Abstract:
The present invention relates to a solvent-free, two component polyurethane coating composition that is suitable for the production of coatings that have long term resistance to temperatures of up to 30° C., have good elongation and withstand cathodic protection, which contains A) a solvent-free polymer mixture containing a component free from OH groups containing at least one of a chlorinated paraffin or dibutoxybenzene, a di-(phenoxy-alkyl) formal, or a polyacrylonitrile, and a component having hydroxyl groups including a component which contains hydroxy groups and ether groups, and optionally a hydroxy-functional polyether polyacrylate and/or another hydroxy-functional compound; and B) a polyisocyanate component containing at least one organic polyisocyanate, where the NCO:OH equivalent ratio is 0.8:1 to 1.5:1.

Description:
FIELD OF THE INVENTION 
     The present invention relates to solvent-free, two-component, polyurethane reactive compositions (2C-PUR) modified with special soft resins, for the production hydrophobic coatings that have good elongation, withstand cathodic protection and have long term temperature resistance. 
     BACKGROUND OF THE INVENTION 
     To protect oil and gas pipelines, and also the ballast tanks of ships, from corrosion, coatings are required that are highly hydrophobic, are impact-resistant, have good elongation and withstand cathodic protection. Fusion bonded epoxide (FBE) systems, applied as a primer (optionally 2 coats) are known for coating pipelines. Here the powder is reacted on the hot pipe. The FBE coating is coated with polyethylene/polypropylene (PE/PP) by the sintering process, or a coating is built up with adhesive, PU foam and polyethylene. PUR systems applied as wet coatings both to the cold pipe or the field joints also known in the prior art. The pre-coated pipes are bent on site before incorporation into the pipeline network. 
     A disadvantage of the prior art is that the FBE coatings are brittle and do not have either stone impact resistance or elongation. The bending stresses arising when laying pipelines lead to the formation of cracks in the coating and thus the loss of corrosion protection. FBE systems can be applied for repairs on site or to coat field joints only at great cost (higher energy requirement) and with low productivity. EP-Wet systems cannot be used on site below 0° C. The disadvantages of the pure some cases have lower tolerance of cathodic protection. The hydrophilic properties of the 2C-PUR systems require layer thicknesses of &gt;1000 μm for corrosion protection of pipes and ballast tanks. 
     An object of the present invention is to provide solvent-free, liquid primers for the corrosion protection of pipes, which 
     a) have a long term temperature resistance of up to 30° C. and at the same time withstand cathodic protection, 
     b) have an elongation at break of at least &gt;5% and are impact resistant, 
     c) provide long term protection even in thinner coats of 600-900 pm because they are more hydrophobic, 
     d) can be applied both on site and in a workshop, and cure at temperatures below 0° C., 
     e) can be used both for the pipe and for the field joints and 
     f) have a longer pot life (up to 15 minutes) and a longer surface-working time (up to 50 minutes). 
     These objects may be achieved with the polyurethane reactive compositions of the present invention as described hereinafter. 
     SUMMARY OF THE INVENTION 
     The present invention relates to a solvent-free, two-component polyurethane coating composition that is suitable for the production of coatings that have long term resistance to temperatures of to 30° C., have good elongation and withstand cathodic protection, which contains 
     A) a solvent-free polymer mixture containing 
     I) 5 to 50 wt. % of a component free from OH groups and containing 
     a) 0 to 100 wt. % of a chlorinated paraffin or dibutoxybenzene, 
     b) 0 to 100 wt. % of a di-[phenoxy-alkyl]formal, 
     c) 0 to 100 wt. % of a polyacrylonitrile, 
     wherein the percentages of I-a), I-b) and I-c) add up to 100 wt. %, based on the weights of I-a) to I-c), and 
     II) 50 to 95 wt. % of a component having hydroxyl groups comprising 
     a) 40 to 100 wt. % of a component which contains hydroxy groups and ether groups, has a functionality of &gt;3.5 and a number average molecular weight of 280 to 1000, and is different from b), 
     b) 0 to 60 wt. % of a hydroxy-functional polyether polyacrylate and 
     c) 0 to 60 wt. % of a hydroxy-functional compound other than a) and b), 
     wherein the wt. % of 11-a) to 11-c) add up to 100 wt. %, based on the weight of component 11) and 
     B) a polyisocyanate component comprising at least one organic polyisocyanate, wherein the NCO:OH equivalent ratio is 0.8:1 to 1.5:1. 
     DETAILED DESCRIPTION OF THE INVENTION 
     In accordance with the present invention component 1) of solvent-free polymer mixture A) preferably contains 
     d) a mixture of a) and b) wherein the weight ratio of a):b) is 99:1 to 1:99, 
     e) a mixture of a) and c) wherein the weight ratio of a):c) is 99:1 to 1:99 
     or 
     f) a mixture of b) and c) wherein the weight ratio of b):c) is 99:1 to 1:99. 
     Suitable OH group-free components I-a) include chlorinated paraffins such as Hordaflex®, Types LC and SP, (Hoechst), Cerechlor®, Types 70/42 (ICI), Rishichlor® (Rishiroop), or polychlorodibutoxybenzene (Rishiroop). 
     Suitable components I-b) include di(phenoxy-ethyl)formal such as Desavin® (Bayer). 
