DE102019110519B4 - Composition, comprising a first composition and a second composition, composition produced therefrom for coating substrate surfaces and their use and method for their production - Google Patents

Abstract

Composition, comprising a first composition and a second composition, wherein the first composition is prepared by reacting at least the components (a) of a compound of the general formula I, wherein R1 is selected from the group consisting of a branched or unbranched alkyl group with 1 to 10 Carbon atoms, an aryl group, and an alkylaryl group; R2, R3, and R4, independently of one another, are each a branched or unbranched alkyl group having 1 to 10 carbon atoms; (b) a (3-glycidyloxypropyl) trialkoxysilane; and (c) water; wherein the first composition does not contain any Q groups; and wherein the second composition is a mixture of at least components (d) an alkanol; (e) a (3-glycidyloxypropyl) trialkoxysilane; and (f) a crosslinker, wherein the crosslinker is selected from the group consisting of Ti (OR5) 4, Zr (OR6) 4, titanium acetylacetonate, and mixtures thereof, wherein R5 and R6 are a branched or unbranched alkyl group having 1 to 10 carbon atoms; is.

Description

The invention relates to compositions which have a first composition and a second composition. It also relates to third compositions produced therefrom which are particularly suitable for coating substrate surfaces. It also relates to uses of the third compositions and methods of making the third compositions.

Lacquers and coating systems for wood substrates, especially in outdoor applications, have become indispensable today. The lacquers or layer systems are used in particular as preservatives in order to protect the wood substrates against environmental influences. In the last few decades, however, a number of conventional preservatives for wood have been banned from the global market for many applications, due to their high toxicity for the environment, humans and animals {Donath 2006}. Various ways of preserving wooden surfaces have been discussed in the past. One possibility is a chemical modification of the wood surface in order to reduce or block the pore size of the pores formed in the wood cell wall {Papadopoulos 2002} Hili 2005 Another possibility that avoids the use of biocides is to reduce the moisture content in the wood because fungi and other harmful organisms need moisture to grow. Water-repellent substances are often combined with biocides in order to achieve optimal protection for the wood substrate. Tetraethoxysilanes and alkyltriethoxysilanes have been described as strong water repellants and moderate fungicides {Donath 2004} {May 2004}. Also from DE 10 2006 003 957 A1 a sol-gel composition is known which is said to be particularly suitable as a coating for metallic surfaces but also as a coating for wood substrates.

In the DE 10 2006 003 957 A1 The sol-gel composition described contains several components, namely at least (i) a glycidyloxypropylalkoxysilane, (ii) an aqueous silica sol, (iii) an organic acid as hydrolysis catalyst and (iv) n-propyl zirconate, butyl titanate or titanium acetylacetonate as crosslinker. However, they have DE 10 2006 003 957 A1 known sol-gel compositions several disadvantages. On the one hand, temperatures of 75 to 80 ° C are required to produce the sol-gel compositions; on the other hand, post-curing of the layer obtained at 100 to 400 ° C is recommended.

Sol-gel compositions to be applied to papers impregnated with an aminoplast resin are off WO 2016/207 072 A1 known. The compositions are said to contain metal alkoxides and fullerene-like nanostructures of molybdenum or tungsten disulfides. Silicic acid esters such as tetraethylorthosilicate (TEOS) are used to produce the gels. The layers produced thus contain Q groups.

the end WO 2015/067 776 A1 a corrosion protection layer and a method for producing this layer are known. CN 1 07 880 773 A describes a water-based coating based on an epoxy-modified silicone resin. U.S. 4,753,827 A1 discloses an abrasion-resistant coating composed of an alkoxysilane and metal oxides.

The object of the invention is to eliminate the disadvantages of the prior art. In particular, compositions are to be specified which enable the production of thermally and mechanically stable layers. Furthermore, a combination that has a first and a second composition, a third composition produced from the combination, uses of the first and third composition and a method for producing the compositions are to be specified.

This object is achieved by the features of claims 1, 12, 13 and 14. Appropriate configurations of the inventions result from the features of the subclaims.

1. (a) einer Verbindung der allgemeinen Formel I,
   
   worin R¹ aus der Gruppe ausgewählt ist, die aus einer verzweigten oder unverzweigten Alkylgruppe mit 1 bis 10 Kohlenstoffatomen, einer Arylgruppe und einer Alkylarylgruppe besteht; R², R³ und R⁴ unabhängig voneinander jeweils eine verzweigte oder unverzweigte Alkylgruppe mit 1 bis 10 Kohlenstoffatomen sind;
2. (b) einem (3-Glycidyloxypropyl)trialkoxysilan; und
3. (c) Wasser; wobei die erste Zusammensetzung keine Q-Gruppen enthält; und wobei die zweite Zusammensetzung ein Gemisch von mindestens den Komponenten
4. (d) einem Alkanol;
5. (e) einem (3-Glycidyloxypropyl)trialkoxysilan; und
6. (f) einem Vernetzer, wobei der Vernetzer aus der Gruppe ausgewählt ist, die aus Ti(OR⁵)₄, Zr(OR⁶)₄, Titanacetylacetonat und Gemischen davon besteht, worin R⁵ und R⁶ eine verzweigte oder unverzweigte Alkylgruppe mit 1 bis 10 Kohlenstoffatomen sind; ist.

