EP0313645A1 - Colle a fusion reticulable sous l'effet de l'humidite - Google Patents

Colle a fusion reticulable sous l'effet de l'humidite

Info

Publication number
EP0313645A1
EP0313645A1 EP19880904940 EP88904940A EP0313645A1 EP 0313645 A1 EP0313645 A1 EP 0313645A1 EP 19880904940 EP19880904940 EP 19880904940 EP 88904940 A EP88904940 A EP 88904940A EP 0313645 A1 EP0313645 A1 EP 0313645A1
Authority
EP
European Patent Office
Prior art keywords
moisture
polyamide
diisocyanate
formula
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.)
Withdrawn
Application number
EP19880904940
Other languages
German (de)
English (en)
Inventor
Heinz-Günther SCHULTE
Jürgen WICHELHAUS
Wolfgang Pille-Wolf
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0313645A1 publication Critical patent/EP0313645A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—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.
EP19880904940 1987-05-04 1988-04-25 Colle a fusion reticulable sous l'effet de l'humidite Withdrawn EP0313645A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19873714763 DE3714763A1 (de) 1987-05-04 1987-05-04 Feuchtigkeitsvernetzende schmelzkleber
DE3714763 1987-05-04

Publications (1)

Publication Number Publication Date
EP0313645A1 true EP0313645A1 (fr) 1989-05-03

Family

ID=6326778

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19880904940 Withdrawn EP0313645A1 (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)

Families Citing this family (9)

* 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
US5135992A (en) * 1990-01-18 1992-08-04 Ppg Industries, Inc. Amide-amine silane resin
DE4032911A1 (de) * 1990-10-17 1992-04-23 Henkel Kgaa Feuchtigkeitshaertende polyamide
US5792881A (en) * 1995-07-06 1998-08-11 Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. Thiolsilanes, method of their production and of their use
FR2776295B1 (fr) * 1998-03-18 2000-06-23 Trl Polyamide thermofusible et reticulable, l'un de ses procedes d'obtention et colle le comprenant
FR2833601B1 (fr) * 2001-12-14 2004-03-12 Trl Polyamides thermofusibles reticulables au moyen de motifs alcoxysilane et colle en comprenant
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
KR20090057413A (ko) 2006-10-02 2009-06-05 미쓰이 가가쿠 폴리우레탄 가부시키가이샤 말단 아이소사이아네이트기 함유 폴리아마이드 수지, 알콕시실레인 변성 폴리아마이드 수지 및 그들의 제조 방법, 가열 용융 접착제 및 수지 경화물
KR20170138492A (ko) * 2015-04-20 2017-12-15 더 거번먼트 오브 더 유나이티드 스테이츠 오브 아메리카, 에즈 레프리젠티드 바이 더 세크러테리 오브 더 네이비 실란으로 말단 캡핑된 폴리아미드 수지

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH634851A5 (de) * 1977-09-09 1983-02-28 Ciba Geigy Ag Verfahren zur herstellung von imidyl- und silylgruppenhaltigen polymeren.
CH660744A5 (de) * 1982-11-05 1987-06-15 Inventa Ag Verfahren zur herstellung hochviskoser bzw. thermisch formstabiler, mindestens teilvernetzter polyamide.
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
DE3518357A1 (de) * 1985-05-22 1986-11-27 Dynamit Nobel Ag, 5210 Troisdorf Feuchtigkeitshaertendes polyestergemisch

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO8808859A1 *

Also Published As

Publication number Publication date
JPH01503149A (ja) 1989-10-26
DE3714763A1 (de) 1988-11-24
WO1988008859A1 (fr) 1988-11-17

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