WO2009074345A2 - Adhésif sans solvants et procédé de collage surfacique de substrats - Google Patents

Adhésif sans solvants et procédé de collage surfacique de substrats Download PDF

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Publication number
WO2009074345A2
WO2009074345A2 PCT/EP2008/010612 EP2008010612W WO2009074345A2 WO 2009074345 A2 WO2009074345 A2 WO 2009074345A2 EP 2008010612 W EP2008010612 W EP 2008010612W WO 2009074345 A2 WO2009074345 A2 WO 2009074345A2
Authority
WO
WIPO (PCT)
Prior art keywords
adhesive
dispersion
substrates
triaminotriazine
derivative
Prior art date
Application number
PCT/EP2008/010612
Other languages
German (de)
English (en)
Other versions
WO2009074345A3 (fr
Inventor
Julian W. Grimme
Heinz Buchholz
Anneliese Buchholz
Original Assignee
Renia-Gesellschaft Mbh
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 Renia-Gesellschaft Mbh filed Critical Renia-Gesellschaft Mbh
Priority to EP08860590A priority Critical patent/EP2222787A2/fr
Publication of WO2009074345A2 publication Critical patent/WO2009074345A2/fr
Publication of WO2009074345A3 publication Critical patent/WO2009074345A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—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
    • 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
    • C08G2170/80—Compositions for aqueous adhesives
    • 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
    • C08G2170/90—Compositions for adhesives used in footwear
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
    • C08L2666/20—Macromolecular compounds having nitrogen in the main chain according to C08L75/00 - C08L79/00; Derivatives thereof

