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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/61—Polysiloxanes
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/80—Masked polyisocyanates
  • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals

Definitions

• the present invention relates to hybrid inorganic-organic polyisocyanates based on polyfunctional organosilanes, metal alkoxides and alkoxysilane-containing blocked polyisocyanates for the production of organic-inorganic coating compositions and adhesives.
• organic-inorganic hybrid materials attempts to combine typical properties of inorganic and organic substances in one material.
• glasses are characterized by their high hardness and acid resistance, while organic polymers are very elastic materials.
• organic-inorganic hybrid materials are known which, on the one hand, are significantly harder than pure organic polymers, but nevertheless do not exhibit the brittleness of purely inorganic materials.
• hybrid materials are classified into different types. An overview can be found in J. Mater. Chem. 6 (1996) 51 1.
• hybrid materials are obtained by hydrolysis and condensation of (semi) Metallalkoxytheticen such as Si (OEt) 4 an inorganic network is formed, which is a mixture with the classic organic polymers such as polyesters or polyacrylates, whose polymer strands interpenetrate A covalent chemical attachment of one network to the other is not present, but there are, if any, only weak interactions (such as van der Waals or hydrogen bonds).)
• Metallalkoxytheticen such as Si (OEt) 4
• an inorganic network is formed, which is a mixture with the classic organic polymers such as polyesters or polyacrylates, whose polymer strands interpenetrate A covalent chemical attachment of one network to the other is not present, but there are, if any, only weak interactions (such as van der Waals or hydrogen bonds).
• Such hybrid materials are described, for example, in WO 93 / 01226 and WO 98/38251.
• WO 98/38251 teaches that transparent hybrid materials are obtainable by mixtures of at least one organic polymer, inorganic particles, an inorganic-organic binder and solvents.
• mixtures are described which are characterized as a hybrid coating, for example by their hardness, optical transparency and crack-free application.
• outdoor weathering resistance ie resistance to UV light under the simultaneous influence of climatic conditions, is of great importance, above all in the field of topcoat coating for outdoor use. This is not solved satisfactorily by the systems described in WO 98/38251.
• no hybrid polyisocyanates are described.
• DE 10 2004 048874 discloses hybrid compositions based on an inorganic binder, metal alkoxides, inorganic UV absorbers and an organic polyol.
• the crosslinking of such systems is carried out with blocked polyisocyanates.
• polyol-free mixtures of the blocked polyisocyanate with the inorganic components are not disclosed or pointed out their advantages.
• the systems described in DE 10 2004 048874 show improved weatherability and acid resistance as well as higher scratch resistance, but their storage stabilities and solvent resistance and chemical resistance are unsatisfactory.
• the present invention relates to hybrid polyisocyanate compositions which are free of organic polyols, comprising
• Inorganic binders of component A) are polyfunctional organosilanes which contain at least 2, preferably at least 3, silicon atoms each having 1 to 3 alkoxy or hydroxyl groups, the silicon atoms each having at least one Si-C bond being bonded to a structural unit linking the silicon atoms.
• linking units in the context of the invention are, for example, linear or branched C 1 to C 10 alkylene chains, C 5 - to Cio-cycloalkylene radicals, aromatic radicals, for example phenyl, naphthyl or biphenyl, or combinations of aromatic and aliphatic radicals mentioned.
• aromatic radicals for example phenyl, naphthyl or biphenyl, or combinations of aromatic and aliphatic radicals mentioned.
• the aliphatic and aromatic radicals may also contain heteroatoms such as Si, N, O, S or F.
• polyfunctional organosilanes are compounds of the general formula (I)
• R 1 alkyl, aryl
• R 2 can also be hydrogen.
• polyfunctional organosilanes are cyclic compounds of the general formula (II)
• R 4 can also be hydrogen
• polyfunctional organosilanes are compounds of the general formula (III)
• R 8 can also be hydrogen
• silanols or alkoxides for example:
• oligomers i. the hydrolysis and condensation products of the abovementioned compounds and of compounds of the formulas (I), (II) and / or (III).
• the inorganic binders of component A) are particularly preferably based on cyclo- [OSiMe [(CH 2 ) 2 Si (OH) Me 2 ] ⁇ 4 and / or cyc / o-OSiMe [(CH 2 ) 2 Si (OEt) 2 me] ⁇ .
