FI96432B - Liquid, radiation curable coating for coating glass surfaces - Google Patents

Description

96432

The present invention relates to a liquid, radiation-curable coating composition for coating glass surfaces, comprising A) 56 to 89% by weight of a coating composition of at least one polyethylated unsaturated polyethylene unsaturated - 30% by weight of the coating mass of at least one ethylenically unsaturated monomer, C) 0.5 to 8% by weight of the coating mass of at least one photoinitiator and D) 0.05 to 6% by weight of the coating mass of alkoxysilane, and E) the usual amounts of amines for photoinitiators as synergists and / or other customary auxiliaries and additives, the sum of components (A) to (E) in each case being 100 to 20% by weight.

The present invention further relates to a method for coating glass surfaces, in particular for coating optical glass fibers using radiation-curable coating compositions.

25 Optical glass fibers are playing an increasingly important role in the field of communication as light-conducting fibers. For this purpose, it is absolutely essential to protect the glass surfaces from moisture and wear. The glass fibers are therefore provided with a protective lacquer layer immediately after their manufacture.

For example, it is known from EP 114 982 to first provide glass fibers with an elastic but slightly hard and slightly tough buffer layer (primer) and then to apply a radiation-curable topcoat with high hardness and toughness. The two-layer 96432 2 structure provides good protection of the glass fibers in the event of mechanical stress, even at low temperatures. EP 114 982 uses radiation curable coating compositions based on polyurethane containing diethylene end groups, a diethylene unsaturated bisphenol diglycidyl ether ester and a monoethylenically unsaturated monomer prepared from this, as a topcoat. However, such fiberglass coatings have the considerable disadvantage that they adhere only poorly to the glass surface. Particularly under the stress of moisture, this adhesion is further aggravated, perhaps even so severely, that the result is complete detachment from the glass surface. The problem of poor adhesion of coating compositions applied to glass-15 tin is known. Therefore, in order to improve the adhesion, organosilanes are often added to the coating compositions as adhesion promoters. For example, it is known from EP 33 043 to add organosilanes as adhesion promoters for radiation-curable coating compositions based on vinyl monomers and reactive polymers (not polyurethanes), it being essential for the invention that either the vinyl monomers or . Examples of suitable compounds include N-aminopropyltriethoxysilane, N, β-aminoethyl-N-aminopropyltrimethoxysilane and / -glycidyloxypropyltrimethoxysilane. The problem of deterioration in the adhesion of fiberglass coatings under moisture stress is not addressed in this publication. JP patent publication 45 138/85, 08.10.1985, (corresponding to JP application publication 42 244/80, 25.03.1980) also discloses the use of organosilanes as adhesion promoters in radiation-curable glass fiber coating materials. Polymers containing azi-35 groups are used as film-forming components. Suitable silanes include Y * -methacryloxypropyltrimethoxysilanes, N-aminopropyltrimethoxysilane and N-glycidyloxypropyltrimethoxysilane. However, in JP 45 138 it is essential for the invention to incorporate azide groups into polymers in order to increase the curing rate. Also, this publication does not discuss the effect of moisture on the adhesion of the fiberglass coating. Finally, EP-A-149 741 also discloses liquid, radiation-curable glass fiber coating materials which contain, in addition to a radiation-curable, polyethylene-unsaturated polymeric compound, 0.5 to 5% of a polyalkoxysilane coating composition.

Suitable are polyalkoxysilanes having an organic substituent having a single active amino or mercaptyl hydrogen tower which can react in the Michaelis addition reaction with ethylenically unsaturated bonds. An example of a suitable silane is V-mercaptopropyltrimethoxysilane. According to the teachings of EP-A-149 741, only the use of such silanes 20 succeeds in improving the adhesion even under moisture loading. In contrast, compounds commonly used as adhesion promoters, such as V'-aminopropyltriethoxysilane and Ν-β- (N-vinylbenzylaminopropyl) trimethoxysilane, prove to be unsuitable for improving soil adhesion according to EP-A-149 741.

It was therefore an object of the present invention to provide radiation-curable coating compositions for coating glass surfaces, in particular optical glass fibers, which have no or only a slight deterioration in adhesion after moisture loading compared to the corresponding freshly prepared and directly cured .

