DE2511077A1 - Turf grass coloration - using hexadentate cobalt phthalocyanine amine complex salts - Google Patents

Abstract

In a process for colouring turf grass, the turf is treated with a hexadentate cobalt phthalocyanine amine complex salt in which the complex consists of (a) a hexadentate cobalt phthalocyanine complex in which the 2 ligands not occupied by the ring system are coordinatively bound to an aliphatic polyamide and (b) an anion of an organic or inorganic acid. The complex is pref. sprayed onto the turf in the form of 1-5 wt. % solution in 1-22% aqueous acetic acid or in the form of an aqueous dispersion. A suitable complex salt is cobalt phthalocyanine ethylenediamine chloride. Application of the specified complexes imparts to turf grass (e.g., on lawns, parks or sports fields) a deep and brilliant green or blue colour with extremely high transparency. Adhesion of the complexes to grass is good without the need to incorporate sticking agents (e.g. resins) into formulations of the complexes.

Description

Process for coloring lawns The invention relates to a process for coloring a lawn, which is characterized in that the lawn with a 6-valent (6-dentate) cobalt phthalocyanine amine complex salt, which is made from a 6-valent (6-dentate) cobalt phthalocyanine complex, in which at Je. both ligands (bonds), those not from the ring system of the 6-valent (6-dentate) cobalt phthalocyanine complex are occupied, an aliphatic polyamark is coordinatively bonded, and an anion an inorganic or organic acid is treated.

Up until now, lawns were often not just for fun and decoration in gardens, parks, factories and airports, sports grounds and the like, but also used to prevent soil erosion and has an interest in turf increased rapidly0 The method according to the invention attempts to achieve the above to comply with the requirements mentioned0 by the method according to the invention is not only possible the human To make life more comfortable it is also very valuable from a turf industry standpoint and supplies made a great contribution to the lawn industry.

The conventional methods that are used to turf a To give more brilliant green or blue color generally consists of that basic, noun or vat dyes or pigment resin dyes or fertilizers and agricultural chemicals that have been previously colored on the lawns be applied. However, all of the above conventional methods are of of low industrial value due to the disadvantages that the dyes used or dyes have poor lightfastness, leak easily when it rains, have a poorer coloring power, kill the lawn itself or the beautiful appearance affect the lawn.

After extensive research, it has now been found that the above mentioned disadvantages of the currently available colorants are avoided can that a 6-valent (6-dentate) eobalt phthalocyanine amine complex salt is used as a coloring agent for lawns used, which consists of a 6-valent (6-dentate) cobalt phthalocyanine complex, in that of the two, of the RingEtm of the 6-valent (6-dentate) eobalt phthalocyanine complex unoccupied ligands (bonds) an aliphatic polyamine bound coordinatively and an anion of an inorganic or organic acid. Characteristic for the method according to the invention is that in the treatment of a lawn with the above-mentioned 6-valent cobalt phthalocyanine amine complex salt (hereinafter referred to as dye according to the invention:? labeled) this a deep and shiny green or blue color with an extremely high transparency can be given, and that the use of the dye according to the invention does not lead to such disadvantages, as they occur in conventional procedures.

The features mentioned above are explained in more detail below.

1.) The dye according to the invention exhibits when it is in an aqueous Solution transferred has a higher viscosity than a solution of another conventional dye and it can therefore adhere well to lawns. Hence needs no resin or similar tackifying agent as in the conventional one Method to be used and the treated with the dye of the invention Turf is not prevented from assimilation.

2.) The dye according to the invention is originally insoluble in water, However, it is made under weakly acidic conditions by using an organic Acid generated, water-soluble 0 This means that the dye according to the invention by volatilization of the acid or by adding a weakly alkaline substance immediately becomes insoluble in water.

