Abstract:
A compound containing cyclic amidine groups and uretdione groups, having the formula: ##STR1## wherein X is O or NR 2 , R is the hydrocarbon radical of isophorone diisocyanate: ##STR2## R 1  is a substituted (cyclo)alkylene radical which is substituted with O-3 CH 3  groups and has 2-14 carbon atoms @ 
     R 2  and R 3  are identical or different (cyclo)alkyl radicals having 1-10 carbon atoms or are phenyl radicals, 
     n is 0-5, and 
     B is 0-1 NCO group and/or 1-0 imidazoline-blocked NCO group of the formula: ##STR3##

Description:
BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention relates to compounds containing cyclic amidine groups and uretdione groups, to a process for their preparation and to use of the compounds. 
     2. Description of the Background 
     DE-A 36 10 758 describes EP hardeners which cure epoxy resins based on bisphenol A both by polymerization of the epoxy groups of the resins (catalytic reaction) and by reaction with the OH groups of the resins (stoichiometric reaction). Relative to the known EP powders, the EP powders produced using these hardeners are notable for outstanding solvent resistance. A disadvantage of the powders of DE-A 36 10 758, however, is that they are not suitable for bonding metals, since the metal sheets bonded therewith exhibit poor lap shear strengths (DIN 53 283) at elevated temperatures. 
     SUMMARY OF THE INVENTION 
     Accordingly, one object of the present invention is to provide a hardener for pulverulent epoxy resin powder adhesives which, when applied to metal sheets, result in improved bonding strength of the metal sheets to each other. 
     Briefly, this object and other objects of the present invention as hereinafter will become more readily apparent can be attained by a compound containing cyclic amidine groups and uretdione groups and having the composition: ##STR4## wherein X is O or NR 2 , R is the hydrocarbon radical of isophorone diisocyanate: ##STR5## R 1  is a substituted (cyclo)alkylene radical which is substituted with O-3 CH 3  groups and has 2-14 carbon atoms 
     R 2  and R 3  are identical or different (cyclo)alkyl radicals having 1-10 carbon atoms or are phenyl radicals, 
     n is 0-5, and 
     B is 0-1 NCO group and/or 1-0 imidazoline-blocked NCO group of the formula: ##STR6## 
     Another aspect of the invention is a process for the preparation of the compound (I) of the invention, which occurs in two stages, wherein, in the first stage, the isophorone diisocyanate uretdione (IPDI uretdione) is chain-extended with a diol or disecondary diamine by the following equation: ##STR7## and, in the second step, the chain-extended isophorone diisocyanate uretdione (II) is partially or completely reacted with cyclic amidines of the formula: ##STR8## where x, R, R 1 , R 2 , R 3  and n are as defined above 
    
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     The compound of formula (I) has a uretdione group content of 1.5-2 mmol/g, a cyclic amidine group (imidazoline) content of 0.3-2% by weight, and a free NCO group content of 0.2-7% by weight, preferably 1-3% by weight. The melting point of the compound is within a range of about 80°-160° C. The present compound further is outstandingly suitable for the preparation of solvent-resistant epoxy resin powder coatings and for bonding metals with enhanced lap shear strength at elevated temperatures. 
     The IPDI uretdione employed in the process according to the invention is described in DE-A 30 30 513 and has an NCO content of 17-18% by weight with a monomer content of &lt;0.7% by weight, after heating at 180° C. (0.5 h) the NCO content is 37-37.6% by weight. 
     The reaction between IPDI uretdione and diol or disecondary diamine is carried out in an inert solvent, for example, an aromatic hydrocarbon, an ester or a ketone. Acetone has proven to be a particularly advantageous solvent. 
     The compounds which are suitable for the chain extension of the IPDI uretdione are, on the one hand, diols as described, for example, in DE-A 27 38 270, p. 10, and on the other hand disecondary diamines, as are obtained, for example, in a known manner from the corresponding diprimary diamines by reaction with a carbonyl compound, for example a ketone or aldehyde, followed by hydrogenation. A particularly simple method of preparing the disecondary compounds is the addition reaction of acrylic esters (CH 2  ═CH--COOR 2 ) with the primary amino groups of the diprimary diamines (H 2  N--R 1  --NH 2 ). 