4,96432

The object underlying the invention is solved with a liquid, radiation-curable coating composition for coating glass surfaces, which contains 5 A) 56 to 89% by weight of the coating mass of at least one diethylenically unsaturated polyurethane optionally containing urea groups, B) 10 to 30% by weight of a coating unsaturated monomer, 10 C) 0.5 to 8% by weight of the coating mass of at least one photoinitiator, D) 0.05 to 6% by weight of the coating mass of alkoxysilane, and E) ordinary amounts of amines as synergists of photoinitiators and / or other customary auxiliaries. and additives, the sum of components (A) to (E) being in each case 100% by weight.

The coating composition is characterized in that β-β-aminoethylaminopropyltrimethoxysilane or N-aminopropyltrimethoxysilane or triaminomodified propyltrimethoxysilane is used as component (D).

Given the variety of organosilicon compounds known as adhesion promoters, it was surprising and unpredictable that using NB-aminoe-25-V'-aminopropyltrimethoxysilane, V-aminopropyltrimethoxysilane, and triaminomodified propyltrimethoxysilane (e.g. ", A commercial product of Dynamit-Nobel Chemie), the adhesion of radiation-curable coatings based on unsaturated polyurethanes to glass surfaces does not deteriorate at all or deteriorates only to a negligible extent under moisture stress, whereas, for example, V-glycidyloxypropyltrimethoxysilane and Np-

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96432 5 In the case of monochloride, a significant deterioration of infection occurs under stress.

The coating composition according to the invention will now be explained in more detail below: Diethylenically unsaturated polyurethanes (A) used as a film-forming component can be obtained by reacting di- or polyisocyanates with a chain extender comprising diols / polyols and / or diamines and / or diamines / polyamines. from a group of polythiols and / -10 or alkanolamines, followed by reacting the remaining free isocyanate groups with at least one hydroxyalkyl acrylate or hydroxyalkyl ester of other ethylenically unsaturated carboxylic acids. The amounts of chain extenders, di- or polyisocyanate, and hydroxyalkyl ester of ethylenically unsaturated carboxylic acid are selected so that 1) the equivalent ratio of NCO groups to the reactive groups of the chain extender (hydroxyl, amino, or meryl); 1: 2, preferably about 2: 1, and 2) the OH groups of the hydroxyalkyl ester of ethylenically unsaturated carboxylic acids is a stoichiometric amount relative to the remaining free isocyanate groups of the prepolymer from the isocyanate and chain extender.

In addition, it is possible to prepare polyurethanes (A) by first reacting a part of the isocyanate groups of the di- or polyisocyanate with at least one hydroxyalkyl ester of an ethylenically unsaturated carboxylic acid, and then reacting the remaining isocyanate groups with a chain extender. Also in this case, the amounts of the chain extender, isocyanate and hydroxyalkyl ester of unsaturated carboxylic acids 35 are selected so that the equivalent ratio of NCO groups to reactive groups of the chain extender is between 3: 1 to 1: 2, preferably about 2: 1, and the equivalent N of the remaining NCO groups. is 1: 1. It goes without saying that all intermediate forms of these two methods are also possible. For example, some of the isocyanate groups of the diisocyanate may be first reacted with the diol, then another part of the isocyanate groups is reacted with the hydroxyalkyl ester of the ethylenically unsaturated carboxylic acid, and finally the remaining isocyanate groups are reacted with the diamine.

These various methods of preparing polyurethanes are known (cf., for example, EP-A-204 161) and therefore do not require a more detailed description.