Definitions

  • the present invention relates to a solvent-free adhesive comprising an aqueous dispersion based on at least one high molecular weight polyurethane and / or polyester polyurethane or more polyurethanes and / or polyester-polyurethane-like construction.
  • the invention is further directed to the use of aqueous polymer dispersions as a contact adhesive for the surface bonding of substrates and to a method for bonding flat substrates.
  • the invention also relates to a crosslinking agent for a solvent-free contact adhesive based on an aqueous, hydroxyl-containing polymer dispersion
  • contact adhesives For bonding two or more layers of flat substrates to an adhesive bond, for example for bonding various shoe components such as shoe soles or shoe inserts, it is usually appropriate contact adhesives, which are applied to the two substrates to be bonded together and cause the surface sticking of the substrates after venting .
  • An important area is the thermal bonding, in which the bonding of the substrates at elevated temperature, namely above the softening temperature of the adhesive takes place.
  • the softening temperature of a contact adhesive is understood to mean a temperature above which a cold-solid state (for example, about 25 ° C.) becomes substantially block-resistant or blunt, ie non-adhesive film of the adhesive becomes tacky again, so that when heated with the Adhesive provided substrates stick together during assembly.
  • Thermoplastic bonding is used, for example, in the furniture industry, in the film coating of wood and medium-density fiberboard, and in the automotive industry in the film coating of molded parts for automotive interior fitting, z. As instrument panels and door panels.
  • the thermal lamination or thermal bonding is used for bonding flat substrates made of leather, polyurethane, polyethylene / vinyl acetate and / or textiles, in particular, for example, when bonding shoe soles or building and gluing shoe insoles.
  • polyurethane adhesives are often used in the shoe industry, which in the past i.A. contained a solvent.
  • aqueous polyurethane dispersions in particular polyester-polyurethane dispersions, which are in principle suitable for bonding shoe components.
  • adhesion of EVA is possible only with the use of a solvent-containing primer.
  • the adhesive dispersions have low softening ranges and are susceptible to hydrolysis by chemical degradation is disadvantageous when using such solvent-free, aqueous polyurethane dispersions as contact or laminating adhesive, so that they are generally secondarily used as a two-component system with an isocyanate crosslinker Component must be processed.
  • the isocyanates used to process the polyurethane dispersions are not only not toxicologically acceptable, but they cause problems in the preparation and processing of the adhesive, because they require a very thorough mechanical mixing of the component isocyanate in the polyurethane dispersion.
  • the limited pot life due to undesirable side reactions of isocyanates and water also complicates the subsequent processing (application of the adhesive and assembly of the substrates provided with adhesive), so that Fehlverklebitch and / or a limited durability of the bond are the result.
  • EP-A 61628 An example of the use of aromatic polyisocyanates in adhesives based on emulsion polymers of ethylenically unsaturated monomers is described in EP-A 61628.
  • EP-A 259679 discloses water-dispersible polyisocyanate preparations which be added to aqueous adhesives based on aqueous polymer dispersions to improve the heat resistance.
  • the stability of such dispersions is limited in time (low dropping time).
  • the object of the present invention is therefore to provide an alternative crosslinker or a contact or laminating adhesive provided therewith, which ensures problem-free and sufficiently long processability in industrial and craft applications, so that bonds with good strength, in particular good heat resistance and high heat resistance Hydrolysis resistance can be obtained.
  • thermoreactive crosslinkers in aqueous dispersions of hydroxyl-containing polymers, in particular polyurethane and / or polyester polyurethane dispersions, gives an adhesive which does not pose any problems with regard to toxicity and / or pot life, by the crosslinking component is inactive at room temperature (about ⁇ 40 0 C), however, when heated to the necessary for the bonding of the substrates following the application of the adhesive and the flash off softening or activation temperature, the crosslinking component is active and the crosslinking reaction thus in Gang sets.
  • the present invention relates to a solvent-free adhesive consisting essentially of:
  • the present invention also relates to a use of a hydroxyl-containing polymer dispersion, in particular a dispersion based on high molecular weight polyurethanes and / or polyester-polyurethanes, containing at least one thermally activatable triaminotriazine derivative and optional additives for defoaming, emulsification, dispersion, wettability and / or modification of rheological properties of the dispersion, as a contact adhesive for the surface bonding of substrates and moreover a method for bonding flat substrates, comprising the following steps:
  • the invention also relates to a crosslinking agent for a solvent-free contact adhesive based on an aqueous, hydroxyl-containing polymer dispersion which is characterized in that it consists of a thermally activatable triaminotriazine derivative.
  • the triaminotriazine derivative consists essentially of a hexa-alkoxylated 2, 4, 6-triamino-1, 3, 5-triazine and / or from etherified melamine derivatives.
  • the adhesive according to the invention may also comprise further additives, as have been used for waterborne polyurethane adhesives in the past.
  • further additives as have been used for waterborne polyurethane adhesives in the past.
  • the following are preferably contained as additives in the adhesive according to the invention:
  • an alkylpolyglycol ether preparation can be used in an advantageous development of the invention.
  • the emulsifier used is preferably one based on an aqueous solution of an arylethylphenyl polyglycol ether.
  • an agent based on an aqueous solution of a succinic acid ester can be used.
  • the rheology modifier is preferably polyurethane-based.
  • the triaminotriazine derivative is preferably contained in an amount of 10 to 15% by weight, based on the amount of solid polymer in the dispersion, in the adhesive of the present invention.
