DE10001443A1 - Thixotropic agent, process for its preparation and its use - Google Patents

Abstract

The invention relates to a thixotropic agent that can be produced by converting at least one primary and/or secondary amine and/or water with at least one polyisocyanate in at least one liquid, low-molecular polyol acting as the reaction medium.

Description

The present invention relates to a novel thixotropic agent. Furthermore it concerns the present invention provides a novel process for its preparation. Furthermore The present invention relates to the use of the novel thixotropic agent for Production of new coating materials, adhesives and sealants.

Coating materials must have a very good stability after their application have, on the one hand, the production of comparatively thick paint layers and Make it possible to paint, without this to the extremely disturbing "runners" especially comes to vertical substrates. On the other hand, the viscosity may the coating materials should not be so high that problems occur during application and no good course of the applied paint layers is possible.

These problems are increasingly associated with coating materials, especially clearcoats high solids content. The use of high-grade coating materials However, solids content is advantageous for environmental reasons, because they are used in the Application and curing emit less volatile organic materials. At the same time, these coating materials must paint, in particular Clearcoats, which in terms of gloss, transparency and clarity, the Scratch resistance, weather resistance and yellowing resistance all Meet the demands of the market.

Comparable problems also occur with adhesives and sealants.

The rheological behavior of coating materials can be determined with the aid of urea group-containing thixotropic agents are positively influenced. These Thixotropic agents are known to consist of polyisocyanates and amines in the Presence of hydroxyl-containing binders prepared in situ. This is why possible because the hydroxyl groups react more slowly with the isocyanate groups than the Amino groups. By way of example, reference is made to the patent specifications DE 23 60 019 B2, DE 235 99 123 B1, DE 235 99 129 B1, DE 198 11 471 A1, DE 27 51 761 C2, EP 0 192 304 B1 or WO 490/22968. Comparable thixotropic agents and methods too their preparation are in the non-prepublished patent applications with the  Reference DE 199 24 170.8, 199 24 172.4 or 199 24 171.6 described.

A disadvantage of these thixotropic agents and the processes for their preparation is that they are essentially used only for the production of coating materials can contain the same binders as they are used for the production of Thixotropic agents were applied.

There is therefore a need for urea group-containing thixotropic agents that are not must be prepared in situ in the presence of hydroxyl-containing binders, but manufactured separately and a variety of coating materials, adhesives and sealants, but especially coating materials can be added. The relevant coating materials are very good application properties, a very good stability and a very good course and paint finishes, in particular clearcoats, which in terms of gloss, transparency and Clarity, scratch resistance, weathering resistance and resistance to yellowing meet all the demands of the market. This also applies mutatis mutandis for the adhesives and sealants.

Low molecular weight liquid polyols, in particular polyhydroxy-functionalized cyclic and / or acyclic alkanes having 9 to 16 carbon atoms in the molecule such as positionally isomeric diethyloctanediols, are already as reactive diluents for the thermal Curing in thermal or thermal and curable with actinic radiation Coating materials, in architectural paints, as reaction medium for the preparation of acrylate copolymers or as a synthetic building block for the preparation of oligomers and polymers have been used. For this is on the not pre-published Patent applications with the file numbers DE 198 50 243, 198 55 167.3, 199 24 674.2, 199 38 758.3, 199 40 855.6 or 199 45 574.0 or the German patent application DE 198 09 643 A1 directed. The use of low molecular weight liquid polyols as Reaction medium for the preparation of urea group-containing thixotropic agents is not described herein.

The object of the present invention is to meet the need described above cover.  

Accordingly, the new thixotropic agent which can be produced has been found by having at least one primary and / or secondary amine and / or water at least one polyisocyanate in at least one liquid, low molecular weight polyol as reaction medium.

The new thixotropic agent is hereinafter referred to as "Inventive Thixotropic agent "referred.

Other inventive objects will be apparent from the description.

In view of the prior art, it was surprising and not for the expert predictably that the object of the present invention is based on the inventive thixotropic agent could be solved. Because with regard to The prior art had actually been expected that the particularly high Excess of hydroxyl groups resulting from the use according to the invention low molecular weight, liquid polyols results in the formation of urea groups suppressed.

The thixotropic agent according to the invention can be obtained by reacting a Polyisocyanate with a primary or secondary amine or a mixture of such Amines and / or water. Preferably, these starting compounds are in such Quantities reacted with each other, that the equivalent ratio between isocyanate-reactive Groups and isocyanate groups between 1.2 and 0.4, preferably between 1.0 and 0.8 lies.

According to the invention, the reaction in at least one liquid, low molecular weight Polyol is carried out as a reaction medium. Preferably, low molecular weight Polyols are used, which are liquid at room temperature.

According to the invention, polyols may be used which are two or more, in particular but have two hydroxyl groups per molecule. Preferably, the Polyols to be used according to the invention have a molecular weight of from 120 to 700, preferably 130 to 650, more preferably 140 to 600, most preferably 150 to 550 and especially 160 to 500 daltons.  

Particular advantages result when the polyol to be used according to the invention polyhydroxy-functionalized cyclic and / or acyclic alkane with 9 to 16 Carbon atoms in the molecule is.

The functionalized alkanes are derived from branched, cyclic or acyclic Alkanes with 9 to 16 carbon atoms, which in each case form the skeleton.

Examples of suitable alkanes of this kind having 9 carbon atoms are 2-methyloctane, 4- Methyloctane, 2,3-dimethylheptane, 3,4-dimethylheptane, 2,6-dimethylheptane, 3,5- Dimethylheptane, 2-methyl-4-ethyl-hexane or isopropylcyclohexane.

