BG97481A - Liquid photo-hardened coating compositions for on 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

It is an object of the present invention to irradiate oligomers with several ethylene unsaturated end groups and several urethane and / or urea groups per molecule derived from

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

b) at least one compound having 2 hydroxyl-s / or amino groups per molecule and a molecular weight average of between 200 and 4000,

c) at least one mono-ethylene unsaturated compound having a group consisting of one active hydrogen atom per molecule and having an average molecular weight between 116 and 1000;

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

• · · ·

It is also an object of the present invention to irradiate roofing masses containing these irradiated oligomers, as well as a method for applying them to glass surfaces, in particular optical glass fibers, using these roofing masses.

Optical glass fibers are of increasing importance in the field of communication systems, such as conducting light wave fibers. For this purpose, glass surfaces must be protected from moisture and phenomena causing their rapid deterioration. Therefore, the glass fibers are provided with at least one protective layer even in their manufacture.

For example, it is known from (1) that the glass fibers are first coated with an elastic but not very rigid and not very tough buffer layer (priming) and then applied with an irradiated hardening lacquer coating characterized by high hardness and toughness.

The two-layer construction provides good protection of the glass fibers against mechanical damage and at low temperatures.

According to (1), primers use irradiation-based coatings based on linear urethane acrylates. For lacquer coating, irradiating curing agents based on linear urethane acrylate, diethylenically unsaturated ester, diglycidyl ether of bisphenol and mono-ethylene unsaturated monomer may be used, wherein the glass transition temperature of the homopolymer obtained from this monomer is greater than 55 .

In addition, according to (2), radiation-curable optical fiber coating means are known. As a binder, these coating agents contain radiation-curable oligomers according to the characteristic part of the main πη Ω T Q mt m / cm

The coating cures described in (2) are irradiated when applied either as a varnish coating or as a single-layer varnish. They are not suitable for priming because of the too high value of the E-module of the hardened coatings.

Radiation-curable optical glass fiber coating masses are also described in (3). As a binder, these coating masses comprise a polyurethane oligomer with acrylate end groups based on a polyfunctional core. These roofing materials can be used for both priming and lacquering. Single-layer processing is also possible.

Also known are (4), (5), (6), (7), and (8), irradiated, curable coating materials for application to optical glass fibers, which contain linear urethane acrylates as a bonding agent. These roofing masses have the disadvantage of unsatisfactory aging resistance. In addition, the mechanical properties of coatings, in particular the elasticity of continuous loading, need improvement.

It is an object of the present invention to provide irradiated, irradiable, coating surfaces for glass surfaces, in particular optical glass fibers, which have better properties than the known coating surfaces. In particular, hardened coatings must have improved aging responses and thus increased stability for a longer period of time than the coated glass fibers.

In addition, hardened coatings must have improved water absorption and desorption reactions. This is particularly important for the optical steam treatment of coated fibers. In addition, hardened coatings must have a good buffering effect at low temperatures. This means that as the temperatures drop, the mechanical properties of the coating deteriorate as little as possible. In particular, the value of the E-module: should be raised as low as possible. The roofing masses must be hardened as quickly as possible. In addition, the coatings obtained should show the most limited development of hydrogen during storage, respectively in straddle breeding, as well as good attachment to the glass surface.

In a more surprising way, the object of the invention is solved by irradiating oligomers with several ethylene unsaturated end groups and several urethane and / or urea groups for a molecule derived from

(a) at least one hydroxy and / or amine function having a functionality between 3 and 4 and a molecular weight average of between 500 and 4000,

b) at least one compound having 2 hydroxyl- and / or amino groups per molecule and having a molecular weight average of between 200 and 4000,

c) at least one mono-ethylene unsaturated compound with one asset a hydrogen atom per molecule and a molecular weight average of between 116 and 1000;

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

The irradiated oligomers are characterized in that the components a) to d) are utilized in such quantities that

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

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

3.

equivalence ratio of isocyanate groups of components

(d) to the hydroxyl and / or amino groups of the sum of the components a) to

c) between 0.9 and 1.0.

The present invention also relates to irradiated curing masses containing these irradiated oligomers, as well as a method for depositing on glass surfaces, in particular optical fiber, using the coating masses.

Surprisingly and unpredictably, it has been found that irradiated curing masses based on the oligomers of the invention lead to coatings with improved cracking reactions over conventional coatings known so far, so that the glass fibers on which these coating masses are applied show increased stability - long period of time. In addition, the coatings obtained from the coating masses according to the invention show improved reactions on the absorption and desorption of water compared to conventional coatings. The good buffering effect of the coatings at low temperatures is also advantageous, so the so-called micro-distortion problem is solved in this way. In addition, the coatings according to the invention have good mechanical properties, such as e.g. in accordance with the purpose of the application, the tensile and expansion resistance, as well as the limited development of hydrogen during storage, respectively. when aging. In addition, they have a good attachment to the glass surface.

The following will first describe in more detail the first irradiated oligomers according to the invention: Components a) for the preparation of oligomers are suitable hydroxy and / or amino-functional compounds with functionality from 3 to 4, preferably • · · · • · • ·

3. These compounds have an average molecular weight of from 500 to 4000, preferably from 750 to 2000.

Examples of suitable compounds are polyoxyalkylated triols, such as e.g. ethoxylated and propoxylated triols, preferably ethoxylated triols, particularly preferably having a molecular weight average molecular weight greater than 1000. For example, trioles. glycerin or trimethylolpropane are used.

Appropriate amino-functional compounds such as e.g. derived from polyalkoxylated triol amino functional compounds. An example of this is Texaco JEFFAMIN products, e.g. JEFFAMIN, T 403, T 3000, T 5000,

C 346, DU 700, BuD 2000.

The amino-functional compounds may contain both primary and secondary amino groups.

Also suitable are compounds that contain both aminotox and hydroxyl groups.

Compounds containing 2 hydroxyl and / or amino groups per molecule are suitable for components b). These compounds have an average molecular weight of from 200 to 4000, preferably from 600 to 2000.

Examples of suitable compounds b) are polyoxyalkylene glycols and polyoxyalkylene amides, preferably alkylene groups having 1 to 6 carbon atoms. For example, suitable are polyoxyethylene glycols having a molecular weight average molecular weight of 1000, 1500, 2000 or 2500 as well as polyoxypropylene glycols with the corresponding molecular weights and polytetramethylene glycols. Polyethoxylated and polypropoxylated diols may also be used, such as e.g. ethoxylated resp. propoxylated butanediol hexanediol derivatives, etc.

Polyester diols may also be used which e.g. are obtained by reacting the glycols just mentioned with dicarboxylic acids, preferably aliphatic and / or cycloaliphatic dicarboxylic acids, such as e.g. hexahydrophthalic acid, adipic acid, acelaic, sebacic and glutaric acid and / or their alkyd substituted derivatives. In place of these acids, their anhydrides can be used as long as they exist. Polycaprolactone diols are also applicable. These products are obtained e.g. by the interaction of caprolactone with diol. Such products are described in US Patent 3 169 945.

The polylactone diols produced by this reaction are distinguished by the presence of a terminal hydroxyl group and by recovered polyester particles which are removed from the lactone. These returning molecular constituents may correspond to the formula

II

- C - (CHR) _n - CH ₂ where η is preferably 4 to 6 and the hydrogen substituent is an alkyl radical, a cycloalkyl radical or an alkoxy radical, wherein no substituent contains more than 12 carbon atoms and the total number of carbon atoms in the the substituents in the lactone ring do not exceed 12.

