MXPA99007814A - Organic-inorganic hybrid materials - Google Patents

Abstract

The present invention relates to mixtures containing organic polymers, inorganic particles and inorganic-organic binding agents, organic-inorganic hybrid materials which can be produced from said mixtures. The invention further relates to the use of said hybrid materials.

Description

ORGANIC-INORGANIC HYBRID MATERIALS DESCRIPTION OF THE INVENTION The present invention refers to mixtures for obtaining organic-inorganic hybrid materials and their use. By means of the synthesis of hybrid organic-inorganic materials it is tried to combine in a material typical properties of inorganic and organic substances. Thus, glass and ceramics are noted in a manner known for their hardness and brittleness, while the organic polymers are elastic but at the same time also essentially softer than the aforementioned substances. Meanwhile, there are known organic-inorganic hybrid materials of many kinds which are significantly harder than organic polymers and otherwise do not show the brittleness of pure organic materials. Depending on the type and mode of interaction between organic and inorganic components, hybrid materials are classified into different types. A review of this is found in J. Mater, Chem, £ (1996), 511. A class of hybrid materials is obtained by reacting a homogeneous mixture of an organic polymer with metal alkoxides, for example Si (OEt), or also CH3 - Si (0Etj3, with water) After the hydrolysis and the condensation of the alkoxides an inorganic network is obtained which is penetrated by the organic polymer ("Interpenetrating network") There is no covalent bond of the polymer to the phase REF .: 31060 inorganic Examples of such hybrid materials are found in US-PS 5 346 939 and WO 93/01226. According to Poly .Mater. Sci .Eng. 74 (1996) 65, the compatibility of the inorganic phase with very polar polymers such as polyamides, polyimides, polyamidimides or polycarbonates, is especially good. In the case of non-polar polymers, for example polyvinyl chlorides or methyl polymethacrylate polymers, which are extremely important technically, phase separation, ie, heterogeneous and turbid materials, are frequently obtained. To improve compatibility, the addition of polyoxazolines is proposed in such systems. Another class of hybrid materials is obtained in an analogous manner, although the organic polymer employed contains reactive groups, for example Si (0Et) 3, which produce a covalent gibbon link to the inorganic network. There are examples of escos in ACS Symp. Ser. 585 (1995) 125, Adv. Mater. 6 (1994) 372 and Mater. Lett. 13 (1992) 261. WO 93/01226 discloses "composite materials" which are formed by an organic and an inorganic polymer, of the glass type. Characteristics of these materials are that the organic polymer can not be extracted and no vitreous or fusion transition point is observed. From the document UP-PS 5,346,939 mixtures are known which consist of non-reactive thermoplastic polymers with organometallic compounds líguidoe. In the presence of water, composite materials are obtained from them in which there is no mixture at the molecular level except that the organic and inorganic phases are separated. Such composite materials are cloudy or white and are therefore not suitable for applications where high transparency materials are needed, for example protective varnishes. Therefore, there is the task of preparing transparent mixtures based on organic polymers, which can be used for the coating of surfaces and which, above all, have good adhesion, durability and resistance to wear and scratching, as well as high transparency. This is made possible by means of the mixtures according to the invention. Therefore the object of the present invention are transparent mixtures consisting of: A) at least one organic polymer B) inorganic particles with a primary particle diameter of 1 to lOOnm C) at least one inorganic-organic binder based on polyfunctional organosilanes which contain at least 2 silicon atoms, each having 1 to 3 alkoxide or hydroxyl groups, the silicon atoms being linked with at least one SiC bond each to a structural unit which is links the silicon atoms, and D) at least one solvent. Organic polymers A) in the sense of the invention can be reactive or inert polymers with respect to components B) and C). The inert organic polymers do not in this case form stable covalent bonds with the inorganic particles or with the inorganic-organic binder. The formation of SI-0-C bonds by reaction of the OH groups of the polymer with alkoxyl groups, for example of the inorganic-organic binder, will not be contemplated as a stable covalent bond in the sense of the invention. It can be dissociated again with water under mild conditions. In essence, a "bond" of the organic polymer to the inorganic components B) and C) will be supported by weak interactions, for example hydrogen bonding. Organic reactive polymers in the sense of the invention contain stable covalent bond forming groups, essentially Si-O-Si or Si-O-Al, with the inorganic components B) and C). The organic polymers with the corresponding reactive groups can be obtained by (co-) polymerization, as described in ACS Symp. Ser. 585 (1995) 125, Adv. Mater. 6 (1994) 372 and Mater. Lett. 13 (1992) 261, or by means of functionalization of an inert polymer. For this purpose, the substances shown are particularly suitable.

