EP2225298A1 - Compositions durcissables à dégagement gazeux réduit - Google Patents

Compositions durcissables à dégagement gazeux réduit

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Publication number
EP2225298A1
EP2225298A1 EP08865653A EP08865653A EP2225298A1 EP 2225298 A1 EP2225298 A1 EP 2225298A1 EP 08865653 A EP08865653 A EP 08865653A EP 08865653 A EP08865653 A EP 08865653A EP 2225298 A1 EP2225298 A1 EP 2225298A1
Authority
EP
European Patent Office
Prior art keywords
atoms
radical
hydrazide
groups
group
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.)
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Application number
EP08865653A
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German (de)
English (en)
Inventor
Urs Burckhardt
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Sika Technology AG
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Sika Technology AG
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Priority to EP08865653A priority Critical patent/EP2225298A1/fr
Publication of EP2225298A1 publication Critical patent/EP2225298A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/72—Hydrazones
    • C07C251/74—Hydrazones having doubly-bound carbon atoms of hydrazone groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C251/76—Hydrazones having doubly-bound carbon atoms of hydrazone groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/302—Water
    • C08G18/307—Atmospheric humidity
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3253—Polyamines being in latent form
    • C08G18/3256—Reaction products of polyamines with aldehydes or ketones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
    • C08G18/503—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups being in latent form
    • 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
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
    • C08K5/24—Derivatives of hydrazine
    • C08K5/25—Carboxylic acid hydrazides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/43—Compounds containing sulfur bound to nitrogen

Definitions

  • the present invention relates to the field of moisture-curing polyurethane compositions and their use, in particular as elastic adhesives in vehicle construction.
  • Curable compositions containing isocyanate groups also referred to as polyurethane compositions
  • polyurethane compositions have long been used in a wide variety of applications, including as one- and two-part elastic adhesives, sealants or coatings.
  • these moisture-activatable amine crosslinking agents so-called “blocked amines” or “latent hardeners”
  • blocked amines can also cause problems, in particular due to the fact that aldehydes or ketones are formed during the curing reaction. These so-called “cleavage products” are not incorporated into the polyurethane matrix and can therefore escape into the environment by evaporation or migration.
  • the aldehydes or ketones formed from the blocked amines often represent odorous and / or harmful substances.
  • WO 2004/013088 A1 and WO 2007/036571 A1 disclose blocked amines in the form of odor-free aldimines and polyurethane compositions containing such aldimines.
  • the aldehydes released during the curing of the compositions are odor-free, relatively low-volatility compounds which largely remain in the hardened composition at room temperature. At elevated temperature, however, it may still lead to outgassing of these aldehydes from the composition.
  • curable compositions according to claim 1 which in addition to a blocked by aldehyde or ketone amine a hydrazide of a carboxylic or sulfonic acid having a sufficiently high melting point, solve this problem.
  • These compositions cure with moisture at room temperature or a slightly elevated temperature, in particular below 40 ° C., without significant involvement of the hydrazide, resulting in aldehydes and / or ketones.
  • the hydrazide Upon heating of the cured compositions, in particular on 80 0 C and higher, the hydrazide begins to react with the resulting aldehydes and / or ketones to low-volatility condensation products that do not outgas even at high temperatures.
  • the cured compositions therefore have particular advantages in fogging behavior.
  • the invention relates to a curable composition
  • a curable composition comprising a) at least one polyisocyanate P, b) at least one amine BA blocked by aldehyde or ketone, c) at least one hydrazide HY of a carboxylic or sulfonic acid having a melting point of at least 100 ° C., in particular of at least 150 ° C, with the proviso that the hydrazide HY is present in an amount of 0.3 to 1.1 equivalent hydrazide groups per equivalent of aldehyde or keto groups by which the amine BA is blocked.
  • hydrazide refers to the condensation product of a carboxylic or sulphonic acid and hydrazine. [H Die]
  • the described curable composition comprises at least one
  • polyisocyanate as used herein includes compounds having two or more isocyanate groups, whether or not These are monomeric diisocyanates, oligomeric polyisocyanates or isocyanate group-containing polymers having a relatively high molecular weight.
  • polymer in the present document comprises, on the one hand, a collective of chemically uniform, but different in terms of degree of polymerization, molecular weight and chain length macromolecules, which was prepared by a polyreaction (polymerization, polyaddition, polycondensation) Such a group of macromolecules from polyreactions, ie compounds which have been obtained by reactions, such as additions or substitutions, of functional groups on predetermined macromolecules and which may be chemically uniform or chemically nonuniform.
  • the term also includes so-called prepolymers, that is to say reactive oligomeric pre-adducts whose functional groups are involved in the construction of macromolecules.
  • Suitable as polyisocyanate P in one embodiment is an isocyanate group-containing polyurethane polymer PUP.
  • polyurethane polymer encompasses all polymers which are prepared by the so-called diisocyanate-polyaddition process, including those polymers which are almost or completely free of urethane groups
  • polyurethane polymers are polyether polyurethanes, polyester polyurethanes, polyethers
  • a suitable polyurethane polymer PUP is obtainable in particular from the reaction of at least one polyol with at least one polyisocyanate, this reaction being possible by the polyol and the polyisocyanate being purified by customary processes, such as polyureas, polyureas, polyureaureas, polyisocyanurates and polycarbodiimides.
  • the polyisocyanate is metered so that its isocyanate groups in relation to the hydroxyl groups of the polyol in stoichiometric excess vorhan
  • the polyisocyanate is metered so that an NCO / OH ratio from 1.3 to 5, in particular one of 1.5 to 3, is complied with.
  • the "NCO / OH ratio” is understood to mean the ratio of the number of isocyanate groups used to the number of hydroxyl groups used.
  • the polyurethane polymer PUP may be made using plasticizers, with the plasticizers used containing no isocyanate-reactive groups.
  • plasticizers used containing no isocyanate-reactive groups.
  • suitable polyols for the preparation of a polyurethane polymer PUP are the following commercial polyols or mixtures thereof:
  • Polyoxyalkylenpolyole also called polyether polyols or oligoetherols, which are polymerization of ethylene oxide, 1, 2-propylene oxide, 1, 2- or 2,3-butylene oxide, oxetane, tetrahydrofuran or mixtures thereof, possibly polymerized with the aid of a starter molecule having two or more active Hydrogen atoms, such as water,
  • Ammonia or compounds with several OH or NH groups such as 1, 2-ethanediol, 1, 2- and 1, 3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols and
  • Tripropylene glycols the isomeric butanediols, pentanediols, hexanediols,
  • Heptanediols Heptanediols, octanediols, nonanediols, decandiols, undecanediols, 1, 3 and 3
  • 1,4-cyclohexanedimethanol bisphenol A, hydrogenated bisphenol A, 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, glycerol, aniline, as well as mixtures of the abovementioned compounds. Can be used both
  • Double Metal Cyanide Complex catalysts DMC catalysts
  • polyoxyalkylene polyols polyoxyalkylene polyols with a higher
  • Catalysts such as NaOH, KOH, CsOH or alkali metal alkoxides.
  • polyoxyalkylenediols or polyoxyalkylenetriols in particular polyoxyethylene and polyoxypropylene di- and triols.
  • polyoxyalkylenediols and -triols having a degree of unsaturation lower than 0.02 meq / g and having a molecular weight in the range from 1 000 to 30 000 g / mol, and also polyoxypropylene diols and triols having a molecular weight of 400-800 g / mol.
  • ethylene oxide-terminated (“EO-endcapped”, ethylene oxide-endcapped) polyoxypropylene polyols
  • EO-endcapped ethylene oxide-endcapped polyoxypropylene polyols
  • polyoxypropylene-polyoxyethylene polyols obtained, for example, by pure polyoxypropylene polyols, especially polyoxypropylene diols and triols, after completion of the polypropoxylation reaction
  • Ethylene oxide are further alkoxylated and thereby have primary hydroxyl groups.
  • Polyesterpolyols also called oligoesterols, prepared for example from dihydric to trihydric alcohols such as 1, 2-ethanediol, diethylene glycol, 1, 2-propanediol, dipropylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1 , 6-hexanediol, neopentyl glycol, glycerol, 1,1,1-trimethylolpropane or mixtures of the abovementioned alcohols with organic dicarboxylic acids or their anhydrides or esters such as succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid , Isophthalic acid, terephthalic acid and hexahydrophthalic acid or mixtures of the abovementioned acids, as well as polyester polyols from lactones such as
  • Polycarbonate polyols as obtainable by reacting, for example, the abovementioned alcohols used to form the polyesterpolyols with dialkyl carbonates, diaryl carbonates or phosgene. At least two hydroxyl-bearing block copolymers which have at least two different blocks of polyether, polyester and / or polycarbonate structure of the type described above.
  • Polyacrylate and polymethacrylate polyols Polyhydrocarbyl polyols, also called oligohydrocarbonols, such as, for example, polyhydroxy-functional ethylene-propylene, ethylene-butylene or ethylene-propylene-diene copolymers, for example produced by Kraton Polymers, or polyhydroxy-functional copolymers of dienes, such as 1,3-butanediene or diene mixtures and vinyl monomers such as styrene, acrylonitrile or isobutylene, or polyhydroxy-functional polybutadiene polyols such as those prepared by copolymerization of 1, 3-butadiene and allyl alcohol and which may also be hydrogenated.
  • Polyhydrocarbyl polyols also called oligohydrocarbonols, such as, for example, polyhydroxy-functional ethylene-propylene, ethylene-butylene or ethylene-propylene-diene copolymers, for example produced by Kraton Polymers,
  • Polyhydroxy-functional acrylonitrile / butadiene copolymers as they can be prepared, for example, from epoxides or aminoalcohols and carboxyl-terminated acrylonitrile / butadiene copolymers (commercially available under the name of Hycar ® CTBN from Hanse Chemie).
  • These stated polyols preferably have an average molecular weight of from 250 to 30,000 g / mol, in particular from 400 to 20,000 g / mol, and preferably have an average OH functionality in the range from 1.6 to 3.
  • Preferred polyols are polyether, polyester, polycarbonate and polyacrylate polyols, preferably diols and triols. Particularly preferred are polyether polyols, especially polyoxypropylene and polyoxypropylene polyoxyethylene polyols.
