LT3332B - Liquid, radiation-cured coating composition for glass surfaces - Google Patents

Abstract

The invention concerns photo-hardened oligomers prepared from a) a hydroxy and/or amino compound with a hydroxy or amino number between 3 and 4 and a mean molecular weight between 500 and 4,000, b) a compound with two hydroxy and/or amino groups and a mean molecular weight between 200 and 4,000, c) a monoethylenically unsaturated compound containing a group with an active hydrogen atom and having a mean molecular weight between 116 and 1,000, d) an aliphatic and/or cycloaliphatic diisocyanate, characterized in that components (a) to (d) are used in amounts such that 1) the molar ratio of component (a) to component (b) is between 0.1 and 1.1, 2) the molar ratio of component (c) to component (a) is between 2.0 and 10, 3) the ratio by equivalent of the isocyanate groups in component (d) to the hydroxy and/or amino groups in components (a) to (c) combined is between 0.9 and 1.0.

Description

The present invention relates to radiation-curable oligomers having several unsaturated ethylene groups and several urethane and / or urea groups per molecule obtained from:

(a) at least one hydroxy- and / or amino-functional compound having 3-4 functional groups and an average molecular weight of 500 to 4000,

b) at least one compound having two hydroxyl and / or amino groups per molecule and having an average molecular weight of 200 to 4000,

(c) at least one monoethylene compound having a group having one active hydrogen atom per molecule and having an average molecular weight of 116 to 1000; and

d) at least one aliphatic and / or cycloaliphatic diisocyanate.

The present invention also relates to radiation curable compositions for forming coatings having these radiation curable oligomers and to a method of coating the glass surface, partially glass fibers, using these compositions.

Optical glass fibers are gaining importance in the field of communications as fiber optics. When used for these purposes, it is necessary to protect the glass surface from moisture and abrasion. The glass fibers are covered with at least one layer of protective varnish.

Thus, for example, it is known from EP-B-114982 that fiberglass is first coated with an elastic low-hard and low-viscosity protective layer (priming) followed by a radiation hardening varnish which is harder and more viscous. The two-layer coating must protect the fiberglass well from mechanical stress and from low temperatures. According to EP-B-11498, a radiation curable coating based on linear urethane acrylates is used as a primer. As coating varnishes used as coatings for radiation curable materials based on linear urethane acrylates, unsaturated diethylene ester, bisphenol diglycidyl ether and unsaturated monoethylene monomer, in addition, the glass transition temperature of the copolymer obtained from this monomer is above 55 ° C.

EP-A-223086 discloses radiation curable coatings for coating optical glass fibers. The binders of these coatings are used to cure the oligomers as reflected in the main claim of the invention.

According to EP-A-223086, these radiation curable coatings are used either as coating varnishes or as one coat varnishes. They are not suitable for priming due to the too high E-modulus value of the curable coatings.

EP-A-209641 discloses curable compositions for coating optical glass fibers. The binder for these coating compositions is a polyurethane oligomer with a terminal acrylic group having a polyfunctional nucleus. These compositions can be used as a primer as well as a coating varnish. One-layer coating is also available.

Finally, radiation-hardening compositions for coating optical glass fibers containing binder linear urethane acrylates are known from European patents EP-A-208845, EP-A-167199, EP-A-204161, EP-A-204160 and EP-A-631.

The disadvantage of these compositions is that their properties change over time. In addition, under long-term loading, their mechanical properties, partly elastic, require an improvement in properties.

It is an object of the present invention to provide radiation curable compositions suitable for coating glass surfaces, partially optical glass fibers, which exhibit improved properties over known compositions. Cured coatings do not change over time and provide greater stability to glass fiber coatings. Further, hardened coatings must increase resistance to water absorption and desorption. This means that the optical fiber is not damaged by the coating.

In addition, cured coatings must have good buffering properties at low temperatures. This means that the mechanical properties of the coating must deteriorate slightly as the temperature drops. In part, the value of the E-module should increase slightly as the temperature decreases. In addition, the composition should harden as soon as possible. In addition, the coating should, as far as possible, emit hydrogen and have good adhesion to the glass surface, with a minimum of storage and aging.

The object is achieved by radiation-curable oligomers having several unsaturated terminal ethylene groups per molecule and several urethane and / or urea groups derived from

(a) at least one hydroxy- and / or amino-containing compound having 3-4 functional groups and an average molecular weight of 500 to 4000,

b) at least one compound having two hydroxyl and / or amino groups per molecule and having an average molecular weight of 200 to 4000,

c) at least one unsaturated monoethylene compound having a group having one active hydrogen atom per molecule and having an average molecular weight of 116 to 1000; and

d) at least one aliphatic and / or cycloaliphatic diisocyanate.

Radiation-curable oligomers differ in that the components a-d are taken in amounts such that:

1. The molar ratio of components a to b is between 0.1: 1 and 1.1: 1, preferably between 0.1 and 0.8.

2. The molar ratio of components c to a is between 2.0: 1 and 10: 1, preferably between 2.5 and 10, and

3. An equivalent ratio of the number of isocyanate groups of component d to the sum of hydroxyl and / or amino group components a to c would be between 0.9 and 1.0.

more resistant

Unexpectedly and so far, radiation hardening compositions have been shown to exhibit enhanced oligomer-based coatings for claimed oligomer based coatings, and optical glass fibers coated with these compositions are also more stable over time. In addition, coatings derived from these compositions have a high water absorption and desorption properties compared to conventional coatings.

The most important characteristic, moreover, is the buffering properties of coatings at low temperatures, since the problem of so-called residual microwaves is solved. The claimed coatings also exhibit good mechanical properties such as tensile strength as well as slight release of hydrogen during storage and aging. Finally, they exhibit good adhesion to the glass surface.

The following radiation-cured oligomers are characterized in more detail.

As the component a for the preparation of the oligomers, hydroxy and / or amino-containing compounds having 34 functional groups are preferred, preferably with 3. These compounds have an average molecular weight of 500 to 4000, preferably 750 to 2000.

Examples of suitable compounds are polyoxyalkylated triols, such as ethoxylated and propoxylated triols, preferably ethoxylated triols, especially with an average molecular weight greater than 1000. The triols may be e.g. glycerin or trimethylolpropane.

Suitable amine-containing compounds, such as derivatives of amino-functional compounds of polyalkoxylated triols, are also suitable. Examples include Texaco products B.JEFAMIN®, T403, T3000, T5000, C346, DU 700 and BuD 2000.

Amine-containing compounds may have both a primary and a secondary amino function.

In addition, compounds having both an amino and a hydroxyl group can be used.

Compounds having two hydroxyl and / or amino groups per molecule may be used as component b. The average molecular weight of these compounds is from 200 to 4000, preferably from 600 to 2000.

Suitable examples of component b are polyoxyalkylene glycols and polyoxyalkylenediamines, with alkylenes having from 1 to 6 carbon atoms being preferred. Polyoxyethylene glycols of average molecular weights of 1000, 1500, 2000 and 2500, as well as polyoxypropylene glycols of appropriate molecular weight and polytetramethylene glycols, may be used. Polyethoxylated and polypropoxylated diols such as ethoxylated propoxylated butanediol, hexanediol, etc. may also be used. derivatives. Further suitable are polyester diols which are obtained, for example, by reaction of already known glycols with dicarboxylic acids, preferably with aliphatic and / or cycloaliphatic dicarboxylic acids such as hexahydro-phthalic acid, adipic acid, azelaic, sebacic and glutaric acids and / or alkyl-substituted derivatives. These acids may be replaced by their anhydrides, if any.

