Aqueous coating composition containing polymer prepared by multistage polymerization and polyurethane

FIELD: polymer materials.

SUBSTANCE: composition contains 5-95% of alkali-swelled polymer prepared by stepped nucleus/shell-type polymerization and 95-5% of at least one polyurethane. Composition is suitable as priming in priming/transparent layer system, which is characterized by high mechanical properties, high "flop", good brightness, essentially lack of "penetration", and good waterproofness.

EFFECT: reduced coating drying time and number of layers.

8 cl, 3 tbl, 17 ex

 

The invention relates to aqueous coating composition containing a polymer obtained stepwise polymerization, and polyurethane. Preferably, the specified aqueous coating composition also contains a metallic pigment such as aluminum, or pigment, such as coated metal oxide mica, which can be obtained coating with a metallic appearance. Thus receive different reflecting effect, called the "flop". The problem of coating systems having a metallic appearance, is getting high "flop", as well as high Shine.

To get high "flop" metallic pigment in the coating composition, the coating should be well focused and stay that way. To obtain a high gloss coating containing a metallic pigment, is provided by the so-called non-pigmented transparent layer. This system is usually called the system "soil/transparent layer. In current practice on the ground sprayed transparent layer without pre-curing of the soil (wet-on-wet"). As a transparent layer usually contains organic solvents, must be provided by stage to prevent disorientation of the metallic pigment in the soil as a result of the softening of the soil organic solvents in a transparent layer (preharden the e inside").

The water composition of the soil is known from EP-A-0287144, i.e. unstitched dispersion of core-shell, where the shell when the swelling provides the desired rheological properties. There is a decrease in the "inside passage". However, it was found that the composition of the coating needs to be improved with respect to some properties of the coating, such as hiding power and drying time.

The present invention now provides an aqueous coating composition, which can be used as a ground in the system soil/transparent layer, which has good mechanical properties, high flop, high gloss, almost without the "inside passage" and good water resistance. Due to the fact that the high solids content can be achieved with the aqueous coating composition of the present invention, obtain a reduction of the drying time and the number of layers. In one or more of the following properties of the aqueous coating composition of the present invention shows improvement with respect to the composition discussed in EP-A-0287144.

The aqueous coating composition according to the invention contains 5 to 95 wt. -%, at least one nabukelevu alkali-polymer (I)obtained stepwise polymerization, type of core-shell and 95-5 wt. -%, at least one polyurethane (II), and the sum of the wt. -%, specified for the polymers (I) and (II)is always 100% of the mass.

Preferably, the aqueous coating composition contains 10-90 wt. -%, at least one polymer (I)obtained stepwise polymerization, and

90-10 wt. -%, at least one polyurethane (II).

More preferably, the aqueous coating composition contains

25-75 wt. -%, at least one polymer (I)obtained stepwise polymerization, and

75-25 wt. -%, at least one polyurethane (II).

Preferably, Nauheim alkali-polymer (I)obtained stepwise polymerization, type of core-shell copolymer is obtained in two or more stages of emulsion polymerization, obtained by copolymerization in the first stage

(A) 60-95 mass (relative to 100 mass polymer obtained step polymerization) of the Monomeric mixture And consisting of

i) 65-100% mol. mixture

a) 60-100 mol%. (cyclo)alkyl(meth)acrylate, (cyclo) alkyl group contains 4-12 carbon atoms, and

b) 0-40 mol%. di(cyclo)alkyllead and/or di(cyclo)alkylphosphate, (cyclo)alkyl groups contain 4 to 12 carbon atoms, and the sum of mol%, the above monomers (a) and (b)is always 100 mol%, and

ii) 0-35 mol%. another copolymerizes monomer with monoalkylphenol the unsaturation, whereby the sum of mol%, these monomers (i) and (ii)is always 100 mol%, and copolymerization at last the blowing stage;

(C) 5-40 mass (relative to 100 mass polymer obtained step polymerization) Monomeric mixture containing

iii) 10 to 60 mol%. (meth)acrylic acid and

iv) 40-90 mol%. another copolymerizes monomer with monoalkylphenol the unsaturation,

moreover, the sum of mol%, these monomers (iii) and (iv)is always 100 mol%.,

with carboxylic acid groups derived from (meth)acrylic acid, at least partially ionized;

with results in seamless nabukelevu alkali-polymer (I)obtained stepwise polymerization, type of core-shell.

Such nabukenya alkali polymers obtained stepwise polymerization, type of core-shell known from EP-A-0287144.

Preferably, the polymer obtained stepwise polymerization, obtained by copolymerization

80-90 mass monomer mixture a and

10-20 mass Monomeric mixture Century.

Optional, can be consistently used in a variety of monomer mixture a and/or B.

Under emulsion polymerization is the polymerization of the monomer with ethylene unsaturation in water in the presence of water-soluble or water-insoluble initiator and using an emulsifier.

