EP3394135A1 - Adhésif thermofusible en polyuréthane à base de polyacrylates présentant une résistance élevée à la chaleur - Google Patents

Adhésif thermofusible en polyuréthane à base de polyacrylates présentant une résistance élevée à la chaleur

Info

Publication number
EP3394135A1
EP3394135A1 EP16820249.7A EP16820249A EP3394135A1 EP 3394135 A1 EP3394135 A1 EP 3394135A1 EP 16820249 A EP16820249 A EP 16820249A EP 3394135 A1 EP3394135 A1 EP 3394135A1
Authority
EP
European Patent Office
Prior art keywords
hot melt
melt adhesive
polyurethane hot
solvent
free
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Withdrawn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
EP16820249.7A
Other languages
German (de)
English (en)
Inventor
Martin Schmider
Kai Paschkowski
Jörg Plaumann
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
Publication of EP3394135A1 publication Critical patent/EP3394135A1/fr
Withdrawn legal-status Critical Current

Links

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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • 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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer

Definitions

  • the invention relates to the field of polyurethane hot melt adhesives (PUR-RHM).
  • compositions without polyacrylates low heat is on the
  • Polyacrylate-containing polyurethane adhesives are used in many industrial sectors, for example in the bonding of sandwich panels.
  • a hot melt adhesive would be desirable, which in addition to the properties favorable for the PUR-RHMs with polyacrylate components improved heat resistance and expediently also has improved mechanical properties.
  • CN 103865465A describes a moisture-curable polyurethane hotmelt adhesive for automotive lamps. Those described in CN 103865465A
  • Polyurethane hot melt adhesives contain from 15 to 25 percent diphenylmethane diisocyanate (MDI), from 25 to 35 percent of a highly crystalline polyester polyol, from 12.5 to 17.5 percent of an aromatic polyester polyol, from 12.5 to 17.5 percent of a non-crystalline MDI (MDI), from 25 to 35 percent of a highly crystalline polyester polyol, from 12.5 to 17.5 percent of an aromatic polyester polyol, from 12.5 to 17.5 percent of a non-crystalline MDI (MDI), from 25 to 35 percent of a highly crystalline polyester polyol, from 12.5 to 17.5 percent of an aromatic polyester polyol, from 12.5 to 17.5 percent of a non-crystalline MDI (MDI), from 25 to 35 percent of a highly crystalline polyester polyol, from 12.5 to 17.5 percent of an aromatic polyester polyol, from 12.5 to 17.5 percent of a non-crystalline MDI (MDI), from 25 to 35 percent of a highly crystalline polyester polyol, from 12.5 to 17.5 percent of
  • Polyesterpolyols 5 to 15% of a tackifying resin, 5 to 10% of a filler and 0.02 to 0.1% of a catalyst.
  • the polyurethane hot melt adhesives according to CN 103865465A are said to have the advantages of being particularly favorable
  • JP 2003-226849 describes hot melt adhesive films for electronic components, which are based essentially on a crystalline polyurethane resin with a
  • Softening temperature in the range of 50 to 90 ° C, a saturated polyester resin having a glass transition temperature Tg in the range of 0 to 1 10 ° C and a filler based.
  • the filler may be incorporated into the composition at 20 to 200 parts based on 100 parts of the crystalline polyurethane resin and 5 to 120 parts of the saturated polyester.
  • CN 103087666 describes polyurethane sealing materials comprising 60 to 90 parts of a polyurethane prepolymer, 0 to 20 parts of a filler, 0.3 to 1.0 parts of a silane coupling agent, 0.2 to 0.9 parts of a catalyst and 5 to 20 parts of a contain thermoplastic polymer.
  • the specified sealant should have the advantages of a particularly favorable connection strength and a significant reduced latency, which has a positive effect on the production efficiency.
  • EP 0 776 342 relates to reactive hot melt adhesives containing a filler whereby, inter alia, improved workability, wettability and improved cure profile times can be set.
  • CN 102477273 describes a process for the preparation of
  • Polyurethane hot melt adhesives based on 50 to 70 wt .-% of a
  • Polyacrylpolymethylenisocyanats 20 to 30 wt .-% of a crystalline
  • Polymer polyols 1 to 2 wt .-% of a blocking agent, 5 to 15 wt .-% of a tackifying resin and 5 to 10 wt .-% of a filler based.
  • the adhesives described should have the advantage of particularly favorable initial and final strength and low coating temperatures and melt viscosities.
  • EP 1 036 103 essentially describes solvent-free
  • Polyurethane hot melt adhesives consisting of (i) 95 to 3% by weight of a reaction product of a polyisocyanate and a low molecular weight polymer based on ethylenically unsaturated monomers, said polymer being active
  • additives selected from the group consisting of tackifying resins, plasticizers, fillers, pigments, stabilizers, tackiness improvers and polyether triols, polyester polyols and mixtures thereof Mixtures thereof are produced.
  • US 5,869,593 discloses polyurethane hot melt adhesives based on polyethers, polyesters, and polyisocyanates.
  • the hot melt adhesives may additionally contain a thermoplastic polymer component of polyurethane, EVA copolymers, ethylene-acrylate copolymers or acrylate polymers and a filler selected from materials such as talc, clays, silica, soot and mica.
