EP1943319A1

EP1943319A1 - Production of coated substrates

Info

Publication number: EP1943319A1
Application number: EP06778205A
Authority: EP
Inventors: Edwin Nun; Heike Bergandt; Hannelore Armoneit; Marie-Theres Wilkes; Thomas Schrief
Original assignee: Evonik Degussa GmbH
Current assignee: Evonik Operations GmbH
Priority date: 2005-11-03
Filing date: 2006-08-10
Publication date: 2008-07-16
Also published as: JP5069243B2; WO2007051662A1; US20080292799A1; JP2009514661A; RU2008121876A; DE102005052939A1; US7993707B2; NO20082450L

Abstract

The invention relates to methods for coating substrates, comprising the following steps: a) a substrate is provided; b) a composition is applied to at least one surface of the substrate, said composition containing a silane of general formula (Z1)Si(OR3), wherein Z1 represents OR or GIy (Gly=3-glycidyloxypropyl), R represents an alkyl radical with 1 to 6 carbon atoms, and all R can be identical or different, an inert solvent, and an initiator, said inert solvent having a boiling point which lies within a range of 50 °C above or below the drying temperature of step c) in the drying conditions of step c), the minimum boiling point of the inert solvent being 80° C in the drying conditions of step c); and c) the composition applied in step b) is dried at a drying temperature of 100 °C to 250 °C. Also disclosed is a coated substrate that is obtained by means of said method.

Description

Production of coated substrates

The present invention relates to a process for coating substrates, as well as coated substrates, obtainable by the aforementioned process.

There is a need in the art to alter or improve the surface properties of substrates through coatings. In particular, the hardness or the resistance to aggressive substances can be improved by coatings. The substrates that may be considered for such a surface treatment can be extremely versatile. First, there is a need for building materials, such as stones or tiles, to prevent contamination. On the other hand, it is also possible that an increased resistance to aggressive substances, such as chemicals, should be achieved. There are also efforts to avoid the tendency of such materials to become soiled by coatings.

On the other hand, there is also the possibility in the field of woven and knitted fabrics of improving surface properties through coatings. This is particularly the case if, for example, the stability of a composite is ensured by the underlying substrate, but the resistance to aggressive substances or the tendency to foul the underlying substrate is low.

One way to apply a coating is the SoI-GeI process. Here, a composition is applied to the substrate, which subsequently hardens and thus forms a stable composite. In particular, in the known sol-gel process has the problem that during curing, the solvent used must be removed from the coating in order to achieve a curing or crosslinking of the coating. Due to the chemical and physical processes that occur during curing, the resulting layer has structural defects which can lead to cracks. This is problematic since the commonly used sol-gel coatings are only a few 100 nm thick. The porosities within the resulting layer due to the curing and crosslinking reactions then often lead to cracks. These resulting cracks and pores can be reduced by targeted sintering, ie a heat treatment. However, with higher layer thicknesses, the problem arises that once cracks have formed can not be removed by further tempering. In the production of thicker layers, it is therefore necessary to apply multiple coatings. One way to positively affect cracking is disclosed in US 5,076,980, which has found suitable drying conditions not only in terms of temperature but also in terms of relative humidity at which the coated substrate dries.

The technical object underlying the present invention is to provide a process for coating substrates with sol-gel coatings, in which high layer thicknesses can be achieved in which no cracks occur, wherein the application of multiple coatings should be avoided , A further object of the present invention is the provision of a coated substrate in which the coating applied with a sol-gel process is free of cracks.

The technical object of the present invention is achieved by a method for coating substrates, comprising the steps:

a) provision of a substrate,

b) application of a composition on at least one surface of the substrate, the composition contains a silane of the general formula (Z1) Si (OR3), wherein Z1 is OR or Gly (Gly = 3-glycidyloxypropyl) and R is an alkyl radical having 1 to 6 carbon atoms and all R may be the same or different, an inert solvent and an initiator, wherein the inert solvent under the drying conditions of step c) has a boiling point in a range of 50 ⁰ C above or below the drying temperature of step c) and the boiling point of the inert solvent under the drying conditions of step c) is at least 80 ⁰ C, and

c) drying the composition applied in step b) at a drying temperature of 100 ^° C. to 250 ^° C.