     Suitable components I-c) include polyacrylonitriles having a average molecular weight of 600 to 3000. 
     Suitable components II-a), which contain hydroxyl groups, are polyether polyols, which can be obtained by known in known manner by the addition of cyclic ethers (such as ethylene oxide, propylene oxide, styrene oxide, butylene oxide or tetrahydrofuran) to starter molecules (such as polyvalent alcohols, aminoalcohols or amines free from ether groups, which have a number average molecular weight of 280 to 1000, preferably 350 to 700 and more preferably 400 to 500. The functionality of the starter molecules, with regard to the reaction with cyclic ethers, must be ≧3.5, preferably ≧4. Polyethers, which contain at least 50%, preferably at least 90%, based on the weight of the repeating units, of —CH(CH 3 )CH 2 O group, are especially preferred. 
     Polyvalent alcohols suitable for use as starter molecules include glycerine, trimethylolpropane, butanetriol-(1,2,4), hexanetriol-(1,2,6), bis(trimethylolpropane), pentaerythritol, mannitol or methylglycoside. 
     Suitable aminoalcohols include 2-aminoethanol, diethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, diisopropanolamine, 2-amino-2-hydroxymethyl-1,3-propanediol and mixtures thereof. 
     Suitable polyvalent amines include aliphatic or cycloaliphatic amines, such as ethylene diamine, 1,2-diaminopropane, 1,3-diamino-propane, 1,4-diaminobutane, 1,3-diamino-2,2-dimethylpropane, 4,4-diaminodicyclohexyl-methane, isophorone diamine, hexamethylene diamine, and 1,12-dodecane diamine; aromatic amines such as the isomers of toluylene diamine; and mixtures thereof. 
     Polyhydroxy component II-b), which is optionally present in the binder mixture according to the invention, can be produced e.g. according to EP-A 825210 (U.S. Pat. No. 6,130,285, herein incorporated by reference). 
     Suitable alcohol components 11-c) have a (number average) molecular weight of 32 to 1000, preferably 32 to 350. Examples include methanol, ethanol, propanol, butanol, hexanol, 2-ethylhexanol, cyclohexanol, stearyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, propanediol-1,2 and -1,3, dipropylene glycol, tripropylene glycol, butanediol-1,2, - 1,3 -1,4  and -2,3, pentanediol-1,5,3-methylpentanediol-1,5, hexanediol-1,6,2-ethylhexanediol-1,3,2-methylpropenediol-1,3, 2,2-dimethylpropanediol-1,3,2-butyl-2-ethylpropanediol-1,3,2,2,4-trimethylpentanediol-1,3, octanediol-1,8, higher molecular weight α-alkanediols containing 9 to 18 carbon atoms, cyclohexanedimethanol, cyclohexanediol, glycerine, trimethylolpropane, butanetriol-1,2,4, hexanetriol-1,2,6, bis(trimethylolpropane), pentaerythritol, mannitol and methylglycoside are preferred. 
     The hydroxy polyesters, hydroxy polyester amides, hydroxy polyethers having a functionality of &lt;3.5, polythioether polyols, hydroxy polycarbonates and hydroxy polyacetals having a number average molecular weight of up to 1,000, which are known from polyurethane chemistry, can optionally also be used as component II-c). 
     Known stabilizers from coatings technology, such as antioxidants and light stabilizers, can optionally be added to polymer mixture A) to further improve the light- and weather stability of the polyether polyacrylates. The binder mixtures according to the invention are preferably used without stabilizers. 
     Suitable antioxidants include stearically-hindered phenols such as 4-methyl-2,6-di-tert.-butylphenol (BHT) or other substituted phenols, thioethers (e.g. Irganox PS®, Ciba Geigy) or phospites (e.g. Irgaphos®, Ciba Geigy) available from Ciba Geigy under the product class name Irganox®. Suitable light stabilizers include HALS (Hindered Amine Light Stabilizers) such as Tinuvin® 622 D or Tinuvin® 765 (Ciba Geigy); and substituted benzotriazoles, such as Tinuvin® 234, Tinuvin® 327 and Tinuvin® 571 (Ciba Geigy). 
     Polyhydroxy component 11 contains 40 to 100 wt. % of component II-a), 0 to 60 wt. % of component II-b) and 0 to 60 wt. % of component II-c). The sum of components II-a) to II-c), without taking account of any antioxidants or light stabilizers, is 100 wt. %. 
     Polyisocyanate component B) according to the invention is an organic polyisocyanate having an average NCO functionality of at least 2 and a molecular weight of at least 140. Suitable polyisocyanates include (i) unmodified organic polyisocyanates having with a molecular weight of 140 to 300, (ii) lacquer polyisocyanates having a number average molecular weight of 300 to 1,000, also (iii) urethane group-containing NCO pre polymers having a number average molecular weight of &gt;1,000, and mixtures thereof. 
     Examples of polyisocyanates i) include 1,4-diisocyanatobutane, 1,6-diisocyanatohexane (HDI), 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- or 2,4,4-trimethyl-1,6-d iisocyanatohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (IPDI), 1-isocyanato-1-methyl-4-(3)-isocyanatomethyl-cyclohexane, bis-(4-isocyanatocyclohexyl)methane, 1,10-diisocyanatodecane, 1,12-diisocyanatodecane, cyclohexane-1,3- and 1,4-diisocyanate, xylylene diisocyanate isomers, 2,4- and 2,6-diisocyanatotoluene or mixtures thereof preferably containing, based on the mixture, up to 35 wt. % 2,6-diisocyanatotoluene, 2,2′-, 2,4′-, 4,4′-diisocyanatodiphenylmethane or polyisocyanate mixtures of the diphenylmethane series and mixtures of the preceding isocyanates. The polyisocyanates of the diphenylmethane series, in particular as isomer mixtures, are preferred. 
