Abstract:
The invention relates to a synergistic fungicidal composition containing more active ingredients comprising 2,3-dihydroxy-6-methyl-5-phenylcarbamoyl-1,4-oxathiine or 2.3-dihydro-6-methyl-5-phenylcarbamoyl-1,4-oxathiine-4,4-dioxide and the zinc and manganese complexes of (8-oxyquinolinate)-(dimethyl dithiocarbamate) as active ingredients, optionally solid and/or liquid carriers and other excipients. The compositions is of value especially in the treatment of infections caused by ustilaginales and yellow rust on cereals.

Description:
FIELD OF THE INVENTION 
     The invention relates to synergistic fungicidal compositions comprising several active ingredients used in the treatment of fungal diseases of cereals, especially infections caused by smuts (ustilaginales), yellow rust of cereals. The invention also discloses a method for combatting or preventing fungal infections by applying the said composition to the locus of the infection. 
     BACKGROUND OF THE INVENTION 
     It is well known from the art, that the most important pathogenic fungi of cereals (e.g. wheat, barley) are as follows: 
     smut diseases, such as bunt smut of wheat (Tilletia foetida), loose smut of barley (Ustilago nuda) and the fusarium species (Fusarium spp.) which infect the plant at the embryo stage partly in the soil, partly internally in the seed; 
     powdery mildew species (e.g. Erypsiphe graminis) which attack the plant at various stages during its life; 
     cereal fusarium fungi (Fusarium graminearum) and rusts (e.g. Puccinia glumarum) which attack the corn after earing. 
     The infections of the plant germs are treated by seed-dressing, while the later fungal attacks are treated with foliar spray application of different kinds of fungicides. 
     So far mercury containing compounds have been used for seed-dressing of corn. However, these compounds have several disadvantages. The health-detrimental and accumulating effect of mercury containing compounds is well known and the compounds do not protect the seeds from internal infections either. 
     Thus new fungicidal agents have become necessary, which are at least so effective as the mercury containing substances but are not that toxic. 
     U.S. Pat. Nos. 3,249,499, 3,393,202 and 3,454,391 and FR Pat. Nos. 1 477 059 and 1 477 060 disclose 2,3-dihydro-5-carboxamido-6-methyl-1,4-oxathiines as fungicidal agents. 
     In FR Pat. Nos. 1 477 061 and 1 477 062 and U.S. Pat. Nos. 3,402,241 and 3,454,391 derivatives are described in which in the ring one or two oxygens are attached to the sulphur atom, i.e. sulfoxides and sulfones. The utility of oxathiines for protection of plants and seeds against plant pathogenic fungi is mentioned. A disadvantage, however is their inefficiency against several species, such as Penicillium sp., Septaria nodorum etc. 
     In Hungarian patent specification No. 171,736 the very favorable fungicidal effect of the mixed liganded (8-oxyquinolate)-(dimethyl dithiocarbamate) metal complexes are described. Said metal complexes are always more effective--especially if the central atom is zinc, manganese, copper, magnesium, iron, cadmium etc.--than the metal complexes of either 8-oxyquinolate or dimethyl dithiocarbamate comprising the same ligand. It is further reported, that a mixture containing 1 part by weight of zinc complex and 1 part by weight of manganese complex is preferred. 
     According to HU-PS 158 608 the fungicidal spectrum off 2,3-dihydro-5-carboxanilid-6-methyl-1,4-oxathiines can be considerably broadened and in many cases an unexpected synergistic activity can be achieved by combining a salt or ester of 8-hydroxyquinoline, such as copper salt thereof, e.g. copper-8-quinolinolate, or its sulphate or benzoate and said oxathiines. Particularly good result was achieved by combining copper-8-quinolinate and carboxanilide-oxathiine at a ratio of 1:15-3:5 against fungi belonging to Basidiomycetes, such as Rhizoctonia Kuhl and Uromyces phasecoli typica Arth (plant pathogen, fungi in soil). These fungicidal agents were especially effective against inner fungi in the seeds of cereals, transferred by seeds, such as Ustilago nuda, against which only hot-water treatment proved to be efficient earlier. No biological activity test result was included in the specification and activity of this composition was confirmed only against Septoria nodorum, Fusarium nivale and Penicillium sp. 
     SUMMARY OF THE INVENTION 
     The composition according to the invention contains 2,3-dihydroxy-6-methyl-5-phenylcarbamoyl-1,4-oxathiine (Carboxin) or 2,3-dihydro-6-methyl-5-phenylcarbamoyl-1,4-oxathiine-4,4-dioxide (Oxicarboxin) and zinc and manganese complexes of (8-oxyquinolate)-(dimethyl dithiobarbamate) as active ingredients in a weight ratio of 1:3 to 3:1 and the weight ratio of the two different metal complexes of (8-oxyquinolinate)-(dimethyl dithiocarbamate) is 1:1. 
     The composition preferably contains 5% to 90% by weight of active ingredients, as well as solid or liquid carriers and other excipients. 
     According to a second aspect of the invention, there is provided a method of treating fungal infections of plants which comprises applying to said plants a fungicidally effective amount of a fungicidal formulation as defined above. 
     DETAILED DESCRIPTION OF THE INVENTION 
     The combinations of active ingredients defined in the above formulation are novel and have been found to be surprisingly effective in controlling or combatting fungal infections of cereals. 
     The composition exhibits synergistic effect in the range of a weight ratio of and the metal complexes being 1:3 to 3:1. The preferred weight ratio of the two metal complexes is 1:1. 
     In the method of treating fungal infections the formulation can be applied by foliar application or it can be used as seed-dresser depending on the fungal attack to be treated. The amount and frequency of application is determined by the severity or expected severity of the fungal disease and, as is well known to those skilled in the art, by the age and condition of the crop. 
     In order to simplify manufacture, storage and transport, the combinations of the active ingredients are normally produced in a concentrate or powder from intended for dilution in a solvent to the degree necessary to enable the above mentioned application rates to be easily achieved. Such formulations are usually in the form of a wettable powder or dust, aqueous or oily suspension, emulsifiable concentrate and granules. The concentrate formulations are intended for appropriate dilution prior to use. This formation of a dispersion can be carried out in conventional spray tanks suitable for the purpose. 
     Wettable powders or dusts comprise an intimate mixture of the active ingredients, one or more inert carriers and appropriate excipients. The inert carrier may be selected from the attapulgite clays, the montmorillonite clays, the diatomaceous earths, kaolins, micas, talcs and purified silicates. 
     Sufficient excipients may be found among the nonionic and ionic surfactants. E.g. sodium or calcium salts of polyacrylic acids and lignin sulphonic acid; the condensation of fatty acids or aliphatic amines or amides with ethylene oxide and/or propylene oxide; fatty acid esters of glycerol, sorbitan, sucrose or pentaerythritol; condensates of these with ethylene oxide and/or propylene oxide; condensation products of fatty alcohols or alkyl phenols with ethylene oxide and/or propylene oxide; sulphates or sulphonates of these condensation products; alkali or alkaline earth metals of sulphuric or sulphonic acid esters; sodium alkylaryl sulphonates; polymers of ethylene oxide and copolymers of ethylene oxide and propylene oxide. 
     The composition according to the invention can be used most preferably in the form of an aqueous dispersion which active ingredient concentration depends on the manner of application, i.e. foliar application or seed-dressing. 
     The invention is illustrated by the following, non-limiting examples. 
    
