Abstract:
A detoxification method for obtaining a pigment compound free from acute and chronic aquatic ecotoxicity by mixing at least one zinc-based component with good anti-corrosive properties but high toxicity-with a phosphate or hydrogen phosphate of a magnesium, sodium, potassium, calcium, strontium, aluminum, ammonium, or organic type or any other compound based on such cations, such as carbonates, oxides, silicates, phosphites, pyrophosphates or phosphonates, said phosphates or hydrogen carbonates or carbonates or oxides or silicates or phosphites or pyrophosphates freed from toxicity enabling a very considerable reduction of the toxic power of said zinc-based component, while maintaining the good anti-corrosive properties thereof.

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This application is a National Stage of International patent application PCT/EP2010/052118, filed on Feb. 19, 2010, which claims priority to foreign French patent application No. FR 09 51104, filed on Feb. 20, 2009, the disclosures of which are incorporated by reference in their entirety. 
     FIELD OF THE INVENTION 
     Zinc containing pigment compounds are confronted with restrictions which are increasingly severe in terms of use in order to meet the various European environmental requirements and directives and notably in fields such as transport, storage and recycling. 
     BACKGROUND OF THE INVENTION 
     Over the past few years, many regulations have appeared, among which mention may be made of the following regulations:
         WEEE—Waste Electrical and Electronic Equipment-2002   ROHS—Restriction of the use of certain Hazardous Substances-2002   End-of-Life Vehicle Recycling—ELV Recycling-2002   REACH—Registration, Evaluation and Authorization of Chemicals-2007   GHS—Globally Harmonized System of Classification and Labelling of Chemicals-2005.       

     Thus, by virtue of their ecotoxicity, the use of zinc containing pigment compounds has become more and more complex over the years. 
     This is notably the case of zinc phosphate and zinc oxide. 
     The classification of zinc salts, including notably zinc phosphate and zinc oxide, was thus established in 2004. Zinc phosphate is particularly mentioned in the 28 th  A.T.P.—Adaptation to Technical Progress—of European directive 67/548/EEC. Zinc phosphate is labeled N/dangerous for the aquatic environment, and R50/53—“Very toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment”. 
     Table 1 recapitulates, according to the amounts of zinc phosphate Zn 3 (PO 4 ) 2 , 2 to 4H 2 O that are used in a product, the labeling restriction and also the associated working code risk phrases in accordance with directive 99/45/EC. 
     
       
         
               
             
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Labeling and risk phrases for zinc phosphate 
               
               
                 use in a product according to 1999/45/EC. 
               
             
          
           
               
                 Quantity of 
                   
                   
               
               
                 Zn 3 (PO 4 ) 2   
                 Labeling 
                 Risk phrase 
               
               
                   
               
               
                 &gt;25% 
                   
                 R50/53 
               
               
                   
                   
                 Very toxic to aquatic organisms, 
               
               
                   
                   
                 may cause long-term adverse effects in 
               
               
                   
                   
                 the aquatic environment 
               
               
                 2.5%-25% 
                   
                 R51/53 
               
               
                   
                   
                 Toxic to aquatic organisms, may 
               
               
                   
                   
                 cause long-term adverse effects in the 
               
               
                   
                   
                 aquatic environment 
               
               
                 0.25%-2.5%  
                 None 
                 R52/53 
               
               
                   
                   
                 Harmful to aquatic organisms, may 
               
               
                   
                   
                 cause long-term adverse effects in the 
               
               
                   
                   
                 aquatic environment. 
               
               
                 &lt;0.25%   
                 None 
                 None 
               
               
                   
               
             
          
         
       
     
     Thus, any formulation which contains more than 2.5% by weight of this compound is consequently labeled N/Dangerous for the aquatic environment. A new need has thus emerged since certain markets do not accept this labeling and require pigment and compounds which do not lead to the N labeling. 
     In accordance with directive 99/45/EC, the formulator, in order to avoid the N labeling, is restricted to the use of less than 2.5% by weight of a product N, R50/53 such as zinc phosphate; however, in the case of anti-corrosion paints and coatings, resistance effectiveness increases with the zinc phosphate content. 
     It should be noted that, conventionally, according to European directive 1999/45/EC, the term “substances” defines chemical elements and their compounds in the natural state or as obtained by any method of production, including any additive necessary for preserving the stability of the product and any impurity deriving from the method, but with the exclusion of any solvent which can be separated without affecting the stability of the substance or modifying its composition. 
     It should also be noted that, conventionally, the term “preparations” defines mixtures or solutions composed of two substances or more. 
     In this context, Zinc free pigment and compounds used in anti-corrosion paints, which had been developed over the past few years, are of renewed interest. Patents have notably been filed on β-tricalcium phosphate (Budenheim, 1991, DE 4014523 A1), and on mixtures of β-tricalcium or dicalcium phosphate and trimagnesium phosphate (Budenheim, 1996-1997, DE 195 41 895 A1-U.S. Pat. No. 5,665,149A). 
     It has also been demonstrated that anti-corrosion pigments containing magnesium phosphate have an advantageous appeal in paint (Albright and Wilson, 1976, U.S. Pat. No. 3,960,611A), without however equaling zinc phosphate. 
     These zinc-free pigments are effective in certain paint systems but are not as universal as zinc phosphate. Indeed, zinc phosphate is effective in most of the formulations used in anti-corrosion paint. 
     SUMMARY OF THE INVENTION 
     In this context, the objective sought is to develop a detoxification method for obtaining a pigment compound free from acute and chronic aquatic ecotoxicity comprising at least one zinc-based component with good anti-corrosive properties but high toxicity, such as: powder of zinc metal, or zinc oxide or hydroxide, or phosphate, borate, stearate, laurate, carbonate, hydroxycarbonate, polyphosphate, phosphite, pyrophosphate, phosphonate, silicate or ferrite, characterized in that it comprises a mixture of said zinc-based component with at least one phosphate or hydrogenophosphate of the following type:
         magnesium, which can be MgHPO 4 .3H 2 O or Mg 3 (PO 4 ) 2 .5H 2 O;   sodium, which can be Na 3 PO 4 .10H 2 O or Na 3 PO 4 .12H 2 O or Na 2 HPO 4 .7H 2 O or   Na 2 HPO 4 .12H 2 O;   potassium, which can be K 3 PO 4  or K 2 HPO 4 ;   calcium, which can be CaHPO 4 .2H 2 O or Ca 3 (PO 4 ) 2 ;   strontium, which can be SrHPO 4  or Sr 3 (PO 4 ) 2 ;   aluminum AlPO 4 ;   ammonium, which can be (NH 4 ) 3 PO 4 .3H 2 O or (NH 4 ) 2 HPO 4 ;   organic, which can be of guanidine type,
 
or any other compound based on said cations Mg, Ca, Sr, etc, such as carbonates, oxides, silicates, phosphites, pyrophosphates or phosphonates, said phosphates or hydrogenocarbonates or carbonates or oxides or silicates or phosphites or pyrophosphates free from toxicity enabling to strongly decrease the toxic power of said zinc-based component, while maintaining the good anti-corrosive properties thereof.
       