     Suitable polyisocyanates ii) include the known solvent-free lacquer polyisocyanates. Within the context of the invention, the term “lacquer polyisocyanates” is understood to mean compounds or mixtures of compounds, which are obtained, by oligomerizing diisocyanates 1) in known manner. 
     Suitable oligomerization reactions include allophanatization, biuretization, carbodiimidization, cyclization, dimerization, urea formation, trimerization and/or urethanization. “Oligomerization” often refers to several of the stated reactions taking place concurrently or consecutively. “Lacquer polyisocyanates” are preferably polyisocyanates containing uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and/or oxadiazinetrione groups. 
     The production of lacquer polyisocyanates is known and disclosed, for example, in DE-A 1 595 273, DE-A 3 700 209, DE-A 3 900 053, EP-A-0 330 966, EPAO 259 233, EP-A-0 377 177, EP-A-0 496 208, EP-A-0 524 501 and U.S. Pat. No. 4,385,171. 
     The urethane group-containing lacquer polyisocyanates ii) can be obtained by the reaction of low molecular weight polyhydroxyl compounds with excess quantities of the preceding di- or polyisocyanates by using a large excess of the di- and polyisocyanates and subsequently removing the excess polyisocyanate, e.g. by thin layer distillation. The prepolymers are preferably produced at 40 to 140° C., optionally using suitable catalysts. 
     Suitable polyhydroxyl compounds for preparing the prepolymers are those having a molecular weight of 62 to 299, such as ethylene glycol, propylene glycol-1,3, butanediol-1,4, hexanediol-1,6, neopentylglycol, 2-ethylhexanediol-1,3, glycerine, trimethylolpropane, pentaerythritol, low-molecular weight esters of these polyols with dicarboxylic acids (such as those disclosed hereinafter), low molecular weight ethoxylation or alkoxylation products of these polyols and mixtures thereof. 
     Polyisocyanates iii) are the known prepolymers having isocyanate groups and prepared by reacting diisocyanates i) and/or lacquer polyisocyanates ii) with organic polyhydroxyl compounds having a number average molecular weight greater than or equal to 300. These polyhydroxyl compounds are known and preferably have a number average molecular weight of 300 to 20,000, more preferably 1,000 to 8,000. 
     Suitable high molecular weight polyhydroxyl compounds for the production of the prepolymers include polyester polyols prepared from the low molecular weight alcohols previously described and polybasic carboxylic acids such as adipic acid, sebacic acid, phthalic acid, isophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, the anhydrides of these acids and any mixtures thereof. Polylactones having hydroxyl groups, in particular polycaprolactones, are also suitable for the production of the prepolymers. 
     Polyether polyols, such as those obtained in the known manner by the alkoxylation of suitable starter molecules, are also suitable for the production of the NCO prepolymers. Suitable starter molecules are the low molecular weight polyols previously described, water, organic polyamines with at least two N—H bonds and mixtures there. Alkylene oxides suitable for the alkoxylation reaction are preferably ethylene oxide and/or propylene oxide, which can be used in any order or in admixture in the alkoxylation reaction. 
     Polytetramethylene glycol polyethers, such as those obtained in known manner by cationic polymerization of tetrahydrofuran, are also suitable for the production of the prepolymers. 
     Polycarbonates having hydroxyl groups, such as those prepared, for example, by the reaction of low molecular diols with phosgene or diaryl carbonates such as diphenylcarbonate, are also suitable for the production of the prepolymers. 
     Polythioetherpolyols, such as those obtained, for example, by the polycondensation of the thiodiglycol with itself, or with diols and/or polyols, are also suitable for the production of prepolymers having NCO groups. 
     Polyacetals, such as polycondensation products of formaldehyde and diols or polyols that can be obtained using acid catalysts (e.g., phosphoric acid or p-toluenesulfonic acid), are also suitable for the production of prepolymers having NCO groups. 
     Mixtures of the preceding polyhydroxyl compounds can also be used to produce the prepolymers. 
     To produce the coating compositions according to the invention, components A) and B) are mixed with each other in amounts sufficient to provide an NCO:OH equivalent ratio of 0.8:1 to 1.5:1, preferably 0.9:1 to 1.3:1. 
     Known additives from coatings technology may optionally be added. Examples include levelling agents, viscosity-controlling additives, pigments, fillers, matting agents, UV stabilizers, antioxidants and catalysts for the crosslinking reaction. These compounds are normally added to and mixed with component A) before components A) and B) are mixed together. 
     The solvent-free, long term temperature resistant, two-component polyurethane coatings according to the invention can be used to protect any metal substrate, even under cathodic protection conditions at long term temperature loads of up to 30° C. The metallic substrates are preferably sheet pilings, locks, ships, pipes and other metal objects in the marine, offshore and onshore industries. 
     The invention is further illustrated but is not intended to be limited by the following examples in which all parts and percentages are by weight unless otherwise specified. 
    