Polycaprolactone diols may also be used. These products are obtained, for example, by reaction of ε-caprolactone with a diol. Such products are described in U.S. Patent No. 3169945.

Polylactondhiols obtained in this manner are characterized by having terminal hydroxyl groups and repeating moieties of polyesters derived from lactone. The following repeating portions of the molecule correspond to the formula:

O

II

-C- (CHR) _n -CH ₂ -, where n is usually 4 to 6, R-alkyl, cycloalkyl or alkoxy moiety, and no R value has more than 12 carbon atoms and the total number of substituted carbon atoms in the lactone does not exceed 12 in the ring.

The starting lactone can be any lactone or lactone derivatives, and must have at least 6 carbon atoms in the ring, e.g. 6-8 carbon atoms, plus at least two R substituents per carbon atom.

The starting lactone can be defined by the general formula

CH ₂ - (CR ₂ ) _n -c = o,

I

O__ where n and R have the values already mentioned.

In the present invention, the best lactone for the production of polyester diols is caprolactones, where n = 4. The best lactone is the ε-caprolactone, where n = 4, and all the R substituents are hydrogen. This lactone is the best because it is available in bulk and gives the best quality coatings. In addition, various other lactones may be used alone or in combination. Examples of aliphatic diols which are suitable for reaction with lactones are the same diols mentioned in interaction with carbonic acids.

As the component b, it is understood that the corresponding diamines, as well as compounds with an OH group and an amino group, can be used. Examples of such compounds are Texaco products - D230, D400, D2000, D4000, ED600, ED900, ED2001 and ED4000 on behalf of JEFFAMIN®.

In component b, it is best to use a mixture consisting of b!) From 0 to 90 mol. % of at least one polyetherdiol, b ₂ ) from 10 to 100 mol. % of at least one modified polyetherdiol, b ₂₁ ) at least one polyetherdiol, b ₂₂ ) at least one aliphatic and / or cycloaliphatic dicarboxylic acid, and b ₂₃ ) at least one aliphatic, saturated, epoxy group and 8 to 21 carbon atoms per in addition, the sum of the components b ₂₁ -b _{23 is in} each case 100 mol. %.

In accordance with conventional techniques for obtaining modified polyetherdiols components b ₂₁ -b ₂₃ used in amounts such that the equivalent ratio of the component _b-21 OH groups carboxylate groups of component b ₂₂ side is made up of 0.45 to 0.55, preferably 0.5, and the equivalent ratio of epoxy groups to component b ₂₃ , of carboxyl groups to component b ₂ 2 ranges from 0.45 to 0.55, preferably at a ratio of 0.5.

Examples of suitable polyether diols b _x and b _2i are the aforementioned polyoxyalkylene glycols and the alkylene groups have from 1 to 6 carbon atoms.

Preferably, component b _x polioksipropilenglikoliai used, having an average molecular weight of from 600 to 2000. Component B ₂₁ is best used polioksibutilenglikolius (Poly - THF) number average molecular weight> 1000th

In component b ₂₂ , aliphatic as well as cycloaliphatic dicarboxylic acids with 8-36 carbon atoms per molecule are preferably used, such as hexahydrophthalic acid. Component b ₂₃ uses, for example, epoxidized vinylcyclohexane compounds, epoxidized, unsaturated monoolefinic fatty acids and / or polybutadienes.

Component b ₂₃ uses glycerol esters - branched monocarboxylic acids such as versatic acid.

For the introduction of unsaturated ethylene groups into polyurethane oligomers, unsaturated monetylene compounds having a single active hydrogen moiety having an average molecular weight of from 116 to 1000, preferably from 116 to 400, are used. Examples of component c may be, for example, unsaturated ethylene moieties. hydroxyalkyl esters of carboxylic acids such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyamyl acrylate, hydroxyhexyl acrylate, hydroxy octyl acrylate, as well as the methacrylic, fumaric, maleic, itaconic, esteric, ester, and crude esters of hydroxy.

Component c may include caprolactone adducts and the hydroxy acyl ester of one of the above unsaturated ethylene acids. Additives of hydroxyalkyl esters of acrylic acid having an average molecular weight of 300 to 1000 are preferred.

Aliphatic and / or cycloaliphatic diisocyanates such as 1,3-cyclopentane, 1,4-cyclohexane, 1,2-cyclohexanediisocyanate, 4,4'-GB 3332 B can be used to obtain oligomers which could be used as component d. methylene-bis- (cyclohexylisocyanar) and isophorone diisocyanate, trimethylene, tetramethylene, pentamethylene, hexamethylene and trimethylhexamethylene-1,6-diisocyanate, as well as the European patent EP-A-204161 in column 4, lines 42-49. , which are derivatives of dimeric fatty acids.

Isophorone diisocyanate and trimethylhexamethylene-1,6-diisocyanate are commonly used.

According to the invention, the components a-d are used in the following amounts for the preparation of oligomers

The molar ratio of components a to b is between 0.1: 1 and 1.1: 1, respectively, preferably between 0.1 and 0.8.

2. The molar ratio of components c to a is between 2: 1 and 10: 1, respectively, preferably between 2.5 and 10, and

3. Equivalent ratio of component d isocyanate groups to active hydrogen atoms of components a plus b plus c is equal to 0.91.0.

The claimed oligomers can be obtained in various ways. For example, the reaction between the isocyanate d and the substances extending the chain a and b can be carried out initially, followed by the reaction of the remaining free isocyanate groups with unsaturated ethylene compounds.

In addition, oligomers may be obtained by reacting a portion of the isocyanate groups of component d with an unsaturated ethylene compound c, followed by reacting the remaining free isocyanate groups with chain extenders a and b.

Polyurethane oligomers can be obtained according to European Patent EP-A-223086, p. 5.

Polyurethane oligomers are best prepared by the two-step process, which initially comprises poly (a) to (d) coupling until more than 85% of the d NCO groups of component (d) react. In the first step, the amount of components a to d is taken such that the equivalent ratio between the NCO groups of component d and the active hydrogen of components a to c is 1: 1.

In the second step, the remaining components (corresponding to the desired ratio NCO: OH) are added and the reaction is continued until the NCO groups have reacted at> 99%. The addition of component c at this stage and the addition of this component c ensure that the equivalent ratio of NCO: OH groups is maintained.

The proposed urethane oligomers generally have an average molecular weight of 2500 to 10,000, preferably of 3,000 to 6,000 (as measured by GPC polystyrene as standard), an average molecular weight of 5,000 to 50,000, preferably of 7,000 to 20,000, and double bonds of from 5,000 to 5,000. 0.45 to 1.5, preferably 0.45 to 0.9 mol / kg, and more preferably 0.45 to 0.63, and more preferably 0.5 to 0.63 mol / kg. kg, and functionality> 2 to 3.5, preferably 2.2 to 2.8, respectively, for each statistical average polymer molecule.

The proposed oligomers are used as a film forming component in A curing compositions for coating. Coating compositions generally contain from 10 to 78% by weight of these oligomers, preferably from 15 to 75% by weight, more preferably from 63 to 73% by weight, based on the total weight of the coating composition.

