EP1966264A1 - Adhesif pour thermoenduction durcissant a l'humidite contenant au moins un prepolymere de polyurethane a fonctions silane - Google Patents

Adhesif pour thermoenduction durcissant a l'humidite contenant au moins un prepolymere de polyurethane a fonctions silane

Info

Publication number
EP1966264A1
EP1966264A1 EP06830810A EP06830810A EP1966264A1 EP 1966264 A1 EP1966264 A1 EP 1966264A1 EP 06830810 A EP06830810 A EP 06830810A EP 06830810 A EP06830810 A EP 06830810A EP 1966264 A1 EP1966264 A1 EP 1966264A1
Authority
EP
European Patent Office
Prior art keywords
moisture
silane
melt adhesive
adhesive composition
formula
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Withdrawn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
EP06830810A
Other languages
German (de)
English (en)
Inventor
Sven Krause
Kai Paschkowski
Urs Burckhardt
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.)
Sika Technology AG
Original Assignee
Sika Technology AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sika Technology AG filed Critical Sika Technology AG
Priority to EP06830810A priority Critical patent/EP1966264A1/fr
Publication of EP1966264A1 publication Critical patent/EP1966264A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • 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
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31598—Next to silicon-containing [silicone, cement, etc.] layer
    • Y10T428/31601—Quartz or glass
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31609—Particulate metal or metal compound-containing
    • Y10T428/31612—As silicone, silane or siloxane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31663—As siloxane, silicone or silane

