EP4214255A1 - Reaktivmasse zur herstellung von polyurethanschichten mit thermisch aktivierbaren katalysatorsystemen - Google Patents

Reaktivmasse zur herstellung von polyurethanschichten mit thermisch aktivierbaren katalysatorsystemen

Info

Publication number
EP4214255A1
EP4214255A1 EP21769054.4A EP21769054A EP4214255A1 EP 4214255 A1 EP4214255 A1 EP 4214255A1 EP 21769054 A EP21769054 A EP 21769054A EP 4214255 A1 EP4214255 A1 EP 4214255A1
Authority
EP
European Patent Office
Prior art keywords
metal
reactive composition
isocyanate
polyol
polyurethane
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
EP21769054.4A
Other languages
German (de)
English (en)
French (fr)
Inventor
Andreas Gerken
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Benecke Kaliko AG
Original Assignee
Benecke Kaliko AG
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 Benecke Kaliko AG filed Critical Benecke Kaliko AG
Publication of EP4214255A1 publication Critical patent/EP4214255A1/de
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/227—Catalysts containing metal compounds of antimony, bismuth or arsenic
    • 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
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/222—Catalysts containing metal compounds metal compounds not provided for in groups C08G18/225 - C08G18/26
    • 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
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/225—Catalysts containing metal compounds of alkali or alkaline earth metals
    • 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
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • 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
    • C09D175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers

