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
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
  • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
• • 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
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
  • C09D133/12—Homopolymers or copolymers of methyl methacrylate

Definitions

• the present invention relates to a coating composition, a preparation method for the same and a use of the same.
• the present invention relates to coating composition for interior and exterior application, especially for exterior application.
• the present invention relates to a preparation method for the same and a use of the same.
• Coating compositions are widely used for various substrates for such as decorating and /or protecting.
• a coating film is exposed to contamination from the atmosphere.
• This contamination is comprised of dirt and dust which are carried to the coating film surface by rain, airborne moisture droplets, wind currents or direct physical contact with people, animals or other objects.
• the microorganism on a coated wall may accelerate the accumulation of the dusts. It is desirable that the coating film remain clean and free of dirt, soil or other contaminants throughout the useful service life of the coating film. Therefore, it is desirable that the coating film formed from a coating composition will have excellent dirt pick-up resistance (DPUR), stain resistance, blocking resistance, etc.
• DPUR dirt pick-up resistance
• a substrate on which a coating is applied may have defects, such as cracks and rough surfaces, which requires the coating film has bridging ability to cover those defects.
• new defects could be generated and/or the existing defects could further develop over the time as the substrate being aged, which may lead to cracks on the formed coating film if the flexibility of the coating is not sufficient. Therefore, it is desirable that the coating has excellent flexibility such that the coating film defects caused by the defects of the substrate or caused from being aged will be avoided.
• dirt pick-up resistance requires a hard coating on a substrate, while to avoid the coating film defects on a substrate, it is desirable that the coating film has excellent flexibility. They are usually a pair of contradicting properties.
• WO 2010105938 Al describes incorporation of surface modified silica particles into the coating to improve the hardness of the film, such that to obtain an improved DPUR.
• the final coating doesn't have sufficient flexibility to bridge the cracks of the substrate.
• CN 1256295 A describes a method to balance DPUR and flexibility by using dispersions of multi-staged emulsion polymers. It uses multi-staged emulsion polymerization to have both hard and soft polymer domains in the final film. However, CN 1256295 A obtains DPUR to certain extent at the cost of flexibility. The final coating film of CN1256295A has moderate DPUR and flexibility performance, neither of them is outstanding.
• US 8993667 describes a redox polymerization to improve DPUR for elastomeric wall coatings.
• the glass transition temperature of the obtained polymer is low for obtaining good flexibility.
• DPUR is still poor because the bulk polymer is too soft.
• JP2007224084A discloses a photo-curable composition for coating film used for flooring of kitchen and passage.
• the photo-curable composition contains a photopolymerizable oligomer having two or more radically polymerizable double bonds, wherein the photopolymerizable oligomer (a) should contain specially selected photopolymerizable oligomer (al) and photopolymerizable oligomer (a2) with defined ratio.
• the composition of JP2007224084A contains high level of volatile organic compounds, and needs additional UV-lamp to help curing. Due to high level of photo-initiator and bi-/multi-functional monomers dosage, the final film obtained from the composition of JP2007224084A is too rigid to provide sufficient flexibility.
• An objective of this invention is to provide a composition, which will form a coating film having both good DPUR and good flexibility at the same time.
• the invention relates to a composition
• a composition comprising:
• component A is physically mixed with component C, or is chemically bonded to the polymer of component C to form a modified polymer having chemically bonded component A.
• Another object of this invention is to provide a process for preparing the composition of the invention, comprising:
• Step 1 forming a polymer-containing coating
• Step 2 incorporating a photo-curable component and a photo -initiator into the polymer-containing coating during step 1 or after the polymer-containing coating is formed,
• photo-curable component is physically mixed with the polymer-containing coating, or is chemically bonded to the polymer of the polymer-containing coating.
• the present invention relates to a process for applying the composition of the invention, comprising applying the composition of the invention to a substrate.
• the present invention relates to a coating film formed from the composition of the invention.
• the coating film formed from the composition of the invention has excellent dirt pick-up resistance (DPUR), stain resistance, blocking resistance, etc. At the same time, the coating film of the present invention has excellent flexibility.
• polymer includes both homopolymers, that is, polymers prepared from a single reactive compound, and copolymers, that is, polymers prepared by reaction of at least two polymer forming reactive, monomeric compounds.
