Patent Document

RELATED APPLICATIONS 
       [0001]    This Application is a Continuation application of International Application PCT/RU2015/000251, filed on Apr. 20, 2015, which in turn claims priority to Russian Patent Applications No. RU 2014121530, tiled May 27, 2014, both of which are incorporated herein by reference in their entirety. 
     
    
     FIELD OF THE INVENTION 
       [0002]    The invention relates to new chemical compounds—zinc and copper salts with organic acids, which can find application as biocides. 
       BACKGROUND OF THE INVENTION 
       [0003]    Various zinc and copper compounds exhibiting biocidal activity are known in the art, in particular, zinc and copper oxides and inorganic salts (U.S. Pat. No. 5,540,954, A01N 59/16, A01N 59/20, B27K 3/52, B05D 07/06, A01N 31/08, A01N 31/00, 1996; U.S. Pat. No. 6,858,658, A01N 59/20, A01N 59/16, C09D 5/16, C08K 03/10, C08K 03/18, C08K 03/22, 2005; US 20080219944, C09D 5/16, 2008; US 20090223408, C09D 5/16, C09D 5/14, 2009), zinc and copper naphthenates or resinates (EP 2161316, C09D 133/06, C09D 133/12, C09D 143/04, C09D 5/16, C09D 7/12, 2010; EP 2360214, C09D 143/04, C09D 193/04, C09D 5/16, 2011; U.S. Pat. No. 4,258,090, C04B 41/45, C04B 41/52, C04B 41/60, C04B 41/70, B05D 03/02, 1981), ammonia complexes of zinc salts (U.S. Pat. No. 5,460,644, C08K 3/10, C08K 3/00, C09D 5/14, C09D 5/00, 1995), zinc and copper pyrithionates-bis-(2-pyridylthio)-1,1′-dioxides (U.S. Pat. No. 5,298,061, C09D 5/16, C09D 5/14, 1994; U.S. Pat. No. 5,717,007, C09D 5/16, C08L, 33/10, C08K 05/17, C08K 05/18, 1998; U.S. Pat. No. 6399560, A01N 43/40, A01N 43/34, A61L 2/18, C11D 3/48, 2002; U.S. Pat. No. 7,410,553, D21C 5/02, B32B 27/04, D21G 1/02, 2008). The above mentioned compounds were used with various degrees of efficiency as biocide of different purpose. 
         [0004]    Zinc salt with acetic and methacrylic acids, i.e. zinc methacrylate-acetate (hereinafter referred to as ZMA) exhibiting a certain biocidal activity when compounded with aqueous styrene-acrylic dispersion being used as polymer primer for applying paint coatings to various surfaces is also known (RU 2315793, C09D 5/14, C09D 131/02, C09D 133/10, 2008). 
         [0005]    The closest analogue of the proposed compounds is zinc or copper (II) salt of the general formula 
         [0000]    
       
                 
         
             
             
         
       
     
         [0006]    wherein M—Zn or Cu, 
         [0007]    R 1  is selected from the group comprising hydrogen and methyl, 
         [0008]    R 2  is selected from the group comprising hydrogen, alkyl and SO 2 OH group. 
         [0009]    R 3  is selected from the group comprising hydrogen and OH (RU 2497857, C09D 5/14, C07C 69/78). 
       SUMMARY OF THE INVENTION 
       [0010]    To provide new means effecting on various biological substrates zinc or copper (II) salt of the general formula is proposed: 
         [0000]    
       
                 
         
             
             
         
       
     
         [0011]    wherein M—Zn or Cu, 
         [0012]    R 1  is selected from the group comprising hydrogen and methyl, 
         [0013]    R 2  is substituted C 1 -C 5  alkyl, 
         [0014]    m=0-5 
         [0015]    n=0-2 
         [0016]    m+n=1-5 
         [0017]    To solve the same problem it is also proposed to use the above compound as biocide. 
         [0018]    It was found that zinc and copper (II) salts corresponding to the above formula exhibit high biocidal activity and wide spectrum of effect on biological matters. Thus, they can be used in disinfectant compositions of various purposes, coating compositions, paper and wood treatment compositions, polymer compositions with higher fungus resistance as well as in many processes preventing organisms and materials from adverse effect of biological matters, in particular crustaceans. 
     
