WO2002102872A1

WO2002102872A1 - Curable mixtures of substances, method for the production and use thereof

Info

Publication number: WO2002102872A1
Application number: PCT/EP2002/006379
Authority: WO
Inventors: Hubert Baumgart; Vincent Cook; Peter Hommes; Elke Westhoff
Original assignee: Basf Coatings Ag
Priority date: 2001-06-15
Filing date: 2002-06-11
Publication date: 2002-12-27
Also published as: DE10128885A1

Abstract

The invention relates to the use of blocked, partially blocked and unblocked polyisocyanates for thermally cross-linking primary and/or secondary carbamate group-containing compounds by the chemical reaction of the isocyanate groups with the carbamate groups. The invention further relates to curable mixtures of substances that contain, as the complementary reactive functional groups, primary and/or secondary carbamate groups and blocked and/or unblocked isocyanate groups that are effectively available for cross-linking the carbamate groups. The invention also relates to the use of the curable mixtures of substances as coating agents, adhesives and sealing compounds as well as to their use for producing the same.

Description

Curable mixtures of substances, processes for their preparation and their use

The present invention relates to the novel use of blocked, partially blocked and / or unblocked polyisocyanates for the thermal crosslinking of compounds containing carbamate groups. In addition, the present invention relates to new curable substance mixtures which crosslink via the reaction of blocked, partially blocked and / or unblocked polyisocyanates with compounds containing carbamate groups. Furthermore, the present invention relates to a new method for producing the new curable mixtures. Last but not least, the present invention relates to the use of the new curable substance mixtures, in particular as coating materials, adhesives and sealants.

The use of blocked, partially blocked and / or unblocked polyisocyanates for the thermal crosslinking of compounds which contain isocyanate-reactive functional groups, such as hydroxyl, thiol and / or primary and / or secondary amino groups, has long been known.

Likewise, the use of aminoplast resins for the thermal crosslinking of compounds, the carbamate groups of the general formula I:

-O-C (O) -NHR (I).

wherein R represents a hydrogen atom or an alkyl group, known. Reference is made, for example, to European patent applications EP 0 594 068 A1, EP 0 594 142 A1 and EP 0 675 141 B1 or the international patent application WO 94/10211. Curable coating materials are known from the European patent application EP 0 915 113 A 1

(1 a) a compound containing hydroxyl and carbamate groups,

(1 b) a polyisocyanate crosslinking agent and

(1 c) an aminoplast crosslinking agent

contains. Alternatively, the curable coating material contains

(2a) a compound containing carbamate groups,

(2 b) a compound containing hydroxyl groups,

(2 c) a polyisocyanate crosslinking agent and

(2 d) an aminoplast crosslinking agent.

It is essential here that

the effective equivalents of the aminoplast crosslinking agent are equal to or less than the equivalents of the carbamate groups and

the effective equivalents of the polyisocyanate crosslinking agent are equal to or less than the equivalents of the hydroxyl groups.

This combination ensures that the viscosity in the initial phase of crosslinking does not drop to such an extent that through strong flow of the coating material form surface defects, such as runners, depressions, "fat edges" or orange peel.

The effect is based on the aminoplast crosslinking agent first reacting with the carbamate groups before the blocked isocyanate groups of the polyisocyanate crosslinking agent react with the hydroxyl groups. The equivalent ratio also ensures that the aminoplast crosslinking agent does not react with the hydroxyl groups and thus forms undesirable ether groups which offer points of attack for aggressive chemicals, such as acid rain, or actinic radiation, such as UV radiation.

If polyisocyanate crosslinking agents with free isocyanate groups are used, they react with the hydroxyl groups before the aminoplast crosslinking agent reacts with the carbamate groups, whereby the same effect is achieved.

The crosslinking of the known coating material by the reaction of the blocked or unblocked isocyanate groups with the carbamate groups is not described in EP 0 915 113 A1.

In the unpublished German patent application DE 100 27 296.7, the following two lists of reactive functional groups are listed in an overview, from which 92 pairs of complementary reactive functional groups can theoretically be derived:

Overview: Examples of complementary reactive functional groups in the

Binders and crosslinking agents or Crosslinking agents and binders

-SH -C (O) -OH

-NH ₂ -C (O) -OC (O) -

-OH -NCO

-O- (CO) - NH- (CO) - NH ₂ -NH-C (O) -OR ^'

-NH-CH ₂ -OH

-N (-CH ₂ -OR ^' ) ₂

-NH-C (O) -CH (-C (O) OR ^' ) ₂

-NH-C (O) -CH (-C (O) OR ^' ) (- C (O) -R')

-NH-C (O) -NR "R ^' "

> Si (OR ^' ) ₂

O -CH-CH ₂ O

C

OO

-C (O) -OH O

-CH-CH2

-C (O) -N (CH ₂ -CH ₂ -OH) ₂

In the overview, the variable R ^'stands for an acyclic or cyclic aliphatic, an aromatic and / or an aromatic-aliphatic (araliphatic) radical; the variables R and R stand for the same or different aliphatic radicals or are linked to one another to form an aliphatic or heteroaliphatic ring.

It is further stated in the unpublished German patent application that preferably thio, hydroxyl, N-methylolamino, N-alkoxymethylamino, imino, carbamate, allophanate and / or carboxyl groups are preferred at crosslinking temperatures of 60 to 180 ° C. Hydroxyl or carboxyl groups, on the one hand and preferably crosslinking agents with anhydride, carboxyl, epoxy, blocked isocyanate, urethane, methylol, methylol ether, siloxane, carbonate, amino, hydroxy and / or beta-hydroxyalkylamide groups, preferably epoxy, beta-hydroxyalkylamide, blocked isocyanate, urethane or alkoxymethylamino groups, on the other hand. The pair »carbamate / isocyanate« is therefore not described expressis verbis, but can at most be derived from a selection from two extensive lists. However, such a selection is opposed by the fact that there is no indication in the prior art that carbamate groups and isocyanate groups could represent complementary reactive functional groups for thermal crosslinking. In addition, in the examples of the unpublished German patent application only the couple

»Carboxyl groups / epoxy groups« applied.

