NZ199674A - Plant conditioning compositions containing titanium-ascorbic acid chelates - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number 1 99674 .1'US1'—TT,r" 1 TJ. kj'f -m*P*Litr*e*i^B'mVTiTrrr-**i^ 1 199674 Patents Form No.5 NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION "PLANT CONDITIONING COMPOSITIONS CONTAINING TITANIUM" -t,WE KERTESZETI EGYETEM, 1118 Budapest, Menesi ut 44, and NITROKEMIA IPARTELEPEK 8184, Fuzfogyartelep, Hungary, both Hungarian companies, hereby declare the invention, for which-5/we pray that a patent may be granted to -rae-/us, .and the method by which it is to be performed, to be particularly described in and by the following statement ^ollowed by page | A.) w t The invention relates to plant conditioning compositions containing titanium, which have an increased physico-chemical and biological stability.

It is well known that titanium plays an important role in the vital processes of plants.

It is further known that though titanium is present in the soil in a high concentration! it is not available for the plants since titanium salts insoluble is water cannot exert their biological activity. is known a solution/containing fouivvalent titanium ions is reacted with ascorbic acid to provide a titanium complex suitable for treating plants. Ascorbic acid is present in the solution in a 50- to 200-fold exoess re-15 lated to titanium. The stability of aqueous solutions oontaining ascorbic acid in an excess suitable for treating plants is, however, not satisfactory. According to microbiological tests for example the strains Clostridium botu-linum, Aspergillus niger, Lactobacillus lactis, Clostridium 20 bytilicum, Thermobacterium mobile decompose ascorbic acid used for forming complexes. The"presence of titanium is supposed to increase this effect. On the other hand, titanium sprayed on the surface of leaves as a thin film may easily be inactivated by environmental effects and therefore in 25 the vegetation period the frequency of treatments should^ considerably be increased to ensure the desired effect."*11--^^^ Due to the high labour costs and energy demand this-haf^^1984 a negative effect on the economy of process. 1^1674- The invention relates to a new plant conditioning composition containing titanium, which is devoid of the above disadvantages, i.e. in which four-valent titanium is resistant to oxidation even in a very dilute solution, in 5 the presence of a high excess of ascorbic acid, after spraying on a large area. The new compositions are resistant to microorganisms as well, •i According to the invention to solutions containing four-valent titanium ions and a high excess of ascorbic acid |10 at least 0.01 % by weight of one or more compounds selected from the following group are added: sorbic acid and salts thereof, benzoic acid and salts thereof, salicylic acid and p-hydroxy-benzoic adid and salts thereof salts thereof,/propionic acid and salts thereof, p-nitro- « -benzoic acid and salts thereof and hexamethylenetetramine. 15 The percentage amount of the above additives is related to the solid substance content of the composition.

Ascorbic acid is used in a 20 to 200-fold excess related to titanium. The above-listed stabilizers are added to the solution up to a concentration of 25 % by weight but k20 in a concentration exceeding 2 % by weight their activity is increased to a relatively low extent and therefore it is generally not economic to increase their amount over this concentration.

It is a considerable advantage of the compositions 25 according to this invention that due to their increased stability the frequency pf treatments can be decreased or if the frequency of treatments is unchanged, the activity is increased by 5 to 8 % in comparision with the known compositions / n%74- - 3 " which do not contain stabilizators. The compositions can be stored for a long time without a noticable loss of activity, in spite of their high ascorbic acid concentration, even in very dilute equeous solutions.

The compositions according to the invention comprise in addition to four-valent titanium ions and a 20 to 200-fold excess of ascorbic aced related to titanium and optionally further conventional additives at least 0.01 % by weight of one or more compounds selected from the following groiro: salicylic acid, p-nitro-Benzoic |10 sorbic acid, benzoic acid ,/p-hydroxy-benzoic acid/propionic acid, salts of these compounds and hexamethylenetetramine optionally in admixture with trace elements and/or vegetable nutriments. Trace elements include magnesium, iron, manganese, zinc, molybdenum and boron while the term "vegetable nutri-15 ments" is used to refer to conventional nitrogene-phosphorus--potassium (NPhP) containing fertilizers, suspensions, etc.