Definitions

  • Hotmelt adhesives are known adhesives. Such adhesives are solid at room temperature and solvent-free adhesives, which are melted for application and applied as a melt on the substrate to be bonded. In contrast to the so-called
  • Hot melt adhesives which pasty adhesives represent and be applied at slightly elevated temperatures up to typically 60 0 C, the application of the hot melt adhesives takes place at temperatures from 85 ° C. Due to the cooling, the adhesives solidify.
  • Such reactive polyurethane hotmelt adhesives are known, for example from EP-A-0 244 608 or US Pat. No. 5,155,180 or EP-A-1 036 103, and are used widely commercially.
  • a disadvantage of the moisture-curing hot melt adhesives having isocyanate groups is that they often lead to excessive blistering, in particular with increased humidity and / or temperature.
  • blisters are usually undesirable, especially when it comes to visible bonds, as they often occur, for example, in packaging applications.
  • Silane-functional polyurethanes have long been used as moisture-curing adhesives and sealants. These silane-functional polyurethanes contain silane groups as reactive groups and are typically prepared by the reaction of isocyanate-group-containing polyurethane prepolymers with aminosilanes.
  • polyurethane adhesives produced in this way have the great disadvantage that the viscosity of the adhesive can increase sharply with prolonged heating.
  • EP-A-0 202 491 mentions silane-functionalized polyester hotmelt adhesives in which an adduct of a polyester polyol and a diisocyanate is reacted with an amino- or mercaptosilane or an adduct of an amino- or mercaptosilane and a diisocyanate is reacted with a polyester polyol.
  • EP-A-0 371 370 discloses moisture-curing postcrosslinking hotmelt adhesives which have terminal alkoxysilane and / or NCO groups. Furthermore, EP-A-0 371 370 discloses that these alkoxysilane end groups can be introduced via mercaptosilane or via a series of aminosilanes. Neither EP-A-0 371 370 nor EP-A-0 202 491 differentiate between aminosilanes and mercaptosilanes for functionalizing the polymer.
  • the object of the present invention is, therefore, moisture-curing
  • compositions cure without bubbles and surprisingly have a very good durability even at high temperatures (viscosity stability).
  • Isocyanate group-containing polyurethane prepolymers can be obtained, which the durability (viscosity stability) of the hotmelt adhesives can be greatly improved at high temperatures. Furthermore, it has been found that the use of silane-functional polyurethane prepolymers of the formula (I) in hot-melt adhesives for improving the durability
  • the invention relates to moisture-curing hot-melt adhesive compositions comprising at least one silane-functional polyurethane prepolymer of the formula (I)
  • R 1 is an n-valent organic radical of a prepolymer P which is prepared from at least one polyol and at least one polyisocyanate and has at least n isocyanate groups, after removal of n isocyanate groups;
  • R 2 is an alkyl group having 1 to 10 C atoms
  • R 3 is a linear or branched alkylene group having 1 to 10 C atoms
  • X is a hydrolyzable radical; a is a value of 0, 1 or 2; n is a value of 2 or more, and wherein the prepolymer P is solid at room temperature and has no further silane group.
  • Polyisocyanate indicates in this document that the respective substance formally contains more than one of the functional group occurring in its name per molecule.
  • silane group refers to a group bonded to an organic radical via a silicon atom, which is hydrolyzable, that is, having from one to three hydrolyzable radicals -OH groups) and, by subsequent condensation reactions of the silanol groups, siloxane groups (Si-O-Si groups).
  • silane refers to low molecular weight organic compounds which carry at least one silane group.
  • silane-functional denotes compounds, in particular polymers, which have silane groups.
  • Hydrolyzable radical is understood as meaning those radicals on a silane group which are displaced integrally from the silicon atom by water in a hydrolysis reaction and are formally replaced there by a hydroxyl group In the hydrolysis reaction, the hydrolyzable group is protonated to a low molecular weight compound which may be organic or inorganic.
  • hydrolyzable radicals X in the silane-functional polyurethane prepolymer of the formula (I) are, above all, those which are customary in silicone chemistry, in particular those which are selected from the group consisting of the formula (X-1), (X-2) , (X-3), (X-4), (X-5), (X-6), (X-7) and (X-8).
  • R 'and R "independently of one another are alkyl or aryl and R 4 is an alkyl group having 1 to 10 C atoms, which optionally contains 1 or 2 ether oxygens, in particular an alkyl group having 1 to 4 C atoms Particularly preferably, the hydrolyzable radical X is an alkoxy group -OR 4 .
