EP1356004A1 - Liant polyurethane a deux composants utilise comme agent adhesif - Google Patents

Liant polyurethane a deux composants utilise comme agent adhesif

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Publication number
EP1356004A1
EP1356004A1 EP02708272A EP02708272A EP1356004A1 EP 1356004 A1 EP1356004 A1 EP 1356004A1 EP 02708272 A EP02708272 A EP 02708272A EP 02708272 A EP02708272 A EP 02708272A EP 1356004 A1 EP1356004 A1 EP 1356004A1
Authority
EP
European Patent Office
Prior art keywords
use according
group
groups
organic
coating
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Withdrawn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
EP02708272A
Other languages
German (de)
English (en)
Inventor
Steffen Hofacker
Markus Mechtel
Wieland Hovestadt
Claus Kobusch
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.)
Covestro Deutschland AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP1356004A1 publication Critical patent/EP1356004A1/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Withdrawn legal-status Critical Current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
    • 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
    • C08G18/8083—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/809—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]

Definitions

  • the invention relates to the use of solvent-containing two-component polyurethane binders as adhesive agents which are applied to a substrate and to which an inorganic or organic coating or an inorganic-organic hydride coating is subsequently applied.
  • Plastics are extremely versatile materials with a number of desirable properties.
  • one disadvantage of these materials is, for example
  • One method of protecting the surface of plastics from such damage is to apply a suitable coating to the plastic
  • Substrate The composition of the coating depends primarily on whether the surface is to be protected from mechanical damage, radiation, the effects of chemicals or other environmental influences (e.g. pollution, etc.).
  • Transparent plastics such as polycarbonate
  • numerous coating materials are known which in particular protect polycarbonates effectively from mechanical damage.
  • These are essentially organically modified, inorganic coatings, which are mostly condensation or UV-curing. Examples can be found in J. Sol-Gel Sei. Techn. 1998, 11, 153-159, Abstr. 23 rd Annual Conference in Organic Coatings, 1997, 271-279, EP-A 0 263
  • adhesion promoters react both with the plastic surface and with the coating and (covalent) chemical bonds are formed.
  • polycarbonates e.g. Aminosilanes, such as aminopropyltrialkoxysilanes (e.g. in DE-A 19 858 998).
  • the amino group reacts with the polycarbonate surface and the alkoxysilyl residues with the organically modified, silicon-containing inorganic coating.
  • these N-H functional new adhesion promoters have the disadvantage that the polycarbonate is considerably damaged by the basic nitrogen function, which is e.g. visually noticeable by a clear yellowing.
  • Another disadvantage is that the adhesion of the inorganic-organic hybrid coatings rapidly decreases when exposed to water, especially warm water. For example, the film becomes cloudy, bubbles form and finally complete
  • the object of the present invention was therefore to provide an adhesion promoter (primer) for silicon-containing coatings on polymeric substrates, which has good adhesion between the organically modified, silicon-containing inorganic
  • Coating and the surface of the polymeric substrate enables and leads neither to optical damage nor to a lability to water.
  • solvent-containing two-component polyurethane binders which contain a hardener component consisting of an addition product of a polyisocyanate with an alkoxysilane and a paint resin reactive towards isocyanate groups can be used as an adhesion promoter.
  • These solvent-based 2-component systems represent an ideal combination of a very high level of adhesion between, for example, a polymeric substrate and an inorganic coating and very good weathering stability.
  • Addition products of, for example, polyisocyanates with aminosilanes are already state of the art.
  • Such moisture-curing, alkoxysilane-terminated polyurethanes are used in flexible, sealing and adhesive compositions which cure at room temperature (for example US Pat. No. 5,700,868, US Pat. No. 4,625,012, US Pat. No. 4,474,933, US Pat. No. 3,979,344, DE-A 4234) 325, DE-A 2 155 259).