When preparing the compositions a four-valent titanium fa salt is dissolved in water in a desired concentration, as- //^f corbic acid is added in a desired excess and the pH of the 20 solution is preferably adjusted to about 5.

To the solution obtained one or more of the above-' listed additives are added. In the .absence of these additives the liquid surface is covered by colonies of microorganisms already after 2 weeks. Microorganisms decrease the active 25 ingredient concentration and make the ordinary use of solutions impossible. The additives according to the invention inhibit the growth of nicroorganism colonies and accordingly preserve the solutions in a condition suitable for application int'74- - t - for a long time and in the same time result in a 5 to 8 % increase in crop yield in comparision with solutions having the same active ingredient concentration but not containing the additives according to the invention. This increase in yield is due to the increased microbiological resistance.

Micro- and macronutriments and plant hormons when added in a given amount to the complex of four-valent titanium with ascorbic acid accelerate the plant growth.

The compositions containing macro- and micronutri-ments.when applied to the plants in a low dose as leaf or spray fertilizers or used for seed dressing have a considerable influence on the development of plants, accelerate the absorption of micronutriments, promote the effect of plant hormons below the toxic threshold value.

The plant conditioning compositions according to the invention comprise 0,1 to 15.0 % by weight, preferably 0,5 to 15.0 % by weight of a titanium-ascorbic acid chelate which contains 14 to 28 g-ttoles of ascorbic acid related to 1 g-a torn of four-valent titanium ions the pH value of which is adjusted 20 to 5 to 7, 0.1 to 2,0 parts by weight of a biochemically essential nutriment related to, 1 part by weight of four-valent titanium ions or a combination of such nutriments and/or 0,001 to 0,01 % of one or more phytohormones and at least ,;|c 0,01 % by weight of one or more of the compounds selected ^ from the following group: sorbic acid and salts thereof, salicylic acid and salts thereof,p-hydroxy-benzoic benzoic acid and salts thereof, /p- nitrogen zoicacid and salts acid & salts thereof thereof, propionic acid and salts thereof, hexamethylene tc oramine related to the total weight of solid ingredients, Itlblf - 5 - . optionally in association with wetting agents, adhesives or further conventional additives.

Aa a nutriment the composition preferably contains boron, magnesium, manganese, iron, sine, molybdenum or a 5 water-soluble salt thereof. Macronutriments include water-soluble nitrogen — phosphorus-potassium fertilizers.

The phytohormon components of the compositions may be auxins , giberellin s*- cytokinins, (alpha-naphthylacetio acid-beta-indolylacetic acid), etc. 10 Phytohormons include 2,4-dichlorophenoxyacetic. acid and salts thereof. The compositions contain 1000 to 200u ppin of ascorbic acid -in one litre of solution and the amount of ascorbic aoid related to four-valent titanium is between 50 000 end 100 000 ppm. Ae a further additive one or more of the sta-15 bilizers referred to hereinabove are added to the solution. Of the microelements the compositions may contain for example 1000 ppm of boron, 500 ppm of manganese, 500 ppm of zinc, 1000 ppm of magnesium and 500 ppm of iron related to 1000 ppm of four-valent titanium, in the form of water-soluble salts. k20 The compositions may contain for example 25 ppm of 2,4-dichloro--phenoxyacetic acid or 10 ppm of giberellic acid or similar additives related to 1000 to 2000 ppm of titanitim. '^73 The plane protecting compositions according to the V • tS invention may be prepared by dissolving a weteis-soluble '-nim salt of four-valent titanium, for example titaDium tetra- ^ chloride or sodium titanate and 14 to 28 g-moles of ascorbic acid calculated for 1 g-atom of titanium in water, adjusting the pH of the aqueous solution to 5 to 7 and adding the I o 199674 aqueous solution of micro- and macro-nutrimenta to the solution obtained. To this solution suitable wetting agents or adhesives and stabilizators may be added. Stabilizing agents stabilize the concentration of titanium and micro-elements on the surface of plants, which have been sprayed by the compositions.