  • small amounts of low molecular weight di- or polyhydric alcohols such as 1, 2-ethanediol, 1, 2- and 1, 3-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, the isomeric dipropylene glycols and tripropylene glycols, the isomeric Butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecanediols, 1, 3- and 1, 4-cyclohexanedimethanol, hydrogenated bisphenol A, dimeric fatty alcohols, 1,1,1-trimethylolethane, 1,1,1, -Tn- methylolpropane, glycerol, pentaerythritol, sugar alcohols such as XyN
  • Aromatic or aliphatic polyisocyanates are used as the polyisocyanate for the preparation of a polyurethane polymer PUP containing isocyanate groups.
  • aromatic isocyanate refers to an organic compound which has exclusively aromatic isocyanate groups.
  • Aromaatic refers to an isocyanate group bonded to an aromatic or heteroaromatic radical.
  • aliphatic isocyanate refers to an organic compound containing aliphatic isocyanate groups.
  • Aliphatic refers to an isocyanate group attached to an aliphatic, cycloaliphatic or arylaliphatic radical.
  • Suitable aromatic polyisocyanates are, for example, monomeric di- or triisocyanates such as 2,4- and 2,6-toluene diisocyanate and any desired mixtures of these isomers (TDI), 4,4'-, 2,4'- and 2,2'-diphenylmethanediisocyanates.
  • MDI monomeric MDI or PMDI
  • NDI 5-diisocyanate
  • TODI 3,3'-dimethyl-4,4'-diisocyanatodiphenyl
  • DADI dianisidine diisocyanate
  • 1,3,5-tris isocyanatomethyl) benzene
  • Tris (4-isocyanatophenyl) methane tris (4-isocyanatophenyl) thiophosphate
  • oligomers and polymers of the abovementioned isocyanates as well as any desired mixtures of the aforementioned isocyanates.
  • MDI and TDI are examples of the abovementioned isocyanates, as well as any desired mixtures of the aforementioned isocyanates.
  • Polyisocyanate PI in the form of a monomeric di- or triisocyanate or an oligomer of a monomeric diisocyanate, wherein, for example, the abovementioned aromatic and aliphatic di- and triisocyanates are suitable as monomeric di- or triisocyanate.
  • Particularly suitable oligomers of a monomeric diisocyanate are the oligomers of HDI, IPDI and TDI. Such oligomers are in practice usually mixtures of substances having different degrees of oligomerization and / or chemical structures.
  • They preferably have an average NCO functionality of 2.1 to 4.0 and in particular contain isocyanurate, iminooxadiazinedione, uretdione, urethane, biuret , Allophanate, carbodiimide, uretonimine or oxadiazinetrione groups.
  • they Preferably, they have a low content of monomeric diisocyanates.
  • HDI biurets for example, Desmodur ® N 100 and Desmodur ® N 3200 (from Bayer), Tolonate ® HDB and Tolonate ® HDB-LV (Rhodia) and Duranate ® 24A-100 (of Asahi Kasei); HDI-Isocyanurates such as Desmodur ® N 3300, Desmodur ® N 3600 and Desmodur ® N 3790 BA (Bayer), Tolonate ® HDT, Tolonate ® HDT LV and Tolonate ® HDT-LV2 (from Rhodia), Duranate ® TPA-100 and Duranate ® THA-100 (by Asahi Kasei) and Coronate HX ® (from Nippon Polyurethane); HDI uretdiones, for example Desmodur ® N 3400 (Bayer); HDI Iminooxadiazindiones, for example Desmodur ® X
  • the polyisocyanate P is a
  • modified MDI Formulated at room temperature forms of MDI (so-called "modified MDI") represent mixtures of MDI with MDI derivatives, such as MDI carbodiimides, MDI uretonimines or MDI urethanes.
  • modified MDI Commercially available types of modified MDI are, for example Desmodur ® CD, Desmodur ® PF and Desmodur ® PC (from Bayer), Lupranat ® MM 103 (from BASF), Isonate ® M 143 (Dow) and Suprasec ® 2020 and Suprasec ® 2388 (from Huntsman).
  • PMDI Homologs designated.
  • Commercially available types of PMDI are, for example Desmodur ® VL, Desmodur ® VL 50, Desmodur ® VL R 10, Desmodur ® VL R 20 and Desmodur ® VKS 20 F (from Bayer), Lupranat ® M 10 R and Lupranat ® M 20 R ( ® from BASF), Isonate ® M 309, Voranate M 229 and Voranate M ® 580 (from Dow) and Suprasec ® 5025, Suprasec 2050 and Suprasec ® ® 2487 (from Huntsman).
  • polyisocyanate PI Preferred as the polyisocyanate PI are PMDI, forms of MDI that are liquid at room temperature, as well as oligomers of HDI, IPDI and TDI, in particular the isocyanurates.
  • Particularly preferred polyisocyanates PI are those having aromatic isocyanate groups.
  • Most preferred as the polyisocyanate PI are MDI, in particular MDI types with a high proportion, in particular 50% by weight or more, of 2,4'-isomer, PMDI, and forms of MDI which are liquid at room temperature.
  • the polyisocyanate P is a
  • Mixture consisting of at least one polyurethane polymer PUP and at least one polyisocyanate PI, as described above.
  • the polyisocyanate P is present in an amount of from 5 to 95% by weight, preferably in an amount of from 10 to 90% by weight, based on the total composition.
  • the polyisocyanate P is preferably present in an amount of 5 to 60% by weight, especially 10 to 50% by weight, based on the total composition.
  • the described curable composition further comprises at least one aldehyde or ketone blocked amine BA.
  • At least one aldehyde or ketone blocked amine BA is a
  • Suitable as blocked amine BA in one embodiment is an aldimine BA1 of the formula (I) where n is an integer from 1 to 5, A is the residue of an amine B after removal of n primary amino groups, and
  • Y is an organic, optionally heteroatom-containing, radical having 1 to 35 carbon atoms.
  • “Secondary amino group” is an NH group which is bonded to two organic radicals, which may also be part of a ring together.
  • aldimines BA1 of the formula (I) are aldimines BA1 of the formula (Ia) and (Ib),
  • R 1 and R 2 are each independently of one another a monovalent hydrocarbon radical having 1 to 12 C atoms, or together represent a bivalent hydrocarbon radical having 4 to 20 C atoms, the part of an optionally substituted, carbocyclic ring having 5 to 8 , preferably 6, is C atoms;
  • Z 1 is a monovalent hydrocarbon radical having 1 to 32 C atoms, which optionally has at least one heteroatom, in particular oxygen in the form of ether, carbonyl or ester groups, or in particular nitrogen in the form of tertiary amino groups;
  • Z 2 is either a substituted or unsubstituted aryl or heteroaryl group which has a ring size of 5 to 8, preferably 6, atoms, O or is CR 8 , wherein R 8 represents a hydrogen atom or an alkoxy group, or represents a substituted or unsubstituted alkenyl or arylalkenyl group having at least 6 C atoms; and A and n have the meanings already mentioned.
  • R 1 and R 2 in formula (I a) each represent a methyl group.
  • Z 1 in formula (I a) preferably represents a radical of the formula (II) or (III) or (IV)
  • R 3 is a hydrogen atom or an alkyl group or a
  • R 4 stands for a hydrocarbon radical having 1 to 30 C atoms, which optionally contains ether oxygen atoms;
  • R 5 is either a hydrogen atom, or a linear or branched alkyl radical having 1 to 30 C atoms, optionally with cyclic moieties and optionally with at least one heteroatom, in particular oxygen in the form of ether, carbonyl or ester groups, is or is a mono- or polyunsaturated, linear or branched hydrocarbon radical having 5 to 30 carbon atoms, or represents an optionally substituted, aromatic or heteroaromatic 5- or 6-membered ring; and R 6 and R 7 are each, independently of one another, each a monovalent aliphatic, cycloaliphatic or arylaliphatic radical having 1 to 20 C atoms and which optionally contains heteroatoms in the form of ether oxygen or tertiary amine nitrogen, or together for a bivalent aliphatic radical having 3 to 20 C atoms, which is part of an optionally substituted heterocyclic ring having 5 to 8, preferably 6, ring atoms and, in addition to the nitrogen atom, optionally contains further
  • R 3 in the formulas (II), (III) and (IV) is a hydrogen atom.
  • R 4 in formula (II) preferably represents a hydrocarbon radical having 6 to 30, in particular having 11 to 30, carbon atoms, which optionally contains ether oxygen atoms.
  • R 5 in formula (III) preferably represents a linear or branched one
  • Alkyl radical having 6 to 30, in particular having 11 to 30, carbon atoms, optionally with cyclic moieties and optionally with at least one heteroatom, or for a mono- or polyunsaturated, linear or branched
  • Hydrocarbon radical having 6 to 30, in particular having 11 to 30, carbon atoms.
  • R 5 in formula (III) is a C 1 alkyl radical.
  • R 6 and R 7 in formula (IV) are each independently of one another methyl, ethyl, propyl, isopropyl, butyl, isobutyl, 2-ethylhexyl,
  • Nitrogen atom - a ring in particular a pyrrolidine, piperidine, Morpholine or N-alkylpiperazine ring, this ring being optionally substituted.
  • An aldimine BA1 of the formula (I) is obtainable by a condensation reaction with elimination of water between at least one amine B of
  • ALD of the formula (VI) is used here with respect to the amino groups of the amine B stoichiometrically or in stoichiometric excess.
  • amine B of formula (V) are suitable in one embodiment polyamines having at least two primary amino groups, such as
  • - Aliphatic, cycloaliphatic or arylaliphatic diamines for example, ethylenediamine, 1, 2-propanediamine, 1, 3-propanediamine, 2-methyl-1, 2-propanediamine, 2,2-dimethyl-1, 3-propanediamine, 1, 3-butanediamine , 1, 4-butanediamine, 1, 3-pentanediamine (DAMP), 1, 5-pentanediamine, 1, 5-diamino-2-methylpentane (MPMD), 1, 6-hexanediamine, 2,5-dimethyl-1, 6 -hexanediamine, 2,2,4- and 2,4,4-trimethylhexamethylenediamine (TMD), 1, 7-heptanediamine, 1, 8-octanediamine, 1, 9-nonanediamine, 1, 10-decanediamine, 1,11-undecanediamine , 1, 12-dodecanediamine and methyl bis (3-aminopropyl) amine, 1, 2, 1, 3 and 1, 4-diamino cyclohexan
  • Ether group-containing aliphatic diamines for example bis (2-aminoethyl) ether, 3,6-dioxaoctane-1, 8-diamine, 4,7-dioxadecane-1, 10-diamine, 4,7-dioxadecane-2.9 -diamine, 4,9-dioxadodecane-1, 12-diamine, 5,8-dioxadodecane-3,10-diamine and higher oligomers of these diamines, bis (3-aminopropyl) -polytetrahydrofurans and other polytetrahydrofuran diamines having molecular weights in the range of, for example, 350 to 5200, as well as polyoxyalkylene diamines.