Suitable for the preparation of polyurethanes (A) are aromatic, aliphatic and cycloaliphatic di- and polyisocyanates, such as, for example, 2,4-, 2,6-tolylene diisocyanate and mixtures thereof, 4,4'-diphenylmethane diisocyanate. cyanate, m-phenylene, p-phenylene, 4,4'-diphenyl, 1,5-naphthalene, 1,4-naphthalene, 4,4'-toluidine, xylene diisocyanate and substituted aromatic systems such as dianisidine diisocyanates, 4,4'-diphenyl ether diisocyanates or chlorodiphenylene diisocyanates and multifunctional aromatic isocyanates such as 1,3,5-triisocyanato-benzene, 4,4'-, " triisocyanate triphenylmethane, 2,4,6-triisocyanatotoluene and 4,4'-diphenyldimethylmethane-2,2 ', 5,5-tetraisocyanate, cycloaliphatic isocyanates such as 1,3-cyclopentane, 1,4- cyclohexane, 1,2-cyclohexane, 4,4'-methylene bis (cyclohexyl isocyanate) and isophorone diisocyanate, aliphatic isocyanates such as for example trimethylene, tetramethylene, pentamethylene, hexamethylene, trimethylhexamethylene 1,6-diisocyanate and tris-hexamethylene-35 triisocyanate, and in EP 204 161 columns.

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96432 The diisocyanates derived from dimer fatty acids described in lanes 4, lines 42-49.

Preferably, 2,4- and 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexa-5 methylene diisocyanate, isophorone diisocyanate and 4,4'-methylenebis (cyclohexyl isocyanate) are used.

Examples of suitable di- and polyols are, for example, ethylene glycol, propylene glycol-1,2 and -1,3-butanediols, pentanediols, neopentyl glycol, hexa-10 nidiols, 2-methylpentanediol-1,5,2-ethylbutanediol-1,4, dimethylol cyclohexane, glycerin, trimethylolethane, trimethylolpropane and trimethylolbutane, erythritol, mesoerythritol, arabite, adonite, xylitol, mannitol, sorbitol, dulcite, hexanetriol, (poly) -15 pentaerythritol; in addition to monoethers such as diethylene glycol and dipropylene glycol and polyethers, adducts of said polyols and alkylene oxides. Examples of alkylene oxides suitable for polyaddition to these polyols to form polyethers include ethylene oxide, propylene oxide, butylene oxide and styrene oxide. These polyaddition products are generally considered to be polyethers having terminal hydroxyl groups. They can be straight-chain or branched. Examples of such polyethers are polyoxyethylene glycols having a molecular weight of 200 to 4000, polyoxypropylene glycols having a molecular weight of 200 to 4000, polyoxytetramethylene glycol, polyoxyhexamethylene glycol and polyoxyethylene glycol, polyoxynonamethylene glycol, polyoxynonamethylene glycol, polyoxynethylene glycol Other types of polyoxyalkylene glycol ether can also be used. Also suitable are polyether polyols obtained by reacting polyols such as ethylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexane-35 diol and mixtures thereof; glycerol trimethylolethane, tri-96432 methylolpropane, 1,2,6-hexanetriol, dipentaerythritol, tripentaerythritol, polypentaerythritol, methylglucosides and sucroses with alkylene oxides such as ethylene oxide, propylene oxide or mixtures thereof. Examples of suitable polyetherdiols are also polymerization products of tetrahydrofuran or butylene oxide. Also useful are polyester polyols, preferably polyester diols, which can be prepared, for example, by reacting the aforementioned glycols with dicarboxylic acids such as phthalic acid, isophthalic acid, hexahydrophthalic acid, adipic acid, azelaic acid, sebacic acid, hexacarboxylate, tetrachloroethaneorta . Instead of these acids, their anhydrides can also be used, if they exist.

Polycaprolactone diols and triols are also useful. These products are obtained, for example, by reacting 6-caprolactone with a diol. Such products are described in U.S. Patent 3,169,945. Poly-20 lactone polyols obtained from such a reaction are characterized by a terminal hydroxyl group and repeating polyester moieties derived from the lactone. These repeating moieties may correspond to formula 25 0

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- C - (CHR) n - CH 2 O- wherein n is preferably 4 to 6 and the substituent is hydrogen, an alkyl-30 group, a cycloalkyl group or an alkoxy group, wherein no substituent contains more than 12 carbon atoms and the total number of carbon atoms in the lactone ring substituent is not more than 12 .

The lactone used as starting material may be an arbitrary lactone or an arbitrary combination of lactones, in which case this lactone must contain at least 6

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96432 9 carbon atoms, for example 6-8 carbon atoms, and wherein at least two hydrogen substituents should be on the carbon atom attached to the oxygen group of the ring. The lactone used as a starting material can be represented by the following general formula.