A reactive reactivity to the organic polymer and at the same time can also be easily linked to the inorganic matrix. By way of example, mention may be made of bifunctional organosilanes, which already find wide application as coupling agents, for example to include glass fibers in polymers. For further details we should mention by way of example the following organosilanes, in which R = alkyl, aryl, preferably it can be methyl or ethyl: a) H2N- (CH2) 3Si (OR) 3 b) H2N- (CH2) 2 -HN- (CH2) 3Si (OR) 3 c) H2N- (CH2) 2-HN- (CH2) 3Si (OR) 3 (CH3) d) C6H5-HN- (CH2) 3YES (OR) 3 e) H2N - (CH2) 2-HN- (CH2) 2-HN- (CH2) 3YES (OR) 3 f) OCN- (CH2) 3Si) (0R) 3 g) HS- (CH2) 3YES (OR) 3 h) H2COCH-CH2-0- (CH2) 3Si (OR) 3 i) H2C = C (CH3) -COO- (CH2) 3Si (OR) 3 j) H2C = CH-Si (OR) 3 The bifunctional organosilanes mentioned above, they can be reacted with organic polymers, for example in the manner and manner represented below, schematically: R, R "" = radicals of a desired polymer chain. However, it is also possible to first react the inorganic components B) and / or C), even further, with the bifunctional organosilanes, essentially with the formation of Si-0-Si bonds, and then carry out the reaction with the organic polymers. As examples of organic polymers there may be mentioned A) polyamides, polycarbonates, polyesters, polyamides, polyketones, polyethers, polyesters, polyacrylonitriles, polyacrylamides, polymethacrylate esters, polyacrylate esters, polyvinyl esters, polyvinyl ether and polyolefins, as well as their copolymers and mixtures ("blends"). Preference is given to using commercially available polyol polymers, for example based on polystyrene esters, polyacrylate esters, polymethacrylate esters and polymers. containing isocyanate groups. Examples of this are polyols based on polyacrylates or polyesters or linear and branched polyesters / polyesters. If several organic polymers A) are used, they can be reacted with one another, for example by adding polymers of polyols with polymers containing isocyanate groups. The inorganic particles B) according to the invention are metal, semi-metallic or non-metallic oxides or oxides with a primary particle diameter of from I to 100 nm, preferably from 5 to 50 nm. The particle diameter (primary particle diameter) was determined by ultracentrifugation according to Colloid. Polym. 267, (1989) 1113. This is a range in which visible light (about 400 to 700 nm) is only scattered, with which materials with high transparency can be obtained. Examples of inorganic particles according to the invention are silica sols (SiO2), boehmite sols (Al (O) OH) and / or TiO2 sols. Silica sols are preferred in organic solvents, since they can be easily mixed with other solvents, which for example contain the organic polymers A). But in order to raise the solids content of the mixtures according to the invention, it is also possible to disperse the inorganic particles B) in the organic polymers without using additional solvents (the solvents which are necessary for the dissolution of the organic polymers, are not "solvents"). "in the sense of the invention are preferably used." I2 particle dispersions are preferably used in polar organic polymers, for example polymers containing OH groups, particularly preferably in polyoids, which are b-reacted naively with organic polymers containing groups The organic-inorganic binders OR according to the invention are polyfunctional organosilanes, which contain at least 2, preferably 3, silicon atoms each having the akoxyl or niaroxyl groups, in which silicon is bonded to at least one Si-C bond to a structural unit linking the silicon atoms As linking structural units according to the invention there can be mentioned, for example, alkeyl chains with from 1 to 10 carbon atoms linear or branched, radicals of cycloalipyl with from 5 to 10 carbon atoms, aromatic radicals, for example phenyl , Naphthyl or Difen io or also combinations of aliphatic and aromatic radicals. The aliphatic and aromatic radicals can also contain heteroatoms such as Si, N, 0, S or F. Examples of polyfunctional organosilanes are compounds of the general formula (I) R% .1S? [(CHa) nSi (OR7) ßRßj. a] 1 (I) being i = 2 to 4, preferably i = 4, n = ia 10, preferably n = 2 to 4, especially preferred n = 2 and R5 = alkyl, aryl, RG = alkyl, aryl, preferably R ° = methyl a = 1 to 3, R7 = alkyl, aryl, preferably R7 = methyl, ethyl, isopropyl, for the case in which a = 1, R "can also mean hydrogen, further examples are the cyclic compounds of the general formula (II) m = 3 to 6, preferably m = 3 or 4, n = 2 to 1U, preferably n = 2, R == Alkyl with 1 to 6 carbon atoms or aryl with 6 to 14 carbon atoms, preferably R5 = methyl, ethyl, especially it is preferred that Rs = methyl, R: = = alkyl, aryl, preferably Ri0 = methyl, c = 1 to 3 R3 = aiguil, aryl, preferably R3 = methyl, ethyl, isopropyl; for the case in which c = 1, R3 can also mean hydrogen. Other examples of polyfunctional organosilanes are compounds of the general formula (III) Si [OSiR11, (CH2) pSi (OR ") dR133, < iJ? (III) where p = ia 10, preferably p = 2 to 4, with special preference p = 2 R "= allyl, aryl, preferably R11 = methyl Ri3 = allyl, aryl preferably Ri3 = methyl d = 1 to 3, R12 = allyl, aryl, preferably R12 = methyl, ethyl, isopropyl; for the case in which d = i, R12 can also be hydrogen. In addition, silanoles or aicóxides can be mentioned as polyfunctional organosilanes, for example: a) Si [(CH2) 2Si (OH) (CH3) 2] 4 b) cyclo-. { OsiMe [(CH2) 2Si (OH) Me2]} 4, or c) cycle-. { Osi e. (CH2) 2S? (OEt) 2Me2j} 4, d) cycle-. { OsiMe [(CH2) 2Si (OMe) Me2]} 4, or e) cycle-. { ? eiMe [(CH2) 2Si (0Et) 3]} Four.