The other coating composition components may contain from 0 to 60%, preferably from 0 to 50% by weight, of the total composition, with at least one unsaturated ethylene oligomer B. In addition to unsaturated polyesters, polyester acrylates and acrylic acrylic copolymers, except for urethane acrylate oligomers, those urethane acrylate polymers used as component A. The amount and type of component B allows for a targeted control of the properties of the curable coating. The greater the proportion of component B in the composition, the greater the E-modulus of the curable coating. Component B is added to the mixture when the composition is used as a coating varnish. The influence of component B on the properties of the resulting coating is known to those skilled in the art. Its proper amount is easily determined by known methods.

Unsaturated ethylene polyurethanes used as component B are already known. They may be obtained by reacting a di- or polyisocyanate with a chain extender of the class of diols / polidiols and / or diamines / polyamines and reacting the remaining free isocyanate groups with at least one hydroxyalkyl ester of hydroxyalkyl acrylate or other unsaturated ethylene carboxylic acids.

The amounts of chain extender, di- or polyisocyanates and hydroxyalkyl esters of unsaturated ethylene carbonic acids are selected so that

1. An equivalent ratio between NCO groups and reactive chain extenders (hydroxyl, amino or mercapto) would be between 3: 1 and 1: 2, preferably between 2: 1, and

2. The OH-groups of hydroxyalkyls of unsaturated ethylene carbonic acids are in stoichiometric relation to the remaining free isocyanate groups in the forpolymer of the isocyanate and the chain extender.

In addition, polyurethanes B can be obtained by reacting a first portion of the isocyanate groups of the dialysis polysocyanate with at least one hydroxyalkyl ester of an unsaturated ethylene carbonic acid, and the remaining isocyanate groups continuing to react with a chain extender. In this case, the hydroxyalkyl ester content of the chain extender, isocyanate, and unsaturated carbonic acid is selected so that the equivalent ratio of NCO groups to the active group of the chain extender is 3: 1 and 1: 2, preferably 2: 1 and the equivalent ratio of residual NCO. groups and OH groups of the hydroxyalkyl ester would be 1: 1.

It goes without saying that intermediate forms are possible in both ways. For example, a portion of the diisocyanate group can be treated with a diol and then another portion of the isocyanate group with a hydroxyalkyl ester of an unsaturated ethylene carbonic acid and finally with the remaining isocyanate group exposed to diamine.

These various methods of preparing polyurethanes are already known (e.g., EP-A-204161) and therefore do not require a more detailed description.

Suitable compounds for the preparation of urethanacrylate oligomer B include those used to obtain component A, as well as the compounds described in DE-OS 3840644.

When using the proposed compositions as coating varnishes, aromatic components are taken up to obtain urethanacrylate oligomer B. Preferably 2,4- and 2,6-toluylenediisocyanate are used as isocyanate components as well as aromatic polyesterols based on phthalic and isophthalic acids and / or polypropylene glycol, ethylene glycol and diethylene glycol as chain extenders.

The other component of the radiation curable coating composition comprises at least one unsaturated ethylene monomer and / or oligomer C, typically 20 to 50% by weight, preferably 23 to 35% by weight, based on the total weight of the coating composition.

The addition of this unsaturated ethylene compound C is known to control the viscosity and cure rate of the coating composition as well as the mechanical properties of the coating as described, for example, in EP-A-223086.

Examples of monomers used include ethoxyethoxyethyl acrylate, N-vinylpyrrolidone, phenoxyethyl acrylate, dimethylaminoethyl acrylate, hydroxyethyl acrylate, isobornyl acrylate, dimethyl acrylamide and dicyclopentyl acrylate. In addition, di- and polyacrylates such as butanediol acrylate, hexanediol acrylate, trimethylol propanediol and triacrylate, pentaerythritol diacrylate, and long chain linear diacrylates having a molecular weight of 400 to 4000, preferably 600 to 2500, may also be used. EP-A-250631. The two acrylic groups can be separated by a polyoxybutylene structure. 1,12-dodecyl acrylate and a product obtained by reacting 2 moles of acrylic acid with 1 mole of fatty dimeric alcohol having 36 carbon atoms may also be used.

Mixtures of the monomers described may also be used. Most commonly used are phenoxyethyl acrylate, hexanediol acrylate, N-vinylpyrrolidone and tripropylene glycol acrylate.

The photoinitiator is used in the coating composition in an amount of from 2 to 8% by weight, preferably 3-5% by weight based on the total weight of the composition, depending on the radiation used to cure the coating (UV radiation, electronic radiation or visible light). Preferred compositions are UV-curable. Most commonly used are ketone-based photoinitiators, such as autophenone, benzophenone, diethoxyautophenone, m-chloroacetophenone, propiophenone, benzoin, benzyl, benzyldimethyl ketal, anthraquinone, thioxanthone and thioxanthone derivatives, triphenylphosphine, 2-hydroxy-2-methyl-l-l onion, hydroxypropyl phenyl phenyl ketone, etc., as well as mixtures of various photoinitiators.

Additionally, coating compositions may additionally contain excipients and additives. They are usually from 0 to 4% by weight, preferably from 0.5 to 2.0% by weight, respectively, based on the total weight of the composition. Examples of such materials are plasticizers that increase the fluidity of the composition, as well as materials that improve adhesion of the particles. Alkoxysilanes, such as N, N-aminoethyl-γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, N-methyl-γ-aminopropyltrimethoxysilane or modified triamine propyltrimethoxysilane (Dynamit Nobel Chemie commercial products Dynasilan®, Typ TRIAMO) are used as adhesives.

The compositions may be applied by a variety of application methods on a substrate, such as spraying, rolling, pouring, dipping, roller coating or recoating.

Hardening of the lacquer film by radiation, preferably by ultraviolet light. Irradiation Devices and Curing Conditions are known in the literature (cf. R. Holmes, U.V. and E.B. Curing Formulations for Printing, Coatings and Paints, SHITA Technology, Academic Press, London, United Kingdom 1984) and need not be described.

The composition is used to cover various surfaces, such as glass, wood, metal or plastic. They are used, in part, to coat the surface of the glass, and are particularly suitable for coating optical glass.

The present invention also relates to a coating method on a glass surface, wherein the proposed composition is coated and cured by UV radiation or electronic radiation, which differs in that said radiation-cured coating composition is used.

The method of coating is particularly recommended for optical glass fibers.

The proposed coating composition can be used as a primer coat and / or as a two coat coat for optical glass fibers.

When the compositions are used as a primer, the E-modulus values of the cured compositions (at 2.5% elongation and room temperature) are in the range of 500 to 1000 MPa.

The following examples further illustrate the invention. All data except parts and percentages are by weight unless there is any ambiguity in the description.

Preparation of Modified Polyetherdiol

In a flask fitted with a stirrer, an inert gas inlet and a probe thermometer, heat 51.1 parts of polytetrahydrofuran with an average molecular weight of 1000 and an OH number of 118 mg KOH / g, 19.1 parts of hexahydro-phthalic anhydride to 120 ° C. the acidity reaches 102 mg KOH / g. Thereafter, 0.02% of chromium octoate, based on the weight of the mixture consisting of poly-THE, glycidyl ester of hexahydrophthalic acid and versatic acid, and 297 parts by weight of glycidyl ester of versatic acid with an epoxide equivalent weight of 266 are added. The mixture is heated to 120 ° C. until the reaction product has gained an epoxy equivalent weight of> 20,000, an acid number of 34 mg KOH / g and an OH number of 60 mg KOH / g.