  • US Pat. No. 5,854,338 discloses a binder combination for water-dilutable two-component polyurethane coatings, which consists of an aqueous hydroxy- and / or amino-functional acrylate dispersion and a hardener component which has isocyanate and alkoxysilyl groups in a certain ratio. The alkoxysilyl groups are reacted by an unmodified
  • Polyisocyanates with corresponding amino-functional alkoxysilyl compounds are available.
  • alkoxysilyl compounds By incorporating the alkoxysilyl compounds into the hardener component, two-component polyurethane coatings with an improved property profile with regard to hardness, acid resistance or adhesion are available.
  • the present invention relates to the use of solvent-containing two-component polyurethane binders containing
  • Q is a group reactive towards isocyanate groups, preferably OH, SH or NHR, where R represents a -C ⁇ -A ⁇ kyl distr or C 6 -C 2 o- aryl group or for -Z-SiX a Y 3 - a ,
  • Z is a linear or branched -C ⁇ -alkylene group, preferably a linear or branched C i -C -alkylene group,
  • X is a hydrolyzable group, preferably C 1 -C 4 alkoxy
  • Y are the same or different C 1 -C 4 alkyl groups and
  • a is an integer from 1 to 3
  • the ratio of the groups of the coating resin (D) reactive towards isocyanate groups to the isocyanate groups of the curing agent (A) is between 0.5: 1 to 2: 1, preferably between 0.7: 1 to 1.3: 1.
  • the polyisocyanate (B) contained in the hardener component (A) preferably has an average NCO functionality of 2.3 to 4.5 and preferably an isocyanate Group content from 11.0 to 24.0 wt .-%.
  • the monomeric diisocyanate content is less than 1% by weight, preferably less than 0.5% by weight.
  • the polyisocyanate (B) consists of at least one organic polyisocyanate with aliphatic, cycloaliphatic, araliphatic and / or aromatically bound isocyanate groups.
  • the polyisocyanates or polyisocyanate mixtures (B) are any polyisocyanates made from at least two diisocyanates and containing uretdione, isocyanurate, allophanate, biuret, biuret, hni, made by modifying simple ahphatic, cycloahphatic, araliphatic and / or aromatic diisocyanates - Nooxadiazinedione and / or oxadiazinetrione structure, as described for example in J Prakt. Chem.
  • Suitable diisocyanates for the preparation of such polyisocyanates are any diisocyanates of the molecular weight range 140 to accessible by phosgenation or by phosgene-free processes, for example by thermal urethane cleavage
  • isocyanate groups such as.
  • the starting components (B) are preferably polyisocyanates or polyisocyanate mixtures of the type mentioned with exclusively aliphatic and / or cycloaliphatic isocyanate groups.
  • Very particularly preferred starting components (B) are polyisocyanates or polyisocyanate mixtures with a biuret or isocyanurate structure based on HDI, EPDI and 7'-or 4,4'-diisocyanatodicyclohexylmethane.
  • Groups of the general formula (I) are, for example, hydroxymethyltri (m) ethoxysilane and alkoxysilyl compounds with secondary amino groups or mercapto groups.
  • secondary aminoalkoxysilanes are N-methyl-3-aminopropyltri (m) ethoxy silane, N-phenyl-3-aminopropyltrimethoxysilane, bis (gamma-tri-methoxysilylpropyl) amine, N-butyl-3-aminopropyltri (m) ethoxysilane , N-ethyl-3-aminoisobutyltri (m) ethoxysilane or N-ethyl-3-aminoisobutylmethyldi (m) ethoxysilane as well as the analogous C 2 -C 4 alkoxysilanes.
  • R 2 and R 3 represent the same or different (cyclo) alkyl radicals having 1 to 8 carbon atoms
  • Preferred compounds of the general formula (II) are dimethyl maleate and diethyl maleate.
  • alkoxysilanes (C) with a functional group of the general formula (I) which is reactive towards isocyanate groups are 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane.
  • Preferred alkoxysilanes (C) are N-butyl-3-aminopropyl-tri (m) ethoxysilane and 3-mercapto-propyltri- (m) ethoxysilane.
  • alkoxysilanes (C) of the general formula (I) mentioned can of course also be used to prepare the hardener (A) used in the use according to the invention.
  • mixtures of alkoxysilanes (C) which contain the same functional group Q which is reactive towards isocyanate groups but different hydrolyzable groups X are possible.
  • the polyisocyanate component (B) is modified with alkoxysilanes (C) in a molar NCO / Q ratio of 1: 0.01 to 0.75, preferably in a molar NCO / Q ratio of 1: 0.05 to 0. 4, where Q has the meaning given in the general formula (I).
  • Polyhydroxyl compounds such as, for example, trifunctional and / or tetrafunctional alcohols and / or the like, are suitable as coating resins (D) which are reactive toward isocyanate groups Suitable polyether polyols, polyester polyols, polycarbonate polyols and / or polyacrylate polyols.