  • two alkoxy groups -OR 4 together represent an alkylenedioxy group -OR 5 O- which form a five- or six-membered ring with the silicon atom, R 5 being an alkylene group having 2 to 10, especially 2 or 3 , C-atoms stands.
  • R 5 being an alkylene group having 2 to 10, especially 2 or 3 , C-atoms stands.
  • the prepolymer P has no further silane group.
  • Silane designations with functional groups as prefixes, such as "aminosilane” or "mercaptosilane” denote silanes which carry the said functional group on the organic radical as a substituent.
  • R 3 is propylene
  • hydrolyzable radical X the radicals -OMethyl, -Oethyl or -O-isoPropyl, in particular -OMethyl, are preferred.
  • the prepolymer P is prepared from at least one polyol and at least one polyisocyanate.
  • Preferred polyols are polyether polyols, polyester polyols and polycarbonate polyols.
  • polyether polyols also called polyoxyalkylene polyols
  • polyoxyalkylene polyols are those which are polymerization products of ethylene oxide, 1,2-propylene oxide, 1,2- or 2,3-butylene oxide, 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 having 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 isomers Butanediols, pentanediols, hexanediols, heptanediols, octanediols, nonanediols, decanediols, undecane
  • Both polyoxyalkylene polyols having a low degree of unsaturation can be used Grams of polyol (mEq / g)) prepared, for example, by means of so-called double metal cyanide complex catalysts (DMC catalysts), as well as polyoxyalkylene polyols having a higher degree of unsaturation, prepared for example with the aid of anionic catalysts such as NaOH, KOH or alkali metal alkoxides.
  • DMC catalysts double metal cyanide complex catalysts
  • polyether polyols are polyoxyalkylene diols or polyoxyalkylene triols, in particular polyoxyethylene diols or polyoxyethylene triols.
  • polyoxyalkylenediols or polyoxyalkylenetriols having a degree of unsaturation lower than 0.02 meq / g and having a molecular weight in the range from 1000 to 30,000 g / mol, and also polyoxypropylenediols and -triols having a molecular weight of from 400 to 8,000 g / mol ,
  • EO-endcapped ethylene oxide-endcapped polyoxypropylene diols or triols
  • polyoxypropylene diols or triols being specific polyoxypropylene polyoxyethylene polyols obtained, for example, by alkoxylating pure polyoxypropylene polyols with ethylene oxide after completion of the polypropoxylation and thereby having primary hydroxyl groups
  • molecular weight or “molar weight” is always understood to mean the molecular weight average M n .
  • Diols having a molecular weight which are generally suitable are polyether polyols
  • such polyethers are sold under the trade name Acclaim® by Bayer.
  • Suitable polyester polyols are in particular those which are prepared from dihydric to trivalent, preferably dihydric, alcohols, for example 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-thmethylolpropane or mixtures of the aforementioned 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 aforementioned acids, as well as polyester polyols from lactones such as ⁇
  • polyester polyols are polyester polyols of adipic acid, sebacic acid or dodecanedicarboxylic acid as the dicarboxylic acid and of hexanediol or neopentyl glycol as the dihydric alcohol.
  • the polyester polyols preferably have a molecular weight of 1500 to 15O00 g / mol, in particular from 1500 to 8000 g / mol, preferably from 2000 to 5500 g / mol.
  • Particularly suitable crystalline or partially crystalline polyester polyols are adipic acid / hexanediol polyester and dodecanedicarboxylic acid / hexanediol polyester.
  • Suitable polycarbonate polyols are those which are obtainable by reacting, for example, the abovementioned alcohols used to form the polyesterpolyols with dialkyl carbonates, diaryl carbonates or phosgene.
  • Preferred polyols are diols, especially polyether diols, polyester diols and polycarbonate diols.
  • polyester diols in particular a mixture of an amorphous and a crystalline or partially crystalline polyester diol.
  • a polyisocyanate contains two or more NCO groups and describes in the present document in each case a low molecular weight compound having a molecular weight of less than 1000 g / mol.
  • polyisocyanates examples include aromatic polyisocyanates, such as 2,4- and 2,6-toluene diisocyanate (TDI) and any mixtures of these isomers, 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate and any Mixtures of these isomers (MDI), mixtures of MDI and MDI homologs (polymeric MDI or PMDI), 1, 3 and 1, 4-phenylene diisocyanate, naphthalene-1, 5-diisocyanate (NDI), 3,3'-dimethyl 4,4'-diisocyanatodiphenyl (TODI), Oligomers and polymers of the aforementioned isocyanates, as well as any mixtures of the aforementioned isocyanates.
  • aromatic polyisocyanates are MDI and TDI.
