WO1992004391A1 - Flüssige, strahlenhärtbare überzugsmasse für die beschichtung von glasoberflächen - Google Patents
Flüssige, strahlenhärtbare überzugsmasse für die beschichtung von glasoberflächen Download PDFInfo
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- WO1992004391A1 WO1992004391A1 PCT/EP1991/001501 EP9101501W WO9204391A1 WO 1992004391 A1 WO1992004391 A1 WO 1992004391A1 EP 9101501 W EP9101501 W EP 9101501W WO 9204391 A1 WO9204391 A1 WO 9204391A1
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Classifications
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- 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
- 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
- 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
Definitions
- Liquid, radiation-curable coating compound for coating glass surfaces Liquid, radiation-curable coating compound for coating glass surfaces
- the present invention relates to radiation-curable oligomers with several ethylenically unsaturated end groups and several urethane and / or urea groups per molecule, which can be prepared from a) at least one hydroxyl and / or amino functional compound with a functionality between 3 and 4 and with a number average molecular weight between 500 and 4000,
- the present invention also relates to radiation-curable coating compositions which contain these radiation-curable oligomers, and to processes for coating glass surfaces, in particular optical glass fibers, in which these coating compositions comprise be set.
- Optical glass fibers have become increasingly important in the field of communication as optical fibers. For this application, it is absolutely necessary to protect the glass surface from moisture and wear and tear.
- the glass fibers are therefore provided with at least one protective lacquer layer immediately after their manufacture.
- EP-B-114 982 it is known from EP-B-114 982 to first provide glass fibers with an elastic, but not very hard and not very tough buffer layer (primer) and then to apply a radiation-curable top coat which has a high hardness and toughness.
- the two-layer structure is intended to provide good protection for the glass fibers against mechanical stress, even at depth
- radiation-hardenable coating compositions 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, a bisphenol and a monoethylenically unsaturated monomer can be used as the topcoat, the glass transition temperature of the homopolymer produced from this monomer being above 55 ° C.
- radiation-curable coating compositions for coating optical glass fibers are also known from EP-A-223 086. These coating compositions contain radiation-hardenable oligomers as binders according to the preamble of the main claim. These radiation-curable coating compositions described in EP-A-223 086 are used either as a topcoat or as a one-coat coating. However, they are not suitable as a primer due to the too high modulus of elasticity of the hardened coatings.
- Radiation-curable coating compositions for the coating of optical glass fibers are also in the
- These coatings contain a polyurethane oligomer with acrylate end groups, which is based on a polyfunctional core. These coating compositions can be used both as a primer and as a top coat. Single-layer processing is also possible.
- EP-A-208 845, EP-A-167 199, EP-A-204 161, EP-A-204 160 and EP-A-250 631 radiation-hardenable coating compositions for the coating of optical glass fibers known as binders contain linear urethane acrylates.
- the present invention is based on the object of providing radiation-hardenable coating compositions for the coating of glass surfaces, in particular of optical glass fibers, which lead to coatings with improved properties in comparison with the known coating compositions.
- the cured coatings should have an improved aging behavior and thus have an increased long-term stability of the coated glass fiber.
- the cured coatings should show improved behavior in the absorption and desorption of water. This is particularly important for the optical attenuation of the coated fiber.
- the cured coatings should have a good buffering effect even at low temperatures.
- the mechanical properties of the coating should deteriorate as little as possible as the temperature drops.
- the modulus of elasticity should only increase as little as possible as the temperature drops.
- the coating materials should harden as quickly as possible.
- the resulting coatings should also show as little hydrogen evolution as possible during storage or aging and have good adhesion to the glass surface.
- the object is surprisingly achieved by radiation-curable oligomers with several ethylenically unsaturated end groups and several urethane and / or urea groups per molecule, which can be prepared from a) at least one hydroxyl and / or amino functional compound with a functionality between 3 and 4 and with a number-average Molecular weight between 500 and 4000, b) at least one compound with 2 hydroxyl and / or amino groups per molecule and with a number average molecular weight between 200 and 4000, c) at least one monoethylenically unsaturated Connect to a group with an active
- 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,
- the molar ratio of component c to component a is between 2.0: 1 and 10: 1, preferably between 2.5 and 10 and
- 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 1.0.
