WO2004020477A1 - Dispersions polymeres aqueuses, leur procede de production et leur utilisation, notamment dans des revetements anticorrosion - Google Patents

Dispersions polymeres aqueuses, leur procede de production et leur utilisation, notamment dans des revetements anticorrosion Download PDF

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WO2004020477A1
WO2004020477A1 PCT/EP2003/007931 EP0307931W WO2004020477A1 WO 2004020477 A1 WO2004020477 A1 WO 2004020477A1 EP 0307931 W EP0307931 W EP 0307931W WO 2004020477 A1 WO2004020477 A1 WO 2004020477A1
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weight
copolymer
acid
monomers
monomer
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PCT/EP2003/007931
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German (de)
English (en)
Inventor
Christian Meiners
Stephan Krieger
Ulrich Désor
Gerhard Merten
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Celanese Emulsions Gmbh
Clariant Gmbh
The Nippon Synthetic Chemical Industry Co., Ltd.
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Application filed by Celanese Emulsions Gmbh, Clariant Gmbh, The Nippon Synthetic Chemical Industry Co., Ltd. filed Critical Celanese Emulsions Gmbh
Priority to JP2004531809A priority Critical patent/JP4979192B2/ja
Publication of WO2004020477A1 publication Critical patent/WO2004020477A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents

Definitions

  • Aqueous polymer dispersions processes for their preparation and their use, in particular in corrosion protection coatings
  • the present invention relates to new aqueous copolymer dispersions, processes for their preparation and their use, in particular in corrosion protection coatings.
  • Aqueous polymer dispersions for use in anti-corrosion coatings are subject to a number of boundary conditions which must be observed in order to ensure adequate protection against rust formation.
  • the coating must have sufficient hydrophobicity to prevent the diffusion of water to the interface between the substrate and the coating, since water is significantly involved in the corrosion process.
  • good adhesion between the substrate and the coating should be ensured in order to minimize the formation of bubbles at the substrate / coating interface due to the infiltration of the anticorrosive protective layer by water.
  • the corrosion protection layer should have a good diffusion barrier effect against carbon dioxide.
  • Unsaturated ß-ketoester compounds, such as allylacetoacetate and acetoacetoxyethyl methacrylate have proven themselves in the literature as adhesion-increasing comonomers.
  • the task of ensuring good adhesion between the substrate and the coating is achieved in WO 99/14278 by acetoacetoxy groups in the polymer.
  • Poly (alkyleneimines) are added to the polymer dispersions, which crosslink with the acetoacetoxy groups during film formation with enamine formation.
  • the premature crosslinking reaction in the polymer dispersion was suppressed by the addition of anionic emulsifiers.
  • nonionic emulsifiers such as Example in WO 99/14275 and WO 99/14279.
  • nonionic emulsifiers are subsequently added as stabilizers.
  • Phosphate emulsifiers are used for the polymerization.
  • the dispersions obtained have little tendency to foam.
  • a disadvantage of these coatings is the need to post-stabilize the dispersions obtained by adding emulsifiers.
  • larger amounts of the emulsifiers are to be added in order to achieve the required storage stability.
  • the addition of poly (alkyleneimine) emulsifier is therefore on the one hand expensive, on the other hand the water absorption increases with an increased emulsifier content in a coating, which is detrimental to the corrosion protection effect.
  • amines tend to form brown-colored degradation products in aqueous solutions, which are undesirable per se and can also apparently lead to discoloration of the coating.
  • the packaging of the dispersions with the described additives and the necessary final pH reduction with a buffer system further increase the costs for the manufacture of the product.
  • crosslinking mechanism of polyamines with acetoacetoxy groups based on aqueous polymer dispersions is i.a. also described in WO 98/54256.
  • US Pat. No. 5,122,566 discloses a process for the preparation of latices which is carried out by means of aqueous emulsion polymerization in the presence of phosphate emulsifiers and at a pH ⁇ 3.5.
  • the dispersions described in this document also contain at least one water-insoluble, nonionic surface-active agent and are adjusted to a pH in the range from 7 to 10.5 after the polymerization.
  • the use of adhesion-increasing acetoacetoxy derivatives of (meth) acrylic acid is not disclosed.