  • the adhesives and sealants described in US Pat. No. 5,869,593 are said to be distinguished by a very high water vapor transmission.
  • Hot melt adhesive of the 2013/020025 A1 underlying polyurethane is made of polyols, hydroxy-functionalized acrylates and a deficit
  • Polyisocyanates based on the NCO / OH ratio, prepared so that a subsequent functionalization with an isocyanatosilane is possible.
  • the aim of the present invention is therefore to propose a polyurethane hot melt adhesive which combines the advantageous properties of the polyacrylate-containing polyurethane hotmelt adhesives having improved heat-conditioning properties and optionally improved mechanical properties.
  • compositions can be solved which correspond to the known polyacrylate-containing polyurethane hot melt adhesives and which additionally contain a filler selected from the group comprising kaolin, fumed silica, carbon black and wollastonite. Accordingly, the invention relates to a filler selected from the group comprising kaolin, fumed silica, carbon black and wollastonite. Accordingly, the invention relates to a filler selected from the group comprising kaolin, fumed silica, carbon black and wollastonite. Accordingly, the invention relates to a filler selected from the group comprising kaolin, fumed silica, carbon black and wollastonite. Accordingly, the invention relates to a filler selected from the group comprising kaolin, fumed silica, carbon black and wollastonite. Accordingly, the invention relates to a filler selected from the group comprising kaolin, fumed silica, carbon black and wollastonite. Accordingly, the invention relates to a filler selected
  • solventless polyurethane hot melt adhesive obtainable by reacting a composition comprising a polyether polyol, a polyester polyol, at least one polyacrylate and one or more fillers selected from kaolin, fumed silica, carbon black or wollastonite with a polyisocyanate.
  • Hot melt adhesives are characterized by significantly improved
  • poly in terms of substance such as “polyol” or “polyisocyanate” refers to substances that formally contain two or more of the functional group per molecule as identified.
  • a polyol is e.g. a compound having two or more hydroxyl groups and a polyisocyanate is a compound having two or more isocyanate groups.
  • a prepolymer is a polymer containing at least one, usually two or more reactive groups, e.g. Isocyanate groups. Via the reactive groups, the prepolymer can be chain extended, crosslinked or cured.
  • the starting components are understood below to mean the polyether polyols, polyisocyanates, polyester polyols and poly (meth) acrylates used for the production of the polyurethane hotmelt adhesive, as well as the fillers mentioned. This refers in particular to the quantities given below. Below the average molecular weight here is the number average of
  • solvent-free means a proportion of compounds which are not reactive toward polyisocyanates or polyols and have a boiling point below 200 ° C. of less than 2% by weight, preferably less than 1% by weight and more preferably less than 0.5% by weight understood. Most preferred is when the solvent-free invention
  • Polyurethane hot melt adhesive with the exception of impurities contained in the starting materials, no solvents are added.
  • these preferably have an average molecular weight Mn of at least 400 g / mol and preferably at least 1000 g / mol.
  • Particularly suitable average molecular weights are in the range from 400 to 30,000 g / mol and preferably from 1000 to 8000 g / mol.
  • a polyether polyol is included, but it is also possible to use a plurality of polyether polyols.
  • the polyether polyols are e.g. to diols or triols or mixtures thereof. Most preferably, the polyether polyol is a polyether diol.
  • Polyether polyols are commercially available.
  • the polyether polyol is also suitably a
  • polyoxyalkylene Particularly suitable polyoxyalkylene polyols are, for example, polymerization products of ethylene oxide, 1, 2-propylene oxide, 1, 2 or 2,3-butylene oxide, tetrahydrofuran or mixtures thereof, optionally polymerized with the aid of a starter molecule having two or more active
  • Hydrogen atoms such as e.g. Water, ammonia or compounds having multiple OH or NH groups, such as e.g. 1, 2-ethanediol, 1, 2 and 1, 3-propanediol,
  • Neopentyl glycol diethylene glycol, triethylene glycol, the isomeric dipropylene glycols and tripropylene glycols, the isomeric butanediols, pentanediols, hexanediols,
  • Heptanediols Heptanediols, octanediols, nonanediols, decandiols, undecanediols, 1, 3- and 1, 4- Cydohexandinnethanol, bisphenol A, hydrogenated bisphenol A, 1, 1, 1 -Thmethylolethan, 1, 1, 1 -Thmethylolpropan, glycerol, aniline and mixtures of the aforementioned compounds.
  • Both polyoxyalkylene polyols having a low degree of unsaturation (measured according to ASTM D-2849-69 and expressed in milliequivalents of unsaturation per gram of polyol (mEq / g)) prepared, for example, by means of so-called double metal cyanide complex catalysts (DMC catalysts) can be used ), as well as polyoxyalkylene polyols having a higher degree of unsaturation (measured according to ASTM D-2849-69 and expressed in milliequivalents of unsaturation per gram of polyol (mEq / g)) prepared, for example, by means of so-called double metal cyanide complex catalysts (DMC catalysts) can be used ), as well as polyoxyalkylene polyols having a higher