- the present invention also relates to radiation-curable coating compositions which contain these radiation-curable oligomers, and to processes for coating glass surfaces, in particular optical glass fibers, in which these coating compositions are used.
- Glass fibers coated with coating compositions have increased long-term stability.
- the coatings produced from the coating compositions according to the invention show improved behavior in the absorption and desorption of water compared to conventional coatings.
- the good buffering effect of the coatings is also advantageous, even at low temperatures, since this solves the problem of so-called microbends.
- the coatings according to the invention are distinguished by good mechanical properties, such as e.g. tensile strength and elongation adapted to the application, as well as low hydrogen evolution during storage and aging.
- Component a for the preparation of the oligomers are hydroxyl- and / or amino-functional compounds with a functionality of 3 to 4, preferably 3. These compounds have number average molecular weights from 500 to 4000, preferably from 750 to 2000.
- suitable compounds are polyoxyalkylated triols, such as. B. ethoxylated and propoxylated triols, preferably ethoxylated triols, particularly preferably with a number average molecular weight greater than or equal to 1000.
- triols for example, glycerol or trimethylolpropane are used.
- the amino-functional compounds can contain both primary and secondary amino groups.
- compounds are also suitable which contain both amino and hydroxyl groups.
- Compounds which contain two hydroxyl and / or amino groups per molecule are suitable as component b. These compounds have number average molecular weights of 200 to 4000, preferably 600 to 2000.
- suitable compounds b are polyoxyalkylene glycols and polyoxyalkylene diamines, alkylene groups having 1 to 6 carbon atoms being preferred.
- polyoxypropylene glycols with the corresponding molecular weights and polytetramethylene glycols are suitable.
- Polyethoxylated and polypropoxylated diols can also be used, such as. B. the ethoxylated or propoxylated
- polyester diols can also be used polyester diols, the z. B. can be produced by reaction of the glycols already mentioned with dicarboxylic acids, preferably aliphatic and / or cycloaliphatic dicarboxylic acids, such as, for example, hexahydrophthalic acid, adipic acid, azelaic, sebacic and glutaric acid and / or their alkyl substituted derivatives.
- dicarboxylic acids preferably aliphatic and / or cycloaliphatic dicarboxylic acids, such as, for example, hexahydrophthalic acid, adipic acid, azelaic, sebacic and glutaric acid and / or their alkyl substituted derivatives.
- dicarboxylic acids preferably aliphatic and / or cycloaliphatic dicarboxylic acids, such as, for example, hexahydrophthalic acid, adipic acid, azelaic, sebac
- Polycaprolactone diols can also be used.
- Products are obtained, for example, by reacting an ⁇ -caprolactone with a diol. Such products are described in U.S. Patent 3,169,945.
- polylactone diols which are obtained by this reaction are distinguished by the presence of a terminal hydroxyl group and by recurring polyester components which are derived from the lactone. These recurring molecular parts can be of the formula
- n is preferably 4 to 6 and the substituent is hydrogen, an alkyl radical, a cycloalkyl radical or an alkoxy radical, where no substituent contains more than 12 carbon atoms and the total number of carbon atoms of the substituents in the lactone ring does not exceed 12.
- the lactone used as the starting material can be any lactone or any combination of lactones, which lactone should contain at least 6 carbon atoms in the ring, for example 6 to 8 carbon atoms and where there should be at least 2 hydrogen substituents on the carbon atom.
- the lactone used as the starting material can be represented by the following general formula: in which n and R have the meaning already given.
- the lactones preferred for the preparation of the polyester diols in the invention are the caprolactones, in which n has the value 4.
- the most preferred lactone is the substituted ⁇ -caprolactone, where n is 4 and all of the R substituents are hydrogen. This lactone is particularly preferred because it is available in large quantities and gives coatings with excellent properties.
- various other lactones can be used individually or in combination. Examples of aliphatic diols suitable for the reaction with the lactone are the diols already listed above for the reaction with the carboxylic acids.
- Suitable compounds are those under the name JEFFAMIL ® D 230, D 400, D 2000, D 4000,
- component b is a mixture of b 1 ) 0 to 90 mol% of at least one polyether diol and
- components b 21 to b 23 are used in amounts such that
- Equivalent ratio of the OH groups of component b 21 to the carboxyl groups of component b 22 is between 0.45 and 0.55, preferably 0.5, and that the equivalent ratio of the epoxy groups of component b 23 to the carboxyl groups of component b 22 is between 0 , 45 and 0.55, preferably 0.5.
