CZ103499A3 - Fertilizer wrapped in foil with aimed release of nutrients, process of its preparation and use - Google Patents

Abstract

Folienumhülltes Düngemittel, umfassend einzeln umhüllte Volumina einer nährstoffhaltigen Substanz, wobei die die nährstoffhaltige Substanz umhüllende Folie ein wasserdurchlässiges Polymer, ein zellstoffhaltiges Material, ein Textilmaterial, ein Lignocellulose-Material oder eine Kombination aus zwei oder mehr davon enthält, sowie ein Verfahren zu dessen Herstellung und ein Düngeverfahren, bei dem das folienumhüllte Düngemittel Verwendung findet.

Description

(57)

The film-coated fertilizer in the form of individually wrapped volumes of a nutrient-containing substance, wherein the film is a water-permeable polymer, a cellulose-containing material, a textile material, a lignocellulosic material, or a combination thereof. A method of producing such a fertilizer and a method of fertilizing by applying said fertilizer.

CZ 1034-99 A3 ZOJ Ϊ-Μ

- ι · · · · ·

I · • <* * * *

Fertilizer wrapped with foil with targeted release of nutrients, method of its production and its use

Technical field

The invention relates to a fertilizer wrapped foil formed of individually coated volumes of a nutrient-containing substance, wherein the foil, which is a nutrient-containing substance, is a water-permeable polymer. a cellulose-containing material, a textile material, a lignocellulose material, or a combination of two or more Lacquer materials. The invention further relates to a process for the production of such a fertilizer and to a method of fertilization in which the fertilizer according to the invention is used.

L 1 Imanns Enzykifallie

10. p. 3 b 3 and z 3 69,

It is generally known to use fertilizer granules which are coated with a polymer layer as fertilizers to improve fertilizer efficiency. The increase in efficiency results from the fact. that the coated fertilizer releases substances that act as plant nutrients in a prolonged manner so that the fertilizer can be active for a longer period of time. Such slow-release fertilizers are described, for example, in der technischen Chemie, Vol. 1987 and their merits are summarized in

i e r t. kes. p. 3 5. p t r. 1 and z 12, 1 9 9 3 1 and ko v e sv s t émv o b i e n eho i ád i 'a. which may include the- ke fertilizer ivo j a k o u c ι η n o u 1 o z k u. J s o u po ps and ny in liters and hikes l n ap rik1 ad e v r o p s k y patent p S p 1 1 1 č 1 s í o EP-A-1523 ° C) a Ε P - AND- 8 3 8 1 1 8 i). Other manure i a, k l e i 'and J show coated with b i o 1 ogi i c k y

polymers, such as are described, for example, in the world-wide publication of cis-WO ⁽ ) 5 ⁽ 13).

The disadvantage of the tickled granulated fertilizers. which are coated, they are an additional load in their inlet and complicated.

I · · <

storage of large quantities of different fertilizers. In addition, different coating thicknesses are caused by irregular yeast. intended for the release of nutrients, particle surface and wide granulation micrometry, bring some inaccuracy in

The possibility of avoiding these deficiencies is the coating of fertilizers. or nutrient-containing substances, films.

For example, U.S. Pat. No. 4,224,048 discloses a fertilizer in the form of tubes or tubing consisting of polymers and polymers or a water swelling polymer. Inside these tubes or tubes are stored substances containing nutrients at regular intervals. The disadvantage of this system is the fact that the amount of latk. introduced during preparation, they are not detachable from each other so that they can move freely inside the tubing, which can lead to irregular distribution of the amount of substance, in addition to incorporating such tubing into or onto the soil. to prevent such tubing from breaking.

German Patent No. Lili-A 40 35 223 discloses a composition with an active ingredient, for example for fertilization and soil treatment, wherein the ingredients present therein are stored or

dispersed in the matrix b i o 1 ogicky demolish 1 polymer. After- written matrices are pou z e water permeable rna t r i c e. of which s e o b s a n u v 1 n u j e e r all those who L y iee subjected to bio- i o g i e k e degradation. V ý s 1 edkem is that before biological rebelled van im with none 1 n e u v o 1 n i, j and k m i but e biol og i cke o d b o u v a n i z o p o c e. t e d y j a k m i 1 e rna i r i c e A n d e c t i n e s holes or holes , p o s t r e d e k. k t e r v is inside, u- in 1m in 1m i to r time. so release is no longer controlled and the result of the museum was di i Cl po s k O Z C N 1 axis L řo a n in 1 i n at 1 i s

large amounts of active ingredient.

Yippee • · · · ·· ·· • · · · • · · ·

A very similar system in which it releases only when the patent specification WO 91 / 0108t> is destroyed.

again the active ingredient described in the world

U.S. Pat. No. 4,845,888 discloses a water-soluble synthetic resin based mulation foil which also contains nutrients or an active ingredient. Again, such a film has the disadvantage that the film must first dissolve in a water-containing medium and once certain perforations or holes have been formed, the active ingredient or nutrients are released in a very short time.

In view of the prior art, the invention provides a film coated fertilizer. which allows a controlled release of the nutrient-containing substance over an extended period of time. Nutrient release begins immediately after being applied to the soil or after incorporation into the soil or substrate by diffusion through the osmotic process and is maintained for a defined period of time. The ground or substrate is continuously supplied with sufficient quantity and selected to match the dosed amounts of nutrients required for collection by the respective plant.

moreover, the preparation of such a film coated with fertilizer, especially in comparison with fertilizer in the form of coated granules. a substantial cost advantage, since the complicated coating operations of maximum uniformity on the granules are saved when nutrient-containing substances are used in the form of, for example, pig, since the granules and nutrient-containing granules are not suitable.

in addition, substances containing nutrients that are normally non-incompatible, for example, substances containing ammonium nitrate and urea, may be used. i in the lorme granuli, because their hveroscopicity i> v normally causes i and their conversion to the lekuie sta v.

