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EP2675830A1 - Résines aminoplaste silylées - Google Patents

Résines aminoplaste silylées

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Publication number
EP2675830A1
EP2675830A1 EP12747530.9A EP12747530A EP2675830A1 EP 2675830 A1 EP2675830 A1 EP 2675830A1 EP 12747530 A EP12747530 A EP 12747530A EP 2675830 A1 EP2675830 A1 EP 2675830A1
Authority
EP
European Patent Office
Prior art keywords
radical
radicals
formula
alkyl
independently
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.)
Withdrawn
Application number
EP12747530.9A
Other languages
German (de)
English (en)
Inventor
Christina Haaf
Markus Hickl
Rüdiger STARK
Horst HINTZE-BRÜNING
Bernd Bruchmann
Dirk Schmelter
Thomas Gloege
Christine RÖSCH
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
Priority claimed from PCT/EP2011/052094 external-priority patent/WO2011101301A1/fr
Application filed by BASF SE filed Critical BASF SE
Priority to EP12747530.9A priority Critical patent/EP2675830A1/fr
Publication of EP2675830A1 publication Critical patent/EP2675830A1/fr
Withdrawn legal-status Critical Current

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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
    • 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
    • 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
    • C08G12/421—Chemically modified polycondensates by etherifying of polycondensates based on acyclic or carbocyclic compounds
    • C08G12/422—Chemically modified polycondensates by etherifying of polycondensates based on acyclic or carbocyclic compounds based on urea or thiourea
    • 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
    • C08G12/40—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
    • C08G12/427—Melamine
    • 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 silylated aminoplast resins, processes for their preparation, their use and coating compositions containing them.
  • Pigmented paints and clearcoats of or based on aminoplast 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. Plastified 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 crosslinkers as the sole formulation component form only brittle networks.
  • crosslinkers as the sole formulation component form 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 commercial products contain mostly methanol as alcohol, but mixed etherified or fully butylated types are also known.
  • the completely etherified melamine-formaldehyde resins are used in practice preferably in coatings of cans (can-coating) and metal strips (coil coatings) worldwide and in NAFTA also for all layers of automotive painting.
  • 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 content of free formaldehyde of 0.5 to 1, 5% standard, but there are also products with a content of free formaldehyde from 0.3 to 3% by weight.
  • 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.
  • Methylolation i. Formaldehyde Einbaumol symposium of less than 1: 5.5
  • the high-imino types differ from the methylol types in that they have a high degree of alkylation, ie. the proportion of etherified methylol groups on the incorporated formaldehyde equivalents, usually up to 80%, whereas the methylol types generally have ⁇ 70%.
  • Fields of application for the partially methylolated melamine-formaldehyde resins extend over all areas of application, also in combination with HMMM types for reactivity adjustment, where Curing temperatures of 100 to 150 ° C are required. Additional catalysis using weak acids is possible and common practice.
  • EP 1784466 describes coating compositions of melamine-formaldehyde resins with hydroxy-functional silanes.
  • a disadvantage of these compounds is that these functionalized silanes in the reaction with the melamine-formaldehyde resin produce an additional functionality, for example a hydroxy or urea group, which in turn reacts with the melamine-formaldehyde resin (hydroxy group) or the Solubility of the product reduced (urea group).
  • Alkoxysilane-modified melamine-formaldehyde resins have already been described in WO 201 1/042377.
  • a disadvantage of these compounds is the aminic nitrogen, which binds acids used to accelerate the curing and thus reduces their catalytic activity.
  • the modified amino resins thus obtained exhibit good properties in coatings, but these can be further improved.
  • Another group of aminoplast resins which are very similar in structure and properties to the melamine-formaldehyde resins, are the benzoguanamine resins (benzoguanamine / formaldehyde resins). Free OH groups can also be at least partially substituted by lower Al groups.
  • urea resins examples include urea resins, ie polycondensation products of urea and formaldehyde (short name UF, according to DIN EN ISO 1043-1: 2002-6).
  • Free OH groups may also be at least partially etherified with lower alcohols, especially C 1 -C 4 -alcohols, particularly preferably methanol or n-butanol.
  • the object of the present invention was to provide novel aminoplast resin modifications which have an additional curing mechanism via tethered silyl groups and give coatings with improved properties.
  • radicals R 9 to R 11 are each independently an alkyl radical or
  • R 14 to R 18 may independently represent alkyl, aryl and cycloalkyl, and q is a positive integer of at least 1, and compounds (Cb) of the formula
  • radical of the formula (IIIa) a radical of the formula (IIIb) in which at least one of the radicals R 9 to R 11 or R 14 to R 18 is a radical OR 12 , where R 12 is an alkyl or aryl radical, and the other radicals are each independently an alkyl radical and
  • q is a positive integer of at least 1, wherein the molar ratio of (Ca): (Cb) is from 5.5: 0.5 to 0.5: 5.5.
  • amino resins obtained according to the invention do not contain the abovementioned interfering amine structures.
  • the aminoplast resins (A) may preferably be melamine-formaldehyde resins, benzoguanamine / formaldehyde resins and urea / formaldehyde resins, each of which may optionally be at least partially etherified and are preferably at least partially etherified. Particularly preferred are at least partially etherified melamine-formaldehyde resins or benzoguanamine / formaldehyde resins, very particularly preferably at least partially etherified melamine-formaldehyde resins.
  • Melamine-formaldehyde resins which can be used according to the invention as amino resins (A) are, for example, constructed as follows:
  • melamine-formaldehyde resins are frequently characterized by the incorporation ratio melamine: formaldehyde: alcohol.
  • the alcohol is preferably selected from the group consisting of methanol, ethanol, isobutanol and n-butanol or mixtures thereof, preferably selected from the group consisting of methanol and n-butanol.
  • Melamine-formaldehyde resins which can be used according to the invention can have a built-in oil ratio of 1: 2 to 6: 1 to 6, and in some cases a formaldehyde incorporation ratio of up to 8 can be conceivable by formation of oligoformalcohols.
  • the melamine-formaldehyde resins that can be used can not only have one melamine group per polycondensate, but quite possibly more, preferably up to six, more preferably up to four, very preferably up to three and in particular up to two.
