Multifunctional coating films that can be applied in liquid form

Abstract

Multifunctional coating films that can be applied in liquid form are provided for compressing, sealing, covering and preserving surfaces. The films include a composition of polysaccharide materials and/or homo- or heteroglycan water-soluble polysaccharide derivatives, polyol spacers, and crosslinkers with carbonyl or carboxylic function(s). As-applied, the composition is water-soluble and reactive, but after hardening it is capable of absorbing water or swelling, impermeable to water vapour, stable against water and UV and can be biologically degraded in a controlled manner. By reacting polysaccharide materials, polysaccharide derivatives and polyol spacers with cross linkers having carbonyl or carboxylic function(s), mechanically stable flexible films are obtained, which retain their mechanical properties up to a foreign material content of 80%. The films can swell in a controlled manner and can bind up to 75% water relative to their dry weight, corresponding to the degree of crosslinking and the spacer that is used.

Claims

1. Multifunctional coating films that can be applied in liquid form for consolidation and waterproofing, for covering and also for preserving surfaces, wherein said films comprise a composition of water-insoluble, polysaccharidic materials and/or homo- or heteroglycan water-soluble polysaccharide derivatives, polyol spacers and crosslinkers having at least one carbonyl or carboxyl function, wherein the crosslinkers are dialdehydes, ketones, diketones, di-, tri- or tetracarboxylic acids and the dialdehydes comprise glyoxal, glutardialdehyde or terephthaldialdehyde, the composition at the time of the application thereof is water soluble and reactive, after the curing thereof remains water absorbent or swellable, water vapor permeable, water stable and UV stable, is biodegradable and has incorporated functional additives, and the polysaccharidic materials and/or polysaccharide derivative and polyol spacers have been reacted with the crosslinkers to a degree that leaves free crosslinker functionalities which can crosslink with functional groups of the surfaces that are to be coated.

2. The multifunctional coating films that can be applied in liquid form as claimed in claim 1, wherein the polyol spacers are aliphatic, cyclic or aromatic polyols.

3. The multifunctional coating films that can be applied in liquid form as claimed in claim 2, wherein the polyol spacers are ethylene glycol, propanetriol, triethylene glycol, polyethylene glycol, sorbitol, glucose, fructose, galactose, cyanidin, corilagin, digallic acid, gallic acid or tannic acid.

4. The multifunctional coating films that can be applied in liquid form as claimed in claim 2, wherein the polyol spacer is tannic acid, and the resulting film exhibits herbicidal and fungicidal properties.

5. The multifunctional coating films that can be applied in liquid form as claimed in claim 1, wherein the crosslinkers are ketones.

6. The multifunctional coating films that can be applied in liquid form as claimed in claim 5, wherein the crosslinkers are acetone or acetylacetone.

7. The multifunctional coating films that can be applied in liquid form as claimed in claim 1, wherein the polysaccharidic materials are of natural or synthetic origin.

8. The multifunctional coating films that can be applied in liquid form as claimed in claim 7, wherein the polysaccharidic materials are recycled cellulose in the form of milled waste paper.

9. The multifunctional coating films that can be applied in liquid form as claimed in claim 1, wherein the water-soluble polysaccharide derivatives are cellulose ethers or starch derivatives.

10. The multifunctional coating films that can be applied in liquid form as claimed in claim 9, wherein the cellulose ethers are hydroxyalkyl celluloses, methyl celluloses or carboxymethyl celluloses and the starch derivative is hydroxyethyl starch.

11. The multifunctional coating films that can be applied in liquid form as claimed in claim 1, wherein the films are a swellable waterproofing layer, the film swellability is affected by the polyol spacer type and, as hydrogel, can bind up to 75% by weight water, based on dry matter thereof, corresponding to a degree of crosslinking, without losing its waterproofing layer property.

12. The multifunctional coating films that can be applied in liquid form as claimed in claim 1, wherein the films retain their mechanical properties up to a foreign matter content of 80% by weight.

13. The multifunctional coating films that can be applied in liquid form as claimed in claim 1, wherein a concentrated aqueous dispersion having a viscosity>2.0 Pa s is storable for at least two years without change in properties, the films comply with construction material class B2, the films have an airtightness, at a material usage of 1 l/m.sup.2, that reaches a value of 0.7-1.2 /h, an so value of 0.7-1.4 m is measured for the resistance to diffusion of the films, and the films have an extensibility, without detachment from a surface, at a stress up to 55 N/mm.sup.2, of between 30 and 60%.

14. The multifunctional coating films that can be applied in liquid form as claimed in claim 1, wherein the films in solid form have overpaintability or overworkability, and adhere to wood, paper, glass, plaster and metal.

15. The multifunctional coating films that can be applied in liquid form as claimed in claim 1, wherein said films are applied as a functional layer for consolidation and waterproofing, for covering and also for preserving surfaces.

16. The multifunctional coating films that can be applied in liquid form as claimed in claim 15, wherein the surfaces are building claddings and wood structures in the roof region or at sites of elevated formation of condensate water.

