Aqueous coating composition

Abstract

The present invention relates generally to the field of crosslinkable aqueous vinyl polymer dispersions, coating compositions comprising said crosslinkable aqueous vinyl polymer dispersions, paint formulations comprising said crosslinkable aqueous vinyl polymer dispersions, and articles coated with the coating compositions or paint formulations. In particular, the present invention relates to an aqueous vinyl polymer dispersion PD, comprising an aqueous dispersion of the following polymer: 1) a vinyl polymer P1, comprising: a) 5-20 wt % of an acid-functional ethylenically unsaturated monomer M1 or a precursor thereof; a) an aqueous dispersion or solution of a vinyl polymer P1 obtained by free radical emulsion polymerization of a monomer mixture comprising: a) 5-25 wt. % of an ethylenically unsaturated monomer M2 containing a polyethylene glycol or monoalkoxypolyethylene glycol moiety; c) up to 90 wt. % of a nonionic ethylenically unsaturated monomer M3 other than M1 or M2; d) 0-10 wt. % of an ethylenically unsaturated monomer M4 having a functional group for crosslinking after film formation; and e) 0-10 wt. % of at least one chain transfer agent CTA, wherein the sum of the wt. % of M1 + M2 + M3 + M4 + CTA = 100 wt. %; and 2) an aqueous dispersion or solution of a vinyl polymer P2, comprising: a) a vinyl polymer P1 having the general structure [Formula 1] JPEG2023520805000007.jpg4644 (wherein R1 and R2 are C1-C5 alkyl and can be linked to form a ring structure, preferably N-vinylpyrrolidone or N-vinylcaprolactam), b) 25-95 wt % of an ethylenically unsaturated monomer M5 selected from the group consisting of N-vinylamides having the formula: (wherein R1 and R2 are C1-C5 alkyl and can be linked to form a ring structure, preferably N-vinylpyrrolidone or N-vinylcaprolactam), b) 5-75 wt % of a nonionic ethylenically unsaturated monomer M3' other than M5, c) 0-5 wt % of an ethylenically unsaturated monomer M4' having a functional group for crosslinking after film formation, d) 0-10 wt % of an acid-functional ethylenically unsaturated monomer M1' or a precursor thereof, and e) 0-5 wt % of an ethylenically unsaturated monomer M2' having a functional group for crosslinking after film formation, % of at least one chain transfer agent CTA', wherein the sum of the wt % of M5+M3'+M4'+M1'+CTA'=100 wt %, and 3) a film-forming vinyl polymer P3 in the form of an aqueous dispersion, comprising: i) 1) at least one acid-functional ethylenically unsaturated monomer M1'', 2) at least one ethylenically unsaturated monomer M4'', other than M1'', which has a functional group for crosslinking during film formation; 3) at least one ethylenically unsaturated monomer M5'', other than M1'' and M2'', which has a functional group for crosslinking during film formation; 1) optionally one acid-functional ethylenically unsaturated monomer M1''', 2) optionally one or more ethylenically unsaturated monomers M4''', other than M1''', having a functional group for crosslinking during film formation, 3) M1''', and M2', in the presence of ii) a water-soluble or water-dispersible crosslinkable vinyl oligomer OL obtained by emulsion polymerization of a monomer mixture containing an acid-functional ethylenically unsaturated monomer M3'', and 5) optionally at least one chain transfer agent CTA'', and 4) a film-forming vinyl polymer P3 comprising 40 to 80 wt % of a high molecular weight vinyl polymer P4 prepared by emulsion polymerization of a monomer mixture comprising at least one ethylenically unsaturated monomer M3''' other than M5''', and optionally one or more polyfunctional ethylenically unsaturated monomers M5''', preferably in an amount of less than 5 wt %, for pre-crosslinking, wherein the total weight of the film-forming vinyl polymer P3 = wt % of the water-soluble or water-dispersible crosslinkable vinyl oligomer OL + wt % of the high molecular weight vinyl polymer P4 = i) + ii) = 100 wt %,The total weight of vinyl polymers in the aqueous vinyl polymer dispersion PD = wt% of vinyl polymer P1 + wt% of vinyl polymer P2 + wt% of film-forming vinyl polymer P3 = 100 wt%.

Description

Technical Field

[0001] The present invention relates to a crosslinkable aqueous vinyl polymer dispersion, a coating composition containing the crosslinkable aqueous vinyl polymer dispersion, a paint formulation containing the crosslinkable aqueous vinyl polymer dispersion, and an article coated with the coating composition or the paint formulation.

Background Art

[0002] Laws regarding the emission of volatile compounds are promoting the switch from solvent-based coating compositions to water-based coating compositions. However, water-based coating compositions still need improvement in order to achieve or balance the advantageous properties of their solvent-based counterparts. A particular problem with water-based coating compositions is that the newly applied coating layer has a short reworkable period without leaving visible defects such as brush marks, roller marks, spray dust (commonly known as "overspray") or visible lines at the joints between adjacent coating layers in the cured coating.

[0003] A layer of a coating composition newly applied to a substrate is said to be "open" if it can still be manipulated during drying without leaving substantial visible defects in the dried coating. The open time is the period between the initial application of the coating layer and the time when corrections can no longer be made without leaving visible defects in the wet coating film.

[0004] Improving the open time of water-based paints based on aqueous film-forming coating compositions has been a long-standing desire. The film-forming polymer in an aqueous coating composition typically has a glass transition temperature low enough to form an adherent film on the substrate at the ambient use temperature, preferably having a minimum film-forming temperature in the range of 0 to 60°C.

[0005] It is considered that a longer open time can be achieved by using a water-soluble additive or a covalent binder in the coating formulation. For example, water-soluble co-solvents such as alkylene glycols (e.g., ethylene glycol, propylene glycol, 2-methyl-2,4-pentanediol) are regarded as having a beneficial effect on the open time. Alternatively, water-soluble polymers such as polyvinyl alcohol, polyethylene glycol, poly(meth)acrylamide, and poly-2-ethyloxazoline have been suggested to be useful for extending the open time of aqueous coatings. However, the resulting coatings showing insufficient water resistance is a common problem of known water-soluble polymer open time improvers. This means that they can only be used at very low levels in practice, thus reducing the effectiveness of the improvement in open time or wet edge time. Water-soluble additives also cause problems when, for example, it is necessary to overcoat a first paint layer with a second layer of the same paint to adequately conceal the substrate. Generally speaking, the recoatability of these paints is insufficient.

[0006] EP136025B1 discloses a paint formulation comprising a water-soluble copolymer containing both ionic and non-ionic moieties. These blends can improve the open time and brushability of decorative paints, but no data or claims related to such uses are mentioned.

[0007] EP0593151B1 describes a method for improving the open time of aqueous coatings. The method involves blending an acrylic latex containing reactive functional groups with a modified amphiphilic low molecular weight compound containing reactive groups complementary to the reactive groups of the polymer latex. The addition of the modified compound actually improved the open time of a reference paint prepared using only the acrylic latex. However, the open time only reached a maximum of 15 minutes, and no data regarding the open time of the second layer and its recoatability are mentioned.

[0008] US2001 / 0031826A1 describes the use of an emulsion polymer for the formulation of a high gloss paint with improved open time. An emulsion polymer was prepared using a mixture of (meth)acrylic monomers and polyalkylene oxide functional monomers. The open time of the paints made with these copolymers was, in some instances, actually significantly longer than 20 minutes. Nevertheless, no data regarding the recoatability of the paints was presented.

[0009] WO2012130817A1 describes an aqueous composition made from a blend of two film-forming polymer dispersions, which exhibits an extended open time of the first layer, as well as excellent chemical resistance and blocking, compared to conventional commercially available trim paints. The first polymer dispersion contains groups for ambient crosslinking and carboxylic acid / polyethylene oxide functional groups. The second polymer dispersion is from the group of polyurethanes, vinyl polymers or alkyds.

[0010] Despite the progress made in the art, the focus has mainly been on the open time and the dry film performance of the first paint layer applied. However, trim and architectural paints are usually applied as multi-layer systems to obtain sufficient hiding of the substrate. Therefore, the open time during the application of the second layer must be at the same level as that of the first paint layer. WO2015107163A1 discloses a technique that enables the open time of the first paint layer to be 22 to 25 minutes. Nevertheless, this property no longer exists when subsequent paint layers are applied and the open time is reduced by approximately 30 to 50%. Also, the flow and leveling of the second applied paint layer of the paint are insufficient. Therefore, there is a need for an aqueous coating having good open time, flow and leveling in paints applied in multiple layers. SUMMARY OF THE INVENTION