  • lacquer binders or lacquer binder components with groups that are reactive toward isocyanates as hydroxyl groups are also suitable as reactants (D) for the hardener (A) used in the use according to the invention.
  • reactants (D) include, for example, polyurethanes or polyureas, which can be crosslinked with polyisocyanates due to the active hydrogen atoms present in the urethane or urea groups.
  • Suitable reactants (D) are, for example, polyamines whose amino groups are blocked, such as e.g.
  • Preferred coating resins (D) are polyacrylate polyols and polyester polyols.
  • the polyisocyanate and / or binder components are generally used in a form diluted with solvents.
  • solvents are, for example, butyl acetate, ethyl acetate, 1-methoxy-2-propyl acetate, toluene, 2-butanone, xylene, 1,4-dioxane, diacetone alcohol, N-methylpyrrolidone,
  • Dimethylacetamide Dimethylfor amid, Dimethylsulfoxid or any mixture of such solvents.
  • Preferred solvents are butyl acetate, ethyl acetate and diaceto alcohol.
  • the solvent-containing 2-component PU binder used according to the invention can optionally be added as further components, the auxiliaries customary in coating technology.
  • auxiliaries are all additives known for the production of lacquers and paints, such as, for example, inorganic or organic pigments, light stabilizers, lacquer additives, such as dispersing, leveling, thickening, defoaming and other auxiliaries, adhesives, fungicides, bactericides, stabilizers. catalysts or inhibitors and catalysts.
  • auxiliaries are all additives known for the production of lacquers and paints, such as, for example, inorganic or organic pigments, light stabilizers, lacquer additives, such as dispersing, leveling, thickening, defoaming and other auxiliaries, adhesives, fungicides, bactericides, stabilizers. catalysts or inhibitors and catalysts.
  • several of the auxiliaries mentioned can also be added.
  • the 2-component PUR binder used according to the invention is applied to a substrate by the application methods customary in coating technology, such as Spraying, flooding, diving, spinning or knife coating.
  • polymeric substrates such as e.g. ABS, polyamide or polyurethane, metals, which may optionally have an organic coating, or also glass.
  • the 2-component PUR binder used according to the invention as an adhesion promoter is particularly suitable for transparent polymeric substrates, for example for thermoplastic polymers such as polycarbonates, polymethyl methacrylates, polystyrene, polyvinylcyclohexane and its copolymers or polyvinyl chloride or their blends.
  • thermoplastic polymers such as polycarbonates, polymethyl methacrylates, polystyrene, polyvinylcyclohexane and its copolymers or polyvinyl chloride or their blends.
  • inorganic coatings such as, for example, purely inorganic paint systems or also organically modified inorganic paint systems or else layers deposited by a plasma process (for example Al 2 O 3 , ⁇ O 2 , SiO x ,
  • TiC etc. can be applied.
  • Such monomer units are, for example, tetraalkoxysilanes such as tetra (m) ethoxysilane or metal alkoxides such as aluminum, titanium or zirconium alkoxide.
  • inorganic coating systems can of course also contain inorganic filler articles, for example SiO 2 , Al 2 O 3 or A1OOH.
  • Organically modified inorganic coating systems include e.g. to understand such coatings produced by the sol-gel process, which are built up from monomer units, which ask organic groups, which remain as constituents in the forming network. These organic groups can be functional or non-functional.
  • Monomer building blocks with non-functional organic groups are e.g. alkylalkoxysilanes, such as, for example, methyltri (m) ethoxysilane, arylalkoxysilanes or phenyltri (m) ethoxysilane, and also carbosilane compounds, such as those e.g. in US-A 5 679 755, US-A 5 677410, US-A 6 005 131, US-A 5 880305 or in EP-A 947 520.
  • alkylalkoxysilanes such as, for example, methyltri (m) ethoxysilane, arylalkoxysilanes or phenyltri (m) ethoxysilane
  • carbosilane compounds such as those e.g. in US-A 5 679 755, US-A 5 677410, US-A 6 005 131, US-A 5 880305 or in EP-A 947 520.
  • Monomer building blocks with functional organic groups are e.g. alkoxy silanes containing vinyl, acrylic or else methacrylic groups, such as vinyl tri (m) ethoxysilane, acryloxypropyl tri (m) ethoxysilane or methacryloxypropyl tri (m) ethoxysilane, and also epoxy-functional alkoxysilanes, for example glycidyloxypropyl tri (m) ethoxysilane, or also NCO-functional alkoxysilanes such as