The mixtures according to the invention may contain, for example, to increase the resistance to abrasion, other metal oxides or additional non-metals. As examples, alkoxides of the general formula (IV) R3x-yM (OR2) and (IV) are mentioned where M = Si, Sn, Ti, Zr (x = 4, y = ia 4) or M = B, Al (x = 3, y = 1 to 3), R2, R3 = alger, aryl preferably R2, R3 = methyl, ethyl, isopropyl, n-butyl, sec-butyl, tere-butyl, phenyl, especially preferably R2, R3 = methyl and ethyl. Examples are Si (Oet) 4, Si (OMe) 4, H3C-Si (OEt) 3, CSH5-Si (OEt) 3, AKO'PrJj or Zr (OiPr) 4, preferably used Yes ( 4. Instead of the aicoxide, its condensation products can also be used. Commercially obtainable are, for example, Si (OEt) 4 condensates. The mixtures according to the invention on the other hand can also contain catalysts F) for the acceleration of the hydrolysis and condensation reactions and / or pigments for coloring or for protection against corrosion. Suitable solvents D) are, for example, alcohols such as methanol, ethanol, isopropanol, l-butanol, 2-butanol, 1,2-ethanediol and giieerine, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone and butanone, esters such as ethyl acetate or isobutyl acetate, aromatic compounds, such as toluene or xylene, esters, such as tere. -butylmethylether, as well as aliphatic hydrocarbons. As catalysts F, organic and inorganic acids or bases, as well as organometallic compounds or alkoxide metals can be used. In a preferred embodiment of the invention, the mixture without taking into account the solvent D) and all other additional constituent parts, such as for example catalysts and / or pigments, has the following composition: 3 to 80% by weight of polymer organic A) 1 to 60% by weight of inorganic polymer B) 1 to 80% by weight of inorganic organic binder C) and 0 to 60% by weight of metallic and non-metallic alkoxide E), completing parts A), B ), C) and E) 100%. In a particularly preferred embodiment of the invention, the mixture without taking into account the solvent D) and all other additional constituent parts, such as for example catalysts and / or pigments, has the following composition: 8 to 50% by weight of organic polymer A) 5 to 40% by weight of inorganic polymer B) 3 to 50% by weight of inorganic organic binder C) and 0 to 50% by weight of metallic and non-metallic alkoxide E), completing parts A), B), C) and E) 100%. The amounts of the solvent D) is preferably selected in such a way that the solids content of the mixture is between 5 and 80%, especially between 10 and 60% is preferred. For the preparation of mixtures according to the invention, the components are mixed in any sequence. The organic polymers are preferably used in a solvent. For the preparation of mixtures that lead to materials in which the organic polymer and the inorganic components are not covalently bound, the following embodiment is preferred: the organic polymer A) is placed in a solvent D) are added with stirring the inorganic particles B), preferably as a transparent dispersion in a solvent and the organic-inorganic binder C) and thereafter alkoxides, other solvents, water, catalysts and / or pigments. For mixtures, from which materials must be obtained, in which they are covalently bound to the hydrolysis, the organic polymer and the inorganic components, in a preferred embodiment, the organic polymer is first reacted A) with a bifunctional organosilane. After the transformation has been complete, the inorganic particles B) are then added, preferably as a transparent dispersion in a solvent and the organic-inorganic binder C), and finally optionally other solvents, water, catalysts and / or pigments. In another embodiment, the bifunctional organosilanes can also be reacted first with the inorganic particles B) and / or with the organic-inorganic binder C). The organic polymer A) is then added and optionally alkoxides, other solvents, water, catalysts and / or pigments are added. In the mentioned embodiments, the inorganic particles B) can also be used as dispersions to the organic polymers A), if necessary in the presence of solvents. The mixtures according to the invention are ready for use immediately after the mixing of the starting components and can be used, for example, for varnishing. Preferably, however, the mixtures are stirred for a certain time, in particular in the presence of water and condensation catalysts, so that polycondensates of the organic-inorganic binder or possibly the alkoxides of added metals are formed. The mixtures thus hardened harden significantly more quickly than freshly prepared ones. By eliminating the volatile components, organic-inorganic hybrid materials can be obtained from the mixtures according to the invention.