As examples of (cyclo)alkyl(meth)acrylates suitable for use in the monomer mixture a and having (cyclo)and kilou group with 4-12 carbon atoms, can be shown as: butyl acrylate, butylmethacrylate, 2-hexyl acrylate, 2-ethylhexylacrylate, octylacrylate, octylacrylate, isobutylacetate, isobornylacrylat, dodecylamine, dodecylammonium, cyclohexylacetate, cyclohexylmethyl and mixtures thereof. Preferably, the monomer mixture And must contain 70-95 mol%, more preferably 80-95 mol%, above (cyclo)alkyl(meth)acrylate. The preferred monomers are butyl acrylate, butylmethacrylate and mixtures thereof.

As examples of di(cyclo)alkylamino and/or di(cyclo)alkylphenolate with (cyclo)alkyl group having 4-12 carbon atoms, are suitable for use in the monomer mixture And can be specified: dibutylated, dibutylphtalate, 2-ethylhexylamine, 2-ethylhexylamine, octisalate, isobornylacetate, dodecylsulfate, cyclohexylurea and mixtures thereof.

As appropriate copolymerizate monomers with monoalkylphenol the unsaturation, most 35 mol%, and preferably 5-20 mol%, which can be used in the monomer mixture a, can be shown as: alkyl(meth)acrylates having at least 4 carbon atoms in the alkyl group, such as methyl methacrylate, methyl acrylate, acrylate, methacrylate, propylacetate, papermaterial and isopropylmalate; alkyllead and-fumarate having less than 4 carbon atoms in killnig groups, such as dimethylmaleic, diethylmaleate, diethylfumarate and DIPROPYLENE; (meth)acrylates having ether groups, such as 2-methoxyethylamine, 2-ethoxyethylacetate, 3-methoxypropylamine; hydroxyalkyl(meth)acrylates, for example, 2-hydroxyethylacrylate, 2-hydroxyethylmethacrylate, 2-hydroxypropylmethacrylate, 2-hydroxypropylmethacrylate, 4-hydroxyethylacrylate, 6-hydroxyhexyloxy, para-hydroxycyclohexyl, para-hydroxypaclitaxel, hydroxypregnenolone(meth)acrylates, hydroxypropranolol(meth)acrylates and their corresponding alkoxybenzenes; epoxy(meth)acrylates, such as glycidylmethacrylate and glycidylmethacrylate; monovinyl aromatic hydrocarbons such as styrene, vinyltoluene, α-methylsterol and vinylnaphthalene; acrylamide and methacrylamide, Acrylonitrile, Methacrylonitrile, N-methylolacrylamide and N-methylolmethacrylamide; N-alkyl(meth)acrylamide, such as N-izopropilakrilamid, N-isopropylacrylamide, N-tert-butyl-acrylamide, N-tert-octylacrylamide, N,N-dimethylaminoethylmethacrylate and N.N-diethylaminoethylmethacrylate; monomers such as vinyl chloride, vinyl acetate, vinyl pyrrolidone and finalproject, and monomers containing one or more urea or urethane groups, for example, the interaction product of 1 mole of isocyanatoacetate and 1 mole of butylamine, 1 mole of benzylamine is, 1 mole of butanol, 1 mole of 2-ethylhexanol and 1 mole of methanol, respectively. Can also be used mixtures of these compounds. Preferred are alkyl(meth)acrylates such as methyl acrylate, methyl methacrylate, acrylate, methacrylate and mixtures thereof, and hydroxyalkyl(meth)acrylates, such as 2-hydroxyethylacrylate, 2-hydroxyethylmethacrylate, 2-hydroxypropylmethacrylate, 2-hydroxy-propylbetaine and mixtures thereof.

Since the polymer (I)obtained step polymerization is unstitched, the choice of monomers in the monomer mixtures a and b is such that other than bonds present functional groups cannot communicate with each other under the reaction conditions obtaining polymer obtained stepwise polymerization.

As examples copolymerizate monomers with monoalkylphenol the unsaturation, which can be used in the monomer mixture In addition to (meth)acrylic acid, can be specified: monovinyl aromatic hydrocarbons such as styrene, vinyltoluene, α-methylsterol and vinylnaphthalene; NITRILES, such as Acrylonitrile and Methacrylonitrile; complex acrylic or methacrylic esters such as methyl methacrylate, methyl acrylate, acrylate, methacrylate, propylacetate, propylbetaine, isopropylacetate, butyl acrylate, butylmethacrylate and 2-cilexetil; hydroxyalkyl(meth)acrylates, for example, 2-hydroxyethylacrylate, 2-hydroxyethylmethacrylate, 2-hydroxypropylmethacrylate, 2-hydroxypropylmethacrylate, 4-hydroxyethylacrylate, 6-hydroxyhexyloxy and para-hydroxycyclohexyl; (meth)acrylates having ether groups, such as 2-methoxyethylamine, 2-ethoxyethylacetate and 3-methoxypropylamine; hydroxypregnenolone(meth)acrylates, hydroxypropranolol(meth)acrylates and their respective alkoxybenzenes; monocarboxylic acid with ethylene unsaturation, such as crotonic acid and taconova acid, and compounds such as vinyl chloride, vinyl acetate, finalproject, vinyl pyrrolidone, acrylamide, methacrylamide and N-alkyl(meth)acrylamide, such as N-izopropilakrilamid, N-tert-butylacrylamide and N-tert-octylacrylamide. Can also be used mixtures of these compounds. The preferred monomers are methyl acrylate, methyl methacrylate, butyl acrylate and butylmethacrylate and mixtures thereof.