Definitions

  • the present invention relates to reactive compositions for the production of polyurethane layers, an isocyanate component from at least one polyfunctional isocyanate, an oligomer of a polyfunctional isocyanate or an isocyanate prepolymer, a polyol component from at least one polyol, and a catalyst system with a metal-based catalyst based on a salt or an organometallic compound and a diketo compound having a melting point of >15°C.
  • the present invention further relates to processes for the production of such polyurethane layers, polyurethane layers produced from the reactive masses and composite structures which contain such polyurethane layers.
  • the present invention relates to the use of the specified catalyst systems for the conversion of polyols and polyisocyanates.
  • Polyurethane systems are used because of their high durability in artificial leather materials as a topcoat or bulk material to produce durable products of leather-equivalent caliper or greater.
  • polyurethane artificial leather is often manufactured in such a way that at least one of the textile coating layers consists of a relatively thick low-solvent or solvent-free reactive polyurethane system.
  • PVC-based synthetic leather is also used in large quantities due to the significantly lower price compared to leather and polyurethane synthetic leather.
  • plasticizers for processing, which have been the subject of public debate for years and whose use is viewed increasingly critically. Accordingly, the use of plasticizers has been increasingly restricted in recent years, e.g. by REACH regulations or the GADSL list of automobile manufacturers.
  • plasticizers are not firmly embedded in the PVC matrix. Over time, plasticizers can therefore migrate out of the polymer matrix, resulting in a change in the flexibility properties of PVC synthetic leather.
  • PVC artificial leather tends to discolour, particularly when exposed to elevated temperatures for a longer period of time, which can occur, for example, when a car is left in the blazing sun for a long time, and the associated deterioration in mechanical stability.
  • polyurethanes are therefore preferred as a coating system over other PVC plastisols, especially since textiles coated with polyurethanes also have a haptic similar to that produced by touching leather.
  • Coatings containing polyurethanes can be prepared by solidifying polyurethanes from solution or by preparing the polyurethanes directly on a substrate from the isocyanate and polyol precursors. Direct preparation is advantageous here for a number of reasons compared to the use of polyurethanes dissolved in solvents or dispersed in water. For example, the production of defect-free parts or webs with dissolved or dispersed polyurethanes can be difficult, since the solvents or water in a manufacturing process must be defined and evaporated as quickly as possible from an economic point of view. In addition, a considerable amount of energy is required for the evaporation process. at When using solvent-based polyurethane systems, solvent residues often remain in the polyurethane, which can still be detected in the finished product and/or can adversely affect the odor of the finished product.
  • dissolved or dispersed polyurethanes are generally only commercially available with specified polyurethane systems.
  • the production speed represents a significant economic factor. Additional catalysts are used to increase this speed. Their profile of requirements is such that a reaction at room temperature is suppressed as far as possible so that the reactive components and any other additives can be mixed well and the mass can be brought into the desired shape before "curing", e.g. by spreading the reactive mass on a On the other hand, the conversion of isocyanates and polyols at the process temperature should take place as quickly as possible.
  • blocked polyisocyanate prepolymers in a mixture with a polyamine, the reaction of which forms a polyurethane urea, is established.
  • Blocked polyisocyanates have the advantage that the reactive mixtures can be left at room temperature for a long time and Processing no special mixing head system is necessary, which mixes the reactive components just before processing.
  • blocking agents used for the reactive isocyanate groups are oximes or caprolactams, which are split off from the blocked polyisocyanate at elevated temperature and release the reactive isocyanate group.
  • the disadvantage here in addition to the sometimes high temperature required for splitting off the blocking agent, is that some of the split-off groups are classified as toxic and remain in the product, particularly in thicker products, where they are visually and functionally disruptive due to their odor or undesirable tendency to migrate to surfaces.
  • blocked polyisocyanate systems usually contain high-boiling solvents such as methoxypropyl acetate to reduce viscosity, which remain in the end product as residues and have to be removed in an energy-intensive manner.
  • EP 1 059 379 B1 describes a polyurethane system with a
  • EP 1 927 466 B1 describes a similar system in which a metal acetylacetonate, for example a tin-based catalyst, is used in conjunction with additional acetylacetone in the reaction mass. This suppresses the reaction at room temperature and the acetylacetone is only vaporized at higher temperatures in order to increase the reactivity of the catalyst system.