• the present invention relates to a composition
• a composition comprising:
• the present invention relates to a composition
• a composition comprising:
• component A is physically mixed with component C, or is chemically bonded to the polymer of component C to form a modified polymer having chemically bonded component A.
• the component A of the composition of the present invention is a photo-curable component.
• Said photo-curable component includes monomers, oligomers and/or polymers having two or more radically polymerizable double bonds.
• Any photo-curable material that can be used in a coating composition may be applicable in the composition of the present invention.
• the component A may be photo-curable (meth)acrylates, photo-curable (poly)urethanes, photo-curable epoxide polymers and the like.
• the component A of the inventive composition are monomers and/or oligomers of polyester acrylates, polyether acrylates, epoxy acrylates, polyurethane acrylates or mixtures thereof.
• component A of the inventive composition can be selected from the group consisting of monomers and/or oligomers of polyurethane acrylates, Laromer ® PE55WIN, Laromer ® LR8765, Laromer ® LR 8983, Laromer ® LR 8889, Laromer ® LR8949, and 1,4-butanediol diacrylate, all of them are available from BASF SE, Ludwigshafen, Germany. More preferably component A of the composition of the invention is Laromer ® WA9057 or Laromer ® LR8949.
• component A comprises, monomers and/or oligomers and/or polymers of allyl ester, vinyl ester of (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid; allyl, vinyl - vinyl ether or thioether; and the like. More preferably, component A comprises monomers and/or oligomers of allyl ester, vinyl ester of (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid; allyl, vinyl - vinyl ether or thioether or mixtures thereof.
• the amount of component A in the composition of the invention may be in the range of 0.01 to 9.9 wt%; preferably in the range of 0.05 to 8 wt%; more preferably in a range of 0.1 to 6 wt%; most preferable in a range of 0.5 to 5 wt%, based on the total weight of the solid components of the composition of the invention.
• the amount of component A in the composition of the invention may be in the range of 0.1 to 9.9 wt%; preferably in the range of 0.1 to 8 wt%; more preferably in a range of 0.1 to 6 wt%, such as in the range of 0.5 to 5 wt%, based on the total weight of the solid components of the composition of the invention.
• the amount of component A in the composition of the invention may be in the range of 0.01 to 9.9 wt%; preferably in the range of 0.05 to 8 wt%; more preferably in a range of 0.1 to 6 wt%, such as in the range of 0.5 to 5 wt%, based on the total weight of the solid components of the composition of the invention.
• any photo-initiator can be used as the component B of the composition for the purpose of the invention, provided that it can be used in a coating composition.
• the photo-initiator can be selected without limitation from benzophenone or acetophenone or derivatives with benzophenone or acetophenone substructures, such as substituted benzophenones, for instance 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, thioxanthones, such as isopropylthioxanthone, or olefmically unsaturated derivatives of benzophenone or of acetophenone, examples being those with a (meth)acrylic radical such as (meth)acryloxyethoxybenzophenone, or with a vinyl group such as 4-vinyloxybenzophenone, or mixtures of these active ingredients, such as 4-methylbenzophenone and 2,4,6-trimethylbenzophenone.
• Component B may either be added before, during or after the actual formulating of A and/
• component B of the composition of the invention may be selected from the group consisting of Benzophenone, IRGACURE ® 754, IRGACURE ® 500 from BASF, and Esacure ® TZM, Esacure ® TZT from Lamberti SPA Company. More preferably, component B of the composition of the invention may be selected from the group consisting of Esacure ® TZM, and IRGACURE ® 500.
• the amount of component B in the composition of the invention may be in the range of 0.01 to 5 wt%; preferably in the range of 0.01 to 1 wt%; more preferable in a range of 0.01 to 0.5 wt%; most preferable in a range of 0.1 to 0.5 wt%, based on the total weight of the solid components of the composition of the invention.
• the component A and component B of the composition of the present invention may be used in an appropriate ratio in a range of 1 to 990 by weight.
• the component A and component B may be used in a component A/component B ratio up to 200, more preferably up to 100.
• the component A and component B may be used in a component A/component B ratio equal to or more than 1.6, preferably equal to or more than 2, more preferably equal to or more than 5.
• the component C of the composition of the invention may be any polymer-containing coating.
• the component C per se is a coating composition that can be used directly to a substrate to form a coating film.
• the component C is directly applicable for exterior application, such as for an exterior wall of a building.