^ H2 "(CR2 ^ rT I

0 - * where n and R have already been assigned a meaning. In the context of the invention, the preferred lactones for the preparation of polyester diols are caprolactones in which n has a value of 4. The most preferred lactone is a substituted G-caprolactone in which n has a value of 4 and all R substituents denote hydrogen. This lactone is particularly advantageous because it is available in large quantities and provides coatings with excellent properties. In addition, various other lactones may be used alone or in combination.

Examples of suitable diols for reacting with lactones are the diols already described above for the reaction with carboxylic acids.

Examples of suitable amines are ethylenediamine, tri-, tetra-, penta-, hexa-, hepta-, nona-, deca- and dodecamethylenediamine, 2,2,4- or 2,4,4-trimethyl-hexamethylenediamine, propylenediamine and corresponding polyalkylenediamines such as polypropylenediamine, polyetherdiamines having a molecular weight of 200 to 4000, for example polyoxyethylenediamine, polyoxypropylenediamine, polytetramethylenediamine, 1,3- and 1,4-butylenediamine, isophoronediamine, 1,2- and 1,4- diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis- (4- ['aminocyclohexyl) propane, 4,7-dioxadecane-1,10-diamine, 4,9-dioxadodecane-1,12-diamine, 7-methyl-4,10-dioxatridecane-1,13-diamine, nitrile tris (ethane-35-amine), ethanolamine, propanolamine, N- (2-aminoethyl) -10 96432 ethanol, polyether polyamines, bis- (3-aminopropyl) methylamine, 3-amino-1- (methylamino) propane, 3-amino-1-cyclohexylamine o) propane, N- (2-hydroxyethyl) ethylenediamine, tris- (2-aminoethylamine) and polyamines of the formula I-N-iRj-NH- ^ R ^ NHj. n is an integer from 1 to 6, preferably from 1 to 3. R 1 and R 2 are the same or different alkylene groups or alkylene groups containing cycloalkylene groups or ether groups having 2 to 6, preferably 2 to 4, C atoms. Examples of such polyalkylene poly-10 amines are diethylenetriamine, triethylenetetramine, tetraethylenetrentamine, dipropylene triamine, tripropylene tretramine, tetrapropylene trentamine and dibutylenetriamine.

Also useful as chain extenders are di-15 and polythiols such as dithioethylene glycol, 1,2- and 1,3-propanedithiol, butanedithiols, pentanediylthiols, hexanedithiols, and other S-H analogs of the disclosed di- and polyols.

Suitable for attaching ethylenically unsaturated groups to polyurethane are hydroxyalkyl esters of ethylenically unsaturated carboxylic acids such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, methoxyacrylate, hydroxyamyl acrylate, hydroxyamyl acrylate, hydroxyhexyl, hydroxyhexyl and hydroxyalkyl esters of isocrotonic acid.

Unsaturated polyurethane is used in the coating compositions in amounts of 56 to 89% by weight of the coating composition.

In addition to the polyurethane (A) just described, the coating composition according to the invention further contains from 10 to 30% by weight of at least one ethylenically unsaturated monomer (B) by weight of the coating composition. Examples of suitable monomers are ethoxyethoxyethyl acrylate, N-vinylpyrrolidone-35, phenoxyethyl acrylate, dimethylaminoethyl acrylate

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96432 11 teaspoons of hydroxyethyl acrylate, butoxyethyl acrylate, isobornyl acrylate, dimethyl lacrylamide and dicyclopentyl acrylate. Also suitable are di- and polyacrylates such as, for example, butanediol diacrylate, trime-5-tolylpropane diacrylate and triacrylate, pentaerythritol diacrylate and the long-chain straight-chain diacrylates with a molecular weight of 400 to 4000, preferably from 400 to 4000, described in EP-A-250 631. - 2500. Both acrylate groups can be separated, for example, by the structure of polyoxybutylene-10. Also useful are 1,12-dodecyl diacrylate and reaction products obtained from 2 moles of acrylic acid and 1 mole of a dimeric fatty alcohol, usually having 36 carbon atoms. Mixtures of the monomers just described are also suitable.