  • a metal acetylacetonate for example a tin-based catalyst
  • WO 2013/087682 A1 describes bismuth-containing catalysts for polyurethane systems in which bismuth salts or complexes have been reacted with a 1,3-ketoamide in a preceding reaction.
  • the resulting catalysts are oily/liquid, but still lead to relatively short processing times at room temperature, which translates into short skinning times.
  • the formulations and the use of these formulations should enable the production of a film with at least one polymeric layer, which can optionally also be foamed, which is a component of a decorative material such as a film or artificial leather as the only film layer or as one of a plurality of film layers.
  • a polymeric layer which can optionally also be foamed, which is a component of a decorative material such as a film or artificial leather as the only film layer or as one of a plurality of film layers.
  • the formulation should enable the production of decorative films with a pleasant tactile feel, and the thickness applied should also prevent the textile structure from being found on the surface.
  • the present invention addresses this need.
  • the present invention is based on the surprising finding that these properties can be imparted by a catalyst system that contains a metal-based catalyst based on a salt or an organometallic compound and a diketo compound with a melting point of >15.degree. Mixtures of these catalyst systems with polyisocyanates and polyols have a relatively stable viscosity at room temperature and can be activated by increasing the temperature, so that, for example at 150° C., tacky polyurethane layers no longer form within 120 seconds. Accordingly, in a first aspect, the present invention relates to a catalyst system that contains a metal-based catalyst based on a salt or an organometallic compound and a diketo compound with a melting point of >15.degree. Mixtures of these catalyst systems with polyisocyanates and polyols have a relatively stable viscosity at room temperature and can be activated by increasing the temperature, so that, for example at 150° C., tacky polyurethane layers no longer form within 120 seconds. Accordingly, in
  • a catalyst system comprising a metal-based catalyst based on a salt or an organometallic compound and a diketo compound with a melting point of >15°C.
  • the "metal-based catalyst” in the reactive mass is a substance that, when added to a mixture of polyisocyanates and polyols, can accelerate the reaction to form a polyurethane (compared to a reaction without the catalyst).
  • the "catalyst system” is conveniently prepared by intimately mixing the metal-based catalyst with the diketo compound, where a solvent may be added.
  • a solvent it is also possible to use short-chain esters of mono-, di- and tricarboxylic acids, which are liquid at room temperature, with aliphatic monofunctional polyols having a molar mass of less than 1000 g/mol. It is assumed that the diketo compound binds to the metal of the metal-based catalyst, with the anions of the salt being able to be displaced.
  • the particular advantage of the reactive materials described here over the prior art explained above is that the mixture has a particularly long processing time (pot life) at room temperature, without that the activity of the catalyst is significantly influenced at elevated processing or process temperatures.
  • Diketo compounds preferred for the reactive composition are those with a melting point of >25°C and more preferably >30°C. Diketo compounds in the form of 1,3-diketo compounds are particularly preferred.
  • the carbon atom positioned between the two CO groups can be substituted or unsubstituted (in this case it is present as a CH2 group).
  • a structure R 1 -CO-CH 2 -CO-R 2 is very particularly preferred, where R 1 and R 2 are preferably selected independently of one another from aliphatic and aromatic radicals, which can optionally be substituted.
  • a preferred aliphatic radical in this connection is an alkyl or alkenyl radical, which can be linear, branched or cyclic.
  • a preferred aromatic radical is an aryl radical and especially a phenyl radical, or a heteroaryl radical, especially a pyridyl radical.
  • Substituents which can be present in the respective radicals are, in particular, halogens which are non-reactive towards the metal center in the catalyst, in particular in the form of fluorine atoms, and nonpolar substituents such as methoxy groups, aryl groups (if the primary radical is an aliphatic radical) or alkyl or alkenyl radicals (when the primary radical is an aromatic radical) into consideration.
  • substituents are also conceivable.
  • Possible substituents of the diketo compound are, for example, alkyl and alkenyl groups with 1 to 18 carbon atoms, cycloalkyl, cycloalkenyl and cycloalkyl alkylenes and alkylcycloalkyl groups with 5 to 18 carbon atoms, and non-fused aryl groups (including aralkyl and alkyaryl) of 6 to 18 carbon atoms, for example methyl, ethyl, propyl, isopropyl, isobutyl, n-butyl, s-butyl, t-butyl, 1-pentyl, 3-pentyl, 1-hexyl, 1- Heptyl, 3-heptyl, 1-octyl, 2,4,4-trimethylpentyl, t-octyl, nonyl, decyl, tridecyl, pentadecyl, h
  • one of the ketone functionalities of the diketo compounds is present in a ring, such as in 2-acetyl-1-tetralone, 1-palmitoyl-2-tetralone, 2-stearoyl-1-tetralone, 2-benzoyl-1-tetralone , 2-acetyl-cyclohexanone, and 2-benzoylcyclohexanone.