The compositions according to the invention are generally applied to the plants by spraying. Experimental, observations show that the nutriments penetrate into the chloroplastises of leaves and as a result phytosynthetic and enzyme activity are increased.

In field trials and greene house experiments under controlled conditions (e.g. illumination) it has been established that the use of the compositions according to the invention accelerates the absorption of biochemically essential nutriments. The absorption of magnesium, manganese, iron and zinc which play an important role in photosynthesis, has a direct influence on the yield of fruit trees and cereals and increases the food value as well. When spraying papilionaceae and grasses, molybdenum and when treating beets the presence of boron increases crop yield, improves the conditions of carbohydrate formation and has a fabourable effect on the formation of cell walls. In case of soils poor in nutriments it is advisable to give also water-soluble nitrogen, phosphorus and potassium compounds to the plant conditioning compositions according to the invention, Small concentrations of phytohormons and herbicides having a hormon activity considerably increase the growth I 99&7f of young plants, seedlings and promote the growth of sprouths and buds.

The optimum doses of the plant conditioning compositions according to the invention are depending on the plant varieties to be treated. When treating vegetables in their vegetation period, 5 to 10 lit./ha. doses may be employed 3- or 4-times. j'or treating cereals after blooming a single 1 lit./hal dose is generally sufficient. If.young seedlings are treated starting from their 3 to 4-Ieaf stage every 10 days, their growth is efficiently increased.

Spraying can be performed by planes , helicopters or sprayers. Before use the compositions are diluted with water to the desired concentration and are used in an amount of 1 to 5 lit./ha, depending on the way of application. From economical point of view it is advisable to connect treatments by the instant compositions with other plant protection works. The compositions according to the invention are compatible with any neutral or slightly acidic plant protecting agents.

The preparation and use of the compositions according to the invention are illustrated by the following examples.

Example 1 • . • A four-valent titanium salt corresponding to 1 g. of ♦ titanium and 100 g. of ascorbic acid are dissolved in water. The solution is made up to 1 lit., the pH is adjusted to 5 and 1 g. of salycilic acid is added. The storability of the composition obtained is at least 2 years.

To the above composition a soluble ammonium salt y-, 1111,74- corresponding to 3 % by weight of nitrogen, phosphoric acid corresponding to 4 % by weight of phosphorous pentoxide and a potassium salt corresponding to 5 % by weight of 1^0 are added where the percentage values relate to the total weight of the solution. The storability of the composition obtained is identical with the storability of the above composition but the latter one contains also essential nutriments in addition to the components used for conditioning plants.

The activity of the composition described above was tested on wheat /Rana-1/ in the vegetation period, in a dose of 3 x 1 g. titanium/ha. The yield of the treated plants was compared with that of the untreated control. The following results were obtained.

Yield ^ kg./ha. .% Wheat treated by the above composition 47.25 121.4 Untreated control 38.93 100.0 Example 2 A four-valent titanium salt corresponding to 1 g. of 'titanium and 95 g. of ascorbic acid are dissolved in 1 lit. of water. The solution is made up to 1 lit., the pH is adjusted to about 5 and 0.5 g. of sodium benzoate are added. The composition obtained can be stored for more than 2 years without any loss in activity.

I 99674- The activity of the composition was tested in maize germination tests (TC 3344/a variety). The following treatments were carried out: Control I: untreated control Control II: treatment carried out with a composition having the above ingredients except sodium benzoate Test solution: the composition prepared according to this example The compositions were used in the same dose as in Example 1.

