[go: up one dir, main page]

WO2007014900A1 - Resines melamine-formaldehyde etherifiees mixtes - Google Patents

Resines melamine-formaldehyde etherifiees mixtes Download PDF

Info

Publication number
WO2007014900A1
WO2007014900A1 PCT/EP2006/064729 EP2006064729W WO2007014900A1 WO 2007014900 A1 WO2007014900 A1 WO 2007014900A1 EP 2006064729 W EP2006064729 W EP 2006064729W WO 2007014900 A1 WO2007014900 A1 WO 2007014900A1
Authority
WO
WIPO (PCT)
Prior art keywords
melamine
acid
formaldehyde
alkanol
etherified
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2006/064729
Other languages
German (de)
English (en)
Inventor
Rainer Erhardt
Andreas Eichfelder
Eva RÜBA
Günter Scherr
Martin Reif
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of WO2007014900A1 publication Critical patent/WO2007014900A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/40—Chemically modified polycondensates
    • C08G12/42—Chemically modified polycondensates by etherifying
    • C08G12/424—Chemically modified polycondensates by etherifying of polycondensates based on heterocyclic compounds
    • C08G12/425—Chemically modified polycondensates by etherifying of polycondensates based on heterocyclic compounds based on triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
    • C08G12/32—Melamines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09D161/32—Modified amine-aldehyde condensates