  • organic groups are also to be understood as meaning those which do not necessarily serve for the establishment of an organic crosslink, such as, for example, halogens, acid groups, alcohol or thiol groups.
  • Suitable organic coatings are, for example, polyurethane or melamine resin crosslinking systems or alkyd resin coating systems.
  • inorganic-organic hybrid coatings are also preferred. These are characterized by the fact that they have both an organic polymer system and an inorganic polymer system which are present side by side or linked.
  • Possible inorganic-organic hybrid coatings are, for example, those in which an organic polymer matrix is modified by adding or incorporating inorganic building blocks.
  • Inorganic building blocks can be, for example, silica sol dispersions in water or in organic solvents and / or hydrolyzates of (organofunctional) alkoxysilanes.
  • a particularly high abrasion resistance and scratch resistance as well as a very good resistance to solvents are achieved if a coating system based on organofunctional alkoxysilanes and / or siloxanes is applied to the polymeric substrate coated with the adhesion promoter used according to the invention.
  • a well-known method for producing such paint binders is the sol-gel process, as described by CJ Blinker and W. Scherer in “Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing, Academic Press, New York (1990) is described in detail. Suitable sol-gel coatings with high mechanical resistance are state of the art and are described, for example, in US Pat. No. 4,624,870, US Pat. No. 3,986,997, US Pat. No.
  • Polymer substrates can thus be effectively protected against mechanical damage and / or against environmental influences such as UV light and / or contamination.
  • a polycarbonate sheet which is coated with the 2-component PU binder used according to the invention as an adhesion promoter and an inorganic coating which has been organically modified and prepared in accordance with the teaching of EP-A 947 520 (example 14) can be effective against mechanical damage and against radiation damage to be protected.
  • the protective effect remains intact even after intensive weathering.
  • a polycarbonate plate coated with the described coating structure can be exposed to boiling demineralized water for several days without a loss of adhesion or an optical change being discernible. After 1000 hours of weathering in a UV-A test with an intensity of 1.35 W / m 2 (ASTM G 154-97, cycle 4), no optical change can be observed on the substrate, on the primer or on the inorganic coating.
  • the 2-component PU binder used according to the invention can be dried and hardened between the ambient temperature and the softening temperature of the polymeric substrate.
  • the curing temperature range is preferably between 20 ° C and 130 ° C (Makrolon ® , Bayer AG, Leverkusen, or Lexan ® , GE Plastics, USA) or 20 to 160 ° C for Apec HT ® (Bayer AG, Leverkusen) with a curing time between 1 minute and 60 minutes.
  • the curing temperature range for Makrolon® is particularly preferably between 100 ° C and 130 ° C and for Apec HT® between 100 ° C and 160 ° C with a curing time between 30 and 60 minutes.
  • the application and curing conditions of the inorganic coatings depend on the respective binder system.
  • PUR binders and the organically modified, inorganic coating can be applied and hardened one after the other. Wet-on-wet application is also possible, followed by a single hardening in the above-mentioned temperature and time interval. For special applications, curing at ambient temperature may also be sufficient.
  • N- (3-Trimethoxysilylpropyl) aspartic acid diethyl ester is produced, according to the teaching of US Pat. No. 5,364,955, Example 5, by reacting equimolar amounts of 3-aminopropyltrimethoxysilane with maleic acid diethyl ester.
  • Example 2 The same procedure as in Example 2. Table 1 shows the polyisocyanate and alkoxysilane used in the amounts used. The resulting NCO content of the addition product is given in%.
  • IPDI isocyanurate
  • Alkoxysilane 1 N- (3-trimethoxysilylpropyl) aspartic acid diethyl ester from Example 1
  • Alkoxysilane 2 N-butyl-3-amino ⁇ ropyltrimethoxysilane, (Dynasilan® 1189, Degussa-Hüls AG)
  • Alkoxysilane 3 bis (trimethoxysilylpropyl) amine, (Silquest A-l 170, Fa. Wite)
  • Alkoxysilane 4 N-methyl-3-aminopropyltrimethoxysilane, (Dynasilan® 1110, from Degussa-Hüls AG)
  • Alkoxysilane 5 3-mercaptopropyltrimethoxysilane, (Dynasilan® NTNS, from Degussa-Hüls AG) Table 1: Examples 3 to 20
