[go: up one dir, main page]

EP1155062A1 - Agent de revetement et procede permettant de le produire - Google Patents

Agent de revetement et procede permettant de le produire

Info

Publication number
EP1155062A1
EP1155062A1 EP99967921A EP99967921A EP1155062A1 EP 1155062 A1 EP1155062 A1 EP 1155062A1 EP 99967921 A EP99967921 A EP 99967921A EP 99967921 A EP99967921 A EP 99967921A EP 1155062 A1 EP1155062 A1 EP 1155062A1
Authority
EP
European Patent Office
Prior art keywords
ring structure
alkyl
coating composition
composition according
component 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Withdrawn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
EP99967921A
Other languages
German (de)
English (en)
Inventor
Hubert Baumgart
Heinz-Peter Rink
Simone Bitter
Fritz Bartol
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 Coatings GmbH
Original Assignee
BASF Coatings GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF Coatings GmbH filed Critical BASF Coatings GmbH
Publication of EP1155062A1 publication Critical patent/EP1155062A1/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Withdrawn legal-status Critical Current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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C08G18/8093—Compounds containing active methylene groups
    • 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
    • C08G18/8096—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with two or more compounds having only one group containing active hydrogen

Definitions

  • the present invention relates to a scratch-resistant one-component coating agent (IC system) which contains (A) at least one blocked polyisocyanate as crosslinking agent and (B) at least one binder with functional groups which react with isocyanate groups, and the use thereof.
  • IC system which contains (A) at least one blocked polyisocyanate as crosslinking agent and (B) at least one binder with functional groups which react with isocyanate groups, and the use thereof.
  • One-component coating agents - IC systems for short - are coating agents in which the crosslinking agents (A) and the binders (B) are present next to one another and do not react with one another under the storage conditions, but rather only at elevated temperatures.
  • so-called two-component coating agents which contain containers made of two different, separately manufactured and stored paint components that are always traded in conjunction with one another, they do not have to be used by a user who wants to produce a coating from a coating agent before the coating is produced first mixed into the coating agent and then processed as quickly as possible.
  • topcoats is understood to mean lacquers that are used to produce the top lacquer layer.
  • the uppermost lacquer layer can be single-layer or multi-layer, in particular two-layer.
  • Two-coat top coats consist of a pigmented basecoat and an unpigmented clearcoat applied to the basecoat or pigmented only with transparent pigments.
  • Two-coat coatings are now produced using the wet-on-wet process, in which a pigmented basecoat is pre-coated and the basecoat layer thus obtained is overcoated with a clearcoat without a baking step and then the basecoat film and clearcoat film are cured together.
  • the process is economically very advantageous, but places high demands on the basecoat and the clearcoat.
  • the clear lacquer applied to the not yet hardened basecoat must not dissolve or otherwise interfere with the basecoat layer, because otherwise coatings with poor appearance are obtained. This applies in particular to paints in which basecoats containing effect pigments (for example metal pigments, in particular aluminum flakes or pearlescent pigments) are used.
  • Scratch-resistant IC systems which also have good acid resistance, are known from international patent application WO 94/22969.
  • the high scratch resistance and acid resistance results from the use of a combination of 4-hydroxybutyl acrylate and / or methacrylate as well as from special neutral, i.e. H. Hydroxyl-free and acid group-free, olefinically unsaturated monomers, so that these known IK systems cannot be varied as broadly as would be desirable in view of the different requirements of the market.
  • DE 195 05 351 AI describes isocyanurate polyisocyanates suitable for use in 1-component paints, which are prepared by trimerization of 1,3-diisocyanatoalkanes with tran-containing isocyanate groups.
  • the isocyanates described in DE 195 05 351 are known isocyanates whose isocyanate groups are not separated from the ring structure via alkyl or ether groups and are therefore not widely varied in terms of material.
  • the blocked polyisocyanurates known from DE 195 19 396 A1 are suitable as hardener components for compounds containing higher functional OH groups.
  • DE 195 19 396 also does not describe any isocyanates whose isocyanate groups are separated from the ring structure via alkyl or ether groups. This means that these isocyanurates also do not give material variability.
  • DE 196 50 044 AI describes a process for the preparation of oxime-blocked lacquer polyisocyanates which are suitable as hardeners for 1-component polyurethane lacquers however, monoblocked diisocyanates are used in the manufacture. However, these isocyanates are also clearly limited in their variability.
  • the object of the present invention is therefore to propose new scratch-resistant and acid-resistant IC systems which vary widely in terms of material and can therefore be adapted extremely well to the needs of the market without their scratch resistance and acid resistance being affected.
  • the new one-component coating composition which contains (A) at least one blocked polyisocyanate as crosslinking agent and (B) at least one binder with functional groups which react with isocanate groups and which is characterized in that it is in the blocked polyisocyanate ( A) um
  • AI the completely blocked derivative of a polyisocyanate (al) which contains at least one diisocyanate structural unit which
  • A2) the completely blocked derivative of an oligomer (a2) of the polyisocyanate (a1) with 2 to 10 isocyanate units, in particular the completely blocked derivative of a trimer (a2);
  • the new one-component coating composition is referred to below as the "IC system according to the invention".
  • the blocked component of the IK system according to the invention is the blocked polyisocyanate (A).
  • the blocked polyisocyanate (A) to be used according to the invention is the completely blocked derivative of a polyisocyanate (a1).
  • This polyisocyanate (al) which serves as a starting material for the production of the blocked polyisocyanate (AI), has at least one diisocyanate structural unit with a special structure.
  • the polyisocyanate (a1) can have two or more of these diisocyanate structural units, it has proven useful to use only one.
  • the diisocyanate structural unit has the following essential features:
  • both isocyanate groups are connected to the ring structure via linear C 1 -C 9 -alkyl and / or linear C 1 -C 10 -etheralkyl.
  • (al32) one isocyanate group is directly linked and the other isocyanate group is linked to the ring structure via linear C -C 9 alkyl and / or linear C -C 1 o ether alkyl.
  • At least one of the two isocyanate groups is or is via linear C2-C9-alkyl or linear C2-Ci 0-ether alkyl, which two radicals are not benzylic
  • the ring structure can basically be hetero rings. Then the ring structure contains not only C atoms but also different ring atoms, such as N atoms, O atoms or Si atoms. These can be saturated or unsaturated or aromatic hetero rings. Examples of suitable saturated hetero rings are the silacyclopentane, silacyclohexane, oxolane, oxane, dioxane, morpholine, pyrrolidine, imidazolidine, pyrazolidine, piperidine or quinuclidine rings.
  • Suitable unsaturated or aromatic hetero rings are pyrrole, imidazole, pyrazole, pyridine, pyrimidine, pyrazine, pyridazine or triazine rings. It is preferred if the ring structure consists of carbon atoms.
  • the ring structure can be free of bridges.