The object of the present invention is to find new curable substance mixtures which can be produced in a simple manner and can be used widely, in particular as coating materials, adhesives and sealing compounds.

The new coating materials, adhesives and sealants are intended to provide coatings, adhesives and seals, in particular coatings, which have excellent etch resistance and chemical resistance, high gloss, high abrasion and scratch resistance and a very high surface hardness, so that in the case of their Repairs can be sanded and polished without problems.

Accordingly, the new use of blocked, partially blocked and unblocked polyisocyanates for the thermal crosslinking of compounds containing primary and / or secondary carbamate groups was found by the chemical reaction of the isocyanate groups with the carbamate groups, which is referred to below as the use according to the invention. In addition, the new curable substance mixtures have been found containing primary and / or secondary carbamate groups as complementary reactive functional groups on the one hand and blocked and / or unblocked isocyanate groups available on the other hand for crosslinking the carbamate groups.

The new curable mixtures of substances are referred to below as "mixtures according to the invention".

Further methods, connections and objects according to the invention are evident from the description below

In view of the prior art, it was surprising and unforeseeable for the person skilled in the art that the object on which the present invention is based could be achieved by the use according to the invention. The use according to the invention led to a new crosslinking chemistry which made it possible to produce the substance mixtures according to the invention. The mixtures of substances according to the invention can be used outstandingly as coating materials, adhesives and sealing compounds or for their production. These supplied new coatings, adhesive layers and seals, with an excellent property profile, which comprised combinations of important application properties, which could not yet be achieved in this advantageous form by the coating materials, adhesives and sealants of the prior art.

In the context of the present invention, “complementary reactive functional groups” means a pair of reactive functional groups which crosslink with one another, such as for example the frequently used pair

"Isocyanate group / hydroxyl group".

In the case of the use according to the invention, this is the "isocyanate group / carbamate group" pair.

The substance mixtures according to the invention contain blocked and / or unblocked isocyanate groups which are effectively available for crosslinking the carbamate groups. This means that so many blocked and / or unblocked isocyanate groups are always made available that even after their reaction with any further isocyanate-reactive functional groups, such as hydroxyl groups, there are still sufficient blocked and / or unblocked isocyanate groups to trigger the crosslinking reaction according to the invention ,

The ratio of equivalent of blocked and / or unblocked isocyanate groups which are effectively available for crosslinking with carbamate groups to carbamate groups is preferably at least 0.1, preferably at least 0.2, particularly preferably at least 0.3, very particularly preferably at least 0, 4 and in particular at least 0.5. The upper limit for the equivalent ratio is in itself arbitrary, but an excessive excess of blocked and / or unblocked isocyanate groups should be avoided. The upper limit is therefore preferably 2, preferably 1.5, particularly preferably 1.2, and in particular 1.

The mixtures of substances according to the invention can be of any composition, as long as they have the features of the invention listed above. The substance mixtures according to the invention preferably contain at least one, preferably one, compound (A) with at least one group, preferably at least two and in particular at least three groups of the general formula I:

-0-C (0) -NHR (I).

In the general formula I, the variable R represents a hydrogen atom or an alkyl group, in particular a linear or branched alkyl group with 1 to 10 carbon atoms or a cycloaliphatic group with 4 to 8 carbon atoms. R is preferably a hydrogen atom.

The compound (A) can be of low molecular weight. Examples of suitable low molecular weight compounds (A) are found in the literature references

EP 0 710 707 A 2, page 4, lines 1 to 27, or EP 0 915 113 A 1st page 2, lines 44 to 48, and page 6, lines 21 to 25,

EP 0 636 660 B1, column 1, line 41, to column 2, line 3, column 2,

Row 12 to column 3, row 32, and column 5, row 43, to column 6, row 36, or

WO 87/00851, page 13, line 11, to page 15, line 8 and Example 1 to Example 33, pages 17 to 27,

described in detail. These low molecular weight compounds (A) allow the preparation of mixtures of substances according to the invention which are particularly high in solids.

The compound (A) can be oligomeric and / or polymeric. Suitable oligomers and polymers (A) come from the polymer classes of the random, alternating and / or block-like linear and / or branched and / or comb-like (co) polymers of ethylenically unsaturated monomers, or polyaddition resins and / or polycondensation resins. These terms are supplemented by Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart, New York, 1998, page 457, "Polyaddition" and "Polyaddifionsharze (polyadducts)", and pages 463 and 464, "Polycondensates", "Polycondensation" and "Polycondensation Resins".

Examples of highly suitable (co) polymers (A) are (meth) acrylate copolymers and partially saponified polyvinyl esters, in particular (meth) acrylate copolymers.

Examples of suitable polyaddition resins and / or

Polycondensation resins (A) are polyesters, alkyds, polyurethanes, polylactones, polycarbonates, polyethers, epoxy resin-amine adducts, polyureas, polyamides or polyimides, in particular polyesters.

The oligomers and / or polymers (A) very particularly preferably originate from the polymer classes of the (meth) acrylate copolymers and polyester.