• R 10, R 11 independently alkyl or aryl groups are preferably methyl, ethyl, I- sopropyl-, n-butyl, sec-butyl, tert-butyl or phenyl, particularly preferably methyl or Ethyl groups and
• Examples are Si (OEt) 4 , Si (OMe) 4 , H 3 C-Si (OEt) 3 , H 3 C-Si (OMe) 3 , B (OEt) 3 , Al (O 1 Pr) 3 , or Zr (O 1 Pr) 4 .
• Si (OEt) 4 instead of the monomeric alkoxides, their hydrolysis and condensation products can also be used.
• Commercially available are, for example, Si (OEt) 4 condensates.
• component B) Particular preference is given in component B) to using Si (OEt) 4 and its hydrolysis and / or condensation products.
• the inorganic UV absorbers of component C) preferably have an average particle size of ⁇ 30 nm.
• At least 98%, particularly preferably at least 99.5%, of all the particles used have the required average particle size.
• inorganic UV absorbers can be used both as a substance but preferably in the form of dispersions (sols).
• solvent can be used both water, aqueous acids or bases as well as organic solvents or mixtures thereof.
• the blocked polyisocyanates of component D) are based on the NCO-functional compounds known per se to the person skilled in the art with more than one NCO group per molecule. These preferably have NCO functionalities of 2.3 to 4.5, contents of NCO groups of 1 1, 0 to 24.0 wt .-% and contents of monomeric diisocyanates of less than 1 wt .-%, preferably less than 0 , 5 wt .-% on.
• Such polyisocyanates are obtainable by modifying simple aliphatic, cycloaliphatic, aromatic and / or aromatic diisocyanates and may have uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structures.
• polyisocyanates can be used as NCO-containing prepolymers.
• Such polyisocyanates are described, for example, in Laas et al. (1994), J. prakt. Chem. 336, 185-200 or in Bock (1999), Polyurethanes for coatings and coatings, Vincentz Verlag, Hannover, pp. 21-27.
• Suitable diisocyanates for the preparation of such polyisocyanates are any diisocyanates of the molecular weight range 140 to 400 g / mol with aliphatic, cycloaliphatic, araliphatic and / or aromatically bound isocyanate groups, such as by phosgenation or by phosgene-free processes, for example by thermal urethane cleavage 1,4-diisocyanatobutane, 1,6-diisocyanatohexane (HDI), 2-methyl-1,5-diisocyanatopentane, 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- and 2,4,4, respectively Trimethyl-1,6-diisocyanatohexane, 1,10-diisocyanatodecane, 1,3- and 1,4-diisocyanatocyclohexane, 1,3- and 1,4-bis- (isocyanatomethyl) -cyclo
• the blocked polyisocyanates of component D) are preferably based on EPDI, MDI, TDI, 4,4'-diisocyanatodicyclohexylmethane, HDI and mixtures thereof. With particular preference they are based on IPDI and / or HDI.
• the blocked polyisocyanates of component D) are usually obtainable in which polyisocyanates of the abovementioned type are reacted with aminoalkoxysilanes and the free NCO groups are then subsequently reacted with blocking agents known to the person skilled in the art (Houben Weyl, Methoden der organischen Chemie XIV / 2, pp. 61-70).
• the isocyanate-reactive alkoxysilanes used are preferably compounds of the formula (V)
• Q is an isocyanate-reactive group
• X is a hydrolyzable group
• Y are identical or different alkyl groups
• Z is a C 1 -C 12 -alkylene group
• a is an integer of 1 to 3.
• the group Q is preferably a group which reacts with isocyanates with urethane, urea or thiourea formation. These are preferably OH, SH or primary or secondary amino groups.
• Preferred amino groups correspond to the formula -NHR 1 , wherein R 1 is hydrogen, a C r C
• the group X is preferably an alkoxy or hydroxy group, more preferably methoxy, ethoxy, propoxy or butoxy.
• Y in formula (I) preferably represents a linear or branched C 1 -C 4 -alkyl group, preferably methyl or ethyl.
• Z in formula (V) is preferably a linear or branched C 1 -C 4 -alkylene group.
• a in formula (V) is 1 or 2.