· ► ► ► ► ► ► ► ► ► ► ► ► ►

Subnet and exterior

The nutrient-coated foil fertilizer coated according to the invention consists in that it consists of one or more individually coated volumes of at most 20 cm @ -1 ^; at least one nutrient-containing substance, wherein the film coating of the at least one nutrient-containing substance is a water-permeable polymer, a cellulose-containing material, a textile material, a glucose material or a combination of two or more such materials.

Such a water permeable polymer is preferably biodegradable.

Another important feature of the film used in the present invention is that it allows the release of the nutrient-containing substance as desired with respect to the nutrients.

All commercially available polymers that are water permeable and capable of forming films can be used for the purposes of the invention.

The term water-permeable is always mini. of films which can be used according to the invention and which form a water-permeable polymer (hereinafter often referred to as polymer films), have vapor permeability values higher than that of polyethylene.

Value for dropping water vapor foil. made of polymers. which can be used according to the invention is preferably greater than 1 g / (day ² ). measured on an IDO µm film at 25 ° C and

p i g r a d i e η t u r e 1 and t i in her 90% and w O Vo. H o r n i mez hodηο- t y p o r s t no s i i in from n i pa polymers O lil, k t e r y c h 1 of e po - used under 1e y y and 1 e z u • Yippee with the advantage of p rib i and z n e 1 oo g / (m ² . day). Polymerovyth i o i 1 I, j e z have ice ob of v and and š 1 v y s o k o u value throughput t i vo d n i P a r y, or bo r e j s o u in e s k ulev n o s i i water ro desolate, p p i k l ad s k i ob, po 1y sac ha rid y not him Mon 1 y vin y 1 and whom-

in, him of

i) y l has been used for the purposes of the invention since bv is

I have released or disintegrated too quickly in the environment and therefore cannot guarantee controlled release for the purposes of the invention, i.e., the long-term supply of nutrients over an extended period of time that meets plant requirements.

It is also possible for the purposes of the invention to use laminated films or barrier films consisting of two or more polymers which meet the above criteria.

Examples of polymers which can be used according to the invention are:

aliphatic polyesters, especially polyesters of dicarboxylic acids having from 2 to 10 carbon atoms, or based on cycloalkyl acids of 7 to 10 carbon atoms and carbon atoms, such as glutaric acid. adipic, puneiic, azelainic.

based on aliphatic carbon, preferably with dicarboxylic acids, in particular with S-Maionic acids. amber, baba. ťumarová.

4-cyclohexanediocarboxylic, itaconic and maleic. described, for example, in the European Infor - mation on E - P - A - 5? 2,682; polyesters based on aromatic dicarboxylic acids usually having 8 to 12 carbon atoms, preferably 8 carbon atoms, such as, for example, terephthalic acid, isobutyric acid, 2.b-naphthoic acid and

1.5-naphtha:

copolyesters with structural units derived from derivatives of both aliphatic n and p i k 1 and d copol; y e s t e r y 'a

t ci k and iomat i ckýc h k a r b o x w n éi even z i acid 1 i n y and more n e b o ba z i i k y s e 1 i n v fumarove a terci

i. succinic and tereitioic acids. as described, for example, in U.S. Pat. No. 5,444,079 and in parallel worldwide publication of the invention of Wu < 2 &gt; / &gt; and {> 5 &lt; 4 &gt; -.- A-44 .i 2 1 0 1 and in a number of applications it is possible to climb in the open

P 4 4 4 O 8 a1). 1, lh OO 5 (i.5.

P 4 4 4o 8,1 (1 ..

5 (H)

I a5 o and 18a.8 las o 5 | 8 (i) (i);

Organic polyacids, such as polylactic acid. polyhydroxyinases, polyamino acids and hydroxycarboxylic acid polymers hereinafter referred to as component (b1) in the characterization of the copolyester (B1) which may be used according to the invention; polyamides such as nylon 6, nylon 66, nylon 12 and nylons 610, 612, as well as copolymers based on polyamides;

polyvinyl compounds such as polystyrene, polyvinyl chloride, polyvinylidene chloride, and styrene-diene copolymers such as butadiene or similar styrene / acrylonitrile / butadiene copolymers;

poly (methyl acrylates), for example poly (methyl meth) acrylate or poly (methyl acrylate) polycarbonates;

a cellulose acetate or parv in acetobutyrate and mixtures thereof.

It is recalled that the molecular weight of the polymers used according to the invention must always be sufficiently high to allow the formation of the polymer.

according to a preferred embodiment, the above-defined poly (cyclo) and lithium dicarboxylic acid copolymers and copolymers containing structural units derived from derivatives of both aliphatic and aromatic carboxylic acids are used. In addition, the acids and esters are particularly suitable. since these polyesters provide good films. iiiiiji a sufficiently high water vapor permeability value in a

J s o u addition biol O g 1 c k .v от bo u r a t e 1 n e. V binding cm b i o 1 o v i c k y from the storm 1 e 1 n e s e here always m i π i. e 1 o l ic also by the tax After po ii z. i l 1 under 1 e v y n a 1 e z u pii sobe ni III v 1 i in the course of - s t i c d even after the influx on and me r i l e lne time. goats fall J e z p and' and in i d i a z p ii - s o be n by hydrolysis and / n e bo ox 1 d a c t, but ve l s 1 no u p with o be n i iii iii i k - 1 O O 1 '0 au i .amϋ, j and ko i with O 11 ba k l e i i e, k v a s i ii k y, mushrooms fl r a St. koz- pud v sa l by t L a k e o v 1 i vneri e n z ymat i c k y. how O J c ¹ described

w * ► ► ^{1 1 1 1 1 1 1 1 1 1 1 1 1 1 1} «« «« «« ^{1 1 1 1 1 1 1 1} In the literature (for example, pp. 76-78, 1977).