Oligomers and polymers (A) containing carbamate groups, which originate from the abovementioned polymer classes, and processes for their preparation are disclosed in the patent applications

EP 0 594 068 A 1, page 2, line 45, to page 4, line 27, page 5,

Lines 36 to 57, and page 7, lines 1 to 22, EP 0 594 142 A 1, page 3, line 1, to page 4, line 37, page 5, line 49, to page 6, line 12, and page 7, lines 5 to 26,

- EP 0 675 141 B1, page 2, line 44, to page 5, line 15, page 8,

Line 5, to page 10, line 41,

WO 94/10211, page 4, line 18, to page 8, line 8, page 12, line 30, to page 14, line 36, page 15, line 35, to page 17, line 32, and page 18, line 16 , to page 19, line 30,

WO 01/23439, page 3 lines 13 to 29, page 4, line 25, to page 19, line 18, i. V. m. the manufacturing examples 1 to 3, page 36, line 16, to page 38, line 12, and

EP 0 915 113 A 1, page 6, line 26, to page 8, line 49, and Example 1, page 11, lines 3 to 15,

known.

The oligomers and / or polymers (A) are preferably prepared by using a monomer mixture which contains at least one olefinically unsaturated carboxylic acid, for example methacrylic acid, in the presence of a glycidyl ester of Versatic © acid (cf.Römpp Lexikon Lacke und Druckfarben, Georg Thieme Verlag, Stuttgart New York, 1998 "Versatic © acids", pages 605 and 606) copolymerized, after which the resulting hydroxyl group-containing (meth) acrylate copolymer is reacted with at least one alkyl carbamate, such as methyl, propyl or butyl carbamate. Or else hydroxyl group-containing (meth) acrylate copolymers and polyesters are combined with phosgene in chloroformate groups (Meth) acrylate copolymers converted, after which the chloroformate groups with ammonia or primary amines

Carbamate groups are implemented. It is also possible to react (meth) acrylate copolymers containing isocyanate groups or polyesters with at least one hydroxyalkyl carbamate, such as 2-hydroxyethyl carbamate.

The oligomers and polymers (A) preferably have a number average molecular weight of 600 to 20,000, preferably 800 to 15,000, particularly preferably 1,000 to 10,000, very particularly preferably 1,200 to 8,000 and in particular 1,200 to 6,000 daltons.

In addition to the carbamate groups, the low molecular weight compounds, the oligomers and / or the polymers (A) can also contain at least one, preferably at least two and in particular at least three, reactive functional groups which differ from the carbamate groups. These reactive functional groups are preferably selected from the group consisting of isocyanate-reactive and non-isocyanate-reactive functional groups.

Examples of suitable isocyanate-reactive functional groups are hydroxyl, thiol and primary and secondary amino groups, especially hydroxyl groups.

Non-isocyanate-reactive functional groups are understood to mean those groups which, under the customary and known conditions of thermal crosslinking, do not react, or react only to a very small extent, with blocked and unblocked isocyanate groups. Examples of suitable non-isocyanate-reactive groups are carboxyl groups, epoxy groups and cyclic carbonate groups, especially carboxyl groups. Compounds (A) preferably contain hydroxyl groups.

Examples of suitable low molecular weight compounds (A) which contain hydroxyl groups can be found in European patent application EP 0 915 113 A1, page 6, lines 21 to 25, or international patent application WO 87/00851, page 13, line 11 to page 15 , Line 8 and Example 1 to Example 33, pages 17 to 27.

Examples of suitable oligomeric and polymeric compounds (A) which contain hydroxyl groups can be found in European patent applications EP 0 915 113 A1, Example 1, page 11, lines 3 to 15, and European patent EP 0 675 141 B1 1, page 2 , Line 44, to page 5, line 15, page 8, line 5, to page 10, line 41.

If the compounds (A) contain reactive functional groups that are different from the carbamate groups, they are preferably present in minor amounts, so that the substance mixtures according to the invention are mainly crosslinked via the crosslinking reaction according to the invention. A minor amount of the compounds (A) in the reactive functional groups other than the carbamate groups is <50, preferably <45, preferably <40, particularly preferably <35, very particularly preferably <30 and in particular <25 equivalents. %, each based on the total amount of reactive functional groups in the compound (A), understood. If the reactive functional groups different from the carbamate groups are isocyanate-reactive functional groups, the amount of polyisocyanates (B) should be selected such that an effective amount of blocked and / or unblocked isocyanate groups is used for the crosslinking of the carbamate groups, i.e. for the crosslinking reaction according to the invention is available. The content of the compounds (A) described above in the substance mixtures according to the invention can vary widely and depends on the requirements of the individual case, in particular on the functionality of the complementary reactive groups in the compounds (A) on the one hand and the crosslinking agents (B) on the other. The content is preferably 20 to 80, preferably 22 to 75, particularly preferably 25 to 70, very particularly preferably 25 to 65 and in particular 25 to 60% by weight, in each case based on the solids of the substance mixture according to the invention.

The substance mixtures according to the invention preferably contain at least one crosslinking agent (B) which is selected from the group consisting of blocked, partially blocked or unblocked polyisocyanates.

Statistically, the polyisocyanates (B) contain at least 2.0, preferably more than 2.0 and in particular more than 2.5 isocyanate groups per molecule. There is basically no upper limit to the number of isocyanate groups; According to the invention, however, it is advantageous if the number does not exceed 15, preferably 12, particularly preferably 10, very particularly preferably 8.0 and in particular 6.0.

The polyisocyanates (B) can have aliphatic, cycloaliphatic or aromatic basic structures. However, at least two of these basic structures can also be present in a polyisocyanate (B). For example, a polyisocyanate (B) is considered to be aliphatic if its isocyanate groups are exclusively connected directly to aliphatic groups. Are the isocyanate groups with both aliphatic and cycloaliphatic groups direct connected, it is an aliphatic-cycloaliphatic polyisocyanate (B).

Aliphatic, aliphatic-cycloaliphatic, cycloaliphatic and aromatic polyisocyanates (B) are preferably used.