[0011] The present invention relates to an aqueous polymer vinyl dispersion for use in a coating composition according to the present invention. This aqueous vinyl polymer dispersion PD is composed of the following polymers: 1) An aqueous dispersion of vinyl polymer P1, a) 5 to 20 wt% of an acid-functional ethylenically unsaturated monomer M1 or its precursor, b) 5 to 25 wt% of an ethylenically unsaturated monomer M2 containing a polyethylene glycol or monoalkoxypolyethylene glycol moiety, c) Up to 90 wt% of a nonionic ethylenically unsaturated monomer M3 other than M1 or M2, d) 0 to 10 wt% of an ethylenically unsaturated monomer M4 having a functional group for crosslinking after film formation, and e) 0 to 10 wt% of at least one chain transfer agent CTA obtained by free radical emulsion polymerization of a monomer mixture containing, where the total wt% of M1 + M2 + M3 + M4 + CTA = 100 wt%, an aqueous dispersion of vinyl polymer P1, and 2) An aqueous dispersion or solution of vinyl polymer P2, a) General structure [Chemical formula] (wherein R1 and R2 are C1 - C5 alkyls and can be linked to form a ring structure, preferably N - vinylpyrrolidone or N - vinylcaprolactam) 25 to 95 wt% of an ethylenically unsaturated monomer M5 selected from the group of N - vinylamides having, b) 5 to 75 wt% of a nonionic ethylenically unsaturated monomer M3', c) 0 to 5 wt% of an ethylenically unsaturated monomer M4' having a functional group for crosslinking after film formation, d) 0 to 10 wt% of an acid-functional ethylenically unsaturated monomer M1' or its precursor, and e) 0 to 5 wt% of at least one chain transfer agent CTA' obtained by free radical copolymerization of, Here, an aqueous dispersion or solution of vinyl polymer P2, where the total wt% of M5 + M3’ + M4’ + M1’ + CTA’ = 100 wt%, and 3) A film-forming vinyl polymer P3 in the form of an aqueous dispersion, i) 1) At least one acid-functional ethylenically unsaturated monomer M1’’, 2) At least one ethylenically unsaturated monomer M4’’ other than M1’’ and having a functional group for crosslinking during film formation, 3) At least one ethylenically unsaturated monomer M3’’ other than M1’’ and M2’’, and 5) Optionally, at least one chain transfer agent CTA’’ A 20 - 60 wt% water-soluble or water-dispersible crosslinkable vinyl oligomer OL obtained by emulsion polymerization of a monomer mixture containing, and ii) In the presence of the water-soluble or water-dispersible crosslinkable vinyl oligomer OL, 1) Optionally, one acid-functional ethylenically unsaturated monomer M1’’’, 2) Optionally, one or more ethylenically unsaturated monomers M4’’’ other than M1’’’ and having a functional group for crosslinking during film formation, 3) At least one ethylenically unsaturated monomer M3’’’ other than M1’’’ and M2’’’, and 4) Optionally, preferably in an amount of less than 5 wt%, one or more polyfunctional ethylenically unsaturated monomers M5’’’ for pre-crosslinking A 40 - 80 wt% high molecular weight vinyl polymer P4 prepared by emulsion polymerization of a monomer mixture containing, A film-forming vinyl polymer P3 in the form of an aqueous dispersion containing, and containing, - The total weight of the film-forming vinyl polymer P3 = wt% of the water-soluble or water-dispersible crosslinkable vinyl oligomer OL + wt% of the high molecular weight vinyl polymer P4 = i) + ii) = 100 wt%, - The total weight of the vinyl polymer in the aqueous vinyl polymer dispersion PD = wt% of the vinyl polymer P1 + wt% of the vinyl polymer P2 + wt% of the film-forming vinyl polymer P3 = 100 wt%.

[0012] The vinyl polymers P1, P2 and P3 can be synthesized separately, and their respective aqueous dispersions can be combined by blending to form the polymer dispersion PD. The ratio of vinyl polymers P1, P2 and P3 is (1:1:98) to (65:15:20), preferably (9:1:90) to (50:10:40), more preferably (25:1.5:73.5) to (35:4.5:60.5), and most preferably (27:2:70) to (32:4:65).

[0013] The aqueous vinyl polymer dispersion PD consists of 30 wt% to 60 wt% of vinyl polymers P1 + P2 + P3, and the remainder is, inter alia, water, surfactant, neutralizing base and biocide.

[0014] In the present invention, "ethylenically unsaturated monomer" means a monomer having at least one carbon-carbon double bond capable of undergoing radical polymerization.

[0015] When used to name the compounds of the present invention, the prefix "(meth)acryl" encompasses both "acryl" and "methacryl", and refers to compounds containing at least one CH2=CHCOO- group or CH2=C(CH3)COO- group, as well as mixtures thereof and mixtures of such compounds.

[0016] "Vinyl oligomer" means a low molecular weight polymer obtained by radical polymerization of ethylenically unsaturated monomers.

[0017] "Vinyl polymer" means a polymer derived from vinyl monomers containing carbon-carbon double bonds.

[0018] "Here, the total wt% of M1 + M2 + M3 + M4 + CTA = 100 wt%" means that the vinyl polymer P1 consists essentially of monomers M1, M2, M3, M4 and at least one chain transfer agent CTA as defined above. Therefore, the total weight of the vinyl polymer P1 corresponds to the sum of the weight percentages of monomers M1, M2, M3, M4 and at least one chain transfer agent CTA.

[0019] "Here, the total wt% of M5 + M3'+ M4'+ M1'+ CTA' = 100 wt%" means that the vinyl polymer P2 consists essentially of monomers M5, M3', M4', M1' and at least one chain transfer agent CTA'. Therefore, the total weight of the vinyl polymer P2 corresponds to the sum of the weight percentages of monomers M5, M3', M4', M1' and at least one chain transfer agent CTA'.

[0020] "The total weight of the film-forming vinyl polymer P3 = wt% of the water-soluble or water-dispersible crosslinkable vinyl oligomer OL + wt% of the high molecular weight vinyl polymer P4 = i) + ii) = 100 wt%" means that the film-forming vinyl polymer P3 consists essentially of the water-soluble or water-dispersible crosslinkable vinyl oligomer OL and the high molecular weight vinyl polymer P4. Therefore, the total weight of the film-forming vinyl polymer P3 corresponds to the sum of the weight percentages of the water-soluble or water-dispersible crosslinkable vinyl oligomer OL and the high molecular weight vinyl polymer P4.

[0021] "Here, 'the total weight of the vinyl polymer in the aqueous vinyl polymer dispersion PD = wt% of vinyl polymer P1 + wt% of vinyl polymer P2 + wt% of film-forming vinyl polymer P3 = 100 wt%' means that this vinyl polymer consists essentially of vinyl polymer P1, vinyl polymer P2, and film-forming vinyl polymer P3. Therefore, the total weight of the vinyl polymer in the aqueous vinyl polymer dispersion PD corresponds to the sum of the weight percentages of vinyl polymer P1, vinyl polymer P2, and film-forming vinyl polymer P3. Therefore, the aqueous vinyl polymer dispersion PD consists essentially of an aqueous dispersion of vinyl polymer P1, an aqueous dispersion or solution of vinyl polymer P2, and an aqueous dispersion of film-forming vinyl polymer P3."

[0022] The process of emulsion polymerization is described in ''Chemistry and Technology of Emulsion Polymerisation'', Editor A. van Herk, (2005), Blackwell Publishing Ltd.

[0023] Definition of Monomers - Monomers M1, M1', M1'', and M1''' The acid-functional ethylenically unsaturated monomers M1, M1', M1'', and M1''' can each independently be selected from the group consisting of carboxylic acid-functional monomers or their precursors, such as acrylic acid, methacrylic acid, maleic acid or its half ester, fumaric acid or its half ester, and itaconic acid or its half ester. These monomers can be manufactured from petrochemical raw materials. Alternatively, they may be derived from renewable feedstocks. Bio-based acrylic acid can be manufactured from glycerol or hydroxypropionic acid, hydroxypropionic acid derivatives, or mixtures thereof. Itaconic acid is obtained by fermentation of sugars, and bio-based methacrylic acid can be derived from itaconic acid.

[0024] Other acid-functional non-carboxylic acid group-containing monomers may be, for example, sulfate or sulfonic acid monomers. Non-limiting examples include 2-acrylamido-2-methylpropanesulfonic acid or its alkali, ammonia or amine salts, and the sodium salts of the addition products of sodium bisulfite of allyl glycidyl ether, 2-sulfoethyl methacrylate or 1-(allyloxy)-2-hydroxypropane-1-sulfonic acid. Also, phosphate or phosphonate-functional monomers can be used. Non-limiting examples of such monomers are monoacryloxyethyl phosphate, Sipomer® PAM-100 and Sipomer® PAM-200 (both manufactured by Solvay), 10-methacryloyloxydecyl dihydrogen phosphate (Kuraray), dimethyl(2-methacryloyloxyethyl)phosphonate and dimethyl(2-methacryloyloxypropyl)phosphonate or ethyl 2-[4-(dihydroxyphosphoryl)-2-oxabutyl]acrylate.

[0025] - Monomers M2, M2’, M2’’ and M2’’’ The polyethylene oxide containing ethylenically unsaturated monomers M2, M2’, M2’’, and M2’’’ preferably contains monomers of the general formula R3-O-(CH2-CH2-O)n-R2, where R3 is acrylic or methacrylic, R2 is H or alkyl, preferably containing 1 to 4 carbon atoms, and n is an integer from 1 to 35, preferably 2 to 20, and most preferably 3 to 15. The polyethylene oxide ethylenically unsaturated monomer preferably contains 2 to 50, more preferably 2 to 20, and most preferably 2 to 15 ethylene oxide units. The monomer is preferably a polyethylene glycol (meth)acrylate monomer or a monomethoxy (meth)acrylate monomer. Suitable examples of the polyethylene oxide ethylenically unsaturated monomer ii) are methoxypolyethylene glycol 550 methacrylate and methoxypolyethylene glycol 350 methacrylate. Examples are Visiomer® ETMA, Visiomer® MPEG550MA (available from Evonik), Bisomer® S20W, Bisomer® PEA6 (available from GEO Specialty Chemicals).