  • the latter are typically products from the amination of polyoxyalkylene diols, and are available, for example under the name Jeffamine ® (from Huntsman), under the name polyetheramine (from BASF) or under the name PC Amine ® (from Nitroil).
  • Particularly suitable polyoxyalkylene diamines are Jeffamine ® D-230, Jeffamine ® D-400, Jeffamine ® D-2000, Jeffamine ® D-4000, Jeffamine ® XTJ-511, Jeffamine ® ED-600, Jeffamine ® ED-900, Jeffamine ® ED-2003, Jeffamine ® XTJ-568, Jeffamine ® XTJ-569, Jeffamine ® XTJ-523, Jeffamine ® XTJ-536, Jeffamine ® XTJ-542, Jeffamine ® XTJ-559; Polyetheramine D 230, polyetheramine D 400 and polyetheramine D 2000, PC Amine® DA 250, PC Amine® DA 400, PC Amine® DA 650 and PC Amine® DA 2000; aliphatic, cycloaliphatic or arylaliphatic triamines, such as 4-
  • polyoxyalkylenetriamines which are typically products from the amination of polyoxyalkylenetriols and obtainable for example under the trade name Jeffamine ® (from Huntsman), under the name polyetheramine (from BASF) or under the name PC Amine ® (from Nitroil) such as Jeffamine ® T-403, Jeffamine ® T-5000; Polyetheramine T403, polyetheramine T5000; and PC Amine® TA 403, PC Amine® TA 5000;
  • aromatic di- and triamines such as 1, 2, 1, 3- and 1, 4-phenylenediamine, 2,4- and 2,6-toluenediamine (TDA), 3,4-toluenediamine, 3,5-dimethylthio -2,4- and -2,6-toluenediamine, 3,5-diethyl-2,4- and -2,6-toluenediamine diamine (DETDA), 2,4,6-triethyl-1,3-phenylenediamine, 2,4,6-triisopropyl-1,3-phenylenediamine, 3-ethyl-5-methyl-2,4-toluylenediamine, 3,5-diisopropyl-2,4-toluene diamine, 3,5-bis (1-methylpropyl) -2,4-toluenediamine, 3,5-bis (tert-butyl) -2,4-toluenediamine, 3-ethyl-5-isopropyl-2, 4-toluyl
  • a polyamine having at least two primary amino groups selected from the group consisting of 1,6-hexamethylenediamine, MPMD, DAMP, IPDA, TMD, 1,3-xylylenediamine, 1,3-bis (aminomethyl) cyclohexane, Bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, 3 (4), 8 (9) -bis (aminomethyl) -tricyclo [5.2.1.0 2 ' 6 ] decane , 1, 2-, 1, 3- and 1, 4-diaminocyclohexane, 1, 4-diamino-2,2,6-trimethylcyclohexane, 3,6-dioxo-octane-1, 8-diamine, 4,7-dioxadecane -1, 10-diamine, 4-aminomethyl-1, 8-octane diamine, polyoxyalkylene-poly
  • amines which have at least one primary amino group and at least one further reactive group which represents either a hydroxyl group, a secondary amino group or a mercapto group are suitable, for example
  • Amines having one or two primary and one secondary amino group such as, for example, N-methyl-1,2-ethanediamine, N-ethyl-1,2-ethanediamine, N-butyl-1,2-ethanediamine, N-hexylamine 1,2-ethanediamine, N- (2-ethylhexyl) -1,2-ethanediamine, N-cyclohexyl-1,2-ethanediamine, 4-aminomethylpiperidine, 3- (4-aminobutyl) piperidine, N- (2 Aminopropyl) piperazine, diethylenetriamine (DETA), bis-hexamethylenetriamine (BHMT), 3- (2-aminoethyl) aminopropylamine; Di- and triamines from cyanoethylation or cyanobutylation and subsequent hydrogenation of primary mono- and diamines, for example N-methyl-1,3-propanediamine, N-ethyl-1,3-propanediamine, N-butyl-1,3-
  • Hydroxyamines having a hydroxyl group and a primary amino group for example 2-aminoethanol, 2-methylaminoethanol, 1-amino-2-propanol, 3-amino-1-propanol, 4-amino-1-butanol, 4-amino 2-butanol, 2-amino-2-methylpropanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 7-amino-1-heptanol, 8-amino-1-octanol, 10-amino-1 decanol, 12-amino-1-dodecanol, A- (2-aminoethyl) -2-hydroxyethylbenzene, 3-aminomethyl-3,5,5-trimethylcyclohexanol; a primary amino-bearing derivatives of glycols such as diethylene glycol, dipropylene glycol, dibutylene glycol and higher oligomers and polymers of these glycols,
  • Mercaptoamines such as 2-aminoethanethiol (cysteamine), 3-aminopropanethiol, 4-amino-1-butanethiol, 6-amino-1-hexanethiol, 8-amino-1-octanethiol, 10-amino-1-decanethiol, 12- Amino-1-dodecanethiol and aminothio sugars such as 2-amino-2-deoxy-6-thioglucose;
  • Amines having one or more primary and more than one secondary amino group such as N, N'-bis (3-aminopropyl) ethylenediamine, tetramethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine and higher homologs of linear polyethyleneamines, N, N'-bis (3-aminopropyl) ethylenediamine, products of multiple cyanoethylation or cyano-butylation and subsequent hydrogenation of primary di- and polyamines having multiple primary amino groups, such as N, N'-bis (3-aminopropyl) - ethylenediamine, N, N'-bis (3-aminopropyl) -1, 4-diaminobutane, N, N'-bis (3-aminopropyl) -2-methyl-1,5-pentanediamine, N, N ' -Bis- (3-amino-1-ethylpropyl) -2-methyl-1, 5-pen
  • Hydroxyamines having at least one hydroxyl group, at least one secondary and at least one primary amino group such as those obtainable, for example, from cyanoethylation or cyanobutylation and subsequent hydrogenation of simple aliphatic hydroxyamines, for example N-hydroxyethyl-1,2-ethanediamine, N-hydroxypropyl -1, 2-ethanediamine, N-hydroxyethyl-1,3-propanediamine, N3-hydroxyethyl-1,3-pentanediamine; - Hydroxyamine having more than one hydroxyl group and one or more primary amino groups, in particular derivatives of polyalkoxylated trihydric or higher alcohols or polyalkoxylated polyamines, and amino sugars, such as glucosamine or galactosamine.
  • amines which are selected from the group consisting of N-methyl-1, 2-ethanediamine, N-ethyl-1, 2-ethanediamine, N-cyclo-hexyl-1, 2-ethanediamine, N-methyl-1 , 3-propanediamine, N-ethyl-1,3-propanediamine, N-butyl-1,3-propanediamine, N-cyclohexyl-1,3-propanediamine, 4-aminomethylpiperidine, 3- (4-aminobutyl) -piperidine , DETA, DPTA, BHMT, fatty diamines such as N-cocoalkyl-1,3-propanediamine, N-oleyl-1,3-propanediamine, N-soyaalkyl-1,3-propanediamine and N-tallowalkyl-1,3-propanediamine, 5 -Amino-1-pentanol, 6-amino-1-hexanol, 4- (2-amino-1-
  • aldehyde ALD of the formula (VI) are primary and secondary aliphatic aldehydes such as propanal, 2-methylpropanal, butanal, 2-methylbutanal, 2-ethylbutanal, pentanal, 2-methylpentanal, 3-methylpentanal, 4-methylpentanal, 2,3- Dimethyl pentanal, hexanal, 2-ethylhexanal, heptanal, octanal, nonanal, decanal, undecanal, 2-methyl-undecanal, dodecanal, methoxyacetaldehyde, cyclopropanecarboxaldehyde, cyclopentanecarboxaldehyde, cyclohexanecarboxaldehyde and diphenylacetaldehyde.
  • primary and secondary aliphatic aldehydes such as propanal, 2-methylpropanal, butanal, 2-methylbutanal, 2-ethylbutanal
  • aldehyde ALD of the formula (VI) are particularly suitable aldehydes which are not enolisable, since they form aldimino groups in the reaction with primary amines, which can not tautomerize to enamino groups and therefore represent particularly well blocked amino groups.
  • tertiary aliphatic and aromatic aldehydes represent non-enolisable aldehydes.
  • aldehyde ALD of the formula (VI) are tertiary aliphatic aldehydes ALDI of the formula (VI a)
  • Ethers of 2-hydroxy-2-methylpropanal and alcohols such as propanol, isopropanol, butanol and 2-ethylhexanol; Esters of 2-formyl-2-methylpropionic acid or 3-formyl-3-methylbutyric acid and alcohols such as propanol, isopropanol, butanol and 2-ethylhexanol; Esters of 2-hydroxy-2-methylpropanal and carboxylic acids such as butyric, isobutyric and 2-ethylhexanoic acid; and the ethers and esters of 2,2-disubstituted 3-hydroxypropanals, butanals or analogous higher aldehydes, especially of 2,2-dimethyl-3-hydroxypropanal, which are described below as being particularly suitable.
  • aldehydes ALDI of the formula (VI a) are in one embodiment aldehydes ALD2 of the formula (VI b),
  • aldehydes ALD2 of the formula (VI b) are ethers of aliphatic, cycloaliphatic or arylaliphatic 2,2-disubstituted 3-hydroxy aldehydes with alcohols or phenols of the formula R 4 -OH, for example Fatty alcohols or phenols.