  • Benzoguanamine / formaldehyde resins which can be used according to the invention as amino resins are, for example, constructed as follows:
  • Benzoguanamine-formaldehyde resins are also frequently characterized by the incorporation ratio of benzoguanamine: formaldehyde: alcohol.
  • the alcohol is preferably selected from the group consisting of methanol, ethanol, isobutanol and n-butanol or mixtures thereof, preferably selected from the group consisting of methanol and n-butanol.
  • Benzoguanamine-formaldehyde resins which can be used according to the invention can have a built-in molar ratio of 1: 1.5 to 4: 1 to 4, and in some cases a formaldehyde incorporation ratio of up to 6 can also be conceivable by formation of oligoformalcohols.
  • Einbauteoldung of 1: 2 to 4: 1, 5 to 4 are preferred.
  • built-in sol ratios of 1: 2.2 to 3.7: 2.1 to 3.0 are particularly preferred, very particularly preferred incorporation ratios of from 1: 3 to 4: 1, 5 to 4, in particular 1 : 3 to 4: 2.0 to 3.0.
  • n-butyl etherified benzoguanamine-formaldehyde resins Einbaumolixie of 1: 2.2 to 3.7: 1, 3 to 2 are particularly preferred, very particularly preferred Einbaumolixie of 1: 3 to 4: 1, 5 to 4, in particular 1 : 3 to 4: 1, 5 to 2.5.
  • the useable benzoguanamine-formaldehyde resins can not only have one benzoguanamine group per polycondensate but quite possibly more, preferably up to five, particularly preferably up to four, very particularly preferably up to three and in particular up to two.
  • Urea / formaldehyde resins which can be used according to the invention as amino resins are, for example, constructed as follows:
  • Urea-formaldehyde resins which can be used according to the invention can have a built-in molar ratio of urea / formaldehyde / alcohol of 1: 1 to 4: 0.3: 3, preferably 1: 1 to 3: 0.4 to 2, particularly preferably 1: 1, 5 to 2.5: 0.5 to 1, 5, most preferably from 1: 1, 6 to 2.1: 0.6 to 1, 3 have.
  • the alcohol is preferably selected from the group consisting of methanol, ethanol, isobutanol and n-butanol or mixtures thereof, preferably selected from the group consisting of methanol and n-butanol.
  • the urea / formaldehyde resins also include so-called glycoluril resins formed by reacting glycoluril, the reaction product of glyoxal with two equivalents of urea, with formaldehyde, optionally etherified with one or more alcohols. It is a preferred embodiment of the present invention that the aminoplast resins, especially the melamine-formaldehyde resins, are etherified with at least one alkyl group substituted with at least one fluorine atom.
  • the alkyl radical which is substituted by at least one fluorine atom may be C 1 -C 20 -alkyl radicals, particularly preferably C 1 -C 12 -alkyl radicals, very particularly preferably C 1 -C 5 -alkyl radicals and in particular C 1 -C 4 -alkyl radicals which contain at least one, preferably at least two and more preferably at least three fluorine atoms carry.
  • perfluoroalkyl radicals in which all hydrogen atoms have been replaced by fluorine atoms or to those alkyl radicals in which all hydrogen atoms have been replaced by fluorine atoms, except for the hydrogen atoms which are directly at the binding site, usually the two hydrogen atoms in position 1 ,
  • alkyl radicals substituted by at least one fluorine atom include trifluoromethyl, 2,2,2-trifluoroethyl, 2,2-difluoroethyl, pentafluoroethyl, 2,2,3,3,3-pentafluoropropyl, perfluoropropyl, 1,1,1,3,3 , 3-hexafluoroprop-2-yl, 2,2,3,3,4,4,4-heptafluorobutyl, 1,1,2,2,3,3,4,4,4-nonafluorobutyl, 2,2,3 , 3,4,4,5,5-octafluoropentyl, 1, 1, 2,2,3,3,4,4,5,5,6,6,6-perfluorohexyl and
  • the alcohols with which the amino resins can be reacted are then correspondingly the alcohols corresponding to these alkyl radicals.
  • up to 100% of the incorporated alcohols can be alcohols which carry at least one fluorine atom, preferably up to 75%, particularly preferably up to 50% and very particularly preferably up to 33%.
  • Another object of the present invention are silylated melamine-formaldehyde resins of the formula (I)
  • radicals R 1 to R 6 are each independently of one another a) a hydrogen atom (-H) as radical, b) - [- CH 2 -O-] m -H, in which m is a positive integer of at least 1, c) - [- CH 2 -O-] n -R 7 , where n is a positive integer of at least 1 and
  • R 7 is an alkyl radical or optionally an alkyl radical substituted by at least one fluorine atom, d) a radical of the formula (II) wherein p is a positive integer of at least 1, R 9 to R 11 may independently represent an alkyl radical or
  • R 12 is an alkyl or aryl radical, a radical of the formula (IIIa)
  • R 14 to R 18 can independently of one another be alkyl, aryl, alkyloxy, aryloxy, cycloalkyl and cycloalkyloxy, and q is a positive integer of at least 1, e) a radical of the formula (IV)
  • r can be zero or a positive integer of at least 1 and the radicals R 1 'to R 5 ' can each independently be selected from the groups a) to d),
  • radicals R 1 to R 6 and the radicals R 1 'to R 5 ', if they are present, is a radical of the formula (II) and not more than two radicals R 1 to R 6 each represent a radical of formula (IV), wherein the ratio of
  • silylated melamine-formaldehyde resins of the invention exhibit a higher gloss and / or improved scratch resistance as a coating than the unmodified melamine-formaldehyde resins.
  • the mixed residue melamine-formaldehyde resins of formula (II) according to the present invention are capable of forming a gradient (also called stratification) within a coating which can simultaneously improve the hardness and elasticity of the coating.
  • hardness and elasticity are opposite properties, i. as the hardness of a coating increases, its elasticity often decreases and vice versa.
