EP2245080A1 - Adhésif - Google Patents

Adhésif

Info

Publication number
EP2245080A1
EP2245080A1 EP09709573A EP09709573A EP2245080A1 EP 2245080 A1 EP2245080 A1 EP 2245080A1 EP 09709573 A EP09709573 A EP 09709573A EP 09709573 A EP09709573 A EP 09709573A EP 2245080 A1 EP2245080 A1 EP 2245080A1
Authority
EP
European Patent Office
Prior art keywords
isocyanate
tertiary amino
terminated
amino groups
adhesive
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Withdrawn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
EP09709573A
Other languages
German (de)
English (en)
Inventor
Matthias Wintermantel
Christos Karafilidis
Heinz-Werner Lucas
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.)
Bayer Intellectual Property GmbH
Original Assignee
Bayer MaterialScience 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 Bayer MaterialScience AG filed Critical Bayer MaterialScience AG
Publication of EP2245080A1 publication Critical patent/EP2245080A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
    • A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
    • A61L15/42—Use of materials characterised by their function or physical properties
    • A61L15/58—Adhesives
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
    • A61L24/04—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
    • A61L24/046—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three 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
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/482—Mixtures of polyethers containing at least one polyether containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G18/4866—Polyethers having a low unsaturation value
    • 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
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • 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