Examples of suitable alkanes of this type having 10 carbon atoms are 4-ethyloctane, 2,3,4,5-tetramethylhexane, 2,3-diethylhexane or 1-methyl-2-n-propylcyclohexane.

Examples of suitable alkanes of this type having 11 carbon atoms are 2,4,5,6- Tetramethylheptane or 3-methyl-6-ethyl-octane.

Examples of suitable alkanes of this type having 12 carbon atoms are 4-methyl-7-ethyl nonane, 4,5-diethyl-octane, 1'-ethyl-butyl-cyclohexane, 3,5-diethyl-octane or 2,4-diethyl octane.

Examples of suitable alkanes of this type having 13 carbon atoms are 3,4-dimethyl-5 ethyl-nonane or 4,6-dimethyl-5-ethyl-nonane.

An example of a suitable alkane of this type having 14 carbon atoms is 3,4- Dimethyl-7-ethyl-decane.

Examples of suitable alkanes of this type having 15 carbon atoms are 3,6-diethyl undecane or 3,6-dimethyl-9-ethyl undecane.

Examples of suitable alkanes of this type having 16 carbon atoms are 3,7-diethyl dodecane or 4-ethyl-6-isopropyl undecane.  

Of these skeletons are the alkanes with 10 to 14 and especially 12 Carbon atoms are particularly advantageous and are therefore preferably used. From These in turn are the octane derivatives very particularly advantageous.

For the invention, it is advantageous if the functionalized alkanes have a boiling point of over 200, preferably 220 and in particular 240 ° C. Beyond that they have a low evaporation rate.

For the coating materials of the invention, it is advantageous if the funktio nalisierten alkanes are acyclic.

The functionalized alkanes generally have primary and / or secondary Hydroxyl groups on. It is advantageous for the coating materials according to the invention if primary and secondary groups exist in a connection.

Very particularly advantageous coating materials of the invention are obtained when the diols position isomers dialkyloctanediols, in particular position isomers Diethyloctanediols, are.

The positionally isomeric diethyloctanediols to be used according to the invention contain a linear C ₈ -carbon chain.

With respect to the two ethyl groups, the C ₈ carbon chain has the following substitution pattern: 2,3, 2,4, 2,5, 2,6, 2,7, 3,4, 3,5, 3,6 or 4,5 , According to the invention, it is advantageous if the two ethyl groups are in the 2,4-position, ie that they are 2,4-diethyloctanediols.

With respect to the two hydroxyl groups, the C ₈ carbon chain has the following substitution pattern: 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 2.3, 2.4 , 2.5, 2.6, 2.7, 2.8, 3.4, 3.5, 3.6, 3.7, 3.8, 4.5, 4.6, 4.8, 5 , 6, 5, 7, 5, 8, 6, 7, 6, 8 or 7, 8. According to the invention, it is advantageous if the two hydroxyl groups are in the 1,5-position, ie that they are diethyloctane-1,5-diols.

The two substitution patterns are combined in any desired manner, ie, that the diethyloctanediols to be used according to the invention are
2,3-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-, -2, 3, -2,4, -2,5, -2,6, -2,7, 2,8, -3,4, -3,5, -3,6, -3,7-, -3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5 , 8-, 6,7-, 6,8- or -7,8-diol,
2,4-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-, -2, 3, -2,4, -2,5, -2,6, -2,7, 2,8, -3,4, -3,5, -3,6, -3,7-, -3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5 , 8-, 6,7-, 6,8- or -7,8-diol,
2,5-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-, -2, 3, -2,4, -2,5, -2,6, -2,7, 2,8, -3,4, -3,5, -3,6, -3,7-, -3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5 , 8-, 6,7-, 6,8- or -7,8-diol,
2,6-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-, -2, 3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4, -3,5-, -3,6-, -3,7-, -3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5 , 8-, 6,7-, 6,8- or -7,8-diol,
2,7-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-, -2, 3-, -2,4-, -2,5-, -2,6-, -2,7-, -2,8-, -3,4-, -3,5-, -3,6- , -3,7-, -3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, - 5,8-, 6,7-, 6,8- or -7,8-diol,
3,4-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-, -2, 3, -2,4, -2,5, -2,6, -2,7, 2,8, -3,4, -3,5, -3,6, -3,7-, -3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5 , 8-, 6,7-, 6,8- or -7,8-diol,
3,5-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-, -2, 3, -2,4, -2,5, -2,6, -2,7, 2,8, -3,4, -3,5, -3,6, -3,7-, -3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5 , 8-, 6,7-, 6,8- or -7,8-diol,
3,6-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-, -2, 3, -2,4, -2,5, -2,6, -2,7, 2,8, -3,4, -3,5, -3,6, -3,7-, -3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5 , 8-, -6,7-, -6,8- or -7,8-diol or um
4,5-diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-, -2, 3, -2,4, -2,5, -2,6, -2,7, 2,8, -3,4, -3,5, -3,6, -3,7-, -3,8-, -4,5-, -4,6-, -4,7-, -4,8-, -5,6-, -5,7-, -5 , 8-, 6,7-, 6,8- or -7,8-diol
is.

The positionally isomeric diethyloctanediols to be used according to the invention can be used as single compounds or as mixtures of two or more diethyloctanediols be used.

Very particular advantages result from the use of 2,4-diethyloctane-1,5-diol.

The positionally isomeric diethyloctanediols used according to the invention are preferred known compounds and can by means of conventional and well-known Synthetic methods of organic chemistry such as the base-catalyzed aldol condensation or fall as byproducts of major chemical syntheses such as Preparation of 2-ethyl-hexanol.