• Any conventional polymer-containing coating composition in the art may be used as component C.
• the component C may be prepared by a skilled person according to a conventional procedure, or the component C may be commercially available.
• the component C may be available from BASF under the trade name of Acronal ® 290; Acronal ® 7035; Acronal ® 7079.
• the component C may be obtained by the processes disclosed in US2014107249 or US2013079462 (each of these two documents is incorporated by reference in entirety).
• the polymer of the component C of the composition of the invention may be any polymer applicable to be contained in a coating composition.
• the polymer may be polyester, polyurethane, epoxy resin, poly(meth)acrylate, and the like.
• a skilled person will easily select an appropriate polymer of the component C, and will easily obtain it by common technology.
• the glass transition temperatures (Tg) of the polymer of the component C is in the range of from -20°C to 60°C, preferred range of from -10 to 50°C; more preferred range of from -10 to 40°C, most preferred range of from 0 to 30°C.
• the polymer of the component C has a Mw in the range of from 25,000 to 10,000,000 Dalton, preferred range of from 30,000 to 5,000,000 Dalton, more preferred range of from 100,000 to 2,000,000 Dalton, most preferred range of from 300,000 to 1,000,000 Dalton, and a Mn in the range of from 4,000 to 1,000,000 Dalton, preferred range of from 5,000 to 500,000 Dalton, more preferred range of from 10,000 to 200,000 Dalton, most preferred range of from 40,000 to 100,000 Dalton.
• the component C constitutes the balance of the composition of the present invention.
• the component C may further contain additives.
• additives may be pigment, such as TiC"2 CR828 from Kerr-McGee Corporation, Oklahoma, U.S. A; filler, such as CaC0 3 Omyacarb ® 5 from Omya; film-forming aids, such as Texonal ® from Eastman Chemical Company; thickener, such as Natrosol ® 250HBR from Ashland; and antifreeze additive, such as propylene glycol from GuoYao Reagent Company; and the like.
• Any conventional additives for a coating composition may be contained in the component C. Generally, these additives are used in their conventional amount respectively.
• the present invention relates to a process for preparing the composition of the invention, comprising:
• Step 1 forming a polymer-containing coating
• Step 2 incorporating a photo-curable component and a photo -initiator into the polymer-containing coating during step 1 or after the polymer-containing coating is formed,
• photo-curable component is physically mixed with the polymer-containing coating, or is chemically bonded to the polymer of the polymer-containing coating.
• the step 1 of the process for preparing the composition of the invention may be carried out under any conventional temperature and pressure conditions for forming a coating.
• a skilled person can select appropriate conditions for step 1.
• the step 1 is achieved via free-radically initiated aqueous emulsion polymerization. This method has been widely described before now and is therefore sufficiently well known to the skilled person [cf, e.g., Encyclopedia of Polymer Science and Engineering, vol. 8, pages 659 to 677, John Wiley & Sons, Inc., 1987; D. C. Blackley, Emulsion Polymerisation, pages 155 to 465, Applied Science Publishers, Ltd., Essex, 1975; D. C. Blackley, Polymer Latices, 2nd Edition, vol.
• the free-radically initiated aqueous emulsion polymerization is typically accomplished by dispersing the ethylenically unsaturated monomers in the aqueous medium, generally using dispersing assistants, such as emulsifiers and/or protective colloids, and polymerizing them by means of at least one water-soluble free-radical polymerization initiator.
• dispersing assistants such as emulsifiers and/or protective colloids
• the residual amounts of unreacted ethylenically unsaturated monomers are lowered by chemical and/or physical methods that are likewise known to the skilled person [see, for example, EP-A 771328, DE-A 19624299, DE-A 19621027, DE-A 19741184, DE-A 19741187, DE-A 19805122, DE-A 19828183, DE-A 19839199, DE-A 19840586 and 19847115], the polymer solids content is adjusted to a desired level by dilution or concentration, or other customary additives, such as bactericidal, foam-modifying or viscosity-modifying additives, are added to the aqueous polymer dispersion.
• customary additives such as bactericidal, foam-modifying or viscosity-modifying additives
• step 2 of the process it may be carried out under any appropriate temperature and pressure.
• the process for preparing the composition of the invention may be carried out at ambient temperature and ambient pressure, such as room
• the present invention relates to a process for applying the composition of the invention, comprising applying the composition of the invention to a substrate.