  • Suitable polyols and auxiliaries for the 2-component PU binders used according to the invention are listed in Table 2.
  • Components B1 to B5 are produced by combining the individual components listed in Table 2 in any order and then mixing them at room temperature.
  • Polyol I trimethylol propane
  • Polyol 2 Desmophen® 670 (Bayer AG, Leverkusen), which contains a commercially available, weakly branched, hydroxyl-containing polyester 80% in BA with a hydroxyl content of 3.5%, an acid number of 2 mg KOH / g and a viscosity of 2800 mPas (23 ° C)
  • Polyol 3 Desmophen® 800 (Bayer AG, Leverkusen), which is a commercially available, highly branched, hydroxyl-containing polyester, solvent-free with a hydroxyl content of 8.6%, an acid number of 4 mg KOH / g and a viscosity of 850 mPas ( 23 ° C, 70% MPA)
  • Polyol 4 Desmophen® VPLS 2249/1 (Bayer AG, Leverkusen), which is a commercially available, branched, short-chain, solvent-free polyester with a hydroxyl content of 16%, an acid number of 2 mg KOH / g and a viscosity of 1900 mPas (23 ° C) represents.
  • a silicon-modified polyisocyanate from Table 1 is combined with one of the polyol mixtures B 1 to B 5 from Table 2 and mixed in an NCO: OH ratio of 1.2: 1.
  • the 2-component PUR binder used according to the invention is ready for application.
  • Corresponding combinations of the polyol mixture B1 to B5 and the silicon-modified polyisocyanates from Table 1 are possible.
  • Table 3 contains, by way of example, the production of 2-component PU binders used according to the invention for all possible combinations resulting from Table 1 and Table 2.
  • the 2-component PU binder used according to the invention as an adhesion promoter is coated on a steel sheet coated with a commercially available adhesion promoter (Sigma Universal Primer® 7417, Sigmakalan, NL) and epoxy corrosion protection lacquer (Sigma Multiguard®, Fa. Sigakalan, NL) Example 28 applied in a dry layer thickness of about 15 microns and dried for 24 hours at room temperature.
  • a commercially available adhesion promoter Sigma Universal Primer® 7417, Sigmakalan, NL
  • epoxy corrosion protection lacquer Sigma Multiguard®, Fa. Sigakalan, NL
  • An organically modified inorganic lacquer which is composed of 64.6% by weight of an ethoxy-functional siloxane, is produced on the adhesion promoter. according to Example 2 in WO 98/52992, 12.9% by weight of a 50% dispersion of a polycondensation product of tetraethoxysilane in n-butanol, 15.5% by weight of an ⁇ , ⁇ -hydroxy-functional polydimethylsiloxane with an OH content of approx. 6%, 1.3% by weight of 3-mercaptopropyltriethoxysilane and 5.7% by weight of an approx. 2% solution of para-toluenesulfonic acid in n-butanol, applied in a dry layer thickness of approx. 40 ⁇ m and also dried for 24 hours at room temperature.
  • the resulting protective coating shows very good adhesion to the polymeric substrate. It is weather-resistant and provides effective protection against dirt.
  • the coating is not wetted by a permanent marker from Edding (Edding ® 850). The marker can be removed 24 hours after application with a cloth without the use of cleaning agents.
  • Example 30 The same procedure as in Example 30. However, the 2-component PU binder from Example 23 used as an adhesion promoter according to the invention in Table 3 was spun on in a layer thickness of approximately 0.2 ⁇ m Comparative example 1
  • Ratio of 1.2 1 100 g of polyol component B 2 from Table 2 with 5.1 g of a 75% solution in butyl acetate of an HDI biuret with an average ⁇ CO content of 16.5% and a ⁇ CO functionality of 3 , 8 and a viscosity of 160 mPas (23 ° C) and spun in a layer thickness of approx. 0.2 ⁇ m.
  • Table 4 shows that the 2-component PU binder used according to the invention as an adhesion promoter leads to good adhesion and excellent weathering stability of the organically modified, inorganic coatings on polymers Substrates such as polycarbonate, polymethyl methacrylate or polyurethane leads. 3-aminopropyltrimethoxysilane, a primer for polycarbonate known from the prior art, leads to complete detachment when stored in demineralized water. Adhesion promoters based on polyisocyanates not modified according to the invention either do not have sufficient basic adhesion or show a significantly lower resistance to weathering / water storage than the adhesion promoters according to the invention.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Paints Or Removers (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