     In the chain extension of the IPDI uretdione with diols, the diol, for example ethylene glycol, diethylene glycol, butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, decanediol, dodcanediol or 2,2,4(2,4,4)-trimethyl-1,6-hexanediol, is added at 60° C. to the acetone solution of the IPDI uretdione and the mixture is heated further at 60° C. until one NCO group is reacted per OH group employed. In order to accelerate the reaction it has proven advantageous to add 0.01-0.1% by weight of dibutyltin dilaurate (DBTL). In reacting the IPDI uretdione with disecondary diamines, the diamine is metered at room temperature into the acetone solution of IPDI uretdione at a rate such that the temperature of the reaction mixture does not exceed 40° C. After the end of the addition of diamine, the reaction too is also virtually at an end. The addition of a catalyst is not necessary. 
     Then, in order to prepare the compound according to the invention, the reaction product from the first stage, which is the acetone solution of the chain-extended IPDI uretdione, is reacted in a 2nd reaction step with the cyclic amidine at 60° C. The cyclic amidine is added at about 60° C. in portions to the acetone solution of the chain-extended IPDI uretdione. After the end of the addition of amidine, heating is continued for about 1 h in order to complete the reaction. Then the acetone is removed by distillation. Then a vacuum is applied in order to remove the last residues of acetone. It has been found particularly advantageous to isolate the reaction product by removing the acetone in a film extruder under vacuum. 
     By the process according to the invention, 1-2 mol of cyclic amidine are reacted per mol of chain-extended IPDI uretdione (λ2 NCO equivalents). The cyclic amidines which are appropriate for preparing the compounds according to the invention are described in DE-A 22 48 776 and DE-A 28 35 029. Particularly suitable amidines are 2-phenylimidazoline, 2-phenyl-4-methyl-imidazoline and 2,4-dimethylimidazoline. 
     The present invention also provides pulverulent coating compositions of high storage stability and excellent solvent resistance which are based on 1,2-epoxide compounds having more than one 1,2-epoxide group and more than one OH group in the molecule, on curing agents and on customary coatings additives, wherein the coating composition comprises the following compound as a hardener: ##STR9## in which X, R, R 1 , R 2 , R 3 , n and B are as defined supra, having an OH:NCO ratio of from 1:0.25 to 1:1, preferably 1:0.5, the content of cyclic amidine (in bonded form) is from 2 to 8% by weight, preferably from 3 to 6% by weight, based on the sum of epoxide compound and hardener, and the hardener comprises from 0.5 to 1 mol of cyclic amidine per NCO equivalent. 
     The hardener (1) according to the invention is compatible with OH-containing EP resins and at elevated temperatures produces homogeneous melts which are very suitable for preparing pulverulent coating compositions. They are stable on storage at room temperature, with curing times within 30-5 minutes in the temperature range 160°-200° C. 
     Epoxide compounds which are suitable for preparing the pulverulent coating compositions according to the invention, which are to be used as powder coatings, are of course only those containing more than one OH group in the molecule. These are EP resins which are obtained by reacting bisphenol A and epichlorohydrin in a molar ratio of n:(n+1) where n is 2-7. Particularly suitable epoxy resins are those having a EP equivalent weight of about 900 and an OH equivalent weight of 300. 
     The powder coatings are prepared, for example, by grinding and mixing the individual components, which are EP resin, chain-extended IPDI uretdione blocked with cyclic amidines, and, if desired, additives such as levelling agents, pigments, fillers, UV stabilizers and antioxidants and extruding the mixture at 80°-110° C., preferably 90°-100° C. After extrusion, the mass is cooled and is ground to a particle size of less than 100 μm. In the preparation of the binder mixture, the components must be matched to each other such that per OH equivalent of the EP resin there is 0.25-1, preferably 0.5, blocked NCO group of the hardener together with a cyclic amidine content (in blocked form) of 2-8% by weight, preferably 3-6% by weight, based on the sum of resin +hardener. The proportion of hardener, therefore, must be chosen such that its cyclic amidine content is sufficient for catalytic curing of the EP resin (polymerization of the epoxide groups) without the OH groups reacting, and at the same time achieving crosslinking of the EP resin by reaction of the OH groups of the EP resin with the blocked NCO groups of the hardener, the EP groups, however, remaining intact. 