The lactone used as the starting material may be any lactone or any combination of lactones, wherein the lactone must contain at least 6 carbon atoms in the finger of, e.g. from 6 to 8 carbon atoms and wherein at least 2 hydrogen substituents are to be contained in the carbon atom.

• ·

The lactone used as a starting material can be represented by the following general formula:

CH ₂ - (CR ₂ ) ^ ^{C = 0} o --- L where η and R are as defined above. The preferred lactones for the preparation of polyester diols according to the invention are caprolactones having a value of 4. The most preferred lactone is the substituted β-caprolactone at which the value!

of η is 4 and all of the R-substituents are hydrogen. This lactone is particularly preferred because it is present in large quantities and leads to coatings with excellent properties. Of course, other lactones can be used individually and in combination. Examples of suitable lactone-interacting aliphatic diols are given above for the diols mentioned when interacting with carboxylic acids.

Naturally, the corresponding diamines as well as their OH or amino group compounds can also be used as components (b). Examples of suitable compounds are those contained in the Texaco products listed below under the name JEFFAMIN

D 230, D 400, D 2000, D 4000, ED 600, ED 900, ED 2001, ED 4000.

Preferably for components b), a mixture of

0 to 90 mol% by weight of at least one polyether diol and

10 to 100 molar% of at least one modified polyether diol of b ₂ -0 at least one polyether diol

6 ₂₂ ) at least one aliphatic and / or cycloaliphatic dicarboxylic acid and ⁶ ₂₃ ) at least one aliphatic, saturated compound with an epoxy group and from 8 to 21 carbon atoms per molecule,

) and 62) as in which the sum of the components of the components and the sum of the components of the components 62 ^) to 623 is 100 molar%.

For the preparation of modified polyether diodes by the conventional methods, the components 62 ^) to 623) are used in such quantities that the equivalent ratio of the OH-groups of the components 62 ^) relative to the carboxylic groups of the components ^ 22 ^ ^{is between} 0.45 to 0.55, preferably 0.5, and that the equivalent ratio of the epoxy groups of the components 623) to the carboxyl groups of the components 622 ^is between 0.45 and 0.55, preferably 0.5.

Examples of suitable polyether diols (b) and 62 (b) are the polyoxyalkylene glycols mentioned above, wherein the alkylene groups contain from 1 to 6 carbon atoms. Preferably, polyoxypropylene glycols with an average molecular weight of between 600 and 2000 are used as components (N, N). Preferably, polyoxybutylene glycols (Poly-THF) with a molecular weight greater than 1000 are used as components 62P.

Preferably aliphatic as well as cycloaliphatic dicarboxylic acids of 8 to 36 carbon atoms ^{are used} as components, such as e.g. hexahydrophthalic acid. For components 623), for example, epoxidized vinylcyclohexane compounds, epoxidized, monoolefinic unsaturated fatty acids and / or polybutadienes are suitable.

Components 623) are preferably used for the branched monocarboxylic acid glycidyl ester, such as e.g. glycidyl ester of versatic acid.

Mono-ethylene unsaturated compound containing compounds are used to introduce the ethylene unsaturated groups into the polyurethane oligomer

active hydrogen atom groups having a molecular weight average of from 116 to 1000, preferably from 116 to 400. Examples of suitable components c) are e.g. the hydroxyalkyl ester of ethylene unsaturated carboxylic acids, such as e.g. hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyamyl acrylate, hydroxyhexyl acrylate, hydroxyoctyl acrylate, and the corresponding hydroxyalkyl esters of methacrylic, fumaric, maleic, itaconic, crotonic and isocrotonic acids, the hydroxyalkyl esters of acrylic acid being in fact preferred. In addition, for components c), adducts of caprolactone and one of the hydroxyalkyl esters of ethylene unsaturated carboxylic acids mentioned above are also suitable. Adducts of the hydroxyalkyl esters of acrylic acid having an average molecular weight of from 300 to 1000 are preferably used. For the preparation of oligomers according to the invention as a com- D “w” · d) are suitable aliphatic and / or cycloaliphatic diisocyanates such as e.g. 1,3-cyclopentane, 1,4-cyclohexane, 1,2-cyclohexane diisocyanate, 4,4'-methylene-bis- (cyclohexylisocyanate) and isophorondiisocyanate, trimethylene-, tetramethylene-, pentamethylene-, hexamethylene trimethylhexamethylene-1,6- diisocyanate as described in EP-A204 161, col. 4, lines 42-49, dimeric fatty acid diisocyanates. Isophorondiisocyanate and trimethylhexamethylene-1,6-diisocyanate are preferably used. It is essential for the invention that the components a) to d) used to prepare the oligomers of the invention are applied in such quantities that

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

2. the molar ratio of the components c) to the components

(a) be between 2: 1 and 10: 1, preferably between

2.5 and 10 and

3. the equivalent ratio of the isocyanate groups of component d) to the active hydrogen atoms of components a) plus b) plus c) is between 0.9 and 1.0.

The oligomers of the invention can be prepared in various ways. For example, it is possible to first react the isocyanate d) with the chain-extending agents a) and b) and then react the remaining free isocyanate groups with ethylene unsaturated compounds c).

In addition, the preparation of the oligomers, as a first part of the isocyanate groups of components d) is reacted with ethylene unsaturated compounds c) then the remaining free isocyanate groups interact with the chain extending agents a) and b).

In addition, the preparation of the polyurethane oligomers is carried out according to the method described in EP-A-223 086, p.

Preferably, the polyurethane oligomers are obtained by a two-step process, where initially stoichiometric multiple attachment of components a) to d) takes place until more than 85% of the NCO groups of components d) react. first step of the method the components a) to d) are used in such quantities that the equivalent ratio of the NCO groups of the components d) to the active hydrogen atoms of the components a) to c) is 1: 1.

In the second step of the method, the remainder of the remaining components (respectively, to the resulting NCO: OH ratio) is added and the reaction continues until the conversion of the NCO groups is greater than 99%. Preferably, in this second step of the method, more components c) are added and by adding these components c) the desired NCO: OH ratio is adjusted.

Typically, the urethane oligomers of the invention have average molecular weights of 2500 to 10000, preferably 3000 to 6000 (measured by GPC versus polystyrene standard), average weighted molecular weights from 5000 to 50000, preferably 7000 to 20000 (measured by GPC against polystyrene standard) , double bond contents of 0.45 to 1.5, preferably 0.45 to 0.9 mol / k, and particularly preferably 0.45 to 0.63 and very preferably 0.5 to 0.63 mol / k kg as well as functionality of more than 2 to 3.5, preferably 2.2 to 2.8, always for the average polymer a molecule.

* * The oligomers of the invention use kata film-forming components A in irradiated coating masses. Typically, the coating masses comprise 10 to 78% by weight, preferably 15 to 75% by weight, and especially preferably 63 to 73% by weight, always relative to the total weight of the coating masses of the oligomers of the invention.

As another component, the coating masses may contain 0 to wt.%, Preferably 0 to 50 wt.%, Always relative to the total weight of the coating masses, at least one other ethylene unsaturated oligomer B. In addition to unsaturated polyesters, polyester acrylates and acrylate copolymers. are used before all except those used as components A • · • · · ·

W urethane acrylate oligomers, urethane acrylate oligomers. By the type and quantity of these components B, the properties of the hardened coating can be targeted. The greater the content of component B, the greater the value of the E-module of the hardened coating. Therefore, components B are added to the roofing masses when the latter are used for lacquer coating. The effect of components B on the properties of the resulting coating is known to those skilled in the art. The always favorable amount to be used can be obtained through a limited number of routine trials.