The aromatic polyisocyanates (B) are preferably used when the tendency to yellowing can be accepted in the end products, such as coatings, adhesive layers and seals, produced from the substance mixtures according to the invention. However, if freedom from yellowing is crucial, aliphatic, cycloaliphatic and aliphatic-cycloaliphatic polyisocyanates (B) are preferably used.

Examples of suitable polyisocyanates (B) are polyurethane prepolymers containing isocyanate groups, which can be prepared by reaction of polyols with an excess of aliphatic, aliphatic-cycloaliphatic, cycloaliphatic and aromatic diisocyanates and are preferably low-viscosity.

Examples of suitable aromatic diisocyanates are 2,4- or 2,6-tolylene diisocyanate, 1,2-, 1,3- or 1,4-phenylene diisocyanate or 1,2-, 1,3-, 1,4- or 1,4 -Naphthylendiisocyanat.

Examples of suitable aliphatic, cycloaliphatic and aliphatic-cycloaliphatic diisocyanates are isophorone diisocyanate (= 5-isocyanato-1-isocyanatomethyl-1, 3,3-trimethyl-cyclohexane), 5-isocyanato-1- (2-isocyanatoeth-1-yl) -1 , 3,3-trimethyl-cyclohexane, 5-isocyanato-1- (3-isocyanatoprop-1-yl) -1,3,3-trimethyl-cyclohexane, 5-isocyanato- (4-isocyanatobut-1-yl) -1 , 3,3-trimethyl-cyclohexane, 1-isocyanato-2- (3-isocyanatoprop-1-yl) cyclohexane, 1-isocyanato-2- (3-isocyanatoeth-1- yl) cyclohexane, 1-isocyanato-2- (4-isocyanatobut-1-yl) cyclohexane, 1, 2-diisocyanatocyclobutane, 1, 3-diisocyanatocyclobutane, 1, 2-

Diisocyanatocyclopentane, 1,3-diisocyanatocyclopentane, 1,2

Diisocyanatocyclohexane, 1,3-diisocyanatocyclohexane, 1,4-diisocyanatocyclohexane, dicyclohexylmethane-2,4'-diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (HDI),

Ethyl ethylene diisocyanate, trimethyl hexane diisocyanate,

Heptamethylene diisocyanate, methyl pentyldi isocyanate (MPDI), nonanetriisocyanate (NTI) or diisocyanates derived from dimer fatty acids, as sold by Henkel under the trade name DDI 1410 and described in the patents WO 97/49745 and WO 97/49747, in particular 2 Heptyl-3,4-bis (9-isocyanatononyl) -1-pentyl-cyclohexane, or 1, 2-, 1, 4- or 1, 3- bis (isocyanatomethyl) cyclohexane, 1, 2-, 1, 4- or 1, 3-bis (2-isocyanatoeth-1-yl) cyclohexane, 1, 3-bis (3-isocyanatoprop-1-yl) cyclohexane, 1, 2-, 1, 4- or 1,3-bis (4th -Isocyanatobut-1-yl) cyclohexane or liquid bis (4-isocyanatocyclohexyl) methane with a trans / trans content of up to 30% by weight, preferably 25% by weight and in particular 20% by weight, as described in the patent applications DE 44 14 032 A1, GB 1220717 A1, DE 16 18 795 A1 or DE 17 93 785 A1 is described, preferably isophorone di-isocyanate, 5-isocyanato-1 - (2-isocyanatoeth-1-yl) -1 , 3,3-trimethylcyclohexane, 5-isocyanato-1- (3-isocyanatoprop-1-yl) -1 , 3,3-trimethylcyclohexane, 5-isocyanato- (4-isocyanatobut-1-yl) -1,3,3-trimethylcyclohexane, 1-isocyanato-2- (3-isocyanatoprop-1-yl) cyclohexane , 1- isocyanato-2- (3-isocyanatoeth-1-yl) cyclohexane, 1-isocyanato-2- (4-isocyanatobut-1-yl) cyclohexane or HDI, in particular HDI.

It can also have isocyanurate, biuret, allophanate, iminooxadiazinedione, urethane, urea, carbodiimide and / or uretdione groups

Polyisocyanates (B) are used, which are customary and known Be prepared from the diisocyanates described above. Examples of suitable production processes and polyisocyanates (B) are, for example, from the patents CA 2,163,591 A, US-A-4,419,513, US 4,454,317 A, EP 0 646 608 A, US 4,801, 675 A, EP 0 183 976 A 1, DE 40 15 155 A 1, EP 0 303 150 A 1, EP 0 496 208 A 1, EP 0 524 500 A 1, EP 0 566 037 A 1, US 5,258,482 A 1, US 5,290,902 A 1, EP 0 649 806 A 1, DE 42 29 183 A1 or EP 0 531 820 A1 is known or they are described in the unpublished German patent application DE 100 05228.2.

In addition, there are the highly viscous polyisocyanates (B), as described in German patent application DE 198 28 935 A1, which have surface-deactivated polyisocyanate particles by urea formation and / or blocking in accordance with European patent applications EP 0 922 720 A1, EP 1 013 690 A 1 and EP 1 029 879 A 1 or nonyl triisocyanate (NTI).

Furthermore, the adducts of polyisocyanates described in German patent application DE 196 09 617 A 1 with dioxanes, dioxolanes and oxazolidines containing isocyanate-reactive functional groups and which still contain free isocyanate groups or are used in combination with other polyisocyanates (B) come as polyisocyanates (B) into consideration.

The polyisocyanates (B) described above are preferably used in the two- or multi-component systems according to the invention.

The polyisocyanates (B) described above can be partially or completely blocked with suitable blocking agents. The partially blocked polyisocyanates (B) are also preferably in the two- or multi-component systems according to the invention used. The completely blocked polyisocyanates (B) are used in particular in the one-component systems according to the invention.

