EP0482031A1 - Procede d'enduction - Google Patents

Procede d'enduction

Info

Publication number
EP0482031A1
EP0482031A1 EP90910121A EP90910121A EP0482031A1 EP 0482031 A1 EP0482031 A1 EP 0482031A1 EP 90910121 A EP90910121 A EP 90910121A EP 90910121 A EP90910121 A EP 90910121A EP 0482031 A1 EP0482031 A1 EP 0482031A1
Authority
EP
European Patent Office
Prior art keywords
component
acid
mixture
group
cyclic
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Withdrawn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
EP90910121A
Other languages
German (de)
English (en)
Inventor
Brigitte Hase
Ulrich Eicken
Wolfgang Gress
Norbert Stork
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0482031A1 publication Critical patent/EP0482031A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D177/12—Polyester-amides
    • 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
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/02—Polyamines

Definitions

  • the present invention is in the field of surface coating, and again in the field of low solvent coating of solid surfaces.
  • the invention relates to a method for coating solid surfaces, in which a mixture of a) cyclic polyimino ether with ⁇ 2 -oxazoline or ⁇ 2 -5,6-dihydro-4H-1,3-oxazine structure, b) optionally at least one compound from the group of cyclic monoimino ethers with ⁇ 2 -oxazoline or ⁇ 2 -5,5-dihydro-4H-1,3-oxazine structure or from the group of lactones with 4,5,6 or 7 ring members, c) one Catalyst for the cationic polymerization, and d) optionally auxiliaries and additives customary in coatings is applied to the surfaces and polymerized by heating on the surface.
  • the process according to the invention is suitable for surfaces of a wide variety of materials, such as metal, wood, glass and plastic, provided that they tolerate the temperatures required for the hardening. It leads to closed, smooth coatings, which are characterized by high adhesive strength, hardness and elasticity as well as good gloss. Another advantage over known systems is that the finished polymerizable mixture can be stored for a very long time at room temperature.
  • Suitable cyclic polyimino ethers are compounds which group two or more times in their molecule
  • Z is either a direct bond or the group CR 5 R 6 and the radicals R 1 to R 6 each independently of one another H, alkyl or aryl with up to 8 carbon atoms.
  • Those polyiminoethers in which at least 4 of the radicals R 1 to R 6 are hydrogen atoms and the rest of which consist of C 1 -C 3 -alkyl are preferred.
  • I represents a 2- ⁇ 2 oxazoline group, ie Z represents a direct bond. Of these in turn, those with the following substitution patterns are particularly preferred:
  • R 3 CH 3 , C 2 H 5 or phenyl
  • R 1 , R 2 and R 4 H
  • Polyiminoethers in which all of the radicals R 1 to R 6 are hydrogen are very particularly preferred.
  • the cyclic polyimonoethers used preferably contain group I 2, 3 or 4 times and are also used as bis, tris and tetrakis oxazolines or bis, tris and tetrakis (5,6-dihydro-4H-1,3-oxazines) designated. Bisiminoethers are particularly preferred.
  • Cyclic polyiminoethers suitable according to the invention are known per se. They are usually prepared from di- or polycarboxylic acids or their derivatives and correspondingly substituted alkanolamines or equivalent reaction partners by cyclizing condensation, analogously to the production of cyclic monoiminoethers from monocarboxylic acids and their derivatives. Examples of suitable polyiminoethers and their preparation can be found, for example, in DE 2029 524, DE-OS 2 158615, DE-OS 3047 759 and EP-OS 273368. Typical representatives are tetramethylene bisoxazoline; called p-phenylenebisoxazoline and 1,4-cyclohexylenebis (5,6-di-hydro-4H-1,3-oxazine).
  • cyclic polyiminoethers Another way of producing cyclic polyiminoethers is based on cyclic monoiminoethers which contain group I only once and carry a reactive group on the substituent in the 2-position.
  • monoiminoethers are also known per se and are generally obtainable by conventional methods from monocarboxylic acids or their derivatives (see, for example, A. Levy and M. Litt, J. Polym. Sei AI, 6.1883 (1968); S. Kobayashi and T. Saegusa in Ring-Opening Polymerization Vol. 2, Ed. KJ Irvin, T. Saegusa, London 1984, p. 761; and
  • Di- and polyiminoethers according to PCT / EP90 / 00733 are particularly preferred for the process according to the invention, these polyiminoethers, depending on the preparation, also containing small amounts of free or blocked polyisocyanate.
  • these polyiminoethers arise only in the coating process from monoiminoethers containing hydroxyl groups and the necessary amounts of polyisocyanate, but this would mean handling the toxicologically unsafe polyisocyanates, which can be avoided in the manner described above.
  • the mixtures used according to the invention can contain compounds from the group of the cyclic monoiminoethers, from the group of the lactones or mixtures of both.
  • Suitable monoimino ethers are substituted ⁇ 2 -O ⁇ azolines and ⁇ 2 -Oxazines, which are also more precisely referred to as 5,6-dihydro-4H-1,3-oxazines. They correspond to Formula II:
  • Z represents a direct bond or the group CR ⁇ R ⁇ and R 1 - R 6 have the meaning given above for the formula I, with, of course, in the polyiminoethers (a) and the monoiminoethers (b) Z and R 1 to R 6 can be chosen independently within the scope of the terms.