    
     EXAMPLE 1 
     A seed-dressing suspension concentrate containing a film forming polymer is prepared with a total active ingredient concentration of 300 g/1000 ml by admixing the components given in Table 1. The solution containing solid particles is wet-milled until the diameter of the solid particles is less than 4 micron. 
     The combination can preferably be used for wet seed-dressing. 
     
                                           TABLE 1__________________________________________________________________________Compound  Amount of the compound added to the composition__________________________________________________________________________     (g)Carboxin  300        -- -- -- -- -- 75  100                              150                                 200                                    225(8-oxyquinolate)-        300   75 150                    225                       112.5                           100                              75 50 37.5(dimethyl dithio-carbamate)Zn complex(8-oxyquinolate)-     -- -- 300              225                 150                    75 112.5                           100                              75 50 37.5(dimethyl dithio-carbamate)Mn complexethyleneglycol     90 90 90 90 90 90 90   90                              90 90 90Tamol MD  40 40 40 40 40 40 40   40                              40 40 40Pluriol PE 10500     20 20 20 25 25 25 30   30                              30 30 30Poligen ASN     150        150           150              150                 150                    150                       150 150                              150                                 150                                    150Rhodamin 2BU Plu      5  5  5  5  5  5 5    5  5  5 5__________________________________________________________________________ ion exchanged water filled to 1000 ml. 
    