Y. Tokiwa and T. Suzuki, Nature ”270,

According to a preferred embodiment of the invention, when using the copolyester, by selecting a suitable ratio between the repeating units derived from aliphatic carboxylic acids and those derived from aromatic carboxylic acids, the biodegradation rate can be changed, i.e. when the polyesters used according to the invention are substantially completely disintegrated. According to pure practice, the greater the proportion of repeating units derived from aliphatic carboxylic acids, the higher the rate of biodegradation of the copolyesters. In addition, the higher the proportion of sections with the alternating succession of repeating units derived from derivatives of amino acids and amino acids, the greater the biodegradation of the copolyester.

the films used according to the invention are films which form a biodegradable copolyester (B) having structural units derived from derivatives of both aliphatic and aromatic carboxylic acids, which are obtainable by reaction of a mixture comprising:

(a1) a mixture of (ail) 10 to 95 mol% of an aliphatic dicarboxylic acid or cycloaliphatic dicarboxylic acid or ester derivative thereof, or a mixture thereof; (a 1 2) 5 to 9 moles of aromatic dicarboxylic acid or ester derivative thereof or mixture thereof, (1 J) Oaz mol lo '7, compounds containing Suli Love her group or mixture thereof, wherein the sum of the individual mole' 7, i.e. _they LOO.

(az) dihydroxy or aminoalcohol or mixtures thereof with each other.

i / i ii i 1 and ι η i p i i i i k (a2) is 0.4: 1 and z 2.5: 1.

(a 5) 11 ni o t n o s n o a /. 1 o 7, based on the extension (a1) of the extender • · * ίί • 4 ···· · · ·

Β · · · ·

(A4) by weight of 0 to 20 O, based on mixture (a1), of compounds having at least three groups capable of forming esters or their a clear laughter.

wherein the repeating units derived from (cvk 1 o) and 1 ifatic aromatic carboxylic acids are statistically divided and the copolvester has a viscosity number of 5 to 450 g / ml (measured in o-dichlorobenzene / flax 1 system (50/50 weight ratio) at a concentration of 0.5% by weight of the copolyester at 25 DEG C.).

In general, the aliphatic dicarboxylic acids which can be used to prepare the copolyester (B) have 2 to 10 carbon atoms, preferably 4 to 6 carbon atoms. Cyclic and fatal dicarboxylic acids which can be used for the same purpose have up to 10 carbon atoms, in particular 8 carbon atoms. In principle, however, it is also possible to use di-carboxylic acids having a greater number of carbon atoms, for example up to 30 carbon atoms.

Examples are: malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid. íumarová. 2,2-dimethylgutarate. suber, 1,3-cyclopentanediocarboxylate. 1. 4 - c k 1 o h e x a n d i k a r b o x y l, 1, 3 - c y k 1 o h e x a n d i k a r b o x y l. diglycolic, itaconic, maleic and 2,5-norbornane dicarboxylic acids. with adipic acid being preferred.

As the ester derivatives of said di-carboxylic acids, mention may be made of dialkyl esters of 1 to 6 carbon atoms, for example dimethyl ester, diethyl ester, dipropyl ester, dibutyl ester. di-nylyl s t r and di-hexyl ester.

The bioreactors may be used alone or in the form of fine mixtures.

Preferably, adipic acid or its ester derivatives and beechic acid or its ester derivatives, in particular adipic acid or its ester derivatives, are used.

Generally, the amount of (cyclo) alithatic dicarboxylic acids or ester derivatives thereof is about 10 to 95, preferably about 20 to about 50 and especially about 25 to about 35 mol%. compounds (all) to (and 13) are always based on the total amount

As aromatic dicarboxylic acids, acids having 8 to 12 carbon atoms, preferably 8 atoms, are referred to as carbon.

Examples are terephthalic acid, isophthalic acid. 2,6-naphtho and 1,5-naphtho and their ester derivatives. Particular mention is made of alkyl esters of 1 to 6 carbon atoms, for example dimethyl ester, diethyl ester, dipropyl ester, dibutyl ester, dipentyl or hexyl esters.

In principle, however, it is also possible to use aromatic dicarboxylic acids having a plurality of carbon atoms.

The aromatic dicarboxylic acids and their ester derivatives may be used alone or in admixture with each other.

Generally, the amount or esters thereof is preferably about 50 to about 5 molar%, aromatic dicarboxylic acid derivatives of about 5 to about 90, about 80, and especially about e >

Used with sulfur (a l 3 containing sulphonate group)

p inu. j c 1) been é s u i and 1 k and 1 i c k ho ko v u neb o alkali metal salt e m i n y d i ka r bo x h lly y y sel n y, o bsa hu J i c í sul f o n o t o p c u piny ne bo Yippee J ‘<- h e s t e r o y c h d e i i v t t . with the salt and the salt k o v u ky s e 1 i n y 5 - sui i oi sii f t and 1 o e nc bo j e j i eh mixture i. from the name sodium s ů i. Qty. with L o s 1 o u e n iny, o b s and h u J ^{1 c} t su 1 1 on t a t e group (a 1 3) .i c p i 'i b 1 harvest or o p f i b 1 s i of the n 1O, with the advantage of the ordinary o and z Ex b 1 i no 5 and especially p r i b 1 i /. No 3 to p i b 1 i ž. n 5 5 πιο 1 A ·.

99

9 9 9 9 based on the total amount of compound (all) to (a13).

Compounds containing sulfonate groups may be used alone or in admixture with each other.

According to the invention, the component (a2) used is a dihydroxy compound or an amino alcohol or mixtures thereof. In general, alkanediols (a21) of 2 to 12 carbon atoms, preferably 4 to 6 carbon atoms, or 5 to 10 carbon atoms of cyclohexanediols, in each case a 1-diether diol may be used for the preparation of esters of all known diols or aminoalcohols. (a22), i.e. ether groups containing hydroxyl compounds and amino alcohols having 2 to 12 carbon atoms (a23), preferably 2 to 4 carbon atoms and amino groups having 5 to 10 carbon atoms.

