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WO1988008859A1 - Colle a fusion reticulable sous l'effet de l'humidite - Google Patents

Colle a fusion reticulable sous l'effet de l'humidite 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
Authority
WO
WIPO (PCT)
Prior art keywords
moisture
polyamide
diisocyanate
formula
group
Prior art date
Application number
PCT/EP1988/000347
Other languages
German (de)
English (en)
Inventor
Heinz-Günther SCHULTE
Jürgen WICHELHAUS
Wolfgang Pille-Wolf
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO1988008859A1 publication Critical patent/WO1988008859A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—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.

Landscapes

  • 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)
  • Polyurethanes Or Polyureas (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polyamides (AREA)

Abstract

On produit des colles à fusion réticulables sous l'effet de l'humidité ayant une stabilité thermique remarquable jusqu'à 200° et davantage et une bonne adhérence initiale, en convertissant des diisocyanates avec des alkoxy-alkylénaminosilanes ou des alkoxy-mercaptosilanes et en faisant réagir les dérivés d'urée ainsi obtenus avec des polyamides ayant des groupes amino et/ou carboxyles libres, de façon à obtenir des polyamides silanisés.
PCT/EP1988/000347 1987-05-04 1988-04-25 Colle a fusion reticulable sous l'effet de l'humidite WO1988008859A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP3714763.3 1987-05-04
DE19873714763 DE3714763A1 (de) 1987-05-04 1987-05-04 Feuchtigkeitsvernetzende schmelzkleber

Publications (1)

Publication Number Publication Date
WO1988008859A1 true WO1988008859A1 (fr) 1988-11-17

Family

ID=6326778

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1988/000347 WO1988008859A1 (fr) 1987-05-04 1988-04-25 Colle a fusion reticulable sous l'effet de l'humidite

Country Status (4)

Country Link
EP (1) EP0313645A1 (fr)
JP (1) JPH01503149A (fr)
DE (1) DE3714763A1 (fr)
WO (1) WO1988008859A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991010697A1 (fr) * 1990-01-18 1991-07-25 Ppg Industries, Inc. Resine amido-amine de silane
WO1999047584A1 (fr) * 1998-03-18 1999-09-23 Trl Polyamide thermofusible et reticulable, l'un de ses procedes d'obtention et colle le comprenant
FR2833601A1 (fr) * 2001-12-14 2003-06-20 Trl Polyamides thermofusibles reticulables au moyen de motifs alcoxysilane et colle en comprenant
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

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3840220A1 (de) 1988-11-29 1990-05-31 Henkel Kgaa Verfahren zur herstellung und applikation von unter feuchtigkeitseinwirkung nachvernetzenden schmelzkleber- und/oder dichtmassen
DE4032911A1 (de) * 1990-10-17 1992-04-23 Henkel Kgaa Feuchtigkeitshaertende polyamide
DE19627198C2 (de) * 1995-07-06 1997-11-20 Fraunhofer Ges Forschung Hydrolysierbare und polymerisierbare bzw. polyaddierbare Silane, ein Verfahren zu deren Herstellung und deren Verwendung
DE102005026085A1 (de) 2005-06-07 2006-12-14 Construction Research & Technology Gmbh Silan-modifizierte Harnstoff-Derivate, Verfahren zu ihrer Herstellung und deren Verwendung als Rheologiehilfsmittel
US20100022717A1 (en) 2006-10-02 2010-01-28 Mitsui Chemicals Polyurethanes, Inc. A terminal isocyanate group-containing polyamide resin, alkoxysilane-modified polyamide resin, processes for production of the resins, hot-melt adhesive agent, and cured resin product

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2402662A1 (fr) * 1977-09-09 1979-04-06 Ciba Geigy Ag Polymeres contenant des groupes imidyles et silyles, utilisables notamment comme adjuvants d'adherence
GB2131037A (en) * 1982-11-05 1984-06-13 Inventa Ag Processing polyamides with cross-linking
JPS59147066A (ja) * 1983-02-10 1984-08-23 Toyo Ink Mfg Co Ltd グラビア印刷インキ
GB2137638A (en) * 1983-04-05 1984-10-10 Bostik Ltd Adhesive compositions
EP0202491A2 (fr) * 1985-05-22 1986-11-26 Hüls Aktiengesellschaft Mélange de polyesters durcissant sous l'action de l'humidité

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2402662A1 (fr) * 1977-09-09 1979-04-06 Ciba Geigy Ag Polymeres contenant des groupes imidyles et silyles, utilisables notamment comme adjuvants d'adherence
GB2131037A (en) * 1982-11-05 1984-06-13 Inventa Ag Processing polyamides with cross-linking
JPS59147066A (ja) * 1983-02-10 1984-08-23 Toyo Ink Mfg Co Ltd グラビア印刷インキ
GB2137638A (en) * 1983-04-05 1984-10-10 Bostik Ltd Adhesive compositions
EP0202491A2 (fr) * 1985-05-22 1986-11-26 Hüls Aktiengesellschaft Mélange de polyesters durcissant sous l'action de l'humidité

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Patent Abstracts of Japan, Band 8, Nr. 279 (C-257)(1716), 20. Dezember 1984; & JP-A-59147066 (TOYO INK SEIKO K.K.) 23. August 1984 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991010697A1 (fr) * 1990-01-18 1991-07-25 Ppg Industries, Inc. Resine amido-amine de silane
WO1999047584A1 (fr) * 1998-03-18 1999-09-23 Trl Polyamide thermofusible et reticulable, l'un de ses procedes d'obtention et colle le comprenant
FR2776295A1 (fr) * 1998-03-18 1999-09-24 Trl Polyamide thermofusible et reticulable, l'un de ses procedes d'obtention et colle le comprenant
FR2833601A1 (fr) * 2001-12-14 2003-06-20 Trl Polyamides thermofusibles reticulables au moyen de motifs alcoxysilane et colle en comprenant
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 (fr) * 2015-04-20 2019-04-24 The Government of the United States of America, as represented by the Secretary of the Navy Résines polyamide coiffées à leurs extrémités par des 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

Also Published As

Publication number Publication date
DE3714763A1 (de) 1988-11-24
JPH01503149A (ja) 1989-10-26
EP0313645A1 (fr) 1989-05-03

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