  • polyisocyanates are aliphatic and cycloaliphatic polyisocyanates, such as 1,6-hexamethylene diisocyanate (HDI), 2-methylpentamethylene-1,5-diisocyanate, 2,2,4- and 2,4,4-trimethyl-1,6.
  • HDI 1,6-hexamethylene diisocyanate
  • 2-methylpentamethylene-1,5-diisocyanate 2,2,4- and 2,4,4-trimethyl-1,6.
  • hexamethylene diisocyanate TMDI
  • 1,1-dodecamethylene diisocyanate cyclohexane-1, 3- and 1,4-diisocyanate and any desired mixtures of these isomers
  • IPDI isophorone diisocyanate or IPDI
  • HMDI 1,4-diisocyanato-2,2,6-trimethylcyclohexane
  • TMCDI m- and p-xylylene diisocyanate
  • m- and p-XDI m- and p-tetramethyl-1, 3- and -1
  • 4-xylylene diisocyanate m- and p-TMXDI).
  • the polyisocyanate is a diisocyanate having a molecular weight of less than 400 g / mol.
  • the preparation of the prepolymer P takes place in a known manner and
  • the prepolymers P have free isocyanate groups and are solid at room temperature.
  • the number of isocyanate groups is very dependent on the desired end properties of the cured adhesive.
  • the polyurethane prepolymer is prepared via a reaction of at least one polyisocyanate and at least one polyol, preferably an amorphous and a crystalline polyester polyol, with a stoichiometric excess of isocyanate groups.
  • the prepolymer P has a molecular weight of preferably more than 2000 g / mol, in particular such between 2000 and 50,000 g / mol, preferably one between 4000 and 30,000 g / mol.
  • the prepolymer P n has isocyanate groups. Depending on the functionality of the polyols and polyisocyanates used, n assumes a value of 2 or higher. It is advantageous if n has a value of 2 to 4. In a preferred embodiment, n is 2. It is clear to the person skilled in the art that the polyols and polyisocyanates used are usually mixtures with different functionalities.
  • a technical "diol” actually contains not only the diol but also monols, so that the average functionality is not 2 but less than 2.
  • technical "diols” can also deplete additions of triplets, so that the middle Functionality is not 2 but more than 2.
  • the preparation of the silane-functional polyurethane prepolymer of the formula (I) is preferably carried out by the reaction of a prepolymer P, as just described, with a mercaptosilane of the formula (II)
  • Suitable mercaptosilanes are, for example, mercaptomethyltrimethoxysilane, mercaptomethylethethoxysilane, mercaptomethyldimethoxymethylsilane, mercaptomethyldiethoxymethylsilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltriisopropoxysilane, 3-mercaptopropyl- methoxy (1, 2-ethylenedioxy) silane, 3-mercaptopropylmethoxy (1,2-propylenedioxy) silane, 3-mercaptopropylethoxy (1,2-propylenedioxy) silane, 3-mercaptopropyldimethoxymethylsilane, 3-mercaptopropyl -diethoxymethylsilane, 3-mercapto-2-methylpropyl-trimethoxysilane, 4-mercapto-3,3-dimethylbutyl-thmethoxysi
  • Suitable mercaptosilanes are 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane, in particular 3-mercaptopropyltrimethoxysilane.
  • the reaction of the isocyanate group-containing prepolymer P with the mercaptosilane is carried out in a known manner.
  • the mercaptosilane is used stoichiometrically or superstoichiometrically and a silane-functional polyurethane prepolymer of the formula (I) is obtained which has no isocyanate groups, that is to say that all n isocyanate groups of the prepolymer P have reacted.
  • the mercaptosilane is used substoichiometrically and there is a silane-functional polyurethane prepolymer of the formula (I) which, in addition to the silane groups, still has isocyanate groups, that is to say that not all n isocyanate groups of the prepolymer P have reacted.
  • silane-functional polyurethane prepolymer of formula (I) still has isocyanate groups.
  • silane-functional polyurethane prepolymer of the formula (I) has no isocyanate groups.
  • the silane-functional polyurethane prepolymer of the formula (I) preferably has no isocyanate groups.
  • the moisture-curing hot-melt adhesive composition may contain further additives such as plasticizers, fillers, adhesion promoters, UV absorbers, UV or heat stabilizers, antioxidants, flame retardants, optical brighteners, catalysts, color pigments or dyes.
  • plasticizers such as plasticizers, fillers, adhesion promoters, UV absorbers, UV or heat stabilizers, antioxidants, flame retardants, optical brighteners, catalysts, color pigments or dyes.
  • Particularly suitable catalysts are those which catalyze the hydrolysis and / or crosslinking of silane groups.
  • Such catalysts include, for example, titanates, organotin compounds such as di-butyltin dilaurate and dibutyltin diacetylacetonate, bismuth organic compounds or bismuth complexes, amino-containing compounds, for example 1,4-diazabicyclo [2.2.2] octane or 2,2'-dimorpholinodiethyl ether.
