WO1994017005A1 - Masses de recouvrement liquides et oligomeres durcissables au rayonnement pour le revetement de surfaces de verre - Google Patents

Masses de recouvrement liquides et oligomeres durcissables au rayonnement pour le revetement de surfaces de verre Download PDF

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Publication number
WO1994017005A1
WO1994017005A1 PCT/EP1994/000134 EP9400134W WO9417005A1 WO 1994017005 A1 WO1994017005 A1 WO 1994017005A1 EP 9400134 W EP9400134 W EP 9400134W WO 9417005 A1 WO9417005 A1 WO 9417005A1
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WIPO (PCT)
Prior art keywords
radiation
component
weight
curable
amino
Prior art date
Application number
PCT/EP1994/000134
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German (de)
English (en)
Inventor
Horst HINTZE-BRÜNING
Martin Lobert
Original Assignee
Basf Lacke + Farben Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Lacke + Farben Aktiengesellschaft filed Critical Basf Lacke + Farben Aktiengesellschaft
Priority to JP6516645A priority Critical patent/JPH08509252A/ja
Priority to BR9405817A priority patent/BR9405817A/pt
Priority to AU58848/94A priority patent/AU672672B2/en
Priority to KR1019950703109A priority patent/KR960700201A/ko
Priority to EP94905095A priority patent/EP0681562A1/fr
Priority to CA002153581A priority patent/CA2153581A1/fr
Publication of WO1994017005A1 publication Critical patent/WO1994017005A1/fr
Priority to BG99789A priority patent/BG99789A/xx
Priority to FI953577A priority patent/FI953577A0/fi
Priority to NO952979A priority patent/NO952979L/no

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Classifications

    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • 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
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to radiation-curable oligomers with several ethylenically unsaturated end groups and several urea and optionally urethane groups per molecule, which can be prepared from
  • Components a to d are used in such amounts that
  • the molar ratio of component a to the component component b is between 0.1: 1 and 1.1: 1,
  • the molar ratio of component c to component a is between 2: 1 and 10: 1 and
  • the equivalent ratio of the isocyanate groups of component d to the amino and possibly hydroxyl 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.
  • Optical glass fibers have become increasingly important in the field of communication as optical waveguide 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-A-223 086 radiation-curable coating agents for the coating of optical glass fibers are known.
  • These coating compositions contain, as binders, radiation-curable oligomers which can be prepared from polyether triols or triamines with an average molecular weight of 300 to 4000, polyether diols or diamines with an average molecular weight of 200 to 4000, OH-functional acrylate monomers and diisocyanates, the molar ratio of triol or triamine to diol or diamine used to prepare the oligomers being between 2.5: 1 and 20: 1.
  • radiation-curable coating agents 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 described in EP-A-209 641. These coating compositions contain, as binders, a polyurethane oligomer with acrylate end groups, which is based on a polyfunctional core. These coating compounds can be used both as a primer and as a top coat. Single-layer processing is also possible.
  • Oligomers according to the preamble of the main claim contain Due to the low modulus of elasticity, these coating agents are used in particular as primers for glass fibers. However, the manufacturers of optical glass fibers have demanded to further improve the mechanical properties of the coatings. In particular, the buffer effect of the coatings should be further optimized and the buffer properties should remain as constant as possible over a wide temperature range. The reactivity of the coating compositions should not be impaired and easy assembly of the coated glass fibers should be ensured.
  • the object of the present invention is to provide radiation-curable coating compositions for the coating of glass surfaces, in particular optical glass fibers, which, compared to the known coating compositions, result in coatings with improved properties.
  • the cured coatings should have an improved buffer effect due to lower modulus of elasticity at higher elongation at break values, the buffer properties being supposed to remain approximately the same over the largest possible temperature range. This means that the mechanical properties of the coating should deteriorate as little as possible as the temperature drops. In particular, the modulus of elasticity should rise as little as possible as the temperature drops.
  • the coating materials should harden as quickly as possible.