Definitions

  • the present invention relates to mixed etherified melamine-formaldehyde resins, processes for their preparation, their use and coating compositions containing such.
  • Pigmented paints and clearcoats of or based on melamine-formaldehyde resins have been known for several decades.
  • Unplasticized melamine-formaldehyde resins are used either alone or in combination with further chemically different crosslinkers, for example blocked polyisocyanates, trisalkylcarbamoyltriazines (TACT) or epoxides, as crosslinking component in binder mixtures. After curing of the paint components to obtain a coating which is resistant to chemical, mechanical and weather-related influences. Plasticized melamine-formaldehyde resins may have modifications with carbamate structures, blends with polyesters or alkyd resins or precondensations with these. Unplasticized melamine-formaldehyde resins, when used on non-rigid flexible coating substrates, require external elastication to prevent the coating from cracking; the crosslinker as the sole formulation component forms only brittle networks.
  • crosslinker as the sole formulation component forms only brittle networks.
  • Melamine-formaldehyde resins can be characterized according to fields of application (molding compounds, glues, impregnating resins, lacquers), alkylating agents (etherification with butanol, methanol, mixed etherification) or, as stated here, according to the ratio of triazine: formaldehyde: etherifying alcohol:
  • the free formaldehyde can be easily reduced due to the low viscosity of the amino resin.
  • the completely etherified melamine-formaldehyde resins are preferred in practice in coating of cans (can-coating) and metal strips (CoN).
  • the second large group of partially etherified melamine-formaldehyde resins which in practice usually have a built-in molar ratio of melamine: formaldehyde: alcohol of 1: 3 to 5.4: 2 to 4.3, are markedly increased compared to the first group thermal reactivity without acid catalysis.
  • a self-condensation takes place, which leads to a higher viscosity (lower high-solids behavior) and thus makes it more difficult to remove the free formaldehyde during the distillation.
  • a free formaldehyde content of 0.5 to 1.5% is standard, but there are also products containing 0.3 to 3% by weight of free formaldehyde.
  • methylated, butylated and mixed etherified types are widely used as commercial products.
  • the etherification with further alkylating agents is described in the literature or available as special products.
  • the high-imino types are distinguished from the methylol types by a high degree of alkylation, i. the proportion of etherified methylol groups on the incorporated formaldehyde equivalents, usually up to 80%, whereas the methylol types are generally ⁇ 70%.
  • a disadvantage of this process is that a molecular weight build-up takes place during the entire reaction time due to the presence of the acidic catalyst.
  • KR 2002043072 (CAS-RN 142: 156542) describes the preparation of methylated melamine-formaldehyde resins with the aid of paraformaldehyde and subsequent transetherification.
  • the disadvantage is that the paraformaldehyde is unfavorable to handle as a solid.
  • JP 52103493 (CAS-RN 88: 24317) describes the transetherification of a Hexamethylolme- laminhexamethylethers (HMMM) with butanol in the acid, then adjusting a basic pH and distillation of the excess butanol.
  • HMMM Hexamethylolme- laminhexamethylethers
  • a disadvantage of the process disclosed therein is that several times must be filtered and despite repeated addition of butanol only a small part of the methyl groups is exchanged pen.
  • the process disclosed therein operates at a low pH of about 2.0 to 2.2.
  • the reaction time extends for at least 220 minutes and several filtration steps, so that the reaction mixture is thermally stressed for a long time, which results in an increased molar mass structure, which causes an increase in viscosity.
  • DE-OS 1669593 describes the transetherification of substantially fully etherified hexamethylol melamines with other alcohols, of which of the six methyl groups at least two are replaced by other groups.
  • the object of the present invention was to provide a partially methylolated, completely etherified, mixed etherified melamine-formaldehyde resin which has a low viscosity at a high solids content, a low free formaldehyde content, and only low formaldehyde emission during crosslinking caused.
  • it should have improved storage stability, in particular a reduced viscosity increase during storage.
  • the object was achieved by using a lower alkanol R 1 OH and a higher alkanol R etherified 2 OH melamine-formaldehyde resins having a solids content of at least 90 wt%, a viscosity according to ISO 3219 / B of not more than 7 Pas at 23 0 C at a solids content of 90%, a content of free formaldehyde of not more than 0.2 wt% obtainable by
  • MeI-N 3 is a melamine radical resulting from mental abstraction of the six hydrogen atoms bound to the amino groups in melamine
  • FA is a group -Chfe-O-
  • R 1 is a Ci - C ⁇ -alkyl group
  • R 2 is a different from R 1 Ci - C 8 alkyl group
  • f E is a number from 3.4 to 5.5, preferably 3.5 to 5.2 and particularly preferably 3.9 to 4.9,
  • MeI-N 3 , FA and R 1 are as defined above,
  • the resulting mixed-etherified melamine-formaldehyde resins have a solids content of at least 85% by weight, preferably at least 90, more preferably at least 92 and most preferably at least 95.
  • the solids content is determined in accordance with ISO 3251 by heating 2 g of the sample material and 2 ml of n-butanol flat in a well-ventilated drying oven at 125 ° C. for a period of 2 hours. The sample is weighed before and after, and the ratio indicates the solids content.
  • the content of free formaldehyde is according to the invention not more than 0.2% by weight, preferably not more than 0.15% by weight and more preferably not more than 0.1% by weight.
  • the content of free formaldehyde is determined according to EN ISO 9020.
  • the melamine-formaldehyde resin used in the transetherification is a melamine-formaldehyde resin which is substantially exclusively etherified, preferably exclusively with alkyl groups R 1 , and carries no other alkyl groups. Impurities through the use of reclaimed or technical alcohol R 1 OH are tolerable.
  • the melamine-formaldehyde resin used further has the following formula:
  • MeI-N 3 , FA and R 1 have the above meaning.
  • fA can take any values from 3.6 to less than 6.0.
  • f A is at least 4.1, more preferably at least 4.2, and most preferably at least 5.0.
  • f A assumes values of preferably not more than 5.9, particularly preferably not more than 5.8, very particularly preferably not more than 5.6 and in particular not more than 5.4.
  • ITI A can not be larger than f A.
  • m A assumes values of at least 2.0, preferably at least 2.4, more preferably at least 2.9, and most preferably at least 3.4.
  • ⁇ IA is not greater than 4.6, preferably not greater than 4.4, more preferably not greater than 4.2, and most preferably not greater than 4.0.
  • MeI-ISb FAfA R 1 mA H ⁇ -tA is considered to be a general description and is calculated from the resin analyzes without consideration of any bridging formation due to condensation.
  • the incorporated formaldehyde is calculated as total formaldehyde (determined after acid digestion) minus the free formaldehyde (DIN 16746-A, SuIfit method) molar based on melamine. This is the number fA.
  • the incorporated alcohol is determined from difference of the total alcohol content according to gas chromatography after acid digestion and the content of free alcohol according to gas chromatography molar based on melamine.
  • GPC Gel-permeation chromatography
  • GPC-MS Gel-permeation chromatography
  • the resins may contain di- and trimers as well as higher oligomers up to a mass fraction of 90%.
  • melamine-formaldehyde resin used in a preferred embodiment of the present invention of the contained in the molecule introduced by formaldehyde methylol groups whose number is represented by fA, usually at least 50% etherified by groups R 1 , so that applies ⁇ IA> 0.5 x fA, preferably at least 55%, more preferably at least 60%, and most preferably at least 65%.
