WO2000005290A1 - Monomerarmes polyurethanbindemittel mit verbesserter gleitmittelhaftung - Google Patents
Monomerarmes polyurethanbindemittel mit verbesserter gleitmittelhaftung Download PDFInfo
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- WO2000005290A1 WO2000005290A1 PCT/EP1999/004890 EP9904890W WO0005290A1 WO 2000005290 A1 WO2000005290 A1 WO 2000005290A1 EP 9904890 W EP9904890 W EP 9904890W WO 0005290 A1 WO0005290 A1 WO 0005290A1
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- isocyanate
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- polyurethane
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G18/4808—Mixtures of two or more polyetherdiols
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
-
- 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
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
Definitions
- the present invention relates to a polyurethane binder, process for the preparation of a low-viscosity, isocyanate group-bearing polyurethane binder which has only a low content of volatile residual monomers, forms essentially no migrates and has improved lubricant adhesion.
- the invention further relates to the use of a low-viscosity polyurethane binder containing isocyanate groups (NCO groups) in the production of adhesives, in particular one- and two-component adhesives, for example for the bonding of sheet-like materials made of e.g. Paper, plastic and / or aluminum, coatings, in particular paints, emulsion paints and casting resins as well as moldings.
- NCO groups isocyanate groups
- Polyurethane prepolymers with isocyanate end groups have been known for a long time. With suitable compounds - usually with polyfunctional alcohols - they can easily be chain-extended or cross-linked to high-molecular substances. Polyurethane prepolymers have gained importance in many areas of application, for example in the production of adhesives, coatings, casting resins and moldings.
- polyurethane prepolymers with terminal isocyanate groups it is customary to react polyfunctional alcohols with an excess of polyisocyanates, generally at least predominantly diisocyanates.
- the molecular weight can be controlled at least approximately via the ratio of OH groups to isocyanate groups. While a ratio of OH groups to isocyanate groups of 1: 1 or close to 1: 1 leads to generally high molecular weights when the reaction is complete, for example at a ratio of about 2: 1 when using diisocyanates statistical means attached a diisocyanate molecule to each OH group, so that in the course of the reaction there is no oligomer formation or chain extension in the ideal case.
- a content of such substances is particularly disruptive when the diisocyanates are volatile.
- the vapors of these diisocyanates are often harmful to health, and the use of products with a high content of such volatile diisocyanates requires extensive measures on the part of the user to protect the person processing the product, in particular expensive measures to keep the air breathed clean.
- volatile means substances which have a vapor pressure of more than about 0.0007 mmHg or a boiling point of less than about 190 ° C (70 mPa) at about 30 ° C.
- polyurethane binders are generally obtained a viscosity that is usually outside the range usable for simple processing methods. In these cases, the viscosity of the polyurethane prepolymers can be reduced by adding suitable solvents, which contradicts the often required absence of solvents of such binders.
- a further possibility for lowering the viscosity while avoiding solvents is to add an excess of monomeric polyisocyanates, which are incorporated into the coating or adhesive bond during a later curing process (after the addition of a hardener or by curing under the influence of moisture) (reactive thinner) .
- Migrates are often intolerable, particularly in the packaging sector, since migration of the migrates through the packaging material would lead to contamination of the packaged goods and the consumer would inevitably have to come into contact with the migrants when the goods are consumed.
- EP-A 0 118 065 proposes to produce polyurethane prepolymers in a two-stage process.
- a monocyclic diisocyanate with a reacted polyfunctional alcohol in the ratio OH groups: isocyanate groups ⁇ 1 and then in a second step reacted a bicyclic diisocyanate with polyfunctional alcohols in the ratio OH groups: isocyanate groups ⁇ 1 in the presence of the prepolymer prepared in the first step.
- a ratio of OH groups: isocyanate groups of 0.65 to 0.8, preferably 0.7 to 0.75 is proposed.
- the prepolymers obtainable in this way still have viscosities of 2500 mPas or 7150 mPas and 9260 mPas at high temperatures (75 ° C. or 90 ° C.); nothing is said about the compatibility with lubricants.
- EP-A 0 019 120 relates to a method for producing elastic, weather-resistant flat structures.
- a two-stage process is proposed in which tolylene diisocyanate (TDI) is reacted with at least equimolar amounts of a polyol in a first stage and the reaction product obtained is then reacted with diphenylmethane diisocyanate (MDI) and a polyol.
- MDI diphenylmethane diisocyanate
- MDI diphenylmethane diisocyanate
- the polyurethane binders obtainable in this way should be able to cure with water or with atmospheric moisture.
- the unpublished German patent application with the file number 197 49 834.5 relates to low-monomer polyurethane binders.
- a two-component polyurethane binder with a low monomer content and a low migratory content is disclosed.
- a common lubricant is, for example, erucic acid amide (ESA), which is often contained in the film in amounts of more than about 400 ppm.
- ESA erucic acid amide
- the films used here generally have a significantly increased lubricant content, which can often be 600 ppm or more, compared to slower-running packaging machines.
- many conventional adhesives leave something to be desired in terms of their adhesive strength in films with a lubricant content of this magnitude. As a result, film composites produced in this way often show inadequate seal seam adhesion, especially after curing.
- the object of the invention was therefore to provide a polyurethane binder which has the lowest possible viscosity and the lowest possible residual content of less than about 1% by weight of volatile diisocyanates, the residual content of volatile isocyanate in the case of tolylene diisocyanate (TDI ) should be less than about 0.1% by weight.
- Another object of the invention was to provide a polyurethane binder which has the lowest possible proportion of "migrates", i. that is, has the lowest possible proportion of monomeric polyisocyanates.
- Another object of the invention was to provide a method with which a polyurethane binder with the above-mentioned properties can be produced.
- a further object of the invention was to provide a polyurethane binder and an adhesive which, in addition to the properties already mentioned with regard to its content of volatile isocyanates and the lowest possible migratory content, also have an improved compatibility with lubricants, that is to say, for example, an improved bond or an improved bond Seal seam adhesion when gluing films with a high lubricant content.