  • the coating agents should enable improved assembly of the coated glass fibers.
  • the coatings In particular at the connection points of various glass fibers, it is therefore necessary for the coatings to have reduced adhesion to the glass fiber in order to be easily removable in the connection area. On the other hand, the The coating on the glass fiber does not deteriorate too much when exposed to moisture in order to ensure that there is no delamination due to moisture exposure when the optical fiber ages.
  • the object is surprisingly achieved by radiation-curable oligomers with several ethylenically unsaturated end groups and several urea and optionally urethane groups per molecule, which can be prepared from
  • Components a to d are used in such amounts that
  • 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 3.
  • the equivalent ratio of the isocyanate groups of component d to the amino and possibly hydroxyl groups of the sum of components a to c is between 0.9 and 1.0.
  • component a at least one a ino group-containing compound a- j ⁇ with a number average molecular weight of more than 4,000 to 10,000 and / or at least one amino and / or hydroxyl group-containing compound a 2 with a number average molecular weight of 400 to 4,000 has been used
  • component b at least one amino group-containing compound h- ⁇ with a number average molecular weight of more than 4,000 to 10,000 and / or at least one amino and / or hydroxyl group-containing compound b 2 with a number average molecular weight of 200 to 4000 has been used
  • the oligomers have double bond contents of 0.25 to 0.44 mol / kg and
  • 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. with which these coating compositions are used.
  • radiation-curable coating compositions based on the oligomers according to the invention form coatings with an improved buffer effect compared to conventional coatings, i.e. lower modulus of elasticity with higher elongation at break values.
  • Another advantage is the good buffering effect of the coatings, 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 intended use, and by a reduced adhesion of the coatings to the glass fiber, which enables improved assembly of the coated glass fibers.
  • the adhesion of the coating does not deteriorate too much after exposure to moisture, so that it is ensured that, as the optical fiber ages, no delamination occurs due to exposure to moisture.
  • the coating agents according to the invention harden quickly.
  • oligomers compounds containing amino groups a ⁇ __ ⁇ ** - * - * - * with a functionality of 3 to 4 and with a number average molecular weight of more than 4,000 to 10,000, preferably of more than 4,000 up to 6,000 and / or difunctional compounds b.-L containing amino groups with a number average molecular weight of more than 4,000 to 10,000, preferably of more than 4,000 to 6,000, are used.
  • Component a 1 and / or component b- ⁇ compounds with secondary are preferred .Amino groups, especially polyethers with terminal secondary amino groups, are used.
  • Polyalkoxylated triols having terminal, secondary .amino groups are particularly preferably used as component a.
  • suitable as component a ⁇ ⁇ compounds containing primary .Amino phenomenon derived from polyalkoxilier- th triplets aminofunctional Verbindun ⁇ are gen, such as those sold under the name JEFFAMINE " ⁇ Texaco commercially available, such as
  • the secondary .amines used as component a ⁇ can be prepared, for example, by reacting the corresponding polyethers containing primary amino groups with aliphatic ketones, such as, in particular, methyl isobutyl ketone and subsequent hydrogenation of the ketimine formed.
  • Polyethers suitable for this reaction and containing primary amino groups are, for example, the products available under the name JEFFAMIN * ⁇ from Texaco, such as JEFFAMIT ⁇ T 5000.
  • component a- ⁇ are those on the market available products, such as NOVAMI.N®N 60.
  • the amino-functional compounds derived from polyalkoxylated diols such as JEFFAMINE ⁇ D 4000, for example, which are available under the name JEFFi ⁇ MIN ⁇ from Texaco, are used as component b- ⁇ .
  • the secondary amines used as component b ⁇ can be prepared analogously to the compounds a- ⁇ by reacting the corresponding polyether containing primary amino groups with aliphatic ketones, such as in particular methyl isobutyl ketone, and subsequently hydrogenating the ketimine formed.
  • Suitable polyethers containing primary amino groups for this reaction are, for example, those listed under b- ⁇ JEFFAMI1® types.