Ethylene unsaturated polyurethanes used as component B are known

They may be obtained by reacting a di-or polyisocyanate with a chain-extending agent of the group of diols / polyols and / or diamines / polyamines and subsequent reaction of the remaining, free isocyanate groups with at least one hydroxyalkyl acrylate or hydroxyalkyl ester of other ethylene unsaturated carboxylic acids.

The quantities of the extension chain means, respectively. the polyisocyanate and hydroxyalkyl ester of ethylene unsaturated carboxylic acid are selected such that

1. the equivalent ratio of NCO groups to the reactive groups of the extending agent (hydroxyl, amine, or mercaptyl groups) is between 3: 1 and 1: 2, preferably 2: 1, and

2. the OH groups of the hydroxyalkyl ester of ethylene unsaturated carboxylic acids are present in a stoichiometric amount relative to the still free isocyanate groups of the isocyanate prepolymer and the extending chain agent.

In addition, it is possible to obtain polyurethanes B as the initial part of the di-or polyisocyanate isocyanate groups is reacted with at least one ethylene unsaturated carboxylic acid hydroxyalkyl ester and then the other isocyanate groups are reacted with the chain extending agent. Also in this case, the amounts of the extending chain agent, isocyanate and

the hydroxyalkyl ester is selected such that the equivalent ratio of the NCO groups to the reactive groups of the extending chain is in the range between 3: 1 and 1: 2, preferably 2: 1, and the equivalent ratio of the other NCO groups to the OH groups of the hydroxyalkyl ester to amount to 1: 1.

Of course, in both methods some intermediate forms are also possible. For example, part of the isocyanate groups of diisocyanate may first react with diol, then another part of the isocyanate groups may react with the hydroxyl ester of ethylene unsaturated carboxylic acid, and subsequently the other isocyanate groups may interact with diamine.

These various methods of producing polyurethanes are known (eg compare EP-A-204 161) and therefore do not need to be described in detail.

For the preparation of urethanacrylate oligomers B, compounds such as the compounds used for the preparation of components A, as well as those specified in DE-OS 38 40 644, are suitable.

In particular, when using the coating materials according to the invention as a varnish coating for the preparation of urethane acrylate oligomers B, it is preferable to use aromatic additives.

components. Particularly preferred in this case are 2,4- and 2,6-toluylenediisocyanate as an isocyanate component as well as aromatic polyester-polyols based on phthalic acid and isophthalic acid and / or polypropylene glycol, ethylene glycol and diethylene glycol as a chain-extending agent.

As another component, the irradiating curing masses also contain at least one ethylene unsaturated monomer and / or oligomer compound B, typically in an amount of 20 to 50% by weight, preferably from 23 to 35% by weight, always relative to the total weight of roofing tables.

By the addition of this ethylene unsaturated compound B, the viscosity and hardening speed of the coating masses as well as the mechanical properties of the resulting coating are regulated, as is known to those skilled in the art and is described, for example, in EP-A-223 086 and therefore does not require More details.

Examples of monomers that may be used may be cited toxoethoxyethyl acrylate, N-vinylpyrrolidone, phenoxyethyl acrylate, dimethylaminoethyl acrylate, hydroxyethyl acrylate, butoxyethyl acrylate, isobornyl acrylate, dimethylacrylate acrylate dicrylate acrylate. Also suitable are di-and polyacrylates, such as e.g. butanediol diacrylate, hexanediol diacrylate, trimethylolpropane diacrylate and trimethylolpropane triacrylate, pentaerythritol diacrylate, as well as those described in EP-A-250 631 long-chain linear diacrylates with molecular weights from 400 to 4000, preferably from 600 to 2500 groups. polyoxybutylene structure. In addition, 1,12-dodecyl diacrylate and the product of the reaction of 2 moles of acrylic acid with 1 mol of dimeric fatty alcohol, which shows the presence of 36 carbon atoms, were also administered.

• · · · · · · · · · ·

Mixtures of the monomers described above are also suitable.

Preferably, phenoxyethyl acrylate, hexanediol diacrylate, N-vinylpyrrolidone and tripropylene glycol diacrylate are used. Usually used in the roofing masses in an amount of 2 to 8% by weight, preferably from 3 to 5% by weight relative to the total weight of the roofing mass, the photoinitiator varies depending on the radiation used for curing the coating (ultraviolet radiation, electron radiation, visible light ).

Preferably, the roofing masses according to the invention are cured by UV rays. In this case, ketone-based photoinitiators, for example, acetophenone, benzophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-funnylpropan-1-one, hydroxypropylphenyl ketone, m-chloroacetophenone, propiophenone, benzoyltin, benzoyltin, benzoquinone, benzoyltin, benzoyltin, benzoin , thioxanthon and thioxanthon derivatives as well as mixtures of various photoinitiators.

In addition, in this case, the roofing masses may also contain the usual excipients and additives

Typically, they are used in an amount of from 0 to weight%, preferably from 0.5 to 2.0% by weight, based on the total weight of the roof masses.

Examples of such substances are flowing agents, softeners, and in particular fixing agents

Alkoxysilanes, such as e.g.

Nβaminoethyl

aminopropyltrimethoxysilane aminopropyltrimethoxysilane

-methylaminopropyltrimethoxysilane or triamino-modified propyltrimethoxy silane (eg DYNASYLAN 'Tur Triamo fixing agent, Dynamit Nobel commercial product).

The coating masses can be applied to the substrate by known application methods, such as pouring, spraying, dipping, scraping, grinding or spreading.

Curing of the lacquer coating is carried out by irradiation, preferably by UV rays. The installations and conditions for these curing methods are known in the literature (R. Holmes, UV and EV Curing Formulations for Printing Inks, Coating and Paints, SITA Technology, Academic Press, London, United Kingdom, 1984) and are not needed from a further detailed description.

Roofing masses are suitable for application to various substrates such as e.g. glass, wood, metal and artificial surfaces. In particular, they are used to apply a coating layer to glass surfaces, especially preferably to optical glass fibers.

It is also an object of the present invention to provide a coating layer on glass surfaces in which radiation-curable coating masses are applied, which are cured by UV or electron irradiation, characterized in that the radiation-curable coating tables are used roofing tables according to the invention.

The method according to the invention is particularly suitable for applying a coating layer on optical glass fibers.

In this case, the coating masses according to the invention can be applied to the glass fibers as a primer and / or varnish coating with two-layer varnishing. When using primers for priming, hardened coatings typically have an E-modulus value (at 2.5% expansion and room temperature) of less than 10 MPa.

When using coating materials as a lacquer, hardened coatings typically have an E-module value (at 2.5% expansion and room temperature) of 500 to 1000 MPa.

The invention will be explained in more detail by way of the examples below. All parts and percentages data are weight data unless explicitly stated otherwise.

Preparation of modified polyether diol

In a cylindrical vessel equipped with an inert gas and a temperature sensor parts polytetrahydrofuran with a stirrer, the inlet device is heated to a temperature of 120 ° C 51.1 with a molecular weight of 1000 and an OH number

118 mg KOH / g and

19.1 parts of hexahydrophthalic acid anhydride and the number is maintained at this temperature until the acidity reaches 102 mg KOH / g. Then they are added

0.02% chromoctoate, relative to the weight of the mixture of poly-THF, hexahydrophthalic acid and glycidyl ester of versatic acid, and 29.7 parts of glycidyl ester of versatic acid with epoxy equivalent weight of 266. The mixture was heated to 12 C until then. achieved an epoxy equivalent weight of more than 20,000, an acidity number of 4 mg KOH / g and an OH number of 60 mg KOH / g.

