Novel cationic epoxy resin esters and process of producing same
The present invention is directed to cationic epoxy resin esters containing basic amino groups and which, after protonation of their basic amino groups with inorganic or organic acids give water-dilutable paint binders, and to a process of producing the resin esters. The binders may be used to particular advantage for cathodic electrodeposition (CED). A special application is their use in pigment pastes for the formulation of CED paints. 
     U.S. Pat. Nos. 4,349,655 and 4,327,200 disclose CED binders carrying oxazolidine groups as protonizable groups. These groups, according to the aforesaid patents, are introduced into hydroxy group containing polymers either through urethane linkages, i.e., via a mono-adduct of an N-hydroxyalkyloxazolidine and a diisocyanate, or by means of a dicarboxylic acid semiester of an N-hydroxyalkyloxazolidine. 
     A number of other background documents, some of them not yet published, for example U.S. patent application Ser. No. 433,984 filed Oct. 12, 1982, now U.S. Pat. No. 4,431,781 corresponding to European Patent Application No. 00 76955, published Apr. 20, 1983; U.S. patent application Ser. No. 503,027 filed June 10, 1983; Austrian Patent Specification No. 372,689, and German Patent Application No. P 33 24 960.1 filed July 11, 1983, disclose the introduction of basic groups into the epoxy resin molecules in the form of oxazolidine groups, either totally or partially, in various ways. Thus, hydroxy group carrying oxazolidines are reacted to advantage with the epoxy groups of the epoxy resins via a carboxy group remaining free after reaction with dicarboxylic acid anhydrides. The double ester bond linking the oxazolidine radical to the epoxy resin introduces into the molecule hydrophilic and, moreover, splitable groups which, in various cases, may have a negative effect on the properties of the products and on the paint films produced therefrom. 
     It has now been found that hydroxy-free 5- and 6-membered ring systems carring the structure- ##STR2## in the ring can be reacted with diacarboxylic acid anhydrides. Thus, the present invention is concerned with cationic epoxy resin esters, and a process for producing the resin esters, wherein resin-like compounds carrying at least two 1,2-epoxy groups are reacted with carboxylic acids and, optionally, with primary and/or secondary alkyl- and/or alkanolamines. The carboxylic acid employed is totally or partially the reaction product of a dicarboxylic acid anhydride and a tertiary amine which has the structure- ##STR3## wherein R and R x  are a hydrogen atom or an alkyl radical or an aryl radical which may be substituted, R y  is an alkyl radical, an amino-alkyl radical having the primary amino groups, if present, blocked (as a ketimine) or the moiety remaining after the reaction with an active hydrogen atom of an acrylic or methacrylic monomer monofunctional with regard to the double bond, and wherein n is 2 or 3, the quantity of basic component being chosen in order that the epoxy-group-free final product has an amine value of at least 35 and preferably of from 40 to 140 mg KOH/g. 
     Suitable resinous epoxy group carrying compounds with at least two 1,2-epoxy groups, in particular, are the known epoxy resins obtained through reactions of bisphenols, novolaks, glycols, and the like, with epichlorohydrin or methylepichlorohydrin. There is a variety of the aforesaid products commercially available and which have been described in detail in publications. Products based on bisphenol A or on novolaks with an epoxide equivalent weight of from 170 to 1000 are particularly preferred. Besides these, other resins carrying epoxy groups can be employed, such as copolymers containing glycidyl(meth)acrylate. 
     The epoxy groups of these resin-like compounds are totally or partially reacted with carboxylic acids obtained through reaction of a dicarboxylic acid anhydride with a tertiary amine, the tertiary amine having a structure of the formula- ##STR4## wherein the radicals R and R x  stand for a hydrogen atom or an alkyl radical or an aryl radical, optionally substituted, R y  is an alkyl radical, an amino-alkyl radical having the primary amino groups, if present, blocked (as a ketimine) or the moiety remaining after the reaction with an active hydrogen atom of an acrylic or methacrylic monomer monofunctional with regard to the double bond, and the index n being 2 or 3. Compounds defined by the formula are known as oxazolidines in the event n=2, i.e., 5-members in the ring, or as perhydro-1,3-oxazines in the event n-3, i.e., 6-members in the ring. 