  • EP-A-0 476 528 discloses a process for the (industrial) production of latices, in which copolymers of vinyl aromatics are used by means of aqueous emulsion polymerization in the presence of a seed polymer at pH ⁇ 3.5 in the presence of phosphate emulsifiers and a water-insoluble, nonionic surface-active agent and acrylates. Except for the presence of at least one seed polymer, this method is identical to that disclosed in US Pat. No. 5,122,566. According to EP-A-0 476 528, polymers with a very high coagulum content are obtained on an industrial production scale in the absence of at least one seed polymer, ie the process according to US Pat. No. 5,122,566.
  • the present invention was therefore based on the object of providing aqueous polymer dispersions which, in corrosion protection coatings, have a high resistance to corrosion in the condensation water test in accordance with DIN 50017, are accessible on an industrial scale and can be prepared without the complex synthetic methods described in the prior art.
  • the films of the polymers should be distinguished by high transparency, that is to say the absence of disruptive scattering centers due to the formation of aggregates during the polymerization, so that they can also be used in clearcoats.
  • aqueous polymer dispersion having a solids content of 20 to 74% by weight, preferably 40 to 70% by weight, containing at least one copolymer A) which
  • the copolymer A) used according to the invention usually has a copolymer at least one glass transition temperature T g in the range from -35 to 80 ° C., preferably one T g in the range from 0 to 40 ° C. or two T g 's in the range from -30 to +20 ° C (first T fl ) and from +40 to + 80 ° C (second T g ).
  • the glass transition temperature of the copolymer A) used according to the invention is set by selecting the type and amount of the comonomers.
  • the proportions by weight of the monomers a) to c) are preferably chosen so that a copolymer composed only of them would have a glass transition temperature T g in the range from -35 to 80.degree.
  • the aqueous dispersions according to the invention have a significantly improved resistance of the resulting corrosion protection coatings in the condensation test according to DIN 50017. Furthermore, the aqueous dispersions according to the invention have reduced coagulum formation during the polymerization. The dispersions obtained can be produced perfectly on an industrial scale and the corrosion protection primer coatings formulated with them have increased (storage) stability. Finally, coatings with a high gloss can be produced with the dispersions according to the invention.
  • Preferred building blocks a) of the at least one copolymer are the esters ⁇ , ⁇ -ethylenically unsaturated carboxylic acids with alkanols containing 1 to 18 carbon atoms, preferably the esters of acrylic and methacrylic acid with methanol, ethanol, propanols, butanols, pentanols, 2- Ethyl hexanol, iso-octanol, n-decanol and n-dodecanol.
  • vinyl aromatic monomers such as styrene and its alkyl derivatives such as methyl styrene, ethyl styrene and oligo (alkyl) styrenes are preferred monomers.
  • alkenes such as ethene, propene, isobutene and derivatives of these compounds, such as vinyl chloride, vinyl ether and esters of (aliphatic) carboxylic acids with alkenes, preferably vinyl acetate, or ethylenically unsaturated esters of versatic acid as building blocks a).
  • Mono- or oligoethylenically unsaturated mono- or oligocarboxylic acids and their anhydrides or their salts are used as building blocks b).
  • Acrylic acid, methacrylic acid, itaconic acid, maleic acid and / or fumaric acid and their salts are preferably used. If the pH of the aqueous monomer emulsion template containing the building blocks b) and c) is ⁇ 4.7, it must be raised to at least pH> 4.7.
  • building blocks b) and (if used) c) in water, optionally together with building blocks d) and emulsifiers and optionally initiators, in the aqueous monomer emulsion template and the monomer emulsion template by adjusting the pH to bases with pH> 4 , 7 is neutralized before the rest of the monomers are added.
  • Partially water-soluble building blocks d) such as, for example, AAEMA, can be added to the aqueous initial charge of the monomer emulsion.
  • the mixture of the following is used as the monomer emulsion template Substances in the storage vessel for the production of monomer emulsions: water, building blocks b), building blocks c) (if present), emulsifiers and optionally building blocks d) and optionally initiators.
  • Sodium and potassium hydroxide are preferably used to raise the pH of the monomer emulsion template.
  • Ammonia is particularly preferably used for the neutralization of the monomer emulsion charge, since the base volatilizes after the film formation of the polymer, which results in less water absorption by the polymer.