  • the diketo compound comprises one of these substances.
  • Preferred diketo compounds in which both keto functionalities are present outside of a ring include, for example, benzoyl-p-chlorobenzoylmethane, bis(4-methylbenzoyl)methane, bis(2-hydroxybenzoyl)methane, benzoylacetylmethane, tribenzoylmethane, diacetylbenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, lauroylbenzoylmethane, dibenzoylmethane , 4-Methoxybenzoyl-benzoylmethane, Bis(4- methoxybenzoyl)methane, Bis(4-chlorobenzoyl)methane, Bis(3,4-methylenedioxybenzoyl)methane, Benzoylacetyloctylmethane, Benzoyl- acetylphenylmethane, Stearoy
  • the diketo compound preferably contains 5 to 30 carbon atoms.
  • Very particularly preferred diketo compounds for use in the reactive materials according to the invention are steaorylbenzoylmethane (Tm 56-59° C.), palmitoylbenzoylmethane, 1-phenyl-1,3-butanedione (Tm 54-56° C.), dibenzolymethane (Tm 77-79° C.) , 1,3-bis(4-methoxyphenyl)-1,3-propanedione (Tm 108-115°C), 1,3-di-(2-pyridyl)-1,3-propanedione (Tm 104-109° C), 5,5'-dimethyl-1-3-cyclohexanedione (Tm 146-148 ° C), 1, 3-cyclohexanedione (101-105 ° C) or mixtures of these diketo compounds, especially in the form of a mixture of stearoyl benzoyl methane and palmitoyl be
  • the metal contained in the metal-based catalyst is a metal capable and capable of catalyzing the reaction of isocyanates and alcohols, the catalysis occurring in most cases via attachment of the metal to the oxygen atom of the isocyanate , which reduces the electron density at the carbon atom of the isocyanate.
  • Metals which promote such activation and which are therefore preferred as the metal of the metal-based catalyst are selected from the group comprising the following metals: tin, zinc, bismuth, potassium, cobalt, manganese, titanium, iron, zirconium and nickel.
  • Very particularly preferred metals are zinc and/or bismuth (as sufficiently active and non-toxic metals), of which bismuth is particularly preferred.
  • metals mentioned can be included in the catalyst system as a metal salt or organometallic compound, preference being given to metal salts because they are usually more stable.
  • Preferred metal salts for use in the catalyst system according to the invention are organic metal salts, in particular selected from the group consisting of metal acetylacetonates, metal ethylhexanoates, metal octoates, metal naphthenates, metal acetates, metal neodecanoates, metal malonates and metal carboxylates, and inorganic metal salts, in particular selected from the group consisting of metal nitrates, metal pyrophosphates and metal halides.
  • Bismuth carboxylate or bismuth neodecanoate are very particularly preferred in the reactive materials according to the invention because of its very good reactivity at elevated temperature and because it is not classified as toxic.
  • the amount of the catalyst system is not subject to any relevant restrictions and can generally be adjusted by those skilled in the art so that on the one hand the desired reactivity is established but on the other hand the amount of the catalyst system is as small as possible. Preference is given here to a proportion of the catalyst system in the reactive composition in the range from 0.01 to 1% by weight and preferably from 0.02 to 0.5% by weight. Any solvent added for the formation of the catalyst system or an added low molecular weight carboxylic acid ester which is liquid at room temperature need not be taken into account here, since this is not active as such in the catalysis of the formation of polyurethanes.
  • the ratio of metal-based catalyst to diketo compound is preferably in the range of about 1:2 to 1:20, and more preferably in the range of about 1:4 to 1:15.
  • the isocyanate component is not subject to any relevant restrictions in the reactive compositions according to the invention, with the proviso that the isocyanates in combination with the polyols in the reactive composition are not so reactive that a significant reaction takes place even under ambient conditions (room temperature) without a catalyst.
  • Polyfunctional isocyanates which can be used in the isocyanate component are aliphatic and/or aromatic polyisocyanates, in particular selected from the group comprising 2,2'-, 2,4'- and 4,4'-methylenediphenyl isocyanate (MDI), 2,4-toluene and -2,6-diisocyanate (TDI), naphthylene-1,5-diisocyanate, 1,6-hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), 1,4-cyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane and dicyclohexylmethane-4,4' -diisocyanate, an oligomer or polymer of such a polyfunctional isocyanate Isocyanate prepolymer obtained from the reaction of such a polyfunctional isocyanate with polyol, or mixtures thereof.
  • MDI 2,2'-, 2,
  • Oligomers of polyfunctional isocyanates include, for example, isocyanurates, uretdiones, and biurets.
  • a useful polyisocyanate polymer is, for example, poly-MDI.
  • an isocyanate prepolymer is used at least in part as the isocyanate component.
  • An isocyanate prepolymer is understood as meaning the reaction product of a polyisocyanate with a polyol, the polyisocyanate preferably being used in a ratio to the polyol such that the NCO/OH ratio is at least 2.
  • the polyol used to produce the isocyanate prepolymer is a polyol with an average functionality in the range from 1.85 to 2.5, in particular 1.9 to 2.2 and very particularly preferably from about 2 ,0 is.