     EXAMPLE 2 
     A formulation containing a total 400 g/1000 ml of active ingredients is prepared. The combination of the composition is shown by Table 2. After the compounds are charged, the composition is filled with ion exchanged water to 1000 ml. and wet-milled until the particle size in the suspension achieves the size not higher than 5 micron. 
     The formulation is applied by foliar spray application after earing of corn. 
     Similarly were prepared the suspensions containing active ingredients separately for comparative tests. 
     
                                           TABLE 2__________________________________________________________________________Compounds Charged amounts of the compounds (g)__________________________________________________________________________Oxicarboxin     400 --  --  --  --  --  100 133.4                                     200 266.7                                             300(8-oxyquinolate)-     --  400 --  100 200 300 150 133.3                                     100 66.65                                             50(dimethyl di-thiocarbamate)Zn complex(8-oxyquinolate)-     --  --  400 300 200 100 150 133.3                                     100 66.65                                             50(dimethyl dithio-carbamate)Mn complexethyleneglycol     80  80  80  80  80  80  80  80  80  80  80Borresperse 3A     40  40  40  40  40  40  45  45  45  45  45Tensiofix CD 5     15  15  15  15  15  15  10  10  10  10  10Rhodopol 23     0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1Bentonit  0.15         0.15             0.15                 0.15                     0.15                         0.15                             0.1 0.1 0.1 0.1 0.1__________________________________________________________________________ 
    
     EXAMPLE 3 
     Wettable powder of 80-90% by weight of total active ingredients is prepared for dressing of seeds of cereals pea and potato. The compounds are charged in an amount shown by Table 3, the composition is mixed, homogenized and milled until the size of the particles is 4 micron. 
     
                       TABLE 3______________________________________           Charged amounts of theCompounds       compounds (g)______________________________________Carboxin        22.5   40       30   60(8-oxyquinolate)-           33.75  20       30   15(dimethyl di-thiocarbamate)Zn complex(8-oxyquinolate)-           33.75  20       30   15(dimethyl dithio-carbamate)Mn complexZeolex 444      6      16       6    6Netzer IS       1.5    1.5      1.5  1.5Dispersing agent 1494           2.5    2.5      2.5  2.5______________________________________ 
    
     EXAMPLE 4 
     Wettable powder suitable for use in foliar application of field crops, mainly cereals were prepared. The amounts of the compounds charged are listed in Table 4. 
     The concentration of the active ingredients in the compositions were 5, 15 20 and 50% by weight. The substances were homogenized and milled as described in Example 3, until a particle size of 4 micron. 
     
                       TABLE 4______________________________________           Amounts of theCompounds       compounds charged (g)______________________________________Carboxin        1.5    10       15   25a 1:1 mixture of           3.5     5        5   25Zn and Mn complexesof (8-oxyquinolate)-(dimethyldithiocarbamate)Zeolex 444      10     10       10   10silica earth    78     68       60   33Netzer IS       2       2        3    2sulfit lye powder           5       5        7    5______________________________________ 
    
     EXAMPLE 5 
     Against pathogenic fungi damaging the crop plants after earing compositions for use in foliar application are prepared with a total active ingredient content of 5, 10, 15 and 20% by weight by admixing substances shown in Table 5 and stirring until all the solid material is dissolved. 
     
                       TABLE 5______________________________________           Amounts of the chargedCompound        compounds (g)______________________________________Carboxin        3      5         5   10an 1:1 mixture of           2      5        15   5Zn and Mn complexesof (8-oxyquinolate)-(dimethyldithiocarbamate)xylene          67     62       50   55dimethyl sulfoxide           20     20       20   20Tensiofix AS    5      5         5   5Tensiofix IS    3      3         5   5______________________________________ 
    
     EXAMPLE 6 
     Seed dressing of spring barley against Ustilago nuda (loose smut of barley). 
     The test was performed on 100 m 2  plots in three replicates by using Fertodi 053 type seeds subjected to wet-dressing, using compositions disclosed in Example 1, and seeding was performed on March 17. The dressing agents contained 300 g/l active ingredient (total), and the used amount was 5 l/t seed. 
     Part of the seeds was not treated, as these served as control. The efficiency of the dressing agents was determined between June 5 to 10 by counting the ears infected by loose smut. The results are shown in Table 6. 
     