  • Preferred building blocks c) are ethylenically unsaturated derivatives of sulfuric, sulfonic, phosphoric and / or phosphonic acid in the form of their sodium, potassium and ammonium salts. Particularly preferred are sodium ethenesulfonate, 2-acrylamido-2-methylpropanesulfonic acid (AMPS ®) salts and Kaliumsulfopropyl methacrylate.
  • AMPS ® 2-acrylamido-2-methylpropanesulfonic acid
  • Kaliumsulfopropyl methacrylate The ammonium salts are particularly preferably used since after
  • Film consolidation the free acids are present in the polymer, which have a lower water absorption of the polymer than the corresponding salts.
  • the aqueous polymer dispersions according to the invention further contain at least 0.3% by weight, preferably 0.3 to 5% by weight, based on the weight of the monomers used to prepare the copolymer, of emulsifiers containing phosphate and / or phosphone groups.
  • the emulsifiers are preferably used as ammonium, sodium and potassium salts of the phosphoric acid esters and / or the phosphonic acid esters.
  • the salts of these compounds with other bases can also be used.
  • the free phosphoric acid and / or phosphonic acid esters are used as raw material, they can be neutralized to pH> 7 (in part) in situ by reacting an aqueous solution of the emulsifier with a base, preferably with ammonia.
  • Emulsifiers containing phosphate groups are preferred, in particular esters of phosphoric acid with alcohols and phenols (also as mixtures of mono-, di- and triesters of phosphoric acid), esters of phosphoric acid with adducts of alcohols or (alkyl) phenols and ethylene oxide and / or propylene oxide and the sodium -, Potassium and ammonium salts of these compounds used.
  • the compounds are commercially available, for example, under the trade name ® Berol 522 (alkylphosphoric acid potassium salt), ® Hostaphat1306 (alkyloligoethoxylate phosphoric acid ester and ® Berol 733 (alkylphenololigoethoxylate phosphate potassium salt).
  • phosphate group-containing emulsifiers ethylenically unsaturated esters of phosphoric acid and hydrocarbons derived therefrom with hydrocarbons can also be used Neutralization products with bases can be used.
  • the at least one copolymer of the aqueous dispersion additionally contains 0.05 to 10% by weight, particularly preferably 0.5 to 3% by weight, based on the weight of the monomers used to prepare the copolymer, of a free-radically polymerizable one Monomers d) with at least one acetoacetoxy group in copolymerized form.
  • Acetoacetoxyethyl methacrylate (AAEMA) and acetoacetoxyethyl acrylate (AAEA) are preferably used as preferred monomers d). Also
  • Acetoacetic acid vinyl ether can be used.
  • the monomers d) can also be introduced with the monomers b) and c) in the initial charge of the monomer emulsion if they, e.g. AAEMA, are partially water-soluble.
  • the at least one copolymer of the aqueous dispersion can additionally, based in each case on the weight of the monomers used to prepare the copolymer, from 0 to 10% by weight, preferably 0 to 2% by weight and particularly preferably 0.05 to 1 Wt .-%, at least one (mono) - or (oligo) - ethylenically unsaturated reactive crosslinking monomers e) copolymerized, in addition to it 0 to 30 wt .-%, preferably 0 to 5 wt .-%, other copolymerizable (mono ) - or (oligo) ethylenically unsaturated monomers f) copolymerized and additionally 0 to 5% by weight, preferably 0 to 2 % By weight, particularly preferably 0 to 0.5% by weight, of molecules g) which react with the polymer by polymer-analogous reactions.
  • Monomers that crosslink during film formation are preferably ethylenically unsaturated derivatives of silane, such as, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, (methacrylicoxypropyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane and (methacryoxoxy-2-oxypropyl-methoxysiloxysilane ) silane, used.
  • silane such as, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, (methacrylicoxypropyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane and (methacryoxoxy-2-oxypropyl-methoxysiloxysilane ) silane, used.
  • glycidyl (meth) acrylates and / or other ethylenically unsaturated derivatives of glycidol such as, for example, glycidyl vinyl ether.
