optional tensio-active agent represents: coating composition can comprise " one or more " carrier and " one or more " optional tensio-active agent.
When using about monomer or polymer lateral chain, term " anionic group " represents: when being dissolved or dispersed in aqueous carrier, have the organic group of net negative charge, preferably pH dependent form net negative charge.
When using about liquid coating composition, term " tackiness agent " represents: the natural polymer or the synthetic polymer (when needing, the coalescing agent with suitable) that are applicable to the film forming in this composition.
Term " mass polymer " represents: the polymkeric substance formed by homogeneous reaction mixture, described homogeneous reaction mixture be by suitable initiator is dissolved in make in one or more reactive monomers and existence without the need to solvent can be polymerized.
When using about pigment grind dispersion or coating composition, term " carrier " represents: for volatile dispersing agent or other vehicle of the remaining ingredient of dispersion or composition.
When using about monomer or polymer lateral chain, term " cation group " represents: when being dissolved or dispersed in aqueous carrier, have the organic group of clean positive charge, the preferably clean positive charge of pH dependent form.
Term " emulsion polymers " represents: the polymkeric substance formed by heterogeneous reaction mixture, and the initial form of described heterogeneous reaction mixture is for comprising the emulsion of water, emulsifying agent (such as, surfactant) and one or more monomers.As use alpha nerein, term " polymeric dispersions of coated pigment " refers to granules of pigments coated by polymer layer at least partly.This term can exchange with " pigment dispersion of polymer overmold " and use.
When using about non-soluble polymer, term " film forming " represents that the aqueous dispersion of polymkeric substance is (when needing, coalescing agent with suitable) can be formed on suitable base material or upholder, paint thin wet layer (such as, the wet layer of about 25 μm of thickness, and when needing, at temperatures greater than room temperature), and dry or harden in addition, to form continuous print coating in fact on base material or upholder.
Term " contrast ratio " represents by shrinking sheet (drawdownchart in LenetaCo.Form3B opaqueness, from BYK-GardnerUSA) black and white part top casting 51 μm (2 mil) dry thickness film, as L* is measured in definition in ASTMInternationalStandardsonColorandAppearanceMeasuremen t the 8th edition, and be used in the value that L* value that black part is measured measures divided by the L* value measured on white portion.
When using about the organic group in monomer or polymkeric substance, term " functional group " represents to be enable this monomer or polymkeric substance participate in chemical reaction or helps pigment suspension or dispersion group in the carrier.
Term " group " and " fragment " are used to distinguish those chemical species allowing to replace the chemical species that maybe can be substituted and do not allow maybe can not be so substituted.Therefore, when using term " group " to describe chemical substituents, described substituting group comprises unsubstituted group and has the group of O, N, Si or S atom (such as in chain (such as, as in alkoxyl group)) and have the group of carbonyl or other customary substituents.When using term " fragment " to describe chemical compound or substituting group, be only intended to comprise unsubstituted chemical substance or substituting group.Such as; phrase " alkyl " is intended to not only comprise pure open chain saturated hydrocarbon alkyl substituent (such as methyl, ethyl, propyl group, the tertiary butyl etc.), and comprises also with the alkyl substituent of other substituting groups known in the art (such as hydroxyl, alkoxyl group, alkyl sulphonyl, halogen atom, cyano group, nitro, amino, carboxyl etc.).Therefore, " alkyl group " comprises ether, haloalkyl, 4-nitro alkyl, carboxyalkyl, hydroxyalkyl, sulphoalkyl etc.On the other hand, phrase " alkyl moiety " is only limitted to comprise pure open chain saturated hydrocarbon alkyl substituent, such as methyl, ethyl, propyl group, the tertiary butyl etc.Term " alkyl group " covers term " alkyl moiety ", and the disclosure of any special groups is also intended to the respective segments specifically disclosing this special groups.
When the number about the atom between two organo-functional groups uses, term " between " refers to the atom number in the shortest path between described group, and does not calculate the atom of described group.
When using about polymkeric substance, term " latex " represents the emulsion of polymer beads in water, and wherein polymkeric substance self can not be dispersed in water; On the contrary, emulsion polymer needs the second emulsifying agent (such as, tensio-active agent) to form emulsion.This term and term " aqueous polymer dispersions " synonym commutative use.
When using about paint and other coating composition, term " low VOC " represents: the gross weight of coating based composition, coating composition contains the volatile organic compounds being less than about 1 % by weight, preferably be less than the volatile organic compounds of about 0.5 % by weight, be more preferably less than the volatile organic compounds of about 0.05 % by weight and be most preferably less than the volatile organic compounds of about 0.005 % by weight.
Term " monomer " represents: as required under the existence of suitable initiator or comonomer, can react to be formed to comprise 3 or more the polymkeric substance derived from the repeating unit of monomer or comonomer.
When using about latex, term " multistage " represents that this emulsion polymer utilizes dispersion (discrete) to dose two or more monomers and obtained, or doses two or more monomers and obtained with utilizing consecutive variations.Usually, when utilizing dsc measurement, multistage latex will not show single Tg flex point.Such as, the DSC curve utilizing dispersion to dose two or more monomers and obtained multistage latex can show two or more Tg flex points.In addition, two or more monomers are dosed with utilizing consecutive variations and the DSC curve of obtained multistage latex can not show Tg flex point.As further explanation, utilize a kind of monomer to dose or dose two or more monomers unchangeably and obtained single phase latex DSC curve only can show a Tg flex point.Once in a while, when only observing a Tg flex point, may be difficult to judge whether this latex represents multistage latex.In this case, sometimes lower Tg flex point can be detected after checking more accurately, or the synthetic schemes for the manufacture of latex can be checked to produce multistage latex to judge whether to be expected to.
When using about coating composition or pigment grind dispersion, term " pigment " represents the microparticle material giving composition or one or more colors of dispersion (comprising white or black) or other vision or the impact of performance.Term " pigment " includes but not limited to pigment extender, opacifying pigments, tinting pigment etc.As use alpha nerein, term " pigment extender " or " filler " refer to in coating composition with strengthening and inertia (the usually colourless and translucent) pigment reducing total cost." opacifying pigments " refers to one or more and joins in paint composite to make its opaque pigment.As use alpha nerein, term " opaque " represents: the contrast ratio of coating composition dry film under the build of 51 μm (2 mils) is higher than 95%.Usually, the specific refractory power of pigment extender is assumed that and is less than about 1.8, and the specific refractory power of opacifying pigments is assumed that and is greater than about 1.8.
When using about coating composition, term " pigment volume concentration (PVC) " or " PVC " represent the percent of total of the dry coatings volume that all pigment species occupy in coating.PVC can calculate according to following fraction: PVC=pigment volume/(pigment volume+non-pigment volume).
Term " polymer " " comprise both homopolymer and multipolymer (namely; the polymkeric substance of two or more different monomers), they contain two or more repeating units and its weight-average molecular weight (Mw) utilizing gel permeation chromatography and polystyrene standards to measure is minimum 500.
Term " preferably " and " preferably " refer to the embodiments of the present invention that can provide some benefit in some cases.But other embodiment also can be preferred in identical or other situation.In addition, one or more are described in detail in detail and preferred embodiment do not represent that other embodiment is unavailable, and and not intended to be gets rid of other embodiment from scope of the present invention.