The modified polyether diol shows an average molecular weight

M _n = 1860 (calculated from the OH number), determined by

M 1500 and / M _n = 1.67. The viscosity of the 80% solution in butyl acetate contains 3.8 d Pas (measured at 23 ° C with a viscometer).

Example 1

In a cylindrical vessel equipped with a stirrer, tidal devices, a thermosensor and an air intake device, 0.35 mol of ordinary ethoxylated trimethylolpropane with a molecular weight of 1000, 0.65 mol of ordinary polyoxypropylene glycol with • · · · · · · · average molecular weight of 600, 0,65 moles of the above modified polyether diol, 1,75 moles of hydroxyethyl acrylate, 0,05¾ dibutyltin dilaurate (relative to the total weight of the components a), b), c) and d)), 0 , 1¾ 2,6-diter-butyl cresol (relative to total weight of the components a), b), c) and d)) and 30 rrtp relative to the total weight of the sum of components a, b, c and d) and heated to 60 ° C. Then θ

at 50 C, 2.70 moles of isophorondiisocyanate are added over 2.5 h. It is then diluted with phenoxyethyl acrylate on a theoretical solid of 90¾ (the sum of the components a, b, c and d) and the temperature is maintained at 60 ° C until the NCO value reaches 1¾. 0.05 ¾ dibutyltin dilaurate and 0.51 mol of ordinary hydroxyethyl acrylate of the caprolactone oligomer with a molecular weight of 344 (Union Carbide commercial grade TONE M 100) were then added at 80 ° C and 80 ° C. maintained until the NCO value is less than 0.1¾. The oligomer thus obtained exhibits a double bond content of 0.6 mol / kg and a functionality of 2.5.

The 40¾ solution (relative to the theoretical solids content) of the resulting oligomer 1 in phenoxyethyl acrylate shows a viscosity of 4.9 dPas (measured at 23 ° C with a viscometer).

Of the 78.1 parts of the above-described 90% solution of urethane oligomer 1, 12.1 parts of phenoxyethyl acrylate, 6.2 parts of N-vinylpyrrolidone, 1.6 parts of β-β-aminoethyl- aminopropyltrimethoxysilane and 2.0 parts of diethoxyacetophenone is obtained by mixing an irradiated curing sheet 1.

Well cleaned, above all grease, glass panels of dimensions: width x length = 98 x 161 mm are glued along the edge with Tesakrepp Nr.4432 adhesive tape (width 19 mm) and a covering mass 1 (dry film thickness 180 µm) is applied to them.

Hardening is performed using an ultraviolet irradiation device equipped with two medium pressure Hg emitters with a lamp power of 80 W / cm at a bandwidth of 40 m / min in two cycles at half load mode (= 40 W / cm).

The irradiation dose was 0.08 J / cm (measured with a UVICURE dosimeter, Eltosch EIT system).

Hardened coatings are obtained with very good mechanical properties, which are also distinguished by good aging resistance, good low temperature reactions as well as improved absorption response and water desorption.

The results of the determination of the E-module at 0,5- and 2,5% -stretching (according to DIN 53 455 respectively) as well as the results of the tests on long-term stretching sa are given in Table 2. In addition, Table 2 shows the results of measurement of E-module values (2.5% stretching) after different aging stages of the hardened coatings.

The temperature dependence of the E-module is shown in Figure 1. Measurements were made with a DMTA instrument from Polymer Laboratories Ltd.

The absorption and desorption responses of the hardened coatings to water are depicted in Figure 2.

Comparative Example 1

In a cylindrical vessel equipped with a stirrer, tidal gear, thermosensor and air inlet, 2.0 mol of isophorondiisocyanate and 0.5% dibutyltin dilaurate (relative to the total weight of the component AB and c) are added and cured to 60 ° C. Then • · · · · · · · · · ·

are added for 120 to 180 minutes at a temperature of 60 ° C, a mole of ordinary polyoxypropylene glycol with a molecular weight of 600. The temperature was maintained at 60 ° C until a NCO value of 4.5% was reached. Then 0.1% 2,6-di-tert-butyl cresol (relative to the total weight of the sum of the components of a to d). 1.54 moles of hydroxyethyl acrylate are then added at 60 ° C for 30 minutes. It is then dissolved with phenoxyethyl acrylate on a theoretical solids content of 90% (referring to the total weight of the sum of components 1 to d). The temperature is maintained at 60 ° C until a NCO value of less than 0,1% is reached.

The oligomer 2 thus obtained shows the content of double bonds

1.01 mol / kg and a functionality of 2.0. A 50% solution (relative to the theoretical solids content) of the obtained viscomer oligomer at a temperature in phenoxyethyl acrylate shows a viscosity of 10 dPas (measured 23 ° C).

Analogous to Example 1 of parts of the above described 90% solution of urethane oligomer 2, parts of phenoxyethyl acrylate, 6.2 parts of N-vinyl-pyrrolidone, piltrimethoxysilane and 2.0

1.6 parts of β-β-aminoethyl-^- ^7- aminopropoethoxyacetophenone are obtained by mixing irradiated curing masses 2.

The application of the roof mass 2 as well as the tests of the hardened coating are carried out analogously to example 1. The results are described in Table 2 as shown in Figures 3 and 4.

TABLE 1: Composition of urethane-oligomers (in mole) example 1 Comparison 1

a) ethoxylated trimethylol- 0.35 - propane (M _n = 1000) b) polyoxypropylene 0.65 1,30 glycol CM _P = 600) b ₂ ) modified poly- 0.65 - ether diol ( _Mn = 1860) c) hydroxyethyl acrylate 1,75 1.54 c) hydrohexyethyl acrylate 0.51 - caprolactone oligomer d) isophorondiisocyanate 2.70 2.0 molar ratio a / b 0.27 0 molar ratio in / a 6.46 oo equivalence ratio 0.91 0.97 NCO / OH

TABLE 2: test results long stretching tests in%

E05-module (0,5¾-stretch) in MPa

E25-module (2.5-stretch) in MPa

E25 after 800 h, 55 ° C in MPa

E25 after 800h. , 90 ° C in MPa

E25 after 800 h, 120 ° C in MPa

1 VI 53,1 58 3.1 2, 75 2.9 2.6 3 2.7 4.2 7.5

F ^1:

Example 2

In the cylindrical vessel described in Example 2, 2 moles of isophorondiisocyanate were added, 0.05% dibutyl colloyl dilaurate and 330 ppm phenothiazine were added and heated to 60 ° C. 2 moles of hydroxyethyl acrylate are then added dropwise, so that the temperature does not exceed 60 ° C. Then, 1 mole of trimethoxyethylolpropane (20 mole of ethoxylene oxide per mole of trimethylolpropane) is also added dropwise at 60 ° C. The temperature is maintained at 60 ° C until a NCO content of 0% is reached. The intermediate thus obtained is then further processed.

moles of isophorondiisocyanate and dibutyl tin dilaurate are added and a mixture of 0.65 moles of polyoxytetramethylene glycol with a molecular weight of 1000 and 0.65 mol of modified polyether diol is added, the temperature being maintained at 60 ° C until the NCO content is reached by 2,7%

Phenothiazine is then added as a stabilizer.

Finally, a mixture of 1.05 mol of hydroxyethyl acrylate and 0.35 mol of intermediate 1 described above was added while maintaining the temperature at 60 ° C until an NCO content of less than 0.1% was reached.