  • m A ⁇ 0.99 xf ⁇ is preferably not more than 95%, more preferably not more than 90 and most preferably not more than 87%.
  • the solids content may be, for example, at least 50%, preferably at least 60, more preferably at least 70, and most preferably at least 75% by weight.
  • the solids content will not exceed 97% and preferably does not exceed 95%.
  • the melamine-formaldehyde resin used may contain at least one solvent, for example water, for example, methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, sec-butanol or tert-butanol, or aromatic hydrocarbons, such as, for example, toluene or xylene isomer mixtures.
  • the content of free formaldehyde of the melamine-formaldehyde resin used is generally more than 0.3% by weight, for example it may be 0.5 or more, preferably 0.6 or more, more preferably 1, 0 or more and most especially preferably 1, 5 wt% or more.
  • R 1 is a C 1 -C 6 -alkyl group, preferably a C 1 -C 4 -alkyl group, particularly preferably a methyl or ethyl group and very particularly preferably a methyl group.
  • R 2 is a C 1 -C 8 -alkyl group, preferably a C 1 -C 4 -alkyl group, particularly preferably an n-butyl or isobutyl group, and very particularly preferably an n-butyl group.
  • C 1 -C 6 -alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 2-butyl, tert-butyl, 1-pentyl, 2-pentyl, iso-amyl, n-hexyl, n -octyl or 2-ethylhexyl.
  • C 1 -C 4 -alkyl is understood as meaning methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, 2-butyl or tert-butyl.
  • butanol is taken to mean n-butanol, isobutanol, sec-butanol and mixtures thereof, preferably n-butanol or isobutanol and more preferably n-butanol.
  • R 1 should contain at least one carbon atom less than R 2 , particularly preferably the boiling point of the alkanol R 2 OH under the selected reaction conditions at least 10, most preferably at least 20 0 C are above that of R 1 OH.
  • the process according to the invention comprises at least two steps which take place at different pH values:
  • step I the transetherification of the used, with residues R 1 -alkylated melamine-formaldehyde resin with the alkanol R 2 OH takes place.
  • the transetherification takes place at a pH of not more than 5.0, preferably not more than 4.0, particularly preferably between 2 and 4, very particularly preferably between 2.5 and 3.5 and in particular between 3.0 and 3.5.
  • the pH can be measured, for example, with a commercially available glass electrode with a diaphragm.
  • Suitable acidic catalysts are sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid, para-toluenesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, methanesulfonic acid or mixtures thereof, and acidic ion exchangers are also conceivable.
  • Preferred are mineral acids, particularly preferred are sulfuric acid, nitric acid and phosphoric acid.
  • the acid catalyst is generally added in amounts of 0.1 to 10% by weight, preferably 0.5 to 7.5, more preferably 1 to 6 and most preferably 3 to 5% by weight. It may be useful to enter the catalyst in several portions.
  • the molar stoichiometric ratio between the alkanol R 2 OH and melamine-formaldehyde resin used (based on melamine units in the melamine-formaldehyde resin) in the transetherification is generally from 1: 3 to 50, preferably 1: 5 to 40, particularly preferably 1: 6 to 30, very particularly preferably 1: 7 to 25 and in particular 1: 9 to 20.
  • alkanol R 2 OH does not play a significant role whether alkanol R 2 OH is initially charged and the melamine-formaldehyde resin is added or the melamine-formaldehyde resin is initially introduced in part of the alkanol R 2 OH and the remainder of the alkanol R 2 OH is continuously or in portions is added or presented the melamine-formaldehyde - resin and then the alkanol is added.
  • the temperature in the transetherification generally reaches as the lower temperature limit 25 ° C below the boiling point of the lower boiling alcohol under the reaction conditions, preferably 20, more preferably 15 and most preferably 10 0 C below the boiling point of the lower boiling alcohol up to an upper temperature limit , which is up to 20 0 C, preferably up to 15, more preferably up to 10 and most preferably up to 5 0 C above the boiling point of the higher-boiling alcohol.
  • the temperature ranges in Umethe- tion from 40 to 130 0 C, preferably from 50 to 125 0 C and more preferably from 60 to 120 0 C.
  • the reaction time during the transetherification is from 2 to 180 minutes, preferably from 5 to 120 minutes and particularly preferably from 10 to 90 minutes.
  • the transetherification is carried out under reaction conditions under which the alkanol R 1 OH displaced from the melamine-formaldehyde resin used is separated from the reaction mixture, for example by distillation.
  • the alkanol R 1 OH displaced from the melamine-formaldehyde resin used is separated from the reaction mixture, for example by distillation.
  • methanol as alkanol R 1 OH and n-butanol as alcohol R 2 OH this means at atmospheric pressure at a temperature above 65 and below 117 0 C.
  • the reaction may be carried out at atmospheric pressure, slightly superatmospheric or slightly reduced pressure, preferably at normal or slightly reduced pressure, and more preferably at normal pressure.
  • the pressure is preferably chosen so that the desired reaction temperature is adjusted depending on the solvent mixture used.
  • a distillation column having 1 to 20 theoretical plates can be placed on the reaction vessel, in which the return can be adapted to Trennerfodernissen.
  • the separation of the low-boiling components from the reaction mixture can be carried out by passing a gas stream which is essentially inert under the reaction conditions
  • Stripping e.g. an oxygen-depleted mixture of air and nitrogen (lean air) or preferably nitrogen or carbon dioxide are supported.
  • the removal of the alkanol R 1 OH is then preferably carried out continuously or stepwise in a manner known per se, for example by vacuum, azeotropic removal, absorption, pervaporation and diffusion over membranes.
  • Molecular sieves or zeolites are preferred for absorption, alternatively separation by distillation or by means of suitable semipermeable membranes.
  • step II the reaction mixture obtained from step I) is worked up by distillation.
  • the pH is adjusted to at least 6.0, preferably to 6.0 to 10.0, particularly preferably to 6.0 to 9.0 and most preferably to 6.0 to before the beginning of the distillation or at the beginning thereof 8.0 set.
  • This can in principle be carried out with any basic compounds, preferably with metal oxides or hydroxides, particularly preferably with alkali metal or alkaline earth metal oxides, hydroxides, carbonates or bicarbonates and very particularly preferably with alkali metal or alkaline earth metal hydroxides.
  • Examples are lithium, sodium, potassium, magnesium or calcium oxide or hydroxide, preference is given to lithium, sodium, potassium, magnesium or calcium hydroxide and particular preference to sodium, potassium or calcium hydroxide.
  • the distillation of the reaction mixture thus obtained is carried out at a temperature of 60 to 120 0 C and a pressure of 1 hPa to atmospheric pressure over a period of up to 5 hours.
  • the distillation is usually carried out until the desired formaldehyde content and the desired alcohol content is achieved.
  • a simple distillation is sufficient, but it can also be carried out a rectification, which can be carried out for example via a column up to 20 theoretical plates.
  • the distillation or rectification can for example be carried out directly from the reaction vessel or by passing the reaction mixture over a continuously operated distillation apparatus, such as a falling film or thin film evaporator.
  • a continuously operated distillation apparatus such as a falling film or thin film evaporator.