When using about the component that can find in coating composition or pigment grind dispersion, term " does not contain in fact " and represents: the weight of coating based composition or pigment grind dispersion, comprises the component being less than about 1 % by weight.
When using about monomer, term " vinyl " represents the site with the olefinic nonsaturation (preferably, terminal ethylenic nonsaturation) of formula-CH=CH2-.
When using about coating composition or pigment grind dispersion, term " water type " represents that main carrier is water.
When using about pigment grind dispersion or coating composition, term " solvent-borne type " represents that main carrier is the mixture of non-aqueous solvent or non-aqueous solvent.
When using about polymkeric substance, term " water dispersible " represents: without the need to using independent tensio-active agent, polymkeric substance self can be dispersed in water, or can add water to form aqueous dispersion in polymkeric substance.Described aqueous dispersion polymers can comprise non-ionic type on polymer or ionic functional group to help to make polymkeric substance have water dispersible.For such polymkeric substance, usually need outside acid or alkali for ion stabilizedization, but not all like this in all cases.Such as, water-soluble composition (that is, highly hydrophilic polymer composition or system) does not need this type of stabilization.But these external acid are not the second emulsifying agents that the second emulsifying agent (such as, tensio-active agent) is such as used to form emulsion polymer emulsion.
When using about monomer or polymer lateral chain, term " amphoteric ion type " represents that monomer or polymer lateral chain have at least one anionic group and at least one cation group.
The numerical range that use side point is enumerated comprises all numerical value (such as, 1 to 5 comprise 1,1.5,2,2.75,3,3.80,4,5 etc.) contained within the scope of this.
Multiple granules of pigments can be used in disclosed dispersion, method and coating composition.Described particle provides scattering of light site in disclosed coating composition dry film, and gives dry film covering or opaqueness.The light scattering ability of pigment describes by its specific refractory power.Therefore, in one aspect, the ranges of indices of refraction of granules of pigments as herein described is wide, and from about 1.2 to about 2.7.Be not limited to theory, the specific refractory power of pigment extender is less than about 1.8 usually, and the specific refractory power of opacifying pigments will be greater than about 1.8.
Exemplary pigments particle comprises opacifying pigments particle such as treated or not processed mineral dye or its mixture, and such as metal oxide comprises the ferriferous oxide of titanium dioxide, multiple color (comprising black); Other oxide compound comprises zinc oxide, weisspiessglanz, zirconium white, chromic oxide and plumbous oxide; Vitriol, sulfide and composition thereof, comprise barium sulfate, zinc sulphide and lithopone; With sheet metal (flake) such as aluminum slice, pearl flake etc.Representative pigment can have various ways, when TiO 2 pigment, and such as rutile, anatase octahedrite and brookite form.Granules of pigments can have various shape and size, but desirably scattering has the photon of about 300nm to the wavelength of (in such as about 700nm to about 1000nm region of ultra-red, in about 380nm to about 700nm visible light region or its part or combination) in about 1000nm SPECTRAL REGION.The suitable shape of granules of pigments comprises spherical, such as regular spherical, oblate spherical, long ball shape and irregular spherical; Cube, such as regular cube and rhombus; Plate sample shape, comprises flat board, notch board and flange; And it is irregularly shaped.The particle with spherical form has about 5nm to about 5000nm ideally, the mean diameter of such as about 10nm to about 1000nm, about 100nm to about 500nm, about 200nm to about 300nm or about 220nm to about 280nm.The particle with non-spherical shape has up to about 1 micron, such as, up to about 500nm or the maximum diameter up to about 300nm ideally.Granules of pigments can comprise one or more coating or surface treatment, such as, inorganic or organic coating or surface treatment such as silicon-dioxide, aluminum oxide, zirconium white, hydrous titanium oxide, stannic oxide, zinc oxide, cerium oxide, phosphoric acid salt, nitrate, polyvalent alcohol, amine, amine salt, silicone, siloxanes and combination (such as silica dioxide coating and aluminum oxide coating layer) thereof.Granules of pigments can be not coated and unprocessed, but as described hereinly fully can be coated with and be can be used in exterior coating simultaneously compared to by not by the coating that so coated granules of pigments is made as the granules of pigments be wrapped by, need to fall low-level UV absorption agent, antioxidant or other weathering resistance additive.Suitable pigment is commercially available from multiple supplier, comprise BASF, LANXESSInorganicPigmentBusinessUnitofBayerCorp., CabotCorp, CibaSpecialtyChemicals, Clariant, FerroCorporation, ShepherdColorCompany, SunChemical and TomatecAmerica, Inc.Titanium dioxide pigment particles is preferred, it comprise prepared by chlorination process those, by standby those of sulfuration legal system and prepare with slurry or dry form those.Exemplary titanium dioxide pigment particles comprises the KRONOS from Kronos, Inc. tM1071,2020,2044,2090,2101,2102,2131,2160,2210,2310,4102,4310 and 4311, from the TIONA of MillenniumSpecialtyChemicalsInc. tM595 and 596i, from the TIPURE of E.I.duPontdeNemoursandCompany tMtS-6200, R-706, R-741, R-746, R-900, R-902+, R-931 and R-960, from the TRONOX of TronoxCorporation tMcR-813, CR-813S, CR-826, CR-826S, CR-828, CR-834 and CR-880, and from the product of other supplier, comprise BluestarNewChemicalMaterialsCo., Ltd., Hebei Chuan Hui Chemical Co., Ltd. (HebeiChuanghuiChemicalsCo., Ltd.), Henan Baililian Chemical Co., Ltd. (HenanBillionsChemicalsCo., Ltd.), IshiharaSangyoKaisha, Ltd., the graceful Chemical Co., Ltd. (NanjingHengsimanChemicalCo., Ltd.) of Nanjing Hensel, Pan Gangtai industry limited liability company (PangangTitaniumIndustryCo., Ltd.), QingdaoGracecorpCo., Ltd., SakaiChemicalIndustryCo., Ltd., Shanghai jumps river titanium white heavy chemicals company limited (ShanghaiYuejiangTitaniumChemicalManufacturerCo., Ltd.), Shijiazhuang section makes every effort to achieve new Chemical Co., Ltd. (ShijiazhuangKelichuangxinChemicalsCo., and Xuzhou Zhong Lian Chemical Co., Ltd. (XuzhouZhonglianChemicalTechnologyCo. Ltd.), Ltd.), with and composition thereof.
Disclosed pigment grind dispersion also can comprise multiple pigment extender or packing material comprises talcum, potter's clay, barite, carbonate, silicate and composition thereof.Exemplary this kind of material comprises Magnesium Silicate q-agent, calcium carbonate, pure aluminium silicate, silicon-dioxide and various clay.