- the invention relates to a polyurethane binder with a low
- component C an at least difunctional isocyanate which has no nitrogen atom which is not part of an NCO group, or a mixture of two or more thereof, as component B and c) an at least difunctional isocyanate or a mixture of two or more isocyanates with an average Functionality of at least two, which has at least one nitrogen atom per isocyanate molecule, which is not part of an NCO or urethane group, is present as component C.
- low viscosity means a viscosity (measured according to Brookfield) which is less than 5000 mPas at 50 ° C.
- polyurethane binder is understood to mean a mixture of at least two isocyanate group-containing molecules in which the proportion of molecules with a molecular weight of more than 500 is at least about 50% by weight, preferably at least about 60% by weight. -% or at least about 70 wt .-%.
- Component A is a polyurethane prepolymer which carries at least two isocyanate groups, or a mixture of two or more polyurethane prepolymers which carries at least two isocyanate groups, which is preferably obtainable by reacting a polyol component with an at least different isocyanate.
- a “polyurethane prepolymer” is understood to mean a compound which results, for example, from the reaction of a polyol component with an at least difunctional isocyanate.
- the term "polyurethane prepolymer” thus encompasses both compounds with a relatively low molecular weight, such as arise, for example, from the reaction of a polyol with an excess of polyisocyanate, but it also includes oligomeric or polymeric compounds.
- Also encompassed by the term “polyurethane prepolymers” are compounds such as those used for. B. from the reaction of a 3- or 4-valent polyol with a molar excess of diisocyanates, based on the polyol. In this case, one molecule of the resulting compound carries several isocyanate groups.
- molecular weight data relating to polymeric compounds relate to the number average molecular weight (M n ).
- the polyurethane prepolymers used in the context of the present invention have a molecular weight of approximately 150 to approximately 15,000, or approximately 500 to approximately 10,000, for example approximately 5,000, but in particular approximately 700 to approximately 2,500.
- the polyurethane prepolymer carrying two isocyanate groups, or at least one of the polyurethane prepolymers present in a mixture of two or more isocyanate group-carrying polyurethane prepolymers has at least two differently bound types of isocyanate groups, at least one of which is a lesser one Has reactivity towards groups reactive with isocyanates than that other type or the other types of isocyanate groups.
- Isocyanate groups with a comparatively lower reactivity towards groups reactive with isocyanates are also referred to in the following text as “less reactive isocyanate groups", the corresponding isocyanate group with a higher reactivity towards compounds reactive with isocyanate groups is also referred to as “more reactive isocyanate group”.
- a difunctional polyurethane prepolymer for example, can therefore be used as component A, which has two differently bonded isocyanate groups, one of the isocyanate groups being more reactive towards isocyanate-reactive groups than the other isocyanate group.
- a polyurethane prepolymer can be obtained, for example, from the reaction of a difunctional alcohol with two different, for example difunctional, compounds containing isocyanate groups, the reaction being carried out, for example, in such a way that on average each molecule of the difunctional alcohol with one molecule each of the different isocyanate group-bearing compounds responds.
- component A It is also possible to use a tri-functional or higher-functional polyurethane prepolymer in component A, it being possible for one molecule of the polyurethane prepolymer to have, for example, a different number of less reactive and more reactive isocyanate groups.
- mixtures of two or more different polyurethane prepolymers can be used as component A.
- the mixtures mentioned can be polyurethane prepolymers in which individual polyurethane molecules each carry identically bound isocyanate groups.
- at least one more reactive and one less reactive type of isocyanate groups ie, a poly- urethane molecule with at least two reactive and one polyurethane molecule with at least two less reactive isocyanate groups.
- the mixture contains, in addition to molecules which carry one or more identically bound isocyanate groups, further molecules which carry both one or more identically bound isocyanate groups and one or more differently bound isocyanate groups.
- reaction products of di- or higher-functional alcohols with an at least equimolar amount (based on the OH groups of the di- or higher-functional alcohol) of low molecular weight diisocyanates with a molecular weight of up to about 400 are also suitable as component A or at least as a component of component A.
- the polyurethane prepolymer used as component A or the mixture of two or more polyurethane prepolymers per molecule has at least one urethane group.
- component A is produced by an at least two-stage reaction in which c) in a first stage a polyurethane prepolymer is prepared from an at least difunctional isocyanate and at least one first polyol component, the NCO / OH ratio being less than 2 and there are still free OH groups in the polyurethane prepolymer, and d) in a second stage a further at least difunctional isocyanate is reacted with the polyurethane prepolymer from the first stage, the isocyanate groups of the isocyanate added in the second stage being higher Have reactivity towards compounds reactive with isocyanates than at least the predominant proportion of the isocyanate groups present in the polyurethane prepolymer from the first stage.
- component A is produced by an at least two-stage reaction in which e) in a first stage a polyurethane prepolymer is prepared from an at least difunctional isocyanate and at least one first polyol component, the NCO / OH ratio being less than 2 and there are still free OH groups in the polyurethane prepolymer, and f) in a second stage a further at least difunctional isocyanate and another polyol component is reacted with the polyurethane prepolymer from the first stage, the isocyanate groups being added in the second stage Isocyanates have a higher reactivity towards compounds reactive with isocyanates than at least the predominant proportion of the isocyanate groups present in the polyurethane prepolymer from the first stage.
- the OH: NCO ratio in the preparation of component A in the second stage is about 0.001 to less than 1, in particular 0.005 to about 0.8.
- the OH: NCO ratio in the second stage is approximately 0.2 to 0.6
- the ratio OH: NCO in the first stage is less than 1, in particular 0.5 to 0.7, it being possible, if appropriate, to maintain the ratios described for the second stage.
- polyol component in the context of the present text encompasses a single polyol or a mixture of two or more polyols which can be used for the production of polyurethanes.
- a polyol is understood to mean a polyfunctional alcohol, ie a compound with more than one OH group in the molecule.
- a large number of polyols can be used as the polyol component for the production of component A. For example, these are aliphatic alcohols with 2 to 4 OH groups per molecule. The OH groups can be bound either primary or secondary.
- Suitable aliphatic alcohols include, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol and their higher homologs or isomers, such as for the person skilled in the art they result from a stepwise extension of the hydrocarbon chain by one CH 2 group each or by introducing branches into the carbon chain.