  • reaction mixture can first be passed through a falling film evaporator and the distillation bottoms are then passed into a thin-film evaporator.
  • the separation of the low boilers from the reaction mixture may be accomplished by passing a stream of gas substantially inert under the distillation conditions (stripping), e.g. an oxygen depleted mixture of air and nitrogen (lean air) or preferably nitrogen or carbon dioxide are supported ..
  • a stream of gas substantially inert under the distillation conditions e.g. an oxygen depleted mixture of air and nitrogen (lean air) or preferably nitrogen or carbon dioxide are supported .
  • the separated in the distillation mixture of the liberated alkanol R 1 OH with the excess of the alkanol R 2 OH can then be recycled, for example, by leading to the production of mixed etherified melamine-formaldehyde resins and there used for etherification.
  • the melamine-formaldehyde resin obtained by the process according to the invention has the following formula:
  • MeI-N 3 , FA, R 1 and R 2 have the meanings described above.
  • f E is a number from 3.4 to 5.5, preferably 3.5 to 5.2 and particularly preferably 3.9 to 4.9,
  • IOE: b ⁇ 1: 8 to 1: 1, especially 1: 7 to 1: 2.5 and especially 1: 6.5 to 1: 3.5.
  • the resulting mixed-etherified melamine-formaldehyde resin has, as a preparation with 90% by weight of melamine-formaldehyde resin in n-butanol, a viscosity at 23 ° C. according to ISO 3219 / B of not more than 7 Pas, preferably not more than 5 Pas.
  • the shear rate should preferably be 20 S -1 .
  • MeI-N 3 FAfE R 1 mE R 2 b E H ⁇ -f ⁇ is considered to be a general description analogous to the formula MeI-N 3 FA fA R 1 mA H 6 -fA described above.
  • the number average molecular weight M n of the resulting mixed-etherified melamine-formaldehyde resins is generally less than 1500 g / mol, preferably less than 1000 g / mol and more preferably less than 850 (determined by gel permeation chromatography with tetrahydrofuran and polystyrene as standard, DIN 55672, part 1).
  • the acid number of the melamine-formaldehyde resins obtained is less than 3, more preferably less than 1 mg KOH / g, determined according to ISO 3682.
  • the color number of the resulting melamine-formaldehyde resins is less than 100, more preferably less than 50, determined according to DIN EN 1557.
  • the content of free alkanol R 1 OH after distillation is generally less than 1% by weight, preferably less than 0.75% by weight, more preferably less than 0.5% by weight and most preferably less than 0.4% by weight.
  • the content of free alkanol R 2 OH can after distillation generally be less than 7% by weight, preferably less than 5% by weight, more preferably less than 3% by weight and most preferably less than 2% by weight.
  • the mixed-etherified melamine-formaldehyde resin obtained according to the invention can then be mixed with common solvents.
  • solvents examples include aromatic and / or (cyclo) aliphatic hydrocarbons and mixtures thereof, halogenated hydrocarbons, esters, ethers and alcohols.
  • aromatic hydrocarbons (cyclo) aliphatic hydrocarbons, alkanoic acid alkyl esters, alkoxylated alkanoic acid alkyl esters and mixtures thereof.
  • Particularly preferred are mono- or polyalkylated benzenes and naphthalenes, Alkanklarealkylester and alkoxylated Alkanklarealkylester and mixtures thereof.
  • aromatic hydrocarbon mixtures preferred are those which comprise predominantly aromatic C 7 - may comprise up Ci4-hydrocarbons and comprise a boiling range from 110 to 300 0 C, particularly preferably toluene, o-, m- or p-xylose lol, trimethylbenzene isomers, tetramethylbenzene , Ethylbenzene, cumene, tetrahydronaphthalene and mixtures containing such.
  • Solvesso® brands of ExxonMobil Chemical especially Solvesso® 100 (CAS No. 64742-95-6, predominantly C 9 and Cio-aromatics, boiling range about 154-178 0 C), 150 (boiling range about 182 - 207 0 C) and 200 (CAS No. 64742-94-5), as well as the Shellsol® brands of Shell.
  • Hydrocarbon mixtures of paraffins, cycloparaffins and aromatics are also available under the designations crystal oil (for example, crystal oil 30, boiling range about 158-198 0 C or Crystal oil 60: CAS No. 64742-82-1.), White spirit (for example likewise CAS No. 64742-.
  • the aromatic content of such hydrocarbon mixtures is generally more than 90% by weight, preferably more than 95, more preferably more than 98, and very preferably more than 99% by weight. It may be useful to use hydrocarbon mixtures with a particularly reduced content of naphthalene.
  • the density at 20 0 C in accordance with DIN 51757 of the hydrocarbons may comprise less than 1 g / cm 3, preferably less than 0.95 and particularly preferably less than 0.9 g / cm 3.
  • the content of aliphatic hydrocarbons is generally less than 5, preferably less than 2.5 and more preferably less than 1% by weight.
  • Halogenated hydrocarbons are, for example, chlorobenzene and dichlorobenzene or isomeric mixtures thereof.
  • esters are n-butyl acetate, ethyl acetate, 1-methoxypropyl acetate-2 and 2-methoxyethyl acetate, and the mono- and diacetyl esters of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol or tripropylene glycol, for example butyl glycol acetate.
  • Further examples are also carbonates, such as preferably 1, 2-ethylene carbonate, 1, 2-propylene carbonate or 1, 3-propylene carbonate.
  • Ethers are, for example, tetrahydrofuran (THF), dioxane and the dimethyl, ethyl or n-butyl ethers of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol or tripropylene glycol.
  • THF tetrahydrofuran
  • dioxane dioxane
  • dimethyl, ethyl or n-butyl ethers of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol or tripropylene glycol.
  • Examples of (cyclo) aliphatic hydrocarbons include decalin, alkylated decalin and isomer mixtures of straight-chain or branched alkanes and / or cycloalkanes.
  • Such mixtures can be prepared in a volume ratio of 10: 1 to 1:10, preferably in a volume ratio of 5: 1 to 1: 5 and more preferably in a volume ratio of 1: 1, where appropriate still in the reaction mixture of the transetherification solvent, in particular the alcohols R 1 OH and R 2 OH are not included ..
  • Preferred examples are butyl acetate / xylene, methoxypropyl acetate / xylene 1: 1, butyl acetate / solvent naphtha 100 1: 1, butyl acetate / Solvesso® 100 1: 2 and crystal oil 30 / Shellsol® A 3: 1.
  • Alcohols are, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, pentanol isomer mixtures, hexanol isomer mixtures, 2-ethylhexanol or octanol. Also suitable is water.
  • the content of the resulting melamine-formaldehyde resins in the solvents after mixing can generally be up to 98% by weight, based on the sum of methylamine-formaldehyde resin and solvent, preferably up to 95% by weight, particularly preferably up to 90% by weight, most preferably up to 86% by weight and in particular up to 80% by weight.
  • the melamine-formaldehyde resins according to the invention give comparable properties to completely etherified melamine-formaldehyde resins.
  • weak acids are understood as meaning monovalent or polyvalent, organic or inorganic, preferably organic acids having a pKa of between 1.6 and 5.2, preferably between 1.6 and 3.8.
  • Examples thereof are carbonic acid, phosphoric acid, formic acid, acetic acid and maleic acid, glyoxylic acid, bromoacetic acid, chloroacetic acid, thioglycolic acid, glycine, cyanoacetic acid, acrylic acid, malonic acid, hydroxypropanedioic acid, propionic acid, isoic acid, 3-hydroxypropionic acid, glycerylic acid, alanine, sarcosine, fumaric acid, acetoacetic acid , Succinic acid, isobutyric acid, pentanoic acid, ascorbic acid, citric acid, nitrilotriacetic acid, cyclopentanecarboxylic acid, 3-methylglutaric acid, adipic acid, hexanoic acid, benzoic acid, cyclohexanecarboxylic acid, heptanedioic acid, heptanoic acid, phthalic acid, isophthalic acid,
  • organic acids preferably mono- or polybasic carboxylic acids. Particularly preferred are maleic acid, acetic acid, maleic acid or fumaric acid.
  • strong acids are understood as meaning monovalent or polyvalent, organic or inorganic, preferably organic acids having a pKa of less than 1.6, and more preferably less than 1.
