DE102009000570A1 - Copolymer, useful as a binder for coatings and in coating agent, which is useful as a clear or topcoat for coating substrates, comprises (meth)acrylic acid ester compounds, and (meth)acrylic acid - Google Patents

Abstract

Copolymer comprises: 20-40 wt.% of at least one (meth)acrylic acid ester compound (1a); 5-20 wt.% of at least one (meth)acrylic acid ester compound (2a); 30-50 wt.% of at least one (meth)acrylic acid ester compound (3a); 2-10 wt.% of (meth)acrylic acid; and 0-15 wt.% of at least one (meth)acrylic acid ester compound (4a). Copolymer comprises: 20-40 wt.% of at least one (meth)acrylic acid ester compound of formula (CH 2=CR 1>-COO-C nH 2n+1) (1a); 5-20 wt.% of at least one (meth)acrylic acid ester compound of formula (CH 2=CR 1>-COO-R 2>) (2a); 30-50 wt.% of at least one (meth)acrylic acid ester compound of formula (CH 2=CR 1>-COO-R 3>) (3a); 2-10 wt.% of (meth)acrylic acid; and 0-15 wt.% of at least one (meth)acrylic acid ester compound of formula (CH 2=CR 1>-COO-R 4>) (4a). R 1>H or CH 3; n : 10-55, where C nH 2n+1is linear or branched; R 2>optionally substituted 1-6C alkyl; R 3>hydroxy-2-10C-alkyl; and R 4>optionally substituted 4-12C cycloalkyl. An independent claim is included for a coating agent comprising: 50-90 wt.% of the copolymer; 10-50 wt.% of one or more monomeric, oligomeric or polymeric isocyanate compounds; and one or more organic solvents, and optionally one or more pigments, fillers and/or conventional additives, in which the molar ratio of hydroxyl groups of the copolymer to the reactive groups of the isocyanate compounds is 0.5-1.5, where the solid content of the coating agent is 45-85 wt.%, and the solution viscosity of the coating agent according to DIN 4 (23[deg] C) is 10-40 sec.

Description

The The present invention relates to copolymers of long chain alkyl esters of (meth) acrylic acid and its use as a binder for coating agents.

Field of the invention

Solvent-based Coating resins based on polyacrylates are according to the state of Technology common materials for the production of coatings. The coating resins form in combination with crosslinkers such as melamine compounds or isocyanates on thermal curing a polymer network. Due to the technical application conditions must certain viscosity limits with the coating formulation be respected. These in turn lead to the limit the solids content in the solution of the polyacrylate and the coating formulation. To the solvent emission to decrease as much as possible in the paint application, is a high solids content in the polyacrylate resin and sought in the coating formulation. On the one hand, this will be in the prior art by adherence to low molecular weights ensured at the polyacrylates. On the other hand Monomers used by their structure a coil conformation which lead to low solution viscosities leads. The structure of the substituent in the side chain The (meth) acrylate monomer is usually based on cyclic compounds such as cyclohexanol, isoborneol or similar structures.

State of the art

In the DE-C-19524787 describes a coating agent having a solids content of 50 to 65 wt .-%, which contains A) hydroxyl-containing copolymers based on (meth) acrylic acid esters, B) polyisocyanates and C) solvent and optionally pigments, fillers and / or paint additives. The copolymers contain mainly hydroxyalkyl (32-42 wt .-%), C ₁ -C ₆ alkyl (25-40 wt .-%) and cycloalkyl esters (12-24 wt .-%) of (meth) acrylic acid and have a T _G of 30-80 ° C. The molar ratio of the hydroxyl groups of component A) to the isocyanate groups of component B) is 0.5-2.

EP-A-0 638 591 (Epple et al.) Discloses "high-solid" varnishes containing copolymers of A) glycidyl esters and B) a mixture of mainly sterically hindered monomers and hydroxyl-containing (meth) acrylates and crosslinked with polyisocyanates. As sterically hindered monomers in addition to styrene and styrene derivatives in particular (meth) acrylates with bulky side groups such as t-butyl methacrylate (t-BMA), isobornyl methacrylate (IBMA), cyclohexyl methacrylate (cHMA) and tert-butylcyclohexyl methacrylate (TBCHMA) are used. The copolymers are used for the production of coatings and as binders for paints and have a T _G above 20 ° C. The "high-solid" coatings have a solids content of about 75% and a solution viscosity of 21 seconds (outlet cup DIN 53211 ).

In the WO 96/20968 describes a coating composition in which a hydroxyl-containing (meth) acrylate copolymer, in addition to a highly branched oligoester containing a plurality of hydroxyl groups, is contained as binder. The (meth) acrylate copolymer contains 10-90% by weight of alkyl-substituted cycloaliphatic (meth) acrylate monomers and / or alkyl-substituted vinyl aromatic monomers, 10-50% by weight of a hydroxyalkyl (meth) acrylate, and 0-80% by weight, preferably 25% -50 wt .-% of a further comonomer, as which inter alia alkyl methacrylates are called with 1 to 12 hydrocarbon atoms.

