CA2090450C - Photo-hardened liquid coating composition for glass surfaces - Google Patents
Photo-hardened liquid coating composition for glass surfacesInfo
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- CA2090450C CA2090450C CA002090450A CA2090450A CA2090450C CA 2090450 C CA2090450 C CA 2090450C CA 002090450 A CA002090450 A CA 002090450A CA 2090450 A CA2090450 A CA 2090450A CA 2090450 C CA2090450 C CA 2090450C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
- C03C17/322—Polyurethanes or polyisocyanates
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/104—Coating to obtain optical fibres
- C03C25/106—Single coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/104—Coating to obtain optical fibres
- C03C25/1065—Multiple coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4887—Polyethers containing carboxylic ester groups derived from carboxylic acids other than acids of higher fatty oils or other than resin acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
- C08G18/6725—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing ester groups other than acrylate or alkylacrylate ester groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
- C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
- C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
- C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Paints Or Removers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polyurethanes Or Polyureas (AREA)
- Surface Treatment Of Glass Fibres Or Filaments (AREA)
- Surface Treatment Of Glass (AREA)
- Medicinal Preparation (AREA)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Glass Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention relates to radiation-curable oligomers which can be prepared from a) one hydroxy- and/or aminofunctional compound having a functionality between 3 and 4 and a number-average molecular weight between 500 and 4000, b) one compound having 2 hydroxy and/or amino groups and a number-average molecular weight between 200 and 4000, c) one monoethylenically unsaturated compound having a group containing one active hydrogen atom and having a number-average molecular weight between 116 and 1000, and d) one aliphatic and/or cycloaliphatic diisocyanate, which comprises using components a to d 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, and 3. the equivalent ratio of the isocyanate groups of component d to the hydroxyl and/or amino groups of the sum of components a to c is between 0.9 and 1Ø
Description
`- 2090i50 Liquid, radiation-curable coating composition for the coatinq of qlass surfaces The present invention relates to radiation-curable oligomers having several ethylenically unsaturat-ed end groups and several urethane and/or urea groups per molecule, which oligomers can be prepared from a) at least one hydroxy- and/or aminofunctional com-pound having a functionality between 3 and 4 and a number-average molecular weight between 500 and 4000, b) at least one compound having 2 hydroxyl and/or amino groups per molecule and a number-average molecular weight between 200 and 4000, c) at least one monoethylenically unsaturated compound having a group contA;ning one active hydrogen atom per molecule and having a number-average molecular weight between 116 and 1000, and d) at least one aliphatic and/or cycloaliphatic diiso-cyanate.
The present invention also relates to radiation-curable coating compositions contAin;ng these radiation-curable oligomers, and to processes for the coating of glass surfaces, in particular optic glass fibers, in '~' 2û~4SI~
which these coating compositions are used.
Optic glass fibers have acquired constantly increasing importance in the commlln;cations sector as light waveguide fibers. For this particular application, it is absolutely necessary to protect their glass surface from moisture and wear. Accordingly, directly after their manufacture, the glass fibers are provided with at least one protective surface coating.
Thus it is known, for example from EP-B-114,982, to provide glass fibers first with a buffer layer (primer) which is elastic but has low hardness and low toughness and then to apply a radiation-curable top coat which has high hardness and toughness. The two-layered structure is intended to ensure good protection of the glass fibers upon exposure to mechanical stress even at low temperatures.
According to EP-B-114,982, radiation-curable coating agents based on linear urethane acrylates are used as the primer. Radiation-curable coating agents based on a linear urethane acrylate, a diethylenically unsaturated ester, a diglycidyl ether of a bisphenol and a monoethylenically unsaturated monomer, the glass transition temperature of the homopolymer prepared f om this monomer being above 55C, can be used as the top coat.
EP-A-223,086 furthermore discloses radiation-curable coating agents for the coating of optic glass 209û450 fibers. These coating agents contain radiation-curable oligomers according to the preamble of the main claim as the binder.
These radiation-curable coating agents described in EP-A-223,086 are used either as top coat or as single-layer coating. However, they are not suitable as primer due to the excessively high modulus of elasticity value of the cured coatings.
Radiation-curable coating compositions for the coating of optic glass fibers are also described in EP-A-209,641. These coating compositions contain a polyure-thane oligomer contAin;ng acrylate end groups and based on a polyfunctional core as the binder. These coating compositions can be used not only as primer but also as top coat. Single-layer processing is also possible.
Finally, for example EP-A-208,845, EP-A-167,199, EP-A-204,161, EP-A-204,160 and EP-A-250,631 disclose radiation-curable coating compositions for the coating of optic glass fibers which contain linear urethane acry-lates as binders. These coating compositions have the disadvantage of unsatisfactory ageing behavior. Further-more, the mechanical properties of the coatingR, in particular elasticity, still need to be improved upon long-term exposure.
The object of the present invention is to provide radiation-curable coating compositions for the coating of glass surfaces, in particular of optic glass fibers, 2~9~
_ - 4 which, compared with the known coating compositions, lead to coatings having improved properties. In particular, the cured coatings should have improved ageing behavior and correspondingly increased long-term stability of the coated glass fibers. Furthermore, the cured coatings should have improved behavior in the absorption and desorption of water. This is of particular importance for the optical damping of the coated fibers. Moreover, the cured coatings should have a good buffer effect even at low temperature. This means that the mechanical properties of the coating should deteriorate only as little as possible with decreasing temperature. In particular, the increase in the modulus of elasticity value with decreasing temperature should be as little as possible. On the other hand, the coating compositions should cure as quickly as possible. Moreover, the resulting coatings should have only very slight evolution of hydrogen upon storage and ageing and show good ad-hesion on the glass surface.
Surprisingly, the object is achieved by radia-tion-curable oligomers cont~;ning several ethylenically unsaturated end groups and several urethane and/or urea groups per molecule in dissolved form, which oligomers can be prepared from a) at least one hydroxy- and/or aminofunctional com-pound having a functionality between 3 and 4 and a number-average molecular weight between 500 and _ 5 _ 2~9~
4000, b) at least one compound having 2 hydroxyl and/or amino groups per molecule and a number-average molecular weight between 200 and 4000, c) at least one monoethylenically unsaturated compound having a group contA;n;ng one active hydrogen atom per molecule and having a number-average molecular weight between 116 and 1000, and d) at least one aliphatic and/or cycloaliphatic diiso-cyanate.
Components a to d are used in the radiation-curable oligomers in amounts such that 1. the molar ratio of component a to component b is between 0.1 : 1 and 1.1 : 1, preferably between 0.1 and 0.8, 2. the molar ratio of component c to component a is between 2.0 : 1 and 10 : 1, preferably between 2.5 and 10, and 3. the equivalent ratio of the isocyanate groups of component d to the hydroxyl and/or amino groups of the sum of components a to c is between 0.9 and 1Ø
The present invention furthermore relates to radiation-curable coating compositions cont~; n; ng these - 6 - 2~9Q450 radiation-curable oligomers and to processes for the coating of glass surfaces, in particular optic glass fibers, in which these coating compositions are used.
It is surprising and was not foreseeable that radiation-curable coating compositions based on the oligomers according to the invention give coatings having improved ageing behavior compared with conventional coatings, as a result of which the glass fibers coated with these coating compositions have increased long-term stability. Moreover, the coatings prepared from the coating compositions according to the invention have improved behavior, compared with conventional coatings, in the absorption and desorption of water. Another advantage is the good buffer effect of the coatings even at low temperatures, thus solving the problem of the so-called microbends. Furthermore, the coatings according to the invention are distinguished by good mechanical properties, such as, for example, tensile strength and elongation adapted to the particular application, and by only a slight evolution of hydrogen upon storage or ageing. Finally, they have good adhesion on the glass surface.
Hereinafter, first the radiation-curable oligo-mers according to the invention will be defined in more detail: suitable components a for the preparation of the oligomers are hydroxy- and/or aminofunctional compounds having a functionality of 3 to 4, preferably 3. These 2D9~-~5û
compounds have number-average molecular weights of 500 to 4000, preferably 750 to 2000.
Examples of suitable compounds are polyalkoxy-lated triols, such as, for example, ethoxylated and propoxylated triols, preferably ethoxylated triols, particularly preferably having a number-average molecular weight of greater than or equal to 1000. Examples of the triols used are glycerol and trimethylolpropane.
The corresponding aminofunctional compounds such as, for example, aminofunctional compounds derived from polyalkoxylated triols, are also suitable. Examples of such products are obt~;nAhle from Texaco under the name JEFFAMIN(R), for example JEFFAMIN~R) T 403, T 3000, T 5000, C 346, DU 700 and BuD 2000.
These aminofunctional compounds can contain both primary and secondary amino groups.
In addition, compounds containing both amino and hydroxyl groups are also suitable.
Suitable components b are compounds contAin;ng two hydroxyl and/or amino groups per molecule. These compounds have number-average molecular weights of 200 to 4000, preferably 600 to 2000.
Examples of suitable compounds b are polyoxy-alkylene glycols and polyoxyalkylenediamines, alkylene groups of 1 to 6 C atoms being preferred. Thus, for example, polyoxyethylene glycols having a number-average molecular weight of 1000, 1500, 2000 or 2500 and polyoxy-2~904 ~11 propylene glycols having corresponding molecular weightsand polytetramethylene glycols are suitable.
Polyethoxylated and polypropoxylated diols can also be used, such as, for example, ethoxylated and propoxylated derivatives of butanediol, hexanediol, and the like.
Furthermore, polyesterdiols, which can be prepared, for example, by reacting the already mentioned glycols with dicarboxylic acids, preferably aliphatic and/or cyclo-aliphatic dicarboxylic acids, such as, for example, hexahydrophthalic acid, adipic acid, azelaic, sebacic and glutaricor cycloaliphakyl-substituted derivatives thereof, can also be used. Instead of these acids, it is possible to use their anhydrides, if they exist.
Polycaprolactonediols can also be used. These products are obtained, for example, by reacting an ~-caprolactone with a diol. Products of this type are described in US Patent No. 3,169,945.
The polylactonediols obtained by this reaction are distinguished by the presence of a terminal hydroxyl group and by recurring polyester portions derived from the lactone. These recurring molecular portions can have the formula - C _ (CHR)n ~ CH2 - 20904~
g in which n is preferably 4 to 6 and the substituent is hydrogen, an alkyl radical, a cycloalkyl radical or an alkoxy radical, no substituent cont~;ning more than 12 carbon atoms and the total number of carbon atoms of the substituents in the lactone ring not exceeding 12.
The lactone used as starting material can be any desired lactone or any desired combination of lactones, in which this lactone should contain at least 6 carbon atoms in the ring, for example 6 to 8 carbon atoms, and in which at least 2 hydrogen substituents should be present on the carbon atom. The lactone used as starting material can be described by the following general formula:
CH2 -- ( CR2 ) n C ~ o in which n and R are as already defined. The lactones which are preferred in the invention for the preparation of polyesterdiols are caprolactones in which n has a value of 4. The most preferred lactone is substituted ~-caprolactone in which n has a value of 4 and all R
substituents are hydrogen. This lactone is particularly preferred since it is available in large amounts and gives coatings having excellent properties. It is also possible to use various other lactones by themselves or 2~0g~p combined. Examples of aliphatic diols suitable for the reaction with the lactone are the diols already mentioned above for the reaction with the carboxylic acids.
It is of course also possible to use the cor-responding diamines and compounds having an OH and an amino group as component b. Examples of suitable com-pounds are the products available from Texaco under the name JEFFAMIN~ D 230, D 400, D 2000, D 4000, ED 600, ED 900, ED 2001 and ED 4000.
A mixture comprising bl) 0 to 90 mol % of at least one polyetherdiol and b2) 10 to 100 mol % of at least one modified poly-etherdiol composed of b21) at least one polyetherdiol b22) at least one aliphatic and/or cycloaliphatic dicarboxylic acid and b23) at least one aliphatic, saturated compound having an epoxy group and 8 to 21 C atoms per molecule, in which the sum of the amounts of components bl and b2 and the sum of the amounts of components b2l to b23 is in each case 100 mol %, is preferably used as component b.
For preparing the modified polyetherdiols by conventional methoas, components b2l to b23 are used in amounts such that the equivalent ratio of the OH groups of component b2l to the carboxyl groups of component b22 is between 0.45 and 0.55, preferably 0.5, and that the equivalent ratio of the epoxy groups of component b23 to 2Q9û~0 the carboxyl groups of component b22 is between 0.45 and 0.55 and preferably 0.5.
Examples of suitable polyetherdiols b1 and b21 are the polyoxyalkylene glycols already listed in which the alkylene groups have 1 to 6 C atoms. Polyoxypropylene glycols having a number-average molecular weight between 600 and 2000 are preferably used as component b1. Polyoxy-butylene glycols (poly-THF) having a number-average molecular weight of > 1000 are preferably used as com-ponent b21-Aliphatic and cycloaliphatic dicarboxylic acids having 8 to 36 C atoms per molecule, such as, for example, hexahydrophthalic acid, are preferably used as component b22. Examples of suitable components b23 are epoxidized vinylcyclohexane compounds, epoxidized, monoolefinically unsaturated fatty acids and/or polybuta-dienes.
Glycidyl esters of branched monocarboxylic acids, such as, for example, the glycidyl ester of Versatic Acid, are preferably used as component b23.
For introducing the ethylenically unsaturated groups into the polyurethane oligomer, monoethylenically unsaturated compounds having a group containing an active hydrogen atom and having a number-average molecular weight of 116 to 1000, preferably 116 to 400, are used.
Examples of suitable components c are, for example, hydroxyalkyl esters of ethylenically unsaturated 20~04~
_ - 12 -carboxylic acids, such as, for example, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyamyl acrylate, hydroxyhexyl acrylate, hydroxyoctyl acrylate, and the corresponding hydroxalkyl esters of methacrylic, fumaric, maleic, itaconic, crotonic and isocrotonic acid, the hydroxyalkyl esters of acrylic acid being, however, preferred.
Furthermore, adducts of caprolactone with one of the abovementioned hydroxyalkyl esters of ethylenically unsaturated carboxylic acids are suitable as component c. Adducts of the hydroxyalkyl esters of acrylic acid having a number-average molecular weight of 300 to 1000 are preferably used.
Suitable components d for the preparation of the oligomers according to the invention are aliphatic and/or cycloaliphatic diisocyanates, such as, for example, 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,2-cyclohexane diisocyanate, 4,4'-methylene-bis(cyclo-hexane isocyanate) and isophorone diisocyanate, tri-methylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate and trimethyl-1,6-hexamethylene diisocyanate and the diisocyanates derived from dimeric fatty acids and described in EP-A-204,161, column 4, lines 42 to 49.
Isophorone diisocyanate and trimethyl-1,6-hexa-methylene diisocyanate are preferably used.
~ 09~4~
It is essential to the invention that components a to d for preparing the oligomers are used in amounts such that 1. the molar ratio of component a to component b is between 0.1 : 1 and 1.1 : 1, preferably between 0.1 and 0.8, 2. the molar ratio of component c to component a is 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 from components a plus b plus c is between 0.9 and 1Ø
The oligomers according to the invention can be prepared by various methods. Thus, for example, it is possible first to react diisocyanate d with chain-length-ening agents a and b and then to react the remAining free isocyanate groups with the ethylenically unsaturated compound c.
