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
  • 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
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic
• • 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
  • C09D7/66—Additives characterised by particle size
  • C09D7/67—Particle size smaller than 100 nm
• • 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
  • C08K3/32—Phosphorus-containing compounds
  • C08K2003/321—Phosphates
  • C08K2003/325—Calcium, strontium or barium phosphate

Definitions

• the present invention relates to a composition containing binder and metal inorganic salt cluster, its preparation, and the use thereof for coating, more specifically use thereof for surface coating, including but not limited to flooring coating.
• Hardness is one of the most important properties for many kinds of coatings, especially the surface coating, including but not limited to floor coating, industrial coating, and wood coating, etc..
• 2K system with isocyanate crosslinking is often used in suface coating.
• 1 K system is always more attractive because of the convenience in application.
• it is also desireable to have good performance regarding modulus, abrasion resisitance, scratch resistance and chemcial resistance for the surface coating.
• a surface coating with good performance on at least one of the properties of hardness, modulus, abrasion resistance, scratch resistance and chemical resistance preferably having good performance on both hardness as well as modulus, abrasion resistance, scratch resistance and chemical resistance.
• One objective of the present disclosure is to provide a composition comprising at least one binder and at least one metal inorganic salt cluster, wherein said at least one metal inorganic salt cluster is represented by M a Xb, wherein M is metal cation, X is inorganic anion, a, b each independently is an integer of 1 to 3.
• Another objective of the present disclose is to provide a method to prepare the composition of the present disclosure.
• the third objective of the present disclose is to provide the use of said composition in coating, preferably surface coating.
• polymer or “polymers”, as used herein, includes both homopolymer(s), that is, polymers prepared from a single reactive compound, and copolymer(s), that is, polymers prepared by reaction of at least two polymer forming reactive, monomeric compounds.
• salt means a chemical compound consisting of an ionic assembly of cations and anions.
• One objective of the present disclosure is to provide a composition comprising at least one binder and at least one metal inorganic salt cluster, wherein said at least one metal inorganic salt cluster is represented by M a Xb, wherein M is a metal cation, X is inorganic anion, a, b each independently is an integer of 1 to 3.
• composition comprising at least one binder and at least one metal inorganic salt cluster of the present disclose
• the resulted composition shows good hardness as well as at least one of the properties of modulus, abrasion resistance, scratch resistance and chemical resistance.
• the term “binder” as used herein refers to organic, polymeric compounds which are responsible for forming film among other components of the coating composition.
• the coating composition may comprise at least one binder.
• the binder may be present in an amount of 1 to 90 wt.%, more preferably 20 to 80 wt.%, most preferably 50 to 70 wt.%, based on the total weight of the coating composition.
• the binder may be present in an amount of 1 to 80 wt.%, or 3 to 50 wt.%, based on the total weight of the coating composition.
• Binders which are useful for the composition include, but are not limited to, alkyd resins, epoxy resins, polyurethanes, vinyl acetate/ethylene copolymers, water glasses, more particularly potassium waterglasses, and also binders based on (meth)acrylate, styrene and/or vinyl esters such as styrene acrylates or butyl acrylates.
• the binder comprises polymer and/or co-polymer of vinyl acetate, ethylene, styrene, (meth)acrylates, butyl acrylates or mixtures of these polymers and/or copolymer.
• the binder comprises polyurethanes, (meth)acrylates, alkyd resins, epoxy resins and any mixture thereof.
• the binder comprises (meth)acrylates, polyurethanes, or any mixture thereof.
• the solid content of binder in the present disclosure is 20 to 65%, preferably 25 to 60%, more preferably 30 to 50%.
• the metal cation M in the metal inorganic salt cluster is monovalent, divalent or tervalence metal cation.
• Example of such metal cation include but not limited to Na + , K + , Be 2+ , Ca 2+ , Mg 2+ , Sr 2+ , Ba 2+ and Al 3+ .
• the metal cation M is divalent metal.
• Example of such metal cation include but not limited to Ca 2+ , Mg 2+ , Sr 2+ and Ba 2+ . More preferably the metal cation M is Ca 2+ , Mg 2+ and Ba 2+ ; most preferably Ca 2+ .
• the anion X in the metal inorganic salt cluster is a divalent or tervalence anion.
• Example of such anion include but not limited to CCh 2 ' and PO 4 3 ', preferably the anion X is PO 4 3 ’.
• the particle size of metal inorganic salt cluster is 0.4 to 9 nm or 0.4 to 7nm, preferably 0.4 to 5nm or 0.6 to 5nm, more preferably 0.4 to 3 nm or 0.6 to 2nm, most preferably 0.6 to 1 ,5nm or 0.8 to 1 ,2nm.
• the particle size of metal inorganic salt is measured by transmission electron microscopy (TEM, HT-7700, Hitachi, Japan).
• the particle size of metal inorganic salt of the present disclosure is calculated by the average particle size of the particle size of 100 particles obtained from TEM image.