                                           TABLE 6__________________________________________________________________________                        Ears infected by                        loose smut per  Dose g/t     Active ingredient                        plotTreatment  Carboxin       Zn  Mn  ratio    (average pieces)__________________________________________________________________________Carboxin  1500 --  --  --       165zinc complex  --   1500           --  --       376manganese  --   --  1500               --       398complexmixture of  --   375 1125               1:3      274zinc and  --   750 750 1:1      235manganese  --   1125           375 3:1      282complexcomposition  375  562.5           562.5               1:3      147according to  500  500 500 1:2       98the invention  750  375 375 1:1       51  1000 250 250 2:1       33  1125 187.5           187.5               3:1       60untreated  --   --  --  --       3114control__________________________________________________________________________ 
    
     The table shows that the 1:3-3:1 mixture of carboxin and (8-oxyquinolinate)-dimethyl-dithiocarbamate Zn and Mn complexes exhibit synergistic activity and a protective activity when using 1500 g/t against infection by loose smut of spring barley. 
     EXAMPLE 7 
     The test shows the protective activity of the combinations on winter wheat against yellow rust (Puccinia glumarum). The tested combinations were applied as foliar sprays in field tests. 
     NS-Rona 2 type wheat seeds were seeded on plots of 5 ha. on October 25th into the soil adequately prepared. 
     The well emerged plants saved from winterkill were weed controlled by a herbicide containing MCPA as active ingredient, generally used in cultivation of cereals by spraying by airoplane, thereafter a sulphur comprising formulation (Sulphur 900 FW) was applied as a foliar spray at the end of tillage (on 5th May) in order to supress the incipient (powdery mildew) infection. 
     Later the selected plots were treated the first time at the end of earing (on 30th May), when the first signs of yellow rust were already observed. In the treatment Oxicarboxin, zinc and manganese complexes of (8-oxyquinolate)-(dimethyl dithiocarbamate) and the combination according to the invention were used in 400 FW formulation, described in Example 2. 50 l/ha. of water were used for spraying, the amount of the active ingredients applied was 0.75 to 1.5 kg/ha. 
     The efficiency of the combinations against yellow rust was evaluated on 12th June. 100 productive plants selected by randomised method from each plots were examined, and the infection index was determined according to the following scale: 
     0=symptom-free 
     1=the infection is 5% or less 
     2=the infection is within the range of from 6% to 10% 
     3=the infection is within the range of from 11% to 25% 
     4=the infection is within the range of from 26% to 50% 
     5=the infection is within the range of from 51% to 75% 
     6=the infection is within the range of from 76% to 100% 
     The percent of the infection expresses the rate of the healthy and infected leaf surfaces or the average coverage of the leaf surface of the four leaf nodes by mycelium. 
     The infection index was calculated from the data obtained according to the following formula: 
     
         F.sub.i =(a.sub.1 ·f.sub.i)/n 
    
     wherein a i  stands for the infection values according to the above scale, f i  represents the frequency of a certain scale value, while n stands for the number of the plants examined. 
     The experimental results are listed in Table 7. 
     
                                           TABLE 7__________________________________________________________________________                         Number of the infected plants   Dosage kg/ha.                Rate of the                         belonging to each scale valuesTreatment   Oxicarboxin          Zn Mn active ingredients                         0 1 2 3 4  5 6 F.sub.1__________________________________________________________________________Oxicarboxin   0.75   -- -- --       18                           29                             34                               19                                 --     1.54   1.50   -- -- --       36                           28                             23                               13                                 --     1.13zinc complex   --     0.75             -- --       --                           12                             58                               18                                 12     2.30   --     1.50             -- --       --                           36                             35                               22                                 7      2.00manganese   --     -- 0.75                --       --                           10                             57                               19                                 14     2.37complex --     -- 1.50                --       --                           36                             33                               23                                 8      2.03the mixture of   --     0.375             1.125                1:3       5                           36                             33                               20                                 6      1.86the zinc and   --     0.75             0.75                1:1      10                           32                             32                               21                                 5      1.79manganese   --     1.125             0.375                3:1      --                           37                             34                               24                                 5      1.97complexesthe composition   0.375  0.562             0.563                1:3      43                           25                             21                                8                                 3      1.03according to   0.5    0.5             0.5                1:2      53                           32                             14                                1                                 --     0.63the invention   0.75   0.375             0.375                1:1      54                           31                             15                               --                                 --     0.61   1.0    0.25             0.25                2:1      52                           23                             17                                8                                 --     0.81   1.125  0.187             0.188                3:1      48                           25                             18                                9                                 --     0.88untreated   --     -- -- --       --                           15                             15                               22                                 20 10                                      18                                        3.49control__________________________________________________________________________ 
    