[0026] - monomers M3, M3’, M3’’, and M3’’’ The nonionic ethylenically unsaturated monomers M3, M3', M3'', M3''', and M3'''' are preferably styrene and styrene derivatives, such as alpha-methylstyrene, t-butylstyrene, vinyltoluene, o-, m-, and p-methylstyrene, o-, m-, and p-ethylstyrene, alkyl esters of (meth)acrylic acid, vinyl esters, vinyl monomers containing a hydroxyl group. Preferred monomers include esters of acrylic acid and methacrylic acid, such as n-butyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cycloalkyl (meth)acrylate, such as cyclohexyl (meth)acrylate. Esters of itaconic acid, such as dimethyl itaconate and di-butyl itaconate. These monomers can be produced from petrochemical raw materials. Alternatively, they may be derived from renewable feedstocks such as bio-based acrylic acid and methacrylic acid. The alkanol used in the (trans)esterification may be of biological origin. Non-limiting examples of such monomers are Visiomer® Terra C13-MA, Visiomer® Terra C17.4-MA, n-octyl acrylate, and isobornyl (meth)acrylate. Also, dienes, such as 1,3-butadiene or isoprene, or mixtures thereof. Also, vinyl esters, such as vinyl acetate, vinyl alkanoate, or derivatives or mixtures thereof can be used in the monomer composition. Nitriles such as (meth)acrylonitrile can also be used.

[0027] - Monomers M4, M4', M4'', and M4''' Monomers M4, M4’, M4’’, M4’’’ and M4’’’’ having functional groups other than acidic groups can be used for crosslinking after film formation. M4, M4’, M4’’, M4’’’ and M4’’’’ may be the same or different. Examples of these monomers include hydroxy-functional monomers such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and monomers having latent hydroxy groups such as glycidyl methacrylate. The hydroxy-functional group can crosslink with polyisocyanate at a temperature slightly higher than ambient temperature. Further examples include derivatives of (meth)acrylamide such as N-methylol (meth)acrylamide. Other examples of monomers include those containing a carbonyl group, such as acrolein, methacrolein, crotonaldehyde, 4-vinylbenzaldehyde, vinyl alkyl ketones having 4 to 7 carbon atoms such as vinyl methyl ketone. Further examples include acrylamide pivalaldehyde, methacrylamide pivalaldehyde, 3-acrylamidomethyl-anisaldehyde, diacetone acrylate and diacetone methacrylate, and keto-containing amides such as diacetone acrylamide. Monomers having an acetoacetoxy-functional group can also be used. Examples of such monomers are acetoacetoxyethyl methacrylate, acetoacetoxyethyl acrylate, acetoacetoxypropyl acrylate, allyl acetoacetate and acetoacetoxybutyl acrylate. The preferred functional groups of monomer M4, each of M4’, M4’’, M4’’’ and M4’’’’ are preferably a carbonyl group or an acetoacetic acid group.

[0028] In a particularly preferred embodiment, monomers M4, M4’, M4’’, M4’’’ and M4’’’’ are selected from acetoacetoxyethyl methacrylate and diacetone acrylamide, or mixtures thereof. Crosslinking agents for use in combination with the above functional groups are known to those skilled in the art and include diamines or polyamines and dicarboxylic acid hydrazides or polycarboxylic acid hydrazides. Crosslinking may occur at ambient temperature or at a slightly elevated temperature. The crosslinking agent may be pre-incorporated into the dispersion of polymer P1, P2 or P3, or may be added at a later stage.

[0029] - Monomer M5 Monomers M5 can each independently be selected from the group of N-vinylamides having the general structure: [Chemical formula] (wherein R1 and R2 are C1-C5 alkyls and may be linked to form a ring structure, preferably N-vinylpyrrolidone or N-vinylcaprolactam).

[0030] - Chain transfer agents CTA, CTA’ and CTA’’ To control the molecular weights of polymers P1, P2, and OL, chain transfer agents CTA, CTA’, CTA’’ are used. Exemplary chain transfer agents are butyl mercaptan, mercaptopropionic acid, 2-ethylhexyl mercaptopropionate, n-dodecyl mercaptan, t-dodecyl mercaptan, n-butyl mercaptopropionate, 2-mercaptoethanol, octyl mercaptan, isodecyl mercaptan, octadecyl mercaptan, mercaptoacetic acid, allyl mercaptopropionate, allyl mercaptoacetate, crotyl mercaptopropionate, crotyl mercaptoacetate. Other non-sulfur-based chain transfer agents include halogenated hydrocarbons or catalytic chain transfer agents. Also, α-methylstyrene dimer or an oligomer of α-methylstyrene dimer can be used. Yet another method for synthesizing polymers with a well-defined molecular weight is the use of diarylethene. A commonly used diarylethene is diphenylethene.

[0031] Definition of vinyl polymers P1, P2, and P3 - Vinyl polymer P1 Vinyl polymer P1 can be obtained by free radical aqueous emulsion polymerization in the presence of at least one free radical initiator and at least one surfactant containing a free radical-reactive double bond, optionally a copolymerizable surfactant.

[0032] The vinyl polymer P1 has a number average molecular weight Mn of 2,000 to 120,000 g / mol, preferably 4,000 to 12,000, and most preferably 5,000 to 10,000. The weight average molecular weight (Mw) is preferably 8,000 to 50,000, and most preferably 10,000 to 25,000. The molecular weight and molecular weight distribution were determined using size exclusion chromatography (SEC) with THF and 2% acetic acid as the eluent. The vinyl polymer P1 has a preferred polydispersity defined by a ratio of Mn / Mw of 1.2 to 3.0, preferably 1.5 to 2.5. The vinyl polymer P1 contains 5 to 25 wt%, preferably 7 to 20 wt%, and most preferably 9 to 15 wt% of a polyethylene oxide ethylenically unsaturated monomer M2. The vinyl polymer P1 preferably has an acid value of 30 to 150 mgKOH / g as determined by ISO3682. When aqueous emulsion polymerization is used, the acid functional groups of the polymer are neutralized to an α value of 0.05 to 0.70, preferably 0.10 to 0.25, and a polymer dispersion of the polymer vinyl polymer P1 in the form of an aqueous dispersion having a pH of 6.0 to 8.0, most preferably 6.5 to 7.5, is obtained.

[0033] According to one embodiment, the vinyl polymer P1 has a number average molecular weight of 2,000 to 120,000 g / mol as determined by size exclusion chromatography using tetrahydrofuran and 2% acetic acid as the eluent and a polystyrene standard, an acid value of 30 to 150 mgKOH / g as determined by ISO3682, and 5 to 25 wt% of an ethylenically unsaturated monomer M2 relative to the total weight of the polymer P1, selected from the group consisting of polyethylene oxide and monoalkoxypolyethylene glycol (meth)acrylate.

[0034] - Vinyl polymer P2 Vinyl polymer P2 is an addition polymer that can be prepared by free radical copolymerization techniques known in the art at temperatures in the range of 0 to 200 °C, at atmospheric pressure or high pressure. Preferably, vinyl polymer P2 is a random copolymer. Block copolymers or gradient copolymers in which the pendant groups derived from monomer A are not uniformly distributed in the second polymer are not preferred as they are suspected not to form a substantially Newtonian solution that is water-soluble. Preferably, vinyl polymer P2 is produced by solution polymerization in an organic solvent that can be easily removed by distillation, such as methyl ethyl ketone, acetone or isopropanol, or in a water-miscible solvent, such as butyl glycol, diethylene glycol monobutyl ether or diethylene glycol monoethyl ether.

[0035] Vinyl polymer P2 generally has a weight average molecular weight Mw of 1,000 to 50,000, preferably 2,000 to 40,000, more preferably 4,000 to 25,000, and most preferably 8,000 to 12,500 gr / mol (determined by gel permeation chromatography using hexafluoro - iso - propanol as the eluent and a poly(methyl methacrylate) standard for the calibration curve).

[0036] Preferably, vinyl polymer P2 has a glass transition temperature Tg of - 30 to 180 °C. Preferably, Tg is at least 0 °C, preferably at least 20 °C, more preferably at least 35 °C, and most preferably at least 45 °C. Good results were also obtained when Tg exceeded 60, 70, 80 as well as 90 and 100 °C. Preferably, the second polymer has a Tg of 0 to 180 °C.

[0037] As described above, vinyl polymer P2 has a non - ionic but hydrophilic functional group resulting from monomer M5 that provides water - solubility.

[0038] From the perspective of the coating properties envisaged, it is preferred that at least 80, preferably 90 or even more preferably 95% of the monomer M3' in the vinyl polymer P2 has a monomer Tg of less than 120, preferably less than 100, 50 or 20, and more preferably less than -10 °C.

[0039] The vinyl polymer P2 further contains 0 to 5 wt% of a crosslinkable monomer M4', which is different from the monomers M1' and M2'. The effective amount of the monomer M3' is in the range of 5 to 75 wt%.

[0040] The vinyl polymer P2 further contains 0 to 5 wt% of a chain transfer agent CTA'.

[0041] In the most preferred embodiment, the vinyl polymer P2 is a copolymer of N-vinylpyrrolidone and ethyl acrylate. Also preferred is a copolymer of N-vinylcaprolactam and ethyl acrylate.

[0042] - Film-forming vinyl polymer P3 The vinyl polymer P3 is a film-forming polymer obtained by polymerizing a vinyl polymer P4 in the presence of a water-soluble or water-dispersible vinyl oligomer OL.

[0043] - Water-soluble or water-dispersible crosslinkable vinyl oligomer OL The water-soluble or water-dispersible crosslinkable vinyl oligomer OL is usually an acid-functional oligomer constructed from monomers M1'', M3'' and M4'' and a chain transfer agent CTA''. The oligomer preferably has a number average molecular weight Mn in the range of 500 g / mol to 50,000 g / mol, more preferably 2,500 g / mol to 25,000 g / mol, and most preferably 5,000 g / mol to 15,000 g / mol. The number average molecular weight and weight average molecular weight (Mn and Mw) of the oligomer can be measured using gel permeation chromatography with THF containing 2% acetic acid as the eluent, using a polymer such as polystyrene with a known molecular weight as a standard. The crosslinkable vinyl oligomer OL preferably has a glass transition temperature in the range of 10 to 150 °C, more preferably 20 to 125 °C, and most preferably 25 to 115 °C.