  • Suitable 2,2-disubstituted 3-hydroxy aldehydes are in turn obtainable from aldol reactions, in particular crossed aldol reactions, between primary or secondary aliphatic aldehydes, in particular formaldehyde, and secondary aliphatic, secondary cycloaliphatic or secondary arylaliphatic aldehydes, such as, for example, isobutyraldehyde, 2- Methylbutyraldehyde, 2-ethylbutyraldehyde, 2-methylvaleraldehyde, 2-ethylcaproic aldehyde, cyclopentanecarboxaldehyde, cyclohexanecarboxaldehyde, 1,2,3,6-tetrahydrobenzaldehyde, 2-methyl-3-phenylpropionaldehyde, 2-phenylpropionaldehyde (hydratropaldehyde) or diphenylacetaldehyde , Examples of suitable 2,2-disub
  • aldehydes ALD2 of the formula (VI b) are 2,2-dimethyl-3-phenoxypropanal, 3-cyclohexyloxy-2,2-dimethylpropanal, 2,2-dimethyl-3- (2-ethylhexyloxy) -propanal , 2,2-dimethyl-3-lauroxy-propanal and 2,2-dimethyl-3-stearoxy-propanal.
  • aldehydes ALDI of the formula (VI a) are aldehydes ALD 3 of the formula (VI c) in a further embodiment,
  • R 1 , R 2 , R 3 and R 5 have the meanings already mentioned.
  • the aldehydes ALD3 of the formula (VI c) are esters of 2,2-disubstituted 3-hydroxy aldehydes already described, such as 2,2-dimethyl-3-hydroxypropanal, 2-hydroxymethyl-2-methyl-butanal, 2-hydroxy methyl 2-ethyl-butanal, 2-hydroxymethyl-2-methyl-pentanal, 2-hydroxymethyl-2-ethyl-hexanal, 1-hydroxymethyl-cyclopentanecarboxaldehyde, 1-hydroxy Methyl-cyclohexanecarboxaldehyde i-hydroxymethylcyclohex-3-enecarboxalde- hyd, 2-hydroxymethyl-2-methyl-3-phenyl-propanal, 3-hydroxy-2-methyl-2-phenyl-propanal and 3-hydroxy-2,2
  • suitable carboxylic acids for this reaction are saturated aliphatic carboxylic acids, such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric
  • aldehydes ALDI of the formula (VI a) are aldehydes ALD4 of the formula (VI d) in a further embodiment, wherein R 1 , R 2 , R 3 , R 6 and R 7 have the meanings already mentioned.
  • An aldehyde ALD4 of the formula (VI d) is in particular obtainable as the product of a Mannich reaction or of a Mannich reaction analogous ⁇ -aminoalkylation, as known from the literature; it can therefore also be called a Mannich base.
  • a secondary aldehyde A1, another aldehyde A2 and a secondary aliphatic amine A3 are reacted with elimination of water to form an aldehyde ALD4.
  • Suitable aldehyde A1 are, for example, isobutyraldehyde, 2-methylbutyraldehyde, 2-ethylbutyraldehyde, 2-methylvaleraldehyde, 2-ethylcapronaldehyde, cyclopentanecarboxaldehyde, cyclohexanecarboxaldehyde,
  • aldehyde A2 examples include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, phenylacetaldehyde, benzaldehyde and substituted benzaldehydes, and also glyoxylic acid esters, in particular ethyl glyoxylate.
  • formaldehyde acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, phenylacetaldehyde, benzaldehyde and substituted benzaldehydes, and also glyoxylic acid esters, in particular ethyl glyoxylate.
  • formaldehyde is formaldehyde.
  • Suitable as a secondary aliphatic amine A3 are, for example, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, di-sec-butylamine, dihexylamine, di (2-ethylhexyl) amine, dicyclohexylamine, N-methylbutylamine, N-ethylbutylamine, N- Methylcyclohexylamine, N-ethylcyclohexylamine, di-2-methoxyethylamine, pyrrolidine, piperidine, N-methylbenzylamine, N-isopropylbenzylamine, N-tert-butylbenzylamine, dibenzylamine, morpholine, 2,6-dimethylmorpholine, Bis (3-dimethylaminopropyl) amine, N-methyl or N-ethylpiperazine.
  • Aldehydes ALD5 of the formula (VI e) are particularly suitable as aldehyde ALD of the formula (VI) in a further embodiment.
  • aldehydes ALD5 are for example aromatic aldehydes, such as benzaldehyde, 2- and 3- and 4-tolualdehyde, 4-ethyl- and 4-propyl- and 4-
  • Preferred aldehyde ALD of the formula (VI) are those mentioned
  • aldehydes ALD3 of the formula (VI c) particularly preferred are the aldehydes ALD3 of the formula (VI c), in particular those in which the radical R 5 has 6 to 30 carbon atoms.
  • odorless aldehydes ALD3 of the formula (VIc) in which the radical R 5 has 11 to 30 carbon atoms.
  • aldehyde ALD 2,2-dimethyl-3-lauroyloxypropanal.
  • suitable as a blocked amine BA is a ketimine BA2 of the formula (VII)
  • Z 3 and Z 4 are each, independently of one another, each a monovalent hydrocarbon radical having 1 to 12 C atoms, or together represent a bivalent hydrocarbon radical having 4 to 20 C atoms, the part of an optionally substituted, carbocyclic ring with 5 to 8, preferably 6, C atoms are; and n and A have the meanings already mentioned.
  • a ketimine BA2 of the formula (VII) is obtainable by a condensation reaction with elimination of water between at least one amine B of the formula (V) and at least one ketone of the formula (VIII).
  • the ketone of the formula (VIII) is used in this case with respect to the amino groups of the amine B stoichiometric or in stoichiometric excess.
  • Z 3 and Z 4 have the meanings already mentioned.
  • ketones of the formula (VIII) are acetone,
  • Diisopropyl ketone, dibutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone and actetophenone Diisopropyl ketone, dibutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone and actetophenone.
  • Suitable amine B of the formula (V) are the abovementioned amines B.
  • Suitable commercial diketimines example, Epikure ® Curing Agent 3502 (from Resolution Performance Products) and Desmophen ® LS 2965A (Bayer).
  • Suitable as blocked amine BA in another embodiment is an enamine BA3 which has at least one enamine group of the formula (IX) and which is obtainable, for example, from the reaction of at least one secondary amine C with at least one aliphatic or cycloaliphatic aldehyde or ketone of the formula (X) with elimination of water.
  • Z 5 and Z 6 are each, independently of one another, each a hydrogen atom or a monovalent hydrocarbon radical having 1 to 12 C atoms, or together represent a bivalent hydrocarbon radical having 3 to 20 C atoms, which is part of an optionally substituted carbocyclic ring having 5 to 8, preferably 6, C atoms; and Z 7 represents a hydrogen atom or a monovalent hydrocarbon radical having 1 to 12 C atoms.
  • Suitable as secondary amine C in one embodiment are amines having at least two secondary amino groups, such as, for example, piperazine, tetramethylpiperazine, homopiperazine, 1,3-di (piperidin-4-yl) -propane, N, N'-dimethylhexamethylenediamine and homologues with higher alkyl or cycloalkyl groups in place of the methyl groups, N, N'-dimethyl-diethylenetriamine and N, N'-dimethyl-dipropylenetriamine.
  • secondary amino groups such as, for example, piperazine, tetramethylpiperazine, homopiperazine, 1,3-di (piperidin-4-yl) -propane, N, N'-dimethylhexamethylenediamine and homologues with higher alkyl or cycloalkyl groups in place of the methyl groups, N, N'-dimethyl-diethylenetriamine and N, N'-dimethyl-diprop
  • amines having a hydroxyl group and a secondary amino group are suitable as secondary amine C in another embodiment and monoalkoxylated primary monoamines, ie reaction products of primary monoamines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, 2-ethylhexylamine, benzylamine and fatty amines such as laurylamine or stearylamine, with stochiometric ratios of epoxides such as ethylene oxide, propylene oxide or butylene oxide 1: 1, for example N-methylethanolamine, N-ethyl-ethanolamine, N-butyl-ethanolamine and N-butyl-isopropanolamine.
  • monoalkoxylated primary monoamines ie reaction products of primary monoamines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, 2-ethylhexylamine, benzy
  • amines having a mercapto group and a secondary amino group such as, for example, N- (2-mercaptoethyl) piperazine, 4-mercapto-piperidine and 2-mercaptoethyl-butylamine, are suitable as secondary amine C.
  • Suitable aldehyde or ketone of the formula (X) are aldehydes which have at least one hydrogen atom in the ⁇ -position to the carbonyl group and are thus enolizable, for example propanal, 2-methylpropanal, butanal, 2-methylbutanal, 2-ethylbutanal, pentanal, 2 Methylpentanal, 3-methylpentanal, 4-methylpentanal, 2,3-dimethylpentanal, hexanal, 2-ethylhexanal, heptanal, octanal, nonanal, decanal, undecanal, 2-methyl-undecanal, dodecanal, methoxyacetaldehyde, cyclopropanecarboxaldehyde, cyclopentanecarboxaldehyde, cyclohexanecarboxaldehyde and diphenylacetaldehyde; and ketones which have at least one hydrogen atom in ⁇
  • Suitable as a blocked amine BA in another embodiment is an oxazolidine BA4 of the formula (XI) in which
  • a 2 is the residue of an amine after removal of n secondary amino groups
  • G 2 is an optionally substituted C 2 - or C 3 -alkylene radical;
  • Z 8 and Z 9 independently represents a hydrogen atom or a monovalent hydrocarbon radical having 1 to 12 C atoms; and n has the meanings already mentioned.
  • oxazolidino group in this document both tetrahydrooxazole groups (5-membered ring) and tetrahydrooxazine groups (6-membered ring) are referred to.
  • An oxazolidine BA4 of the formula (XI) is obtainable, for example, from the reaction of at least one amine D of the formula (XII) with at least one aldehyde or ketone of the formula (XIII) with elimination of water.
  • Suitable amine D of the formula (XII) are aliphatic hydroxyamines having a secondary amino group, such as, for example, diethanolamine,
  • Dipropanolamine and diisopropanolamine Preferred as the amine D is diethanolamine, which can be reacted with an aldehyde or ketone of the formula (XIII) to give an oxazolidine of the formula (XI a).
  • Z 8 and Z 9 have the meanings already mentioned.
  • An oxazolidine of the formula (XI a) can be reacted with a polyisocyanate such that the hydroxyl groups react with isocyanate groups. In this way, polyoxazolidines are available.
