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WO1988008859A1 - Hot-melt adhesives characterized by moisture-induced cross-linking - Google Patents

Hot-melt adhesives characterized by moisture-induced cross-linking Download PDF

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Publication number
WO1988008859A1
WO1988008859A1 PCT/EP1988/000347 EP8800347W WO8808859A1 WO 1988008859 A1 WO1988008859 A1 WO 1988008859A1 EP 8800347 W EP8800347 W EP 8800347W WO 8808859 A1 WO8808859 A1 WO 8808859A1
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Prior art keywords
moisture
polyamide
diisocyanate
formula
group
Prior art date
Application number
PCT/EP1988/000347
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German (de)
French (fr)
Inventor
Heinz-Günther SCHULTE
Jürgen WICHELHAUS
Wolfgang Pille-Wolf
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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Publication of WO1988008859A1 publication Critical patent/WO1988008859A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/8083—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/809—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
    • 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
    • C08G18/60—Polyamides or polyester-amides
    • C08G18/603—Polyamides
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/48—Polymers modified by chemical after-treatment
    • 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
    • C08G2170/00—Compositions for adhesives
    • C08G2170/20—Compositions for hot melt adhesives

Definitions

  • the invention relates to moisture-curing hot melt adhesives.
  • Moisture-crosslinking hot-melt adhesives are generally understood to mean solvent-free adhesives which, after being applied to a substrate, achieve their final strength and heat resistance by curing with water from the atmosphere or the substrate.
  • the groups reacting with water are generally NCO groups, cf. DE-B 24 01 320, EP-B 00 19 159, DE-A 32 36 313, DE-A 33 39 981, US-B 3 991 025, US-B 3 931 077, US-B 4 166 873, EP -A 0 125 008, EP-A 0 125 009.
  • moisture-curing hotmelt adhesives can be obtained if free NCO groups of prepolymers are reacted with ⁇ -aminoalkyl-trialkoxysilanes, the curing then taking place via the Si (OR) 3 end groups, cf. DE-OS 35 18 357.
  • This lecture also presented a moisture-curing hotmelt adhesive which was built up from a polyester as a backbone with free OH groups, in such a way that the OH groups were first reacted in excess with polyfunctional isocyanates . The free NCO groups then present were then reacted with ⁇ -aminoalkyl trialkoxysilanes to give so-called silane hotmelt adhesives.
  • a similarly structured melting stick Super systems are from Japanese patent applications 80 160 074 (CA 94, 15 79 92p (1981)), 59 24 767 (CA 101, 73 931t (1984)), 59 221 366 (CA 102, 150611p (1985)), 59 172 573 (CA 102, 96632f (1985)) and 59 174 674 (CA 102, 63283q (1985 known.
  • Moisture-crosslinking hotmelt adhesives that contain free NCO groups are temperature-sensitive and crosslink to insoluble and infusible polymers when a permissible maximum temperature is exceeded.
  • the application temperatures for these adhesives are therefore relatively low.
  • the invention is directed to moisture-crosslinking hotmelt adhesives whose heat resistance after crosslinking exceeds 200 ° C. and which give excellent adhesive performance both before and after crosslinking.
  • the moisture crosslinking hot melt adhesives of the invention contain silanized polyamides and are obtainable by reacting a diisocyanate of the formula (I)
  • R 1 is a radical selected from the group consisting of C 5 -C 14 -alkylene, arylene, diarylenealkane and dialkylene-substituted aryl, with an alkoxyalkyleneamino- or mercaptosilane of the general formulas (Ila or Ilb)
  • R 2 is a substituent from that of hydrogen
  • n is a number from 1-4
  • R 3 is a C 1 -C 4 alkyl group
  • R 4 is a radical from that of C 1 -C 4 alkyl and alkoxyalkylene with 2-4
  • p is a number of 0, 1 or 2
  • R 1 , R 2 , R 3 , R 4 , n and p are as defined above and X denotes the group -NH- or -S-,
  • x is a number which gives amine or acid numbers between 5 and 50 for the polyamides.
  • polyamides Homopolyamides, copolyamides, polyamide alloys, so-called elastomeric polyamides and polyamides containing other thermoplastics can be used as polyamides.
  • these are the following basic types:
  • Suitable aliphatic polyamides are, for example, from amino acids, lactams or aliphatic dicarboxylic acids of the formula HOOC- (CH 2 ) n -COOH with diamines H 2 N (CH 2 ) n -NH 2 , where n is 4 to 13.
  • Suitable elastomeric polyamides can be composed of polyamide and polyether blocks, the polyamide and the polyether blocks being linked, for example, by esters or amine bonds or using a di-isocyanate or di-epoxide.
  • Amorphous polyamides are said to be preferably a glass conversion point below 200 ° C.
  • the copolyamides can be constructed, for example, from aliphatic, aromatic and / or branched-chain monomers and from monomers with additional heteroatoms which have no polyamide-forming function.
  • the polyamides to be used as the starting material can contain free amino and / or carboxyl groups. They can also contain end groups that are polyamide-forming and, in addition to aliphatic chain links and amide groups, secondary amino groups and other groups with heteroatoms such as -O-, -S-, -SO 2 -, - NCH 3 - or -CO- in the chain.
  • PA polyamide
  • PA-6 polyamide
  • PA-11 PA-12
  • PA-66 PA-69
  • PA-6.10 PA-6.12
  • PA-6.13 amorphous PA according to ÜS-B 4 233 145 or US-B 4 268 661
  • amorphous PA from isophthalic acid, hexanediamine and optionally other polyamide monomers
  • transparent polyamide from trimethylhexamethylene diamine and texephthalic acid
  • Carboxyl-terminated polyamides of the formula (IVb) are prepared like amino-terminated polyamides, but with an excess of dicarboxylic acid, cf. Houben-Weyl, Vol. 14/2, Thieme-Verlag, and Ullmann's Encyclopedia of Technical Chemistry, Vol. 19, Verlag Chemie 1980.
  • the polyamide of the formula (IVa) has amine numbers between 5 and 50.
  • Polyamides of the formula (IVb) preferably have acid numbers between 5 and 50.