- polyether diols b 1 and b 21 examples are the polyoxyalkylene glycols already listed, the alkylene groups having 1 to 6 carbon atoms.
- Component b 1 is preferably polyoxypropylene glycols with a number average molecular weight between 600 and 2000.
- Component b 22 is preferably aliphatic and cycloaliphatic dicarboxylic acids having 8 to 36 carbon atoms per molecule, such as. B. hexahydrophthalic acid.
- Suitable as component b 23 are, for example, epoxidized vinylcyclohexane compounds, epoxidized, monoolefinically unsaturated fatty acids and / or polybutadienes.
- Preferred as component b 23 are glycidyl esters of branched monocarboxylic acids, such as. B. the glycidyl ester of versatic acid used.
- monoethylenically unsaturated compounds having a group with an active hydrogen atom and having a number-average molecular weight of 116 to 1000, preferably 116 to 400, are used.
- suitable components c.
- Adducts of caprolactone and one of the above-mentioned hydroxyalkyl esters of ethylenically unsaturated carboxylic acids are also suitable as component c.
- Adducts of the hydroxyalkyl esters of acrylic acid with a number average molecular weight of 300 to 1000 are preferably used.
- Suitable for the preparation of the oligomers according to the invention as component d are aliphatic and / or cycloaliphatic diisocyanates, such as, for. B. 1,3-cyclopentane, 1,4-cyclohexane, 1,2-cyclohexane diisocyanate, 4, 4 '-methylene-bis- (cyclohexyl isocyanate) and isophorondiisoeyanate, trimethylene, tetramethylene, pentamethylene -, Hexamethylene and trimethylhexamethylene-1, 6-diisocyanate and those described in EP-A-204 161, column 4, lines 42 to 49, from Dimer fatty acid-derived diisocyanates.
- Isophorone diisocyanate and trimethylhexamethylene -1,6-diisocyanate are preferably used.
- 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
- 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 1.0.
- the oligomers according to the invention can be prepared in different ways. For example, it is possible first to react the diisocyanate d with the chain extenders a and b and then to react the remaining free isocyanate groups with the ethylenically unsaturated compound c.
- oligomers by first reacting some of the isocyanate groups of component d with the ethylenically unsaturated compound c and then subsequently reacting the remaining free isocyanate groups with chain extenders a and b. It is also possible to prepare the polyurethane oligomers by the processes described in EP-A-223 086 on page 5.
- the polyurethane oligomers are preferably produced by means of a two-stage process in which the stoichiometric polyaddition of components a to d is carried out until more than 85% of the NCO groups of component d have reacted.
- components a to d are used in amounts such that the equivalent ratio of the NCO groups of component d to the active hydrogen atoms of components a to c is 1: 1.
- a second process step the rest of the remaining components (corresponding to the desired NGO: OH ratio) are then added and the reaction is continued until the NCO groups have converted> 99%.
- further component c is preferably added and the desired NCO: OH equivalent ratio is set by adding this component c.
- the urethane oligomers according to the invention usually have number average molecular weights of
- the oligomers according to the invention are used as film-forming component A in radiation-curable coating compositions.
- the coating compositions usually contain 10 to 78% by weight, preferably 15 to 75% by weight and particularly preferably 63 to 73% by weight, based in each case on the total weight of the coating composition, of these oligomers according to the invention.
- the coating compositions can contain 0 to 60% by weight, preferably 0 to 50% by weight, based in each case on the total weight of the coating composition, of at least one further ethylenically unsaturated oligomer B.
- unsaturated polyesters polyester acrylates and acrylate copolymers
- urethane acrylate oligomers in particular are used, with the exception of the urethane acrylate oligomers used as component A.
- the type and amount of this component B can be used to control the properties of the cured coating in a targeted manner. The higher the proportion of this component B, the higher the modulus of elasticity of the cured coating in general.
- Component B is therefore added to the coating compositions especially when the coating compositions are used as a topcoat.
- the influence of this component B on the properties of the resulting coating is known to the person skilled in the art. The cheapest amount can be easily determined using a few routine tests.