The results obtained are given in the following table: Mean stem % length /cm/ Control I 4.09 100.0 Control II 4.65 113.7 Test Solution 4.74 115.9 The same test was repeated in field trials on silo maize. The following results were obtained: Yield 102 kg./ha. % Control I Control II Test composition Example 3 A four-valent titanium salt corresponding to 1000 ppm of titanium, 100 000 ppm of ascorbic acid, 500 ppm of manganese 406.0 471.0 484.0 100.0 116.0 119.2 - 1996 7 500 ppm of zinc and 700 ppm of iron in the form of water-soluble salts are dissolved in water and the solution is made up to 1 lit. The pH is adjusted to 5 and 0.5 g. of sodium benzoate and 1000 ppm of sodium ligninsulfonate (wetting agent) are added.

The composition obtained is used in a 200-fold dilution for treating paprika and in a 500 to 1000-fold dilution for treating apples..Paprika is treated in a 4 to 5-leaf stage three times, by spraying. The apple trees are sprayed when the petals are falling and the treatment is repeated two more times, in the third and sixth week. Peach, apricot, pear and cherry can also successfully be treated in an analogeous way. The results obtained on paprika and apples, respectively are shown in the following tables.

Paprika test Treatment Average weight Pieces/ Ascorbic acid content kg./plant % 100 plants % iqg./lOO g. % Control Treated 7.46 9.19 100.0 123.5 280 324 100.0 72 115.7 266 100.0 369.4 Variety and treatment Apple teat Yield kg./ha. % Glucose content Starking Jonathan Control Treated Control Treated 3540 5960 7262 11066 100.0 168.3 100.0 152.3 9.1 9.8 8.3 10.6 199674- - ii - 020 Example 4 A four-valent titanium salt corresponding to 1000 ppm of titanium, a 28-times molar excess of ascorbic acid and 0,5 g of salycilic acid are dissolved in water and the solution ia made up to 1 lit. The pH is adjusted to 5 and 10 ppm. of giberellic acid and 2000 ppm. of sodium dodecylbenzonesulfonate (wetting agent) are added.

The composition obtained was tested in wheat germination tests and was used for treating Saintpaulis ionantha plants. VJheat grains were dressed by a solution containing 0.02 ppm titanium. The Saintpaulis ionantha plants were sprayed by a 0.2 % dilution of the above solution every ten day, « 4 altogether twice.

The results obtained are given in the following tables.

Wheat germination test Variety and treatment Average length of plant cm % Lublajnaja Control Treated .46 12.18 100.0 116 ^4 Treatment Saintpaulis ionantha test Plant diameter Dry substance Formation of /average of 100 plants/ cm dL /» bulbs % Control Treated .75 21.20 3.96 4.58 23 1^67^ The results show that the wheat grains treated by the compositions according to the invention germinated in a shorter time and the growth of the treated Saintpaulis ionantha plants was accelerated in comparision with the control grains and plants, respectively. The same growth accelerating affect can be observed when ornamental plants are treated. The treated plants flower earlier and consequently cen be sold about 2 weeks earlier than the control plants.

Example 5.

A four-valent titanium salt corresponding to 2000 ppm. of titanium and 100 000 ppm, of ascorbic acid are dissolved in 1 lit, of water, 0,5 g of sodium benzoate and 500 ppm, of a water-soluble molybdenum salt and 1000 ppm, of polyethylene-polypropylene block polymer (wetting agent) are added. The pH of the solution is adjusted to 5. to 6-leaf lucerne plants were treated by the above compositions before every mowing once, in a dose of 2 lit,/ha.

Green peas were treated by the above composition during budding and at the first by a dose of 2 lit./ha, altogether twice.

Grass was sprayed by 1 lit,/ha, of the above composition-once. The results of the above treatments are shown in the following tables, \ ' \ * \ • ■ \ . p „ / TO Treating green peas 199674 Variety and treatment Yield kg./ha.