  • Diacetone acrylamide can also be used as monomer e). In this case, however, a dihydrazide should be added as a co-crosslinker. Masked derivatives of N-methylolacrylamide, such as N-butoxymethylmethacrylamide, can also be used as crosslinking agents.
  • monomers f) which can be used include, for example, unsaturated nitrogen-containing monomers, such as methacrylamide and dimethylaminoethyl (meth) acrylate, derivatives of urea, such as ß-ureidoethyl acrylate, ß-ureidovinyl ether, and ⁇ -hydroxyalkyl (meth) acrylates, where Methacrylamide is preferred.
  • unsaturated nitrogen-containing monomers such as methacrylamide and dimethylaminoethyl (meth) acrylate
  • derivatives of urea such as ß-ureidoethyl acrylate, ß-ureidovinyl ether, and ⁇ -hydroxyalkyl (meth) acrylates, where Methacrylamide is preferred.
  • bifunctional (meth) acrylates such as 1, 4- and 1, 3-butanediol di (meth) acrylate and 1, 6-hexanediol di (meth) acrylate
  • bifunctional ethylene derivatives such as divinylbenzene, butadiene
  • trifunctional (meth) acrylates such as trimethylolpropane trimethacrylate
  • Epoxysilanes are preferably used here, particularly preferably glycidyloxypropyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltriethoxysilane, ⁇ - (3,4- Epoxycyclohexyl) ethyltrimethoxysilane, furthermore oligofunctional silanes such as 1 - (triethoxysilyl) -2- (diethoxymethylsilyl) ethane or tris- [3- (trimethoxysilyl) propyljisocyanurate.
  • the aqueous composition according to the invention contains
  • UV crosslinking substances which are not ethylenically unsaturated are.
  • Preferred UV crosslinkers are acetophenone, benzophenone and acetophenone or benzophenone derivatives which do not contain an ethylenically unsaturated polymerizable group.
  • Derivatives of benzophenone which are present as a liquid mixture at room temperature, optionally with the addition of suitable auxiliary substances, are particularly preferred since these are advantageous in terms of application technology.
  • Phosphine oxide derivatives can also be used.
  • the aqueous polymer dispersion according to the invention can also contain further emulsifiers.
  • the total amount of emulsifiers is preferably in the range from 0.3 to 10% by weight, particularly preferably 0.3 to 3.5% by weight, based on the total amount of the monomers of the copolymer.
  • Preferred further emulsifiers are those which contain alkyl, aryl or alkylaryl groups.
  • a poly (ethylene oxide), a poly (propylene oxide) or a poly (ethylene oxide / propylene oxide) can be used as a spacer between the hydrocarbon radical and the polar head group.
  • ionic emulsifiers based on sulfate, sulfonate or carboxylate in addition to the phosphate or phosphonate emulsifiers is less preferred.
  • Nonionic co-emulsifiers in addition to the phosphate and / or phosphone emulsifiers can also be used.
  • the emulsifiers are preferably added before and / or during the polymerization.
  • ionic and nonionic emulsifiers can also be added to the finished dispersion in order to increase their stability.
  • the amount of emulsifiers used should be kept as low as possible in order to minimize the water absorption of the coatings.
  • the aqueous polymer dispersion according to the invention contains 0 to 5% by weight, preferably 0 to 1% by weight, based on the weight of the monomers used to prepare the copolymer, of protective colloids.
  • All protective colloids known to the person skilled in the art and suitable for the present purpose can be used as protective colloids.
  • water-soluble carboxymethyl celluloses are preferably used, particularly preferably in the form of their ammonium or alkali salts.
  • Commercially available products are, for example, ® Blanose 7M, ® Blanose 7UL, ® Blanose 7EL and ® Ambergum 3021 (Aqualon).
  • carboxymethyl celluloses can optionally carry further substituents, such as, for example, alkyl or hydroxyalkyl radicals, alkyloxyalkyl radicals and dialkylamino groups.
  • substituents such as, for example, alkyl or hydroxyalkyl radicals, alkyloxyalkyl radicals and dialkylamino groups. Examples include methylcarboxymethyl cellulose, ethyl carboxymethyl cellulose, hydroxyethyl carboxymethyl cellulose, hydroxypropyl carboxymethyl cellulose, methoxyethyl carboxymethyl cellulose and ethoxyethyl carboxymethyl cellulose.