  • Suitable aldehydes or ketones of the formula (XIII) are the abovementioned aldehydes or ketones of the formula (XI), and also, for example, formaldehyde, benzaldehyde and substituted benzaldehydes. Preference is given to 2-methylpropanal.
  • Suitable commercial oxazolidines are for example Hardener OZ TM (Bayer), Zoldine ® RD-20, Zoldine ® MS-52 and Zoldine ® MS Plus (from Angus Chemical), and lncozol ® 2, lncozol ® 3, lncozol ® LV, lncozol ® 4 , Incozol ® HP and Incozol ® NC (from Industrial Copolymers).
  • blocked amine BA are compounds having two or more of the described blocked amino groups, which differ from one another.
  • the blocked amino groups in the form of aldimino groups, keto-imino groups, enamino groups and / or oxazolidino groups of the blocked amine BA react to the exclusion of moisture with isocyanate groups not or only very slowly.
  • the blocked amine BA is advantageously present in the curable composition in an amount such that the ratio between the number of blocked amino groups and optionally present hydroxyl, mercapto and secondary amino groups and the number of isocyanate groups 0.1 to 1.1, preferably 0.2 to 0.9, in particular 0.5 to 0.9. If blocked amino groups are present in the form of oxazolidino groups, these are counted twice since these are formally difunctional after hydrolysis to isocyanate groups.
  • Preferred as the blocked amine BA in the described curable composition are the aldimines BA1 of the formula (I), the ketimines BA2 of the formula (VII), the enamines BA3 containing enamino groups of the formula (IX) and the oxazolidines BA4 of the formula (Xl).
  • blocked amine BA Particularly preferred as blocked amine BA are the aldimines BA1, the ketimines BA2 and the oxazolidines BA4. Particularly preferred are the aldimines BA1 of the formula (I a) and the formula (I b) and the oxazolidines BA4. Most preferred as blocked amine BA are the aldimines BA1 of the formula (Ia) in which Z 1 is a radical of the formula (II) or (III) or (IV), in particular a radical of the formula (III) ,
  • the described curable composition furthermore comprises at least one hydrazide HY of a carboxylic or sulfonic acid which has a melting point of at least 100 ° C., in particular of at least 150 ° C., having.
  • the melting point of the hydrazide HY is preferably below 300 ° C.
  • carboxylic acid also includes carbonic acid.
  • a hydrazide HY of a carboxylic acid has in particular the formula
  • X for the q-valent radical of a hydrazide HY a sulfonic acid which has a melting point of at least 100 0 C, in particular of at least 150 0 C, after removal of q Sulfonklarehydrazid phenomenon;
  • m is zero or 1
  • p is 1 or 2 or 3 or 4
  • q is 1 or 2 or 3 or 4.
  • p is 2.
  • the hydrazide HY is obtainable, for example, by the condensation of suitable carboxylic or sulfonic acids with hydrazine or hydrazine hydrate.
  • suitable carboxylic or sulfonic acid hydrazides having a melting point above 100 ° C. are, for example, the following:
  • Hydrazides of aliphatic and arylaliphatic carboxylic acids such as lauric acid, palmitic acid, stearic acid, cyanoacetic acid, 2,4-dichlorophenoxyacetic acid, 4-nitrophenoxyacetic acid, 1-naphthylacetic acid; Hydrazides of aromatic and heteroaromatic carboxylic acids such as benzoic acid, 2-, 3- and 4-chlorobenzoic acid, 2-, 3- and 4-bromobenzoic acid, 2- and 4-toluic acid, 2-, 3- and 4-nitrobenzoic acid, salicylic acid, 4- tert -butylbenzoic acid, 4-methoxybenzoic acid, 4-ethoxybenzoic acid, 4-trifluorobenzoic acid, 4-dimethylaminobenzoic acid, the isomeric dichlorobenzoic acids, dimethoxybenzoic acids and trimethoxybenzoic acids, monomethyl terephthalate, 1-naphthylcarboxylic acid,
  • Monohydrazines and dihydrazides of dicarboxylic acids such as oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, isophthalic acid, terephthalic acid; Mono-, di- and trihydrazides of tricarboxylic acids such as benzenetricarboxylic acid; the dihydrazide of carbonic acid (carbodihydrazide); Hydrazides of sulfonic acids such as benzenesulfonic acid, 4-toluenesulfonic acid; Dihydrazides of disulfonic acids such as propylene disul
  • hydrazide HY cyclic hydrazides of dicarboxylic acids which represent N-aminoimides, for example N-aminophthalimide, N-aminosuccinimide, 2-amino-3a, 4,7,7-tetrahydro-isoindole-1,3-dione, Amino-4-aza-tricyclo [5.2.1.0 2 ' 6 ] dec-8-ene-3,5-dione, 4-amino-4-aza-10-oxa-tricyclo [5.2.1.0 2 ' 6 ] decyl 8-en-3,5-dione.
  • N-aminoimides for example N-aminophthalimide, N-aminosuccinimide, 2-amino-3a, 4,7,7-tetrahydro-isoindole-1,3-dione, Amino-4-aza-tricyclo [5.2.1.0 2 ' 6 ] dec-8-ene-3,5-dione, 4-a
  • Preferred hydrazides HY are carboxylic acid hydrazides.
  • carboxylic acid dihydrazides particular preference is given to carboxylic acid dihydrazides.
  • the carboxylic acid dihydrazide HY is selected from the
  • HY most preferred is adipic dihydrazide.
  • Hydrazide groups can in principle react both with isocyanate groups and with aldehyde and keto groups.
  • carboxylic acid hydrazide groups with isocyanate groups acylsemi- carbazide groups of the formula (XVI a) are formed, while in the reaction with aldehyde or keto groups with elimination of water, groups of the formula (XVII a) are formed.
  • Sulfonic acid hydrazide groups form analogous groups of the formula (XVI b) and (XVII b).
  • the hydrazide HY is solid at room temperature and has a melting point of at least 100 ° C., preferably of at least 150 ° C. Its reactivity toward isocyanate groups and its reactivity toward aldehyde and keto groups is severely limited at temperatures well below its melting point. At room temperature, it reacts neither with isocyanate groups nor with aldehyde or keto groups to any significant extent.
  • the hydrazide HY is storage-stable with isocyanate groups at room temperature or slightly elevated temperature. Only with stronger elevated temperature, especially at 80 0 C and higher, find the reactions mentioned to a considerable extent.
  • the hydrazide HY is present in the curable composition in an amount of 0.3 to 1.1 equivalent hydrazide groups per equivalent of aldehyde and keto groups by which the amine BA is blocked.
  • the hydrazide HY is present in the curable composition in an amount of from 0.5 to 1.0 equivalent, more preferably from 0.75 to 1.0 equivalent of hydrazide groups per equivalent of aldehyde or keto groups by which the amine BA is blocked.
  • the hydrazide HY is present in an amount smaller than 0.3 equivalent of hydrazide groups per equivalent of aldehyde and keto groups, by means of which the amine BA is blocked, the aldehyde or ketone outgassing is reduced only to a slight extent due to the stoichiometry. If the hydrazide HY is present in an amount greater than 1.1 equivalents of hydrazide groups per equivalent of aldehyde and keto groups by means of which the amine BA is blocked, then no additional reduction of the aldehyde or ketone outgassing is achieved.
  • the hydrazide HY is advantageously present in a stoichiometric or nearly stoichiometric amount relative to the aldehyde and keto groups by means of which the amine BA is blocked.
  • the curable composition may contain, in addition to at least one polyisocyanate P, at least one aldehyde or ketone-blocked amine BA and at least one hydrazide HY of a carboxylic or sulfonic acid further auxiliaries and additives.
  • the curable composition may be in the form of a one-part composition or in the form of a two-part composition.
  • a curable composition whose components in mixed form can be stored in the same container, and which is storage stable at room temperature for a long period of time, ie not or only slightly changed by the storage in their application or use properties, and which cures after application by the action of moisture.
  • a "two-component composition” refers to a curable composition whose constituents are present in two different components which are stored in separate containers and are each stable on their own, and only shortly before or during the application of the composition do the two components become intertwined is mixed, whereupon the mixed composition hardens, wherein the curing may take place or be completed only by the action of moisture.
  • One-component compositions have the advantage that they can be applied without mixing, while two-component compositions have the advantage that they can cure faster and as ingredients may contain substances which are not storable together with isocyanates.
  • the curable composition is in the
  • polyurethane polymer PUP a polyurethane polymer PUP, or a mixture of a polyurethane polymer PUP and a polyisocyanate PI, as described above, is preferred.
  • a blocked amine BA in the one-component composition is an aldimine BA1 of the formula (Ia), in particular having a radical Z 1 of the formula (II) or (III) or (IV), or an aldimine BA1 of the formula (Ib), or an oxazolidine BA4 of the formula (XI) is preferred.
  • the blocked amine is opposite to the amine part
  • Isocyanate-reactive groups such as hydroxyl groups, mercapto groups or unblocked amino groups, their number per molecule is preferably one.
  • Blocked amines BA with isocyanate-reactive Groups react on mixing with the polyisocyanate P by forming adducts.
  • the blocked amine BA preferably contains no isocyanate-reactive groups, such as hydroxyl groups, mercapto groups or unblocked amino groups.