If expected, disclosed pigment grind dispersion can comprise other pigment, comprises dyestuff, treated or not processed pigment dyestuff, glass and composition thereof.Exemplary this kind of material comprises various carbon black, azo pigment, Benzimidazolinone, carbazole (such as carbazole violet), indanthrone, isoindolinone, isoindoline (isoindolons), perylene, phthalocyanine, quinacridone, thioindigo red; Pigment dyestuff comprises plastic pigment such as solid bead pigment (such as, polystyrene or polyvinyl chloride bead) and comprise microballoon pigment (such as, United States Patent (USP) 4,427,835,4 of one or more hole and blister polymer beads, 920,160,4,594,363,4,469,825,4,468,498,4,880,842,4,985,064,5,5157,084,5,041,464,5,036,109,5,409,776 and 5,510, those described in 422).Other exemplary this kind of material comprises EXPANCEL tM551DE20 vinyl cyanide/vinylchlorid expanded beads (from ExpancelInc.), SIL-CEL tM43 glass microporous fillers (from SilbricoCorporation), FILLITE tM100 ceramic spherical particles (from TrelleborgFilliteInc.), SPHERICEL tMhollow glass ball (from PotterIndustriesInc.), 3M ceramic microsphere comprise G-200, G-400, G-600, G-800, W-210, W-410 and W-610 grade (from 3M), 3M hollow microsphere comprises 3MPerformanceAdditivesiM30K (equally from 3M), INHANCE tMuH1900 polyethylene particle (from Fluoro-SealInc.) and BIPHOR aluminum phosphate (from BungeFertilizantesS.A., Brazil).
The consumption of pigment be enough to provide under the coat-thickness level expected adequate colouration, the coating composition of suitable opaque solidification if necessary, such as reach the pigment volume concentration (PVC) (PVC) of about 0.25 to about 95 volume percent.Under the PVC value of multiple expectation, granules of pigments can improve the opaqueness or opacifying property of prepared coating composition.Preferably, the PVC of disclosed coating composition is about 5%-about 85%, and is more preferably about 10%-about 60%.
Disclosed pigment grind dispersion manufactures by disclosed granules of pigments, polymeric dispersant, carrier and optional tensio-active agent being blended together.Do not want to be bound by any theory, Ginding process can comprise makes granules of pigments loose (such as, caused by the shearing force in the pigment grind dispersion of stirring or other stress), and polymeric dispersant can help to soak new surface of pigments region, for electrostatically (or otherwise) exposed makes loose particle stabilization and prevent or stop them again coalescent.Therefore, polymeric dispersant can promote more effectively to utilize granules of pigments and improves the degree of described particle refracted light and make the opaque degree of disclosed coating composition.Polymeric dispersant can be such as mass polymer, solution polymer or aqueous dispersion polymers or aqueous polymer dispersions, and can such as by under the existence of initiator, make the ethylenically unsaturated monomer in suitable carrier, and the polymerization of mixtures of the unsaturated amphoteric ion type monomer of olefinic manufactures.Polymeric dispersant can such as account for Opacifying pigment particle weight at least about 0.1 % by weight, at least about 0.2 % by weight, at least about 0.3 % by weight or at least about 0.5 % by weight, and at the most about 25 % by weight, at the most about 10 % by weight, at the most about 5 % by weight or at the most about 2 % by weight.
Multiple olefinic unsaturated amphoteric ion type monomer can be used to form disclosed polymeric dispersant.Olefinic unsaturated amphoteric ion type monomer can comprise one or more (and preferably, one) ethylenically unsaturated group, preferred terminal ethylenyl groups.Olefinic unsaturated amphoteric ion type monomer also can comprise one or more (and preferably, one) anionic group and one or more (and preferably, one) cation group.Anionic group and cation group provide side chain for amphoteric ion type polymkeric substance, and wherein every bar side chain comprises anionic group in polymeric dispersant and cation group; And can the wetting and stabilization of auxiliary polyalcohol dispersion agent as mentioned above.In presence of water, Exemplary anionic group forms negatively charged ion.The limiting examples of anionic group comprises acid or anhydride group, sulfate group (the such as ,-OSO of neutralization 3 -), sulfonic acid group (such as ,-SO 2o -), phosphate group (such as ,-PO 4 2-), phospho acid group (such as ,-POO -), phosphonyl group (such as ,-PO 3 -) or hydroxy-acid group (such as ,-COO -).In presence of water, Exemplary cationic group forms positively charged ion.The limiting examples of cation group comprises quaternary ammonium group (such as ,-NH 3+,-NH 2r1+ or-NHR1R 2+, wherein R1 and R2 is organic group), quaternary phosphine group (such as ,-PR1R2R 3+, wherein R1, R2 and R3 are organic groups) or uncle (tertiary) sulfate group (such as ,-SR1R 2+, wherein R1 and R2 is organic group).In the monomer of amino-contained, add water usually amido can not be converted into quaternary ammonium cation, the monomer therefore only comprising positively charged ion and this kind of amido can not be considered amphoteric ion type monomer.The unsaturated amphoteric ion type monomer of exemplary olefinic comprises sultaine (methyl) acrylate, phosphoric acid ester trimethyl-glycine (methyl) acrylate and carboxylic acid trimethyl-glycine (methyl) acrylate, and (No. CAS is 3637-26-1 to comprise sultaine methacrylic ester, have another name called 3-dimethyl (methylacryoyloxyethyl) amino propane sulfonic acid ester, N-(3-sulfopropyl)-N-(methylacryoyloxyethyl)-N, N-dimethylamino trimethyl-glycine) or [2-(methacryloxypropyl) ethyl] dimethyl-(3-sulfopropyl) amino hydroxylate)), 2-methylacryoyloxyethyl Phosphorylcholine (No. CAS is 67881-98-5), with those as described in U.S. Patent Application Publication No.US2011/0137001Al (people such as Prat) of the monomer with betaine group, comprise the commercially available monomer from Raschig mERSPE, mERSPP, mERSPDA and mERSPV.Also the mixture of the unsaturated amphoteric ion type monomer of olefinic can be utilized.Olefinic unsaturated amphoteric ion type monomer such as can account at least about 0.5 % by weight and at the most about 99.5 % by weight of disclosed polymeric dispersant.
In one embodiment, disclosed polymeric dispersant can be formed by various of monomer, and described monomer comprises hydrophobicity or hydrophilic monomer.The unsaturated hydrophobic monomer of multiple olefinic can be used to form disclosed polymeric dispersant.The unsaturated hydrophobic monomer of olefinic can comprise one or more (and preferably, comprising one) ethylenically unsaturated groups, preferred terminal ethylenyl groups.The unsaturated hydrophobic monomer of olefinic also comprises one or more (and preferably, comprising one) hydrophobic groups, and it does not preferably comprise hydrophilic radical.Hydrophobic group is provided in the hydrophobic polymer side chain in polymeric dispersant.Exemplary hydrophobic group comprises alkyl, aryl, fatty acid residue, fluorocarbon and the silicone compounds with 3 or more carbon atoms.The unsaturated hydrophobic monomer of exemplary olefinic comprises methacrylic acid n-propyl ester, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacrylic acid tertiary butyl ester, methacrylic acid 2-(ethyl hexyl) ester, isodecyl base ester, vinylbenzene, vinylbenzene (such as, the Vinyl toluene be substituted, alpha-methyl styrene, p-methylstyrene, p-tert-butylstyrene and Vinylstyrene), allylic cpd (such as, diallyl phthalate and 2,4,6-, tri-allyloxys-1,3,5-triazines), lauryl methacrylate, methacrylic acid stearyl-ester, methacrylic acid mountain Yu base ester, methacrylic acid trimethylcyclohexyl, cyclohexyl methacrylate, t-butyl cyclohexyl base ester, IBOMA, t-butyl cyclohexyl base ester, phenyl methacrylate, benzyl methacrylate, its acrylate counterpart and composition thereof.The unsaturated hydrophobic monomer of olefinic such as can account at least about 0.5 % by weight and at the most about 99.5 % by weight of disclosed polymeric dispersant.