Particularly advantageous thixotropic agents according to the invention are obtained when as amines primary and / or secondary amines, preferably primary amines and in particular primary monoamines be used as starting compounds. Further Benefits result from the use of araliphatic or aliphatic primary Monoamines, in particular aliphatic primary monoamines with at least 6 Carbon atoms in the molecule. Examples of suitable primary monoamines are Benzylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, tert. Butylamine, pentylamine, n-hexylamine, n-octylamine, iso-nonanylamine, iso-tridecylamine, n- Decylamine, stearylamine or ethanolamine.

Furthermore, primary and secondary acyclic or cyclic amines containing ether groups can be used. These are, for example, morpholine or substances of the general formula (CH ₃ - (CH ₂ ) _a -O- (CH ₂ ) _b ) _c NH _d , where a is an integer from 0 to 10, b is an integer from 1 to 20, c is 1 or 2 and the sum of c and d is always 3. Preferably, a = 0, b = 3, c = 1 and d = 2 (= methoxypropylamine).

In addition, column 3, page 3, lines 25 to 47, European Patent 0 192 304 B1 directed.

Examples of suitable polyisocyanates to be used according to the invention are diisocyanates, such as tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, 2,2,4- Trimethylhexamethylene-1,6-diisocyanate, omega, omega'-dipropyl-ether-diisocyanate, Cyclohexyl-1,4-diisocyanate, cyclohexyl-1,3-diisocyanate, cyclohexyl-1,2-diisocyanate, Dicyclohexylmethane-4,4'-diisocyanate, 1,5-dimethyl-2,4-di (isocyanato-methyl) -benzene, 1,5-dimethyl-2,4-di (isocyanatoethyl) benzene, 1,3,5-trimethyl-2,4-di (isocyanatomethyl) - benzene, 1,3,5-triethyl-2,4-di (isocyanatomethyl) benzene, isophorone diisocyanate, Dicyclohexyldimethylmethane-4,4'-diisocyanate, 2,4-tolylene diisocyanate, 2,6- Toluylene diisocyanate, diphenylmethane-4,4'-diisocyanate.

Further examples of suitable polyisocyanates are

• 1. isocyanates having at least one diisocyanate structural unit, which
  • a) an unsaturated or aromatic or non-aromatic ring structure having 5-10 ring atoms and
  • b) has two bonded to the ring structure isocyanate groups, wherein
  • c) in the case of a non-aromatic ring structure
    • a) both isocyanate groups via linear C ₁ -C ₉ alkyl and / or linear C ₂ -C ₁₀ -ether alkyl or
    • b) one isocyanate group directly and the other via linear C ₂ -C ₉ alkyl and / or linear C ₂ -C ₁₀ ether alkyl and
  • d) in the case of an unsaturated aromatic ring structure at least one of the two isocyanate groups is attached via linear C ₂ -C ₉ -alkyl and / or linear C ₂ - C ₁₀ -ether-alkyl having two radicals no benzylic hydrogen atoms connected to the ring structure or;

and or

• 1. at least one oligomer of this isocyanate Ia) having 2 to 10 isocyanate units, in particular a trimer;

and or

• 1. at least one partially blocked isocyanate Ia) and / or at least one partially blocked oligomers Ib).

The isocyanates Ia) may contain two or more of these diisocyanate structural units However, it has been proven to use only one.

With respect to the diisocyanate structural unit of the diisocyanate Ia), there are various Possibilities of further education, which are described below.

With regard to the ring structure (i), it is possible in principle that they are hetero rings is. Then, the ring structure (i) contains C atoms as well as ring atoms thereof as well various ring atoms, such as N atoms, O atoms or Si atoms. in this connection it may 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. Examples of suitable unsaturated or aromatic hetero rings are pyrrole, imidazole, pyrazole, pyridine, pyrimidine, pyrazine, pyridazine or Triazine rings. It is preferred if the ring structure (i) as ring atoms exclusively C- Contains atoms.

The ring structure (i) can be bridge-free on the one hand. In the case that the ring structure (i) is a bicyclic terpene backbone, decalin, adamantane or quinuclidine however, bridges may be included. Examples of suitable terpene backbones are caran, Norcaran, Pinane, Camphane or Norbonan backbones.

The hydrogen atoms of a diisocyanate structural unit Ia), in particular the ring structure (i) may be substituted by groups or atoms which are free of isocyanates  still react with the amine and / or the binder. Examples of suitable groups are Nitro, alkyl, cycloalkyl, perfluoroalkyl, perfluorocycloalkyl or aryl groups. Examples suitable atoms are halogen atoms, in particular fluorine.

Advantageously, the ring structure (i) consists of 6 C atoms, in particular in the form of Cyclohexane or benzene.

Examples of suitable linear C ₁ -C ₉ -alkyl are methylene or ethylene and tri, tetra, penta, hexa, hepta, octa or nonamethylene radicals, in particular methylene radicals.

The linear C ₂ -C ₁₀ ether alkyls are connected to the ring structure either via the oxygen atoms or via the alkanediyl radicals contained therein. Preferably, they are linked via the oxygen atoms. The indices 2 to 10 mean that 2 to 10 C atoms are contained in the ether alkyls.

The ether alkyls may contain only 1 oxygen atom. It is an advantage if 2 to 10, in particular 2 to 5 oxygen atoms in the chain is present. Then there are 1 or more, but especially 2, C atoms between 2 oxygen atoms.

Examples of suitable C ₂ -C ₁₀ etheralkyls are
- (O-CH ₂ ) _m -, where m = 1 to 10,
- (OC ₂ H ₄ ) _p -, where p = 1 to 5,
- (OC ₃ H ₆ ) _q -, where q = 1 to 3 or
- (OC ₄ H ₈ ) _r -, where r = 1 to 2.