  • the polyether polyol is preferably a polyoxyethylene diol, polyoxyethylene triol, polyoxypropylene diol, polyoxypropylene triol, or a mixture thereof.
  • Polyether polyol is more preferably a polyethylene oxide and / or a polypropylene oxide. Most preferably, the polyether polyol is polypropylene oxide.
  • Polyether polyols are sold, for example, under the trade name Acclaim® by Bayer. Also suitable are so-called ethylene oxide-capped (ethylene oxide-endcapped) polyoxypropylene diols or triols, which are polyoxypropylene polyoxyethylene polyols obtained, for example, by alkoxylating polyoxypropylene polyols after completion of the polypropoxylation with ethylene oxide and thereby primary hydroxyl groups exhibit.
  • Polyether polyols especially polypropylene oxide, have e.g. a middle one
  • the polyether polyol is advantageously included in the polyurethane hot melt adhesive of the invention at a level in the range of from 15 to 45% by weight and preferably from 20 to 40% by weight, based on the total weight of the starting components.
  • the solvent-free polyurethane hot melt adhesive according to the invention contains only one polyether polyol.
  • the solvent-free polyurethane hotmelt adhesives according to the invention furthermore include a polyester polyol, although these may also be several polyesterpolyols.
  • Suitable polyester polyols are liquid, amorphous or crystalline polyester polyols, such as polyester triols and especially polyester diols, and mixtures of these
  • Polyester polyols wherein the polyester polyol is preferably a crystalline polyester polyol.
  • the division into liquid, amorphous and crystalline polyester polyols is customary and known to the person skilled in the art.
  • Corresponding products are commercially available, eg the Dynacoll ® 7000 series from Evonik.
  • the liquid polyester polyols have a glass transition temperature of below 0 ° C, preferably -5 ° C or below.
  • the amorphous polyester polyols have a glass transition temperature of at least 0 ° C.
  • the crystalline polyester polyols have a melting point, the melting point being preferably at least 35 ° C, more preferably at least 50 ° C.
  • the glass transition temperature (Tg) and the melting point (Smp) can be determined according to DIN 53765.
  • Suitable polyester polyols are e.g. are prepared from di- or trihydric, preferably dihydric, alcohols, such as. 1, 2-ethanediol, diethylene glycol,
  • Triethylene glycol 1, 2-propanediol, 1, 3-propanediol, dipropylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 10-decanediol, 1, 12- dodecanediol,
  • Dimer fatty alcohol neopentyl glycol, glycerol, 1,1,1-trimethylolpropane or
  • Polyester polyols from lactones such as ⁇ -caprolactone also benzoate resins.
  • polyester polyols in particular crystalline polyester polyols, are polyester polyols of adipic acid, sebacic acid or dodecanedicarboxylic acid as dicarboxylic acid and of hexanediol or neopentyl glycol as dihydric alcohol.
  • Particularly suitable as crystalline polyester polyols are adipic acid / hexanediol polyester and dodecanedicarboxylic acid / hexanediol polyester.
  • polyester polyols are polyester polyols
  • polyester polyols may e.g. by complete ring opening of epoxidized triglycerides of a fat mixture containing at least partially olefinically unsaturated fatty acid with one or more
  • Alcohols having 1 to 12 carbon atoms and subsequent partial transesterification of the triglyceride derivatives to alkyl ester polyols having 1 to 12 carbon atoms in the alkyl radical can be produced.
  • Polyester polyols which are particularly suitable for the purposes of the present invention are crystalline polyester polyols at room temperature, which are preferably a middle one
  • the polyester polyol is useful at a level in the range of 5 to
  • the solvent-free polyurethane hot melt adhesive according to the invention contains only one polyester polyol.
  • Polyurethane hot melt adhesives forms a polyisocyanate.
  • the polyisocyanate may comprise one or more diisocyanates, especially monomeric diisocyanates.
  • diisocyanates e.g. aliphatic, cycloaliphatic or aromatic
  • Diisocyanates especially monomeric diisocyanates, are used, with aromatic monomeric diisocyanates are preferred.
  • the usual, commercially available diisocyanates can be used.
  • a monomeric di- or polyisocyanate in contrast to, for example, isocyanate prepolymers, in particular contains no urethane groups.
  • Non-monomeric diisocyanates are, for example, oligomeric or polymeric products of monomers
  • Diisocyanates e.g. Adducts of monomeric diisocyanates, which are also commercially available. However, the use of monomeric diisocyanates is preferred.
  • monomeric diisocyanates are 1, 6-hexamethylene diisocyanate (HDI), 2-methylpentamethylene-1, 5-diisocyanate, 2,2,4- and 2,4,4-trimethyl-1,6-hexamethylene diisocyanate (TMDI) and mixtures of these Isomers, 1, 10-deca methylene diisocyanate, 1, 12-dodecamethylene diisocyanate, lysine and
  • MDI MDI
  • TDI TDI
  • HDI High-density polyethylene
  • MDI Diphenylmethane diisocyanate
  • 4,4'-diphenylmethane diisocyanate (4,4'-MDI).
  • Diisocyanates can often contain isomeric mixtures or other isomers as impurities.