All customary and known blocking agents are suitable as blocking agents for the isocyanate groups. The blocking agents are preferably selected from the group consisting of

i) phenols, such as phenol, cresol, xylenol, nitrophenol, chlorophenol, ethylphenol, tert-butylphenol, hydroxybenzoic acid, esters of these

Acid or 2,5-di-tert-butyl-4-hydroxytoluene;

ii) lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam or ß-propiolactam;

iii) active methylenic compounds, such as diethyl malonate,

Dimethylmalonate, ethyl or methyl acetoacetate or

acetylacetone;

iv) 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 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, 1, 4-cyclohexyldimethanol or acetocyanhydrin; v) mercaptans, such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, t-dodecyl mercaptan, 2-mercaptobenzothiazole, thiophenol, methylthiophenol or ethylthiophenol;

vi) acid amides, such as acetoanilide, acetoanisidinamide, 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, carbazole, aniline, naphthylamine, butylamine, dibutylamine or butylphenylamine;

ix) imidazoles, such as imidazole or 2-ethylimidazole;

x) ureas, such as urea, thiourea, ethylene urea, ethylene thiourea or 1,3-diphenylurea;

xi) carbamates, such as phenyl N-phenylcarbamate or 2-oxazolidone;

xii) imines such as ethyleneimine;

xiii) oximes, such as acetone oxime, formal doxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diisobutyl ketoxime, diacetyl monoxime,

Benzophenone oxime or chlorohexanone oximes;

xiv) salts of the sulfurous acid, such as sodium bisulfite or potassium bisulfite; xv) hydroxamic acid esters, such as benzyl methacrylohydroxamate (BMH) or allyl methacrylohydroxamate; or

xvi) substituted pyrazoles, especially dimethylpyrazole, or triazoles; such as

xvii) mixtures of these blocking agents,

selected. Mixtures xvii) are preferably used, in particular malonic esters and acetoacetic acid esters, malonic esters and dimethylpyrazoles and succimide and dimethylpyrazoles.

The amount of the polyisocyanates (B) described above in the mixtures of substances according to the invention can vary widely and depends on the requirements of the individual case, in particular on the functionality of the complementary reactive groups in the compounds (A) on the one hand and the polyisocyanates (B) on the other hand. The content is preferably 10 to 80, preferably 15 to 70 and in particular 20 to 60% by weight, in each case based on the solid of the substance mixture according to the invention.

In addition to the essential constituents (A) and (B) described above, the substance mixtures according to the invention can also contain at least one compound (C) which contains at least one reactive functional group which differs from the carbamate group. Examples of suitable reactive functional groups of this type are those described above. Hydroxyl groups are particularly preferably used

The compounds (C) which contain the particularly preferred hydroxyl groups can be of low molecular weight. They are usually used by the

Experts referred to as reactive thinners for thermal crosslinking. Examples of suitable thermally curable reactive diluents are positionally isomeric diethyloctanediols or hydroxyl group-containing hyperbranched compounds or dendrimers, as are described in German patent applications DE 198 09 643 A1, DE 198 40 605 A1 or DE 19805421 A1.

The polymeric and oligomeric compounds (C) which contain the particularly preferred hydroxyl groups come from the polymer classes described above. The (meth) acrylate (co) polymers and the polyesters are preferably used.

Examples of suitable hydroxyl-containing polymeric and oligomeric compounds (C) are found in the literature

- EP 0 915 113 A 1, page 3, line 55, to page 6, page 12,

EP 0 675 141 B1, page 8, pages 36 to 52, page 9, and page 48, to page 10, page 5,

- EP 0 710 707 A 2, page 3, lines 17 to 48, i. V. m. Page 5, line

43, to page 7, line 19,

WO 34/10211, Example C, page 11, page 30, to page 12, line 28, Example N, and page 19, line 32, to page 20, line 30,

WO 01/23439, page 5, line 14, to page 14, line 23, i. V. m. the manufacturing example 1, pages 36, line 16, to page 37, line 5, or

DE 4421 823 A 1, page 4, line 4, to page 11, line 15,

described in detail. If they are used, the compounds (C) are contained in minor amounts in the substance mixtures according to the invention, so that the substance mixtures according to the invention are mainly crosslinked via the crosslinking reaction according to the invention. A minor amount of the compounds of the invention in the compounds (C) of <50, preferably <45, preferably <40, particularly preferably <35, very particularly preferably <30 and in particular <25 wt .-%, each based on the total amount of (A) and (C) understood. If the compounds (C) contain isocyanate-reactive functional groups, the amount of polyisocyanates (B) should be selected such that an effective amount of blocked and / or unblocked isocyanate groups is still available for the crosslinking of the carbamate groups, ie for the crosslinking reaction according to the invention stands.

Furthermore, the substance mixtures according to the invention can contain at least one crosslinking agent (D) with reactive functional groups which are predominantly or exclusively complementary to the reactive functional groups different from the carbamate group. This means that the reactive functional groups in question do not, or only very slowly, react with the carbamate groups under the customary and known conditions of thermal crosslinking. Examples of suitable reactive functional groups of this type are carboxyl groups, epoxy groups and cyclic carbonate groups. Examples of suitable crosslinking agents (D) are described in German patent application DE 199 24 171 A1, page 7, line 67, to page 8, line 46, or in German patent application DE 199 08 018 A1, page 7, lines 40 to 56, and page 16, line 59. If used, the crosslinking agent (D) is also used in minor amounts, depending on the content of the reactive functional groups of the carbamate groups according to the invention, so that the crosslinking of the inventive mixtures mainly takes place via the crosslinking reaction according to the invention.