According to the invention, an assembly is provided which has a first composition and a second composition, the first composition being produced by reacting at least the components

1. (a) a compound of the general formula I,
   
   wherein R ¹ is selected from the group consisting of a branched or unbranched alkyl group having 1 to 10 carbon atoms, an aryl group, and an alkylaryl group; R ² , R ³ and R ⁴ are each independently a branched or unbranched alkyl group having 1 to 10 carbon atoms;
2. (b) a (3-glycidyloxypropyl) trialkoxysilane; and
3. (c) water; wherein the first composition does not contain any Q groups; and wherein the second composition is a mixture of at least the components
4. (d) an alkanol;
5. (e) a (3-glycidyloxypropyl) trialkoxysilane; and
6. (f) a crosslinker, wherein the crosslinker is selected from the group consisting of Ti (OR ⁵ ) ₄ , Zr (OR ⁶ ) ₄ , titanium acetylacetonate and mixtures thereof, wherein R ⁵ and R ^{6 are} a branched or unbranched alkyl group with 1 are up to 10 carbon atoms; is.

1. (a) einer Verbindung der allgemeinen Formel I,
   
   worin R¹ aus der Gruppe ausgewählt ist, die aus einer verzweigten oder unverzweigten Alkylgruppe mit 1 bis 10 Kohlenstoffatomen, einer Arylgruppe und einer Alkylarylgruppe besteht; R², R³ und R⁴ unabhängig voneinander jeweils eine verzweigte oder unverzweigte Alkylgruppe mit 1 bis 10 Kohlenstoffatomen sind;
2. (b) einem (3-Glycidyloxypropyl)trialkoxysilan, und
3. (c) Wasser.

hergestellt. Es ist vorgesehen, dass die erste Zusammensetzung keine Q-Gruppen aufweist. Es kann daher vorgesehen sein, dass keine der Komponenten, aus denen die erste Zusammensetzung hergestellt ist, ein Kieselsol ist.The first composition is by reacting at least the components

1. (a) a compound of the general formula I,
   
   wherein R ¹ is selected from the group consisting of a branched or unbranched alkyl group having 1 to 10 carbon atoms, an aryl group, and an alkylaryl group; R ² , R ³ and R ⁴ are each independently a branched or unbranched alkyl group having 1 to 10 carbon atoms;
2. (b) a (3-glycidyloxypropyl) trialkoxysilane, and
3. (c) water.

manufactured. It is envisaged that the first composition will not have any Q groups. It can therefore be provided that none of the components from which the first composition is produced is a silica sol.

Unless otherwise stated, the term “alkyl” relates in particular to a saturated aliphatic hydrocarbon group with a branched or unbranched carbon chain with 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms and particularly preferably 1 to 6 carbon atoms. The alkyl group is preferably unsubstituted.

Unless otherwise stated, the term “aryl” relates in particular to a monovalent cyclic aromatic hydrocarbon group which can comprise a mono-, bi- or tricyclic aromatic ring. Examples of aryl groups are - optionally substituted - phenyl, naphthyl, phenanthryl, fluorenyl, indenyl, azulenyl, oxydiphenyl, biphenyl, methylenediphenyl, aminodiphenyl, diphenylsulphidyl, diphenylsulphonyl, diphenylisopropylidenyl, benzo-dioxanyl, benzo-peroxadioxylylynyl, benzo-azolene-ylidenyl, benzo-piper-dioxylylynyl, benzo-azol-dioxylyinyl, benzo-azoledioxylylynyl, benzo-piper-dioxylylynyl, benzo-piperidoxy-ylynyl, benzo-pipero-dioxylylynyl, benzo-azido Methylenedioxyphenyl, ethylenedioxyphenyl and the like, the list being not exhaustive. Preferably, aryl includes optionally substituted phenyl and optionally substituted naphthyl, with phenyl being particularly preferred. The aryl group is preferably unsubstituted.

Unless stated otherwise, the term “alkylaryl” relates in particular to a monovalent aryl group bearing one or more alkyl groups, the aryl group and the alkyl group being as defined above. The aryl group is preferably a phenyl group, it being possible for the alkyl group to be, for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl or tert-butyl. The aryl group preferably carries only one alkyl group.

It can be provided that R ¹ is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl and phenyl. ^{R 1} is preferably methyl or phenyl, particularly preferably methyl.

It can be provided that R ² , R ³ and R ^{4 are} independently selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert- Butyl. Preferably R ² , R ³ and R ^{4 are} each methyl or ethyl, particularly preferably each ethyl. Preferably R ² , R ³ and R ^{4 are the} same alkyl groups.

Component (a) is preferably a methyltriethoxysilane (MTEOS).

Component (b) is a (3-glycidyloxypropyl) trialkoxysilane. Preferably the alkoxy group of the (3-glycidyloxypropyl) trialkoxysilane is selected from the group consisting of methoxy, ethoxy, propoxy and butoxy. (3-Glycidyloxypropyl) trialkoxysilane (3-Glycidyloxypropyl) triethoxysilane (GLYEO) is particularly preferred.

In a preferred embodiment of the first composition, component (a) is methyltriethoxyoxysilane, component (b) (3-glycidyloxypropyl) triethoxysilane and component (c) is water.