Examples which may be mentioned are: et al., 1, 2, 2-piperidiol. 1,3-propanediol, 1,2-, 1,4-butanediol, 1,5-pentanediol, 2,4-dimethyl-2-ethylhexane-1,3-diol, 2,2-diene t 1 - 1,3-propanediol. 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2- isobutyl-1,3-propanediol. 2,2,4-trimethyl-1,6-hexanediol, in particular ethylene glycol, 1,3-propanediol, 1,4-butanediol and 2,2-dimethyl-1,3-propanediol (n-propentylglycyl), cyclopentanediol, 1,4-cyclohexanediol.

1,2-, 1,3- and 1,4-cyclohexanedimethanol and 2,2,4,4-tetramethyl-13-cyclobutanilio;

dicih y1e n g1 in ko I, triel hy1e ngIyko1, po 1ye t hy1e ng1 in ko 1, po 1 in rp 1 eng I yko I apo I ytetrahydro 1 ura η, z e ni n l on diet li y 1 eng 1 y kol, three hy1e ng I y ko 1 and after Iye l hy1e ngI y kol or is south we are with, or bo

s 1 o u e n i n y in a j i c i p r o less i v ý number of ether 1 ed n o Lek, n a p i i - k1 ad po 1 y e t hy 1 e n g 1 y k o I, k t e r y o b s a n o n e n o n e n o n e single - pieces and k 1 e i y ί e 7. 1 S Cat n and at 1 ad in a familiar way Mon 1 ymer a c i n e j p r v e e l hy 1 e nox i d u a on 1 e (1 n e p ropy 1 c n o x i d u. Mo 1 e k u 1 o v a mass hand, i After 1 y c t h y 1 e ng1y ko 1 ) e from rule of law and ib1 i reap 2 5 o and from 1) 1 • and her; (> 1 advantage ex i b 1 i z n e (> OO a /, i i b 1 i /, n e J () (K) g / mo1;

·· ···· · · · · · ·

4-Aminomethyl-hexane-1,2,3-amino-1,3-aminopropanol, 4-aminobutano-5-amino-pentano-1,6-aminohexano-1, aminocyclopentano-1 and aminocylohexano-1 and mixtures thereof.

The dihydroxy compound or aminoalcohol may be used alone or in admixture with each other.

The molar ratio of (a1) and (a2) is usually selected from about 0.4: 1 to 2.5: 1, preferably about 0.5: 1 to about 1.5: 1, more preferably about 0.5: 1 to about 1.2: 1, especially about 0.5: 1 to about 1: 1.

The molar ratios of (a1) and (a2) in the isolated copolyester (optionally after removal of the required amount of excess component (a2)) are about 0.4: 1 to about 1.5: 1, preferably about 0.5: 1 to about 1 2: 1, especially about 0.5: 1 to about 1: 1.

All of the commonly used chain extenders used to produce polyester can be used as chain extenders (ad). Optionally, the chain extenders are used in an amount by weight of about 0.01 to about 10, preferably about 0.05 to about 5, more preferably about 0.07 and about 3 to about 3, and especially about 0.1 to about 1%, each based on the composition. (a 1).

Suitable chain extenders are: diisocyanates, for example tosylene-2,4-diisocyanate, 4-isocyanate, b-diisocyanate, 4,4- and 2,4'-di-isocyanates. nv1meihand ii soky anáι, na ftyi e η - 1, 5 - diis oky anai, xy ly lend i isocyndl, he x aine L hy ie nd iisokya ná, i s foi oncl ii soky a námet thy I enbis (4 isocyanates and, in particular, hexamethylenediocyanate: three functional and isocyanate compounds which may contain isocyanurate and / or biuret with a moiety other than Li 3; divi nyle L hery, for example 1,4bula nd io Id ivi η in Iclher, 1,0-hexand io I divi η v 1 el h a r, 4-c v I hexanedimethano 1di in inyl ether and 2,2'-bisoxazole of formula (I)

-O

Compounds of formula (I) are generally obtained as described in the literature (Angew. Chem. Int. Edit, Vol. 11, pp. 287-288 (1972)). The bisoxazolines of formula 1 are particularly preferred, wherein R ¹ is a single bond. (CIO) qa quinenyl group wherein q is 2, 3 or 4, such as methylene, ethane-1,2-diyl, propane-1,3-diyl, propane-1,2-diyl, butane Especially preferred are 2,2'-bis (2-oxazoline), bis (2-oxazolinylmethane), 1,2-bis (2-oxazolidinyl) ethane, 1,3- (1,4-diyl or phenylene). bis (2-oxazolidinyl) (propane, 1,4-bis (2-oxazolidinyl) bu L and η, 1,4-bis (2-oxazolinyl) benzene, 1,2-bis {2 -oxazolinyl) benzene; and 1,3-bis (2-oxazolinyl) benzene.

1 ´ r o d 1 t o o t o c t (a. Fine mixtures.

can also be used in an exemplary manner, compounds having at least three groups capable of forming esters (a 4) or their mutual with one another, optionally in a weight amount of about 0.01 to about 2o, preferably about 1 to about 2 up to about 10, especially about 3 to about 7, especially about 3 to about 5, each based on mixture (a1).

The compounds used as (n4) contain:. preferably 3 to 3 for functional groups capable of forming an ester linkage, in particular has a higher cost (a 4) and has it in the molecule 3 and in the thirty-one of the luliolo type, in particular 3 and e. ydiosyl groups and / or carboxyl groups. 1 and with advantageous use are three ·· ···· ♦ ·

I · · ·

l.J • • ·. J J J J J

functional and / or tetrafunctional carboxylic acids or their derivatives. Examples of acids such as tartaric acid, citric acid, malic acid, trimethylol propane, trimethylthane, pentaerythritol, polyglycerol, glycerol. trimesic acid, tritilic acid, trifluoric anhydride, pyromellitic acid, pyromotyric acid dianhydride and hydroxyisphthalic acid.