  • the isocyanate prepolymer also preferably has an isocyanate group content (determined as a proportion by weight) of between about 2 and 20%, and in particular between about 4 and 13%.
  • isocyanate group content (determined as a proportion by weight) of between about 2 and 20%, and in particular between about 4 and 13%.
  • these isocyanate prepolymers can also have other functional groups such as
  • Ether, thioether, ester and carbonate groups which can be incorporated into the isocyanate prepolymer via the polyol, or urea groups.
  • isocyanate-containing compounds in which the isocyanate group is temporarily chemically blocked and can be reactivated again by heating and splitting off a blocking group.
  • a blocking agent for example, ketoximes such as butanone oxime or acetone oxime, or Caprolactam used. Mixtures of the aforementioned constituents of the isocyanate component can also be used.
  • the polyol component is also not subject to any relevant restrictions in the reactive compositions according to the invention, but here too it must be ensured that the polyols do not form such a relative mixture with the isocyanates that a significant reaction takes place even under ambient conditions (room temperature) without a catalyst.
  • Suitable polyols for use in the reactive compositions according to the invention have a molecular weight in the range from 62 to 20,000, in particular from 250 to 10,000 g/mol and particularly preferably in the range from 2000 to 8000 g/mol.
  • the molecular weight refers to the average molecular weight Mw and is to be determined by GPC and the inclusion of suitable standards (e.g. polystyrene).
  • aliphatic polyols which are preferably bifunctional or higher.
  • the term "aliphatic” is to be understood here as meaning that the polyol does not contain any aromatic components, while functional groups such as ether, ester, carbonate and urea groups can be contained in the polyol.
  • polymer-based polyols and in particular polyols selected from the group comprising polyester polyols, polyether polyols, polythioether polyols, polycarbonate polyols, polyols having a plurality of the functional groups contained in the aforementioned polymers, aliphatic polyacetals containing hydroxyl groups and aliphatic polycarbonates containing hydroxyl groups are therefore preferred. It is very particularly preferred if the polyol component contains at least one polyether polyol and it is most preferred if the polyol component contains only polyether polyols.
  • the reactive composition according to the invention preferably contains a proportion of higher-functional and in particular trifunctional polyols. Further it is preferred that the reactive composition does not contain polyols with a functionality higher than trifunctional.
  • the reactive mass contains trifunctional and difunctional polyol in the polyol component or is formed from trifunctional and difunctional polyol, it is preferred that the trifunctional polyol accounts for at least 50% by weight and more preferably in the range of 65 to 90% by weight. on the polyol component. It is very particularly preferred here if polyether polyols are used as the trifunctional and difunctional polyol.
  • the polyisocyanate component and the polyol component are expediently used in a ratio in which there is an excess of isocyanate groups over OH groups, in particular if the polyol component contains polyols with a functionality of >2.
  • excess of isocyanate groups as far as possible a conversion of all the OH groups in the reactive composition is then achieved; excess NCO groups remain, but these can subsequently react with atmospheric moisture and thus be broken down to -NH2 groups.
  • polystyrene resin In addition to the polyols, other compounds which react with isocyanates and which contain reactive hydrogen atoms by which some of the polyols are substituted can also be used to modify the properties of the fully reacted system in the reactive composition according to the invention.
  • Such compounds contain, for example, two or more reactive groups which are present as OH groups, SH groups, NH groups, NH2 groups or CH-acidic groups, for example in beta-diketo compounds.
  • the reactive composition according to the invention can contain one or more additives that are conventionally used for the production of polyurethane layers and polyurethane artificial leather, e.g. to optimize certain properties or to increase the reactivity even further.
  • An additive to increase the reactivity is, for example, a co-catalyst, for example in the form of a base, one of polyols or other H-acidic compounds stabilized proton released during polyurethane formation.
  • suitable bases are, for example, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,4-diazabicyclo[2.2.2]octane (DABCO), dimethylaminoethanol, etc.
  • liquid additives that Delay reactivity of the metal catalyst for example acetylacetone or 2-ethylhexanoic acid, are added, but this is not necessary for the purposes of the invention.
  • Such liquid additives are preferably not contained in the reactive compositions according to the invention, since acetylacetone-containing reactive compositions smell pungent after conversion to polyurethanes and 2-ethylhexanoic acid is classified as teratogenic and remains in the product due to its boiling point of 228° C. during the formation of the polyurethanes.