The process of the present invention is not limited to any specific substrates. The substrates can be both open-pored and closed-pore. The substrates should show no change at the selected drying temperature of step c), ie be thermally stable at these drying temperatures.

The substrate may be an open-pore or closed-pore substrate. In particular, it is possible that the substrate may be a woven fabric, a knitted fabric, a film, a tile, a stone or a metallic substrate.

In a preferred embodiment, the composition of step b) contains a second silane having the general formula (Z2) zSi (OR) 4-z, wherein R is an alkyl radical having 1 to 6 carbon atoms and Z2 is HaFbCn, where a and b are integers, all Rs may be the same or different, a + b = 1 + 2n, z = 1 or 2, and n is 1 to 16, or in the case where Z1 is GIy, Z2 Am (Am = 3-aminopropyl) with z = 1.

The composition of step b) preferably comprises 3-glycidyloxypropyltriethoxysilane and / or 3-glycidyloxypropyltrimethoxysilane as the silane and / or 3-aminopropyltrimethoxysilane and / or 3-aminopropyltriethoxysilane as the second silane.

More preferably, in the composition of step b), the silane is tetraethoxysilane and the second silane is a silane of the formula (HaFbCn) zSi (OR) 4-z, where a and b are integers, a + b = 1 + 2n is, z is 1 or 2, n is 1 to 16 and all R may be the same or different, preferably all R are the same and contain from 1 to 6 carbon atoms. Preferably in the composition of step b) tetraethoxysilane, methyltriethoxysilane, octyltriethoxysilane and / or hexadecyltrimethoxysilane as silane and / or 3,3,4,4,5,5,6,6,7,7,8,8,8 Tridecafluorooctyltriethoxysilane as the second silane.

As the inert solvent, any solvent having a corresponding boiling point can be used. The inert solvent in a preferred embodiment does not substantially react with the other components of the composition of step b). Rather, surprisingly, a homogeneous, pore and crack-free surface is produced on the substrate by the inert solvent. At the selected drying temperatures of step c), the inert solvent evaporates from the coating. It is believed that the evaporation of the inert solvent, the flexibility of the curing and crosslinking composition of step b) is guaranteed longer, so that initially forms a solid structure and only completely evaporated after formation of the solid structure, the inert solvent.

In a preferred embodiment, the inert solvent under the drying conditions of step c) has a boiling point in the range of 4O ⁰ C above or below the drying temperature of step c), more preferably in the range of 30 ⁰ C above or below the Drying temperature of step c), more preferably in the range of 2O ⁰ C above or below the drying temperature of step c) and most preferably, the boiling point of the inert solvent is in a range of 10 ⁰ C above or below the drying temperature of step c). Preferably, the boiling point of the inert solvent under the drying conditions of step c) is almost identical to the drying temperature of step c).

The inert solvents used can be any of a wide variety of inert solvents. The inert solvent may be selected depending on the drying temperature of step c). In a preferred embodiment, the inert solvent is selected from the group consisting of alcohols, formamides, ketones, ethers and mixtures thereof. In a further preferred embodiment the inert solvent is not water.

The amount of inert solvent in the composition of step b) is not further limited. In a preferred embodiment, based on the total molar amount of silane of the composition of step b), 0.1 to 200 mol% of inert solvent. In a further preferred embodiment, 0.2 to 160 mole%, more preferably 0.5 to 150 mole%, and most preferably 1.0 to 100 mole% of inert solvent is included in the composition of step b).

Preferably, the inert solvent under the drying conditions of step c) has a boiling point of at least 90 ⁰ C, more preferably of at least 100 ⁰ C, in particular of at least 11O ⁰ C and most preferably of at least 120 ° C.