Therefore it is the one used in the method according to the invention Acid to make the dye according to the invention water-soluble, preferably a volatile acid such as formic acid or acetic acid. Because a lawn in one acidic soil grows strongest, the method according to the invention is most suitable best for applying to lawn. It was previously common practice to direct a lawn to spray, in some cases with a small amount of lime or magnesium oxide, to control the acidity of the soil. When using the invention Procedure on a lawn must therefore, if necessary, the lawn with lime, magnesium oxide or an alkaline fertilizer such as urea.

3o) The dye according to the invention adheres firmly and not only colors Lawn seedlings, but also the buds, leaves and stems of lawn and its bear capacity is far better than that of conventional dyes. That is, the inventive Dye adheres and colors a lawn with such high speed, about 3 to about 5 times the speed of coloring with malachite green with practically the same coloring power edBpriit, whereby malachite green is a dye with is the best coloring power for a lawn. The dye according to the invention converts within a short period of time under the action of ultraviolet radiation in the air into an insoluble xobalt phthalocyanine without the risk of that it flows out by rain or by spraying with water or other substances contaminated.

To apply the dye according to the invention to a lawn can a very simple process can be used, in which the lawn with a 1 to 5% strength by weight solution of the dye according to the invention in a 1 to 2% strength aqueous solution Acetic acid solution or with an aqueous dispersion of the dye according to the invention is sprayed using an anionic or non-ionic surface active Has been manufactured by means of. Needless to say, in the above case the solution or dispersion of the dye according to the invention with any agricultural chemicals, fertilizers, other chemicals and the like. Can be added or that the dye according to the invention in a solution this substance can be dissolved or dispersed. In addition, it is not a disadvantage the dye according to the invention in a mixture with methanol or cellosolve as a dissolution aid to be used, or it is expedient in combination with another dye or pigment used.

Examples of the polyamine which the dye of the invention are ethylenediamine, propylenediamine, dimethylaminopropylamine and diethylaminopropylamine, while examples of the anion are acid residues of various hydrohalic acids, Mineral acids such as nitric acid, sulfuric acid, carbonic acid, dicarbonic acid, phosphoric acid and phosphorous Acid and lower fatty acids such as acetic acid and Propionic acid, although the invention is not limited thereto. A preferred one Polyamine is ethylenediamine or 1-amino-3-dimethylaminopropane and a preferred one Anion is the remainder of hydrogen chloride, hydrogen bromide, hydrogen iodide, nitric acid, Dicarbonic acid, phosphoric acid or acetic acid.

Lawns generally become coarse in Japanese and western lawns Lawn divided, however, they can be divided into about 50 types and the current one State of the art is that various facilities and procedures are used to to obtain more preferred lawns of newer species0 It can therefore be assumed that increasingly new types of lawn are being produced. In each case, however, is that according to the invention Procedure applicable to any lawn.

The invention is illustrated by the following examples in which all parts and percentages are based on weight, further discussed but not limited to to be limited.

Example 1 Using a golf green made of pentgrass The following experiment was carried out on the lawn: Two square ones were placed in the lawn Areas A and B formed with a side length of 15 cm. The areas A and B were individually using a spray device evenly with 50 ml of a solution of 2 parts of a 6-valent cobalt phthalocyanine amine complex salt, which is used as the polyamine 1-Amino-3-dimethylaminopropane and containing chlorine as the anion, in 100 ml of a 2% strength sprayed aqueous acetic acid solution. Immediately after spraying with the above called dye solution, area A was also mixed with 50 ml of 1% aqueous Ammonia sprayed after the lawn (the sod and the surface of Soil) was colored and dried, the color of the lawn quickly turned bluish green. After 1 day (24 hours), small amounts of the colored sward appeared on both areas A and B cut out and recorded and then a 1 hour leach test in warm water (30 to 400C), but in both cases none was subjected Leaching of the dye from the sward of areas A and B observed Density and the brilliance of the color shade of the colored lawns in areas A and B were identical and they were far better than those of the surrounding lawns, that had not been sprayed with the dye solution. Also, the lawns were in the two areas A and B which had been subjected to the coloring treatment, Hardly changed in color when left for two months.