  • component b- ⁇ are the products commercially available under the name NOVAMIl ⁇ from CONDEA Chemie GmbH, such as NOVAMIN®N 50.
  • Poly- alkoxylated diols with terminal, secondary amino groups are particularly preferably used as component b.
  • Oligomers optionally also amino and / or hydroxyl group-containing compounds a 2 with a functionality of 3 to 4, preferably 3, and with a number average molecular weight of 400 to 4,000, preferably 750 to 2,000, are used.
  • Suitable amino and / or hydroxyl group-containing compounds a 2 are polyoxyalkylated triols, such as, for example, ethoxylated and propoxylated triols, preferably ethoxylated triols, particularly preferably with a number average molecular weight greater than or equal to 1,000. Glycerol or trimethylolpropane, for example, are used as triols.
  • Suitable as component a 2 also shows the corresponding amino-functional compounds, such as those derived from poly- alkoxylated triols amino-functional compounds.
  • Examples are the products available under the name JEFFAMIN ** ⁇ from Texaco, for example JEFFAMIN - * - * * , T 403 and T 3000 and the products available under the name N0VAMI.N® from CONDEA Chemie GmbH, eg NOVAMI .N®N 30.
  • the amino-functional compounds a 2 can contain both primary and secondary amino groups. In addition, compounds which contain both amino and hydroxyl groups are also suitable. For the preparation of the oligomers according to the invention it is also possible, if appropriate, to use compounds b 2 containing amino and / or hydroxyl groups and containing two hydroxyl and / or amino groups per molecule.
  • These compounds b 2 have number average molecular weights of 200 to 4,000, preferably 600 to 2,000.
  • Suitable amino and / or hydroxyl group-containing compounds b 2 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, e.g. the ethoxylated or propoxylated derivatives of butanediol, hexanediol, etc., polyester diols which e.g. can be produced by reacting the glycols already mentioned with dicarboxylic acids, preferably aliphatic and / or cycloaliphatic dicarboxylic acids, such as e.g.
  • Hexahydrophthalic acid, adipic acid, azelaic, sebacic and glutaric acid and / or their alkyl-substituted derivatives instead of these acids, their anhydrides, if they exist, can also be used.
  • Polycaprolactone diols can also be used. These products are obtained, for example, by reacting a £ -caprolactone with a diol. Such products are described in U.S. Patent 3,169,945.
  • polylactone diols that are obtained by this reaction holds, are characterized by the presence of a terminal hydroxyl group and by recurring polyester portions 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, this lactone should contain at least 6 carbon atoms in the ring, for example 6 to 8 carbon atoms and at least 2 hydrogen substituents on the carbon atom should be.
  • the lactone used as the starting material can be represented by the following general formula:
  • n and R have the meaning already given.
  • the lactones preferred for the preparation of the polyester diols in the invention are the caprolactones, where n is 4.
  • the most preferred lactone is the substituted c-caprolactone, where n is 4 and all 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 the products available under the name JEFFAMIN®D 230, D 400, D 2000, ED 600, ED 900, ED 2001, ED 4000, BUD 2000 and C 346 from Texaco and those under the name NOVAMIN - ⁇ products available from CONDEA Chemie GmbH, such as, for example, NOVAMI-Ni ⁇ N 10, N 20 and N 40.
  • components a to V are used in amounts such that the equivalent ratio of the OH groups of component ⁇ to the carboxyl groups of component ⁇ is between 0.45 and 0.55, preferably 0.5 , and that the equivalent ratio of the epoxy groups of component Y * to the carboxyl groups of component ß is between 0.45 and 0.55, preferably 0.5.
  • polyether diols b 21 and ⁇ examples are the polyoxyalkylene glycols already listed, the alkylene groups having 1 to 6 carbon atoms.
  • Component b 21 is preferably polyoxypropylene glycols with a number average molecular weight between 600 and 2,000.
  • Polyoxibutylene glycols (poly-THF) with a number-average molecular weight> 1,000 are preferably used as component ⁇ .