    
     EXAMPLES 
     The coating materials were milled in the mixture having OH groups using a vacuum dissolver. The solvent-free coating compositions were applied with a 2C airless spray machine in layer thicknesses of 500 to 1200 μm, to 3 mm thick, SA 2½ blasted steel sheets. After storage for one week under laboratory conditions, the coatings were tested for tolerance of cathodic protection and also elongation and impact resistance. The pot life and surface-working time (repair, field joints) of the coatings were also determined. 
     Cathodic Protection Test to ASTMG8 
     
       
         
               
               
             
           
               
                   
               
             
             
               
                 Medium: 
                 5% NaCl solution 
               
               
                 Temperature: 
                 30° C. 
               
               
                 Voltage: 
                 U H  = −1260 mV 
               
               
                 Duration: 
                 28 days 
               
               
                 Judgement criteria: 
                 Film decomposition on surface 
               
               
                   
                 Constancy of current consumption 
               
               
                   
                 Infiltration up to 10 mm in artificially 
               
               
                   
                 damaged area 
               
               
                 Impact resistance: 
                 ASTM D 2794-93 
               
               
                 Shore D hardness: 
                 DIN 53505 
               
               
                 Elongation at break of free 
                 DIN EN ISO 527 
               
               
                 films: 
               
               
                 Pot life 
                 (min or sec) 
               
               
                 Surface-working 
                 (min) 
               
               
                   
               
             
          
         
       
     
     Examples 1 to 5 
     Zero Values 
     
       
         
               
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE I 
               
               
                   
               
               
                   
                   
                 Ex. 1 
                 Ex. 2 
                 Ex. 3 
                 Ex. 4 
                 Ex. 5 
               
               
                   
                   
                 (Parts) 
                 (Parts) 
                 (Parts) 
                 (Parts) 
                 (Parts) 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Comp. 1 
               
             
          
           
               
                 Desmophen ® 
                 (Bayer) 
                 22.7 
                 12.75 
                 73.84 
                 45.4 
                 22.7 
               
               
                 LS 2358 
               
               
                 Desmophen ® 
                 (Bayer) 
                 — 
                 12.75 
                 — 
                 45.4 
                 — 
               
               
                 VP LS 2285 
               
               
                 1,4-butanediol 
                 (Bayer) 
                 — 
                 — 
                 14.4 
                 6.92 
                 — 
               
               
                 Baylith ® 
                 (Talke) 
                 5.4 
                 5.4 
                 21.6 
                 21.6 
                 5.4 
               
               
                 L-Paste 
               
               
                 Anti-Terra 204 ® 
                 (Byk Chemie) 
                 0.4 
                 0.4 
                 1.6 
                 1.6 
                 0.0 
               
               
                 Hardener DT 
                 (Bayer) 
                 0.4 
                 0.4 
                 1.6 
                 1.6 
                 0.4 
               
               
                 Crayvallac ® Super 
                 (Langer &amp; Co) 
                 0.4 
                 0.4 
                 1.6 
                 1.6 
                 0.4 
               
               
                 Talc BC- 
                 (Naintsch 
                 — 
                 — 
                 22.4 
                 22.4 
                 — 
               
               
                 Standard ® 
                 Mineralwerke) 
               
               
                 Naintsch ® 
                 (Naintsch 
                 5.6 
                 5.6 
                 — 
                 — 
                 5.6 
               
               
                 BC Standard 
                 Mineralwerke) 
               
               
                 Plastorit ® 
                 (Naitsch 
                 7.7 
                 7.7 
                 30.8 
                 30.8 
                 7.7 
               
               
                 Naintsch 0 
                 Mineralwerke) 
               
               
                 Schwerspat 
                 (Sachtleben) 
                 18.9 
                 18.9 
                 75.6 
                 75.6 
                 18.9 
               
               
                 EWO ® 
               
               
                 Bayertitan ® 
                 (Bayer) 
                 3.7 
                 3.7 
                 — 
                 — 
                 3.7 
               
               
                 R-KB-4 
               
               
                 Tronox ® 
                 (Kerr Mc Gee) 
                 — 
                 — 
                 14.8 
                 14.8 
                 — 
               
               
                 R-KB-4 
               
               
                 Comp. 2 
               
               
                 Desmodur ® VL 
                 (Bayer) 
                 32.05 
                 27.5 
                 128.2 
                 128.2 
                 31.5 
               
               
                 Desmodur ® 
                 (Bayer) 
                 — 
                 — 
                 — 
                 — 
                 5.0 
               
               
                 E 14 
               
               
                 CD Test 
               
               
                 (30° C.) 
               