- Highly functional alcohols such as, for example, glycerol, trimethyloipropane, pentaerythritol and oligomeric ethers of the substances mentioned with themselves or as a mixture of two or more of the ethers mentioned are also suitable.
- reaction products of low molecular weight polyfunctional alcohols with alkylene oxides can be used as the polyol component for the production of component A.
- the alkylene oxides preferably have 2 to 4 carbon atoms.
- the reaction products of ethylene glycol, propylene glycol, the isomeric butanediols or hexanediols with ethylene oxide, propylene oxide and / or butylene oxide are suitable.
- polyethene polyols are also suitable with the alkylene oxides mentioned to give polyethene polyols.
- polyethene polyols with a molecular weight of about 100 to about 10,000, preferably from about 200 to about 5,000.
- polypropylene glycol with a molecular weight of approximately 300 to approximately 2500 is very particularly preferred.
- polyethene polyols as arise, for example, from the polymerization of tetrahydrofuran.
- the polyethers are prepared in a manner known to the person skilled in the art by reacting a starter compound having a reactive hydrogen atom with alkylene oxides, for example ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran or epichlorohydrin or mixtures of two or more thereof.
- alkylene oxides for example ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran or epichlorohydrin or mixtures of two or more thereof.
- Suitable starting compounds are, for example, water, ethylene glycol, propylene glycol 1,2 or 1,3, butylene glycol 1,4 or 1,3 hexanediol 1,6, octane diol 1,8, neopentyl glycol, 1,4-hydroxymethylcyclohexane, 2 -Methyl-1,3-propanediol, glycerol, trimethyloipropan, hexanetriol-1,2,6, butanetriol-1,2,4 trimethylolethane, pentaerythritol, mannitol, sorbitol, methylglycosides, sugar, phenol, isononylphenol, resorcinol, hydroquinone, 1, 2,2- or 1,1,2-tris (hydroxyphenyl) ethane, ammonia, methylamine, ethylenediamine, tetra- or hexamethyleneamine, triethanolamine, aniline, phenylenediamine, 2,
- polyethers which have been modified by vinyl polymers. Such products are obtainable, for example, by polymerizing styrene and / or acrylonitrile in the presence of polyethers.
- polyesters polyols with a molecular weight of about 200 to about 10,000.
- polyesters can be used which are formed by reacting low molecular weight alcohols, in particular ethylene glycol, diethylene glycol, neopentyl glycol, hexanediol, butanediol, propylene glycol, glycerol or trimethyloipropane with caprolactone.
- polyester polyols can be produced by polycondensation. So difunctional and / or trifunctional alcohols with a deficit of dicarboxylic acids and / or tricarboxylic acids, or their reactive derivatives, can be condensed to Polyeste ⁇ olyolen.
- Suitable dicarboxylic acids are, for example, succinic acid and its higher homologues with up to 16 C- Atoms, also unsaturated dicarboxylic acids such as maleic acid or fumaric acid and aromatic dicarboxylic acids, especially the isomeric phthalic acids, such as
- Phthalic acid isophthalic acid or terephthalic acid.
- Citric acid or trimellitic acid are suitable as tricarboxylic acids.
- Polyester polyols of at least one of the dicarboxylic acids and glycerol mentioned, which have a residual content of OH groups, are particularly suitable according to the invention.
- Particularly suitable alcohols are hexanediol, ethylene glycol,
- Diethylene glycol or neopentyl glycol or mixtures of two or more of them Diethylene glycol or neopentyl glycol or mixtures of two or more of them.
- Particularly suitable acids are isophthalic acid or adipic acid or their
- polyols used particularly preferably as polyol components for the production of component A are, for example, dipropylene glycol and / or polypropylene glycol with a molecular weight of approximately 400 to approximately 2500, and also polyol polyols, preferably polyol polyols, obtainable by polycondensation of hexanediol, ethylene glycol, diethylene glycol or neopentyl glycol or Mixtures of two or more thereof and isophthalic acid or adipic acid, or mixtures thereof.
- High molecular weight polyesters include, for example, the reaction products of polyfunctional, preferably difunctional alcohols (optionally together with small amounts of trifunctional alcohols) and polyfunctional, preferably difunctional carboxylic acids.
- polyfunctional preferably difunctional alcohols
- polyfunctional preferably difunctional carboxylic acids.
- the corresponding polycarboxylic anhydrides or corresponding polycarboxylic esters with alcohols with preferably 1 to 3 carbon atoms can also be used (if possible).
- the polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic. They can optionally be substituted, for example by alkyl groups, alkenyl groups, ether groups or halogens.
- polycarboxylic acids examples include succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalohydride anhydride, endophthalide anhydride
- Glutaric anhydride maleic acid, maleic anhydride, fumaric acid, dimer fatty acid or trimer fatty acid or mixtures of two or more thereof are suitable. If necessary, minor amounts of monofunctional fatty acids can be present in the reaction mixture.
- polyesters can optionally have a small proportion of carboxyl end groups.
- Polyesters obtainable from lactones, for example ⁇ -caprolactone or hydroxycarboxylic acids, for example ⁇ -hydroxycaproic acid, can also be used.
- Polyacetals are also suitable as polyol components.
- Polyacetals are understood to mean compounds such as are obtainable from glycols, for example diethylene glycol or hexanediol, with formaldehyde.
- Polyacetals which can be used in the context of the invention can likewise be obtained by polymerizing cyclic acetals.
- Polycarbonates are also suitable as polyols for the production of component A.
- Polycarbonates can be obtained, for example, by the reaction of diols such as propylene glycol, 1,4-butanediol or 1,6-hexanediol, diethylene glycol, triethylene glycol or tetraethylene glycol or mixtures of two or more thereof with diaryl carbonates, for example diphenyl carbonate or phosgene.
- OH-bearing polyacrylates are also suitable as a polyol component for the production of components A.
- These polyacrylates can be obtained, for example, by the polymerization of ethylenically unsaturated monomers which carry an OH group.