The composition of step b) further contains an initiator. The initiator in a preferred embodiment is an acid or a base which is preferably an aqueous acid or base.

If an acid is used as the initiator, so much acid is preferably used that the resulting sol has a calculated pH of 2 to 6. If a base is used as the initiator, so much base is preferably used that the resulting sol has a calculated pH of 8 to 11. The aqueous base or acid is preferably added in such a way that the molar ratio of water to compounds of the formula (Z1) 1Si (OR) 3, in particular GlySi (OR) 3 in the preparation of the mixture of 100,000: 1 to 10: 1, preferably from 1000: 1 to 100: 1.

In the composition of step b), in a preferred embodiment at least one further solvent may be present, which preferably has a lower boiling point than the inert solvent. Preferred further solvents are low-boiling alcohols, such as, for example, ethanol or isopropanol. In the composition of step b) at least one further additive may be included. As additives, it is possible to use all compounds which are familiar to the person skilled in the art in connection with sol-gel coatings.

More preferably, in the composition of step b) oxide particles, selected from the oxides of Ti, Si, Zr, Al, Y, Sn, Ce or mixtures thereof, may be contained. The oxide particles may preferably have a hydrophobic surface. Preferably, on the surface of the oxide particles are bonded to silicon atoms bonded organic radicals X1 + 2nCn, wherein n is 1 to 20 and X is hydrogen and / or fluorine.

If the oxide particles have a hydrophobic surface, it is preferable to partially hydrolyze the surface of the oxide particles under the reaction conditions of the sol-gel formation of the present invention. In this case, reactive centers are preferably formed which react with the organic silicon compounds of the composition from step b). These organic silicon compounds are covalently bound to the oxide particles during curing by z. B. -O bonds bound. As a result, the oxide particles are covalently crosslinked with the hardening sol-GeI. Surprisingly, the layer thickness of the cured layer can be further increased thereby.

The oxide particles may have an average particle size of 10 to 1,000 nm, preferably 20 to 500 nm, more preferably 30 to 250 nm.

If the coating is to be transparent and / or colorless, it is preferred to use only oxide particles which have an average particle size of from 10 to 250 nm. The mean particle size refers to the size of the primary particles or, if the oxides are present as agglomerates, to the size of the agglomerates. The particle size is determined by light scattering methods, for example by a device of the type HORIBA LB 550® (Retsch Technology).

The composition of step b) may be applied to the substrate by various well-known methods. In particular, the composition may, for example, be doctored, brushed, rolled up, sprayed on or by immersing the substrate in the composition.

The drying of the composition in step c) can be carried out by any method known to those skilled in the art. In particular, the drying can be carried out in an oven. Particularly preferred are a convection oven, an infrared field and / or a microwave radiator. In a preferred embodiment, the drying temperature during the drying in step c) is substantially constant and preferably constant. This means that preferably, for example, an oven is heated to the desired drying temperature, and that the substrate on which the composition of step b) is applied is introduced into the preheated oven. After the desired drying time, which is necessary to dry and optionally cure the applied composition, the coated substrate is removed from the drying unit.

The drying times are not limited. However, they should be chosen so that complete removal of the solvent from the applied coating is possible. The drying time of step c) is preferably between 1 minute and 3 hours.

In a preferred embodiment, so much of the composition is applied to the substrate in step b) that after drying in step c) a layer of the dried composition having a layer thickness of 0.05 to 10 μm is present on the substrate. Preferably, a layer having a layer thickness of from 0.1 μm to 9 μm, more preferably from 0.2 μm to 8 μm, and most preferably from 0.3 μm to 7 μm, is present on the dried substrate.

The coated substrate of the present invention surprisingly shows a very high freedom from cracks, wherein in a preferred embodiment substantially no cracks are present in the coating.

The chromium oxide oil test according to DIN EN ISO 10 545-14 is a test for the proof of crack-freeness. Here, chromium oxide, which has a green color, to the applied coating. After removal of the chromium oxide in accordance with the procedure specified in DIN EN ISO 10 545-14, the degree of discoloration of the coating is an indicator for the pore or crack-free surface. The coatings of the invention show a very high pore and crack-free surface, so that the chromium oxide oil can be removed almost without residue.