To produce the first composition, components (a), (b) and (c) are _{reacted in a mass ratio m a} : m _b : m _c of preferably 14 to 24: 0.1 to 2: 0.2 to 4, stronger preferably 16 to 22: 0.5 to 1.5: 0.1 to 3, even more preferably 17 to 21: 0.8 to 1.2: 1.5 to 2.5 and particularly preferably 19: 1: 2. Here, m _{a is} the mass of component (a), m _{b is} the mass of component (b) and m _{c is} the mass of component (c).

1. (a) Methyltriethoxysilan;
2. (b) (3-Glycidyloxypropyl)triethoxysilan; und
3. (c) Wasser

hergestellt, wobei die Komponenten (a), (b) und (c) in einem Masseverhältnis m_a : m_b : m_c = 19 : 1 : 2 umgesetzt werden.In a preferred embodiment, the first composition is by reacting at least the components

1. (a) methyltriethoxysilane;
2. (b) (3-glycidyloxypropyl) triethoxysilane; and
3. (c) water

produced, the components (a), (b) and (c) _{being reacted in a mass ratio m a} : m _b : m _c = 19: 1: 2.

To produce the first composition, at least components (a), (b) and (c) are reacted with one another. For this purpose it can be provided that component (a) is mixed with component (b) to obtain a first mixture. Water is then added to the first mixture to obtain a second mixture. An organic or inorganic acid can then be added to the second mixture will. The organic or inorganic acid can catalyze the conversion of components (a), (b) and (c) to form the first composition. It catalyzes the hydrolysis of components (a) and (b), both of which are silanes. The organic or inorganic acid serves as a catalyst in making the first composition. An inorganic acid is preferably used. The inorganic acid can be, for example, hydrochloric acid (HCl), nitric acid or sulfuric acid, hydrochloric acid being preferred. The first composition can thus be prepared at least from components (a), (b) and (c) in the presence of an inorganic acid.

The organic or inorganic acid is preferably used in a volume ratio V _H2O : V _acid equal to 1 to 3: 2 to 4, more preferably 1.5 to 2.5: 2.5 to 3.5 and particularly preferably 2: 3, where V _{H2O is} the volume of component (c) and V _{acid is} the volume of the organic or inorganic acid. If hydrochloric acid is used as the inorganic acid, the volume ratio V _H2O : V _{HC1 is} preferably 2: 3.

No solvent is required to make the first composition. The first composition can be a sol. In one embodiment, the first composition can only consist of components (a), (b) and (c).

The first composition can be used to form one or more layers. In particular, the first composition can be used for coating substrate surfaces, for example for coating wooden surfaces. The curing can take place in the air. The first composition can be cured at room temperature or elevated temperature. Hardening at elevated temperature shortens the time required for hardening. Hardening at an elevated temperature can take place, for example, at a temperature of 80 to 100.degree. At such a temperature, curing can take place, for example, for a period of 30 minutes to 2 hours. Curing at room temperature may take a long time.

The curing of the first composition can be accelerated by adding a crosslinker. The crosslinker is preferably selected from the group consisting of Ti (OR ⁵ ) ₄ , Zr (OR ⁶ ) ₄ , titanium acetylacetonate and mixtures of one, two or more of these crosslinkers, R ⁵ and R ⁶ each being a branched or unbranched alkyl group having 1 to 10 carbon atoms. A more preferred crosslinker is selected from the group consisting of titanium (IV) butoxide, n-propyl zirconate, titanium acetylacetonate, and mixtures thereof. A particularly preferred crosslinker is titanium (IV) n-butoxide (TBOT). Titanium (IV) -n-butoxide is a compound, also known as titanium tetrabutanolate, with the empirical formula C ₁₆ H ₃₆ O ₄ Ti. The crosslinking agent can be dissolved in a solvent, for example an alkanol. The alkanol can be a monohydric alcohol having 1 to 6 carbon atoms. The alkanol is preferably selected from the group consisting of methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol and tert-butanol. A preferred alkanol is ethanol. Methanol is not preferred because of its toxicity. The crosslinker enables components (a) and (b) to be crosslinked with one another and with one another. Another compound or a mixture of one or more of the crosslinkers described here with one or more other crosslinkers can also be used as crosslinkers. The term “other crosslinker” can refer, for example, to a Ti or Zr compound that is chemically related to the Ti (OR ⁵ ) ₄ , Zr (OR ⁶ ) ₄ or titanium acetylacetonate described here.

The addition of the crosslinker enables the first composition to cure at room temperature. It is therefore advisable to add the crosslinker to components (a), (b) and (c) only immediately before using the first composition. It is therefore expedient to provide components (a), (b) and (c) separately from the crosslinker.

In addition to components (a), (b) and (c), the first composition can contain further components, for example one or more additives. An additive can be a filler, for example. The filler or fillers can impart a color to a layer produced using the first composition, but also carry other functions that influence the electrical, mechanical, magnetic, thermal, chemical, biological-medical and / or other properties of the produced layer and / or can determine. However, it is not necessary that the first composition be prepared using a filler. Examples of a filler are zinc stearate and silicon dioxide. The mass fraction of the filler (s) in the first composition is preferably not more than 35% by weight, more preferably not more than 30% by weight and particularly preferably not more than 20% by weight. In one embodiment, the first composition can only consist of components (a), (b) and (c) and one or more additives.