If the isocyanate Ia) contains at least one diisocyanate structural unit having a non-aromatic ring structure (i), in particular cyclohexane, both isocyanate groups can be bonded via -CH ₂ -, preferably to the positions 1 and 3 of the ring structure. But it is also possible to bind to positions 1,2 and 1,4. The diisocyanate structural unit or the isocyanate Ia) then has, for example, the formula C ₆ H ₁₀ (-CH ₂ -NCO) ₂ .

But it is also possible that one of the two isocyanate groups directly to a ring atom of a non-aromatic ring structure (i), in particular cyclohexane, is bound and that the second isocyanate group via C ₂ -C ₉ alkyl, in particular C ₃ alkyl to another Ring atom, preferably in 1,2-configuration, is bound. The diisocyanate structural unit or the isocyanate Ia) then has, for example, the formula C ₆ H ₁₀ (-NCO) (- C ₃ H ₆ -NCO).

If the isocyanate Ia) contains at least one diisocyanate structural unit having an unsaturated or aromatic ring structure (i), in particular benzene, both isocyanate groups can be connected via C ₂ -C ₉ -alkyl. It is important that the alkanediyl radicals contain no benzylic hydrogen atoms, but instead carry substituents R ¹ and R ² , which react neither with isocyanates nor with the amine or the binder. Examples of suitable substituents R ¹ and R ² are C ₁ -C ₁₀ -alkyl, aryl or halogen, preferably -CH ₃ .

Examples of suitable alkanediyl groups are accordingly -CR ¹ R ² - (CH ₂ ) _n -, where n = 1 to 8, in particular 1 to 4, and R ¹ and R ² = the abovementioned substituents.

The alkanediyl groups described above are preferably bonded to positions 1 and 3 of the benzene ring. However, binding to positions 1, 2 and 1.4 is also possible in this case. The diisocyanate structural unit or the isocyanate Ia) to be used according to the invention then has, for example, the formula C ₆ H ₄ (--C (CH ₃ ) ₂ -C ₂ H ₄ -NCO) ₂ .

However, the two isocyanate groups may also be linked to the unsaturated or aromatic ring structure, in particular benzene, via the above-described C ₂ -C ₁₀ -etheralkyls. It is important that the ether alkyls carry no benzylic hydrogen atoms. This can be achieved in the event that the ether alkyls are linked via C atoms to the aromatic ring structure, that the benzylic carbon atoms carry the substituents R ¹ and R ^{2 described} above. When the ether alkyls are linked via oxygen atoms to the aromatic ring structure, there are no benzylic hydrogen atoms present, which is why this variant is preferred.

It is also possible here for one of the two isocyanate groups to be bonded directly to a ring atom of an unsaturated or aromatic ring structure (i), preferably a benzene ring, and for the second isocyanate group to have, for example, C ₃ -C ₉ -alkyl which has no benzylic hydrogen atoms , is bonded to another ring atom, preferably in 1,2-configuration. The diisocyanate structural unit or the isocyanate Ia) to be used according to the invention then has, for example, the formula C ₆ H ₄ (-NCO) (--C (CH 3) 2 - (CH 2) 2 -NCO).

Instead of the isocyanate Ia) or in addition to this, at least one oligomer Ib) be used. The oligomer Ib) is prepared from the isocyanate Ia), wherein advantageously 2 to 10 monomer units are reacted and wherein the Trimerization is particularly preferred. The oligomerization and trimerization can with the aid of customary and known suitable catalysts for the formation of uretdione, Biuret, isocyanurate, iminooxadiazinedione, urea and / or allophanate groups. However, oligomerization is also possible by reaction with low molecular weight Polyols such as trimethylolpropane or homotrimethylolpropane, glycerol, neopentyl glycol, Dimethylolcyclohexane, ethylene glycol, diethylene glycol, propylene glycol, 2-methyl-2- propylpropanediol-1,3,2-ethyl-2-butylpropanediol-1,3,2,2,4-trimethylpentanediol-1,5 and 2,2,5-trimethylhexane-diol-1,6, which, if necessary, optionally partially ethoxylated and / or propoxylated or otherwise hydrophilized.

Oligomers of this type, other than those described above, may also be used Diisocyanates, for example hexamethylene diisocyanate, are used become.

In addition to the diisocyanates and / or their oligomers and / or the isocyanates Ia) and / or their oligomers Ib), at least one partially blocked diisocyanate and / or its partially blocked oligomer and / or at least one partially blocked Isocyanate Ia) and / or its partially blocked oligomer Ib) (= isocyanate Ic)) become. Furthermore, instead of the diisocyanates and / or their oligomers and / or the isocyanates Ia) and / or their oligomers Ib) at least partially blocked oligomer and / or at least one partially blocked oligomer Ib) (= Isocyanate Ic)) can be used.  

In addition, on page 3, lines 10 to 51, the German patent DE 198 11 471 A 1 or on page 8, lines 4 to 23 of international patent application WO 94/22968 directed.