It is also possible to prepare the oligomers by first reacting a portion of the isocyanate groups of component b with the ethyle~icAlly unsaturated compound c and then reacting the remaining free isocyanate groups with chain-lengthening agents a and b.
~ - 14 - 2 ~ ~q 5Q
Furthermore, it is possible to prepare the polyurethane oligomers by the process described in EP-A-223,086 on page 5.
The polyurethane oligomers are preferably prepar-ed by a two-step process by first carrying out the stoichiometric polyaddition reaction of components a to d until more than 85 % of the NCO groups of component d have been converted. In this first process step, com-ponents a to d are used in amounts such that the equival-ent ratio of the NCO groups of component d to the active hydrogen atoms of components a to c is 1:1.
In a second process step, the remainder of the other components (in accordance with the desired NCO: OH
ratio) is then added, and the reaction is continued up to an NCO group conversion of > 99 %. In this second process step, it is preferred to add more of component c and to achieve the desired NCO: OH equivalent ratio by adding this component c.
The urethane oligomers according to the invention usually have number-average molecular weights of 2500 to 10000, preferably 3000 to 6000 (measured by GPC against a polystyrene st~n~Ard), weight-average molecular weights of 5000 to 50000, preferably 7000 to 20000 (measured by GPC against a polystyrene stAn~Ard), double-bond contents of 0.45 to 1.5, preferably 0.45 to 0.9, mol/kg and particularly preferably 0.45 to 0.63, and very particularly preferably 0.5 to 0.63 mol/kg, and a - 15 - 20~5~
functionality of >2 to 3.5, preferably 2.2 to 2.8, in each case per statistic average polymer molecule.
The oligomers according to the invention are used in radiation-c~rable coating compositions as film-forming component A. The coating compositions usually contain 10 to 78 % by weight, preferably at least 15 % by weight, and particularly preferably 63 to 73 % by weight, in each case relative to the total weight of the coating composi-tion, of these oligomers according to the invention.
As further component, the coating compositions can contain O to 60 % by weight, preferably O to 50 % by weight, in each case relative to the total weight of the coating composition, of at least one further ethylenical-ly unsaturated oligomer B. Apart from unsaturated poly-esters, polyester acrylates and acrylate copolymers, in particular urethane acrylate oligomers, with the excep-tion of the urethane acrylate oligomers used as component A, are used. The properties of the completely cured coating can be selectively adjusted by means of the type and amount of this component B. The higher the amount of this component B, the higher in general the modulus of elasticity value of the completely cured coating. Com-ponent B is therefore added to the coating composition especially if the coating compositions are used as top coat. However, the effect of this component B on the properties of the resulting coating is known to one Replacement sheet ~ - 16 - 20 9 Q4 ~o skilled in the art. The most favorable amount to be used in each case can therefore be simply determined by a few routine experiments. These ethylenically unsaturated polyurethanes used as component B are known. They can be obtained by reacting a di- or polyisocyanate with a chain-lengthening agent from the group of diols/polyols and/or diamines/polyamines, followed by reaction of the remaining free isocyanate groups with at least one hydroxyalkyl acrylate or hydroxyalkyl ester of other ethylenically unsaturated carboxylic acids.
The amounts of chain-lengthening agent, di- or polyisocyanate and hydroxyalkyl ester of an ethylenically unsaturated carboxylic acid are selected in such a manner that 1. the equivalent ratio of the NCO groups to the reactive groups of the chain-lengthening agent (hydroxyl, amino or mercapto groups) is between 3:1 and 1:2, preferably 2:1, and 2. the OH groups of the hydroxyalkyl esters of the ethylenically unsaturated carboxylic acids are present in a stoichiometric amount with respect to the still free isocyanate groups of the prepolymer composed of isocyanate and chain-lengthening agents.
Replacement sheet _ - 17 - 2~ Q
Furthermore, it is possible to prepare the polyurethanes B by first reacting a portion of the iso-cyanate groups of a di- or polyisocyanate with at least one hydroxyalkyl ester of an ethylenically unsaturated carboxylic acid and then reacting the remaining isocya-nate groups with a chain-lengthening agent. In this case too, the amounts of chain-lengthening agent, isocyanate and hydroxyalkyl ester of unsaturated carboxylic acids are selected in such a manner that the equivalent ratio of the NCO groups to the reactive group of the chain-lengthening agent is between 3:1 and 1:2, preferably 2:1, and the equivalent ratio of the remaining NCO groups to the OH groups of the hydroxyalkyl ester is 1:1.
All intermediate forms of these two processes are of course also possible. For example, a portion of the isocyanate groups of a diisocyanate can first be reacted with a diol, a further portion of the isocyanate groups can then be reacted with the hydroxyalkyl ester of an ethylenically unsaturated carboxylic acid, and this can be followed by reacting the remaining isocyanate groups with a ~ ;ne.
These various preparation processes for poly-urethanes are known (cf. for example, EP-A-204,161) and therefore need not be described in more detail.
Compounds which are suitable for the preparation of these urethane-acrylate oligomers B are the compounds Replacement sheet - 18 - 2 ~ 5~
.
already used in the preparation of component A and further the compounds mentioned in German Offenlegungs-schrift 3,840,644.
Especially when the coating compositions accord-ing to the invention are used as top coat, aromatic structural components are preferably used for preparing the urethane-acrylate oligomers B. In this case, 2,4- and 2,6-toluylene diisocyanate are preferably used as isocya-nate components and aromatic polyester polyols based on phthalic acid and isophthalic acid and/or polypropylene glycol, ethylene glycol and diethylene glycol as chain-lengthening agents.
As further component, the radiation-curable coating compositions additionally contain at least one ethylenically unsaturated monomeric and/or oligomeric compound C, usually in an amount of 20 to 50 % by weight, preferably 22 to 35 ~ by weight, in each case relative to the total weight of the coating composition.
By adding this ethylenically unsaturated compound C, the viscosity and the curing rate of the coating compositions and the mechanical properties of the result-ing coating are controlled, as is known to one skilled in the art and described, for example, in EP-A-223,086 and which should be consulted for further details.
Examples of monomers which can be used are ethoxyethoxyethyl acrylate, N-vinylpyrrolidone, phenoxyethyl acrylate, dimethylaminoethyl acrylate, Replacement sheet 2 0 ~
hydroxyethyl acrylate, butoxyethyl acrylate, isobornyl acrylate, dimethylacrylamide and dicyclopentyl acrylate.
Di- and polyacrylates, such as, for example, butanediol diacrylate, hexanediol diacrylate, trimethylolpropane di-and triacrylate, pentaerythritol diacrylate and the long-chain linear diacrylates having a molecular weight of 400 to 4000 or preferably 600 to 2500, and described in EP-A-250,631, are also suitable. The two acrylate groups can be, for example, separated by a polyoxybutylene structure. Furthermore, 1,12-dodecyl diacrylate and the reaction product of 2 mol of acrylic acid with one mol of a dimeric fatty alcohol, which in general has 36 C atoms, can also be used.
Mixtures of the monomers just described are also suitable. Phenoxyethyl acrylate, hexanediol diacrylate, N-vinylpyrrolidone and tripropylene glycol diacrylate are preferably used.
The photoinitiator usually used in the coating compositions according to the invention in an amount of 2 to 8 % by weight, preferably 3 to 5 % by weight, relative to the total weight of the coating composition, varies with the radiation used for curing the coating agents ( W radiation, electron radiation, visible light).
The coating compositions according to the invention are preferably cured by means of W radiation. In this case, ketone-based photoinitiators are usually used, for example acetophenone, benzophenone, diethoxyacetophenone, 2as~4so 2-hydroxy-2-methyl-1-phenyl-1-propanone, hydroxypropyl phenyl ketone, m-chloroacetophenone, propiophenone, benzoin, benzil, benzil dimethyl ketal, anthraquinone, thioxanthone and thioxanthone derivatives and triphenyl-phosphine and the like, as well as mixtures of variousphotoinitiators.
Furthermore, the coating compositions can addi-tionally contain, if desired, customary auxiliaries and additives. These are usually used in an amount of 0 to 4 % by weight, preferably 0.5 to 2.0 % by weight, in each case relative to the total weight of the coating composi-tion. Examples of substances of this type are flow-improving agents, plasticizers and in particular adhesion promoters. Adhesion promoters used for this are alkoxy-silanes, such as, for example, N-~-aminoethyl-~-amino-propyltrimethoxysilane, ~-aminopropyltrimethoxysilane, N-methyl-~-aminopropyltrimethoxysilane or triamino-modified propyltrimethoxysilane (for example adhesion promoter DYNASYLAN~ of "TRIAMO type", commercial product from Dynamit Nobel Chemie).
The coating compositions can be applied to the substrate by means of known application methods, such as, for example, spraying, rolling, flooding, dipping, knife-or brush-application.
The coating films are cured by means of radiation, preferably by means of W radiation.
Apparatuses and conditions for these curing methods are 29904~P
known from the literature (cf. for example, R. Holmes, U.V. and E.B. Curing Formulations for Printing Inks, Coatings and Paints, SITA Technology, Academic Press, London, United Kingdom 1984~ and need no further description.
The coating compositions are suitable for the coating of a wide range of substrates, for example glass, wood, metal and plastic surfaces. However, they are in particular used for the coating of glass surfaces, particularly preferably of optic glass fibers.
Accordingly, the present invention also relates to a process for the coating of a glass surface, in which a radiation-curable coating composition is applied and cured by means of W or electron radiation, which process comprises using the coating compositions according to the invention as the radiation-curable coating compositions.
The process according to the invention is par-ticularly suitable for the coating of optic glass fibers.
For this purpose, the coating compositions according to the invention can be applied to the glass fibers as a primer and/or top coat of a two-layer coat. When the coating compositions are used as a primer, the completely cured coatings usually have a modulus of elasticity value (at 2.5 % elongation and room temperature) of less than 10 MPa.
When the coating compositions are used as top coat, the completely cured coatings usually have a 20 904~0 modulus of elasticity value (at 2.5 % elongation and room temperature) of 500 to 1000 MPa.
The invention will be illustrated in more detail in the examples which follow. All parts and percentages given are by weight, unless stated expressly otherwise.
PreParation of a modified polyetherdiol In a boiler equipped with stirrer, inert gas inlet and temperature sensor, 51.1 parts of polytetra-hydrofuran having a number-average molecular weight of 1000 and an OH number of 118 mg of KOH/g and 19.1 parts of hexahydrophthalic anhydride are heated to 120C and maintained at this temperature until an acid number of 102 mg of KOH/g has been reached. 0.02 % of chromium octoate, relative to the weight of the mixture composed of poly-THF, hexahydrophthalic acid and glycidyl ester of Versatic Acid, and 29.7 parts of the glycidyl ester of Versatic Acid having an epoxy equivalent weight of 266 are then added. The mixture is heated at 120C until the reaction product has an epoxy equivalent weight of > 20,000, an acid number of 4 mg of KOH/g and an OH
number of 60 mg of KOH/g.
The modified polyether diol has an average molecular weight ~ of 1860 (calculated from the OH
nunber), an Mn z 1500 determined by GPC and an MW/M~ = 1.67. The viscosity of an 80 % strength solution in butyl acetate is 3.8 dPas (measured at 23C with the 2 a ~
plate/cone viscometer).
ExamPle 1 In a boiler equipped with stirrer, inlet means, temperature sensor and air inlet, 0.35 mol of a commercially available ethoxylated trimethylolpropane having a number-average molecular weight of 1000, 0.65 mol of a commercially available polyoxypropylene glycol having a number-average molecular weight of 600, 0.65 mol of the modified polyetherdiol described above, 1.75 mol of hydroxyethyl acrylate, 0.05 % of dibutyltin dilaurate (relative to the total weight of the sum of components a, b, c and d), 0.1 % of 2,6-ditert.-butylcresol (relative to the total weight of the sum of components a, b, c and d) and 30 ppm of phenothiazine (relative to the total weight of the sum of components a, b, c and d) are initially introduced, and the mixture is heated to 60C.
2.70 mol of isophorone diisocyanate are then metered in at 50C over a period of 2.5 h. The mixture is then diluted with phenoxyethyl acrylate to a theoretical solids content of 90 % (sum of components a to d), and the temperature is maintained at 60C until an NCO value of 1 % has been reached. 0.05 % of dibutyltin dilaurate and 0.51 mol of a commercially available hydroxyethyl acrylate/caprolactone oligomer having a number-average molecular weight of 344 (commercial product TONE M 100 from Union Carbide) are added at a temperature of 80C, and the temperature is maintained at 80C until an NCO
2~90~0 value of < 0.1 % has been reached. The oligomer thus obtained has a double-bond content of 0.6 mol/kg and a functionality of 2.5.
A 40 % solution (relative to the theoretical solids content) of the oligomer 1 obtained in phenoxy-ethyl acrylate has a viscosity of 4.9 d Pas (measured at 23C with the plate/cone viscometer.
78.1 parts of the 90 % strength solution of the urethane oligomer 1 described above, 12.1 parts of phenoxyethyl acrylate, 6.2 parts of N-vinylpyrrolidone, 1.6 parts of N-~-aminoethyl-~-aminopropyltrimethoxysilane and 2.0 parts of diethoxyacetophenone are used to prepare a radiation-curable coating composition 1 by mixing.
Thoroughly cleaned (in particular grease-free) glass plates (width x length = 98 x 161 mm) are covered at the edge with Tesakrepp~ adhesive tape No. 4432 (width 19 mm), and the coating composition 1 is applied by means of a knife (dry-film thickness 180 ~m).
The curing is carried out using a W radiation apparatus equipped with two Hg medium-pressure lamps each of 80 W/cm lamp power at a belt rate of 40 m/minute in two runs at half-load operation (= 40 W/cm).
The dose of this incoming radiation was 0.08 J/cm2 (measured with the WICURE dosimeter, system EIT from Eltosch).
This gave completely cured coatings which have very good mechanical properties and furthermore are - 25 - 2 OgO~ 5~
distinguished by good resistance to ageing, good low-temperature performance and improved performance in the absorption and desorption of water.
The results of the determination of the modulus of elasticity at 0.5 and 2.5 ~ elongation (according to DIN Standard 53 455) and the results of the elongation at break test are listed in Table 2. The results of the measurement of the modulus of elasticity values (2.5 %
elongation) after various ageing treatments of the completely cured coatings are also shown in Table 2.
The dependence of the modulus of elasticity value on the temperature is shown in Figure 1. The measurements were carried out using the DMTA instrument from Polymer Laboratories Ltd.
The absorption and desorption performance of the completely cured coating in contact with water is shown in Figure 2.
ComParative ExamPle 1 2.0 mol of isophorone diisocyanate and 0.05 % of dibutyltin dilaurate (relative to the total weight of the sum of components a to d) are initially introduced into a boiler equipped with stirrer, inlet means, temperature sensor and air inlet, and the mixture is heated to 60C.