• composition of the invention may be applied by conventional application methods such as, for example, brush or roller, spray-coating such as air-atomized spray, air-assisted spray, airless spray, high volume low pressure spray, air-assisted airless spray, electrostatic spray, etc., spin coating, curtain-coating, and the like.
• spray-coating such as air-atomized spray, air-assisted spray, airless spray, high volume low pressure spray, air-assisted airless spray, electrostatic spray, etc.
• spin coating curtain-coating, and the like.
• any appropriate substrate may be used as a substrate for applying the composition of the invention, such as polymeric substrate, cement, concrete, ceramics, metals, woods, leather, and the like, provided that the coated substrate will be exposed to a light, such as sunlight.
• the coating film formed from the composition of the invention may have any appropriate dry film thickness.
• the dry film thickness of the coating film formed from the composition of the invention is up to 2000 ⁇ , preferably up to ⁇ , such as up to 500 ⁇ , more preferably up to 300 ⁇ , and especially up to 200 ⁇ , and no less than ⁇ , preferably no less than 50 ⁇ , more preferably no less than ⁇ .
• the dry film thickness of the coating film formed from the composition of the invention is in the range of 50 ⁇ to 500 ⁇ , more preferably in the range of 50 ⁇ to 300 ⁇ , such as in the range of ⁇ to 300 ⁇ .
• the dry film thickness of the coating film formed from the composition of the invention is in the range of ⁇ to 2000 ⁇ , such as in the range of 30 ⁇ to ⁇ , more preferably in the range of 50 ⁇ to ⁇ , still preferably in the range of 50 ⁇ to 500 ⁇ such as in the range of 50 ⁇ to 300 ⁇ .
• the substrate is wood and the dry film thickness of the coating film formed from the composition of the invention is in the range of 30 ⁇ to 200 ⁇ , more preferably in the range of 50 ⁇ to 150 ⁇ , still preferably in the range of 50 ⁇ to ⁇ .
• the present invention relates to a coating film obtained from the composition of the invention.
• the present invention includes the following embodiments.
• composition comprising
• composition comprising
• component A is physically mixed with component C.
• component A is chemically bonded to the polymer of component C to form a modified polymer having chemically bonded component A.
• the amount of component A in the composition of the invention may be in the range of 0.1 to 9.9 wt%; preferably in the range of 0.1 to 8 wt%; more preferably in a range of 0.1 to 6 wt%, such as in the range of 0.5 to 5 wt%, based on the total weight of the solid components of the composition of the invention.
• Mw in the range of from 25,000 to 10,000,000 Dalton, preferred range of from 30,000 to 5,000,000 Dalton, more preferred range of from 100,000 to 2,000,000 Dalton, most preferred range of from 300,000 to 1,000,000 Dalton, and a Mn in the range of from 4,000 to 1,000,000 Dalton, preferred range of from 5,000 to 500,000 Dalton, more preferred range of from 10,000 to 200,000 Dalton, most preferred range of from 40,000 to 100,000 Dalton, measured by gel permeation chromatography according to ISO 13885-1.
• the amount of component A in the composition of the invention may be in the range of 0.1 to 9.9 wt%; the Tg of the polymer of component C is in the range of -10 to 50°C, the polymer of component C has a Mw in the range of 30,000 to 5,000,000 Dalton, and a Mn in the range of from 5,000 to 500,000 Dalton measured by gel permeation chromatography according to ISO 13885-1.
• the composition of any one of embodiments 1-3 wherein the amount of component A in the composition of the invention may be in the range of 0.1 to 9.9 wt%; the Tg of the polymer of component C is in the range of -10 to 40°C, the polymer of component C has a Mw in the range of 100,000 to 2,000,000 Dalton, and a Mn in the range of from 10,000 to 200,00 Dalton 0 measured by gel permeation chromatography according to ISO 13885-1. 10.
• substituted benzophenones for instance 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, thioxanthones, such as isopropylthioxanthone, olefm
• Step 1 forming a polymer-containing coating
• Step 2 incorporating a photo-curable component and a photo -initiator into the polymer-containing coating during step 1 or after the polymer-containing coating is formed,
• photo-curable component is physically mixed with the polymer-containing coating, or is chemically bonded to the polymer of the polymer-containing coating.