     The preparation of the above N-substituted compounds particularly suited for carrying out the invention can be effected in a simple manner and according to various methods. When using N-substituted secondary ethanol- or propanolamines, the ring is closed with aldehydes, the desired ring-functional oxazolidine or perhydro-1,3-oxazine forming: ##STR5## Suitable substituted amines for the reaction, in addition to N-alkyl-substituted ethanol- or propanolamines, are aminolkylsubstituted ethanol- or propanolamines, such as aminoethylethanolamine or aminoethylpropanolamine, or substances of similar structure. It is understood that primary amino groups must be present in blocked form prior to reaction, for example as ketimines. Alternatively, blocking the primary amino groups may be effected through addition of (meth)acrylic compounds to β- or γ-hydroxy-functional primary amines as follows: 
     
         HO--(CH.sub.2).sub.n --NH.sub.2 +CH.sub.2 =CH--COOR→HO--(CH.sub.2)n--NH--CH.sub.2 --CH.sub.2 --COOR. 
    
     Further, in addition to the normal primary alkanol amines, substituted compounds such as 2-phenyl-2-hydroxy-ethylamine can be used. Suitable acrylic monomers, in addition to the homologous esters of acrylic acid or methacrylic acid with monoalcohols, are monomers carrying tertiary amino groups, such as dimethylaminoethylacrylate and its homologues. 
     A further method of preparing suitable secondary alkanol amines is the reaction of primary alkyl amines with monoepoxy compounds according to the reaction- ##STR6## Suitable primary alkyl amines for use in forming the secondary alkanol amines are the normal straight-chain or branched alkyl amines, including the fatty amines, as well as primary/tertiary amines such as dialkylaminoalkylamines, such as dimethyl- or diethylaminopropylamine. Suitable monoepoxy compounds for use in the reaction are glycidyl esters of carboxylic acids, such as Cardura®E (the glycidyl ester of branched C 9  -C 11  monocarboxylic acids) or glycidylmethacrylate, glycidyl ethers, such as butylglycidyl ether, phenylglycidyl ether, p.-tertiary butylphenol glycidyl ether or allyl glycidyl ether or hydrocarbon oxides, for example the olefin oxides such as- ##STR7## exemplified by octylene oxide, styrene oxide, or cyclohexenevinylmonoxide. 
     Suitable aldehydes for use in closing the ring are aliphatic or aromatic aldehydes such as formaldehyde and its homologues, benzaldehyde, anisaldehyde, and salicylaldehyde. 
     The methods of preparation of the various representatives of the tertiary amines used for carrying out the present invention are described in detail in the experimental section of the present specification. Blends of various types of these compounds may be produced through joint reaction of various hydroxyamines with aldehydes. 
     The amines are reacted with the diacarboxylic acid anhydride at from 50° to 100° C., optionally in the presence of an inert solvent, until the acid value calculated for the monocarboxy compound is attained. 
     Suitable dicarboxylic acid anhydrides are the saturated or unsaturated aliphatic or cycloaliphatic discarboxylic acid anhydrides and the various hydration products of aromatic discarboxylic acids. Exemplary anhydrides are the anhydrides of succinic acid and its homologues; the anhydrides of maleic acid, and the anhydrides of aromatic diacarboxylic acids such as the anhydrides of phthalic acid and naphthocarboxlic acid. Tetrahydrophthalic acid anhydride is particularly preferred. The monocarboxy compounds thus obtained are reacted at from 60° to 75° C. with the compounds carrying epoxy groups, until an acid value of below 3 mg KOH/g is attained. 
     The epoxy groups of the di- or polyepoxy resins not reacting with the intermediates carrying the oxazolidine groups are reacted with other modifying compounds carrying active hydrogen atoms, such as carboxylic acids or amines. 
     The products processed to CED binders are practically free from unreacted epoxy groups. Suitable modifying carboxylic acids are the longer chain carboxylic acids, such as saturated or unsaturated oil fatty acids; α,β-unsaturated monocarboxylic acids such as (meth)acrylic acid, or semiesters of dicarboxylic acids with saturated or unsaturated alcohols or hydroxyalkyloxazolidines or partial esters of tricarboxylic acid anhydrides. Similar modifications are described in U.S. Pat. No. 4,327,200. With simultaneous increase in the molecular weight, subordinate quantities of aliphatic dicarboxylic acids can be used. When using primary or secondary amines, the range of total amine value and the effect on the viscosity have to be considered, since otherwise the parameters for electrodeposition can be detrimentally changed. 