  • Examples are sulfuric acid, pyrophosphoric acid, sulfuric acid and
  • Tetrafluoroboric acid Tetrafluoroboric acid, trichloroacetic acid, dichloroacetic acid, oxalic acid, nitroacetic acid.
  • organic acids preferably organic sulfonic acids. Particularly preferred are methanesulfonic acid, para-toluenesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, cyclododecanesulfonic acid and camphorsulfonic acid.
  • the acids are generally used in amounts of up to 10% by weight, preferably 0.1 to 8, particularly preferably 0.3 to 6, very particularly preferably 0.5 to 5 and in particular from 1 to 3% by weight, based on the melamine used.
  • Formaldehyde resin is used.
  • acids can be used as free acids or blocked.
  • the curing is generally carried out so that after application of the coating of the substrates with the melamine-formaldehyde resins coating compositions or coating formulations according to the invention, optionally mixed with other typical coatings additives and thermally curable resins, optionally at a temperature below 80 0 C, preferably room temperature to 60 0 C and particularly preferably room temperature to 40 0 C over a period up to 72 hours, preferably up to 48 hours, more preferably up to 24 hours, most preferably up to 12 and in particular up to 6 hours dries, and under an oxygen-containing atmosphere, preferably air, or under inert gas at temperatures between 80 and 270, preferably between 100 and 240 and particularly preferably between 120 and 180 0 C thermally treated (cures).
  • a temperature below 80 0 C preferably room temperature to 60 0 C and particularly preferably room temperature to 40 0 C over a period up to 72 hours, preferably up to 48 hours, more preferably up to 24 hours, most preferably up to 12 and in particular up to 6 hours
  • Lacquer curing takes place in dependence on the amount of brushing agent applied and the enmeshed crosslinking energy via high-energy radiation, heat transfer from heated surfaces or via convection of gaseous media over a period of seconds, eg during strip lamination in combination with NIR drying, up to to 5 hours, eg. Thick layer systems on temperature-sensitive materials, usually not less than 10 minutes, preferably not less than 15, more preferably not less than 30 and most preferably not less than 45 minutes. Drying removes substantially any solvent present and, in addition, a reaction with the binder may already take place, whereas the curing essentially involves the reaction with the binder.
  • the curing can also be carried out in addition to or instead of the thermal curing by IR and NIR radiation, wherein as NIR radiation here electromagnetic radiation in the Wavelength range from 760 nm to 2.5 microns, preferably from 900 to 1500 nm is designated.
  • NIR radiation electromagnetic radiation in the Wavelength range from 760 nm to 2.5 microns, preferably from 900 to 1500 nm is designated.
  • Curing takes place in a period of 1 second to 60 minutes, preferably from 1 minute to 45 minutes.
  • Another object of the present invention are coating compositions containing at least one mixed etherified melamine-formaldehyde resin according to the invention.
  • such coating compositions contain at least one binder which contains reactive groups with respect to melamine-formaldehyde resins. These are usually epoxy group- and / or hydroxyl-containing binders and carboxy- and amino-containing resins.
  • the hydroxyl-containing binder is preferably polyetherol, polyesterols, polyacrylate polyols, polycarbonate polyols, alkyd resins or epoxy resins.
  • the binders have on average per molecule at least two, preferably two to ten, particularly preferably three to ten and very particularly preferably three to eight hydroxy groups per molecule.
  • the OH number measured in accordance with DIN 53240-2, is generally from 10 to 200 mg KOH / g, preferably from 30 to 140.
  • the binders may have an acid number according to DIN EN ISO 3682 of 0 to 200 mg KOH / g, preferably 0 to 100 and particularly preferably 0 to 10 mg KOH / g.
  • the polyacrylate polyols are, for example, those copolymers of (meth) acrylic acid esters with at least one compound having at least one, preferably exactly one hydroxyl group and at least one, preferably exactly one (meth) acrylate group.
  • the latter can be, for example, monoesters of ⁇ , ⁇ -unsaturated carboxylic acids, such as acrylic acid, methacrylic acid (referred to in this document as "(meth) acrylic acid”), with diols or polyols which preferably have 2 to 20 C atoms and at least two hydroxyl groups , such as ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 1-dimethyl-1, 2-ethanediol, dipropylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, tripropylene glycol, 1, 4- butanediol,
  • the hydroxy group-carrying monomers are in the copolymerization in admixture with other polymerizable, preferably free-radically polymerizable monomers, preferably those containing more than 50 wt .-% of Ci-C 2 o-alkyl (meth) acrylate, vinyl aromatics with up to 20 C -Atoms, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinyl halides, non-aromatic hydrocarbons having 4 to 8 carbon atoms and 1 or 2 double bonds, unsaturated nitriles and mixtures thereof.
  • Particularly preferred are the polymers which are more than
  • Ci-Cio-alkyl (meth) acrylates 60 wt .-% of Ci-Cio-alkyl (meth) acrylates, styrene or mixtures thereof.
  • the polymers may contain hydroxy-functional monomers corresponding to the above hydroxy group content and optionally further monomers, e.g. ethylenically unsaturated acids, in particular carboxylic acids, acid anhydrides or acid amides.
  • binders are polyesterols, as obtainable by condensation of polycarboxylic acids, in particular dicarboxylic acids with polyols, in particular diols.
  • Polyester polyols are e.g. from Ullmann's Encyclopedia of Industrial Chemistry, 4th Edition, Volume 19, pp. 62-65. Preference is given to using polyesterpolyols which are obtained by reacting dihydric alcohols with dibasic carboxylic acids. Instead of the free polycarboxylic acids, it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof to prepare the polyesterpolyols.
  • the polycarboxylic acids may be aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic, and optionally, e.g. by halogen atoms, substituted and / or unsaturated. Examples include:
  • C 1 -C 4 -alkyl esters preferably methyl, ethyl or n-butyl esters, of the acids mentioned are used.
  • dicarboxylic acids of the general formula HOOC- (CH 2) y -COOH, where y is a number from 1 to 20, preferably an even number from 2 to 20, particularly preferably succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid.
  • Suitable polyhydric alcohols for preparing the polyesterols are 1, 2-propanediol, ethylene glycol, 2,2-dimethyl-1,2-ethanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1, 4-butanediol, 3-methylpentane-1, 5-diol, 2-ethylhexane-1, 3-diol, 2,4-diethyloctane-1, 3-diol, 1, 6-hexanediol, poly-THF with one molecular weight between 162 and 2000, poly-1,3-propanediol having a molecular weight between 134 and 1178, poly-1,2-propanediol having a molecular weight between 134 and 898, polyethylene glycol having a molecular weight between 106 and 458, neopentyl glycol, hydroxypivalic acid neopent
  • Alcohols of the general formula HO- (CH 2) X -OH are preferred, where x is a number from 1 to 20, preferably an even number from 2 to 20.
  • Preferred are ethylene glycol, butane-1, 4-diol, hexane-1, 6-diol, octane-1, 8-diol and dodecane-1, 12-diol. Further preferred is neopentyl glycol.
  • polycarbonate diols e.g. by reaction of phosgene with an excess of the mentioned as synthesis components for the polyester polyols low molecular weight alcohols, into consideration.
  • lactone-based polyesterdiols which are homopolymers or copolymers of lactones, preferably terminal hydroxyl-containing addition products of lactones onto suitable difunctional starter molecules.
  • Suitable lactones are preferably those which are derived from compounds of the general formula HO- (CH 2) z -COOH, where z is a number from 1 to 20 and an H atom of a methylene unit by a C 1 to C 4 alkyl radical may be substituted.