The hydroxyl group-containing (meth) acrylate copolymer preferably has an OH value of 60 to 180, a T _g of at least 30 ° C and a molecular weight (M _n ) of <4000. The coating agent further contains polyisocyanate as a crosslinking agent. The drying time to freedom from sticking and dust dryness is shortened by isobornyl methacrylate (IBMA) and tert-butylstyrene compared to t-BMA and i-BMA. This benefit is accompanied by a reduction in the solids content and leads to an increase in volatile organic compounds (VOC).

US-A-4,242,243 discloses a coating composition comprising a methacrylate copolymer containing 35-65% by weight of C ₁ -C ₁₂ -alkyl methacrylate and 10-30% by weight of a hydroxy-C ₂ -C ₄ -alkyl (meth) acrylate and 25-45% by weight. % of fatty acids. For the preparation of the coating agent, first the methacrylate copolymer is prepared and subsequently the hydroxyl side groups are esterified with fatty acids. The 2-stage production process is complicated because the polymerization requires different temperatures and solvents than the esterification. Side chain modification with fatty acids achieves a variety of requirements, such as low solvent emissions, low solution viscosity, and concurrent shortness Drying times (no adhesive) to meet.

EP-A-0882750 describes the preparation of a (meth) acrylate copolymer and its use as a high solids, low VOC coating with good service life of the coating mixture. These advantageous properties are achieved by the use of 5 to 45% of a (methacrylate) monomer with active hydrogen (OH, NH) such. As HEMA and the use of a reactive solvent for the polymerization achieved. The comonomers used include alkyl (meth) acrylates having 1-18 carbon atoms and styrene. The reactive solvent is understood as meaning, for example, saturated polyester polyols. Also aminoendfunktionalisierte polypropylene glycols are called. The advantage of this procedure should lie in the manufacturability of a coating with self-regenerating properties. If damaged by superficial scratches and traces of abrasion, the gloss of the coating can be restored by simple polishing. The copolymers are preferably crosslinked by isocyanates, so that the coating cures at ambient temperature.

EP 0 676 431 A1 describes the improvement in the viscosity of high-solids paints by the use of 1,4-cyclohexanedimethanol. The varnishes tested contain a hydroxyl group-containing poly (meth) acrylate, a commercial polyisocyanate crosslinker, and 1,4-cyclohexanedimethanol as a viscosity index improver. To improve the effect, a polyester with 1,4-cyclohexanedimethanol structural units is additionally used. The preparation of poly (meth) acrylate resins having various IBMA concentrations is described, with no data on non-volatile content (nfA) and König hardness being available for such resins.

EP 0 676 423 A1 describes the effective combination of 4-HBA and IBMA to increase the nfa while improving the Knoop hardness of the dried film. Each of the combinations MMA / HEMA, IBMA / HEMA, MMA / 4-HBA and IBMA / 4-HBA produces three poly (meth) acrylates with decreasing molar masses in the range between 1300-2500 g / mol. The solutions of the poly (meth) acrylates contain a solids content of ~ 82%. They are crosslinked with dilution of BuAC with HDT90. The crosslinking takes place by drying at room temperature.

task

• – eine möglichst geringe Lösungsmittelemission aufweist,
• – eine Viskosität aufweist, die problemlos mit den üblichen Maschinen verarbeitbar ist und
• – einen möglichst hohen Gehalt an Festkörpern aufweist.

It was now in view of the discussed prior art, the task of developing a copolymer (paint resin), suitable as a binder for a coating agent, and a coating composition prepared therefrom, the

• - has the lowest possible solvent emission,
• - Has a viscosity that can be processed easily with the usual machines and
• - Has the highest possible content of solids.

solution

in the The scope of the present invention has been to solve the Task (meth) acrylate ester with long linear and / or branched Alkyl chains (LACE monomers = long alkyl chain ester methacrylate monomers) used in the paint formulation. The notation (meth) acrylate here means both derivatives of acrylic acid and the Methacrylic acid. This could already lower in the paint resin Solution viscosity at high solids content be achieved. In particular, this effect made in the final Paint formulation, d. H. in the coating resin-containing coating agent, noticeable.

Under Paint resin is understood to mean a polymer which is from the reaction of organic unsaturated molecules, preferably monoethylenically unsaturated carboxylic acids and their esters, by radical polymerization of the C-C double bond evident.

in the Compared to known coating resins can according to the invention by the use of long-chain alkyl (meth) acrylates higher Solid state contents are achieved. The achieved viscosities are in a comparable scope to commercially available Coating resins.