     In a particularly preferred embodiment of the process, the binders prepared according to the invention, subsequent to the reaction of the epoxy resin with the oxazolidine group carrying intermediate and the other modifiers, are subjected to an acidic hydrolysis at from 50° to 80° C., whereby, as is assumed, a part of the oxazolidine rings is opened through the formation of substituted methylol groups. Through the aforesaid post-treatment, reactions are anticipated which otherwise occur in the finished paint or in the coating tank. For this purpose, the reaction product is treated for some hours at the indicated temperature with water and a portion of the acid which is later on used for neutralization. 
     The binders can be milled with pigments in known manner and, for the production of a material ready for application, they are, after partial or total neutralization with inorganic or organic acids to a pH-value of from 4 to 7, diluted with preferably deionized water, to a solids content of between 5% and 20% when used for electrodeposition. The binders prepared according to the invention show excellent dilutability with water, even with a low degree of neutralization. The coemployment of additives and auxiliary substances as well as the conditions for electrodeposition are known to those skilled in the art and need no further explanation. The products produced according to the invention are particularly suited as mill base resins for grinding the pigments. The methods involved are known to the expert and form no part of the present invention. 
     The composition of the binders produced according to the invention by proper selection of components can have self-crosslinking properties and on baking at from 180° to 200° C. wil form homogeneous and resistant films. Self-crosslinking electrodeposition paints can be formulated with the binders of the invention which afford the properties necessary in practice such as high resistance to moisture and salt spray impact. To provide such characteristics, the binders should have a double bond number of at least 0.8, which means that they have to have at least 0.8 chain end double bonds in 1000 molecular weight units. Since the binders also carry free hydroxy groups, film-formation may also be effected through additional crosslinking agents such as blocked di- or polyisocyanates, amino resins, or phenolic resins. When using the resin as mill base for grinding the pigments, the curing tendency is sufficient to give the required resistance characteristics to the whole system when combined with other self-crosslinking resin components. 
     The following examples illustrate the invention without limiting its scope. All data given in parts or percentages refer to parts or percentages by weight unless otherwise stated. All data in the tables refer to the solids content. 
     The following abbreviations are used in the examples: 
     METOLA--N-methylethanolamine 
     ETOLA--N-ethylethanolamine 
     MOLA--monoethanolamine 
     MIPOLA--monoisopropanolamine 
     MPOLA--monopropanolamine 
     BA--n-butylamine 
     HA--n-hexylamine 
     LA--laurylamine 
     DMAPA--dimethylaminopropylamine 
     DEAPA--diethylaminopropylamine 
     AEEA--aminothylethanolamine 
     APEA--aminopropylethanolamine 
     DEA--diethylamine 
     DBA--dibutylamine 
     FA--paraformaldehyde, 91% 
     BZA--benzaldehyde 
     ANA--anisaldehyde 
     SA--salicylaldehyde 
     BUAC--butylacrylate 
     EHAC--2-ethylhexylacrylate 
     EMAC--ethylmethacrylate 
     BUMAC--butylmethacrylate 
     GMAC--glycidylmethacrylate 
     EHGE--2-ethylhexylglycidylether 
     AGE--allylglycidylether 
     CE--Cardura E 
     MIBK--methylisobutylketone 
     APHE--acetophenone 
     CHX--cyclohexanone 
     TMSA--trimellitic acid anhydride 
     THPSA--tetrahydrophthalic acid anhydride 
     PSA--phthalic acid anhydride 
     MSA--maleic acid anhydride 
     BSA--succinic acid anhydride 
     GSA--glutaric acid anhydride 
     HHPSA--hexahydrophthalic acid anhydride 
     HEMA--hydroxyethylmethacrylate 
     HEA--hydroxyethylacrylate 
     MET--methanol 
     ETHEX--2-ethylhexanol 
     BUT--n-butanol 
     ET--ethanol 
     EPH I--epoxy resin based on Bisphenol A having an epoxy equivalent of about 200 
     EPH II--epoxy resin based or Bisphenol A having an epoxy equivalent of about 550 
     EPH III--epoxy resin based on an epoxidized phenol novolak having an epoxy equivalent of about 200. 