  • the hotmelt adhesive composition is free of carbon black. Soot, especially in the polyurethane Chemistry, especially in conventional one-component polyurethane adhesives or one-component polyurethane hot melt, often added as a filler to improve the mechanics of the adhesive, as well as to make the low-viscosity adhesives stable.
  • the adhesive is free of inorganic fillers.
  • carbon black filled adhesives are poorly suited for those applications in which the aesthetics of the bonds are considered important, and where at least one of the substrates to be bonded is transparent or translucent.
  • a soot-free, or a hot melt adhesive composition which is free of inorganic fillers such applications are possible without the mechanics or application being adversely affected.
  • the adhesive is meltable, ie that it has a sufficiently low viscosity at the application temperature that allows a sensible application, and that it quickly solidifies on cooling, so that it quickly Can absorb forces even before the crosslinking reaction is complete with humidity. It has been found that the moisture Heissschmelzklebstoffzusammenset- wetting at a temperature of 150 0 C and in particular a viscosity of less than 100'0OO mPas, in particular of less than 50'0OO mPas and at 70 0 C in particular a viscosity of greater than 20'000 mPas, in particular of more than 50'0OO mPas.
  • silane-functional polyurethane prepolymer of the formula (I) can also be mixed with other polyurethane prepolymers, whereby the stability (viscosity stability) at elevated temperature of the moisture-curing hot-melt adhesive thus formed can be improved.
  • the invention comprises a method for bonding substrate S1 to substrate S2.
  • This method comprises the steps of i) heating a moisture-curing hot-melt adhesive composition, as described above, to a
  • step iii) typically closes
  • Step iv) of chemical curing of the moisture-curing hot melt adhesive composition with atmospheric moisture The person skilled in the art understands that, depending on the system used, temperature and reactivity of the adhesive, crosslinking reactions, and thus chemical curing, can already begin during the application. However, the bulk of networking, and thus in the narrow sense of the term chemical curing, takes place after application.
  • the substrates S1 and / or S2 can be pretreated before applying the hot-melt adhesive composition.
  • Pretreatments include in particular physical and / or chemical
  • the substrates S1 and S2 may be a variety of materials.
  • plastics organic materials such as leather, fabrics,
  • Paper, wood, resin-bonded wood materials, resin-texil composites Fabrics, glass, porcelain, ceramics and metals and metal alloys, in particular painted or powder-coated metals and metal alloys.
  • plastics are polyvinyl chloride (PVC), acrylonitrile-butadiene-styrene copolymers (ABS), SMC (sheet molding composites), polycarbonate (PC), polyamide (PA), polyester (PE), polyoxymethylene (POM), Polyolefins (PO), in particular polyethylene (PE) or polypropylene (PP), preferably with plasma, corona or flame-treated PP or PE.
  • PVC polyvinyl chloride
  • ABS acrylonitrile-butadiene-styrene copolymers
  • SMC sheet molding composites
  • PC polycarbonate
  • PA polyamide
  • PET polyester
  • POM polyoxymethylene
  • PO Polyolefins
  • PE polyethylene
  • PP polypropylene
  • the substrates S1 and S2 are transparent materials, in particular transparent plastic films.
  • Another preferred transparent material is glass, especially in the form of a disk.
  • the moisture-curing hot-melt adhesive composition is used in particular in an industrial manufacturing process.
  • the moisture-curing hot-melt adhesive composition is suitable for bonds in which the bonding site is visible.
  • it is particularly suitable for the bonding of glass, in particular in vehicle and window construction.
  • it is particularly suitable for the gluing of transparent packaging.
  • the adhesive cures substantially free of bubbles.
  • Typical thicknesses of bonds are 10 microns or more.
  • the bond thickness is between 10 microns and 1000 microns, especially between 80 microns and 500 microns. It has been shown that even in bonding layer thicknesses of over 80 microns no bubbles occur.
  • articles are in particular articles of the transport, furniture or textile industry.
  • the automotive industry in particular is preferred.
  • Exemplary such articles are automotive interior trim parts such as headliner, sun visor, instrument panel, door side panel, parcel shelf and the same; Wood fiber materials from the shower and bath area; Furniture decorative films, membrane films with textiles such as cotton, polyester films in the clothing sector or textiles with foams for automotive equipment.
  • such articles are in particular articles from the packaging industry.
  • such an article is a transparent packaging.