This can be done, for example, by evaporating the volatile components at temperatures of -10 to 200 ° C, preferably 15 to 160 ° C. The organic-inorganic hybrid materials thus obtained are formed by interpenetrating lattices or by a molecular mixture of inorganic and organic components. The inorganic network is formed in this case by the inorganic particles B), by the organic-inorganic binder C) and optionally by bifunctional alkoxides and / or organosilanes or by the corresponding hydrolysis and condensation products of all the aforementioned components. It is characteristic of the materials that the inorganic lattice contains structural units in which some silicon atoms are coupled through organic radicals to which they are linked through Si-C bonds. The new materials are suitable, for example, for obtaining coatings and moldings. The bodies molded from the materials according to the invention show less inflammability, for example, compared to moldings made from polyurethanes because of the high fraction of inorganic components. Coatings from materials according to the invention are characterized by good adhesion, high transparency, resistance to solvents and chemicals, resistance to abrasion and elasticity. The coatings are They adhere very well on glass and metals but also on many other organic and ceramic materials. Thus, for example, they can be varnished again, without problems, polyurethane varnish prints. They can also be applied without previous treatment, on transparent plastics such as polycarbonate, coatings that adhere well to improve the scratch resistance. The organic-inorganic hybrid materials according to the invention can be used, for example, as transparent coatings in those places where high resistance to abrasion, elasticity, resistance to chemicals or solvents are required. They are . to mention as examples the varnishes of coating in the automotive field, in the marine field (ships, port facilities) or also in the construction of apparatuses. for chemistry (for example, inner and outer linings of pipelines or reactors). For use in the automotive field, high resistance to abrasion and simultaneously resistance to solvents and chemicals is essential. To avoid a detachment (on large surfaces) of the varnish films in case of deformation damage, the coatings must show a certain elasticity. From the organic-inorganic hybrid materials according to the invention, coatings can be obtained whose resistance to solvents and Guidance products are as good or even partially better than the best coating varnishes well tested in practice, but the materials according to the invention at the same time show essentially better abrasion resistance. In particular, the coatings according to the invention with a high fraction of inorganic components are also suitable, for example, as biological anti-fouling coatings for ships.