- Such monomers can be obtained, for example, by the esterification of ethylenically unsaturated carboxylic acids and difunctional alcohols, the alcohol usually being in a slight excess.
- Suitable ethylenically unsaturated carboxylic acids are, for example, acrylic acid, methacrylic acid, crotonic acid or maleic acid.
- Corresponding esters carrying OH groups are, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate or 3-hydroxypropyl methacrylate or
- the corresponding polyol component is in each case reacted with an at least difunctional isocyanate.
- any isocyanate with at least two isocyanate groups can be used as the at least difunctional isocyanate for the production of component A, but compounds with two to four isocyanate groups, in particular with two isocyanate groups, are generally preferred for the purposes of the present invention.
- At least difunctional isocyanates are described below which are suitable as the at least difunctional isocyanate for the production of components A.
- ethylene diisocyanate 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate (HDI), cyclobutane-1,3-diisocyanate, cyclohexane-1,3, and 1,4-diisocyanate as well as mixtures of two or more thereof, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 2,4- and 2,6-hexahydrotoluylene diisocyanate, tetramethylxylylene diisocyanate (TMXDI), 1,3- and 1,4-phenylene diisocyanate, 2, 4- or 2,6-tolylene diisocyanate, diphenylmethane-2,4'-diisocyanate, diphenylmethane-2,2'-diisocyanate or diphenylmethane-4,
- isocyanates for the production of component A are trivalent or higher-valent isocyanates, such as are obtainable, for example, by oligomerizing diisocyanates.
- trivalent and higher polyisocyanates are the triisocyanurates from HDI or IPDI or their mixtures or their mixed triisocyanurates.
- diisocyanates which have two isocyanate groups with different reactivity are used to prepare component A.
- diisocyanates are 2,4- and 2,6-tolylene diisocyanate (TDI) and isophorone diisocyanate (IPDI).
- TDI 2,4- and 2,6-tolylene diisocyanate
- IPDI isophorone diisocyanate
- Non-symmetrical diisocyanates generally react one isocyanate group significantly faster with groups that are reactive toward isocyanates, for example OH groups, while the remaining isocyanate group is comparatively inert.
- a monocyclic, non-symmetrical diisocyanate is used to produce component A, which has two isocyanate groups of the different reactivity described.
- TDI 2,4- or 2,6-tolylene diisocyanate
- the polyurethane binder according to the invention contains as component B an at least difunctional isocyanate which has no nitrogen atom which is not part of an NCO group, or a mixture of two or more thereof.
- Suitable as component B are, for example, at least difunctional isocyanates or a mixture of two or more such isocyanates, the average functionality of which is at least about two.
- component B contains at least one at least difunctional isocyanate, the NCO groups of which are more reactive than the less reactive isocyanate groups of the compounds in comparison with compounds reactive with NCO groups, for example with urethane, thiourethane, biuret or allophanate formation
- Component A contained polyurethane prepolymers.
- the isocyanate groups of the difunctional isocyanates contained in component B can have a different or essentially identical reactivity. It is also possible in the context of a preferred embodiment of the invention to use at least difunctional isocyanates as component B, the isocyanate groups of which have an identical reactivity.
- component B has a molecular weight of up to about 2,000, but preferably the molecular weight is lower, for example less than about 1,000, less than about 700 or less than about 400 g / mol.
- MDI 4,4'-diphenylmethane diisocyanate
- 2,2'-diphenylmethane diisocyanate 2,4'-diphenylmethane diisocyanate
- HDI 2,4'-diphenylmethane diisocyanate
- IPDI or TMXDI are suitable for use as component B in the context of the present invention.
- MDI 4,4'-diphenylmethane diisocyanate
- 2,2'-diphenylmethane diisocyanate or 2,4'-diphenylmethane diisocyanate are used.
- the polyurethane binder according to the invention contains at least about 3% by weight of component B, based on the total polyurethane binder. In a preferred embodiment, the polyurethane binder contains about 5 to about 25% by weight of component B.
- the polyurethane binder according to the invention preferably has a content of volatile monomers bearing isocyanate groups of less than 2% by weight or less than 1% by weight or preferably less than 0.5% by weight. These limits apply in particular to volatile isocyanate compounds which have only a limited risk potential for persons involved in their processing, for example for isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), tetramethylxylylene diisocyanate (TMXDI) or cyclohexane diisocyanate.
- IPDI isophorone diisocyanate
- HDI hexamethylene diisocyanate
- TMXDI tetramethylxylylene diisocyanate
- cyclohexane diisocyanate cyclohexane diisocyanate.
- the content in the polyurethane binder according to the invention is preferably less than 0.3% by weight and particularly preferably less than 0.1% by weight.
- the latter isocyanate compounds include, in particular, tolylene diisocyanate (TDI).
- TDI tolylene diisocyanate
- the polyurethane binder has a TDI and HDI content of less than 0.05% by weight.
- the polyurethane binder according to the invention contains as component C an at least difunctional isocyanate or a mixture of two or more isocyanates with an average functionality of at least two, which has at least one nitrogen atom per isocyanate, which is not part of an NCO or urethane group.
- Suitable for use in component C are, for example, the carbodiimides bearing NCO groups, as can be obtained by reacting diisocyanates under suitable conditions and with catalysis.
- isocyanates examples include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), hydrogenated MDI (H 12 MDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), 4,4'-diphenyldimethylmethane diisocyanate, di- and tetraalkylene diphenylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, the isomers of tolylene diisocyanate (TDI), 1-methyl-2,4-diisocyanato-cyclohexane, 1,6-diisocyanato 2,2,4-trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane, 1-isocyan
- diisocyanates are, for example, trimethylhexamethylene diisocyanate, 1,4-diisocyanatobutane, 1, 12-diisocyanatododecane and dimer fatty acid diisocyanate. Particularly suitable are: tetramethylene, hexamethylene,
- Cyclohexane 1,3- or 1,4-tetramethylxylene, isophorone, 4,4-dicyclohexylmethane and lysine ester di-isocyanate.
- reaction products of MDI, TDI, HDI or IPDI, or of mixtures of two or more thereof, with formation of carbodimide are particularly suitable.