  • Another aspect of the present invention is the use of mercaptosilanes of formula (II) already described for modifying isocyanate group-containing polyurethane prepolymers to improve the durability (viscosity stability) of a silane-functional uncured
  • radicals have the meanings and preferences already described for formula (I).
  • Preferred mercaptosilanes are 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane, in particular 3-mercaptopropyltrimethoxysilane.
  • silane-functional polyurethane prepolymers can be obtained from isocyanate-group-containing polyurethane urethane prepolymers which can greatly improve the stability (viscosity stability) of the hotmelt adhesives at high temperatures, in particular in comparison with the corresponding silane-functional polyurethane prepolymers be obtained from isocyanate group-containing polyurethane prepolymers and aminosilanes. Furthermore, it has been found that the use of silane-functional polyurethane prepolymers of the formula (I) in hot-melt adhesives leads to an improvement in the stability (viscosity stability) of moisture-curing hot-melt adhesives at high temperatures.
  • Another aspect of the present invention is the use of a silane-functional polyurethane prepolymer of the formula (I) as it already is in hot-melt adhesives for improving the durability (viscosity stability) of the uncured adhesive.
  • a hotmelt adhesive based on silane-functional polyurethane prepolymers of the formula (I) has a significantly better viscosity stability at elevated temperature than a corresponding prior art adhesive which is based on silane-functional polyurethane prepolymers consisting of isocyanate groups. containing polyurethane prepolymers and aminosilanes.
  • the phenomenon that the increase in viscosity with the storage time at high temperature, which corresponds in particular to the application temperature, ie typically at a storage temperature between 120 0 C and 160 0 C, not or only very much weaker or slower increases, is in this document term "durability" or "viscosity stability".
  • Viscosity stabilization found that the UV stability, in particular the yellowing of the moisture-curing hot melt adhesive compositions by the use of cycloaliphatic polyisocyanates in the preparation of the prepolymer P, or the silane-functional polyurethane prepolymer of the formula (I) could be greatly reduced.
  • a 1: 1 (w: w) polyester blend of Dynacoll® 7150 (Degussa) and Dynacoll® 7250 (Degussa) was charged in a 1 liter reaction vessel with non-stick coating and a 4-neck flat ground cover. This was melted in an oil bath with temperature control at 120-125 0 C for 4 hours.
  • the prepolymer P1 thus prepared had an NCO content of 2.2% and a viscosity of 15,500 mPas at 130 0 C.
  • the prepolymer P2 was prepared in an analogous manner as P1, except that for P2, the polyester mixture was stoichiometrically replaced by the polyether polyol Desmophen® 4028 BD (Bayer).
  • the prepolymer P2 prepared in this way had an NCO content of 2.05% and a viscosity of 1875 mPas (10 rpm) at 70 ° C.
  • prepolymer P1 was treated with the corresponding stoichiometric (1 silane reacted with 1 NCO group) silane used according to Table 2 and 0.2 wt .-% dibutyltin dilaurate (DBTL) as catalyst, based on the prepolymer, and after 1 h reaction time in tubes or cartridges filled. This ensured storage in the absence of moisture.
  • DBTL dibutyltin dilaurate
  • the viscosity measurement was carried out continuously at the respective temperature.
  • the viscosity ⁇ [mPas] of the respective composition was measured by means of Rheomat (Brookfield, Thermosel, spindle 27, shear rate 1 min -1 ) after a storage time t L at the respective temperature T.
  • Table 5 Long-term viscosity stability of composition 1 at a storage temperature of 160 ° C.
  • Tables 3 to 5 show that the compositions 1 and 2 are distinguished from the reference examples by an extraordinarily improved storage stability. Even at 160 ° C, the viscosity increase is low even after a long storage time, while the reference examples are already so thick thickened that they are no longer measurable.
  • specimens were prepared in accordance with the preparation of the specimens for the determination of the Shore A hardness.
  • the hot adhesive was in this case filled with a temperature of about 140 0 C in a teflon ring (2mm thickness).
  • the glue was pressed with a weight (5kg) on the starch and cooled.
  • the cooled adhesive was then demolded and cured at 20 0 C and 55% humidity. Blistering was by visual assessment.
  • the prepolymer P1 was used as reference for a reactive hot-melt adhesive.
  • composition 1 Tensile shear strength The tensile shear strength of composition 1 was measured on the basis of DIN EN 1465 on a tensile testing machine from Zwick (Z 020) at a test speed of 100 mm / min. Two specimens of the respective substrate were bonded (overlap 12 ⁇ 25 mm, adhesive layer thickness 2 mm) and tested. The mechanical results of composition 1 are in