1.30 mol of commercially available polyoxypropylene glycol having a number-average molecular weight of 600 are then metered in at 60C over a period of 120 to 180 minutes. The temperature is maintained at 60C until an ~ - 26 - 09 ~5 NCO value of 4.5 % has been reached. 0.1 % of 2.6-di-tert.-butylcresol (relative to the total weight of the sum of components a to d) and 40 ppm of phenothiazine (relative to the total weight of the sum of components a to d) are then added to the boiler. 1.54 mol of hydroxy-ethyl acrylate are then metered in at 60C over a period of 30 minutes. Dissolution of the mixture is then started with phenoxyethyl acrylate until a theoretical solids content of 90 % (relative to the total weight of the sum of components a to d) has been reached. The temperature is then maintained at 60C until an NCO content of < 0.1 % has been reached.
The oligomer 2 thus obtained has a double-bond content of 1.01 mol/kg and a functionality of 2Ø A 50 %
strength solution (relative to the theoretical solids content) of the oligomer 2 obtained in phenoxyethyl acrylate has a viscosity of 10 dPas (measured at 23C
with a plate/cone viscometer).
Analogously to Example 1, 78.1 parts of the 90 %
strength solution of the urethane oligomer 2 described above, 12.1 parts of phenoxyethyl acrylate, 6.2 parts of N-vinylpyrrolidone, 1,6 parts of N-~-aminoethyl-~-amino-propyltrimethoxysilane and 2.0 parts of diethoxyacetophe-none are used to prepare a radiation-curable coating composition 2 by mixing. Application of this coating composition 2 and testing of the completely cured coating is carried out analogously to Example 1. The results are shown in Table 2 and in Figures 3 and 4.
- 27 - 2 0~45~
Table 1 : Composition of the urethane oligomers (in mol) Example 1 Comparison 1 a) Ethoxylated tri- 0.35 methylolpropane 5(Mn = 1000) b1) Polyoxypropylene 0.65 1.30 glycol (Mn = 600) b2) Modified polyetherdiol 0.65 (Mn = 1860) c) Hydroxyethyl acrylate 1.75 1.54 c) Hydroxyethyl acrylate- 0.51 caprolactone oligomer d) Isophorone diisocyanate 2.70 2.0 Molar ratio a/b 0.27 0 Molar ratio c/a 6.46 crO
Equivalent ratio 0.91 0.97 NCO/OH
Table 2: Test results 1 Cl Elongation at break 53.1 58 in %
Modulus of elasticity 3.1 2.75 05 (0.5 %
elongation) in MPa Modulus of elasticity 2.9 2.6 25 (2.5 %
elongation) in MPa E25 after 800 h, 55C, 3 2.7 in MPa E25 after 800 h, 90C, 4.2 7.5 in MPa E25 after 800 h, 120C, 7.3 18.3 in MPa 20904~0 Example 2 2 mol of isophorone diisocyanate are initially introduced into the boiler described in Example 1, and 0.05% of dibutyltin dilaurate and 30 ppm of phenothiazine are added, and the mixture is heated to 60C. 2 mol of hydroxyethyl acrylate are then added dropwise at such a rate that the temperature does not exceed 60C. 1 mol of ethoxylated trimethylolpropane (20 mol of ethylene oxide per mole of trimethylolpropane) are then added dropwise also at 60C. The mixture is maintained at 60C until an NCO content of 0% has been reached. The intermediate 1 thus obtained is then processed further.
2 mol of isophorone diisocyanate and dibutyltin dilaurate are initially introduced, and 0.65 mol of polyoxytetramethylene glycol having a number-average molecular weight of 1,000, and 0.65 mol of the modified polyether diol are then added as a mixture, and the temperature is maintained at 60C until an NCO content of 2.7% has been reached. Phenothiazine is then added as a stabilizer. A mixture of 1.05 mol of hydroxyethyl acrylate and 0.35 mol of the intermediate 1 described above is then metered in, and the temperature is maintained at 60C until an NCO content of less than 0.1%
has been reached.
The radiation-curable coating composition is prepared from 70 parts of the urethane oligomer described above, 20.0 parts of phenoxyethyl acrylate, 6.5 parts of 2~0~!~0 N-vinylpyrrolidone, 1.5 parts of N-~-aminoethyl-7-aminopropyltrimethoxysilane and 2.0 parts of diethoxyacetophenone by mixing. The chemical properties are listed in Table 4. Thoroughly clean (in particular grease-free) glass plates (width x length = 98 x 161 mm) are covered at the edge with Tesakrepp~ adhesive tape No. 4432 (width 19 mm), and the coating composition is applied by means of a knife (dry-film thickness 180 ~m).
Curing is carried out using a W radiation apparatus equipped with two Hg medium-pressure lamps each of 80 W/cm lamp power at a belt rate of 40 m/minute in 2 runs at half-load operation (= 40 W/cm).
The dose of this incoming radiation was O.08 J/cm2 (measured with the UVICURE dosimeter, system EIT from Eltosch).
This gave completely cured coatings which have very good mechanical properties and furthermore are distinguished by good resistance to aging, good low-temperature performance and improved performance in the absorption and desorption of water.
The results of the determination of the modulus of elasticity at 0.5% and 2.5% elongation (according to DIN Standard 53 455) and the results of the elongation at break test are listed in Table 5.
The dependence of the modulus of elasticity value on the temperature is shown in Table 6 and Figures 5 and 7. The measurements were carried out using the DMTA instrument _ - 31 - 2~0450 from Polymer Laboratories Ltd.
Example 3 The intermediate 1 is prepared analogously to Example 2.
2 mol of isophorone diisocyanate and dibutyltin dilaurate are initially introduced, and 0.65 mol of polyoxytetramethylene glycol having a number-average molecular weight of 1,000, and 0.65 mol of the modified polyether diol are added as a mixture, and the tem-perature is maintained at 60C until an NCO content of2.6% has been reached. Phenothiazine is then added as a stabilizer. A mixture of 0.35 mol of hydroxyethyl acrylate and 1.05 mol of the intermediate 1 described above is then metered in, and the temperature is maintained at 60C until an NCO content of less than 0.1 has been reached.
Preparation, application and curing of the radiation-curable coating agent and testing of the coating were carried out analogously to Example 2. The test results are shown in Tables 5 and 6 and in Figures 5 and 8.
ExamPle 4 The intermediate 1 is prepared analogously to Example 2.
2 mol of isophorone diisocyanate are initially introduced, and 1.3 mol of modified polyether diol are added. After addition is complete, the mixture is maintained at 60C for another 6 hours. 1.4 mol of the inter-mediate described above are then metered in, and the temperature is maintained at 60C until an NCO content of less than 0.1% has been reached.
Preparation, application and curing of the radiation-curable coating agent and testing of the coating ~ere carried out analogously to Example 2.
The test results are shown in Tables 5 and 6 and in Figures 5 and 9.
Comparative Examples 2 and 3 Analogously to Example 2, polyurethane acrylate oligomers were prepared from the components listed in Table 3.
These urethane acrylate oligomers were used to prepare radiation-curable coating compositions analogously to Example 2.
Application, curing and testing of the coatings were also carried out analogously to Example 2. The results of the determination of the modulus of elasticity at 0.5% and 2.5%
elongation (according to DIN Standard 53 455) and the results of the elongation at break test are listed in Table 5.
The dependence of the modulus of elasticity value on the temperature is shown in Figures 6, 10 and 11 and in Table 8.
The measurements were carried out using the DMTA instrument from Polymer Laboratories Ltd.
2~9~950 Table 3: Composition of the polyurethane acrylate oligomers in mol Example 2 3 4 C2 C3 p-THF 1000 O. 65 0.65 - 0.65 p 600 mod. PE 0.65 0.65 1.30 0.65 1.30 eth. TMP 7 - - - 0.70 0.70 eth. TMP 20 0.35 1.05 1.40 HEA 1.75 2.45 2.80 2.10 2.10 IPDI 2.70 4.10 4.80 3.40 3.40 The following abbreviations were used in Table 3:
p-THF 1000: polyoxytetramethylene glycol having a number-average molecular weight of 1,000 p 600: polyoxypropylene glycol having a number-average molecular weight of 600 mod. PE: modified polyether diol eth. TMP 7: ethoxylated trimethylolpropane having 7 ethylene oxide units per trimethylol-propane (M~ = 414) eth. TMP 20: ethoxylated trimethylolpropane having 20 e t hy l e ne ox ide u n it s p e r trimethylolpropane HEA: 2-hydroxyethyl acrylate IPDI: isophorone diisocyanate 2~9~4$0 Table 4: Chemical properties of the liquid coating agents 1 2 3 4 Cl C2 C3 Oligomer 1 3 4 5 2 6 7 DBC (coating a.) 2.07 2.02 2.02 1.99 2.31 1.91 2.01 DBC (oligomer) 0.67 0.6 0.61 0.56 0.69 0.6 C = C - R 3.39 3.78 3.73 4.07 2.25 2.80 3.80 Funct. 2.5 2.5 3.5 4 2 3 3 10 DBC (coating a.): concentration of acrylic groups in mol/kg in the coating agent DBC (oligomer): concentration of acrylic groups in mol/kg in the oligomer C = C - R: ratio of acrylic groups of the mono-mers to acrylic groups of the oligomer determined in the coating agent Funct.: average acrylic group functionality of the polymer 2090~50 Table 5: Mechanical test values of the coatings 1 2 ' 3 4 c2 - c3 Elongation at break (%) 53 48 44 42 56 62 Modulus of elasticity (0.5% elongation) in MPa 3.1 2.8 2.7 2.5 17 15 Modulus of elasticity (2.5X elongation) in MPa 2.9 2. 6 2.5 2.2 15.7 13. 5 2~04~
_ - 36 -Table 6 Example 2 Example 3 ~C] ~ log E ~ l-C~ ~ lo9 E
I
-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,S ~'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 -2~,5 "9,035 -28,5 " 8.996 -28.5 ~'8,9618 -27,5 " 8,977 -28 "9,001 -26,5 " 8,957 -27 "8.98t 26 " 8.945 -26 "8.964 -25 " 8,921 -25 "8.898 -24 " 8.899 -24.5 "a .924 -23 " 8,883 - 23,5 "8,908 - 22 " 8,862 -22,5 ~'8,8818 -21 " 8,779 -21.5 "8,861 -20.5 " 8.818 -21 "8.U9 -19,5 " 8,792 -20 "8,829 -18,5 " 8.714 - 19 "8.786 - 18 " 8.745 -18 "8,775 -17 " 8,721 -17,5 "8.748 -16 " 8.613 -16,5 "8.708 -15 " 8.656 -15,5 "8.693 -14,5 " a.636 -~4.5 "8.669 -13 ~' 8.587 - 13 5 "8.617 - 12 " 8.556 -12 5 "8.6 11.5 " 8.528 2090g~
_ - 37 -Continuation of Table 6 Example 2 Example 3 ~ ' log E T~C~ " iog E
-11.5 "8.574 -10.5 " 8.48 -11 "8.525 -9,5 " 8.417 -10 "8.511 -8.5 " 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 " 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 "7.68~ 5 " 7,654 ~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 u ~,311 0 " ~,311 11 " 7,275 11 "7.275 12 " 7,231 2 "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,~51 15 5 u7,051 16 H 6,999 16 u 6.999 17,5 ~' 6,932 17.5 ~ 6.932 18 ~ 6,891 - ~090~5Q
Continuation of Table 6 Example 2 Example 3 ~t-C~ ~ l~ E Tt-cl ~ (~ E
18 ~' 6,~91 18,5 ~6,876 18,5 ~ 6,~76 Z0 ~6.t1S
~ ~,815 20.S 1~6.7'96 20,5 ~ 6,7~6 21,5 ~6.7'S7 21,5 ~ 6,7S7 22,5 ~6~735 22.5 ~ 6,73S Z3 ~6.7~
23 ~ 6,71 24 ~6.698 24 ~ 6,698 25 ~6.67 ~ 6,67 26 ~6,638 26 ~ 6.638 26.5 u6,623 26 5 H 6,623 l 8.5 ~6,491 28 5 ~ 6,491 ~O,S ~6,483 30,5 ~ 6,483 ~2,5 ~6,501 32,5 ~ 6,501 34 ~6~514 34 ~ 6.51~ 37.5 ~6.464 37,5 ~ 6.~64 38 ~6.46 38 ~ 6.46 39 ~6,419 39 ~ 6,419 40.5 ~6~44 40 S ~ 6.44 41,5 u6,426 41 5 ~ 6,426 42,5 ~6,43 42,5 ~ 6.43 43 u6,409 43 ~ 6~09 4L "6,~54 44 ~ 6.454 45 ~6,423 ~ 6~23 46 ~6~366 ~6 ~ 6,366 47 ~6,453 47 ~ 6.453 48 2460368 48 ~ 6.395 u 6,359 51 ~ o.356 5- Ho,4472 ,~ ~ o,429 o,~76 S ~ o, ~83 6 ~ o,434 57~1 ~ o,422 58, ~ 6.408 6~ ~ 6.362 2090~5~
-Table 7 Example 4 Example 1 T~-CI ~ lo~ E ~[-C~ ~ log E
-39 " 9,332 39 " 9,395 -38 " 9,33 -38,5 " 9,39~
-37 " 9,317 -38 " 9,393 -36 " 9,306 -36,5 " 9,39 -35 "9.303 ~35.5 " 9,378 -34 "9,28 -35 " 9.378 ~33.5 "9,276 -34,5 ~ 9,377 -32,5 "9.265 -33.5 " ~,378 -31,5 "9.251 -32,5 " 9.363 -30,5 " 9.232 -31.5 ~' 9.356 -29.5 " 9,223 -31 ~ 9,357 -29 " 9,208 -29,5 " 9.35 -27 5 " 9.19 -28.5 " 9.337 -27 " 9,17 -28 " 9.334--26 " 9.146 -27.5 " 9.332 -25 "9.134 -26 " 9.32 -24 "9.119 -25 " 9.279 -23,5 "9.1 -24 5 " 9.305 -22.5 "9.074 -24 " 9,303 -21.5 "9.052 -22.5 " 9.295 -21 "9.039 -21 " 9.267 -20 " 9.008 -20.5 " 9.263 -19 " 8.981 ~20 " 9.261 -18 " 8.958 -19.5 " 9.256 -17.5 "8,911 -18.5 ~' 9.241 -16.5 "8.896 -17 " 9.205 -15 "8,a64 -16.5 " 9,202 -14 5 ~8,825 -16 " 9,199 -13.5 "8,792 -15 " 9.192 -13 " 8,765 -13.5 ~ 9,136 -12 " 8,654 -13 " 9.129 -11 "8,689 -12.5 " 9.125 ~ o ~
Continuation of Table 7 Example 4 Example 1 T~'C] " l~g E T~C~ " log E
The present invention also relates to radiation-curable coating compositions contAin;ng these radiation-curable oligomers, and to processes for the coating of glass surfaces, in particular optic glass fibers, in '~' 2û~4SI~
which these coating compositions are used.