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
       [0019]    The essence of the invention is illustrated by examples given below. Examples 1-11 describe the preparation and properties of certain representatives of the proposed series of substances, examples 12-28 various types of their biocidal activity, 
       EXAMPLE 1 
       [0020]    10 g of glycolic acid, 100 ml of distilled water are placed into a 500 ml round-bottom flask, and the solution is stirred until glycolic acid is completely dissolved. Then a suspension of 10.6 g of copper (II) oxide in 50 ml of distilled water is gradually added to the solution under constant stirring, whereupon 11.32 g of methacrylic acid is added, and the suspension is stirred until completely dissolving solids. The obtained solution is evaporated to dryness at a temperature of not more than 70° C., and the resulted solid product is subjected to recrystallization from distilled water, 28 g of water-soluble powdered copper methacrylate-glycolate is obtained which corresponds to the above general formula wherein R 1 ═CH 3 , R 2 ═CH 2 , m=1, n=0 (95% yield of the stoichiometric), The results of elemental analysis of salts obtained as described in this and subsequent examples are given in Table 1. 
       EXAMPLE 2 
       [0021]    Copper methacrylate-alutamate (R 1 ═CH 3 , R 2 ═CH(NH 2 )(CH 2 ) 2 , m=0, n=1) with melting point of 200° C. is obtained in 75% yield of the stoichiometric by analogy with Example 1 using glutamic acid instead of glycolic one. 
       EXAMPLE 3 
       [0022]    Copper acrylate-asparaginate (R 1 ═H, R 2 ═CH(NH 2 )CH 2 , m=0, n=1) with melting point of 185° C. is obtained in 82% yield of the stoichiometric by analogy with Example 1 using acrylic and asparaginic acids instead of methacrylic and glycolic ones (respectively). 
       EXAMPLE 4 
       [0023]    Zinc methacrylate-succinate (R 1 ═CH 3 , R 2 ═(CH 2 ) 2 , m=0, n=1) with melting point of 195° C. is obtained in 74% yield of the stoichiometric by analogy with Example 1 using succinic acid instead of alycolic one and zinc oxide instead of copper one. 
       EXAMPLE 5 
       [0024]    Zinc acrylate-malonate (R 1 ═H, R 2 ═CH 2 , m=0, n=1) with melting point of 175° C. is obtained in 78% yield of the stoichiometric by analogy with Example 1 using acrylic and malonic acids instead of methacrylic and glycolic ones (respectively) and zinc oxide instead of copper one. 
       EXAMPLE 6 
       [0025]    Zinc methacrylate-malate (R 1 ═CH 3 , R 2 ═CH 2 CH, m=1, n=1) with melting point of 215° C. is obtained in 78% yield of the stoichiometric by analogy with Example 1 using malic acid instead of glycolic one and zinc oxide instead of copper one. 
       EXAMPLE 7 
       [0026]    Zinc acrylate-citrate(R 1 ═H, R 2 ═C(CH 2 ) 2 , m=1, n=2) with melting point of 155° C. is obtained in 87% yield of the stoichiometric by analogy with Example 1 using acrylic and citric acids instead of methacrylic and glycolic ones (respectively) and zinc oxide instead of copper one. 
       EXAMPLE 8 
       [0027]    Zinc acrylate-amygdalate (R 1 ═R 2 ═CHC 6 H 5 , m=1, n=0) with melting point of 180° C. is obtained in 65% yield of the stoichiometric by analogy with Example 1 using acrylic and amygdalic acids instead of methacrylic and glycolic ones (respectively) and zinc oxide instead of copper one. 
       EXAMPLE 9 
       [0028]    Copper acrylate-tartrate (R 1 ═H, R 2 ═CHCH, m=2, n=1) with melting point of 165° C. is obtained in 78% yield of the stoichiometric by analogy with Example 1 using acrylic and tartaric acids instead of methacrylic and glycolic ones (respectively). 