• the coating film of embodiment 13 wherein the dry film thickness of the coating film is up to ⁇ , preferably up to 500 ⁇ , more preferably up to 300 ⁇ , and especially up to 200 ⁇ , and no less than 30 ⁇ , preferably no less than 50 ⁇ , more preferably no less than 30 ⁇ .
• the dry film thickness of the coating film is in the range of 50 ⁇ to 500 ⁇ , more preferably in the range of 50 ⁇ to 300 ⁇ , such as in the range of ⁇ to 300 ⁇ .
• 50 ⁇ to ⁇ still preferably in the range of 50 ⁇ to 500 ⁇ such as in the range of 50 ⁇ to 300 ⁇ .
• a 4L-reactor was inertized by passing nitrogen through for 10 min, then charged with 600 g of demineralized water, 25 g of a 33% seed latex of polystyrene with a particle size of 33 nm. Then the reactor containing the above charge was heated to 85°C for synthesis with stirring. Then 5 g of 7% sodium peroxosulfate aqueous solution was added at 85°C.
• an emulsion feed obtained by mixing 450 g of demineralized water, 28 g of a sodium salt of a fatty alcohol polyglycol ether sulfate, 705 g of methyl methacrylate, 527 g of n-butyl acrylate, 23 g of methacrylic acid and 13g of Esacure ® TZM, was fed into the reactor over 210 minutes.
• an initiator feed of 95 g of 7wt% sodium peroxosulfate aqueous solution was fed to the reactor over 240 min. After the addition of the initiator feed was finished, the obtained reaction mixture was cooled to 75°C.
• the volume concentration of the total inorganic contents in the resulting composition is around 45%.
• the content of Laromer ® LR 8765 is about 5.01%, and the content of Esacure ® TZM is about 0.25%.
• a 4L-reactor was inertized by passing nitrogen through for 10 min, then charged with 600 g of demineralized water, 25 g of a 33% seed latex of polystyrene with a particle size of 33 nm.
• the reactor containing the above charge was heated to 85°C for synthesis with stirring.
• 5 g of 7% sodium peroxosulfate aqueous solution was added at 85°C.
• an initiator feed of 95g of 7wt% sodium peroxosulfate aqueous solution was fed to the reactor over 240 min. After the addition of the initiator feed was finished, the obtained reaction mixture was cooled to 75°C.
• reaction mixture was then added 45 g of a 8% aqueous solution of sodium hydroxide within 5 min. After that 26 g of a 10% aqueous solution of tert-butyl hydroperoxide solution and 36 g of a 13 % solution of sodium sulfite were added within 60 min then the reaction mixture was cooled to room temperature. A latex was resulted.
• the volume concentration of the total inorganic contents in the in the resulting composition is around 45%.
• a 4L-reactor was inertized by passing nitrogen through for 10 min, then charged with 600 g of demineralized water, 25 g of a 33% seed latex of polystyrene with a particle size of 33 nm.
• the reactor containing the above charge was heated to 85°C for synthesis with stirring.
• 5 g of 7% sodium peroxosulfate aqueous solution was added at 85°C.
• an emulsion feed obtained by mixing 450 g of demineralized water, 28 g of a sodium salt of a fatty alcohol polyglycol ether sulfate, 625 g of methyl methacrylate, 607 g of 2-ethylhexyl acrylate, 23 g of methacrylic acid and 13g of IRGACURE ® 500, was fed into the reactor over 210 minutes.
• an initiator feed of 95g of 7wt% sodium peroxosulfate aqueous solution was fed to the reactor over 240 min. After the addition of the initiator feed was finished, the obtained reaction mixture was cooled to 75°C.
• the volume concentration of the total inorganic contents in the resulting composition is around 45%.
• the content of Laromer ® LR 8765 is about 5.01%, and the content of IRGACURE ® 500 is about 0.25%.
• a 4L-reactor was inertized by passing nitrogen through for 10 min, then charged with 600 g of demineralized water, 25 g of a 33% seed latex of polystyrene with a particle size of 33 nm.
• the reactor containing the above charge was heated to 85°C for synthesis with stirring.
• 5 g of 7% sodium peroxosulfate aqueous solution was added at 85°C.
• an emulsion feed obtained by mixing 450 g of demineralized water, 28 g of a sodium salt of a fatty alcohol polyglycol ether sulfate, 625 g of methyl methacrylate, 607 g of 2-ethylhexyl acrylate, 23 g of methacrylic acid, was fed into the reactor over 210 minutes.