  • the hardness is required on the outside of a coating, for example, to improve the scratch resistance, whereas the elasticity of a coating within the coating to improve e.g. the stone chip resistance is required. This has hitherto been achieved by applying at least two different coating compositions which exhibit the respective desired properties, in separate coating and drying or curing steps.
  • the melamine-formaldehyde resins having mixed radicals of the formula (II) according to the invention can furthermore show improved intermediate adhesion of the coatings to the substrate.
  • the variables in the above formula (I) have the following meaning:
  • R 7 is alkyl, preferably C 1 - to C 4 -alkyl, more preferably methyl, ethyl, / is-butyl or n-butyl, very particularly preferably methyl or n-butyl and especially methyl.
  • alkyl is understood to mean straight-chain or branched alkyl groups having one to 20 carbon atoms, preferably C 1 -C 8 -alkyl groups, ie, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, tyl, iso-butyl, 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.
  • R 7 may also be an alkyl radical substituted by at least one fluorine atom, which may be C 1 -C 20 -alkyl radicals, particularly preferably C 1 -C 12 -alkyl radicals, very particularly preferably C 1 -C -alkyl radicals and in particular C 1 -C 4 -alkyl radicals which carry at least one, preferably at least two and more preferably at least three fluorine atoms.
  • perfluoroalkyl radicals in which all hydrogen atoms have been replaced by fluorine atoms or to those alkyl radicals in which all hydrogen atoms have been replaced by fluorine atoms, except for the hydrogen atoms which are directly at the binding site, usually the two hydrogen atoms in position 1 ,
  • alkyl radicals substituted by at least one fluorine atom are trifluoromethyl
  • up to 100% of the incorporated alcohols may be alcohols which carry at least one fluorine atom, preferably up to 75%, more preferably up to 50% and most preferably preferably up to 33%.
  • R 9 to R 11 are each independently alkyl, a radical of the formula -OR 12 , or of the formula (IIIa) or (IIIb), preferably a radical of the formula -OR 12 , particularly preferably with R 12 alkyl, very particularly preferably methyl or Ethyl and especially ethyl.
  • the radicals R 1 'to R 5 ' can each independently be selected from the groups a) to d). It goes without saying that the radicals R 1 'to R 5 ' are present in the silylated melamine-formaldehyde resins according to the invention only if at least one of the radicals R 1 to R 6 is a radical of the formula (IV).
  • m is a positive integer from 1 to 4, preferably from 1 to 3, more preferably from 1 to 2, and most preferably 1.
  • n is a positive integer from 1 to 4, preferably from 1 to 3, particularly preferably from 1 to 2 and very particularly preferably 1.
  • p is zero or a positive integer from 1 to 4, preferably from 0 to 3, particularly preferably from 0 to 2, very particularly preferably 0 or 1 and in particular 1.
  • q is a positive integer from 1 to 4, preferably from 1 to 3, more preferably from 1 to 2, and most preferably 1.
  • r is zero or a positive integer from 1 to 4, preferably from 0 to 3, particularly preferably from 0 to 2, very particularly preferably zero or 1 and in particular 1.
  • no more than one of the radicals R 1 to R 6 is a Radical of the formula (IV), more preferably only one or none.
  • Another object of the present invention are silylated Benzogua
  • radicals R 3 to R 6 are each independently of one another a) a hydrogen atom (-H) as radical, b) - [- CH 2 -O-] m -H, in which m is a positive integer of at least 1, c) - [- CH 2 -O-] n -R 7 , where n is a positive integer of at least 1 and
  • R 7 is an alkyl radical or optionally an alkyl radical substituted by at least one fluorine atom, d) a radical of the formula (II)
  • p is a positive integer of at least 1,
  • R 9 to R 11 may be independently
  • R 12 is an alkyl or aryl radical
  • R 14 to R 18 can independently of one another be alkyl, aryl, alkyloxy, aryloxy, cycloalkyl and cycloalkyloxy, and q is a positive integer of at least 1, e) a radical of the formula (IVa)
  • r can be zero or a positive integer of at least 1,
  • the radicals R 3 'to R 5 ' can each independently be selected from the groups a) to d), with the proviso that at least one of the radicals R 3 to R 6 and the radicals R 3 'to R 5 ', if they are present, is a radical of the formula (II) and not more than two radicals R 3 to R 6 because they represent a radical of the formula (IVa),
  • the silylated benzoguanamine-formaldehyde resins according to the invention exhibit a higher gloss and / or improved scratch resistance compared with the unmodified benzoguanamine-formaldehyde resins.
  • silylated benzoguanamine-formaldehyde resins according to the invention having mixed radicals of the formula (II) can also exhibit the same advantages described above as the mixed-chain melamine-formaldehyde resins of the formula (II) according to the invention.
  • R 7 is alkyl, preferably C 1 - to C 4 -alkyl, more preferably methyl, ethyl, / is-butyl or n-butyl, most preferably methyl or n-butyl and especially methyl.
  • alkyl is understood to mean straight-chain or branched alkyl groups having one to 20 carbon atoms, preferably C 1 -C 8 -alkyl groups, ie, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, tyl, iso-butyl, 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.
  • R 7 may also be an alkyl radical substituted by at least one fluorine atom, which may be C 1 -C 20 -alkyl radicals, particularly preferably C 1 -C 12 -alkyl radicals, very particularly preferably C 1 -C -alkyl radicals and in particular C 1 -C 4 -alkyl radicals which carry at least one, preferably at least two and more preferably at least three fluorine atoms.
  • fluorine atom may be C 1 -C 20 -alkyl radicals, particularly preferably C 1 -C 12 -alkyl radicals, very particularly preferably C 1 -C -alkyl radicals and in particular C 1 -C 4 -alkyl radicals which carry at least one, preferably at least two and more preferably at least three fluorine atoms.