Optic glass fibers have acquired constantly increasing importance in the commlln;cations sector as light waveguide fibers. For this particular application, it is absolutely necessary to protect their glass surface from moisture and wear. Accordingly, directly after their manufacture, the glass fibers are provided with at least one protective surface coating.
Thus it is known, for example from EP-B-114,982, to provide glass fibers first with a buffer layer (primer) which is elastic but has low hardness and low toughness and then to apply a radiation-curable top coat which has high hardness and toughness. The two-layered structure is intended to ensure good protection of the glass fibers upon exposure to mechanical stress even at low temperatures.
According to EP-B-114,982, radiation-curable coating agents based on linear urethane acrylates are used as the primer. Radiation-curable coating agents based on a linear urethane acrylate, a diethylenically unsaturated ester, a diglycidyl ether of a bisphenol and a monoethylenically unsaturated monomer, the glass transition temperature of the homopolymer prepared f om this monomer being above 55C, can be used as the top coat.
EP-A-223,086 furthermore discloses radiation-curable coating agents for the coating of optic glass 209û450 fibers. These coating agents contain radiation-curable oligomers according to the preamble of the main claim as the binder.
These radiation-curable coating agents described in EP-A-223,086 are used either as top coat or as single-layer coating. However, they are not suitable as primer due to the excessively high modulus of elasticity value of the cured coatings.
Radiation-curable coating compositions for the coating of optic glass fibers are also described in EP-A-209,641. These coating compositions contain a polyure-thane oligomer contAin;ng acrylate end groups and based on a polyfunctional core as the binder. These coating compositions can be used not only as primer but also as top coat. Single-layer processing is also possible.
Finally, for example EP-A-208,845, EP-A-167,199, EP-A-204,161, EP-A-204,160 and EP-A-250,631 disclose radiation-curable coating compositions for the coating of optic glass fibers which contain linear urethane acry-lates as binders. These coating compositions have the disadvantage of unsatisfactory ageing behavior. Further-more, the mechanical properties of the coatingR, in particular elasticity, still need to be improved upon long-term exposure.
The object of the present invention is to provide radiation-curable coating compositions for the coating of glass surfaces, in particular of optic glass fibers, 2~9~
_ - 4 which, compared with the known coating compositions, lead to coatings having improved properties. In particular, the cured coatings should have improved ageing behavior and correspondingly increased long-term stability of the coated glass fibers. Furthermore, the cured coatings should have improved behavior in the absorption and desorption of water. This is of particular importance for the optical damping of the coated fibers. Moreover, the cured coatings should have a good buffer effect even at low temperature. This means that the mechanical properties of the coating should deteriorate only as little as possible with decreasing temperature. In particular, the increase in the modulus of elasticity value with decreasing temperature should be as little as possible. On the other hand, the coating compositions should cure as quickly as possible. Moreover, the resulting coatings should have only very slight evolution of hydrogen upon storage and ageing and show good ad-hesion on the glass surface.
Surprisingly, the object is achieved by radia-tion-curable oligomers cont~;ning several ethylenically unsaturated end groups and several urethane and/or urea groups per molecule in dissolved form, which oligomers can be prepared from a) at least one hydroxy- and/or aminofunctional com-pound having a functionality between 3 and 4 and a number-average molecular weight between 500 and _ 5 _ 2~9~
4000, b) at least one compound having 2 hydroxyl and/or amino groups per molecule and a number-average molecular weight between 200 and 4000, c) at least one monoethylenically unsaturated compound having a group contA;n;ng one active hydrogen atom per molecule and having a number-average molecular weight between 116 and 1000, and d) at least one aliphatic and/or cycloaliphatic diiso-cyanate.
Components a to d are used in the radiation-curable oligomers in amounts such that 1. the molar ratio of component a to component b is between 0.1 : 1 and 1.1 : 1, preferably between 0.1 and 0.8, 2. the molar ratio of component c to component a is between 2.0 : 1 and 10 : 1, preferably between 2.5 and 10, and 3. the equivalent ratio of the isocyanate groups of component d to the hydroxyl and/or amino groups of the sum of components a to c is between 0.9 and 1Ø
The present invention furthermore relates to radiation-curable coating compositions cont~; n; ng these - 6 - 2~9Q450 radiation-curable oligomers and to processes for the coating of glass surfaces, in particular optic glass fibers, in which these coating compositions are used.
It is surprising and was not foreseeable that radiation-curable coating compositions based on the oligomers according to the invention give coatings having improved ageing behavior compared with conventional coatings, as a result of which the glass fibers coated with these coating compositions have increased long-term stability. Moreover, the coatings prepared from the coating compositions according to the invention have improved behavior, compared with conventional coatings, in the absorption and desorption of water. Another advantage is the good buffer effect of the coatings even at low temperatures, thus solving the problem of the so-called microbends. Furthermore, the coatings according to the invention are distinguished by good mechanical properties, such as, for example, tensile strength and elongation adapted to the particular application, and by only a slight evolution of hydrogen upon storage or ageing. Finally, they have good adhesion on the glass surface.
Hereinafter, first the radiation-curable oligo-mers according to the invention will be defined in more detail: suitable components a for the preparation of the oligomers are hydroxy- and/or aminofunctional compounds having a functionality of 3 to 4, preferably 3. These 2D9~-~5û
compounds have number-average molecular weights of 500 to 4000, preferably 750 to 2000.
Examples of suitable compounds are polyalkoxy-lated triols, such as, for example, ethoxylated and propoxylated triols, preferably ethoxylated triols, particularly preferably having a number-average molecular weight of greater than or equal to 1000. Examples of the triols used are glycerol and trimethylolpropane.
The corresponding aminofunctional compounds such as, for example, aminofunctional compounds derived from polyalkoxylated triols, are also suitable. Examples of such products are obt~;nAhle from Texaco under the name JEFFAMIN(R), for example JEFFAMIN~R) T 403, T 3000, T 5000, C 346, DU 700 and BuD 2000.
These aminofunctional compounds can contain both primary and secondary amino groups.
In addition, compounds containing both amino and hydroxyl groups are also suitable.
Suitable components b are compounds contAin;ng two hydroxyl and/or amino groups per molecule. These compounds have number-average molecular weights of 200 to 4000, preferably 600 to 2000.
Examples of suitable compounds b are polyoxy-alkylene glycols and polyoxyalkylenediamines, alkylene groups of 1 to 6 C atoms being preferred. Thus, for example, polyoxyethylene glycols having a number-average molecular weight of 1000, 1500, 2000 or 2500 and polyoxy-2~904 ~11 propylene glycols having corresponding molecular weightsand polytetramethylene glycols are suitable.
Polyethoxylated and polypropoxylated diols can also be used, such as, for example, ethoxylated and propoxylated derivatives of butanediol, hexanediol, and the like.
Furthermore, polyesterdiols, which can be prepared, for example, by reacting the already mentioned glycols with dicarboxylic acids, preferably aliphatic and/or cyclo-aliphatic dicarboxylic acids, such as, for example, hexahydrophthalic acid, adipic acid, azelaic, sebacic and glutaricor cycloaliphakyl-substituted derivatives thereof, can also be used. Instead of these acids, it is possible to use their anhydrides, if they exist.
Polycaprolactonediols can also be used. These products are obtained, for example, by reacting an ~-caprolactone with a diol. Products of this type are described in US Patent No. 3,169,945.
The polylactonediols obtained by this reaction are distinguished by the presence of a terminal hydroxyl group and by recurring polyester portions derived from the lactone. These recurring molecular portions can have the formula - C _ (CHR)n ~ CH2 - 20904~
g in which n is preferably 4 to 6 and the substituent is hydrogen, an alkyl radical, a cycloalkyl radical or an alkoxy radical, no substituent cont~;ning more than 12 carbon atoms and the total number of carbon atoms of the substituents in the lactone ring not exceeding 12.
The lactone used as starting material can be any desired lactone or any desired combination of lactones, in which this lactone should contain at least 6 carbon atoms in the ring, for example 6 to 8 carbon atoms, and in which at least 2 hydrogen substituents should be present on the carbon atom. The lactone used as starting material can be described by the following general formula:
CH2 -- ( CR2 ) n C ~ o in which n and R are as already defined. The lactones which are preferred in the invention for the preparation of polyesterdiols are caprolactones in which n has a value of 4. The most preferred lactone is substituted ~-caprolactone in which n has a value of 4 and all R
substituents are hydrogen. This lactone is particularly preferred since it is available in large amounts and gives coatings having excellent properties. It is also possible to use various other lactones by themselves or 2~0g~p combined. Examples of aliphatic diols suitable for the reaction with the lactone are the diols already mentioned above for the reaction with the carboxylic acids.
It is of course also possible to use the cor-responding diamines and compounds having an OH and an amino group as component b. Examples of suitable com-pounds are the products available from Texaco under the name JEFFAMIN~ D 230, D 400, D 2000, D 4000, ED 600, ED 900, ED 2001 and ED 4000.
A mixture comprising bl) 0 to 90 mol % of at least one polyetherdiol and b2) 10 to 100 mol % of at least one modified poly-etherdiol composed of b21) at least one polyetherdiol b22) at least one aliphatic and/or cycloaliphatic dicarboxylic acid and b23) at least one aliphatic, saturated compound having an epoxy group and 8 to 21 C atoms per molecule, in which the sum of the amounts of components bl and b2 and the sum of the amounts of components b2l to b23 is in each case 100 mol %, is preferably used as component b.
For preparing the modified polyetherdiols by conventional methoas, components b2l to b23 are used in amounts such that the equivalent ratio of the OH groups of component b2l to the carboxyl groups of component b22 is between 0.45 and 0.55, preferably 0.5, and that the equivalent ratio of the epoxy groups of component b23 to 2Q9û~0 the carboxyl groups of component b22 is between 0.45 and 0.55 and preferably 0.5.
Examples of suitable polyetherdiols b1 and b21 are the polyoxyalkylene glycols already listed in which the alkylene groups have 1 to 6 C atoms. Polyoxypropylene glycols having a number-average molecular weight between 600 and 2000 are preferably used as component b1. Polyoxy-butylene glycols (poly-THF) having a number-average molecular weight of > 1000 are preferably used as com-ponent b21-Aliphatic and cycloaliphatic dicarboxylic acids having 8 to 36 C atoms per molecule, such as, for example, hexahydrophthalic acid, are preferably used as component b22. Examples of suitable components b23 are epoxidized vinylcyclohexane compounds, epoxidized, monoolefinically unsaturated fatty acids and/or polybuta-dienes.
Glycidyl esters of branched monocarboxylic acids, such as, for example, the glycidyl ester of Versatic Acid, are preferably used as component b23.
For introducing the ethylenically unsaturated groups into the polyurethane oligomer, monoethylenically unsaturated compounds having a group containing an active hydrogen atom and having a number-average molecular weight of 116 to 1000, preferably 116 to 400, are used.
Examples of suitable components c are, for example, hydroxyalkyl esters of ethylenically unsaturated 20~04~
_ - 12 -carboxylic acids, such as, for example, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyamyl acrylate, hydroxyhexyl acrylate, hydroxyoctyl acrylate, and the corresponding hydroxalkyl esters of methacrylic, fumaric, maleic, itaconic, crotonic and isocrotonic acid, the hydroxyalkyl esters of acrylic acid being, however, preferred.
Furthermore, adducts of caprolactone with one of the abovementioned hydroxyalkyl esters of ethylenically unsaturated carboxylic acids are suitable as component c. Adducts of the hydroxyalkyl esters of acrylic acid having a number-average molecular weight of 300 to 1000 are preferably used.
Suitable components d for the preparation of the oligomers according to the invention are aliphatic and/or cycloaliphatic diisocyanates, such as, for example, 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,2-cyclohexane diisocyanate, 4,4'-methylene-bis(cyclo-hexane isocyanate) and isophorone diisocyanate, tri-methylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate and trimethyl-1,6-hexamethylene diisocyanate and the diisocyanates derived from dimeric fatty acids and described in EP-A-204,161, column 4, lines 42 to 49.
Isophorone diisocyanate and trimethyl-1,6-hexa-methylene diisocyanate are preferably used.
~ 09~4~
It is essential to the invention that components a to d for preparing the oligomers are used in amounts such that 1. the molar ratio of component a to component b is between 0.1 : 1 and 1.1 : 1, preferably between 0.1 and 0.8, 2. the molar ratio of component c to component a is 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 from components a plus b plus c is between 0.9 and 1Ø
The oligomers according to the invention can be prepared by various methods. Thus, for example, it is possible first to react diisocyanate d with chain-length-ening agents a and b and then to react the remAining free isocyanate groups with the ethylenically unsaturated compound c.
It is also possible to prepare the oligomers by first reacting a portion of the isocyanate groups of component b with the ethyle~icAlly unsaturated compound c and then reacting the remaining free isocyanate groups with chain-lengthening agents a and b.
~ - 14 - 2 ~ ~q 5Q
Furthermore, it is possible to prepare the polyurethane oligomers by the process described in EP-A-223,086 on page 5.
The polyurethane oligomers are preferably prepar-ed by a two-step process by first carrying out the stoichiometric polyaddition reaction of components a to d until more than 85 % of the NCO groups of component d have been converted. In this first process step, com-ponents a to d are used in amounts such that the equival-ent ratio of the NCO groups of component d to the active hydrogen atoms of components a to c is 1:1.
In a second process step, the remainder of the other components (in accordance with the desired NCO: OH
ratio) is then added, and the reaction is continued up to an NCO group conversion of > 99 %. In this second process step, it is preferred to add more of component c and to achieve the desired NCO: OH equivalent ratio by adding this component c.
The urethane oligomers according to the invention usually have number-average molecular weights of 2500 to 10000, preferably 3000 to 6000 (measured by GPC against a polystyrene st~n~Ard), weight-average molecular weights of 5000 to 50000, preferably 7000 to 20000 (measured by GPC against a polystyrene stAn~Ard), double-bond contents of 0.45 to 1.5, preferably 0.45 to 0.9, mol/kg and particularly preferably 0.45 to 0.63, and very particularly preferably 0.5 to 0.63 mol/kg, and a - 15 - 20~5~
functionality of >2 to 3.5, preferably 2.2 to 2.8, in each case per statistic average polymer molecule.
The oligomers according to the invention are used in radiation-c~rable coating compositions as film-forming component A. The coating compositions usually contain 10 to 78 % by weight, preferably at least 15 % by weight, and particularly preferably 63 to 73 % by weight, in each case relative to the total weight of the coating composi-tion, of these oligomers according to the invention.
As further component, the coating compositions can contain O to 60 % by weight, preferably O to 50 % by weight, in each case relative to the total weight of the coating composition, of at least one further ethylenical-ly unsaturated oligomer B. Apart from unsaturated poly-esters, polyester acrylates and acrylate copolymers, in particular urethane acrylate oligomers, with the excep-tion of the urethane acrylate oligomers used as component A, are used. The properties of the completely cured coating can be selectively adjusted by means of the type and amount of this component B. The higher the amount of this component B, the higher in general the modulus of elasticity value of the completely cured coating. Com-ponent B is therefore added to the coating composition especially if the coating compositions are used as top coat. However, the effect of this component B on the properties of the resulting coating is known to one Replacement sheet ~ - 16 - 20 9 Q4 ~o skilled in the art. The most favorable amount to be used in each case can therefore be simply determined by a few routine experiments. These ethylenically unsaturated polyurethanes used as component B are known. They can be obtained by reacting a di- or polyisocyanate with a chain-lengthening agent from the group of diols/polyols and/or diamines/polyamines, followed by reaction of the remaining free isocyanate groups with at least one hydroxyalkyl acrylate or hydroxyalkyl ester of other ethylenically unsaturated carboxylic acids.