  • aliphatic and cycloaliphatic dicarboxylic acids with 8 to 36 carbon atoms per molecule are preferably used, such as Hexahydrophthalic acid.
  • Suitable components are, for example, epoxidized, monoolefinically unsaturated fatty acids and / or polybutadienes.
  • Preferred components of olcidyl esters are branched monocarboxylic acids, such as the glycidyl ester of versatic acid.
  • the compounds a- ⁇ , a 2 , b- ⁇ and b 2 are preferably used in such amounts that the molar ratio of
  • Hydroxyl and / or amino groups of components a 2 and b 2 to the amino groups of components a- ⁇ and b- ⁇ is between 0 and 10, preferably between 0.1 and 3.
  • monoethylenically unsaturated compounds with a group with an active hydrogen atom which have a number average molecular weight of 116 to 1,000, preferably 116 to 400.
  • suitable components c are e.g. Hydroxyalkyl esters of ethylenically unsaturated carboxylic acids, e.g.
  • 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 1,000 are preferably used.
  • Aliphatic and / or cycloaliphatic diisocyanates such as 1,3-cyclopentane, 1,4-cyclohexane, 1,2-cyclohexane diisocyanate, 4,4'-methylene, are suitable as component d for the production of the oligomers according to the invention bis (cyclohexyl isocyanate) and isophorone diisocyanate, trimethylene, tetramethylene, pentamethylene, hexethylene and trimethylhexamethylene-l r 6-diisocyanate and those described in EP-A-204 161, column 4, lines 42 to 49, Diisocyanates derived from dimer fatty acids. Isophorone diisocyanate and trimethylhexamethylene-1,6-diisocyanate are preferably used.
  • Components a to d are used to produce the oligomers in such amounts that
  • 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 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 the chain extenders a and b.
  • 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 NCO: 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.
  • an adduct of hydroxyethyl acrylate and caprolactone with a number average molecular weight> .300 is preferably used as component c.
  • the urethane oligomers have double bond contents of 0.25 to 0.44 mol / kg, preferably 0.3 to 0.44 mol / kg.
  • the urethane oligomers according to the invention usually have number average molecular weights of 2,000 to 20,000, preferably 3,500 to 16,000 (measured with GPC against polystyrene standard), weight average molecular weights of 8,000 to 100,000, preferably 10,000 to 40,000 (measured with GPC) against polystyrene standard) and a functionality of 2 to 4, preferably 2.5 to 3.0, each per statistical average polymer molecule.
  • 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 at least 15% 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, in each case based 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 elastic modulus 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.
  • These 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 hydroxyalkyl acrylate or hydroxyalkyl ester of other ethylenic groups unsaturated carboxylic acids. The amounts of chain extender, di- or poly-isocyanate 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 free isocyanate groups of the prepolymer composed 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.
  • the amounts of chain extender, isocyanate and hydroxyalkyl ester of unsaturated carboxylic acids are chosen 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 that Equivalent ratio of the remaining NCO groups to the OH groups of the hydroxyalkyl ester is 1: 1.
  • part of the isocyanate groups of a diisocyanate can first be reacted with a diol, then another part of the isocyanate groups with the hydroxyl alkyl ester of an ethylenically unsaturated carboxylic acid and then the remaining isocyanate groups can be reacted with a diamine.
  • aromatic structural components are preferably used to produce the urethane acrylate oligomers.
  • 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 20 to 50% by weight, preferably 22 to 35% by weight, in each case based on the total weight of the coating mass.
  • Examples of monomers that can be used are ethoxyethoxyethyl acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, phenoxyethyl acrylate, dimethylaminoethyl acrylate, hydroxyethyl acrylate, butoxyethyl acrylate, isobornyl acrylate, dimethyl acrylate and dicyclyl amide and dicyclyl amide.
  • Di- and polyacrylates such as e.g. Butanediol diacrylate,
  • the two acrylate groups can be separated by a polyoxybutylene structure. 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-vinylcaprolactam and tripropylene glycol diacrylate are preferably used.