Due to their repulsion effect against many dyes and their good resistance to solvents, the coatings according to the invention are very suitable as anti-graffiti varnishes. On the one hand the coatings are so wet that the dye film runs and forms drops, and on the other hand the dry dye can be removed without effort. The coatings can be applied on existing coatings to protect vehicles or also constructions in an efficient way.

The following examples serve to illustrate the invention without limiting it.

Examples Polyacrylates used as organic polymers can be obtained commercially under Desmophen ~ commercial name in Bayer AG, D-51386 Leverkusen. Unless otherwise indicated, Desmophen ^ A 665 (3.0% OH groups) is used as a 65% solution in n-butyl acetate / xylene (3: 1) and Desmophen '' A 450 (1, 0% OH groups) as a 50% solution in n-buyl acetate.

They were obtained. { OS iMe [(CH2) 2S i (OH) Me:]} 4 ("D4-silanol"; and ci d o- { OS iMe [(CH); S i (O?) 2Me].}. 4 '"D4-diethoxidc") as described in Example 1 or 2, by means of hydrosylation of cyclic. { OSi - (CH3) (C2H3)} 4 with HSiClMe2 or with HSiCl2Me and subsequent idolysis or alcoholysis. ? í Si ['CH :; : Si (OH) Me «J (" VS-s i lanol ") was prepared in a corresponding manner from etraviniisiiano, HSiClMe; and subsequent hydrolysis as described in DE-CS 19 603 242.

Hydrosiliylation catalysts can be obtained commercially, for example, "Silopren U Kstalisator Pt / S" (68% solution of a Pt complex substituted with cyclic ligands).

. { OSi (CH3) (C2h3)} 4 in isopropanol), Bayer AG, D-51368 Leverkusen, or were prepared as indicated.

The syntheses of the compounds mentioned above were carried out under an argon atmosphere or under vacuum.

The (organo) silicon sol used consisted of a dispersion of about 30% by weight of SiO2 (primary particle diameter of about 9 nm) in isopropanol. The indicated SiO2 content is obtained from the added amounts of (organ) silicon sol (SiO2 content of 30%) and TEOS (content of SiO2 of 28.8 &in the case of complete condensation) referred to the solids totals The films were applied by means of a film nder (leveler) on glass and when not indicated otherwise hardened for 1 hour at 130 ° C in an air circulation oven.

For the verification of the adhesion, a reticular cut test was carried out based on the standard - ISO 2409. The determination of the pencil hardness was made based on ASTM D 3363-92a co pens of the brand "S tabilo-micro 8000" (firm Schwan, Germany) hardness B up to 7H. The degree of hardness of the pencil that does not scratch the film to the base is given. The pendulum hardness was determined according to DIN 53 157 and the richsen drawing according to DIN ISO 1520.

Resistance to solvents was checked visually (1 minute or 5 minutes acting time): "C" (if to alter) "5" altered mean ivamen e: for example, blistering, disintegration c detached, softening; .