  • high-molecular compounds such as, for example, polyvinyl alcohols, polyvinyl pyrrolidones, polyacrylamides, polymethacrylamides or polycarboxylic acids and their alkali metal or ammonium salts can also be used as protective colloids.
  • the aqueous polymer dispersion according to the invention contains 0 to 10% by weight, preferably 0.05 to 3% by weight, based on the weight of the monomers used to prepare the copolymer, of dispersants, preferably of polymeric dispersants.
  • dispersants preferably of polymeric dispersants.
  • All dispersants known to the person skilled in the art and suitable for the present purpose can be used as dispersants. Examples include water-soluble poly (meth) acrylic acids and / or their alkali or ammonium salts.
  • dispersants with hydrophobic components are preferably used, such as, for example, water-soluble copolymers of vinyl aromatics, in particular styrene with ethylenically unsaturated carboxylic acids and / or their anhydrides, in particular maleic anhydride.
  • These copolymers are particularly preferably used in the form of the corresponding ammonium and alkali salts. Some or all of these can also be introduced during or before the polymerization.
  • ® SMA resins such as the ® SMA 3000 HNa from Cray Valley, can be used.
  • the aqueous polymer dispersion according to the invention can, if appropriate, also film-forming auxiliaries, such as, for example, butyl diglycol and white spirit, plasticizers, such as, for example, dimethyl phthalate and dibutyl phthalate, and / or other auxiliaries, such as, for example, corrosion inhibitors, polyurethane and polyacrylate thickeners, preservatives, defoamers, such as Examples include mineral oil or silicone oil defoamers, wetting agents and other additives, as are usually used for the formulation of coating compositions.
  • auxiliaries such as, for example, butyl diglycol and white spirit
  • plasticizers such as, for example, dimethyl phthalate and dibutyl phthalate
  • auxiliaries such as, for example, corrosion inhibitors, polyurethane and polyacrylate thickeners, preservatives, defoamers, such as Examples include mineral oil or silicone oil defoamers, wetting agents and other additives, as are usually used
  • the present invention relates both to the aqueous polymer dispersions and to processes for their preparation and their use, in particular in anti-rust coatings.
  • the copolymers can be prepared by the methods of free radical suspension, mini-emulsion, microemulsion and emulsion polymerization known to the person skilled in the art. However, emulsion polymerization in water is preferred as the production process.
  • the aqueous polymer dispersions prepared therefrom are the preferred delivery form for the copolymers according to the invention.
  • the at least one copolymer is accordingly preferably by free radical emulsion polymerization in an aqueous medium under the
  • the conventional methods of emulsion polymerization emulsify the monomers in the aqueous phase in the presence of the emulsifiers, initiators and, if appropriate, the protective colloid and polymerize them preferably at temperatures in the range from 25 to 95 ° C.
  • the emulsion polymerization can by the processes known to the person skilled in the art, such as, for example, batch or emulsion feed processes, the emulsion feed process being preferred, in which part of the monomer emulsion is initially introduced and polymerized before the remaining monomers are metered in as an aqueous monomer emulsion.
  • a plurality of monomer (emulsion) feeds of different compositions are preferably metered in successively.
  • multi-stage polymers with heterogeneous morphology of the resulting polymer film are obtained.
  • the preparation of such multistage polymers is described, for example, in EP-A-0 795 568.
  • Suitable multistage polymers have lower minimum film formation temperatures (MFTs) than homogeneous polymers of the same monomer composition and are therefore preferred.
  • MFTs minimum film formation temperatures
  • Multi-stage polymers can also be produced in a particularly block-resistant manner. Deviating from this, the monomers can also be metered in according to the so-called power feed technique with a constant or abrupt gradient of the monomer composition.
  • Both the emulsifier (s) and any protective colloids which may be used can be (partly) placed in the reactor and / or (partly) metered in with the monomer emulsion.
  • One or more monomer emulsion templates can be used in the process according to the invention.
  • the pH of the monomer emulsion template comprising the at least one monomer b) and optionally the at least one monomer c) is> 4.7, preferably 4.7 to 11, particularly preferably 4.7 to 8 and very particularly preferably 5 to 7.