L'invention concerne l'utilisation comme agents adhésifs, de liants polyuréthane à deux composants à base de solvant, qui contiennent un composant durcisseur à base d'un produit d'addition d'un polyisocyanate avec un alcoxysilane et une résine pour vernis réagissant vis-à-vis de groupes isocyanate.
EP02708272A 2001-01-24 2002-01-11 Liant polyurethane a deux composants utilise comme agent adhesif Withdrawn EP1356004A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10103027 2001-01-24
DE10103027A DE10103027A1 (de) 2001-01-24 2001-01-24 Zweikomponenten-Polyurethan-Bindemittel als Haftvermittler
PCT/EP2002/000205 WO2002059224A1 (fr) 2001-01-24 2002-01-11 Liant polyurethane a deux composants utilise comme agent adhesif

Publications (1)

Publication Number Publication Date
EP1356004A1 true EP1356004A1 (fr) 2003-10-29

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Application Number Title Priority Date Filing Date
EP02708272A Withdrawn EP1356004A1 (fr) 2001-01-24 2002-01-11 Liant polyurethane a deux composants utilise comme agent adhesif

Country Status (14)

Country Link
US (1) US6756464B2 (fr)
EP (1) EP1356004A1 (fr)
JP (1) JP2004525213A (fr)
KR (1) KR20040030494A (fr)
CN (1) CN1243808C (fr)
CA (1) CA2435430C (fr)
CZ (1) CZ20032033A3 (fr)
DE (1) DE10103027A1 (fr)
HK (1) HK1064697A1 (fr)
HU (1) HUP0302795A3 (fr)
MX (1) MXPA03006536A (fr)
PL (1) PL205153B1 (fr)
SK (1) SK9182003A3 (fr)
WO (1) WO2002059224A1 (fr)

Families Citing this family (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10103026A1 (de) * 2001-01-24 2002-07-25 Bayer Ag Schutzüberzug mit zweischichtigem Beschichtungsaufbau
EP1502927A1 (fr) * 2003-07-31 2005-02-02 Sika Technology AG Composition pour couche primaire, exempte d'isocyanate, pour verre et vitrocéramiques
US20050238899A1 (en) * 2004-04-27 2005-10-27 Isao Nagata High solids clearcoat compositions containing silane functional compounds
DE102004050746A1 (de) * 2004-10-19 2006-04-20 Basf Coatings Ag Hochkratzfeste und hochelastische Beschichtungsmittel auf Basis von Alkoxysilan-funktionellen Komponenten
DE102006006656A1 (de) * 2005-08-26 2007-03-01 Degussa Ag Silan enthaltendes Bindemittel für Verbundwerkstoffe
CN101096472A (zh) * 2006-06-26 2008-01-02 上海飞凯光电材料有限公司 辐射固化材料粘接性能促进剂
US9353287B2 (en) 2006-12-19 2016-05-31 Basf Coatings Gmbh Coating agents having high scratch resistance and weathering stability
CN101050223B (zh) * 2007-05-14 2010-12-01 张群朝 含硅烷或功能聚硅氧烷改性的异氰酸酯类三聚体及其制备方法
DE102007061854A1 (de) 2007-12-19 2009-06-25 Basf Coatings Ag Beschichtungsmittel mit hoher Kratzbeständigkeit und Witterungsstabilität
DE102007061856A1 (de) 2007-12-19 2009-06-25 Basf Coatings Ag Beschichtungsmittel mit hoher Kratzbeständigkeit und Witterungsstabilität
DE102007061855A1 (de) 2007-12-19 2009-06-25 Basf Coatings Ag Beschichtungsmittel mit hoher Kratzbeständigkeit und Witterungsstabilität
US20100266855A1 (en) * 2007-12-27 2010-10-21 E. I. Du Pont De Nemours And Company Adhesion-promoting agent for protective coatings