Examples of suitable blocking agents are those of U.S. Patent 4,444,954 known blocking agents such as i) phenols such as phenol, cresol, xylenol, nitrophenol, Chlorophenol, ethylphenol, t-butylphenol, hydroxybenzoic acid, esters of this acid or 2,5-di-t-butyl-4-hydroxy-toluene; ii) lactams, such as caprolactam, valerolactam, Butyrolactam or propiolactam; iii) active methylenic compounds, such as Diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate or acetylacetone; iv) alcohols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butyl Butanol, n-amyl alcohol, t-amyl alcohol, lauryl alcohol, ethylene glycol monomethyl ether, Ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, Ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, Diethylene glycol monoethyl ether, propylene glycol monomethyl ether, methoxymethanol, Glycolic acid, glycolic acid ester, lactic acid, lactic acid ester methylolurea, Methylolmelamine, diacetone alcohol, ethylene chlorohydrin, ethylene bromohydrin, 1,3- Dichloro-2-propanol or aceto-cyanohydrin; v) mercaptans such as butylmercaptan, Hexylmercaptan, t-butylmercaptan, t-dodecylmercaptan, 2-mercaptobenzothiazole, Thiophenol, methylthiophenol or ethylthiophenol; vi) acid amides such as acetoanilide, Acetoanisidinamid, acrylamide, methacrylamide, acetic acid amide, stearic acid amide or benzamide; vii) imides such as succinimide, phthalimide or maleimide; viii) amines such as Diphenylamine, phenylnaphthylamine, xylidine, N-phenylxylidine, cabazole, aniline, Naphthylamine, butylamine, dibutylamine or butylphenylamine; ix) imidazoles such as imidazole or 2-ethylimidazole, x) ureas such as urea, thiourea, ethyleneurea, Ethylene thiourea or 1,3-diphenylurea; xi) carbamates such as N- Phenylcarbamoyl phenyl ester or 2-oxazolidone; xii) imines such as ethyleneimine, xiii) Oximes such as acetone oxime, formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, Diisobutyl ketoxime, diacetyl monoxime, benzophenone oxime or chlorohexanone oximes; xiv) Salts of sulfurous acid such as sodium bisulfite or potassium bisulfite; xv) Hydroxamic acid esters such as Benzylmethacrylohydroxamat (BMH) or Allyl methacrylohydroxamate or xvi) substituted pyrazoles, imidazoles or triazoles.  

The above-described oligomers advantageously have an NCO Functionality of 2.0-5.0, preferably 2.2-4.0, especially 2.5-3.8.

In the preparation of the thixotropic agent according to the invention can still at least one of the constituents of the invention described below Be present coating materials, adhesives and sealants, in particular at least one binder (see Rompp Lexikon Lacke and Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Binders," pages 73 and 74), at least one another hydroxyl-containing reactive diluent and / or at least one in the German Patent DE 198 11 471 A1, page 3, line 52, to page 5, line 4, described polyol.

Furthermore, the thixotropic agent according to the invention at least one Silica contained. Hydrophilic and hydrophobic silicas are commercially available for example under the trade name Aerosil® and under the product names 200, R972, R974, R805 and R812 from Degussa AG, Hanau.

In addition, the thixotropic agent of the invention may still at least one Wetting agents included. Examples of suitable wetting agents are disclosed in the patent EP 0 154 678 A1 known or are sold under the trade names Disperbyk® 161 by the Byk, Borchigen® from Bayer AG and Tego Disperse® 710 from the company Tego Chemical Services distributed.

The thixotropic agent according to the invention serves to prepare coating materials, adhesives and sealants according to the invention, In particular, solvent-containing coating materials according to the invention, adhesives and Sealants. This shows the particular advantage of the invention Thixotropic agent that they namely the production of inventive Coating materials, adhesives and sealants allow a particular high solids content with the correspondingly low content of volatile have organic ingredients and still apply very well to let. Preferably, the solids content, based on the respective Coating material or adhesive or the respective sealant, at least 40,  preferably at least 45, more preferably at least 50, most preferably 55 and in particular at least 60 wt .-%.

The content of the coating materials, adhesives and sealants according to the invention on the thixotropic agents according to the invention can vary very widely. Downward it is only limited by the fact that the thixotropic agent according to the invention in must be added to such an amount that its advantageous technical Effects still set to the desired and required extent. He is upstairs characterized in that the viscosity of the coating materials according to the invention, Adhesives and sealants should not be so high that a problem-free Application and a very good course are no longer guaranteed. The Thixotropic agent according to the invention is preferably used in an amount of from 0.01 to 10% by weight, preferably 0.02 to 9.0 wt .-%, in particular 0.06 to 8.5 wt .-%, respectively based on the total solids of the coating materials according to the invention, Adhesives and sealants used.

Very particular advantages result in the use of the invention Thixotropic agent for the preparation of the coating materials according to the invention, in particular the pigmented solid-color topcoats or basecoats according to the invention or unpigmented clearcoats, especially the clearcoats of the invention.

In general, the coating materials of the invention contain except the Thixotropic agents according to the invention still at least one binder, the can be self-crosslinking or externally crosslinking. To the terms "self-crosslinking" and "externally cross-linked" is published on Römpp Lexikon Lacke and Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Hardening", pages 274-276.

Accordingly, the chemical nature of the binders can vary widely. According to the invention, it is advantageous if hydroxyl-containing binders are used become.

Examples of suitable hydroxyl-containing binders are thermally curable, random, alternating and / or block-structured linear and / or branched and / or comb-like (co) polymers of ethylenically unsaturated  Monomers, or polyaddition resins and / or polycondensation resins. To this Terms are used in Römpp Lexikon Lacke and Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, page 457, "polyaddition" and "polyaddition resins (Polyadducts) ", and pages 463 and 464," polycondensates "," polycondensation "and Refer to "polycondensation resins".

Examples of suitable binders are hydroxyl-containing linear and / or branched and / or block-like, comb-like and / or statistically structured Poly (meth) acrylates or acrylate copolymers, polyesters, alkyds, polyurethanes, acrylated polyurethanes, acrylated polyesters, polylactones, polycarbonates, polyethers, Epoxy resin-amine adducts, (meth) acrylate diols, partially saponified polyvinyl esters or Polyureas. Of these, the acrylate copolymers and the polyesters are advantageous and are preferably used according to the invention. Examples are especially preferred Acrylate copolymers are described in International Patent Application WO 94/22968, Page 2, line 26, to page 7, line 5 described.