     The application of the powder coatings to the substrates to be coated can be carried out by known methods, for example by electrostatic powder spraying or fluidized-bed sintering. The coated articles are subsequently cured for 5-30 minutes in the temperature range 200°-160° C. Substrates suitable for coating with the pulverulent coating compositions according to the invention are all those which withstand the curing conditions indicated, examples being metals, glass and ceramic. The powder coatings thus prepared are notable for very good coatings properties and outstanding resistance to aggressive solvents such as, for example, methyl isobutyl ketone. 
     The present invention also embodies the use of the compounds of the invention in the preparation of pulverulent, one-component metal adhesives. 
     The resin/hardener mixture suitable for bonding metals is identical with the pulverulent coating compositions, i.e. has the same composition, preparation and application, and in the case of the bonding of metals it is even sufficient to apply the powder to the metal panels by sieving. After the clean surface of one metal has been coated with the resin/hardener mixture according to the invention, it is fixed with the other metal to be bonded with the aid of a screw clamp. Curing takes place, as in the case of the powder-coated substrates, at 160°-200° C. within 30-5 minutes. 
     The metal bonds thus produced differ markedly from the EP-based one component metal adhesives currently available on the market with respect to their strength (lap shear strength as determined by the procedure of DIN 53 283) at elevated temperatures. 
     The pulverulent metal adhesives based on EP resins that are currently on the market consist of a (solid) EP resin which is cured with dicyandiamide. The metal bonds produced therewith exhibit lap shear strengths which are excellent at room temperature but which decrease sharply with rising temperature and are virtually zero at 150° C., in other words, the bond fails at 150° C., whereas bonds with the resin/hardener mixture according to the invention still have lap shear strengths at 150° C. which are about 10 N/mm 2 . 
     A) A Method of Preparation of the Compound of the Invention 
     The diol is metered in over the course of about 1 hour with intensive stirring to an acetone solution of the IPDI uretdione (about 50% acetone based on the sum of IPDI uretdione+chain extender+cyclic amidine), which contains 0.05% by weight dibutyltin dilaurate, and the mixture is heated further at 60° C. until one NCO equivalent has reacted per OH equivalent employed. The cyclic amidine is then added in portions. After the addition of amidine has taken place, heating is continued at 60° C. for about 1 h . 
     The acetone is then removed by distillation. In order to remove the last residues of acetone, vacuum is applied to the reaction mass. If a disecondary diamine is used instead of the diol for chain extension of the IPDI uretdione, the reaction takes place at room temperature and without DBTL. 
     The IPDI uretdione used for chain extension was prepared in accordance with the reaction conditions described in Example 2 of DE-A 30 30 513. The NCO content of the IPDI uretdione was 17.3%; on heating at 180° C. (0.5 h) an NCO content of 37% was found. 