  • bridges can be included.
  • suitable terpene backbones are caran, norcaran, pinan, camphan or norbonan backbones.
  • the hydrogen atoms of a diisocyanate structural unit in particular the ring structure, can be substituted by groups or atoms which do not react either with isocyanates or with the binder (B) described below.
  • suitable groups are nitro, alkyl, cycloalkyl, perfluoroalkyl, perfluorocycloalkyl or aryl groups.
  • suitable atoms are halogen atoms, in particular fluorine.
  • the ring structure advantageously consists of 6 carbon atoms, in particular in the form of cyclohexane or benzene.
  • linear C 1 -C 9 alkyl examples are methylene or ethylene and tri, tetra, penta-, hexa-, hepta, octa or nonamethylene radicals, in particular methylene radicals.
  • the linear C 2 -C 1 o-ether alkyls are connected either via the oxygen atoms or the contained alkanediyl radicals having the ring structure. They are preferably connected to them via the oxygen atoms.
  • the indices 2 to 10 mean that 2 to 10 carbon atoms are contained in the ether alkylene.
  • the ether alkyls can only contain 1 oxygen atom. According to the invention, it is advantageous if 2 to 10, in particular 2 to 5, oxygen atoms are present in the chain. Then there are 1 or more, but in particular 2, C atoms between 2 oxygen atoms.
  • both isocyanate groups can be moved via -CH2-, preferably at positions 1 and 3 of the
  • the diisocyanate structural unit or the polyisocyanate (al) then has, for example, the formula C6Hg (-CH2-NCO) 2 , in which the isocyanatomethylene radicals are in the 1,3-, 1,2- and 1,4-positions to one another.
  • one of the two isocyanate groups can be bonded directly to a ring atom of a non-aromatic ring system, in particular cyclohexane, and for the second isocyanate group to be via C 9 -C 9 -alkyl, in particular
  • the diisocyanate structural unit or the polyisocyanate (al) then has, for example, the formula CöHg -NCOX ⁇ Hg-NCO), in which the Isocyanate and the isocyanatotrimethylene group are in the 1,2 position to each other.
  • both isocyanate groups can be linked to it via C 2 -C 9 alkyl. It is essential that the alkanediyl radicals contain no benzylic hydrogen atoms, but instead carry substituents R 1 and R 2 which do not react with isocyanates or with the binders (B). Examples of suitable substituents R 1 and R 2 are Ci -Ci Q alkyl, aryl or halogen, preferably - CH 3 .
  • the alkanediyl groups described above are preferably attached to positions 1 and 3 of the benzene ring. In this case, too, it is possible to bind to positions 1,2 and 1,4.
  • the diisocyanate structural unit or the polyisocyanate (al) then has, for example, the formula CöH4 (-C (CH3) 2-C2H4-NCO) 2 , in which the 3-isocyanates-1,1-dimethyl-prop-l-yl-
  • Residues are in the 1,2-, 1,3- and 1,4-position to each other.
  • the two isocyanate groups can, however, also be linked to the unsaturated or aromatic ring system, in particular benzene, via the C 2 -C 10 ether alkyls described above. It is essential according to the invention that the ether alkyls do not carry any benzylic hydrogen atoms. In the event that the ether alkyls are linked to the aromatic ring system via carbon atoms, this can be achieved in that the benzylic carbon atoms carry the substituents R 1 and R 2 described above. If the Ether alkyls are linked to the aromatic ring system via oxygen atoms, there are no benzylic hydrogen atoms, which is why this variant is preferred.
  • one of the two isocyanate groups can be bonded directly to a ring atom of an unsaturated or aromatic ring system, preferably a benzene ring, and for the second isocyanate group to be attached, for example via C 2 -C 9 -alkyl which has no benzylic hydrogen atoms further ring atom, preferably in a 1, 2 configuration, is bound.
  • the diisocanate structural unit or the polyisocyanate (al) then has, for example, the formula C6H4 (-NCO) (- C (CH 3 ) 2 - (CH 2 ) 2 -NCO), in which the
  • an oligomer (a2) of the polyisocyanate (a1) can also be used as a starting material for the preparation of the completely blocked derivative (A2) to be used according to the invention.
  • the oligomers (a2) used for this purpose advantageously have an NCO functionality of 2.0-5.0, preferably 2.2-4.0, in particular 2.5-3.8.
  • the oligomer (a2) is produced from the polyisocyanate (al), with advantageously 2-10 monomer units being reacted and with trimerization being particularly preferred.
  • the oligomerization and trimerization can lead to the formation of uretdione, biuret, isocyanurate, iminooxadiazinedione, urea, urethane and / or allophanate groups with the aid of customary and known suitable catalysts.
  • oligomerization is also possible by reaction with low molecular weight polyols such as trimethylolpropane or homotrimethylolpropane, glycerol, neopentylglycol, dimethylolcyclohexane, ethylene glycol, diethylene glycol, propylene glycol, 2-methyl-2-propylpropanediol-1, 3, 2-ethyl-2-butylpropane diol 3,2,2,4- Trimethylpentanediol-1,5 and 2,2,5-trimethylhexanediol-1,6, which, if necessary, are partially ethoxylated and / or propoxylated or otherwise hydrophilized.
  • polyols such as trimethylolpropane or homotrimethylolpropane, glycerol, neopentylglycol, dimethylolcyclohexane, ethylene glycol, diethylene glycol, propylene glycol, 2-methyl-2-prop
  • the polyisocyanates (a1) and (a2) are reacted with blocking agents in a customary and known manner.
  • blocking agents examples include the blocking agents known from US Pat. No. 4,444,954, such as
  • phenols such as phenol, cresol, xylenol, nitrophenol, chlorophenol,
  • lactams such as ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam or ß-propiolactam
  • active methylenic compounds such as diethyl malonate, dimethyl malonate, ethyl or methyl acetoacetate or acetylacetone;
  • alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, n-amyl alcohol, t-amyl alcohol, lauryl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether,
  • Methoxymethanol glycolic acid, glycolic acid ester, lactic acid, lactic acid ester, methylolurea, methylolmelamine, diacetone alcohol, ethylene chlorohydrin, ethylene bromohydrin, l, 3-dichloro-2-propanol, 1,4-cyclohexyldimethanol or acetocyanhydrin; v) mercaptans such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, t-dodecyl mercaptan, 2-mercaptobenzothiazole, thiophenol,
  • acid amides such as acetoanilide, acetoanisidinamide, acrylamide, methacrylamide, acetic acid amide, stearic acid amide or benzamide;
  • imides such as succinimide, phthalimide or maleimide
  • amines such as diphenylamine, phenylnaphthylamine, xylidine, N-phenylxylidine, carbazole, aniline, naphthylamine, butylamine, dibutylamine or butylphenylamine;
  • imidazoles such as imidazole or 2-ethylimidazole
  • ureas such as urea, thiourea, ethylene urea, ethylene thiourea or 1,3-diphenylurea;
  • xi) carbamates such as phenyl N-phenylcarbamate or 2-oxazolidone
  • imines such as ethyleneimine
  • oximes such as acetone oxime, formal doxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diisobutyl ketoxime, diacetyl monoxime, benzophenone oxime or chlorohexanone oxime;
  • xiv) salts of sulfurous acid such as sodium bisulfite or potassium bisulfite
  • hydroxamic acid esters such as benzyl methacrylohydroxamate (BMH) or allyl methacrylohydroxamate; or xvi) substituted pyrazoles, ketoximes, lnidazoles or triazoles; such as
  • the blocked polyisocyanates (AI) and / or (A2) to be used according to the invention can be the only crosslinking agents (A) which are present in the IC system according to the invention.
  • customary and known crosslinking agents can also be used in quantities which do not adversely affect the advantageous property profile of the IC systems according to the invention caused by the blocked polyisocyanates (AI) and / or (A2) to be used, but vary further in an advantageous manner.
  • Suitable customary and known crosslinking agents are all completely blocked monomeric polyisocyanates and / or their trimers and / or oligomers, which are referred to in the art as paint polyisocyanates. These have aliphatic, cycloaliphatic, araliphatic and / or aromatically bound isocyanate groups. Polyisocyanates with 2 to 5 isocyanate groups per molecule are preferably used.