  • perfluoroalkyl radicals in which all hydrogen atoms have been replaced by fluorine atoms or to those alkyl radicals in which all hydrogen atoms have been replaced by fluorine atoms, except for the hydrogen atoms which are directly at the binding site, usually the two hydrogen atoms in position 1 ,
  • alkyl radicals substituted by at least one fluorine atom include trifluoromethyl, 2,2,2-trifluoroethyl, 2,2-difluoroethyl, pentafluoroethyl, 2,2,3,3,3-pentafluoropropyl, perfluoropropyl, 1,1,1,3,3 , 3-hexafluoroprop-2-yl, 2,2,3,3,4,4,4-heptafluorobutyl, 1,1,2,2,3,3,4,4,4-nonafluorobutyl, 2,2,3,3,4, 4,5,5-octafluoropentyl, 1, 1, 2,2,3,3,4,4,5,5,6,6,6-perfluorohexyl and
  • radicals R 7 may be alkyl radicals substituted with at least one fluorine atom, preferably up to 75%, particularly preferably up to 50% and very particularly preferably up to 33%.
  • R 9 to R 11 are each independently alkyl, a radical of the formula -OR 12 , or of the formula (IIIa) or (IIIb), preferably a radical of the formula -OR 12 , particularly preferably with R 12 alkyl, very particularly preferably methyl or Ethyl and especially ethyl.
  • the radicals R 3 'to R 5 ' can each independently be selected from the groups a) to d). It goes without saying that the radicals R 3 'to R 5 ' are present in the silylated benzoguanamine-formaldehyde resins according to the invention only if at least one of the radicals R 3 to R 6 is a radical of the formula (IVa).
  • m is a positive integer from 1 to 4, preferably from 1 to 3, more preferably from 1 to 2, and most preferably 1.
  • n is a positive integer from 1 to 4, preferably from 1 to 3, particularly preferably from 1 to 2 and very particularly preferably 1.
  • p is zero or a positive integer from 1 to 4, preferably from 0 to 3, particularly preferably from 0 to 2, very particularly preferably zero or 1 and in particular 1.
  • q is a positive integer from 1 to 4, preferably from 1 to 3, more preferably from 1 to 2, and most preferably 1.
  • r is zero or a positive integer from 1 to 4, preferably from 0 to 3, particularly preferably from 0 to 2, very particularly preferably 0 or 1 and in particular 1.
  • no more than one of the radicals R 3 to R 6 represents a radical of the formula (IVa), more preferably only one or none.
  • the silylated aminoplast resins according to the invention are obtainable, for example, by two-step reaction of the corresponding aminoplasts, for example the melamine-formaldehyde resins corresponding to the compounds of the formula (I), ie melamine-formaldehyde resins of the formula (I) in which the radical Formula (II) is replaced by a group - [- CH 2 -O-] pH.
  • this compound is reacted with an unsaturated monoalcohol (B), preferably allyl alcohol, at the double bond in the next step by transition metal, preferably platinum catalyzed hydrosilylation a mixture of at least the compounds (Ca) and (Cb) of the formula (V ) is added.
  • B unsaturated monoalcohol
  • transition metal preferably platinum catalyzed hydrosilylation a mixture of at least the compounds (Ca) and (Cb) of the formula (V ) is added.
  • R 9 -R 11 have the meaning given above.
  • at least one alcohol, which carries at least one fluorine atom are reacted.
  • This platinum-catalyzed hydrosilylation is often carried out in the following manner:
  • the reaction product of the aminoplast resin (A) used with the unsaturated monoalko (B) is at ambient temperature in a reaction vessel equipped with an inert gas cover maintenance device, preferably nitrogen or argon added under inert gas cover with the silicon hydride (V), dissolved in an anhydrous inert solvent, added with stirring is a catalyst, such as a transition metal, preferably a noble metal of subgroup VI II, more preferably nickel, nickel salts, iridium salts and most preferably chloroplatinic acid or the so-called Karstedt catalyst, is then added.
  • the temperature is increased under inert gas cover to about 60 ° C.
  • the aminoplast resin used may contain at least one solvent, for example water, C 1 -C 4 -alkyl alcohols, such as, for example, methanol, ethanol, / so-propanol, n-propanol, n-butanol, / so-butanol, sec / butanol or ferric buta -nol, or aromatic hydrocarbons, such as toluene or xylene-iso-merengemische.
  • solvent for example water, C 1 -C 4 -alkyl alcohols, such as, for example, methanol, ethanol, / so-propanol, n-propanol, n-butanol, / so-butanol, sec / butanol or ferric buta -nol, or aromatic hydrocarbons, such as toluene or xylene-iso-merengemische.
  • the content of free formaldehyde of the aminoplast resin used is generally not more than 1, 5 wt%, for example, it may not more than 1, 0, preferably not more than 0.5, more preferably not more than 0.3 and most especially preferably not more than 0, 1 wt% amount.
  • Such sp 3 -hybridized carbon atoms may be, for example, alkyl groups, unsubstituted methylene groups, monosubstituted (1,1-alkylene groups) or disubstituted alkylene groups
  • the aromatic ring system is a carbocyclic ring system, heteroaromatic systems are excluded according to the invention.
  • At least one sp 3 -hybridised carbon atom preferably one to ten, particularly preferably one to five, very particularly preferably one to three, in particular one to two and especially one.
  • Examples of such compounds (B) are allyl alcohol (2-propene-1-ol), methallyl alcohol (2-methyl-2-propene-1-ol), homoallyl alcohol (3-butene-1-ol), 1-butene-3 -ol, 3-methyl-2-buten-1-ol, 2-methyl-3-buten-2-ol, 1-octen-3-ol, 2-hexen-1-ol, 1-penten-3-ol as well as phytol, farnesol and linalool.
  • Allyl alcohol, methallyl alcohol and homoallyl alcohol are preferred, and allyl alcohol is particularly preferred.
  • the stoichiometry of unsaturated alcohol (B) to the ether groups in the aminoplast resin to be replaced is usually from 0.2: 1 to 1: 0.2.
  • the compound (C) are those of the formula (V):
  • compounds (C) are made between compounds (Ca), in which are R 9 to R 11 are alkyl and in the radicals R 14 to R 18 are the radicals are alkyl, aryl and cycloalkyl, and compounds (Cb) carrying at least one group -OR 12 .
  • radicals R 9 to R 11 are each independently
  • R 14 to R 18 can independently of one another be alkyl, aryl and cycloalkyl, preferably alkyl or aryl and particularly preferably alkyl, and q is a positive integer of at least 1.