17. The multifunctional coating films that can be applied in liquid form as claimed in claim 1, wherein said films have herbicidal, fungicidal, insecticidal and acaricidal properties.

18. Soil stabilizer, soil covering and unwanted growth suppressant in the agricultural and gardening sectors comprising the multifunctional coating films that can be applied in liquid form as claimed in claim 1, wherein, and the film's residence time in the soil is adjustable depending on the crosslinker composition/degree of crosslinking and degree of substitution.

19. The multifunctional coating films as claimed in claim 1, wherein the degree of reaction is less than 81%.

20. A method for producing multifunctional coating films that can be applied in liquid form on the basis of polysaccharidic materials, comprising forming an aqueous dispersion by mixing dispersible polysaccharidic materials in solid form with polyol spacers and with crosslinkers which have one or more carbonyl and/or carboxyl functions, wherein the crosslinkers are dialdehydes, ketones, diketones, di-, tri- or tetracarboxylic acids and the dialdehydes comprise glyoxal, glutardialdehyde or terephthaldialdehyde and incorporating functional additives in a one-pot synthesis with water as solvent to form an initially storage-stable aqueous dispersion, wherein the polysaccharidic materials and/or polysaccharide derivatives and polyol spacers have reacted with the crosslinkers to a degree that leaves free crosslinker functionalities which can crosslink with functional groups of the surface that are to be coated, applying the dispersion as a liquid coating film to surfaces in an acid medium, and crosslinking quantitatively via acetals or ketals, wherein all chemical reactions proceed in the solvent water and the crosslinking takes place at temperatures from 10 C.

21. A method as claimed in claim 20 for producing coating films that can be applied in liquid form on the basis of polysaccharide materials, wherein the polysaccharide materials are cellulosic materials and/or water-soluble polysaccharide derivatives.

22. A method as claimed in claim 21 for producing coating films that can be applied in liquid form on the basis of polysaccharide materials, wherein the water-soluble polysaccharide derivatives are hydroxyethyl celluloses, methyl celluloses, carboxymethyl celluloses and hydroxyethyl starches.

Description

EXAMPLE 1

(1) For synthesis of the coating films that can be applied in liquid form, a 0.1 to 1 molar, preferably 0.4 to 0.5 molar, solution of the cellulose derivative in water is produced, mixed with the same amount of recycled cellulose and acidified using concentrated acetic acid to a pH of 2 to 6, preferably 4 to 5, and admixed with 0.05 to 0.5 mol, preferably 0.1 to 0.3 mol, of glyoxal, based on a 40% strength solution, stirred for 10 min at a temperature of 20 to 50 C., preferably 20 to 30 C., and then 0.1 to 0.5 mol, preferably 0.2 to 0.4 mol of the polyol component is added, and the mixture is stirred for 3 hours at 20 to 50 C., preferably 30 to 40 C. The reaction mixtures thus produced are partially crosslinked, still water-soluble products having viscosities between 0.68 and 1.46 Pa s in a temperature gradient from 15 to 30 C. After dilution with water in the ratio 1:5, an atomizable solution is obtained which is suitable as vapor barrier for wood structures. The concentrated product is storable for at least two years without change in properties.

EXAMPLE 2

(2) A 0.1 to 0.5 molar, preferably 0.3 to 0.4 molar, solution of the polyol component in water is adjusted to pH 3 to 6, preferably 4 to 5, using acetic acid and admixed with 0.1 to 0.5 mol, preferably 0.3 to 0.4 mol, of glyoxal, based on a 40% strength solution, stirred for 20 min at a temperature of 20 to 50 C., preferably 30 to 40 C., and admixed with a 0.1 to 1 molar, preferably 0.4 to 0.5 molar, aqueous solution of the cellulose derivative which had been mixed with the same amount of recycled cellulose, and the mixture is stirred for 4 hours at a temperature of 20 to 50 C., preferably 30 to 40 C. The reaction mixtures thus produced are partially crosslinked, still water-soluble products having viscosities between 0.72 and 1.32 Pa s in a temperature gradient from 15 to 30 C. After dilution with water in the ratio 1:6, an atomizable solution is obtained which is suitable as vapor barrier for wood structures. The concentrated product is storable for up to two years without, change in properties.

EXAMPLE 3

(3) A 0.1 to 1 molar, preferably 0.4 to 0.6 molar, aqueous solution of the cellulose derivative is adjusted to pH 3 to 6, preferably pH 4 to 5, using acetic acid and admixed, with 0.5 to 1.5 mol, preferably 0.8 to 1.2 mol, of glyoxal, based on a 40% strength solution, and the mixture is stirred for 10 min at a temperature of 20 to 50 C., preferably 30 to 40 C. Subsequently, 0.1 to 0.6 mol, preferably 0.3 to 0.5 mol, of an aromatic polyol, preferably tannic acid, is added thereto and the mixture is stirred for a further 60 min at a temperature of 20 to 50 C., preferably 30 to 40 C. This partially crosslinked, still water-soluble product, in addition to the property of film formation, still has a herbicidal action against monocotyledonous and dicotyledonous plants.