  • the monomeric diisocyanate has, for example, a molecular weight of not more than 1000 g / mol, preferably not more than 500 g / mol, more preferably not more than 400 g / mol.
  • Polyurethane hot melt adhesive may range from 5 to 40 weight percent, but is preferably from 7 to 20 weight percent, based on the
  • the solvent-free polyurethane adhesives according to the invention contain, in addition to the mentioned polyether polyol and polyester polyol, at least one polyacrylate, which may also be a polymethacrylate.
  • Poly (meth) acrylate should therefore be understood below to mean both polyacrylates and polymethacrylates as well as polymers based on acrylate and methacrylate monomers.
  • One or more polyacrylates and one or more polymethacrylates can be used.
  • Polyacrylates and polymethacrylates are commercially available. A summary of polyacrylates and polymethacrylates can be found, for example, in Ullmann's Enzyklopadie der ischen Chemie, Verlag Chemie, 4th Edition, Vol. 19, pp. 7 to 30.
  • the poly (meth) acrylate is a homopolymer or copolymer of at least one acrylic ester and / or at least one methacrylic acid ester and
  • a copolymer of acrylic ester is referred to as a polyacrylate, even if it comprises a methacrylic acid ester as a comonomer.
  • the poly (meth) acrylate is preferably a bead polymer.
  • Acrylic acid esters and methacrylic acid esters are e.g. C-Ms-alkyl acrylates, preferably C-i-alkyl acrylates, or C-i-is-Alkylnnethacrylate, preferably Ci- alkyl methacrylates.
  • Acrylic acid esters or methacrylic acid esters without an additional functional group are preferred.
  • acrylic acid esters and methacrylic acid esters are methyl acrylate, ethyl acrylate, n-butyl acrylate, tert-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate and n-butyl methacrylate.
  • acrylic acid esters or methacrylic acid esters having an additional functional group examples include maleic acid, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, butanediol mono (meth) acrylate, esters of (meth) acrylic acid and glycol oligomers and polymers, in particular propylene glycol Oligomers and polymers, as well as esters of (meth) acrylic acid and glycol ethers.
  • Preferred polyacrylates or polymethacrylates are copolymers which are obtained by free-radical polymerization of one or more acrylic esters and / or methacrylates, if appropriate in combination with one or more OH-functional acrylic esters and / or OH-functional methacrylic esters.
  • the polyacrylate or polymethacrylate is preferably a homopolymer or
  • Methacrylic acid ester has no additional functional group.
  • the polyacrylate or polymethacrylate is particularly preferably a copolymer of methyl methacrylate and n-butyl methacrylate and optionally at least one another comonomer, such as a hydroxy-functional acrylic ester or a hydroxy-functional methacrylic acid ester.
  • Polyacrylates or polymethacrylates are available, for example under the series name Dynacoll ® AC Evonik.
  • the polyacrylate or polymethacrylate has e.g. an average molecular weight in the range of 10,000 to 200,000 g / mol, preferably from 20,000 to 150,000 g / mol.
  • the polyacrylate or polymethacrylate in a preferred embodiment comprises at least one polyacrylate or polymethacrylate having a weight-average molecular weight Mw in the range from 30,000 to 300,000 g / mol, in particular 40,000 to 250,000 g / mol, more preferably 60,000 to 200,000 g / mol and most preferably 75,000 to 150,000 g / mol. It may be expedient if all polyacrylates or polymethacrylates contained in polyurethane hot melt adhesive meet these requirements. Additionally or alternatively, it is preferred if the polyacrylate or polymethacrylate has a glass transition temperature, determined according to ISO 1 1357-1, in the range of> 60 ° C and especially> 63 ° C.
  • the proportion of the at least one poly (meth) acrylate may, for example, suitably be in the range from 12 to 40% by weight, and preferably from 15 to 30% by weight, based on the total weight of the polyurethane hot melt adhesive
  • the solvent-free Polyurethananschmelzklebstoff at least one poly (meth) acrylate containing a
  • melt flow index at 190 ° C in the range of 0.1 to 10 g / 10 min If in the context of this invention, a melt flow index is mentioned, this is to be determined according to ISO 1 133. As a preferable range for the designated poly (meth) acrylate, a melt flow index in the range of 2 to 9.5 g / 10 min can be given.
  • Polyurethane hot melt adhesives according to the present invention
  • Poly (meth) acrylate which has a melt flow index at 190 ° C of more than 10 g / 10 min.
  • melt flow index at 190 ° C of more than 10 g / 10 min.
  • a range of 15 to 25 g / 10 min can be given.
  • the solvent-free invention contains
  • Polyurethane hot melt adhesive one or more fillers selected from kaolin, fumed silica, carbon black or wollastonite.
  • kaolin, fumed silica and carbon black are preferred because it has been observed that adding wollastonite at higher levels may adversely affect the thermal stability of the adhesive.
  • carbon black is associated with the disadvantage that black products are inevitably obtained, which is not desirable in all cases
  • kaolin and fumed silica are particularly preferred of the mentioned fillers.