               
                 Layer thickness (μm) 
                   
                 1050 
                 840 
                 730 
                 780 
                 1120 
               
               
                 Duration 
                   
                 29 d 
                 29 d 
                 28 d 
                 28 d 
                 29 d 
               
               
                 Evaluation 
               
               
                 Current 
                 [mA] 
                 12.6 
                 14.5 
                 25 
                 32 
                 12 
               
               
                 consumption 
               
               
                 (start) 
               
               
                 Current 
                 [mA] 
                 22.5 
                 17 
                 18.5 
                 33.5 
                 23 
               
               
                 consumption 
               
               
                 after 20 d 
               
               
                 Current 
                 [mA] 
                 22 
                 19 
                 15 
                 37.5 
                 23 
               
               
                 consumption 
               
               
                 [end] 
               
               
                 Appearance of 
                   
                 none 
                 none 
                 none 
                 none 
                 none 
               
               
                 film (surface 
               
               
                 decomposition) 
               
               
                 Infiltration in 
                   
                 0-1 
                 0-1 
                 0 
                 0 
                 2 
               
               
                 artificially 
               
               
                 damaged area 
               
               
                 [ASTMG 
               
               
                 42-85] [mm] 
               
               
                 Impact 
                   
                 7.5 
                 7.8 
                 8.2 
                 8.2 
                 8.5 
               
               
                 resistance 
               
               
                 [J/mm] 
               
               
                 Shore D 
                   
                 82 
                 80 
                 80 
                 81 
                 77 
               
               
                 hardness 
               
               
                 Elongation at 
                   
                 2.0 
                 2.0 
                 2.3 
                 2.3 
                 17 
               
               
                 break [%] 
               
               
                 Pot life [sec] 
                   
                 120 
                 120 
                 90 
                 90 
                 130 
               
               
                 Workability 
                   
                 0 
                 0 
                 0 
                 0 
                 0 
               
               
                 [min] 
               
               
                   
               
             
          
         
       
     
     EXAMPLES 
     According to the Invention 
     The following examples according to the invention (Tables II to VII) are based on the formulations of the 0 values in Table I. PVK and the NCO/OH ratio remain constant. The Desmophenes LS 2358 and/or LS 2285 and/or butanediol 1.4 are exchanged proportionately for the soft resins according to the invention or combinations thereof. 
     
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE II 
               
             
             
               
                   
               
               
                 Examples 1-5 (according to the invention) according to 0 value 
               
               
                 of Example 1, Table I 
               
             
          
           
               
                   
                   
                 Ex. 1 
                 Ex. 2 
                 Ex. 3 
                 Ex. 4 
                 Ex. 5 
               
               
                   
                   
                 (Parts ) 
                 (Parts) 
                 (Parts) 
                 (Parts) 
                 (Parts) 
               
               
                   
               
               
                 Comp. 1 
               
             
          
           
               
                 Desmophen ® LS 
                 (Bayer) 
                 13.6 
                 17.0 
                 15.3 
                 13.6 
                 13.6 
               
               
                 2358 
               
               
                 Hordaflex SP 
                 (Hoechst) 
                 9.1 
                   
                 3.7 
                 9.1 
               
               
                 Desavin ® 
                 (Bayer) 
                 — 
                 5.7 
                 3.7 
                 — 
                 9.1 
               
               
                 Baylith ® 
                 (Talke) 
                 5.4 
                 5.4 
                 5.4 
                 5.4 
                 5.4 
               
               
                 L- Paste 
               
               
                 Anti-Terra 204 ® 
                 (Byk Chemie) 
                 0.4 
                 0.4 
                 0.4 
                 0.4 
                 0.4 
               
               
                 Hardener DT ® 
                 (Bayer AG) 
                 0.4 
                 0.4 
                 0.4 
                 0.4 
                 0.4 
               
               
                 Crayvallac ® 
                 (Langer 
                 0.4 
                 0.4 
                 0.4 
                 0.4 
                 0.4 
               
               
                 Super 
                 &amp; Co) 
               
               
                 Talc BC- 
                 (Naintsch 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 Standard ® 
                 Mineralwerke) 
               
               
                 Naintsch ® 
                 (Naintsch 
                 4.3 
                 4.8 
                 4.5 
                 4.3 
                 4.7 
               
               
                 BC Standard 
                 Mineralwerke) 
               
               
                 Plastorit ® 
                 (Naintsch 
                 5.9 
                 6.6 
                 6.3 
                 5.9 
                 6.4 
               
               
                 Naintsch 0 
                 Mineralwerke) 
               
               
                 Schwerspat 
                 (Sachtleben) 
                 14.6 
                 16.2 
                 15.4 
                 14.6 
                 15.8 
               
               
                 EWO ® 
               
               
                 Bayertitan ® R-KB-4 
                 (Bayer) 
                 2.9 
                 3.2 
                 3.0 
                 2.9 
                 3.1 
               
               
                 Tronox ® 
                 (Kerr Mc Gee) 
                 — 
                 — 
                 — 
                 — 
                 — 
               
               
                 R-KB-4 
               
               
                 Comp. 2 
               
               
                 Desmodur ® 
                 (Bayer) 
                 19.5 
                 24 
                 21.6 
                 19.5 
                 18.6 
               
               
                 VL 
               
               
                 Desmodur ® 
                 (Bayer) 
                 — 
                 — 
                 — 
                 — 
                 3.0 
               
               
                 E 14 
               
               
                 CD Test (30° C.) 
               