The first composition preferably has no Q groups. For this reason, no component should be used for the preparation of the first composition which can lead to the formation of Q groups and / or which contains Q groups. In particular, it can be provided that no tetraethylorthosilicate (TEOS) and no tetramethylorthosilicate (TMOS) are used to produce the first composition. The term “Q group” denotes a silicon atom tetrahedrally coordinated with four oxygen atoms. A Q group can be, for example, an Si (—O — Si) ₄ group. Because neither component (a) nor component (b) contain Q groups, it is ensured that the first composition does not contain a Q group either.

The first composition can be used to make layers. The layers produced can be transparent layers. The first composition can be used directly for coating substrate surfaces. Coating methods known from the prior art can be used for this purpose. For example, the third composition can be applied to a substrate surface by brushing, knife coating, dip coating or spray coating. The substrate surface can be a surface of a substrate such as wood, plastic, glass, ceramic, metal, metal alloys, pressboard, paper, cardboard, layers of lacquer or stone. The first composition is preferably used for coating wood.

Apart from the production of layers using the first composition, the first composition can also be used to produce molded bodies. A shaped body can be produced, for example, by infiltration of a porous material with the first composition or by casting and subsequent curing.

• (d) ein Alkanol;
• (e) ein (3-Glycidyloxypropyl)trialkoxysilan, und
• (f) ein Vernetzer, wobei der Vernetzer aus der Gruppe ausgewählt ist, die aus Ti(OR⁵)₄, Zr(OR⁶)₄, Titanacetylacetonat und Gemischen davon besteht, worin R⁵ und R⁶ eine verzweigte oder unverzweigte Alkylgruppe mit 1 bis 10 Kohlenstoffatomen sind.

The second composition should be a mixture of the following components:

• (d) an alkanol;
• (e) a (3-glycidyloxypropyl) trialkoxysilane, and
• (f) a crosslinker, wherein the crosslinker is selected from the group consisting of Ti (OR ⁵ ) ₄ , Zr (OR ⁶ ) ₄ , titanium acetylacetonate and mixtures thereof, wherein R ⁵ and R ^{6 are} a branched or unbranched alkyl group with 1 to 10 carbon atoms.

It can be provided that the second composition has no Q groups, for example no Si (—O — Si) ₄ units. It can therefore be provided that none of the components comprising the second composition is a silica sol.

Component (d) can be the alkanol described in connection with the first composition. Accordingly, the alkanol can be a monohydric alcohol with 1 to 6 carbon atoms. The alkanol is preferably selected from the group consisting of methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol and mixtures thereof. A preferred alkanol is ethanol. Methanol is not preferred because of its toxicity. Component (d) serves as a solvent for components (e) and (f) in the second composition.

Component (e) is a (3-glycidyloxypropyl) trialkoxysilane. The alkoxy group of the (3-glycidyloxypropyl) trialkoxysilane is preferably selected from the group consisting of methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy and tert-butoxy. Preferably component (e) is the same compound as component (b). Component (e) is therefore particularly preferred (3-glycidyloxypropyl) triethoxysilane (GLYEO). It should be noted that component (e) is included in the assembly in addition to component (b).

Component (f) is the crosslinker already described in connection with the first composition. A particularly preferred crosslinker is titanium (IV) butoxide (TBOT).

The second composition can be used as a hardener component for the first composition, which is the sol component. The second composition contains the crosslinker, that is to say that the first composition - apart from components (a), (b) and (c) - does not contain any further crosslinker. In particular, when the second composition is used as the hardener component, the first composition contains neither Ti (OR ⁵ ) ₄ nor Zr (OR ⁶ ) ₄ nor titanium acetylacetonate.

In a preferred embodiment, the second composition has the following components: component (d) is ethanol, component (e) is (3-glycidyloxypropyl) triethoxysilane and component (f) is titanium (IV) butoxide. In one embodiment, the second composition can only consist of components (d), (e) and (f).

In the second composition, components (d), (e) and (f) _{can be present with one another in a mass ratio m d} : m _e : m _f of 0.5 to 4: 0.5 to 4: 0.1 to 2, more preferably 1 to 3: 1 to 3: 0.5 to 2, even more preferably 1.5 to 2.5: 1.5 to 2.5: 0.7 to 1.5 and particularly preferably 2: 2: 1 Here, m _{d is} the mass of component (d), m _{e is} the mass of component (e) and m _{f is} the mass of component (f).

• (d) Ethanol;
• (e) (3-Glycidyloxypropyl)triethoxysilan (GLYEO); und
• (f) Titan(IV)-butoxid (TBOT); wobei die Komponenten (d), (e) und (f) in einem Masseverhältnis m_d : m_e : m_f = 2 : 2 : 1 in der zweiten Zusammensetzung enthalten sind.

In a preferred embodiment, the second composition is a mixture of at least the components

• (d) ethanol;
• (e) (3-glycidyloxypropyl) triethoxysilane (GLYEO); and
• (f) titanium (IV) butoxide (TBOT); the components (d), (e) and (f) being _{contained in the second composition in a mass ratio m d} : m _e : m _f = 2: 2: 1.