     Preparation Of The Intermediates Used In The Examples 
     1. Preparation Of Cyclic Tertiary Amines (CTA) 
     1.1. Through ring formation with an aldehyde of N-substituted secondary ethanol- or propanol amines, at 80° to 120° C., with azeotropic separation of the reaction water, a compound of Formula (I) resulting- ##STR8## wherein R 1  is an alkyl radical with from 1 to 4 C-atoms, 
     R 2  is a hydrogen atom or a CH 3  -group 
     R 3  is a hydrogen atom, an alkyl radical or a phenyl radical 
     R 4  is a hydrogen atom, an alkyl radical with from 1 to 12 C-atoms or an optionally substituted aryl radical. 
     1.2. From aminoalkyl substituted ethanol- or propanolamines, the primary amino groups of which are blocked through ketimine formation. The amine is charged to a reaction kettle, and at 30° to 60° C., the ketone is added, while the batch is cooled. Subsequently, at 80° to 120° C., the reaction water is removed by azeotropic distillation. The ring formation with the aldehyde is formed in the manner described above to provide a compound with the formula- ##STR9## wherein R 2 , R 3  and R 4  are as above defined, and 
     R 5  is a straight-chain or branched cyclic alkylene radical with from 2 to 12 C-atoms or an aralkyl radical, and 
     R 6  is a straight-chain or branched alkyl radical with from 1 to 4 C-atoms, an aryl radical or a hydrogen atom, or, jointly for both R 6  groups, a ring-forming alkylene radical optionally substituted with alkyl, aryl or alkoxy radicals. 
     1.3. From β- (or γ)-hydroxy functional primary amines, the primary amine groups of which have been reacted with a (meth)acrylic compound. In producing this intermediate, in the first step, the (meth)acrylate is added to the amine at 30° to 35° C., while cooling. The reaction is completed by reacting further at 70° to 80° C. or above (preferably at 140° C., in the event methacrylates are used) for a period of from 1 to 3 hours. Then, at 70° to 80° C., the aldehyde is added and the ring is closed at 80° to 120° C., while entraining the reaction water with an azeotropic agent, to provide a compound with the formula- ##STR10## wherein R 2 , R 3  and R 4  are as above defined, and 
     R 7  is a radical remaining after the reaction with an active hydrogen atom of an acrylic or methacrylic monomer monofunctional with regard to the double bond. 
     1.4. Through reaction with monopoxide compounds and secondary alkyl-alkanol amines derived from primary alkyl amines. Thus, the monoepoxide compound is added at 60° to 120° C. to the amine during a period of from 1 to 2 hours. The reaction is completed by maintaining the temperature for another 3 hours. The ring formation with the aldehyde in the manner above provides a 5-membered cyclic amine of the formula- ##STR11## wherein R 2  and R 4  are as above defined, and 
     R 8  is a straight-chain or branched alkyl radical with from 2 to 18 C-atoms, a cycloalkyl radical or an aralkyl radical or a tertiary amino group carrying the aforesaid groups, and 
     R 9  is saturated or unsaturated aliphatic, cycloaliphatic or aromatic hydrocarbon radical, optionally carrying ether or ester groups. 
     Table 1 lists the starting materials (weight units) for the cyclic tertiary amines according to Formulas I to IV as used in the examples. 
     2. Preparation Of The Monocarboxy Compounds Used According To The Invention (MCC) 
     The reaction partners listed in Table 2 are reacted at the given temperature, until the calculated acid value of the monocarboxy compound is attained. Optionally, the reaction may be carried out in the presence of inert solvent such as xylene or diethylene glycol dimethylether. 
     3. Preparation Of The Polycarboxylic Acid Partial Esters Used As Modifiers (SE) 
     Semiesters or partial esters are produced from the di- and tricarboxylic acid anhydrides and monoalcohols listed in Table 3. Optionally, the reaction may be carried out in the presence of inert solvents as noted in (2) above. 
    
    
     EXAMPLES 1-21 
     Formation Of Paint Binders 
     The starting materials listed in Table 4 are mixed and held at 75° to 80° C., until the acid value has fallen to below 3 mg KOH/g. The reaction may optionally be carried out in the presence of solvents, such as glycol ethers, more particularly ethyleneglycol monoethylether. According to the preferred embodiment, the reaction product, obtained as a 62% to 72% solution, is diluted further with water to 60%, after addition of 10 millimoles (mM) of acetic acid per 100 g of resin solids and held at 50° to 70° C. for about 3 hours, while stirring. Prior to further processing, the binders may be diluted further with solvents such as dieactone alcohol or glycol ethers. 