- ethylenically unsaturated polyurethanes used as component B are known. They can be obtained by reacting a di- or polyisocyanate with a chain extender from the group of the diols / polyols and / or diamines / polyamines and then reacting the remaining free isocyanate groups with at least one Hy hydroxyalkyl acrylate or hydroxyalkyl esters of other ethylenically unsaturated carboxylic acids.
- the amounts of chain extender, di- or polyisocyanate and hydroxyalkyl ester of an ethylenically unsaturated carboxylic acid are chosen so that
- the equivalent ratio of the NCO groups to the reactive groups of the chain extender is between 3: 1 and 1: 2, preferably 2: 1, and
- the OH groups of the hydroxyalkyl esters of the ethylenically unsaturated carboxylic acids are present in a stoichiometric amount in relation to the isocyanate groups of the prepolymer that is still free of isocyanate and chain extender.
- the polyurethanes B by first reacting some of the isocyanate groups of a di- or polyisocyanate with at least one hydroxyalkyl ester of an ethylenically unsaturated carboxylic acid and then reacting the remaining isocyanate groups with a chain extender. In this case too, the amounts of chain extender, isocyanate and hydroxyalkyl ester become more unsaturated
- Carboxylic acids selected so that the equivalent ratio of the NCO groups to the reactive group of the chain extender 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 is.
- part of the isocyanate groups of a diisocyanate can first be reacted with a diol, then another part of the isocyanate groups with the hydroxyalkyl ester of an ethylenically unsaturated carboxylic acid and then the remaining isocyanate groups can be reacted with a diamine.
- EP-A-204 161 EP-A-204 161 and therefore do not require a more detailed description.
- aromatic components are preferably used to produce the urethane acrylate oligomers B.
- 2,4- and 2,6-tolylene diisocyanate are particularly preferably used as the isocyanate component and aromatic polyester polyols based on phthalic acid and isophthalic acid and / or polypropylene glycol, ethylene glycol and diethylene glycol as chain extenders.
- the radiation-curable coating compositions also contain at least one ethylenically unsaturated monomeric and / or oligomeric compound C, usually in an amount of from 20 to 50% by weight, preferably from 23 to 35% by weight, in each case based on the total weight of the coating composition.
- this ethylenically unsaturated compound C controls the viscosity and the rate of curing of the coating compositions and the mechanical properties of the resulting coating, as is known to the person skilled in the art and is described, for example, in EP-A-223 086 and to which reference is made for further details becomes.
- Examples of monomers that can be used include ethoxyethoxyethyl acrylate, N-vinylpyrrolidone, phenoxyethyl acrylate, dimethylaminoethyl acrylate, hydroxyethyl acrylate, butoxyethyl acrylate, isobornyl acrylate, dimethylacrylamide and dicyclopentyl acrylate.
- Di- and polyacrylates such as, for. B.
- the two acrylate groups can by a polyoxibutylene be separated. It is also possible to use 1,12-dodecyl diacrylate and the reaction product of 2 moles of acrylic acid * with one mole of a dimer fatty alcohol, which generally has 36 carbon atoms.
- Phenoxyethyl acrylate, hexanediol diacrylate, N-vinylpyrrolidone and tripropylene glycol diacrylate are preferably used.
- the in the coating compositions according to the invention usually in an amount of 2 to 8 wt .-% before Adds 3 to 5% by weight, based on the total weight of the coating composition, of the photoinitiator used varies with the radiation used to harden the coating compositions (UV radiation, electron beams, visible light).
- the coating compositions according to the invention are preferably cured by means of UV radiation.
- ketone-based photoinitiators are usually used, for example acetophenone, benzophenone, diethoxiacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, hydroxypropylphenyl ketone, m-chloroacetophenone, propiophenone, benzoin, benzil, benzildimethonone ketal, anthrachachone and thioxanthone derivatives and triphenylphosphine and the like. ⁇ . and mixtures of various photoinitiators.
- the coating compositions may also contain 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 based on the total weight of the coating composition. Examples of such substances are leveling agents, plasticizers and, in particular, adhesion promoters.