  • Most preferred of these fillers is kaolin, since it has been observed that it can be incorporated into the melt composition in greater proportions without adversely affecting the properties of the adhesive.
  • particularly inexpensive hot melt adhesives can be produced, since the filler is compared to the other components to be included in the composition of the cheapest component.
  • the said fillers are included in an amount in the solvent-free polyurethane hot melt adhesive of the invention which provides a marked improvement in the heat balance, i. an improvement in the thermal state (intended for bonding two wood substrates) of at least 5 ° C and preferably at least 10 ° C compared to the composition without filler causes.
  • the amount of filler added should not be so great that the viscosity of the hot melt adhesive composition increases too much.
  • the amount of filler should be such that the viscosity of the hot melt adhesive is not more than 50,000 mPa.s and preferably not more than
  • kaolin is included in the adhesive composition of the present invention, its content should be in the range of about 2 to 35%, especially in the range of about 5 to 30 wt .-% and particularly preferably in the range of about 10 to 20 wt .-%, are. With kaolin contents of more than 35% by weight, a marked increase in the viscosity at 130 ° C. was observed, which improved the processability
  • fumed silica When fumed silica is used as the filler, its content in the solvent-free polyurethane hot melt adhesive should be in the range of 0.5 to
  • carbon black When carbon black is included as a filler in the hot-melt adhesive composition of the present invention, its content should be suitably in the range of 2 to
  • Wollastonite contains as filler, its proportion should suitably be in the range of 2 to 8 wt .-% and in particular 3 to 5 wt .-%. At a content of about 10 wt .-% wollastonite, although a further improvement of
  • the hot melt adhesive composition according to the invention contains precisely one of the fillers mentioned, ie kaolin, fumed silica, carbon black or wollastonite. In another Embodiment contains the hot melt adhesive composition according to the invention more of the mentioned fillers.
  • Polyisocyanate preferably with a monomeric diisocyanate, for example, at temperatures in the range of 60 to 160 ° C, preferably 80 to 140 ° C, are performed.
  • the duration of the implementation depends of course on the used
  • Polyester polyols and polyisocyanates may optionally conventional
  • Metal catalysts can be used, for example, bi-catalysts, as well
  • the polyisocyanate is preferably incorporated in an amount such that an NCO / OH ratio in the range of 1, 5: 1 to 3: 1 and more preferably 1, 8: 1 to 2.5: 1 sets.
  • the OH groups in this case essentially or exclusively account for the polyols mentioned, i. in particular the polyester and polyether polyols.
  • the above-mentioned NCO / OH ratios are calculated in each case via the molar ratio of isocyanate to
  • an NCO content of 1 to 5 wt .-% and preferably 1, 8 to 3 wt .-% is set in the adhesive.
  • solvent-free Polyurethananschmelzklebstoffe also contain other auxiliaries, it being preferred, however, if the proportion of these other auxiliaries, if used at all, not more than 10 wt .-% and preferably not more than 5 wt .-%, based on the total weight of the polyurethane hot melt adhesive, accounts.
  • suitable optional auxiliaries are one or more thermoplastic polymers and / or one or more additives.
  • the additives are selected, for example, from catalysts, plasticizers, adhesion promoters, UV absorbers, UV and heat stabilizers, antioxidants, flame retardants, optical brighteners, pigments, dyes and drying agents.
  • catalysts are catalysts which control the reaction of isocyanate groups with atmospheric moisture
  • the optional thermoplastic polymers are preferably non-reactive thermoplastic polymers.
  • examples are homo- or copolymers of unsaturated monomers, in particular from the group comprising ethylene, propylene, butylene, isobutylene, isoprene, vinyl acetate or higher esters thereof.
  • Particularly suitable are ethylene-vinyl acetate copolymer (EVA), atactic poly- ⁇ -olefin (APAO), polypropylene (PP) and polyethylene (PE).
  • EVA ethylene-vinyl acetate copolymer
  • APAO atactic poly- ⁇ -olefin
  • PP polypropylene
  • PE polyethylene
  • Thermoplastic polymers do not include poly (meth) acrylates.
  • the solvent-free polyurethane hot melt adhesives according to the invention comprise isocyanate-terminated polyurethane polymers or polyurethane prepolymers.
  • the polyurethane hot melt adhesive of the invention is meltable, i. he has at the application temperature to a sufficiently low viscosity, so that a suitable application is possible, and he quickly becomes cold on cooling, so that he can absorb forces quickly, even before the crosslinking reaction with
  • the adhesive particularly preferably has a viscosity at 130 ° C. of ⁇ 50,000 mPa.s and in particular ⁇ 20,000 mPa.s.
  • the invention comprises a method for bonding a first substrate to a second substrate, comprising heating a
  • polyurethane hot melt adhesive according to the invention; the application of the heated polyurethane hot melt adhesive to the first substrate; contacting the applied polyurethane hot melt adhesive with the second substrate;