- oligomerization products of the polyisocyanates such as are obtainable with the formation of isocyanurate rings by suitable reaction of polyisocyanates, preferably diisocyanates. If oligomerization products are used, those with an average degree of oligomerization of about 3 to about 5 are particularly suitable.
- Isocyanates suitable for the reaction are those already mentioned above, the trimerization products of the isocyanates HDI, MDI or IPDI being particularly preferred.
- polymeric isocyanates such as those obtained as a residue in the distillation bottoms from the distillation of diisocyanates.
- polymeric MDI is obtainable from the distillation residue in the distillation of MDI and has at least one nitrogen atom per isocyanate which is not part of an NCO or urethane group.
- Component C is added to the polyurethane binder according to the invention in such an amount that the entire polyurethane binder contains about 1 to about 40% by weight of component C.
- the polyurethane binder contains about 5 to about 30% by weight and in particular about 10 to about 22% by weight of component C.
- a polyurethane binder with the advantages according to the invention can in principle be produced in any manner. However, two methods have proven to be particularly advantageous and are described below.
- component A it is possible to produce the polyurethane binder directly by the production of component A, with a subsequent subsequent or simultaneous addition of components B and C.
- Component B can optionally be added together with another polyol component.
- the invention therefore furthermore relates to a process for the preparation of a polyurethane binder containing isocyanate groups, comprising at least three stages, in which h) a polyurethane prepolymer is prepared in a first stage from an at least difunctional isocyanate and at least one polyol component, and i) in a second stage Stage another at least difunctional isocyanate, which has no nitrogen atom which is not part of an NCO group, or a mixture of two or more thereof and j) in a third stage an at least difunctional isocyanate or a mixture of two or more isocyanates with an average Functionality of at least two is added, wherein at least one isocyanate has at least one nitrogen atom which is not part of an NCO group, the majority of the isocyanate groups present after completion of the first stage having a lower reactivity with isocy anate-reactive groups, especially with respect to OH groups, has as the isocyanate groups of the at least difunctional isocyanate added
- OH: NCO ratio is less than 1. The ratio of OH groups to
- isocyanate groups in the first stage are about 0.4 to about 0.7, in particular more than 0.5 to about 0.7.
- the reaction of a polyol component with the at least difunctional isocyanate in a first stage can be carried out in any manner known to the person skilled in the art according to the general rules of polyurethane production.
- the reaction can take place, for example, in the presence of solvents.
- solvents In principle, all solvents commonly used in polyurethane chemistry can be used as solvents, in particular esters, ketones, halogenated hydrocarbons, alkanes, alkenes and aromatic hydrocarbons.
- solvents examples include methylene chloride, trichlorethylene, toluene, xylene, butyl acetate, amyl acetate, isobutyl acetate, methyl isobutyl ketone, methoxybutyl acetate, cyclohexane, cyclohexanone, dichlorobenzene, diethyl ketone, diisobutyl ketone, dioxane, ethyl acetate, ethylene glycol ethylacetyl ethylacetyl ethylacetyl ethylacetyl ethylacetyl ethylacetyl ethylacetyl ethylacetyl ethylacetyl ethylacetyl ethylacetyl ethylacetyl ethylacetyl ethylacetyl ethylacetyl eth
- reaction components themselves are liquid or at least one or more of the reaction components form a solution or dispersion of further, insufficiently liquid reaction components, the use of solvents can be dispensed with entirely. Such a solvent-free reaction is preferred in the context of the present invention.
- the polyol if appropriate together with a suitable solvent, is placed in a suitable vessel and mixed.
- the at least difunctional isocyanate is then added while mixing continues.
- the temperature is usually raised to accelerate the reaction. As a rule, the temperature is raised to about 40 to about 80 ° C.
- the onset of exothermic reaction then causes the temperature to rise.
- the temperature of the The batch is kept at about 70 to about 110 ° C., for example at about 85 to 95 ° C. or in particular at about 75 to about 85 ° C., the temperature is optionally set by suitable external measures, for example heating or cooling.
- customary catalysts can optionally be added to the reaction mixture.
- the addition of dibutyltin dilaurate or diazabicyclooctane (DABCO) is preferred. If it is desired to use a catalyst, the catalyst is generally added to the reaction mixture in an amount of from about 0.005% by weight or from about 0.01% to about 0.2% by weight, based on the overall batch .
- the reaction time for the first stage depends on the polyol component used, the at least difunctional isocyanate used, the reaction temperature and any catalyst present.
- the total reaction time is usually about 30 minutes to about 20 hours.
- IPDI Isophorone diisocyanate
- TXDI tetramethylxylylene diisocyanate
- MDI H12 hydrogenated diphenylmethane diisocyanate
- TDI tolylene diisocyanate
- At least one further at least difunctional isocyanate which has no nitrogen atom and which is not part of an NCO group, or a mixture of two or more such isocyanates is mixed with component A obtained in the first stage, or optionally implemented together with another polyol component.
- Any polyol from the group of the polyols listed above in the course of this text or a mixture of two or more thereof can be used as a constituent of the further polyol component which may be present.
- a polypropylene glycol is preferably used as the polyol component in the second stage of the process according to the invention with a molecular weight of about 400 to about 2500, or a Polyeste ⁇ olyo! with at least a high, in particular a predominant proportion of aliphatic dicarboxylic acids, or a mixture of these polyols.
- At least difunctional isocyanate which has no nitrogen atom and which is not part of an NCO group
- at least one polyisocyanate is used in the second stage of the process according to the invention, the isocyanate groups of which have a higher reactivity than the isocyanate groups in the prepolymer with lower reactivity.
- reactive isocyanate groups which originate from the at least difunctional isocyanate originally used to prepare prepolymer A may still be present in the prepolymer.
- a bicyclic, aromatic, symmetrical diisocyanate is preferably used as the further at least difunctional isocyanate, which has no nitrogen atom and which is not part of an NCO group.
- the bicyclic isocyanates include, for example, the diisocyanates of the diphenylmethane series, in particular the 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate.