EXAMPLE 4

(4) For the synthesis, a 0.1 to 1 molar, preferably 0.4 to 0.5 molar, solution of the cellulose derivative in water is produced, acidified to a pH of 2 to 6, preferably 4 to 5, using concentrated acetic acid and admixed with 0.1 to 0.5 mol, preferably 0.2 to 0.3 mol, of glyoxal or glutardialdehyde, based on a 40% strength solution, the mixture is stirred for 10 min at a temperature of 20 to 50 C., preferably 20 to 30 C., to this solution, then 0.1 to 0.8 mol, preferably 0.3 to 0.6 mol, of an aromatic polyol, preferably tannic acid, is added, and the mixture is stirred for a further 60 min at a temperature of 20 to 50 C., preferably 30 to 40 C. The still water-soluble product, in addition to the property of film formation, still has a fungicidal action against. Ceratocystis sp. Heterobasidium annosum, Disculapinicola, Fungi imperfecti, and Candida albicans. [Table 2] [Determination as specified in DIN 58940-84, issue date: 2002-October Medical microbiologysensitivity testing of microbial pathogens to chemotherapeuticspart 84: Microdilution; special requirements for testing fungi against antimycotics]

(5) TABLE-US-00002 TABLE 2.1 Fungicidal action of HEC-Corilagin at a degree of substitution of 0.35 HEC-Corilagin Ceratocystis Heterobasidion Discula Fungi Candida 10 g sp. annosum pinicola imperfecti albicans Inhibition zone diameter 21 27 22 18 26 [mm]

(6) TABLE-US-00003 TABLE 2.2 Fungicidal action of HEC-Cyanidin at a degree of substitution of 0.35 HEC-Cyanidin Ceratocystis Heterobasidion Discula Fungi Candida 10 g sp. annosum pinicola imperfecti albicans Inhibition zone diameter 16 19 14 13 11 [mm]

(7) TABLE-US-00004 TABLE 2.3 Fungicidal action of HEC-Digallic at a degree of substitution of 0.35 HEC-Digallic acid Ceratocystis Heterobasidion Discula Fungi Candida 10 g sp. annosum pinicola imperfecti albicans Inhibition zone diameter 18 27 29 16 13 [mm]

(8) TABLE-US-00005 TABLE 2.4 Fungicidal action of HEC-Corilagin at a degree of substitution of 0.7 HEC-Corilagin Ceratocystis Heterobasidion Discula Fungi Candida 10 g sp. annosum pinicola imperfecti albicans Inhibition zone diameter 34 41 37 28 39 [mm]

(9) TABLE-US-00006 TABLE 2.5 Fungicidal action of HEC-Cyanidin at a degree of substitution of 0.7 HEC-Cyanidin Ceratocystis Heterobasidion Discula Fungi Candida 10 g sp. annosum pinicola imperfecti albicans Inhibition zone diameter 22 31 21 19 14 [mm]

(10) TABLE-US-00007 TABLE 2.6 Fungicidal action of HEC-Digallic acid at a degree of substitution of 0.7 HEC-Digallic acid Ceratocystis Heterobasidion Discula Fungi Candida 10 g sp. annosum pinicola imperfecti albicans Inhibition zone diameter 28 38 39 21 18 [mm]

EXAMPLE 5

(11) A 0.4 to 1.0 molar, preferably 0.6 to 0.8 molar, aqueous solution of the polysaccharide derivative is acidified to a pH of 2.5 to 6.5, preferably 4 to 5, using concentrated acetic acid, and is then admixed with acetone until the water-soluble polysaccharide derivative starts to precipitate out. The still clear solution is stirred for 1 hour at 35 to 55 C., preferably 50 C., and thereafter admixed with 0.4 to 0.9 mol, preferably 0.7 mol, of an aqueous solution of an aromatic polyol, preferably tannic acid, and stirred for a further 20 to 40 min, preferably 30 min, at this temperature. The still water-soluble product, after the complete removal of water from the reaction system, forms water-insoluble flexible films.

EXAMPLE 6

(12) A 0.2 to 1.2 molar, preferably 0.8 to 1.0 molar, aqueous solution of the polysaccharide is acidified to a pH of 3 to 7, preferably 4 to 6, using concentrated acetic acid and is then admixed with acetylacetone until the water-soluble polysaccharide begins to precipitate out. The still clear solution is stirred for 2 to 6 hours, preferably 4 hours, at a temperature of 40 to 80 C., preferably 60 C., and thereafter admixed with a 0.8 to 1.2 molar, preferably 1 molar, aqueous solution of an aromatic polyol, preferably tannic acid, and stirred for a further 60 to 120 min, preferably 80 min, at this temperature. The still water-soluble product, after the complete removal of water from the reaction system, forms water-insoluble flexible films.