       EXAMPLE 10 
       [0029]    Zinc acrylate-lactate (R 1 ═H, R 2 ═CHCH 3 , m=1, n=0) with melting point of 175° C. is obtained in 65% yield of the stoichiometric by analogy with Example 1 using acrylic and lactic acids instead of methacrylic and glycolic ones (respectively) and zinc oxide instead of copper one. 
       EXAMPLE 11 
       [0030]    Copper acrylate-gluconate (R 1 ═H, R 2 ═(CH) 4 CH 2 , m=5, n=0) with melting point of 195° C. is obtained in 68% yield of the stoichiometric by analogy with Example 1 using acrylic and &amp;conic acids instead of methacrylic and glycolic ones (respectively). 
       EXAMPLE 12 
       [0031]    Bactericidal activity of copper methacrylate-glycolate obtained as described in Example 1, copper acrylate-tartrate obtained as described in Example 9 and zinc acrylate-malonate obtained as described in Example 5 is determined according to the known method (RU 2378363, C12N 1/00, C12Q 1/00, 2010) based on the exposure of a bacterial culture in a solution of bactericidal substance for a certain period of time followed by its neutralization and inoculation of the culture on a solid nutrient medium. The sensitivity of microorganisms to a disinfectant is judged by microorganism growth on the nutrient medium up to 300 CFU/ml (CFU colony-forming unit) while growth up to 100 CFU/ml indicates incomplete bactericidal effect, growth up to 100-300 CFU/ml indicates sub-bactericidal effect and growth up to more than 300 CFU/ml indicates resistance of microorganisms to a disinfectant, The determination is performed on  E. coli  No. 906 and  S. aureus  No. 1257 test strains conventionally used to study the bactericidal activity of biocides as well as on clinical strain  P. aeruginosa  at salt concentrations from 1.5 to 3% and time of exposure from 5 to 60 min. Test results are given in Table 2. It follows from Table 2 that copper methacrylate-glycolate, copper acrylate-tartrate and zinc acrylate-malonate at concentration of 2.0% exhibit stable bactericidal effect against investigated strains at time of exposure from 30 min. 
       EXAMPLES 13-24 
       [0032]    The fungicidal activity of the proposed salts is determined according to GOST 30028.4-2006 by testing samples of various materials treated with these salts for resistance to fungal spores, Test results in terms of tolerance time (in days) are given in Table 3 wherein tolerance time for untreated materials are given for comparison, 
       EXAMPLES 25-26 
       [0033]    The biocidal activity of copper methacrylate-glycolate obtained as described in Example 1 and zinc acrylate-lactate obtained as described in Example 10 against crustaceans (daphnias) is tested according to FR. 1.39.2007,03223 procedure, Test results for salts obtained as described in these and subsequent examples are given in Table 4. 
       Examples 27-28 (comparative). The biocidal activity of known compounds is tested in conditions described in Examples 25-26, 
     INDUSTRIAL APPLICABILITY 
       [0034]    The present invention can be used for production of biocides intended, for example, for incorporation into polymer compositions, disinfectant and antiseptic compositions, treatment of wood, paper, building structures and other materials to prevent their damage caused by biological matters (microorganisms, fungi, algae), manufacture of various articles with biocidal properties, etc. 
         [0000]    
       