The amounts of chain-lengthening agent, di- or polyisocyanate and hydroxyalkyl ester of an ethylenically unsaturated carboxylic acid are selected in such a manner that 1. the equivalent ratio of the NCO groups to the reactive groups of the chain-lengthening agent (hydroxyl, amino or mercapto groups) is between 3:1 and 1:2, preferably 2:1, and 2. the OH groups of the hydroxyalkyl esters of the ethylenically unsaturated carboxylic acids are present in a stoichiometric amount with respect to the still free isocyanate groups of the prepolymer composed of isocyanate and chain-lengthening agents.
Replacement sheet _ - 17 - 2~ Q
Furthermore, it is possible to prepare the polyurethanes B by first reacting a portion of the iso-cyanate groups of a di- or polyisocyanate with at least one hydroxyalkyl ester of an ethylenically unsaturated carboxylic acid and then reacting the remaining isocya-nate groups with a chain-lengthening agent. In this case too, the amounts of chain-lengthening agent, isocyanate and hydroxyalkyl ester of unsaturated carboxylic acids are selected in such a manner that the equivalent ratio of the NCO groups to the reactive group of the chain-lengthening agent is between 3:1 and 1:2, preferably 2:1, and the equivalent ratio of the remaining NCO groups to the OH groups of the hydroxyalkyl ester is 1:1.
All intermediate forms of these two processes are of course also possible. For example, a portion of the isocyanate groups of a diisocyanate can first be reacted with a diol, a further portion of the isocyanate groups can then be reacted with the hydroxyalkyl ester of an ethylenically unsaturated carboxylic acid, and this can be followed by reacting the remaining isocyanate groups with a ~ ;ne.
These various preparation processes for poly-urethanes are known (cf. for example, EP-A-204,161) and therefore need not be described in more detail.
Compounds which are suitable for the preparation of these urethane-acrylate oligomers B are the compounds Replacement sheet - 18 - 2 ~ 5~
.
already used in the preparation of component A and further the compounds mentioned in German Offenlegungs-schrift 3,840,644.
Especially when the coating compositions accord-ing to the invention are used as top coat, aromatic structural components are preferably used for preparing the urethane-acrylate oligomers B. In this case, 2,4- and 2,6-toluylene diisocyanate are preferably used as isocya-nate components and aromatic polyester polyols based on phthalic acid and isophthalic acid and/or polypropylene glycol, ethylene glycol and diethylene glycol as chain-lengthening agents.
As further component, the radiation-curable coating compositions additionally contain at least one ethylenically unsaturated monomeric and/or oligomeric compound C, usually in an amount of 20 to 50 % by weight, preferably 22 to 35 ~ by weight, in each case relative to the total weight of the coating composition.
By adding this ethylenically unsaturated compound C, the viscosity and the curing rate of the coating compositions and the mechanical properties of the result-ing coating are controlled, as is known to one skilled in the art and described, for example, in EP-A-223,086 and which should be consulted for further details.
Examples of monomers which can be used are ethoxyethoxyethyl acrylate, N-vinylpyrrolidone, phenoxyethyl acrylate, dimethylaminoethyl acrylate, Replacement sheet 2 0 ~
hydroxyethyl acrylate, butoxyethyl acrylate, isobornyl acrylate, dimethylacrylamide and dicyclopentyl acrylate.
Di- and polyacrylates, such as, for example, butanediol diacrylate, hexanediol diacrylate, trimethylolpropane di-and triacrylate, pentaerythritol diacrylate and the long-chain linear diacrylates having a molecular weight of 400 to 4000 or preferably 600 to 2500, and described in EP-A-250,631, are also suitable. The two acrylate groups can be, for example, separated by a polyoxybutylene structure. Furthermore, 1,12-dodecyl diacrylate and the reaction product of 2 mol of acrylic acid with one mol of a dimeric fatty alcohol, which in general has 36 C atoms, can also be used.
Mixtures of the monomers just described are also suitable. Phenoxyethyl acrylate, hexanediol diacrylate, N-vinylpyrrolidone and tripropylene glycol diacrylate are preferably used.
The photoinitiator usually used in the coating compositions according to the invention in an amount of 2 to 8 % by weight, preferably 3 to 5 % by weight, relative to the total weight of the coating composition, varies with the radiation used for curing the coating agents ( W radiation, electron radiation, visible light).
The coating compositions according to the invention are preferably cured by means of W radiation. In this case, ketone-based photoinitiators are usually used, for example acetophenone, benzophenone, diethoxyacetophenone, 2as~4so 2-hydroxy-2-methyl-1-phenyl-1-propanone, hydroxypropyl phenyl ketone, m-chloroacetophenone, propiophenone, benzoin, benzil, benzil dimethyl ketal, anthraquinone, thioxanthone and thioxanthone derivatives and triphenyl-phosphine and the like, as well as mixtures of variousphotoinitiators.
Furthermore, the coating compositions can addi-tionally contain, if desired, customary auxiliaries and additives. These are usually used in an amount of 0 to 4 % by weight, preferably 0.5 to 2.0 % by weight, in each case relative to the total weight of the coating composi-tion. Examples of substances of this type are flow-improving agents, plasticizers and in particular adhesion promoters. Adhesion promoters used for this are alkoxy-silanes, such as, for example, N-~-aminoethyl-~-amino-propyltrimethoxysilane, ~-aminopropyltrimethoxysilane, N-methyl-~-aminopropyltrimethoxysilane or triamino-modified propyltrimethoxysilane (for example adhesion promoter DYNASYLAN~ of "TRIAMO type", commercial product from Dynamit Nobel Chemie).
The coating compositions can be applied to the substrate by means of known application methods, such as, for example, spraying, rolling, flooding, dipping, knife-or brush-application.
The coating films are cured by means of radiation, preferably by means of W radiation.
Apparatuses and conditions for these curing methods are 29904~P
known from the literature (cf. for example, R. Holmes, U.V. and E.B. Curing Formulations for Printing Inks, Coatings and Paints, SITA Technology, Academic Press, London, United Kingdom 1984~ and need no further description.
The coating compositions are suitable for the coating of a wide range of substrates, for example glass, wood, metal and plastic surfaces. However, they are in particular used for the coating of glass surfaces, particularly preferably of optic glass fibers.
Accordingly, the present invention also relates to a process for the coating of a glass surface, in which a radiation-curable coating composition is applied and cured by means of W or electron radiation, which process comprises using the coating compositions according to the invention as the radiation-curable coating compositions.
The process according to the invention is par-ticularly suitable for the coating of optic glass fibers.
For this purpose, the coating compositions according to the invention can be applied to the glass fibers as a primer and/or top coat of a two-layer coat. When the coating compositions are used as a primer, the completely cured coatings usually have a modulus of elasticity value (at 2.5 % elongation and room temperature) of less than 10 MPa.
When the coating compositions are used as top coat, the completely cured coatings usually have a 20 904~0 modulus of elasticity value (at 2.5 % elongation and room temperature) of 500 to 1000 MPa.
The invention will be illustrated in more detail in the examples which follow. All parts and percentages given are by weight, unless stated expressly otherwise.
PreParation of a modified polyetherdiol In a boiler equipped with stirrer, inert gas inlet and temperature sensor, 51.1 parts of polytetra-hydrofuran having a number-average molecular weight of 1000 and an OH number of 118 mg of KOH/g and 19.1 parts of hexahydrophthalic anhydride are heated to 120C and maintained at this temperature until an acid number of 102 mg of KOH/g has been reached. 0.02 % of chromium octoate, relative to the weight of the mixture composed of poly-THF, hexahydrophthalic acid and glycidyl ester of Versatic Acid, and 29.7 parts of the glycidyl ester of Versatic Acid having an epoxy equivalent weight of 266 are then added. The mixture is heated at 120C until the reaction product has an epoxy equivalent weight of > 20,000, an acid number of 4 mg of KOH/g and an OH
number of 60 mg of KOH/g.
The modified polyether diol has an average molecular weight ~ of 1860 (calculated from the OH
nunber), an Mn z 1500 determined by GPC and an MW/M~ = 1.67. The viscosity of an 80 % strength solution in butyl acetate is 3.8 dPas (measured at 23C with the 2 a ~
plate/cone viscometer).
ExamPle 1 In a boiler equipped with stirrer, inlet means, temperature sensor and air inlet, 0.35 mol of a commercially available ethoxylated trimethylolpropane having a number-average molecular weight of 1000, 0.65 mol of a commercially available polyoxypropylene glycol having a number-average molecular weight of 600, 0.65 mol of the modified polyetherdiol described above, 1.75 mol of hydroxyethyl acrylate, 0.05 % of dibutyltin dilaurate (relative to the total weight of the sum of components a, b, c and d), 0.1 % of 2,6-ditert.-butylcresol (relative to the total weight of the sum of components a, b, c and d) and 30 ppm of phenothiazine (relative to the total weight of the sum of components a, b, c and d) are initially introduced, and the mixture is heated to 60C.
2.70 mol of isophorone diisocyanate are then metered in at 50C over a period of 2.5 h. The mixture is then diluted with phenoxyethyl acrylate to a theoretical solids content of 90 % (sum of components a to d), and the temperature is maintained at 60C until an NCO value of 1 % has been reached. 0.05 % of dibutyltin dilaurate and 0.51 mol of a commercially available hydroxyethyl acrylate/caprolactone oligomer having a number-average molecular weight of 344 (commercial product TONE M 100 from Union Carbide) are added at a temperature of 80C, and the temperature is maintained at 80C until an NCO
2~90~0 value of < 0.1 % has been reached. The oligomer thus obtained has a double-bond content of 0.6 mol/kg and a functionality of 2.5.
A 40 % solution (relative to the theoretical solids content) of the oligomer 1 obtained in phenoxy-ethyl acrylate has a viscosity of 4.9 d Pas (measured at 23C with the plate/cone viscometer.
78.1 parts of the 90 % strength solution of the urethane oligomer 1 described above, 12.1 parts of phenoxyethyl acrylate, 6.2 parts of N-vinylpyrrolidone, 1.6 parts of N-~-aminoethyl-~-aminopropyltrimethoxysilane and 2.0 parts of diethoxyacetophenone are used to prepare a radiation-curable coating composition 1 by mixing.
Thoroughly cleaned (in particular grease-free) glass plates (width x length = 98 x 161 mm) are covered at the edge with Tesakrepp~ adhesive tape No. 4432 (width 19 mm), and the coating composition 1 is applied by means of a knife (dry-film thickness 180 ~m).
The curing is carried out using a W radiation apparatus equipped with two Hg medium-pressure lamps each of 80 W/cm lamp power at a belt rate of 40 m/minute in two runs at half-load operation (= 40 W/cm).
The dose of this incoming radiation was 0.08 J/cm2 (measured with the WICURE dosimeter, system EIT from Eltosch).
This gave completely cured coatings which have very good mechanical properties and furthermore are - 25 - 2 OgO~ 5~
distinguished by good resistance to ageing, good low-temperature performance and improved performance in the absorption and desorption of water.
The results of the determination of the modulus of elasticity at 0.5 and 2.5 ~ elongation (according to DIN Standard 53 455) and the results of the elongation at break test are listed in Table 2. The results of the measurement of the modulus of elasticity values (2.5 %
elongation) after various ageing treatments of the completely cured coatings are also shown in Table 2.
The dependence of the modulus of elasticity value on the temperature is shown in Figure 1. The measurements were carried out using the DMTA instrument from Polymer Laboratories Ltd.
The absorption and desorption performance of the completely cured coating in contact with water is shown in Figure 2.
ComParative ExamPle 1 2.0 mol of isophorone diisocyanate and 0.05 % of dibutyltin dilaurate (relative to the total weight of the sum of components a to d) are initially introduced into a boiler equipped with stirrer, inlet means, temperature sensor and air inlet, and the mixture is heated to 60C.
1.30 mol of commercially available polyoxypropylene glycol having a number-average molecular weight of 600 are then metered in at 60C over a period of 120 to 180 minutes. The temperature is maintained at 60C until an ~ - 26 - 09 ~5 NCO value of 4.5 % has been reached. 0.1 % of 2.6-di-tert.-butylcresol (relative to the total weight of the sum of components a to d) and 40 ppm of phenothiazine (relative to the total weight of the sum of components a to d) are then added to the boiler. 1.54 mol of hydroxy-ethyl acrylate are then metered in at 60C over a period of 30 minutes. Dissolution of the mixture is then started with phenoxyethyl acrylate until a theoretical solids content of 90 % (relative to the total weight of the sum of components a to d) has been reached. The temperature is then maintained at 60C until an NCO content of < 0.1 % has been reached.
The oligomer 2 thus obtained has a double-bond content of 1.01 mol/kg and a functionality of 2Ø A 50 %
strength solution (relative to the theoretical solids content) of the oligomer 2 obtained in phenoxyethyl acrylate has a viscosity of 10 dPas (measured at 23C
with a plate/cone viscometer).
Analogously to Example 1, 78.1 parts of the 90 %
strength solution of the urethane oligomer 2 described above, 12.1 parts of phenoxyethyl acrylate, 6.2 parts of N-vinylpyrrolidone, 1,6 parts of N-~-aminoethyl-~-amino-propyltrimethoxysilane and 2.0 parts of diethoxyacetophe-none are used to prepare a radiation-curable coating composition 2 by mixing. Application of this coating composition 2 and testing of the completely cured coating is carried out analogously to Example 1. The results are shown in Table 2 and in Figures 3 and 4.
- 27 - 2 0~45~
Table 1 : Composition of the urethane oligomers (in mol) Example 1 Comparison 1 a) Ethoxylated tri- 0.35 methylolpropane 5(Mn = 1000) b1) Polyoxypropylene 0.65 1.30 glycol (Mn = 600) b2) Modified polyetherdiol 0.65 (Mn = 1860) c) Hydroxyethyl acrylate 1.75 1.54 c) Hydroxyethyl acrylate- 0.51 caprolactone oligomer d) Isophorone diisocyanate 2.70 2.0 Molar ratio a/b 0.27 0 Molar ratio c/a 6.46 crO
Equivalent ratio 0.91 0.97 NCO/OH
Table 2: Test results 1 Cl Elongation at break 53.1 58 in %
Modulus of elasticity 3.1 2.75 05 (0.5 %
elongation) in MPa Modulus of elasticity 2.9 2.6 25 (2.5 %
elongation) in MPa E25 after 800 h, 55C, 3 2.7 in MPa E25 after 800 h, 90C, 4.2 7.5 in MPa E25 after 800 h, 120C, 7.3 18.3 in MPa 20904~0 Example 2 2 mol of isophorone diisocyanate are initially introduced into the boiler described in Example 1, and 0.05% of dibutyltin dilaurate and 30 ppm of phenothiazine are added, and the mixture is heated to 60C. 2 mol of hydroxyethyl acrylate are then added dropwise at such a rate that the temperature does not exceed 60C. 1 mol of ethoxylated trimethylolpropane (20 mol of ethylene oxide per mole of trimethylolpropane) are then added dropwise also at 60C. The mixture is maintained at 60C until an NCO content of 0% has been reached. The intermediate 1 thus obtained is then processed further.