The opening tunnel test was performed in a laboratory tunnel consisting of a rotating brush < bristles of pelietiiene) and two nozzles for the shortening of the abrasive edio (quartz sand, average particle size 25 μm). The coated plate to be analyzed was moved 10 times under the brush forwards and backwards and sprayed at the same time with the mixture of water and sand. After 10 cycles the surface was cleaned with ethanol and the loss of brightness was determined (measurement of brightness at 20 ° C).

The effectiveness as an anti-paint coating (antigraffi ti) was checked by means of a one hour action of a 1% fuchsin solution in water-ethanol-butyl glycol (1: 1: 1). The dried film was rubbed with a paper towel soaked in ethanol and the remaining dye was visually classified into the categories "weak rose" and "rose". The absence of recognizable fuchsin residues was given as "eliminated without residues".

When rlc was indicated otherwise, the data in percentaje s or percentage in ceso. ? em lo 1 Coal activated active mask with H-PtClg 49.5 g of Norit CN 1 active carbon were suspended in 300 ml of bidistilled water and 200 ml of an aqueous solution of K; PcCl was added, which contained 0.5 g of Pt calculated as metal. Stirring continued for 10 minutes and the catalyst was suction filtered through a vacuum filter. The crude product (153 g) was dried at 0.1 Pa and 110 ° C and stored under argon. The catalyst contained 1% platinum.

Synthesis of ci cl o-. { OS iMe [(Z? ') 2S iCl.Me2]} -.

To 50 g (145.2 mmol) of cyclin- [OS i (CH-i C; H3) 120 m. of THi were added mmol) of chlorodime t ils i lane and 800 mg of the catalyst (preparation as indicated above). The reaction temperature was heated to 50 ° C, which was not observed ta poc; cab < ae ñoras . err.ee ra t u: n su p development d cale: aoo or another 20 hours, c ° c S? ? rv . eer ura amo 'e is deleted e. talizado : cr filtration through a * reversible frit.

The clear and colored filtrate was released in vacuo from the olfactory components and the product was oozed as a colorless oil.

Synthesis of ci cl o- (CS i e 'Z?' 2) _S i (OH) Me2]} 4 To a mixture consisting of 87.4 ml (63.6 g;; 28, 3 rr.mcl) of trithiamine, 12.1 ml (12.1 g; mmol) of water and 2850 ml of tert-bu tylmethyl ether were added drop wise in the interval of 1 hour 105 g (145.2 mmol) of cyclohexane. { OS iMe [(CH2) 2SiClMe2]} i in 100 ml of diethyl ether. After the addition was complete, an additional hour was stirred and the precipitate of triethyl onium hydrochloride was then filtered. Then, the volatile components were removed in vacuo by means of a rotary evaporator, the oily residue was taken in a portion of THF and filtered through silica gel. After a new elimination of the volatile components, the product was obtained as a viscous oil. Remand: 69.5 g corresponding to 74% of the theoretical. ? i emol e 2 Synthesis of ci cl o -. { OS iMe [(Cp:): SiCl2 (CH3)]} - 249.5 g (725.5 mmol) of cyclohexane (CK3) (C2K3) were placed} 4 in 250 ml of toluene (p.a.) and heated to 100 ° C after the addition of 50 μi of Silopren ü-katalisator. Then, 30 ml of dimethyl ether was added rapidly, so that the temperature rose immediately to 110 ° C. Then, the dropwise addition of the amount of dime ti 1 chlorosilane remaining from the 332.3 ml (367.2 g, 3.19 mol) was started. During the dripping (about 2 hours), the temperature of the reaction mixture rose meanwhile to 120 ° C, but fell in the last 30 ml at 107 ° C. The yellowish reaction mixture was stirred for a further 2 hours at 110 ° C and then cooled to room temperature. After removal by condensation of the volatile components in vacuo a pale yellow oil was obtained.

Rendition: 581.0 corresponding to 99.6% of the theory.