• an initiator feed of 95g of 7wt% sodium peroxosulfate aqueous solution was fed to the reactor over 240 min. After the addition of the initiator feed was finished, the obtained reaction mixture was cooled to 75°C.
• reaction mixture was then added 45 g of an 8% aqueous solution of sodium hydroxide within 5 min. After that 26 g of a 10% aqueous solution of tert-butyl hydroperoxide solution and 36 g of a 13 % solution of sodium sulfite were added within 60 min then the reaction mixture was cooled to room temperature. A latex was resulted.
• the volume concentration of the total inorganic contents in the resulting composition is around 45%.
• a 4L-reactor was inertized by passing nitrogen through for 10 min, then charged with 1000 g of demineralized water, 25 g of a 33% seed latex of polystyrene with a particle size of 33 nm.
• the reactor containing the above charge was heated to 85°C for synthesis with stirring.
• 5 g of 7% sodium peroxosulfate aqueous solution was added at 85°C.
• an initiator feed of 95g of 7wt% sodium peroxosulfate aqueous solution was fed to the reactor over 210 min.
• the obtained reaction mixture was cooled to 75°C.
• 25 g of an 8% aqueous solution of sodium hydroxide was then added within 5 min.
• allyl methacrylate was chemically bonded to the polymers formed in the latex.
• FT-IR analysis showed that in the obtained latex, about 70 % by weight of allyl groups were remained, which is active photo-curable component.
• a 4L-reactor was inertized by passing nitrogen through for 10 min, then charged with 600 g of demineralized water, 25 g of a 33% seed latex of polystyrene with a particle size of 33 nm.
• the reactor containing the above charge was heated to 85°C for synthesis with stirring.
• 5 g of 7% sodium peroxosulfate aqueous solution was added at 85°C.
• an emulsion feed obtained by mixing 450 g of demineralized water, 28 g of a sodium salt of a fatty alcohol polyglycol ether sulfate, 594 g of methyl methacrylate, 577 g of 2-ethylhexyl acrylate, 23 g of methacrylic acid and 13g of IRGACURE ® 500, was fed into the reactor over 210 minutes.
• an initiator feed of 95g of 7wt% sodium peroxosulfate aqueous solution was fed to the reactor over 240 min.
• allyl methacrylate was added during the preparation of the latex.
• FT-IR analysis showed that in the obtained latex, about 70 % by weight of allyl groups were remained, which is active photo-curable component.
• the content of allyl methacrylate is about 1.35%, and the content of IRGACURE ® 500 is about 0.28%.
• a 4L-reactor was inertized by passing nitrogen through for 10 min, then charged with 600 g of demineralized water, 25 g of a 33% seed latex of polystyrene with a particle size of 33 nm.
• the reactor containing the above charge was heated to 85°C for synthesis with stirring.
• 5 g of 7% sodium peroxosulfate aqueous solution was added at 85°C.
• an emulsion feed obtained by mixing 450 g of demineralized water, 28 g of a sodium salt of a fatty alcohol polyglycol ether sulfate, 625 g of methyl methacrylate, 607 g of 2-ethylhexyl acrylate, 23 g of methacrylic acid and 13g of IRGACURE ® 500, was fed into the reactor over 210 minutes.
• an initiator feed of 95g of 7wt% sodium peroxosulfate aqueous solution was fed to the reactor over 240 min. After the addition of the initiator feed was finished, the obtained reaction mixture was cooled to 75°C.
• reaction mixture 45 g of an 8% aqueous solution of sodium hydroxide was then added within 5 min. After that 26 g of a 10%> aqueous solution of tert-butyl hydroperoxide solution and 36 g of a 13 % solution of sodium sulfite were added within 60 min. After the end of the feed the reaction mixture was cooled to room temperature. A latex was resulted.
• the volume concentration of the total inorganic contents in the resulting composition is around 45%.
• the glass transition temperature of the polymer in Latex A was 20°C.
• Molecular weight was measured by gel permeation chromatography according to ISO 13885-1. Mw was around 512,000 Dalton, Mn was around 77,000 Dalton.
• the content of Laromer ® WA9057 is about 5.30%, and the content of Esacure ® TZT is about 0.26%.
• the volume concentration of the total inorganic contents in the resulting composition is around 45%.