• a₁) 20–40 Gew.-% mindestens eines (Meth)acrylsäureesters der Formel (1) CH2=C(R1)-COO-CnH2n+1 (1)worin R¹ = H oder CH₃ ist und n unabhängig voneinander eine ganze Zahl von 10 bis 55 ist, wobei -C_nH_2n+1 linear oder verzweigt sein kann,
• a₂) 5–20 Gew.-% mindestens eines (Meth)acrylsäureesters der Formel (2) CH2=C(R1)-COO-R2 (2),worin R¹ = H oder CH₃ ist und R² lineares oder verzweigtes C₁-C₆-Alkyl ist, welches gegebenenfalls substituiert sein kann;
• a₃) 30–50 Gew.-% mindestens eines (Meth)acrylsäureesters der Formel (3) CH2=C(R1)-COO-R3 (3),worin R¹ = H oder CH₃ ist und R³ ein Hydroxy-(C₂-C₁₀)-Alkylrest ist,
• a₄) 2–10 Gew.-% (Meth)acrylsäure, und
• a₅) 0–15 Gew.-% mindestens eines (Meth)acrylsäureesters der Formel (4) CH₂=C(R¹)-COO-R⁴ (4), worin R¹ = H oder CH₃ ist und R⁴ eine (C₄-C₁₂)-Cycloalkylgruppe ist, die gegebenenfalls substituiert sein kann, wobei die Summe der Komponenten a₁) bis a₅) stets 100 Gew.-% beträgt.

The invention therefore relates to copolymers

• a ₁ ) 20-40% by weight of at least one (meth) acrylic acid ester of the formula (1) CH 2 = C (R 1 ) -COO-C n H 2n + 1 (1) wherein R ¹ = H or CH ₃ and n is independently an integer from 10 to 55, where -C _n H _{2n + 1 may be} linear or branched,
• a ₂ ) 5-20% by weight of at least one (meth) acrylic ester of the formula (2) CH 2 = C (R 1 ) -COO-R 2 (2) wherein R ¹ = H or CH ₃ and R ^{2 is} linear or branched C ₁ -C ₆ alkyl, which may optionally be substituted;
• a ₃ ) 30-50% by weight of at least one (meth) acrylic acid ester of the formula (3) CH 2 = C (R 1 ) -COO-R 3 (3) wherein R ¹ = H or CH ₃ and R ^{3 is} a hydroxy (C ₂ -C ₁₀ ) -alkyl radical,
• a ₄ ) 2-10% by weight of (meth) acrylic acid, and
• a ₅ ) 0-15 wt .-% of at least one (meth) acrylic acid ester of the formula (4) CH ₂ = C (R ¹ ) -COO-R ⁴ (4), wherein R ¹ = H or CH ₃ and R ⁴ is a (C ₄ -C ₁₂ ) -cycloalkyl group, which may optionally be substituted, wherein the sum of components a ₁ ) to a ₅ ) is always 100 wt .-%.

The novel copolymers generally have a hydroxyl number of 100 to 180 mg KOH / g, an acid number of 10 to 20 mg KOH / g, an average molecular weight (number average M _n ) of 1,000 to 10,000 g / mol and a Brookfield viscosity of 500 to 5000 mPa · s, preferably from 2000 to 3500 mPa · s (measured in 75% solution at 23 ° C).

Furthermore, the aforementioned copolymers generally have a glass transition temperature (Tg) below 40 ° C (determined by DSC measurement at extrapolated heating rate of 0 K / min after ISO 11357 ). The Vicat softening temperature, after DIN EN ISO 306 , Aug. 1994 (16h / 80 ° C; B50; Mini Vicat plant) is preferably at least 75 ° C, more preferably at least 85 ° C.

A ₁ ) (meth) acrylic acid esters with long linear and branched alkyl chains of the formula (I) (= LACE monomers) are understood as meaning, for example: isotridecyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, decyl (meth ) acrylate, C ₁₃ - (meth) acrylate, C _17.4 - (meth) acrylate, stearyl (meth) acrylate, hexadecyl (meth) acrylate, 2-methylhexadecyl methacrylate, heptadecyl (meth) acrylate, 5-iso-propylheptadecyl (meth acrylate, 4-tert-butyloctadecyl (meth) acrylate, 5-ethyloctadecyl (meth) acrylate, 3-iso-propyloctadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, eicosyl (meth) acrylate, Cetyleicosyl (meth) acrylate, Stearyleicosyl (meth) acrylate, docosyl (meth) acrylate, Eicosyltetratriacontyl (meth) acrylate, oxiranyl (meth) acrylates such as 10,11-epoxyhexadecyl (meth) acrylate.

It It is also possible to use mixtures of the abovementioned compounds become.

Preference is given to LACE monomers a ₁ ) of the formula (I) in which n is an integer from 13 to 30, very particularly preferably from 17 to 25.

The proportion of the LACE monomers a ₁ ) of the formula (I) to the copolymer is preferably 25 to 35 wt .-%.