By adding the chain extender (aJ) and / or the compounds (a4), it is possible, for example, to vary the number or molecular viscosity of the melts. i.e., increasing the cut-off viscosity number and molecular weight as compared to polyesters without the supplied chain extender (a3) and / or compounds (a4). which, correspondingly, has a limit viscosity number and can be weight and weight

And I vary the mechanical properties of the polyesters accordingly, according to the specific application.

According to the invention, a film comprising biodegradable copolyesters (B1) having structural units derived from derivatives of both aliphatic and aromatic carboxylic acids is obtained by obtaining a reaction mixture comprising:

(a) a mixture

(a 11) 10 to 9 5 mo 1 % a 1 i f and t i c k e <1 i carboxylic acid i n y or c y k i o a 1 i Ial i c k e Boxes and Boxes k y s e 1 i 11 y n e o o e s terového d e r i v a t or j e j i c h and J from the m e n e s m e s i, (a12) 5 to 90 mo 1 3 aroiriat i c k e d i k a r b o x y 1 o e s e l i n v b e her e stero v é h o cl e r or J c J 1 c h h a r i s me s i, (a 13) υ up to 10 mol% s parting e η in y o b p a hu j i c i sul phon o. e s kupin y or him i c h in / a softly mixture i, 1) i m total jednot 1 i v y c h mo 1% Yippee 1 CJO, (a2) dih y d r o x .v p 1 o u c e n inu n customs) a m i no alcohol, or else c ti v z a - j c ni η ó mix with i, m i mo1 and others poillú t (a 1) to ( and 2) J c t), 4: 1 and 2.5: 1,

(a3) by weight and zO2, based on the mixture of the (a1) extender. (A4) 0 to 20% by weight, based on the mixture of (a1) a compound having at least three ester-forming groups, or mixtures thereof with one another (b) from 0.1 to 1% by weight, based on the mixture of (a1) hydroxycarboxylic acid (b1), which is defined by the following formula (IIa) or (IIb)

HO-1-C (O) —GOJ p H (Ha) • [—C (O) —G — O— J r 'where p is 1 to 1500, r is an integer of 1, 2. 3 or 4 and G a phenylene group, a -CHein- group, n an integer of 1, 2, 3, 4 or 5;

wherein the repeating units derived from (cyclo) and 1 ifatic and aromatic carboxylic acids are statistically separated, the copolyester having a viscosity number of 5 to 450 g / ml (measured in the o-dichlorobenzene / phenol system (weight ratio 5Ο / 5υ) at content by weight of 0.5% copolyester at 25 ° C).

In the above formula, p is preferably 1 to about 10000, preferably 1 or 2, preferably 1 or 5.

The trio content of the hydrocarbon acids (til) in the reaction mixture is preferably 1.1 to 30%, based on the mixture (a1).

J: i to o hyd r ox y and r boxes 1 o v y c h mash lin (lil) s e with v ý 1 i n v g1yko1 ové, ii-, 1. - , b, i.e. o - hyd io v e, j j c c y k i i c k y e h 11 e r i v a t u , such as gly k o 1 i d (i 2, 5 -d and he), 1-, L d i 1 and k t i d - i 3, () dime t hy 11.4 al i l i., i 1 II - p- hyd roben. not in and k y sel i n a and her o 1 igomers a [ίο 1 blame r y k y s e 1 i n a .1 Mon 1 y hydroxy has p e 1 n a, po 1 in val i 'o x y in a 1 e r t) In 1

i -al ion) after Iy and k t i d

¹ 9 ^ 9 · 999 999 999 999 999 9 999

9 • * 999 999 999 · 9 999 9 9 9

· * (Commercially available under the designation EcoPLA ^K Cargill) was added and after 3-1yhydroxymáse1 NE and 3-polyhydroxyvaIerové (commercial product El iopo I ^R solečnosti Zeneca) while using the above-defined derivatives of low molecular weight and cyclic derivatives.

Naturally, two or more of the hydroxycarboxylic acids defined above may also be used.

In addition, using cyclic derivatives of the above-described hydroxycarboxylic acids (b1) in reaction with a biodegradable copolymer used according to the invention, the ring-opening polymerization reactions known per se of copolyesters of the above type are obtained which contain block structures consisting of copolyester ( 13) used according to the invention, which are bound to each other by at least one hydroxycarboxylic acid unit (b1) (the ring-opening polymerization reaction is described in Encyk 1, opiate and of Polymer Science and Engineering, vol. 12, 2nd edition, John) Wiley & Sons, vol. 3b-41, 1938).

The opereomers which are preferably used according to the invention comprise components (a11), (a12) and (a2), which copolyesters may contain both the sulfonic acid groups Lac components (a3) and (a4) defined extenders

heavily and / or i tutoring n y. ú d a j e 1 s 1 u š no u s 1 o ž - answer quantity i Lech! O Ingredients in mo 1%: kyše 1 i n a t. e r e 1 1 and 1 o a ( 7 5) , ad i po v a (25) , neopentyIg 1 y k o 1 í 1 OO) acid i n a terci Pilová ( 7 0) , ad l after v a (J <)) . b u r and i o 1 (1 teaching)). k y s e 1 i n a terci 'L a 1 o a ( 70) , ad i (25) , i s o f L and 1 o v á (5), n c o - pe n L y 1 g 1 y k o 1 ( flax), k y s e 1 ι on the target ta 1 o v a ( 1) 0) , adi po v a (4o) , b u t a n d i o 1 (lotto. Ko po 1 y c L c i 'y, pou z i t e under 1 e in y n and c . they have us 1 o d u j i c i c ha -

r and kler i s1 i k v:

• ·

They have a viscosity number of about 5 to 450 g / ml, preferably about 100 to about 350 g / ml, and in particular about 200 to about 350 g / ml, each measured in the o-dichlorobenzene / phenol system (50/50 weight ratio) at weight content of 0.6% copolyester at 25 C.