The unsaturated hydrophilic monomer of multiple olefinic can be used to form disclosed polymeric dispersant.The unsaturated hydrophilic monomer of olefinic can comprise one or more (and preferably, a kind of) ethylenically unsaturated groups, preferred terminal ethylenyl groups.The unsaturated hydrophilic monomer of olefinic also comprises one or more (and preferably, a kind of) hydrophilic radical, such as acidic-group, amino or ethylene oxide groups.Hydrophilic radical provides the side chain of the hydrophilic polymer in polymeric dispersant, and can improve the water-soluble of polymeric dispersant, or can the wetting and stabilization of auxiliary polyalcohol dispersion agent as mentioned above.Exemplary acidic hydrophilic group comprises carboxyl (such as ,-COOH), alkylsulfonyl (such as ,-S (=O) OH) and organophosphorus (such as ,-P (=O) OH2) group and salt thereof and ester.Exemplary ethylenic unsaturated acid monomer comprises vinylformic acid, methacrylic acid, methylene-succinic acid, 2-sulfoethyl (methyl) acrylate, sulfopropyl (methyl) acrylate, styrene sulfonic acid, vinyl sulfonic acid and salt thereof and ester.The ester of exemplary unsaturated acid monomer by making unsaturated acid and there is the straight chain of one or more (such as 1-18) carbon atoms, ring-type or aromatic alcohol or polyvalent alcohol or derivatives thereof react and formed, or by making unsaturated alcohol and there is the straight chain of one or more (such as 1-18 is individual) carbon atoms, ring-type or aromatic carboxylic acid or polyprotonic acid or derivatives thereof reacts and formed.The salt of exemplary unsaturated acid monomer comprises an alkali metal salt and ammonium salt.Exemplary amide group comprises acrylamide (such as ,-C (=O) NH2) group.Exemplary olefinic unsaturated acyl amine monomers comprises 2-(methyl) acrylamide-2-methyl propane sulfonic acid, Methacrylamide, methoxymethyl acrylamide, methoxy methyl butylmethacrylamide and n-butoxy methyl methacrylamide.The mixture of the unsaturated hydrophilic monomer of olefinic can also be used.The unsaturated hydrophilic monomer of olefinic such as can account for about 0 % by weight-Yue 90 % by weight of disclosed polymeric dispersant.
If expected, other ethylenically unsaturated monomer of appropriate amount (such as, vinyl cyanide, Vinyl Ether and those of ordinary skill in the art are familiar with other monomer) can be used to form polymeric dispersant.Can also use and not provide the monomer of polymer lateral chain as discussed above to form disclosed polymeric dispersant, condition is that monomer comprises by the adorned precursor unit of post-polymerization to provide polymer lateral chain as discussed above.Such as, U.S. Patent Application Publication No.US2011/0137001Al mentioned above describes the post polymerization beet alkalization that can be used to provide the polymer lateral chain group that will obtain, and it utilizes above-mentioned amphoteric ion type monomer.Apparent for those of ordinary skills for providing other post-polymerization of other polymer lateral chain group as discussed above.
Polymeric dispersant can be formed under the existence of one or more optional chain growth polymerization starters (that is, catalyzer).Exemplary initiator comprises other initiator that hydroperoxide, persulphate, peroxide and azo derivative and those of ordinary skill in the art are familiar with.Exemplary hydroperoxide initiators includes but not limited to cumene hydroperoxide, tert-butyl hydroperoxide, hydrogen peroxide etc.Exemplary persulfate initiator includes but not limited to Sodium Persulfate, Potassium Persulphate, ammonium persulphate etc.Exemplary peroxy initiator comprises t-butyl peroxy 2-ethylhexanoate, two-tert-butyl peroxide, two-cumyl peroxide, t-amyl peroxy compound, cumene hydroperoxide, two-n-propyl peroxydicarbonate, tert-pentyl peracetic acid ester etc.Exemplary azo initiator comprises 2,2-azo two (2-methyliso-butyronitrile), 2,2-azos two (2-methylbutyronitrile), 2,2-azo two (2,4-methyl pentane nitrile), 2,2-azos two (2,4-dimethyl-4-oxyethyl group valeronitrile) etc.
The technology be familiar with by utilizing those of ordinary skill in the art makes the unsaturated amphoteric ion type of olefinic and non-amphoteric ion type monomer copolymerization to prepare polymeric dispersant.The amount of adjustable often kind of monomer is to provide performance and the further feature of expectation, and wherein at least part of is preferred derived from the polymeric dispersant in one or more vinylbenzene, acrylate or methacrylic ester.Polymeric dispersant forms (or can with one or more solvents or carrier combinations) usually in one or more solvents or carrier.Exemplary solvent or carrier comprise ester class, such as ethyl acetate and butylacetate; Ketone, such as methyl ethyl ketone, methyl iso-butyl ketone (MIBK), methyl-n-amyl ketone and acetone; Alcohols, such as methyl alcohol, ethanol, Virahol and butanols; Glycols, such as ethylene glycol and propylene glycol; Ethers, such as tetrahydrofuran (THF), ethylene glycol monobutyl ether and propylene glycol monomethyl ether; With ether acetic acid ester such as propylene glycol methyl ether acetate, the ethylene glycol monomethyl ether acetate etc. of mixing.In one aspect, when polymeric dispersant comprises aqueous polymer dispersions or water soluble polymer dispersions, carrier or solvent can be water.In some pigment grind dispersion embodiments (such as, in some solvent-borne type embodiments), polymeric dispersant is solution polymer, its acid number such as higher than about 2, higher than about 5, higher than about 10 or higher than about 20.In other pigment grind dispersion embodiment (such as, in some water type embodiments), polymeric dispersant is water dispersible (former state or by adding appropriate neutralizing agent) and its acid number can be such as 0 or higher than about 20, higher than about 30, higher than about 50 or higher than about 100.Acid number also can such as up to about 700, lower than about 500 or lower than about 300.Polymeric dispersant also can be made into solution polymer, then use in water type coating composition, this realizes by the following: polymer solvent is replaced into water after solution polymerization completes to promote mixed polymer dispersion agent and granules of pigments subsequently in aqueous carrier; Or realize by the following: polymkeric substance and polymer solvent separate by the technology that utilizes those skilled in the art to be familiar with (such as, polymkeric substance being precipitated in non-solvent, then dissolution precipitation thing again in aqueous phase carriers).
Polymeric dispersant can have various molecular weights.Preferably, molecular weight is enough low to make polymkeric substance have low viscosity and good pigment wetting feature.The weight-average molecular weight of polymeric dispersant (utilizing cohesion permeation chromatography and polystyrene standards to measure) can such as higher than about 500, higher than about 2000, higher than about 5000 or higher than about 7000.Weight-average molecular weight also can such as lower than about 200000, lower than about 50000, lower than about 20000, lower than about 10000 or lower than about 8000.Express with weight basis, pigment grind dispersion such as can comprise the carrier of the pigment of about 5 % by weight-Yue 80 % by weight, the polymeric dispersant of about 0.01 % by weight-Yue 10 % by weight and about 10 % by weight-Yue 70 % by weight.But these amounts depend on that many factors comprises the type of pigment, density, surface-area and oil-absorption(number).