  • the polyamides of the formula (IVa) are preferably prepared from dimeric fatty acids formed by polymerizing unsaturated fatty acids having 12 to 22 carbon atoms or esters thereof with C 1 -C 4 -aliphatic alcohols; these are polyamides, as described in EP-A 00 61 119, the disclosure of which is included here.
  • the isocyanates are those of isomeric toluylidene diisocyanates, in particular technical mixtures of 2,4- and 2,6-isomers, diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, naphthylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate (2,4,4 -Trimethyl-1,6-diisocyanato-hexane) and dimeric tolylene diisocyanate-2,4 as well as cyclohexylene diisocyanate and dicyclohexylmethane diisocyanate group formed.
  • the trialkoxy-alkyleneaminosilanes of the general formula (Ila) are in particular those which have only one, preferably secondary, amino group.
  • Typical examples are ⁇ -A-inopropyltrimethoxysilane ⁇ -aminopropyltriethoxysilane N-methyl- ⁇ -aminopropyltrimethoxysilane N-cyclohexyl- ⁇ -aminopropyltrimethoxysilane Nn-octyl- ⁇ -aminopropyltrimethoxysilan-3-aminoxysilan-N-phenyl-trimyl-N-phenyl-trimyl-N-phenyl-trimyl-N-phenyl-trimyl-N-phenyl-trimyl-3 ] -amin N-methyl- ⁇ -aminopropylmethyl-dimethoxysilane.
  • alkoxy substituents in particular the monomethyl ethers of glycols such as ethylene or diethylene glycol and the like, can also be used.
  • the moisture crosslinking hot melt adhesives of the invention may contain acidic catalysts selected from the group consisting of tin II octoate, dibutyltin dilaurate, tetrabutyl titanate, zinc acetate and zinc acetylacetonate.
  • acidic catalysts selected from the group consisting of tin II octoate, dibutyltin dilaurate, tetrabutyl titanate, zinc acetate and zinc acetylacetonate.
  • Such catalysts are common, cf. e.g. Ulimann, Enzykl ⁇ püdie der technical chemistry, Vol. 21, page 523 ff or E. Skeisir, Handbook of Adhesives, van Nostrand, 1976, page 630.
  • the moisture-crosslinking hotmelt adhesives of the invention can have a content of 0 to 50% by weight, based on trialkoxysilane-terminated polyamide of the formulas (Va) or (Vb), of resins which are inert to the latter.
  • Va trialkoxysilane-terminated polyamide of the formulas (Va) or (Vb)
  • resins which are inert to the latter are also common, cf. B.E. Skeist, Handbook of Adhesives, van Nostrand, 1976.
  • the preparation of the moisture-crosslinking hotmelt adhesives of the invention in the sequence 1. diisocyanate, 2. alkoxysilane, 3. polymer is compared to the production in the sequence of the prior art, namely 1. polymer, 2. Diisocyanate, 3rd alkoxysilane, cheaper because here only one monoisocyanate formally reacts with the polymer at temperatures above the melting temperature of the polymer.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Polyamides (AREA)

Abstract

Hot-melt adhesives characterized by moisture-induced cross-linking which possesses excellent thermal stability at temperatures equal to or greater than 200°C and good initial adhesive strength are produced by converting diisocyanates with alkyloxy-alkylenamino or alkoxy-mercaptosilanes and reacting the urea derivatives so obtained with polyamides containing free amino and/or carboxyl groups to form silanized polyamides.

Description

Feuchtigkeitsvernetzende Schmelzkleber Moisture-curing hot melt adhesive
Die Erfindung betrifft feuchtigkeitsvernetzende Schmelzkleber.The invention relates to moisture-curing hot melt adhesives.
Unter feuchtigkeitsvernetzenden Schmelzklebern versteht man im allgemeinen lösemittelfreie Klebstoffe, die nach dem Auftragen auf ein Substrat ihre Endfestigkeit und Wärmestandfestigkeit erreichen, indem sie mit Wasser aus der Atmosphäre oder dem Substrat nachhärten. Die mit Wasser reagierenden Gruppen sind im allgemeinen NCO-Gruppen, vgl. DE-B 24 01 320, EP-B 00 19 159, DE-A 32 36 313, DE-A 33 39 981, US-B 3 991 025, US-B 3 931 077, US-B 4 166 873, EP-A 0 125 008, EP-A 0 125 009. Weiterhin ist bekannt, daß man feuchtigkeitshärtende Schmelzkleber erhalten kann, wenn man freie NCO-Gruppen von Prepolymeren mit γ-Aminoalkyl-trialkoxysilanen umsetzt, wobei die Aushärtung dann über die Si(OR)3-Endgruppen erfolgt, vgl. DE-OS 35 18 357. In diesem Vortrag wurde auch ein feuchtigkeitshärtender Schmelzkleber vorgestellt, der aus einem Polyester als Grundgerüst mit freien OH-Gruppen aufgebaut wurde, und zwar in der Weise, daß die OH-Gruppen zunächst mit mehrfunktionellen Isocyanaten im Überschuß umgesetzt wurden. Die dann vorhandenen freien NCO-Gruppen wurden anschließend mit γ -Aminoalkyl-trialkoxysilanen zu sogenannten Silanschmelzklebstoffen umgesetzt. Ähnlich aufgebaute Schmelzkle bersysteme sind aus den japanischen Patentanmeldungen 80 160 074 (C.A 94 , 15 79 92p (1981)), 59 24 767 (C.A 101, 73 931t (1984)), 59 221 366 (C.A 102, 150611p (1985)), 59 172 573 (C.A. 102, 96632f (1985)) und 59 174 674 (C.A. 102, 63283q (1985 bekannt.Moisture-crosslinking hot-melt adhesives are generally understood to mean solvent-free adhesives which, after being applied to a substrate, achieve their final strength and heat resistance by curing with water from the atmosphere or the substrate. The groups reacting with water are generally NCO groups, cf. DE-B 24 01 320, EP-B 00 19 159, DE-A 32 36 313, DE-A 33 39 981, US-B 3 991 025, US-B 3 931 077, US-B 4 166 873, EP -A 0 125 008, EP-A 0 125 009. It is also known that moisture-curing hotmelt adhesives can be obtained if free NCO groups of prepolymers are reacted with γ-aminoalkyl-trialkoxysilanes, the curing then taking place via the Si (OR) 3 end groups, cf. DE-OS 35 18 357. This lecture also presented a moisture-curing hotmelt adhesive which was built up from a polyester as a backbone with free OH groups, in such a way that the OH groups were first reacted in excess with polyfunctional isocyanates . The free NCO groups then present were then reacted with γ-aminoalkyl trialkoxysilanes to give so-called silane hotmelt adhesives. A similarly structured melting stick Super systems are from Japanese patent applications 80 160 074 (CA 94, 15 79 92p (1981)), 59 24 767 (CA 101, 73 931t (1984)), 59 221 366 (CA 102, 150611p (1985)), 59 172 573 (CA 102, 96632f (1985)) and 59 174 674 (CA 102, 63283q (1985 known.