     
                                           TABLE 1__________________________________________________________________________Compounds according to the invention                                      Glass     % NCOComposition of the compounds according to the invention                                      transition                                                (afterIPDI                                  point     heating atExampleUretdione     Chain extender Cyclic amine m.p. (DSC) % NCO                                                180° C.                                                     NH.sub.2No.   mol!      mol!           mol!         °C.!                                       °C.!                                            (free)                                                for 1                                                      mmol/g!__________________________________________________________________________A) 1 1    --                     ##STR10##   66-75                                      35-48/42                                            6.6 28.4 1.6A) 2 3    2 HO(CH.sub.2).sub.6OH                    2 B 31       127-135                                       96-112/100                                            0.1 18.7 1.0A) 3 2    1 HO(CH.sub.2).sub.6OH                    2 B 31       123-130                                      88-112/93                                            0.2 19.8 1.4A) 4 3    2 HO(CH.sub.2).sub.12OH                    2 B 31       116-127                                      80-98/84                                            0.1 17.2 0.9A) 5 2    1 HO(CH.sub.2).sub.12OH                    2 B 31       111-122                                      79-98/82                                            0.1 18.8 1.3A) 6 4    3 HOCH.sub.2CH.sub.2OH (EG)                    2 B 31       146-153                                      123-134/126                                            &lt;0.1                                                19.3 0.8A) 7 3    2 EG           2 B 31       133-141                                      117-128/122                                            &lt;0.1                                                19.7 1.06A) 8 2    1 EG           2 B 31       128-139                                      108-118/115                                            &lt;0.1                                                20.7 1.5A) 9 5      ##STR11##                     ##STR12##   163-175                                      132-145/140                                            1.2 15.4 0.3__________________________________________________________________________ *)R = HC radical of isophoronediamine 
    
     B) Epoxy Resin Powder Coatings General Preparation Procedure 
     The ground products each of hardener, epoxy resin and levelling agent masterbatch, were first of all mixed in dry form with the white pigment in an edge runner mill and then homogenized in an extruder at 80°-120° C. After cooling, the extrudate was crushed and ground in a pinned-disk mill to a particle size of &lt;100 μm. The powder thus produced was applied with an electrostatic powder spraying unit at 60 kV to degreased, optionally pretreated iron panels (1 mm thick) and baked in a laboratory convection oven. 
     Leveling Agent Masterbatch 
     10% by weight of the levelling agent, which is a commercially available acrylate-oligomer, are homogenized in the melt in the epoxy resin and, after solidifying, are comminuted. 
     Epoxy Resin 
     In the epoxy resin coating examples infra, a solid epoxy resin was used of the diglycidyl ether of bisphenol A prepared by reacting epichlorohydrin with bisphenol A, which, according to the manufacturer, has an epoxide equivalent weight of 900-1000, an epoxide value of 0.10-0.11, a hydroxyl value of 0.34 and a melting point of 96°-104° C. 
     Composition of the EP Powder 
     The powder coatings listed in Table 2 contain 40 parts by weight of TiO 2 , 0-5 part by weight of levelling agent, 59.5 parts by weight of binder, with the OH:NCO equivalence ratio of resin to hardener being generally 2:1. 
     The abbreviations in the tables below have the following meanings 
     CD: Coat thickness in μm 
     HK: Konig hardness in sec (DIN 53 157) 
     EI: Erichsen indentation in mm (DIN 53 156) 
     GG 60°≮: Gardner gloss (ASTM-D 523) 
     Imp. rev.:Impact reverse in g·m 
     CH: Cross-hatch test (DIN 53 151) 
     MEK (methyl ethyl ketone) resistance: 
     Number of strokes with an MEK-soaked cottonwool pad under a load of 1 kg until the surface is attacked (matt surface). 
     