The technology that those of ordinary skill in the art can be utilized to be familiar with is to merge granules of pigments and polymeric dispersant.Preferably, they in the carrier of the final carrier by the coating composition become for completing, merged in the mixture being commonly called " abrasive material ".If expected, abrasive material can comprise grinding medium and promote other component or the composition of pigment size reduction and dispersion.Grinding optionally comprises the monomer that one or more are used to the granules of pigments of coated dispersion the most at last, or this kind of monomer can add after granules of pigments has been dispersed in abrasive material.
Once obtain suitable pigment particle size and degree of scatter, next with coated pigment particle at least in part of the polymer layer disclosed in one or more.In one aspect, one or more polymer layers can be chain growth polymer layers.In yet another aspect, one or more polymer layers can be step growth polymerization nitride layer.
In one embodiment, when polymer layer is chain growth polymkeric substance, by by one or more ethylenically unsaturated monomers (such as, monomer as discussed above) and radical initiator is (such as, initiator as discussed above) and carrier extra if necessary or other carrier are (such as, carrier as discussed above) be included in or join in pigment grind dispersion, to form the dispersion of coated pigment, thus it is coated to carry out local expediently.Exemplary olefinic unsaturated monomer for the formation of one or more chain growth polymer layers comprises vinylbenzene, acrylate and methacrylic ester, such as but not limited to, vinylbenzene, vinylbenzene (such as, the Vinyl toluene be substituted, alpha-methyl styrene, p-methylstyrene, p-tert-butylstyrene, Vinylstyrene etc.), methyl methacrylate (MMA), β-dimethyl-aminoethylmethacrylate, HEMA (2-HEMA), methylacryoyloxyethyl phosphoric acid ester, methacrylic acid sulfoethyl ester, methacrylic acid n-propyl ester, isopropyl methacrylate, methacrylic acid 2-hydroxypropyl ester, n-butyl methacrylate, isobutyl methacrylate, methacrylic acid tertiary butyl ester, 4-hydroxybutyl methacrylate, methacrylic acid 2-(ethyl hexyl) ester, isodecyl base ester, lauryl methacrylate, methacrylic acid stearyl-ester, methacrylic acid mountain Yu base ester, ethylene glycol dimethacrylate (EGDMA), TEGDMA (TEGDMA), polypropylene glycol dimethacrylate (PPGDMA), dipropylene, 1,3-and BDO dimethacrylate (Isosorbide-5-Nitrae-butanedioldimethacrylate), polyethylene glycol dimethacrylate (PEGDMA), 1,3-butylen glycol dimethacrylate (1,3-butyleneglycoldimethacrylate), HDDMA (HDDMA), trimethylolpropane trimethacrylate (TMPTMA), tetra methylol propane trimethyl acrylic ester, acetoacetoxyethyl methacrylic ester (AAEM), glycidyl methacrylate, methacrylic acid trimethylcyclohexyl, cyclohexyl methacrylate, t-butyl cyclohexyl base ester, isobornyl methacrylate, t-butyl cyclohexyl base ester, phenyl methacrylate, methylpropenyl benzyl ester, its acrylate counterpart and composition thereof.Extra Exemplary olefinic unsaturated monomer comprises acrylic amide and vinyl cyanide such as, Methacrylamide, methoxymethyl acrylamide, methoxy methyl butylmethacrylamide, n-butoxy methyl methacrylamide, methacrylonitrile etc.In some embodiments, desirably, chain growth polymer layer at least partly derived from one or more lipid acid (methyl) acrylate, such as based on starting olefinic unsaturated monomer at the most about 25 % by weight one or more lipid acid (methyl) acrylate.Preferably, chain growth polymer layer is emulsion polymer (such as, single phase or multistage emulsion polymer).
In one embodiment, when polymer layer is step growth polymerization thing, by one or more can be included in or join in pigment grind dispersion by the highly functional reactive monomer or oligomer progressively growing formation polymkeric substance, to provide the dispersion of coated pigment, thus it is coated to carry out local expediently.Illustrative polymers as described herein by progressively growing formation is drawn together but is not limited to the reaction product of one or more diprotic acid and one or more polyhydroxy-alcohols, described diprotic acid such as succsinic acid, hexanodioic acid, sebacic acid, dimeracid, maleic anhydride, Tetra hydro Phthalic anhydride, m-phthalic acid, terephthalic acid and analogue, described polyhydroxy-alcohol (such as, dibasic alcohol, trivalent alcohol, tetravalent alcohol etc.) such as but not limited to ethylene glycol, Diethylene Glycol, triethylene glycol, trimethylene glycol, dipropylidene diol, three trimethylene glycols, 1,2-PD, 1,3-PD, 1,2-butyleneglycol, 1,3 butylene glycol, BDO, 2,3-butanediol, 2-methyl isophthalic acid, 2-propylene glycol, 1,5-PD, 2-methyl-2,3-butanediol, 1,6-hexylene glycol, 1,2-hexylene glycol, 2,5-hexylene glycol, 2-methyl-2,4-pentanediol, Pinacol, 2-ethyl-hexylene glycol, 1,2-ethohexadiol, 1,2-decanediol, 2,2,4-neopentyl glycol, 2-butyl-2-ethyl-1,3-PD, 2,2-diethyl-1,3-PD, glycerine, TriMethylolPropane(TMP), tetramethylolmethane etc.Modified further by the reaction with one or more aromatic diisocyanate, aliphatic series or alicyclic diisocyanate, polyisocyanates therefrom etc. by progressively growing these formed polymkeric substance.
In one preferred embodiment, the polymer layer of at least one formation as described herein be binder for film formation and granules of pigments coated at least partly at room temperature from coalescent and without the need to the existence of another kind of binder for film formation and the coalescing aid of VOC without the need to measuring containing undesirable (objectionable).
Multiple method can be utilized to comprise U.S. Patent No. 5,171, those described in 772 (people such as Hoy), carry out form layers.The calculated thickness of one or more polymer layers can be such as about 10nm to about 400nm, and pigment particle size is depended on to a certain extent in the interval expected.Such as, be the titanium dioxide granule of 250nm for average particle size particle size, desirably, the thickness of coated polymer layer is about 100nm, with between titanium dioxide granule maintain be spaced apart the lowest wavelength of visible ray at least about 1/2nd (that is, minimum about 200nm).
The dispersion of the coated pigment produced optionally combines with one or more tackiness agents or one or more coating adjuvants (such as, thickening material, rheology modifier, tensio-active agent or coalescing agent) with the coating formed.Exemplary tackiness agent is well known to those of ordinary skill in the art, and can various ways be had, comprise emulsion polymer and solution polymer, such as acrylic copolymer, styrene/acrylic acid co-polymer, vinyl acetate copolymer, vinyl-acetic ester/acrylic copolymer, tertiary ethylene carbonate/acrylic copolymer, ethylene/vinyl acetate, styrene/butadiene copolymers, alkyd, polyester, polyester urethane, the polyester that drying oil-modified polymkeric substance is such as drying oil-modified and urethane, polyethers, polymeric amide, epoxy ester, polyureas, urethane, polysiloxane, silicone, fluorinated copolymers is vinylidene fluoride such as, with the blend of any above-mentioned polymer binder.Tackiness agent can comprise polycomponent (such as, two-pack) one or more components of reaction system, such as, the component of isocyanate-polyol amine, isocyanate-polyol, epoxy-polyamine, carbodiimide-polyprotonic acid, ethylenimine-polyprotonic acid, trimeric cyanamide-polyvalent alcohol or urea aldehyde-polyvalent alcohol coating system.Tackiness agent such as can account for about 5 volume %-about 99 volume % of dry coatings volume.Volume solid content is defined as the volume fraction of dry ingredients in supplied coating composition, and it such as can account for about 5 volume % of coating composition to about 80 volume %.Pigment volume concentration (PVC) is defined as the volume fraction of pigment in dry-coated material, and it such as can account for about 0.1 volume % of base coating to about 95 volume %.In some embodiments, pigment volume concentration (PVC) is desirably about 0.1 volume % to about 30 volume %, about 0.5 volume % to about 25 volume % or about 1 volume % to about 25 volume %.The second-order transition temperature of polymer binder can be such as about-130 DEG C to about 350 DEG C, preferably about-20 DEG C to about 150 DEG C, more preferably about-10 DEG C to about 100 DEG C.Utilize BROOKFIELD tMviscometer and with 20rpm run RTVSpindleNo.4 measure the viscosity of coating composition at 25 DEG C can be such as about 10-100000cps.