To produce the second composition, components (d), (e) and (f) are mixed with one another. In contrast to the production of the first composition, the production of the second composition is not necessarily associated with a chemical reaction. This is reflected in the high long-term stability of the second composition. To produce the second composition, provision can be made for component (e) or a first partial amount of component (d) to be introduced into component (d) and to be mixed with it to obtain a third mixture. Component (f) is then introduced into the third mixture to obtain a fourth mixture. If only a first partial amount of component (d) was used beforehand, the remaining, second partial amount of component (d) can be used to take up any residues of component (f) and to feed both together to the fourth mixture. With regard to the high viscosity of component (f) - this applies in particular when titanium (IV) butoxide is used as component (f), vigorous stirring of the third and fourth mixture is advantageous in order to ensure a homogeneous distribution of the components ( e) and (f) in component (d). Even if the production of the second composition does not necessarily involve a chemical reaction, reactions between the components of the mixture are not completely ruled out. For example, a reaction between OR ⁵ groups of the crosslinker Ti (OR ⁵ ) ₄ with ethanol molecules cannot be completely ruled out.

The volume ratio of the first composition to the second composition can be from 0.5 to 2: 2 to 0.5, a volume ratio of 1: 1 being preferred.

The first composition and the second composition are preferably provided separately from one another in order to avoid premature and undesired curing. A third composition is obtained by combining the first composition and the second composition. This third composition can be used particularly advantageously for the formation of layers, in particular for the formation of layers on substrate surfaces. In one embodiment, the composition according to the invention can only consist of components (a), (b), (c), (d), (e) and (f). In another embodiment, it can only consist of components (a), (b), (c), (d), (e) and (f) and one or more additives.

According to the invention, a composition is thus provided which is produced from the composition according to the invention by reacting the first composition with the second composition. This composition is referred to as the third composition in the present invention. To produce the third composition, the first composition and the second composition are mixed with one another. The volume ratio of the first composition to the second composition can be from 0.5 to 2: 2 to 0.5, a volume ratio of 1: 1 being preferred. Under the action of the crosslinker contained in the second composition, d. H. Component (f), cures the third composition.

The third composition preferably has no Q groups. For this reason, no component should be used for the preparation of the third composition which can lead to the formation of Q groups and / or which contains Q groups. In particular, the first composition and the second composition should not contain any components which can lead to the formation of Q groups and / or which contain Q groups. In particular, it can be provided that the first, second and third compositions contain no tetraethylorthosilicate (TEOS) and no tetramethylorthosilicate (TMOS) or these compounds are used to prepare the first, second or third composition. Because neither component (a) nor component (b) nor component (e) contain Q groups, it is ensured that the third composition does not contain any Q group either. For this reason, it can be provided that none of the components that are used to produce the third composition is a silica sol. It can thus be provided that the first composition does not have any Si (—O — Si) ₄ units.

The third composition can contain one or more additives. An additive can be a filler, for example. The filler or fillers can impart a color to a layer produced using the first composition, but also carry other functions that influence the electrical, mechanical, magnetic, thermal, chemical, biological-medical and / or other properties of the produced layer and / or can determine. However, it is not necessary that the third composition be made using a filler. A filler can be, for example, zinc stearate or silicon dioxide. The mass fraction of the filler (s) in the second composition is preferably not more than 35% by weight, more preferably not more than 30% by weight and particularly preferably not more than 20% by weight. In one embodiment, the third composition can be prepared by reacting the reaction product from only components (a), (b) and (c) with the mixture from only components (d), (e) and (f). In another embodiment, it can be carried out by reacting the reaction product from only components (a), (b) and (c) with the mixture from only components (d), (e) and (f) and then adding one or more additives getting produced.

The third composition can be used to form one or more layers. A layer produced using the third composition is a hybrid material layer based on siloxanes. This layer hardens at room temperature, is biocompatible and mechanically stable.

The third composition can be used for coating substrate surfaces, for example for coating wooden surfaces. The third composition can be cured in air. The third composition can be cured at room temperature. Hardening at elevated temperature is not necessary, but possible. If curing is carried out at an elevated temperature, the time required to achieve complete curing is reduced.

1. (a) Methyltriethoxysilan (MTEOS);
2. (b) (3-Glycidyloxypropyl)triethoxysilan (GLYEO); und
3. (c) Wasser;

(B) mit einer als Härter-Komponente dienenden zweiten Zusammensetzung, die ein Gemisch ist aus

• (d) Ethanol;
• (e) (3-Glycidyloxypropyl)triethoxysilan (GLYEO); und
• (f) Titan(IV)-butoxid (TBOT).

A preferred third composition is made by reacting (A) a first composition serving as a sol component made from

1. (a) methyltriethoxysilane (MTEOS);
2. (b) (3-glycidyloxypropyl) triethoxysilane (GLYEO); and
3. (c) water;

(B) with a second composition serving as hardener component, which is a mixture of

• (d) ethanol;
• (e) (3-glycidyloxypropyl) triethoxysilane (GLYEO); and
• (f) Titanium (IV) butoxide (TBOT).

One or more additives can be added to the third composition.

According to the invention, a method of making a third composition is provided, wherein the first composition is blended with the second composition. Provision can be made for one or more additives to be added to the third composition obtained in this way immediately after the first and second compositions have been mixed.