2 mol of isophorone diisocyanate and dibutyltin dilaurate are initially introduced, and 0.65 mol of polyoxytetramethylene glycol having a number-average molecular weight of 1,000, and 0.65 mol of the modified polyether diol are then added as a mixture, and the temperature is maintained at 60C until an NCO content of 2.7% has been reached. Phenothiazine is then added as a stabilizer. A mixture of 1.05 mol of hydroxyethyl acrylate and 0.35 mol of the intermediate 1 described above is then metered in, and the temperature is maintained at 60C until an NCO content of less than 0.1%
has been reached.
The radiation-curable coating composition is prepared from 70 parts of the urethane oligomer described above, 20.0 parts of phenoxyethyl acrylate, 6.5 parts of 2~0~!~0 N-vinylpyrrolidone, 1.5 parts of N-~-aminoethyl-7-aminopropyltrimethoxysilane and 2.0 parts of diethoxyacetophenone by mixing. The chemical properties are listed in Table 4. Thoroughly clean (in particular grease-free) glass plates (width x length = 98 x 161 mm) are covered at the edge with Tesakrepp~ adhesive tape No. 4432 (width 19 mm), and the coating composition is applied by means of a knife (dry-film thickness 180 ~m).
Curing is carried out using a W radiation apparatus equipped with two Hg medium-pressure lamps each of 80 W/cm lamp power at a belt rate of 40 m/minute in 2 runs at half-load operation (= 40 W/cm).
The dose of this incoming radiation was O.08 J/cm2 (measured with the UVICURE dosimeter, system EIT from Eltosch).
This gave completely cured coatings which have very good mechanical properties and furthermore are distinguished by good resistance to aging, good low-temperature performance and improved performance in the absorption and desorption of water.
The results of the determination of the modulus of elasticity at 0.5% and 2.5% elongation (according to DIN Standard 53 455) and the results of the elongation at break test are listed in Table 5.
The dependence of the modulus of elasticity value on the temperature is shown in Table 6 and Figures 5 and 7. The measurements were carried out using the DMTA instrument _ - 31 - 2~0450 from Polymer Laboratories Ltd.
Example 3 The intermediate 1 is prepared analogously to Example 2.
2 mol of isophorone diisocyanate and dibutyltin dilaurate are initially introduced, and 0.65 mol of polyoxytetramethylene glycol having a number-average molecular weight of 1,000, and 0.65 mol of the modified polyether diol are added as a mixture, and the tem-perature is maintained at 60C until an NCO content of2.6% has been reached. Phenothiazine is then added as a stabilizer. A mixture of 0.35 mol of hydroxyethyl acrylate and 1.05 mol of the intermediate 1 described above is then metered in, and the temperature is maintained at 60C until an NCO content of less than 0.1 has been reached.
Preparation, application and curing of the radiation-curable coating agent and testing of the coating were carried out analogously to Example 2. The test results are shown in Tables 5 and 6 and in Figures 5 and 8.
ExamPle 4 The intermediate 1 is prepared analogously to Example 2.
2 mol of isophorone diisocyanate are initially introduced, and 1.3 mol of modified polyether diol are added. After addition is complete, the mixture is maintained at 60C for another 6 hours. 1.4 mol of the inter-mediate described above are then metered in, and the temperature is maintained at 60C until an NCO content of less than 0.1% has been reached.
Preparation, application and curing of the radiation-curable coating agent and testing of the coating ~ere carried out analogously to Example 2.
The test results are shown in Tables 5 and 6 and in Figures 5 and 9.
Comparative Examples 2 and 3 Analogously to Example 2, polyurethane acrylate oligomers were prepared from the components listed in Table 3.
These urethane acrylate oligomers were used to prepare radiation-curable coating compositions analogously to Example 2.
Application, curing and testing of the coatings were also carried out analogously to Example 2. The results of the determination of the modulus of elasticity at 0.5% and 2.5%
elongation (according to DIN Standard 53 455) and the results of the elongation at break test are listed in Table 5.
The dependence of the modulus of elasticity value on the temperature is shown in Figures 6, 10 and 11 and in Table 8.
The measurements were carried out using the DMTA instrument from Polymer Laboratories Ltd.
2~9~950 Table 3: Composition of the polyurethane acrylate oligomers in mol Example 2 3 4 C2 C3 p-THF 1000 O. 65 0.65 - 0.65 p 600 mod. PE 0.65 0.65 1.30 0.65 1.30 eth. TMP 7 - - - 0.70 0.70 eth. TMP 20 0.35 1.05 1.40 HEA 1.75 2.45 2.80 2.10 2.10 IPDI 2.70 4.10 4.80 3.40 3.40 The following abbreviations were used in Table 3:
p-THF 1000: polyoxytetramethylene glycol having a number-average molecular weight of 1,000 p 600: polyoxypropylene glycol having a number-average molecular weight of 600 mod. PE: modified polyether diol eth. TMP 7: ethoxylated trimethylolpropane having 7 ethylene oxide units per trimethylol-propane (M~ = 414) eth. TMP 20: ethoxylated trimethylolpropane having 20 e t hy l e ne ox ide u n it s p e r trimethylolpropane HEA: 2-hydroxyethyl acrylate IPDI: isophorone diisocyanate 2~9~4$0 Table 4: Chemical properties of the liquid coating agents 1 2 3 4 Cl C2 C3 Oligomer 1 3 4 5 2 6 7 DBC (coating a.) 2.07 2.02 2.02 1.99 2.31 1.91 2.01 DBC (oligomer) 0.67 0.6 0.61 0.56 0.69 0.6 C = C - R 3.39 3.78 3.73 4.07 2.25 2.80 3.80 Funct. 2.5 2.5 3.5 4 2 3 3 10 DBC (coating a.): concentration of acrylic groups in mol/kg in the coating agent DBC (oligomer): concentration of acrylic groups in mol/kg in the oligomer C = C - R: ratio of acrylic groups of the mono-mers to acrylic groups of the oligomer determined in the coating agent Funct.: average acrylic group functionality of the polymer 2090~50 Table 5: Mechanical test values of the coatings 1 2 ' 3 4 c2 - c3 Elongation at break (%) 53 48 44 42 56 62 Modulus of elasticity (0.5% elongation) in MPa 3.1 2.8 2.7 2.5 17 15 Modulus of elasticity (2.5X elongation) in MPa 2.9 2. 6 2.5 2.2 15.7 13. 5 2~04~
_ - 36 -Table 6 Example 2 Example 3 ~C] ~ log E ~ l-C~ ~ lo9 E
I
-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,S ~'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 -2~,5 "9,035 -28,5 " 8.996 -28.5 ~'8,9618 -27,5 " 8,977 -28 "9,001 -26,5 " 8,957 -27 "8.98t 26 " 8.945 -26 "8.964 -25 " 8,921 -25 "8.898 -24 " 8.899 -24.5 "a .924 -23 " 8,883 - 23,5 "8,908 - 22 " 8,862 -22,5 ~'8,8818 -21 " 8,779 -21.5 "8,861 -20.5 " 8.818 -21 "8.U9 -19,5 " 8,792 -20 "8,829 -18,5 " 8.714 - 19 "8.786 - 18 " 8.745 -18 "8,775 -17 " 8,721 -17,5 "8.748 -16 " 8.613 -16,5 "8.708 -15 " 8.656 -15,5 "8.693 -14,5 " a.636 -~4.5 "8.669 -13 ~' 8.587 - 13 5 "8.617 - 12 " 8.556 -12 5 "8.6 11.5 " 8.528 2090g~
_ - 37 -Continuation of Table 6 Example 2 Example 3 ~ ' log E T~C~ " iog E
-11.5 "8.574 -10.5 " 8.48 -11 "8.525 -9,5 " 8.417 -10 "8.511 -8.5 " 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 " 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 "7.68~ 5 " 7,654 ~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 u ~,311 0 " ~,311 11 " 7,275 11 "7.275 12 " 7,231 2 "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,~51 15 5 u7,051 16 H 6,999 16 u 6.999 17,5 ~' 6,932 17.5 ~ 6.932 18 ~ 6,891 - ~090~5Q
Continuation of Table 6 Example 2 Example 3 ~t-C~ ~ l~ E Tt-cl ~ (~ E
18 ~' 6,~91 18,5 ~6,876 18,5 ~ 6,~76 Z0 ~6.t1S
~ ~,815 20.S 1~6.7'96 20,5 ~ 6,7~6 21,5 ~6.7'S7 21,5 ~ 6,7S7 22,5 ~6~735 22.5 ~ 6,73S Z3 ~6.7~
23 ~ 6,71 24 ~6.698 24 ~ 6,698 25 ~6.67 ~ 6,67 26 ~6,638 26 ~ 6.638 26.5 u6,623 26 5 H 6,623 l 8.5 ~6,491 28 5 ~ 6,491 ~O,S ~6,483 30,5 ~ 6,483 ~2,5 ~6,501 32,5 ~ 6,501 34 ~6~514 34 ~ 6.51~ 37.5 ~6.464 37,5 ~ 6.~64 38 ~6.46 38 ~ 6.46 39 ~6,419 39 ~ 6,419 40.5 ~6~44 40 S ~ 6.44 41,5 u6,426 41 5 ~ 6,426 42,5 ~6,43 42,5 ~ 6.43 43 u6,409 43 ~ 6~09 4L "6,~54 44 ~ 6.454 45 ~6,423 ~ 6~23 46 ~6~366 ~6 ~ 6,366 47 ~6,453 47 ~ 6.453 48 2460368 48 ~ 6.395 u 6,359 51 ~ o.356 5- Ho,4472 ,~ ~ o,429 o,~76 S ~ o, ~83 6 ~ o,434 57~1 ~ o,422 58, ~ 6.408 6~ ~ 6.362 2090~5~
-Table 7 Example 4 Example 1 T~-CI ~ lo~ E ~[-C~ ~ log E
-39 " 9,332 39 " 9,395 -38 " 9,33 -38,5 " 9,39~
-37 " 9,317 -38 " 9,393 -36 " 9,306 -36,5 " 9,39 -35 "9.303 ~35.5 " 9,378 -34 "9,28 -35 " 9.378 ~33.5 "9,276 -34,5 ~ 9,377 -32,5 "9.265 -33.5 " ~,378 -31,5 "9.251 -32,5 " 9.363 -30,5 " 9.232 -31.5 ~' 9.356 -29.5 " 9,223 -31 ~ 9,357 -29 " 9,208 -29,5 " 9.35 -27 5 " 9.19 -28.5 " 9.337 -27 " 9,17 -28 " 9.334--26 " 9.146 -27.5 " 9.332 -25 "9.134 -26 " 9.32 -24 "9.119 -25 " 9.279 -23,5 "9.1 -24 5 " 9.305 -22.5 "9.074 -24 " 9,303 -21.5 "9.052 -22.5 " 9.295 -21 "9.039 -21 " 9.267 -20 " 9.008 -20.5 " 9.263 -19 " 8.981 ~20 " 9.261 -18 " 8.958 -19.5 " 9.256 -17.5 "8,911 -18.5 ~' 9.241 -16.5 "8.896 -17 " 9.205 -15 "8,a64 -16.5 " 9,202 -14 5 ~8,825 -16 " 9,199 -13.5 "8,792 -15 " 9.192 -13 " 8,765 -13.5 ~ 9,136 -12 " 8,654 -13 " 9.129 -11 "8,689 -12.5 " 9.125 ~ o ~
Continuation of Table 7 Example 4 Example 1 T~'C] " l~g E T~C~ " log E
-10 " 8.662 -11 "9.103 -9,5 ~ 8.615 -10 "9.04 -8.5 '~8.587 -9,5 ll9-041 -7.5 " 8,515 .9 "9 037 -6.5 " 8.3~3 -6 "8.a92 -6 " 8.4~8 -5,5 "8.921 -5 ~ 8.408 -S "8.919 -4 " 8.321 -.S "8,64 -3 'l8.297 1 "8,491 - 2 " 8.22 1.5 "8.528 -1 " 8.145 2 "8.549 0 " 8.109 3 "8.451 1 " 7,997 6 "8,194 2 " 7.954 9,5 "7,827 3 ~ 7.829 10 "7.9~
4 ~l7,807 12,5 "7.493 S,S ~ 7,722 13.5 "7,657 6 " 7.673 16,5 "7.273 7 ~ ~.627 17 "7,328 7,5 " 7,579 19 '~7,11a 9 " 7,46L 19,S "7,143 10,5 ~ 7.364 21.5 ~6,932 11 U7.313 22.5 "6.924 12 ~7,247 23 "6,ff1 13 H7,213 25 H6.817 ~3.5 ~i,156 25,5 ~6.84 ~4.5 ~7.123 2~,5 U6,741 15.5 ~7,057 32 ~6.599 ~6 "~,022 39 ~6.4a3 ~7 ~6.ff6 38,5 ~6.5 ~8 U6.892 ~2 ~6,486 19 ~6.846 ~2.5 ~6.519 ~6.~a9 ~5.5 ~6.~7~
)2 0 9~ ~5`0 .- - 41 -Continuation of Table 7 Example 4 Example 1 ~l-C~ ~ E ~l-C~ ~ ~ E
20.5 ~ 6.759 ~5 ~6.477 23 6.617 47,5 6.522 24.5 ~ 6.566 ~8. ~6.489 25.5 ~ 6.518 51. u6.536 26,5 ~ 6,5a6 54. u6.472 27,5 ~ 6.~91 57.5 ~6.542 28,5 ~ 6.452 58 u6.52 29.5 ~ 6.439 30,5 ~ 6.3~2 3t ~ 6.366 32 ~ 6.373 33 ~ 6.302 33. " 6~357 ~4, " 6.329 35, ~'6.,86 36,~ ~'6.~83 37 u o~96 38,5 ~' o.. 69 39 u ~,256 " o.137 41 ~ 6,23 42 " 6.24 42.5 " 6,232 43,5 " 6.181 44 ~ 6,262 " 6.215 46 " 6.17 ~6.5 ~ 6,158 .5 u ~.106 ~8.5 ~ 6.007 ~9,5 ~ 6,0 1 ~ 6.154 51 ~ 6. 7 5~ ~ ~.O~S