- Alkoxisilanes such as N- ⁇ -aminoethyl- ⁇ -aminopropyltrimethoxisilane, ⁇ -aminopropyltrimethoxisilane, N-methyl- ⁇ -aminopropyltrimethoxisilane or triamine-modified propyltrimethoxisilane (e.g. adhesion promoter
- the coating compositions can by means of known application methods, such as. B. spraying, rolling, flooding, dipping, knife coating or brushing, are applied to the substrate.
- the coating films are cured by means of radiation, preferably by means of UV radiation.
- the facilities and conditions for these curing methods are known from the literature (see, for example, R. Holmes, UV and EB Curing Formulations for Printing Inks, Coatings and Paints, SITA Technology, Academic Press, London, United Kindom 1984) and do not require any further description .
- the coating compositions are suitable for coating various substrates, for example glass, wood, metal and plastic surfaces.
- they are used for coating glass surfaces, particularly preferably optical glass fibers.
- the present invention therefore also relates to a method for coating a glass surface, in which a radiation-curable coating composition is applied and cured by means of UV or electron radiation, which is characterized in that the coating compositions according to the invention are used as radiation-curable coating compositions.
- the method according to the invention is particularly well suited for the coating of optical glass fibers.
- the coating compositions according to the invention can be applied to the glass fibers as a primer and / or topcoat for a two-coat finish.
- the cured coatings When the coating compositions are used as a primer, the cured coatings usually have a modulus of elasticity (at 2.5% elongation and room temperature) of less than 10 MPa.
- the cured coatings When using the coating compound as a top coat the cured coatings usually have a modulus of elasticity (at 2.5% elongation and room temperature) of 500 to 1000 MPa.
- chromium octoate based on the weight of the mixture of poly-THF, hexahydrophthalic acid and glycidyl ester of versatic acid and 29.7 parts of the glycidyl ester of versatic acid with an epoxide equivalent weight of 266, are added.
- the mixture is heated to 120 ° C. until the reaction product has an epoxide equivalent weight> 20,000, an acid number of 4 mg KOH / g and an OH number of 60 mg KOH / g.
- the viscosity of an 80% solution in butyl acetate is 3.8 d Pas (measured at 23 ° C with the plate / cone viscometer).
- Solids content of the oligomer obtained 1 in Phenoxyethyl acrylate has a viscosity of 4.9 dPas (measured at 23 ° C with the plate and cone viscometer).
- the irradiated dose is 0.08 J / cm 2 (measured with the dosimeter, UVICURE, System EIT from Eltosch).
- Table 2 shows the results of the measurement of the modulus of elasticity (2.5% elongation) after different aging of the cured coatings.
- the oligomer 2 thus obtained has a double bond content of 1.01 mol / kg and a functionality of 2.0.
- a 50% solution (based on the theoretical solids content) of the oligomer 2 obtained in phenoxyethyl acrylate has a viscosity of 10 dPas (measured at 23 ° C. with the plate-cone viscometer).
- Example 2 Analogously to Example 1, 78.1 parts of the 90% solution of urethane oligomer 2 described above, 12.1 parts of phenoxyethyl acrylate, 6.2 parts of N-vinyl-pyrrolidone, 1.6 parts of N- ⁇ -aminoethyl- ⁇ -aminopropyltrimethoxisilan and 2.0 parts of diethoxiacetophenone by mixing a radiation-curable coating mass 2.
- This coating composition 2 is applied and the hardened coating is tested in the same way as in Example 1. The results are shown in Table 2 and in Figures 3 and 4.
- 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 N-vinylpyrrolidone, 1.5 parts of N- ⁇ -aminoethyl-ox-aminopropyltrimethoxisilane and 2.0 parts of diethoxiacetophenone .
- the chemical properties are shown in Table 4.
- the irradiated dose is 0.08 J / cm 2 (measured with the dosimeter, UVICURE, System EIT from Eltosch).
- Phenothiazine 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 kept at 60 ° C. until an NCO content of ⁇ 0.1% is reached.
- polyurethane acrylate oligomers were produced from the components listed in Table 3.
- urethane acrylate oligomers were analogous to Example 2 radiation-curable coating compositions prepared. The application, curing and testing of the coatings was also carried out analogously to Example 2.
- P 600 polyoxypropylene glycol with a number average molecular weight of 600 mod.
- PE modified polyether diol eth.