DE102008030304A1 (de) * 2008-06-25 2009-12-31 Basf Coatings Ag Verwendung teilsilanisierter Verbindungen auf Polyisocyanatbasis als Vernetzungsmittel in Beschichtungszusammensetzungen und Beschichtungszusammensetzung enthaltend die Verbindungen
DE102008050916A1 (de) * 2008-10-10 2010-04-15 Basf Coatings Ag Zweikomponenten-Polyurethan-Lack enthaltend silanisierte Polyisocyanathärter, Verfahren zur Herstellung von silanisierten Polyisocyanathärtern und nach dem Verfahren hergestellte Härter
DE102010005994B4 (de) * 2010-01-27 2022-07-28 Tianjin Shenglong Fibre Co., Ltd. Verfahren zur Hestellung eines Hybrid-Polsterelements, insbesondere eines Sitz- und Lehnenpolsterelements zur Verwendung in einem Kraftfahrzeug, ein Polsterelement und ein Fahrzeugsitz mit einem Polsterelement.
US8133964B2 (en) * 2010-06-29 2012-03-13 Science Applications International Corporation Single-component coating having alkoxysilane-terminated N-substituted urea resins
CN102416373B (zh) * 2011-09-22 2014-03-12 东莞广泽汽车饰件有限公司 一种塑胶基材的表面高光涂装工艺
EP2602109A3 (fr) 2011-12-06 2013-07-10 Alporit AG Corps composite en mousse polymère de styrène
ES2733959T3 (es) * 2012-09-04 2019-12-03 Covestro Deutschland Ag Aglutinantes con funcionalidad silano con estructura de tiouretano
EP2871194B1 (fr) 2013-11-12 2016-08-03 nolax AG Colle à deux composants
KR101688938B1 (ko) * 2014-09-29 2016-12-23 한경대학교 산학협력단 인을 포함하는 환경친화형 난연성 폴리우레탄수지의 제조방법
WO2016064481A1 (fr) * 2014-10-22 2016-04-28 The Government Of The United States Of America, As Represented By The Secretary Of The Navy Revêtements à base de siloxane en deux composants contenant des polymères à liaisons urée et terminaisons alcoxysilane
US10190020B2 (en) 2014-10-22 2019-01-29 The United States Of America, As Represented By The Secretary Of The Navy Siloxane-based coatings containing polymers with urea linkages and terminal alkoxysilanes
KR102555281B1 (ko) * 2015-09-09 2023-07-14 코베스트로 도이칠란트 아게 스크래치-내성 2-성분 폴리우레탄 코팅
ES2870027T3 (es) 2015-09-09 2021-10-26 Covestro Intellectual Property Gmbh & Co Kg Recubrimientos acuosos de PU 2C resistentes a arañazos
FR3054837B1 (fr) * 2016-08-08 2020-06-19 Bostik Sa Procede de synthese de polyurethanes silyles et composition de polyurethanes silyles
EP3505549A1 (fr) * 2017-12-28 2019-07-03 Covestro Deutschland AG Composés polyurées modifiés par un silane à base des polyisocyanates comportant des groupes isocyanurate et des groupes allophanate
WO2019212625A1 (fr) * 2018-04-30 2019-11-07 Dow Global Technologies Llc Compositions adhésives à deux constituants à base de silanes à terminaison isocyanate, et procédés de fabrication associés
EP3760658A1 (fr) * 2019-07-03 2021-01-06 Covestro Deutschland AG Revêtements 2k pur résistants
CN111363460B (zh) * 2020-03-18 2021-11-26 深圳飞扬骏研新材料股份有限公司 喷涂用环保免烘烤罩光清漆、制备方法及固化材料
CN118401616A (zh) * 2020-12-17 2024-07-26 阿克佐 诺贝尔国际涂料股份有限公司 用于聚碳酸酯基材的多层涂层体系
CN114479626B (zh) * 2022-01-26 2023-07-07 广州市捷晟智谷颜料有限公司 一种涂料组合物