• the volume concentration of the total inorganic contents in the resulting composition is around 45%.
• the content of Laromer ® LR 8983 is about 1.16%, and the content of IRGACURE ® 754 is about 0.11%.
• the volume concentration of the total inorganic contents in the resulting composition is around 45%>.
• the volume concentration of the total inorganic contents in the resulting composition is around 45%.
• the content of Laromer ® LR 8949 is about 5.15%, and the content of Benzophenone is about 0.05%>.
• a commercially available dispersion Acronal ® 7079 from BASF (Latex B) with lg of Esacure ® TZM, 25g of Laromer ® PE55
• the volume concentration of the total inorganic contents in the resulting composition is around 45%.
• the glass transition temperature of the polymer in Latex B was 10°C.
• Molecular weight was measured by gel permeation chromatography according to ISO 13885-1. Mw was around 917,000 Dalton, Mn was around 190,000 Dalton.
• the content of Laromer ® PE55 WIN is about 4.49%, and the content of Esacure ® TZM is about 0.18%.
• the volume concentration of the total inorganic contents in the resulting composition is around 34%.
• the content of Laromer ® LR 8889 is about 6.15%, and the content of IRGACURE ® 500 is about 0.22%.
• the volume concentration of the total inorganic contents in the resulting composition is around 34%.
• the volume concentration of the total inorganic contents in the resulting composition is around 34%.
• the content of Laromer ® HDDA is about 2.98%, and the content of Esacure ® TZT is about 0.18%.
• the volume concentration of the total inorganic contents in the resulting composition is around 34%.
• the glass transition temperature of the polymer in Latex C was 23°C.
• Molecular weight was measured by gel permeation chromatography according to ISO 13885-1. Mw was around 394,000 Dalton, Mn was around 62,000 Dalton.
• the content of Laromer ® WA9057 is about 7.93%, and the content of IRGACURE ® 754 is about0.18%.
• the volume concentration of the total inorganic contents in the resulting composition is around 34%.
• Example 3 185g of demineralized water, 5g of dispersant DISPEX ® AA4140 from BASF, lg of defoamer DC065 from Dow Corning, 196g of T1O2 CR828 from Kerr-McGee, 139g of CaC0 3 Omyacarb ® 5 from Omya, 16g of Texonal ® from Eastman, 3g of Natrosol ® 250HBR from Ashland and lOg of propylene glycol from GuoYao Reagent Company, to form a composition.
• the volume concentration of the total inorganic contents in the resulting composition is around 35%.
• the content of allyl methacrylate is about 2.89%, and the content of Benzophenone is about 0.18%.
• the volume concentration of the total inorganic contents in the resulting composition is around 34%.
• Example 13 Formulate 408g of Latex A with 1.3g of Benzophenone, 36g of resulting dispersion from Example 3, 185g of demineralized water, 5g of dispersant DISPEX ® AA4140 from BASF, lg of defoamer DC065 from Dow Corning, 196g of Ti0 2 CR828 from Kerr-McGee, 139g of CaCOs Omyacarb ® 5 from Omya, 16g of Texonal ® from Eastman, 3g of Natrosol ® 250HBR from Ashland and lOg of propylene glycol from GuoYao Reagent Company, to form a composition.
• the volume concentration of the total inorganic contents in the resulting composition is around 35%.
• the content of allyl methacrylate is about 2.32%, and the content of Benzophenone is about 0.23%.
• the volume concentration of the total inorganic contents in the resulting composition is around 35%.
• a 4L-reactor was inertized by passing nitrogen through for 10 min, then charged with 600 g of demineralized water, 25 g of a 33% seed latex of polystyrene with a particle size of 33 nm.
• the reactor containing the above charge was heated to 85°C, and stirred over the complete time of synthesis. 5 g of 7% sodium peroxosulfate aqueous solution was added at 85°C.
• an emulsion feed mixed by 450 g of demineralized water, 28 g of a sodium salt of a fatty alcohol polyglycol ether sulfate, 705 g of methyl methacrylate, 527 g of n-butyl acrylate, 23 g of methacrylic acid and 13g of Esacure ® TZM, was started and fed within 210 minutes.
• 95g of 7wt% sodium peroxosulfate aqueous solution was started and fed to the reactor with 240 min. After the end of the initiator feed the reaction mixture was cooled to 75°C.