The LACE monomers a ₁ ) can be obtained, for example, by reacting (meth) acrylates and / or the corresponding acids with long-chain fatty alcohols, generally resulting in an (isomeric) mixture of (meth) acrylic esters with different long-chain alcohol radicals. These fatty alcohols include Oxo Alcohol ^® 7911 and Oxo Alcohol ^® 7900, Oxo Alcohol ^® 1100 from Monsanto; Alphanol ^® 79 by ICI; Nafol ^® 1620, Alfol ^® 610 and Alfol ^® 810 from Condea; Epal ^® 610 and Epal ^® 810 from Ethyl Corporation, Linevol ^® 79. Linevol ^® 911 and Dobanol ^® 25L of Shell AG; Lial 125 from ^Augusts® Milan; Dehydad® ^® and Lorol ^® of Henkel KGaA and Linopol ^® 7-11 and Acropol ^® 91 Ugine Kuhlmann.

It may also be used to prepare the LACE monomer blends of two or more methacrylates satisfying the above description, be used.

A ₂ ) (meth) acrylic esters of the formula (2) are understood as meaning, for example, methyl, ethyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl and / or hexyl (meth) acrylate.

Under a ₃₎ hydroxyalkyl esters of (meth) acrylic acid of formula (3) is preferably meant hydroxy- (C ₂ -C ₆₎ -alkyl, in particular hydroxyethyl, hydroxypropyl and / or hydroxybutyl (meth) acrylate.

Component a ₄ ) is to be understood as meaning acrylic and / or methacrylic acid.

Under a ₅ ) cycloalkyl esters of (meth) acrylic acid of formula (4) is preferably understood cyclopentyl, cyclohexyl, 4-tert-butylcyclohexyl, 3,3,5-trimethylcyclohexyl, isobornyl, 2-ethylhexyl, Dihydrodicyclopentadienyl -, 2,4,5-tri-t-butyl-3-vinylcyclohexyl and / or 2,3,4,5-tetra-t-butylcyclohexyl (meth) acrylate. Further subject of the invention are copolymers according to claim 1, the total 5-20 wt .-% of (meth) acrylic acid esters of the formulas (2), (3) and / or (4), which are characterized by a glass transition temperature of its homopolymer of more than 90 ° C.

Under (Meth) acrylates are always both derivatives of acrylic acid and the methacrylic acid and mixtures of the two understood above components.

The Preparation of the novel copolymers can be done by the usual methods, such as by a free-radically initiated polymerization, which is preferably in an organic solvent. As a solvent For the polymerization reaction, all inert Solvent with sufficiently high boiling point used such as aromatic hydrocarbons such as benzene, Toluene, xylene or chlorobenzene, either pure or in the form of the mixture of isomers, Esters such as ethyl acetate, butyl acetate, methyl glycol acetate, ethyl glycol acetate or methoxypropyl acetate, ethers, such as butyl glycol, tetrahydrofuran (THF), dioxane or ethyl glycol ether, ketones such as acetone or methyl ethyl ketone (MEK), halogen-containing solvents such as methylene chloride or trichloromonofluoroethane.

The Free-radical initiated polymerization can be carried out by conventional Initiators are triggered whose half-lives of the Radical decay at 80 degrees Celsius to 180 degrees Celsius between 0.01 and 400 minutes are. In general, the copolymerization takes place in the aforementioned temperature range, preferably between 100 degrees Celsius and 160 degrees Celsius and under a pressure between 1,000 to 20,000 mbar, whereby the exact polymerization conditions judge by the type of initiator. The initiators are in quantities from 0.01 to 8 wt .-%, based on the total amount of the monomers used.

suitable Initiators are, for example, aliphatic azo compounds such as Azoisobutyronitrile and peroxides such as dibenzoyl peroxide, tert-butyl perpivalate, tert-butyl per-2-ethylhexanoate, tert-butyl perbenzoate, tert-butyl hydroperoxide, Cumene hydroperoxide and dicyclohexyl and dibenzyl peroxodicarbonate.

to Control of the molecular weight of the copolymers can, for example the usual sulfur-containing regulators are used such as n-dodecylmercaptan, diisopropylxanthogen disulphide, di (methylenetrimethylolpropane) xanthogen disulphide and thioglycol. They are in amounts of about 3 wt .-%, based on the total amount of monomers used.

The average chain length of said monomers is by Forming the arithmetic mean over the distribution determined, whereby the distribution of the chains by gas chromatographic Determination methods is determined.

The Number average molecular weight Mn of the invention Copolymers can vary widely, the molecular weight usually tailored to the purpose and method of processing. In general, Mn ranges between 1,000 and 10,000 g / mol, preferably from 1 000 to 8 000 g / mol and more preferably 1 000 to 6 000 g / mol, without this being a limitation should be done.

The glass transition temperature (Tg) of the novel copolymers is generally below 40 ° C., preferably below 25 ° C., more preferably below 10 ° C. (determined by DSC measurement) ISO 11357 at three different heating rates of 10, 20 and 40 K / min, extrapolated to the heating rate of 0 K / min).