• Suitable alkoxysilanes of the formula (V) are hydroxymethyltri (m) ethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3
• secondary aminoalkoxysilanes are N-methyl-3-aminopropyltri (m) ethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, bis (gamma-trimethoxysilylpropyl) amine, N-butyl-3-aminopropyltri (rn) ethoxysilane, N-ethyl -3- aminoisobutyltri (m) ethoxysilane or N-ethyl-3-aminoisobutylmethyldi (m) ethoxysilane and the analogous C 2 -C 4 alkoxysilanes.
• isocyanate-reactive alkoxysilanes are aspartic acid esters, as obtained, for example, according to US Pat. No. 5,364,955 by the reaction of aminosilanes with maleic or fumaric acid esters, preferably dimethyl maleate or diethyl maleate.
• Particularly preferred isocyanate-reactive alkoxysilanes for modifying the polyisocyanates are secondary aminoalkoxysilanes of the type described above, more preferably aspartic acid esters and aminoalkoxysilanes having one or two alkoxy groups.
• the abovementioned alkoxysilanes can be used individually but also in mixtures for modification.
• the ratio of free NCO groups of the isocyanate to be modified to the NCO-reactive groups Q of the alkoxysilane of the formula (V) is preferably 1: 0.01 to 1: 0.75, particularly preferably 1: 0.05 to 1: 0.4.
• the isocyanates to be blocked as described above are reacted with one or a mixture of a plurality of blocking agents.
• Suitable blocking agents are all compounds which can be eliminated on heating of the blocked (poly) isocyanate, if appropriate in the presence of a catalyst.
• Suitable blocking agents are e.g. sterically demanding amines such as dicyclohexylamine, diisopropylamine, N-tert-butyl-N-benzylamine, caprolactam, butanone oxime, imidazoles with the various conceivable substitution patterns, pyrazoles such as 3,5-dimethylpyrazole, triazoles and tetrazoles, as well as alcohols such as isopropanol, ethanol, Methyl ethyl ketoxime, malonic acid ester.
• Preferred blocking agents are butanone oxime, caprolactam, malonic acid esters, diisopropylamine, cyclopentanone-2-carboxyethyl ester, cyclopentanone-2-carboxymethyl ester, isopropanol, dimethylpyrazole and mixtures thereof. Particularly preferred is dimethylpyrazole.
• the content of free NCO groups in the polyisocyanates of component D) according to the invention is ⁇ 5 wt .-%, preferably ⁇ 0.5 wt .-%, in particular ⁇ 0.1 wt .-%.
• organic solvents may also be added in addition to the components A) to D).
• examples are alcohols, such as methanol, ethanol, isopropanol, 2-butanol, 1, 2-ethanediol or glycerol, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or butanone, esters, such as ethyl acetate or methoxypropyl acetate, aromatics such as toluene or xylene, ethers such as tert-butyl methyl ether, and aliphatic hydrocarbons.
• alcohols such as methanol, ethanol, isopropanol, 2-butanol, 1, 2-ethanediol or glycerol
• ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or butanone
• esters such as ethyl acetate or me
• polar solvents and particularly preferably alcohols of the abovementioned type Preference is given to using polar solvents and particularly preferably alcohols of the abovementioned type.
• solvent mixtures with alcohol and / or ester contents of more than 50% by weight, particularly preferably more than 80% by weight.
• the amount of solvent is preferably selected such that the solids content of the composition is 5 to 75% by weight, particularly preferably 20 to 55% by weight.
• hybrid polyisocyanate compositions according to the invention may also contain catalysts which serve to accelerate the hydrolysis and condensation reactions.
• catalysts organic and inorganic acids and bases as well as organometallic compounds, fluoride compounds or metal alkoxides can be used. Examples which may be mentioned are: acetic acid, p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, ammonia, dibutylamine, potassium hydroxide, sodium hydroxide, ammonium fluoride, sodium fluoride, or aluminum isopropoxide.
• the hybrid polyisocyanate compositions according to the invention based on the components A) to D), have a composition of
• the hybrid polyisocyanate compositions according to the invention based on the components A) to D), have a composition of
• hybrid polyisocyanate compositions according to the invention are typically prepared by initially introducing components A) and B) and, if appropriate, proportions of organic solvent and then, if appropriate, hydrolyzing (partially) by addition of acid and finally component C) and optionally further organic solvents are added with stirring and optionally with cooling. Subsequently, the addition of component D).