Described thickening material, rheology modifier, tensio-active agent and coalescing agent are well known to those of ordinary skill in the art.Exemplary thickening material or rheology modifier comprise precipitating inhibitor, hydrophobic ethoxylated urethane resin (HEUR) thickening material, hydrophobically modified, caustic solubility or alkali swelling emulsion (HASE) thickening material, cellulose thickener, polysaccharide thickening material and composition thereof.Exemplary commercially available rheology modifier comprises the NATROSOL from Ashland tM250 and AQUAFLOW tMseries, from the ATTAGEL of BASFCorp. tM50, from the CELLOSIZE of DowChemicalCo. tMseries and UCARPOLYPHOBE tMt-900 and T-901, from the BENTONE of ElementisSpecialties tMaD and BENTONEEW, LATTICE from FMCBiopolymer tMnTC-61, and all from the ACRYSOL of Rohm & Haas tMrM-6, ACRYSOLRM-8, ACRYSOLRM-12W and ACRYSOLRM-2020NPR.When there is thickening material or rheology modifier, based on final coating composition weight, disclosed coating composition preferably comprises thickening material or the rheology modifier of about 0.1 % by weight-Yue 10 % by weight or about 0.5 % by weight-Yue 3 % by weight.
Exemplary tensio-active agent comprises anionic, anionic, both sexes and nonionic surface active agent.Commercially available tensio-active agent or dispersion agent comprise the TAMOL from DowChemicalCo. tMseries, from the nonyl of DowChemicalCo. and octylphenol ethoxylate (such as, TRITON tMx-45, TRITONX-100, TRITONX-114, TRITONX-165, TRITONX-305 and TRITONX-405) and from the nonyl of other supplier and octylphenol ethoxylate (such as, T-DETN series from HarcrosChemicals), from DowChemicalCo., ElementisSpecialties, Inc. with alkylphenol ethoxylate (APE) substitute of other supplier, from the SURFYNOL of AirProductsandChemicals, Inc. tMeach member of series (such as, SURFYNOL104, SURFYNOL104A, SURFYNOL104BC, SURFYNOL104DPM, SURFYNOL104E, SURFYNOL104H, SURFYNOL104PA, SURFYNOL104PG50, SURFYNOL104S, SURFYNOL2502, SURFYNOL420, SURFYNOL440, SURFYNOL465, SURFYNOL485, SURFYNOL485W, SURFYNOL82, SURFYNOLCT-211, SURFYNOLCT-221, SURFYNOLOP-340, SURFYNOLPSA204, SURFYNOLPSA216, SURFYNOLPSA336, SURFYNOLSE and SURFYNOLSE-F), from 3M, E.I.DuPontdeNemoursandCo. with the various Fluorocarbon surfactants of other supplier, and from Ashland, the phosphoric acid ester of Rhodia and other supplier.When a surfactant is present, based on total composition weight, disclosed coating composition preferably comprises about 0.1 % by weight-Yue 10 % by weight and the tensio-active agent of more preferably about 1 % by weight-Yue 3 % by weight.
Coalescing agent can contribute to making coated granules of pigments or other optional film-forming polymer be agglomerated into continuous print film.Exemplary coalescing agent comprises benzoic ether such as alkyl benzoate, mono benzoate and dibenzoate; Capronate, such as, from the OPTIFILM of EastmanChemicalCo. tM400 3 (ethylene glycol) two (2-ethylhexanoate); Dioctyl maleate; Oleic acid propylene glycol ester, such as, from the EDENOL of Cognis tMeFC-100, it has formula HOCH (CH 3) CH 2oC (O) (CH 2(CH=CH (CH 2) 7cH 3); From UCARFilmerffiT, UCAR n propyl propionate of DOWChemicalCo., UCAR n-butyl propionate and UCAR n-pentyl propionate; With the TEXANOL from EastmanChemicalCo. tMester alcohol; In U.S. Patent No. 6,762,230B2,7,812,079B2 and 8,110, in 624B2 (collective belongs to the people such as Brandenburger) and in U.S. Patent No. 8,106,239B2 (people such as Zhou) and 8, the material discussed in the patent application case No.US2009/0149591Al that announces in 394,496B2 people such as () Foster, in U.S. such as () Yang; Its mixture etc.Other coalescing agent that can join in water type embodiment comprises VOC, comprises glycol ethers, organic ester, aromatic substance and ethylene glycol or trimethylene glycol.When there is coalescing agent, based on final coating composition weight, disclosed coating composition preferably comprises the coalescing agent of about 0.05 % by weight-Yue 10 % by weight or about 0.05 % by weight-Yue 5 % by weight.
Disclosed coating composition can comprise other adjuvant that multiple those skilled in the art are familiar with.Representational adjuvant is people such as Koleske, and PaintandCoatingsIndustry, in April, 2003, describes in the 12 to 86 page.Exemplary adjuvant and commercial example thereof comprise adhesion promotor; Anticrater agent; Antioxidant; Biocide, mycocide, mould inhibitor and sanitas are (such as, from the BUSAN of BuckmanLaboratories, Inc. tM1292, from the NOPCOCIDE of Cognis tMn-40D, KATHON from Rohm & Haas tMlX and the POLYPHASE from TroyCorporation tM663, POLYPHASE678 and POLYPHASEPW-40); Buffer reagent; Solidification indicator; Defoamer; Thermo-stabilizer; Wetting agent; Levelling agent; (such as, hindered amine as light stabilizer, such as, from the TINUVIN of CibaSpecialtyChemicals for photostabilizer tM123-DW and TINUVIN292HP); Optical brightener; Pearling agent (pearlescent); Fluidizer; Polymeric additive; Reactive thinner; Tackifier; UV light absorber (such as, from TINUVIN234 and TINUVIN1130 of CibaSpecialtyChemicals); Wax is (such as, from the AQUACER of Altana tM593, from the HYDROCER of ShamrockTechnologies, Inc. tM303 and MICHEM from Michelman, Inc. tMemulsion 32535); Wetting agent is (such as, from the BYK of Altana tM346 and BYK348, PENTEX from Rhodia tM99 and TROYSOLLAC from Troycorporation tM) etc.Type and the amount of these and other adjuvant are typically empirically selected.