  • the emulsifiers are usually added together with the monomer emulsion templates, it being possible for different monomer emulsion templates to contain different emulsifiers.
  • the monomer template containing the at least one monomer b) preferably contains emulsifiers containing phosphate groups.
  • Monomer templates containing monomers a), b) and optionally c) and emulsifiers containing phosphate groups are particularly preferably used.
  • the polymerization is usually carried out at pH values of> 4.7, preferably 4.7 to 11 and particularly preferably 5 to 7.
  • Oil and / or water-soluble radical formers or redox initiator systems are used to start and carry out the polymerization.
  • potassium, sodium or ammonium peroxodisulfate, hydrogen peroxide, dibenzoyl peroxide, lauryl peroxide, tert-butyl hydroperoxide, azoisobutyronitrile and other azo initiators are preferably used, optionally together with reducing reagents such as sodium bisulfite, ® rongalit, glucose, ascorbic acid or tartaric acid.
  • the polymerization initiators are generally used in amounts of 0.1 to 10% by weight, preferably 0.1 to 1% by weight, in each case based on the total weight of the monomers used to prepare the copolymer.
  • regulators such as thiols
  • n-dodecyl mercaptan thiophenol
  • 2-methyl-5-tert-butylthiophenol being preferably used.
  • the regulator or regulators are generally used in amounts of 0 to 1% by weight, based on the weight of the monomers used to prepare the copolymer.
  • the final pH of the aqueous dispersions is generally adjusted to pH 6 to 10 using aqueous solutions of ammonia or alkali hydroxide solutions.
  • aqueous dispersions according to the invention can be prepared by adding conventional additives, pigments, plasticizers and, if appropriate, other ingredients, for example fillers, dispersants, thickeners, corrosion protection pigments, corrosion inhibitors, wetting agents, UV inhibitors, UV initiators and / or other polymeric binders can be formulated into coating compositions. They are particularly suitable for the production and use of optionally pigmented coatings, such as, for example, anti-rust coatings, clear lacquers, gloss lacquers and decorative coatings, in which increased substrate adhesion is required. The improved substrate adhesion is ensured by the presence of phosphate and, if applicable, wet adhesion promoters such as acetoacetoxy groups in the synthetic resin preparation.
  • AAEMA and / or AAEA are particularly preferably used as functional monomers of the at least one copolymer.
  • Suitable substrates are preferably metals, particularly preferably steel, but also inorganic surfaces containing silicate, and wood. Furthermore, acetoacetoxy groups which may be present ensure that the coatings according to the invention have a low tendency to block, ie have little tendency to block when pressing two drying surfaces which have been treated with the coatings. Good substrate adhesion is also achieved if, instead of the monomers d), reactive-crosslinking monomers e) are used.
  • the determination of the minimum film-forming temperature (MFT) of the polymers was carried out in accordance with DIN-ISO 2115.
  • the glass transition temperatures (T g ) of the polymers were determined by means of DSC (Differential Scanning Calorimetry). The heating and cooling rate was 20 ° C / min in each case, and the recorded temperature range was -60 ° C to + 130 ° C.
  • the specified glass transition temperatures of the polymers were determined in the 2nd heating cycle (mid-point evaluation). By using the Fox equation, the glass transition temperatures of the polymers can be estimated to a good approximation (see TG Fox, Bull. Am. Phys. Soc. (Ser. II), 1, 123 [1956]).
  • the glass transition temperatures of the homopolymers built up from the monomers a), b) and c) are largely known and are listed, for example, in J. Brandrup, EH Immergut, Polymer Handbook, 2 nd Ed., J. Wiley, New York, 1975.
  • Monomer emulsion liquor (monomer emulsion template): Become one after the other
  • Example 11 After storage for one day at room temperature, the dispersions of Examples 1 to 10 (solids content approx. 47%), water and Texanol are added to the paste in the amounts described and the finished coating is stirred for a further 10 minutes at 500 rpm.
  • Example 11 k and 111 (see Table 3) is before Color formulation each 1.44 wt .-% based on the polymer dispersions gross SMA ⁇ 3000 HNa solution (Cray Valley, delivery form about 25% solids) added to the dispersion.
