Epoxy(meth)acrylates, a process for their production and their use as binders

Abstract

The present invention relates epoxy(meth)acrylates which are substantially free from epoxide groups and are the reaction products of organic compounds containing epoxide groups and having a number average molecular weight (Mn) of 130 to 1000 withI) compounds containing carboxyl and ester groups at an equivalent ratio of carboxyl groups to epoxide groups of 0.7:1.0 to 1.0:1.0, wherein compounds I) are reaction products ofA) organic dicarboxylic acids or dicarboxylic acid anhydrides having a molecular weight of 98 to 164 withB) reaction products containing alcoholic hydroxyl groups and prepared at a COOH/OH equivalent ratio of 0.6 to 0.95 froma) (meth)acrylic acid andb) tri- or tetrahydric ether alcohols having a molecular weight of 180 to 1000, which contain at least two ethylene oxide units -CH2-CH2-O- as part of one or more ether structures and which contain up to 20 mole %, based on the total moles of alkylene oxide units, of propylene oxide units, -CH2-CH (CH3)-O-, andII) basic nitrogen compounds selected from ammonia and (cyclo)aliphatic primary and secondary mines at an NH/epoxide equivalent ratio of 0:1.0 to 0.3:1.0.The present invention also relates to a process for preparing these epoxy(meth)acrylates and to their use in radically hardenable coating, putties or sealing compositions, or for the production of moldings.

What is claimed is:  
     
       1. An epoxy(meth)acrylate which is substantially free from epoxide groups and is the reaction product of an organic compound containing epoxide groups and having a number average molecular weight (M n ) of 130 to 1000 with 
       I) a compound containing carboxyl and ester groups at an equivalent ratio of carboxyl groups to epoxide groups of 0.7:1.0 to 1.0:1.0, wherein compound I) is the reaction product of  
       A) an organic dicarboxylic acid or dicarboxylic acid anhydride having a molecular weight of 98 to  164 or a member slected from the group consisting of sebacic acid anhydride, tetrahydrophthalic acid, hexahydrophthalic acid, norbornene dicarboxylic acid, norbornene dicarboxylic acid anhydride, phthalic acid, isophthalic acid and terephthalic acid,  with  
       B) a reaction product containing alcoholic hydroxyl groups and prepared at a COOH/OH equivalent ratio of 0.6  6.0:1 to 0.95  0.95:1 from  
       a) (meth)acrylic acid and  
       b) a tri- or tetrahydric ether alcohol having a molecular weight of 180 to 1000, which contains at least two ethylene oxide units —CH 2 —CH 2 —O— as part of one or more ether structures and which contains up to 20 mole %, based on the total moles of alkylene oxide units, of propylene oxide units, —CH 2 —CH(CH 3 )—O—, and  
       II) a basic nitrogen compound selected from ammonia and (cyclo)aliphatic primary and secondary amines at an NH/epoxide equivalent ratio of 0:1.0 to 0.3:1.0.  
     
     
       2. The epoxy(meth)acrylate of claim  1  wherein the epoxy(meth)acrylate is the reaction product of said organic compound containing epoxide groups with compound I) at an equivalent ratio of carboxyl groups to epoxide groups of 0.8:1.0 to 0.98:1.0 and with basic nitrogen compound II at an NH/epoxide equivalent ratio of 0.02:1.0 to 0.2:1.0. 
     
     
       3. The epoxy(meth)acrylate of claim  2  wherein said tri- or tetrahydric ether alcohol contains 2 to 20 ethylene oxide units. 
     
     
       4. The epoxy(meth)acrylate of claim  1  wherein said tri- or tetrahydric ether alcohol contains 2 to 20 ethylene oxide units. 
     
     
       5. A binder-containing, radically hardening composition wherein the binder comprises the epoxy(meth)acrylates of claim  1 . 
     
     
       6. A process for preparing an epoxy(meth)acrylate, which is substantially free from epoxide groups, which comprises reacting an organic compound containing epoxide groups and having a number average molecular weight (M n ) of 130 to 1000 with 
       I) a compound containing carboxyl and ester groups at an equivalent ratio of carboxyl groups to epoxide groups of 0.7:1.0 to 1.0:1.0, wherein compound I) is the reaction product of  
       A) an organic dicarboxylic acid or dicarboxylic acid anhydride having a molecular weight of 98 to  164 or a member slected from the group consisting of sebacic acid anhydride, tetrahydrophthalic acid, hexahydrophthalic acid, norbornene dicarboxylic acid, norbornene dicarboxylic acid anhydride, phthalic acid, isophthalic acid and terephthalic acid,  with  
       B) a reaction product containing alcoholic hydroxyl groups and prepared at a COOH/OH equivalent ratio of 0.6  0.6:1 to 0.95  0.95:1 from  
       a) (meth)acrylic acid and  
       b) a tri- or tetrahydric ether alcohol having a molecular weight of 180 to 1000, which contains at least two ethylene oxide units —CH 2 —CH 2 —O— part of one or more ether structures and which contains up to 20 mole %, based on the total moles of alkylene oxide units, of propylene oxide units, —CH 2 —CH(CH 3 )—O—, and  
       II) a basic nitrogen compound selected from ammonia and (cyclo)aliphatic primary and secondary amines at an NH/epoxide equivalent ratio of 0:1.0 to 0.3:1.0.  
     
     
       7. The process of claim  6  wherein said tri- or tetrahydric ether alcohol contains 2 to 20 ethylene oxide units. 
     
     
       8. The process of claim  2   6 wherein the epoxy(meth)acrylate is the reaction product of said organic compound containing epoxide groups with compound I) at an equivalent ratio of carboxyl groups to epoxide groups of 0.8:1.0 to 0.98:1.0 and with basic nitrogen compound II at an NH/epoxide equivalent ratio of 0.02:1.0 to 0.2:1.0. 
     
     
       9. The process of claim  8  wherein said tri- or tetrahydric ether alcohol contains 2 to 20 ethylene oxide units.