Family Cites Families (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1954093C3 (de) 1968-11-15 1978-12-21 Mobay Chemical Corp., Pittsburgh, Pa. (V.St.A.) Verfahren zur Herstellung von polymeren organischen Isocyanaten
BE790977A (fr) 1971-11-06 1973-05-07 Bayer Ag Procede de preparation de produits de poly-addition silicies
NL7408473A (fr) 1973-06-27 1974-12-31
US3979344A (en) 1974-11-19 1976-09-07 Inmont Corporation Vulcanizable silicon terminated polyurethane polymer composition having improved cure speed
DE2641380C2 (de) 1976-09-15 1989-11-23 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von Polyisocyanaten mit Isocyanuratstruktur
DE2845514A1 (de) * 1978-10-19 1980-04-30 Bayer Ag Isocyanatgemisch und seine verwendung als bindemittel in einkomponenten-lacken
DE2914427A1 (de) 1979-04-10 1980-10-23 Bayer Ag Beschichtung fuer thermoplasten
DE3119151A1 (de) * 1981-05-14 1982-12-02 Bayer Ag, 5090 Leverkusen Verfahren zur splittersicheren beschichtung von glasoberflaechen
DE3220866A1 (de) 1982-06-03 1983-12-08 Dynamit Nobel Ag, 5210 Troisdorf Vernetzbare harzmischungen
US4625012A (en) 1985-08-26 1986-11-25 Essex Specialty Products, Inc. Moisture curable polyurethane polymers
JPH0784574B2 (ja) * 1986-04-22 1995-09-13 ナトコペイント株式会社 塗料組成物
IL84025A0 (en) 1986-10-03 1988-02-29 Ppg Industries Inc Organosiloxane/metal oxide coating compositions and their production
DE3700209A1 (de) 1987-01-07 1988-07-21 Bayer Ag Verfahren zur herstellung von polyisocyanaten mit biuretstruktur
DE3811350A1 (de) 1988-04-02 1989-10-19 Bayer Ag Verfahren zur herstellung von isocyanuratpolyisocyanaten, die nach diesem verfahren erhaltenen verbindungen und ihre verwendung
DE3814167A1 (de) 1988-04-27 1989-11-09 Bayer Ag Verfahren zur herstellung von isocyanuratgruppen aufweisenden polyisocyanaten und ihre verwendung
JP2772002B2 (ja) 1988-11-28 1998-07-02 サンスター技研株式会社 プライマー組成物
DE3900053A1 (de) 1989-01-03 1990-07-12 Bayer Ag Verfahren zur herstellung von uretdion- und isocyanuratgruppen aufweisenden polyisocyanaten, die nach diesem verfahren erhaeltlichen polyisocyanate und ihre verwendung in zweikomponenten-polyurethanlacken
DE3928503A1 (de) 1989-08-29 1991-03-07 Bayer Ag Verfahren zur herstellung von loesungen von isocyanuratgruppen aufweisenden polyisocyanaten in lackloesungsmitteln und ihre verwendung
EP0489688B1 (fr) 1990-12-04 1996-03-06 Ciba-Geigy Ag Agent de couplage
JPH04239537A (ja) * 1991-01-23 1992-08-27 Nissan Motor Co Ltd 耐擦傷性を向上させた透明樹脂基板
DE4234325A1 (de) 1992-10-12 1994-04-14 Basf Magnetics Gmbh Magnetische Aufzeichnungsträger
DE4338361A1 (de) 1993-11-10 1995-05-11 Inst Neue Mat Gemein Gmbh Verfahren zur Herstellung von Zusammensetzungen auf der Basis von Epoxidgruppen-haltigen Silanen
DE19517838A1 (de) 1995-05-16 1996-11-21 Bayer Ag Carbosilan-Dendrimere, ein Verfahren zur Herstellung und deren Verwendung
US5677410A (en) 1995-05-16 1997-10-14 Bayer Ag Carbosilane-dendrimers, carbosilane-hybrid materials, methods for manufacturing them and a method for manufacturing coatings from the carbosilane-dendrimers
US5700868A (en) * 1995-07-25 1997-12-23 Dainichiseika Color & Chemicals Mfg. Co., Ltd. Back-side coating formulations for heat-sensitive recording materials and heat-sensitive recording materials having a back layer coated therewith
US6005131A (en) 1996-01-30 1999-12-21 Bayer Aktiengesellschaft Multi-functional, cyclic organosiloxanes, process for the production thereof and use thereof
DE19611849A1 (de) 1996-03-26 1997-10-02 Bayer Ag Neue Isocyanattrimerisate und Isocyanattrimerisatmischungen, deren Herstellung und Verwendung
CA2219610A1 (fr) * 1996-11-18 1998-05-18 Takeda Chemical Industries, Ltd. Composition d'appret
DE19711650C1 (de) 1997-03-20 1998-06-10 Bayer Ag Verfahren zur Herstellung SiOH-funktioneller Carbosilan-Dendrimere
DE19715427A1 (de) 1997-04-14 1998-10-15 Bayer Ag Wäßrige 2-Komponenten Bindemittel und deren Verwendung
DE19814060A1 (de) 1998-03-30 1999-10-07 Bayer Ag Borhaltige Mischungen, Hybridmaterialien und Beschichtungen
DE19818998B4 (de) 1998-04-28 2008-12-24 Giesecke & Devrient Gmbh Verfahren zum Schutz vor Angriffen auf den Authentifizierungsalgorithmus bzw. den Geheimschlüssel einer Chipkarte
WO2001098393A1 (fr) * 2000-06-22 2001-12-27 Basf Corporation Compositions de revetement pourvues d'une adherence amelioree a des substrats d'aluminum

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO02059224A1 *

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CN1243808C (zh) 2006-03-01
CA2435430A1 (fr) 2002-08-01
HK1064697A1 (en) 2005-02-04
MXPA03006536A (es) 2004-06-25
US20020142169A1 (en) 2002-10-03
WO2002059224A1 (fr) 2002-08-01
PL361766A1 (en) 2004-10-04
PL205153B1 (pl) 2010-03-31
CZ20032033A3 (cs) 2003-10-15
CN1487982A (zh) 2004-04-07
DE10103027A1 (de) 2002-07-25
SK9182003A3 (en) 2003-11-04
US6756464B2 (en) 2004-06-29
CA2435430C (fr) 2011-12-13

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