For further details of (cyclo) aliphatic dicarboxylic acids, aromatic dicarboxylic acids, diols and / or aminoalcohol which may be used according to the invention and other components (a3), (a4) and (b1) reference is made to the aforementioned prior art, as well as to U.S. Patent No. 5,446,079 and to the parallel world publication WO 92/09654.

Optionally, a cellulose-containing material, a textile or oligocellulose material may be used as the film material in combination with a water-permeable polymer as described above. The cellulose-containing material useful in the present invention as a film comprises paper pulp and cellulose pulp, wherein the paper pulp raw materials may be wood, straw, cane, bamboo and bagasse. Pulp based on cellulose ethers and cellulose esters can be used as pulp for the production of man-made fibers. Such materials are described in detail in the literature (Cllmans Encyklopolisic der technischen Che-

lily, 4. tax , p. 17, p. 5 3 1 to 6 3 1 1979 pod header  l'ap i e r J e j í ž obsah j e taken over c e into context with Line 1 - 1 e earth. As f ó 1 i e under 1 e v y n á i e Z u 1 of: e L a usin g x L i 1ni ho ho- t e r i á l u. you suddenly text i int ma l e r i a l is always sick all three m a t e r i a y v e form i o u n a of 1 e X 1! 1 n e h v 1 á k e n v e f about the felt felt, all p lsti and ro him i. Text i 1 n i v 1 and k n i t mal mal e r i and 1 of which 1 z e po u z i l under 1 e you to 1 e z u k p i 'i p i a l e e x l i fed him t e r i a 1u pou - z i t c n e h o under 1 e v y n a 1 e Z ll J sou J ak p ri r from n even in 1 acna, like is- at k1 and b and in 1 n a and kapok t a k of names and p r umy a love pulled out in 1 anak,

• • ι __ __ __ __ __ __ __ __ __ __ ι __ __ __ __ __ __ __ __ __ __ __ __ __ __ Fibers such as regenerated cellulose fibers, cellulose acetate fibers, aiginates and 1-isoprene fibers, synthetic fibers such as fibers made from the above-defined polymers but also water-impermeable fibers of the water-impermeable polymers of the invention, such as polyethylene and polypropylene.

It is also possible to use an oligocellulose material.

The rate at which the nutrients are released from the manure according to the invention can be controlled not only by the film material, but also by the film thickness of about 500 μηι or less, preferably about approx. About 10 to about 100 μιη.

a selection-coated film which is normally harvested at most 200,

V dependent! At the same time, the nutrients contained in the intended purpose according to the invention are needed so that the foil both the crop, the crop and the vegetative volume of the ivu-containing substance are approximately at most 20 cm @ -1. approximate nejvzv 1 and s is preferably seams HODO 5 CTN ³ pi · ib 1 i of the n é provide a varnish of small quantities of NO U is controlled UVO 1ß s and Ni lat alkyl, approximately not more than 10 cm ^3, especially approximately at most 3 O, 5 cm ³ to about 2 cm more preferably cm ³ and ob. whereas nutrient-containing substances in nutrient-containing quantities in such quantities as to avoid unintentionally high doses or fillings of substances and to damage to the atrium. The lower volume limit of the wrapped according to the invention is about 0.01 tin ³ , preferably about 0.5 cm ³ .

The nutrient-containing substances which are contained in the foil of the packaged fertilizer according to the invention may be in the form of a powder, a granule, a capsule or a sugar.

Suitable nutrient-containing substances which can be used according to the invention are, in particular, oiganic or mineral fertilizers, as described, for example, in the book Dllmanns hrizyclopiidie der. chen Chemie, 5th edition, vol. A10, pp. 323-34, 1987 (particularly in Chapters 2.1 and 4).

Suitable fertilizers are, for example, direct and multicomponent fertilizers which contain either a single nutrient or a combination of nutrients such as nitrogen, potassium or phosphorus, optionally in the form of their salts. An example is NP fertilizer. NK, PK, and NPK, nitrogen containing direct fertilizers such as calcium nitrate, ammonium sulphate, ammonium nitrate and urea, as well as slow-release fertilizers, especially those based on urea, for example sobuty1 idendimocene, crotones 1 idend1urea and urea no / form 1dehyde condensate.

Other plant nutrients as well as trace elements may also be used, in addition to the aforementioned main constituents, lacquer fertilizers contain small amounts of magnesium, calcium, sulfur, iron, manganese, copper, zinc, cobalt, molybdenum and / or boron compounds. fertilization requirements.

Nutrient-containing substances can be used alone or in admixture with each other.

In addition to the nutrient-containing substances or mixtures thereof, the product may further comprise other additives, for example nitrification inhibitors, which have been described in the literature (for example, German Patent Application No. IJE-A 41 28 828, DE 195 03 8 2, 7,4 and DE < 31 > 764.9 and in the prior art cited in these publications) in particular pyrazoles or derivatives

pyr and zo i u, r e gu 1; t o i y r i s a a In this case it is used to o c h r a n grate 1 i n. for example1 ad 1 u n g i e i d y ins e k th i e y y hc r b i c d v. V y n a i e z, s also b 1 fo ii coated e h manure i , t V o r e n y e li ř a d o u i n d j v i d u a 1 n e po in 1 ee ny e h o b y e n y y s y s o s 2O cm ³ and I e s p o ii j e tl n e ! and t o i) and if u i i v i z i v y, is from J s o s e r /. e n v v J e d i) c ne bo v néko 1 i ka rov n o be z n yeti rad ach . 1 o z name on that h no j 1 in o O ba 1 e no 1 o 1 i i under 1 e v y n a 1 e / u miles of flat to [i tikl ad ve 1 o r me s η ů r in pe te 1

• · · · · · · · · · · · · · · · · · ·

I · · · ·

A series of such lines of beads arranged side by side, but also individual after cutting with a suitable device.