  • Additives used in polyurethane coatings and polyurethane synthetic leathers include, in particular, aging inhibitors, flame retardants, fillers, preferably in the form of chalk (CaCOs) or cellulose derivatives, pigments, flow, ventilation and processing aids, rheological aids, flow aids, foaming aids, solvents, carboxylic acid esters and crosslinker under consideration.
  • the reactive composition according to the invention therefore preferably contains one or more of such additives.
  • Suitable flame retardants are aluminum trihydrate or organic phosphinates such as aluminum diethylphosphinate.
  • Suitable leveling agents are e.g. silicone oils.
  • the reactive composition according to the invention is preferably adjusted to a suitable viscosity, preferably in the range from 1 Pa.s to 120 Pa.s, in particular from 5 Pa.s to 15 Pa.s, with this viscosity being present, for example, in the composition a squeegee gap through which the mass is applied to a substrate, can be determined according to ISO 2555:2018.
  • the present invention relates to a polyurethane layer which can be obtained by applying a reactive composition, as described above, to a substrate and reacting the isocyanate component with the polyol component to form polyurethane. Due to the catalyst system used for the reaction, which contains high-boiling diketo compounds, these are present in the polyurethane layer after the reaction and can be detected by extraction and detection, e.g. using GC or HPLC-MS.
  • thick layers for example in an artificial leather or a film composite, can also be produced with the reactive composition according to the invention from 200 to 350 pm.
  • the polyurethane layer has a visually recognizable structure on one side. Structuring in the form of an embossing that imitates the skin side of leather is preferred.
  • the polyurethane layer is provided with a layer of lacquer.
  • This has the task, for example, of improving the surface properties, in particular the abrasion resistance.
  • the optical properties of the surface for example the gloss, can be controlled as desired by means of a lacquer layer.
  • a layer of lacquer is applied to the surface of the polyurethane layer in a manner known in the art, while this is freely accessible from above.
  • the polyurethane layer is solid and has no voids.
  • the cover layer is foamed and has isolated cavities.
  • the cover layer is foamed and has interconnected cavities.
  • the polyurethane layer may be planar or in the form of an object onto or into which it is applied or incorporated, e.g.
  • the present invention relates to a method for producing a polyurethane layer, as described above, wherein
  • the reactive composition is heated to convert the isocyanate and polyol components to form the polyurethane layer, preferably to a temperature above the melting temperature of the diketo compound contained in the reactive composition,
  • the substrate is subsequently removed from the polyurethane layer.
  • the substrate can have a structure that corresponds to the negative of the structure to be produced on the polyurethane layer.
  • Such a method is also referred to in the prior art as reverse coating.
  • Thick polyurethane layers which form the top layer of an artificial leather (i.e. the layer forming the visible side, which can optionally be coated with a layer of lacquer), are particularly advantageous for the production of artificial leather, since the high layer thickness means that a textile structure of a carrier layer is not possible pressed through to the surface and the overall composite has a pleasant "handle" or feel.
  • the present invention therefore relates to a composite structure that has a polyurethane layer as described above, a carrier layer, in particular a textile carrier layer or a carrier layer made of PVC, polyolefin, thermoplastic polyurethane or a polyurethane foam, and optionally an adhesive layer arranged between these layers and/or or a lacquer layer applied to the side of the polyurethane layer opposite the carrier layer.
  • a carrier layer in particular a textile carrier layer or a carrier layer made of PVC, polyolefin, thermoplastic polyurethane or a polyurethane foam
  • an adhesive layer arranged between these layers and/or or a lacquer layer applied to the side of the polyurethane layer opposite the carrier layer.
  • the polyurethane layer in the composite structure is composed essentially (i.e. at least 98% by weight, preferably at least 99% by weight and even more preferably at least 99.5% by weight) of aliphatic polyols and polyisocyanates.
  • Such polyurethanes have the advantage of high resistance to yellowing and aging.
  • the polyurethane layer in the composite is colored dark or black, or the polyurethane layer does not form the top layer of the composite (here, a paint layer is not counted as a top layer).
  • aromatic polyisocyanates were used also or even exclusively for the formation of the polyurethane layer.
  • the present invention relates to the use of a mixture of a metal-based catalyst based on a salt or an organometallic compound and a diketo compound with a melting point of >15° C., preferably as described above, as a catalyst system for the conversion of polyols and polyisocyanates.
  • the composite structures which contain at least one polyurethane layer from a reactive composition according to the invention, can be produced in the same thickness as leather, which is already used today, for example, in automobile interiors.