The modified polyetherdiol has an average molecular weight of M _n = 1860 (based on OH-number), the average weight of GPC is known as M _n «1500 M _n / M _n = 1.67. The viscosity of 80% solution of butyl acetate is 3.8 d Pas (measured At ° C with flat / cone viscometer).

Place a sample of 0.35 mol in a flask fitted with a stirrer, an oxygen inlet and a probe thermometer. of conventional ethoxylated trimethylolpropane having an average molecular weight of 1000, 0.65 mol. of conventional polyoxypropylene glycol having an average molecular weight of 600, 0.65 mol. of the modified polyetherdiol, 1.75 mol. of hydroxyethyl acrylate 0.05% (based on the sum of the total weights of d and d) and ppm of the phenothiazine (based on the sum of the weights of the components a, b, c and d) and the mixture is heated to 60 ° C. After that 2.5 hours. adding tin dibutyl dilaurate components a, b, c

50 ° C.

After that, so that 90% (amount of temperature

2.70 mol. Dilute the isophorone diisocyanate to phenoxyethyl acrylate to give a theoretical amount of the components a to d) and maintain the reaction at 60 ° C until the NCO value reaches 1%. This is followed by the addition of 0.05% tin dibutyl dilaurate and 0.51 mol. of a conventional hydroxyethyl acrylate caprolactone oligomer having an average molecular weight of 344 (Union Carbide product TONE M100) and raising the temperature to 80 ° C until the NCO value is <0.1%. The oligomer thus obtained has a double bond content of 0.6 mol / kg and a functionality of 2.5.

The viscosity of the 40% solution of oligomer I (based on the theoretical solids content) in phenoxyethyl acrylate is 4.9 dPas in a cone viscometer.

(measured with 23 ^U C flat /

The liquid, radiation curable composition is prepared by mixing 78.1 parts of the above 90% urethane oligomer 1 solution, 12.1 parts phenoxyethyl acrylate, 6.2 parts N-vinylpyrrolidone, 1.6 parts Ν-β-aminoethyl-γ-aminopropyltrimethoxysilane and 2, 0 part diethoxyacetophenone.

A well-cleaned (necessarily degreased) glass plate (width x length = 98 x 161 mm) is fastened at the edges with adhesive tape Tesakrepp No. 4432 (width 19 mm) and applied with a squeegee 1 (dry film thickness 180 µm).

The curing is performed by means of a device for irradiation with UV light, equipped with two medium-pressure mercury emitters with a lamp power of 80 W / cm and a sliding speed of 40 m / min, irradiated in 2 transitions at half the load (= 40 W). / cm).

The radiation dose is 0.08 J / cm ² (measured by a dosimeter UVICURE system EIT company Eltosch).

Cured coatings with very good mechanical properties are obtained which, moreover, have resistance to aging and low temperatures, as well as water absorption and desorption.

The results of the E-module for elongation from 0.5 to 2.5% (in accordance with DIN 53455) as well as the results of the elongation break tests are given in Table 2. In addition, Table 2 shows the E-modulus results (for 2.5% elongation) when the cured coating is aged.

The temperature dependence of E-module values is presented in Fig. 1. Measurements were made by Polymer Laboratories Ltd. devices DMTA.

The characteristics of cured coatings under water absorption and desorption are shown in Fig. 2.

example of comparison

Place 2.0 mol in a flask fitted with a stirrer, an air inlet and a probe thermometer. isophorone diisocyanate and 0.05% tin dibutyl dilaurate (based on the sum of the weight of the components a-d) and heated to 60 ° C. Thereafter, 1.30 mol was added over 120-180 min. of ordinary polyoxypropylene glycol having an average molecular weight of 600, the temperature is maintained at 60 ° C until the NCO value is 4.5%. Next, 0.1% of 2,6-ditret-butyl-cresol (based on the sum of the weight of the components a-d) and 40 ppm of phenothiazine (based on the sum of the weight of the components a-d) are added. Then, 1.54 mol of hydroxyLT 3332 B ethyl acrylate are added at 60 ° C over a period of 30 min. It is then dissolved in phenoxyethyl acrylate to a theoretical solid content of 90 ° C (based on the sum of the weight of the components a-d). The temperature of 60 ° C is maintained until the NCO value is <0.1%.

The oligomer 2 obtained in this manner has a double bond content of 1.1 µmol / kg and a functionality of 2.0. The viscosity of the resulting oligomer 2 in phenoxyethyl acrylate 50% (based on the theoretical solids content) is 10 d Pas (measured at 23 ° C in a plate / cone viscometer).

In analogy to Example 1, from 90.1 parts of a 90% solution of urethane oligomer 2, 12.1 parts of phenoxyethyl acrylate, 6.2 parts of N-vinylpyrrolidone, 1.6 parts of Np-aminoethyl-γ-aminopropyltrimethoxysilane and 2.0 parts of diethoxyphenone are obtained. radiation curing coating composition 2. Application 2 of this composition, as well as inspection of the cured coating, is carried out analogously to Example 1. The results are shown in Table 2 and Figures 3 and 4.

table

Composition of urethane oligomer (in moles)

Figure 1 1 comparison example (a) Ethoxylated trimethylolpropane (Mn = 100) 0.35 - b _x ) polyoxypropylene glycol (Mn = 600) 0, 65 1.30 b ₂ ) Modified polyetherdiol 0, 65 - (e) hydroxyethyl acrylate 1.75 1.54 c) hydroxyethyl acrylate caprolactone oligoner 0.51 - (d) isophorone diisocyanates 2.70 2.0 molar ratio a / b 0.27 0 molar ratio c / a 6, 46 00 equivalent ratio NCO / OH 0, 91 0, 97

table

Test results

Figure 1 1 comparison example Intermittent Extension,% 53, 1 58 E 05 - modulus (0.5% elongation), MPa 3, 1 2.75 E 25 - modulus (2.5% elongation), MPa 2, 9 2.6 E 25 at 800 or 55 ° C, MPa 3 2.7 E 25 at 800 or 90 ° C, MPa 4.2 7.5 E 25 after 800 or 120 ° C, MPa 7.3 18.3

example

Place 2 mol of the flask described in Example 1. isophorone diisocyanate and 0.05% tin dibutyl dilaurate, and 30 ml. parts of phenothiazine and heated to 60 ° C. This is followed by the dropwise addition of 2 mol. hydroxyethyl acrylate so that the temperature does not rise above 60 ° C. Further, 1 mol. of ethoxylated trimethylpropane (20 moles ethylene oxide per mole trimethylol propane) at 60 ° C. The mixture is heated at 60 ° C until the NCO groups are 0%. Intermediate 1 thus obtained is involved in further reactions.

2 mol mol. of isophorone diisocyanate and tin dibutyl dilaurate and a mixture of 0.65 mol. of polyoxytetramethylene glycol having an average molecular weight of 1000 and 0.65 mol. modified polyetherdiol and maintained at 60 ° C until the number of NCO groups reaches 2.7%. Thereafter, the stabilizer phenothiazine is added. A mixture of 1.05 mol was then added. of hydroxyethyl acrylate and 0.35 mol. Intermediate 1 described above; The temperature is maintained at 60 ° C until the number of NCO groups is <0.1%

The liquid radiation curable coating composition is prepared by mixing 70 parts of the above urethane oligomer, 20.0 parts of phenoxyethyl acrylate, 6.5 parts of N-vinylpyrrolidone, 1.5 parts of N-p-aminoethyl-γ-aminopropyltrimethoxysilane and 2.0 parts of diethoxyacetophenone. The chemical properties are given in Table 4.