Feuchtigkeitsvernetzende Schmelzkleber, die freie NCO-Gruppen aufweisen, sind temperaturempfindlich und vernetzen beim Überschreiten einer zulässigen Höchsttemperatur zu unlöslichen und unschmelzbaren Polymeren. Die Anwendungstemperaturen für diese Kleber sind daher relativ niedrig. Zudem lassen sich häufig auch unmittelbar nach der Applikation noch keine besonderen Festigkeiten bei Raumtemperatur erzielen, obwohl dies ein wesentliches Kriterium für Schmelzkleber darstellt.Moisture-crosslinking hotmelt adhesives that contain free NCO groups are temperature-sensitive and crosslink to insoluble and infusible polymers when a permissible maximum temperature is exceeded. The application temperatures for these adhesives are therefore relatively low. In addition, it is often not possible to achieve any particular strengths at room temperature immediately after application, although this is an important criterion for hot melt adhesives.
Die aus dem Stand der Technik bekannte Synthese in der Reihenfolge 1. Polymer, 2. Diisocyanat und 3. Alkoxysilan, wie sie in den obengenannten japanischen Patentanmeldungen beschrieben wird, birgt die Gefahr der Viskositätszunahme infolge einer breiteren Molekulargewichtsverteilung während der Reaktion, welche die zur Applikation erforderliche Temperatur erhöht sowie das Abkühlverhalten negativ beeinflußt.The synthesis known from the prior art in the order of 1st polymer, 2nd diisocyanate and 3rd alkoxysilane, as described in the above-mentioned Japanese patent applications, harbors the risk of an increase in viscosity as a result of a broader molecular weight distribution during the reaction, which is the reason for the application required temperature increased and the cooling behavior negatively affected.
Demgemäß ist die Erfindung auf feuchtigkeitsvernetzende Schmelzkleber gerichtet, deren Wärmestandfestigkeit nach Vernetzung 200°C überschreitet und die sowohl vor als auch nach dem Vernetzen ausgezeichnete Klebleistungen ergeben.Accordingly, the invention is directed to moisture-crosslinking hotmelt adhesives whose heat resistance after crosslinking exceeds 200 ° C. and which give excellent adhesive performance both before and after crosslinking.
Die feuchtigkeitsvernetzenden Schmelzkleber der Erfindung enthalten silanisierte Polyamide und sind erhältlich durch Umsetzung eines Diisocyanats der Formel (I)The moisture crosslinking hot melt adhesives of the invention contain silanized polyamides and are obtainable by reacting a diisocyanate of the formula (I)
OCN-R1-NCO ( I ) in der R1 ein aus der von C5-C14-Alkylen, Arylen, Diarylenalkan und dialkylen-substituiertes Aryl gebildeten Gruppe ausgewählter Rest ist, mit einem Alkoxy-alkylenamino- oder -mercaptosilan der allgemeinen Formeln (Ila bzw. Ilb)OCN-R 1 -NCO (I) in which R 1 is a radical selected from the group consisting of C 5 -C 14 -alkylene, arylene, diarylenealkane and dialkylene-substituted aryl, with an alkoxyalkyleneamino- or mercaptosilane of the general formulas (Ila or Ilb)
Figure imgf000005_0001
in der R2 ein Substituent aus der von Wasserstoff,
Figure imgf000005_0001
in which R 2 is a substituent from that of hydrogen,
C1-C4-Alkyl, Aryl und dem Rest der FormelC 1 -C 4 alkyl, aryl and the rest of the formula
Figure imgf000005_0002
gebildeten Gruppe ist,
Figure imgf000005_0002
educated group is
n eine Zahl von 1-4,n is a number from 1-4,
R3 eine C1-C4-Alkylgruppe,R 3 is a C 1 -C 4 alkyl group,
R4 ein Rest aus der von C1-C4-Alkyl und Alkoxyalkylen mit 2-4R 4 is a radical from that of C 1 -C 4 alkyl and alkoxyalkylene with 2-4
Kohlenstoffatomen gebildeten Gruppe undCarbon atoms formed group and
p eine Zahl von 0, 1 oder 2p is a number of 0, 1 or 2
oderor
Figure imgf000005_0003
in der R 3, R4, n und p wie oben definiert sind, bedeuten ,
Figure imgf000005_0003
in which R 3 , R 4 , n and p are as defined above, mean
zu einem Harnstoffderivat der allgemeinen Formel (III)to a urea derivative of the general formula (III)
Figure imgf000006_0001
Figure imgf000006_0001
in der R 1, R2, R3, R4, n und p wie oben definiert sind und X die Gruppe -NH- oder -S- bedeutet,in which R 1 , R 2 , R 3 , R 4 , n and p are as defined above and X denotes the group -NH- or -S-,
sowie Umsetzung im wesentlichen sämtlicher freien Aminogruppen oder Carboxylgruppen eines Polyamids bzw. carboxylterminierten Polyamids der Formeln (IVa) bzw. (IVb)and reaction of essentially all free amino groups or carboxyl groups of a polyamide or carboxyl-terminated polyamide of the formulas (IVa) or (IVb)
Polyamid(NH2)x (IVa)Polyamide (NH 2 ) x (IVa)
Polyamid(COOH)x (IVb)Polyamide (COOH) x (IVb)
in der x eine Zahl bedeutet, die für die Polyamide Amin- bzw. Säurezahlen zwischen 5 und 50 ergibt.in which x is a number which gives amine or acid numbers between 5 and 50 for the polyamides.