Of the 70 parts of the urethane oligomer described above, 20.0 parts of phenoxyethyl acrylate, 6.5 parts of N-vinylpyrrolidone, 1.5 parts of N-β-aminoethyl-N-aminopropyltrimethoxysilane and 0.2 parts of diethoxyacetophenone are obtained by mixing curing is when irradiated roofing mass. The chemical properties are shown in Table 4. Glass plates (width x length = 98x161 mm) are well cleaned (primarily of grease) and adhered to the edge with Tesakrepp adhesive tape No. 4423 (width 19 mm and cover (stretch) (thickness) to a dry layer of 180 pm).

• · · ·

Curing is carried out using an UV irradiation installation equipped with two Hg emitters with 80 W / cm lamp power at a bandwidth of 40 m / min in two cycles at half load (= 40 W mode) / cm).

The irradiation dose was 0.08 J / cm (measured with a UVICURE dosimeter, Eltosch EIT system).

Hardened coatings are obtained with very good mechanical properties, which are also characterized by good aging resistance, good low temperature reactions and improved response to water absorption and desorption.

The results of the determination of the E-module at 0.5 and 2.5% elongation (DIN respectively) as well as the results of the elongation are given in Table 5.

The temperature dependence of the E-module is shown in Table 6 and Figures 5 and 7. Measurements were taken with a DMTA apparatus of Polymer Laboratories Ltd.

W ··

Example 3

Preparation of intermediate 1 was carried out analogously to the method described in example 2.

2 moles of isophorondiisocyanate and dibutyl tin dilaurate were added and a mixture of 0.65 moles of polyoxytetramethylene glycol with a molecular weight of 1000 and 0.65 mol of modified polyether diol was then added. keeping the temperature at 60 ° C until a NCO content of 2.6% is reached. Phenothiazine is then added as a stabilizer. A mixture of 0.35 mol of hydroxyethyl acrylate and 1.05 mol of intermediate 1 above was then added while maintaining the temperature at 60 ° C until an NCO content of less than 0.1% was reached. · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

· · · · ·

The preparation, application and quenching of the irradiating curing agent as well as the coating tests were performed analogously to Example 2.

The test results are shown in Tables 5 and 6 and are shown in Figures 5 and 8.

Example 4

Preparation of intermediate 1 was carried out analogously to that described in example 2.

Add a mole of isophorondiisocyanate and add 1.3 mol of modified polyether diol. After the addition was complete, the mixture was maintained at 60 ° C for 6 h.

1.4 moles of the above intermediate at 60 ° C are then added until a content is reached and the temperature is maintained at NCO less than 0.1¾.

The hardening of the irradiating curing agent as well as the coating tests were obtained, applied, and quenched analogously to Example 2.

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

Comparative Examples 2 and 3

Analogous to Example 2, the polyurethane acrylate oligomers were prepared from the components listed in Table 3.

These urethanacrylate oligomers were prepared analogously to Example 2, irradiated curing masses. Hardening applications and coating tests were performed analogously to Example 2.

• · · · · · · · ·

The temperature dependence of the E-module is shown in Figure 5 and shown in Table 8. Measurements were taken with a DMTA instrument from Polymer Laboratories Ltd.

Table 3: Composition of polyurethane acrylate oligomers in mole

Example 2 3 4 V2 V3 p-THF 1000 0.65 0.65 - 0.65 - P 600 - - - - - mod.RE 0.65 0.65 1,30 0.65 1,30 fl. TMP 7 - - - 0.70 0.70 fl. TMP 20 0.35 1,05 1,40 - - NEA 1,75 2.45 2.80 2.10 2.10 IPDI 2.70 4.10 4.80 3,40 3,40 Table 3 the following abbreviations have been used: p-THF 1000 : polyoxytetramethylene glycol with average molecular weight 1000 P 600 : polyoxypropylene glycol with average molecular weight 600 mod.RE : modified polyether diol et al. TMP 7 : ethoxylated trimethylolpropane with 7 units

ethylene oxide for trimethylolpropane

(M _n = 414) et al. TMP 20 : ethoxylated trimethylolpropane with 20 units ethylene oxide for trimethylolpropane NEA : 2-hydroxyethyl acrylate IPDI : isophorondiisocyanate

to>

Table 4: Chemical properties of the liquid coating agent

MS>

t-1>

'tG

Midrange

rt X and X rt S Rf R. rt Η rt f rt & in x F. X ffl s X X X ο Midrange rt X P ρ X α > h and X Rf φ Rf ο sch a s U p ο rt ο in Fr. and and rt X in X Midrange X R. R. ο X ι — 1 Fr. and rt Midrange Fr. \ Oh 00 υ rt X ech «X Midrange years rt X Rf r *. Midrange Fr. that him Fr. ο s W S s X rt rt X J. ffl B « τ — 1 σ> Fr. rt Rf magazine what oo X X X U in ech • h e. p X ffl and what 1—1 ο Midrange him > h X f Fr. Rf Rf Rf in X R. R. X Midrange o X rt 1—1 Yu f F. X X X him Midrange in Η X Fr. · * • X X X ffl Rf X Midrange Midrange Midrange Midrange X X and X Midrange Midrange F. rt and X X X X ΟΊ Thu. years Rf X Fr. > 4 magazine Ln Fr. F. S Γθ < ech ech • X rt rt 3 ss Yu 1—1 Ο * 3 · o Rf rt rt rt X X X X X B and Rf Midrange ι-l that o f Fr. Ό Yu SS ss ffl f S • h ech • X ex X X in in X Midrange Fr. him that HH a X Midrange rt rt o Rf Fr. He is Ri X f X Midrange 00 IN in F. S Fr. Yu X X Midrange Fr. rt • X • X * x ex F. f F. X X him Midrange Fr. him Midrange R. years and Fr. and X X F. S f Fr. Fr. Rf Rf Yu Mr- and X rt and Fr. H © that Yu ο X • X • X ex ex ι — 1 Midrange Fr. him Midrange • ·

S NW X J. X RF <υ s ο εύ S J. X E X Ίρ φ S ο ρ q4 Rf R. in Rf X f X 1 J. Midrange 1 S Fr. Midrange • ο ο • Fr. X ο Ο Ρ X ⁴ - ' Ο Ρ in '-' W '-' X and and II X υ υ II X Midrange pq pq > 4 pq pq Fr. pi η Ο θ Q Q Ο θ

Table 5: mechanical values for coating tests

MS>

midnight Mr

LD hH

LD

Midrange midrange m · to * 3 · midrange * 3 * e

oo sch-I *

yo r ^)

LG r-L O o \ <= X ⁴ --- 'Sat.