Well-cleaned (necessarily degreased) glass plates (width x length = 98 x 161 mm) are fastened at the edges with Tesakrepp® No. 4432 (width 19 mm) adhesive tape and applied with a squeegee (dry film thickness 180 µm).

The curing is performed by means of a device for irradiation with UV light, equipped with two medium-pressure mercury emitters with a lamp power of 80 W / cm and a sliding speed of 40 m / min, irradiated in 2 transitions at half the load (= 40 W). / cm).

table

Composition of polyurethane acrylate oligoraer (in moles)

An example 2 3 4 2 for comparison example 3 for comparison example P-THF 1000 0, 65 0, 65 - 0, 65 - P 600 - - - - - mod. PE 0, 65 0, 65 1.30 0, 65 1.30 ethoxy TMP 7 - - - 0.70 0.70 ethoxy TMP 20 0.35 1.05 1.40 - - Hi 1.75 2.45 2.80 2, 10 2, 10 IPDI 2.70 4, 10 4.80 3, 40 3, 40

Abbreviations used in Table 3:

P-THF 1000:

polyoctetramethylene glycol having an average molecular weight of 1000

P 600:

polyoxypropylene glycol having an average molecular weight of 600 mod. PE:

modified polyetherdiol ethoxy TMP 7:

ethoxylated trimethylolopropane with 7 units of ethylene oxide for trimethylol propane (Mn = 414) ethoxy TMP 20: ethoxylated trimethylolopropane with 20 units of ethylene oxide for trimethyl lolpropane

GOOD:

- hydroxyethyloxylate

IPDI:

isophorondiisocyanate table

Chemical Properties of Coating Liquid Compositions

1 2 3 4 1 Comparison Fig. 2 Comparison Fig. 3 Comparison Fig. The oligomer CBC (coatings 1 3 4 5 2 6th 7th position) 2.07 2.02 2.02 1, 99 2.31 1.91 2.01 DBC (oligomer) 0.67 0.60 0.61 0.56 0.69 0, 60 C = C-R 3.39 3.78 3.73 4.07 2.25 2.80 3.80 Functionality 2.5 2.5 3.5 4.0 2.0 3.0 3.0

DBC (Coating Composition): Concentration of acrylic groups in mol / kg coating composition

DBC (oligomer): concentration of acrylic groups in mol / kg oligomer

C = C-R:

ratio of monomer acrylic groups to oligomer acrylic groups found in the composition

Functionality: Table of average polymer functionality in acrylic groups

Mechanical characteristics of tested coatings

1 2 3 4 2 Comparison Fig. 3 Comparison Fig. Elongation at break (%) 53 48 44 42 56 62 E - Module (0.5%) elongation), MPa 3.1 2, 8 2.7 2.5 17th 15th Module E (2.5%) elongation), MPa 2.9 2.6 2.5 2.2 15.7 13.5

The radiation dose is 0.08 J / cm (measured by a dosimeter UVICURE system EIT company Eltosch).

Cured coatings with very good mechanical properties are obtained which, moreover, have resistance to aging and low temperatures, as well as water absorption and desorption.

The results of the E-module for elongation from 0.5 to 2.5% (in accordance with DIN 53455) as well as the results of elongation break tests are given in Table 5. In addition, Table 5 shows the E-modulus results (for 2.5% elongation) when the cured coating is aged.

The temperature dependence of the E-module values is shown in Table 6 and Figures 5 and 7. Measurements were made by Polymer Laboratories Ltd. devices DMTA.

example

Intermediate 1 is obtained under the same conditions as described in Example 2.

Placed in 2 mol. isophorone diisocyanate and tin dibutyl dilaurate and a mixture of 0.65 mol. polyoxytetramethylene glycol having an average molecular weight of 1000 and 0.65 mol. modified polyetherdiol and maintained at 60 ° C until the NCO content reaches 2.6%. Phenothiazine is then added as a stabilizer. Then 0.35 mol was added. of hydroxyethyl acrylate and 1.05 mol. Intermediate 1, described above, maintained at 60 ° C until the number of NCO groups reached <0.1%.

The preparation, application and hardening of the composition, as well as the coating inspection, are carried out in the same manner as described in Example 2.

The test results are shown in Tables 5 and 6, as well as in Figure 8.

example

Intermediate 1 is obtained under the same conditions as described in Example 2.

Placed in 2 mol. isophorone diisocyanate and 1.3 mol. of modified polyetherdiol.

When all is added, the mixture is heated at 60 ° C for a further hour. This is followed by the addition of 1.4 mol. the temperature of the intermediate described above and 60 ° C is maintained until the NCO group content reaches <0.1%.

The preparation, application and compositions are cured by irradiation and coating screening in the same manner as in Example 2.

The test results are shown in Tables 5 and 6, as well as in Figures 5 and 9.

and 3 comparison examples

Analogously to Example 2, the polyurethane acrylate oligomers are prepared from the components shown in Table 3.

From these urethanacrylate oligomers, analogous to Example 2, radiation-curable coating compositions are obtained.

The application, curing and coating test are performed in the same manner as in Example 2.

The results of setting the E-module at 0.5% elongation (corresponding to DIN 53455) as well as the elongation at break are given in Table 5.

The temperature dependence of E-module values is presented in Fig. 5. and Table 8. Measurements were made by Polymer Laboratories Ltd. device VDMTA.

table example Example 3

T £ ° C] log E Ti'C] ⁵³ log e i I L -41 II 9,204 -39 B 9,174 -40 II 9,191 -38.5 II 9,161 39 II 9,178 -37.5 II 9.1 • f * o -38.5 II 9,173 -36.5 u 9.1 's. »j j r \? i i i ! i —1 i -5 it 9.16 -55.5 II 9.1 22nd to - '6.5 n 9,143 . '' S II 9,107 | -55.5 H 9,134 -34 i! 9.0 ______________J

- '4 S ^!) Tf J 9.122 -32.5 - 9,074 -33.5 B 9,099 -32 II 9,054 -32.5 H 9,072 -31 B 9,043 -51 U 9,063 -30 ί i 9,032 to -50.5 ie 9,045 -59 ? l 9,011 - 4 I ß -29.5 n 9,035 -23.5 B 3,996 i -23.5 II 3,963 -27.5 B 3,977 ΐ -28 ii 9,001 -26.5 B 3,957 to i -27 H 8,981 -26 U 8,945 At -26 II 3,964 -25 U 8,921 At -25 B 3,398 -24 u 3,899 j -24.5 B 3,924 -23 ii 3,833 -23.5 II 8,908 -22 S! 3,862 * 22.5 II 3,888 -21 i! 3,779 -21.5 II 3,861 -20.5 U 3,818 -21  ; 3,849 -19.5 H 8,792 1 -20 n 3,829 -13.5 n 3,714 -19 II 3,786 -13 si 3.745 i -18 II 8,775 -17 > 1 3,721 i -17.5 II 8,748 -16 3,613 -16.5 II 3,708 -15 SI 3,656 —T -15.5 II 3,693 -14.5 : i 8,636 -14.5 II 3,669 -13 II 8,587 -13.5 II 8,617 -12 II 8,556 -12.5 II 8.6 -11.5 II 8,528

table (continued) sample example

TC ° c3 1 og E TC ° c3 log E * 11.5 M 8,574 -10.5 lt 8.48 -11 II 8.525 -9.5 11th 8,417 -10 II 8,511 -8.5 > 1 8,415 -9.5 : i 3,448 -7.5 H 8.338 -3.5 JI 3,426 -7 11th 3,327 i -5 u 3,403 -6 u 3,299 i 3.35 -5 II 3,153