  • isocyanates of this type are, for example, in "Methods of Organic Chemistry", Houben-Weyl, volume 14/2, 4th edition, Georg Thieme Verlag, Stuttgart 1963, pages 61 to 70, W. Siefken, Liebigs Annalen der Chemie, volume 562, pages 75 to 136, European patent specification EP-A-0 101 832 or the US patent specifications US-A-3, 290,350, US-A-4, 130,577 and US-A-4,439,616.
  • polyisocyanates examples include phenylene diisocyanate, tolylene diisocyanate, xylylidene diisocyanate, 1,3-bis (2-isocyanatoprop-2-yl) benzene (tetramethylxylylidene diisocyanate), bisphenylene diisocyanate,
  • Tetramethylene diisocyanate pentamethylene diisocyanate, hexamethylene diisocyanate, propylene diisocyanate, ethylethylene diisocyanate and trimethylhexane diisocyanate.
  • customary and known completely blocked isocyanate-containing polyurethane prepolymers which can be prepared by reacting the above-mentioned polyols with an excess of these polyisocyanates and which are preferably of low viscosity. It is also possible to use the customary and known completely blocked isocyanurate, biuret, allophanate, iminooxadiazinedione, urethane, urea groups and or polyisocyanates containing uretdione groups. Polyisocyanates containing urethane groups are obtained, for example, by reacting some of the isocyanate groups with the above-mentioned polyols.
  • Aliphatic or cycloaliphatic polyisocyanates in particular tetramethylene diisocyanate, hexamethylene diisocyanate, dimerized and trimerized tetramethylene diisocyanate or hexamethylene diisocyanate, isophorone diisocyanate, 2-isocyanatopropylcyclohexyl isocyanate, are preferably used,
  • Dicyclohexylmethane-2,4'-diisocyanate or dicyclohexylmethane-4,4'-diisocyanate or mixtures of these polyisocyanates are used as starting materials.
  • Mixtures of polyisocyanates based on hexamethylene diisocyanate and containing uretdione, isocyanurate and / or allophanate groups, as are formed by catalytic oligomerization of hexamethylene diisocyanate using suitable catalysts, are very particularly preferably used as starting materials.
  • suitable blocking agents are those mentioned above.
  • suitable customary and known crosslinking agents are polyepoxides, in particular all known aliphatic and / or cycloaliphatic and / or aromatic polyepoxides, for example based on bisphenol-A or bisphenol-F.
  • polyepoxides are, for example, the polyepoxides commercially available under the names Epikote® from Shell, Denacol® from Nagase Chemicals Ltd., Japan, such as e.g.
  • Denacol EX-411 penentaerythritol polyglycidyl ether
  • Denacol EX-321 trimethylolpropane polyglycidyl ether
  • Denacol EX-512 polyglycerol polyglycidyl ether
  • Denacol EX-521 polyglycerol polyglycidyl ether
  • Tris (alkoxycarbonylamino) triazines of the formula can also be used as crosslinking agents
  • aminoplast resins for example melamine resins
  • Any aminoplast resin suitable for topcoats or transparent clearcoats or a mixture of such aminoplast resins can be used.
  • the usual and known aminoplast resins come into consideration, the methylol and or methoxymethyl groups z. T. are defunctionalized by means of carbamate or allophanate groups.
  • Crosslinking agents of this type are described in the patents US-A-4 710 542 and EP-B-0 245 700 and in the article by B. Singh and co-workers "Carbamylmethylated Melamines, Novel Crosslinkers for the Coatings Industry" in Advanced Organic Coatings Science and Technology Series, 1991, Volume 13, pages 193 to 207.
  • suitable customary and known crosslinking agents are beta-hydroxyalkylamides such as N, N, N ', N'-tetrakis (2-hydroxyethyl) adipamide or N, N, N', N'-tetrakis (2-hydroxypropyl) adipamide or siloxanes , in particular siloxanes with at least one trialkoxy or dialkoxysilane group.
  • the further essential component of the IK system according to the invention is at least one binder (B) based on polymers which contain functional groups which react with isocyanate groups.
  • binders (B) which are highly suitable according to the invention are polyacrylates, polyesters, polyurethanes, acrylated polyurethanes or acrylated polyesters, but in particular polyacrylates.
  • An example of a functional group which is particularly suitable according to the invention is the hydroxyl group.
  • binders (B) which are particularly suitable according to the invention are the polyacrylate resins (B) with an OH number in the range 20-400, in particular in the range 60-250, especially in the range 80-200.
  • polyacrylate resins (B) are preferably used, the hydroxyl numbers from 40 to 240, preferably 60 to 210, very particularly preferably 100 to 200, acid numbers from 0 to 35 and preferably 0 to 23, glass transition temperatures from -35 to +70 ° C. and preferably -20 to +40 ° C, and number-average molecular weights M n of 1500 to 30,000, preferably 2000 to 15,000, very particularly preferably 2500 to 10,000, the ratio M w / M n being between 1.2 and 5.0, is preferably 1.2 and 4.0.
  • the glass transition temperature of the polyacrylate resins (B) is determined by the type and amount of the monomers used. The selection of the monomers can be carried out by a person skilled in the art with the aid of the following formula, with which the glass transition temperatures of polyacrylate resins can be approximately calculated:
  • Tg glass transition temperature of the polyacrylate resin
  • Wn weight fraction of the nth monomer
  • Measures to control the molecular weight are also part of the specialist knowledge of the average person skilled in the art and need not be explained in more detail here.
  • Polyacrylate resins (B) which are obtainable by polymerization in an organic solvent or a solvent mixture and in the presence of at least one polymerization initiator and, if appropriate, in the presence of regulators are particularly preferably used
  • bl one different from (b2), (b3), (b4), (b5), (b6) and (b7), with (b2), (b3), (b4), (b5), (b6) and (b7) copolymerizable, essentially acid group-free (meth) acrylic acid esters or a mixture of such monomers,
  • b3) optionally one ethylenically unsaturated monomer or at least one acid group which can be converted into the corresponding acid anion group and which carries (bl), (b2), (b4), (b5), (b6) and (b7) a mixture of such monomers, b4) optionally one or more vinyl aromatic hydrocarbons,
  • b6) optionally a polysiloxane macromonomer which is copolymerizable with (bl), (b2), (b3), (b4), (b5) and (b7) and
  • component (bl) which can be copolymerized with (b2), (b3), (b4), (b5), (b6) and (b7), essentially acid group-free esters of (meth) acrylic acid or a mixture of such (meth) acrylic acid esters are used, in particular (meth) acrylic or alkyl cycloalkyl esters with up to 20 Carbon atoms in the alkyl radical, in particular methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, hexyl, ethylhexyl, stearyl and lauryl acrylate or methacrylate; or cycloaliphatic (meth) acrylic acid esters, in particular cyclohexyl, isobomyl, dicyclopentadienyl, octahydro-4,7-methano-1H-indene m
  • Component (b2) which can be copolymerized with (bl), (b3), (b4), (b5), (b6) and (b7) and is different from (b5) is ethylenically unsaturated monomers which carry at least one hydroxyl group per molecule and are essentially free of acid groups or a mixture of such monomers is used.
  • HydroxyUcylester of acrylic acid, methacrylic acid or another alpha, beta-ethylenically unsaturated carboxylic acid are mentioned as examples.
  • These esters can be derived from an alkylene glycol esterified with the acid, or they can be obtained by reacting the acid with an alkylene oxide.
  • hydroxyethyl esters of acrylic acid or methacrylic acid in which the hydroxyalkyl group contains up to 20 carbon atoms, reaction products of cyclic esters, such as, for example, epsilon-caprolactone and these hydroxyalkyl esters, or mixtures of these hydroxyalkyl esters or epsilon-caprolactone-modified hydroxyalkyl esters.
  • hydroxyacyl esters examples include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxyethyl methacrylate,