               
                 ASTMG 42-85 
               
               
                 Layer thickness 
                   
                 850 
                 810 
                 790 
                 600 
                 820 
               
               
                 (μm) 
               
               
                 Duration (d) 
                   
                 28 
                 28 
                 28 
                 28 
                 28 
               
               
                 Current 
                 [mA] 
                 18 
                 19.5 
                 21 
                 35 
                 27 
               
               
                 consumption 
               
               
                 (start) 
               
               
                 Current 
                 [mA] 
                 25 
                 19 
                 19 
                 29.5 
                 22 
               
               
                 consumption 
               
               
                 (end) 
               
               
                 Appearance 
                 0 
                 0 
                 0 
                 0 
                 0 
                 Slight 
               
               
                 of film (surface 
               
               
                 decomposition) 
               
               
                 Infiltration in 
                   
                 0-1 
                 0-1 
                 0-1 
                 0 
                 1 
               
               
                 artificially 
               
               
                 damaged area 
               
               
                 Impact 
                 [J/mm] 
                 12 
                 15 
                 12 
                 13 
                 17 
               
               
                 resistance 
               
               
                 [J/mm] 
               
               
                 Shore D 
                   
                 69 
                 68 
                 65 
                 65 
                 65 
               
               
                 hardness 
               
               
                 Elongation at 
                   
                 15 
                 17 
                 17 
                 17 
                 20 
               
               
                 break (%) 
               
               
                 Pot life (min) 
                   
                 15 
                 15 
                 14 
                 15 
                 17 
               
               
                 Workability 
                   
                 45 
                 45 
                 45 
                 45 
                 55 
               
               
                 (min) 
               
               
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
             
           
               
                 TABLE III 
               
             
             
               
                   
               
               
                 Examples 1-4 (according to the invention) 
               
               
                 according to 0 value of Example 2, Table I 
               
             
          
           
               
                   
                   
                 Ex. 1 
                 Ex. 2 
                 Ex. 3 
                 Ex. 4 
               
               
                   
                   
                 (Parts) 
                 (Parts) 
                 (Parts) 
                 (Parts) 
               
               
                   
               
             
          
           
               
                 Comp. 1 
               
             
          
           
               
                 Desmophen ® LS 
                 (Bayer) 
                 7.65 
                 9.56 
                 8.65 
                 7.65 
               
               
                 2358 
               
               
                 Desmophen ® VP 
                 (Bayer) 
                 7.65 
                 9.56 
                 8.65 
                 7.65 
               
               
                 LS 2285 
               
               
                 Hordaflex SP 
                 (Hoechst) 
                 11.1 
                 — 
                 4.1 
                 11.1 
               
               
                 Desavin ® 
                 (Bayer) 
                 — 
                 5.38 
                 4.1 
                 — 
               
               
                 Desmodur ® VL 
                 (Bayer) 
                 16.50 
                 20.6 
                 18.7 
                 16.50 
               
               
                 Desmodur ® E 14 
                 (Bayer) 
                 — 
                 — 
                 — 
                 — 
               
               
                 CD Test (30° C.) 
               
               
                 ASTMG 42-85 
               
               
                 Layer thickness 
                   
                 880 
                 820 
                 890 
                 650 
               
               
                 (μm) 
               
               
                 Duration (d) 
                   
                 28 
                 28 
                 28 
                 28 
               
               
                 Current 
                 [mA] 
                 15 
                 19 
                 13 
                 19 
               
               
                 consumption 
               
               
                 start 
               
               
                 Current 
                 [mA] 
                 22 
                 27 
                 14 
                 24 
               
               
                 consumption end 
               
               
                 Appearance of 
                 None 
                 None 
                 None 
                 None 
                 None 
               
               
                 film, surface 
               
               
                 decomposition 
               
               
                 Infiltration in 
                   
                 1 
                 1-2 
                 1 
                 2-3 
               
               
                 artificially 
               
               
                 damaged area 
               
               
                 [mm] 
               
               
                 Impact 
                 [J/mm] 
                 11 
                 14 
                 15 
                 15 
               
               
                 resistance 
               
               
                 [J/mm] 
               
               
                 Shore D 
                   
                 69 
                 70 
                 69 
                 68 
               
               
                 hardness 
               
               
                 Elongation at 
                   
                 14 
                 17 
                 15 
                 14 
               
               
                 break (%) 
               
               
                 Pot life (min) 
                   
                 15 
                 14 
                 13 
                 13 
               
               
                 Surfacing resins 
                   
                 45 
                 45 
                 45 
                 45 
               
               
                 (min) 
               
               
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
             
           
               
                 TABLE IV 
               
             
             
               
                   
               
               
                 Examples 1-4 (according to the invention) 
               
               
                 according to 0 value of Example 3, Table I 
               
             
          
           
               
                   
                   
                 Ex. 1 
                 Ex. 2 
                 Ex. 3 
                 Ex. 4 
               
               
                   
                   
                 (Parts) 
                 (Parts) 
                 (Parts) 
                 (Parts) 
               
               
                   
               
             
          
           
               
                 Comp. 1 
               
             
          
           
               
                 Desmophen ® LS 
                 (Bayer) 
                 44.30 
                 55.38 
                 44.30 
                 50.2 
               
               
                 2358 
               
               
                 Butanediol 1.4 
                 (Bayer) 
                 8.64 
                 10.80 
                 8.64 
                 9.8 
               
               
                 Hordaflex SP ® 
                 (Hoech 
                 35.30 
                 — 
                 — 
                 — 
               
               
                   
                 st) 
               
               
                 Desavin ® 
                 (Bayer) 
                 — 
                 22.06 
                 — 
                 14.12 
               
               
                 Polyacrylonitrile 
                 (Bayer) 
                 — 
                 — 
                 35.30 
                 14.12 
               
               
                 Comp. 2 
               
               
                 Desmodur ® VL 
                 (Bayer) 
                 76.92 
                 96.15 
                 76.92 
                 87.2 
               
               
                 CD Test (30° C.) 
               