- diphenylmethane diisocyanate in particular 4,4'-diphenylmethane diisocyanate
- the use of diphenylmethane diisocyanate, in particular 4,4'-diphenylmethane diisocyanate is particularly preferred as the further at least difunctional isocyanate in the second stage of the process according to the invention.
- the further at least difunctional isocyanate which has no nitrogen atom and which is not part of an NCO group, is in a second stage Amount of about 1 to about 50% by weight, preferably about 10 to about 30% by weight and in particular in an amount of about 15 to about 25% by weight, based on the total amount of the polyisocyanates used in all stages of the invention Procedure used.
- the ratio OH: NCO in the second stage is about 0.2 to about 0.6, in particular up to about 0.5. This is to be understood as the ratio OH: NCO of the components added in the second stage; isocyanate groups originating from prepolymer A are not taken into account here.
- a polyurethane binder with the advantages according to the invention can also be produced by mixing individual components D, E, F and G.
- the invention therefore also relates to a process for the preparation of a low-viscosity, isocyanate group-bearing polyurethane binder with a low content of volatile, isocyanate group-containing monomers, comprising the mixing of four components D, E, F and G, in which k) component D is an isocyanate group load-bearing polyurethane prepolymer, obtainable by reacting a polyol component with an at least difunctional isocyanate, I) as component E another polyurethane prepolymer carrying isocyanate groups, obtainable by reacting a polyol component with a further at least difunctional isocyanate, the isocyanate groups of which are more reactive towards isocyanates Groups have as the isocyanate groups of component D, m) as component F an at least difunctional isocyanate which has no nitrogen atom which is not part of an NCO group, or a mixture of two or more thereof, and n) as component G a further at least difunctional isocyan
- the polyurethane binders according to the invention and the polyurethane binders produced according to the invention preferably have a viscosity of less than 5000 mPas (measured with Brookfield RT DVII (Thermosell), spindle 27, 20 rpm, 50 ° C.).
- all reactions which may possibly occur between components D, E, F and G are understood to mean reactions of isocyanate groups with functional groups which have hydrogen atoms which are reactive toward isocyanates.
- the addition of component F generally leads to a reaction of the isocyanate groups of component F with the free OH groups. This results in a reduction in the content of component F. Accordingly, if reactions are to be expected which can lead to a reduction in the proportion of component F, component F must be added in such an amount that, after all of these reactions have ended, the required minimum amount of component F is present in the polyurethane binder.
- polyols and mixtures of two or more of the polyols mentioned can be used as the polyol component for producing components D and E in the process according to the invention.
- the polyol components which were mentioned as particularly suitable for the production of component A in the context of this text are preferably also used in the process according to the invention.
- the statements regarding component B apply analogously to the at least difunctional isocyanate to be used as component F, which has no nitrogen atom which is not part of an NCO group, or a mixture of two or more such isocyanates.
- component C apply analogously to the at least difunctional isocyanate to be used as component G or a mixture of two or more isocyanates with an average functionality of at least two, at least one isocyanate having at least one nitrogen atom which is not part of an NCO group .
- the polyurethane binder according to the invention and the polyurethane binders produced according to the invention are distinguished in particular by the fact that they have an extremely low content of volatile monomers bearing isocyanate groups, which is less than 2% by weight, or less than 1% by weight, less than 0%. 5 wt .-% and in particular less than about 0.1 wt .-%. It should be particularly emphasized that the process according to the invention manages without separate process steps for removing volatile diisocyanate components.
- polyurethane binders produced by the process according to the invention have a viscosity which is in a very favorable range for processing.
- the viscosity of the polyurethane binders produced by the process according to the invention is in particular less than 5,000 mPas (measured using Brookfield RT DVII (Thermosell), spindle 27, 20 rpm, 50 ° C.).
- the polyurethane binders according to the invention are suitable in bulk or as a solution in organic solvents, for example in solvents as described above, for coating objects, in particular for gluing objects.
- the invention therefore also relates to the use of a polyurethane binder according to the invention or a polyurethane binder which has been produced by a process according to the invention in the production of adhesives, in particular one and two-component adhesives, coatings, in particular paints, emulsion paints and casting resins and moldings, and for coating and in particular gluing objects, in particular for gluing films and for producing film composite materials.
- the polyurethane binder according to the invention or the polyurethane binder produced by one of the methods according to the invention is used in particular for bonding plastics and particularly preferably for laminating plastic foils, plastic foils vapor-coated with metal or metal oxides, and metal foils, in particular aluminum foils.
- the curing, d. H. the crosslinking of the individual polyurethane binder molecules via the free isocyanate groups can only be brought about by adding atmospheric moisture without the addition of further compounds, for example hardener.
- polyfunctional crosslinking agents for example amines or in particular polyfunctional alcohols, are added as hardeners (two-component systems).
- Foil composites produced with the products produced according to the invention show high processing reliability when heat-sealing. This is due to the reduced proportion of migratable, low-molecular products in the polyurethane binders.
- an advantageous processing temperature for the adhesives produced according to the invention is between approximately 30 and approximately 90 ° C.
- the invention also relates to an adhesive comprising two components
- component H where o) a polyurethane binder according to the invention containing isocyanate groups or a polyurethane binder containing isocyanate groups, prepared according to one of the processes according to the invention described above, as component H, and p) a compound having at least two functional groups which are reactive towards the isocyanate groups of component H and a Molecular weight of up to 50,000, or a mixture of two or more such compounds, is used as component I.
- Any polyurethane binder according to the invention can be used as component H, as described in the context of the above text.
- Component I is preferably a compound having at least two functional groups with a molecular weight of up to 2,500 which are reactive towards the isocyanate groups of component F, or a mixture of two or more such compounds. At least two functional groups which are reactive toward the isocyanate groups of component F are particularly suitable for amino groups, mercapto groups or OH groups, it being possible for compounds which can be used in component G to have amino groups, mercapto groups or OH groups in each case exclusively or in a mixture.
- component I The functionality of the compounds that can be used in component I is generally at least about two.
- Component I preferably has a proportion of more highly functional compounds, for example with a functionality of three, four or more.
- the total (average) functionality of component I is, for example, about two (e.g. if only difunctional compounds are used as component I) or more, for example about 2.1, 2.2, 2.5, 2.7, or 3. If necessary, component I can have an even higher functionality, for example about four or more.