Synthesis of c i ci c-. { OS iMe [(CH:): S i (OE t) ~ (CH3)] 581.0 g (722.2 mmol) of cyclohexane were dissolved. { OSiMe [(CH2) 2SiCi2 (CH3)]} i (preparation as described above) and 500 μl and gctra was added dropwise with stirring to 476.0 g (10.33 mol) of eta ol (p.a.). After dripping (about 2 hours) during which the reaction mixture was heated to about 32 ° C, it was heated to reflux for a further two hours, still releasing gas vigorously. hydrochloric. At the end, the volatile components were removed by distillation first under normal pressure and then under vacuum. A weakly yellow oil was obtained.

E j em o l 3 D4-Silanol / Desmophen To 665 if dissolves additional entities g of cyclic were stirred. { CSiMe [(CHc): Si (OH) Me-]} ^ with 108.4 of Desmochen / A 665 that a mixture was obtained or ogénea, 135.5 ml of Organosol, 75 ml of TOS and 12 l of 0.1 hydrochloric acid were added. Ogénea is agitated for 2 more hours. Co having in solids: 3%.

After application and hardening, a transparent film was obtained, without cracks, which exhibited a weak dry film.

E j emolo 4 D4-Silanol / Desmophen A 665 with a low fraction of Orsanosol. 150 g of a 10% solution of ci cl or -. { OS i and í (CK z) 2S i (OH) e:} ^ ob e ida en r.-butar.ol, 108.4 g of Desmoche 'A 665, 68 ml of Organosol, 75 ml of TEOS and 12 ml of 0.1 N hydrochloric acid.

After the application and hardening, a transparent film was obtained, without cracks.

Example 5 D4 -Silanol / Desmophen® A 665 with a high fraction of Organosol. 150 g of a 10% solution of citric acid were mixed. { OSiMe [(CH2) 2Si (OH) Me2]} 4 in n-butanol, 108.4 of Desmophen®, A 665, 135.5 ml of Organol, 75 ml of TEOS and 12 ml of hydrochloric acid, 0.1 N and were stirred for 2 hours. A homogeneous mixture was obtained.

The application was made by spraying (carrier gas: Nitrogen); Specific tests for automobile: *) Xylene, MPA, ethyl acetate, acetone (1 minute acting time), benzine (10 minutes).

Tree resin, brake fluid, pancreatin (50%), NaOH (1%), sulfuric acid (1%); the indicated temperature corresponds to the first visible damage.

Loss of brightness after 10 washes, determined at 20 ° C of incidence angle (starting brightness, final brightness, difference).

As a comparison: loss of gloss of a 2C polyurethane coating varnish: 35.2.

Example 6 D4-Silanol / Desmophen ™ A 665 with a pre-reaction of the inorganic components. 150 g of a 10% solution of cyclo- were mixed. { 0siMe [((CH2) 2Si (OH) e.) .4 in n-butanol, 69 ml of Organosol, 75 ml of TEOS and 12 ml of 0.1 N hydrochloric acid and stirred for 2 hours, then 108.4 g of water were added. Desmophen ™ A 665 and stirred for a further 15 minutes to obtain a homogeneous mixture.

After application and hardening a transparent film was obtained, without cracks.

Example 7 D4-Silanol / Desmophen® A 665 (70% in n-butyl acetate) 1.5 g of cyclohexane was stirred. { OSiMe [[(CH2) 2Si (0H) Me2]} 4 with 10.08 g of Desmophen® A 665 until a homogeneous mixture was obtained. Then 13.6 ml of Organosol, 7.5 ml of TEOS and 1.2 ml of 0.1 N hydrochloric acid and the homogeneous mixture was stirred for a further 2 hours.

After application and hardening a transparent film was obtained, without cracks.

Examples 8-10 D -Diet oxide / Desmophen® A 665 In the sequences indicated in the table, the ingredients were mixed and stirred for 2 h. Homogeneous mixtures were obtained.

After the application and hardening, transparent films were obtained, with only cracks.

E j empl o 11 and 12 D4 -Diet oxide / Desmophen® A 665 with pre-reaction of the inorganic components.

The (inorganic) components indicated in the table were mixed and stirred for 2 hours; the Desmophen ™ A 665 organic polymer was then added and stirring was continued until homogeneous mixtures were obtained.