The third composition can be used to make layers. The layers produced can be transparent layers. The third composition obtained by mixing the first and the second composition can be used directly for coating substrate surfaces. Coating methods known from the prior art can be used for this purpose. For example, the third composition can be applied to a substrate surface by brushing, knife coating, dip coating or spray coating. The substrate surface can be a surface of a substrate such as wood, plastic, glass, Ceramics, metal, metal alloys, pressboard, paper, cardboard, layers of lacquer or stone. The third composition is preferably used for coating wood.

Apart from the production of layers using the third composition, the third composition can also be used to produce molded articles. A shaped body can be produced, for example, by infiltrating a porous material with the third composition or by pouring the third composition and then curing it.

The layers which are obtained using the third composition according to the invention have a large number of advantageous properties. It is possible to produce layers that are free from Q groups. This can be seen in particular in ²⁹ Si-CP / MAS-NMR spectra of the layers. The freedom from Q groups is advantageous because the layers produced have greater flexibility, since no rigid framework, in particular no rigid framework composed of Si (—O — Si) ₄ units, is formed, and so stresses and cracks are avoided.

The third composition cures at room temperature. In particular, this is not the case with many sol-gel systems known from the prior art. The layers produced using the third composition according to the invention are mechanically very stable and strongly adherent. An examination of such layers according to DIN EN ISO 2409: 2013-06 resulted in the highest stability on wood substrates.

Layers can be created using the third composition. These layers can be thin layers, but also comparatively thick layers. A thin layer is understood to mean a layer with a layer thickness of 15 micrometers or less, 10 micrometers or less, or 1 micrometer or less. The layer thickness of a thin layer is preferably in a range from 0.1 to 10 micrometers. A thick layer is understood to mean a layer with a layer thickness of 100 micrometers or more, preferably more than 100 micrometers, wherein a thick layer can also have a layer thickness of 500 micrometers or more. However, a layer can also have a layer thickness of 15 micrometers to 100 micrometers. It has been found that the third composition according to the invention can be used to produce thick layers which are completely free of cracks.

It has also been found that the layers produced using the third composition according to the invention are thermally stable, specifically up to temperatures of 200.degree. The layers only begin to decompose significantly from 200 ° C, as was shown by means of thermogravimetry measurements. The layers produced using the third composition according to the invention also have a high optical transparency. They can therefore be viewed as optically transparent layers. In addition, the layers absorb in the NIR and UV range.

The first composition and the second composition, that is to say both the sol component and the hardener component, are advantageously storage-stable for several months. All customary application methods such as knife coating, brushing, dipping and spraying can be used to produce layers from the third composition, the list not being exhaustive.

According to the invention, the use of the third composition is provided for coating a substrate surface or for forming a shaped body. The third composition is preferably used for coating wood.

• 1 ein ²⁹Si-NMR-Spektrum einer Schicht, die aus einer erfindungsgemäßen Zusammensetzung hergestellt wurde;
• 2 eine fotografische Aufnahme einer Schicht, die aus einer erfindungsgemäßen Zusammensetzung hergestellt wurde und einem Gitterschnitt unterzogen wurde;
• 3 eine mittels 3D-Laser-Scanning-Mikroskopie erhaltene Aufnahme der in 2 gezeigten Schicht;
• 4 ein Diagramm, das Ergebnisse thermogravimetrischer Messungen an pulverisierten erfindungsgemäßen Zusammensetzungen zeigt; und
• 5 ein Diagramm, das Messungen der Transparenz von Schichten, die aus erfindungsgemäßen Zusammensetzungen hergestellt wurden, zeigt.

The invention is explained in more detail below using exemplary embodiments, which are not intended to restrict the invention, with reference to the drawings. Show it

• 1 a ²⁹ Si-NMR spectrum of a layer produced from a composition according to the invention;
• 2 a photograph of a layer which has been produced from a composition according to the invention and has been cross-cut;
• 3 a picture of the in 2 layer shown;
• 4th a diagram showing results of thermogravimetric measurements on pulverized compositions according to the invention; and
• 5 Figure 3 is a graph showing measurements of the transparency of layers made from compositions according to the invention.

In the following, the term “vigorous stirring” denotes the maximum possible stirring speed at which the stirring tool used, for example a magnetic stirring bar known as a stirring bar, still rotates stably, but at least 600 revolutions per minute (rpm). The stirring speed should not be changed until the end of the reaction.

Example 1 not according to the invention: Production of the sol component

The starting materials were used in the ratio m _MTEOS : m _GLYEO : m _H2O = 19: 1: 2. Water and 1 M HCl in the ratio V _H2O : V _HC1 = 2: 3 were used.

The MTEOS was weighed into a three-necked flask. The MTEOS was cooled to 5 ° C. in an ice bath while stirring. The GLYEO was weighed into a syringe and added with vigorous stirring. The mixture was then stirred at a maximum of 5 ° C. for 30 minutes. Water was slowly added dropwise via a dropping funnel to ensure that the temperature did not increase significantly. 1 M HCl was added dropwise very slowly (approx. 30 drops per minute) in order to prevent the temperature from rising above 5 ° C. After the end of the dropwise addition, the mixture was stirred for a further 30 minutes while cooling with an ice bath. The ice bath was then removed and the mixture was stirred for a further 24 hours.