Glass transition temperatures (Tg) can be z. See, for example, the reference Brandrup and EH Immergut, "Polymer Handbook", Interscience 1966, pIII-61 to III-63, or the "Plastics Handbook", Volume IX, Editors R. Vieweg and F. Esser, Carl-Hanser-Verlag , Munich 1975, pp. 333-339 and TG Fox in Bull. At the. Physics soc, Vol. I, (3) p 123 (1956). Furthermore, one can determine the glass transition temperature of the polymers by measuring differential scanning calorimetry (DSC), z. B. after ISO 11357 . make.

The Copolymers of the invention are suitable as Binders for the preparation of paint formulations for all practical fields of application in which solvent-containing, solvent-free or other aqueous Painting and coating systems with an improved property profile be used.

Another The invention therefore relates to coating compositions containing the copolymers according to the invention as a binder component contain.

The Copolymers may be used in the presence of suitable crosslinkers be cured cold or at elevated temperature.

When Hardener component are suitable in these coating compositions Aminoplast resins, monomeric, oligomeric or polymeric isocyanates and Anhydride-containing compounds individually or in combination. The crosslinker is added in each case in such an amount that the molar ratio of the OH groups of the copolymer to the reactive groups of the crosslinker is between 0.5 to 1.5. As a hardener component suitable amino resins are in particular Urea, melamine and / or benzoguanamine resins. It is about here to etherified urea, melamine or benzoguanamine-formaldehyde condensation products. These crosslinkers result in the presence of acids such as B. p-toluenesulfonic acid to cure the coating.

According to the invention however, preferred as crosslinking agents are monomeric, oligomeric or polymeric Isocycanate used. As isocyanate component come in principle all known from polyurethane chemistry aliphatic, cycloaliphatic or aromatic polyisocyanates individually or in mixtures. For example Low molecular weight polyisocyanates such as, for example, are very suitable Hexamethylene diisocyanate, 2,2,4- and / or 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, Dodecamethylene diisocyanate, tetramethyl-p-xylylene diisocyanate, 1,4-diisocyanatocyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,4'- and / or 4,4'-di-isocyanato-diphenylmethane or mixtures of these Isomers with their higher homologs.

However, particular preference is given to using derivatives of these simple polyisocyanates, as are customary in coating technology. These include polyisocyanates which have, for example, biuret groups, uretdione groups, isocyanurate groups, urethane groups, carbodiimide groups or allophanate groups, as described, for example, in US Pat. B. in the EP-A-0470461 to be discribed.

• i. 50–90 Gew.-% des erfindungsgemäßen Copolymeren,
• ii. 10–50 Gew.-% einer oder mehrerer monomerer, oligomerer oder polymerer Isocyanatverbindungen, und
• iii. ein oder mehrere organische Lösemittel, sowie gegebenenfalls übliche Hilfs- und Zusatzmittel,

in welchem
sich die Anteile von i) und ii) zu 100 Gew.-% ergänzen, das molare Verhältnis der Hydroxylgruppen des Copolymeren zu den reaktiven Gruppen der Isocycanatverbindungen 0,5 bis 1,5 ist; der Festkörperanteil 45 bis 85 Gew.-% und die Lösungsviskosität nach DIN 4 (23°C) 10 bis 40 sec beträgt.Another object of the invention is therefore a coating composition containing

• i. 50-90% by weight of the copolymer according to the invention,
• ii. 10-50% by weight of one or more monomeric, oligomeric or polymeric isocyanate compounds, and
• iii. one or more organic solvents, and optionally conventional auxiliaries and additives,

in which
if the proportions of i) and ii) are 100% by weight, the molar ratio of the hydroxyl groups of the copolymer to the reactive groups of the isocyanate compounds is 0.5 to 1.5; the solids content 45 to 85 wt .-% and the solution viscosity after DIN 4 (23 ° C) is 10 to 40 sec.

The solids content of the coating composition according to the invention is preferably from 50 to 80% by weight, more preferably from 55 to 75% by weight. The solution viscosity after DIN 4 (23 ° C) of the coating composition according to the invention is preferably 15 to 35 seconds, more preferably 20 to 30 seconds.

suitable Organic solvents are, for example, those already mentioned above in the preparation of the copolymers.

Catalysts, leveling agents, silicone oils, plasticizers, pigments such as iron oxides, lead oxides, lead silicates, titanium dioxide, barium sulfate, zinc sulfide, phthalocyanine complexes, etc., fillers such as talc, in particular, belong to the auxiliaries and admixtures customary in coating technology , Mica, kaolin, chalk, quartz, asbestos, slate, various silicas, silicates, etc., viscosity control additives, matting agents, high molecular weight, fusible organic compounds such as waxes, UV absorbers and light stabilizers such as low molecular weight organic compounds to protect the coating from the weather and UV Radiation, antioxidants and / or Peroxidzersetzer, defoamers and / or wetting agents, active diluents and the like.