[0044] The Tg of the oligomer OL in this specification represents the calculated glass transition temperature, and it is well known that it is the temperature at which the polymer changes from a glassy brittle state to a rubbery state. The Tg value can be calculated using Fox's equation (T.G. Fox, Bull. Am. Phys. Soc. 1, 123 (1956)), which is well known in the art, and is represented by the following equation: 1 / Tg = W1 / Tg(1) + W2 / Tg(2) + W3 / Tg(3) +..... (where W1, W2, W3, etc. are the weight fractions of comonomers (1), (2), and (3), etc., and Tg(1), Tg(2), Tg(3) are the glass transition temperatures of the respective homopolymers). For the calculation, the glass transition values of the homopolymers described in Polymer Handbook, 4th edition (editors: J. Brandrup, E.H. Immergut, E.A. Grulke, John Wiley & Sons, Inc. 1999) are used. The calculated Tg (unit: Kelvin) can be easily converted to Celsius.

[0045] The vinyl oligomer OL preferably has an acid value of at least 45 mg KOH / g, more preferably at least 50 mg KOH / g, and most preferably at least 55 mg KOH / g.

[0046] Methods for influencing the molecular weight in emulsion polymerization to achieve the desired number average molecular weight are well known to those skilled in the art. The molecular weight control of the oligomer can be provided by using chain transfer agents such as mercaptans and halogenated hydrocarbons. Suitable mercaptans include n-dodecyl mercaptan, n-octyl mercaptan, t-dodecyl mercaptan, 2-mercaptoethanol, isooctyl thioglycolate, C2-C8 mercaptocarboxylic acids and their esters, such as 3-mercaptopropionic acid and 2-mercaptopropionic acid.

[0047] The crosslinkable vinyl oligomer OL can be prepared by any known technique, including direct synthesis of the oligomer by an aqueous process, i.e., in the presence of water (e.g., by emulsion polymerization, suspension polymerization, micro-suspension polymerization or mini-emulsion polymerization), or by solution polymerization where the solvent is water, or miscible with water, or any organic solvent that is removed by distillation after transferring the oligomer into water. When the oligomer is a macromonomer, it can be prepared by several methods including but not limited to the use of reversible addition-fragmentation (RAFT) agents by using catalyst chain transfer agents such as cobalt chain transfer. Also, as described in US2007 / 0043156A1 and US6,872,789, alpha-methylstyrene dimer or oligomers of alpha-methylstyrene dimer can also be used. Yet another method for synthesizing polymers with a well-defined molecular weight is the use of diaryl ethenes such as diphenylethene or high temperature processes.

[0048] Preferably, the vinyl oligomer OL is prepared by solution polymerization, emulsion polymerization or suspension polymerization. Preferably, the oligomer is prepared by an aqueous process. Preferably, the continuous phase of the aqueous process contains >50 wt%, more preferably >80 wt%, most preferably >95 wt% water.

[0049] Most preferably, the vinyl oligomer OL is prepared by an aqueous free radical emulsion polymerization process.

[0050] Free radical polymerization can be carried out as a batch or semi - continuous polymerization process.

[0051] Free radical emulsion polymerization usually requires the use of a free radical generating initiator to initiate the polymerization. Suitable free radical generating initiators include inorganic peroxides such as potassium, sodium or ammonium persulfate, hydrogen peroxide, or percarbonates; organic peroxides such as acyl peroxides including benzoyl peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide and cumene hydroperoxide; dialkyl peroxides such as di-t-butyl peroxide; peroxy esters such as t-butyl perbenzoate, etc., and mixtures can also be used. Peroxy compounds are sometimes advantageously used in combination with suitable reducing agents (redox systems) such as sodium or potassium pyrosulfite or bisulfite, Bruggolite® FF6 (trade name of L. Brueggemann GmbH & Co. KG) and isoascorbic acid. Metal compounds such as Fe.EDTA (EDTA is ethylenediaminetetraacetate) can also be used as part of a redox initiator system. Azofunctional initiators such as azobis(isobutyronitrile), 2,2’-azo-bis(2-methylbutanenitrile) (ANBN); and 4,4’-azobis(4-cyanovaleric acid) can also be used. It is possible to use an initiator system that partitions between the aqueous and organic phases, such as a combination of t-butyl hydroperoxide, isoascorbic acid or Bruggolite® FF6 and Fe.EDTA. The amount of initiator or initiator system used is conventional and is, for example, in the range of 0.05 to 6 wt% based on the total vinyl monomer used. Preferred initiators for preparing crosslinkable oligomers include ammonium persulfate, sodium persulfate, potassium persulfate, azobis(isobutyronitrile) and / or 4,4’-azobis(4-cyanovaleric acid). The most preferred initiators for preparing crosslinkable oligomers include the above redox systems and persulfates. An additional amount of initiator may optionally be added at the end of the polymerization process to assist in the removal of any residual vinyl monomer.

[0052] When the crosslinkable vinyl oligomer OL is prepared by emulsion polymerization, a surfactant (even if it is self-dispersible) can be used to assist in the dispersion or emulsification of the vinyl copolymer in water. Suitable surfactants are ionic or non-ionic surfactants. Examples of anionic emulsifiers are potassium laurate, potassium stearate, potassium oleate, sodium decyl sulfate, sodium dodecyl sulfate, and sodium rosinate. Examples of non-ionic emulsifiers are linear and branched alkyl and alkylaryl polyethylene glycol ethers and thioethers, and linear and branched alkyl and alkylaryl polypropylene glycol ethers and thioethers, alkylphenoxypoly(ethyleneoxy)ethanol, for example, an adduct of 1 mole of nonylphenol and 5 to 50 moles of ethylene oxide, or an alkali or ammonium salt of the sulfate or phosphate of the said adduct.

[0053] Moreover, a surfactant containing an olefinically unsaturated group capable of participating in free radical polymerization can also be used. Suitable polymerizable surfactants include hemiesters of maleic anhydride of the formula M+OOC-CH=CHCOOR (wherein R is C6-C22 alkyl and M+ is Na+, K+, Li+, NH4+, or a protonated or quaternary amine). Polyoxyethylene alkyl phenyl ethers having an ethylenically unsaturated bond sold under the trade name Noigen® RN (e.g., Montello, Inc.), such as NOIGEN® RN-10, NOIGEN® RN-20, NOIGEN® RN-30, NOIGEN® RN-40, and NOIGEN® RN-5065, or its sulfates sold under the trade name Hitenol® BC (e.g., Montello, Inc.), such as HITENOL® BC-10, HITENOL® BC-1025, HITENOL® BC-20, HITENOL® BC-2020, HITENOL® BC-30. MAXEMUL® 6106 (available from Croda) having both phosphonate ester and ethoxy hydrophilicity (a nominal C18 alkyl chain having an acrylate reactive group). Other representative reactive surfactants having a phosphate ester functional group suitable for such reactions include, but are not limited to, MAXEMUL® 6112, MAXEMUL® 5011, MAXEMUL® 5010 (all available from Croda Industrial Specialties).Alternative reactive surfactants suitable for use in various embodiments of the present invention include sodium allyloxyhydroxypropyl sulfonate (available from Solvay as SIPOMER® COPS-1), ADEKA REASOAP® SR / ER series, such as ADEKA REASOAP® ER-10, ER-20, ER-30 and ER-40, Akeda Reasoap SR-10, SR-20, SR-30 (all available from Asahi Denka Co., Ltd.) and allyl sulfosuccinate derivatives (e.g., TREM® LT-40 (available from BASF)).

[0054] The amount of surfactant used in the synthesis of the oligomer is preferably 0 to 15 wt%, more preferably 0 to 8 wt%, even more preferably 0 to 5 wt%, particularly 0.1 to 3 wt%.

[0055] - High molecular weight vinyl polymer P4 Preferably, vinyl polymer P4 is prepared in an aqueous process in the presence of crosslinkable vinyl oligomer OL. Prior to the polymerization of vinyl polymer P4, the crosslinkable vinyl oligomer may be partially or completely solubilized. Most preferably, vinyl polymer P4 is prepared by an aqueous emulsion polymerization process.

[0056] The method for preparing vinyl polymer P4, although not limited, includes polymerizing all of vinyl oligomer OL, monomer M3''', and optionally M1''', and / or M2''', and / or M4''' in one batch, pre-filling the reactor with solubilized or partially solubilized vinyl oligomer OL, and subsequently feeding the monomer in one or more steps and / or using gradient feeding techniques (or vice versa), feeding both the oligomer OL and the monomer to the reactor (optionally with some oligomers pre-filled), feeding the monomer to the oligomer being fed to the reactor simultaneously to prepare the vinyl polymer (optionally with some vinyl oligomers pre-filled), or continuously feeding a mixture of vinyl oligomer and monomer to the reactor, and can be carried out in several ways.

[0057] Preferably, the free radical polymerization for obtaining vinyl polymer P4 is caused by heating the contents of the reactor to a temperature in the range of 30 °C to 100 °C, more preferably in the range of 50 °C to 90 °C.

[0058] Vinyl polymer P4 has a glass transition temperature of -70 °C to 50 °C, more usually -25 °C to 40 °C, and should be at least 25 °C, more preferably at least 40 °C lower than the Tg of vinyl oligomer OL. The weight average molecular weight of vinyl polymer P4 should be higher than at least 60,000 g / mol, preferably higher than 100,000 g / mol.

[0059] The film-forming vinyl polymer P3 containing oligomer OL and polymer P4 is preferably in the form of an aqueous polymer dispersion.

[0060] Vinyl polymer P3 contains 20 to 60 wt% of vinyl oligomer OL, preferably 25 to 55 wt% of vinyl oligomer OL, and most preferably 25 to 52.5 wt% of vinyl oligomer OL.