               
                 ASTMG 42-85 
               
               
                 Layer thickness 
                   
                 880 
                 790 
                 770 
                 820 
               
               
                 (μm) 
               
               
                 Duration (d) 
                   
                 28 
                 28 
                 28 
                 28 
               
               
                 Current 
                 [mA] 
                 23 
                 21 
                 25 
                 25 
               
               
                 consumption 
               
               
                 start 
               
               
                 Current 
                 [mA] 
                 28 
                 28 
                 31 
                 30 
               
               
                 consumption 
               
               
                 end 
               
               
                 Appearance of 
                 None 
                 None 
                 None 
                 None 
                 None 
               
               
                 film, surface 
               
               
                 decomposition 
               
               
                 Infiltration in 
                   
                 0-1 
                 1 
                 1 
                 0-1 
               
               
                 artificially 
               
               
                 damaged area 
               
               
                 [mm] 
               
               
                 Impact 
                 [J/mm] 
                 11 
                 16 
                 14 
                 14 
               
               
                 resistance 
               
               
                 [J/mm] 
               
               
                 Shore D 
                   
                 72 
                 70 
                 71 
                 71 
               
               
                 hardness 
               
               
                 Elongation at 
                   
                 12 
                 14 
                 13 
                 15 
               
               
                 break (%) 
               
               
                 Pot life 
                 (min) 
                 15 
                 15 
                 14 
                 12 
               
               
                 Workability 
                 (min) 
                 45 
                 45 
                 45 
                 45 
               
               
                 (min) 
               
               
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
             
           
               
                 TABLE V 
               
             
             
               
                   
               
               
                 Examples 1-4 (according to the invention) 
               
               
                 according to 0 value of Example 4, Table I 
               
             
          
           
               
                   
                   
                 Ex. 1 
                 Ex. 2 
                 Ex. 3 
                 Ex. 4 
               
               
                   
                   
                 (Parts) 
                 (Parts) 
                 (Parts) 
                 (Parts) 
               
               
                   
               
             
          
           
               
                 Comp. 1 
               
             
          
           
               
                 Desmophen ® LS 
                 (Bayer) 
                 27.25 
                 34.05 
                 30.9 
                 27.25 
               
               
                 2358 
               
               
                 Desmophen ® LS 
                 (Bayer) 
                 27.25 
                 34.05 
                 30.9 
                 27.25 
               
               
                 2285 
               
               
                 Butanediol 1.4 
                 (Bayer) 
                 4.15 
                 5.19 
                 4.7 
                 4.15 
               
               
                 Hordaflex SP ® 
                 (Hoechst) 
                 39.1 
                 — 
                 15.6 
                 — 
               
               
                 Polyacrylonitrile 
                 (Bayer) 
                 — 
                 — 
                 — 
                 39.1 
               
               
                 Comp. 2 
               
               
                 Desmodur ® VL 
                 (Bayer) 
                 76.9 
                 96.15 
                 87.2 
                 76.9 
               
               
                 CD Test (30° C.) 
               
               
                 ASTMG 42-85 
               
               
                 Layer thickness 
                   
                 830 
                 800 
                 700 
                 810 
               
               
                 (μm) 
               
               
                 Duration (d) 
                   
                 28 
                 28 
                 28 
                 28 
               
               
                 Current 
                 [mA] 
                 14.5 
                 16 
                 21 
                 22 
               
               
                 consumption 
               
               
                 start 
               
               
                 Current 
                 [mA] 
                 19 
                 15 
                 20 
                 25 
               
               
                 consumption end 
               
               
                 Appearance of 
                   
                 None 
                 None 
                 None 
                 None 
               
               
                 film, surface 
               
               
                 decomposition 
               
               
                 Infiltration in 
                   
                 0-1 
                 1-2 
                 2 
                 2 
               
               
                 artificially 
               
               
                 damaged area 
               
               
                 [mm] 
               
               
                 Shore D 
                   
                 71 
                 70 
                 70 
                 72 
               
               
                 hardness 
               
               
                 Elongation at 
                   
                 14 
                 18 
                 13 
                 15 
               
               
                 break (%) 
               
               
                 Pot life (min) 
                   
                 15 
                 15 
                 14 
                 12 
               
               
                 Workability (min) 
                   
                 45 
                 45 
                 45 
                 45 
               
               
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
             
           
               
                 TABLE VI 
               
             
             
               
                   
               
               
                 Examples 1-4 (according to the invention) 
               
               
                 according to 0 value of Example 5, Table I 
               
             
          
           
               
                   
                   
                 Ex. 1 
                 Ex. 2 
                 Ex. 3 
                 Ex. 4 
               
               
                   
                   
                 (Parts) 
                 (Parts) 
                 (Parts) 
                 (Parts) 
               
               
                   
               
             
          
           
               
                 Comp. 1 
               
             
          
           
               
                 Desmophen ® LS 
                 (Bayer) 
                 13.6 
                 15.4 
                 15.4 
                 13.6 
               
               
                 2358 
               
               
                 Hordaflex SP ® 
                 (Hoechst) 
                 4.55 
                 3.6 
                 — 
                 — 
               
               
                 Desavin ® 
                 (Bayer) 
                 — 
                 3.6 
                 3.6 
                 — 
               
               
                 Polyacrylonitrile 
                 (Bayer) 
                 4.55 
                 — 
                 3.6 
                 9.1 
               
               
                 Comp. 2 
               
               
                 Desmodur ® VL 
                 (Bayer) 
                 18.5 
                 21.4 
                 21.4 
                 18.9 
               
               
                 Desmodur ® E 14 
                 (Bayer) 
                 3.0 
                 3.4 
                 3.4 
                 3.0 
               
               
                 CD Test (30° C.) 
               