Preferably, N-vinylpyrrolidone, phenoxyethyl acrylate, isobornyl acrylate and mixtures of these monomers are used.

The photoinitiator used in the coating compositions according to the invention in an amount of 0.5 to 8% by weight, preferably 2 to 5% by weight, of the coating composition varies according to the radiation used to cure the coating material (UV radiation, electron radiation, visible light). Preferably, the coating compositions according to the invention are cured by means of UV radiation. In this case, ketone-based photo-initiators are usually used, for example, acetophenone, benzophenone, diethoxyacetophenone, m-chloroacetophenone, propiophenone, benzoin, benzyl, benzyldimethyl ketal, anthraquinone, thioxanthene and thioxanthene derivatives and various photoinate derivatives. It is possible to use in combination with said photoinitiators various amines, for example diethylamine and triethanolamine, which act as synergists in amounts of up to 4% by weight of the coating mass.

As an essential ingredient of the invention, the coating compositions 35 contain 0.05 to 6% by weight of the coating composition of β, β-amino-12,946,32-ethyl-2-aminopropyltrimethoxysilane, N'-aminopropyltrimethoxysilane, or a triaminomodified propyltrimethoxysilane (e.g. type TRIAMO, Dynamit-Nobel Chemie kaup-5 product). These alkoxysilanes are common commercial products and therefore do not need to be further described. Preferred coating materials are obtained when either 0.5-2% by weight of the coating mass of N, β-aminoethylaminopropyltrimethoxysilane or 2-4% by weight of the coating mass of V-aminopropyltrimethoxysilane or 4-6% by weight of the coating mass is used as component (D). triaminomodified propyltrimethoxysilane (e.g. the adhesion promoter DYNASYLAI®, type TRIAMO, a commercial product of Dynamit Nobel Chemie).

In addition, the coating compositions according to the invention may optionally also contain other customary auxiliaries and additives in customary amounts, preferably from 0.05 to 10% by weight, based on the coating composition. Examples of such substances are fluxes and plasticizers. The coating compositions can be applied to the glass surface by known methods, for example by injection molding, rolling, a-flow, dipping, granulating or brushing.

The curing of the lacquer films is carried out by means of radiation, preferably UV radiation. The equipment and conditions required for these curing methods are known in the literature (cf., e.g., R. Holmes, U.V. and E.B. Curing Formulation for Printing Inks, Coatings and Paints, SITA Technology, Academic Press, London, UK 1984) and do not require further description.

The present invention also relates to a process for coating glass surfaces, I.) applying a radiation-curable coating composition comprising li 96432 13 A) 56 to 89% by weight of the coating composition of at least one diethylenically unsaturated polyurethane, optionally containing urea groups, B) 10 to 30% by weight of the coating mass of at least 5 equal ethylenically unsaturated monomers, C) 0.5 to 8% by weight of the coating mass of at least one photoinitiator, D) 0.05 to 6% by weight of the coating mass of alkoxysilane, 10 E) ordinary amounts of amines as synergists of photoinitiators and / or other customary auxiliaries and additives, the sum of components (A) to (E) in each case being 100% by weight, II.) the coating mass is cured by means of UV or electron radiation.

The process is characterized in that the coating composition contains N, β-aminoethylaminopropyltrimethoxysilane or Ϋ-aminopropyltrimethoxysilane or triaminomodified propyltrimethoxysilane as component (D).

For a more detailed description of the coating composition used in the method according to the invention and for carrying out this method, reference is made to pages 5-13 of this description. The method according to the invention is particularly well suited for coating optical glass fibers. Especially when using 25 optical glass fibers as light guides, it is important that the coating compositions used to protect the surface have good adhesion to the glass surface even under moisture stress. Reductions in the adhesion of the coating after moisture stress - which cannot be avoided when using glass fibers as light guides - (for example, the glass fibers are free in the air at the switching stations *) lead to varnish damage on the surface of the glass fiber. This then unprotected surface can now be damaged very easily, for example by dust particles, leading to a deterioration of the optical properties. However, it is with the aid of the method according to the invention and the coating compositions according to the invention that it is possible to avoid these disadvantages and to provide coatings which have very good stability even after moisture stress.