     According to one variant of the invention, said pigment component free from toxicity has an algae inhibition rate of less than 50% according to OECD protocol 201, a  daphnia  immobilization rate of less than 50% according to OECD protocol 202, a fish mortality rate of less than 50% according to OECD protocol 203, which results in LC50s (lethal concentration by ingestion for 50% of the population) and EC50s (lethal concentration by inhalation for 50% of the population) above 100 mg/l, and an NOEC (No Observed Effect Concentration) strictly above 1 mg/l on  daphnia  reproduction according to OECD protocol 211. 
     According to one variant of the invention, the mixing is carried out with zinc phosphate Zn 3 (PO 4 ) 2 .0 to 4H 2 O and/or zinc oxide, and magnesium phosphate MgHPO 4 .3H 2 O, the weight ratio between the zinc salts and the magnesium phosphate being non-zero and included respectively between approximately 0 and 99.5%. 
     According to one variant of the invention, the weight ratio between the zinc phosphate and the magnesium phosphate is approximately 90%/10%, and the weight ratio between the zinc phosphate, the magnesium phosphate and the zinc oxide is approximately 80%/10%/10%. 
     The subject of the invention is also a method for producing an anti-corrosion paint, characterized in that it uses the pigment compound obtained by means of the detoxification method according to the invention. 
     According to one variant of the invention, the method for producing paint comprises the use of a pigment compound in combination with a non-ecotoxic filler, for instance talc, barite, kaolin, silica, aluminum silicates or carbonates, calcium silicates or carbonates, magnesium silicates or carbonates, potassium silicates or carbonates, iron oxide, chromium oxide green, mica, titanium dioxide, carbonate or ferrite, for producing a paint. 
     According to one variant of the invention, the detoxification method for obtaining a pigment compound comprises a mixing process via a physical or a chemical process, such as sequential precipitation, sequential crystallization, coprecipitation, cocrystallization, grinding, kneading, dispersion, extrusion, forming a slurry, or granulation. 
     The subject of the invention is also a method for obtaining a coating comprising a polymer of epoxy, alkyd, acrylic, vinyl, polyurethane, polyester, aminoplast, polyolefin, phenolic, butyral, butadiene, PVDF, rubber, or synthetic or natural oil type, characterized in that it uses the pigment compound obtained by means of the detoxification method of the invention. 
     A subject of the invention is also the use of an anti-corrosion coating obtained according to the method of the present invention, for treating a metal part or object such as a motor vehicle, ship, aircraft, bridge, civil engineering vehicle, rail vehicle, agricultural building, industrial building, coil coating, electronic, computer and household appliances materials, gas plant and oil plant. 
     A subject of the invention is also a method for obtaining a plastic, characterized in that it uses the pigment compound obtained by means of the detoxification method according to the invention. 
     A subject of the invention is also a method for obtaining a mastic, characterized in that it uses the pigment compound obtained by means of the detoxification method according to the invention. 
     A subject of the invention is also a method for obtaining an adhesive, characterized in that it uses the pigment compound obtained by means of the detoxification method according to the invention. 
     A subject of the invention is also a method for obtaining an ink, characterized in that it uses the pigment compound obtained by means of the detoxification method according to the invention. 
     A subject of the invention is also a method for obtaining a natural or synthetic rubber material, characterized in that it uses the pigment compound obtained by means of the detoxification method according to the invention. 
     A subject of the invention is also a method for obtaining a solid or liquid lubricant, characterized in that it uses the pigment compound obtained by means of the detoxification method according to the invention. 
     A subject of the invention is also a method for obtaining a fertilizing substance, characterized in that it uses the pigment compound obtained by means of the detoxification method according to the invention. 
     A subject of the invention is also a method for obtaining an anti-UV compound for plastics, characterized in that it uses the pigment compound obtained by means of the detoxification method according to the invention. 
     Finally, a subject of the invention is a method for obtaining an anti-UV compound for cosmetics, characterized in that it uses the pigment compound obtained by means of the detoxification method according to the invention. 
     A subject of the invention is also the use of an anti-corrosion coating according to the invention, for treating a metal part or object such as a motor vehicle, ship, aircraft, bridge, heavy construction machine, rail vehicle, agricultural building, industrial building, coil coating, electronic, computer and household appliance material, gas plant and oil plant. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       The invention will be understood more clearly and other advantages will become apparent on reading the description which follows and which is given without implied limitation, and by virtue of the appended figures among which: 
         FIG. 1  illustrates paint tests for evaluating the anti-corrosion performance levels, carried out according to the ASTM 1654 standards for plate blistering and degree of rusting, of a coating comprising an anti-corrosion adhesion primer of a first type of epoxy amide incorporating a standard zinc phosphate, of a coating comprising an anti-corrosion adhesion primer of a first type of epoxy amide incorporating a first compound according to the invention, and of a coating comprising an anti-corrosion adhesion primer of a second type of epoxy amide incorporating a second compound according to the invention; 
         FIG. 2  illustrates paint tests for evaluating the anti-corrosion performance levels, carried out according to the ASTM 1654 standards for plate blistering and degree of rusting, of a coating comprising an anti-corrosion adhesion primer of a first type of epoxy amine incorporating a standard zinc phosphate, of a coating comprising an anti-corrosion adhesion primer of a first type of epoxy amine incorporating a first compound of the invention, and of a coating comprising an anti-corrosion adhesion primer of a first type of epoxy amine incorporating a second compound according to the invention. 
     