  • R 9 to R 11 are each independently of one another
  • radical of the formula (IIIb) in which at least one, preferably at least two and more preferably at least three of the radicals R 9 to R 11 and R 14 to R 18 is a radical OR 12 , where R 12 is an alkyl or aryl radical, and the other radicals independently of one another are each an alkyl radical or, in the case of R 14 to R 18, additionally a cycloalkyl or aryl radical and
  • q is a positive integer of at least 1.
  • Preferred alkyl radicals are C 1 -C 20 -alkyl radicals, particularly preferably C 1 -C 12 -alkyl radicals, very particularly preferably C 1 -C 5 -alkyl radicals and in particular C 1 -C 4 -alkyl radicals.
  • alkyl radicals are methyl, ethyl, iso-propyl, n-propyl, n-butyl, iso-butyl, sec-butyl, fer-butyl, n-hexyl, n-heptyl, n-octyl, n-decyl , n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl, 2-ethylhexyl and 2-propylheptyl.
  • aryl radicals are phenyl, p-tolyl, ⁇ -naphthyl and ⁇ -naphthyl, preferred is phenyl.
  • R 9 to R 11 are independently selected from the group consisting of methyl, ethyl, iso-propyl, n-butyl, tert-butyl, most preferably from the group consisting of methyl, ethyl and n-butyl.
  • Preferred radicals R 12 are methoxy, ethoxy, isopropoxy, n-butyloxy, tert-butyloxy and phenoxy, more preferably methoxy, ethoxy, n-butyloxy, tert-butyloxy and phenoxy, most preferably methoxy, ethoxy and phenoxy and especially ethoxy , Preferred radicals R 14 to R 18 , unless they are OR 12, are independently selected from the group consisting of methyl, ethyl, isopropyl, n-butyl, tert-butyl, very particularly preferably from the group consisting of methyl, Ethyl and n-butyl.
  • the silanes (Ca) used are very particularly preferably trimethylsilane, triethylsilane, tert. Butyl dimethylsilane, tri-iso-propylsilane, Bistrimethylsilyloxymethylsilan, Bistriethylsilyloxymethylsilan or mixtures thereof.
  • the silanes (Cb) used are preferably tris (alkyloxy) silanes or alkylbis (alkyloxy) silanes, particularly preferably tris (C 1 -C 4 -alkyloxy) silanes or C 1 -C 4 -alkyl bis (C 1 -C 4 -alkyloxy ) silanes.
  • the silanes (Cb) used are very particularly preferably diethoxymethylsilane, dimethoxymethylsilane, methoxydimethylsilane, ethoxydimethylsilane,
  • the silanes (C) are used as a mixture of compounds (Ca): (Cb) in a ratio of 5.5: 0.5 to 0.5: 5.5, preferably 5: 1 to 1: 5 and more preferably from 4: 2 to 2: 4 and most preferably from 3: 3 to 2: 4 used.
  • the stoichiometry of silane (C) of the formula (V) to give double bonds in the aminoplast resin which has been converted in this way by reaction with an unsaturated alcohol is generally from 0.1: 1 to 1, 0: 1, preferably from 0 , 5: 1 to 1, 0: 1, more preferably from 0.6: 1 to 1, 0: 1, and most preferably from 0.8: 1 to 1, 0: 1.
  • At least 75% of the double bonds of the unsaturated alcohol incorporated into the aminoplast resin are preferably reacted with a silane (C), preferably at least 80%, more preferably at least 85% and most preferably at least 90%.
  • Conceivable although less preferred, is also the use of compounds (C) which carry more than one Si-H bond, for example at least two, preferably two to four, more preferably two or three, and most preferably two.
  • R 9 and R 10 may have the above meanings.
  • Examples of these are 1, 1, 3,3-tetramethyldisiloxane, 1, 1, 3,3-tetraethyldisiloxane and 1, 1, 3,3-tetraphenyldisiloxane.
  • the conversion into the silylated aminoplast resins according to the invention may preferably be carried out in the first stage at between 40 and 120.degree. C., more preferably between 60 and 110.degree. C. and very preferably between 80 and 100.degree. C. and in the second stage preferably between 40.degree and 80 ° C, more preferably between 50 and 70 ° C, and most preferably at 60 ° C.
  • the reaction can be carried out in bulk, but preferably in an inert, anhydrous solvent.
  • the reaction of the aminoplast resin used with the unsaturated alcohol can be catalyzed or uncatalyzed, with or without the addition of an entrainer, for example toluene.
  • an entrainer for example toluene.
  • a catalyst it is preferably an acid. Examples of acids are listed below.
  • the unsaturated alcohol is used in a ratio of 1: 1 to 20: 1 (molar) with respect to aminoplast resin, preferably in a ratio of 6: 6 to 15: 6, particularly preferably in a ratio of about 10: 6.
  • the excess alcohol is removed after the reaction under reduced pressure at a maximum of 50 ° C from the reaction mixture. Further heating of the reaction mixture can lead to the polymerization of the aminoplast resin.
  • the reaction of the unsaturated alcohol (B) with the aminoplast resin (A) can be carried out in the sense of a transetherification in which cleaved in the aminoplast resin alkyl groups and replaced by the unsaturated alcohol (B), or in the sense of etherification, wherein contained in the aminoplast resin free Hydroxy groups are substituted by the unsaturated alcohol (B).
  • esterification and transetherification take place simultaneously, as far as free hydroxy groups are present.
  • condensation of the aminoplast resins to form polynuclear melamine-formaldehyde or benzoguanamine condensates may also take place.
  • more or more nucleated aminoplast resins are built up, which can enhance the inventive gradient formation in the coating composition.
  • transition metal-catalyzed As transition metals are preferably those of the eighth subgroup in question, particularly preferably platinum, rhodium, palladium, cobalt and nickel metallic or in the form of the complexes.
  • a preferred catalyst is e.g. the so-called Karstedt catalyst (platinum divinyltetramethyldisiloxane) or Hexachloroplatinklahydrat, for example, in the form of Speier catalyst, ie in the form of the solution in iso-propanol, and platinum on activated carbon.