  • Examples are ⁇ -caprolactone, ⁇ -propiolactone, gamma-butyrolactone and / or methyl- ⁇ -caprolactone, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthalenic acid or pivalolactone and mixtures thereof.
  • Suitable starter components are, for example, the low molecular weight dihydric alcohols mentioned above as the synthesis component for the polyesterpolyols.
  • the corresponding polymers of ⁇ -caprolactone are particularly preferred.
  • Lower polyester diols or polyether diols can also be used as starters for the preparation of the lactone polymers.
  • polyetherols which are prepared by addition of ethylene oxide, propylene oxide or butylene oxide to H-active components.
  • polycondensates of butanediol are suitable.
  • the polymers may of course also be compounds with primary secondary amino groups.
  • polycarbonate polyols e.g. by reaction of phosgene with an excess of the mentioned as synthesis components for the polyester polyols low molecular weight alcohols, into consideration.
  • Alkyd resins are polycondensation resins of polyols, polybasic carboxylic acids and fatty oils or free natural and / or synthetic fatty acids; at least one polyol must be tri- or higher-functional.
  • polyols and polybasic carboxylic acids for example, the components may be used, which are mentioned above in the polyesterols.
  • Preferred polyhydric alcohols are glycerol, pentaerythritol, trimethylolethane, trimethylolpropane, various diols, such as ethane / propanediol, diethylene glycol, neopentyl glycol.
  • Preferred polybasic carboxylic acids are phthalic acid (anhydride) (PSA), isophthalic acid, terephthalic acid, trimellitic anhydride, adipic acid, azelaic acid, sebacic acid.
  • the oil component or fatty acid are, for example, drying oils, such as linseed oil, oiticica oil or wood oil, semi-drying oils, such as soybean oil, sunflower oil, safflower oil, ricinoleic oil or tall oil, non-drying oils, such as castor oil, coconut oil or peanut oil, or free fatty acids of the above oils or synthetic monocarboxylic acids into consideration.
  • drying oils such as linseed oil, oiticica oil or wood oil
  • semi-drying oils such as soybean oil, sunflower oil, safflower oil, ricinoleic oil or tall oil
  • non-drying oils such as castor oil, coconut oil or peanut oil
  • free fatty acids of the above oils or synthetic monocarboxylic acids into consideration such as castor oil, coconut oil or peanut oil.
  • the molecular weight of typical alkyd resins is between 1500 and 20,000, preferably between 3500 and 6000.
  • the acid number is preferably 2 to 30 mg KOH / g, with water-dilutable resins also 35-65 mg KOH / g.
  • the OH number is usually up to 300, preferably up to 100 mg KOH / g.
  • Such polyacrylate polyols, polyesterols and / or polyetherols preferably have a molecular weight M n of at least 1000, more preferably at least 2000 and most preferably at least 5000 g / mol.
  • the molecular weight M n may be, for example, up to 200,000, preferably up to 100,000, particularly preferably up to 80,000 and very particularly preferably up to 50,000 g / mol.
  • the melamine-formaldehyde resins according to the invention can also be used together with non-crosslinkable binders, i. such without against melamine-formaldehyde resins reactive groups used.
  • the melamine-formaldehyde resins of the present invention do not function as crosslinkers but, e.g. as a plasticizer.
  • antioxidants for example, antioxidants, stabilizers, activators (accelerators), fillers, pigments, dyes, antistatic agents, flame retardants, thickeners, thixotropic agents, surface-active agents, viscosity modifiers, plasticizers or chelating agents can be used.
  • chelating agents e.g. Ethylenediamine and their salts and ß-diketones are used.
  • Suitable fillers include silicates, e.g. Example by hydrolysis of silicon tetrachloride available silicates such as Aerosil ® the Fa. Degussa, silica, talc, aluminum silicates, magnesium silicates, calcium carbonates, etc.
  • silicates e.g. Example by hydrolysis of silicon tetrachloride available silicates such as Aerosil ® the Fa. Degussa, silica, talc, aluminum silicates, magnesium silicates, calcium carbonates, etc.
  • Suitable stabilizers include typical UV absorbers such as oxanilides, triazines and benzotriazole (the latter available as Tinuvin ® grades from Ciba-Spezialitatenchemie) and benzophenones. These may be used alone or together with suitable radical scavengers, for example sterically hindered amines such as 2,2,6,6-tetramethylpiperidine, 2,6-di-tert-butylpiperidine or derivatives thereof, eg. B. bis (2,2,6,6-tetra-methyl-4-piperi- dyl) sebacinat be used. Stabilizers are usually used in amounts of 0.1 to 5.0 wt .-%, based on the solid components contained in the preparation.
  • suitable radical scavengers for example sterically hindered amines such as 2,2,6,6-tetramethylpiperidine, 2,6-di-tert-butylpiperidine or derivatives thereof, eg.
  • Pigments may also be included. Pigments are according to CD Römpp Chemie Lexikon - Version 1.0, Stuttgart / New York: Georg Thieme Verlag 1995 with reference to DIN 55943 particulate "in the application medium practically insoluble, inorganic see or organic, colorful or achromatic colorants ".
  • practically insoluble means a solubility at 25 ° C. of less than 1 g / 1000 g of application medium, preferably less than 0.5, particularly preferably less than 0.25, very particularly preferably less than 0.1 and in particular less than 0.05 g / 1000 g application medium.
  • pigments include any systems of absorption and / or effect pigments, preferably absorption pigments. Number and selection of the pigment components are not subject to any restrictions. They can be adapted to the particular requirements, for example the desired color impression, as desired.
  • Effect pigments are to be understood as meaning all pigments which have a platelet-like structure and impart special decorative color effects to a surface coating.
  • the effect pigments are, for example, all effect pigments which can usually be used in vehicle and industrial coating.
  • Examples of such effect pigments are pure metal pigments; such as. Aluminum, iron or copper pigments;
  • Interference pigments such as e.g. titanium dioxide coated mica, iron oxide coated mica, mixed oxide coated mica (e.g., with titanium dioxide and Fe2O3 or titanium dioxide and O2O3), metal oxide coated aluminum, or liquid crystal pigments.
  • the coloring absorption pigments are, for example, customary organic or inorganic absorption pigments which can be used in the coatings industry.
  • organic absorption pigments are azo pigments, phthalocyanine, quinacridone and pyrrolopyrrole pigments.
  • inorganic absorption pigments are iron oxide pigments, titanium dioxide and carbon black.
  • compositions according to the invention are thus composed as follows:
  • Resin optionally at least either a strong or a weak acid, at least one binder, - optionally at least one paint typical additive, optionally at least one solvent and optionally at least one pigment.
  • the coating of the substrates with the coating compositions according to the invention is carried out by customary methods known to the person skilled in the art, at least one coating composition or coating formulation according to the invention being applied to the substrate to be coated in the desired thickness and the volatile constituents parts of the coating composition, optionally with heating, removed (drying). If desired, this process can be repeated one or more times.
  • the application to the substrate can in a known manner, for. B. by spraying, filling, doctoring, brushing, rolling, rolling or pouring done.
  • the coating thickness is generally in a range of about 3 to 1000 g / m 2 and preferably 10 to 200 g / m 2 .
  • Suitable substrates for the coating compositions according to the invention are, for example, thermoplastic polymers, in particular polymethyl methacrylates, polybutyl methacrylates, polyethylene terephthalates, polybutylene terephthalates, polyvinylidene fluorides, polyvinyl chlorides, polyesters, polyolefins, acrylonitrile-ethylene-propylene-tolylene copolymers (A-EPDM), polyetherimides, polyether ketones, polyphenylene sulfides, polyphenylene ethers or mixtures thereof.