The content of the coating materials of the invention to the binder can be very broad vary and depend primarily on the purpose of the respective coating material of the invention. Preferably, the binders are in one Amount of, based on the total solids of the coating material, 5.0 to 95, preferably 10 to 90, more preferably 15 to 85, most preferably 20 to 80 and in particular 25 to 75 wt .-%.

Should the coating materials according to the invention also with actinic radiation to be curable, which is also referred to by experts as dual cure, they contain with actinic radiation curable components such as (meth) acrylic functional (Meth) acrylate copolymers, polyether acrylates, polyester acrylates, unsaturated polyesters, Epoxy acrylates, urethane acrylates, amino acrylates, melamine acrylates, silicone acrylates and the corresponding methacrylates.

In the context of the present invention is actinic radiation electromagnetic radiation such as visible light, UV radiation or X-radiation, in particular UV radiation, or corpuscular radiation such as electron radiation Roger that.  

Furthermore, the coating material of the invention color and / or effect Pigments (see Rompp Lexikon Lacke and Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, "Effect Pigments", page 176, "Metal Oxide Mica Pigments" to "Metallic Pigments", pages 380 and 381, "iron blue pigments" to "iron oxide black", Pages 180 and 181, "Pigments" to "Pigment Volume Concentration", pages 451 to 453, "Thioindigo Pigments", page 563, and "Titanium Dioxide Pigments", page 567); organic and inorganic, transparent or opaque fillers (see Rompp Lexikon Lacke and Printing inks, Georg Thieme Verlag, 1998, "Fillers", pages 250 ff.); nanoparticles; thermally curable reactive diluents, such as in positionally isomeric diethyloctanediols or Hydroxyl-containing hyperbranched compounds or dendrimers; With Actinic radiation curable reactive diluents (see Rompp Lexikon Lacke and Printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, "Reaktivverdünner" page 491); Crosslinking agents for thermal curing such as aminoplast resins, anhydride group-containing compounds or resins, epoxy group-containing compounds or resins, tris (alkoxycarbonylamino) triazines, carbonate group-containing compounds or resins, blocked and / or unblocked polyisocyanates and / or Hydroxyalkylamides (see also Rompp Lexikon Lacke and printing inks, Georg Thieme Verlag, Stuttgart, New York, 1998, "Hardening", pages 274 to 276); low and high-boiling organic solvents ("long solvents"), such as ketones Methyl ethyl ketone or methyl isobutyl ketone, esters such as ethyl acetate or butyl acetate, ethers such as dibutyl ether or ethylene glycol, diethylene glycol, propylene glycol, Dipropylene glycol, butylene glycol or dibutylene glycol dimethyl, diethyl or dibutyl ether, N-methylpyrrolidone or xylenes or mixtures of aromatic Hydrocarbons such as Solvent Naphtha® or Solvesso®; Water; UV absorbers; Light stabilizers; Radical scavengers; thermolabile radical initiators; Photoinitiators; Catalysts for thermal crosslinking; Venting means; slip additives; polymerization inhibitors; defoamers; emulsifiers; Wetting and dispersing agents; Adhesion promoters; Leveling agents; film-forming aids; rheology-controlling additives (Thickener); Flame retardants; driers; desiccant; Skinning agents; Corrosion inhibitors; Waxes and matting agents included.

As far as the cross-linking agents are concerned, they can, depending on their reactivity coating materials according to the invention are added directly, whereby a  One-component system results. Is it, however, a particularly reactive one? Crosslinking agents, such as a polyisocyanate or an epoxide, this is generally only added shortly before use the coating materials of the invention. in this connection results in a two- or multi-component system.

Further examples of suitable additives of the type described above are described in the textbook "Lackadditive" by Johan Bieleman, Wiley-VCH, Weinheim, New York, 1998, described in detail.

The additives are used in conventional and known, effective amounts.

The above-described binders and additives can also be used in the Be contained adhesives and sealants according to the invention, provided that they are suitable, which the skilled person will easily determine by his general knowledge can.

The preparation of the coating materials of the invention has no special features but is done in a conventional manner by mixing the above components described in suitable mixing units such as stirred tank, dissolver, Agitator mills or extruders.

The coating material of the invention, in particular the inventive Water-based paint, is excellent for the production of color and / or effect Multilayer coatings on primed and unprimed substrates after wet-in Wet method suitable. Furthermore, the coating material according to the invention, in particular the solid-color topcoat according to the invention, outstanding for the production of single-coat color and / or effect paints suitable.

Special advantages unfolds the coating material of the invention in his Use as a clearcoat according to the invention in the context of the wet-on-wet process a basecoat is applied to the primed or unprimed substrate and dried, however, it is not cured, after which the clearcoat is applied to the basecoat film and the resulting clearcoat film together with the basecoat film thermally or thermally and with actinic radiation (dual cure) hardens.  

The substrates are all surfaces to be painted, which by curing the layers thereon under the application of heat or the combined Application of heat and actinic radiation (dual cure) can not be harmed in consideration; these are z. B. metals, plastics, wood, ceramics, stone, textile, fiber composites, Leather, glass, glass fibers, glass and rock wool, mineral- and resin-bound building materials, such as Gypsum and cement boards or roof tiles, as well as composites of these materials. Therefore the multicoat paint systems of the invention are also for applications outside the automotive OEM and automotive refinishing suitable. Come here in particular for the coating of furniture and for industrial application, including coil coating and container coating or the coating of electrotechnical Components, into consideration. In industrial applications, they are suitable for the Painting of virtually all parts for private or industrial use such as Radiators, household appliances, small metal parts such as nuts and bolts, Hubcaps, rims, packing or coils or windings of stators and rotors of electric motors.