• the metal inorganic salt cluster is present in the amount of 0.1 to 10 wt.%, preferably 0.3 to 8 wt.%, more preferably 0.5 to 5 wt.%, most preferably 1 to 3 wt.% based on the weight of the composition.
• the metal inorganic salt cluster is prepared according to the process disclosed in CN110157132B.
• the metal inorganic salt cluster of Cas(PO 4 )2 could be preared via the process as below: adding triethylamine as stablizer, CaCl2'2H2O as Ca source, HsPO 4 as phosphorus source into the organic solvent to generate the metal inorganic salt cluster of Cas(PO 4 )2, wherein the reaction temperature is around 25°C .
• the organic solvent could be any of commonly used organic solvent, examples of such organic solvent are ethanol, glycol and glycerol or the mixture thereof.
• the solid content of the composition in the present disclosure is 10 to 80%, preferably 20 to 65%, more preferably 25 to 60%, most preferably 25 to 50%.
• Another objective of the present disclose is to provide a method to prepare the composition of the present invention.
• the composition is prepared by mixing at least one binder and at least one metal inorganic cluster under room temperature; optionally other components of at least one of pigment, filler, solvent, preservative, thickener, dispersant and defoamer are added under agitation.
• the third objective of the present disclose is to provide the use of such composition in surface coating.
• the surface coating composition may contain further components, such as pigment, filler, solvent, water, and further additives such as preservative, thickener, dispersant and defoamer.
• Suitable pigment includes, for example, inorganic white pigments, such as titanium dioxide, barium sulfate, zinc oxide, zinc sulfide, basic lead carbonate, antimony trioxide, and lithopones; inorganic colored pigments, such as iron oxides, carbon black, graphite, zinc yellow, zinc green, Ultramarin, manganese black, antimony black, and manganese violet; organic color pigments, such as indigo, azo dyes, anthraquinoids and indidental dyes, as well as dioxazine, quinacridone, phthalocyanine, isoindolinone and metal complex pigments. Also suitable are synthetic white pigments with air inclusions for increasing light scattering, such as the Rhopaque® dispersions.
• inorganic white pigments such as titanium dioxide, barium sulfate, zinc oxide, zinc sulfide, basic lead carbonate, antimony trioxide, and lithopones
• inorganic colored pigments such as iron oxides, carbon
• the pigment may be present, if present, in an amount of 20 to 80 wt.%, preferably 50 to 75 wt.% in the case of wall paints, or in an amount of no more than 25 wt.%, preferably no more than 15 wt.%, most preferably no more than 10 wt.% in the case of transparent or semi-transparent coatings, based on the total weight of the coating composition.
• Suitable filler includes, for example, kaolin, talc, mica, magnesite, alkaline earth carbonates such as calcite or chalk, magnesium carbonate, dolomite, alkaline earth sulfates such as calcium sulfate, silicon compounds such as silicon dioxide or aluminum silicates or magnesium aluminum silicates, and aluminum oxide or aluminum oxide hydrate.
• the filler may be present, if present, in an amount of 1 to 90 wt.%, preferably 20 to 60 wt.% in the case of wall paint, or in an amount of no more than 5 wt.%, preferably no more than 2 wt.%, most preferably no more than 1 wt.% in the case of transparent or semi-transparent coatings, based on the total weight of the coating composition.
• Suitable organic solvent includes, for example, trimethylpentane, propylene glycol or dipropylene glycol butyl ether.
• the organic solvent may be present, if present, in an amount of less than 5 wt.%, based on the total weight of the coating composition.
• Suitable preservative includes, for example, isothiazolinone preparations such as 2-methyl-2H- isothiazol-3-one or 1 ,2-benzisothiazolin-3H-one.
• the preservative may be present in an amount of less than 2 wt.%, preferably less than 0.3 wt.%, based on the total weight of the coating composition.
• Suitable thickener includes, for example, cellulose ethers, bentonite, polysaccharides, fumed silica, phyllosilicates, or polyurethane thickeners.
• the thickener may be present in an amount of less than 1 wt.%, preferably less than 0.6 wt.%, based on the total weight of the coating composition.
• Suitable dispersant includes, for example, alkylbenzenesulfonates, polycarboxylates, fatty acid amines or salts of polyacrylic acids.
• the dispersant may be present in an amount of less than 2 wt.%, preferably 0.001 to 0.5 wt.%, based on the total weight of the coating composition.
• Suitable defoamer includes, for example, poly(organo)siloxanes, silicone oils or mineral oils. The defoamer may be present in an amount of less than 1 wt.%, more preferably 0 to 0.5 wt.%, based on the total weight of the coating composition.
• Triethylamine (TEA, ⁇ Hs ⁇ N; 99%) from Sinopharm Chemical Reagent Co., Ltd..China.
• HAP Hydroxyapatite nanoparticles from Aladdin’s Reagent Co., Ltd., China
• Anticide MBS from Thor
• Omyacarb 2 powder from Omya
• Omyacarb 5 powder from Omya
• Talc 800 mesh powder from Shandong jinqi minerals Co., Ltd.