mit dem Harnstoffderivat der Formel (III) zu einem trialkoxysilanterminierten Polyamid der Formeln (Va) bzw. (Vb)with the urea derivative of the formula (III) to give a trialkoxysilane-terminated polyamide of the formulas (Va) or (Vb)
Figure imgf000006_0002
Figure imgf000006_0003
in der R1, R3, X, n, p und x wie oben definiert sind,
Figure imgf000006_0002
Figure imgf000006_0003
in which R 1 , R 3 , X, n, p and x are as defined above,
sowie sauren oder basischen Katalysatoren und üblichen Hilfsstoffen.as well as acidic or basic catalysts and customary auxiliaries.
Als Polyamide können Homopolyamide, Copolyamide, Polyamid-Legierungen, sogenannte elastomere Polyamide sowie Polyamide mit einem Gehalt an anderen Thermoplasten eingesetzt werden. Mit anderen Worten gesagt, handelt es sich hierbei um folgende Grundtypen:Homopolyamides, copolyamides, polyamide alloys, so-called elastomeric polyamides and polyamides containing other thermoplastics can be used as polyamides. In other words, these are the following basic types:
- aliphatische Homo- oder Copolyamide,aliphatic homo- or copolyamides,
- aliphatisch-aromatische Homo- oder Copolyamide,aliphatic-aromatic homo- or copolyamides,
- amorphe Polyamide,- amorphous polyamides,
- elastomere Polyamide,- elastomeric polyamides,
- Mischungen verschiedener Polyamide oder- Mixtures of different polyamides or
- Polyamid-Legierungen, welche mindestens 50 Gew.-% Polyamide enthalten.- Polyamide alloys which contain at least 50% by weight of polyamides.
Geeignete aliphatische Polyamide sind z.B. von Aminosäuren, Lactamen oder aliphatischen Dicarbonsäuren der Formel HOOC-(CH2)n-COOH mit Diaminen H2N(CH2)n-NH2 ab, wobei n 4 bis 13 bedeutet. Geeignete elastomere Polyamide können aus Polyamid-und Polyether-Blöσken zusammengesetzt sein, wobei die Polyamid- und die Polyether-Blöcke z.B. durch Ester oder Aminbindungen oder unter Verwendung eines Di-isocyanats oder Di-epoxids verknüpft sind.Suitable aliphatic polyamides are, for example, from amino acids, lactams or aliphatic dicarboxylic acids of the formula HOOC- (CH 2 ) n -COOH with diamines H 2 N (CH 2 ) n -NH 2 , where n is 4 to 13. Suitable elastomeric polyamides can be composed of polyamide and polyether blocks, the polyamide and the polyether blocks being linked, for example, by esters or amine bonds or using a di-isocyanate or di-epoxide.
Amorphe Polyamide sollen vorzugsweise einen Glasumwandlungs punkt unter 200°C aufweisen.Amorphous polyamides are said to be preferably a glass conversion point below 200 ° C.
Die Copolyamide können beispielsweise aus aliphatischen, aromatischen und/oder verzweigtkettigen Monomeren sowie aus Monomeren mit zusätzlichen Heteroatomen, welche keine polyamidbildende Funktion ausüben, aufgebaut sein. Die als Ausgangsstoff zu verwendenden Polyamide können freie Amino- und/oder Carboxylgruppen enthalten. Sie können auch polyamidbildungsinerte Endgruppen sowie in der Kette neben aliphatischen Kettengliedern und Amidgruppen noch sekundäre Aminogruppen sowie andere Gruppen mit Heteroatomen wie -O-, -S-, -SO2-,-NCH3- oder -CO- enthalten.The copolyamides can be constructed, for example, from aliphatic, aromatic and / or branched-chain monomers and from monomers with additional heteroatoms which have no polyamide-forming function. The polyamides to be used as the starting material can contain free amino and / or carboxyl groups. They can also contain end groups that are polyamide-forming and, in addition to aliphatic chain links and amide groups, secondary amino groups and other groups with heteroatoms such as -O-, -S-, -SO 2 -, - NCH 3 - or -CO- in the chain.
Für die Herstellung der feuchtigkeitsvernetzenden Schmelzkleber der Erfindung sind insbesondere die folgenden (Co)polyamide geeignet (PA = Polyamid): PA-6, PA-11, PA-12, PA-66, PA-69, PA-6.10, PA-6.12, PA-6.13, amorphes PA gemäß ÜS-B 4 233 145 oder US-B 4 268 661, amorphes PA aus Isophthalsäure, Hexandiamin und gegebenenfalls anderen Polyamid-Monomeren, transparentes Polyamid aus Trimethylhexamethylendiamin und Texephthalsäure, weitere bekannte transparente Polyamide, elastomere Polyamide mit einem Teil kristallinen Polyamid-Anteil aus z.B. PA-6, PA-11 oder PA-12, welche z.B. über Amid- oder Esterverbindungen mit einem Polyether-Block verknüpft sein können, wobei der Polyether-Block bevorzugt die Struktur -(O-(CH2)4-)n, n = 2 - 50, aufweist oder wobei die Sauerstoffatome durch Isopropylgruppen verknüpft sind.The following (co) polyamides (PA = polyamide) are particularly suitable for producing the moisture-crosslinking hotmelt adhesives of the invention: PA-6, PA-11, PA-12, PA-66, PA-69, PA-6.10, PA-6.12 , PA-6.13, amorphous PA according to ÜS-B 4 233 145 or US-B 4 268 661, amorphous PA from isophthalic acid, hexanediamine and optionally other polyamide monomers, transparent polyamide from trimethylhexamethylene diamine and texephthalic acid, other known transparent polyamides, elastomeric polyamides a portion of crystalline polyamide from, for example, PA-6, PA-11 or PA-12, which can be linked, for example via amide or ester compounds, to a polyether block, the polyether block preferably having the structure - (O- (CH 2 ) 4 -) n , n = 2 - 50, or where the oxygen atoms are linked by isopropyl groups.