  • R represents a carbon-bonded aliphatic, aromatic or araliphatic radical having 1 to 21 carbon atoms, preferably 6 to 17 carbon atoms, which may contain ether groups and can carry further substituents that do not interfere with the polymerization reaction.
  • Monoimino ethers in which at least 4 of the radicals R 1 to R 6 are hydrogen atoms and the rest of which consist of C 1 -C 3 -alkyl are preferred. Also preferred are the compounds in which Z is a direct bond. Of these in turn, those with the following substitution patterns are particularly preferred:
  • Monoiminoethers in which all of the radicals R 1 to R 6 are hydrogen are very particularly preferred.
  • the monoiminoethers of the formula II which are suitable according to the invention are known per se and by customary processes, primarily from monocarboxylic acids or their derivatives and corresponding alkanolamines or equivalent compounds by cyclizing condensation , producible. With regard to the details, reference is made to the literature cited above for a) for monoimino ethers.
  • lactones with a 4-membered, 5-membered, 6-membered or 7-membered ring are suitable as component b.
  • the unsubstituted compounds butyrolactone, valerolactone and caprolactone are particularly preferred, but these lactones can optionally also be substituted, preferably by alkyl groups having 1 to 3 carbon atoms.
  • the molar ratio of components a and b and the valency of a largely determine the curing rate in the polymerization reaction and also the mechanical properties of the coating produced.
  • Components a and b are therefore preferably in the equivalent ratio of 95: 5 to 5:95, in particular 80:20 to 20:80, the equivalent weight here being understood to mean the molecular weight divided by the number of imino ether groups present in the molecule (valence) .
  • Suitable catalysts for the polymers of components a and b are generally all catalysts which can trigger a cationic polymerization and which are also known for the polymerization of cyclic iminoethers, for example from DE 12 06 585. These are generally Lewis or Bronsted acids or alkylating agents which can form salt-like compounds with the imino ethers, and these salt-like compounds themselves. Examples include methyl trifluoromethanesulfonate, ortho- and para-toluenesulfonic acid and N-methyl 2-phenyl-oxazolinium trifluoromethanesulfonate called.
  • cationic polymerization of cyclic iminoethers is a so-called living polymer which can in principle be continued at any time at the chain ends by adding further monomers, such "still living” polymers, which can be prepared from component b alone, are also suitable as catalysts for the method according to the invention.
  • coatings of excellent quality can be produced from components a and c or a, b and c alone, the choice of the individual components and their quantities also making it possible to vary individual properties of the coatings, in particular the elasticity, within wide limits.
  • the properties of the mixture to be processed and the finished coating can also be varied by further additives.
  • all auxiliaries and fillers can be used here as additives, as are known for conventional lacquers and paints, for example dyes, pigments, thickeners, light stabilizers, solvents, plasticizers, resins and other binders.
  • resins and other binders as are common in paint technology, the exposure properties can be adapted to the requirements of the substrate and the intended protective function to an even greater extent.
  • resins and binders are polyacrylate, polyester, chlorinated rubber, alkyd resin, polyurethane and polymeric imino ethers (linear polymer of monoimino ethers of the formula II).
  • the amount of resins and binders added depends on the desired effect and can be freely selected within wide limits.
  • Thickeners and solvents serve primarily to adjust the rheological properties of the mixture to be polymerized when it is liquid.
  • Suitable organic solvents are especially aromatic hydrocarbons and chlorinated hydrocarbons. Solvents which evaporate below the curing temperature are preferably used.
  • binders Their share in the total mixture is usually not more than 50% by weight, preferably between 1 and 20% by weight, but it is particularly preferred to work entirely without organic solvents.
  • Both low molecular weight substances such as modified, hardened fats, and polymeric compounds, for example polyester, are suitable as thickeners.
  • the transition from polymeric thickeners to the paint components commonly referred to as binders is fluid.
  • the color and transparency of the coatings can be changed as desired by adding dyes, pigments and fillers. While the polymers from a or a and b alone result in transparent and practically colorless top layers, these additives can be used to produce highly opaque lacquers or transparent glazes. The amount used depends on the desired effect.
  • auxiliaries and additives it is of course important to ensure that there is no disruption to the polymerization of components a and b.
  • substances with a basic action cannot generally be used.
  • the amount of auxiliaries and additives in the mixture to be polymerized can be chosen to be quite high without the advantages of the process according to the invention being lost.
  • the total content of component d is preferably not more than 70% by weight, in particular not more than 50% by weight, based on the total mixture of components a, b, c and d.
  • the lower limit depends on the desired effect and can , for example with dyes, 0.001 wt .-% and below.