  • the inventive method may preferably for bonding different Shoe components for example made of leather, PVC, PUR and / or thermoplastic rubber are used.
  • During the execution of the process step is preferably carried c) at a temperature of at least 40 ° C and particularly preferably at a temperature of 70 0 C to 90 0 C, because it has been shown that this is the obtuse not only for the reactivation, On the substrates applied adhesive film, but at the same time also leads to a rapid decomposition of Triaminotriazinderivats and thus a triggering of the adhesive condensation, ie it arises from the initially inactive triamine reactive intermediates which can condense with the hydroxyl groups of the polymer to form a network.
  • the aqueous polymer dispersion used according to the invention may contain one or more thermoplastic polymers finely dispersed in the dispersion, as are commonly used in contact and / or laminating adhesives.
  • the dispersion contains essentially polyurethane as the polymer.
  • Suitable aqueous polyurethane or polyester-polyurethane dispersions are known and, for example, ® under the trade names of BASF AG or Luphen ® Dispercoll U from Bayer AG available commercially.
  • the coating of the substrates with the aqueous dispersion of the copolymer CP is expediently carried out by customary methods such as spraying, pouring, brushing or knife coating.
  • spraying the dispersion can often be dispensed with a separate drying step, since during spraying already a large proportion of the dispersion water evaporates, so that step a) and step b) then substantially coincide.
  • the application rate of the adhesive is generally dimensioned so that after drying in step b) the then blunt adhesive coating on each of the two substrates has an average basis weight in the range of 5 to 100 g / mm 2 , preferably in the range from 5 to 50 g / mm 2 and in particular in the range of 10 to 40 g / mm 2 .
  • Step b) of the process according to the invention can be carried out both at room temperature (flash off) and at a slightly elevated temperature, for. B. at temperatures ranging from 30 to 40 0 C, z. B. by irradiation with infrared light or other heat source.
  • the coating usually contains less than 5% by weight of water.
  • the subsequent to the drying heat activation for bonding the two substrates is usually carried out at temperatures above 40 0 C and in particular in the range of 70 to 90 0 C. If drying is also to be carried out at this temperature, fall step b) and step c) of course together, or merge into each other.
  • the melting of the adhesive film and simultaneous activation of the crosslinking component at or immediately before the bonding of the substrates can also be carried out by irradiation with infrared light or by heating in a hot air stream. Processes for this are known to the person skilled in the art.
  • the bonding of the flat substrates to a two-dimensional adhesive composite according to step c) takes place in the customary devices, ie in two flexible substrates in calenders or in presses, for.
  • the customary devices ie in two flexible substrates in calenders or in presses, for.
  • if one of the substrates is rigid.
  • at least one of the substrates is flexible.
  • the production of the adhesive bond naturally takes place at a temperature above the activation temperature. Separate heating (preheating step) is not required. Therefore, usually heated presses or heated calenders are used.
  • pressure is usually applied to the substrates, which is usually in the range of 0.05 to 5 N / mm 2 .
  • the optionally subsequent cooling can be done by switching off the heater to the press or the calender are effected. Under certain circumstances, an additional cooling device, for example, a water or air cooling can be used.
  • the inventive method is suitable for bonding a variety of substrates.
  • Suitable substrates are for example those of wood, wood fibers, metal, leather or plastic, for.
  • Schub Anlagenmaschinener such as soles, Obermaterialledermaschine, insoles, etc.
  • the rule is that the substrates to be bonded are absorbent only to a limited extent.
  • the inventive method is of course not limited to the production of adhesive composites of two substrates, but is of course also suitable for the production of multi-layer adhesive composites, for example by repeating steps a) to d) of the process according to the invention or several one-sided or two-sided coated substrates simultaneously or one after the other joins together to form an adhesive bond.
  • the adhesive according to the invention can be stored even over a prolonged period, even at a storage temperature which is elevated in comparison with conventional ambient temperatures (25.degree. C.), as long as this storage temperature is below the decomposition temperature of the triaminotriazine derivative used as the crosslinking component.
  • the adhesive composites produced with the adhesive used according to the invention have good heat resistance and are storage-stable even at elevated temperature over a relatively long period of time.
  • the submitted polyurethane dispersion is added with stirring at low speed, the triaminotriazine. After a stirring time of 20 minutes, the additives defoamers, emulsifiers Tor and wetting and dispersing agents at intervals of 10 minutes added. The entire mixture is stirred for about 20 minutes. The speed is increased and the rheology modifier is added slowly. The mixture is continued for about 20 to 30 min. stirred until the Rheologiemodofizleiters- agent distributed and a homogeneous mixture is formed. The formulation thus obtained is allowed to rest for about 12 hours before its viscosity is adjusted by mixing in water. Usually, the viscosity is thereafter at 1500-2000 mPa-s, the solids content is about 35 wt.% To 50 wt.%. The amounts of starting materials are given in the table below.
  • the solvent-free, aqueous contact adhesive is prepared by means of one of those described above Application methods applied.
  • the moist adhesive layer is dried by venting / evaporating the water at room temperature or removing the water by supplying heat (evaporation in a drying tunnel or similar aids) or underpressure.
  • the dried adhesive film is heated on the substrates to a temperature equal to and / or higher of the softening range of the polymer dispersion and the decomposition temperature of the triaminotriazine and thereby at room temperature non-adhesive adhesive film activated. This is followed by the bonding of usual bonding of the substrates provided with the adhesive and subsequent pressing and cooling of the bond.