    
    
     The rest of the description is more particularly presented in the context of magnesium monohydrogen phosphate, which is very suitable because it has very good compatibility with zinc phosphate. 
     DETAILED DESCRIPTION 
     Example of an Anti-Corrosion Compound Based on Zinc Phosphate, on Zinc Oxide and on Magnesium Phosphate 
     The following compound was tested:
         PZATB: 80% PZ/10% PAT30/10% ZnO with PZ: Zn 3 (PO 4 ) 2 .0 to 4H 2 O and   PAT30: MgHPO 4 .3H 2 O       

     1) Ecotoxicity Tests on the Anti-Corrosion Compounds based on Zinc Phosphate, on Zinc Oxide and on Magnesium Phosphate 
     There are two possible routes for determining the “dangerous for the environment” labeling of preparations:
         a first route governs the determination according to the substance mixture rule, i.e. according to the composition of the product. By this route, any product containing zinc is consequently dangerous for the environment;   a second route governs the determination according to the ecotoxicity tests in accordance with OECD protocols 201, 202 and 203 for acute ecotoxicity on the preparation containing dangerous materials, this second possible route prevailing over the first route as defined in regulations 1999/45/EC and 1272/2008/EC reiterating the criteria for classification of a tested preparation or mixture containing at least one dangerous material.       

     According to the second route, the tests are carried out on the following three species: algae,  daphnia  and fish. 
     From a regulatory point of view, the applicant followed amended annex 5 of directive 67/548/EEC, directive 99/45/EEC relating to modified preparations, and the GHS report prepared in 2003—part 3, paragraph 3.10.3 relating to the criteria for the classification of mixtures, and tests were carried out according to the OECD guidelines 201 adopted on Mar. 23, 2006, 202 adopted on Apr. 13, 2004, and 203 adopted on Jul. 17, 1992. 
     The conventional labeling of a compound is subsequently carried out in relation to the poorest result of the three acute tests and makes it possible to provide the results recapitulated in table 2, in which the labelings possibly imposed are defined according to a concentration C, a test duration expressed in hours and a rate of 50 percent of species succumbing at the end of the number of hours identified. 
     
       
         
               
             
               
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 Labeling and risk phrases according to the results obtained 
               
               
                 in the ecotoxicity tests according to 1999/45/EC 
               
             
          
           
               
                   
                 Concen- 
                   
                   
               
               
                 Tests 
                 tration C 
                 Labeling 
                 Risk phrase 
               
               
                   
               
               
                 96H LC50 (fish) 
                  ≦1 mg/l 
                   
                 R50/53 
               
               
                 48H EC50 ( daphnia ) 
                   
                   
                 Very toxic to aquatic 
               
               
                 72H LC50 (algae) 
                   
                   
                 organisms, may cause 
               
               
                   
                   
                   
                 long-term adverse 
               
               
                   
                   
                   
                 effects in the aquatic 
               
               
                   
                   
                   
                 environment 
               
               
                 96H LC50 (fish) 
                 between 
                   
                 R51/53 
               
               
                 48H EC50 ( daphnia ) 
                 1 and 
                   
                 Toxic to aquatic organisms, 
               
               
                 72H LC50 (algae) 
                 10 mg/l 
                   
                 may cause long-term 
               
               
                   
                   
                   
                 adverse effects in the 
               
               
                   
                   
                   
                 aquatic environment 
               
               
                 96H LC50 (fish) 
                 between 
                 None 
                 R52/53 
               
               
                 48H EC50 ( daphnia ) 
                 10 and  
                   
                 Harmful to aquatic 
               
               
                 72H LC50 (algae) 
                 100 mg/l 
                   
                 organisms, may  
               
               
                   
                   
                   
                 cause long-term 
               
               
                   
                   
                   
                 adverse effects in the  
               
               
                   
                   
                   
                 aquatic environment 
               
               
                 96H LC50 (fish) 
                 &gt;100 mg/l 
                 None 
                 R53 or no risk phrase 
               
               
                 48H EC50 ( daphnia ) 
                   
                   
                 according to the chronic 
               
               
                 72H LC50 (algae) 
                   
                   
                 ecotoxicity 
               
               
                   
               
             
          
         
       
     
     The globally harmonized labeling system GHS, in its latest revision of 2009, reiterates and confirms the maximum limits of 1 (category 1) 10 (category 2 [1 to 10 mg/l]) and 100 mg/l (category 3 [10 to 100 mg/l]) as criteria for classification of acute aquatic toxicity of categories 1 to 3. Above 100 mg/l for acute toxicity, the substance or the preparation is not classified for its toxicity. 
     In addition, the GHS also specifies that, when the chronic toxicity exhibits a no observed effect concentration of greater than 1 mg/l, then this substance or this mixture is not subject to classification for its chronic nature. 
     The tests were carried out at the CIT, Centre International de Toxicologie [International Center for Toxicology] in Evreux (France). 
     The preparation was produced by physical mixing. 
     The term GLP denotes tests carried out according to Good Laboratory Practice. 
     The following terms are used:
         the reference LC50 denotes: the lethal concentration by ingestion for 50% of the population;   the reference EC50 denotes: the lethal concentration by inhalation for 50% of the population.       

     1.1. Acute ecotoxicity on  Pseudokirchneriella subcapitata  algae 
     
       
         
               
             
               
               
               
               
               
             
           
               
                 TABLE 3 
               
             
             
               
                   
               
               
                 Results of acute ecotoxicity on  Pseudokirchneriella subcapitata   
               
               
                 algae 
               
             
          
           
               
                   
                   
                 GLP/non GLP 
                 Inhibition 
                 LC50 
               
               
                   
                 Preparation 
                 test 
                 algae (%) 
                 (mg/l) 
               
               
                   
               
               
                   
                 PZATB 
                 Non GLP 
                 36.2 
                 &gt;100 
               
               
                   
               
             
          
         
       
     
     Table 3 shows that the inhibition of the algae is less than 50%. The preparation is not therefore ecotoxic to the algae owing to an acute ecotoxicity LC50&gt;100 mg/l according to OECD protocol 201. 
     1.2. Acute ecotoxicity on  Daphnia magna  crustaceans 
     
       
         
               
             
               
               
               
               
               
             
           
               
                 TABLE 4 
               
             
             
               
                   
               
               
                 Results of acute ecotoxicity on  Daphnia magna  crustaceans 
               
             
          
           
               
                   
                   
                 GLP/non GLP 
                 Immobilization 
                 EC50 
               
               
                   
                 Preparation 
                 test 
                   daphnia  (%) 
                 (mg/l) 
               
               
                   
               
               