  • an intimate mixture of components a, b and c and, if appropriate, d is first prepared.
  • the order of addition is arbitrary. In general, this mixture can be kept at room temperature for several days to several weeks, so that it is not necessary to mix the components immediately before use.
  • mixtures which are liquid at room temperature or at a slightly elevated temperature so that they can be applied to the surface using the customary application techniques for liquid lacquers, for example by brushing, spraying or dipping.
  • mixtures of solid components to the surface using powder coating technology, for example by electrostatic processes.
  • the application of the components a - d to the surfaces is followed by a heat treatment, since the curing of the mixture at room temperature generally takes too long for a practical application.
  • the necessary tempera Tures and hardening times can be varied within wide limits primarily by the amount of component c, but also depend on the reactivity and concentration of components a and b.
  • Temperatures between approximately 80 and approximately 250 ° C. and polymerization times between approximately 5 and approximately 120 minutes can serve as guidelines. The choice of temperature and thus of time naturally also depends on the sensitivity of the substrate and the other coating components. Under certain circumstances, it may be appropriate to carry out the heat treatment under inert gas. Various methods can be used to heat the mixture, for example heating with warm air, heating by radiation, such as infrared or microwave, or contact heating of the surface to be coated from the rear. The choice of the suitable heating process can therefore be determined entirely by external parameters of the process in practice, for example whether the process is carried out continuously or discontinuously.
  • mixtures of components a and c and, if appropriate, b and d were prepared and applied to plates made of different materials using a doctor blade. After heat treatment in a forced-air drying cabinet, the properties of the films obtained were examined using the test methods known in paint technology.
  • the polyiminoethers al-a9 used were prepared according to the earlier patent application PCT / EP90 / 00733 from equivalent amounts of commercially available polyisocyanates and monoiminoethers bearing hydroxyl groups. These monoiminoethers were in turn prepared from hydroxycarboxylic acids or their esters and ethanolamine or 3-aminopropan-1-ol according to the earlier patent applications EP 88 118 090.5 and EP-90 107 481.5. Tetramethylene bisoxazoline (a 15) was obtained according to DOS 2 158 615; m-phenylenebisoxazoline was commercially available (Showa Denko, Tokyo).
  • TXDl (R) 12-hydroxystearic acid isophorone diisocyanate
  • the mixtures to be polymerized contained additives which were thickeners and / or binders: d1 polyester (Grilesta (R) P 7205, EMS-Chemie)
  • d3 rilanite (R) HT modified, hardened fatty acid, Henkel
  • d4-d12 copolymers of monooxazolines according to formula II prepared by cationic polymerization analogously to the information in example part A of PCT / EP90 / 00019. See Table 3 for details.
  • the molecular weights given are weight averages determined by gel chromatography against the polystyrene standard.
  • Table 4 contains the composition of the mixtures used for coating and gives the polymerization conditions.
  • concentration of c in% by weight, based on a + b, and the concentration of d in weight%, based on b, were given. The curing took place in a circulating air drying cabinet.
  • Example 1 component component a b component c component d
  • Example component component a b component c component d
  • Example component component a b component c component d
  • Example component component a b component c component d
  • Example component component a b component c component d
  • the coatings according to Examples 1-78 were examined on steel sheets, aluminum sheets and in some cases on glass for their mechanical properties and for their adhesive strength.
  • the layer thickness was 30-35 ⁇ m in all cases.
  • the pendulum hardness was tested at room temperature in accordance with the regulations of the German standard DIN 53 157, the deepening (reverse) in accordance with the regulations of the US standard ASTM-D 2795-69 and the cross cut in accordance with HJ Peters (in Zeidler-Bleisch, laboratory book for the lacquer - und Anstrichstoff industrie, pp. 309-310, W. Knopp Verlag, Düsseldorf 1967).
  • pendulum hardness and impact depth correspond to greater hardness or better flexibility of the coating.
  • the cross-cut is assessed visually with a rating between 0 (best adhesion) and 4 (poor adhesion). Particularly noteworthy is the excellent adhesion even with films of particularly high hardness.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Des polyiminoéthers cycliques à structure DELTA2-oxazoline ou DELTA2-5,6-dihydro-4H-1,3-oxazine sont appliqués sur des surfaces solides, seuls ou conjointement avec des monoiminoéthers du même type ou avec des lactones, en mélange avec des catalyseurs pour la polymérisation cationique, et polymérisés par chauffage. Il se forme des revêtements lisses et brillants présentant de bonnes propriétés d'adhérence, de dureté et d'élasticité.
EP90910121A 1989-07-21 1990-07-12 Procede d'enduction Withdrawn EP0482031A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3924163A DE3924163A1 (de) 1989-07-21 1989-07-21 Beschichtungsverfahren
DE3924163 1989-07-21