Carboxyl-terminierte Polyamide der Formel (IVb) werden wie Amino-terminierte Polyamide hergestellt, jedoch mit einem Überschuß an Dicarbonsäure, vgl. Houben-Weyl, Bd. 14/2, Thieme-Verlag, sowie Ullmanns Enzyklopädie der technischen Chemie, Bd. 19, Verlag Chemie 1980. Gemäß bevorzugten Ausführungsformen der Erfindung weist das Polyamid der Formel (IVa) Aminzahlen zwischen 5 und 50 auf. Polyamide der Formel (IVb) weisen vorzugsweise Säurezahlen zwischen 5 und 50 auf.Carboxyl-terminated polyamides of the formula (IVb) are prepared like amino-terminated polyamides, but with an excess of dicarboxylic acid, cf. Houben-Weyl, Vol. 14/2, Thieme-Verlag, and Ullmann's Encyclopedia of Technical Chemistry, Vol. 19, Verlag Chemie 1980. According to preferred embodiments of the invention, the polyamide of the formula (IVa) has amine numbers between 5 and 50. Polyamides of the formula (IVb) preferably have acid numbers between 5 and 50.
Bevorzugt werden die Polyamide der Formel (IVa) aus durch Polymerisation ungesättigter Fettsäuren mit 12 bis 22 Kohlenstoffatomen bzw. Estern derselben mit C1-C4-aliphatischen Alkoholen gebildeten dimeren Fettsäuren hergestellt; dies sind Polyamide, wie sie in der EP-A 00 61 119 beschrieben sind, deren Offenbarung hier eingeschlossen ist.The polyamides of the formula (IVa) are preferably prepared from dimeric fatty acids formed by polymerizing unsaturated fatty acids having 12 to 22 carbon atoms or esters thereof with C 1 -C 4 -aliphatic alcohols; these are polyamides, as described in EP-A 00 61 119, the disclosure of which is included here.
Gemäß einer weiteren vorteilhaften Ausführungsform der Erfindung sind die Isocyanate aus der von isomeren Toluylidendiisocyanaten, insbesondere technischen Gemischen des 2,4- und 2,6-Isomeren, Diphenylmethandiisocyanat, 1,6-Hexamethylendiisocyanat, Naphthylendiisocyanat, Xylylendiisocyanat, Isophorondiisocyanat (2,4,4-Trimethyl-1,6-diisocyanato-hexan) und dimerem Toluylendiisocyanat-2,4 sowie Cyclohexylendiisocyanat und Dicyclohexylmethandiisocyanat gebildeten Gruppe ausgewählt.According to a further advantageous embodiment of the invention, the isocyanates are those of isomeric toluylidene diisocyanates, in particular technical mixtures of 2,4- and 2,6-isomers, diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, naphthylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate (2,4,4 -Trimethyl-1,6-diisocyanato-hexane) and dimeric tolylene diisocyanate-2,4 as well as cyclohexylene diisocyanate and dicyclohexylmethane diisocyanate group formed.
Die Trialkoxy-alkylenamino-silane der allgemeinen Formel (Ila) sind insbesondere solche, die nur eine, vorzugsweise sekundäre, Aminogruppe aufweisen. Typische Beispiele sind γ-A-inopropyltrimethoxysilan γ-Aminopropyltriethoxysilan N-Methyl-γ-aminopropyltrimethoxysilan N-Cyclohexyl-Υ-aminopropyltrimethoxysilan N-n-Octyl-γ-aminopropyltrimethoxysilan N-Phenyl-γ-aminopropyltrimethoxysilan Di-[1-propyl-3(trimethoxysilyl)]-amin N-Methyl-γ-aminopropylmethyl-dimethoxysilan. Typische Vertreter der Mercaptosilanester der allgemeinen Formel (Ilb) sind Mercaptopropyl-trimethoxysilan und Mercaptopropyl-triethoxysilan.The trialkoxy-alkyleneaminosilanes of the general formula (Ila) are in particular those which have only one, preferably secondary, amino group. Typical examples are γ-A-inopropyltrimethoxysilane γ-aminopropyltriethoxysilane N-methyl-γ-aminopropyltrimethoxysilane N-cyclohexyl-Υ-aminopropyltrimethoxysilane Nn-octyl-γ-aminopropyltrimethoxysilan-3-aminoxysilan-N-phenyl-trimyl-N-phenyl-trimyl-N-phenyl-trimyl-N-phenyl-trimyl-N-phenyl-trimyl-3 ] -amin N-methyl-γ-aminopropylmethyl-dimethoxysilane. Typical representatives of the mercaptosilane esters of the general formula (IIb) are mercaptopropyl-trimethoxysilane and mercaptopropyl-triethoxysilane.
Außer Methoxy- und Ethoxysilanen sind auch andere Alkoxy- substituenten, insbesondere die Monomethylether von Glykolen wie Ethylen- oder Diethylenglykol und dergleichen verwendbar.In addition to methoxy and ethoxysilanes, other alkoxy substituents, in particular the monomethyl ethers of glycols such as ethylene or diethylene glycol and the like, can also be used.
Die Reaktion der Harnstoffderivate der Formel (III) mit den Polyamiden der Formeln (IVa) und (IVb) erfolgt in einer Schmelze der Polyamide.The reaction of the urea derivatives of the formula (III) with the polyamides of the formulas (IVa) and (IVb) takes place in a melt of the polyamides.