The composition obtained is an example of a first composition and is not per se the subject of the invention.

Example 2 not according to the invention: Production of the hardener component:

The compounds were mixed in the ratio m _ethanol : m _GLYEO : m _TBOT = 2: 2: 1. Mixing was carried out with vigorous stirring. 90% by weight of the ethanol was placed in a flask. GLYEO was weighed into a syringe and added with vigorous stirring. It was stirred for 5 minutes. TBOT was weighed and slowly added dropwise via a dropping funnel (approx. 1 drop per second). The remaining ethanol was used to completely transfer the TBOT into the dropping funnel and then to rinse the dropping funnel. It was stirred for 2 more hours at room temperature.

The composition obtained is an example of a second composition and is not per se the subject of the invention.

Example 3: Mixing the sol component with the hardener component

The sol component and the hardener component, which together represent an example of a composition according to the invention, were placed in a volume ratio of 1: 1 in a beaker and then stirred using a magnetic stirrer until a clear, suspended matter-free solution was formed. This could then be used directly for coating. The mixture obtained is an example of a third composition.

Example 4: Proof of freedom from Q groups

The solution prepared in Example 3 was used to produce a layer. The layer is ^{examined by means of 29} Si-LC-NMR spectroscopy. This in 1 The spectrum shown confirms that the layer did not have any Q groups.

Example 5: Mechanical stability of a coating

The solution prepared in Example 3 was applied to wooden surfaces by means of dip coating. The layers formed were cured at room temperature and were free of cracks and defects, colorless to slightly yellowish and transparent. The layers were then examined using a cross-cut according to DIN EN ISO 2409: 2013-06 ( 2 and 3 ). The results are in Table 1 shown. Table 1 Current number Substrate Layer thickness [µm] Adhesion strength according to the cross-cut test 1 Spruce 61 0 2 Spruce 96 1 3 Spruce 42 0 4th jaw 49 0 5 jaw 87 2 6th jaw 75 1

It can be seen that the layers exhibited good to very good adhesive strength, with a rating of “0” for the adhesive strength being the best rating, while a rating of “5” is the worst rating.

Example 6: Proof of the thermal stability of a coating

The solution produced in Example 3 was used to produce layers. The thermal resistance of the layers was proven by thermogravimetric tests on powdered layers. It is in 4th It can be seen that the layers are thermally stable up to over 200 ° C. This in 4th The diagram shown has the temperature T in ° C. as the abscissa and the percentage mass fraction of the undecomposed coating in relation to the mass of the coating originally used as the ordinate.

Example 7: Detection of the optical transparency and adsorption in the UV and NIR range

The solution prepared in Example 3 was transferred to a cuvette to produce layers. The transparency of the layers was examined by means of UV / Vis-NIR measurements. It is in 5 to recognize that the layers have a high optical transparency and absorb in the NIR and UV range. In 5 indicates the indication “1. Attempt "the measurement on a first shift, the indication" 2. Try “the measurement on a second shift. The indication "Difference 1" is the difference between the measured values of the glass plate and the measured values of the first layer, the indication "Difference 2" is the difference between the measured values of the glass plate and the measured values of the second layer. This in 5 The diagram shown has the wavelength in nm as the abscissa and the transmittance as the ordinate.

Example 8: Proof of miscibility with a filler

To demonstrate the miscibility with a filler of the first and third compositions according to the invention, a filler was added to solutions prepared according to Example 3, specifically immediately after preparation of the solution, ie before the start of curing. Either zinc stearate or silicon dioxide was added as filler. Both fillers are commercially available and widely used in the paints and coatings industry. Both fillers were used as filler powder. The results are shown in Table 2 filler Mass fraction [%] Miscibility Layer generation possible? comment Zinc stearate 9.3 Completely mixable Yes Usable without restrictions Zinc stearate 14.8 Completely mixable Yes Usable without restrictions Zinc stearate 30.1 Completely mixable Yes Viscosity significantly increased, but manageable by redilution with ethanol. Silicon dioxide 20.4 Completely mixable Yes Increased mixing had to be ensured (ultrasound) Silicon dioxide 33.1 Completely mixable Yes

It can be seen in Table 2 that the addition of a filler does not impair the formation of the layer. The mass fraction of the filler relates to the sum of the mass of the solution used and the mass of the filler added in percent, the mass of the solution used being its mass before the start of curing.

Literature cited

• Donath, S.; Militz, H.; Mai, C. (2004): Wood modification with alkoxysilanes. In: Wood Sci. Technol. 38 (7), S. 555-566.001: 10.1007/s00226-004-0257-1 .
• Donath, S.; Militz, H.; Mai, C. (2006): Treatment of wood with aminofunctional silanes for protection against wood destroying fungi. In: Holzforschung 60 (2), S. 210-216. DOI: 10.1515/HF.2006.035 .
• Hili, C. A.S.; Forster, S. C.; Farahani, M. R.M.; Haie, M. O.C.; Ormondroyd, G. A.; Williams, G. R. (2005): An investigation of cell wall micropore blocking as a possible mechanism for the decay resistance of anhydride modified wood. In: Int. Biodeterior. Biodegrad. 55 (1), S. 69-76. DOI: 10.1016/j.ibiod.2004.07.003 .
• Mai, C.; Militz, H. (2004): Modification of wood with silicon compounds. Treatment systems based on organic silicon compounds? A review. In: Wood Sci. Technol. 37 (6), S. 453-461. DOI: 10.1007/s00226-004-0225-9 .
• Papadopoulos, A. N.; Hili, C. A. S. (2002): The biological effectiveness of wood modified with linear chain carboxylic acid anhydrides against Coniophora puteana. In: Eur. J. Wood Wood Prod. 60 (5), S. 329-332. DOI: 10.1007/s00107-002-0327-8 .