In the case of electrically conductive substrates primers may be used which are in customary and known manner of electrocoating (ETL) are produced. Therefor come both anodic (ATL) and cathodic (KTL) electrodeposition paints, but especially KTL, into consideration. Usually, especially in the Automobackackierung, then a filler coating or Anticaking primer applied, considered as part of the primer can be.

It may also be primed or unrounded plastic parts of z. ABS, AMMA, ASA, CA, CAB, EP, UF, CF, MF, MPF, PF, PAN, PA, PE, HDPE, LDPE, LLDPE, UHMWPE, PC, PC / PBT, PC / PA, PET, PMMA, PP, PS, SB, PUR, PVC, RF, SAN, PBT, PPE, POM, PUR-RIM, SMC, BMC, PP-EPDM and UP (abbreviated to DIN 7728T1) can be painted, glued or sealed. In the case of non-functionalized and / or non-polar substrate surfaces, these can be known in prior art prior to coating Subjected to a pretreatment, such as with a plasma or with flames, or be provided with a hydro primer.  

The application of the clearcoats according to the invention can be carried out by all customary Application methods, such. As spraying, knife coating, brushing, pouring, dipping, watering, Dripping or rolling done. In this case, the substrate to be coated as such rest, wherein the application device or system is moved. But that too can to be coated substrate, in particular a coil to be moved, wherein the Application plant rests relative to the substrate or is moved in a suitable manner. Contain the clearcoats of the invention components containing actinic radiation can be activated, the application is preferably in the absence of light carried out. Of course, these application methods in the context of Wet-in-wet process according to the invention also for the application of the basecoat film be used.

The applied basecoat films and clearcoat films can be used in conventional and known manner - possibly after a certain rest period, the course of the Layers and / or the evaporation of volatiles serves - thermal or be cured thermally and with actinic radiation.

Methodically, the thermal curing has no special features, but it will be the usual and known temperatures in the range of room temperature to 200 ° C, Curing times ranging from one minute to three hours and devices such as Radiant heaters or convection ovens applied.

Curing with actinic radiation also has no special methodological features but is done in a conventional manner by irradiation with UV lamps and / or electron beam sources, preferably under inert gas.

In the case of joint curing of the clearcoat films according to the invention with the Basecoat films can be thermally cured and cured with actinic radiation be used simultaneously or alternately. Be the two curing methods used alternately, for example, can be started with the thermal curing and be terminated with the curing with actinic radiation. In other cases it can be prove to be advantageous to begin with the curing with actinic radiation and hereby to end. The person skilled in the art can use the curing method which is suitable for the individual case  is most advantageous, due to its general expertise, where appropriate To find help with simple preliminary tests.

This shows, as a further particular advantage of the clearcoats of the invention, that all customary and known basecoats (cf., for example, the patents EP 0 089 497 A1, EP 0 256 540 A1, EP 0 228 003 A1, EP 0 397 806 A1, DE-A-43 28 092 A1, EP 0 522 420 A1, EP 0 522 419 A1, WO 97/49745, WO 97/49747, EP 0 401 565 A1, EP 0 730 613 B1 or WO 95/14721) in the wet-in-wet process with the Clearcoat film according to the invention can be combined.

Within the multicoat system according to the invention, the thickness of the individual can Layers vary widely. According to the invention, however, it is advantageous if the Basecoat layer has a thickness of 5 to 25 .mu.m, in particular 7 to 20 .mu.m, and the Clearcoat layer has a thickness of 15 to 120 .mu.m, preferably 30 to 80 .mu.m and especially 40 to 60 microns.

The coatings produced by the process according to the invention, in particular the one- and multi-layer clearcoats and color and / or effect paints are what color, effect, gloss and D.O.I. (distinctiveness of the reflected image), of the highest optical quality, have a smooth, structure-free, hard, flexible and scratch-resistant surface, are odorless and weatherproof, chemical and etch resistant, do not yellow and show no cracking and Delamination of the layers.

The primed or unprimed substrates coated with these coatings therefore have a particularly high service life and a particularly high Use value, what they are for manufacturers, users and end users technically and economically very attractive. The same applies to the primed or ungrounded substrates, by means of the adhesives of the invention and Bonding adhesives produced adhesive layers and seals glued and / or are sealed.

Examples Production Example 1 The preparation of the thixotropic agent according to the invention

In a suitable reaction vessel, 10.1 parts by weight of benzylamine and 480 Parts by weight of 2,4-diethyloctane-1,5-diol and with the help of a dissolver mixed. To the resulting mixture was added a solution of 7.9 Parts by weight of hexamethylene diisocyanate in 102 parts by weight of butyl acetate Room temperature dropped for two minutes. The resulting reaction mixture was stirred for ten minutes.

The thixotropic agent according to the invention had the following pseudoplastic behavior:

Schernfeld viscosity (s ^-1 ) (DPas) 1 8080 10 1920 100 685 1000 308

Production Example 2 The preparation of a binder based on polyester

In a 4 liter steel reactor, 134 parts by weight of trimethylolpropane and 462 Parts by weight of hexahydrophthalic presented and 6.5 hours under Stirring heated to 120 ° C. Subsequently, 684 parts by weight of Versatic® acid were added Glycidylester added and heated the resulting reaction mixture with stirring so long at 120 ° C until an acid number of 6.6 was reached. The polyester was at 90 ° C dissolved with butyl acetate to a solids content of 84.4 wt .-%. Its number-average Molecular weight was 1499 daltons, its mass-average molecular weight was 2,485 Dalton.  