Die feuchtigkeitsvernetzenden Schmelzkleber der Erfindung können saure Katalysatoren enthalten, die aus der von Zinn-II-octoat, Dibutylzinn-dilaurat, Tetrabutyl-titanat, Zinkacetat und Zinkacetylacetonat gebildeten Gruppe ausgewählt sind. Derartige Katalysatoren sind üblich, vgl. z.B. Ulimann, Enzyklαpüdie der technischen Chemie, Bd. 21, Seite 523 ff oder E. Skeisir, Handbook of Adhesives, van Nostrand, 1976, Seite 630.The moisture crosslinking hot melt adhesives of the invention may contain acidic catalysts selected from the group consisting of tin II octoate, dibutyltin dilaurate, tetrabutyl titanate, zinc acetate and zinc acetylacetonate. Such catalysts are common, cf. e.g. Ulimann, Enzyklαpüdie der technical chemistry, Vol. 21, page 523 ff or E. Skeisir, Handbook of Adhesives, van Nostrand, 1976, page 630.
Gemäß einem weiteren vorteilhaften Merkmal der Erfindung können die feuchtigkeitsvernetzenden Schmelzkleber der Erfindung einen Gehalt an 0 bis 50 Gew.-%, bezogen auf Trialkoxysilan-terminiertes Polyamid der Formeln (Va) bzw. (Vb), gegenüber diesem inerte Harze aufweisen. Diese Harze und Weichmacher sind ebenfalls üblich, vgl. B.E. Skeist, Handbook of Adhesives, van Nostrand, 1976.According to a further advantageous feature of the invention, the moisture-crosslinking hotmelt adhesives of the invention can have a content of 0 to 50% by weight, based on trialkoxysilane-terminated polyamide of the formulas (Va) or (Vb), of resins which are inert to the latter. These resins and plasticizers are also common, cf. B.E. Skeist, Handbook of Adhesives, van Nostrand, 1976.
Die Herstellung der feuchtigkeitsvernetzenden Schmelzkleber der Erfindung in der Reihenfolge 1. Diisocyanat, 2. Alkoxysilan, 3. Polymer ist gegenüber der Herstellung in der Reihenfolge des Standes der Technik, nämlich 1. Polymer, 2. Diisocyanat, 3. Alkoxysilan, günstiger, weil hier formal nur ein Monoisocyanat mit dem Polymeren bei Temperaturen oberhalb der Schmelztemperatur des Polymeren reagiert. The preparation of the moisture-crosslinking hotmelt adhesives of the invention in the sequence 1. diisocyanate, 2. alkoxysilane, 3. polymer is compared to the production in the sequence of the prior art, namely 1. polymer, 2. Diisocyanate, 3rd alkoxysilane, cheaper because here only one monoisocyanate formally reacts with the polymer at temperatures above the melting temperature of the polymer.
Die Erfindung wird im folgenden anhand bevorzugter Ausführungsbeispiele näher erläutert.The invention is explained in more detail below on the basis of preferred exemplary embodiments.
Beispiel 1.Example 1.
a) Herstellung eines Diisocyanat/Aminoalkoxysilan-Adduktesa) Preparation of a diisocyanate / aminoalkoxysilane adduct
In einem Rührreaktor wurden unter Schutzgas 222 Gew.-Teile Isophoron-Diisocyanat vorgelegt und 222 Gew.-Teile Y-Aminopropyl-triethoxysilan so rasch zugetropft, daß die Innentemperatur bei Kühlung 40°C nicht überschritt. Die Viskosität des Produktes betrug 300 Pa.s, die NCO-Zahl 9,2.222 parts by weight of isophorone diisocyanate were placed in a stirred reactor under a protective gas, and 222 parts by weight of Y-aminopropyl-triethoxysilane were added dropwise so rapidly that the internal temperature did not exceed 40 ° C. when cooled. The viscosity of the product was 300 Pa.s, the NCO number 9.2.
b) Herstellung eines Trialkoxysilan-terminierten Polyamidsb) Preparation of a trialkoxysilane-terminated polyamide
25 Gew.-Teile eines Polyamids (I) aus Dimerfettsäure und Ethylendiamin (Aminzahl 35 bis 50 , Erweichungspunkt 93 º C , DIN 52 011) wurden bei 120°C aufgeschmolzen und 1 h zur Entfernung von Feuchtigkeit evakuiert. Unter Schutzgas wurden dann 8,4 Gew. -Teile des Reaktionsproduktes aus Beispiel la zugegeben. Nach 45 min war die NCO-Zahl auf 0 abgesunken und die Reaktion somit beendet.25 parts by weight of a polyamide (I) made from dimer fatty acid and ethylenediamine (amine number 35 to 50, softening point 93 ° C., DIN 52 011) were melted at 120 ° C. and evacuated for 1 hour to remove moisture. 8.4 parts by weight of the reaction product from Example 1a were then added under protective gas. After 45 min the NCO number had dropped to 0 and the reaction was thus ended.
Danach wurden 0,33 Gew.-Teile Dibutylzinn-dilaurat bis zur Homogenität untergerührt.Then 0.33 part by weight of dibutyltin dilaurate was stirred in until homogeneous.
Beispiel 2.Example 2.
Herstellung eines Trialkoxysilan-terminierten PolyamidsPreparation of a trialkoxysilane-terminated polyamide
70 Gew.-Teile eines Polyamids (II) aus Dimerfettsäure und Piperazin (Aminzahl 5,8, Erweichungspunkt 100°C) wurden bei 160 C aufgeschmolzen und 1 h zur Entfernung von Feuchtigkeit evakuiert. Unter Schutzgas wurden dann 30 Gew.-Teile des Diisocyanat/Aminoalkoxysilan-Adduktes nach Beispiel la zugegeben. Nach 45 min war die NCO-Zahl auf 0 abgesunken und die Reaktion beendet. Danach wurden 0,2 Gew.-Teile Dibutylzinn-dilaurat bis zur Homogenität untergerührt.70 parts by weight of a polyamide (II) made from dimer fatty acid and piperazine (amine number 5.8, softening point 100 ° C.) were melted at 160 ° C. and evacuated for 1 hour to remove moisture. Then 30 parts by weight of the Diisocyanate / aminoalkoxysilane adduct according to Example la added. After 45 min the NCO number had dropped to 0 and the reaction had ended. Then 0.2 part by weight of dibutyltin dilaurate was stirred in until homogeneous.