[0061] The solid content of the aqueous dispersion of vinyl polymer P3 is preferably in the range of 20 to 60 wt%, most preferably in the range of 30 to 50 wt%.

[0062] - Initiator Free radical polymerization requires the use of a free radical generating initiator to initiate the polymerization. Suitable free radical generating initiators include inorganic peroxides such as potassium, sodium or ammonium persulfate, hydrogen peroxide, or percarbonates; organic peroxides such as acyl peroxides including benzoyl peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide and cumene hydroperoxide; dialkyl peroxides such as di-t-butyl peroxide; peroxy esters such as t-butyl perbenzoate, etc., and mixtures can also be used. Peroxy compounds are advantageously used in combination with suitable reducing agents (redox systems) such as sodium or potassium pyrosulfite or sodium or potassium bisulfite, and sodium formaldehyde sulfoxylate and isoascorbic acid in some cases. Also, non-formaldehyde releasing reducing agents such as Bruggolite® FF6 can be used. Metal compounds such as Fe.EDTA (EDTA is ethylenediaminetetraacetate) can also be used as part of a redox initiator system. Azofunctional initiators such as azobis(isobutyronitrile), 2,2'-azo-bis(2-methylbutanenitrile) (ANBN); and 4,4'-azobis(4-cyanovaleric acid) can also be used. It is possible to use an initiator system that partitions between the aqueous and organic phases, for example, a combination of t-butyl hydroperoxide, isoascorbic acid and Fe.EDTA. The amount of initiator or initiator system used is conventional and is, for example, in the range of 0.05 to 6 wt% based on the total vinyl monomer used. Preferred initiators for preparing vinyl polymers P1, P3, and P4 and vinyl oligomer OL include ammonium persulfate, sodium persulfate, potassium persulfate, azobis(isobutyronitrile) and / or 4,4'-azobis(4-cyanovaleric acid). An additional amount of initiator may optionally be added at the end of the polymerization process to assist in removing any residual vinyl monomer.

[0063] - Surfactant When the free radical polymerization for synthesizing P1 and P3 is carried out as emulsion polymerization, it is necessary to use a surfactant. Suitable surfactants are ionic or nonionic surfactants. Examples of anionic emulsifiers are potassium laurate, potassium stearate, potassium oleate, sodium decyl sulfate, sodium dodecyl sulfate and sodium rosinate. Examples of nonionic emulsifiers are linear and branched alkyl and alkylaryl polyethylene glycol ethers and thioethers and linear and branched alkyl and alkylaryl polypropylene glycol ethers and thioethers, alkylphenoxypoly(ethyleneoxy)ethanol, for example an adduct of 1 mole of nonylphenol and 5 to 50 moles of ethylene oxide, or an alkali or ammonium salt of the sulfate or phosphate of said adduct.

[0064] Moreover, a surfactant containing an olefinically unsaturated group that can participate in free radical polymerization can also be used. Suitable polymerizable surfactants include hemiesters of maleic anhydride of the formula M+-OOC-CH=CHCOOR (wherein R is C6-C22 alkyl and M+ is Na+, K+, Li+, NH4+, or a protonated or quaternary amine). Polyoxyethylene alkyl phenyl ethers having an ethylenically unsaturated bond sold under the trade name Noigen® RN (e.g., Montello, Inc.), such as NOIGEN® RN-10, NOIGEN® RN-20, NOIGEN® RN-30, NOIGEN® RN-40, and NOIGEN® RN-5065, or its sulfates sold under the trade name Hitenol® BC (e.g., Montello, Inc.), such as HITENOL® BC-10, HITENOL® BC-1025, HITENOL® BC-20, HITENOL® BC-2020, HITENOL® BC-30. MAXEMUL™ 6106 (available from Uniquema) having both phosphonate ester and ethoxy hydrophilicity (nominal C18 alkyl chain with acrylate reactive groups). Other representative reactive surfactants having a phosphate ester functional group suitable for such reactions include, but are not limited to, MAXEMUL® 6112, MAXEMUL® 5011, MAXEMUL® 5010 (all available from Croda Industrial Specialties).Alternative reactive surfactants suitable for use in various embodiments of the present invention include sodium allyloxyhydroxypropyl sulfonate (available from Solvay as SIPOMER® COPS-1), ADEKA REASOAP® SR / ER series, such as ADEKA REASOAP® ER-10, ER-20, ER-30 and ER-40, Akeda Reasoap SR-10, SR-20, SR-30 (all available from Asahi Denka Co., Ltd.) and allyl sulfosuccinate derivatives (e.g., TREM® LT-40 (available from BASF)).

[0065] The present invention also relates to a coating composition COA comprising an aqueous vinyl polymer dispersion PD.

[0066] The coating composition COA can have a pH of 2.0 to 9.0, preferably 4.5 to 8.5, most preferably 7.5 to 8.0. The coating composition COA can preferably be formulated into a paint by adding ordinary paint additives. Such a composition can still be called a coating composition. The coating composition COA may further comprise one or more organic solvents that assist in film formation, pigments (organic or inorganic) and / or other additives and fillers known in the art. When using an organic solvent, a water-miscible solvent is preferred. The amount of the organic solvent should be selected to provide a coating composition with a low volatile organic content (VOC), and preferably less than 50 g / liter, preferably less than 30 g / liter of the coating composition, including water of volatile organic compounds, as calculated by the ISO method 11890-2 in the ready-to-use form.

[0067] According to one embodiment, the coating composition COA containing the aqueous vinyl polymer dispersion PD may further contain at least one or a plurality of conventional components selected from pigments, dyes, emulsifiers, surfactants, plasticizers, thickeners, heat stabilizers, leveling agents, anti-crushing agents, fillers, anti-settling agents, UV absorbers, antioxidants, desiccant salts, organic co-solvents, wetting agents, etc., or mixtures thereof.

[0068] According to another embodiment, the coating composition COA may also contain, but is not limited to, leveling agents, rheology agents, anti-blocking agents, and flow control agents, such as silicone, fluorocarbon, urethane, or cellulose-based; extenders; flattening agents; pigment wetting and dispersing agents and surfactants; ultraviolet (UV) absorbers; UV light stabilizers; colored pigments; defoaming and foam-stopping agents; anti-settling agents, anti-dripping agents, and bodying agents; anti-skinning agents; flood and float resistance agents; fungicides and anti-mildew agents; corrosion inhibitors; thickeners; plasticizers; reactive plasticizers; desiccants; catalysts; or fusing agents. The present invention also relates to a coating composition and a paint composition containing 1 to 70 wt% of a pigment or filler. Preferably, the pigment used is rutile-type titanium dioxide, and most preferably, it has an oil absorption of less than 25 g of oil / 100 g of pigment as determined by ASTM D281-12(2016).

[0069] The coating composition COA according to the present invention may further contain a maximum of 20 wt%, preferably a maximum of 15, 10, or 5 wt% of an isocyanate crosslinking agent; a maximum of 20 wt%, preferably a maximum of 5 wt% of a polyhydrazide crosslinking agent; a maximum of 10 wt% of a silane crosslinking agent; and a maximum of 10% of a (meth)acryloyl oligomer.

[0070] As described above, the coating composition according to the present invention is suitable for various coating uses such as, for example, paints, impregnating compositions, sealing compositions and adhesive compositions. Preferred uses are primers, topcoats, or clearcoats. The coating composition can be applied to a substrate by any convenient method such as, for example, brushing, spraying or dipping. Suitable substrates include metals, woods, papers, plastics and leathers.

[0071] The present invention also relates to a method of making a coating composition COA, the method comprising the step of mixing an aqueous vinyl polymer dispersion PD with at least one or more conventional components selected from pigments, dyes, emulsifiers, surfactants, plasticizers, thickeners, heat stabilizers, leveling agents, anti-crushing agents, fillers, anti-settling agents, UV absorbers, antioxidants, drying agent salts, organic co-solvents, wetting agents, etc., or mixtures thereof.

[0072] Preferably, the coating composition COA is an aqueous coating composition.

[0073] The present invention also relates to a paint formulation comprising the coating composition COA or comprising the vinyl polymer dispersion PD. According to one embodiment, the paint formulation is preferably a pigment formulation.

[0074] The present invention also relates to the use of the aqueous vinyl polymer dispersion PD for increasing the open time, wet edge time and / or hardness of the coating composition.

[0075] The present invention also relates to an article coated with the coating composition COA or the paint formulation.

[0076] The present invention is illustrated in more detail by the following non-limiting examples.

[0077] All of the foregoing embodiments can be combined to the extent reasonable.

[0078] Example Test method The solid content (SC) is measured by weighing 1 gram of the dispersion into a tin cup and placing the cup in an air-circulation oven at 125 °C for 60 minutes. The difference in weight is related to the volatile content, and the remaining non-volatile part is the solid content. If the viscosity is high, 1 gram of water is added before heating. If the polymer contains a co-solvent, the described method does not give the correct solid content value. As a result, the theoretical solid content is used.

[0079] The molecular weight and molecular weight distribution were determined using size exclusion chromatography (SEC). The SEC apparatus used consists of a pump, an autosampler, and a He-degasser (Degasys DG-1210 manufactured by Uniflows) equipped with a PLgel 5μm MIXED-C 600×7.5 mm column and a PLgel 5μm guard column (50×7.5 mm - Polymer Laboratories). The column oven (Separations Analytical Instruments)5 was set at 30 °C. Tetrahydrofuran (THF - extra dry, Biosolve 206347) + 2% acetic acid (Baker 6052) was used as the eluent at a flow rate of 0.8 ml / min. Carbon disulfide (Backer) was used as a marker. The refractive index of Waters 410 was used as a detector. The injection volume was 100 μl at a concentration of 1.5 mg / ml. Poly(styrene) standards (Polymer Laboratories, Easical PS-1, 2010-0501 (M range 580 g / mol to 8,500,000 g / mol) and Easical PS-2, 2010-0601 (M range 580 g / mol to 400,000 g / mol)) were used to calibrate using a third-order polynomial. The software used for data analysis is Empower (Waters). For the analysis of the molecular weight of polymer P2, the eluent is changed to hexafluoroisopropanol and the poly(styrene) standards are replaced with poly(methyl methacrylate) standards.