  • the photoinitiator typically used in the coating compositions according to the invention in an amount of 2 to 8% by weight, preferably 3 to 5% by weight, based on the total weight of the coating composition, varies with the jet used to harden the coating compositions lung (UV radiation, electron radiation, 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, ⁇ , ⁇ -dimethyl- ⁇ -hydroxiacetophenone, diethoxiacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, Hy - Droxipropylphenyl ketone, m-chloroacetophenone, propiophenone, benzoin, benzil, benzil dimethyl ketal, anthraquinone, thioxanthone and thioxanthone derivatives and triphenylphosphine and others as well as 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 and plasticizers.
  • the coating compositions can be applied using known application methods, such as e.g. 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.
  • radiation preferably by means of UV radiation.
  • the systems 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 need no 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, especially preferably used of 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 composition.
  • 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 in particular as a primer, but possibly also as a topcoat for a two-layer coating.
  • the coating compositions 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 the coating compositions are used as topcoat, the cured coatings usually have a modulus of elasticity (at 2.5% elongation and room temperature) of 500 to 1,000 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 epoxy 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 dPas (measured at 23 ° C. with a plate / cone viscometer).
  • a 40% solution (based on the theoretical solids content) of the oligomer 1 obtained in phenoxyethyl acrylate has a viscosity of 4.9 dPas (measured at 23 ° C. with the plate-cone viscometer).
  • a radiation-curable coating composition 1 is prepared from 66.8 parts of the urethane oligomer 1 described above, 29.3 parts of phenoxyethyl acrylate and 3.9 parts of ⁇ , ⁇ -dimethyl- ⁇ -hydroxiacetophenone.
  • Curing is carried out with the help of a UV irradiation system, equipped with two Hg medium pressure lamps each with 80 W / cm lamp power, at a belt speed speed of 14 m / minute, in 1 pass at full load.
  • the irradiated dose is 0.15 J / cm 2 (measured with the UVICURE dosimeter, System EIT from Eltosch).
  • Table 3 shows the results of the modulus of elasticity determination at 0.5 and 2.5% elongation (according to the DIN 53 455 standard) and the results of the elongation at break test.
  • the liability test was carried out in accordance with DIN standard 53289.
  • a 40% solution (based on the theoretical solids content) of the oligomer obtained in phenoxyethyl acrylate has a viscosity of 4.1 dPas (measured at 23 ° C. with the plate-cone viscometer).
  • a radiation-curable coating composition 2 is prepared from 66.8 parts of the urethane acrylate oligomer 2 described above, 29.3 parts of phenoxyethyl acrylate and 3.9 parts of ⁇ , ⁇ -dimethyl- ⁇ -hydroxiacetophenone.
  • Example 2 The coating composition 2 is applied and cured analogously to Comparative Example 1. The test results of the coating obtained are shown in Table 3.
  • Example 2 The coating composition 2 is applied and cured analogously to Comparative Example 1. The test results of the coating obtained are shown in Table 3.
  • ⁇ 5000, amine equivalent weight 1890 g, commercial product JEFFAMIN-S-'T 5000 from Texaco
  • the temperature was kept at 60 ° C. until an NCO value of 1.8% was reached. Thereafter, the mixture was also heated to 80 ° C. and the temperature was held at 80 ° C. until an NCO value of 0.9% was reached.
  • a 40% solution of the intermediate product thus obtained has a viscosity of 2.9 dPas, measured at 23 "C with the plate-cone viscometer using phenoxyethyl acrylate as solvent.
  • the reaction with the amine is carried out analogously to Example 1.
  • a 40% solution (based on the theoretical solids content) of the oligomer 3 obtained in phenoxyethyl acrylate has a viscosity of 5.1 dPas (23 ° C., plate-cone viscometer) ).
  • the preparation, application and curing of the coating composition 3 is carried out analogously to Example 1.
  • the test results of the coating obtained are shown in Table 3.