                                           TABLE 2__________________________________________________________________________Composition of the pigmented (40% by weight TiO.sub.2) powders and thecoatings data (after curing)              Temp.  °C.!NCO       OH       200         180     170Exampleequiv.     equiv.   Duration  min!No.  hardener     EP       10  20  30  15  25  25  30__________________________________________________________________________B) 1 1 A) 2     2   HK   138 150 140 154 152 155 153         GG 60°&lt;)              29  29  30  26  26  25  28         CH   0   0   1   0   0   1   0         El   3.1 3.4 6   1   1.3 1.8 1.3         Bl rev.              20  10  &lt;10 &lt;10 &lt;10 &lt;10 &lt;10         MEK  120 180 200 &gt;200                              &gt;200                                  200 200B) 2 1 A) 3     2   HK   147 153 154 155 168 163 158         GG 60°&lt;)              40  53  56  42  44  38  45         CH   1   1   0   1   1   1   1         El   4.5 3.8 4.1 1.8 1.8 2.6 2.8         Bl rev.              20  10  10  &lt;10 &lt;10 &lt;10 &lt;10         MEK  &gt;200                  &gt;200                      &gt;200                          &gt;200                              &gt;200                                  &gt;200                                      &gt;200B) 3 1 A) 4     2   HK   185 183 175 192 184 179 180         GG 60°&lt;)              78  82  84  85  83  78  88         CH   1   1   1   1   1   0   0         El   7   7.8 7.4 6.7 6.4 7.1 6.7         Bl rev.              60  50  50  50  50  40  40         MEK  &gt;200                  &gt;200                      &gt;200                          &gt;200                              &gt;200                                  150 180B) 4 1 A) 5     2   HK   164 169 169 180 177 170 170         GG 60°&lt;)              80  76  68  68  69  60  70         CH   4   3   3   0   0   0   0         El   4.5 4.3 4.5 4.5 3.1 5.1 5.2         Bl rev.              30  20  20  &lt;10 &lt;10 &lt;10 &lt;10         MEK  80  120 200 130 180 80  110B) 5 1 A) 6     2   HK   101 130 109 133 140 139 128         GG 60°&lt;)              11  10  11  13  12  12  12         CH   0   0   0   0   0   0   0         El   1.1 1   0.8 0.9 0.8 0.6 0.7         Bl rev.              &lt;10 &lt;10 &lt;10 &lt;10 &lt;10 &lt;10 &lt;10         MEK  200 200 200 16  40  20  26B) 6 1 A) 7     2   HK   117 110 116 153 141 137 136         GG 60°&lt;)              19  18  19  21  20  20  21         CH   1   0   0   0   0   0   0         El   1.1 1.0 1.4 0.9 0.9 0.9 1         Bl rev.              &lt;10 &lt;10 &lt;10 &lt;10 &lt;10 &lt;10 &lt;10         MEK  200 &gt;200                      &gt;200                          26  80  46  60B) 7a1 A) 1     2   HK   179 183 186 175 174 179 183         GG 60°&lt;)              68  69  70  62  61  60  62         CH   0   0   0   0   1   0   0         El   2.5 3.0 3.1 3   4   2.8 3         Bl rev.              &lt;10 &lt;10 &lt;10 &lt;10 &lt;10 &lt;10 &lt;10         MEK  &gt;200                  &gt;200                      &gt;200                          &gt;200                              &gt;200                                  &gt;200                                      &gt;200B) 7b1 A) 1     4   HK   151 151 151 150 146 170 159         GG 60°&lt;)              30  32  32  25  20  60  25         CH   0   0   0   0   0   0   0         El   3.3 4.2 3.8 3   3.5 5.1 2         Bl rev.              &lt;10 &lt;10 &lt;10 &lt;10 &lt;10 &lt;10 &lt;10         MEK  90  100 110 80  100 80  30__________________________________________________________________________ 
    
     C) Use of the Compounds of the Invention for the Preparation of Pulverulent One-Component Adhesives 
     The hardener of the invention and an EP resin with an EP value of 0.1 are subjected to intensive kneading in a plastograph for 5 minutes at 100° C. After cooling, the product is ground and applied by sieving to steel panels (1.5 mm thick) cleaned with Scotch-Brite, and bonding is conducted in accordance with the procedure of DIN 53 283. The lap shear strengths of these steel bonds (after curing at 200° or 180° C.) are listed in the table infra. 
     
                                           TABLE 3__________________________________________________________________________Metal bonds (DIN 53 283) with the hardener/EP mixtures according to theinventionAdhesive composition           Curing   Lap shear strength (DIN 53 283)  N/mm.sup.2 !ExampleNCO equiv.      OH equiv.           Temperature                 Time                    RoomNo.  Hardener      EP    °C.!                  min!                    temperature                          100° C.                              130° C.                                  150° C.__________________________________________________________________________C) 1 1 A) 7      2    180   30 20    16  10  9C) 2 1 A) 7      1    180   30 21    19  9   9C) 3 1 A) 8      2    180   30 20    17  8   7C) 4 1 A) 8      1    180   30 18    19  16  15C) 5 1 A) 4      2    180   30 21    19  7   6           200   15 20    18  9   7C) 6 1 A) 4      1    180   30 17    13  13  12           200   15 18    14  14  15C) 7 1 A) 5      2    180   30 21    18  17  14           200   15 20    18  16  16Comparison ExampleAT 1 (Ciba)     200   30 29    14  3   1__________________________________________________________________________ 
    
     Having now fully described the invention, it will be apparent to one of ordinary skill in the art that many changes and modifications can be made thereto without departing from the spirit or scope of the invention as set forth herein.