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  • 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 un adhésif à base d'une dispersion polymère aqueuse dans lequel un dérivé triaminotriazine thermoactivable est employé en tant qu'agent réticulant. La triaminotriazine est inactive à température ambiante. Lors du chauffage de la triaminotriazine à la température d'activation, il y a toutefois décomposition de la triamine et donc formation de produits intermédiaires réactifs pouvant fusionner avec des groupes hydroxyl du polymère, de telle manière qu'il peut y avoir réticulation de l'adhésif.
PCT/EP2008/010612 2007-12-13 2008-12-12 Adhésif sans solvants et procédé de collage surfacique de substrats WO2009074345A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08860590A EP2222787A2 (fr) 2007-12-13 2008-12-12 Adhésif sans solvants et procédé de collage surfacique de substrats

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007060889A DE102007060889A1 (de) 2007-12-13 2007-12-13 Lösemittelfreier Klebstoff sowie Verfahren zum flächigen Verkleben von Substraten
DE102007060889.8 2007-12-13

Publications (2)

Publication Number Publication Date
WO2009074345A2 true WO2009074345A2 (fr) 2009-06-18
WO2009074345A3 WO2009074345A3 (fr) 2009-12-03

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Application Number Title Priority Date Filing Date
PCT/EP2008/010612 WO2009074345A2 (fr) 2007-12-13 2008-12-12 Adhésif sans solvants et procédé de collage surfacique de substrats

Country Status (3)

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EP (1) EP2222787A2 (fr)
DE (1) DE102007060889A1 (fr)
WO (1) WO2009074345A2 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102014005170A1 (de) * 2014-04-09 2015-10-15 Grammer Ag Verfahren und Vorrichtung zum Kaschieren eines Fahrzeugteils der Innenausstattung mit einem Lederbezug

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4758615A (en) * 1986-05-26 1988-07-19 Hoechst Ag Polymers containing urethane groups prepared by the reaction of polyamino compounds and cyclic carbonates
DE3903796A1 (de) * 1989-02-09 1990-08-16 Stockhausen Chem Fab Gmbh Waessrige polyurethan- bzw. polyurethanharnstoffdispersionen, verfahren zum beflocken elastomerer formkoerper sowie zur heissversiegelung von textilen flaechengebilden unter verwendung dieser dispersionen

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3112117A1 (de) 1981-03-27 1982-10-07 Bayer Ag, 5090 Leverkusen Verwendung von in wasser dispergierbaren polyisocyanat-zubereitungen als zusatzmittel fuer waessrige klebstoffe
DE3630045A1 (de) 1986-09-04 1988-03-17 Bayer Ag Klebstoff und die verwendung des klebstoffs zur herstellung von verklebungen
DE19907988A1 (de) * 1999-02-25 2000-08-31 Bayer Ag Wäßrige Sperrschicht auf Basis von Polyurethan-Dispersionen
DE19914898C2 (de) * 1999-04-01 2002-10-24 Basf Coatings Ag Vernetzungsmittel für auf der Basis von Pyrimidin für thermisch härtbare Zusammensetzungen und deren Verwendung
US6437036B1 (en) * 1999-11-17 2002-08-20 Basf Corporation Waterborne primer with improved chip resistance

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4758615A (en) * 1986-05-26 1988-07-19 Hoechst Ag Polymers containing urethane groups prepared by the reaction of polyamino compounds and cyclic carbonates
DE3903796A1 (de) * 1989-02-09 1990-08-16 Stockhausen Chem Fab Gmbh Waessrige polyurethan- bzw. polyurethanharnstoffdispersionen, verfahren zum beflocken elastomerer formkoerper sowie zur heissversiegelung von textilen flaechengebilden unter verwendung dieser dispersionen

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Publication number Publication date
DE102007060889A1 (de) 2009-06-18
EP2222787A2 (fr) 2010-09-01
WO2009074345A3 (fr) 2009-12-03

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