- TMP7 ethoxylated trimethylolpropane with 7
- IPDI isophorone diisocyanate
- DBC concentration of the acrylic groups in mol / kg in the coating agent
- DBC (oligomer) concentration of the acrylic groups in mol / kg in the oligomer
- C C - R: ratio of the acrylic groups in the coating agent determined
Landscapes
- 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)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (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)
- Medicines Containing Antibodies Or Antigens For Use As Internal Diagnostic Agents (AREA)
- Medicinal Preparation (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Glass Compositions (AREA)
Abstract
Description
Claims
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR919106811A BR9106811A (pt) | 1990-09-01 | 1991-08-08 | Massa de revestimento liquida,endurecivel por radiacao para o revestimento de superficies de vidro |
DE59103926T DE59103926D1 (de) | 1990-09-01 | 1991-08-08 | Flüssige, strahlenhärtbare überzugsmasse für die beschichtung von glasoberflächen. |
KR1019930700632A KR930702411A (ko) | 1990-09-01 | 1991-08-08 | 유리 표면용 광-경화성 액체 피복 조성물 |
AU83314/91A AU648099B2 (en) | 1990-09-01 | 1991-08-08 | Photo-hardened liquid coating composition for glass surfaces |
EP91914598A EP0545969B1 (de) | 1990-09-01 | 1991-08-08 | Flüssige, strahlenhärtbare überzugsmasse für die beschichtung von glasoberflächen |
BG97481A BG60917B1 (bg) | 1990-09-01 | 1993-02-25 | Течни, втвърдяващи се при облъчване, покривни маси за нанасяне върху стъклени повърхности |
FI930851A FI930851A (fi) | 1990-09-01 | 1993-02-25 | Vaetskeformiga, medelst straolning haerdbara belaeggningsmassor foer belaeggning av glasytor |
NO93930689A NO930689L (no) | 1990-09-01 | 1993-02-26 | Flytende, straaleherdbar overtrekksmasse for overtrekning av glassoverflater |
LVP-93-428A LV10463B (en) | 1990-09-01 | 1993-05-27 | Thermal hardening composition for covering of glass surfaceod of milk producing cows |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4027770A DE4027770A1 (de) | 1990-09-01 | 1990-09-01 | Fluessige, strahlenhaertbare ueberzugsmasse fuer die beschichtung von glasoberflaechen |
DEP4027770.4 | 1990-09-01 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1992004391A1 true WO1992004391A1 (de) | 1992-03-19 |
Family
ID=6413412
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1991/001501 WO1992004391A1 (de) | 1990-09-01 | 1991-08-08 | Flüssige, strahlenhärtbare überzugsmasse für die beschichtung von glasoberflächen |
Country Status (18)
Country | Link |
---|---|
EP (1) | EP0545969B1 (de) |
JP (1) | JP2509409B2 (de) |
KR (1) | KR930702411A (de) |
AT (1) | ATE115598T1 (de) |
AU (1) | AU648099B2 (de) |
BG (1) | BG60917B1 (de) |
BR (1) | BR9106811A (de) |
CA (1) | CA2090450C (de) |
DE (2) | DE4027770A1 (de) |
DK (1) | DK0545969T3 (de) |
ES (1) | ES2068603T3 (de) |
FI (1) | FI930851A (de) |
LT (1) | LT3332B (de) |
LV (1) | LV10463B (de) |
MD (1) | MD940197A (de) |
NO (1) | NO930689L (de) |
WO (1) | WO1992004391A1 (de) |
YU (1) | YU47699B (de) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1994017005A1 (de) * | 1993-01-28 | 1994-08-04 | Basf Lacke + Farben Aktiengesellschaft | Strahlenhärtbare oligomere sowie flüssige, strahlenhärtbare überzugsmasse für die beschichtung von glasoberflächen |