Beispiel 3.Example 3.
a) Herstellung eines Diisocyanat/Mercaptoalkoxysilan-Adduktes.a) Preparation of a diisocyanate / mercaptoalkoxysilane adduct.
In einem Rührreaktor wurden unter Schutzgas 222 Gew.-Teile Isophorondiisocyanat und 196 Gew.-Teile γ-Mercaptopropyl-triethoxysilan gemischt und ca. 3 Stunden bei 130°C umgesetzt, bis der theoretische NCO-Wert von 10,0 erreicht war.In a stirred reactor, 222 parts by weight of isophorone diisocyanate and 196 parts by weight of γ-mercaptopropyl-triethoxysilane were mixed under protective gas and reacted for about 3 hours at 130 ° C. until the theoretical NCO value of 10.0 was reached.
b) Herstellung eines- Trialkoxysilan-terminierten Polyamids.b) Preparation of a trialkoxysilane-terminated polyamide.
30 g eines Polyamids (III) aus Dimerfettsäure und Piperazin mit einer Säurezahl von 7,8 wurden bei 180°C aufgeschmolzen und eine Stunde zur Entfernung von Feuchtigkeit evakuiert. Unter Schutzgas wurden anschließend 12 Gew.-Teile des Reaktionsproduktes aus Beispiel 3a sowie 0,4 Gew.-Teile Dibutylzinn-dilaurat zugegeben und bei dieser Temperatur gehalten, bis der NCO-Gehalt unter 0,3 abgesunken war (ca. 1 Stunde).30 g of a polyamide (III) from dimer fatty acid and piperazine with an acid number of 7.8 were melted at 180 ° C. and evacuated for one hour to remove moisture. 12 parts by weight of the reaction product from Example 3a and 0.4 part by weight of dibutyltin dilaurate were then added under protective gas and the mixture was kept at this temperature until the NCO content had dropped below 0.3 (about 1 hour).
Die Warmestandfestigkeit und die Klebleistungen auf Holz nach 24 h der in der oben beschriebenen Weise hergestellten Schmelzkleber der Erfindung wurden bestimmt, wobei die Werte jeweils mit denjenigen der nicht-modifizierten Polyamide verglichen wurden. Die Werte sind in der nachfolgenden Tabelle zusammengefaßt. TabelleThe heat resistance and the adhesive performance on wood after 24 h of the hot-melt adhesive of the invention produced in the manner described above were determined, the values in each case being compared with those of the unmodified polyamides. The values are summarized in the table below. table
Klebleistungen auf Holz nach 24 hAdhesive performances on wood after 24 h
Wärmestandfestigkeit ZugscherfestigkeitHeat resistance tensile shear strength
(Aufheizgeschwindigkeit: [N/mm2](Heating rate: [N / mm 2 ]
5°C/10 min) 23°C 60°C5 ° C / 10 min) 23 ° C 60 ° C
Polyamid (1) 70°C 3,2 0,3 Beispiel 1 > 200°C 10,2 4,9 Polyamid 2 125°C 5,6 2,2 Beispiel 2 > 200°C 9,3 3,6 Polyamid 3 110°C 6,5 1,6 Beispiel 3 200°C 7,1 2,5 Polyamide (1) 70 ° C 3.2 0.3 Example 1> 200 ° C 10.2 4.9 Polyamide 2 125 ° C 5.6 2.2 Example 2> 200 ° C 9.3 3.6 Polyamide 3 110 ° C 6.5 1.6 Example 3 200 ° C 7.1 2.5

Claims

Patentansprüche Claims
1. Feuchtigkeitsvernetzende Schmelzkleber, gekennzeichnet durch einen Gehalt an silanisierten Polyamiden, erhältlich durch Umsetzung eines Diisocyanats der Formel (I)1. Moisture-crosslinking hotmelt adhesive, characterized by a content of silanized polyamides, obtainable by reacting a diisocyanate of the formula (I)
OCN-R1-NCO (I)OCN-R 1 -NCO (I)
in der R1 ein aus der von C5-C14-Alkylen, Arylen, Diarylenalkan und dialkylen-substituiertes Aryl gebildeten Gruppe ausgewählter Rest ist, mit einem Alkoxy-alkylenamino- oder -mercaptosilan der allgemeinen Formeln (Ila bzw. Ilb)in which R 1 is a radical selected from the group consisting of C 5 -C 14 -alkylene, arylene, diarylenealkane and dialkylene-substituted aryl, with an alkoxyalkyleneamino- or mercaptosilane of the general formulas (Ila or Ilb)
Figure imgf000015_0001
in der R 2 ein Substituent aus der von Wasserstoff,
Figure imgf000015_0001
in which R 2 is a substituent from that of hydrogen,
C1-C4-Alkyl, Aryl und dem Rest der FormelC 1 -C 4 alkyl, aryl and the rest of the formula
Figure imgf000015_0002
gebildeten Gruppe ist, n eine Zahl von 1-4,
Figure imgf000015_0002
educated group is n is a number from 1-4,
R3 eine C1-C4-Alkylgruppe,R 3 is a C 1 -C 4 alkyl group,
R 4 ein Rest aus der von C1-C4-Alkyl und Alkoxyalkylen mitR 4 is a radical from that of C 1 -C 4 alkyl and alkoxyalkylene
2-4 Kohlenstoffatomen gebildeten Gruppe und2-4 carbon atoms formed group and
p eine Zahl von 0, 1 oder 2p is a number of 0, 1 or 2
oderor
in der R 3, R4, n und p wie oben definiert sind, in which R 3 , R 4 , n and p are as defined above,
bedeuten,mean,
zu einem Harnstoffderivat der allgemeinen Formel (III)to a urea derivative of the general formula (III)
Figure imgf000016_0002
Figure imgf000016_0002
in der R1 , R2 , R3 , R4 , n und p wie oben definiert sind undin which R 1 , R 2 , R 3 , R 4 , n and p are as defined above and
X die Gruppe -NH- oder -S- bedeutet,X represents the group -NH- or -S-,
sowie Umsetzung im wesentlichen sämtlicher freien Aminogruppen oder Carboxylgruppen eines Polyamids bzw. carboxylterminierten Polyamids der Formeln (IVa) bzw. (IVb)and reaction of essentially all free amino groups or carboxyl groups of a polyamide or carboxyl-terminated polyamide of the formulas (IVa) or (IVb)
Polyamid(-NH2)x (IVa) Polyamid(COOH)x (IVb)Polyamide (-NH 2 ) x (IVa) Polyamide (COOH) x (IVb)
in der x eine Zahl bedeutet, die für die Polyamide Amin- bzw. Säurezahlen zwischen 5 und 50 ergibt,in which x denotes a number which gives amine or acid numbers between 5 and 50 for the polyamides,
mit dem Harnstoffderivat der Formel (III) zu einem trialkoxysilanterminierten Polyamid der Formeln (Va) bzw. (Vb)with the urea derivative of the formula (III) to give a trialkoxysilane-terminated polyamide of the formulas (Va) or (Vb)
Figure imgf000017_0001
in der R 1, R3, X, n, p und x wie oben definiert sind,
Figure imgf000017_0001
in which R 1 , R 3 , X, n, p and x are as defined above,
sowie sauren oder basischen Katalysatoren und üblichen Hilfsstoffen.as well as acidic or basic catalysts and customary auxiliaries.