  • auxiliaries and additives for a one-component composition for example, the following substances are suitable:
  • Plasticizers for example carboxylic esters, such as phthalates, for example dioctyl phthalate, diisononyl phthalate or diisodecyl phthalate, adipates, for example dioctyl adipate, azelates and sebacates, organic phosphoric and sulfonic acid esters or polybutenes;
  • carboxylic esters such as phthalates, for example dioctyl phthalate, diisononyl phthalate or diisodecyl phthalate
  • adipates for example dioctyl adipate, azelates and sebacates
  • organic phosphoric and sulfonic acid esters or polybutenes for example carboxylic esters, such as phthalates, for example dioctyl phthalate, diisononyl phthalate or diisodecyl phthalate, adipates, for example dioctyl adipate
  • thermoplastic polymers for example homopolymers or copolymers of unsaturated monomers, in particular from the group comprising ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate and alkyl (meth) acrylates, in particular polyethylenes (PE), polypropylenes (PP) , Polyisobutylenes, ethylene-vinyl acetate copolymers (EVA) and atactic poly- ⁇ -olefins (APAO);
  • PE polyethylenes
  • PP polypropylenes
  • EVA ethylene-vinyl acetate copolymers
  • APAO atactic poly- ⁇ -olefins
  • inorganic and organic fillers for example ground or precipitated calcium carbonates, which are optionally coated with fatty acids, in particular stearates, baryta (BaSO 4 , also called barite), quartz flours, calcined kaolins, aluminum oxides, aluminum hydroxides, silicic acids, in particular finely divided silicas from pyrolysis processes , Russian, in particular industrially produced Russian (hereinafter referred to as "soot”), PVC powder or hollow spheres;
  • fatty acids in particular stearates
  • baryta BaSO 4 , also called barite
  • quartz flours calcined kaolins
  • aluminum oxides aluminum hydroxides
  • silicic acids in particular finely divided silicas from pyrolysis processes
  • Russian in particular industrially produced Russian (hereinafter referred to as "soot"), PVC powder or hollow spheres;
  • Fibers such as polyethylene
  • Pigments for example titanium dioxide or iron oxides
  • Catalysts which accelerate the hydrolysis of the blocked amino groups in particular acids or compounds hydrolyzable to acids, for example organic carboxylic acids such as benzoic acid, salicylic acid or 2-nitrobenzoic acid, organic carboxylic anhydrides such as phthalic anhydride, hexahydrophthalic anhydride and hexahydromethyl phthalic anhydride, silyl esters of organic carboxylic acids, organic Sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid or 4-dodecylbenzenesulfonic acid, sulfonic acid esters, other organic or inorganic acids, or mixtures of the abovementioned acids and acid esters;
  • organic carboxylic acids such as benzoic acid, salicylic acid or 2-nitrobenzoic acid
  • organic carboxylic anhydrides such as phthalic anhydride, hexahydrophthalic anhydride and hexahydromethyl phthalic an
  • Catalysts which accelerate the reaction of the isocyanate groups with water in particular metal compounds, for example organotin compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dibutyltin diacetylacetonate and dioctyltin dilaurate, bismuth compounds such as bismuth trioctoate and bismuth tris (neodecanoate), and compounds containing tertiary amino groups such as 2,2 '-Dimorpholinodiethyl ether and 1,4-diazabicyclo [2.2.2] octane;
  • organotin compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dibutyltin diacetylacetonate and dioctyltin dilaurate, bismuth compounds such as bismuth triocto
  • Rheology modifiers such as thickeners or thixotropic agents, for example urea compounds, polyamide waxes, bentonites or pyrogenic silicas;
  • Reactive diluents and crosslinkers for example monomeric diisocyanates and oligomers and derivatives of these diisocyanates, adducts monomeric
  • Drying agents such as, for example, molecular sieves, calcium oxide, highly reactive isocyanates, such as p-tosyl isocyanate, orthoformic acid esters, tetraalkoxysilanes, such as tetraethoxysilane; Trialkoxysilanes such as methyltrimethoxysilane, isooctyltrimethoxysilane and vinyltrimethoxysilane;
  • Adhesion promoters in particular organoalkoxysilanes, also referred to below as "silanes", for example epoxysilanes, such as 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane, (meth) acrylsilanes, such as 3-methacryloxypropyltrimethoxysilane, isocyanatosilanes, such as 3-isocyanatopropyltrimethoxysilane, S- (alkylcarbonyl ) mercaptosilanes, such as S-octanoyl-3-mercaptopropyltriethoxysilane, and aldimino silanes, such as N-benzylidene-3-aminopropyltrimethoxysilane, and oligomeric forms of these silanes;
  • silanes for example epoxysilanes, such as 3-glycidoxypropyltrimethoxysilane
  • the one-component composition contains at least one catalyst.
  • the composition contains as catalyst a carboxylic acid such as benzoic acid or salicylic acid and / or a tin compound and / or a bismuth compound. It may be advantageous if different catalysts or different types of catalysts, such as, for example, an acid and a metal compound, are mixed with one another.
  • the one-component composition contains at least one further auxiliary and additive, in particular selected from the group comprising plasticizers, fillers and thickeners.
  • the one-component composition described is preferably prepared in the absence of moisture and stored at room temperature or slightly elevated temperature.
  • a suitable climate-proof packaging or arrangement such as a keg, a bag or a cartridge, it has a good storage stability.
  • the terms "storage-stable” and “storage stability” in the context of a curable composition in this document refers to the fact that the viscosity of the composition does not increase or at most rises so much at a given application temperature and with suitable storage during the time considered that the composition remains usable in the intended manner.
  • the curable composition is in the form of a bicomponent composition.
  • the two-component composition consists of a component K1 and a component K2, which are stored separately from each other and mixed together shortly before application.
  • the polyisocyanate P and the blocked amine BA are part of the component K1
  • the component K2 contains isocyanate-reactive compounds, especially water and / or polyols and / or polyamines and / or amino alcohols and / or polythiols
  • the hydrazide HY is contained either in the component K1 or in the component K2 or in both components.
  • the polyisocyanate P is part of component K1
  • component K2 contains the blocked amine BA and isocyanate-reactive compounds, especially water and / or polyols and / or polyamines and / or amino alcohols and / or polythiols and the hydrazide HY is contained either in the component K1 or in the component K2 or in both components.
  • the component K2 contains at least one blocked amine
  • the hydrazide HY is a component of the component K2.
  • polyisocyanate P in the two-component composition a polyisocyanate PI, or a mixture of a polyurethane polymer PUP and a polyisocyanate PI, as described above, are preferred.
  • Suitable polyols in component K2 are the same commercial polyols as have already been mentioned as suitable for the preparation of a polyurethane polymer PUP, as well as those low molecular weight dihydric or polyhydric alcohols, such as previously suitable for use in the preparation of a polyurethane polymer PUP were mentioned.
  • Suitable polyamines in component K2 are commercially available aliphatic or aromatic polyamines having primary and / or secondary amino groups, such as are commonly used in two-component polyurethane compositions, such as, for example, 1, 5-diamino-2-methylpentane (MPMD), 1, 3-xylylenediamine (MXDA), N, N'-dibutylethylenediamine, 3,5-diethyl-2,4 (6) -diaminotoluene (DETDA), 3,5-dimethylthio-2,4 (6) -diaminotoluene (available, for example, as Ethacure ® 300 from Albemarle) and primary and secondary polyoxyalkylene-diamines, such as are obtainable for example under the name Jeffamine ® (from Huntsman).
  • MPMD 1, 5-diamino-2-methylpentane
  • MXDA 1, 3-xylylenediamine
  • N N'-dibutylethylenediamine
  • Suitable amino alcohols in component K2 are compounds which have at least one primary or secondary amino group and at least one hydroxyl group, for example 2-aminoethanol, 2-methyl-aminoethanol, 1-amino-2-propanol and diethanolamine.
  • Suitable polythiols in component K2 are for example those known under the trade name Thiokol ® liquid mercapto-terminated polymers, and polyesters of thiocarboxylic acids.
  • both components may contain other auxiliaries and additives, as already mentioned above for a one-component composition.
  • additional auxiliaries and additives are additionally possible.
  • these are those auxiliaries and additives which are not or only briefly storable together with aromatic isocyanate groups.
  • the two-component composition contains at least one catalyst.
  • the composition contains as Catalyst a carboxylic acid such as benzoic acid or salicylic acid and / or a tin compound and / or a bismuth compound. It may be advantageous if different catalysts, or different types of catalysts, such as an acid and a metal compound, are mixed together.
  • the two-component composition contains at least one further auxiliary and additive, in particular selected from the group comprising plasticizers, crosslinkers, fillers and thickeners.
  • the component K2 preferably contains no isocyanate groups.
  • the preparation of the described components K1 and K2 is carried out separately from each other, at least for the component K1 in the absence of moisture.
  • the two components K1 and K2 are storage-stable separately from one another at room temperature or slightly elevated temperature, i. they may each be stored in a suitable packaging or arrangement, such as a keg, hobbock, pouch, bucket or cartridge, for several months to a year and longer before being used, without being in their respective ones Change properties to a degree that is relevant to their use.
  • the mixing ratio between the components K1 and K2 is preferably selected such that the isocyanate-reactive groups of the components K1 and K2 are in a suitable ratio to the isocyanate groups of the component K1.
  • 0.1 to 1.1 preferably 0.5 to 0.95, particularly preferably 0.6 to 0.95 equivalent of the sum of the isocyanate-reactive groups per equivalent of isocyanate groups are present before curing, the blocked amino groups being counted among the isocyanate-reactive groups and water is not expected to be isocyanate-reactive groups.
  • Excess isocyanate groups react in particular directly with water, for example with atmospheric moisture.
  • the described curable composition is suitably applied at a temperature below 40 ° C.
  • the application temperature of the composition is advantageously well below the melting point of the hydrazide HY present in order to avoid a premature reaction of the hydrazide HY with the isocyanate groups present.
  • the application is carried out by contacting the composition with a solid surface, optionally by means of a suitable auxiliary agent. If the composition is in pasty form, the application can be carried out, for example, from commercially available cartridges, which are preferably operated manually for smaller applications. An application by means of compressed air from a cartridge or from a barrel or hobbock by means of a feed pump or an extruder, optionally by means of an application robot, is also possible. Such types of application are particularly preferred in industrial manufacturing applications or in large applications.
  • components K1 and K2 are mixed together before or during application by a suitable method.
  • the mixing can be continuous or batchwise. If mixing takes place before application, care must be taken that there is not too much time between blending components K1 and K2 and the application, as this can lead to disturbances, such as a slow or incomplete buildup of adhesion to the solid surface ,
  • the curable composition reacts with water or moisture and is thereby crosslinked. If enough water is present to react most or all of the isocyanate groups, a cured composition results which has good mechanical properties.
  • the composition may therefore be termed "moisture-curing.”
  • this process also referred to as “curing” or “crosslinking,” takes place at room temperature or slightly elevated temperature, in particular below 40 ° C.
  • the blocked amine BA begins to react with existing isocyanate groups to release aldehydes and / or ketones as soon as it comes into contact with water. Existing aldimino groups can hydrolyze upon access of moisture, or water, via intermediates to primary amino groups, the corresponding aldehyde is released.