- Component I preferably contains a polyol carrying at least two OH groups. All polyols mentioned in the context of the present text are suitable for use in component I, provided that they meet the restrictive criterion of the upper limit of the molecular weight.
- Component I is generally used in an amount such that the ratio of isocyanate groups of component H to functional groups in component I which are reactive with isocyanate groups of component H is about 5: 1 to about 1: 1, in particular about 2: 1 to about 1 : 1 is.
- the adhesive according to the invention generally has a viscosity of about 250 to about 10,000 mPas, in particular about 500 to about 8,000 or up to about 5,000 mPas (Brookfield RVT DVII, spindle 27, 20 rpm, 40 ° C.).
- the adhesive according to the invention can also contain additives.
- the additives can make up up to about 30% by weight of the total adhesive.
- additives which can be used in the context of the present invention include, for example, plasticizers, stabilizers, antioxidants, dyes, photostabilizers or fillers.
- plasticizers based on phthalic acid are used as plasticizers, in particular dialkyl phthalates, phthalic esters which have been esterified with a linear alkanol having about 6 to about 12 carbon atoms being preferred as plasticizers.
- Dioctyl phthalate is particularly preferred.
- plasticizers for example sucrose benzoate, diethylene glycol benzoate and / or diethylene glycol benzoate about 50 to about 95% of all hydroxyl groups have been esterified, phosphate plasticizers, for example t-butylphenyl diphenyl phosphate, polyethylene glycols and their derivatives, for example diphenyl ether of poly (ethylene glycol), liquid resin derivatives, for example the methyl ester of hydrogenated resin, vegetable and animal oils, for example glycerol esters of fatty acids and their polymerization products.
- benzoate plasticizers for example sucrose benzoate, diethylene glycol benzoate and / or diethylene glycol benzoate about 50 to about 95% of all hydroxyl groups have been esterified
- phosphate plasticizers for example t-butylphenyl diphenyl phosphate
- polyethylene glycols and their derivatives for example diphenyl ether of poly (ethylene glycol)
- liquid resin derivatives for example the methyl
- Stabilizers or antioxidants which can be used as additives in the context of the invention include sterically hindered phenols of high molecular weight (M n ), polyfunctional phenols and sulfur- and phosphorus-containing phenols.
- Phenols which can be used as additives in the context of the invention are, for example, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene; Pentaerythritol tetrakis 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate; n-octadecyl-3,5-di-tert-butyl-4-hydroxyphenyl) propionate; 4,4-methylenebis (2,6-di-tert-butylphenol); 4,4-thiobis (6-tert-butyl-o-cresol); 2,6-di-tert-butylphenol; 6-
- Suitable photostabilizers are, for example, those which are commercially available under the name Thinuvin® (manufacturer: Ciba Geigy).
- thermoplastic polymers can be present in the adhesives according to the invention, for example ethylene vinyl acetate (EVA), ethylene acrylic acid, ethylene methacrylate and ethylene-n-butyl acrylate copolymers, which optionally give the adhesive additional flexibility, toughness and strength.
- EVA ethylene vinyl acetate
- ethylene acrylic acid ethylene methacrylate
- ethylene-n-butyl acrylate copolymers which optionally give the adhesive additional flexibility, toughness and strength.
- hydrophilic polymers for example polyvinyl alcohol, hydroxyethyl cellulose, hydroxypropyl cellulose, polyvinyl methyl ether, polyethylene oxide, polyvinyl pyrrolidone, polyethyloxazoline or Starch or cellulose esters, especially the acetates with a degree of substitution of less than 2.5, which increase the wettability of the adhesives.
- PE1 polyether based on propylene glycol
- PE2 polyether based on propylene glycol
- MDI-P polymer MDI (residue from distillation bottoms)
- F2 film made of polyethylene (PE) with a thickness of 70 ⁇ and a plasticizer content of 400 ppm erucic acid amide (ESA)
- F3 film made of polyethylene (PE) with a thickness of 60 ⁇ and a plasticizer content of 800 ppm erucic acid amide
- the mixing ratio of adhesive preparation / hardener was 1/1 for B1 to B8 and 100 to 70 for V1 and V2.
- the application amount in all examples was 2 g / m 2 .
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Lubricants (AREA)
- Paints Or Removers (AREA)
Abstract
Description
Claims
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000561244A JP2003519243A (ja) | 1998-07-20 | 1999-07-10 | 改善された滑剤接着を有する低モノマーのポリウレタン結合剤 |
SK99-2001A SK992001A3 (en) | 1998-07-20 | 1999-07-10 | MONOMER-POOR POLYURETHANE BONDING AGENT HAVING AN IMPROVEDì (54) LUBRICANT ADHESION |
KR1020017000850A KR20010053584A (ko) | 1998-07-20 | 1999-07-10 | 개선된 윤활 접착성을 갖는, 단량체의 함량이 낮은폴리우레탄 결합제 |
BR9912309-6A BR9912309A (pt) | 1998-07-20 | 1999-07-10 | Aglutinante de poliuretano pobre em monÈmeros com aperfeiçoada aderência do agente deslizante |
EP99932867A EP1100839A1 (de) | 1998-07-20 | 1999-07-10 | Monomerarmes polyurethanbindemittel mit verbesserter gleitmittelhaftung |