  • the reaction in the first stage is carried out so that the unsaturated alcohol used may optionally be initially charged together with the catalyst, brought to the desired temperature and the aminoplast resin, if appropriate dissolved in a suitable solvent, is slowly added thereto. It would also be conceivable for the reduction in temperature, the application of negative pressure. This would reduce self-condensation of the aminoplast resins and lead to smaller, lower viscosity molecules. Conversely, one could extend the duration of the reaction and / or perform at elevated temperature to build up polynuclear aminoplast resins.
  • the released methanol is collected continuously in a water separator and the reaction is stopped after the theoretical amount of methanol has been deposited.
  • water is contained in the reaction mixture, it is advantageous to use a short Vigreux column effective separation of the azeotrope of unsaturated alcohol and water used by the methanol formed.
  • the reaction is preferably carried out in the absence of water.
  • the unsaturated alcohol used is distilled before use over potassium carbonate or another suitable desiccant.
  • the resulting reaction product can be purified by column chromatography on silica gel (silica gel Si 60, 40-63 ⁇ , Merck) with a mobile phase mixture of ethyl acetate and pentane in the ratio 1: 2.
  • silica gel silica gel Si 60, 40-63 ⁇ , Merck
  • the crude product usually contains only minor impurities and can be used without further purification in the following synthesis.
  • the second reaction stage is carried out so that the precursor from the first reaction stage is preferably initially charged under inert atmosphere together with the corresponding silane in an anhydrous, inert solvent and mixed with vigorous stirring with a solution of the transition metal catalyst in the same solvent.
  • the reaction mixture is stirred at the abovementioned temperature for 30 minutes to 200 hours, preferably 1 to 150, more preferably 2 to 100 hours, and if appropriate subsequently freed of solvent under reduced pressure. A work-up of the product is not required.
  • Suitable acidic catalysts are sulfuric acid, nitric acid, phosphoric acid, hydrochloric acid, para-toluenesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, methanesulfonic acid, nonylnaphthalene disulfonic acid or mixtures thereof, including acidic ion exchangers. Preference is given to sulfonic acids, particular preference is given to para-toluenesulfonic acid.
  • the acidic catalyst is generally added in amounts of from 0.1 to 1% by weight, preferably from 0.1 to 0.5% by weight. It may be useful to enter the catalyst in several portions.
  • the silylated aminoplast resin obtained has a viscosity at 23 ° C. according to ISO 3219 / B of preferably between 100 and 50,000 mPas, more preferably between 500 and
  • the shear rate should preferably be 250 s _1 .
  • the number average molecular weight M n of the resulting silylated aminoplast resins is generally less than 3500 g / mol, preferably less than 3000 g / mol and more preferably less than 2500 (determined by gel permeation chromatography Tetrahydrofuran and polystyrene as standard,
  • the acid number of the aminoplast resins obtained, especially of the melamine-formaldehyde resins, is less than 3, more preferably less than 2 mg KOH / g, determined in accordance with ISO 3682.
  • the content of free formaldehyde in the silylated aminoplast resins according to the invention is generally 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.
  • silylated aminoplast resin obtained in accordance with the invention is preferably subsequently mixed with common solvents or mixtures thereof.
  • 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.
  • aromatic hydrocarbon mixtures are those which comprise predominantly aromatic C 7 - to C 4 -hydrocarbons and may have a boiling range of from 1 10 to 300 ° C., particular preference is given to toluene, o-, m- or p-xyol, trimethylbenzene isomers, tetramethylbenzene isomers , Ethylbenzene, cumene, tetrahydronaphthalene and mixtures containing such.
  • Solvesso® grades from ExxonMobil Chemical, in particular Solvesso® 100 (CAS No. 64742-95-6, predominantly C9 and C10 aromatics, boiling range about
  • 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 particularly 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 ° C. in accordance with DIN 51757 of the hydrocarbons may be 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, for example, 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 butylglycol 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.
  • (Cyclo) aliphatic hydrocarbons are, for example, decalin, alkylated decalin and isomer mixtures of straight-chain or branched alkanes and / or cycloalkanes.
  • n-butyl acetate ethyl acetate, 1-methoxypropyl 2, 2-methoxyethyl acetate, and mixtures thereof, in particular with the above-listed aromatic hydrocarbon mixtures.
  • 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.
  • 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,
  • silylated aminoplast resins according to the invention show comparable or even improved properties with regard to gloss and hardness to the unsilylated aminoplast resins.
  • they have a further crosslinking mechanism via the silyl groups contained.
  • silylated aminoplast resins according to the invention are capable of forming a gradient in a coating composition (see below), in which the cured coating has a higher hardness on the surface or in the upper coating region than in the lower region (side to the substrate). the coating shows.
  • the cured coating has an average change in the modulus of elasticity perpendicular to the surface of at least 1 MPas per ⁇ , preferably at least 2.5 MPas per ⁇ and particularly preferably at least 5 MPas per ⁇ .
  • a preferred method for measuring such a gradient is listed in the examples.
  • the curing is generally carried out so that after application of the coating of the substrates with the aminoplast resins containing coating compositions or coating formulations, optionally mixed with other typical additives and thermally curable resins, preferably at a temperature below 80 ° C, preferably room temperature to 60 ° C and particularly preferably room temperature to 40 ° C over a period of 1 minute and not more than 72 hours, preferably not more than 48 hours, more preferably not more than 24 hours, most preferably not more than 12 and in particular of not more than 6 hours, 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 ° C thermally treated (cures).
  • a temperature below 80 ° C preferably room temperature to 60 ° C and particularly preferably room temperature to 40 ° C over a period of 1 minute and not more than 72 hours, preferably not more than 48 hours, more preferably not more than 24 hours, most preferably not more than 12 and in particular of not
  • the amount of solvent contained in the coating composition prior to application should be removed from the applied coating composition.
  • the lacquer curing takes place, depending on the amount of coating material applied, via high-energy radiation, heat transfer from heated surfaces or via convection of gaseous media over a period of seconds, e.g. in tape coating in combination with NIR drying, up to 5 hours, e.g. 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 essentially removes any solvent present, moreover, a reaction with the binder may already take place, whereas the curing essentially involves the reaction with the binder.