  • olefinically unsaturated polyols as component (b2).
  • Suitable polyacrylate resins (B) are also obtained if trimethylolpropane monoallyl ether is at least partially used as component (b2).
  • the proportion of trimethylolpropane monoallyl ether is usually 2 to 10% by weight, based on the total weight of the monomers (bl) to (b7) used to prepare the polyacrylate resin.
  • the olefinically unsaturated polyols such as in particular
  • Trimethylolpropane monoallyl ethers can be used as the sole monomers containing hydroxyl groups, but in particular proportionally in combination with other of the monomers mentioned (b2) containing hydroxyl groups.
  • each can carry at least one acid group, preferably one carboxyl group, per molecule, with (bl), (b2), (b4), (b5), (b6) and (b7), ethylenically unsaturated monomer or a mixture of such monomers can be used.
  • Acrylic acid and / or methacrylic acid are particularly preferably used as component (b3).
  • other ethylenically unsaturated carboxylic acids with up to 6 carbon atoms in the molecule can also be used. Examples of such acids are ethacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid.
  • ethylenically unsaturated sulfonic or phosphonic acids or their partial esters can be used as component (b3).
  • component (b3) can also be used as component (b3).
  • Maleic acid mono (meth) acryloyloxyethyl ester, succinic acid mono (meth) acryloyloxyethyl ester and phthalic acid mono (meth) acryloyloxyethyl ester can be used.
  • As optional component (b4) vinyl aromatic hydrocarbons such as styrene, alpha-alkyl styrenes and vinyl toluene are used.
  • the reaction product of acrylic acid and / or methacrylic acid with the glycidyl ester of a monocarboxylic acid branched in the alpha position with 5 to 18 C atoms per molecule is used.
  • the reaction of acrylic or methacrylic acid with the glycidyl ester of a carboxylic acid with a tertiary alpha carbon atom can take place before, during or after the polymerization reaction.
  • the reaction product of acrylic and / or methacrylic acid with the glycidyl ester of versatic acid is preferably used as component (b5).
  • This glycidyl ester is commercially available under the name "Cardura E10".
  • vinyl esters of saturated aliphatic monocarboxylic acids having 9 to 11 carbon atoms which are branched on the alpha carbon atom are particularly preferably used.
  • polysiloxane macromonomers which have a number average molecular weight Mn of 1,000 to 40,000, preferably 2,000 to 20,000, particularly preferably 2,500 to 10,000 and in particular 3,000 to 7,000 and on average 0.5 to 2.5, preferably 0,
  • Mn number average molecular weight
  • DE-A-38 07 571 on pages 5 to 7, DE-A-37 06 095 in columns 3 to 7, EP-B -0 358 153 on pages 3 to 6, in US-A 4,754,014 in columns 5 to 9, in DE-A 44 21 823 or in international patent application WO 92/22615 on page 12, line 18 to Page 18, line 10, or vinyl monomers containing acryloxysilane can be prepared by reacting hydroxy-functional silanes with epichlorohydrin and then reacting the reaction product with methacrylic acid and / or hydroxyalkyl esters of (meth) acrylic acid.
  • Component (b7) can be one or more vinyl esters of monocarboxylic acids having 5 to 18 carbon atoms in the molecule and branched in the alpha position.
  • the branched monocarboxylic acids can be obtained by
  • Crack products of paraffinic hydrocarbons such as mineral oil fractions, and can contain both branched and straight-chain acyclic and / or cycloaliphatic olefins.
  • olefins When such olefins are reacted with formic acid or with carbon monoxide and water, a mixture of carboxylic acids is formed in which the carboxyl groups are predominantly located on a quaternary carbon atom.
  • Other olefinic starting materials are, for example, propylene trimer, propylene tetramer and diisobutylene.
  • the vinyl ester can also be prepared from the acids in a manner known per se, for example by allowing the acid to react with acetylene.
  • monomers (b7) come olefins such as ethylene, propylene, but-1-ene, pent-1-ene, hex-1-ene, cyclohexene, cyclopentene, norbornene, butadiene, isoprene, cyclopentadiene or dicyclopentadiene;
  • (Meth) acrylic acid amides such as (meth) acrylic acid amide, N-methyl, N, N-dimethyl, N-ethyl, N, N-diethyl, N-propyl, N, N-dipropyl, N-butyl, N, N-dibutyl, N-cyclohexyl or N, N-cyclohexyl-methyl- (meth) acrylic acid amide;
  • Monomers containing epoxy groups such as the glycidyl ester of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or ita
  • Examples of other highly suitable polyacrylate resins (B) are known from European patents EP-A-0 666 780 or EP-A-0 767 185 or US Pat. Nos. 5, 480,943, 5,475,073 or 5,534,598.
  • copolymerization of the monomers described above has no special features in terms of method, but instead takes place with the aid of the methods known and known in the plastics field of continuous or discontinuous copolymerization in bulk, solution, carbon dioxide or emulsion under normal pressure or excess pressure in stirred tanks, autoclaves, tubular reactors or Taylor reactors.
  • suitable cooling polymerization processes are described in the patents DE-A-197 09 465, DE-C-197 09 476, DE-A-28 48 906, DE-A-195 24 182, EP-A-0 554783, WO 95/27742 or WO 82/02387.
  • Taylor reactors which are used to convert substances under the conditions of the Taylor flow are known. They essentially consist of two coaxial, concentrically arranged cylinders, the outer of which is fixed and the inner of which rotates. The volume formed by the gap between the cylinders serves as the reaction space. With increasing angular velocity (Oi of the inner cylinder, a number of different flow forms occur, which are characterized by a dimensionless characteristic number, the so-called Taylor number Ta.
  • the Taylor number is also dependent on the kinematic viscosity v of the fluid in the gap and on the geometric parameters, the outer radius of the inner cylinder n, the inner radius of the outer cylinder r a and the gap width d, the difference between the two radii, according to the following formula:
  • the laminar Couette flow a simple shear flow, forms. If the speed of rotation of the inner cylinder is further increased, opposite rotating (counter-rotating) vortices with axes along the circumferential direction occur alternately above a critical value. These so-called Taylor vortices are rotationally symmetrical and have a diameter that is approximately as large as the gap width. Two adjacent vertebrae form a pair of vertebrae or a vertebral cell. This behavior is based on the fact that when the inner cylinder rotates with the outer cylinder at rest, the fluid particles near the inner cylinder are subjected to a stronger centrifugal force than those which are further away from the inner cylinder.
  • each pair of vortices travels through the gap, with only a small mass exchange occurring between adjacent pairs of vortices.
  • the mixing within such vortex pairs is very high, whereas the axial mixing beyond the pair boundaries is only very low.
  • a pair of vortices can therefore be regarded as a well-mixed stirred kettle.
  • the flow system thus behaves like an ideal flow tube in that the vortex pairs move through the gap with a constant dwell time like ideal stirred tanks.
  • Taylor reactors with an outer reactor wall and a concentrically or eccentrically arranged rotor, a reactor bottom and a reactor cover, which together define the annular-shaped reactor volume, at least one device for metering in educts and a device for the product outflow, with the reactor wall and / or the rotor is or are geometrically designed such that the conditions for the Taylor flow are met over essentially the entire length of the reactor in the reactor volume, ie the annular gap widens in the direction of flow.
  • Free-radical initiators are preferably used as (co) polymerization initiators. Initiator type and amount are usually chosen so that the available radicals are as constant as possible at the polymerization temperature during the feed phase.