~3. ~ o.1 4 4, ~ o,l85 5,5 ~ 6,073 ~6,5 ~6.0183 57 ~ ~.132 58 ~6. ~ 05 59 ~ o,125 59.5 ~ o.142 60,5 ~o .202 20904~0 Table 8 Comparative Comparative Comparative Example 2 Example 3 Example 1 tC~ ~ E ~ ~-C~ ~ ~ E ~ ~-C~ ~ E
40.5 "9,237 -38 '~9.363 -38.5 '~9,~03 -~1.5 "9.26L -37,5 '~9.366 -38 '~9,40 -40 "9,28 -37 "9.37 -37.5 " 9,~1 -37.5 "9.223 36.5 "9.37 -37 ~ 9.40 -37 "9.241 36 "9.368 -36.5 " 9~408 -37.5 "9.257 35.5 "9.367 -36 " 9.406 -38 "9,267 -34 "9.3~1 -35 ~l9.403 -35 "9.24 -33 "9.334 -33.5 " 9.38~
-33,5 "9,22 -32.5 "9.333 -33 " 9.382 -33 "9.229 -32 "9.33 -32.5 " 9,382 -31 "9.203 -30.5 "9.312 -32 " 9.38 -30.5 "9.2 -28.5 "9.291 -31 ~ 9.376 -30 "9.199 -28 "9,29~ -29.5 " 9,355 -29.5 "9.203 -27.5 "9.289 -28.5 " 9.353 -27.5 "9,175 -27 "9,287 -28 '~9.35 -26.5 "9.157 -26 "9.264 -27.5 '~9.351 -26 "9.159 -25 "9.255 -26 " 9.327 -25,5 "9.158 -24,5 "9.251 -24.5 " 9.317 -23,5 "9.133 -23,5 "9.251 -24 " 9~317 -22,5 "9,116 -22 "9.~15 -23.S " 9.317 -22 "9.115 -21 "9.~ 07 -23 " 9.313 -21,5 "9.117 -20.5 "9.; 06 -22.5 " 9.313 -21 "9.117 -20 "9.202 -~1 " 9.279 19 "9.075 - 19 "9.1t6 -~0 " 9.274 -18,5 "9.071 -17.5 '~9.156 -19.5 " 9,273 -lt "9.071 .17 U9,155 -19 '~9.271 -17,5 "9.07 -16~5 "9,153 -18 " 9.256 -16 "9.0~7 -15 ~9.125 -16.5 "~.2, ~
-15 "~,989 -14 "9.1 16 " ~.2,2 .14,5 U9.02 -13.5 "9.099 -15. " 9.~2 -14 U9.02 -13 "9.096 -1~,~ " 9.2~7 .13,5 U9.02 11~5 -9.061 -1~ '~9.165 20904~0 ., Continuation of Table 8 Comparative Comparative Comparative Example 2 Example 3 Example 1 lcg E ~ 3 ~ T r~
-ll,S ~l8,967 11 '~9,0~8 -12~5 "9.162 ~ 8,961 -10.5 "9.045 12 "9,16 -lO S "8,96 9 ll9~007 1l.5 I~9~157 ~lO ~8,958 -8 ~8.99 -9~5 ~'9.085 -8~5 ~8~917 ~7 5 ~t~988 a.s ~9~081 7,5 ~'8,898 -7 ~'8~987 8 "9~08 ~7 "8,89~ ~5.5 "8.922 -7.5 "9,079 6 5 8 !896 5 8,917 6 8.998 -5 ~8~8L6 -~.5 ~8.918 -5 ~'8~982 -4 "8.83 -3,5 "8.91 -4. S "8.986 ~3.5 "8,798 -1~5 "8~822 -~ "8.985 ~3 "8,825 ~1 " 8.~ -2 "t~827 8.7~1 S ~ 8~t- -t~S ~'8~8~6 ~ S ~8.74~ 8,75, ~ 1 ~8.8&8 0 ~8.747 2 ~ 17 S ~'8,~03 1,5 ~8.708 2,5 ~ 25 1 ~8,761 3 "8 62 3 ".728 1.5 "8.768 3,5 "8,635 5 "8.531 2 "8.767 4 "8.6L3 6 "8,556 5 "8.573 6 "8,508 6,5 "1~577 7 ",~22 6.5 ~t.S01 7 ~.591 9 u.372 ~ ~8,52 ~ .597 12~5 u,097 7.5 ~~.524 10~ .266 16~5 ~~~757 ~~,2~5 1 ~ 41 19 ~7,359 10.5 ~~331 12.5 ~8,04 20 ~7~14 11 u.-63 14 ~,164 20. ~7,46 ~5 u~89 14~5 ~~209 23~ u7.15 12~5 ~~ 01 16~5 ~,~791 2 ~t.~O
14 ~.132 17 u7~98 23. ~7, 44 1~,5 ~~.165 17.5 ~t~02- 26 ~o,~O9 14 ~~,196 20~5 u7.67 26,5 ~a.989 16 ~ 67 21 ~7~06 28 ~o,911 17.5 ~~,908 23~5 ~7~76 29.5 ~6.~44 Continuation of Table 8 Comparative Comparative Comparative Example 2 Example 3 Example 1 T l-C~ ~ l~ E ~ ~-C~ ~ l~ E ~ ~-C~ ~ l~ E
~8 ~7~954 ;4 ~ 7~534 29 ~ 6.~71 8.5 ~o,016 ;6 ~ ~,256 31.5 ~ 6.685 2~ 6~6 ~7 ~ 7,229 32~5 ~ 6~698 21~5 u7,722 ~6,5 ~ 7,289 32 ~ 6~733 21 ~7~774 ~7~5 ~ ~297 34~5 ~ 6~391 23~ 5 ~?~8a 30, S ~ 7~011 35 ~ 6~604 24~5 ~7~452 30 ~ ?~072 35~5 ~ 6~58 ~?~498 30,5 ~ 7~102 38 ~ 6~464 24~5 ~ 541 33~5 ~ 6~79 38~5 ~ ~SS4 26~5 ~7~363 3~ ~ 6~28 8 ~ o~S41 27~ 5 ~7~273 33.5 ~ o~73 40,5 ~o ~46~
28 u7~312 ~4 ~ o.~97 ~1~5 ~ o~69 28~5 u7~313 ~6 ~ ~712 ~1 ~ o~502 30 ~ 5 u7.081 ,7 ~o j 674 43 ~ 6~497 31 ~7~115 36~5 u O~71 ~5 ~ 6~449 30~5 ~7~162 39 ~ o~59 44.5 ~ 6~432 33 ~6~988 47~ 5 ~ 6~ 99 45 ~ a~462 34~ 5 ~6~ 971 50 ~ 5 UD.~ 09 47~ 5 u O~43, 34 ~7~013 51 u O,~09 48~5 ~ o~45 37 ~6.85 54.5 ~ o.~99 ~ u ~41~
38 ~6.831 55 ~ 6~89 51~ ~ 6~339 7~ 5 ~6~ 86 58 ~ 6.29 5~ ~ 6~ 4 ~8,5 ~6,795 57~5 u 6~374 u o~36 ~O~S ~6,767 58.5 u 6.425 4 ~ o~42 41 ~6,776 5 ~ o~466 ~O~S ~6.m 54~5 u O~39 42,5 ~6~74~ 55 ~ o,~19 44 ~6,712 57 ~ o.388 44,5 ~o.716 58 ~ o~394 44 uo ,714 57~ S ~~ ~382 46 ~o,681 58~5 ~ o~453 47~5 ~6.688 47 ~6.6~8 48 u6 693 50.5 ~6.657 51 u6~66 50,5 H6~641 52 ~6.68 54 u6.646 5~,5 u6~633 53~5 ~6.637 55,5 u~ ~672 57,5 ~o,644 58 ~o,636 57 uo~651 5~.5 ~o,676 60.5 ~o~64~
4 ~l7,807 12,5 "7.493 S,S ~ 7,722 13.5 "7,657 6 " 7.673 16,5 "7.273 7 ~ ~.627 17 "7,328 7,5 " 7,579 19 '~7,11a 9 " 7,46L 19,S "7,143 10,5 ~ 7.364 21.5 ~6,932 11 U7.313 22.5 "6.924 12 ~7,247 23 "6,ff1 13 H7,213 25 H6.817 ~3.5 ~i,156 25,5 ~6.84 ~4.5 ~7.123 2~,5 U6,741 15.5 ~7,057 32 ~6.599 ~6 "~,022 39 ~6.4a3 ~7 ~6.ff6 38,5 ~6.5 ~8 U6.892 ~2 ~6,486 19 ~6.846 ~2.5 ~6.519 ~6.~a9 ~5.5 ~6.~7~
)2 0 9~ ~5`0 .- - 41 -Continuation of Table 7 Example 4 Example 1 ~l-C~ ~ E ~l-C~ ~ ~ E
20.5 ~ 6.759 ~5 ~6.477 23 6.617 47,5 6.522 24.5 ~ 6.566 ~8. ~6.489 25.5 ~ 6.518 51. u6.536 26,5 ~ 6,5a6 54. u6.472 27,5 ~ 6.~91 57.5 ~6.542 28,5 ~ 6.452 58 u6.52 29.5 ~ 6.439 30,5 ~ 6.3~2 3t ~ 6.366 32 ~ 6.373 33 ~ 6.302 33. " 6~357 ~4, " 6.329 35, ~'6.,86 36,~ ~'6.~83 37 u o~96 38,5 ~' o.. 69 39 u ~,256 " o.137 41 ~ 6,23 42 " 6.24 42.5 " 6,232 43,5 " 6.181 44 ~ 6,262 " 6.215 46 " 6.17 ~6.5 ~ 6,158 .5 u ~.106 ~8.5 ~ 6.007 ~9,5 ~ 6,0 1 ~ 6.154 51 ~ 6. 7 5~ ~ ~.O~S
~3. ~ o.1 4 4, ~ o,l85 5,5 ~ 6,073 ~6,5 ~6.0183 57 ~ ~.132 58 ~6. ~ 05 59 ~ o,125 59.5 ~ o.142 60,5 ~o .202 20904~0 Table 8 Comparative Comparative Comparative Example 2 Example 3 Example 1 tC~ ~ E ~ ~-C~ ~ ~ E ~ ~-C~ ~ E
40.5 "9,237 -38 '~9.363 -38.5 '~9,~03 -~1.5 "9.26L -37,5 '~9.366 -38 '~9,40 -40 "9,28 -37 "9.37 -37.5 " 9,~1 -37.5 "9.223 36.5 "9.37 -37 ~ 9.40 -37 "9.241 36 "9.368 -36.5 " 9~408 -37.5 "9.257 35.5 "9.367 -36 " 9.406 -38 "9,267 -34 "9.3~1 -35 ~l9.403 -35 "9.24 -33 "9.334 -33.5 " 9.38~
-33,5 "9,22 -32.5 "9.333 -33 " 9.382 -33 "9.229 -32 "9.33 -32.5 " 9,382 -31 "9.203 -30.5 "9.312 -32 " 9.38 -30.5 "9.2 -28.5 "9.291 -31 ~ 9.376 -30 "9.199 -28 "9,29~ -29.5 " 9,355 -29.5 "9.203 -27.5 "9.289 -28.5 " 9.353 -27.5 "9,175 -27 "9,287 -28 '~9.35 -26.5 "9.157 -26 "9.264 -27.5 '~9.351 -26 "9.159 -25 "9.255 -26 " 9.327 -25,5 "9.158 -24,5 "9.251 -24.5 " 9.317 -23,5 "9.133 -23,5 "9.251 -24 " 9~317 -22,5 "9,116 -22 "9.~15 -23.S " 9.317 -22 "9.115 -21 "9.~ 07 -23 " 9.313 -21,5 "9.117 -20.5 "9.; 06 -22.5 " 9.313 -21 "9.117 -20 "9.202 -~1 " 9.279 19 "9.075 - 19 "9.1t6 -~0 " 9.274 -18,5 "9.071 -17.5 '~9.156 -19.5 " 9,273 -lt "9.071 .17 U9,155 -19 '~9.271 -17,5 "9.07 -16~5 "9,153 -18 " 9.256 -16 "9.0~7 -15 ~9.125 -16.5 "~.2, ~
-15 "~,989 -14 "9.1 16 " ~.2,2 .14,5 U9.02 -13.5 "9.099 -15. " 9.~2 -14 U9.02 -13 "9.096 -1~,~ " 9.2~7 .13,5 U9.02 11~5 -9.061 -1~ '~9.165 20904~0 ., Continuation of Table 8 Comparative Comparative Comparative Example 2 Example 3 Example 1 lcg E ~ 3 ~ T r~
-ll,S ~l8,967 11 '~9,0~8 -12~5 "9.162 ~ 8,961 -10.5 "9.045 12 "9,16 -lO S "8,96 9 ll9~007 1l.5 I~9~157 ~lO ~8,958 -8 ~8.99 -9~5 ~'9.085 -8~5 ~8~917 ~7 5 ~t~988 a.s ~9~081 7,5 ~'8,898 -7 ~'8~987 8 "9~08 ~7 "8,89~ ~5.5 "8.922 -7.5 "9,079 6 5 8 !896 5 8,917 6 8.998 -5 ~8~8L6 -~.5 ~8.918 -5 ~'8~982 -4 "8.83 -3,5 "8.91 -4. S "8.986 ~3.5 "8,798 -1~5 "8~822 -~ "8.985 ~3 "8,825 ~1 " 8.~ -2 "t~827 8.7~1 S ~ 8~t- -t~S ~'8~8~6 ~ S ~8.74~ 8,75, ~ 1 ~8.8&8 0 ~8.747 2 ~ 17 S ~'8,~03 1,5 ~8.708 2,5 ~ 25 1 ~8,761 3 "8 62 3 ".728 1.5 "8.768 3,5 "8,635 5 "8.531 2 "8.767 4 "8.6L3 6 "8,556 5 "8.573 6 "8,508 6,5 "1~577 7 ",~22 6.5 ~t.S01 7 ~.591 9 u.372 ~ ~8,52 ~ .597 12~5 u,097 7.5 ~~.524 10~ .266 16~5 ~~~757 ~~,2~5 1 ~ 41 19 ~7,359 10.5 ~~331 12.5 ~8,04 20 ~7~14 11 u.-63 14 ~,164 20. ~7,46 ~5 u~89 14~5 ~~209 23~ u7.15 12~5 ~~ 01 16~5 ~,~791 2 ~t.~O
14 ~.132 17 u7~98 23. ~7, 44 1~,5 ~~.165 17.5 ~t~02- 26 ~o,~O9 14 ~~,196 20~5 u7.67 26,5 ~a.989 16 ~ 67 21 ~7~06 28 ~o,911 17.5 ~~,908 23~5 ~7~76 29.5 ~6.~44 Continuation of Table 8 Comparative Comparative Comparative Example 2 Example 3 Example 1 T l-C~ ~ l~ E ~ ~-C~ ~ l~ E ~ ~-C~ ~ l~ E
~8 ~7~954 ;4 ~ 7~534 29 ~ 6.~71 8.5 ~o,016 ;6 ~ ~,256 31.5 ~ 6.685 2~ 6~6 ~7 ~ 7,229 32~5 ~ 6~698 21~5 u7,722 ~6,5 ~ 7,289 32 ~ 6~733 21 ~7~774 ~7~5 ~ ~297 34~5 ~ 6~391 23~ 5 ~?~8a 30, S ~ 7~011 35 ~ 6~604 24~5 ~7~452 30 ~ ?~072 35~5 ~ 6~58 ~?~498 30,5 ~ 7~102 38 ~ 6~464 24~5 ~ 541 33~5 ~ 6~79 38~5 ~ ~SS4 26~5 ~7~363 3~ ~ 6~28 8 ~ o~S41 27~ 5 ~7~273 33.5 ~ o~73 40,5 ~o ~46~
28 u7~312 ~4 ~ o.~97 ~1~5 ~ o~69 28~5 u7~313 ~6 ~ ~712 ~1 ~ o~502 30 ~ 5 u7.081 ,7 ~o j 674 43 ~ 6~497 31 ~7~115 36~5 u O~71 ~5 ~ 6~449 30~5 ~7~162 39 ~ o~59 44.5 ~ 6~432 33 ~6~988 47~ 5 ~ 6~ 99 45 ~ a~462 34~ 5 ~6~ 971 50 ~ 5 UD.~ 09 47~ 5 u O~43, 34 ~7~013 51 u O,~09 48~5 ~ o~45 37 ~6.85 54.5 ~ o.~99 ~ u ~41~
38 ~6.831 55 ~ 6~89 51~ ~ 6~339 7~ 5 ~6~ 86 58 ~ 6.29 5~ ~ 6~ 4 ~8,5 ~6,795 57~5 u 6~374 u o~36 ~O~S ~6,767 58.5 u 6.425 4 ~ o~42 41 ~6,776 5 ~ o~466 ~O~S ~6.m 54~5 u O~39 42,5 ~6~74~ 55 ~ o,~19 44 ~6,712 57 ~ o.388 44,5 ~o.716 58 ~ o~394 44 uo ,714 57~ S ~~ ~382 46 ~o,681 58~5 ~ o~453 47~5 ~6.688 47 ~6.6~8 48 u6 693 50.5 ~6.657 51 u6~66 50,5 H6~641 52 ~6.68 54 u6.646 5~,5 u6~633 53~5 ~6.637 55,5 u~ ~672 57,5 ~o,644 58 ~o,636 57 uo~651 5~.5 ~o,676 60.5 ~o~64~
Claims (16)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A radiation-curable oligomer having several ethylenically unsaturated end groups and several urethane or urea groups per molecule, which oligomer can be prepared from a) at least one hydroxy- or aminofunctional compound having a functionality between 3 and 4 and a number-average molecular weight of more than 750 to 4000, polyester polyols being excepted, b) at least one compound having 2 hydroxyl or amino groups per molecule and a number-average molecular weight between 200 and 4000, polyesterdiols being excepted, c) at least one monoethylenically unsaturated compound having a group containing one active hydrogen atom per molecule and having a number-average molecular weight between 116 and 1000, and d) at least one aliphatic or cycloaliphatic diisocyanate, which comprises using components a to d in amounts such that 1) the molar ratio of component a to component b is between 0.1 : 1 and 1.1 : 1, 2) the molar ratio of component c to component a is between 2 : 1 and 10 : 1, and 3) the equivalent ratio of the isocyanate groups of component d to the hydroxyl or amino groups of the sum of components a to c is between 0.9 and 1Ø
2. A radiation-curable oligomer as claimed in claim 1, wherein a compound having a functionality of 3 has been used as component a.