         
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 1 
               
               
                   
               
               
                 Results of elemental analysis of salts 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                   
                   
                 Empirical 
                 Sample 
                 C, g 
                 H, g 
               
             
          
           
               
                 Example 
                 Name 
                 formula 
                 weight, g 
                 calculated 
                 determined 
                 calculated 
                 determined 
               
               
                 1 
                 2 
                 3 
                 4 
                 5 
                 6 
                 7 
                 8 
               
               
                   
               
               
                 1 
                 Copper 
                 C 6 H 8 O 5 Cu 
                 0.5 
                 0.1609 
                 0.161 
                 0 0180 
                 0.0179 
               
               
                   
                 methacrylate- 
                   
                   
                   
                 0.1609 
                   
                   
               
               
                   
                 glycolate 
                   
                   
                   
                   
                   
                   
               
               
                 2 
                 Copper 
                 C 9 H 13 O 6 NCu 
                 0.5 
                 0.183 
                 0.18 
                 0.022 
                 0.021 
               
               
                   
                 methacrylate- 
                   
                   
                   
                 0.184 
                   
                 0.02 
               
               
                   
                 glutamate 
                   
                   
                   
                   
                   
                   
               
               
                 3 
                 Copper 
                 C 7 H 9 O 6 NCu 
                 0.5 
                 0.1575 
                 0.157 
                 0.0168 
                 0.016 
               
               
                   
                 acrylate- 
                   
                   
                   
                 0.151 
                   
                 0.017 
               
               
                   
                 asparginate 
                   
                   
                   
                   
                   
                   
               
               
                 4 
                 Zinc 
                 C 8 H 10 O 6 Zn 
                 0.5 
                 0.1795 
                 0.18 
                 0.0187 
                 0.019 
               
               
                   
                 methacrylate- 
                   
                   
                   
                 0.178 
                   
                 0.0185 
               
               
                   
                 succinate 
                   
                   
                   
                   
                   
                   
               
               
                 5 
                 Zinc acrylate- 
                 C 6 H 6 O 6 Zn 
                 0.5 
                 0.15 
                 0.148 
                 0.0125 
                 0.013 
               
               
                   
                 malonate 
                   
                   
                   
                 0.151 
                   
                 0.0125 
               
               
                 6 
                 Zinc 
                 C 8 H 10 O 7 Zn 
                 0.5 
                 0.1695 
                 0.169 
                 0.0176 
                 0.0179 
               
               
                   
                 methacrylate- 
                   
                   
                   
                 0.17 
                   
                 0.0177 
               
               
                   
                 malate 
                   
                   
                   
                   
                   
                   
               
               
                 7 
                 Zinc acrylate- 
                 C 9 H 10 O 9 Zn 
                 0.5 
                 0.165 
                 0.164 
                 0.0153 
                 0.0153 
               
               
                   
                 citrate 
                   
                   
                   
                 0.167 
                   
                 0.0151 
               
               
                 8 
                 Zinc acrylate- 
                 C 11 H 10 O 5 Zn 
                 0.5 
                 0.2295 
                 0.23 
                 0.0174 
                 0.0175 
               
               
                   
                 amygdalate 
                   
                   
                   
                 0.229 
                   
                   
               
               
                 9 
                 Copper  
                 C 7 H 8 O 8 Cu 
                 0.5 
                 0.148 
                 0.15 
                 0.014 
                 0.014 
               
               
                   
                 acrylate- 
                   
                   
                   
                 0.149 
                   
                 0.0145 
               
               
                   
                 tartrate 
                   
                   
                   
                   
                   
                   
               
               
                 10 
                 Zinc acrylate- 
                 C 6 H 8 O 5 Zn 
                 0.5 
                 0.159 
                 0.16 
                 0.0177 
                 0.018 
               
               
                   
                 lactate 
                   
                   
                   
                   
                   
                   
               
               
                 11 
                 Copper  
                 C 9 H 14 O 9 Cu 
                 0.5 
                 0.1638 
                 0.164 
                 0.0212 
                 0.021 
               
               
                   
                 acrylate- 
                   
                   
                   
                 0.165 
                   
                   
               
               
                   
                 gluconate 
               
               
                   
               
             
          
           
               
                   
                   
                 Zn, g 
                 Cu, g 
                 N, g 
               
             
          
           
               
                   
                 Example 
                 calculated 
                 determined 
                 calculated 
                 determined 
                 calculated 
                 determined 
               
               
                   
                 1 
                 9 
                 10 
                 11 
                 12 
                 13 
                 14 
               