WO2003091346A1 (en) | 2002-04-24 | 2003-11-06 | Dsm Ip Assets B.V. | Radiation curable coating composition for optical fiber with reduced attenuation loss |
WO2003091177A1 (en) * | 2002-04-24 | 2003-11-06 | Pirelli & C. S.P.A. | Optical fiber with reduced attenuation loss |
US7085466B2 (en) | 2002-04-24 | 2006-08-01 | Pirelli & C. Spa | Method for controlling microbending induced attenuation losses in an optical fiber |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19715382C1 (de) * | 1997-04-14 | 1998-11-19 | Synthopol Chemie Dr Koch | Wasserdispergierte, strahlenhärtbare Polyurethane |
BR112020024462A2 (pt) | 2018-06-01 | 2021-03-16 | Dsm Ip Assets B.V. | Composições curáveis por radiação para revestir fibra óptica através de oligômeros alternativos e os revestimentos produzidos a partir das mesmas |
EP4003927A1 (de) * | 2019-07-31 | 2022-06-01 | Covestro (Netherlands) B.V. | Strahlungshärtbare zusammensetzungen mit multifunktionellen langarmigen oligomeren zur beschichtung von optischen fasern |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4131602A (en) * | 1977-09-29 | 1978-12-26 | Union Carbide Corporation | Radiation curable acrylated polyurethane |
EP0207257A2 (de) * | 1985-05-07 | 1987-01-07 | Hüls Aktiengesellschaft | Strahlenhärtbare Makromere auf der Basis von (meth)acrylfunktionellen Polyestern und deren Verwendung |
EP0209641A2 (de) * | 1985-07-22 | 1987-01-28 | DeSOTO, INC. | Mittels Ultraviolettstrahlen härtbare auf einem polyfunktionellen Kern basierte Beschichtungen für optische Glasfasern |
EP0223086A1 (de) * | 1985-10-29 | 1987-05-27 | DeSOTO, INC. | Mittels Ultraviolettstrahlung härtbare Beschichtungen für optische Glasfaser |
EP0228854A2 (de) * | 1985-12-16 | 1987-07-15 | INTEREZ, Inc.(a Delaware corporation) | Strahlungshärtbare, akrylierte Polyurethanoligomerzusammensetzungen |
EP0323546A2 (de) * | 1988-01-04 | 1989-07-12 | DeSoto, Inc. | Auf einem mit substituierten Dikarbonsäuren kettenverlängerten Polyoxytetramethylenglykol basierte acrylierte Polyurethane |
Family Cites Families (6)
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 |
JPS5940102B2 (ja) | 1978-11-17 | 1984-09-28 | 日本クラウンコルク株式会社 | 剥離可能な接着構造物 |
NL8401981A (nl) | 1984-06-22 | 1986-01-16 | Philips Nv | Optische glasvezel voorzien van een kunststofbedekking en werkwijze voor de vervaardiging daarvan. |
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 |
-
1990
- 1990-09-01 DE DE4027770A patent/DE4027770A1/de not_active Withdrawn
-
1991
- 1991-08-08 DE DE59103926T patent/DE59103926D1/de not_active Expired - Fee Related
- 1991-08-08 CA CA002090450A patent/CA2090450C/en not_active Expired - Fee Related
- 1991-08-08 AT AT91914598T patent/ATE115598T1/de not_active IP Right Cessation
- 1991-08-08 KR KR1019930700632A patent/KR930702411A/ko not_active Application Discontinuation
- 1991-08-08 BR BR919106811A patent/BR9106811A/pt not_active Application Discontinuation
- 1991-08-08 WO PCT/EP1991/001501 patent/WO1992004391A1/de active IP Right Grant
- 1991-08-08 DK DK91914598.7T patent/DK0545969T3/da active
- 1991-08-08 AU AU83314/91A patent/AU648099B2/en not_active Ceased
- 1991-08-08 EP EP91914598A patent/EP0545969B1/de not_active Expired - Lifetime
- 1991-08-08 ES ES91914598T patent/ES2068603T3/es not_active Expired - Lifetime
- 1991-08-08 JP JP3513482A patent/JP2509409B2/ja not_active Expired - Lifetime
- 1991-08-30 YU YU146191A patent/YU47699B/sh unknown
-
1993