The invention further relates to a method for producing the foil coated fertilizer according to the invention, wherein:

a) at least one first and at least one second film consisting of a water-permeable polymer as defined above is introduced into the application device,

(b) depositing, with the aid of an application device, a series of volumes of not more than 2µ cm ^{3 of} at least one nutrient-containing substance on at least one first film, such that the volumes are separated by gaps;

c) joining at least one first film and at least one second film in the spaces between the volumes so that each of the volumes is individually coated, yielding a film-coated fertilizer.

For the method of the invention, the films are fed to the application device by means of a conventional feeding device, for example by means of a roller.

Once the film of water-containing polymer has been placed in the application device for applying the nutrient-containing substance, a suitable amount of the substance is applied to the first one of the first film, and it is essential that the volumes applied are in each case separated. of ram i.

According to Unity O p i o e d e n i v y n a 1 e z, u Yippee and 1 e one Surface and ρ1 i k and turn it from a i i z e n i • o b e e e at least j ed e 11 s h a n d e t h o o t metal surface. na k t e i e s e k 1 i I J 1 '(I c s po a one beers and and 1 e s po a n i d i u ha f o 1 i e, a n a k t e r e s c b c ti o in and [> 1 i duck i him P r o e s u z a - vřide j i p r i s 1 u s n e f o 1 i e d Vil i 1 I and p i i k and v and i him z a r i z n i k o n s t r u o a n la k that e has o pa l i e n y Fri o h 1 u b e n and us, t - I t and c and blows here n ad a 1e like 1. in general se za v á d ene 1 o 1 i o, k! _ U í c of'. , l k i y v d i d i s 1, v 1 i s ii - 1 i (1 o t e v L o dimples help wall OJI 'L i <i k u ii and ρ r i k i ad d i o is you 1 ·; -

• ·

·. · Η · _. Preferably, it is preferably a source of vacuum. The apertures of said surfaces preferably have at least a volume that corresponds to half the volume of the nutrient-containing substance to be applied. If the volume of the pits with which the first film is provided corresponds to half the volume of the nutrient-containing substance, at least the second film is introduced onto the surface within the applicator device. or is placed during the application process on a lacquer surface which is also provided with depressions, referred to herein as pits, whose volumes correspond to at least half the volume of the nutrient-containing substance.

Naturally, the process according to the invention can also be carried out

so that the surfaces on at least j e d n a p r v n i foil, at least one d r uhá foil. or a 1 e s p o ri j e d n a p r v n i and at least one mate foil inside and p 1 i k a c η í h o z i i z e n i. is ο- belonging to children 1 k y o b j e m is bigger i than half o b i c m u Ι <i i ky containing the nutrients it has b a t a p 1 and forged will. on at k- ice volume applied 1 and t k y contain i c i nutrients. v k t e 1 No. 111 7. t O When - The fall may be second foil o p a th e n a proportionately smaller d u i k y n e b o

has no indentations when applied to the first film

It's Led y po u z e need to post written f ó i e, klet po v 1 e k a j i h n o j i v o, t v o i y c e 1 c o s o c e, c klér čm mii ze by 1 here no of s t '' i h no j i v a saved o. Po c o n c o. 11 i p 1 n c n i a p 1 i k a c e s e s ho r a U v c d c 11 c i by 1 i Ι- in z - gently join at the limit era between volumes, which is general pi ο V C d C s 1 c - peri i m or v a r c n i in f o 1 i i ob y 1 yrn i z. [i u s o b y . hrome 1 o llo IIIO h o u 1> yL 1 o i i c Paint on in /, iem with bonded vacuum vc or c 1 c k i z o. i and i. i c k vin n and bo j cm. According to Jal. i h o z o c d c i i y a 1 e z, u se a years, pon j c ilna i ’1 May 11 1 1 o 1 i c a and 1 c a po ii j cd on d i ha ha 1 o 1 i c z, a they lead and Zaica. i z and c Z po v r c h j c o ρ a l i c n d k 1 k y. ob j cm k a z, d c ho d ϋ 1 k u from to Vlil a pel t i v 1 11 c o b j emu a ρ1 i metal a n c 1 a t o y b s a l i u j i c i z. I v i ny.

An apparatus, i.e. machines, with a series of dual-heated dies. which or side by side.

is preferably used are calenders. of said rollers, which are generally arranged above one another

In general, the process proceeds as follows:

In each case, at least one first film and at least one second film are fed from two sides onto a roll, the surface of which is provided with suitable dimples. The films are then introduced into the wells by a suitable device, for example a vacuum. Before being filled with a nutrient-containing substance, the films are brought into contact with each other at one point in the equipment used and joined together on one side. An appropriate amount (volume) of the nutrient-containing substance is then introduced.

the two films are brought into contact again once the application of the nutrient-containing substance is complete and re-bonded to one another, for example by gluing, welding, applying vacuum or electrostatic charge.

The invention with fertilizers, as in the above manner:

The invention also relates to a process for the preparation of film-coated films in which:

and) d o z a t r u b i proceeding from e a d e and 1 e s o d u p r o p u j e d n a sine 11 o p p r v π í f o 1ymer u ó 1 i e In this case c k. y which is from v (b) z a d C 'J i to help for in á d é c i h o z a i z e n i ř a d v ob him s e 20 cm ³ at least one 1 and L k y o b s a h u j j c i live ny do a i e s [i o n j e d n é fol 1ie in the form of i r u b i c k y so that o b j e m y J s o u o d d e 1 n y me z e r am i (c) u z and v i i á is preferably s 1 e g e in or sv a r e n i m < 1 e s after n) refilling 1 '6 1 i e in form L r ti 0 i c k .v s mez i pros Lor .In lile of 1 ob j cniy 11 i k. C k a ž d v of volumes is even nti i v i d u a 1 n e po v 1 e prices. Fri i mu /, 3 u /. i:. k i i manure i v o both 1 o 1 i i.