3. A radiation-curable oligomer as claimed in claim 1 wherein compounds having a number-average molecular weight of more than 750 to 2000 have been used as component a or compounds having a number-average molecular weight between 600 and 2000 as component b or compounds having a number-average molecular weight between 116 and 400 as component c.
4. A radiation-curable oligomer as claimed in claim 1 wherein components a to d have been used in amounts such that 1) the molar ratio of component a to component b is between 0.1 and 0.8 or 2) the molar ratio of component c to component a is between 2.5 and 10.
5. A radiation-curable oligomer as claimed in claim 4, wherein the oligomer has an acrylic group content of 0.45 to 0.63 mol/kg.
6. A radiation-curable oligomer as claimed in claim 1 wherein an ethoxylated triol having a number-average molecular weight of > 1000 has been used as component a.
7. A radiation-curable oligomer as claimed in claim 1 wherein a mixture comprising b1) 0 to 90 mol % of a polyetherdiol and b2) 100 to 10 mol % of a modified polyetherdiol composed of b21) at least one polyetherdiol b22) at least one aliphatic or cycloaliphatic dicarboxylic acid and b23) at least one aliphatic, saturated compound having epoxy group and 8 to 21 C atoms per molecule, in which the sum of the amounts of components b1 and b2 and the sum of the amounts of components b21 to b23 is in each case 100 mol %.
8. A radiation curable oligomer as claimed in claim 7 wherein said mixture of b1 and b2 is used as component b.
9. A radiation-curable oligomer as claimed in any one of claims 1 to 8, which has been prepared by 1) carrying out the polyaddition reaction of components a to d up to a conversion of more than 85 % of the NCO groups, in which components a to d have been used in amounts such that the equivalent ratio of the isocyanate groups of component a to the hydroxyl or amino groups of components a to c is 1:1 and 2) the polyaddition reaction of components a to d has been continued with addition of more of component c up to a conversion of more than 99 % of the NCO groups.
10. A radiation-curable coating composition, which contains at least one radiation-curable oligomer as claimed in any one of claims 1 to 8.
11. A buffer coating of an optical glass fibre comprising a radiation-curable coating composition which contains A) 10 to 78 % of at least one radiation-curable oligomer as claimed in any one of claims 1 to 7, B) 0 to 60 % by weight of at least one further ethylenically unsaturated oligomer, C) 20 to 50 % by weight of at least one ethylenically unsaturated monomeric or oligomeric compound, D) 2 to 8 % by weight of at least one photoinitiator and E) 0 to 4 % by weight of an auxiliary or additive, the % by weight given being in each case relative to the total weight of the coating composition.
12. A radiation-curable coating composition which contains A) at least 15 % of at least one radiation-curable oligomer as claimed in one of claims 1 to 7, B) 0 to 50 % by weight of at least one further ethylenically unsaturated oligomer, C) 23 to 35 % by weight of at least one ethylenically unsaturated monomeric or oligomeric compound, D) 3 to 5 % by weight of at least one photoinitiator and E) 0.5 to 2.0 % by weight of an auxiliary or additive, the % by weight given being in each case relative to the total weight of the coating composition.
13. A radiation-curable coating composition as claimed in claim 12 which contains a further ethylenically unsaturated polyurethane as component b.
14. A buffer coating of an optical fibre according to claim 11 which contains a further ethylenically unsaturated polyurethane as component b.
15. A process for the coating of a glass surface, in which 1) applying a radiation-curable primer to said glass surface and curing said primer by means of UV or electron radiation and 2) applying a radiation-curable top coat to said glass surface and curing said top coat by means of UV or electron radiation, which comprises using a radiation-curable coating composition as claimed in claim 10 as primer or topcoat.
16. An optic glass fibre coated with a radiation-curable coating composition as claimed in claim 10.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4027770A DE4027770A1 (en) | 1990-09-01 | 1990-09-01 | LIQUID, RADIANT-COVERABLE COATING MEASUREMENT FOR THE COATING OF GLASS SURFACES |
| DEP4027770.4 | 1990-09-01 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2090450A1 CA2090450A1 (en) | 1992-03-02 |
| CA2090450C true CA2090450C (en) | 1996-07-02 |
Family
ID=6413412
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002090450A Expired - Fee Related CA2090450C (en) | 1990-09-01 | 1991-08-08 | Photo-hardened liquid coating composition for glass surfaces |
Country Status (18)
| Country | Link |
|---|---|
| EP (1) | EP0545969B1 (en) |
| JP (1) | JP2509409B2 (en) |
| KR (1) | KR930702411A (en) |
| AT (1) | ATE115598T1 (en) |
| AU (1) | AU648099B2 (en) |
| BG (1) | BG60917B1 (en) |
| BR (1) | BR9106811A (en) |
| CA (1) | CA2090450C (en) |
| DE (2) | DE4027770A1 (en) |
| DK (1) | DK0545969T3 (en) |
| ES (1) | ES2068603T3 (en) |
| FI (1) | FI930851A (en) |
| LT (1) | LT3332B (en) |
| LV (1) | LV10463B (en) |
| MD (1) | MD940197A (en) |
| NO (1) | NO930689L (en) |
| WO (1) | WO1992004391A1 (en) |
| YU (1) | YU47699B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4302327A1 (en) * | 1993-01-28 | 1994-08-04 | Basf Lacke & Farben | Radiation-curable oligomers as well as liquid, radiation-curable coating mass for the coating of glass surfaces |
| DE19715382C1 (en) * | 1997-04-14 | 1998-11-19 | Synthopol Chemie Dr Koch | Water-dispersed, radiation-curable polyurethanes |
| CN100573205C (en) | 2002-04-24 | 2009-12-23 | 普雷斯曼电缆及系统能源有限公司 | Can control the optical fiber of the attenuation losses of little Qu Yinqi |
| WO2003091346A1 (en) | 2002-04-24 | 2003-11-06 | Dsm Ip Assets B.V. | Radiation curable coating composition for optical fiber with reduced attenuation loss |
| DE60223597T2 (en) | 2002-04-24 | 2008-11-13 | Prysmian Cavi E Sistemi Energia S.R.L. | OPTICAL FIBER WITH REDUCED DAMPING LOSSES |
| EP3802453A1 (en) * | 2018-06-01 | 2021-04-14 | DSM IP Assets B.V. | Radiation curable compositions for coating optical fiber and the coatings produced therefrom |
| US11530163B2 (en) * | 2019-07-31 | 2022-12-20 | Covestro (Netherlands) B.V. | Radiation curable compositions with multi-functional long-armed oligomers for coating optical fibers |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4121089A (en) | 1977-07-29 | 1978-10-17 | International Business Machines Corporation | Apparatus for the reversal of a hot roll in a fusing assembly |
| US4131602A (en) * | 1977-09-29 | 1978-12-26 | Union Carbide Corporation | Radiation curable acrylated polyurethane |
| JPS5940102B2 (en) | 1978-11-17 | 1984-09-28 | 日本クラウンコルク株式会社 | Peelable adhesive structure |
| US4607084A (en) * | 1984-06-11 | 1986-08-19 | Celanese Specialty Resins, Inc. | Radiation curable acrylated polyurethane oligomer compositions |
| NL8401981A (en) | 1984-06-22 | 1986-01-16 | Philips Nv | OPTICAL GLASS FIBER PROVIDED WITH A PLASTIC COATING AND METHOD FOR THE MANUFACTURE THEREOF. |
| DE3613082A1 (en) * | 1985-05-07 | 1986-11-13 | Hüls AG, 45772 Marl | ADHESIVE ADHESIVES ON THE BASIS OF RADIANT, POLYESTERS CONTAINING (METH) ACRYLIC GROUPS |
| US4609718A (en) | 1985-05-08 | 1986-09-02 | Desoto, Inc. | Ultraviolet curable buffer coatings for optical glass fiber based on long chain oxyalkylene diamines |
| US4608409A (en) | 1985-05-08 | 1986-08-26 | Desoto, Inc. | Polyacrylated oligomers in ultraviolet curable optical fiber coatings |
| US4690502A (en) | 1985-07-08 | 1987-09-01 | Desoto, Inc. | Ultraviolet curable optical glass fiber coatings from acrylate terminated, end-branched polyurethane polyurea oligomers |
| US4806574A (en) * | 1985-07-22 | 1989-02-21 | Desoto, Inc. | Ultraviolet curable coatings for optical glass fiber based on a polyfunctional core |
| CA1292752C (en) * | 1985-10-29 | 1991-12-03 | John M. Zimmerman | Ultraviolet curable coatings for optical glass fiber |
| US4782129A (en) * | 1988-01-04 | 1988-11-01 | Desoto, Inc. | Acrylated polyurethanes based on polyoxytetramethylene glycol chain extended with substituted diacids |
-
1990
- 1990-09-01 DE DE4027770A patent/DE4027770A1/en not_active Withdrawn
-
1991
- 1991-08-08 AT AT91914598T patent/ATE115598T1/en not_active IP Right Cessation
- 1991-08-08 BR BR919106811A patent/BR9106811A/en not_active Application Discontinuation
- 1991-08-08 CA CA002090450A patent/CA2090450C/en not_active Expired - Fee Related
- 1991-08-08 DE DE59103926T patent/DE59103926D1/en not_active Expired - Fee Related
- 1991-08-08 EP EP91914598A patent/EP0545969B1/en not_active Expired - Lifetime
- 1991-08-08 KR KR1019930700632A patent/KR930702411A/en not_active Application Discontinuation
- 1991-08-08 WO PCT/EP1991/001501 patent/WO1992004391A1/en active IP Right Grant
- 1991-08-08 DK DK91914598.7T patent/DK0545969T3/en active
- 1991-08-08 ES ES91914598T patent/ES2068603T3/en not_active Expired - Lifetime
- 1991-08-08 AU AU83314/91A patent/AU648099B2/en not_active Ceased
- 1991-08-08 JP JP3513482A patent/JP2509409B2/en not_active Expired - Lifetime
- 1991-08-30 YU YU146191A patent/YU47699B/en unknown
-
1993
- 1993-02-25 BG BG97481A patent/BG60917B1/en unknown
- 1993-02-25 FI FI930851A patent/FI930851A/en not_active Application Discontinuation
- 1993-02-26 NO NO93930689A patent/NO930689L/en unknown
- 1993-05-06 LT LTIP531A patent/LT3332B/en not_active IP Right Cessation
- 1993-05-27 LV LVP-93-428A patent/LV10463B/en unknown
-
1994
- 1994-07-14 MD MD94-0197A patent/MD940197A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| YU47699B (en) | 1996-01-08 |
| KR930702411A (en) | 1993-09-09 |
| EP0545969B1 (en) | 1994-12-14 |
| FI930851A0 (en) | 1993-02-25 |
| AU8331491A (en) | 1992-03-30 |
| DE4027770A1 (en) | 1992-03-05 |
| JPH06502435A (en) | 1994-03-17 |
| ATE115598T1 (en) | 1994-12-15 |
| BG97481A (en) | 1994-03-24 |
| BR9106811A (en) | 1993-08-24 |
| LV10463A (en) | 1995-02-20 |
| JP2509409B2 (en) | 1996-06-19 |
| LT3332B (en) | 1995-07-25 |
| LV10463B (en) | 1996-04-20 |
| FI930851A (en) | 1993-02-25 |
| AU648099B2 (en) | 1994-04-14 |
| WO1992004391A1 (en) | 1992-03-19 |
| MD940197A (en) | 1996-01-31 |
| DK0545969T3 (en) | 1995-04-18 |
| DE59103926D1 (en) | 1995-01-26 |
| CA2090450A1 (en) | 1992-03-02 |
| LTIP531A (en) | 1994-11-25 |
| NO930689D0 (en) | 1993-02-26 |
| YU146191A (en) | 1994-06-10 |
| BG60917B1 (en) | 1996-06-28 |
| NO930689L (en) | 1993-02-26 |
| ES2068603T3 (en) | 1995-04-16 |
| EP0545969A1 (en) | 1993-06-16 |
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Legal Events
| Date | Code | Title | Description |
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| EEER | Examination request | ||
| MKLA | Lapsed |