  • the curing can also take place in addition to or instead of the thermal curing by IR and NIR radiation, wherein NIR radiation here electromagnetic radiation in the wavelength range of 760 nm to 2.5 ⁇ , preferably from 900 to 1500 nm is designated.
  • the curing takes place in a period of 1 second to 120 minutes, preferably from 1 minute to 60 minutes.
  • coating compositions containing at least one inventive silylated aminoplast resin contain at least one binder which contains groups reactive with amino resins. These are generally selected from the group consisting of epoxy groups-containing binders, hydroxyl-containing binders, binders containing carboxy groups and binders containing amino groups.
  • the hydroxyl-containing binder is preferably polyetherols, polyesterols, polyacrylate polyols, polycarbonate polyols, alkyd resins or epoxy resins. Particular preference is given to polyesterols and polyacrylate polyols, very particular preference to polyacrylate polyols.
  • 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 according to DI N 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 di- or polyols, which preferably have 2 to 20 C atoms and have 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-C2o-alkyl (meth) acrylate, vinyl aromatics having up to 20 carbon atoms , Vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinyl halide iden, 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 consist of more than 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 other monomers, e.g. ethylenically unsaturated acids, in particular carboxylic acids, acid anhydrides or acid amides.
  • Further 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. Polyester polyols are preferably used, 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:
  • 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.
  • 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 low molecular weight alcohols mentioned as synthesis components for the polyesterpolyols, into consideration.
  • lactone-based polyesterdiols which are homopolymers or copolymers of lactones, preferably terminal hydroxyl-containing addition products of lactones to suitable difunctional starter molecules.
  • Preferred lactones are 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 is also denoted by a d- to C 4 - Alkyl radical may be substituted.
  • Examples are ⁇ -caprolactone, ⁇ -propiolactone, gamma-butyrolactone and / or methyl-s-caprolactone, 4-hydroxybenzoic acid, 6-hydroxy-2-naphthoic 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 the ⁇ -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 can 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.
  • 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 or tallol, 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 or tallol
  • 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 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 or tallol, non-drying oils
  • 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 generally 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, particularly preferably at least 2000 and very particularly 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.
  • TACT trisalkylcarbamoyltriazines
  • aminoplast resins of the invention especially the melamine-formaldehyde resins, may also be used together with non-crosslinkable binders, i. such without reactive against melamine-formaldehyde resins groups used.
  • the amino resins according to the invention crosslink by condensation of their silane groups with one another. The crosslinking is accelerated by adding acids and other catalysts.
  • weak acids are understood to mean 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 of these 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.
  • 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 of these are sulfuric acid, pyrophosphoric acid, sulfurous acid and tetrafluoroboric acid, trichloroacetic acid, dichloroacetic acid, oxalic acid, nitroacetic acid.
  • organic acids preferably organic sulfonic acids. Particular preference is given to 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 aminoplast resin used , Furthermore, the acids can be used as free acids or blocked.
  • amines such as DBN, DBU and aliphatic amines
  • tin-containing catalysts for example: DBTL
  • an acid must always be added for the melamine crosslinking.
  • 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.
  • Suitable thickeners besides free-radically (co) polymerized (co) polymers, customary organic and inorganic thickeners such as hydroxymethylcellulose or bentonite.
  • customary organic and inorganic thickeners such as hydroxymethylcellulose or bentonite.
  • chelating agents e.g. Ethylenediamine acetic acid and its salts as well
  • Suitable fillers include silicates, e.g. B. obtainable by hydrolysis of silicon tetrachloride silicates, such as Aerosil ®. From Degussa, siliceous earth, talc, aluminum silicates, magnesium silicates, calcium carbonates, etc.
  • Suitable stabilizers include typical UV absorbers such as oxanilides, triazines and Benzotri- azol (the latter available as Tinuvin ® brands Ciba Specialty Chemicals) and benzophenones.
  • radical scavengers for example sterically hindered amines such as 2,2,6,6-tetramethylpiperidine, 2,6-di-tert-butylpiperidine or derivatives thereof, eg. As bis (2,2,6,6-tetra-methyl-4-piperi-dyl) sebacinate used.
  • Stabilizers are usually used in amounts of 0.1 to 5.0 wt .-%, based on the solid components contained in the preparation.
  • 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 or organic, colored 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, more preferably less than 0.25, very preferably less than 0.1 and in particular less than 0.05 g / 1000 g of 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 respective 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 titanium dioxide coated mica, iron oxide coated mica, mixed oxide coated mica (eg with titanium dioxide and Fe2O3 or titanium dioxide and Cr20s), 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.
  • the coating compositions according to the invention are thus composed as follows: at least one silylated aminoplast resin according to the invention, preferably a silylated melamine-formaldehyde resin,
  • a further crosslinker which is capable of reacting with the binder (s), preferably selected from the group consisting of polyisocyanates, melamine-formaldehyde resins and ketone-formaldehyde resins.
  • the coating of the substrates with the coating compositions of the invention is carried out according to customary methods Processes known to those skilled in the art, wherein at least one coating composition or paint formulation according to the invention is applied to the substrate to be coated in the desired thickness and the volatile constituents 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 . Subsequently, it can be hardened as described above.
  • 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 diene glycol 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 diene glycol 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 of it.
  • 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, PUR, PVAC, PVAL, PVC, PVDC, PVP, SAN, SB, SMS, UF , UP plastics (abbreviated to DIN 7728) and aliphatic polyketones.
  • Particularly preferred substrates are glass and 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. It 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. Also conceivable is the use of the coating compositions according to the invention for the treatment of tinned iron / steel (tinplate).
  • 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 molded bricks 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 molded bricks and fiber cement boards, or metals or coated metals, preferably plastics or metals, especially in the form of films, more preferably metals.
  • aminoplast resins, coating compositions or paint formulations according to the invention are suitable as or in exterior coatings, ie applications that are exposed to daylight, preferably building components, interior coatings, coatings on vehicles and aircraft.