In special cases, the substance mixtures according to the invention can also contain crosslinking agents (E), as are usually used for the crosslinking of compounds (A) containing carbamate groups. Examples of suitable crosslinking agents (E) are amino resins, such as those from German patent application DE 199 24 171 A1, page 8, pages 36 to 42, or European patent application EP 0 915 113 A1, page 9, pages 5 to 16, are known. The amount of crosslinking agents (E) are chosen so that the crosslinking takes place via the carbamate groups, mainly via the polyisocyanates (B). The equivalent ratio of complementary reactive functional groups in the crosslinking agents (E) to the carbamate groups present is preferably at most 0.2, preferably at most 0.15 and in particular at most 0.1.

Depending on the intended use, the substance mixtures according to the invention can contain at least one pigment (F).

In the case of two- and multi-component systems, the pigments (F) can be mixed in via the binder component (A) and / or the crosslinking agent component (B). They are preferably mixed in via the binder component (A).

The pigments (F) from the group consisting of color and / or effect, fluorescent, electrically conductive and magnetically shielding pigments, metal powders, organic and inorganic, transparent and opaque fillers and nanoparticles.

Instead of or in addition to the pigments (F), the coating materials of the invention may also contain at least one additive (G). In the case of two- or multi-component systems, the additives (G) can be mixed in via the binder component (A) and / or the crosslinking agent component (B). They are preferably mixed in via the binder component (A).

Examples of suitable additives (G) are molecularly soluble

dyes; Light stabilizers, such as UV absorbers and reversible radical scavengers (HALS); antioxidants; low and high boiling ("long") organic solvents; Venting means; Wetting agents; emulsifiers;

slip additives; polymerization inhibitors; Thermal catalysts

Networking; thermolabile free radical initiators; Photoinitiators and coinitiators; thermally curable reactive thinners; reaction thinners curable with actinic radiation; curable with actinic radiation

Binder; Adhesion promoters; Leveling agents; film-forming aids;

Rheology aids (thickeners and / or sag control agents);

Flame retardants; Corrosion inhibitors; anti-caking agents; waxes; driers;

Biocides and / or matting agents; as for example in the textbook "Lackadditive" by Johan Bieleman, Wiley-VCH, Weinheim,

New York, 1998, in German patent application DE 199 14 896 A1,

Column 14, page 26, until column 15, line 46, are described in detail.

In addition, reference is made to DE 199 04 317 A1 and DE 198 55 125 A1. Actinic radiation means electromagnetic radiation, such as near infrared (NIR), visible light, UV radiation and X-rays, in particular UV radiation, and corpuscular radiation, such as electron beams.

In terms of method, the preparation of the substance mixtures according to the invention has no special features, but takes place by mixing and homogenizing the constituents described above with the aid of customary and known mixing methods and devices, such as stirred kettles, agitator mills, extruders, kneaders, Ultraturrax, in-line dissolvers, static mixers , Gear rim dispersers,

Pressure relief nozzles and / or microfluidizers. If additives (G) curable with actinic radiation are also used, the mixtures according to the invention are preferably prepared with the exclusion of actinic radiation.

The resulting substance mixtures according to the invention can be conventional, organic solvent-containing curable substance mixtures, aqueous curable substance mixtures, essentially or completely solvent-free and water-free liquid curable substance mixtures (100% systems), essentially or completely solvent-free and water-free solid curable substance mixtures (powder) or be essentially or completely solvent-free powder suspensions (powder slurries).

They are excellently suited as coating materials, adhesives and sealants or for their manufacture.

The coating materials according to the invention can be used as fillers, stone chip protection primers, basecoats and solid-color topcoats and as clearcoats, in particular as clearcoat, or for the production of films. Above all, the coating materials of the invention are outstandingly suitable for the production of single- and multi-layer clear coats, as well as single- and multi-layer, color and / or effect, electrically conductive, magnetically shielding and / or fluorescent coatings, especially after the wet-on-wet process a basecoat, in particular a waterborne basecoat, is applied to the surface of a substrate, after which the resulting basecoat film is dried without curing and covered with a clearcoat film. The two layers are then hardened together (see also international patent application WO 01/23439, page 29, page 17, to page 32, line 30, and pages 33, line 25, to page 34, page 5, line 2). ,

In terms of method, the application of the coating materials, adhesives and sealants according to the invention has no peculiarities, but can be done by all customary application methods, such as Spraying, knife coating, brushing, pouring, dipping, trickling or rolling. Spray application methods are preferably used for the coating materials according to the invention, unless it is powder coatings which are applied, for example, with the aid of the fluidized-bed processes typical of powder coatings. In general, it is advisable to work with the exclusion of actinic radiation in order to avoid premature crosslinking of the coating materials, adhesives and sealants according to the invention.

All substrates whose surface is covered by the

Use of heat in the hardening of the layers on it is not damaged. The substrates preferably consist of metals,

Plastics, wood, ceramics, stone, textile, fiber composite, 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.

In the case of electrically conductive substrates, primers can be used which are produced in a customary and known manner from electrocoat materials. Both anodic and cathodic electrocoat materials, but in particular cathodic electrocoat materials, are suitable for this. In the case of non-functionalized and / or non-polar plastic surfaces, these can be subjected to a pretreatment in a known manner, such as with a plasma or with flame treatment, or can be provided with a hydro primer before coating.

Accordingly, the coating materials, adhesives and sealants according to the invention for coating, gluing and sealing motor vehicle bodies or parts thereof, of motor vehicles indoors and outdoors, of buildings indoors and outdoors, of furniture, windows and doors and in the context of industrial painting Excellent for coating, gluing and sealing small parts, such as nuts, screws, such as hubcaps or rims, coils, containers, packaging, electrical components, such as motor windings or transformer windings, and white goods such as household appliances, boilers and radiators.

The curing of the applied substance mixtures according to the invention also has no special features in terms of method, but is carried out using the customary and known thermal methods, such as heating in a forced-air oven or irradiation with IR lamps, and, if appropriate, using the customary and known methods of radiation curing, such as those used for example in the German patent application DE 198 18 735 A1, column 10, page 31, to column 11, line 33.