• »»

Claims (7)

If fertilizer coated 16111 in the form of individually coated nutrient-containing volumes is to be applied, the film-coated fertilizer obtained in operation c) of the process can be separated by cutting or perforating the film in the space gaps using a cutting or perforating device to obtain individual films of coated fertilizers, each having a volume of approximately not more than 20 cm ^{3 of the} nutrient-containing substance; in the case of perforations, the fertilizer coated units are separated when fertilizer is applied. The process according to the invention is advantageous. that performed continuously or after The invention also relates to films which are as follows: coated fertilizer, a) at least one first and one second film having a polymer of the above defined polymer is introduced into the application device; (b) application by means of an application device of a series of volumes not exceeding 20 cm ³ at least: one in it {'oh 1 anyway, that volumes j are separated we are not even l, c i connections is with e a 1 e s p o j e d n a p r v n i f o 1 i c and at least j e d n a d r u h a f ó1 i e in me crách between o bjemy Lak - Z c each of the ob j c ni u j e i n - d i v i d u á 1 n e coated, ex and that is of 1 s k a f o 1 i i o b a 1 e n e h n o j i v o and it further concerns k c f o i i i o 1) a 1 e n e ho li n o J i v a . k t c r e j e v y r o b i i 1 n e following from [) s o e e: a) to the equipment will be introduced at least j e d on p i v n i 1 o 1 i e of form tubes k .v, k l c z a j e /. Introduction to the im pii s i 11 e ii U po iymei U. b) .the porn has been introduced, whether or not the country of the highest volume of sc • • · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · 20 cm @ -1 of at least one nutrient-containing substance in at least one tube-like foil such that the volumes are separated by an c) is preferably closed by gluing or welding at least one film in the form of a tube with intermediate spaces between the volumes such that each of the volumes is individually wrapped around the film. coated to obtain The invention further relates to a fertilization method in which the fertilizer-coated film according to the invention or the film-coated fertilizer prepared by the process according to the invention is applied, mixed with or incorporated into the substrate or with the ground. in iůmysloya yyuz i iei nost The production of a fertilizer, wrapped foil, which slows the release of nutrients to the soil, the rate of release of the nutrients being controlled by the choice of coating and its thickness. • * -11 • • • · · · • · • · • · · £ 4 · - • • • · • · • • • • • · · • · • · • • · • • • · • · · • · · • • • • • • • • • • · · • · «· i A T ί. X CLAIMS 1. Fertilizer wrapped with a foil with a targeted release of nutrients, characterized by: comprising one or more individually coated volumes of not more than 2υ cm ^{3 of} at least one nutrient-containing substance, wherein the film-coating of at least one nutrient-containing substance is a water permeable polymer, cellulose-containing material, textile material, lignocellulosic material or a combination of two or more such materials . 2. Foil wrapped fertilizer according to claim 1, characterized in that the water-permeable polymer is biodegradable. ii. The film-coated fertilizer according to claim 1 or 2, characterized in that the film-coated fertilizer is in the form of a series of individually coated volumes of at most 20 cm ^{3 of} at least one nutrient-containing substance arranged in a row or in several parallel rows. Way z n a v y rob y h n o j i v a e i s wrapped foil according to claim 1 to 2, c u J 1 e by that e v i i p AND cl o a p 1 i k and C η i him equipment at least one first and a- e with it j e d n a d r u h á f o i i e of assemblies and j i e í z v o d u p o [i u s t h o s h o - a d e i i O1 o v and n e him po i yme r u, and n o š o n í s e help ap1 i k and k it him z a i i z e n even a series of volumes at most υ cm ³ ί e s po n j e d n e substances containing nutrients for a 1e with po e d n u p r in 11 1 Id 1 ii lak. from volumes j SHOW odd 1 e n y me z e r am i, poJ U J O :E and forest p rd to pi in it ld 1 i e ťi and 1 e s to <1 r u há o 1 i c v ine /. e i. i c h not z i ob | emy lak, /. e k a d y o o j j jiiii j e i n - i v i d u a i ii e po v 1 e e e ii, i s e z i k a 1 o 1 i i both 1 e e e e t i i o i • · The method according to claim 4, characterized in that at least one first film, at least one second film or at least one first film and at least one second film film are each introduced on at least one surface disposed within the applicator and provided with a pulp and p1. The pleats that cover the pits of the at least one first film and the at least one second film or the at least one first and at least one second film are pressed into the pits by a pressure source. A method according to claim 4 or 5, characterized in that at least one first film and at least one second film are fed to a roll having a surface provided with dimples. 7. A method according to claim 4, characterized in that, after filling with at least one nutrient-containing substance, at least one first film and at least one second film are bonded together by vacuum, electrostatic charge, gluing or welding the film in gaps between volumes. A process for the production of a film-coated fertilizer according to claims 1 to 1, characterized in that it is screened. ž e a) at least one first film in the form of a water-polymeric tube is introduced into the apparatus, b) introducing the insertion device by means of a series of not more than 20 ^cm-1 at least once laymen containing nutrients into at least one sheet in the form of a tube so that the volumes are separated me that the frame i, C) u z a v i i a is preferably . 1 e pe n i iii or sva r e η í m at least j f o 1 i e v lrub i c k \ ii ic of i p i o s L o r y not from i o b j em y Lak everybody from ob is π iii is i nd i v i il u a 1 and c po v e e c e n, p i ieemz. se z hno j i o o coated with 1 i I. z. i skli i 'u j i i Z ϋ o pod Ic r ii Ic Ic ► ► ► _ _ _ _ _ _ · · · · · · · · · < that they come in a long time d) cuts or perforates the sheets in the gaps between the volumes of the fertilizer wrapped with the sheet, the cutting or perforating device. 10. A fertilizer method according to claim 1, wherein the film-coated fertilizer according to claim 1 is applied to the soil, mixed with or incorporated into the soil. or up to 3 or a sheet of claim 4 to 4 9, with the ground or