• the inorganic UV absorbers C) are preferably introduced by stirring into the inventive component A) and / or B) in the composition according to the invention. Stirring in the organic polyisocyanate component is not preferred.
• Another object of the present invention are coating compositions, at least containing
• the polyurethane systems of the present invention contain polyhydroxy and / or polyamine compounds for crosslinking.
• other polyisocyanates which are different from the polyisocyanates according to the invention and also auxiliaries and additives may be present.
• Suitable polyhydroxyl compounds are, for example, tri- and / or tetrafunctional alcohols and / or the polyether polyols, polyester polyols and / or polyacrylate polyols customary in coating technology.
• polyurethanes or polyureas which can be crosslinked with polyisocyanates because of the active hydrogen atoms present in the urethane or urea groups can also be used for crosslinking.
• polyamines whose amino groups may be blocked such as polyketimines, polyaldimines or oxazolanes.
• Polyisocyanate polyols and polyester polyols are preferably used for crosslinking the polyisocyanates according to the invention.
• catalysts for the reaction of the compositions according to the invention with the polyisocyanates it is possible to use catalysts such as commercially available organometallic compounds of the elements aluminum, tin, zinc, titanium, manganese, iron, bismuth or else zirconium, for example dibutyltin laurate, zinc octoate, titanium tetraisopropylate.
• tertiary amines such as l, 4-diazabicyclo [2.2.2] octane are also suitable.
• compositions of a) according to the invention in which they are preferably between 60 and 180 ° C., preferably between 70 and 150 ° C., at temperatures between 20 and 200 ° C. C is performed.
• the ratio of a) to b) is such that an NCO / OH ratio of the free and optionally blocked NCO groups from a) to the OH groups of component b) is from 0.3 to 2, preferably 0, 4 to 1, 5 particularly preferably 0.5 to 1.0 results.
• auxiliaries such as inorganic or organic pigments, other organic light stabilizers, radical scavengers, paint additives, such as dispersing, leveling, thickening, defoaming and other aids, adhesives, fungicides, bactericides, stabilizers or inhibitors and Further catalysts can be prepared from the composition according to the invention, in particular in the form of the coating compositions of the invention, highly resistant paints for the automotive industry.
• coating compositions according to the invention can also be used in the fields of synthetic finish coating, floor coating and / or wood / furniture coating.
• Desmodur ® VPLS 2253 3,5-dimethylpyrazole-blocked polyisocyanate (trimer) based on HDI; 75% in MPA / SN 100 (8:17), viscosity at 23 ° C about 3600 mPas, blocked NCO content 10.5%, equivalent weight 400, Bayer MaterialScience AG, Leverkusen, DE
• Desmodur ® N3300 hexamethylene diisocyanate trimer; NCO content 21, 8 +/- 0.3 wt .-%, viscosity at 23 ° C about 3000 mPas, Bayer MaterialScience AG, Leverkusen, DE
• Desmophen A665 BA polyacrylate, 70% in butyl acetate, OH content 3.2%, viscosity at 23 0 C for about 8500 mPas, product of Bayer MaterialScience AG, Leverkusen, DE
• Baysilone ® Paint Additive OL 17 Leveling Aid, 100% Lff. (Borchers GmbH, Langenfeld, Germany)
• BYK ® 070 defoamers, 10% in MPA / BA / xylene Lff. (BYK-Chemie GmbH, Wesel, Germany)
• Tinuvin® 123 radical scavenger, 100% Lff. (Ciba Specialty Chemicals Lampertheim GmbH, Lampertheim, Germany)
• Tinuvin® 384-2 UV stabilizer, 100% Lff. (Ciba Specialty Chemicals Lampertheim GmbH, Lampertheim, Germany)
• MPA / SN mixture 1: 1 mixture of 1-methoxypropyl acetate and Solvent Naphta 100 (Kraemer & Martin GmbH, St. Augustin, Germany)
• the test tube rack is removed from the paint surface. Subsequently, the solvent residues are removed immediately by means of an absorbent paper or textile fabric. Immediately examine the test surface after careful scratching with the fingernail visually for changes. The following levels are distinguished:
• the order of the numbers describes the sequence of the tested solvents (xylene, methoxypropyl acetate, ethyl acetate, acetone)
• Storage stability To determine the storage stability, the samples were stored at appropriate temperatures and regularly assessed visually for gelling, sedimentation and discoloration.