  • the heating of the Polyurethananschmelzklebstoffs can be carried out for example to a temperature in the range of 80 ° C to 200 ° C, in particular from 120 ° C to 160 ° C.
  • the first substrate and the second substrate may be made of the same or different material.
  • the first and / or second substrate may be pretreated prior to application of the polyurethane hot melt adhesive.
  • Such pretreatments include in particular physical and / or chemical cleaning and
  • Activation methods for example grinding, sandblasting, brushing, corona treatment, plasma treatment, flaming, etching or the like, or treatment with cleaners or solvents or the application of an adhesion promoter, a primer solution or a primer.
  • the first and second substrates or their surface may e.g. made of plastic, organic material such as leather, fabric, paper, wood, resin-bound
  • Wood material resin-textile composite material, glass, porcelain, ceramic and metal and metal alloy, in particular painted or powder-coated metal and metal alloy.
  • plastics are polyvinyl chloride (PVC), acrylonitrile-butadiene-styrene copolymers (ABS), SMC (sheet molding composites), polycarbonate (PC), polyamide (PA), polyester (PE), polyoxymethylene (POM), polyolefin ( PO), in particular polyethylene (PE) or polypropylene (PP), preferably PP or PE surface-treated with plasma, corona or flame.
  • PVC polyvinyl chloride
  • ABS acrylonitrile-butadiene-styrene copolymers
  • SMC sheet molding composites
  • PC polycarbonate
  • PA polyamide
  • PET polyester
  • POM polyoxymethylene
  • PO polyolefin
  • PE polyethylene
  • PP polypropylene
  • at least one of the first and second substrates is a plastic film, a textile or glass.
  • Preferred materials for the first and / or second substrate are transparent materials, in particular transparent ones
  • Plastic films Another preferred transparent material is glass,
  • the solvent-free polyurethane hot melt adhesive of the invention is particularly suitable for industrial applications, e.g. in vehicle construction, in particular in the automotive industry, in the textile industry, e.g. as a textile adhesive, and in the
  • Packaging industry e.g. as a film adhesive.
  • the solvent-free polyurethane hot melt adhesive according to the invention is suitable for bonds in which the bonding site is visible. So it is particularly suitable for the bonding of glass, especially in vehicle and window construction, and for the gluing of transparent packaging.
  • the thickness of the adhesive layer formed from the polyurethane hot melt adhesive of the present invention is e.g. 10 ⁇ or more, preferably the thickness is in the range of 10 to 1000 ⁇ , more preferably from 80 to 500 ⁇ .
  • the invention also relates to articles which are according to the invention
  • Gluing be glued.
  • Such articles are in particular articles of the transport industry, in particular the automotive industry, furniture or textile industry.
  • bonded articles are automobile interior trim parts such as gutter, sun visor, instrument panel, door side panel, parcel shelf and the like;
  • Wood fiber materials from the shower and bath area 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.
  • Further examples of bonded articles are articles from the packaging industry, in particular one
  • the articles are sandwich panels.
  • another aspect of the present invention relates to the use of the polyurethane hot melt adhesives of the invention for industrial purposes
  • the viscosity was measured at 130 ° C. by means of Rheomat (Brookfield, Thermosel, spindle 27, shear rate 1 min -1 ).
  • the hot melt adhesive was preheated at 150 ° C for 30 minutes. Meanwhile, a squeegee was placed on a Sicol paper strip (length about 30 cm). Both were then placed on a hot plate and preheated. There were at least 20
  • the initial strength of the hot melt adhesive was tested with a tensile shear wood specimen.
  • the standard wood is beech (Fagus sylvatica) (specimen: 2 pieces: 100 mm x 25 mm x 5 mm, thickness of the adhesive layer: 1 mm).
  • the initial strength was measured 6, 10, 20 and 30 minutes after assembly of the samples.
  • the force at break of the test specimen was determined at a defined test speed.
  • the heat resistance was determined by means of wood test specimens with dimensions of 1, 5 cm ⁇ 1.5 cm by applying the compositions with a layer thickness of 1 mm to the first specimen and then bringing them into contact with the second specimen. After complete curing, the specimen was loaded in a tensile shear tester weighing 1 kg. The temperature was initially set to about 40 ° C below the expected thermal state and then increased at a distance of 1 h by 10 ° C. The temperature (in ° C) at which the test specimen failed in the tensile shear test was taken as the heat balance of the composition.
  • the stability of the adhesive was determined by the viscosity of the adhesive as% increase after storage for 16 h at 140 ° C (with exclusion of moisture). A viscosity increase of more than 150% was considered unacceptable.
  • Test condition 23 ° C / 50% RH The maximum tensile force absorbed by the sample was measured. The tensile strength and elongation at break were determined from this, the mean value of each of the five test pieces being determined.
  • Polyurethane melt adhesives made with varying amounts of kaolin made with varying amounts of kaolin.