  • the aminoplast resins and coating compositions of the invention are used as or in automotive clearcoat and topcoat (s). Further preferred fields of use are can-coating and coil-coating.
  • the coating compositions are particularly suitable for applications in which A particularly high application security, outdoor weather resistance, appearance, solvent and / or chemical resistance are required.
  • the solvent was removed in vacuo. Then the substance was dissolved in acetone and filtered through silica gel 60 (040-0.063 mm), 1 cm high and 7 cm diameter. The resulting solution was evaporated.
  • the formulations were applied to different substrates (aluminum foil, Bonder sheet (Gardobond), glass and Stamylan (polypropylene)). After application, between 0-120 min at room temperature in the trigger pre-stored without cover. In this case, separation by the surface tension of the solvent can take place by evaporation of the solvent / solvent mixture. The formation of a gradient is faster, the lower the surface tension of the crosslinker. The more polar the substrate, the greater the gradient formation. Subsequently, the thermal curing of the upstream film was carried out without further manipulation for 2 h at 140 ° C.
  • siloxane-crosslinking components of the crosslinker higher crosslinking of the cured coating composition at the top than at the bottom and thus the union of two opposing paint properties such as hardness and elasticity in only one film.
  • a blank sample without siloxane-containing melamine was prepared and measured analogously.
  • compositions of the stratifying formulations are given in the table.
  • the employed Luwipal® 066LF from BASF SE is a highly to completely methyletherified melamine-formaldehyde resin with a nonvolatile content (according to ISO 3251, 2 g sample with 2 ml butanol are heated for 2 hours at 125 ° C) from 93 to 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 ° C and a shear rate D of 41.3 s -1 .
  • Joncryl® 500 is a commercially available polyacrylate polyol.
  • Nacure® 2500 from King Industries is para-toluenesulfonic acid (p-TsOH), 25% dissolved in isopropanol.
  • the film thickness was between 10-150 ⁇ . Stratification was demonstrated on chemical (analytical-spectroscopic) and physical (mechanical hardness measurement by nano-indentation) pathways. Chemical detection:
  • ATR-IR spectroscopy of the peeled cured coating films (top and bottom) was made on Bonder sheet. Scaling was automatically scaled to the largest band of the spectrum.
  • a comparative example (system 4) was measured without stratifying siloxane melamine. Visible in the ATR-IR measurements are differences in the spectral shape (wavenumbers and intensities) between top and bottom. This indicates a chemical difference in the cured paint between the top and bottom. This effect is particularly pronounced on Bonderblech compared to the described comparative example. See Figure 1: System 1: top: solid line, bottom: broken line. Differences in the range of 800-1700 cm- 1 . See Figure 2: System 2: top: solid line, bottom: broken line. Very pronounced differences in the range of 800-1600 cm first
  • the coating compositions were applied to bonder and aluminum sheet, stored at room temperature (see table) and thermally cured. Subsequently, the films were peeled off, embedded in an epoxy resin and subjected to a microtome cut. The resulting microtome cut is then examined with a nano-indenter device:
  • Figure 6 System 1
  • Figure 6 The top of the coating begins at about 10 ⁇ and ends at about 95 ⁇ . Before and after, there is the epoxy resin. The coating has been embedded in an epoxy resin and cut in the microtome.
  • FIG. 7 System 2
  • the top of the coating begins at about 0 ⁇ and ends at about 100 ⁇ . Before and after, there is the epoxy resin.
  • the coating has been embedded in an epoxy resin and cut in the microtome.
  • FIG. 8 System 3
  • the top of the coating starts at about ⁇ and ends at about 130 ⁇ . Before and after, there is the epoxy resin.
  • the coating has been embedded in an epoxy resin and cut in the microtome.
  • FIG. 9 System 4
  • the top of the coating begins at about 0 ⁇ and ends at about 170 ⁇ . Before and after, there is the epoxy resin.
  • the coating has been embedded in an epoxy resin and cut in the microtome.
  • the gradient in the desired systems in hardness is> 0.15 MPa / ⁇

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  • 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)
  • Phenolic Resins Or Amino Resins (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne des résines aminoplaste silylées, leur procédé de fabrication, leur utilisation, ainsi que des matières de revêtement contenant lesdites résines.
EP12747530.9A 2011-02-14 2012-02-10 Résines aminoplaste silylées Withdrawn EP2675830A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP12747530.9A EP2675830A1 (fr) 2011-02-14 2012-02-10 Résines aminoplaste silylées

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
PCT/EP2011/052094 WO2011101301A1 (fr) 2010-02-16 2011-02-14 Résines aminoplastes silylées
EP11177369 2011-08-12
EP12747530.9A EP2675830A1 (fr) 2011-02-14 2012-02-10 Résines aminoplaste silylées
PCT/IB2012/050600 WO2012110926A1 (fr) 2011-02-14 2012-02-10 Résines aminoplaste silylées

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EP2675830A1 true EP2675830A1 (fr) 2013-12-25

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CN105732988B (zh) * 2014-12-08 2018-04-10 海洋化工研究院有限公司 一种有机硅改性饱和聚酯树脂的制备
DE102015209794B4 (de) * 2015-05-28 2017-07-27 Carl Zeiss Vision International Gmbh Verfahren zur Herstellung eines optischen Glases mit Antifog-Beschichtung und optisches Glas mit Antifog-Beschichtung
CN113603893B (zh) * 2021-08-13 2022-11-22 苏州市兴业化工有限公司 多元改性氨基树脂、其制备方法与应用

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US20040214017A1 (en) * 2003-04-28 2004-10-28 Uhlianuk Peter William Coatings that contain monomeric and polymeric melamines with attached functional silane groups
CN101338157B (zh) * 2008-08-14 2010-08-11 常熟理工学院 可直焊聚酯亚胺漆包线漆及其制备方法
ES2466821T3 (es) * 2010-02-16 2014-06-11 Basf Se Resinas aminoplásticas sililadas
CN101817913A (zh) * 2010-03-11 2010-09-01 浙江奥仕化学有限公司 高度甲基醚化氨基树脂的制备方法

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