                   
                 PZATB 
                 Non GLP 
                 0 
                 &gt;100 
               
               
                   
               
             
          
         
       
     
     Table 4 shows that no  daphnia  is immobilized. The preparation is not therefore ecotoxic to crustaceans owing to an acute ecotoxicity EC50 &gt;100 mg/l according to OECD protocol 202. 
     1.3. Acute ecotoxicity on  Oncorhynchus mykiss  fish 
     
       
         
               
             
               
               
               
               
               
             
           
               
                 TABLE 5 
               
             
             
               
                   
               
               
                 Results of acute ecotoxicity on  Oncorhynchus mykiss  fish 
               
             
          
           
               
                   
                   
                 Number 
                 Trout 
                   
               
               
                   
                 GLP/non GLP 
                 of 
                 mortality 
                 LC50 
               
               
                 Preparation 
                 test 
                 trout 
                 (%) 
                 (mg/l) 
               
               
                   
               
               
                 PZATB 
                 Non GLP 
                 10 
                 0 
                 &gt;100 
               
               
                   
               
             
          
         
       
     
     Table 5 shows that no trout died. The preparation does not exhibit any toxicity to the fish owing to an acute ecotoxicity LC50 &gt;100 mg/l according to OECD protocol 203. 
     It thus emerges from these test that PZATB does not exhibit any acute toxicity. 
     Example of Anti-Corrosion Compounds Based on Zinc Phosphate and on Magnesium Phosphate 
     Various compounds were produced and tested with weight ratios between zinc phosphate and magnesium monohydrogen phosphate ranging from 99%/1%) to 4.3%/95.7%, and identified as follows: 
     PZAT 99:PZ 99%/PAT30 1% 
     PZAT 95:PZ 95%/PAT30 5% 
     PZAT 90:PZ 90%/PAT30 10% 
     PZAT 80:PZ 80%/PAT30 20% 
     PZAT 70:PZ 70%/PAT30 30% 
     PZAT 60:PZ 60%/PAT30 40% 
     PZAT 50:PZ 50%/PAT30 50% 
     PZAT 40:PZ 40%/PAT30 60% 
     PZAT 04:PZ 4.3%/PAT30 95.7% 
     with PZ:Zn 3 (PO 4 ) 2 ,0 to 4H 2 O and 
     PAT30:Mg HPO 4 ,3H 2 O 
     2) Acute Ecotoxicity Tests on the Anti-Corrosion Compounds based on Zinc Phosphate and on Magnesium Phosphate 
     Tests were carried out at the CIT, Centre International de Toxicologie [International Center for Toxicology] in Evreux (France). 
     The preparations were produced by physical mixing. 
     The term GLP denotes tests carried out according to Good Laboratory Practice. 
     The following terms are used:
         the reference LC50 denotes: the lethal concentration by ingestion for 50% of the population;   the reference EC50 denotes: the lethal concentration by inhalation for 50% of the population.       

     2.1. Acute Ecotoxicity on  Pseudokirchneriella subcapitata  algae 
     
       
         
               
             
               
               
               
               
             
               
               
               
               
             
           
               
                 TABLE 6 
               
             
             
               
                   
               
               
                 Results of acute ecotoxicity on  Pseudokirchneriella subcapitata   
               
               
                 algae 
               
             
          
           
               
                   
                 GLP/non GLP 
                 Inhibition 
                 LC50 
               
               
                 Preparation 
                 test 
                 algae (%) 
                 (mg/l) 
               
               
                   
               
             
          
           
               
                 PZ 99%/PAT30 1% 
                 GLP 
                 16.29 
                 &gt;100 
               
               
                 PZ 95%/PAT30 5% 
                 GLP 
                 6.76 
                 &gt;100 
               
               
                 PZ 90%/PAT30 10% 
                 GLP 
                 11.67 
                 &gt;100 
               
               
                 PZ 80%/PAT30 20% 
                 Non GLP 
                 23.58 
                 &gt;100 
               
               
                 PZ 70%/PAT30 30% 
                 Non GLP 
                 19.16 
                 &gt;100 
               
               
                 PZ 60%/PAT30 40% 
                 Non GLP 
                 17.5 
                 &gt;100 
               
               
                 PZ 50%/PAT30 50% 
                 Non GLP 
                 13.72 
                 &gt;100 
               
               
                 PZ 40%/PAT30 60% 
                 Non GLP 
                 6.58 
                 &gt;100 
               
               
                 PZ 4.3%/PAT30 95.7% 
                 GLP 
                 12.24 
                 &gt;100 
               
               
                   
               
             
          
         
       
     
     Table 6 shows that the inhibition of the algae is less than 50%. The preparation is not therefore ecotoxic to the algae owing to an acute ecotoxicity LC50&gt;100 mg/l according to OECD protocol 201. 
     2.2. Acute Ecotoxicity on  Daphnia magna  crustaceans 
     
       
         
               
             
               
               
               
               
             
           
               
                 TABLE 7 
               
             
             
               
                   
               
               
                 Results of acute ecotoxicity on  Daphnia magna  crustaceans 
               
             
          
           
               
                   
                 GLP/non GLP 
                 Immobilization 
                 EC50 
               
               
                 Preparation 
                 test 
                   daphnia  (%) 
                 (mg/l) 
               
               
                   
               
               
                 PZ 99%/PAT30 1% 
                 GLP 
                 0 
                 &gt;100 
               
               
                 PZ 95%/PAT30 5% 
                 GLP 
                 0 
                 &gt;100 
               
               
                 PZ 90%/PAT30 10% 
                 GLP 
                 0 
                 &gt;100 
               
               
                 PZ 80%/PAT30 20% 
                 Non GLP 
                 0 
                 &gt;100 
               
               
                 PZ 70%/PAT30 30% 
                 Non GLP 
                 0 
                 &gt;100 
               
               
                 PZ 60%/PAT30 40% 
                 Non GLP 
                 0 
                 &gt;100 
               
               
                 PZ 50%/PAT30 50% 
                 Non GLP 
                 0 
                 &gt;100 
               
               
                 PZ 40%/PAT30 60% 
                 Non GLP 
                 0 
                 &gt;100 
               
               
                 PZ 4.3%/PAT30 95.7% 
                 GLP 
                 0 
                 &gt;100 
               
               
                   
               
             
          
         
       
     