  • One or more layers can optionally be used to produce the necessary thicknesses.
  • a polyurethane layer or a composite structure with such a layer, which is formed from the reactive composition according to the invention, can also be produced in a continuous process such as, for example, a continuous coating process (direct or transfer coating).
  • the discoloration of a polyurethane layer produced from them after prolonged exposure to heat or UV radiation can be kept so low that even light-colored artificial leather based on the invention can be used in vehicle instrument panels without any problems .
  • the manufactured products can remain dimensionally stable even after prolonged exposure to heat (e.g. climate storage at temperatures of up to 105°C for 26 weeks).
  • the polyurethane layers according to the invention can also be so abrasion-resistant and flexible that they can be used for the usual seat applications in the furniture and automotive sectors and pass the necessary qualification tests (robot test, entry and exit test).
  • the polyurethane layers according to the invention can also be flexible over a wide temperature range (from ⁇ 20° C.), so that the risk of imitation leather breaking due to brittleness when the seat is cold is minimized.
  • the invention is illustrated in more detail below using a few examples, which, however, are not to be regarded as limiting the scope of protection of the application in any way.
  • nickel acetylacetonate Sigma-Aldrich
  • bismuth neodecanoate Borchikat 315 EU, Borchers
  • zinc neodecanoate Reaxis C616, Reaxis
  • bismuth carboxylate Reaxis C716, Reaxis
  • tin dioctylbis( 2,4-pentanedionato- KO2-KO4) Reaxis C2013, Reaxis
  • bismuth/zinc neodecanoate mixture Bicat 8, Shepherd
  • zinc salt of a C12-C14 fatty acid Kosmos 54, Evonik
  • Acetylacetone from Sigma-Aldrich
  • Rhodiastab 55 P from Rhodia/Solvay
  • the amount of catalyst used corresponds to the sum of the numerical values in the respective line in Table 1.
  • the isocyanate component was used in excess (NCO/OH ratio 1.29).
  • the comparison mixtures 1-6, 13, 19 and 25 show that (with the exception of the zinc-based catalyst V3, whose catalytic activity is not sufficient here) a dry film can be produced from the reactive mass with the catalysts tested.
  • the possible processing time is very short, since the viscosity increases so much within 30 minutes that it is no longer possible to process the reactive masses.
  • the toxically questionable catalyst V1 (Example 1) is a processable mass viscosity obtained after 30 minutes, but here too this has increased very sharply compared to the initial viscosity. In all cases, these masses can hardly be processed without technically complex mixing head systems.
  • the comparison mixtures 7 to 12 show that the processing time can be significantly extended by using the liquid 1,3-diketo compound “acetylacetone” in combination with the reactive catalyst bismuth neodecanoate.
  • the reason for this is that the acetylacetone complexes the metal catalyst and only fully releases it for catalysis again through evaporation.
  • An application of this principle is also described, for example, in EP 1 927 466 B1.
  • comparison mixtures 7 to 12 also show a relatively clear increase in viscosity, in particular when the amounts of catalyst are increased, so that processing without mixing head systems is also difficult here.
  • relatively large amounts of acetylacetone must be used for an effective effect which, due to the high boiling point of acetylacetone of 140°C at 150°C, means that parts of this odor-intensive substance, which is classified as toxic, remain in the end product.
  • Mixtures 14 to 18, 20 to 24 and 26 to 30 show the effectiveness of the solid diketo compound (here mixture of stearoyl benzoyl methane and palmitoyl benzoyl methane) in the mass using bismuth neodecanoate as a catalyst as an example.
  • the solid diketo compound here mixture of stearoyl benzoyl methane and palmitoyl benzoyl methane
  • the reactivity of the composition is not adversely affected and a dry film can be produced in all cases at 150° C. in 2 minutes.
  • the proportion of catalyst can be greatly increased without the viscosities or pot lives of the composition increasing as a result (see mixtures 16, 22 and 28). This shows that the amount of catalyst can easily be increased for faster processing without adversely affecting the
  • Mixtures 31 to 34 show that, even when using other metal catalysts with diketo compounds that are solid at room temperature, long processing times are achieved at room temperature and the mass viscosities are still low even after 60 minutes. Apart from the two (even without the addition of diketo compound) insufficiently reactive mixtures with zinc catalysts 31 and 33, dry films are also produced here at 150° C. in 2 minutes.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)
EP21769054.4A 2020-09-15 2021-08-19 Reaktivmasse zur herstellung von polyurethanschichten mit thermisch aktivierbaren katalysatorsystemen Pending EP4214255A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102020211572.9A DE102020211572A1 (de) 2020-09-15 2020-09-15 Reaktivmasse zur Herstellung von Polyurethanschichten mit thermisch aktivierbaren Katalysatorsystemen
PCT/DE2021/200113 WO2022057985A1 (de) 2020-09-15 2021-08-19 Reaktivmasse zur herstellung von polyurethanschichten mit thermisch aktivierbaren katalysatorsystemen