In addition, the areas A and B were individually divided into squares with a Side length of 25 cm divided to form areas C and Do. The areas C and D were treated in the same way as the first time0 That is, the Area C was treated in the same way as Area A, while Area D in the same way as area B was treated. Because of the second treatment the lawns in areas C and D were colored a little deeper greenish-blue than that Areas A and B and their brilliance were slightly better when visually observed. The lawns in areas C and D were left for 5 months, it was however, no significant visual change was observed. During this period new buds of the turf germinated in relation to the state of growth of the buds and those of the lawns, however, no change was observed.

The same treatment as above was applied to a Korean turf grass Applied to existing golf green turf, with virtually the same results as obtained above.

In the case of the Korean lawn grass, the lawn grass was discolored, if it froze and it turned brown during the winter time, However, when the lawn grass one was subjected to such treatment as above, such discoloration was hardly likely to occur watch.

Example 2 A solution of 5 g of a 6-valent eobalt phthalocyanine amine complex salt dye, which contained ethylenediamine as the polyamine and the anion-chlorine, in 100 ml of a 3% strength aqueous acetic acid solution was admixed with 0.1 g of an organic sulfur fungicide. This solution was sprayed onto lawn grass using a sprayer, that had been planted in a sloping surface of the ground to prevent erosion of the soil and maintain the appearance of the environment. the The consequence of this is that the lawn grass has a brilliant and deep greenish-blue color Color has been dyed0 It is particularly preferred to spray the dye solution on carried out during the transition from autumn to winter, when the discoloration of the Lawn grass occurs.

Comparative Example 1 Using withered Japanese turf grass as a material, the three dyes described below were used with respect to their coloring properties, their water degradation and their lightfastness tested.

Material to be dyed: The withered Japanese grass engraving was made cut into pieces less than about 1 mm in length and the pieces were mixed sufficiently to produce a substantially homogeneous material; Dyes: a) Malachite green b) Direct Fast Green c) a 6-valued (6-tooth) Cobalt phthalocyanine amine complex salt, which is ethylenediamine as a polyamine and ethylenediamine as an anion Contained chlorine.

The dyes a) and b) were individually using water transferred into a 3% aqueous solution and the dye c) was using a 2% aqueous acetic acid solution into a 3% aqueous acetic acid solution and 100 ml of each of the solutions thus prepared was poured into a beaker. 5 g of the sample material was poured into the solution in each beaker and the at the same time obtained mixture was slowly stirred at room temperature for 30 minutes and then filtered using a filter paper. The stained material on the filter paper was immediately dried as it was, whereby it was found that the materials treated with the dyes a) and c) in deep colors in practically the same extent had been stained as that with the dye b) treated material was hardly stained.

Then in each case 1 part of the dried material was dissolved in 50 ml of water introduced and the resulting mixture was slowly stirred and then filtered, It was found that the filtrate of the material treated with the dye a) the deepest color was the filtrate of the material treated with dye b) had a relatively deep color and the filtrate of the dye c) treated material was colorless and transparent. Subsequently, the filtration residues immediately dried on the filter papers to find that the color density the residue of the material treated with the dye a) by water extraction decreased to about half that of the material treated with the dye b) was practically the same as that of the material treated with dye a) and that the material treated with the dye c) did not change. aside from that were these three residues exposed to sunlight under certain conditions, whereby it was found that the residue of the material treated with the dye a) apparently became discolored and faded within 5 hours that the one of the material treated with the dye b) difficult with regard to its discoloration was judged because it was originally low in coloration, though fading was observed within 5 hours and that of the material treated with the dye c) practically none even after 100 hours Had discoloration.