The coating compositions according to the invention can then be applied either as a single-layer varnish or as a primer for a two-layer varnish on a glass fiber. Suitable topcoats in connection with a two-layer varnish are described, for example, in EP 114 982.

The invention is further elucidated in the following examples. All figures and percentages are by weight unless otherwise indicated.

Example 1 (comparison)

A radiation-curable coating composition consisting of 75.8 parts of unsaturated polyurethane, 9.2 parts of trimethylolpropane triacrylate, 12 parts of phenoxyethyl acrylate and 0.5 parts of benzylide is prepared by known methods (cf., for example, EP-A-114 982). 2.5 parts of benzophenone so that 4 moles of 4,4'-methylene bis (cyclohexyl isocyanate) are first reacted with 2 moles of polyoxypropylene glycol (molecular weight 1000) in the presence of trimethyllipropane triacrylate and phenoxyethyl acrylate. This intermediate obtained is reacted with 2 moles of 2-hydroxyethyl acrylate and then with 1 mole of polyoxypropylenediamine (molecular weight 230).

Photoinitiators are then added to the mixture. Well-cleaned (above all non-greasy) glass sheets (width x length = 98 x 151 mm) are glued from the edge with Tesakrepp® ~ adhesive tape no. 4432 (width 19 mm) and the coating mass le-30 is coated by granulation (dry film thickness 180 μm).

The curing is carried out with a UV irradiator with two medium Hg radiators, each with a power of 80 W / cm, using a belt speed of 40 m / min and two passes and a half power (= 40 W / m). The irradiation dose is then

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96432 15 0.08 J / cm2 (measured with a dosimeter UVICURE, System EIT, manufactured by Eltosch).

Immediately afterwards, the infection is examined as follows: 5 - Peel the beginning of the film somewhat out of the glass with a blade.

- Attach a wire loop to the film part removed with adhesive tape.

- Hang the spring balance and pull it out as evenly as possible at the right angle.

- Read the required gravity in grams from the scale.

The evaluation of the adhesion test is performed by reporting the values obtained from the parallel assays and checking the reproducibility of the good (= large) adhesion values by means of several replicates.

The result of the adhesion test is shown in Table 1. In addition to this adhesion test, it is also possible to perform a roller peel test in accordance with DIN 55 289, but 20 it was not performed. In addition, to test for infection after moisture stress, the glass sheets are stored immediately after curing for 12 hours in suitable weather cabinets with a humidity adjusted to 90% relative humidity (r.F.) (equivalent to DIN 50005) at room temperature. 25 (25 ° C). As soon as the treatment is completed, the tensile test is carried out on a spring balance in the same way as immediately after irradiation.

The evaluation of the adhesion test is also performed in this case by averaging the parallel determinations. 30 With good (= high) adhesion values, at least two repeat measurements are performed to determine reproducibility. The result of this experiment is also shown in Table 1.

The adhesion test performed on the window glass gives good, reliable results as a laboratory method. This method 35 is also carried out by glass fiber manufacturers because it gives 16,96432 practical results which hold very well with the adhesion values of optical glass fibers (typical fiber thickness 125 .mu.m).

Example 2 (Comparative) According to Comparative Example 1, a radiation-curable coating material based on an unsaturated polyurethane is prepared. In contrast to Comparative Example 1, the coating agent further contains 2% by weight of the total composition of γ-glycidyloxypropyltrimethoxysilane.

10 According to Comparative Example 1, this coating agent is applied by means of a Rake to glass sheets (dry film thickness 180 μm) and cured by means of a medium mercury pressure lamp (dose rate also 0.08 J / cm 2). Immediately after curing of the coating material and storage for 12 hours at 90% relative humidity and room temperature, the adhesion of the coating is measured as shown in Comparative Example 1. The results are shown in Table 1.