  • initiators which can be used are: dialkyl peroxides, for example di-tert-butyl peroxide, di-tert-amyl peroxide and dicumyl peroxide, hydroperoxides, for example cumene hydroperoxide and tert-butyl hydroperoxide, peresters, for example tert-butyl perbenzoate, tert-butyl perpivalate, tert-Butylper-3,5,5-trimethylhexanoate and tert-Butylper-2-ethylhexanoate, or bisazo compounds such as azobisiobutyronitrile.
  • the polymerization conditions (reaction temperature, feed time of the monomer mixture and polymerization initiators, possibly also the use of molecular weight regulators, for example mercaptans, thioglycolic acid esters, alpha-diphenylethene, compounds containing nitroxyl radicals or hydrogen chloride) are selected such that in particular the polyacrylate resins (B) have a number-average molecular weight indicated (determined by gel permeation chromatography using polystyrene as calibration substance).
  • molecular weight regulators for example mercaptans, thioglycolic acid esters, alpha-diphenylethene, compounds containing nitroxyl radicals or hydrogen chloride
  • All reactive diluents are suitable as reaction medium which are incorporated into the binder (B) in the known crosslinking reactions between the hydroxyl groups of the binders (B) and the blocked isocyanate groups of the crosslinking agent (A) to be used according to the invention and which do not affect the copolymerization. or even prevent it.
  • the person skilled in the art can therefore select the most suitable reactive diluents with the help of his general specialist knowledge, if necessary with the aid of simple preliminary tests.
  • Suitable reactive diluents are oligomeric polyols which can be obtained from oligomeric intermediates which are obtained by metathesis reactions of acyclic monoolefins and cyclic monoolefins by hydroformylation and subsequent hydrogenation;
  • suitable cyclic monoolefins are cyclobutene, cyclopentene, cyclohexene, cyclooctene, cycloheptene, norbones or 7-oxanorbones;
  • suitable acyclic monoolefins are contained in hydrocarbon mixtures which are obtained in petroleum processing by cracking (Cs cut);
  • suitable oligomeric polyols to be used according to the invention have a hydroxyl number from 200 to 450, a number average molecular weight Mn from 400 to 1000 and a mass average molecular weight Mw from 600 to 1100;
  • suitable polyols are branched, cyclic and / or acylated clische C9-C 16 alkanes functionalized with at least two hydroxyl groups, especially diethyloctanediols.
  • polyols to be used are hyperbranched compounds with a tetrafunctional central group, derived from ditrimethylolpropane, diglycerol, ditrimethylolethane, pentaerythritol, tetrakis (2-hydroxyethyl) methane, tetrakis (3-hydroxypropyl) methane or 2,2-bis-hydroxymethyl-butanediol- ( 1,4) (homopentaerythritol).
  • These reactive diluents can be prepared by the customary and known methods of producing hyperbranched and dendrimeric compounds.
  • Suitable synthesis methods are described, for example, in the patent specifications WO 93/17060 or WO 96/12754 or in the book by GR Newkome, CN Moorefield and F. Vögtle, "Dendritic Molecules, Concepts, Syntheses, Perspectives", VCH, Weinheim, New York, 1996 , described.
  • the IK systems according to the invention can still contain up to 25% by weight.
  • % based on the total amount of binders (B) of one or more of (B) different, hydroxyl group-containing binders, such as linear and / or contain branched and / or block-like, comb-like and / or randomly constructed poly (meth) acrylates, polyesters, polyurethanes, acrylated polyurethanes, acrylated polyesters, polylactones, polycarbonates, polyethers, (meth) acrylate diols or polyureas.
  • binders (B) of one or more of (B) different, hydroxyl group-containing binders such as linear and / or contain branched and / or block-like, comb-like and / or randomly constructed poly (meth) acrylates, polyesters, polyurethanes, acrylated polyurethanes, acrylated polyesters, polylactones, polycarbonates, polyethers, (meth) acrylate diols or polyureas.
  • IK systems according to the invention may vary
  • UV absorber and Radical scavenger; Crosslinking catalysts, in particular organometallic compounds, preferably tin and / or organism bismuth or tertiary amines; Rheological agents, in particular those known from the patents WO 94/22968, EP-A-0 276 501, EP-A-0 249 201 or WO 97/12945; Pigments and FüUstoffe any kind, for example, color pigments such as azo pigments, phthalocyanine pigments, carbonyl, dioxazine pigments, titanium dioxide, carbon black, iron oxides, or chromium or cobalt oxides, effect pigments such as metal flake pigments, especially aluminum flake pigments and pearlescent pigments or fillers such as chalk, calcium sulfates, barium sulfate, Siükate as talc or kaolin, silicas, reactive and inert nanon particles, oxides such as aluminum hydroxide or magnesium hydroxide or organic fillers such
  • the IC system according to the invention can contain up to 40% by weight of constituents which are curable with actinic light, in particular UV radiation, and / or electron radiation. This offers the advantage that the IC system according to the invention is both thermally curable and radiation-curable.
  • UV-curable or electron-curable coating compositions are suitable as constituents of this type.
  • These radiation-curable coating compositions usually contain at least one, preferably more, radiation-curable binders, in particular based on ethylenically unsaturated prepolymers and / or ethylenically unsaturated oligomers, optionally one or more reactive diluents and optionally one or more photoinitiators.
  • the radiation-curable binders are advantageously used as constituents.
  • suitable radiation-curable binders are (meth) acrylic functional units (meth) acrylic copolymers, polyether acrylates,
  • Polyester acrylates unsaturated polyesters, epoxy acrylates, urethane acrylates, amino acrylates, melamine acrylates, silicone acrylates and the corresponding methacrylates. It is preferred to use binders which are free from aromatic structural units. Urethane (meth) acrylates and / or polyester (meth) acrylates are therefore preferably used, particularly preferably aliphatic urethane acrylates.
  • the IC system according to the invention in particular for its use as a coating agent, is selected so that the hardened IC system, in particular the clear lacquer according to the invention, has a memory module E 'of at least 10 ⁇ > 6 p a? preferably of at least 10 ⁇ 0 Pa, particularly preferably of at least 10 ⁇ Pa, and a loss factor at 20 ° C of a maximum of 0.10, preferably of a maximum of 0.06, the memory module W and the loss factor tan ⁇ with the dynamic Mechanical thermal analysis on homogeneous free films with a layer thickness of 40 + 10 ⁇ m have been measured.
  • the loss factor tan ⁇ is defined as the quotient of the loss module E "and the memory module E '.
  • Dynamic mechanical thermal analysis is a well-known measurement method for determining the viscoelastic properties of
  • the measurements can be carried out, for example, with the devices MK ⁇ ,
  • the storage module E 'and the loss factor tan ⁇ are measured on homogeneous free films.
  • the free films are produced in a known manner in that the coating composition according to the invention is applied and cured to substrates on which the coating composition does not adhere.
  • Glass, Teflon and in particular polypropylene may be mentioned as examples of suitable substrates.
  • Polypropylene has the advantage of good availability and is therefore normally used as a carrier material.
  • the layer thickness of the free films used for the measurement is generally 40 + 10 ⁇ m.
  • the special selection of the IK systems according to the invention based on the value of the memory module in the rubber-elastic range and the loss factor at 20 ° C. of the hardened IK systems enables the IC systems according to the invention with a further optimized property profile to be provided with a very good scratch resistance at the same time very good PoUrley, chemical and moisture resistance as well Weather resistance, since both parameters can be determined by simple DMTA measurements.