Landscapes

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

Abstract

L'invention concerne des additifs thermofusibles en polyuréthane, exempts de solvant, qui sont obtenus par transformation d'une composition comprenant un polyétherpolyol, un polyesterpolyol, au moins un poly(méth)acrylate et une ou plusieurs charges, choisies parmi le kaolin, la silice pyrogène, la suie ou la wollastonite, avec un polyisocyanate. Par rapport aux adhésifs analogues sans teneur en charge, ces additifs se caractérisent par des propriétés de résistance thermique significativement améliorées tout en présentant pour le reste des propriétés comparables. De plus, dans certains cas, on a pu observer des propriétés mécaniques améliorées, telles qu'en particulier une résistance à la déchirure améliorée, grâce à l'addition des charges. Les compositions d'adhésif thermofusible décrites se caractérisent par conséquent en particulier pour des applications dans la construction automobile, dans l'industrie textile et dans l'industrie des emballages et en particulier pour le collage de panneaux sandwich.
EP16820249.7A 2015-12-23 2016-12-21 Adhésif thermofusible en polyuréthane à base de polyacrylates présentant une résistance élevée à la chaleur Withdrawn EP3394135A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP15202474 2015-12-23
PCT/EP2016/082049 WO2017108873A1 (fr) 2015-12-23 2016-12-21 Adhésif thermofusible en polyuréthane à base de polyacrylates présentant une résistance élevée à la chaleur

Publications (1)

Publication Number Publication Date
EP3394135A1 true EP3394135A1 (fr) 2018-10-31

Family

ID=55068850

Family Applications (1)

Application Number Title Priority Date Filing Date
EP16820249.7A Withdrawn EP3394135A1 (fr) 2015-12-23 2016-12-21 Adhésif thermofusible en polyuréthane à base de polyacrylates présentant une résistance élevée à la chaleur

Country Status (4)

Country Link
US (1) US10800957B2 (fr)
EP (1) EP3394135A1 (fr)
CN (1) CN108431068A (fr)
WO (1) WO2017108873A1 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107523255A (zh) * 2017-09-08 2017-12-29 广州市极威新材料有限公司 一种用于贴面装饰的湿固化聚氨酯热熔胶
CN107955127A (zh) * 2017-11-09 2018-04-24 湖南优冠体育材料有限公司 一种新型无溶剂聚氨酯微孔弹性球场材料的制备及使用方法
WO2019100357A1 (fr) * 2017-11-27 2019-05-31 烟台德邦科技有限公司 Procédé de préparation d'un adhésif thermofusible de polyuréthane résistant aux températures élevées
EP4021706A1 (fr) 2019-08-26 2022-07-06 H.B. Fuller Company Composition adhésive thermofusible durcissable à l'humidité à durcissement rapide et articles comprenant celle-ci
EP4077574A4 (fr) 2019-12-17 2023-09-06 Henkel AG & Co. KGaA Composition de colle polyuréthane thermofusible et son procédé de préparation
CN111303824A (zh) * 2020-04-20 2020-06-19 常州威斯敦粘合材料有限责任公司 湿固化聚氨酯热熔胶及其制备方法、应用和钢构件
CN112322244A (zh) * 2020-11-23 2021-02-05 西安航空职业技术学院 一种耐高温胶粘剂及其制备方法
CN112745794A (zh) * 2020-12-29 2021-05-04 烟台德邦科技股份有限公司 一种湿固化聚氨酯热熔胶及其制备方法
JP2024505523A (ja) * 2021-01-28 2024-02-06 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン ゲル化及び相分離抑制剤を充填ポリウレタン反応性ホットメルト接着剤に組み込む方法
CN114989772B (zh) * 2021-07-05 2024-03-01 无锡博锦高分子研究发展有限公司 一种低硬度纺织品聚氨酯热熔胶粘剂及其制备方法
WO2023044665A1 (fr) * 2021-09-23 2023-03-30 Sika Technology Ag Adhésif thermofusible en polyuréthane durcissable à l'humidité présentant une stabilité thermique améliorée