The monomer mixture preferably contains from 15 to 50 mol%, in particular, 20 to 40 mol%. (meth)acrylic acid and 50-85 mol%, in particular, 60-80 mol%. copolymerizes monomer with monoalkylphenol the unsaturation.

The copolymerization of a Monomeric mixture usually gives a copolymer having an acid number of 30-450 and preferably 60-350, and a hydroxyl number of 0-50, and preferably 60-300. As the acid number and hydroxyl number are expressed in mg KOH per g of the copolymer.

The polymer (I)obtained stepwise polymerization, has MP from 50,000 to 2000000, preferably from 100000 to 1000000.

The emulsifiers preferably used in the emulsion polymerization, are anionic or non-ionic nature. Examples of anionic emulsifiers include: potassium laurate, potassium stearate, potassium oleate, matricellular, nitrilotriacetate, nitrilotriacetonitrile and resinat sodium. Examples of nonionic emulsifiers include linear and branched ethers and thioethers alkyl - and alkalinebatteries and-polypropylenglycol, alkylphenoxy(ethyleneoxy)ataneli, such as the adduct of 1 mole of Nonylphenol with 3-12 by moles of ethylene oxide; alkyl(ethylenoxy)ataneli with 8-18 carbon atoms in the alkyl groups, such as the adduct of 1 mole of dodecanol with 3-12 by moles of ethylene oxide. Examples of emulsifiers containing anionic and non-ionic groups are ammonium or sodium salt of sulfate alkylphenoxy(ethyleneoxy)atenolol, such as the adduct of 1 mole of Nonylphenol with 3-12 by moles of ethylene oxide, and ammonium or sodium salt of alkyl sulfate(ethylenoxy) atenolol with 8-18 carbon atoms in the alkyl groups, such as the adduct of 1 mole of C12-14-alcohol 3-12 by moles of ethylene oxide. Preferred is the ammonium or sodium sulfate salt of the adduct of 1 mole of C 12-14-alcohol 3-12 by moles of ethylene oxide.

In addition, emulsion polymerization traditional radical initiators can be used in conventional amounts. Examples of suitable radical initiators include water-soluble initiators such as ammonium persulfate, sodium persulfate, potassium persulfate and tert-butylhydroperoxide, and water-insoluble initiators such as bis(2-ethylhexyl)PEROXYDICARBONATE, di-n-butylperoxybenzoate, tert-butylacetat, Gidropress hydroperoxide, peroxide Dibenzoyl, peroxide Dilauroyl, 2,2'-azobisisobutyronitrile and 2,2'-azobis-2-methylbutyronitrile.

As reducing agents that may be used in combination with, for example, hydropredict can be specified: ascorbic acid, nitrosulfonic-formaldehyde, thiosulfate, bisulfite-hydrosulfate, water-soluble amines, such as Diethylenetriamine, Triethylenetetramine, Tetraethylenepentamine, N,N'-dimethylethanolamine and N.N-diethylethanolamine, and reducing salts such as sulfate, cobalt, iron, Nickel and copper.

Optionally, a growth regulator circuit, for example, n-octyl mercaptan, dodecylmercaptan and 3-mercaptopropionic acid, can also be used.

The copolymerization of monomer mixtures usually carried out at atmospheric pressure at a temperature of 40-100°C, p is edocfile, 60-90°With, in the atmosphere of inert gas, such as nitrogen. Not necessarily, however, the copolymerization can also be performed at elevated pressure, in any case, the reaction conditions for monomer mixtures a and b must be chosen so that other than bonds, functional groups present in the monomer mixtures may not interact with each other.

According to the invention the carboxylic acid group derived from acrylic acid and/or methacrylic acid, at least 40-100% neutralized by addition of a neutralizing agent. As neutralizing agents are carboxylic acids may be mentioned ammonia and amines, such as N,N-dimethylethanolamine, N,N-diethylethanolamine, 2-(dimethyl)-amino-2-methyl-1-propanol, triethylamine and morpholine. Preferably, the neutralization of the carboxylic acid groups is carried out after the polymerization.

The mixture nabukenya in alkali polymers obtained stepwise polymerization, type of core-shell can be used in (I).

An example of a dispersion containing such nabuhay alkali-polymer obtained stepwise polymerization, is the variance of Setalux 6801 AQ-24 supplied by the company Akzo Nobel Resins.

The polyurethane (II) in the General case can be obtained from polyisocyanates and polyols, as known to the expert. Their examples include Neorez R970 (provider NeoResins) and Daota VTW 2275 (provider Vianova Resins). Also included in the definition of the polyurethane (II) are hybrids of polyurethane, such as polyurethanacrylate hybrids. Their examples include Neopac E115 (provider NeoResins) and Daotan VTW 6460 (provider Vianova Resins).