  • Example 12 Testing of anti-rust coatings in a constant condensation test according to DIN 50017 and storage stability of the primer formulations
  • the primers from Example 11 are applied to galvanized steel sheets with a 100 ⁇ m spiral doctor blade (wet layer thickness approx. 100 ⁇ m, dry layer thickness approx. 50 ⁇ m) and then 14 days at 23 ° C and 50% rel. Humidity dried. Then the dry layer thickness is determined and the sheets parallel to the long axis in the middle of the substrate are scored over the entire length of the test specimen using a scribe tool so that there is a distance of 30 mm from the sheet edges. The test is carried out in a climate change test device from Weiss at 40 ° C. and 100% rel. Humidity carried out at an exposure duration of 864 hours.
  • KSW (4 x bubble quantity + 1 x bubble size + 1 x degree of rust) / 6
  • the bubble quantity, bubble size and degree of rust were determined in accordance with DIN 53209 and DIN 53210.
  • Storage stability is ensured by storing the primers for 3 months at room temperature determined in closed PE vessels.
  • the assessment is carried out on a scale from 1 to 5, 1 meaning excellent storage stability without any settling of the fillers and pigments and 5 very strong settling with considerable serum formation.
  • V comparative example
  • P example according to the invention
  • 3 phosphate emulsifier
  • 4 sulfate emulsifier
  • the use of the dispersions according to the invention which are produced at pH 5 of the monomer emulsion liquor and thus (partially) neutralized carboxylic acid monomer groups, results in increased stability of the anti-rust primer. While the primer 11i coagulates immediately when the binder is added during the primer preparation, the formulation 11j according to the invention is stable.
  • the dispersions according to the invention surprisingly produce a significantly increased rust protection effect in the constant climate condensation water test in rust protection primers, compared to polymers in which the monomer emulsion template containing carboxylic acid groups b) was not adjusted to at least pH> 4.7. Only by combining the features of the presence of a phosphate emulsifier and using a monomer emulsion template containing the building blocks b) with a pH> 4.7 are the inventive

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Abstract

L'invention concerne des dispersions polymères destinées à la protection contre la corrosion et présentant de bonnes propriétés antirouille, leur production et leur utilisation. Les dispersions polymères selon l'invention comprennent des émulsifiants contenant des groupes phosphate ou phosphonate et les groupes d'acide (carboxylique) ajoutés en tant que stabilisants sont (partiellement) neutralisés avant la polymérisation par l'ajout de bases. On obtient ainsi des dispersions polymères à propriétés antirouille améliorées selon le test à eau de condensation DIN 50017 et à teneur faible en coagulat pour une production à l'échelon industriel. Les dispersions polymères selon l'invention améliorent en outre la stabilité des apprêts anticorrosion produits avec elles ; elles permettent de formuler des revêtements à brillance élevée.
PCT/EP2003/007931 2002-08-08 2003-07-21 Dispersions polymeres aqueuses, leur procede de production et leur utilisation, notamment dans des revetements anticorrosion WO2004020477A1 (fr)

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DE2002136395 DE10236395A1 (de) 2002-08-08 2002-08-08 Wässrige Polymerdispersionen, Verfahren zu ihrer Herstellung sowie ihre Verwendung, insbesondere in Korrosionsschutzbeschichtung