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5869593A (en) 1991-07-01 1999-02-09 H. B. Fuller Licensing & Financing, Inc. High moisture vapor transmission hot melt moisture cure polyurethane adhesive
US5525663A (en) 1994-08-18 1996-06-11 Minnesota Mining And Manufacturing Company Reactive hot-melt adhesive and/or sealing composition and method of using same
US6465104B1 (en) * 1997-12-01 2002-10-15 Henkel Kommanditgesellschaft Auf Aktien Modified polyurethane hotmelt adhesive
AU742870B2 (en) * 1997-12-01 2002-01-17 Henkel Kommanditgesellschaft Auf Aktien Modified polyurethane hotmelt adhesive
DE10149142A1 (de) * 2001-10-05 2003-04-24 Henkel Kgaa Modifizierter reaktiver Schmelzklebstoff und dessen Verwendung
JP4171221B2 (ja) 2002-02-05 2008-10-22 日東シンコー株式会社 電子部材用ホットメルト接着シート
JP5893000B2 (ja) * 2010-03-16 2016-03-23 ヘンケル アイピー アンド ホールディング ゲゼルシャフト ミット ベシュレンクテル ハフツング シラン湿気硬化性ホットメルト
CN102477273A (zh) 2010-11-26 2012-05-30 上海恩意材料科技有限公司 一种聚氨酯热熔胶黏剂的制备方法
JP5734092B2 (ja) * 2011-05-24 2015-06-10 ヘンケルジャパン株式会社 湿気硬化型ホットメルト接着剤
CN103865465A (zh) 2012-12-14 2014-06-18 江苏天顺新材料有限公司 汽车车灯用湿固化聚氨酯热熔胶及其制备方法
CN103087666B (zh) * 2013-03-05 2014-11-12 河南省科学院化学研究所有限公司 一种反应型聚氨酯热熔密封胶
CN104974707B (zh) * 2015-07-07 2017-12-05 上海天洋热熔粘接材料股份有限公司 一种湿固化聚氨酯热熔胶及其制备方法

Also Published As

Publication number Publication date
WO2017108873A1 (fr) 2017-06-29
US20180346775A1 (en) 2018-12-06
US10800957B2 (en) 2020-10-13
CN108431068A (zh) 2018-08-21

Similar Documents

Publication Publication Date Title
WO2017108873A1 (fr) Adhésif thermofusible en polyuréthane à base de polyacrylates présentant une résistance élevée à la chaleur
EP3288992B1 (fr) Procédé en deux étapes destiné à la fabrication d'une colle polyuréthane à fondre à chaud à faible teneur en diisocyanates monomères et à durcissement rapide
EP3116930B1 (fr) Adhésif thermofusible en polyuréthane avec une faible teneur en diisocyanates monomères et une bonne vitesse de réticulation
EP2585510B1 (fr) Adhésif à contrecoller à base de tpu
EP2038360B1 (fr) Colle à chaud réactive à l'humidité avec temps de pleine ouverture accru
EP2493945B1 (fr) Adhésif bicomposant en dispersion aqueuse
EP1250394B1 (fr) Compositions de polyurethanne a base de copolymeres de polyester-polyether
EP2336261B1 (fr) Compositions de colle de fusion à chaud ayant une bonne adhésion tant sur les substrats polaires qu'apolaires
EP1432748A1 (fr) Colle fusible reactive modifiee et son utilisation
DE112008000237T5 (de) Reakitver Schmelzklebstoff mit bitumenhaltigem Additiv
WO2009086069A1 (fr) Composition adhésive thermofusible durcissable à l'humidité
WO2008059056A1 (fr) Composition d'adhésif fondant à chaud, durcissant à l'humidité contenant de la polyaldimine
EP3315528B1 (fr) Procédé de réduction d'adhérence au repos d'adhésifs polyuréthanes thermofusibles durcissant à l'humidité
WO2017009310A1 (fr) Colle thermofusible polyuréthane, contenant des dialdimines, offrant une meilleure adhérence sur l'acier inoxydable
WO2018228936A1 (fr) Composition de polyuréthane à deux composants
TW202130688A (zh) 反應性熱熔黏著劑組合物及其用途
DE10235090A1 (de) Segmentierte Polyurethan-Schmelzklebstoff-Zusammensetzungen
EP2145909B1 (fr) Procédé de fabrication d'alcools bloqués
CN117794971A (zh) 具有耐热性和耐湿性的可湿固化聚氨酯热熔粘合剂
WO2023168622A1 (fr) Adhésif thermofusible de polyuréthane durcissable à l'humidité ayant une résistance initiale améliorée
WO2023044665A1 (fr) Adhésif thermofusible en polyuréthane durcissable à l'humidité présentant une stabilité thermique améliorée
WO2023139067A1 (fr) Adhésif thermofusible en polyuréthane durcissable à l'humidité présentant une stabilité thermique améliorée

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20180723

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20200717

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20230701