Preferably, the polyurethane (II) is poliuretanoviy. More preferably, poliuretanoviy contains:

v) not less than 200 mEq per 100 g of solids of chemically introduced carbonate group-O-CO-O - and

vi) the combined total of up to 320 mEq per 100 g of solids of chemically introduced urethane groups-NH-CO-O - and chemically introduced urea groups-NH-CO-NH-.

Such dispersion poliuretanoviy known from DE 3936794.

Preferably, poliuretanoviy contains not less than 250 mEq per 100 g of solids of chemically introduced carbonate group-O-CO-O -, and the combined total of 200-300 mEq per 100 g of solids urethane groups-NH-CO-O -, and urea groups-NH-CO-NH.

Poliuretanoviy can be obtained in a known manner by the interaction of:

a) organic polyisocyanates, which contain no hydrophilic groups or groups becoming hydrophilic group, with

b) relatively high molecular weight organic polyhydroxylated compounds that have no hydrophilic groups or groups becoming hydrophilic group,

c) optionally, discobolus the diversified compositions containing at least two interacting with isocyanate groups, but no hydrophilic groups or groups capable of conversion into hydrophilic groups;

d) optionally, a nonionic hydrophilic source components containing at least one isocyanate group or at least one interacting with the isocyanate group, and

e) optionally, source components, containing at least one ionic group or at least one group capable of conversion into ionic group and at least one interacting with the isocyanate hydrogen atom,

provided that the number of non-ionic groups and ionic groups present in components (d) and (e)are sufficient to ensure the dispersion of poliuretanoviy in the water.

The interaction between isocyanate groups and hydroxyl groups gives a urethane group, whereas urea groups present in the interaction products, formed from amidofunctional source components and/or interaction between the isocyanate groups and dispersing water, which is always possible in the process of obtaining aqueous polyurethane dispersions.

Polyisocyanate component a) includes any polyisocyanate, known in polyurethane chemistry. These polyisocyanates generally have a molecular mA is su 112-1000, preferably, 140-400. Suitable polyisocyanates are polyisocyanates which correspond to the formula Q(NCO)nin which Q represents an organic group obtained by removing isocyanate groups from an organic MDI having a molecular weight of 112-1000, preferably, 140-400, and p represents a number from 2 to 4, preferably 2 or 3, and more preferably 2. In the above formula, Q preferably represents a divalent aliphatic hydrocarbon group having 4-18 carbon atoms, a divalent cycloaliphatic hydrocarbon group having 5-15 carbon atoms, divalent aromatic hydrocarbon group having 6-15 carbon atoms, or analiticheskoy hydrocarbon group having 7-15 carbon atoms. Examples of suitable polyisocyanates include tetramethyldisilane, 1,6-diisocyanatohexane (HDI) dodecyltrimethoxysilane, 2,2,4-tri-methylhexadecanoic, underinvestment-(1,11), lysine -(ester)diisocyanate, cyclohexane-1,3 - and -1,4-diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (IPDI) and 4,4'-diisocyanatobutane. Also suitable are aromatic diisocyanates, such as 2,4-diisocyanate and/or 2,6-diisocyanate, 4,4"-diisocyanatobutane and 1,4-diisocyanatobutane. HDI, IPDI and a mixture of these is diisocyanates are particularly preferred.

Component (b) includes organic polyhydroxylated compounds having a molecular weight of 300-5000, preferably from 500 to 3,000 and containing at least 50 wt. -%, preferably more than 70 wt. -%, polyhydroxyalkanoates. Polyhydroxyalkanoate are esters of carboxylic acids, obtained by the interaction of derivatives of carboxylic acids, for example, diphenylcarbonate or phosgene, with dialami. Examples of these diols include ethylene glycol, propane-1,2 - and -1,3-diol, butane-1,4 - and -1,3-diol, hexane-1,6-diol, octane-1,8-diol, neopentylglycol, 1,4-bis-hydroxymethylcellulose, 2-methylpropane-1,3-diol, 2,2,4-trimethylpentane-1,3-diol, diethylene glycol, tri - and tetraethylene glycol, dipropyleneglycol, polypropyleneglycol, dibutylamino, polietilenglikoli, bisphenol a and tetrabromobisphenol A. Diol component preferably contains 40 to 100 wt%. hexandiol, preferably, hexane-1,6-diol and/or derivatives hexandiol, preferably containing ether or a complex ester group in addition to the limit HE-groups, for example, products obtained by the interaction of 1 mol of hexanediol with ≥1 mole, preferably 1-2 mol caprolactone according to DE 1770245, or products obtained by sumatriptane of hexandiol education digoxin or tridecylalcohol according to DE 1570540. Poly(a simple ether)poly is urbanatomy, described in DE 3717060, are also very suitable.