Examples 3 and 4 (comparison)

Glass coatings are prepared according to Example 2, but the difference is that instead of 2% by weight of the total composition, γ-glycidyloxypropyltrimethoxysilane is now used in 2% by weight of 3-butenyltriethoxysilane (Example 3) and 2% by weight of Np- (N-vinylbenzyl). -amino) ethyl-γ-aminopropyltrimethoxysilane monohydro-25 chloride (formula (CH 3 O) 3 Si (CH 2) 3 NH (CH 2) 2 NH-CH 2 - ζθ} -CH * CH 2 · HCl (Example 4) always with respect to the total composition. the results of the forging test are shown in Table 1.

Examples 5-7 ** Glass coatings are prepared according to Example 2, but the difference is that instead of 2% by weight, γ-glycidyloxypropyltrimethoxysilane is now used in 35 (Example 5) and 2 (Example 6) and 3 (Example 7) 96432 17 no-% Ν-β-aminoethyl-γ-aminopropyltrimethoxysilane always relative to the total composition. The results of the adhesion test are shown in Table 1.

Examples 8-9 Glass coatings are prepared according to Example 2, but with the difference that instead of 2% by weight of Y'-glycidyloxypropyltrimethoxysilane, 2% by weight of Y'-aminopropyltrimethoxysilane (Example 10) and 2% by weight of triaminomodified propyltrimethoxysilane are now used. (adhesion promoter DYNASYLAl · / ®, type "TRIAMO", commercial product of Dynamit-Nobel Chemie) always in relation to the total composition. The results of the adhesion test are shown in Table 1.

18 96432

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Examples 1-11 show that by adding β-β-aminoethyl-β-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane and triaminomodified propyltrimethoxysilane (adhesive DYNASYLAhi®, 5 "type" TRIAMO "), Dynamit-Nobel Chemien no there is little or no deterioration in infection after exposure to moisture, while the addition of other known silane-based infectious agents, such as Y'-glycidyloxypropyltrimethoxysilysane, 3-butenyltriethoxysilane and Ν-β-β-vinyl-aminobenzylaminopropyl-γ-ylamethyl-γ-ethyl significant deterioration of infection is observed under moisture stress.

Claims (11)

1. Liquid, by straining curable coating material for coating glass surfaces and containing A) at least one and optionally urea groups containing, diethylenically unsaturated polyurethane in an amount of 56 - 89% by weight, calculated pci coating mass, B) at least one ethylenically unsaturated monomer in an amount of 10-30% by weight, calculated on the coating mass, C) at least one photoinitiator in an amount of 0.5 - 8% by weight, calculated on the coating mass, and D) an alkoxysilane in an amount of 0.05 - 6% by weight, calculated on the coating mass, and E) usual amounts amines as synergists for the photoinitiators and / or conventional auxiliaries and additives, the sum of components (A) - (E) being in each case up to 100% by weight, characterized in that as component D) is inserted NB-aminoethyl-γ-amino-propyltrimethoxysilane or γ-aminopropyltrimethoxysilane or triaminomodified propyltrimethoxysilane. Coating composition according to claim 1, characterized in that, as component (D), it contains N-B-aminoethyl-γ-aminopropyl trimethoxysilane in an amount of 0.5-2% by weight, calculated on the coating mass. Coating composition according to claim 1, characterized in that, as component (D), it contains γ-aminopropyl trimethoxysilane in an amount of 2-4% by weight, calculated on the coating mass. Coating composition according to claim 1, characterized in that it contains as a component (D) 4-6% by weight of N-methyl-Y-aminopropyl trimethoxysilane. Coating composition according to any one of claims 1-4, characterized in that the monomer (B) is N-vinylpyrrolidone and / or phenoxyethyl acrylate and / or isobornyl acrylate. A coating composition according to any one of claims 1 to 5, characterized in that it further contains a synergist and / or conventional auxiliary and additive material. A method of coating a glass surface according to which (I) a radiation-curable coating composition is applied and (II) the coating composition is cured by UV or electron irradiation, characterized in that a coating composition according to any of the claims is applied. 1 - 6. 8. A method according to claim 7, characterized in that the glass surface is the surface of an optical glass fiber. 9. Optical fiberglass, characterized in that it is coated with a coating material according to any of claims 1 to 6. Use of the optical fiber of claim 9 as a light path conductor. Use of the radiation curable coating composition according to claims 1-6 for coating optical glass fibers.