After application and hardening, transparent films were obtained which did not show cracks.

Examples 13 and 14 Reaction of Desmophen ™ A 665 (70% in n-butyl acetate) with OCN- [(CH2) 3-Si (OEt) 3. 100 g of Desmophen ™ A 665 were each stirred with 0.7 g (example 13) or with 3.5 (example 14) of OCN- (CH 2) 3-Si (OEt) 3 and after that they were heated in the drying oven to 45 ° C. ° C for 5 hours. A colorless mixture with an unmodified viscosity was obtained in an appreciable manner.

D4-Silanol / Desmophen ™ A 665 (functionalized with OCN- (CH2) 3-Si (OEt) 3.

The educts were mixed together with each of the others in the sequence given in the table and stirred for 2 hours. Homogeneous mixtures were obtained.

After application and hardening transparent films were obtained, without cracks.

Examples .15-17 TVS-Silanol / Desmophen® A 450 (at 50- 'in n-butyl acetate / xylene (1: 1)) 2.0 g of S i [(CH 2) 2 S i (OH) e 2] 4, 4.0 ml of TEOS, 5.0 ml of ethanol and 1.0 ml of 0.1 N hydrochloric acid were mixed and stirred for 1 hour.

After that, 2 g of Desmophen® A 450 (Example 15), 1.0 g of Desmophen® A 450 (Example 16), or 0.5 g of Desmophen® A 450 were added to each 2 ml of this solution. (Example 17), and stirred until homogeneous mixtures were obtained.

With the solutions thus obtained, a polycarbonate plate and an ABS plate were coated (90 μm) and the coating hardened for 1 hour at 130 ° C or at 90 ° C.

The reticular cut test gave: E j emplo 1 < ' D -Silanol / Desmophen "A 450 1.5 g of citric acid was mixed. { OSiMe [(CH2) 2Si (OH) Me2]} 4 10 g of me tiletil ce tona, g of Desmophen® A 450, 13.6 ml of Organosol, 7.5 ml of TEOS and 1.2 ml of 0.1 N hydrochloric acid were stirred for 2 hours. A homogeneous mixture was obtained.

After application and hardening a transparent film was obtained, without cracks.

Examples of comparison la - lg TEOS, H C-Si (OEt) 3 or Ph-Si (OEt) 3 / Desmophen® A 665 (no organic-inorganic binder) The ingredients were mixed in the sequence indicated in the table and stirred for 2 hours. Homogeneous mixtures were obtained.

With the solutions thus obtained, a glass plate was coated in each case (wet film thickness 240 μm) and the coating hardened for 15 minutes at 130 ° C.

Comparison example 2a and 2b TEOS, H3C-Si (OEt) 3 or Ph-Si (OEt) 3 / Desmophen® A 665 of Example 14 (no organic-inorganic binder) The ingredients were mixed in the sequence indicated in the table and stirred for 2 hours. Homogeneous mixtures were obtained.

With the solutions thus obtained, a vxdry plate (thickness of the wet film 240 μm) was coated and the coating was cured for 15 minutes at 130 ° C.

It is noted that with regard to this date, the best method known to the applicant to carry out the aforementioned invention is that which is clear from the present description of the invention. Having described the invention as above, the content of the following is claimed as property.

Claims (3)

1. CLAIMS 1.- Transparent mixtures, characterized in that they contain: A) one or several organic polymers B) inorganic particles with a primary particle diameter of 1 to 100 nm, C) one or more inorganic-organic binders based on polyfunctional organosilanes, which they contain at least 2 silicon atoms with 1 to 3 alkoxy or hydroxy groups, wherein the silicon atoms are linked with at least one SiC bond to a structural unit linking the silicon atoms, and D) at least one solvent.
2. 2.- Hybrid organic-inorganic materials, characterized in that they are obtained by means of the separation of the volatile constituent parts of the mixtures according to claim 1.
3. 3.- Use of organic-inorganic hybrid materials according to claim 2 for the preparation of molded bodies or surface coatings.