  • thermoplastic polymers in particular polymethyl methacrylates, polybutyl methacrylates, polyethylene terephthalates, polybutylene terephthalates, polyvinylidene fluorides, polyvinyl chlorides, polyesters, polyolefins, acrylonitrile-ethylene-propylene-tolylene copolymers (A-EPDM), polyetherimides, polyether ketones, polyphenylene sul
  • polyethylene polypropylene, polystyrene, polybutadiene, polyesters, polyamides, polyethers, polycarbonate, polyvinyl acetal, polyacrylonitrile, polyacetal, polyvinyl alcohol, polyvinyl acetate, phenolic resins, urea resins, melamine resins, alkyd resins, epoxy resins or polyurethanes, their block or graft copolymers and blends from that.
  • ABS ABS, AES, AMMA, ASA, EP, EPS, EVA, EVAL, HDPE, LDPE, MABS, MBS, MF, PA, PA6, PA66, PAN, PB, PBT, PBTP, PC, PE, PEC, PEEK , PEI, PEK, PEP, PES, PET, PETP, PF, PI, PIB, PMMA, POM, PP, PPS, PS, PSU,
  • Particularly preferred substrates are polyolefins, e.g. PP (polypropylene), which may optionally be isotactic, syndiotactic or atactic and optionally non-oriented or oriented by uni- or bis-axial stretching, SAN (styrene-acrylonitrile copolymers), PC (polycarbonates), PVC (polyvinyl chlorides), PMMA (Polymethylmethacrylate), PBT (poly (butylene terephthalate) s), PA (polyamides), ASA (acrylonitrile-styrene-acrylic ester copolymers) and ABS (acrylonitrile-butadiene-styrene copolymers), and their physical blends (blends).
  • PP polypropylene
  • SAN polypropylene
  • PC polycarbonates
  • PVC polyvinyl chlorides
  • PMMA Polymethylmethacrylate
  • PBT poly (butylene terephthalate) s
  • Blends of ABS or ASA with PA or PBT or PC Very particular preference is given to polyolefins, PMMA and PVC.
  • ASA in particular according to DE 196 51 350 and the blend ASA / PC.
  • PMMA polymethyl methacrylate
  • a further preferred substrate for coating with the coating compositions of the invention are metals which may optionally be pretreated with a primer.
  • the type of metal can in principle be any metals. In particular, however, are such metals or alloys, which are commonly used as metallic construction materials, and must be protected from corrosion.
  • they are surfaces of iron, steel, Zn, Zn alloys, Al or Al alloys. These may be the surfaces of bodies made entirely of said metals or alloys. However, the bodies can also be coated only with these metals and themselves consist of different materials, for example of other metals, alloys, polymers or composite materials. It may be surfaces of castings, galvanized iron or steel. In a preferred embodiment of the present invention are steel surfaces.
  • Zn or Al alloys are known to the person skilled in the art. Depending on the desired application, the skilled person will select the type and amount of alloying components. Typical components of zinc alloys include in particular Al, Pb, Si, Mg, Sn, Cu or Cd. Typical constituents of aluminum alloys include, in particular, Mg, Mn, Si, Zn, Cr, Zr, Cu or Ti. These may also be Al / Zn alloys in which Al and Zn are present in approximately the same amount , Steel coated with such alloys is commercially available. The steel may contain the usual alloying components known to those skilled in the art.
  • the coating compositions and coating formulations according to the invention are furthermore suitable for coating substrates such as wood, paper, textile, leather, fleece, plastic surfaces, glass, ceramics, mineral building materials, such as cement molding stones and fiber cement boards, or metals or coated metals, preferably plastics or metals, especially in the form of films, more preferably metals.
  • substrates such as wood, paper, textile, leather, fleece, plastic surfaces, glass, ceramics, mineral building materials, such as cement molding stones and fiber cement boards, or metals or coated metals, preferably plastics or metals, especially in the form of films, more preferably metals.
  • the melamine-formaldehyde resins, coating compositions or paint formulations according to the invention are suitable as or in exterior coatings, ie those applications which are exposed to daylight, preferably building components, interior coatings, coatings on vehicles and aircraft.
  • the melamine-formaldehyde resins and coating compositions according to the invention as or used in automotive clearcoats and topcoats (s). Further preferred fields of use are can-coating and coil-coating.
  • primers are particularly suitable as primers, fillers, pigmented topcoats and clearcoats in the field of industrial, wood, automotive, in particular OEM paintwork, or decorative lacquering.
  • coating compositions for applications in which a particularly high application safety, outdoor weathering resistance, appearance, solvent and / or chemical resistance are required.
  • a particular advantage of the coating compositions according to the invention with a mixture-etherified melamine-formaldehyde resin according to the invention is the reduced formaldehyde emission from the coating composition during firing compared with commercially available melamine-formaldehyde resins of comparable reactivity.
  • the starting material used was a melamine-formaldehyde resin which had been etherified with methanol, having a composition MeI-ISb where Me is methyl.
  • Vacuum distillation was carried out to 120 0 C and 90 mbar. The product was filtered.
  • the reaction product had a viscosity of 5700 mPas (23 0 C).
  • the content of free formaldehyde was 0.06% by weight, of free methanol less than 0.1% by weight and of free butanol about 0.8% by weight.
  • the nonvolatile content after two hours of heating at 125 0 C was 97.2%.
  • the starting material used was a melamine-formaldehyde resin which had been etherified with methanol, having a composition MeI-ISb where Me is methyl.
  • the pH was adjusted to 7 with sodium hydroxide solution and a vacuum distillation was carried out to 120 0 C and 90 mbar.
  • the product was filtered.
  • the reaction product had a viscosity of 7000 mPas (23 0 C).
  • the content of free formaldehyde was 0.05% by weight, of free methanol less than 0.1% by weight and of free butanol about 5% by weight.
  • the nonvolatile content after heating at 125 ° C. for 2 hours was 90.2%.
  • the ratio of crosslinker to binder was 30:70 (based on solid parts by weight).
  • the solvent used was a mixture of xylene to methoxypropanol in the ratio 70:30.
  • the formaldehyde emission is calculated on the solids content of the mixture.
  • Luwipal® 072 from BASF AG is a partially methyl-etherified melamine-formaldehyde resin with a nonvolatile content (according to ISO 3251) of 73-77% by weight in isobutanol.
  • the viscosity (ISO 3219 B) is 4.0 - 7.0 Pas at 23 0 C and a shear rate D of 20.6 s- 1 .
  • Luwipal® 018 from BASF AG is a partially butyl-etherified melamine-formaldehyde resin with a non-volatile content (according to ISO 3251) of 71-75% by weight in n-butanol.
  • the viscosity (ISO 3219 B) is 4.0 - 7.0 Pas at 23 0 C and a shear rate D of 21, 0 s- 1 .
  • Luwipal® 052 from BASF AG is a mixed methyl / butyl partially etherified melamine-formaldehyde resin with a non-volatile content (according to ISO 3251) of 69-72% by weight in n-butanol.
  • the viscosity (ISO 3219 B) is 4.0 - 6.0 Pas at 23 0 C and a shear rate of 20.6 D 1 s.
  • Luwipal® 066LF from BASF AG is a highly to completely methyl-etherified melamine-formaldehyde resin with a non-volatile content (according to ISO 3251) of 93-96% by weight with a low content of free formaldehyde of not more than 0.3% by weight.
  • the viscosity (ISO 3219 B) is 2.0 - 6.0 Pas at 23 0 C and a shear rate D of 41, 3 S 1 .
  • the viscosity of the resin according to Example 1 after storage at 40 0 C in 8 months increased by only 10% based on the initial viscosity. Comparable reactive resins showed a viscosity doubling over the same period.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Abstract