The resulting coatings and films according to the invention, in particular the single- or multi-layer color and / or effect coatings and clearcoats, in particular the clearcoats, according to the invention are simple to produce and have excellent optical properties and very high levels of light, chemicals, water and condensation water -, weather resistance and etch resistance. In particular, they are free from cloudiness and inhomogeneities. They have excellent scratch resistance and abrasion resistance with excellent surface hardness.

The adhesive layers according to the invention permanently bond a wide variety of substrates to one another and have high chemical and mechanical stability even in the case of extreme temperatures and / or temperature fluctuations.

Likewise, the seals according to the invention permanently seal the substrates, and they also have high chemical and mechanical stability even at extreme temperatures and / or temperature fluctuations. V. m. exposed to aggressive chemicals.

Accordingly, the primed or unprimed substrates which are usually used in the technological fields listed above, which are coated with at least one coating according to the invention, bonded with at least one adhesive layer according to the invention and / or sealed with at least one seal according to the invention, have a particularly long profile with a particularly advantageous application properties Service life, which makes them economically and ecologically particularly attractive.

Examples

Production Example 1

The Production of a Methacrylate Copolymer (A) Containing Carbamate Groups

A primary carbamate group-containing methacrylate copolymer (A) was first prepared for the preparation of the clearcoat materials of the invention.

For this purpose, 27.75 parts by weight of Solventnaphtha ® were placed in a reaction vessel suitable for radical copolymerization, equipped with a stirrer, reflux condenser, two inlet vessels for the monomer inlet and the initiator inlet, controllable heating and nitrogen inlet tube, and heated to 140 ° C. with stirring. After the temperature had been reached, a monomer mixture of 4.05 parts by weight of styrene, 28.75 parts by weight of 2-ethylhexyl acrylate, 4.05 parts by weight of 2-ethylhexyl methacrylate and 20.55 parts by weight of 2-

Hydroxyethyl methacrylate evenly metered into the reaction vessel for three hours. At the same time, an initiator solution composed of 8.15 parts by weight of Solventnaphtha ® and 4.62 parts by weight of the commercially available initiator of the radical polymerization Vazo ® 67 was evenly metered into the reaction vessel. Dosing was started at the same time. The temperature of the reaction mixture was kept at 140 ° C. during the feeds. After the feeds had ended, the feed vessels were rinsed with 0.5 part by weight of Solventnaphtha ® each. Subsequently, at Postpolymerized 140 ° C until the solids content of the polymer solution was 60% by weight (one hour / 130 ° C) and the viscosity was 3.3 to 3.8 dPas (original viscosity, 23 ° C). The polymer solution was then cooled and 1.08 parts by weight of Solventnaphtha ® were added. It had a hydroxyl number of 155 mg KOH / g solids.

78.9 parts by weight of the polymer solution described above, 12.7 parts by weight of methyl carbamate and 2.5 parts by weight of cyclohexane (entrainer) were weighed in the order given into a reaction vessel equipped with a stirrer, column, column top and separation device with phase separation, and stirring to 130 ° C heated. A mixture of 1.5 parts by weight of Solventnaphtha ® and 0.08 part by weight of dibutyltin oxide was then added. The temperature of the reaction mixture was kept at 130 ° C. for three hours, and the column top temperature was kept at a maximum of 85 ° C. during this period. A mixture of 1.5 parts by weight of Solventnaphtha® and 0.08 part by weight of dibutyltin oxide was then added. The resulting reaction mixture was stirred at 130 ° C. and at a maximum column head temperature of 85 ° C. until the hydroxyl number was 10 to 20 mg KOH / g solids. The reaction mixture was then cooled to 100 ° C. and methanol and excess methyl carbamate were distilled off in vacuo. The temperature of the reaction mixture was raised to 115 ° C. over an hour and kept at this temperature under vacuum until no more methyl carbamate distilled off. The resulting polymer solution (A) was mixed with 1.16 parts by weight of solvent naphtha. Their solids content was 70% by weight (one hour / 130 ° C), their viscosity was 7.0 to 8.0 dPas (60 percent in Solventnaphtha ®, 23 ° C). The methacrylate copolymer (A) containing carbamate groups had a hydroxyl number of 18 mg KOH / g solids and a carbamate equivalent weight of 452 g.

Examples 1 to 3

The preparation of the clearcoats 1 to 3 and clearcoats 1 to 3 according to the invention

The clearcoats of Examples 1 to 3 according to the invention were produced by mixing and homogenizing the constituents given in Table 1.

Table 1: The material composition of the clearcoats 1 to 3 according to the invention

Component examples

(Parts by weight):

1 2

3

Solution of the methacrylate copolymer (A) 41, 76 53.36

43.28

Trimers of isophorone diisocyanate ^a) 57.24 47.47 blocked with dimethylpyrazole Trimers of hexamethylene diisocyanate ^b) blocked with dimethylpyrazole ^b) - -

8.25

Trimeres of isophorone diisocyanate ^c) - 45.64

Dibutyltin dilaurate 0.5 0.5

0.5

Byk Chemie) 0.5 0.5

0.5

Solventnaphtha ® 11, 33 21

13.83

a) Desmodur © VP LS 2252 from Bayer AG; Solids content: 60% by weight; Blocked isocyanate group content: 7.3% by weight, based on the solution; Isocyanate equivalent weight of the solution: 572 g;

b) Desmodur ® VP LS 2253 from Bayer AG; Solid content: 75% by weight; Blocked isocyanate group content: 10.5% by weight, based on the solution; Isocyanate equivalent weight of the solution: 400 g;

c) Desmodur® Z 4470 SN from Bayer AG, solids content: 71% by weight; Isocyanate group content: 11.8% by weight, based on the solution); The clearcoats 1 and 3 according to the invention (one-component systems) had a theoretical solids content of 60% by weight. They were stable in storage and transport and had very good ring line stability. They were easy to apply without any problems.