• Binder A Acronal EDGE 6283 from BASF, acrylic dispersion with butyl acrylate, styrene and acrylic acid as monomers, solid content is 42.1%
• Binder B HPUD 1591 from Si.m, polyurethane dispersion with isophorone diisocyanate, polycarbonate and dimethylolpropionic acid, solid content is 36%
• binder A 72.68 g of binder A was mixed uniformly with 30.5 g of CPOs obtained from above process to form a homogeneous emulsion.
• 6 g of BDG was charged to the above-mentioned emulsion with agitation and mixing for 2 minutes; 2 g of AMP 95 was slowly charged with agitation and mixing until homogenous emulsion was obtained.
• 0.4 g of Anticide MBS and 1.32 g of water were charged with agitation and mixing for 1 minute.
• binder B 85 g was mixed uniformly with 71.4 g of CPOs obtained from above process to form a homogeneous emulsion.
• 3 g of DPND and 2 g of Texonal were charged to the above- mentioned emulsion with agitation and mixing for 2 minutes; 2 g of AMP 95 was slowly charged with agitation and mixing until homogenous emulsion was obtained.
• 0.4 g of Anticide MBS was charged with agitation and mixing for 1 minute.
• 4.12 g of Dispex CX 4320 was added with agitation and mixing for 2 minutes, 0.6 g of Foamstar SI 2210 was added with agitation and mixing for 2 minutes.
• binder A 72.68 g of binder A was charged with agitation, 6 g of BDG was further charged with agitation and mixing for 2 minutes; 2 g of AMP 95 was slowly charged with agitation and mixing until homogenous emulsion was obtained. After blending for 2 minutes, 0.4 g of Anticide MBS and 1.32 g of water were charged with agitation and mixing for 1 minute.
• binder A 72.68 g of binder A was mixed uniformly with 1.525 g of HAP to form a homogeneous emulsion, 6 g of BDG was further charged with agitation and mixing for 2 minutes; 2 g of AMP 95 was slowly charged with agitation and mixing until homogenous emulsion was obtained. After blending for 2 minutes, 0.4 g of Anticide MBS and 1.32 g of water were charged with agitation and mixing for 1 minute.
• binder B 85 g of binder B was charged with agitation, 3 g of DPND and 2 g of Texonal were charged to the above-mentioned emulsion with agitation and mixing for 2 minutes; 2 g of AMP 95 was slowly charged with agitation and mixing until homogenous emulsion was obtained. After blending for 2 minutes, 0.4 g of Anticide MBS was charged with agitation and mixing for 1 minute.
• binder B 85 g was mixed uniformly with 3.57 g of HAP to form a homogeneous emulsion, 3 g of DPND and 2 g of Texonal were charged to the above-mentioned emulsion with agitation and mixing for 2 minutes; 2 g of AMP 95 was slowly charged with agitation and mixing until homogenous emulsion was obtained. After blending for 2 minutes, 0.4 g of Anticide MBS was charged with agitation and mixing for 1 minute.
• compositions were applied to the non-asbestos fiber cement plate using a manual film applicator and the thickness of scraping coating was150 pm.
• the intermediate drying time between the first and the second coating was 24 h. Then drying the samples at the condition of 23 °C and 50% relative humidity for 1 week after application of the last composition.
• the testing instrument and operating procedures were preceded according to GB/T 6739-2006.
• the type of rubber grinding wheel chosen was CS-17 and the load of each rubber grinding wheel was 750 g. All the compositions were pre-ground for 100 rotations and the weight was set as wi. After abrasion for 500 rotations, the weight of the sample was set as W2. The value difference between wi and W2 reflect the abrasion resistance ability.
• sample preparation was consistent with hardness test. Adding a few drops of liquid to the test plate, including water, oil, 10% of H2SO4 solution and 20% of NaOH solution. The testing times were 168 h, 72 h, 48 h and 72 h for each liquid, respectively. After the testing, washing the test area with water, and the discoloration of the samples were checked.
• Nanoindentation modulus test were carried out by an Agilent G200 Nano Indenter equipped with continuous stiffness measurement modulem, the average value was calculated according to the five tests.
• Microscratch tests were performed using a microscratch tester (UNHT/MCT/MST, Anton Paar GmbH, Austria). All scratch testing samples were conducted at a constant normal load of 100 mN with a velocity of 200 pm min -1 . For each sample, five scratches were made in each test region. The scratch distance was 500 pm and each scratch was at least 50 pm away from the next scratch. The average scratching contact depth value at different distance of each scratch was calculated. Finally, the average value was calculated again according to the five scratches.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Nanotechnology (AREA)
• Paints Or Removers (AREA)

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• 2023
  • 2023-05-02 EP EP23724704.4A patent/EP4519366A1/de active Pending
  • 2023-05-02 AU AU2023265376A patent/AU2023265376A1/en active Pending
  • 2023-05-02 CN CN202380038320.3A patent/CN119894994A/zh active Pending
  • 2023-05-02 WO PCT/EP2023/061507 patent/WO2023213792A1/en not_active Ceased

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