     The test results very expressively show that hte combinations containing oxicarboxin, zinc and manganese complexes of (8-oxyquinolinate)-(dimethyl-dithiocarbamate) at the weight ratio of 1:3 to 3:1 can adequately prevent the yellow rust infection of winter wheat and exhibit a synergistic effect in these ratios of the active ingredients. 
     EXAMPLE 8 
     This Example illustrates the typical synergistic activity observed when combinations of the invention are employed for control of fungal organisms, such as Fusarium spp. and Tilletia foetida. 
     NS-Rona 2 type winter wheat seeds infected with Fusarium spp. in 50.5% were infected with 0.2% by weight of Tilletia foetida spora calculated for the weight of the wheat. 
     The thus prepared seeds were seed-dressed with a combination according to Example 3 at a dosage of 900 g/t. 
     Further seed-dressing liquids were prepared containing only carboxin or only zinc or manganese complexes of (8-oxyquinolate)-(dimethyl-dithiocarbamate). The compositions were similarly prepared as in Example 3. As comparative formulation Quinolate V-4X was used in an amount of 900 g/t. This formulation contained 50% Carboxin and 15% copper oxyquinolate as active ingredient. 
     A part of the infected seeds was not seed-dressed and served as control in the experiments. 
     2×100 pieces of the treated and untreated seeds were incubated on Papavizas-type selective medium at 20° C. for 8 days and the Fusarium spp. infection was determined according to the developed sporulation and expressed in %. 
     Another part of the seeds was seeded on November 17 to plots of 2 m 2  prepared previously. 150 seeds were seeded to each line. The extent of the Tilletia foetida infection was determined on July 2 in the period of complete maturity by counting the ears one by one. 
     The results obtained by randomised block design method in three replicates are listed in Table 8. 
     The results show, that the combinations exhibit synergistic activity in the range of a weight ratio of 3:1 to 1:3 of carbendazime and the metal complexes; they reduce the Fusarium spp. infection and the Tilletia foetida infection to 0. The fungicidal activity thereof exceeds that of Quinolate V-4X. 
     
                                           TABLE 8__________________________________________________________________________                     Fusarium spp.                            Number of the               Rate of                     infection                            ears/plot infected    Dosage g/t the active                     %      with TilletiaTreatment    Carboxin         Zn Mn ingredients                     (laboratory)                            foetida__________________________________________________________________________Carboxin 900  -- -- --    31.0   3(8-oxyquino-    --   900            -- --    26.0   7late-(dimethyldithiocarbamate)Zn complex(8-oxyquino-    --   -- 900               --    22.5   4late)-(dimethyldithiocarbamate)Mn complexzinc and --   225            675               1:3   18.0   5manganese    --   450            450               1:1   13.5   3complex  --   675            225               3:1   20.2   2Carboxin +    225  338            337               1:3   0      0zinc and 300  300            300               1:2   0      0manganese    450  225            225               1:1   0      0complexes    600  150            150               2:1   0      0in 1:1 ratio    675  112            113               3:1   0      0infected with -- -- --    50.5   93ustilaginalesControlNon-infected    --   -- -- --    49.8   10controlOuinolate    900  -- -- --    17.5   4V-4X__________________________________________________________________________ 
    
     EXAMPLE 9 
     Winter barley was seed-dressed against the infection of Fusarium spp., Aspergilus, Penicillium and Tilletia foetida. The experiments were carried out similarly to Example 8, the combinations described in Example 3 were used and Quinolate V-4X (15% of oxyquinolate copper complex+50% of carboxine) well known in the art was applied as control. 
     The experimental results are listed in Table 9. 
     The test results show, that the combinations according to the invention in the weight ratio of 1:3 to 3:1 of the active ingredients exhibit synergistic activity, they supress the Fusarium spp. and Aspergilus infection below 2%, while completely control the Penicillium and Tilletia foetida infection. Their antifungal effect is significantly higher than that of Quinolate V-4X widely used as a fungicide. 
     