     As will be apparent to one skilled in the art, various modifications can be made within the scope of the aforesaid description. Such modifications, being within the ability of one skilled in the art, form a part of the present invention and are embraced by the appended claims. 
     
                                           TABLE 1                                 
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PREPARATION OF INTERMEDIATE TERTIARY AMINES (CTA)                         
                                     Reaction Temp.                       
CTA                                                                       
   Formula                                                                
        Amine   (Meth)acrylate                                            
                        Monoepoxide                                       
                               Ketone                                     
                                     h/°C.                         
                                             Aldehyde                     
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1  I     75 METOLA                                                        
                --      --     --    --      106 BZA                      
2  I     89 ETOLA                                                         
                --      --     --    --      136 ANA                      
3  I     89 ETOLA                                                         
                --      --     --    --       33 FA                       
4  III   61 MOLA                                                          
                128 BUAC                                                  
                        --     --    1/70     33 FA                       
5  III   75 MIPOLA                                                        
                184 EHAC                                                  
                        --     --    2/75    106 BZA                      
6  III   61 MOLA                                                          
                114 EMAC                                                  
                        --     --    2/120   136 ANA                      
7  III   61 MOLA                                                          
                184 EHAC                                                  
                        --     --    1/75    106 BZA                      
8  III   75 MPOLA                                                         
                184 EHAC                                                  
                        --     --    1/70     33 FA                       
9  III   75 MPOLA                                                         
                142 BUMAC                                                 
                        --     --    2/140   136 ANA                      
10 IV    73 BA  --      186 EHGE                                          
                               --    2/120    33 FA                       
11 IV   101 HA  --      114 AGE                                           
                               --    1/110   106 BZA                      
12 IV    73 BA  --      142 GMA                                           
                               --    1/100   136 ANA                      
13 IV   102 DMAPA                                                         
                --      240 CE --    1/120    33 FA                       
14 IV   130 DEAPA                                                         
                --      186 EHGE                                          
                               --    1/115   122 SA                       
15 IV    73 BA  --      240 CE --    2/130   106 BZA                      
16 IV   188 LA  --      114 AGE                                           
                               --    2/130    33 FA                       
17 II   104 AEEA                                                          
                --      --     100 MIBK                                   
                                     --       33 FA                       
18 II   118 APEA                                                          
                --      --     120 APHE                                   
                                     --      106 BZA                      
19 II   104 AEEA                                                          
                --      --      98 CHX                                    
                                     --      136 ANA                      
__________________________________________________________________________
 Column 1 represents preparations 1-19; and column 2 refers to the graphic
 formulations I-IV at pages 14, 15, 16, and 17 of the specification.      
 
    
     
                       TABLE 2                                                     
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PREPARATION OF INTERMEDIATE                                               
MONOCARBOXY COMPOUNDS (MCC)                                               
      Dicarboxylic                                                        
                  Cycl. Tert. Amine                                       
MCC   Anhydr.     Table 1      Reaction Temp. °C.                  
______________________________________                                    
 1    114 GSA     101 VP 3     80                                         
 2     98 MSA     347 VP 5     60                                         
 3    152 THPSA   271 VP 8     85                                         
 4    148 PSA      354 VP 13   70                                         
 5    100 BSA     333 VP 7     80                                         
 6    154 HHPSA   207 VP 2     90                                         
 7     98 MSA      401 VP 15   65                                         
 8    148 PSA      302 VP 19   70                                         
 9    152 THPSA    271 VP 10   85                                         
10    114 GSA      198 VP 17   75                                         
11    148 PSA     335 VP 9     90                                         
12     98 MSA     293 VP 6     65                                         
13    100 BSA      420 VP 14   65                                         
14    152 THPSA   163 VP 1     70                                         
15    148 PSA      308 VP 18   75                                         
16    100 BSA     201 VP 4     75                                         
17    114 GSA      303 VP 11   80                                         
18    148 PSA      333 VP 12   75                                         
19    152 THPSA    198 VP 17   75                                         
20     98 MSA     101 VP 4     60                                         
                  167 VP 7                                                
21    100 BSA      157 VP 16   85                                         
                   82 VP 1                                                
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                       TABLE 3                                                     
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PREPARATION OF INTERMEDIATE                                               
PARTIAL ESTER MODIFIERS (SE)                                              
                                 Reaction                                 
SE    Carboxylic Anhydride                                                
                      Monoalcohol                                         
                                 Temp. °C.                         