Average delicacy Saccharose % (T) % Paget Control 4450 100.0 140.5 .35 Treated 5250 118.0 127.5 .88 Griine Control 4210 100.0 136.2 .35 Treated 5260 124.9 123.8 .75 Lucerne teat Treatment Green weight Dry substanpe Raw protein Digest- Starch .3 kg./m* content g./kg. g./kg. able pro- value tein g./kg g./kg.

Control Treated 1.25 1.87 Treatment Yield kg./ha. % 905 915 Grass test Raw protein g./kg. 128 93 171 124 Starch value g./kg. 301 316 Control 4300 100.0 46 110 Treated 6500 151.2 47 106 The above results show that the yield and delicacy of green peas are greatly improved by the treatment according to the invention.

In the case of lucerne in addition to the improvement of quantitative and qualitative characteristics the number of roots is also considerably increased and the activity of hitrogenase epaym is accelerated. When spraying grass a V. striking increase of green mass can be observed while the I n&74- raw protein and starch, values remain substantially unchanged.

Example 6 A water-soluble four-valent titanium salt corresponding to 1000 ppm of titanium and 900 000 ppm, of ascorbic acid are dissolved in water and the solution is made up to 1 lit. The pH of the solution is adjusted to 5 and 25 ppm, of 2,4--dichlorophenoxyacetic acid sodium salt, 0.5 g« of sodium benzoate and petroleum sulfonate sodium salt (wetting agent) are added, £7 the composition obtained, after dilution, vine plants were sprayed three times in their vegetation period. The results are shown in the following table.

Vine test Sugar/acid ratio % Variety and treatment Glucose g./lOO ml.

"Treasure of Fannonia" Control Treated "Italian riesling" Control 8,0 9.4 12.6 17*6. 100.0 117.5 100,0 139.6 13.2 19.2 .1 28.3 The above results show that the treatment increases the carbohydrate content of grapes and accordingly, the sugar/ 25 acid ratio is also increased. *sMAYi ^6*74-

Claims (8)

WHAT WE CLAIM IS: 10 15 20

1. Plant conditioning composition containing a titanium-ascorbic acid chelate, substantially for spraying foliage or seed treatment, which comprises 0.1 to 15.0 % by weight of a titanium-ascorbic acid chelate containing 14 to 28 g.moles of ascorbic acid related to 1 g.atom of titanium, the pH of which is adjusted to 5 to 7, 0.1 to 2.0 parts by weight of one or more biochemically essential nutriments and/or 0.0001 to 0.001 parts by weight of one or more phytohormones related to 1 part by weight of titanium and at least 0.01 % by weight of one or more of the compounds selected from the following group: sorbic acid and salts thereof, benzoic acid and salts thereof, salicylic acid and salts thereof, p-hydroxy-benzoic acid and salts thereof, £-nitro-benzoic acid and salts thereof, propionic acid and salts thereof, hexamethylenetetramine related to the total weight of solid ingredients, optionally in association with wetting agents, adhesives and/or further conventional additives.

2. A composition as claimed in claim 1 which comprises as a biochemically essential nutriment a water-soluble salt of boron, magnesium, manganese, iron, zinc or molybdenum.

3. A composition as claimed in claim 1 or claim 2 which comprises as a biochemically essential nutriment a nitrogen-phosphorus-potassium-containing fertilizer.

4. A composition as claimed in claim 1, which comprises as phytohormones auxins, giberellins and cytokinins, e.g. ilpha-naphthylacetic acid or beta-indolylacetic acid. - 16 - W67£

5. A composition as claimed in claim 1 or 4, which comprises 2,4-dichlorophenoxyacetic acid or salts thereof as a phytohormone.

6. A composition as claimed in claim 1 substantially as specifically described herein in any one of the Examples.

7. A method of preparation of a composition as claimed in claim 1 substantially as specifically described herein in any one of the Examples.

8. A method of acceleration of plant growth which comprises the use of a composition as claimed in claim 1, substantially as specifically described herein in any one of the Examples.