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

Abstract

La présente invention concerne des compositions d’adhésif pour thermoenduction durcissant à l'humidité, lesdites compositions contenant au moins un prépolymère de polyuréthane à fonctions silane de formule (I). Les compositions ne présentent pas de bulles lors du chauffage ou du durcissement et se distinguent par une excellente stabilité de viscosité à haute température. Cet adhésif pour thermoenduction convient donc particulièrement pour la production industrielle, notamment de matériaux transparents.
EP06830810A 2005-12-23 2006-12-22 Adhesif pour thermoenduction durcissant a l'humidite contenant au moins un prepolymere de polyurethane a fonctions silane Withdrawn EP1966264A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP06830810A EP1966264A1 (fr) 2005-12-23 2006-12-22 Adhesif pour thermoenduction durcissant a l'humidite contenant au moins un prepolymere de polyurethane a fonctions silane

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP20050112960 EP1801138A1 (fr) 2005-12-23 2005-12-23 Adhésifs thermofusibles durcissant par l'humidité contenant au moins un prépolymere de polyuréthane ayant des fonctions silans
PCT/EP2006/070161 WO2007074143A1 (fr) 2005-12-23 2006-12-22 Adhesif pour thermoenduction durcissant a l’humidite contenant au moins un prepolymere de polyurethane a fonctions silane
EP06830810A EP1966264A1 (fr) 2005-12-23 2006-12-22 Adhesif pour thermoenduction durcissant a l'humidite contenant au moins un prepolymere de polyurethane a fonctions silane

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EP1966264A1 true EP1966264A1 (fr) 2008-09-10

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EP06830810A Withdrawn EP1966264A1 (fr) 2005-12-23 2006-12-22 Adhesif pour thermoenduction durcissant a l'humidite contenant au moins un prepolymere de polyurethane a fonctions silane

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EP (2) EP1801138A1 (fr)
JP (1) JP5254804B2 (fr)
KR (1) KR101352257B1 (fr)
CN (1) CN101437861B (fr)
BR (1) BRPI0620429A2 (fr)
CA (1) CA2634837A1 (fr)
RU (1) RU2482136C2 (fr)
WO (1) WO2007074143A1 (fr)

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CA2634837A1 (fr) 2007-07-05
WO2007074143A1 (fr) 2007-07-05
JP5254804B2 (ja) 2013-08-07
US8263226B2 (en) 2012-09-11
BRPI0620429A2 (pt) 2011-11-08
RU2482136C2 (ru) 2013-05-20
KR20080081985A (ko) 2008-09-10
JP2009533486A (ja) 2009-09-17
CN101437861A (zh) 2009-05-20
RU2008130407A (ru) 2011-02-20
KR101352257B1 (ko) 2014-02-17
EP1801138A1 (fr) 2007-06-27
US20100040894A1 (en) 2010-02-18
CN101437861B (zh) 2011-12-14

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