The Coating agents can be prepared by known methods, for example by brushing, dipping, flooding or with the help of rollers or Doctoring, but especially by spraying, to the respective substrate be applied. You can also in the heat be applied. The curing of the invention Coating agent can already be carried out at room temperature or but to speed up the process at elevated temperatures for example 100-150 ° C. This affects also the use of a catalyst such as dibutyltin laurate advantageous.

The Coating compositions of the invention are for Coating, painting or sealing of substrates such as mineral-bound building material surfaces such as lime and / or Cement-bound plasters, gypsum-containing surfaces, fiber-cement building materials and concrete; Wood and wooden materials such as chipboard, wood fiber boards or medium density fiberboard; asphalt and bituminous road and asphalt Industrial flooring; Plastic, glass and metal surfaces suitable. The coating compositions of the invention For example, as automotive refinish paints, both in the intermediate layer as well as pigmented or non-pigmented (Clearcoat) topcoat can be used. You are also to the area Bonding of various materials / substrates suitable, with similar and / or different materials are interconnected can.

following the invention is explained in detail by examples, without the invention being limited thereto.

Production process of the invention coating agents

In a 2L four-necked round bottom flask, equipped with reflux condenser, saber stirrer, stirrer motor, dosing pump, Pt100 digital thermometer in oil bath, contact thermometer in the sump, (T = 140-150 ° C sump temperature) relay, oil bath with stirring motor for mixing, nitrogen bottle with supply line and Flow meter, the polymerization is carried out under nitrogen atmosphere (0.25 L / min). The solvent is initially charged, the monomer mixture is added within 4 h, then stirred for 30 min. The regulator used is 1.23% by weight of mercaptoethanol. The initiator used is 5.18% by weight of tert-butyl per-2-ethylhexanoate. It is then cooled to 80 ° C, addition of 0.07% initiator for after-reaction, stirring for 2 h at 80 ° C. Subsequently, additional solvent is added, it is cooled to room temperature and bottled. As the solvent, a mixture of 66.66 wt .-% Solvesso ^® 100 (Exxon Mobile) and 33.33 wt .-% used n-butyl acetate. The polymer content of the solution is 75% by weight. Table 1: Compositions of the polymers Polymer LACE monomer A1 - A2 - B ITMA C IDMA D C13 methacrylate E C17,4-methacrylate F SMA G C18-22 methacrylate TMCHMA 30% 10.0% 10.0% 10.0% 10.0% 10.0% 10.0% 10.0% EHMA - 10.0% 10.0% 10.0% 10.0% 10.0% 10.0% 10.0% Butyl acrylate (BA) 20% 27.0% 7.0% 7.0% 7.0% 7.0% 7.0% 7.0% HEA - 40.0% 40.0% 40.0% 40.0% 40.0% 40.0% 40.0% HEMA 20% - - - - - - - Methacrylic acid (MAS) 3% 3.0% 3.0% 3.0% 3.0% 3.0% 3.0% 3.0% LACE monomer - - 30.0% 30.0% 30.0% 30.0% 30.0% 30.0% MMA 27% 10.0%

Explanation of abbreviations:

• 2-hydroxyethyl methacrylate = HEMA
• Trimethylcyclohexylmethacrylate = TMCHMA
• Isotridecyl-MA = ITMA
• Isodecyl MA = IDMA
• Stearyl MA = SMA
• 2-ethylhexyl methacrylate = EHMA
• 2-hydroxyethyl acrylate = HEA
• Methyl methacrylate = MMA

The Determination of the OH number was carried out by acetylation with acetic acid in DMF / THF solution at room temperature with catalysis of 4- (dimethylamino) pyridine. The unreacted acetic anhydride was hydrolyzed with water to acetic acid and combined with the acetic acid formed during the acetylation, potentiometric back titrated with aqueous NaOH.

The Determination of the acid number was carried out by potentiometric Titration.

The Viscosity was in a solvent mixture Solvesso 100 and butyl acetate (ratio 2: 1) with a Brookfield viscometer at 23 ° C, 12 rpm with a spindle III measured.

The molecular weight determination of M _w and M _{n was} carried out by gel permeation chromatography (GPC) with an eluent based on N, N-dimethylacetamide, LiBr and acetic acid at a temperature of 35 ° C. against a PMMA standard.