  • a radiation-curable oligomer 4 was prepared analogously to Example 1, with the difference that instead of 0.35 mol of the polyether triamine with secondary amino groups (NOVAMIL> i * S>) N 60) in Comparative Example 2, 0.35 mol of a commercially available propoxylated Glycerins with an average of 3 primary .amino groups per Molecule with a number average molecular weight of 3,000 (amine equivalent weight 1060 g, commercial product JEFF-AMII-S T 3000 from Texaco) were used. After the addition of the isophorone diisocyanate, the temperature was kept at 60 ° C. until one
  • a 40% solution (based on the theoretical solids content) of the oligomer obtained in phenoxyethyl acrylate has a viscosity of 4.6 dPas, measured at 23 ° C. with the plate-cone viscometer.
  • the production, application and curing of the rays ⁇ curable coating composition 4 is carried out analogously to Example 1.
  • the test results of the coatings obtained are shown in Table 3.
  • the oligomer 5 obtained in this way has a double bond content of 0.414 mol / kg and a functionality of 2.5.
  • a 40% solution (based on the theoretical solids content) of the oligomer obtained in phenoxyethyl acrylate has a viscosity of 3.7 dPas (measured at 23 ° C. with the plate-cone viscometer).
  • the radiation-curable coating composition 5 is produced, applied and cured analogously to Example 1. The test results of the coating obtained are shown in Table 3. Comparative Example 3
  • a radiation-curable oligomer is produced with the only difference that instead of 0.65 mol of the polyether diamine with secondary amino groups with a number average molecular weight of 4150 (NOVAMINE ⁇ N 50), now 0.65 mol of a commercially available one ⁇ Lichen polyoxypropylene diamine with primary amino groups with a number average molecular weight of 4000 (amine equivalent weight 2220 g, commercial product JEFFAMIN * - * 'D 4000 from Texaco) were used.
  • a 40% solution (based on the theoretical solids content) of the oligomer obtained in 6 Phe ⁇ noxiethylacrylat has a viscosity of 6.6 dPas (measured at 23 C with the ⁇ cone and plate viscometer).
  • the coating composition is prepared, applied and cured analogously to Example 1. The test results of the coating obtained are shown in Table 3.
  • Polyoxypropylene 600 0.65 mod. PE 1860 1.30 0.65 1.30 1.30 0.65 0.65
  • TMP ethoxylated trimethylolpropane PE-triamine 1 'propoxylated glycerol with primary amino groups
  • PE-diamin 1 ° polyoxypropylene diamine with primary amino groups
  • PE-diamine 2 polyoxypropylene diamine with secondary amino groups
  • IPDI isophorone diisocyanate
  • Table 3 Test results of the coatings (coating composition in each case from 66.8 parts by weight of urethane acrylate oligomer, 29.3 parts of phenoxyethyl acrylate and 3.9 parts of ⁇ , ⁇ -dimethyl-ct-hydroxiacetophenone)
  • Example 1 and 2 As the comparison of Examples 1 and 2 with Comparative Examples 1 and 2 and the comparison of Example 3 with Comparative Example 3 shows, when using amino group-containing chain extenders with a number average molecular weight M n of more than 4,000, the buffering effect the resulting coating significantly improved.