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• Donath, S .; Militz, H .; Mai, C. (2004): Wood modification with alkoxysilanes. In: Wood Sci. Technol. 38 (7), pp. 555-566.001: 10.1007 / s00226-004-0257-1 .
• Donath, S .; Militz, H .; Mai, C. (2006): Treatment of wood with aminofunctional silanes for protection against wood destroying fungi. In: Holzforschung 60 (2), pp. 210-216. DOI: 10.1515 / HF.2006.035 .
• Hili, CAS; Forster, SC; Farahani, MRM; Sharks, MOC; Ormondroyd, GA; Williams, GR (2005): An investigation of cell wall micropore blocking as a possible mechanism for the decay resistance of anhydride modified wood. In: Int. Biodeterior. Biodegradation. 55 (1), pp. 69-76. DOI: 10.1016 / j.ibiod.2004.07.003 .
• Mai, C .; Militz, H. (2004): Modification of wood with silicon compounds. Treatment systems based on organic silicon compounds? A review. In: Wood Sci. Technol. 37 (6), pp. 453-461. DOI: 10.1007 / s00226-004-0225-9 .
• Papadopoulos, AN; Hili, CAS (2002): The biological effectiveness of wood modified with linear chain carboxylic acid anhydrides against Coniophora puteana. In: Eur. J. Wood Wood Prod. 60 (5), pp. 329-332. DOI: 10.1007 / s00107-002-0327-8 .

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Claims (14)

Composition comprising a first composition and a second composition, the first composition being prepared by reacting at least the components (a) of a compound of the general formula I,

wherein R ¹ is selected from the group consisting of a branched or unbranched alkyl group having 1 to 10 carbon atoms, an aryl group, and an alkylaryl group; R ² , R ³ and R ⁴ are each independently a branched or unbranched alkyl group having 1 to 10 carbon atoms; (b) a (3-glycidyloxypropyl) trialkoxysilane; and (c) water; wherein the first composition does not contain any Q groups; and wherein the second composition is a mixture of at least the components (d) an alkanol; (e) a (3-glycidyloxypropyl) trialkoxysilane; and (f) a crosslinker, wherein the crosslinker is selected from the group consisting of Ti (OR ⁵ ) ₄ , Zr (OR ⁶ ) ₄ , titanium acetylacetonate and mixtures thereof, wherein R ⁵ and R ^{6 are} a branched or unbranched alkyl group with 1 are up to 10 carbon atoms; is. Compilation according to Claim 1 , characterized in that R ¹ is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl and phenyl, and that R ² , R ³ and R ^{4 are} independently selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl. Compilation according to Claim 1 or Claim 2 , characterized in that, based on the first composition, the alkoxy group of the (3-glycidyloxypropyl) trialkoxysilane is selected from the group consisting of methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy , sec-butoxy and tert-butoxy. Composition according to one of the preceding claims, characterized in that component (a) is methyltriethoxysilane and component (b) is (3-glycidyloxypropyl) triethoxysilane. Composition according to one of the preceding claims, characterized in that components (a), (b) and (c) in a mass ratio m _a : mb: m _c = 14 to 24: 0.1 to 2: 0.2 to 4 implemented. Composition according to one of the preceding claims, characterized in that components (a), (b) and (c) _{are reacted in a mass ratio m a} : mb: m _c = 19: 1: 2. Composition according to one of the preceding claims, characterized in that the first composition is produced at least from components (a), (b) and (c) in the presence of an organic or inorganic acid. Composition according to one of the preceding claims, characterized in that the first composition has a crosslinker as a further component, the crosslinker being selected from the group consisting of Ti (OR ⁵ ) ₄ , Zr (OR ⁶ ) ₄ , titanium acetylacetonate and mixtures thereof where R ⁵ and R ^{6 are} a branched or unbranched alkyl group having 1 to 10 carbon atoms. Composition according to one of the preceding claims, characterized in that the alkanol is selected from the group consisting of ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol and mixtures thereof . Composition according to one of the preceding claims, characterized in that component (d) is ethanol, component (e) is (3-glycidyloxypropyl) triethoxysilane and component (f) is titanium (IV) butoxide. Composition according to one of the preceding claims, characterized in that the volume ratio of the first composition to the second composition is 0.5 to 2: 2 to 0.5. Composition made from a composition according to one of the Claims 1 until 11 by reacting the first composition with the second composition. Use of a composition according to Claim 12 for the coating of a substrate surface or the formation of a shaped body. Process for the preparation of a composition according to Claim 12 , characterized in that the first composition is blended with the second composition.

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