• N- (3-trimethoxysilylpropyl) aspartic acid diethyl ester was prepared according to the teaching of US Pat. No. 5,364,955, Example 5, by reacting equimolar amounts of 3-aminopropyltrimethoxysilane with diethyl maleate.
• Example 1 Based on DE 01004048874 A1, Example 1, 204.7 g of D4 diethoxide, 1054.1 g of tetraethoxysilane, 309.7 g of ethanol, 929.2 g of 2-butanol and 103.3 g of butylglycol were initially charged in a 4 l multi-necked flask, homogenized and then initially added 108.4 g of 0.1 molar hydrochloric acid with stirring. After a stirring time of 30 minutes, a further 111.2 g of 0.1 molar hydrochloric acid were added with stirring and stirred for 60 minutes. Thereafter, 56.8 g of ceria particles (Cerium Colloidal 20%, Fa.
• ceria particles Cerium Colloidal 20%, Fa.
• Example 3 Preparation of a Composition According to the Invention
• the mixture was translucent / yellowish and sedimentation free at room temperature for about 2 weeks, homogeneous.
• a colorless, liquid, blocked polyisocyanate having the following characteristics was obtained: solids content 80% by weight, viscosity 2450 mPas at 23 ° C., equivalent weight 652.6 g / val and 6.44% blocked NCO content based on DMP.
• Example 6
• the mixture was transparent / yellowish and stable at room temperature for about 10 days against sedimentation or sedimentation-free.
• Example 7 (Comparative Example to Examples 4 and 6)
• Desmodur® VPLS 2253 (3,5-dimethylpyrazole-blocked polyisocyanate (trimer) based on HDI, 75% in MPA / SN 100 (8:17), viscosity at 23 ° C. about 3600 mPas, blocked NCO Content 10.5%, equivalent weight 400, Bayer MaterialScience AG, Leverkusen, DE) were mixed with 75.1 g of the compound from Example 2, homogenized and then filtered off through a 10 ⁇ m filter. The resulting mixture had a theoretical solids of 40.7% in 2-butanol / ethanol / MPA / SN100 and a theoretical, blocked NCO content of 2.6%.
• the mixture became cloudy and showed phase separation.
• the mixture was transparent / yellowish and stable at room temperature for approx. 30 days against sedimentation or sedimentation free.
• Example 10 comparative example, unblocked polyisocyanate:
• Desmodur ® N3300 hexamethylene diisocyanate trimer; NCO content 21.8 +/- 0.3% by weight, viscosity at 23 ° C 3000 mPas, Bayer MaterialScience AG, Leverkusen, DE
• the resulting mixture had a theoretical Festkö ⁇ er of 40% in 2-butanol / ethanol / butyl acetate and a theoretical NCO content of 3.43%.
• the mixture was cloudy and separated into two phases.
• Example 1 hybrid polyisocyanate according to the invention from Example 4 was shown in Table 1 with Desmophen ® A665 BA / X in the ratio NCO / OH 1/1 as well as paint additives off mixed and stirred well.
• the Festkö ⁇ er of the hybrid paint was about 30% and were optionally adjusted with a solvent mixture MP A / SN 1: 1.
• Baysilone OL 17 (solid / BM solid) used as 10% solution in MPA 2.0% Byk 070 (Lff./BM solid), used in Lff. (10% solution) 1.0% Tinuvin 123 (solid / BM solid), used in Lff. (100%) 1, 5% Tinuvin 384-2 (solid / BM solid) used in Lff. (100%) about 0.5% DBTL (solid / solid) used as a 10% solution in MPA
• Example 1 1 shows in addition to the colloidal stability and thus formability significantly improved chemical and solvent resistance, as well as an increased scratch resistance compared to the non-hybrid, blocked polyisocyanate (Example 12). Furthermore, the crosslinking could be carried out at much lower temperatures.

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• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Polyurethanes Or Polyureas (AREA)
• Paints Or Removers (AREA)
• Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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  • 2007-05-09 DE DE102007021630A patent/DE102007021630A1/de not_active Withdrawn
• 2008
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  • 2008-04-26 WO PCT/EP2008/003401 patent/WO2008138471A1/de active Application Filing
  • 2008-04-26 EP EP08749175A patent/EP2155799A1/de not_active Withdrawn
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