  • the coatings of Examples 1 and 2 according to the invention have a number-average molecular weight of only when using an amino group-containing chain extender compared to the analogue structure
  • Example 1 brings a further improvement in the mechanical properties of the coatings compared to chain extenders with primary amino groups (Example 2). Also the comparison of example 3 with the analog one
  • Comparative Example 3 in which a primary amine with a number average molecular weight of 4,000 was now used instead of the A ins according to the invention with a number average molecular weight of 4,150, confirms the improved mechanical properties of the coatings according to the invention.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Paints Or Removers (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention a pour objet des oligomères durcissables au rayonnement fabriqués à partir de polyéthertriols ou de polyéthertriamines (a), de polyétherdiols ou de polyétherdiamines (b), de monomères acrylates à fonctions OH (c) et de diisocyanates (d), le rapport molaire de (a) à (b) étant compris entre 0,1 et 1,1, le rapport molaire de (c) à (a) étant compris entre 2,0 et 10, et le rapport d'équivalence des groupes NCO de (d) aux groupes hydroxyle ou amino de la somme de (a) à (c) étant compris entre 0,9 et 1,0, caractérisés en ce qu'on utilise, pour la fabrication des oligomères, au moins un composé de 3 à 4 groupes amino et d'un poids moléculaire moyen en nombre de plus de 4.000 et jusqu'à 10.000, et/ou au moins un composé à 2 groupes amino et d'un poids moléculaire moyen en nombre de plus de 4.000 et jusqu'à 10.000, et en ce que les oligomères présentent des teneurs en doubles liaisons de 0,25 à 0,44 mol/kg.
PCT/EP1994/000134 1993-01-28 1994-01-20 Masses de recouvrement liquides et oligomeres durcissables au rayonnement pour le revetement de surfaces de verre WO1994017005A1 (fr)

Priority Applications (9)

Application Number Priority Date Filing Date Title
JP6516645A JPH08509252A (ja) 1993-01-28 1994-01-20 放射線硬化性オリゴマーならびにガラス表面の被覆のための液状の放射線硬化性被覆材料
BR9405817A BR9405817A (pt) 1993-01-28 1994-01-20 Oligómeros endureciveis por radiaçao massa de revestimento endurecivel por radiação processo de revestimento de uma superficie de vidro especialmente de uma de fibra de vidro e fibra ótica de vidro
AU58848/94A AU672672B2 (en) 1993-01-28 1994-01-20 Radiation-hardenable oligomers and liquid, radiation-hardenable coating masses for glass surfaces
KR1019950703109A KR960700201A (ko) 1993-01-28 1994-01-20 방사-경화 올리고머 및 유리표면 코팅용 액체 방사-경화 코팅 조성물(radiation-hardenable oligomers and liquid, radiation-hardenable coating masses for glass surfaces)
EP94905095A EP0681562A1 (fr) 1993-01-28 1994-01-20 Masses de recouvrement liquides et oligomeres durcissables au rayonnement pour le revetement de surfaces de verre
CA002153581A CA2153581A1 (fr) 1993-01-28 1994-01-20 Oligomeres reticulables et composition liquide pour revetement photoreticulable de surfaces en verre
BG99789A BG99789A (en) 1993-01-28 1995-07-18 Oligomers and liquid composition for glass surface coating, hardening under the solar rays effect
FI953577A FI953577A0 (fi) 1993-01-28 1995-07-26 Säteilyn vaikutuksesta kovettuvia oligomeerejä sekä nestemäisiä, säteilyn vaikutuksesta kovettuvia päällystysmassoja lasipintojen päällystämiseen
NO952979A NO952979L (no) 1993-01-28 1995-07-27 Stråleherdbare oligomerer samt flytende, stråleherdbar overtrekksmasse for overtrekning av glassoverflater

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4302327A DE4302327A1 (de) 1993-01-28 1993-01-28 Strahlenhärtbare Oligomere sowie flüssige, strahlenhärtbare Überzugsmasse für die Beschichtung von Glasoberflächen
DEP4302327.4 1993-01-28

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JP (1) JPH08509252A (fr)