Publications (1)

Publication Number Publication Date
EP0482031A1 true EP0482031A1 (fr) 1992-04-29

Family

ID=6385544

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90910121A Withdrawn EP0482031A1 (fr) 1989-07-21 1990-07-12 Procede d'enduction

Country Status (5)

Country Link
US (1) US5240744A (fr)
EP (1) EP0482031A1 (fr)
JP (1) JPH04506821A (fr)
DE (1) DE3924163A1 (fr)
WO (1) WO1991001354A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4140333A1 (de) * 1991-12-06 1993-06-09 Henkel Kgaa, 4000 Duesseldorf, De Neue cyclische polyiminoether (ii)
DE4403953A1 (de) * 1994-02-08 1995-08-10 Henkel Kgaa Verlaufsmittel für Pulverlacke
US20040067313A1 (en) * 2002-10-03 2004-04-08 Hauser Brian T. Process for applying a coating to untreated metal substrates
DE102011079991A1 (de) 2011-07-28 2012-09-13 Bayer Crop Science Ag Verwendung von Saatgutbehandlungs-Wirkstoffen aus der Gruppe der Nicotinoid-Insektizide als Safener
US9708188B1 (en) * 2016-02-22 2017-07-18 Air Products And Chemicals, Inc. Method for argon production via cold pressure swing adsorption
EP3885387A1 (fr) 2020-03-25 2021-09-29 Covestro Deutschland AG Composés de polyaddition à base de polyisocyanate comportant des éléments structuraux d'iminoéther cyclique à cinq-chaînons

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3373194A (en) * 1965-07-26 1968-03-12 Allied Chem Poly(n-acylethylenimines) from 2-substituted-2-oxazolines
DE1595381B2 (de) * 1966-01-29 1974-11-07 Chemische Werke Huels Ag, 4370 Marl Verfahren zur Polymerisation von Gemischen verschiedener Delta hoch 2 -Oxazoline
FR2174360A6 (en) * 1971-02-03 1973-10-12 Inst Francais Du Petrole Bisoxazoline cpd coating compsns - hardened by irradiation
BE790572A (fr) * 1971-10-27 1973-04-26 Bayer Ag 2,2'-bis- ou 2,2',2''-tris-(5,6-dihydro-4h-1,3-oxazines
DE3036119A1 (de) * 1980-09-25 1982-04-08 Chemische Werke Hüls AG, 4370 Marl Verfahren zur herstellung von 2-isopropyl- und 2n-propyl-(delta)-oxazolin-copolymeren
JPS59229926A (ja) * 1983-06-10 1984-12-24 Mitsubishi Electric Corp 半導体集積回路装置
JPS6090219A (ja) * 1983-10-21 1985-05-21 Takeda Chem Ind Ltd 熱硬化性樹脂の製造法
DE3402280C1 (de) * 1984-01-24 1985-07-25 Dynamit Nobel Ag, 5210 Troisdorf Waermehaertbare Klebstoff- und Dichtungsmassen
EP0273368A3 (fr) * 1986-12-26 1989-09-06 Teijin Limited Procédé de préparation de résines thermodurcissables

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9101354A1 *

Also Published As

Publication number Publication date
WO1991001354A1 (fr) 1991-02-07
JPH04506821A (ja) 1992-11-26
US5240744A (en) 1993-08-31
DE3924163A1 (de) 1991-01-24

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