The dispersion of coated pigment is preferably general dispersion, and its vehicle and other composition make them be applicable in solvent-borne type and water type coating composition.The dispersion of coated pigment can be used to form or can be added in multiple coating composition, and described coating composition comprises priming paint, surfacer (primersurfacers), finish paint (comprising single coating) and basic unit's paint (basecoat) for varnish/basic unit's paint facing.These coating compositions can comprise linking agent, comprise the isocyanic ester of end-blocking, alkylating trimeric cyanamide, polyisocyanates, epoxy resin etc., and these coating compositions can be solvent type or water type.Various kinds of media thing or carrier can be used in solvent-borne type or water type embodiment.Exemplary solvent and carrier comprise above-mentioned those.Disclosed coating composition is low VOC dispersion preferably, it comprises, based on total liquid composition weight, 0.01 % by weight to be less than 5 % by weight VOC, more preferably 0.01 % by weight to be less than 2.5 % by weight VOC, most preferably 0.01 % by weight to the VOC being less than 0.5 % by weight.
Disclosed coating can be coated on multiple base material.Exemplary base material comprises cement, cement fibrolite plate, concrete, metal, plastics and timber (comprising monoblock timber, composite wood and veneer(ed) wood).Multiple measurement can be utilized to assess paint and the staining agent of drying or sclerosis, and described measurement comprises adhesivity (such as utilizing ASTMD3359-07 to measure), resistance to caking (such as utilizing " ASTMD4946-89 reviews for 2003 " to measure), efflorescence (such as utilizing ASTMD4214-07 to measure), cracking (such as utilizing ASTMD661-93 to measure), contrast ratio (CR measures as mentioned above), incrustation (such as utilizing ASTMD3719-00 to measure), fade or variable color (such as utilizing ASTMD2244-11 to measure), gloss or loss of gloss (such as utilizing ASTMD523-08 to measure), shock-resistance (such as utilizing " ASTMD2794-93 reviews for 2010 " to measure), low temperature coalescent (LTC such as utilizes ASTMD3793-06 to measure), pendulum hardness (such as utilizing ASTMD-4366-95 to measure), scrub test (such as utilizing ASTMD2486-06 to measure), actual washability (such as utilizing ASTMD4828-94 to measure), tinctorial strength (TS such as utilizes ASTMD-2066-07 to measure), water tolerance (such as utilizing ASTMD870-09 to measure) or the measurement standard (such as described in ASTMD3730-10 and ASTMD5324-10 those) collected.
Further describe the present invention in the examples below, wherein unless otherwise noted, otherwise all numbers and per-cent are all by weight.
Abbreviation
BA n-butyl acrylate
MMA methyl methacrylate
MAA methacrylic acid
AA vinylformic acid
AAm acrylamide
DMAEMA dimethylaminoethyl methacrylic ester
BzCl benzyl chloride
SBMA sultaine methacrylic ester
DMAEMA-BzCl dimethylaminoethyl methacrylic ester benzyl chloride quaternary amine
APS ammonium persulphate
MEK methyl ethyl ketone
NVM non-volatile matter in mass (percentage of solids)
2ME2-mercaptoethanol
TBHP tert-butyl hydroperoxide (70% aqueous solution)
FF6BRUGGOLITE tMfF6 (from BruggemannChemical)
Preparative Example 1
The preparation of amphoteric ion type copolymer dispersant aqueous dispersion
The deionized water of a 173.92g and 1.94gRhodacalDS-4 are joined and is equipped with in four neck 2L flasks of condenser, mechanical agitating vane, purging with nitrogen gas adapter and thermopair and is heated to 82 DEG C.At such a temperature and when stirring under a nitrogen, join in reaction flask by pre-for 28.93g monomer emulsion, the pre-emulsion of this monomer comprises 49.61g deionized water, 8.01gRhodacalDS-4,72.78gBA, 121.29gSBMA, 36.39gMAA and 1.21g2ME.After 2 minutes, in flask, add the premixture of 10.0g deionized water and 2.43gAPS.At 81-82 DEG C, the content of stirred flask continues 20 minutes, is then added in reaction vessel by pre-for remaining monomer emulsion with uniform rate through the process of 62 minutes.After the pre-emulsion charging of monomer completes, use the 10.0g pre-emulsion beaker of deionized water rinsing monomer and feed-pipe.Then, keep the constant temperature of the content of reaction flask to stir for 18 minutes simultaneously.Then, in reaction flask, add 0.33gtBHP, and then add the premixture of 10.0g deionized water and 0.25gFF6.Add latter 17 minutes for the last time, make a batch cooling.Measure produce product NVM be 48.1%.
Preparative Example 2
Amphoteric ion type monomer sultaine methacrylic ester (SBMA)
In 200mLErlenmeyer flask, at room temperature merge 30.01gDMAEMA and 30.03gMEK.In ice bath, cool produced solution continue 10 minutes, once add 23.27g1 subsequently, 3-propane sultone.In ice bath, cooling reaction continues other 20 minutes, then makes it be warming up to room temperature gradually.Reaction flask is kept to uncap.After 2 hours, product precipitates, is then collected by filter paper.Product S BMA is transferred in aluminium foil ship also dry.
Preparative Example 3
Hydrophobic water-soluble monomer DMAEMA-BzCI
In 200mLErlenmeyer flask, 40.03gDMAEMA, 32.27gBzCl and 40.07gMEK are merged into portion.Stir the mixture that produces and be heated to about 40-50 DEG C and continue 2 hours, then stay overnight at room temperature.On filter, the product D MAEMA-BzCl of collecting precipitation is also dry.
Preparative Example 4
Amphoteric ion type copolymer dispersant is prepared in water
The deionized water of a 100.45g is joined and is equipped with in four neck 1L stills of condenser, mechanical agitating vane, purging with nitrogen gas adapter and 2 hole rubber septums.30 minutes are continued with purging with nitrogen gas still at 91 DEG C.At this temperature and mechanical stirring, added through 31 minutes the monomer solution be made up of 6.01gDMAEMA-BzCl, 10.00gSBMA, 3.03gMAA, 0.10g2ME, 0.20gAPS and 50.04g deionized water.The additional solution be made up of 0.15gAPS and 9.89g deionized water is added through 11 minutes.Reaction mixture is remained on 90 DEG C and continue other 100 minutes to remove excessive initiator.Measuring NVM is 11.30%.
Embodiment 1
The preparation of titanium dioxide dispersion
Following preparation titanium dioxide dispersion: add 500.0gTI-PURE gradually in the aqueous solution that 5 points of clockwise stir tMr706 titanium dioxide, described aqueous solution is containing useful 125.3g deionization water-reducible 21.8g Preparative Example 1 amphoteric ion type copolymer dispersant aqueous dispersion.This mixture of high-speed stirring continues other 30 minutes, is then diluted to 73%NVM with 51.5g deionized water, to produce the titanium dioxide slurry containing 71.57 % by weight titanium dioxide and 1.43 % by weight copolymer dispersants.
Embodiment 2
The preparation of titanium dioxide dispersion
Prepare titanium dioxide grinding distribution body as follows: in the aqueous solution that 5 points of clockwise stir, add 750.30gTI-PURE gradually tMr706 titanium dioxide, described aqueous solution is containing useful 191.55g deionization water-reducible 109.49g Preparative Example 4 polymer dispersed agent solution.This mixture of high-speed stirring continues other 60 minutes, to produce the titanium dioxide slurry containing 71.4 % by weight titanium dioxide and 1.14 % by weight polymeric dispersants.