                                           TABLE 9__________________________________________________________________________                        Infection                             Infection                                   Infection                                         Number of the ears per                  Rate of the                        with with  with  plots     Dosage g/t   active                        Fusarium                             Aspergilus                                   Penicillium                                         infected with TilletiaTreatment Carboxin          Zn  Mn  ingredients                        spp. (%)                             (%)   (%)   foetida__________________________________________________________________________Carboxin  1800 --  --  --    30.4 20.7  17.6  0.6(8-oxyquinolate)-     --   1800              --  --    27.1 17.3  15.2  0.7(dimethyl di-thiocarbamate)Zn complex(8-oxyquinolate)-     --   --  1800                  --    23.2 12.9  10.3  0.4(dimethyl di-thiocarbamate)Mn complexthe mixture of     --   450 1350                  1:3   18.7 9.3   8.1   0.7the zinc and     --   900 900 1:1   13.0 7.5   6.5   0.5manganese --   1350              450 3:1   16.5 8.4   9.0   0.3complexesCarboxin +      450 675 675 1:3   0    0     0     0zinc and   600 600 600 1:2   0.5  0     0     0manganese  900 450 450 1:1   0.94 0.7   0     0complex   1200 300 300 2:1   1.0  0.9   0     0     1350 225 225 3:1   1.36 1.2   0     0untreated --   --  --  --    50.3 40.5  32.4  10.8controlQuinolate V-4X     2000 --  --  --    8.0  14.4  6.0   2.5__________________________________________________________________________ 
    
     EXAMPLE 10 
     Seed-dressing of peas against Fusarium spp., Alternaria, Penicillium and Aspergilus. 
     We proceed as disclosed in Example 8 but incubation is carried out for 10 days instead of 8. Compositions of Example 1 were used for dressing at a dose of 900 g/t. As comparison Orthocid 50 WP (50% Captane) was used similarly at a dose of 900 g/t. Results are shown in Table 10. 
     
                                           TABLE 10__________________________________________________________________________       Active             Fusarium spp.                    Alternaria                          Penicillium                                Aspergilus       ingredient             infection                    infection                          infection                                infectionTreatment  Dose g/t       rate  %      %     %     %__________________________________________________________________________Carboxin  900  --    4.0    1.8   3.0   4.2Zn complex  900  --    2.7    1.7   1.5   1.8Mn complex  900  --    2.3    1.3   1.0   1.5mixture of  900  1:3   1.9    0.9   0.8   1.3zinc andmanganesecomplexescomposition  900  1:2   0      0     0     0according to  900  1:1   0      0     0     0the invention  900  2:1   0      0     0     0  900  3:1   0      0     0     0untreated  --   --    9.5    4.5   12.0  9.5controlOrthocid  900  --    1.0    2.0   2.0   3.550 WP__________________________________________________________________________ 
    
     Test results show the efficient protective activity against the four types of fungi by using a 3:1-1:3 mixture of Carboxin and zinc and manganese complexes (1:1 mixture) of (8-oxyquinolate)-(dimethyl-dithiocarbamate). 
     The compositions according to the invention are further suitable against the following fungi: Ustilago triciti (wheat), Ustilago hordei (barley), Ustilago avenae (oats) and Septorium, Fusarium and Penicillium of corn, wheat, barley and oat. Good results were obtained against Rhizoctonia infection of potato buds and seeds and fusarium tilting of scotch fir and black pine. 
     The chemical names and producers of the additives used in Examples 1 to 5 are as follows: 
     
         ______________________________________Trade name     Producer   Chemical name______________________________________Tamol MD  BASF       sodium salt of a copolymer of                maleinic acid and olephinePluriol   BASF       condensating product ofPE 10500             ethylene oxide and propylene                oxidePoligen ASN     BASF       acrylate-styrene copolymerRhodamin  BASF       xanthene type lye2BU FluBorresperse     Borresgaard                sodium lignine sulphonate3ATensiofix CD5     Tensia     cocoanut alcohol polyglycol                etherRhodopol 23     Rhone-     polysacharide     PoulencNetzer IS Hoechst    aliphatic sulphonic acid NaDisperger-           cresol-formaldehyde condensatemittel 1494Tensiofix AS     Tensia     octylphenol-polyglycol-etherTensiofix IS     Tensia     nonylphenol-polyglycol-ether______________________________________