  • ketimino groups may hydrolyze via intermediates to primary amino groups on entry of moisture, liberating the corresponding ketone. In the presence of isocyanate groups also urea groups are formed. Also present Enamino phenomenon react upon access of moisture to release the corresponding aldehyde or ketone with isocyanate groups to urea groups. In the hydrolysis of existing oxazolidino groups formally release a aldehyde or ketone per oxazolidino group a secondary amino group and a hydroxyl group. In the presence of isocyanate groups, the secondary amino groups react to urea groups and the hydroxyl groups to urethane groups.
  • Oxazolidino phenomenon are thus formally difunctional in their hydrolysis to isocyanate groups.
  • the water needed to cure the composition is either already present in the applied composition, for example - in the case of a two-part composition - being a component of component K2 or by adding it to the composition shortly before or during application, or the water diffuses into the composition in the form of atmospheric moisture.
  • the reaction of the blocked amine BA with the isocyanate groups takes place from the outside inwards, parallel to the penetration of the atmospheric moisture into the composition.
  • a two-component composition which has hydroxyl, mercapto or primary or secondary amino groups, these also react with the isocyanate groups present.
  • Excess isocyanate groups react in particular directly with water. As a result of these reactions, the mixed composition cross-links and eventually hardens to a solid material.
  • the curing is generally free of bubbles, especially at high curing rate.
  • the curing rate can be influenced by the type and amount of one or more optionally present catalysts and / or by the air humidity or, if appropriate, by the amount of water introduced via a component K2.
  • the curing is carried out at room temperature or slightly elevated temperature, in particular below 40 0 C.
  • the hydrazide HY does not react at these conditions due to its high melting point to any significant extent with isocyanates, but remains largely unreacted in the cured composition.
  • the hydrazide HY When the cured composition is heated, in particular to 80 ° C. and higher, the hydrazide HY begins to react with the aldehydes and / or ketones present, in particular with the aldehydes and / or ketones liberated in the hydrolysis of the blocked amine BA.
  • the resulting in the reaction between hydrazides and aldehydes or ketones Condensation products, also called hydrazones, are referred to in the present document as "aldazides" or as "ketazides”.
  • the heating of the cured composition can be carried out, for example, in the course of normal use of the cured composition, for example, by an automobile whose windshield is bonded by means of the described composition is strongly heated by solar radiation.
  • the heating of the cured composition can also be brought about deliberately by, for example, the abovementioned automobile - or an attachment thereof containing the glued windshield - specifically heated to 80 0 C, for example, so that existing aldehydes and / or ketones react with the hydrazide HY.
  • the targeted heating can represent a process step in the manufacturing process.
  • the described curable composition hardly differs in its curing behavior and the mechanical properties of suitable compositions without hydrazide HY at a suitable application and curing temperature.
  • the isocyanate groups react, as already described, with the hydrolyzing blocked amino groups of the blocked amine BA and optionally present hydroxyl groups, mercapto groups and unblocked amino groups, and finally with water, while the hydrazide HY due to its high melting point not to a significant extent at the Curing reaction participates.
  • the curable composition described has a significantly reduced outgassing, especially at elevated temperature.
  • Emissions caused by the outgassing of aldehydes or ketones can be disruptive, especially indoors, for example by causing an unpleasant odor, or by causing irritation to the skin or respiratory tract, or by forming fittings on surfaces. In vehicles, such fittings can lead to clouding of the discs, which is also referred to as "fogging" (and as described in DIN 75201 determined can be). In the automotive industry in particular, there are often limits for the materials used in the vehicle interior, for example adhesives, volatiles escaping through outgassing.
  • the hydrazide begins to react with the aldehydes and / or ketones liberated in the hydrolysis of the blocked amine BA.
  • the aldazides or ketazides formed in this case are low volatility enough not to outgas even at higher temperatures.
  • the hydrazide HY described can be used to reduce the aldehyde or ketone outgassing from the cured composition.
  • the hydrazide HY has, as already mentioned, a melting point of at least 100 0 C, in particular of at least 150 0 C, on. Too low a melting point of the hydrazide used can result in premature reaction with isocyanate groups, which can lead to incomplete curing of the composition and / or inadequate storage stability of the hydrazide together with isocyanate groups.
  • the storage stability of a one-component composition is related to the melting point of the hydrazide present.
  • a curable composition which, in addition to at least one polyisocyanate P, as hydrazide HY the particular preferred adipic dihydrazide in the amount already mentioned, and as a blocked amine BA an aldimine BA1 of the formula (I a) with Z 1 of the formula (II) or (III) with radicals R 4 or R 5 having 11 to 30 carbon atoms, has particularly advantageous properties. It has a very good storage stability, cures at room temperature or slightly elevated temperature quickly and odor-free and has in the cured state good mechanical properties. At elevated temperature, it shows a surprisingly low aldehyde outgassing; their weight loss at 80 ° C. is very low compared to that of a corresponding composition without hydrazide HY.
  • the described curable composition especially when containing aromatic isocyanate groups or reaction products thereof, exhibits a markedly reduced tendency to yellowing compared with corresponding compositions without Hydrazide HY.
  • the reduced yellowing tendency is particularly evident in the cured composition, especially when it is heated for a few hours or days, for example to temperatures of 80 to 130 0 C.
  • a described hydrazide HY or Aldazid thereof for reducing the yellowing of a cured Polyurethane composition can be used.
  • Preferred applications of the curable composition described, in particular of the preferred embodiments thereof, are adhesives, sealants, potting compounds, coatings, floor coverings, paints, lacquers, primers or foams.
  • curable compositions described are particularly suitable as one-component or two-component elastic adhesives in vehicle construction, in particular as
  • the curable compositions described are furthermore particularly suitable as one-component or two-component floor coverings.
  • a further aspect of the present invention relates to a method for bonding a substrate S1 to a substrate S2, which comprises the steps of: i) applying a previously described curable composition to a substrate S1 at a temperature below 40 ° C.; ii) contacting the applied composition with a substrate S2 within the open time of the composition; iii) curing the applied composition in a
  • the substrate S2 is made of the same or a different material as the substrate S1.
  • Another aspect of the present invention relates to a method of sealing. This comprises the following steps: i) application of a previously described curable composition at a temperature below 40 ° C. between a substrate S1 and a substrate S2 such that the composition is in contact with the substrate S1 and the substrate S2; Curing the applied composition in a
  • the substrate S2 is made of the same or a different material as the substrate S1.
  • the composition is pressed into a so-called joint.
  • Another aspect of the present invention relates to a method of coating a substrate S1. This comprises the steps: i '") application of a previously described curable composition at a temperature below 40 ° C. to a substrate S1 within the open time of the composition; ii'") hardening of the applied composition at a temperature below 40 ° C.
  • suitable substrates S1 and / or S2 are, for example, inorganic substrates such as glass, glass-ceramic, concrete, mortar, Brick, brick, plaster and natural stones such as granite or marble; Metals or alloys such as aluminum, steel, non-ferrous metals, galvanized metals; organic substrates such as leather, fabrics, paper, wood, resin-bonded wood materials, resin-Texil composites, plastics such as polyvinyl chloride (hard and soft PVC), acrylonitrile-butadiene-styrene copolymers (ABS), SMC (Sheet Molding Composites ), Polycarbonate (PC), polyamide (PA), polyesters, PMMA, polyesters, epoxy resins, polyurethanes (PUR), polyoxymethylene (POM), polyolefins (PO), in particular plasma-corona or flame-treated polyethylene (PE) or polypropylene ( PP), ethylene / propylene copolymers (EPM) and ethylene / propylene
  • the substrates can be pretreated before applying the composition.
  • pretreatments include, in particular, physical and / or chemical cleaning methods, for example grinding, sandblasting, brushing or the like, or treatment with cleaners or solvents or the application of an adhesion promoter, a primer solution or a primer.
  • This article is in particular a building, in particular a building of civil engineering, or an industrial good or a consumer good, in particular a window, a household machine, or a means of transport, in particular a vehicle on water or on land, preferably an automobile, a bus , a truck, a train or a ship, or an attachment of a means of transport, or an article of the furniture, textile or packaging industry.
  • Another object of the present invention is a cured composition AZ, obtained by the curing of the previously described curable composition at a temperature below 40 0 C by the action of water, for example in the
  • Q 1 is a hydrogen atom or Z 3 or Z 5 or Z 8 , wherein if Q 1 is a hydrogen atom, Q 2 is Y, or if Q 1 is Z 3 , Q 2 is Z 4 , or
  • Q 1 is Z 5
  • Q 2 is or if Q 1 is Z 8
  • Q 2 is Z 9 .
  • W, X, m, p, q, Y, Z 3 , Z 4 , Z 5 , Z 5 , Z 6 , Z 7 , Z 8 and Z 9 have the meanings already described.
  • the compounds of the formula (XVIII a), (XVIII b) and (XIX) are aldazides or ketazides of carboxylic or sulfonic acid hydrazides.
  • the compounds of the formula (XVIII a) and (XVIII b) are formed by the reaction of a hydrazide HY in the form of a carboxylic acid hydrazide with an aldehyde or ketone, while the compound of formula (XIX) is formed by the reaction of a hydrazide HY in the form of a sulfonic acid hydrazide with an aldehyde or ketone, and wherein the aldehyde or ketone precipitates upon curing of the composition the blocked amine BA was released.
  • the cured composition AZ contains a
  • Carboxylic acid dihydrazide is preferably selected from the group consisting of carbodihydrazide, oxalic dihydrazide, succinic dihydrazide, adipic acid dihydrazide, suberic dihydrazide, azelaic dihydrazide, sebacic dihydrazide, dodecanoic dihydrazide and isophthalic dihydrazide. Of these, most preferred is adipic dihydrazide.
  • Q 1 is preferably a hydrogen atom and Q 2 is -C (R 1 ) (R 2 ) (Z 1 ), where Z 1 is, in particular, a radical of the formula (II) or (III) or (IV).
  • Another object of the present invention is an aldazide of the formula (XX a) or (XX b),
  • W 1 represents the p'-valent radical of a hydrazide HY of a carboxylic acid which has a melting point of at least 100 ° C., in particular of at least 150 ° C., after removal of p 'carboxylic acid hydrazide groups; p 'is 2 or 3 or 4; and m, R 1 , R 2 and Z 1 have the meanings already mentioned.