CA002338378A CA2338378A1 (en) | 1998-07-20 | 1999-07-10 | Monomer-poor polyurethane bonding agent having an improved lubricant adhesion |
AU49096/99A AU4909699A (en) | 1998-07-20 | 1999-07-10 | Monomer-poor polyurethane bonding agent having an improved lubricant adhesion |
HU0102626A HUP0102626A2 (hu) | 1998-07-20 | 1999-07-10 | Monomerekben szegény poliuretán kötőanyagok javított felületi tapadással |
HR20000902A HRP20000902A2 (en) | 1998-07-20 | 2000-12-28 | Monomer-poor polyurethane bonding agent having an improved lubricant adhesion |
NO20010327A NO20010327L (no) | 1998-07-20 | 2001-01-19 | Monomer-fattig polyuretanbindemiddel med forbedret smøremiddel-adhesjon |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19832556.8 | 1998-07-20 | ||
DE19832556 | 1998-07-20 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/137,884 Continuation US6809171B2 (en) | 1998-07-20 | 2002-05-02 | Monomer-poor polyurethane bonding agent having an improved lubricant adhesion |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000005290A1 true WO2000005290A1 (de) | 2000-02-03 |
Family
ID=7874664
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1999/004890 WO2000005290A1 (de) | 1998-07-20 | 1999-07-10 | Monomerarmes polyurethanbindemittel mit verbesserter gleitmittelhaftung |
Country Status (15)
Country | Link |
---|---|
EP (1) | EP1100839A1 (de) |
JP (1) | JP2003519243A (de) |
KR (1) | KR20010053584A (de) |
CN (1) | CN1310733A (de) |
AU (1) | AU4909699A (de) |
BR (1) | BR9912309A (de) |
CA (1) | CA2338378A1 (de) |
DE (1) | DE19931997A1 (de) |
HR (1) | HRP20000902A2 (de) |
HU (1) | HUP0102626A2 (de) |
ID (1) | ID30020A (de) |
NO (1) | NO20010327L (de) |
SK (1) | SK992001A3 (de) |
TR (1) | TR200100058T2 (de) |
WO (1) | WO2000005290A1 (de) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
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KR100586132B1 (ko) * | 1999-04-23 | 2006-06-02 | 닛폰 폴리우레탄 고교 가부시키가이샤 | 라미네이트용 접착제 |
DE50309990D1 (de) | 2002-02-22 | 2008-07-31 | Jowat Ag | Polyurethan-Zusammensetzungen mit geringem Anteil an Diisocyanatmonomer(en) |
JP4783276B2 (ja) * | 2006-12-25 | 2011-09-28 | 三洋化成工業株式会社 | ポリエステル系ウレタン樹脂。 |
DE102008027914A1 (de) | 2008-06-12 | 2009-12-17 | Henkel Ag & Co. Kgaa | Vernetzende 2K-Isocyanat-Zusammensetzungen |
CN103270067B (zh) * | 2010-12-20 | 2015-01-28 | 阿克佐诺贝尔国际涂料股份有限公司 | 来自具有非常低游离单体异氰酸酯的预聚物的mdi基衬里和膜 |
RU2599250C2 (ru) * | 2011-04-15 | 2016-10-10 | Х.Б. Фуллер Компани | Адгезивы на основе модифицированного дифенилметандиизоцианата |
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1999
- 1999-07-09 DE DE19931997A patent/DE19931997A1/de not_active Withdrawn
- 1999-07-10 TR TR2001/00058T patent/TR200100058T2/xx unknown
- 1999-07-10 JP JP2000561244A patent/JP2003519243A/ja active Pending
- 1999-07-10 ID IDW20010162D patent/ID30020A/id unknown
- 1999-07-10 EP EP99932867A patent/EP1100839A1/de not_active Withdrawn
- 1999-07-10 SK SK99-2001A patent/SK992001A3/sk unknown
- 1999-07-10 WO PCT/EP1999/004890 patent/WO2000005290A1/de not_active Application Discontinuation
- 1999-07-10 HU HU0102626A patent/HUP0102626A2/hu unknown
- 1999-07-10 AU AU49096/99A patent/AU4909699A/en not_active Abandoned
- 1999-07-10 BR BR9912309-6A patent/BR9912309A/pt not_active Application Discontinuation
- 1999-07-10 CN CN99808826A patent/CN1310733A/zh active Pending
- 1999-07-10 KR KR1020017000850A patent/KR20010053584A/ko not_active Application Discontinuation
- 1999-07-10 CA CA002338378A patent/CA2338378A1/en not_active Abandoned
-
2000
- 2000-12-28 HR HR20000902A patent/HRP20000902A2/hr not_active Application Discontinuation
-
2001
- 2001-01-19 NO NO20010327A patent/NO20010327L/no unknown
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EP0019120A1 (de) * | 1979-04-28 | 1980-11-26 | Häger & Kässner GmbH | Verfahren zur Herstellung elastischer, wetterbeständiger Flächengebilde |
EP0118065A2 (de) * | 1983-02-25 | 1984-09-12 | Henkel Kommanditgesellschaft auf Aktien | Verfahren zur Herstellung von Polyurethan-Präpolymeren mit endständigen Isocyanatgruppen und vermindertem Restmonomergehalt |
EP0150444A2 (de) * | 1984-01-14 | 1985-08-07 | Henkel Kommanditgesellschaft auf Aktien | Verfahren zur Herstellung gemischter Polyurethan-Prepolymerer |
GB2268180A (en) * | 1992-05-12 | 1994-01-05 | Basf Corp | Polymethylene polyphenyl polyisocyanate based prepolymers |
WO1998029466A1 (de) * | 1997-01-02 | 1998-07-09 | Henkel Kommanditgesellschaft Auf Aktien | Monomerenarmes pu-prepolymer |
WO1999024486A1 (de) * | 1997-11-11 | 1999-05-20 | Henkel Kommanditgesellschaft Auf Aktien | Polyurethanbindemittel mit einem niedrigen gehalt an leichtflüchtigen monomeren |
Also Published As
Publication number | Publication date |
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DE19931997A1 (de) | 2000-01-27 |
EP1100839A1 (de) | 2001-05-23 |
NO20010327L (no) | 2001-03-13 |
JP2003519243A (ja) | 2003-06-17 |
HRP20000902A2 (en) | 2001-08-31 |
CN1310733A (zh) | 2001-08-29 |
NO20010327D0 (no) | 2001-01-19 |
CA2338378A1 (en) | 2000-02-03 |
AU4909699A (en) | 2000-02-14 |
TR200100058T2 (tr) | 2001-05-21 |
KR20010053584A (ko) | 2001-06-25 |
BR9912309A (pt) | 2001-05-08 |
SK992001A3 (en) | 2001-08-06 |
ID30020A (id) | 2001-11-01 |
HUP0102626A2 (hu) | 2001-11-28 |
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