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CN103773142A (zh) * 2014-01-20 2014-05-07 南通华新环保设备工程有限公司 一种设备用环保防锈涂料及其制备方法
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CN105541225A (zh) * 2015-12-25 2016-05-04 常熟市奇越新型建材科技有限公司 抹墙干粉涂料
CN106867347A (zh) * 2017-04-05 2017-06-20 武汉迪赛环保新材料股份有限公司 一种热轧h型钢临时防锈液
CN108017972A (zh) * 2017-11-24 2018-05-11 鹤山市信兴化工有限公司 有机硅改性丙烯酸聚氨酯杂合乳液及由其制成的水性涂料
CN111286312A (zh) * 2020-02-20 2020-06-16 中国石油天然气股份有限公司 一种油井用缓释型缓蚀阻垢剂胶囊及其制备方法
CN113201087A (zh) * 2020-11-20 2021-08-03 联固新材料科技(广州)有限公司 羟基丙烯酸分散体及其制备方法和双组分聚氨酯漆
CN114591665A (zh) * 2021-12-28 2022-06-07 天津市新丽华色材有限责任公司 一种低voc乳液型水性铝镜镜背涂料
FR3117794A1 (fr) * 2020-12-23 2022-06-24 L'oreal Dispersion aqueuse d’un copolymère spécifique et ses applications cosmétiques
WO2022136114A1 (fr) * 2020-12-23 2022-06-30 L'oreal Dispersion aqueuse d'un copolymère spécifique et ses applications cosmétiques
CN117567688A (zh) * 2024-01-15 2024-02-20 星宇新材料股份有限公司 一种丁腈乳液及其合成方法和应用

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DE102007033595A1 (de) 2007-07-19 2009-01-22 Celanese Emulsions Gmbh Polyvinylesterdispersionen, Verfahren zu deren Herstellung und deren Verwendung
DE102007033596A1 (de) 2007-07-19 2009-01-22 Celanese Emulsions Gmbh Beschichtungsmittel mit hoher Bewitterungsbeständigkeit, Verfahren zu deren Herstellung und deren Verwendung
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CA2971498A1 (fr) * 2016-07-14 2018-01-14 Dow Global Technologies Llc Latex fonctionnalise avec de l'acide phosphorique et des groupes photoinitiateurs
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CN107478767B (zh) * 2017-09-05 2019-09-06 中国科学院长春应用化学研究所 一种测定有机膦酸溶液中长链脂肪醇含量的方法
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EP1926787B2 (fr) † 2005-09-12 2013-07-10 Basf Se Procédé pour augmenter la résistance à la pénétration de taches de compositions de revêtement aqueux
US9102848B2 (en) 2011-02-28 2015-08-11 Basf Se Environmentally friendly, polymer dispersion-based coating formulations and methods of preparing and using same
CN103773142A (zh) * 2014-01-20 2014-05-07 南通华新环保设备工程有限公司 一种设备用环保防锈涂料及其制备方法
CN103773142B (zh) * 2014-01-20 2015-12-02 南通华新环保设备工程有限公司 一种设备用环保防锈涂料及其制备方法
CN105541225A (zh) * 2015-12-25 2016-05-04 常熟市奇越新型建材科技有限公司 抹墙干粉涂料
CN106867347A (zh) * 2017-04-05 2017-06-20 武汉迪赛环保新材料股份有限公司 一种热轧h型钢临时防锈液
CN108017972A (zh) * 2017-11-24 2018-05-11 鹤山市信兴化工有限公司 有机硅改性丙烯酸聚氨酯杂合乳液及由其制成的水性涂料
CN111286312A (zh) * 2020-02-20 2020-06-16 中国石油天然气股份有限公司 一种油井用缓释型缓蚀阻垢剂胶囊及其制备方法
CN113201087A (zh) * 2020-11-20 2021-08-03 联固新材料科技(广州)有限公司 羟基丙烯酸分散体及其制备方法和双组分聚氨酯漆
FR3117794A1 (fr) * 2020-12-23 2022-06-24 L'oreal Dispersion aqueuse d’un copolymère spécifique et ses applications cosmétiques
FR3117788A1 (fr) * 2020-12-23 2022-06-24 L'oreal Dispersion aqueuse d’un copolymère spécifique et ses applications cosmétiques
WO2022136114A1 (fr) * 2020-12-23 2022-06-30 L'oreal Dispersion aqueuse d'un copolymère spécifique et ses applications cosmétiques
CN114591665A (zh) * 2021-12-28 2022-06-07 天津市新丽华色材有限责任公司 一种低voc乳液型水性铝镜镜背涂料
CN114591665B (zh) * 2021-12-28 2022-11-01 天津市新丽华色材有限责任公司 一种低voc乳液型水性铝镜镜背涂料
CN117567688A (zh) * 2024-01-15 2024-02-20 星宇新材料股份有限公司 一种丁腈乳液及其合成方法和应用
CN117567688B (zh) * 2024-01-15 2024-04-05 星宇新材料股份有限公司 一种丁腈乳液及其合成方法和应用

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CN1688614A (zh) 2005-10-26
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JP2011225893A (ja) 2011-11-10
CN100345869C (zh) 2007-10-31

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