               
                   
               
               
                   
                 1 
                   
                   
                 0.1421 
                 0.1421 
                   
                   
               
               
                   
                   
                   
                   
                   
                 0.1420 
                   
                   
               
               
                   
                 2 
                   
                   
                 0.108 
                 0.11 
                 0.0237 
                 0.024 
               
               
                   
                 3 
                   
                   
                 0.1193 
                 0.119 
                 0.0262 
                 0.027 
               
               
                   
                 4 
                 0.122 
                 0.12 
                   
                   
                   
                   
               
               
                   
                   
                   
                 0.116 
                   
                   
                   
                   
               
               
                   
                 5 
                 0.137 
                 0.14 
                   
                   
                   
                   
               
               
                   
                 6 
                 0.115 
                 0.115 
                   
                   
                   
                   
               
               
                   
                   
                   
                 0.117 
                   
                   
                   
                   
               
               
                   
                 7 
                 0.0998 
                 0.1 
                   
                   
                   
                   
               
               
                   
                   
                   
                 0.099 
                   
                   
                   
                   
               
               
                   
                 8 
                 0.1137 
                 0.1138 
                   
                   
                   
                   
               
               
                   
                 9 
                   
                   
                 0.112 
                 0.1125 
                   
                   
               
               
                   
                 10 
                 0.145 
                 0.147 
                   
                   
                   
                   
               
               
                   
                 11 
                   
                   
                 0.0964 
                 0.0968 
                   
                   
               
               
                   
                   
                   
                   
                   
                 0.0962 
                   
                   
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
             
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 Bactericidal activity of salts 
               
             
          
           
               
                   
                 Time of 
                 Copper methacrylate-glycolate 
                 Copper acrylate-tartrate 
                 Zinc acrylate-malonate 
               
             
          
           
               
                 Concentration, 
                 exposure, 
                 
                   E. coli  
                 
                 
                   S. aureus 
                 
                   
                 
                   E.coli  
                 
                 
                   S. aureus 
                 
                   
                 
                   E.coli  
                 
                 
                   S.aureus 
                 
               
               
                 % wt. 
                 min. 
                 906 
                 1257 
                 
                   P. aeruginosa 
                 
                 906 
                 1257 
                 
                   P. aeruginosa 
                 
                 906 
                 1257 
               
               
                   
               
             
          
           
               
                 3.0 
                 30 
                 NG 
                 NG 
                 NG 
                 NG 
                 NG 
                 NG 
                   
                   
               
               
                   
                 15 
                 NG 
                 NG 
                 NG 
                 NG 
                 NG 
                 NG 
                   
                   
               
               
                   
                 5 
                 NG 
                 NG 
                 NG 
                 NG 
                 NG 
                 NG 
                   
                   
               
               
                 2.0 
                 60 
                 NG 
                 NG 
                 NG 
                 NG 
                 NG 
                 NG 
                 NG 
                 NG 
               
               
                   
                   
                 NG 
                 NG 
                 NG 
                 NG 
                 NG 
                 NG 
                 NG 
                 NG 
               
               
                   
                   
                 NG 
                 NG 
                 NG 
                 NG 
                 NG 
                 NG 
                 NG 
                 NG 
               
               
                   
                   
                 NG 
                 NG 
                 NG 
                 NG 
                 NG 
                 NG 
                 NG 
                 NG 
               
               
                   
                 30 
                 NG 
                 NG 
                 NG 
                 NG 
                 NG 
                 NG 
                 NG 
                 NG 
               
               
                   
                   
                 NG 
                 NG 
                 &gt;300 CFU 
                 NG 
                 NG 
                 NG 
                 NG 
                 NG 
               
               
                   
                   
                 NG 
                 NG 
                 &gt;300 CFU 
                 NG 
                 NG 
                 &gt;300 CFU 
                 NG 
                 NG 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                   
                 NG 
               
               
                   