  • the resulting clearcoats of the invention also have a high gloss and an acid and base resistance.
  • the IC systems according to the invention can be used not only for the production of clearcoats and topcoats, but also for the production of adhesives and sealants.
  • crosslinking agents (A) or binders (B) to be used for the production of powders, solid, liquid from solvent-free liquids, water-soluble or water-dispersible from aqueous solutions or dispersions or correspondingly soluble for solutions in organic solvents.
  • the production of the IC systems according to the invention has no special procedural features, but the usual methods such as combining the individual components and mixing them with stirring are used.
  • the IC system according to the invention is used primarily for the production of coated molded parts, composite parts or complex components, in particular vehicle bodies, which contain or consist of foils, glass, wood, paper and / or metal, by applying the coating agent, for example by coil coating the corresponding molded parts, composite parts or complex components and curing the resulting coating.
  • the IC system according to the invention is preferably used for the production of single- or multi-layer coatings and particularly preferably for the production of top coats.
  • it can also be used to produce a clearcoat to be applied over a basecoat film, for example a clearcoat of a multi-coat paint system produced by the wet-on-wet process.
  • a primer for underbody protection.
  • the plastics or the other substrates can also be coated directly with the clear coat or top coat.
  • the IC system according to the invention is used above all in the serial painting of vehicle bodies, in particular automobile bodies.
  • the adhesive according to the invention is used to produce bonded composite parts which contain or consist of foils, plastics, glass, wood, paper and / or metal by placing the adhesive on the surface (s) to be bonded of a foil or a plastic, glass, Wood, paper and / or metal containing or consisting of molded part and / or the surface (s) of the part that is to be glued, is applied and optionally pre-hardened, after which the relevant surfaces to be glued are brought into contact and accordingly Adhesive is cured.
  • the coating agent according to the invention and the adhesive according to the invention are generally applied using customary methods, for example by spraying, knife coating, dipping or brushing.
  • the sealing compound according to the invention serves to hermetically seal the joints in composite parts and complex components, in particular vehicle bodies, which are composed of different molded parts and composite parts.
  • the sealing compound according to the invention is introduced into the joints, for example by spraying or pouring, and if appropriate thermally hardened with the coating agents and / or adhesives also used.
  • the coating compositions, adhesives or sealants according to the invention are preferably cured at temperatures from 100 to 240 ° C. Temperatures between 100 and 180 ° C. are particularly preferred. In special application forms of the coating compositions according to the invention, lower curing temperatures of 100 to 160 ° C. can also be used.
  • the IC systems according to the invention contain constituents which are curable with actinic light, in particular UV radiation, and / or electron radiation, thermal curing is preceded or followed by radiation curing.
  • Curing by radiation in particular UV radiation, has no special features in terms of method, but is carried out in customary and known systems under the conditions, as described, for example, by R. Holmes in UV and EB Curing Formulations for Printing Inks, Coatings and Paints, SITA Technology, Academic Press, London, United Kindom 1984, or by D. Stoye and W. Freitag (editors) in Paints, Coatings and Solvents, Second Completely Revised Edition, Wiley-VCH, Weinheim, New York, 1998.
  • Molded parts, composite parts and complex components which contain or consist of foils, plastics, glass, wood, paper and / or metal and at least one layer of the hardened binder, at least one layer of the hardened adhesive and / or at least one sealed with a hardened sealing compound according to the invention Contain joints, have clear advantages over conventional molded, composite and components in terms of thermal stability, light resistance, scratch resistance and weather resistance, so that the overall result is a longer service life.
  • the resulting polymer solution has a solids content of 65% determined in a forced air oven for 1 h at 130 ° C., an acid number of 17 and a viscosity of 16 dPas (measured on a 60% solution of the polymer solution in the aromatic solvent described, using an ICI -Plate-cone viscometer at 23 ° C).
  • Example 1 An inventive (example 1) and conventional IK systems (comparative experiments VI and V2) were produced from the constituents listed in table 1 by mixing and applied to test panels. Steel panels made of body steel, which had been pretreated with commercially available zinc phosphate solution, were used as test panels.
  • Table 1 Composition of the IK system according to the invention (Example 1) and the conventional IK systems (comparative experiments VI and V2)
  • Methyl etherified melamine-formaldehyde resin (90% in iso-
  • test panels To produce the test panels, an electro dip coating with a layer thickness of 18-22 ⁇ m and a filler with a layer thickness of 35-40 ⁇ m were applied and baked in succession. A black water-based paint was then applied with a layer thickness of 12 - 15 ⁇ m and flashed off at 80 ° C for 10 min. Finally, the IC system to be tested from Example 1 and Comparative Experiments VI and V2 was applied with a layer thickness of 40-45 ⁇ m, after which the basecoat and the IK systems were cured for 20 minutes at 140 ° C. (wet-on-wet -Method). The test boards according to the invention and the test boards VI and V2 not according to the invention were stored at room temperature for 2 weeks after application of the paints before the test was carried out.
  • the lacquer surface was damaged with a sieve fabric, which was loaded with a mass.
  • the screen fabric and the varnish surface were wetted liberally with a detergent solution.
  • the test panel was moved back and forth under the screen fabric in a lifting motion by means of a motor drive.
  • the test specimen was an eraser (4.5 x 2.0 cm, wide side perpendicular to the direction of scratching) covered with nylon mesh (No. 11, 31 ⁇ m mesh size, Tg 50 ° C.).
  • the coating weight was 2000 g.
  • the scratch resistance was determined after the sand test.
  • the paint surface was loaded with sand (20g quartz-silver sand 1.5-2.0 mm).
  • Test board was attached. The same test boards were used as in the above
  • Table 2 Scratch resistance of the coatings produced from the IC system of Example 1 according to the invention and the conventional IC systems of comparative experiments VI to V2
  • the BART (BASF ACID RESISTANCE TEST) was used to determine the
  • test substances sulfuric acid 15%, 10%, 36%; sulfuric acid 6%, hydrochloric acid 10%, sodium hydroxide solution 5%, VE
  • Every single mark (spot) was evaluated and the result for each coating was recorded in a suitable form (e.g. sums of notes for a temperature).
  • Table 3 The acid resistance of the coatings produced from the IC system according to the invention (example 1) and from the conventional IC systems (comparative experiments VI and V2)
  • Demineralized water 2 0 0 0 1 0 0 0 0.5 0 0 0 0.5
  • Demineralized water 3 0 0 0.5 1 0 0 0 0.5 0 0 0 0.5
  • Demineralized water 4 0 0 0.5 1 0 0 0 0.5 0 0 0 1
  • the test panels of the example and of the comparative experiments VI and V2 were exposed to the damage caused by sulfuric acid.
  • the sulfuric acid 1% p.A.
  • a pipette 25 ⁇ l per drop
  • the test panels were loaded on a gradient oven (e.g. type: 2615 from BYK-Gardner) for 30 minutes.
  • the temperature at which the first visible change occurred was determined.