1> e n hey co Vol n t Rf sj is \ ° Rf LG Fr. • h Well Oh <D '-' N. S and P. AZ hours Fr. Rf S n 1 W m

O *

LD sch *

sch

U0 mSh mSh σ> mSh

Ф X Сб

Rn

Bb CO sat

PH about X

I about \ °

1_Fr r;

H o s o sc ι

And ffl · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

-31 TABLE 6

Tabelle 6

Example 2

Example 3

Beispiel 2

Beispiel 3

TCC] * log E TCC] log E -41 ·· 9,204 -39 · '9,174 -40 ·· 9.191 -38.5 · '9.161 -39 9,178 -37.5 9,148 -38.5 9,173 -36.5 9,132 -37.5 9.16 -35.5 · '9.122 -36.5 9,148 -35 «9,107 -35.5 9,134 -34 ·· 9,092 -34.5 9,122 -32.5 ·· 9,074 -33.5 · '9,099 -32 9,054 -32.5 ·· 9,072 -31 ·· 9.043 -31 9,063 -30 9,032 -30.5 '· 9.045 -29 ·· 9.011 -29.5 9,035 -28.5 8,996 -28.5 8,968 -27.5 · '8.977 -28 9,001 -26.5 8,957 -27 8,981 -26 ·· 8,945 -26 8,964 -25 ·· 8.921 -25 8,898 -24 8,899 -24.5 8,924 -23 · '8,883 -23.5 ·· 8,908 -22 8,862 -22.5 8,888 -21 8,779 -21.5 8,861 -20.5 8,818 -21 8,849 -19.5 8,792 j -20 8,829 -18.5 8,714 -19 8,786 -18 · '8,745 i -18 · '8,775 <7 ^ 8/721 I -17.5 8,748 -16 8,613 | -16.5 8,708 8/656 -15.5 8,693 -14.5 8,636 -14.5 8,669 -13 8,587 -13.5 8,617 -12 · '8,556 -12.5 · '8.6 -11.5 "8.528

• · · · · · · · · · ·

-3235

Continuation of Table

Fortsetzung Tabelle 6

Example 2

Example 3

Beispiel 2

Beispiel 3

TG ° C] log E TE ° NW log E -11.5 8,574 -10.5 ·· 8.48 -11 · '8,525 -9.5 8,417 -10 8,511 -8.5 ¹¹ 8.415 -9.5 · '8,448 -7.5 ·· 8,382 -8.5 · '8.426 -7 '· 8.327 -7.5 · '8,403 -6 8,299 -6.5 · '8.35 -5 '· 8,153 -6 8,317 -4 ¹¹ 8,205 -4.5 8.24 -3.5 ·· -3.5 8,208 -3 ·· 8,034 -3 · '8,034 -2 · '8,109 -2 »8,109 -1 8,076 -1 ·· 8,076 -, 5 ·· 7,997 -, 5 7,997 1 “7,955 1 ·· 7,955 1.5 · '7.86 1.5 · '7.86 2.5 · '7.836 2.5 · '7.836 3 · '7.79 3 '7.79 4 · '7,681 4 · 7,681 5 · '7,654 5 «7,654 6 7,618 6 · '7,618 7,5 · '7,503 7,5 · '7,503 8 · '7,464 8 · '7,464 9 · 7,425 9 7,425 10 · 7,311 10 7,311 11 7,275 11 7,275 12 7,231 12 7,231 13 7,185 13 7,185 13.5 ·· 7.15 13.5 ·· 7.15 14.5 7,099 14.5 · '7,099 15.5 «7,051 15.5 7,051 16 6,999 16 · '6,999 17.5 6,932 17.5 6,932 18 6,891

• · · · · · • · · • · · · • · · · 36 · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · • · · · · · · · · · · · · · -33- Sequel Table 6 1 Fortsetzung Tabelle 6 Example 2 Example 3 Beispiel 2 Beispiel 3

T ['C] * log E 1 [• C] log 'E 18 6,891 18.5 6.876 18.5 6.876 20 6,815 20 6,815 20.5 6.796 20.5 6.796 21.5 6.757 21.5 ·· 6,757 22.5 ·· 6,735 22.5 6.735 23 6.71 23 · '6.71 24 6,698 24 6,698 25 ^and 6.67 25 6.67 26 6,638 26 · '6,638 26.5 * 6.623 26.5 6.623 28.5 6.491 28.5 6.491 30.5 6.483 30.5 6.483 32.5 · '6.501 32.5 6,501 34 '· 6,514 34 · '6,514 37.5 · '6.464 37.5 · '6.464 38 6.46 38 «6.46 39 6,419 39 6,419 40.5 6.44 40.5 6.44 41.5 ·· 6,426 41.5 6.426 42.5 ·· 6.43 42.5 '· 6.43 43 6,409 43 6,409 44 · '6,454 44 6,454 45 '· 6.423 45 6,423 46 · '6,366 46 '· 6,366 47 · '6,453 47 6,453 48 2460368 48 6,395 50 6,359 51 ”6,356 52 · '6,472 53 6,429 54 6,376 55 6,383 56 6,434 57.5 ·· 6,422 58.5 6,408 60 * 6,362

• · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · ·

Table 7

Tabelle Ί Example 4

Beispiel 4 example 1

Beispiel 1

T [-C] - log E T [“C] - log E -39 9,332 th most common -39 9,395 -38 9.33 -38.5 · '9,394 -37 · ' 9,317 th most common -38 · '9,393 -36 9,306 th most common -36.5 ·· 9.39 -35 '· 9,303 th most common -35.5 ·· 9.378 -34 9.28 -35 9,378 -33.5 9,276 th most common -34.5 · '9,377 -32.5 '· 9,265 th most common -33.5 ·· 9.378 -31.5 9,251 th most common -32.5 · '9,363 -30.5 9,232 th most common -31.5 9,356 -29.5 ·· 9,223 th most common -31 · '9,357 -29 9,208 th most common -29.5 · '9.35 -27.5 · ' 9.19 -28.5 ·· 9.337 -27 · ' 9.17 -28 «9,334 -26 « 9,146 th most common -27.5 '· 9.332 -25 · ' 9,134 th most common -26 '· 9.32 -24 9,119 th most common -25 · '9,279 -23.5 ·· 9,1 -24.5 9,305 -22.5 9,074 th most common -24 9,303 -21.5 · ' 9,052 th most common -22.5 9,295 -21 9,039 th most common -21 · '9,267 -20 · ' 9,008 th most common -20.5 · '9.263 -19 ·· 8,981 th most common -20 · '9,261 -18 ·· 8,958 th most common -19.5 9,256 -17.5 8,911 th most common -18.5 9,241 -16.5 8,896 th most common -17 9,205 -15 8,864 th most common -16.5 ·· 9,202 -14.5 8,825 th most common -16 · '9,199 -13.5 8,792 th most common -15 '· 9.192 -13 8,765 th most common -13.5 9,136 -12 · ' 8,654 th most common -13 ·· 9.129 I -11 · ' 8,689 th most common -12.5 ·· 9.125

• · · · · ·

-35example 4 example 1

Beispiel 4 Beispiel 1

Continuation of Table 7

Fortsetzung Tabelle 7

T £ ° C] 1o 9 E. ^T C ° ^C 2 log Well -10 II 8,662 th most common -11 II 9,103 th most common -9.5 II 8,615 th most common -10 II 9,044 th most common '8.5 II 8,587 th most common -9.5 II 9,041 th most common -7.5 II 8,515 th most common -9 II 9,037 th most common -6.5 II 8,393 th most common -6 II 8,892 th most common -6 II 8,448 th most common '5.5 II 8,921 th most common -5 II 8,408 th most common -5 II 8,919 th most common -4 II 8,321 th most common -, 5 II 8.64 -3 II 8,297 th most common 1 II 8,491 th most common -2 II 8.22 1.5 II 8,528 th most common -1 II 8,145 th most common 2 II 8,549 th most common 0 II 8,109 th most common 3 II 8,451 th most common 1 II 7,997 th most common 6 II 8,194 th most common 2 II 7,954 th most common 9.5 II 7,827 th most common 3 II 7,829 th most common 10 II 7.94 4 II 7,807 th most common 12.5 II 7,493 th most common 5.5 II 7,722 th most common 13.5 II 7,657 th most common 6 II 7,673 th most common 16.5 II 7,273 th most common 7 II 7,627 th most common 17 II 7,328 th most common 7.5 II 7,579 th most common 19 II 7,118 th most common 9 II 7,464 th most common 19.5 II 7,143 th most common 10.5 II 7,364 th most common 21.5 II 6,932 th most common 11 II 7,313 th most common 22.5 II 6,924 th most common 12 II 7,247 th most common 23 II 6,951 th most common 13 II 7,213 th most common 25 II 6,817 th most common 13.5 II 7,156 th most common 25.5 II 6.84 14.5 II 7,123 th most common 27.5 II 6,741 th most common 15.5 II 7,057 th most common 32 II 6,599 th most common 16 II 7,022 th most common 39 • 1 6,483 th most common 17 • I 6,956 th most common 38.5 II 6.5 18 • 1 6,892 th most common 42 II 6,486 th most common 19 m 6,846 th most common 42.5 m 6,519 th most common 20 N 6,789 th most common «E II 6,474 th most common