2. Feuchtigkeitsvernetzende Schmelzkleber nach Anspruch 1, dadurch gekennzeichnet, daß die Isocyanate aus der von isomeren Toluylendiisocyanaten, insbesondere technischen Gemischen des 2,4- und 2 ,6-Isomeren, Diphenylmethandiisocyanat, 1,6-Hexamethylendiisocyanat, Naphthylendiisocyanat, Xylylendiisocyanat, Isophorondiisocyanat2. Moisture-crosslinking hot-melt adhesive according to claim 1, characterized in that the isocyanates from the isomeric tolylene diisocyanates, in particular technical mixtures of 2,4- and 2,6-isomers, diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, naphthylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate
(2,4,4-Trimethyl-1,6-diisocyanato-hexan), dimerem Toluylendiisocyanat-2,4, Cyclohexylendiisocyanat und Dicyclohexylmethandiisocyanat gebildeten Gruppe ausgewählt sind.(2,4,4-trimethyl-1,6-diisocyanato-hexane), dimeric tolylene diisocyanate-2,4, cyclohexylene diisocyanate and dicyclohexylmethane diisocyanate group are selected.
3. Feuchtigkeitsvernetzende Schmelzkleber nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Polyamid der Formel (IVa) Aminzahlen zwischen 5 und 30 aufweist.3. Moisture-crosslinking hot melt adhesive according to claim 1 or 2, characterized in that the polyamide of formula (IVa) has amine numbers between 5 and 30.
4. Feuchtigkeitsvernetzende Schmelzkleber nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Polyamid der Formel (IVb) Säurezahlen zwischen 5 und 30 aufweist.4. Moisture-crosslinking hot-melt adhesive according to claim 1 or 2, characterized in that the polyamide of formula (IVb) has acid numbers between 5 and 30.
5. Feuchtigkeitsvernetzende Schmelzkleber nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Polyamide der Formel (IVa) aus durch Polymerisation ungesättigter Fettsäuren mit 12 bis 22 Kohlenstoffatomen bzw. Estern derselben mit C1-C4-aliphatischen Alkoholen gebildeten dimeren Fettsäuren hergestellt sind.5. Moisture-crosslinking hot-melt adhesive according to one of claims 1 to 3, characterized in that the polyamides of the formula (IVa) are produced from dimeric fatty acids formed by polymerization of unsaturated fatty acids having 12 to 22 carbon atoms or esters thereof with C 1 -C 4 -aliphatic alcohols are.
6. Feuchtigkeitsvernetzende Schmelzkleber nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß die sauren Katalysatoren aus der von Zinn-II-octoat, Dibutylzinn-dilaurat, Tetrabutyltitanat, Zinkacetat und Zinkacetylacetonat gebildeten Gruppe ausgewählt sind.6. Moisture-crosslinking hot-melt adhesive according to one of claims 1 to 5, characterized in that the acidic catalysts are selected from the group formed by tin (II) octoate, dibutyltin dilaurate, tetrabutyl titanate, zinc acetate and zinc acetylacetonate.
7. Feuchtigkeitsvernetzende Sehntelzkleber nach einem der Ansprüche 1 bis 6, gekennzeichnet durch einen Gehalt an 0-50 Gew.-%, bezogen auf Alkoxysilan-terminiertes Polyamid der Formel (Va) bzw. (Vb), gegenüber diesem inerten Harzen. 7. Moisture-crosslinking tendon adhesive according to one of claims 1 to 6, characterized by a content of 0-50 wt .-%, based on alkoxysilane-terminated polyamide of the formula (Va) or (Vb), compared to this inert resins.
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WO1991010697A1 (en) * 1990-01-18 1991-07-25 Ppg Industries, Inc. Amide-amine silane resin
WO1999047584A1 (en) * 1998-03-18 1999-09-23 Trl Thermofusible and crosslinkable polyamide and one of the methods for obtaining same and adhesive comprising same
FR2776295A1 (en) * 1998-03-18 1999-09-24 Trl Thermofusible and crosslinkable polyamide
FR2833601A1 (en) * 2001-12-14 2003-06-20 Trl Composition used in adhesives and for electrical encapsulation comprises a polyamide resin crosslinkable in water by condensation then hydrolysis, and obtained from polyacid and polyamine monomers
US20170240704A1 (en) * 2015-04-20 2017-08-24 The Government Of The United States Of America, As Represented By The Secretary Of The Navy Silane endcapped polyamide resins
EP3286249A4 (en) * 2015-04-20 2019-04-24 The Government of the United States of America, as represented by the Secretary of the Navy POLYAMIDE RESINS CURVED AT THEIR END WITH SILANES
US10669448B2 (en) 2015-04-20 2020-06-02 The Government Of The United States Of America, As Represented By The Secretary Of The Navy Silane endcapped polyamide resins

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DE3714763A1 (en) 1988-11-24
EP0313645A1 (en) 1989-05-03

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