Landscapes

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

Abstract

L'invention concerne un agent de revêtement à un seul composant, qui contient (A) comme agent de réticulation au moins un polyisocyanate séquencé et (B) au moins un liant ayant des groupes fonctionnels. Il se caractérise en ce que le polyisocyanate séquencé (A) est (A1) le dérivé entièrement séquencé d'un polyisocyanate (a1), qui contient au moins une unité structurale de di-isocyanate, présentant (a11) une structure cyclique insaturée ou aromatique ou non aromatique ayant entre 5 et 10 atomes cycliques et (a12) deux groupes isocyanate liés à la structure cyclique. A cet effet, (a13) en cas de structure cyclique non aromatique, (a131) les deux groupes isocyanate sont liés à la structure cycliquear l'intermédiaire d'alkyle C1-C9 linéaire et/ou d'étheralkyle C2-C10 linéaire ou (a132) un groupe isocyanate est lié directement et l'autre groupe isocyanate est lié par l'intermédiaire d'alkyle C2-C9 linéaire ou d'étheralkyle C2-C10; (a14) en cas de structure cyclique insaturée ou aromatique, au moins un des deux groupes isocyanate est lié à la structure cyclique par l'intermédiaire d'alkyle C2-C9 linéaire et/ou d'étheralkyle C2-C10 linéaire, les deux restes ne présentant pas d'atome d'hydrogène benzylique. Dans le cas du polyisocyanate séquencé (A), il s'agit notamment (A2) du dérivé entièrement séquencé d'un oligomère (a2) du polyisocyanate (a1) ayant entre 2 et 10 unités d'isocyanate, notamment le dérivé entièrement séquencé d'un trimère (a2).
EP99967921A 1998-11-30 1999-11-24 Agent de revetement et procede permettant de le produire Withdrawn EP1155062A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19855152 1998-11-30
DE1998155152 DE19855152C2 (de) 1998-11-30 1998-11-30 Beschichtungsmittel und Verfahren zu dessen Herstellung
PCT/EP1999/009083 WO2000032670A1 (fr) 1998-11-30 1999-11-24 Agent de revetement et procede permettant de le produire