Thus, the substrates coated with the process of the present invention show an improved coating compared to the prior art coatings. In particular, it is surprisingly possible to apply thicker coatings, avoiding multiple application in a multi-coating process. The coatings of the present invention can be used as scratch-resistant coatings on polymeric fabrics as well as for the sealing of natural stones.

In a preferred embodiment, at least one further coating can be applied before application of the composition in step b). This coating can, for example, a print, such. B. be a design print.

In a further preferred embodiment, at least one further coating can be applied after application of the composition in step b). This further coating can also be applied after the drying in step c). This further coating can, for example, a printing, such. B. be a design print.

Thus, a coated substrate obtainable by the method described herein has many uses. In particular, avoiding multiple coatings makes it possible to manufacture coated substrates more efficiently. Examples

Example 1: From 25.5 g of 3, 3,4,4,5,5,6,6, 7,7,8,8,8-tridecafluorooctyltriethoxysilane, 4.45 g of 3-glycidyloxypropyltriethoxysilane and 83.2 g of tetraethylorthosilicate a mixture made.

To the o. A. 17.44 g of a dispersion of 4 g of a hydrophobic flame-hydrolytically produced silica (AEROSIL® R8200 of

Degussa AG) in 2-pentanone (b.p .: 102 ⁰ C). The dispersion of silica and 2-pentanone was prereacted by mixing the silica for 1 minute and 2-

Pentanone produced under ultrasound and has a concentration of 10 wt .-% on. The particle size distribution of the dispersion was determined by means of light scattering on a particle size measuring device from Horiba. Here are the following

Values found: D50 = 109 nm, 10% = 61 nm, 90% = 189 nm. The dispersion has a zeta potential of -6.03 mV at a magnitude of 211674 mV.

After adding the dispersion to the mixture, 5.45 μl of 63% nitric acid are added with stirring. Subsequently, 3.2 g of 3-aminopropyltriethoxysilane are added with vigorous stirring, care being taken that the temperature of the reaction mixture does not exceed 40 ^° C. The resulting sol is stirred for 48 h.

A marble slab "Carrara Antik" measuring 7.5 x 7.5 cm is cleaned with a detergent using a brush and water, then the slab is dried for 24 h at 60 ^° C. and then cooled in a desiccator.

The SoI applies a 50 μm thick layer to the stone plate in a hand-held frame. The coated stone slab was allowed to stand for 1 h at room temperature and then heated to 150 ^° C. for 15 minutes. After 24 h, the coating was characterized. The coating shows after drying and hardening a mean layer thickness of about 20 microns.

Assessment of surface properties:

A drop of water is applied to the coating. This water droplet does not penetrate the coating, but remains on the coating.

The chromium oxide oil test according to DIN EN ISO 10 545-14 shows that Cr2O3 can be completely removed after an exposure time of 24 h. There are no discolorations.

Comparative Example 2:

With the exception that instead of 2-pentanone ethanol (bp.: 78 ° C) is used for the preparation of the silica dispersion, a stone slab is otherwise coated according to Example 1.

Assessment of surface properties:

A drop of water is applied to the coating. This water droplet penetrates into the coating.

The chromium oxide oil test in accordance with DIN EN ISO 10 545-14 shows that Cr2O3 can not be completely removed after an exposure time of 24 hours. The Cr2O3 leaves green patches in the resulting pores and holes of the coating.

In summary, it can be stated that substrates can be provided with a crack-free coating by the method of the present invention. The coating of the present invention is resistant to environmental influences and provides secure protection of the underlying substrate.