     Table 7 shows that no  daphnia  is immobilized. The preparation is not therefore ecotoxic to crustaceans owing to an acute ecotoxicity EC50 &gt;100 mg/l according to OECD protocol 202. 
     2.3. Acute Ecotoxicity on  Oncorhynchus mykiss  fish 
     
       
         
               
             
               
               
               
               
               
             
           
               
                 TABLE 8 
               
             
             
               
                   
               
               
                 Results of acute ecotoxicity on  Oncorhynchus mykiss  fish 
               
             
          
           
               
                   
                   
                 Number 
                 Trout 
                   
               
               
                   
                 GLP/non GLP 
                 of 
                 mortality 
                 LC50 
               
               
                 Preparation 
                 test 
                 trout 
                 (%) 
                 (mg/l) 
               
               
                   
               
               
                 PZ 99%/PAT30 1% 
                 GLP 
                 10 
                 0 
                 &gt;100 
               
               
                 PZ 95%/PAT30 5% 
                 GLP 
                 10 
                 0 
                 &gt;100 
               
               
                 PZ 90%/PAT30 10% 
                 GLP 
                 10 
                 0 
                 &gt;100 
               
               
                 PZ 80%/PAT30 20% 
                 Non GLP 
                 10 
                 0 
                 &gt;100 
               
               
                 PZ 70%/PAT30 30% 
                 Non GLP 
                 10 
                 0 
                 &gt;100 
               
               
                 PZ 60%/PAT30 40% 
                 Non GLP 
                 10 
                 0 
                 &gt;100 
               
               
                 PZ 50%/PAT30 50% 
                 Non GLP 
                 10 
                 0 
                 &gt;100 
               
               
                 PZ 40%/PAT30 60% 
                 Non GLP 
                 10 
                 0 
                 &gt;100 
               
               
                 PZ 4.3%/PAT30 95.7% 
                 GLP 
                 10 
                 0 
                 &gt;100 
               
               
                   
               
             
          
         
       
     
     Table 8 shows that no trout died. The preparation does not exhibit any toxicity to the fish owing to an acute ecotoxicity LC50&gt;100 mg/l according to OECD protocol 203. 
     Various compounds were produced and tested with weight ratios between zinc phosphate and magnesium monohydrogen phosphate ranging from 99%/1% to 25%/75%, and identified as follows: 
     PZAT 99:PZ 99%/PAT30 1% 
     PZAT 92:PZ 92%/PAT30 8% 
     PZAT 25:PZ 75%/PAT30 25% 
     with PZ:Zn 3 (PO 4 ) 2 .0 to 4H 2 O and 
     PAT30:MgHPO 4 .3H 2 O 
     3) Chronic Ecotoxicity Tests on the Anti-Corrosion Compounds based on Zinc Phosphate and on Magnesium Phosphate 
     There are two possible routes for determining the “dangerous for the environment in the long term” labeling of preparations:
         a first route governs the determination according to the substance mixture rule, i.e. according to the composition of the product. Via this route, any product containing more than 25% of an R53 product (1999/45/EC) consequently exhibits a chronic ecotoxicity;   a second route governs the determination according to ecotoxicity tests on the most sensitive species, which, in the case of zinc salts, is  daphnia , in accordance with OECD protocol 211 relating to preparations containing dangerous materials, this possible second route prevailing over the first.       

     From a regulatory point of view, the applicant followed amended annex 5 of directive 67/548/EEC, directive 99/45/EEC relating to modified preparations in table 9, regulation 1272/2008 EC resulting from the recommendations of the UNO report of the GHS prepared in 2003 modified—part 3, paragraph 3.10.3 in table 10 relating to the criteria for the classification of mixtures, and tests were carried out according to the OECD guidelines 211 adopted on Oct. 3, 2008. 
     The term “NOEC” denotes the No Observed Effect Concentration. 
     
       
         
               
             
               
               
               
             
           
               
                 TABLE 9 
               
             
             
               
                   
               
               
                 Chronic ecotoxicity labeling and risk phrases according to the GHS 
               
             
          
           
               
                   
                   
                 Labeling and risk phrases according 
               
               
                   
                 Tests 
                 to the GHS 
               
               
                   
               
               
                   
                 If NOEC &lt; or = 1 mg/l 
                 May cause long-term adverse effects 
               
               
                   
                   
                 in the aquatic environment 
               
               
                   
                 If NOEC &gt; 1 mg/l 
                 No labeling 
               
               
                   
                   
                 No risk phrase 
               
               
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
             
           
               
                 TABLE 10 
               
             
             
               
                   
               
               
                 Chronic ecotoxicity labeling and risk phrases according 
               
               
                 to regulation 1999/45/EC for preparations or mixtures 
               
             
          
           
               
                   
                 Labeling and risk phrases according 
               
               
                 Content 
                 to current regulations 
               
               
                   
               
               
                 If the content of R53 
                 R53 
               
               
                 substance &gt;25% (in the 
                 May cause long-term adverse effects 
               
               
                 absence of R50 or 51 or 52) 
                 in the aquatic environment 
               
               
                 If the content of R53 
                 No labeling 
               
               
                 substance &lt;25% (in the 
                 No risk phrase 
               
               
                 absence of R50 or 51 or 52) 
               
               
                   
               
             
          
         
       
     
     Tests were carried out at the CIT, Centre International de Toxicologie [International Center for Toxicology] in Evreux (France). 
     The preparations were produced by physical mixing. 
     The tests were carried out under GLP. The term GLP denotes tests carried out according to Good Laboratory Practice. 
     