-4.5 ^si 3.24 -3.5 ”to -3.5 U 3,208 -3 II 3,034 to -3 ? a 8,034 -? u 3,109 i i -7 1 ϋ 3,109 -1 II 3,076 i -1 '·· 3,076 -, 5 u 7,997 i i -, 5 U 7,997 1 II 7,955 i 1 H 7,955 1.5 u 7.86 I 1.5 ^u 7.36 2.5 II 7,836 I 2.5 II 7,336 J II 7.79 -Yeah I 3 u 7.79 4 tl 7,681 I 4 91 7,681 5 II 7,654 5 ii 7,654 6th II 7,618 6th II 7,618 7.5 M 7,503 7.5 II 7,503 8th II 7,464 8th II 7,464 9th II 7,425 9th SI 7,425 10th h 7,311 10th 31st 7,311 11th u 7.275 11th II 7.275 12th M 7,231 To 12 II 7,231 13th II 7,185 I 15 u 7,185 13.5 ii 7.15 I B, 5 u 7.15 14.5 11th 7,099 14.5 II 7,099 15.5 II 7,051 15.5 II 7,051 16th u 6,999 16th 1 « 6,999 17.5 M 6,932 17.5 M 6,932 13th M 6,891

table (continued) example Example ³

i rcj ⁸ logE T necessarilyCJ * log 'E 13 «6,391 18.5 ^M 6.876 13.5 6.376 20 ^H 6.815 to <0 · '6,315 20.5 · ’6,796 {20.5 6.796 21.5 6.757 1 21.5 »5.757 22.3 6, '735 | 22.5 ”6.735 23 6.71 j 23 ♦ '6.71 24 ^{: I} 6,693 At 24 6,693 25 '6.67 • 25 ¹¹ 6.67 26 6,633 ! 25 6,633 26.5 ^u 6,623 to 26.5 ^;! 6,623 28.5 «5.491 j 23.5 ^{: 1} 6.691 30.5 · '6,433

32.5 " 6,501 34 »' 6,514 j 64 ¹¹ 6,514 57.5 6,464 | 37.5 6,464 38 ,4 6.46 33 6.46 39 " 6,419 I 3? · ' 6,419 40.5 " 6.44 In 40.5 6.44 41.5 " 6,426 to b 5 ⁵¹ 6,426 42.5 '· 6.43 j ^z, 2.5 " o, 4 o 43 ¹ 6,409 To 43 6,409 44 " 6,454 i 44 '' 6,454 45 ⁵¹ 6,423 i 45 6,423 46th 6,366; 46th 6,366 47 " 6,453 to 47 ^{! 1} 6,453 48 2460368 »' 48 6,395 50 '6,359 1 j j 51 h 6,356 i to 52 ^w 0.472 33 " . 6,429 to 54 » 6,376 55 * 6,383 56 " 6,434 57.5 6,422 58.5 » 6,408 60 * 6,362

table example Example 1

i [° C3 « tog E Ti'C] » tog E -39 II 9,332 -39 II 9,395 -38 lt 9.33 -38.5 II 9,394 • -37 lt 9,317 -38 II 9,393 -36 II 9,306 -36.5 lt 9.39 -35 II 9,303 -35.5 lt 9,378 -34 II 9.28 -35 II 9,378 -33.5 u 9,276 -34.5 it 9.377 j -32.5 11th 9,265 -33.5 II 9,378 j -31.5 ΪΙ 9,251 -32.5 II 9,363 -30.5 11th 9,232 -31.5 1 « 9,356

-29.5; »____ 9,223 to -51» 9,357

-29 11th 9,208 -29.5 II 9 35 '• -'J -27.5 9.19 -28.5 n 9,337; -27 lt 9.17 -28 II 9,334 i to -26 31st 9,146 -27.5 n 9,332 J -25 II 9,134 -26 u 9.32 i -24 II 9,119 -25 II 9,279 ί To -23.5 II 9.1 -24.5 II 9,305 1 _i -22.5 II 9,074 -24 II 9,303 i -21.5 II 9,052 -22.5 II 9,295 j -21 u 9,039 -21 u 9,267 ! _! -20 II 9,008 -20.5 II 9,263 1 i -19 ! l 3,981 -20 II 9,261 j -13 U 3,958 -19.5 1 « 9,256 -17.5 Ί 3,911 -13.5 II 9,241 To -16.5 II 8,896 -17 u 9,205 -15 II 3,364 -16.5 II 9,202 -14.5 II 8.825 -16 II 9,199 -13.5 ; i 3,792 -15 al 9,192 _ί -13 II 3,765 -13.5 II 9,136 -j -12 II 3,654 -13 II 9.129 -11 II 8,689 -12A- II 9,125 .. J

table (continued) sample example

T £ ° c] log e T £ ° c3 log E -10 n 3,662 -11 II 9,103 -9.5 II 3,615 -10 11th 9,044 -3.5 M 8,587 -9.5 II 9,041 -7.5 11th 3,515 -9 n 9,037 -6.5 1! 8.339 -6 u 8,892 -6 h 3,443 -5.5 » 8,921 -5 u 3,408 • 5 ii 8.919 j -4 it 3,321 -, 5 5Ϊ 3, M I -3 n 8.297 1 II 8.491 -2 n 3.22 1.5 II 8,528 | -1 u 3,145 2 31st o, 549 i δ tl 8,109 3 K 3,451 | ϊ ii 7,997 6th 31st 3,194 j 2 ii 7,954 9.5 II 7,827 j 3 II 7,829 10th 11th 7.94: · to ⁰ n 7,807 12.5 SI 7.493 j 5.5 tl 7,722 13.5 II 7,657 | 6th 11th 7,673 16.5 II 7,273 | 7th H 7,627 ' 17th ii 7,328 7.5 SI 7,579 19th «1 7,118 9th tl 7,464 19.5 11th 7,143 10.5 II 7,364 21.5 lt 6,932 11th II 7,313: 22.5 11th 6,924 12th 7,247 In 23rd II 6,951 13th » 7,213 25th II 6,317 13.5 H 7,156 25.5 91 "6784 H.5 u 7.123 27.5 U 6,741 15.5 II 7,057 32 H 6,599: 16th H 7,022 39 II 6,483 17th H 6,956 38.5 M 6.5 18th II 6,892 42 H 6,486 19th H 6,846 42.5 H 6,519 20th M 6,789 «, 5 M 6,474

table (continued) sample example

rfC) ^α iog E T PC] “Ic-g E 20.5 «6.759 43 6,477 23 6,617 47.5 "6.522 24.5 * 6.566 48.5 * 6.489 25.5 * 6.513 51.5 6.536 26.5 6.506 54.5 6.472 27.5 ^a 6.491 37.5 * 6.542 28.5 ^and 6.452 58 " 6.52 29.5 ^y 4.439 30.5 * 6.382 i 31 5,366 32 6,373 33 ^u 6.302 ~~ 33.5 - · 6.357) » 34.5 6.329 35,5 '' 6,226 I 36.5 ^M 6.283 37 ^M 6.296 38.5 "6.269 39 * 6.256 40 "6.137 41 ^H 6.23 42 "6,247 42.5 6.232 43.5 »6.181 44 6,262 45 ·· 6,215 46 6.17 46.5 ^M 5.1 SS 47.5 ^M 5.166 43.5 * 6.067 49.5 6.031 50 ¹ 6.154 51 «6.07 53 6.025 53.5 6.114 54 ^ 5 6.185 55 ^ 5 "6,073 56.5 * 6.083 57 ^M 6.132 58 ^M 6,105 To “59 * 6,125 Γ 59.5 6.142 SoT ^-5 6,202