Publications (1)

Publication Number Publication Date
EP4214255A1 true EP4214255A1 (de) 2023-07-26

Family

ID=77710420

Family Applications (1)

Application Number Title Priority Date Filing Date
EP21769054.4A Pending EP4214255A1 (de) 2020-09-15 2021-08-19 Reaktivmasse zur herstellung von polyurethanschichten mit thermisch aktivierbaren katalysatorsystemen

Country Status (5)

Country Link
US (1) US20230406990A1 (zh)
EP (1) EP4214255A1 (zh)
CN (1) CN116096772A (zh)
DE (1) DE102020211572A1 (zh)
WO (1) WO2022057985A1 (zh)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2957716B2 (ja) * 1991-01-17 1999-10-06 三共有機合成 株式会社 ウレタン重合物の製造法
DE19931323B4 (de) 1999-07-07 2008-10-16 Benecke-Kaliko Ag Verbundgebilde mit einer oder mehreren Polyurethanschichten, Verfahren zu deren Herstellung und ihre Verwendung
DE102006056956A1 (de) 2006-11-30 2008-06-05 Benecke-Kaliko Ag Verbundgebilde mit einer Polyurethanschicht, Verfahren zu deren Hersellung und Verwendung
CA2775975C (en) 2009-09-30 2016-11-08 Dow Global Technologies Llc Heat stabilized polymeric composition with epoxidized fatty acid ester plasticizer
EP2604615A1 (de) 2011-12-12 2013-06-19 Sika Technology AG Bismuthaltiger Katalysator für Polyurethan-Zusammensetzungen

Also Published As

Publication number Publication date
WO2022057985A1 (de) 2022-03-24
DE102020211572A1 (de) 2022-03-17
CN116096772A (zh) 2023-05-09
US20230406990A1 (en) 2023-12-21

Similar Documents

Publication Publication Date Title
DE69821536T2 (de) Urethan Katalysator enthaltend Zirkoniumacetylacetonat
DE19931323B4 (de) Verbundgebilde mit einer oder mehreren Polyurethanschichten, Verfahren zu deren Herstellung und ihre Verwendung
DE2637115C3 (de) Verfahren zur Herstellung von Polyurethanharnstoffen
EP1927466B1 (de) Verbundgebilde mit einer Polyurethanschicht, Verfahren zu deren Herstellung und Verwendung
DE10037157A1 (de) Mehrschichtige Beschichtungssysteme aus einer dickschichtigen, gelartigen Grundschicht und einer Deckschicht aus Polyurethan-Lack, deren Herstellung und Verwendung
WO2000059974A1 (de) Polyurethanlösungen mit alkoxysilanstruktureinheiten
DE2221756C3 (de) Verfahren zur Herstellung von lösungsmittelbeständigen, lichtechten, knick- und reibfesten Polyurethanüberzügen auf textlien Substraten, Leder oder Kunstleder oder von Folien
EP3526268B1 (de) Beschichtungsmittelsystem basierend auf salzen einer aliphatischen monocarbonsäure
DE102009027394A1 (de) Verwendung von Isocyanaten auf der Basis von nachwachsenden Rohstoffen
DE102009051445A1 (de) Verwendung spezieller Katalysatoren für die Herstellung von Polyurethanbeschichtungen
WO2011000585A1 (de) Zusammensetzungen auf der basis von diisocyanaten aus nachwachsenden rohstoffen
DE2304893B1 (de) Verfahren zur Herstellung von Überzügen
EP3247757B1 (de) Beschichtungsmittelsystem basierend auf li/bi-katalysatoren
WO2014048854A1 (de) Polyisocyanat-polyadditionsprodukte
DE1092190B (de) Verfahren zur Herstellung hochmolekularer vernetzter Kunststoffe
EP3445827A1 (de) Thermolatent katalysiertes zwei-komponenten-system
EP3334773A1 (de) Beschichtungsmittelsystem basierend auf bi-katalysatoren und aromatischen carbonsäuren
DE2448133C2 (de) Verfahren zur Beschichtung von Substraten
EP2035517B1 (de) In-mold-coating verfahren zur herstellung von formteilen unter verwendung wässriger 2-komponenten-lackformulierung
WO2011018162A1 (de) Isocyanatgruppen enthaltende prepolymere mit guter lagerstabilität
WO2022057985A1 (de) Reaktivmasse zur herstellung von polyurethanschichten mit thermisch aktivierbaren katalysatorsystemen
EP2305727A1 (de) Neue 2K-PUR-Systeme
EP3628694A1 (de) Lösemittelarme beschichtungssysteme für textilien
DE3536017A1 (de) Ganz oder teilweise mit epsilon-caprolactam blockiertes trans-cyclohexan-1,4-diisocyanat, dessen herstellung und verwendung
WO2001064767A1 (de) Polyurethan-beschichtungen auf basis uretdion- und/oder oxadiazintrion-gruppen enthaltender polyisocyanate

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20230417

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)