  • p ' is 2.
  • Z 1 is preferably a radical of the formula (II) or (III) or (IV).
  • Infrared spectra were measured on a Perkin-Elmer 1600 FT-IR instrument, solids as KBr compacts in direct jet, liquids as undiluted films, and cured polymers as pressed films on a ZnSe crystal horizontal ATR measuring unit; the absorption bands are given in wavenumbers (crrf 1 ) (measurement window: 4000-650 cm -1 ); the suffix sh indicates a band appearing as a shoulder, the suffix br on a broad band.
  • the viscosity was measured on a thermostatically controlled cone-plate viscometer Physica UM (cone diameter 20 mm, cone angle 1 °, cone peak-to-plate distance 0.05 mm, shear rate 0 to 1000 s -1 ).
  • the amine content ie the total content of free amino groups and blocked amino groups (aldimino groups) in the compounds prepared, was determined titrimetrically (with 0.1 N HClO 4 in glacial acetic acid, against crystal violet) and is always given in mmol N / g.
  • a standard climate at a temperature of 23 ⁇ 1 0 C at a relative humidity of 50 ⁇ 5% is referred to.
  • polymer P-1 In a screw cap polypropylene cup, polymer P-1, whose preparation is described below, was prepared using a centrifugal mixer (Speed Mixer TM DAC 150, FlackTek Inc, 1 min at 2500 rpm) with the ingredients listed in Table 1 the specified parts by weight mixed to a homogeneous mass.
  • a centrifugal mixer Speed Mixer TM DAC 150, FlackTek Inc, 1 min at 2500 rpm
  • Polymer P-1 was prepared as follows:
  • Table 1 Composition of Examples 3 to 7 and Comparative Examples 8 to 9. a 5 wt .-% salicylic acid in dioctyl adipate. b 2,2'-Dimorpholinodi- ether (DABCO ® DMDEE Catalyst, Air Products). c ratio between aldimino groups and isocyanate groups. d ratio between hydrazide groups and aldimino groups.
  • DABCO ® DMDEE 2,2'-Dimorpholinodi- ether
  • compositions thus obtained were tested for viscosity, storage stability, skinning time, blistering, mechanical properties, outgassing loss and degree of gassing of the aldehyde.
  • Storage stability was determined by the change (increase) in viscosity during storage in the heat.
  • the composition was stored in the sealed tube in the oven at 60 0 C and measured the viscosity at 20 0 C a first time after 6 hours and a second time after 7 days of storage.
  • the storage stability results from the percentage increase of the second viscosity value compared to the first.
  • tack free time To measure the skin formation time (time to freedom from tack, "tack free time") a few grams of the stored during 6 hours at 60 0 C, room-temperature warm composition in a layer thickness of approximately 2 mm were applied to cardboard, and the time under standard conditions, It took until the slightest tap of the surface of the composition by means of a pipette of LDPE for the first time left no residues on the pipette more.
  • Bubble formation was assessed qualitatively by the amount of bubbles that occurred during cure of the composition. As mechanical properties were the tensile strength
  • the aldehyde content of a composition can be calculated directly from the aldimine content The lower the degree of gasification of the aldehyde, the less aldehyde was outgassed.
  • a piece of the film produced as described above was cut into pieces of about 2 ⁇ 2 mm in size. About 5 g of these pieces were weighed into a crystallizing dish, covered with a tared watch glass and the shell at low immersion depth in the oil bath for 24 hours at 100 0 C or 12 hours heated to 130 0 C, which formed a condensation fitting on the watch glass , The amount of condensate was determined by reweighing the fogged watch glass and expressed in percent of the weighed film amount as "fogging".
  • FIG. 1 shows infrared spectra.
  • the spectrum designated IR-1 was taken up by the polyurethane composition of Example 3 after curing under standard conditions.
  • the spectrum designated IR-2 was absorbed by the polyurethane composition of Example 3 after curing under standard conditions and subsequent heating for 24 hours at 100 0 C.
  • the spectrum designated IR-R1 is the spectrum of the aldazide of Example 1 (condensation product of adipic dihydrazide and 2,2-dimethyl-3-lauroyloxypropanal).
  • an infrared spectrum was recorded subsequent to the determination of the fogging at 130 0 C by the respective condensate on the watch glass.
  • the spectrum designated IR-3 shows the condensate of Example 3
  • the spectrum designated IR-R2 shows the condensate of Example 8.
  • the spectrum designated IR-R3 is derived from 2,2-dimethyl-3-lauroyloxy-propanal, ie the aldehyde released from aldimine A-2.
  • Table 3 Composition of the adhesives of Examples 10 to 12 and Comparative Examples 13 to 14.
  • a diisodecyl phthalate (DIDP; Palatinol ® Z, BASF).
  • DIDP diisodecyl phthalate
  • b dried at 130 ° C. 0 hydrophobic fumed silica (Aerosil ® R972, Degussa).
  • d p-toluene sulfonyl isocyanate additive Tl, Bayer
  • e 3-Glycidoxypropyltrieth- oxysilane (Dynasylan ® GLYEO, Degussa).
  • the stability and the thread tension were used.
  • the adhesive was applied by means of a caulking gun via a triangular nozzle as a horizontally extending triangular bead with a base diameter of 8 mm and a height (distance of the triangular tip from the base) of 20 mm on a vertical piece of cardboard. After 5 minutes, it was measured how far the tip was lowered, i. moved away from the original position in the middle of the triangle caterpillar. When the tip was in a fully or nearly unchanged position, it was considered “very good” to be “good” if the tip was between the middle and the base end.
  • the thread tension was determined qualitatively by applying some adhesive to a wall-mounted piece of cardboard by means of a caulking gun, pulling the caulking gun away from the applied adhesive at the end of the job and measuring the length of the thread remaining at the break-off point.
  • Shore A hardness was determined according to DIN 53505 on test specimens cured for 14 days under standard conditions.
  • Example 3 The other properties were tested as described in Example 3, wherein the Ausgasungsberg was also determined after 7d / 80 0 C.
  • the outgassing loss of the aldimine-free Comparative Example 14 was used as the zero value to calculate the degree of gasification.
  • Table 4 Properties of the adhesives of Examples 10 to 12 and Comparative Examples 13 to 14.
  • a 1st figure Testing after curing under standard conditions; 2nd figure: test after condensation (7d / 70 ° C) ("cataplasm") of the material cured in standard climates, 3rd figure: test after heat load (7d / 80 ° C) of the material cured in standard atmosphere; after heat load (7d / 100 ° C) of the material cured under standard conditions
  • upper number after 7d / 80 ° C
  • lower figure after 7d / 100 ° C.
  • Polymer P-1 was prepared as described in Example 3.
  • the polyurethane polymer P-2 was prepared as follows: 590 g of polyol Acclaim ® 4200 N (polypropylene oxide diol having an OH number of 28.5 mg KOH / g; Bayer), 1180 g of polyol Caradol ® MD34-02 (polypropylene oxide-polyethylene triol, OH -number 35.0 mg KOH / g; Shell) and 230 g of isophorone diisocyanate (IPDI; Vestanat ® IPDI, Degussa) were according to a known method at 80 0 C to give an NCO-terminated polyurethane polymer having a titrimetrically determined free isocyanate groups of 2.1% by weight reacted.
  • IPDI isophorone diisocyanate
  • the urea thickener was prepared as follows:
  • Table 5 Composition of the adhesives of Examples 15 to 16 and Comparative Examples 17 to 18.
  • a Urea thickener b 3-glycidoxypropyltriethoxysilane (Dyna Sylan GLYEO ®, Degussa).
  • c 5% by weight of salicylic acid in dioctyl adipate.
  • dibutyltin dilaurate 5% by weight in diisodecyl phthalate).
  • DABCO ® DMDEE Catalyst, Air Products
  • the adhesives thus obtained were tested for application properties, skin formation time, mechanical properties, outgassing loss and degree of aldehyde's exhaustion as described in Example 10.
  • the outgassing loss of aldimine-free Comparative Example 18 was used as the zero value to calculate the degree of gasification.
  • the blistering was tested as described in Example 3.
  • Table 6 Properties of the adhesives of Examples 15 to 16 and Comparative Examples 17 to 18.
  • nb not determined From Table 6 it can be seen that the invention
  • Adhesives of Examples 15 to 16 which in addition to the aldimine A-2 adipic acid dihydrazide, compared to the adhesive of Comparative Example 17 without hydrazide have a significantly reduced Ausgasungsmann.
  • the hydrazide is used stoichiometrically with respect to the aldimine (Example 15)
  • the outgassing loss at 80 ° C. drops to less than half the value measured for Comparative Example 17 and reaches approximately that for Reference Example 18 which does not contain aldimine at 100 ° C. measured value.
  • the thermal stability of the adhesives of Examples 15 and 16 is comparable to that of Comparative Example 17.

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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)
  • Paints Or Removers (AREA)
  • Sealing Material Composition (AREA)

Abstract

L'invention concerne notamment des compositions durcissables contenant au moins un polyisocyanate, au moins une amine bloquée par aldéhyde ou cétone, et au moins un hydrazide d'un acide carboxylique ou sulfonique, présentant un point de fusion d'au moins 100 °C, notamment d'au moins 150 °C. Il s'est avéré que de telle compositions, après avoir été durcies sous l'effet de l'humidité à température ambiante, présentent, lors du chauffage à des températures élevées, un dégagement gazeux de composants volatils bien plus faible que celui de compositions correspondantes ne contenant pas d'hydrazide.
EP08865653A 2007-12-21 2008-12-19 Compositions durcissables à dégagement gazeux réduit Withdrawn EP2225298A1 (fr)

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EP07150364A EP2072550A1 (fr) 2007-12-21 2007-12-21 Compositions durcissables à dégazage réduit
EP08865653A EP2225298A1 (fr) 2007-12-21 2008-12-19 Compositions durcissables à dégagement gazeux réduit
PCT/EP2008/067985 WO2009080738A1 (fr) 2007-12-21 2008-12-19 Compositions durcissables à dégagement gazeux réduit

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EP2072550A1 (fr) 2009-06-24
US20100273924A1 (en) 2010-10-28
JP2011506733A (ja) 2011-03-03
CN101903432A (zh) 2010-12-01

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