The hydroxyl polycarbonates should be essentially linear, although they can be, if necessary, slightly branched introduction of multi-functional components, in particular low molecular weight polyols, such as glycerin, trimethylolpropane, hexane-1,2,6-triol, butane-1,2,4-triol, trimethylolpropane, pentaerythritol, hinit, mannitol and sorbitol, methyl glycoside and 1,4,3,6-diaminohexane.

In addition polyhydroxyalkanoates source component b) may contain other known polyhydroxylated connection with the above-mentioned molecular weight, for example,

b1) a compound dihydroxyflavone derived from dicarboxylic acids such as succinic acid, adipic acid, subernova acid, azelaic acid, sabotinova acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophtalic acid, and diols, such as ethylene glycol, propane-1,2-diol, propane-1,3-diol, diethylene glycol, butane-1,4-diol, hexane-1,6-diol, octane-1,8-diol, neopentylglycol, 2-methylpropane-1,3-diol and the various isomers of bishydroxycoumarin;

b2) polylactones, such as polymers ε-caprolactone initiated above diatomic alcohols; and

b3) polyethers, for example, polymers and copolymers of tetrahydrofuran, stimulated is, of propylene oxide, ethylene oxide, butyleneglycol or epichlorohydrin, initiated divalent starter molecules such as water, the above-mentioned diols or amines containing 2 NH-linkages, in particular, polymers and copolymers of propylene oxide and, optionally, ethylene oxide. The ethylene oxide may be used as part of the total number of ether molecules, provided that the resulting poly(simple ether)diol contains not more than 10% of the mass. ethylenoxide links. It is preferable to use poly(a simple ether)diols, which is obtained without the introduction of ethylene oxide, especially, poly(simple ether)diols based on propylene oxide and tetrahydrofuran.

Optional, used original components) are known low molecular weight compounds that have a molecular weight below 300, contain hydroxyl groups and/or amino groups and are at least bifunctionality in the addition reactions of isocyanate. Compounds that are disfunctionality in the addition reactions of isocyanate (extension chain), compounds that are at least trifunctional in the addition reactions of isocyanate (crosslinking agents), and mixtures of these compounds can be used as original components). Examples of these compounds include low molecular weight is nagatani alcohols, such as ethylene glycol, propane-1,2 - and -1,3-diol, butane-1,4 - and -1,3-diol, hexane-1,6-diol, octane-1,8-diol, neopentylglycol, 1,4-bishydroxycoumarin, 2-methylpropane-1,3-diol, 2,2,4-trimethylpentane-1,3-diol, glycerol, trimethylolpropane, trimethylacetyl, isomers hexanetriol and inharited; low molecular weight diamines, such as Ethylenediamine, 1,2 - and 1,3-diaminopropane, 1,3-, 1,4 - and 1,6-diaminohexane, 1,3-diamino-2,2-DIMETHYLPROPANE, isophorondiamine, 4,4'-diaminodicyclohexylmethane, 4,4-diamino-3,3'-dimethylcyclohexylamine, 1,4-bis-(2-amino-prop-2-yl)cyclohexane, hydrazine, hydrazide, and mixtures of such diamines and hydrazines; more highly functional polyamine, such as Diethylenetriamine, Triethylenetetramine, dipropylenetriamine and dipropylenetriamine; hydrogenated addition products of Acrylonitrile to aliphatic or cycloaliphatic the diamines, preferably obtained by joining Acrylonitrile groups to the molecule of the diamine, for example, hexamethylpropyleneamine, tetramethylpropylenediamine, ISOPHORONEDIAMINE or 1,3 - or 1,4-cyclohexylpropionate and mixtures of such polyamines.

Hydrophilic source components d) are compounds containing ethylenoxide links entered in a simple polyester chain, in particular:

d1) diisocyanates and/or compositions that contain interacting with isocyanate waters is their atoms and are disfunctionality in the reactions of isocyanate polyaddition, the diisocyanates and the composition also contains a simple polyester side chains containing ethylenoxide links, and

d2) monoisocyanates and/or compositions which are monofunctional in the polyaddition reaction of the isocyanate and contain interacting with isocyanate hydrogen atom, monoisocyanates and compositions containing simple end of the polyester chain containing ethylenoxide links, and

d3) a mixture of d1) and d2).

Obtaining mentioned hydrophilic starting components is carried out by methods similar to the methods described in U.S. patent No. 3920598, 3905929, 4190566 and 4237264.

The compounds used as starting components (e)have at least one interacting with the isocyanate group and at least one (potentially) ionic group. They include alcohols containing tertiary amino groups, hydroxycarbonate acid, hydroxysulfonic acid, aminocarbonyl acid and aminosulfonic acid discussed in U.S. patent No. 3479310. Instead of these starting components containing potentially ionic groups, can be used in their salt derivatives type, i.e. ionic group formed by quaternization or neutralization of potentially ionic groups. Examples of suitable quaternionic and neutralizing agents for converting potentially and is the R groups in the ionic groups are also described in U.S. patent No. 3479310. When using potentially ion source components, at least partial transformation of the potentially ionic groups into ionic groups is carried out by quaternization or neutralization after or in the process of obtaining poliuretanoviy.