Table 8 2 for comparison 3 for comparison 1 comparison example example example

T PC) Ic-g'E 1 PC] ^H log S. T PC] " leg E -40.5 9,237 -38  9,363 -38.5 h 9,403 -41.5 9,264 | -37.5  9,366 -33 n 9,403 -40 9.23 to -37  9.37 -37.5 n 9.41 -37.5 9,223 I -36.5  9.37 -37 tl 9,409 -37 9,241 -36 »'9,363 -30.5 lt 9,408 -37.5 9.257 l -35.5 · 9,367 -36 II 9,406 -33 " 9,267 | -34  9,341 -35 II 9,403 -35 9.24 -33  9,334 -3.5 II 9.33-4 -33.5 ¹¹ 9.22 -32.5  9,333 -33 : i 9,332 -33 « 9,229 -32 "9.33 -32.5 h 9,332 ; -31> · 9,203 -30.5 9,312 -32 :> 9.33 i -30.5 9.2 -23.5 9,291 -31 u 9.3 / 6 j -30 " 0 K.O /, 1 /, -23  9,294 -29.5 9,355 To -29.5 " 9,203 -27.5 * '9,239 -23.5 ii 9,353 i -27.5 ·· 9.175 -27 · 9,237 -23 u -λ 354 ! -26.5 '· 9,157 · 2ό "9,264 -27.5 II 9,351 s -26 » 9, 559 -25  9,255 - 26th u 9,327 to -25.5 ·· 9.158 -24.5  9,251 -24.5 II 9,317 | -23.5 ·· 9,133 -23.5 '· 9,251 -24 II 9,317 | -22.5 ·· 9,116 -22 «9,215 -23.5  2,317 -22 » 9,115 -21 "9,207 -23 II 9,313 -21.5 " 9,117 -20.5 ^M, 9.206 -22.5 M 9,313 -21 " 9,117 O f \ l 1 ! 9,202 -21 ii 9,279 -19 9,075 -19 '· 9,136 I » o. II 9,274 -13.5 » 9,071 -17.5 9,156 -19.5 JI 9,273 to -13 9,071 -17 ^M, 9.155 -19 II 9,271 1 -> 7.5 « 9.07 ί -16.5  9,153 -18 u 9,256 -16 » 9,047 -15 9,125 -16.5 ; i 9,226 (-15 · » • 3.'39 -14 9.1 -16 II 9,222 j -14.5 9.02 -13.5 «9.09 * 9 -15.5 : · Ι 9.22 I - 14 M. i 9.02 -13 ^M, 9.096 -H, 5 ? l 9.207 I -13.5 « 9.02 -11.5 ^M, 9.061 -13 II 9.165

table (continued) comparison example comparison example comparison example

T UCJ 1 og E Yeah 1 og E T pc] ¹¹ log E -n, 5 ·· 8,967 -11 tl '9,048 -12.5 II 9,162 -11 ·· 8,961 -10.5 11th 9,045 -12 11th 9.16 -10.5 ¹¹ 8.96 -9 lt 9,007 -11.5 lt 2,157 -10 S, 958 -8 ii 8.99 -9.5 K 9,035 -8.5 ·· 8,917 -7.5 II 3.9SS . -3.5 II 9,021

-7.5 »'8,898__H -7 ¹¹ 8,987' ___ Γ ___- 3» 9.08

- 7 II 8,894 i -5.5 II 3,922 i -7.5 II 9,079 to -6.5 ^!! 3,396 i -5 II 8,917 -6 II 3,998 j -5 II 8,846 -h, 5 II 3,913 -5 II 3.982 -4 II 8.33 -3.5 II 3.91 -4.5 it 8.9c6 to I -3.5 II 8,793 i -1.5 II 3,822 -4 tl 3,935 to - 7 n 3.825 j -1 <1 8.83 - z SI 3,327 j -1 II 3,741 j -, 5 II 3.83 -1.5 II 3,036 ', 5 II 3,744 1 II 8.757 -1 II 3,833 0 II 8,747 2 II 8,717 , 5 II 3,703 1.5 II 8,708 2.5 II 3.725 1 tl 3,761 to 3 lt 3.62 II 3,728 1.5 lt 3.768 3.5 n 3,635 5 > 1 8,531 2 lt 3,767 to 4 • 1 3,643 6th II 8,556 5 M 3,573 ~ 1 6th K 3,508 6.5 II 8,577 7th u 3,422 6.5 H 3,501 7th II 8,591 9th M 8,372 7th M S, 52 7.5 II 8,597 12.5 H 8,097 7.5 M 8,524 10.5 II 8,266 16.5 M 7,757 10th II 3,245 11th II 3.41 19th Oops 7,359 to 10.5 M 8.331 12.5 tl 3.04 20th M ~ 7? 4Ϊ4 j 11 H 8.336 14th ii 3,164 20.5 U 7.468 j i 10, ' U 3,339 i · '{ 3,209 23.5 ii 7,158 i Ϊ 12.5 M 3,101 16.5 H 7,791 23rd M 7,209 in i ^u 3,132 17th 41 7,982 23.5 Λ 7,244 j ί 14.5 U 3,165 17.5 H 3,023 26th M 5,909 to i M 3,196 20.5 M 7,679 26.5 H 6,989 to 16th M 3,067 21st M 7,806 28th H 6,911 i '7.5 n 23.5 M 7,476 M 6,844

table (continued) comparison example comparison example comparison example

T C ° cj log E τ p c] log E T pc] " log E -11.5 8,967 -11 9,048 -12.5 9,162 -11 3,961 -10.5 9,045 -12 9.16 -10.5 8.96 I .9h 9,007 -11.5 9,157 -10 8,958 | -8 8.99 -9.5 9,035 -8.5 ·· 8,917 i -7.5 » 8,988 -8.5 9,081 -7.5 ·· 8,893 I -7 '· 8,987 -8 9.08 -7 '· 8,894 i -5.5 8,922 -7.5 · ' 9,079 -6.5 " 8,896 -5 · ' 8,917 -6 8,998 -5 · ' 8,846 -4.5 ·· 8,918 -5 8,982 -4 n 8.83 -3.5 3.91 -4.5 3,936 -3.5 ¹¹ 8,798 -1.5 3,822 -4 · 3,985 -3 ¹¹ 3,825 -1 " 8.83 -2 3,827 -1 · ' 8,741 -, 5 ··· 8.83 -1.5 h 8,886 -, 5 · ' 8,744 1 3,757 -1 '· 3,588 0 8,747 2 · ' 8,717 »5 ·· 3,703 1.5 " 8,708 2.5 8.725 1 3,761 3 · ' 3.62 3 8,728 1.5 '· 3,768 3.5 ··· 3,635 5 3,531 2 3,767 4 8,643 6th 8,556 5 8,573 6 " 3,508 6.5 " 8,577 7th 8,422 6.5 · ' 3,501 7th 8,591 9 " 8.372 7 « 3.52 7.5 '· 8,597 12.5 8,097 7.5 8,524 10.5 ^H 8,266 16.5 - 7,757 10th 8,245 11 · ' 3.41 19 " 7,359 10.5 « 3,331 12.5 · ' 8.04 20 " 7,414 11 * 3,363 14th 3,164 20.5 " 7,468 10.3 " 3,389 14.5 3,209 23.5 " 7,158 12.5 " 8,101 16.5 " 7,791 23 * 7,209 14th 3,132 17 * · 7,982 23.5 * 7,244 14.5 - 3,165 17.5 " 3,023 26 * 6,909 14 « 8,196 20.5 7,679 26.5 * 6,989 16th 3,067 21st 7,806 28 - 6,911 17.5 » 7,908 23.5 " 7,476 29.5 - 6,844