Publications (1)

Publication Number Publication Date
EP1155062A1 true EP1155062A1 (fr) 2001-11-21

Family

ID=7889473

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99967921A Withdrawn EP1155062A1 (fr) 1998-11-30 1999-11-24 Agent de revetement et procede permettant de le produire

Country Status (7)

Country Link
EP (1) EP1155062A1 (fr)
JP (1) JP2002531611A (fr)
AU (1) AU2430600A (fr)
BR (1) BR9916147A (fr)
DE (1) DE19855152C2 (fr)
MX (1) MXPA01005407A (fr)
WO (1) WO2000032670A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8802771B2 (en) 2010-11-22 2014-08-12 Dow Global Technologies Llc Two component polyurethane coating compositions comprising isocyanurate compositions from bis(isocyanatomethyl) cyclohexane and from aliphatic diisocyanates

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19924171A1 (de) 1999-05-25 2000-11-30 Basf Coatings Ag Beschichtungsstoff mit einer Mischung aus mindestens einem Netzmittel und Harnstoffen und/oder Harnstoffderivaten als Thixotropiermittel
DE19924170A1 (de) 1999-05-25 2000-11-30 Basf Coatings Ag Thixotropierungsmittel
DE10042152A1 (de) 2000-08-26 2002-03-28 Basf Coatings Ag Mit aktinischer Strahlung aktivierbares Thixotropierungsmittel, Verfahren zu seiner Herstellung und seine Verwendung
US8686090B2 (en) 2003-12-10 2014-04-01 Basf Coatings Gmbh Use of urea crystals for non-polymeric coatings
JP7288858B2 (ja) * 2017-11-21 2023-06-08 三井化学株式会社 ブロックイソシアネート組成物、および、コーティング剤
CN120941788A (zh) * 2025-10-14 2025-11-14 飞琳科新材料(南通)有限公司 一种基于表面微纳结构的仿生减阻保护膜及其制备方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5420560B2 (fr) * 1971-11-20 1979-07-24
DE3000662A1 (de) * 1980-01-10 1981-07-16 Chemische Werke Hüls AG, 4370 Marl Einkomponenten-einbrennlacke
DE3001060A1 (de) * 1980-01-12 1981-07-16 Chemische Werke Hüls AG, 4370 Marl Blockierte polyisocyanato-isocyanurate und ihre herstellung und verwendung
US4375539A (en) * 1981-07-22 1983-03-01 Eastman Kodak Company Solid blocked crosslinking agents based on 1,4-cyclohexane bis(methylisocyanate)
JPH0780984B2 (ja) * 1987-05-29 1995-08-30 武田薬品工業株式会社 プレコートメタル用一液性熱硬化型樹脂組成物
DE19505351A1 (de) * 1995-02-17 1996-08-22 Bayer Ag Isocyanurat-Polyisocyanate auf Basis von 1,3-Düsocyanatocycloalkanen
DE19519396A1 (de) * 1995-05-26 1996-11-28 Huels Chemische Werke Ag Neue blockierte Polyisocyanate sowie ein Verfahren zu ihrer Herstellung
DE19650044A1 (de) * 1996-12-03 1998-06-04 Huels Chemische Werke Ag Verfahren zur Herstellung von oximblockierten Lackpolyisocyanaten

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0032670A1 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8802771B2 (en) 2010-11-22 2014-08-12 Dow Global Technologies Llc Two component polyurethane coating compositions comprising isocyanurate compositions from bis(isocyanatomethyl) cyclohexane and from aliphatic diisocyanates

Also Published As

Publication number Publication date
DE19855152A1 (de) 2000-05-31
WO2000032670A1 (fr) 2000-06-08
BR9916147A (pt) 2001-09-04
AU2430600A (en) 2000-06-19
DE19855152C2 (de) 2001-02-01
MXPA01005407A (es) 2002-03-14
JP2002531611A (ja) 2002-09-24

Similar Documents

Publication Publication Date Title
EP1423449B1 (fr) Matieres de revetement durcissables thermiquement et par rayonnement actinique et leur utilisation
EP1232221B1 (fr) Agent d'application contenant un solvant et utilisation
WO1992015405A1 (fr) Procede de production d'un revetement de vernis multicouche protecteur et/ou decoratif
DE19909894A1 (de) Sol-Gel-Überzug für einschichtige oder mehrschichtige Lackierungen
EP1190003B1 (fr) Substance de revetement comportant un melange constitue d'au moins un agent mouillant et d'urees et/ou de derives d'uree en tant qu'agent thixotrope
EP0940459B1 (fr) Agent de revêtement et adhésifs, leur utilisation et procédé pour leur préparation
EP1156890B1 (fr) Laquage multicouche hautement resistant aux rayures, son procede de realisation et son utilisation
EP0856019A1 (fr) Agent de recouvrement compose d'au moins 3 constituants, procede permettant de le preparer et utilisation
DE10042152A1 (de) Mit aktinischer Strahlung aktivierbares Thixotropierungsmittel, Verfahren zu seiner Herstellung und seine Verwendung
DE10021139B4 (de) Mehrkomponentenbeschichtungsstoffe, -klebstoffe und -dichtungsmassen und ihre Verwendung
EP0998508B1 (fr) Agent de recouvrement et procede permettant de le preparer
DE19855152C2 (de) Beschichtungsmittel und Verfahren zu dessen Herstellung
DE10305115B4 (de) Beschichtungsstoffe, Verfahren zu ihrer Herstellung und ihre Verwendung
EP3107972B1 (fr) Compositions de produits de revêtement, revêtements ainsi fabriqués et leur utilisation
EP1311580A1 (fr) Systemes a composante unique durcissable par reaction thermique et par rayonnement actinique et leur utilisation
EP1131362B1 (fr) Utilisation de methylpropane-1,3-diol-mono(meth)acrylate pour la production d'agents de revetement, de colles et de materiaux d'etancheite durcissables par voie oxydative et/ou thermique
EP1163303B1 (fr) Utilisation de tricyclodecane dimethanol pour la production de peintures multicouches
WO2016000952A1 (fr) Produits de réaction à base de polyéther et peintures de base aqueuses contenant lesdits produits de réaction
DE10305119B4 (de) Beschichtungsstoffe, Verfahren zu ihrer Herstellung und ihre Verwendung
EP1616925A1 (fr) Sytème aqueux à plusieurs composants, sa préparation et son utilisation
DE10004750A1 (de) Die Verwendung von Tricyclodecandimethanol zur Herstellung von Mehrschichtlackierungen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20010519

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

17Q First examination report despatched

Effective date: 20020130

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20030704

RBV Designated contracting states (corrected)

Designated state(s): DE ES FR IT