The hexavalent (6-tooth) used in the previous examples Cobalt phthalocyanine amine complex salt dye was prepared as follows: A mixture from 12.8 parts of phthalonitrile, 3.3 parts of anhydrous cobalt chloride, 6 parts Urea, 1.3 parts of ammonium chloride and 60 parts of ethylene glycol was in one with A reaction vessel equipped with a stirrer and having a capacity of 200 parts was introduced and slowly heated to 1200C over a period of about 1 hour, the Reaction mixture gradually became viscous and turned into a liquid portion with it a deep brown color and a precipitate with a purplish blue color separated. After that, the reaction continued at 130-13500 for another 3 hours had been, the deep brown color of the liquid portion changed to pale yellow and the amount of precipitate increased and the reaction mixture became more viscous and took on an even, deep, purplish-blue color. After the fact that the color of the liquid portion had turned pale by a filter paper spot test was confirmed, the internal temperature of the reaction vessel was lowered to 80 ° C and the reaction mixture was added with 27 parts of 30% hydrochloric acid added and then stirred for 30 minutes at 80 to 90 ° C, the color of the reaction mixture turned dark green and the liquid portion became practically colorless. The reaction mixture continued stirring until the liquid portion became completely colorless. The for it required Time was about 1 hour. Thereafter, the temperature of the reaction mixture rose Reduced a value below 1000 and there were slowly 80 parts of dimethylaminopropylamine admitted.

Since the reaction was exothermic, the system was turned off if necessary cooled so that the temperature did not rise above 300C.

The end point of the reaction can be determined by the complete dissolution of the Reaction mixture can be determined in an aqueous acetic acid solution.

After the reaction, the precipitates were collected by filtration and washed with water and then the filter cake at room temperature in 200 Parts of 3% acetic acid dissolved. Subsequently, small amounts of insoluble Materials separated by filtration and the filtrate was washed with a 20% aqueous sodium chloride solution was added to precipitate the precipitates. The rainfall were separated by filtration and then dried at 4000, leaving 13 parts of a greenish blue cobalt phthalocyanine complex salt. This complex salt was easily soluble in methanol or in water acidified with acetic acid and showed it had a nice greenish blue color, but it was in hydrocarbon solvents insoluble0 The wavelength of the absorption maximum of the product thus produced was 671 mp, measured in a 2% acetic acid solution, and the elemental analysis yielded 60.7% C, 5.22% II, 20.4% N, 6.46% Cl and 7.15% Co.

Patent claims:

Claims (4)

A method for coloring a lawn, characterized in that that the lawn with a hexavalent (6-dentate) cobalt phthalocyanine amine complex salt treated, which consists of a 6-valent (6-dentate) cobalt phthalocyanine complex, in that of the ring system of the 6-valent (6-dentate) cobalt phthalocyanine complex unoccupied two ligands (bonds) coordinate an aliphatic polyamine is bound, and an anion of an inorganic or organic acid. 2. The method according to claim 1, characterized in that the 6-valent (6-dentate) cobalt phthalocyanine amine complex salt in the form of a 1 to 5% strength by weight Solution in a 1 to 2% aqueous acetic acid solution or in the form of an aqueous one Sprayed dispersion on the lawn. 3. Use of a hexavalent (6-tooth) cobalt phthalocyanine amine complex salt, that from a 6-valent (6-dentate) cobalt phthalocyanine complex, in which to the from the ring system of the 6-valent (6-dentate) cobalt phthalocyanine complex occupied both ligands (bonds) an aliphatic polyamine coordinatively bound and an anion of an inorganic or organic acid for dyeing of a lawn. 4. Use of a hexavalent (6-tooth) cobalt phthalocyanine amine complex salt, that by condensing phthalonitrile with a cobalt metal donor in one Alcohol solvents with a boiling point above 1000C at a Reaction temperature from 100 to 150, preferably from 115 to 1350C, adding a aqueous solution of an inorganic or organic acid at a temperature of 0 temperature of more than 50, preferably from 70 to 100 ° C. to the reaction mixture obtained and subsequent reaction of the reaction mixture as such or after the separation the same has been produced by filtering with an aliphatic polyamine, for the purpose specified in claim 3.