OQ

Continued Table 7

Fortsetzung Tabelle 7 Example 4

Beispiel 4

-36example 1

Beispiel 1

TI'CJ log E 1 rfci · log'E 20.5 «6,759 45 6,477 23 * 6,617 47.5 ·· 6.522 24.5 * 6.566 48.5 6.489 25.5 * 6.518 51.5 * 6.536 26.5 * 6.550 54.5 ·· 6,472 27.5 6.491 57.5 - 6.542 28.5 * 6.452 58 ·· 6.52 29.5 * 6.439 30.5 * 6.382 31 * 6,366 32 6,373 33 6,302 33.5 6,357 34,5 6,329 35.5 6.286 36.5 6.283 37 “6,296 38.5 6.269 39 6,256 40 6,137 41 6.23 42 6,247 42.5 6.232 43,5 6,181 44 6,262 45 6,215 46 6.17 46.5 6,158 47.5 6,166 48.5 6.067 49.5 6.081 50 * 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 6,132 58 “6,105 59 * 6,125 59.5 * 6.142 60.5 * 6.202

Table 8

Tabelle 8

comparative comparative comparative Example 2 Example 3 Example 1 Verg1 еисhs- Vergleichs- Vergleichs- beispiel 2 beispiel 3 beispiel 1

T [° C] " log * E T [° C] ^M log E T [° C] log E I -40.5 II 9,237 th most common -38 II 9,363 th most common -38.5 II 9,403 th most common -41.5 II 9,264 th most common -37.5 II 9,366 th most common -38 II 9,408 th most common -40 II 9.28 -37 II 9.37 -37.5 II 9.41 -37.5 II 9,223 th most common -36.5 II 9.37 -37 II 9,409 th most common -37 II 9,241 th most common -36 II 9,368 th most common -36.5 II 9,408 th most common -37.5 II 9,257 th most common -35.5 II 9,367 th most common -36 II 9,406 th most common -38 II 9,267 th most common -34 II 9,341 th most common -35 II 9,403 th most common -35 II -33 II 9,334 th most common -33.5 II 9,384 th most common -33.5 II 9.22 -32.5 II 9,333 th most common -33 II 9,382 th most common -33 II 9,229 th most common -32 II 9.33 -32.5 II 9,382 th most common -31 II 9,203 th most common -30.5 II 9,312 th most common -32 II 9.38 -30.5 II 9.2 -28.5 II 9,291 th most common -31 II 9,376 th most common -30 II 9,199 th most common -28 II 9,294 th most common -29.5 II 9,355 th most common -29.5 II 9,203 th most common • 27.5 II 9,289 th most common -28.5 II 9,353 th most common '27, 5 II 9,175 th most common -27 > 1 9,287 th most common -28 II 9,354 th most common -26.5 • 1 9,157 th most common -26 II 9,264 th most common -27.5 II 9,351 th most common -26 II 9,159 th most common -25 II 9,255 th most common -26 II 9,327 th most common -25.5 II 9,158 th most common -24.5 II 9,251 th most common -24.5 II 9,317 th most common -23.5 II 9,133 th most common -23.5 II 9,251 th most common -24 It 9,317 th most common -22.5 II 9,116 th most common -22 II 9,215 th most common -23.5 II J9.317 -22 II 9,115 th most common -21 II 9,207 th most common -23 II 9,313 th most common -21.5 II 9,117 th most common -20.5 II 9,206 th most common -22.5 II 9,313 th most common -21 II 9,117 th most common 1 -20 II 9,202 th most common -21 II 9,279 th most common -19 II 9,075 th most common ί -19 II 9,186 th most common -20 II 9,274 th most common -18.5 II 9,071 th most common -17.5 II 9,156 th most common -19.5 II 9,273 th most common -18 II 9,071 th most common -17 II 9,155 th most common -19 II 9,271 th most common -17.5 II 9.07 -16.5 II 9,153 th most common -18 II 9,256 th most common -16 II 9,047 th most common -15 II 9,125 th most common -16.5 II 9,226 th most common -15 II 8,989 th most common -14 II 9,1 -16 II 9,222 th most common -14.5 II 9.02 -13.5 II 9,099 th most common -15.5 II 9.22 -14 II 9.02 -13 II 9,096 th most common -14.5 II 9,207 th most common -13.5 It 9.02 -11.5 II 9,061 th most common -13 It 9,165 th most common

• · · · · · · · · · - '41 • ·

-3g

continued table 8 Fortsetzung Tabel le 8 comparative comparative comparative Example 2 Example 3 Example 1 Vergleichs- Vergleichs- Vergleichs- beispiel 2 beispiel 3 beispiel 1

TC ° cj ¹¹ log E T pcj log E r pc] log E I -11.5 8,967 th most common -11 9,048 th most common -12.5 9,162 th most common -11 ·· 8,961 th most common -10.5 '· 9,045 th most common -12 9.16 -10.5 ·· 8.96 -9 i. 9,007 th most common -11.5 9,157 th most common -10 · ' 8,958 th most common -8 8.99 -9.5 9,085 th most common -8.5 · ' 8,917 th most common -7.5 · 8,988 th most common -8.5 · ' 9,081 th most common -7.5 ·· 8,898 | -7 '· 8,987 th most common -8 9.08 -7 ·· 8,894 i -5.5 · * 8,922 th most common -7.5 ·· 9,079 th most common -6.5 8,896 th most common -5 8,917 th most common -6 '· 8,998 th most common -5 ·· 8,846 th most common -4.5 8,918 th most common -5 8,982 th most common -4 II 8.83 -3.5 8.91 -4.5 8,986 th most common -3.5 ·· 8,798 th most common -1.5 ·· 8,822 th most common .4 II 8,985 th most common -3 ·· 8,825 th most common -1 8.83 -2 ·· 8,827 th most common -1 · ' 8,741 th most common -.5 ·· 8.83 -1.5 · 8,886 th most common -, 5 ·· 8,744 th most common 1 · ' 8,757 th most common -1 8,888 th most common 0 8,747 th most common 2 ·· 8,717 th most common »5 - 8,703 th most common 1.5 ·· 8,708 th most common 2.5 ·· 8,725 th most common 1 8,761 th most common 3 8.62 3 · ' 8,728 th most common 1.5 ·· 8,768 th most common 3,5 » 8,635 th most common 5 ·· 8,531 th most common 2 '· 8,767 th most common 4 II 8,643 th most common 6 ' 8,556 th most common 5 8,573 th most common 6 8,508 th most common 6.5 '· 8,577 th most common 7 8,422 th most common 6.5 · ' 8,501 th most common 7 · ' 8,591 th most common 9 8,372 th most common 7 8.52 7.5 ·· 8,597 th most common 12.5 ·· 8,097 th most common 7.5 ·· 8,524 th most common 10.5 · 8,266 th most common 16.5 " 7,757 th most common 10 · ' 8,245 th most common 11 · ' 8.41 19 7,359 th most common 10.5 ·· 8,331 th most common 12.5 ·· 8.04 20 7,414 th most common 11 ·· 8,363 th most common 14 · ' 8,164 th most common 20.5 7,468 th most common 10.5 8,389 th most common 14.5 ·· 8,209 th most common 23.5 ·· 7,158 th most common 12.5 ·· 8,101 th most common 16.5 7,791 th most common 23 ·· 7,209 th most common 14 and 8,132 th most common 17 · ' 7,982 th most common 23.5 ·· 7,244 th most common 14,5 " 8,165 th most common 17.5 ·· 8,023 th most common 26 6,909 th most common 14 · ' 8,196 th most common 20.5 · ' 7,679 th most common 26.5 · ' 6,989 th most common 16 · ' 8,067 th most common 21 7,806 th most common 28 6,911 th most common 17,5 « 7,908 th most common 23.5 ·· 7,476 th most common 29.5 6,844 th most common