The preferred source components (e) include 2,2-bis-(hydroxymethyl)alcanlinoterreos acid having a total of 5-8 carbon atoms, and/or their salts, obtained by partial or complete neutralization of the organic amines or NH3. 2,2-dimethylpropionic acid (2,2-bishydroxycoumarin acid) and/or its salts are especially preferred for use as the source component (e).

Obtaining polyurethanes of the starting components a)to (e) is carried out in a known manner in one or more stages using the reactants in such proportions that the equivalent ratio of isocyanate groups present in source components for interacting with the isocyanate groups present in source components, is 0.8:1 to 2:1, preferably from 0.95:1-1,5:1 and more preferably from 0.95:1 to 1.2:1.

Component d) is used in such quantity that poliuretanoviy contains 0-30 wt. -%, preferably, from 1 to 20 wt. -%, ethylenoxide links entered into the end or side of a simple polyester chain.

The number to mponent e) and the degree of neutralization, necessary for the formation of ionic groups, are calculated to ensure that the final polyurethane contains 0-120, preferably 1-80 mEq of ionic groups per 100 g of solids. The total number ethylenoxide links and ionic groups must be sufficient to ensure the dispersion of poliuretanoviy in the water.

The interaction of the starting components a)to (e) can be carried out in one or more stages, optionally, in the presence of inert to isocyanate vadomarius solvent, so that the products interactions get in the form of a solution in such a solvent. In this context, the term "solution" refers to either a true solution or a water in oil emulsion, which may be formed, for example, if a separate source components are used in the form of aqueous solutions. Examples of suitable solvents include acetone, methyl ethyl ketone, N-organic and any mixtures of these solvents. These solvents are usually used in such quantities that the products of interaction of the starting components a)to (e) are obtained in the form of 10-70% of the mass.

When receiving poliuretanoviy carried out in the form of a single-stage interaction, the source components containing interacting with isocyanate groups, preferably mixed together and then carry out the interaction with the source components containing isocyanate groups. This interaction is, preferably, carried out initially in the absence of solvents at temperatures of 50-150°optionally in the presence of known catalysts.

The viscosity of the mixture increases during the reaction, and one of the above solvents, therefore, gradually add to the mixture. The content of the polyurethane in the finally obtained organic solution is regulated to a concentration of 10-70 wt. -%, in particular, 15-55% of the mass.

When using the two-stage method, the isocyanate prepolymer, preferably, first get free from solvent at about 50-150°With excessive amounts isocyanatomethyl source components and the hydroxyl-containing starting components at equivalent ratio of NCO:OH of 1.1:1-3,5:1, preferably, 1,2:1-2,5:1, with or without solvent, and specified the isocyanate prepolymer selected from the solvent, if the solvent is not used at this stage. The resulting solution was then further interacts with the chain extenders or crosslinking agents (C)which are optionally used in the form of aqueous solutions and are, preferably, the original components of the above type containing primary and/or secondary amino groups. The number of source components)used in the second stage, R is Skitalets with ensuring that the equivalent ratio of all the starting components used in the first and second stages, corresponds to the previously established conditions.

The end products of both variants (single-stage and two-stage) solutions are the products of interaction in the above solvent, having a solids content in the above range.

If there are any ionic group, at least partial conversion into ionic groups by quaternization or neutralization mainly carried out before adding the dispersing water. If the source component (e) contains hydroxyl group, which is preferred, in particular, dimethylolpropionic acid used neutralizing agents, preferred are tertiary amines, such as triethylamine, tri-n-butylamine, N,N,N-trimethylcyclohexylamine, N-methylmorpholine, N-methylpiperazine, N,N-dimethylethanolamine, N-methylpiperidin and triethanolamine. To neutralize the hydroxyl group is also preferable to use ammonia under conditions defined in EP-A-0269972.

After adding water as solvent or dispersing medium, at least the major proportion of the used auxiliary solvent optionally removed by distillation. Water is used in an amount which is is fast enough to ensure a product with a solids content of 10-60 wt. -%, preferably 20-45% of the mass.

Poliuretanoviy can also be obtained by other methods known in the art, for example, when using hydrazine or diamines as chain extenders (C) in blocked form, i.e. in the form of the corresponding azines or ketimines, as discussed in U.S. patent No. 4269748 and 4829122.

Alternatively, it may be used the so-called method of mixing the prepolymer (see D. Dieterich, Angew. Makromol. Chem., 9A, 142 (1981)). In this way NCO-prepolymer initially receive, as described above, and after at least partial conversion of any present potentially ionic groups into ionic groups, the prepolymer is mixed with water with the formation of the emulsion. NCO groups of the prepolymer then interact in the aqueous phase of the accession amidofunctional of chain extenders or crosslinking agents (C) and/or by interaction with water.

One example of such a dispersion poliuretanoviy is Bayhydrol VPLS 2952 (supplier Bayer).

Mixtures of polyurethanes can be used in (II).