L'invention concerne des résines mélamine-formaldéhyde éthérifiées mixtes, leur procédé de fabrication et leur utilisation, ainsi que des produits de revêtement contenant de telles résines.
PCT/EP2006/064729 2005-08-01 2006-07-27 Resines melamine-formaldehyde etherifiees mixtes Ceased WO2007014900A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005036584.1 2005-08-01
DE200510036584 DE102005036584A1 (de) 2005-08-01 2005-08-01 Gemischtveretherte Melamin-Formaldehyd-Harze

Publications (1)

Publication Number Publication Date
WO2007014900A1 true WO2007014900A1 (fr) 2007-02-08

Family

ID=36939218

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2006/064729 Ceased WO2007014900A1 (fr) 2005-08-01 2006-07-27 Resines melamine-formaldehyde etherifiees mixtes

Country Status (2)

Country Link
DE (1) DE102005036584A1 (fr)
WO (1) WO2007014900A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9039927B2 (en) 2005-12-09 2015-05-26 Basf Se Etherified melamine/formaldehyde condensates having a high solid content and low viscosity
CN109680537A (zh) * 2018-12-12 2019-04-26 济宁明升新材料有限公司 一种新型层间结合胶和制备方法及其在造纸层间喷淋中的应用
CN112500547A (zh) * 2020-12-25 2021-03-16 南京长江涂料有限公司 一种水性高性能丁醚化改性hmmm树脂及其制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2973510T3 (es) 2015-12-16 2024-06-20 Prefere Melamines Gmbh Proceso de fabricación de soluciones de resinas amino-formaldehídicas alquiladas con un bajo contenido de formaldehído libre

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2709693A (en) * 1950-12-04 1955-05-31 Ciba Ltd Etherified condensation products of formaldehyde with amino-1:3:5-triazines containing at least two aminogroups
GB888473A (en) * 1957-05-03 1962-01-31 Rheinpreussen Ag Air-drying aminoplast-alkyd coating composition
GB1195087A (en) * 1966-10-06 1970-06-17 Reichhold Albert Chemie Ag Method for the Production of Salts of Amino Triazine Carboxylic Acids Soluble in Water
DE2221367A1 (de) * 1972-05-02 1973-12-13 Cassella Farbwerke Mainkur Ag Verfahren zur herstellung von mischaethern methylolierter aminotriazine
EP0653468A2 (fr) * 1993-11-12 1995-05-17 Herberts Gesellschaft mit beschränkter Haftung Revêtement pour les couches de couverture transparentes et utilisation dans des procédés de préparation des revêtements multicouches

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2709693A (en) * 1950-12-04 1955-05-31 Ciba Ltd Etherified condensation products of formaldehyde with amino-1:3:5-triazines containing at least two aminogroups
GB888473A (en) * 1957-05-03 1962-01-31 Rheinpreussen Ag Air-drying aminoplast-alkyd coating composition
GB1195087A (en) * 1966-10-06 1970-06-17 Reichhold Albert Chemie Ag Method for the Production of Salts of Amino Triazine Carboxylic Acids Soluble in Water
DE2221367A1 (de) * 1972-05-02 1973-12-13 Cassella Farbwerke Mainkur Ag Verfahren zur herstellung von mischaethern methylolierter aminotriazine
EP0653468A2 (fr) * 1993-11-12 1995-05-17 Herberts Gesellschaft mit beschränkter Haftung Revêtement pour les couches de couverture transparentes et utilisation dans des procédés de préparation des revêtements multicouches

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; NOWAK, DOMINIK ET AL: "Ethers of polymethylolmelamine", XP002398056, retrieved from STN Database accession no. 1976:422253 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9039927B2 (en) 2005-12-09 2015-05-26 Basf Se Etherified melamine/formaldehyde condensates having a high solid content and low viscosity
CN109680537A (zh) * 2018-12-12 2019-04-26 济宁明升新材料有限公司 一种新型层间结合胶和制备方法及其在造纸层间喷淋中的应用
CN109680537B (zh) * 2018-12-12 2021-06-15 济宁明升新材料有限公司 一种新型层间结合胶和制备方法及其在造纸层间喷淋中的应用
CN112500547A (zh) * 2020-12-25 2021-03-16 南京长江涂料有限公司 一种水性高性能丁醚化改性hmmm树脂及其制备方法

Also Published As

Publication number Publication date
DE102005036584A1 (de) 2007-02-15

Similar Documents

Publication Publication Date Title
EP3201280B1 (fr) Composition de revêtement aminoplaste en un composant
EP1756197B2 (fr) Polyesters hautement fonctionnels, hautement ramifies ou hyper ramifies, leur production et leur utilisation
DE2317874C3 (de) Schichtstoff auf der Grundlage von Polycarbonat mit beschichteter Oberfläche
EP2350154B1 (fr) Résines mélamine-formaldéhyde (méth)acrylées
EP2046906A2 (fr) Laques à base aqueuse renfermant des polycarbonates hautement ou hyper-ramifiés hautement fonctionnels
EP2853551A1 (fr) Additif liquide améliorant l'adhérence et son procédé de fabrication
EP2536773B1 (fr) Résines aminoplastes silylées
EP2379656A1 (fr) Compositions de revêtement à séchage rapide
EP2225338A1 (fr) Matières de revêtement aux propriétés améliorées
WO2007014900A1 (fr) Resines melamine-formaldehyde etherifiees mixtes
WO2011042377A1 (fr) Résines mélamine-formaldéhyde silylées
EP2675830A1 (fr) Résines aminoplaste silylées
DE2505246C2 (de) Nichtwäßrige Einbrennlacke enthaltend epsilon-Caprolactam als Reaktivverdünner
DE1900414B2 (de) Ueberzugsmittel
WO2014090647A2 (fr) Résines aminiques (méth)acrylées
DE1805196C3 (de) Überzugsmittel
KR102101224B1 (ko) 신규 바이오기반 폴리에스테르
DE102009046713A1 (de) Strahlungshärtbare Beschichtungsmassen
WO2008022922A1 (fr) Nouvel agent de revêtement
DE1644766C3 (de) Überzugsmittel
DE1644761A1 (de) Verfahren zur Herstellung von schlagfesten,elastischen und harten UEberzuegen
DE102006006130A1 (de) Polyole auf der Basis von modifizierten Aminoplastharzen, Verfahren zu ihrer Herstellung und Ihre Verwendung
DE102007058979A1 (de) Neue Beschichtungsmittel
DE1805197B2 (de) Ueberzugsmittel
DE1805189B (de) Überzugsmittel

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 06764260

Country of ref document: EP

Kind code of ref document: A1