• Erläuterungen: siehe Tabelle 1

Tabelle 3: Eigenschaften des Beschichtungsmittels Copolymer A2 B C D E F G LACE-Monomer - ITMA IDMA C13-Methacrylat C17,4-Methacrylat SMA C18-22-Methacrylat OH-Zahl Harz/ Isocyanat 1/1 1/1 1/1 1/1 1/1 1/1 1/1 Vernetzer 1 9 4 3 3 3 3 3 Vernetzer 2 1 6 7 7 7 7 7 Katalysator 0,002% 0,005% 0,005% 0,005% 0,005% 0,005% 0,005% Viskosität DIN 4 , 23 °C (sec) 19 20 22 21 21 22 19 Festkörpergehalt (Gew.-%) 54,4 57,8 58,0 58,3 58,0 59,4 56,3 Schichtdicke (μm) 26–33 24–31 26–31 23–27 37–48 30–39 26–34 Pankreatin-Test (°C) < 32 65 77 68 37 66 41 Eindruckhärte DIN 53156 111 118 118 118 111 105 111 Glanz (20°) DIN 6753 80,4 80,2 77,4 79,5 79,0 70,6 75,0 Δ Glanz nach Kratzen 24,0 34,2 31,7 37,2 37,7 38,7 39,2 Δ Glanz nach reflow 1 10,1 30,8 28,3 33,5 32,4 34,3 34,2 Δ Glanz nach reflow 2 1,7 23,6 23,1 25,7 23,1 24,9 22,1 The glass transition temperature was confirmed by DSC measurement ISO 11357 measured at three different heating rates (K / min). The evaluation of the measurement curves was done electronically according to the tangent method. The measured values obtained were extrapolated to the heating rate 0 K / min. Table 2: Copolymer Properties Polymer LACE monomer A1 - A2 - B ITMA C IDMA D C13 methacrylate E C17,4-methacrylate F SMA G C18-22 methacrylate Acid number [mgKOH / g] 14.7 16.2 16.2 16.3 16.6 16.0 16.7 16.7 OH number [mgKOH / g] 68.4 141 141 141 144 143 142 144 Viscosity (23 ° C) [mPas], 75% resins 25200 3240 2540 2740 2190 2440 2840 3140 Mn [g / mol] (GPC) 2870 2180 2110 2130 2300 2230 2330 2380 Mw [g / mol] (GPC) 6660 5560 5120 5420 5690 5670 6020 6260 Tg [° C], (DSC, measured with three heating rates (10 K / min, 20 K / min, 40 K / min)) 55 16 8th 4 4 -6 -7 -2

• Explanations: see Table 1

Table 3: Properties of the coating agent copolymer A2 B C D e F G LACE monomer - ITMA IDMA C13 methacrylate C17,4 methacrylate SMA C18-22 methacrylate OH number resin / isocyanate 1.1 1.1 1.1 1.1 1.1 1.1 1.1 Crosslinker 1 9 4 3 3 3 3 3 Crosslinker 2 1 6 7 7 7 7 7 catalyst 0.002% 0.005% 0.005% 0.005% 0.005% 0.005% 0.005% viscosity DIN 4 , 23 ° C (sec) 19 20 22 21 21 22 19 Solids content (wt.%) 54.4 57.8 58.0 58.3 58.0 59.4 56.3 Layer thickness (μm) 26-33 24-31 26-31 23-27 37-48 30-39 26-34 Pancreatin test (° C) <32 65 77 68 37 66 41 indentation hardness DIN 53156 111 118 118 118 111 105 111 Shine (20 °) DIN 6753 80.4 80.2 77.4 79.5 79.0 70.6 75.0 Δ shine after scratching 24.0 34.2 31.7 37.2 37.7 38.7 39.2 Δ gloss after reflow 1 10.1 30.8 28.3 33.5 32.4 34.3 34.2 Δ gloss after reflow 2 1.7 23.6 23.1 25.7 23.1 24.9 22.1

The Amount of the copolymer was such that the molar amount of contained therein hydroxyl groups of the molar amount of isocyanate groups in the crosslinker mixture was equivalent.

Crosslinker 1 is Vestanat ^® HT 2500 L, produced by Degussa AG, crosslinking agent 2 is Vestanat ^® T 1.890 E, also manufactured by Degussa AG.

The Crosslinkers were in different mass ratios used (see Table 3). The networking of the components was at 140 ° C and over 25 min. carried out.

The catalyst used is dibutyltin dilaurate (DBTL); Type: Tegokat ^® used 218, manufactured by Goldschmidt TIB GmbH.

The viscosity was with the DIN 4 Outflow cup determined at 23 ° C.

The shine was after DIN 6753 with a device of Byk Gardner, type: hazegloss.

The Layer thickness was measured with the device Mini Test 3001 of the company Measured electro physics.

Of the Pancreatin test was performed as follows: on coated steel sheets is the topcoat to be tested applied and cured according to the respective instructions, At a distance of about 2 cm, drops (about 1 cm) of a 50% Pancreatin slurry applied and then the sheet is in a gradient oven (Byk Gardner, type 2601) 60 min at 30 to 85 ° C tempered.

To Rinsing the test medium is an attack of Coating (first visible trace or destruction of the Paint film) assessed visually.

The impression hardness became after DIN 53156 determined.