In the case of the clearcoat material 2 according to the invention (two-component system, solids content 60% by weight), the polyisocyanate was added to the binder component shortly before application. The two-component system had an excellent pot life (processing time).

To test the application properties of the clearcoats 1 to 3 according to the invention, test panels were produced as follows:

A commercially available aqueous filler from BASF Coatings AG was first applied and baked onto a steel pistol coated with a commercially available electrocoat (electrocoat with a layer thickness of 18-22 μm). Filler layers with a layer thickness of 35 to 40 μm resulted. A commercial black uni base coat from BASF Coatings AG was then applied in the same way to the filler coating and predried at 80 ° C. for 10 minutes. After the panels had been cooled, one layer each of the clearcoats 1 to 3 according to the invention was applied with pneumatic spray guns and predried for 10 minutes at 50 ° C. and then crosslinked together with the basecoat layers for 30 minutes at 140 ° C. object temperature. The result was basecoat layers with a thickness of 15 μm and clear lacquer layers with a thickness of 40 μm. The black uni base coat was chosen because of the was able to best observe the formation of scratches on the corresponding test boards.

The multicoat paint systems of Examples 1 to 3 according to the invention had an excellent overall optical impression. The gloss measured according to DIN 67530 with a reflectometer from BYK reflectometrically at an angle of 20 ° was 85 in all cases.

The micro penetration hardness (universal hardness at 25.6 mN, Fischerscope 100V with diamond pyramid according to Vickers) was 155.5 in Example 1, 156.9 in Example 2 and 134.5 in Example 3.

The scratch resistance of the multilayer coating of Example 2 was determined in accordance with the sand test described in international patent application WO 01/23439, page 41, pages 1 to 13. As a result of the damage, the gloss only dropped to 60, which underpinned the high scratch resistance of the multilayer coating 2.

The etch resistance and chemical resistance, in particular to organic solvents, tree resin, pancreatin and acids such as sulfuric acid, were excellent and at the level of customary and known two-component clearcoats based on binders containing hydroxyl groups and polyisocyanates or on the basis of binders containing carbamate groups and aminoplasts, such as they are sold, for example, by the BASF Corporation under the Ureclear ® brand.

Claims

Curable mixtures of substances, processes for their preparation and their use

1. Use of blocked, partially blocked and unblocked polyisocyanates for the thermal crosslinking of compounds containing primary and / or secondary carbamate groups by the chemical reaction of the isocyanate groups with the carbamate groups.

2. Curable substance mixtures containing primary and / or secondary carbamate groups as complementary reactive functional groups on the one hand and blocked and / or unblocked isocyanate groups available on the other hand for crosslinking the carbamate groups.

3. Curable substance mixtures according to claim 2, characterized in that the equivalent ratio of blocked and / or unblocked isocyanate groups which are responsible for the crosslinking

Carbamate groups are effectively available to carbamate groups is at least 0.1.

4. Curable substance mixtures according to claim 3, characterized in that the equivalent ratio is at least 0.5.

5. Curable substance mixtures according to claim 3 or 4, characterized in that the upper limit for the equivalent ratio is 2.

6. Curable mixtures of substances according to one of claims 2 to 5, characterized in that they

(A) at least one compound having at least one carbamate group of the general formula I:

-O-C (O) -NHR (I),

in which R represents a hydrogen atom or an alkyl group,

(B) at least one crosslinking agent selected from the group consisting of blocked, partially blocked or unblocked polyisocyanates,

contain.

7. Curable substance mixtures according to claim 6, characterized in that the compound (A) also contains at least one further reactive functional group which is different from the carbamate group.

8. Curable substance mixtures according to claim 6 or 7, characterized in that it contains at least one compound (C) with at least one reactive functional group different from the carbamate group.

9. Curable substance mixtures according to claim 7 or 8, characterized in that the reactive functional groups from the group different from the carbamate groups, consisting of isocyanate-reactive functional groups.

10. Curable substance mixtures according to claim 9, characterized in that the isocyanate-reactive functional groups are selected from the group consisting of hydroxyl, thiol and primary and secondary amino groups.

11. Curable substance mixtures according to one of claims 7 to 10, characterized in that they contain minor amounts of at least one crosslinking agent (D) with reactive functional groups which are predominantly or exclusively complementary to the reactive functional groups different from the carbamate group.

12. Curable substance mixtures according to claim 11, characterized in that the complementary reactive functional groups are selected from the group consisting of carboxyl groups, epoxy groups and cyclic carbonate groups.

13. Curable substance mixtures according to one of claims 2 to 12, characterized in that they contain small amounts of at least one crosslinking agent (E), such as is used for the crosslinking of compounds containing carbamate groups (A).

14. Curable mixtures of substances according to one of claims 2 to 13, characterized in that they are one-component systems or two- or multi-component systems.

15. Use of the curable substance mixtures according to one of claims 2 to 14 as coating materials, adhesives and sealing compounds or for their production.

16. Use according to claim 15, characterized in that

the coating materials for the production of single- and multi-layer clear coats and foils as well as single- and multi-layer, color and / or effect-giving, electrically conductive, magnetically shielding and / or fluorescent coatings and foils,

the adhesives for the production of adhesive layers and

- The sealants for the production of seals

be used.

17. Use according to claim 15 or 16, characterized in that the coating materials, adhesives and sealants

Coating, gluing and sealing of

Motor vehicle bodies and parts thereof, motor vehicles in interior and exterior areas, structures in interior and exterior areas, furniture, windows and doors and in the context of industrial painting the coating, gluing and sealing of

Small parts, coils, containers, packaging, electrical components and white goods.