The coating composition of the present invention, as the aqueous coating composition, consists essentially of water. However, about 20% of the mass. the content of the liquid coating composition may be an organic solvent. As suitable organic solvents can be specified with arty, containing ether group as hexillion, butoxyethanol, 1-methoxypropanol-2, 1-ethoxypropanol-2, 1-propoxyphenol-2, 1-butoxypropan-2 and 1-isobutoxide-2; alcohols such as methanol, ethanol, propanol, butanol, pentanol and hexanol; diols, such as ethylene glycol and diethylene glycol.

The coating composition according to the present invention can be overiden physical drying. Alternatively, however, the coating composition can be solidified in the presence of a curing agent which reacts with hydroxyl and/or carboxyl groups.

Examples of suitable curing agents include aminos containing N-methylol groups and/or groups of simple ether N-methylol obtained by the interaction of the aldehyde, such as formaldehyde with a compound containing amino or aminogroup, such as melamine such as Cymel 328 (provider Cytek), urea, N,N'-etilenmocevina, dicyanodiamide, benzoguanamine. The resulting compound, preferably fully or partially aeriferous alcohols having 1-6 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, Isobutanol, amyl alcohol, hexanol or mixtures thereof. Particularly favorable results can be obtained when using methylaniline with 4-6 methyl groups per molecule of melamine, the rich at least 3 methylol groups tarifitsirovana butanol, or product butanilicaine condensation of formaldehyde and N,N'-Ethylenediamine. Examples of other suitable curing agents include polyisocyanates or water-dispersible blocked polyisocyanate, such as blocked by methylethylketoxime containing the isocyanate group of the adduct MDI with hydroxycarbonic acid, for example, dimethylolpropionic acid, and aliphatic or aromatic carbodiimide.

In addition nabukelevu alkali-polymer (I)obtained stepwise polymerization, type of core-shell and polyurethane (II) a binder composition may also contain water soluble materials, such as alkyd resins, polyesters, polyacrylates and mixtures thereof.

In addition, the coating composition may contain conventional additives and activating agents such as dispersing agents, dyes, accelerators for the curing reaction and rheology modifiers, such as Acrysol RM 2020, Acrysol ASE 60, Coatex Rheo 3000 u Viscalex HV 30.

Used pigments can be acidic, neutral or alkaline. Optionally, pigments can be pre-treated to modify the properties. Examples of suitable pigments include metallic pigments, such as aluminum and stainless steel; pearlescent pigments such as mica coated with metal oxide, such as oxide yellow is for and/or titanium dioxide; inorganic pigments such as titanium dioxide, iron oxide, carbon black, silica, kaolin, talc, barium sulfate, lead silicate, strontium chromate and chromium oxide; and organic pigments such as phthalocyanine pigments.

The solids content of the coating composition is in the range from 5 to 60 wt. -%, preferably, from 10 to 40% of the mass. It depends on whether you are using a metallic pigment, or not. The presence of metallic pigments gives a lower solids content compared with when there are non-metallic pigments. However, compared with traditional water priming systems, the solids content of the coating composition of the present invention is higher in both cases.

Preferably, the coating composition according to the present invention is used as a primer in the so-called soil system/transparent layer to provide a metallic appearance with a high gloss. In this case, the coating composition according to the invention contains the so-called "non-living" aluminum paste or any other metallic pigment. Using the coating composition according to the invention as soil can prevent the softening of the soil layer after spraying them, so that the metallic effect is not those who aetsa.

A transparent layer in the system soil/transparent layer can be, for example, a transparent primer lacquer traditional compositions of polyacrylate/melamine. The transparent layer may also be a two-component composition is a complex polyester or polyacrylate/polyisocyanate. The polyisocyanate may be, for example, the trimer of 1,6-hexamethylenediisocyanate. The transparent layer may also be a slurry containing hydrophilic polyisocyanates.

The coating composition according to the invention can be applied to the substrate in any desired way, such as applying by roller, spray, brush application, spraying, application by spray, dipping, electrostatic spraying or electrophoresis, preferably by sputtering.

Suitable substrates can be made of wood, metal and synthetic material, optional, pre-treated, for example, a primer or filler. Curing can be performed at ambient temperature or optionally at an elevated temperature to reduce the curing time. Optionally, the coating composition can be overiden at high temperatures in the range of, for example, 60-160°C in an oven for a period of 10-60 minutes Transparent layer can be applied wet-on-wet on the ground. Optionally, the primer can bitcasting overiden to the deposition of the transparent layer. Also soil can be fully overiden to the deposition of the transparent layer.

The compositions are particularly suitable for obtaining a coated metal substrates, such as in the finishing industry, in particular, in the body shop for repair of vehicles and transportation means such as trains, trucks, buses and airplanes. Compositions of the present invention can also be used in the first finish of cars.

The invention is additionally described in the following examples, which should not be construed as limiting the scope of the present invention.

Examples

The test methods used in examples are described below.

The viscosity of the spray solution is determined by the funnel No. 4 DIN.