               
                 ASTMG 42-85 
               
               
                 Layer thickness 
                   
                 830 
                 770 
                 800 
                 790 
               
               
                 (μm) 
               
               
                 Duration (d) 
                   
                 28 
                 28 
                 28 
                 28 
               
               
                 Current 
                 [mA] 
                 17 
                 24 
                 13 
                 20 
               
               
                 consumption 
               
               
                 start 
               
               
                 Current 
                 [mA] 
                 20 
                 21 
                 29 
                 24 
               
               
                 consumption end 
               
               
                 Appearance of 
                   
                 None 
                 None 
                 None 
                 None 
               
               
                 film, surface 
               
               
                 decomposition 
               
               
                 Infiltration in 
                   
                 0 
                 1-2 
                 0 
                 1 
               
               
                 artificially 
               
               
                 damaged area 
               
               
                 [mm] 
               
               
                 Shore D 
                   
                 16 
                 17 
                 17 
                 15 
               
               
                 hardness 
               
               
                 Elongation at 
                   
                 65 
                 63 
                 63 
                 66 
               
               
                 break (%) 
               
               
                 Pot life (min) 
                   
                 17 
                 19 
                 19 
                 17 
               
               
                 Workability (min) 
                   
                 15 
                 12 
                 12 
                 14 
               
               
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
               
               
               
               
               
             
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE VII 
               
             
             
               
                   
               
               
                 Examples 1-5 (according to the invention) 
               
               
                 according to 0 value of Example 2, Table I 
               
             
          
           
               
                   
                   
                 Ex. 1 
                 Ex. 2 
                 Ex. 3 
                 Ex. 4 
                 Ex. 5 
               
               
                   
                   
                 (Parts) 
                 (Parts) 
                 (Parts) 
                 (Parts) 
                 Parts) 
               
               
                   
               
             
          
           
               
                 Comp. 1 
               
             
          
           
               
                 Desmophen ® 
                 (Bayer) 
                 7.65 
                 7.65 
                 7.65 
                 7.65 
                 7.65 
               
               
                 LS 2358 
               
               
                 Desmophen ® 
                 (Bayer) 
                 7.65 
                 7.65 
                 7.65 
                 7.65 
                 7.65 
               
               
                 LS 2285 
               
               
                 Cerachlor 
                 (Akzo-ICL) 
                 11.1 
                 — 
                 — 
                 11.1 
                 — 
               
               
                 70/42 ® 
               
               
                 Rishichlor ® 
                 (Rishiroop) 
                 — 
                 11.1 
                 — 
                 — 
                 — 
               
               
                 Polychlrodibutyl- 
                 (Rishiroop) 
                 — 
                 — 
                 11.1 
                 — 
                 11.1 
               
               
                 oxybenzene 
               
               
                 Comp. 2 
               
               
                 Desmodur ® VL 
                 (Bayer) 
                 16.5 
                 16.5 
                 16.5 
                 — 
                 — 
               
               
                 Desmodur ® N 3600 
                 (Bayer) 
                 — 
                 — 
                 — 
                 22.6 
                 22.6 
               
               
                 CD Test 
               
               
                 (30° C.) 
               
               
                 ASTMG 42-85 
               
               
                 Layer 
                   
                 780 
                 730 
                 740 
                 800 
                 710 
               
               
                 thickness (μm) 
               
               
                 Duration (d) 
                   
                 28 
                 28 
                 28 
                 28 
                 28 
               
               
                 Current 
                 [mA] 
                 24 
                 20 
                 35 
                 21 
                 24 
               
               
                 consumption 
               
               
                 (start) 
               
               
                 Current 
                 [mA] 
                 31 
                 23 
                 27 
                 30 
                 38 
               
               
                 consumption 
               
               
                 (end) 
               
               
                 Appearance of 
                   
                 None 
                 None 
                 None 
                 Slight 
                 Slight 
               
               
                 film (surface 
               
               
                 decomposition) 
               
               
                 Infiltration in 
               
               
                 artificially 
               
               
                 damaged area 
               
               
                 Damage [mm] 
                   
                 0 
                 0 
                 0-1 
                 2-3 
                 2-3 
               
               
                 Impact 
                   
                 11 
                 11 
                 12 
                 15 
                 16 
               
               
                 resistance 
               
               
                 [J/mm] 
               
               
                 Shore D 
                   
                 69 
                 69 
                 68 
                 64 
                 64 
               
               
                 hardness 
               
               
                 Elongation at 
                   
                 14 
                 13 
                 14 
                 17 
                 18 
               
               
                 break (%) 
               
               
                 Pot life (min) 
                   
                 15 
                 15 
                 14 
                 19 
                 19 
               
               
                 Surfacing 
                   
                 45 
                 45 
                 45 
                 55 
                 55 
               
               
                 resins (min) 
               
               
                   
               
             
          
         
       
     
     Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.