                 15 
                 &gt;300 CFU 
                 &gt;300 CFU 
                 &gt;300 CFU 
                 NG 
                 NG 
                 &gt;300 CFU 
                 NG 
                 NG 
               
               
                   
                 5 
                 CG 
                 CG 
                 CG 
                 NG 
                 NG 
                 CG 
                  1 CFU 
                 NG 
               
               
                 1.5 
                 60 
                 &gt;300 CFU 
                 &gt;300 CFU 
                 CG 
                 NG 
                 NG 
                 CG 
                  5 CFU 
                  1 CFU 
               
               
                   
                   
                   
                   
                   
                 NG 
                 NG 
                   
                  4 CFU 
                  3 CFU 
               
               
                   
                   
                   
                   
                   
                 NG 
                 NG 
                   
                   
                   
               
               
                   
                 30 
                 CG 
                 CG 
                 CG 
                   
                   
                 CG 
                 45 CFU 
                 35 CFU 
               
               
                   
                   
                   
                   
                   
                   
                   
                   
                 53 CFU 
                 43 CFU 
               
               
                   
                 15 
                   
                   
                   
                   
                   
                 — 
                 78 CFU 
                 85 CFU 
               
               
                   
                 5 
                   
                   
                   
                   
                   
                 — 
                 &gt;300 CFU     
                 &gt;300 CFU     
               
               
                   
               
               
                 Note: 
               
               
                 NG—no growth; 
               
               
                 CFU—number of colony-forming units in 1 ml; 
               
               
                 CG—confluent growth 
               
             
          
         
       
     
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                 TABLE 3 
               
             
             
               
                   
               
               
                 Fungicidal activity of salts 
               
             
          
           
               
                 Exam- 
                   
                 Additive 
                 Tolerance 
               
             
          
           
               
                 ple 
                   
                   
                 Content, 
                 time, 
               
               
                 No. 
                 Test material 
                 Name 
                 % wt. 
                 days 
               
               
                   
               
             
          
           
               
                 13 
                 Polyvinyl  
                 Copper  
                 5 
                 10 
               
               
                   
                 chloride 
                 methacrylate- 
                   
                   
               
               
                   
                 emulsion 
                 glycolate 
                   
                   
               
               
                 14 
                 Polyvinyl  
                 Copper 
                 5 
                 17 
               
               
                   
                 chloride 
                 acrylate- 
                   
                   
               
               
                   
                 emulsion 
                 tartrate 
                   
                   
               
               
                 15 
                 Polyvinyl  
                 Zinc  
                 5 
                 9 
               
               
                   
                 chloride 
                 methacrylate- 
                   
                   
               
               
                   
                 emulsion 
                 malate 
                   
                   
               
               
                 16 
                 Polyvinyl  
                 Zinc  
                 5 
                 17 
               
               
                   
                 chloride 
                 acrylate- 
                   
                   
               
               
                   
                 emulsion 
                 citrate 
                   
                   
               
               
                 17 
                 Polyvinyl  
                 Zinc  
                 5 
                 18 
               
               
                   
                 chloride 
                 acrylate- 
                   
                   
               
               
                   
                 emulsion 
                 malonate 
                   
                   
               
               
                 18 
                 Polyvinyl  
                 — 
                 — 
                 6 
               
               
                 (com 
                 chloride 
                   
                   
                   
               
               
                 par.) 
                 emulsion 
                   
                   
                   
               
               
                 19 
                 Paper impregnated 
                 Copper 
                 5 
                 8 
               
               
                   
                 with latex SKS 
                 methacrylate- 
                   
                   
               
               
                   
                 65 GP 
                 glycolate 
                   
                   
               
               
                 20 
                 Paper impregnated 
                 Copper 
                 5 
                 16 
               
               
                   
                 with latex SKS  
                 acrylate- 
                   
                   
               
               
                   
                 65 GP 
                 tartrate 
                   
                   
               
               
                 21 
                 Paper impregnated 
                 Zinc  
                 5 
                 20 
               
               
                   
                 with latex SKS  
                 acrylate- 
                   
                   
               