The solids content of the binder content and the volumetric concentration of VOC calculated theoretically. In the calculation of VOC by the presence of water is neglected. Drying time is determined visually. The specified time starts with the deposition substrate to cover, and ends at the moment when the appearance of the coating becomes opaque.

Use the following connections:

PAD - Setalux 6801 AQ-24 (supplier Akzo Nobel Resins).

PUR - Bayhydrol VPLS 2952 (provider Voeg).

Examples 1-9

To test the coating compositions of the present invention receive several colored formulations. In this case the binder is, pigments, solvents, water and conventional additives are mixed together. The selected color formulations are shown in table 1.

Metal plates get with a traditional primer. Black and white binder is applied on primed plate, in order to determine the hiding power of the coating composition. The composition of the soil color formulations are shown in table 1, sprayed on the plate. Plate utverjdayut at ambient temperature.

As can be seen from the results shown in table 2, the compositions of the coatings of the present invention noticeably dry quickly, enabling fast application and setting time. In addition, only a small amount of material required to provide full cover. Finally, ready-to-spray viscosity depending on the VOC is excellent.

Table 2
ExampleThe viscosity of the houses. solution (C)The number of layersDrying time (min)The use of the material (g)
1the concentration is2,513182,5
2the concentration is2+VP10,5149,7
3the concentration is 2+VP11100
4362,5+VP11184
528,52+VP8138
624,52+VP9157
7262,5+VP14211
825413204
926,5417231
VP - viamichelin floor
the concentration is not defined

Examples 10-13 and comparative examples A-D

Several colored recipes receive as described in example 1. As comparative examples get the same colored the recipe, except that a binder composition instead of a mixture of Setalux 6801 AQ 24 and Bayhydrol VPLS 2952 use 100% Setalux 6801 AQ 24 so that the ratio of pigment:binder remains the same.

In the composition of the coatings impose traditional solvents in such a way that each has the same ready-to-spray viscosity and is applied as described in example 1. The results are shown in table 3.

As you can see from the t is blitz 3 results ready to spray viscosity with respect to the solids content is excellent. Unexpectedly, the compositions of the coatings of the present invention have a higher solids content at the same ready-to-spray viscosity. In addition, the coating composition of the present invention to dry much faster, enabling fast application and setting time. Finally, only a small amount of material required to provide full cover.

1. Aqueous composition for coating containing 5 to 95 wt.%, at least one nabukelevu in the alkali type polymer core-shell (I) and 95-5 wt.%, at least one polyurethane (II), and the sum of the wt.%, specified for the polymers (I) and (II)is always 100 wt.%, where Nauheim in alkali-type polymer core-shell copolymer is obtained in two or more stages of emulsion polymerization and obtained by copolymerization in the first stage

(A) 60-95 parts by weight (relative to 100 parts by weight of a polymer obtained step polymerization) of the Monomeric mixture And consisting of

i) 65-100 mole% mixture

a) 60-100 mol.% (cyclo)alkyl(meth)acrylate, (cyclo)alkyl group contains 4-12 carbon atoms, and

b) 0-40 mol.% di(cyclo)alkyllead and/or di(cyclo)alkylphosphate, (cyclo)alkyl group containing 4-12 carbon at the MOU

moreover, the sum of the mol.%, the above monomers (a) and (b)is always 100 mol.%, and

ii) 0-35 mol.% another copolymerizes monomer with monoalkylphenol the unsaturation, and the sum of the mol.%, these monomers (i) and (ii)is always 100 mol.%, and

the copolymerization at a later stage

C) 5-40 parts by weight (relative to 100 parts by weight of a polymer obtained step polymerization) Monomeric mixture containing

iii) 10 to 60 mol.% (meth)acrylic acid and

iv) 40-90 mol.% another copolymerizes monomer with monoalkylphenol the unsaturation,

moreover, the sum of the mol.%, these monomers (iii) and (iv)is always 100 mol.%,

with carboxylic acid groups derived from (meth)acrylic acid, at least partially ionized;

with results in seamless nabukelevu in the alkali type polymer core-shell (I).

2. Aqueous composition for coating according to claim 1, characterized in that the polyurethane (II) is poliuretanoviy.

3. Aqueous composition for coating according to claim 2, characterized in that the polyurethane (II) is poliuretanoviy containing:

v) not less than 200 mEq per 100 g of solids of chemically introduced carbonate group-O-CO-O-, and

vi) the combined total of up to 320 mEq per 100 g of solids of chemically Annot is the R urethane groups-NH-CO-O - and chemically introduced urea groups-NH-CO-NH-.

4. Aqueous composition for coating according to claim 1, characterized in that it contains pigments.

5. Aqueous composition for coating according to claim 4, characterized in that the pigment is a metallic pigment.

6. A method of obtaining a multilayer coating on a substrate containing a stage of coating the substrate aqueous composition for coating according to any one of claims 1-5.

7. The method according to claim 6, characterized in that the aqueous composition for coating is ground.

8. Aqueous composition for coating according to any one of claims 1 to 5, used for decoration of cars.



 

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