Production Example 3 The preparation of an acrylic-based binder

In a 4 liter steel reactor, equipped with two feed vessels and one Reflux condenser, was added 218 parts by weight of 2,4-diethyloctane-1,5-diol, 108.95 Parts by weight of VeoVa® (see Rompp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, page 598), 250.3 parts by weight of methyl amyl ketone and Submitted 192.3 parts by weight of ethoxyethyl propionate and with stirring under nitrogen Heated to 145 ° C. To the resulting mixture was metered at 145 ° C - simultaneously starting - during 4.0 hours evenly a mixture of 326.5 parts by weight Styrene, 217.7 parts by weight of tert-butylcyclohexyl acrylate, 653 parts by weight Butyl methacrylate and 870.6 parts by weight of hydroxypropyl methacrylate and during 5.0 Evenly a mixture of 97.9 parts by weight of di-tert-butyl peroxide and 65.3 parts by weight of methyl amyl ketone. The resulting acrylate copolymer was washed with a mixture of 8.0 parts by weight butyl acetate, 1.0 parts by weight xylene and 1.0 Parts by weight of methyl amyl ketone adjusted to a solids content of 69.0 wt .-%. The resulting solution had a viscosity of 35 dPas.

example 1 The preparation of a clearcoat according to the invention and an inventive clearcoat

From the constituents described below, a two-component clearcoat was prepared in the usual and known manner:
25.8 parts by weight of the binder solution of Preparation Example 2,
19.6 parts by weight of the binder solution of Preparation Example 3,
5.0 parts by weight of 2,4-diethyloctane-1,5-diol,
9.6 parts by weight of the thixotropic agent of Preparation Example 1,
0.07 parts by weight of a 10% strength by weight solution of dibutyltin dilaurate in butyl acetate,
0.07 parts by weight of the commercially available BYK® 331 additive from Byk Chemie,
0.4 parts by weight of a commercially available additive for extending the service life,
0.02 of a commercially available silicone leveling agent,
0.8 parts by weight of the commercially available light stabilizer Tinuvin® 400,
0.7 parts by weight of the commercial light stabilizer Tinuvin® 292,
17.5 parts by weight of butyl acetate,
25.1 parts by weight of the commercial polyisocyanate Desmodur® 3600 and
3.3 parts by weight of the commercial polyisocyanate Desmodur® 3390.

The resulting clearcoat had a pot life of about two Hours up. Its viscosity was 29 s in the DIN 4-cup. Its solids content was 72% by weight (one hour / 130 ° C).

The clearcoat provided clearcoats, even at relatively high layer thicknesses a gloss of over 85 (reflectometric measurement at an angle of 20 ° with a reflectometer from BYK). In addition, the rest fulfilled performance characteristics of the clearcoats all the requirements of Market.

Claims (16)

1. Thixotropic agent, producible by at least one primary and / or secondary amine and / or water with at least one polyisocyanate in at least one liquid, low molecular weight polyol as the reaction medium implements. 2. thixotropic agent according to claim 1, characterized in that the polyol a polyhydroxy-functionalized cyclic and / or acyclic alkane with 9 bis 16 carbon atoms in the molecule. 3. thixotropic agent according to claim 2, characterized in that the alkane is functionalized with two hydroxyl groups. 4. thixotropic agent according to claim 2 or 3, characterized in that the functionalized alkane is acyclic. 5. thixotropic agent according to one of claims 2 to 4, characterized the functionalized alkane is primary and / or secondary, especially primary and secondary, hydroxyl groups. 6. thixotropic agent according to one of claims 2 to 5, characterized the functionalized alkanes are positionally isomeric dialkyloctanediols. 7. thixotropic agent according to claim 6, characterized in that the positionally isomeric dialkyloctanediols are isomeric diethyloctanediols. 8. thixotropic agent according to claim 7, characterized in that the diethyloctanediol, a 2,3-, 2,4-, 2,5-, 2,6-, 2,7-, 3,4-, 3,5-, 3,6- or 4,5-diethyloctanediol.   9. thixotropic agent according to claim 8, characterized in that the diethyloctanediol is a 2,4-diethyloctanediol. 10. thixotropic agent according to one of claims 7 to 9, characterized that the positionally isomeric diethyloctanediol is a diethyloctane-1,2-, -1,3-, -1,4-, -1,5-, -1,6-, -1,7-, -1,8-, -2,3-, -2,4-, -2,5-, -2,6-, -2,7-, -2 , 8-, -3,4-, -3,5-, -3,6-, -3,7-, -3,8-, -4.5, -4.6, -4.7, -4.8, -5.6, -5.7, -5.8, -6.7, -6 , 8- or -7,8-diol. 11. thixotropic agent according to claim 10, characterized in that the diethyloctanediol is diethyloctan-1,5-diol. 12. Thixotropic agent according to claim 11, characterized in that the diethyloctanediol is 2,4-diethyloctan-1,5-diol. 13. thixotropic agent according to any one of claims 1 to 12, characterized characterized in that primary monoamines are used. 14. thixotropic agents according to any one of claims 1 to 13, characterized characterized in that diisocyanates are used. 15. Use of the thixotropic agents according to one of claims 1 to 14 for the production of coating materials, adhesives and sealants with a high solids content. 16. Use of thixotropic agents according to claim 15, characterized characterized in that the solids content, based on the respective Coating material or adhesive or the respective sealant, at least 40 wt .-% is.