[0080] The Brookfield viscosity is measured using a Brookfield RVT viscometer at a temperature of 23 ± 1°C in accordance with ISO 2555-1974.

[0081] The particle size was determined by dynamic light scattering using a Malvern Zetasizer model Nano-S90. The Z-average value was reported as the particle size. The z-average diameter is the average hydrodynamic diameter and is calculated in accordance with the international standard ISO 13321 for dynamic light scattering.

[0082] The initial water resistance (EWR) is measured by applying an 80 μm wet film on a Leneta flat chart. After drying at 23°C for 24 hours at a relative humidity of 45 - 55%, water droplets are placed on the surface of the paint and left for 0.5, 1, and 2 hours. After this time, the water is removed with a cloth. Damage in the form of blisters is judged immediately and after 24 hours of recovery. The reported EWR is either for 1 hour of water contact and 24 hours of recovery. A scale of 1 (completely removed or completely blistered) - 5 (no damage) is used.

[0083] The open time of the paint was determined by applying the paint on a Leneta flat chart FORM WH with a 125 micron bar applicator under conditioning conditions of 23°C and a relative humidity of 45 - 55%. The evaporation rate of the water-based paint is 22 mg / m 2per second. Using an eraser for pencils with a width of at least 2 mm, an X-shaped cross is applied to the paint layer immediately after application. A new paint and a brush filled with excess paint (Elma acryl 93-14 or Pro-Gold Exclusive 7200-12) are removed by scraping along the edge of the can. The newly filled brush is moved twice in the vertical direction of the width of the substrate and twice in the horizontal direction of the length of the substrate at the position of the X-shaped cross. This movement is repeated 10 times ( "10 cross brushes") on the same cross. This procedure is repeated at intervals of 1 minute or 2 minutes until the next cross until the cross can still be seen even after 10 "cross brushes" (one movement = twice in the width direction of the substrate and twice in the length direction of the substrate). The open time is reported as the time within the next interval of 1 minute or 2 minutes after 10 "cross brushes" that can completely remove the X-cross shape damage of the newly applied film. A 2-minute interval can be selected to obtain the first indication of the open time, and then a 1-minute interval can be used to obtain a more accurate open time.

[0084] The König hardness was measured according to ASTM D2457, wet-coated at 100 μm on glass, and dried at room temperature and at 50 °C for 16 hours.

[0085] The initial blocking resistance was measured by applying a coating with a wet layer thickness of 150 μm on a test chart. The coating is dried at room temperature for 24 hours. Blocking is tested at a temperature of 50 °C for 4 hours using a pressure of 1 kg / cm 2 of pressure.

[0086] Example 1. Preparation of an aqueous dispersion of vinyl polymer P1 by emulsion polymerization. In an emulsion polymerization reactor equipped with a cooler, a stirrer, a monomer feed tank, and an initiator feed tank, a pre-emulsion was prepared as follows: 454 grams of water and 5 grams of an anionic polymerizable surfactant (Resoap® SR-1025) were added and heated to 70 °C. In the feed tank, a mixture of 117 grams of water, 22.8 grams of the anionic polymerizable surfactant Reasoap® SR-1025 (e.g., Adeka Corporation), and 0.3 grams of sodium lauryl sulfate was mixed for 5 minutes. The monomer pre-emulsion was prepared by adding the following raw materials to the feed tank: 109.5 grams of methyl methacrylate, 24.2 grams of Visiomer® ETMA (ethyl triglycol methacrylate, Rohm GmbH), 24.2 grams of methacrylic acid, 145.7 grams of n-butyl methacrylate, 3.56 grams of octyl mercaptan, and 1.75 grams of 2-mercaptoethanol. The contents of the feed tank were stirred until a stable pre-emulsion was obtained.

[0087] A 5% wt pre-emulsion is charged into the reactor. The reactor is heated to 80 °C. Once this temperature is reached, a solution prepared by dissolving 0.3 g of ammonium persulfate in 6.3 g of water is added to the reactor. After waiting for 5 minutes, the reactor is heated to 85 °C. The supply of the pre-emulsion monomer to the reactor is started. At the same time, the supply of an initiator solution prepared by dissolving 0.75 grams of ammonium persulfate in 15.2 grams of water is started. The charging of the monomer feed is completed in 60 minutes. The charging of the initiator feed takes 70 minutes. The following finishing steps were carried out: The feed tank was rinsed with 21.0 grams of water, and the initiator tank was rinsed with 6.7 grams of water. After the supply was completed, the temperature was maintained for an additional 60 minutes. The batch was cooled to 65 °C, and a slurry prepared by mixing 4.0 g of water and 0.75 g of tertiary butyl hydroperoxide (70% wt aqueous solution) was added. A solution of 16.0 grams of water and 0.35 grams of sodium formaldehyde sulfoxylate was charged into the reactor over 15 minutes. The contents of the reactor were maintained at a temperature of 65 °C for an additional 30 minutes. Thereafter, the reactor was cooled to 25 °C. At a temperature of 25 °C, a solution prepared by dissolving 3.1 grams of Proxel® AQ (10% solution of benzisothiazolone, e.g., Lonza) in 4.0 grams of water was added, and the beaker was rinsed with 4.0 grams of water. A solution prepared by dissolving 1.65 grams of 25 wt% ammonia solution in 4.0 grams of water was added to the reactor. The beaker was rinsed with 4.0 grams of water. An aqueous polymer vinyl dispersion polymer having both ethylene oxide functional groups and carboxylic acid functional groups with the following properties was obtained: SC = 32%; pH = 7.5; residual monomer < 100 ppm; particle size = 122 nm. When the molecular weight was measured, Mn = 5,000 and Mw = 13,200.

[0088] Example 2. Preparation of an aqueous solution of vinyl polymer P2. 930.80 grams of methyl ethyl ketone was added to the polymerization reactor and heated to reflux (86 °C). Subsequently, a mixture of 31.90 grams of methyl ethyl ketone and 3.20 grams of the initiator Perkadox® AMBN (2,2’-azobis(2-methylbutyronitrile), e.g., Nouryon) was added to the reactor in parallel with 1438.00 grams of (N)-vinylpyrrolidone and 359.30 grams of ethyl acrylate over 3 hours. The reactor was held at reflux temperature for 30 minutes after the reaction. The reactor was cooled to 75 °C and 1237 grams of demineralized water was added. Methyl ethyl ketone distillation was initiated until the residual methyl ethyl ketone reached <0.1%. Finally, additional water was added to reach 50% theoretical solids. The resulting second polymer was a clear solution with slight haze and had a solids content of 49.7%. The weight average molecular weight was 51,300 and the number average molecular weight was 12,600 g / mol.

[0089] Example 3. Preparation of an aqueous dispersion of polymer P3. The first step is the synthesis of vinyl oligomer OL. A 7-liter reactor was charged with 3,089 grams of demineralized water and 35.44 grams of Reasoap® SR-1025. While maintaining a nitrogen atmosphere in the reactor, the contents of the reactor were heated to 80 °C. A nitrogen atmosphere was maintained throughout the polymerization process. A pre-emulsion was prepared by dissolving 99.21 grams of Reasoap® SR-1020 in 779.8 grams of demineralized water. To this, 1,297 grams of methyl methacrylate, 231 grams of diacetone acrylamide, 164.5 grams of methacrylic acid, 294.7 grams of n-butyl methacrylate, 22.1 grams of n-octyl mercaptan and 11.34 grams of 2-mercaptoethanol were added with stirring.

[0090] 5% of this pre-emulsion was added to the reactor. When the temperature reached 80 °C, 1.754 grams of ammonium persulfate dissolved in 85.03 grams of deionized water was added to the reactor. The temperature was raised to 85 °C and the remainder of the pre-emulsion was added over 60 minutes. The beaker containing the pre-emulsion was rinsed with 177.2 grams of deionized water. The beaker of the initiator solution was rinsed with 42.51 g of water. The batch was held at 85 °C for 30 minutes, after which 124.8 g of ammonia (25% concentration) dissolved in 255.3 g of water was added over 30 minutes. The pH of the solution was 8.2. The batch was held at 85 °C for an additional 120 minutes. After this holding period, the contents of the reactor were cooled to room temperature. The product was filtered through a filter bag and stored in a polyethylene recipient. As a result of the analysis, the number average molecular weight of the crosslinkable oligomer was 7,000 g / mol and the weight average molecular weight was 16,500 g / mol.