KR (1) KR960700201A (fr)
AU (1) AU672672B2 (fr)
BG (1) BG99789A (fr)
BR (1) BR9405817A (fr)
CA (1) CA2153581A1 (fr)
DE (1) DE4302327A1 (fr)
FI (1) FI953577A0 (fr)
NO (1) NO952979L (fr)
TW (1) TW249818B (fr)
WO (1) WO1994017005A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10350861B2 (en) 2015-07-31 2019-07-16 Corning Incorporated Laminate structures with enhanced damping properties

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU4969697A (en) * 1996-11-08 1998-06-03 Dsm N.V. Radiation-curable optical glass fiber coating compositions, coated optical glass fibers, and optical glass fiber assemblies
US6110593A (en) 1998-05-21 2000-08-29 Dsm N.V. Radiation-curable optical fiber primary coating system
DE19920799A1 (de) 1999-05-06 2000-11-16 Basf Coatings Ag Thermisch und mit aktinischer Strahlung härtbarer Beschichtungsstoff und seine Verwendung
US6835759B2 (en) 2001-08-28 2004-12-28 Basf Corporation Dual cure coating composition and processes for using the same
US6852771B2 (en) 2001-08-28 2005-02-08 Basf Corporation Dual radiation/thermal cured coating composition
US20030077394A1 (en) * 2001-08-28 2003-04-24 Bradford Christophen J. Dual cure coating composition and process for using the same
WO2013181484A1 (fr) 2012-05-31 2013-12-05 Corning Incorporated Couches intermédiaires rigides pour structures de verre feuilleté
KR102466478B1 (ko) 2013-08-30 2022-11-11 코닝 인코포레이티드 경량, 고강성 유리 적층체 구조물
WO2020096055A1 (fr) * 2018-11-09 2020-05-14 住友電気工業株式会社 Fibre optique

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EP0193092A2 (fr) * 1985-02-20 1986-09-03 DeSOTO, INC. Polyacrylates de polyuréthane polyurée solides et élastiques et revêtements durcissables par des rayons d'électrons contenant ceux-ci
EP0223086A1 (fr) * 1985-10-29 1987-05-27 DeSOTO, INC. Revêtements pour des fibres optiques en verre durcissables par le rayonnement ultra-violet
EP0290623A1 (fr) * 1986-11-21 1988-11-17 Nippon Kayaku Kabushiki Kaisha Melange de (meth)acrylate de polyurethane, composition de resine et agent de revetement
WO1992004391A1 (fr) * 1990-09-01 1992-03-19 Basf Lacke + Farben Aktiengesellschaft Melange liquide photodurcissable d'enduction de surfaces en verre
WO1992006846A1 (fr) * 1990-10-19 1992-04-30 Dsm Desotech, Inc. Composition de resine liquide durcissable

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EP0193092A2 (fr) * 1985-02-20 1986-09-03 DeSOTO, INC. Polyacrylates de polyuréthane polyurée solides et élastiques et revêtements durcissables par des rayons d'électrons contenant ceux-ci
EP0223086A1 (fr) * 1985-10-29 1987-05-27 DeSOTO, INC. Revêtements pour des fibres optiques en verre durcissables par le rayonnement ultra-violet
EP0290623A1 (fr) * 1986-11-21 1988-11-17 Nippon Kayaku Kabushiki Kaisha Melange de (meth)acrylate de polyurethane, composition de resine et agent de revetement
WO1992004391A1 (fr) * 1990-09-01 1992-03-19 Basf Lacke + Farben Aktiengesellschaft Melange liquide photodurcissable d'enduction de surfaces en verre
WO1992006846A1 (fr) * 1990-10-19 1992-04-30 Dsm Desotech, Inc. Composition de resine liquide durcissable

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Publication number Priority date Publication date Assignee Title
US10350861B2 (en) 2015-07-31 2019-07-16 Corning Incorporated Laminate structures with enhanced damping properties

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AU5884894A (en) 1994-08-15
TW249818B (fr) 1995-06-21
JPH08509252A (ja) 1996-10-01
CA2153581A1 (fr) 1994-08-04
AU672672B2 (en) 1996-10-10
EP0681562A1 (fr) 1995-11-15
NO952979D0 (no) 1995-07-27
NO952979L (no) 1995-07-27
BR9405817A (pt) 1996-01-16
KR960700201A (ko) 1996-01-19
BG99789A (en) 1996-03-29
FI953577A (fi) 1995-07-26
FI953577A0 (fi) 1995-07-26
DE4302327A1 (de) 1994-08-04

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