               
                   
                 65 GP 
                 malonate 
                   
                   
               
               
                 22 
                 Paper impregnated 
                 — 
                 — 
                 4 
               
               
                 (com 
                 with latex SKS  
                   
                   
                   
               
               
                 par.) 
                 65 GP 
                   
                   
                   
               
               
                 23 
                 Paper impregnated 
                 Copper 
                 5 
                 8 
               
               
                   
                 with petrolatum  
                 methacrylate- 
                   
                   
               
               
                   
                 base 
                 glycolate 
                   
                   
               
               
                 24 
                 Paper impregnated 
                 — 
                 — 
                 5 
               
               
                 (com 
                 with petrolatum  
                   
                   
                   
               
               
                 par.) 
                 base 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
           
               
                 Table 4 
               
             
             
               
                   
               
               
                 Biocidal activity of compounds against crustaceans 
               
             
          
           
               
                   
                   
                   
                   
                 Number of 
                   
               
               
                   
                   
                   
                   
                 survived  
                 Daphnia 
               
               
                   
                   
                   
                   
                 daphnias 
                 death  
               
               
                   
                   
                   
                   
                 (the average  
                 rate 
               
               
                   
                   
                 Concen- 
                   
                 over 
                 in test 
               
               
                   
                   
                 tration in  
                   
                 parallel set of 
                 sample,  
               
               
                   
                   
                 aqueous 
                 Test  
                 samples) 
                 % of  
               
             
          
           
               
                 Example 
                   
                 medium,  
                 time,  
                 Control 
                 Test 
                 control 
               
               
                 No. 
                 Compound 
                 % wt. 
                 h 
                 sample 
                 sample 
                 sample 
               
               
                   
               
             
          
           
               
                 25 
                 Zinc  
                 1 
                 96 
                 10 
                 0 
                 100 
               
               
                   
                 acrylate- 
                 0.1 
                   
                   
                 0 
                 100 
               
               
                   
                 lactate 
                 0.01 
                   
                   
                 0 
                 100 
               
               
                   
                   
                 0.001 
                   
                   
                 0 
                 100 
               
               
                   
                   
                 0.0001 
                   
                   
                 1 
                 90 
               
               
                   
                   
                 0.001 
                   
                   
                 3 
                 70 
               
               
                 26 
                 Copper 
                 1 
                 96 
                 10 
                 0 
                 100 
               
               
                   
                 methacrylate- 
                 0.1 
                   
                   
                 0 
                 100 
               
               
                   
                 glycolate 
                 0.01 
                   
                   
                 0 
                 100 
               
               
                   
                   
                 0.001 
                   
                   
                 0 
                 100 
               
               
                   
                   
                 0.0001 
                   
                   
                 0 
                 100 
               
               
                   
                   
                 0.00001 
                   
                   
                 1 
                 90 
               
               
                 27 
                 Copper 
                 1 
                 96 
                 10 
                 8 
                 20 
               
               
                 (compar.) 
                 acrylate- 
                 0.1 
                   
                   
                 9 
                 10 
               
               
                   
                 benzoate 
                 0.01 
                   
                   
                 10 
                 0 
               
               
                   
                   
                 0.001 
                   
                   
                 10 
                 0 
               
               
                   
                   
                 0.0001 
                   
                   
                 10 
                 0 
               
               
                   
                   
                 0.00001 
                   
                   
                 10 
                 0 
               
               
                 28 
                 Zinc 
                 1 
                 96 
                 10 
                 10 
                 0 
               
               
                 (compar.) 
                 methacrylate- 
                 0.1 
                   
                   
                 10 
                 0 
               
               
                   
                 salicylate 
                 0.01 
                   
                   
                 10 
                 0 
               
               
                   
                   
                 0.001 
                   
                   
                 10 
                 0 
               
               
                   
                   
                 0.0001 
                   
                   
                 10 
                 0 
               
               
                   
                   
                 0.00001 
                   
                   
                 10 
                 0

Technology Category: c