[0091] In the second step, vinyl polymer P4 was prepared in the presence of the above vinyl oligomer. 4.549 grams of the oligomer solution from the first step was charged into a 7-liter reactor, heated to 45 °C with stirring under a nitrogen atmosphere. A monomer mixture consisting of 391.3 grams of methyl methacrylate, 933.3 grams of n-butyl acrylate, 20.71 grams of divinylbenzene and 43.58 grams of styrene was prepared. 50% of this mixture was added to the reactor. After mixing for 30 minutes, 0.59 gram of tertiary-butyl hydroperoxide (70% aqueous solution) was added, followed by 50% of a solution prepared by dissolving 0.0382 gram of iron(II) sulfate heptahydrate and 0.0478 gram of disodium ethylenediaminetetraacetate dihydrate in 58.16 grams of demineralized water. A solution prepared by dissolving 2.533 grams of Bruggolite® FF6M (e.g., L. Brueggemann GmbH & Co. KG) in 290.5 grams of demineralized water was prepared, and 43.95 grams of this solution was added to the reactor. The batch exothermed to 54.9 °C and was held at 55 °C for 45 minutes. After the holding period, the reactor was cooled to 50 °C and the remaining monomer was added. The batch was held at 50 °C for 30 minutes. The beaker containing the monomer mixture was rinsed with 316.4 grams of demineralized water and this was added to the reactor. 2.46 grams of tertiary-butyl hydroperoxide (70% aqueous solution) and the remaining iron(II) sulfate heptahydrate / ethylenediamine disodium solution were added to the reactor, followed by 43.95 grams of Bruggolite® FF6M solution. The batch exothermed and the temperature rose to 60 °C. After 15 minutes, the remaining Bruggolite® FF6M solution was charged to the reactor over 30 minutes. 64.63 grams of adipic acid dihydrazide was added via an addition funnel. The funnel was rinsed with 316.4 grams of demineralized water. The batch was cooled to ambient temperature. 21.31 grams of Proxel® AQ was added to the reactor, followed by rinsing with 21.78 grams of demineralized water. The batch was filtered through a filter bag and stored in a suitable recipient. The dispersion had a solids content of 39.8, a pH of 8.1, a Brookfield viscosity of 198 cPa.s and a particle size of 49 nm. The MFFT was 17 °C.

[0092] Examples 4 and 5 (comparison): Aqueous coating composition A white pigment coating formulation was prepared using the components in Table 1.

[0093] The mill base is prepared in a cooling container at room temperature. Deionized water, an antifoaming agent, a dispersant, and a surfactant are charged into a container equipped with a stirring device having a dissolver blade. Subsequently, titanium dioxide is slowly added under high-speed stirring (2,000 - 3,000 rpm, disk size 50 mm, container diameter 80 mm). After the addition, stirring is continued for 30 minutes, and the fineness of pulverization is less than 10 μm.

[0094] Once the mill base is prepared, it is then added to a binder (having the composition according to the present invention) under stirring (1,000 - 1,500 rpm, disk size 80 mm, container diameter 150 mm) in a dropping container pre-filled with a coating composition containing a binder. When ready, deionized water, an antifoaming agent, an anti-slip agent, a co-solvent, an amine, a biocide, a thickener, and the co-solvent again are added under stirring.

[0095] After overnight stabilization, additional thickener is added until the ICI viscosity reaches 2.7 - 3.0 poise (10,000 s-1). For all tests, the paint is applied the next day. [Table 1]

[0096] Table 2 shows the performance of the pigment coating formulations presented in Table 1. [Table 2]

[0097] It is apparent from Table 2 that the coating composition according to the present invention has an excellent open time during the application of the second coating layer without impairing other coating properties. The present invention has been described above. Although overlapping with other descriptions, aspects of the present invention are shown below. However, the present invention is not limited thereto. [1] An aqueous vinyl polymer dispersion PD, 1) An aqueous dispersion of a vinyl polymer P1, a) 5 to 20 wt% of an acid-functional ethylenically unsaturated monomer M1 or its precursor, b) 5 to 25 wt% of an ethylenically unsaturated monomer M2 containing a polyethylene glycol or monoalkoxypolyethylene glycol moiety, c) Up to 90 wt% of a nonionic ethylenically unsaturated monomer M3 other than M1 or M2, d) 0 to 10 wt% of an ethylenically unsaturated monomer M4 having a functional group for crosslinking after film formation, and e) 0 to 10 wt% of at least one chain transfer agent CTA obtained by free radical emulsion polymerization of a monomer mixture containing, where the total wt% of M1 + M2 + M3 + M4 + CTA = 100 wt%, an aqueous dispersion of vinyl polymer P1, and 2) An aqueous dispersion or solution of a vinyl polymer P2, a) The general structure [Chemical formula 1] JPEG0007701937000005.jpg4644 (wherein R 1 and R 2 are C 1 ~C 5 alkyls and may be linked to form a ring structure, preferably N-vinylpyrrolidone or N-vinylcaprolactam) 25 to 95 wt% of an ethylenically unsaturated monomer M5 selected from the group of N-vinylamides having, b) 5 to 75 wt% of a nonionic ethylenically unsaturated monomer M3' other than M5, c) 0 to 5 wt% of an ethylenically unsaturated monomer M4' having a functional group for crosslinking after film formation, d) 0 to 10 wt% of an acid-functional ethylenically unsaturated monomer M1' or its precursor, and e) 0 to 5 wt% of at least one chain transfer agent CTA' obtained by free radical copolymerization of, where the total wt% of M5 + M3' + M4' + M1' + CTA' = 100 wt%, an aqueous dispersion or solution of vinyl polymer P2, and 3) A film-forming vinyl polymer P3 in the form of an aqueous dispersion, i) 1) At least one acid-functional ethylenically unsaturated monomer M1'', 2) At least one ethylenically unsaturated monomer M4'' having a functional group for crosslinking during film formation other than M1'', 3) At least one ethylenically unsaturated monomer M3'' other than M1'' and M2'', and 5) Optionally, at least one chain transfer agent CTA'' An aqueous dispersion of a film-forming vinyl polymer P3, obtained by emulsion polymerization of a monomer mixture containing 20 to 60 wt% of a water-soluble or water-dispersible crosslinkable vinyl oligomer OL, and ii) in the presence of a water-soluble or water-dispersible crosslinkable vinyl oligomer OL, 1) optionally, one acid-functional ethylenically unsaturated monomer M1''', 2) optionally, one or more ethylenically unsaturated monomers M4''' having a functional group for crosslinking during film formation, other than M1''', 3) at least one ethylenically unsaturated monomer M3''', other than M1''' and M2''', and 4) optionally, one or more polyfunctional ethylenically unsaturated monomers M5''' for pre-crosslinking, preferably in an amount of less than 5 wt% A 40 to 80 wt% high molecular weight vinyl polymer P4, prepared by emulsion polymerization of a monomer mixture containing Including, - The total weight of the film-forming vinyl polymer P3 = wt% of the water-soluble or water-dispersible crosslinkable vinyl oligomer OL + wt% of the high molecular weight vinyl polymer P4 = i) + ii) = 100 wt%, - The total weight of the vinyl polymer in the aqueous vinyl polymer dispersion PD = wt% of the vinyl polymer P1 + wt% of the vinyl polymer P2 + wt% of the film-forming vinyl polymer P3 = 100 wt%, An aqueous vinyl polymer dispersion PD. The aqueous vinyl polymer dispersion PD according to [1], wherein the weight ratio of the vinyl polymers P1, P2 to P3 is in the range of (1:1:98) to (65:15:20). [2] The vinyl polymer P1 has a number average molecular weight of 2,000 to 120,000 g / mol determined by size exclusion chromatography using tetrahydrofuran and 2% acetic acid as eluents and a polystyrene standard, an acid value of 30 to 150 mg KOH / g determined by ISO 3682, and an ethylenically unsaturated monomer M2 of 5 to 25 wt% compared to the total weight of the vinyl polymer P1, selected from the group consisting of polyethylene oxide or monoalkoxy polyethylene glycol (meth)acrylate. The aqueous vinyl polymer dispersion PD according to [1] or [2]. [3] ​ [4] The vinyl polymer P2 is the aqueous vinyl polymer dispersion PD according to any one of [1] to [3], which is determined by gel permeation chromatography using hexafluoro-isopropanol as an eluent and a polymethyl methacrylate standard for the calibration curve, and has a number average molecular weight Mn of 1,000 to 50,000 g / mol. [5] The vinyl polymer P2 is the aqueous vinyl polymer dispersion PD according to any one of [1] to [4], which contains at least 80% of a monomer M3' having a monomer glass transition temperature Tg lower than 120°C. [6] The vinyl polymer P2 is the aqueous vinyl polymer dispersion PD according to any one of [1] to [5], which is a copolymer of N-vinylpyrrolidone and ethyl acrylate, or a copolymer of N-vinylcaprolactam and ethyl acrylate. [7] The water-soluble or water-dispersible crosslinkable vinyl oligomer OL is the aqueous vinyl polymer dispersion PD according to any one of [1] to [6], which has an acid value of at least 45 mgKOH / g. [8] The water-soluble or water-dispersible crosslinkable vinyl oligomer OL is the aqueous vinyl polymer dispersion PD according to any one of [1] to [7], which is determined by size exclusion chromatography using tetrahydrofuran and 2% acetic acid as an eluent and a polystyrene standard for the calibration curve, and has a number average molecular weight of 500 to 50,000 g / mol. [9] The water-soluble or water-dispersible crosslinkable vinyl oligomer OL is the aqueous vinyl polymer dispersion PD according to any one of [1] to [8], which preferably has a glass transition temperature (Tg) in the range of 10 to 150°C.

[10] The high molecular weight vinyl polymer P4 is the aqueous vinyl polymer dispersion PD according to any one of [1] to [9], which has a glass transition temperature of -70°C to 50°C and is at least 25°C lower than the glass transition temperature of the water-soluble or water-dispersible crosslinkable vinyl oligomer OL.

[11] The high molecular weight vinyl polymer P4 is the aqueous vinyl polymer dispersion PD according to any one of [1] to

[10] , which has a number average molecular weight of 60,000 g / mol or more.

[12] The film-forming vinyl polymer P3 is in the form of an aqueous polymer dispersion and contains 20 to 60 wt% of the water-soluble or water-dispersible crosslinkable vinyl oligomer OL, which is the aqueous vinyl polymer dispersion PD according to any one of [1] to

[11] .