______________________________________                                    
1     98        MSA      130  HEMA   85                                   
2     148       PSA      32   MET    70                                   
3     152       THPSA    116  HEA    85                                   
4     58        TMSA     130  ETHEX  100                                  
      106       PSA                                                       
5     100       BSA      130  HEMA   85                                   
6     98        MSA      65   ETHEX  95                                   
                         37   BUT                                         
7     152       TMPSA    32   MET    75                                   
8     148       PSA      74   BUT    95                                   
9     98        MSA      116  HEA    85                                   
10    100       BSA      46   ET     80                                   
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                                           TABLE 4                                 
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EXAMPLES OF BINDER PREPARATIONS                                           
Epoxy Resin MCC    SE or Monocarboxylic Acid                              
                                 Amine     Amine                          
Example                                                                   
     g Type                                                               
         Val                                                              
            g/Type                                                        
                Mol  g/Type                                               
                           Val   g      Val                               
                                           mg KOH/g                       
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1    400 I                                                                
         2.0                                                              
            542/17                                                        
                1.3  144/2 0.8   22 DEA 0.3                               
                                           75                             
     500 II                                                               
         1.0                     31 DMAPA                                 
                                        0.6                               
2    532 III                                                              
         2.8                                                              
            482/16                                                        
                1.6  257/9 1.2   --     -- 70                             
3    200 I                                                                
         1.0                                                              
            280/19                                                        
                0.8  138/MACS                                             
                           1.6   44 DEA 0.6                               
                                           91                             
     500 II                                                               
         1.0                                                              
     190 III                                                              
         1.0                                                              
4    500 II                                                               
         1.0                                                              
            898/7                                                         
                1.8  --    --    29 DEA 0.4                               
                                           87                             
     342 III                                                              
         1.8                     39 DEAPA                                 
                                        0.6                               
5    600 I                                                                
         3.0                                                              
            866/5                                                         
                2.0  --    --    73 DEA 1.0                               
                                           109                            
6    300 I                                                                
         1.5                                                              
            676/13                                                        
                1.3  402/3 1.5   --     -- 72                             
     650 III                                                              
         1.3                                                              
7    1200 II                                                              
         2.4                                                              
            254/9                                                         
                0.6   86/MACS                                             
                           1.0   103 DBA                                  
                                        0.8                               
                                           48                             
8    300 I                                                                
         1.5                                                              
            407/21                                                        
                1.2  115/5 0.5   44 DEA 0.6                               
                                           111                            
     228 III                                                              
         1.2                     20 DMAPA                                 
                                        0.4                               
9    1050 II                                                              
         2.1                                                              
            757/2                                                         
                1.7  --    --    29 DEA 0.4                               
                                           64                             
10   456 III                                                              
         2.4                                                              
            483/11                                                        
                1.0  120/6 0.6   41 DMAPA                                 
                                        0.8                               
                                           92                             
11   260 I                                                                
         1.3                                                              
            274/12                                                        
                0.7  146/10                                               
                           1.0   39 DBA 0.3                               
                                           90                             
     247 III                                                              
         1.3                     31 DMAPA                                 
                                        0.6                               
12   440 I                                                                
         2.2                                                              
            592/3                                                         
                1.4  222/8 1.0   39 DEAPA                                 
                                        0.6                               
                                           66                             
     400 II                                                               
         0.8                                                              
13   560 I                                                                
         2.8                                                              
            593/15                                                        
                1.3  300/6 1.5   --     -- 100                            
14   1100 II                                                              
         2.2                                                              
            337/18                                                        
                0.7  129/7 0.7   15 DEA 0.2                               
                                           52                             
                                 39 DEAPA                                 
                                        0.6                               
15   475 III                                                              
         2.5                                                              
            406/10                                                        
                1.3   86/ACS                                              
                           1.2   --     -- 151                            
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