table (continued) comparison example comparison example comparison example

f CC3 »log E 1 rci «log T ['C] »log E 18th 7,954 24 «7,534 29th 6,371 18.5 * 8,016 26 * 7,256 31.5 6,635 21 » 7,666 27 « 7,229 32.5 6,698 21.5 · ' 7,722 26.5 x 7.289 32 « 6,733 21st 7,774 27.5 * 7.297 34.5 » 6,391 23.5 7,463 30.5 ^M 7,011 35 « 6,604 24.5 7,452 30 "7,072 35.5 « 6.58 25 ^M 7,493 30.5 * 7,102 38 " 6,464 24.5 7,541 33.5 « 6.79 38.5 ^H 6,554 26.5 " 7,363 34 * 6,828 33 - 6,541 27.5 " 7,273 33.5 * 5,373 40.5 - 6,464 28 ^M 7,312 34 »6.397 41.5 " 6,469 23.5 " 7,313 36 5,712 41 ^{! 1} 6,502 j 30.5 " 7,021 37 «6,674 43 · 6,497 31st 7,115 36.5 6.71 45 6,449 30.5 7,162 39 ··· 6.59 44.5 6,432 33 " 6,983 47.5 «'6,299 45 * 6,462 34.5 6,971 50.5 6,309 47,5 '» 6,432 34 '· 7,013 51 * 6,309 43.5 6,452 37 ··· 6.85 54.5 6,299 48 6,417 38 · ' 6,331 55 " 6,389 51.5 6,339 37.5 · ' 6.86 58 ^u 6.29 52 « 6.42 38.5 6,795 57.5 ·· 6,374 51 - 6,368 40.5 6,767 58.5 6,425 54 " 6,421 41 6,776 55 6,466 40.5 '· 6,773 54.5 6,393 42.5 6,744 55 - 6,419 ? 44 »' 6,712 _ 57 » 3,388 ! 44.5 6,716 53 « 6,394 to 44 years 6,714 57.5 * 6,382 ; 46 » 6,631 58.5 » 6,453 i 47.5 · ' 6,688 to 47 « 6,668 | 43 " 6,693 50.5 - 6,657 51 ^M 6.66 50.5 ^M 6,641 52 « 6.63 54 6,646 54.5 ^J 6,633 53.5 " 6,637 55.5 6,672 57.5 " 6,644 58 6,636 57 6,651 58.5 « 6,675 60.5 * 6.64 '? _____. — V. , ... I ....._...... ——— ----. _η ,

Claims (13)

DEFINITION OF INVENTION 1) the poly-addition of components a to d is carried out until 85% of the NCO groups are reacted, and the components a to d are added in amounts such that the equivalent ratio of the isocyanic groups component a to the sum of hydroxyl and / or amino groups a to c 1: 1, and 1) the molar ratio between components a and b is 0, 1 to 0.8, 1) the molar ratio between components a and b is 0.1: 1 and 1.1: 1, 1. Radiation-curable oligomers with several terminal unsaturated ethylene groups and several urethane and / or urea groups per molecule obtained from (a) at least one hydroxy- and / or amino-functional compound with 34 functional groups and an average molecular weight of 500 to 4000, b) at least one compound having two hydroxyl and / or amino groups per molecule having a molecular weight of 200 to 4000, c) at least one unsaturated monoethylene compound having an active hydrogen group per molecule having a molecular weight of 116 to 1000, d) at least one aliphatic and / or cycloaliphatic diisocyanate, characterized in that the components a to d are present in a ratio such that 2.0% by weight of additives, in addition to the total weight of the conventional auxiliaries, to give a coating composition by weight 2) Polyphenylation of components a to d is carried out by adding component c until 99% of the NCO groups are reacted. 2) the molar ratio between components c and a is between 2.5 and 10. 2. A process according to claim 2 wherein the component a uses compounds having an average molecular weight of 750 to 2000 and / or the component b uses compounds having an average molecular weight of 600 to 2000 and the component c uses compounds having an average molecular weight of 116 to 400. . 2. Radiation-curable oligomers according to claim 1, characterized in that the component a uses compounds having 3 functional groups. 2) the molar ratio between components c and a is 2.0: 1 and 10: 1, 3. Radiation-curable oligomers according to either 1 or 3) the equivalent ratio between the diisocyanate groups of the component and the hydroxyl and / or amino groups of the sum of the components a to c is between 0.9 and 1.0. Radiation-curable oligomers according to claim 13, characterized in that the components a to d are added in amounts such that Radiation-curable oligomers according to claim 4, characterized in that the oligomer has acrylic groups of from 0.45 to 0.63 mol / kg. Radiation-curable oligomers according to one of claims 1 to 5, characterized in that the component a uses ethoxylated triols having an average molecular weight of> 1000. Radiation-curable oligomers according to one of claims 1 to 6, characterized in that component b uses a mixture of b!) From 0 to 90 mol% of polyetherdiol and b ₂ ) from 100 to 10 mol% of modified polyetherdiol of b ₂₁ ). at least one polyetherdiol b ₂₂ ) at least one aliphatic and / or cycloaliphatic dicarboxylic acid and b ₂₃ ) at least one aliphatic saturated epoxy group containing from 8 to 21 C atoms per molecule, in addition to the sum of the components b _r and b ₂ , the sum of the components b ₂₁ -b ₂₃ is 100 mol% in each case. Radiation-curable oligomers according to one of claims 1 to 7, characterized in that they are obtained under conditions in which 9. A radiation curable composition comprising at least one radiation curable oligomer according to any one of claims 18 to 9. The radiation-curable coating composition of claim 9, partially for buffering optical glass fibers, wherein that it consists of A) 10 to 78% by weight of at least one radiation curable oligomer according to one of the 1-8 points, B) 0 to 60% by weight at least of another unsaturated ethylene oligomer, C) from 20 to 50% by weight of at least one unsaturated an ethylene monomeric and / or oligomeric compound, D) from 2 to 8% by weight of at least one photoinitiator, and E) from 0 to 4% by weight of conventional excipients or additives in addition to the% by weight based on the total weight of the coating composition. 11. A radiation curable coating composition according to claim 9, characterized in that it consists of A) 15 to 8 points to be hardened, 75% by weight of at least one non-saturated ethylene oligomer of at least one of 1B) from 0 to 50% by weight, C) 22 to 35% by weight of at least one unsaturated ethylene monomeric and / or oligomeric compound, D) from 3 to 5% by weight of at least one photoinitiator, and E) from 0.5 to the materials and calculate the masses. A radiation-curable coating composition according to claim 10 or 11, characterized in that: 15 that component B is unsaturated ethylene polyurethane. Use of a radiation curable composition according to any one of claims 9 to 12 as a primer and / or varnish for coating a glass surface, in particular a glass fiber.