Claims

claims

1) Method for coating substrates, comprising the steps:

a) provision of a substrate,

b) application of a composition on at least one surface of the

Substrates, the composition contains a silane of the general formula (Z1) Si (OR3), wherein Z1 is OR or Gly (Gly = 3-glycidyloxypropyl) and R is an alkyl radical having 1 to 6 carbon atoms and all R may be the same or different, an inert solvent and an initiator, wherein the solvent under the drying conditions of step c) has a boiling point which is in a range of 50 ⁰ C above or below the drying temperature of step c) and the boiling point of the inert solvent among the Drying conditions of step c) is at least 80 ⁰ C, and

2. The method of claim 1, wherein the substrate is an open cell or closed cell substrate.

3. The method according to claim 1 or 2, characterized in that the composition of step b) contains a second silane of the general formula (Z2) zSi (OR) 4-z, wherein R is an alkyl radical having 1 to 6 carbon atoms and Z2 is HaFbCn, where a and b are integers, all R may be the same or different, a + b = 1 + 2n, z = 1 or 2, and n is 1 to 16, or in the case that Z1 is GIy, Z2 Am (Am = 3-aminopropyl) with z = 1.

4. The method according to at least one of claims 1 to 3, characterized in that contained in the composition of step b) based on the total molar amount of silane 0.1 to 200 mol% of inert solvent.

5. The method according to at least one of claims 1 to 4, characterized in that the inert solvent is selected from the group consisting of alcohols, formamides, ketones, ethers and mixtures thereof.

6. The method according to at least one of claims 1 to 5, characterized in that the inert solvent is not water.

7. The method according to at least one of claims 1 to 6, characterized in that in the composition of step b) 3-glycidyloxypropyltriethoxysilane and / or 3-glycidyloxypropyltrimethoxysilane as silane and / or 3-aminopropyltrimethoxysilane and / or 3-aminopropyltriethoxysilane as second silane are included.

8. The method according to at least one of claims 1 to 7, characterized in that in the composition of step b) as the silane tetraethoxysilane and as the second silane, a silane of the formula (HaFbCn) zSi (OR) 4-z is included, wherein a and b are integers, a + b = 1 + 2n, z is 1 or 2, n is 1 to 16 and all Rs may be the same or different, preferably all Rs are the same and contain from 1 to 6 carbon atoms.

9. The method according to at least one of claims 1 to 8, characterized in that in the composition of step b) tetraethoxysilane, methyltriethoxysilane, octyltriethoxysilane and / or hexadecyltrimethoxysilane as silane and / or 3,3,4,4,5, 5,6,6,7,7,8,8,8-tridecafluorooctyltriethoxysilane are contained as the second silane.

10. The method according to at least one of claims 1 to 9, characterized in the composition of step b), the initiator is an acid or base, which is preferably an aqueous acid or base.

11. The method according to at least one of claims 1 to 10, characterized in that in the composition of step b) at least one further solvent is present, which preferably has a lower boiling point than the inert solvent.

12. The method according to at least one of claims 1 to 11, characterized in that in the composition of step b) at least one further additive is contained.

13. The method according to at least one of claims 1 to 12, characterized in that in the composition of step b) oxide particles selected from the oxides of Ti, Si, Zr, Al, Y, Sn, Ce or mixtures thereof are included.

14. The method according to claim 13, characterized in that the surface of the oxide particles is hydrophobic.

15. The method according to claim 13 or 14, characterized in that on the surface of the oxide particles to silicon atoms bound organic radicals X1 + 2nCn are present, wherein n is 1 to 20 and X is hydrogen and / or fluorine.

16. The method according to claim 1, characterized in that in step b) so much of the composition is applied to the substrate that after drying in step c) a layer of the substrate is deposited on the substrate. dried composition having a layer thickness of 0.05 to 10 microns is present.

17. The method according to at least one of claims 1 to 16, characterized in that during the drying in step c) the drying temperature is substantially constant and preferably constant.

18. The method according to at least one of claims 1 to 17, characterized in that prior to the application of the composition in step b) at least one further coating is applied.

19. The method according to at least one of claims 1 to 18, characterized in that after application of the composition in step b) at least one further coating is applied.

20. A coated substrate obtainable according to at least one of claims I to 19.