• reaction mixture was then added 45 g of a 8% aqueous solution of sodium hydroxide within 5 min. After that 26 g of a 10% aqueous solution of tert-butyl hydroperoxide solution and 36 g of a 13 % solution of sodium sulfite were added within 60 min followed by adding 870g of Laromer ® 8765. After the end of the feed the reaction mixture was cooled to room temperature.
• the volume concentration of the total inorganic contents in the resulting composition of around 45%.
• a 4L-reactor was inertized by passing nitrogen through for 10 min, then charged with 600 g of demineralized water, 25 g of a 33% seed latex of polystyrene with a particle size of 33 nm.
• the reactor containing the above charge was heated to 85°C, and stirred over the complete time of synthesis. 5 g of 7% sodium peroxosulfate aqueous solution was added at 85°C.
• an emulsion feed mixed by 450 g of demineralized water, 28 g of a sodium salt of a fatty alcohol polyglycol ether sulfate, 998 g of methyl methacrylate, 304 g of n-butyl acrylate, 23 g of methacrylic acid and 13g of Esacure ® TZM, was started and fed within 210 minutes.
• 95g of 7wt% sodium peroxosulfate aqueous solution was started and fed to the reactor with 240 min. After the end of the initiator feed the reaction mixture was cooled to 75°C.
• the volume concentration of the total inorganic contents in the resulting composition of around 45%.
• a 4L-reactor was inertized by passing nitrogen through for 10 min, then charged with 600 g of demineralized water, 25 g of a 33% seed latex of polystyrene with a particle size of 33 nm.
• the reactor containing the above charge was heated to 85°C, and stirred over the complete time of synthesis. 5 g of 7% sodium peroxosulfate aqueous solution was added at 85°C.
• an emulsion feed mixed by 450 g of demineralized water, 28 g of a sodium salt of a fatty alcohol polyglycol ether sulfate, 247 g of methyl methacrylate, 1055 g of n-butyl acrylate, 23 g of methacrylic acid and 13g of Esacure ® TZM, was started and fed within 210 minutes.
• 95g of 7wt% sodium peroxosulfate aqueous solution was started and fed to the reactor with 240 min. After the end of the initiator feed the reaction mixture was cooled to 75°C.
• the volume concentration of the total inorganic contents in the resulting composition of around 45%.
• a 4L-reactor was inertized by passing nitrogen through for 10 min, then charged with 600 g of demineralized water, 25 g of a 33% seed latex of polystyrene with a particle size of 33 nm.
• the reactor containing the above charge was heated to 85°C, and stirred over the complete time of synthesis. 5 g of 7% sodium peroxosulfate aqueous solution was added at 85°C.
• an emulsion feed mixed by 450 g of demineralized water, 28 g of a sodium salt of a fatty alcohol polyglycol ether sulfate, 705g of methyl methacrylate, 527 g of n-butyl acrylate, 23 g of methacrylic acid, 52g of n-dodecyl mercaptan and 13g of Esacure ® TZM, was started and fed within 210 minutes.
• 95g of 7wt% sodium peroxosulfate aqueous solution was started and fed to the reactor with 240 min. After the end of the initiator feed the reaction mixture was cooled to 75°C.
• the volume concentration of the total inorganic contents in the resulting composition of around 45%.
• compositions samples from above examples and comparative examples are casted and cured into dry film according to the method described in SS500:2002, for mechanical test and outdoor exposure in BASF Advanced Chemicals Company, Shanghai Site.
• the mechanical test is in accordance with ASTM D412 using die C with the pulling rate of 50 mm/min.
• Tg is determined by Differential Scanning Calorimetrie (TA DSC Q100, Waters TA, -80 to 120°C, "midpoint temperature" of second heating curve, heating rate 10°C /min).
• the Elongation at Break values obtained by the inventive examples are around 100% or higher, which means a sufficient flexibility of the coating film obtained from the inventive composition.
• the highest Lab DPUR ⁇ value obtained by the inventive examples is 7.34 (example 6), which is still lower than comparative examples 2-9.
• the lower value of the Lab DPUR ⁇ value means the better the dirt pick-up resistance.
• Comparative example 1 though it obtains the low DPUR value of 6.04, the obtained film of comparative example 1 has Elongation at Break of 16%, which is too low to be applicable.
• the coating films obtained from the composition of the invention achieve both excellent flexibility and dirt pick-up resistance.

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• 2016
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