       
         
               
             
               
               
               
               
               
             
           
               
                 TABLE 11 
               
             
             
               
                   
               
               
                 Results of the chronic ecotoxicity tests 
               
             
          
           
               
                 Preparation 
                 Mortality 
                 Growth 
                 Reproduction 
                 NOEC 
               
               
                   
               
               
                 PZAT99 
                 No effect 
                 No effect 
                 No effect 
                 &gt; or = 1.5 mg/l 
               
               
                 PZAT92 
                 No effect 
                 No effect 
                 No effect 
                 &gt; or = 1.5 mg/l 
               
               
                 PZAT25 
                 No effect 
                 No effect 
                 No effect 
                 &gt; or = 1.5 mg/l 
               
               
                   
               
             
          
         
       
     
     Table 11 shows that the preparations do not exhibit chronic ecotoxicity owing to an NOEC&gt;1 mg/l according to OECD protocol 211. 
     None of the preparations containing zinc phosphate and magnesium phosphate have any dangerous for the environment labeling (no acute or chronic toxicity). 
     Since preparations containing 0 to 25% of zinc phosphate do not exhibit any chronic ecotoxicity according to the substance mixture rule, it was demonstrated that any compound containing from 0 to 99% of zinc phosphate as a mixture with magnesium phosphate is consequently exempt from dangerous for the environment labeling. 
     It thus emerges from these analyses that none of these preparations mentioned above in points 2 and 3 are dangerous for the environment, in terms of both acute and chronic characteristics. 
     The corresponding compounds listed above were evaluated in terms of toxicity and, by way of industrial illustration, are also evaluated in terms of anti-corrosion performance levels. 
     For this, conventional anti-corrosion adhesion primers of solvent-phase epoxy system type, incorporating the various pigment compounds, were prepared without there being any notable losses of performance levels compared with PZ. 
     Indeed, in the context of the problem of anti-corrosion coating, it is sought to develop anti-corrosion adhesion primers corresponding to the first coat intended to coat a metal surface, itself intended to support in a conventional manner a second coat of paint generally carrying the color of said coating and frequently called topcoat. 
     4) Anti-Corrosion Tests in Paint 
     Thus, the applicant carried out tests in paint proving the good anti-corrosion performance levels in paint of the compounds. These tests were carried out with solvent-phase epoxy primers. 
     Illustration 1: Tests of the Preparation in a Solvent-Phase Vinyl Alkyd Primer 
     The formula of table 12 was prepared. 
     
       
         
               
             
               
               
               
               
             
               
               
               
               
             
           
               
                 TABLE 12 
               
             
             
               
                   
               
               
                 Formula of a solvent-phase vinyl alkyd primer 
               
             
          
           
               
                   
                 % 
                   
                   
               
               
                 STARTING MATERIALS 
                 WEIGHT 
                 DESCRIPTION 
                 SUPPLIERS 
               
               
                   
               
             
          
           
               
                 SETAL 199-SS-55 
                 25.5 
                 Medium oil alkyd 
                 NUPLEX 
               
               
                 ACETONE 
                 5.00 
                 solvent 
                 SHELL 
               
               
                 NUODEX 10% Ca 
                 0.50 
                 Dispersant 
                 ELEMENTIS Specialities 
               
               
                 BENTONE SD2 
                 0.30 
                 Rheological additive 
                 NL Chemicals 
               
               
                 SOLVESSO 100 
                 7.5 
                 Aromatic solvent 
                 EXXON CHEMICAL 
               
               
                 ZINC PHOSPHATE PZ20 
                 8.00 
                 Corrosion inhibitor 
                 SNCZ 
               
               
                 TALC 10 M2 
                 4.00 
                 filler 
                 RIO TINTO Minerals 
               
               
                 MICA MU M 2/1 
                 9.00 
                 filler 
                 CMMP 
               
               
                 MICRONOX 
                 11.00 
                 Micronized natural iron 
                 KEYSER AND MACKAY 
               
               
                   
                   
                 oxide 
                   
               
               
                 THIXATROL ST 
                 0.30 
                 Thixotropic additive 
                 NL Chemicals 
               
               
                 grinding for 40 minutes until 
                   
                   
                   
               
               
                 Hegman fineness of 6 is 
                   
                   
                   
               
               
                 obtained 
                   
                   
                   
               
               
                 LAROFLEX MP35/S100 at 
                 21.10 
                 Vinyl chloride copolymer 
                 BASF 
               
               
                 28.5% 
                   
                   
                   
               
               
                 SOLVESSO 100 
                 2.93 
                 Aromatic solvent 
                 EXXON CHEMICAL 
               
               
                 ISOPROPYL ALCOHOL 
                 1.20 
                 solvent 
                 SHELL 
               
               
                 CERECLOR 42 
                 0.60 
                 Chloroparaffin, plasticizer 
                 INEOS 
               
               
                 NUODEX 8% Co 
                 0.05 
                 siccative 
                 ELEMENTIS Specialities 
               
               
                 NUODEX 10% Zr 
                 0.12 
                 siccative 
                 ELEMENTIS Specialities 
               
               
                 DUOMEEN TDO 
                 0.30 
                 Cationic surfactant 
                 AKZO Chemie 
               
               
                 MEKO 
                 0.50 
                 Methyl ethyl ketoxime, 
                   
               
               
                   
                   
                 anti-skinning agent 
                   
               
               
                 % PVC 
                 30.21 
                   
                   
               
               
                 (pigment volume 
                   
                   
                   
               
               
                 concentration) 
                   
                   
                   
               
               
                 Dry extract, % by weight 
                 60.49 
                   
                   
               
               
                 Dry extract, % by volume 
                 41.62 
                   
                   
               
               
                 Pigment/binder ratio 
                 0.43 
                   
                   
               
               
                 (by volume) 
               
               
                   
               
             
          
         
       
     
     Comparison of the Compounds PZ, PZATB, and PZAT90 in Alkyd Primer 
     PZ, the preparation PZ 80%/PAT30 10%/ZnO 10%, and the preparation PZ 90%/PAT30 10% were compared. PZATB and PZAT90 were prepared by physical mixing. 
     A metal surface was given a coat of anti-corrosion primer incorporating the pigment compounds in an alkyd resin, having a thickness of 40 μm. This coat is covered with a film of an alkyd coat having a thickness of 25 μm, also commonly called topcoat. 
     The whole is exposed to a salt fog (standard ASTM B117) for 300 hours. 
       FIG. 1  illustrates the results obtained. 
     A rating made it possible to evaluate the degree of rusting and the degree of blistering. 
     For the degree of rusting, standard NF ISO 4628-3 T30-140-3 was used. 
     Ri0: no rusting, 0% rusted surface area 
     Ri1: very little rusting, 0.5% rusted surface area 
     Ri5: highly rusted, 40 to 50% rusted surface area 
     For the degree of blistering, standards NF ISO 4628-1 T30-140-2 and NF ISO 4628-3 T30-140-2 were used. 
     DOS0: no detectable defect of size invisible at 10× magnification 
     D2S2: small amount of small blisters 
     D5S5: large amount of large blisters. 
     The “scribe rating” and the “global rating” are produced according to standard ASTM D 1654 January 2005—“Standard Test Method for Evaluation of Painted or Coated Specimens Subjected to Corrosive Environments”—tables 1 and 2 respectively, page 3. 
     Rating at Scribe:
         10 represents 0 mm at scribe   0 represents 16 mm and more at scribe       

     Global Rating:
         10 represents 0% degradation   0 represents more than 75% degradation.       