Of the Scratch test is performed as follows: on the paint surface becomes one in a surfactant solution soaked and weighted screen mesh moved in a lift-shaped manner by means of a motor drive; it will 80 double strokes per 80 s performed.

to Determination of Reflow 1, the sheet is 2 h at 40 ° C in Conditioned drying oven, to determine the reflow 2 is the Sheet metal conditioned at 60 ° C for a further 2 h. The shine is measured before, after the scratch test and after reflow 1 and 2, as a result, the difference (delta) becomes the initial value specified.

The Results listed in Table 3 (Copolymer B-G) show clearly, even in comparison to the prior art (Copolymer A2) that the desired combination of beneficial Properties such as high solids content, good resistance in the pancreatin test and good reflow values by the invention Coating is achieved.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - DE 19524787 C [0003]
• - EP 0638591 A [0004]
• WO 96/20968 [0005]
• - US 4242243 A [0007]
• EP 0882750 A [0008]
• EP 0676431 A1 [0009]
• EP 0676423 A1 [0010]
• EP 0470461A [0042]

Cited non-patent literature

• - DIN 53211 [0004]
• - ISO 11357 [0017]
• - DIN EN ISO 306 [0017]
• - ISO 11357 [0035]
• - ISO 11357 [0036]
• - DIN 4 [0043]
• - DIN 4 [0044]
• - ISO 11357 [0055]
• - DIN 4 [0055]
• - DIN 53156 [0055]
• - DIN 6753 [0055]
• - DIN 4 [0060]
• - DIN 6753 [0061]
• - DIN 53156 [0065]

Claims (10)

Copolymers of a ₁ ) 20-40% by weight of at least one (meth) acrylic ester of the formula (1) CH 2 = C (R 1 ) -COO-C n H 2n + 1 (1) wherein R ¹ = H or CH ₃ and n is independently an integer from 10 to 55, wherein -C _n H _{2n + 1 may be} linear or branched, a ₂ ) 5-20 wt .-% of at least one (meth ) acrylic ester of the formula (2) CH 2 = C (R 1 ) -COO-R 2 (2) wherein R ¹ = H or CH ₃ and R ^{2 is} linear or branched C ₁ -C ₆ alkyl, which may optionally be substituted; a ₃ ) 30-50% by weight of at least one (meth) acrylic acid ester of the formula (3) CH 2 = C (R 1 ) -COO-R 3 (3) wherein R ¹ = H or CH ₃ and R ^{3 is} a hydroxy (C ₂ -C ₁₀ ) alkyl, a ₄ ) 2-10 wt .-% of (meth) acrylic acid, and a ₅ ) 0-15 wt. % of at least one (meth) acrylic acid ester of the formula (4) CH ₂ = C (R ¹ ) -COO-R ⁴ (4), wherein R ¹ = H or CH ₃ and R ^{4 is} a C ₄ -C ₁₂ cycloalkyl group which may optionally be substituted, wherein the sum of the components a ₁ ) to a ₅ ) is always 100 wt .-%. Copolymers according to Claim 1, characterized in that they have a hydroxyl number of 100 to 180 mg KOH / g, an acid number of 10 to 20 mg KOH / g, a number average molecular weight M _n of 1,000 to 10,000 g / mol and a Brookfield Viscosity of 500 to 5000 mPa · s (measured in 75% solution at 23 ° C) have. Copolymers according to Claim 1 or 2, characterized in that it has a glass transition temperature, determined according to DSC (ISO 11357) at heating rate 0 K / min, below of 40 ° C. Copolymers according to claims 1-3, characterized in that the average molecular weight (number average M _n ) is 1,000 to 6,000 g / mol. Copolymers according to the claims 1 to 4, characterized in that they contain 5-20% by weight of (meth) acrylic acid esters of the formulas (2), (3) and / or (4), which by a glass transition temperature their homopolymer of more than 90 ° C characterized are. Use of the copolymers according to claim 1-5 as a binder for paints. Coating composition containing i. 50-90 % By weight of the copolymer according to the claims 1 to 5, ii. 10-50% by weight of one or more monomeric, oligomeric or polymeric isocyanate compounds, and iii. one or more organic solvents, and optionally one or more pigments, fillers and / or conventional additives  in which  the molar ratio of Hydroxyl groups of the copolymer to the reactive groups of Isocycanatverbindungen 0.5 to 1.5; the solids content 45 wt .-% to 85 Wt .-% and  the solution viscosity according to DIN 4 (23 ° C) is 10 to 40 sec. Coating composition according to claim 7, characterized in that the solids content 50 Wt .-% to 80 wt .-% and the solution viscosity 15 to 35 sec. Coating composition according to claim 7 or 8, characterized in that the solids content 55 wt .-% to 75 wt .-% and the solution viscosity 20 to 30 sec. Use of the coating composition according to Claims 7 to 9 as clear or topcoat for coating of substrates.