Embodiment 3
The formation of coated titanium dioxide latex
The titanium dioxide slurry obtained in embodiment 1 by 470.53g is transferred in 2L still also with 189.77g deionized water and 25.65gRHODACAL tMdS-4 surfactivity dilution agent.Still is heated to 50 DEG C, adds the sodium feredetate solution of 0.18gtBHP and 0.15g7% subsequently.Then, added the first monomer emulsion containing 11.74g deionized water, 37.69gBMA, 25.96gMMA, 1.36gMAA, 0.90gtBHP and 12.83gRhodacalDS-4 tensio-active agent through 20 minutes and added through 120 minutes and the reductive agent mixture deposited.Reductive agent mixture is included in the 2.49gFF6 reductive agent in 81.25g deionized water.With 10.0g deionized water rinsing first monomer emulsion, and then add second comonomer emulsion, second comonomer emulsion comprises 150.77gBA, 106.53gMMA, 2.71gMAA, 49.07gRhodacalDS-4,51.46g deionized water and 3.61gtBHP.Added second comonomer charging through 84 minutes and use 15.0g deionized water rinsing.Be about 8.2 by adding aqueous ammonium hydroxide solution by the pH regulator of product.Reaction product is the coated titanium dioxide latex containing 55.7%NVM almost without grumeleuse or reactor fouling.
Embodiment 4
The formation of coated titanium dioxide latex
The titanium dioxide slurry obtained in example 2 by 939.55g to be transferred in 3L still and with 382g deionized water and the 51.29g RHODACAL from Solvay tMdS-4 surfactivity dilution agent.Still is heated to 50 DEG C, add the 200g first monomer emulsion containing 45.65g deionized water subsequently, then added the monomer mixture containing 58%/40%/2%BA/MMA/MAA and 25.65gRHODACALDS-4 tensio-active agent through 20 minutes and added through 126 minutes and the redox initiator mixture deposited.After the first monomer emulsion and redox initiator charging, added the second comonomer emulsion of 750g containing 58%/41%/l1%BA/MMA/MAA charging through 70 minutes.The volume ratio of the first monomer emulsion and second comonomer emulsion is 20: 8, and based on total monomer weight, redox initiator material comprises 1.0 % by weight tBHP and 0.76 % by weight FF6.Be about 9 by adding aqueous ammonium hydroxide solution by the pH regulator of product.Reaction product is containing 55.5%NVM and the average particle size particle size with monomodal particle distribution of sizes is the coated titanium dioxide latex of 470nm.
After description the preferred embodiment of the present invention like this, those skilled in the art will easily recognize: other embodiment in the scope of the claim appended by instruction herein can be applicable to herein.The entire disclosure of all patents, patent document and publication is merged in herein, as being incorporated to separately all by reference.

Claims (7)

1. pigment grind dispersion, it comprises the mixture of following material:
A) carrier;
B) granules of pigments, its specific refractory power is at least 1.8; With
C) polymeric dispersant, it has:
I) polymer backbone; With
Ii) the amphoteric ion type polymer lateral chain of anionic group and cation group is comprised.
2. the pigment dispersion of polymer overmold, it comprises the mixture of following material:
A) carrier;
B) granules of pigments, described particle is coated by least one polymer layer at least partly; With
C) polymeric dispersant, it has:
I) polymer backbone; With
Ii) the amphoteric ion type polymer lateral chain of anionic group and cation group is comprised.
3. make paints the method for grinding distribution body, and described method comprises the following material of mixing:
A) carrier;
B) granules of pigments; With
C) polymeric dispersant, it has:
I) polymer backbone; With
Ii) the amphoteric ion type polymer lateral chain of anionic group and cation group is comprised.
4. manufacture the method for the pigment dispersion of polymer overmold, described method comprises:
A) form the dispersion of carrier, granules of pigments and polymeric dispersant, wherein said polymeric dispersant has:
I) polymer backbone; With
Ii) the amphoteric ion type polymer lateral chain of anionic group and cation group is comprised;
B) described dispersion comprised or in described dispersion, add radical initiator and one or more ethylenically unsaturated monomers; With
C) described ethylenically unsaturated monomer is made to be polymerized to make described granules of pigments coated by least one polymer layer at least partly.
5. coating composition, it comprises the dispersion of following component:
A) carrier;
B) granules of pigments, described granules of pigments is coated by least one polymer layer at least partly; With
C) polymeric dispersant, it has:
I) the first polymer backbone; With
Ii) the amphoteric ion type polymer lateral chain of anionic group and cation group is comprised;
D) one or both in following material:
I) binder for film formation, it comprises the polymkeric substance being different from described first polymkeric substance; Or
Ii) one or more in thickening material, rheology modifier, tensio-active agent or coalescing agent.
6. dispersion, composition or method according to any one of front claim, the specific refractory power of wherein said granules of pigments is at least about 1.8.
7. dispersion, composition or method according to any one of front claim, the specific refractory power of wherein said granules of pigments is lower than about 1.8.
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CN109415576A (en) * 2016-09-06 2019-03-01 Dic株式会社 Resin-coated inorganic or metallic pigments
CN110337454A (en) * 2017-03-15 2019-10-15 株式会社Adeka Water-soluble composition, the manufacturing method of its solidfied material and its solidfied material and acyl group phosphinates
CN111518417A (en) * 2020-05-08 2020-08-11 重庆大学 Method for modifying titanium dioxide by adopting urea-formaldehyde resin
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WO2021207956A1 (en) * 2020-04-15 2021-10-21 Solvay Sa Use of coating compositions for making a substrate frost resistant, compositions and methods useful therefor
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CN107001814A (en) * 2014-12-08 2017-08-01 威士伯采购公司 The granules of pigments of polymer overmold
CN109415576A (en) * 2016-09-06 2019-03-01 Dic株式会社 Resin-coated inorganic or metallic pigments
CN110337454A (en) * 2017-03-15 2019-10-15 株式会社Adeka Water-soluble composition, the manufacturing method of its solidfied material and its solidfied material and acyl group phosphinates
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CN115397930A (en) * 2020-04-15 2022-11-25 索尔维公司 Coating composition, use and method for anti-frosting a substrate
WO2021207956A1 (en) * 2020-04-15 2021-10-21 Solvay Sa Use of coating compositions for making a substrate frost resistant, compositions and methods useful therefor
CN115427746A (en) * 2020-04-15 2022-12-02 索尔维公司 Use of a coating composition to render a substrate anti-frosting, compositions and methods therefor
CN111518417A (en) * 2020-05-08 2020-08-11 重庆大学 Method for modifying titanium dioxide by adopting urea-formaldehyde resin
CN111518417B (en) * 2020-05-08 2021-08-13 重庆大学 Method for modifying titanium dioxide by adopting urea-formaldehyde resin
CN113248944A (en) * 2020-06-24 2021-08-13 广西七色珠光材料股份有限公司 Pearlescent pigment for powder coating, preparation method and reaction device thereof
CN114410131A (en) * 2021-12-14 2022-04-29 河南河大纳米材料工程研究中心有限公司 Water-phase instant titanium dioxide material and preparation method and application thereof
CN115109198A (en) * 2022-05-24 2022-09-27 厦门路桥翔通建材科技有限公司 High-workability double-comb type amphoteric polycarboxylate superplasticizer and preparation method thereof

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