[13] The aqueous dispersion of the vinyl polymer P3 is the aqueous vinyl polymer dispersion PD described in

[12] having a solid content in the range of 20 to 60 wt%.

[14] Use of the aqueous vinyl polymer dispersion PD described in any one of [1] to

[13] for increasing the open time, wet edge time and / or hardness of the coating composition.

[15] A coating composition COA comprising the aqueous vinyl polymer dispersion PD described in any one of [1] to

[14] and at least one or more conventional components selected from non-vinyl polymers, pigments, dyes, emulsifiers, surfactants, plasticizers, thickeners, heat stabilizers, leveling agents, anti-crushing agents, fillers, anti-settling agents, UV absorbers, antioxidants, desiccant salts, organic co-solvents, wetting agents, etc., or mixtures thereof.

[16] A method for producing the coating composition COA described in

[15] , comprising the step of blending the aqueous vinyl polymer dispersion PD described in any one of [1] to

[13] with at least one or more conventional components selected from non-vinyl polymer pigments, dyes, emulsifiers, surfactants, plasticizers, thickeners, heat stabilizers, leveling agents, anti-crushing agents, fillers, anti-settling agents, UV absorbers, antioxidants, desiccant salts, organic co-solvents, wetting agents, etc., or mixtures thereof.

Claims

1. An aqueous vinyl polymer dispersion PD, comprising: 1) An aqueous dispersion of a vinyl polymer P1, comprising: a) 5 to 20 wt% of an acid-functional ethylenically unsaturated monomer M1 or its precursor; b) 5 to 25 wt% of an ethylenically unsaturated monomer M2 containing a polyethylene glycol or monoalkoxypolyethylene glycol moiety; c) Up to 90 wt% of a nonionic ethylenically unsaturated monomer M3 other than M1 or M2; d) 0 to 10 wt% of an ethylenically unsaturated monomer M4 having a functional group for crosslinking after film formation; and e) 0 to 10 wt% of at least one chain transfer agent CTA obtained by free radical emulsion polymerization of a monomer mixture, wherein the total wt% of M1 + M2 + M3 + M4 + CTA = 100 wt%, an aqueous dispersion of vinyl polymer P1; and 2) An aqueous dispersion or solution of a vinyl polymer P2, comprising: a) 25 to 95 wt% of an ethylenically unsaturated monomer M5 selected from the group of N-vinylamides having the general structure 【Chemical 1】 (wherein, R １ and R ２ are C １ - C ５ alkyls and may be linked to form a ring structure) ; b) 5 to 75 wt% of a nonionic ethylenically unsaturated monomer M3' other than M5; c) 0 to 5 wt% of an ethylenically unsaturated monomer M4' having a functional group for crosslinking after film formation; d) 0 to 10 wt% of an acid-functional ethylenically unsaturated monomer M1' or its precursor; and e) 0 to 5 wt% of at least one chain transfer agent CTA' obtained by free radical copolymerization, wherein the total wt% of M5 + M3' + M4' + M1' + CTA' = 100 wt%, an aqueous dispersion or solution of vinyl polymer P2; and 3) A film-forming vinyl polymer P3 in the form of an aqueous dispersion, comprising: i) 20 to 60 wt% of a water-soluble or water-dispersible crosslinkable vinyl oligomer OL obtained by emulsion polymerization of a monomer mixture comprising: 1) At least one acid-functional ethylenically unsaturated monomer M1''; 2) At least one ethylenically unsaturated monomer M4'' having a functional group for crosslinking during film formation other than M1''; 3) At least one ethylenically unsaturated monomer M3'' other than M1'' and M2''; and 5) Optionally, at least one chain transfer agent CTA''; and ii) In the presence of the water-soluble or water-dispersible crosslinkable vinyl oligomer OL, 1) Optionally, one acid-functional ethylenically unsaturated monomer M1''' 2) Optionally, one or more ethylenically unsaturated monomers M4''' having functional groups for crosslinking during film formation, other than M1'''; 3) At least one ethylenically unsaturated monomer M3''' other than M1''' and M2''', and 4) Optionally, one or more polyfunctional ethylenically unsaturated monomers M5''' for pre-crosslinking A high molecular weight vinyl polymer P4 of 40 to 80 wt% prepared by emulsion polymerization of a monomer mixture containing A film-forming vinyl polymer P3 in the form of an aqueous dispersion containing Including, - The total weight of the film-forming vinyl polymer P3 = the wt% of the water-soluble or water-dispersible crosslinkable vinyl oligomer OL + the wt% of the high molecular weight vinyl polymer P4 = i) + ii) = 100 wt%; - The total weight of the vinyl polymer in the aqueous vinyl polymer dispersion PD = the wt% of the vinyl polymer P1 + the wt% of the vinyl polymer P2 + the wt% of the film-forming vinyl polymer P3 = 100 wt%. An aqueous vinyl polymer dispersion PD. **Claim 2**: The aqueous vinyl polymer dispersion PD according to claim 1, wherein the ring structure of the ethylenically unsaturated monomer M5 is N-vinylpyrrolidone or N-vinylcaprolactam. **Claim 3**: The aqueous vinyl polymer dispersion PD according to claim 1, wherein one or more polyfunctional ethylenically unsaturated monomers M5''' for pre-crosslinking are present in an amount of less than 5 wt%. **Claim 4** The aqueous vinyl polymer dispersion PD according to claim 1, wherein the weight ratio of the vinyl polymers P1, P2 to P3 is included in the range of (1:1:98) to (65:15:20). **Claim 5** The vinyl polymer P1 has a number average molecular weight of 2,000 to 120,000 g / mol determined by size exclusion chromatography using tetrahydrofuran and 2% acetic acid as eluents and a polystyrene standard, an acid value of 30 to 150 mg KOH / g determined by ISO 3682, and is selected from the group consisting of polyethylene oxide or monoalkoxypolyethylene glycol (meth)acrylate, and has 5 to 25 wt% of the ethylenically unsaturated monomer M2 compared to the total weight of the vinyl polymer P1. The aqueous vinyl polymer dispersion PD according to any one of claims 1 to 4. **Claim 6** The vinyl polymer P2 has a number average molecular weight Mn of 1,000 to 50,000 g / mol as determined by gel permeation chromatography using hexafluoro - iso - propanol as an eluent and a polymethyl methacrylate standard for the calibration curve, and the aqueous vinyl polymer dispersion PD according to any one of claims 1 to 5.

7. The vinyl polymer P2 contains at least 80% of a monomer M3' having a monomer glass transition temperature Tg lower than 120°C, and the aqueous vinyl polymer dispersion PD according to any one of claims 1 to 6.

8. The vinyl polymer P2 is a copolymer of N - vinylpyrrolidone and ethyl acrylate, or a copolymer of N - vinylcaprolactam and ethyl acrylate, and the aqueous vinyl polymer dispersion PD according to any one of claims 1 to 7.

9. The water - soluble or water - dispersible cross - linkable vinyl oligomer OL has an acid value of at least 45 mgKOH / g, and the aqueous vinyl polymer dispersion PD according to any one of claims 1 to 8.

10. The water - soluble or water - dispersible cross - linkable vinyl oligomer OL has a number average molecular weight of 500 to 50,000 g / mol as determined by size exclusion chromatography using tetrahydrofuran and 2% acetic acid as an eluent and a polystyrene standard for the calibration curve, and the aqueous vinyl polymer dispersion PD according to any one of claims 1 to 9.

11. The water - soluble or water - dispersible cross - linkable vinyl oligomer OL has a glass transition temperature (Tg) in the range of 10 to 150°C, and the aqueous vinyl polymer dispersion PD according to any one of claims 1 to 10.

12. The high - molecular - weight vinyl polymer P4 has a glass transition temperature of - 70°C to 50°C, which is at least 25°C lower than the glass transition temperature of the water - soluble or water - dispersible cross - linkable vinyl oligomer OL, and the aqueous vinyl polymer dispersion PD according to any one of claims 1 to 11.

13. The high - molecular - weight vinyl polymer P4 has a number average molecular weight of 60,000 g / mol or more, and the aqueous vinyl polymer dispersion PD according to any one of claims 1 to 12.

14. The film-forming vinyl polymer P3 is in the form of an aqueous polymer dispersion and contains 20 to 60 wt% of a water-soluble or water-dispersible crosslinkable vinyl oligomer OL, the aqueous vinyl polymer dispersion PD according to any one of claims 1 to 13.

15. The aqueous dispersion of the vinyl polymer P3 has a solid content within the range of 20 to 60 wt%, the aqueous vinyl polymer dispersion PD according to claim 14.

16. Use of the aqueous vinyl polymer dispersion PD according to any one of claims 1 to 15 for increasing the open time, wet edge time and / or hardness of a coating composition.

17. A coating composition COA comprising the aqueous vinyl polymer dispersion PD according to any one of claims 1 to 15 and at least one or more conventional components selected from non-vinyl polymers, pigments, dyes, emulsifiers, surfactants, plasticizers, thickeners, heat stabilizers, leveling agents, anti-crushing agents, fillers, anti-settling agents, UV absorbers, antioxidants, desiccant salts, organic co-solvents, wetting agents, or mixtures thereof.

18. A method for producing the coating composition COA according to claim 17, comprising the step of blending the aqueous vinyl polymer dispersion PD according to any one of claims 1 to 15 with at least one or more conventional components selected from non-vinyl polymer pigments, dyes, emulsifiers, surfactants, plasticizers, thickeners, heat stabilizers, leveling agents, anti-crushing agents, fillers, anti-settling agents, UV absorbers, antioxidants, desiccant salts, organic co-solvents, wetting agents, or mixtures thereof.

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