- 1993-02-25 BG BG97481A patent/BG60917B1/bg unknown
- 1993-02-25 FI FI930851A patent/FI930851A/fi not_active Application Discontinuation
- 1993-02-26 NO NO93930689A patent/NO930689L/no unknown
- 1993-05-06 LT LTIP531A patent/LT3332B/lt not_active IP Right Cessation
- 1993-05-27 LV LVP-93-428A patent/LV10463B/lv unknown
-
1994
- 1994-07-14 MD MD94-0197A patent/MD940197A/ro unknown
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4131602A (en) * | 1977-09-29 | 1978-12-26 | Union Carbide Corporation | Radiation curable acrylated polyurethane |
EP0207257A2 (de) * | 1985-05-07 | 1987-01-07 | Hüls Aktiengesellschaft | Strahlenhärtbare Makromere auf der Basis von (meth)acrylfunktionellen Polyestern und deren Verwendung |
EP0209641A2 (de) * | 1985-07-22 | 1987-01-28 | DeSOTO, INC. | Mittels Ultraviolettstrahlen härtbare auf einem polyfunktionellen Kern basierte Beschichtungen für optische Glasfasern |
EP0223086A1 (de) * | 1985-10-29 | 1987-05-27 | DeSOTO, INC. | Mittels Ultraviolettstrahlung härtbare Beschichtungen für optische Glasfaser |
EP0228854A2 (de) * | 1985-12-16 | 1987-07-15 | INTEREZ, Inc.(a Delaware corporation) | Strahlungshärtbare, akrylierte Polyurethanoligomerzusammensetzungen |
EP0323546A2 (de) * | 1988-01-04 | 1989-07-12 | DeSoto, Inc. | Auf einem mit substituierten Dikarbonsäuren kettenverlängerten Polyoxytetramethylenglykol basierte acrylierte Polyurethane |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1994017005A1 (de) * | 1993-01-28 | 1994-08-04 | Basf Lacke + Farben Aktiengesellschaft | Strahlenhärtbare oligomere sowie flüssige, strahlenhärtbare überzugsmasse für die beschichtung von glasoberflächen |
WO2003091346A1 (en) | 2002-04-24 | 2003-11-06 | Dsm Ip Assets B.V. | Radiation curable coating composition for optical fiber with reduced attenuation loss |
WO2003091177A1 (en) * | 2002-04-24 | 2003-11-06 | Pirelli & C. S.P.A. | Optical fiber with reduced attenuation loss |
US7085466B2 (en) | 2002-04-24 | 2006-08-01 | Pirelli & C. Spa | Method for controlling microbending induced attenuation losses in an optical fiber |
US7200310B2 (en) | 2002-04-24 | 2007-04-03 | Prysmian Cavi E Sistemi Energia S.R.L. | Optical fiber |
US7317858B2 (en) | 2002-04-24 | 2008-01-08 | Prysmian Cavi E Sistemi Energia S.R.L. | Optical fiber with reduced attenuation loss |
KR100849975B1 (ko) * | 2002-04-24 | 2008-08-01 | 피렐리 앤 씨. 에스.피.에이. | 감소된 감쇠 손실을 갖는 광섬유 |
Also Published As
Publication number | Publication date |
---|---|
LV10463A (lv) | 1995-02-20 |
EP0545969A1 (de) | 1993-06-16 |
EP0545969B1 (de) | 1994-12-14 |
KR930702411A (ko) | 1993-09-09 |
JPH06502435A (ja) | 1994-03-17 |
NO930689D0 (no) | 1993-02-26 |
DK0545969T3 (da) | 1995-04-18 |
DE4027770A1 (de) | 1992-03-05 |
NO930689L (no) | 1993-02-26 |
AU648099B2 (en) | 1994-04-14 |
YU146191A (sh) | 1994-06-10 |
LV10463B (en) | 1996-04-20 |
AU8331491A (en) | 1992-03-30 |
ATE115598T1 (de) | 1994-12-15 |
DE59103926D1 (de) | 1995-01-26 |
CA2090450C (en) | 1996-07-02 |
BR9106811A (pt) | 1993-08-24 |
MD940197A (ro) | 1996-01-31 |
FI930851A0 (fi) | 1993-02-25 |
LT3332B (en) | 1995-07-25 |
ES2068603T3 (es) | 1995-04-16 |
CA2090450A1 (en) | 1992-03-02 |
YU47699B (sh) | 1996-01-08 |
BG97481A (bg) | 1994-03-24 |
JP2509409B2 (ja) | 1996-06-19 |
BG60917B1 (bg) | 1996-06-28 |
LTIP531A (en) | 1994-11-25 |
FI930851A (fi) | 1993-02-25 |
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