     The rating in table 13 is produced according to the standards described above. 
     
       
         
               
             
               
               
               
               
               
             
           
               
                 TABLE 13 
               
             
             
               
                   
               
               
                 Rating of the solvent-phase vinyl alkyd primer 
               
             
          
           
               
                   
                 Degree of 
                 Degree of 
                   
                   
               
               
                   
                 rusting 
                 blistering 
                   
                   
               
               
                   
                 NF-ISO 
                 NF-ISO 
                 Scribe 
                 Full plate 
               
               
                   
                 4828-3 
                 4828-3 
                 corrosion 
                 global rating 
               
               
                   
                 T 30140-3 
                 T 30140-3 
                 ASTM 1654 
                 ASTM 1654 
               
               
                   
               
               
                 PZ 
                 RI1 
                 D2S2 
                 6 
                 6 
               
               
                 PZAT90 
                 RI1 
                 D3S2 
                 4 
                 4 
               
               
                 PZATB 
                 RI0 
                 D0S0 
                 8 
                 9 
               
               
                   
               
             
          
         
       
     
     PZATB is as effective as PZ, and more effective than PZAT90. 
     Illustration 2: Tests of the preparation in a solvent-phase epoxy amide primer 
     The formula of table 14 was prepared. 
     
       
         
               
             
               
               
               
               
             
               
               
               
               
             
           
               
                 TABLE 14 
               
             
             
               
                   
               
               
                 Formula of a solvent-phase epoxy amide 
               
             
          
           
               
                   
                 % 
                   
                   
               
               
                 STARTING MATERIALS 
                 WEIGHT 
                 DESCRIPTION 
                 SUPPLIERS 
               
               
                   
               
             
          
           
               
                 PART A 
                   
                   
                   
               
               
                 Introduce with mixing in 
                   
                   
                   
               
               
                 the following order 
                   
                   
                   
               
               
                 EPIKOTE 1001/XYLENE 
                 22.90 
                 Epoxy resin 
                 HEXION 
               
               
                 50/50 weight/weight 
                   
                   
                   
               
               
                 SOLVESSO 100 
                 7.20 
                 Aromatic hydrocarbon 
                 TOTAL Chimie 
               
               
                   
                   
                 solvent 
                   
               
               
                 ISOBUTYL ALCOHOL 
                 1.60 
                 Solvent 
                 SHELL 
               
               
                 DOWANOL PMA 
                 7.30 
                 Glycol ester, solvent 
                 DOW 
               
               
                 NUODEX 10% Ca 
                 0.50 
                 Dispersant 
                 ELEMENTIS Specialities 
               
               
                 BENTONE SD2 
                 0.15 
                 Rheological additive 
                 ELEMENTIS Specialities 
               
               
                 TiO 2  TR92 
                 4.30 
                 Rutile 
                 HUNSTMANN 
               
               
                 ZINC PHOSPHATE PZ20 
                 8.00 
                 Corrosion 
                 SNCZ 
               
               
                   
                   
                 inhibitor 
                   
               
               
                 YELLOW IRON OXIDE 
                 5.10 
                 Pigment, colorant 
                 BAYER 
               
               
                 3920 
                   
                   
                   
               
               
                 TALC 10 M2 
                 9.30 
                 Filler 
                 RIO TINTO Minerals 
               
               
                 MICA MU 2/1 
                 10.70 
                 Filler 
                 CMMP 
               
               
                 THIXATROL ST 
                 0.20 
                 Thixotropic additive 
                 ELEMENTIS Specialities 
               
               
                 Grinding in ball mill for 40 
                   
                   
                   
               
               
                 minutes until Hegman 
                   
                   
                   
               
               
                 fineness of 5 obtained 
                   
                   
                   
               
               
                 BUTYL ACETATE 
                 2.50 
                 Ester, solvent 
                 TOTAL chimie 
               
               
                 CERECLOR M50 
                 2.40 
                 Chloroparaffin, plasticizer 
                 INEOS 
               
               
                 DUOMEEN TDO 
                 0.15 
                 Cationic surfactant 
                 AKZO Chemie 
               
               
                 PART B 
                   
                   
                   
               
               
                 XYLENE 
                 3.00 
                 Aromatic 
                 TOTAL Chimie 
               
               
                   
                   
                 hydrocarbon, 
                   
               
               
                   
                   
                 solvent 
                   
               
               
                 EPILINK 230 
                 0.30 
                 Accelerator 
                 AKZO Chemie 
               
               
                 ARADUR 115 X70 BD 
                 14.40 
                 Polyamidoamide 
                 VANTICO 
               
               
                   
                   
                 hardener 
                   
               
               
                 % PVC 
                 34.5 
                   
                   
               
               
                 (pigment volume 
                   
                   
                   
               
               
                 concentration) 
                   
                   
                   
               
               
                 Dry extract, % by weight 
                 62.39 
                   
                   
               
               
                 Dry extract, % by volume 
                 44.75 
                   
                   
               
               
                 Pigment/binder ratio 
                 0.53 
                   
                   
               
               
                 (by volume) 
               
               
                   
               
             
          
         
       
     
     Comparison of the compounds PZ, PZATB and PZAT90 in epoxy amide primer 
     PZ, the preparation PZ 80%/PAT30 10%/ZnO 10%, and the preparation PZ 90%/PAT30 10% were compared. PZATB and PZAT90 were prepared by physical mixing. 
     A metal surface was given a coat of anti-corrosion primer incorporating the pigment compounds in an epoxy amide resin, having a thickness of 50 μm. This coat is covered with a film of polyurethane PU having a thickness of 100 μm, also commonly called topcoat. 
     The whole is exposed to a salt fog (standard ASTM B117) for 600 hours. 
       FIG. 2  illustrates the results obtained. 
     The rating in table 15 is produced according to the same standards as mentioned above. 
     