• · · · · · · · · · · ·

Ji »· <

Continued Table 8

-39Forsetzung Tabelle 8 compare example 2 compare example 3 compare example 1 ¹ Vergleichsbeisp. 2 VergleicnsDeisp. 3 Vergleichsbeisp. 1

T i'C] “log E G [* C] * tog E D GS] log E 18 ·· 7,954 24 7,534 29 * 6,871 18.5 · '8,016 26 * 7.256 31.5 6.685 21 7,666 27 * 7,229 32.5 «6,698 21.5 7,722 26.5 7.289 32 * 6,733 21 · '7,774 27.5 · '7.297 34.5 “6,391 23.5 7.488 30.5 “7,011 35 * 6,604 24.5 7.452 30 7,072 35.5 ^and 6.58 25 · '7,498 30.5 7,102 38 «6,464 24.5 · '7.541 33.5 * 6.79 38.5 * 6.554 26.5 ·· 7.363 34 6,828 38 * 6,541 27.5 7.273 33.5 * 6.873 40.5 * 6.464 28 ·· 7,312 34 6,897 41.5 * 6.469 28.5 ·· 7,313 36 6,712 41 * 6,502 30.5 · '7.081 37 · '6,674 43 ·· 6,497 31 7,115 36.5 6.71 45 * 6,449 30.5 7.162 39 · '6.59 44.5 '· 6.432 33 · '6,988 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 48,5 «6,452 37 6.85 54.5 · '6.299 48 .4,417 38 · 6,831 55 6,389 51.5 “6.339 37.5 6.86 58 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 · '6,388 44.5 · '6,716 58 6,394 44 · '6,714 57.5 6,382 46 · '6,681 58.5 '· 6.453 47.5 · '6.688 47 6,668 48 6,693 50.5 ^and 6.657 51 6.66 50.5 6.641 52 6.68 54 · '6,646 54.5 6.633 53.5 6.637 55.5 '· 6.672 57.5 6.644 58 6,636 57 · '6,651 58.5 * 6.676 60.5 ^m 6,648

• ·

Claims (3)

1. Irradiated oligomers with several ethylene unsaturated end groups and several urethane and / or urea groups for a molecule derived from (a) at least one hydroxy and / or amino-functional compound having functionality between 3 and 4 and having a molecular weight average of between 500 and 4000, (b) at least one compound having two hydroxyl and / or amino groups per molecule and having a molecular weight average of between 200 and 4000, c) at least one mono-ethylene unsaturated compound having an active hydrogen atom group for a molecule with a molecular weight between 116 and 1000; d) at least one aliphatic and / or cycloaliphatic diisocyanate, characterized in that the components a through d are used in such quantities that 1) the fashion ratio of components a to components b is between 0.1: 1 and 1.1: 1, 2) the molar ratio of the components to the components of a is between 2: 1 and 10: 1 and 3) the equivalence ratio of the isocyanate groups of the components d to the hydroxyl and / or amino groups of the sum of the components a to c is between 0.9 and 1.0. 2. Irradiated oligomers according to claim 1, characterized in that compounds a have functionality of component 3. • · · · · Irradiated oligomers according to claim 1 or 2, characterized in that compounds with a molecular weight of between 750 and 2000 and / or components b with a molecular weight of between 600 and 2000 are used as components a and / or compounds with a molecular weight average of between 116 and 400 are used as components in. Irradiated oligomers according to one of claims 1 to 3, characterized in that the components a to d are used in such quantities that 1) the molar ratio of found between 0.1 and 0.8 the components and / or a and the components b se 2) the molar ratio of the components in and the components a se found between 2.5 and 10. 5. Irradiated oligomers according to claim 4, characterized in that the oligomer exhibits an acrylic group content of 0.45 to 0.63 mol / kg. Irradiating oligomers according to one of claims 1 to 5, characterized in that ethoxylated triol having a molecular weight greater than 1000 is used as component a. Irradiating oligomers according to one of the claims! 1 to 6, characterized in that a mixture of b) 0 to 90 mol% polyether diol is used as component b; 62) 100 to 10 mol% modified polyether diol of 62P at least one polyether diol 622) at least one aliphatic and / or cycloaliphatic carbon • 62 ^) at least one aliphatic, unsaturated compound with one epoxy group and 8 to 21 carbon atoms per molecule, such that as the sum of the constituent components b | and, so does the sum of the component parts 621 to 622 always amounts to 100 moles Irradiating oligomers according to one of claims 1 to 7, characterized in that they are obtained as 1) polyaddition of the components a to d to a volume of more than 85¾ NCO groups is carried out, whereby the components a to d are used in such quantities that the equivalent ratio of the isocyanate groups of the components a to the hydroxyl and / or amino groups of the components a through c are 1: 1 and 2) the polyaddition of the components a to d with the addition of other components continues until a volume of more than 99¾ NCO groups is obtained. An irradiating curing compound comprising at least one irradiated curing oligomer according to any one of claims 1 to 8. 10. The irradiating coating mass according to claim 9, in particular for a buffer coating of optical glass fibers, characterized in that it contains A) 10 to 78% by weight of at least one radiation-curable oligomer according to any one of claims 1 to 8, B) 0 to 60 weight ¾ of at least one other ethylene unsaturated oligomer, B) 20 to 50% by weight of at least one ethylene unsaturated monomer and / or oligomer compound, D) 2 to 8% by weight of at least one photoinitiator and E) 0 to 4% by weight of the usual excipients and additives, with the weight% always referring to the total weight of the roof mass. An irradiated roofing mass according to claim 10 9, characterized in that it contains A) 15 to 75% by weight of at least one radiation-curable oligomer according to claims 1 to 8, B) 0 to 50% by weight of at least another ethylene unsaturated oligomer, B) 22 to 35% by weight of at least one ethylene unsaturated monomer and / or oligomer compound, D) 3 to 5% by weight of most branded photoinitiator and E) 0.5 to 2.0% by weight of the usual excipients and additives, with the weight% always referring to the total weight of the roof mass. 12. The irradiated roofing mass according to claim 10 or 11, characterized in that it contains, as component B, other ethylene unsaturated polyurethane. 13. A method for applying a coating layer to a glass surface, in particular glass fibers, in which 1) a hardening primer is applied and UV-cured or electronically cured; and 2) irradiating the lacquer coating and curing by means of ultraviolet or electronic irradiation, characterized in that the irradiated curing coating according to one of claims 9 to 12 is used as a primer and / or lacquer coating. Optical glass fibers, characterized in that they are coated with a radiation-curable coating according to one of claims 9 to 12.