       
         
               
             
               
               
               
               
               
             
           
               
                 TABLE 15 
               
             
             
               
                   
               
               
                 Rating of the solvent-phase epoxy amide primer 
               
             
          
           
               
                   
                 Degree of 
                 Degree of 
                   
                   
               
               
                   
                 rusting 
                 blistering 
                   
                   
               
               
                   
                 NF-ISO 
                 NF-ISO 
                 Scribe 
                 Full plate 
               
               
                   
                 4828-3 
                 4828-3 
                 corrosion 
                 global rating 
               
               
                   
                 T 30140-3 
                 T 30140-3 
                 ASTM* 1654 
                 ASTM* 1654 
               
               
                   
               
               
                 PZ 
                 RI1 
                 D2S2 
                 4 
                 7 
               
               
                 PZAT90 
                 RI1 
                 D2S2 
                 6 
                 8 
               
               
                 PZATB 
                 RI1 
                 D2S2 
                 3 
                 6 
               
               
                   
               
             
          
         
       
     
     PZAT90 is as effective as PZ, and more effective than PZATB. 
     Illustration 3: Tests of the Preparation in a Solvent-Phase Epoxy Amine Primer 
     The formula in table 16 was prepared. 
     
       
         
               
             
               
               
               
               
             
               
               
               
               
             
           
               
                 TABLE 16 
               
             
             
               
                   
               
               
                 Formula of a solvent-phase epoxy amine primer 
               
             
          
           
               
                   
                 % 
                   
                   
               
               
                 STARTING MATERIALS 
                 WEIGHT 
                 DESCRIPTION 
                 SUPPLIERS 
               
               
                   
               
             
          
           
               
                 PART A 
                   
                   
                   
               
               
                 Introduce with stirring in the 
                   
                   
                   
               
               
                 following order 
                   
                   
                   
               
               
                 EPIKOTE 1001/XYLENE 
                 25.40 
                 Epoxy resin 
                 HEXION 
               
               
                 50/50 weight/weight 
                   
                   
                   
               
               
                 SOLVESSO 100 
                 7.90 
                 Aromatic hydrocarbon, 
                 TOTAL chimie 
               
               
                   
                   
                 solvent 
                   
               
               
                 ISOBUTYL ALCOHOL 
                 1.80 
                 Solvent 
                 SHELL 
               
               
                 DOWANOL PMA 
                 8.00 
                 Glycol ester, solvent 
                 DOW 
               
               
                 NUODEX 10% Ca 
                 0.50 
                 Dispersant 
                 ELEMENTIS Specialities 
               
               
                 BENTONE SD2 
                 0.20 
                 Rheological additive 
                 ELEMENTIS Specialities 
               
               
                 TiO 2  TR92 
                 4.80 
                 Rutile 
                 HUNSTMANN 
               
               
                 ZINC PHOSPHATE PZ20 
                 8.00 
                 Corrosion 
                 SNCZ 
               
               
                   
                   
                 inhibitor 
                   
               
               
                 YELLOW IRON OXIDE 
                 5.70 
                 Pigment, colorant 
                 BAYER 
               
               
                 3920 
                   
                   
                   
               
               
                 TALC 10 M2 
                 9.00 
                 Filler 
                 RIO TINTO Minerals 
               
               
                 MICA MU 2/1 
                 10.00 
                 Filler 
                 CMMP 
               
               
                 THIXATROL ST 
                 0.20 
                 Thixotropic additive 
                 ELEMENTIS Specialities 
               
               
                 Grinding in bead mill for 40 
                   
                   
                   
               
               
                 minutes until Hegman 
                   
                   
                   
               
               
                 fineness of 5 obtained 
                   
                   
                   
               
               
                 BUTYL ACETATE 
                 2.60 
                 Ester, solvent 
                 TOTAL chimie 
               
               
                 CERECLOR M50 
                 2.60 
                 Chloroparaffin, plasticizer 
                 INEOS 
               
               
                 DUOMEEN TDO 
                 0.20 
                 Cationic surfactant 
                 AKZO Chemie 
               
               
                 PART B 
                   
                   
                   
               
               
                 XYLENE 
                 4.10 
                 Aromatic hydrocarbon, 
                 TOTAL chimie 
               
               
                   
                   
                 solvent 
                   
               
               
                 DOWANOL PMA 
                 4.10 
                 Glycol ester, solvent 
                 DOW 
               
               
                 EFFIDUR 433 
                 4.90 
                 Cycloaliphatic polyamine 
                 France INDUSTRIE 
               
               
                 % PVC 
                 39.27 
                   
                   
               
               
                 (pigment volume 
                   
                   
                   
               
               
                 concentration) 
                   
                   
                   
               
               
                 Dry extract, % by weight 
                 58.56 
                   
                   
               
               
                 Dry extract, % by volume 
                 39.27 
                   
                   
               
               
                 Pigment/binder ratio 
                 0.65 
                   
                   
               
               
                 (by volume) 
               
               
                   
               
             
          
         
       
     
     Comparison of the Compounds PZ, PZATB and PZAT90 in Epoxy Amine Primer 
     An anti-corrosion primer based on epoxy amine incorporating the pigment preparations is prepared, having a thickness of 50 μm. This coat is covered with a film of polyurethane PU having a thickness of 100 μm, also commonly called topcoat. 
     The whole is exposed to a salt fog—standard ASTM B117—for 600 hours. 
       FIG. 3  illustrates the results obtained. 
     The rating in table 17 is produced according to the same standards as mentioned above. 
     
       
         
               
             
               
               
               
               
               
             
           
               
                 TABLE 17 
               
             
             
               
                   
               
               
                 Rating of the solvent-phase epoxy amine primer 
               
             
          
           
               
                   
                 Degree of 
                 Degree of 
                   
                   
               
               
                   
                 rusting 
                 blistering 
                   
                 Complete 
               
               
                   
                 NF-ISO 
                 NF-ISO 
                 Scribe 
                 plate 
               
               
                   
                 4828-3 
                 4828-3 
                 corrosion 
                 general rating 
               
               
                   
                 T 30140-3 
                 T 30140-3 
                 ASTM* 1654 
                 ASTM* 1654 
               
               
                   
               
               
                 PZ 
                 RI1 
                 D0S0 
                 6 
                 6 
               
               
                 PZAT90 
                 RI0 
                 D0S0 
                 8 
                 9 
               
               
                 PZATB 
                 RI1 
                 D0S0 
                 6 
                 6 
               
               
                   
               
             
          
         
       
     
     PZATB is as effective as PZ, PZAT90 is more effective than these other two compounds. 
     A comparison of PZ and of the PZAT90 pigment in an epoxy amide system, and solvent-phase epoxy amide shows very satisfactory results regarding the performance of the PZAT90 pigment.