Definitions

  • the invention relates to the use of specific isocyanate-terminated polyurethane prepolymers in adhesive formulations. These adhesive formulations can be used in applications where the direct or indirect contact of the adhesive layer with sensitive substrates requires the avoidance or minimization of migrates.
  • These sensitive substrates may be, for example, the human skin or composite films.
  • the latter are used extensively for the production of packaging for all types of goods. Since monofilms, coextruded multilayer films or extrusion-laminated film composites can not cover all requirements such as transparency / opacity, printability, barrier properties, sealability and mechanical properties, composite films in which the individual layers are bonded together by adhesive make up the largest share in the market and thus have an immense commercial significance. Of particular importance is the production of food packaging from composite films. Since some layers used on the food-facing side have low barrier properties compared to the adhesive constituents used, special attention must be paid to the possible migration of adhesive constituents into the foodstuff. In surgery, adhesives are increasingly used for wound closure and care. It is particularly important that no harmful substances from the adhesive layer migrate into the skin or the system.
  • the laminated films must be stored after their preparation before packaging the food until the reaction has progressed so far that no migration of PAA's is more detectable or the prescribed limits are exceeded.
  • the method according to ⁇ 35 LMBG Food and Commodities Act
  • a pouch from the film composite to be examined with a food simulant usually 3% strength by weight aqueous acetic acid solution
  • the contents of PAA are photometrically checked after derivatization.
  • contents of less than 0.2 ⁇ g of PAA per 100 ml of food simulant can be achieved. This corresponds to 2 ppb and at the same time the detection limit of the described method.
  • the term “free from matte” or "migrattransport Folienverbünde” is used, if this limit was exceeded.
  • EP-A 0 590 398 describes the use of low-monomer isocyanate-terminated polyurethane prepolymers obtained by removal of the monomeric polyisocyanates by distillation in solvent-free 2K adhesive formulations for the production of flexible film composites.
  • the film composites produced thereby are determined free from migrat within three days according to the method according to ⁇ 35 LMBG.
  • this procedure requires a time-consuming distillation step which increases the production costs and can not be carried out with conventional stirred kettles without plant-technical modifications.
  • the viscosity of the low-monomer isocyanate-terminated polyurethane prepolymers is higher than the conventional isocyanate-terminated polyurethane prepolymers.
  • low-monomer diphenylmethane diisocyanate polyurethane prepolymers having an isocyanate content of> 6% by weight have a viscosity of> 10,000 mPas at 50 ° C.
  • this viscosity is too high for use in flexible packaging adhesive formulations.
  • the content of monomeric polyisocyanate must be controlled, which means a logistical and financial overhead.
  • DE-A 3 401 129 describes the preparation of low-monomer isocyanate-terminated polyurethane prepolymers in a two-stage process using at least two differently reactive polyisocyanates (for example tolylene diisocyanate and diphenylmethane diisocyanate).
  • polyisocyanates for example tolylene diisocyanate and diphenylmethane diisocyanate.
  • the use of a "customary accelerator" is disclosed The use of low-monomer prepolymers in adhesive formulations for bonding films is described, with the disadvantageous use and metering of two differently reactive isocyanates and the necessary control the content of monomeric polyisocyanate.
  • US 2006/0078741 describes the use of catalysts in order to shorten the curing time of adhesive formulations for the production of film composites.
  • the shortened curing time correlates with the storage time that is necessary to obtain a migrato-free film composite.
  • a disadvantage of the use of a catalyst are its migration ability and the undesirable heavy metal content in the usually metallic catalysts.
  • an isocyanate-terminated polyurethane prepolymer which is not necessarily low in monomer content but contains tertiary amino groups, gives adhesive preparations which can be used advantageously in an adhesive formulation with a polyol or a polyol mixture.
  • adhesive preparations which can be used advantageously in an adhesive formulation with a polyol or a polyol mixture.
  • these are suitable, inter alia, for the production of adhesive bonds in which it is important that they do not diffuse out of any monomers because they come into contact, for example, with the skin or with foodstuffs.
  • the adhesive formulations according to the invention are used, for example, for producing composite films which, according to ⁇ 35 LMBG, are free from migratine after three days or more.
  • adhesive preparations according to the invention are used as surgical adhesives for wound closure and supply or in the production of adhesive and plaster systems for wound closure and care, as are known as patches, for example from EP-A 0 897 406, or US Pat even without textile carrier directly as a wound adhesive or wound closure agent.
  • active ingredients which have a positive influence on the wound behavior can be incorporated into these adhesive preparations. These include, for example, antimicrobial agents such as antimycotics and antibacterial substances (antibiotics), corticosteroids, chitosan, dexpanthenol and chlorhexidine gluconate.
  • the present invention relates to the use of isocyanate-terminated polyurethane prepolymers containing tertiary amino groups in adhesive formulations for the production of film composites, which yield migrato-free film composites after three days at the latest, as well as in the manufacture of medical wound care systems.
  • an advantage over the prior art is that the preparation of the isocyanate-terminated prepolymers in contrast to the prior art in a 1-stage process in a conventional stirred tank, without complicated distillation, without the use of an asymmetric isocyanate (its availability is not always given is) and without quality control of the content of monomeric polyisocyanate is possible and leads after equal or shorter time to migratelle film composites.
  • the isocyanate-terminated polyurethane prepolymers of the present invention have a lower viscosity compared to the low-monomer isocyanate-terminated polyurethane prepolymers described above, and no addition of a catalyst which is usually capable of migration, reduces storage stability, and requires possibly heavy metal content in food packaging is undesirable.
  • the invention therefore preferably relates to the use of an isocyanate-terminated and tertiary amino-containing polyurethane prepolymers in adhesive formulations which are migratrile after three days and are particularly preferably used for the production of film composites.
  • the polyurethane prepolymer and the adhesive formulation preferably have the following characteristics:
  • the adhesive formulation preferably consists of an isocyanate-terminated polyurethane urethane prepolymer A) and a polyol or a polyol formulation B) and optionally further additives C).
  • the isocyanate-terminated polyurethane prepolymer is a reaction product of a polyisocyanate or a polyisocyanate formulation a) and at least one polyol or a polyol mixture b): a) The polyisocyanate bz ⁇ V.
  • the polyisocyanate formulation generally contains polyisocyanates having a functionality of from 2 to 3.5, preferably from 2 to 2.7, more preferably from 2 to 2.2, and most preferably from 2 to an NCO content of 21 to 50 wt. -%, preferably from 21 to 49 wt .-%, particularly preferably from 29 to 34 wt .-% and most preferably from 33.6 wt .-%.
  • the polyol or the polyol mixture generally contains at least one polyether containing tertiary amino groups, a number average molecular weight M n of 320 to 20,000 g / mol, preferably from 330 to 4500 g / mol, particularly preferably from 340 to 4200 g / mol and most preferably from 3400 to 4100 g / mol and has a nominal functionality of from 2 to 4.5, preferably from 2.5 to 4.5, more preferably from 3 to 4.5, and most preferably from 4 and optionally one or more further polyethers and / or polyesters and / or polycarbonates having an average molecular weight M n of from 300 to 20 000 g / mol, preferably from 430 to 17 300 g / mol, more preferably from 590 to 8000 g / mol, and very particularly preferably from 1000 to 4000 g / mol.
  • the polyol or the polyol formulation a) has a hydroxyl number of 40 to 300 mg KOH / g, preferably from 80 to 270 mg KOH / g and more preferably from 180 to 240 mg KOH / g. b) has a nominal average functionality of 2 to 4, preferably 2 to 3.4, and more preferably from 2 to 2.9.
  • c) is a polyol, polyether polyol, polycarbonate polyol or a polyester polyol or a mixture of two or more of said polyols.
  • the isocyanate-terminated polyurethane prepolymer is characterized in that it a) an NCO content of 5-20% by weight, preferably an NCO content of 9-19% by weight, particularly preferably an NCO content of 12-18% by weight and very particularly preferably an NCO Content of 13-17 wt .-% has. b) a nominal average functionality of 2 to 3, preferably from 2 to 2.7, more preferably from 2 to 2.4, and most preferably from 2 to
  • the preparation of isocyanate-terminated and tertiary amino-containing polyurethane prepolymers A) is known in the art from polyurethane chemistry per se.
  • the reaction of components A) a) and A) b) in the preparation of the polyurethane prepolymers A) takes place, for example, in such a way that the polyols which are liquid at reaction temperatures are mixed with an excess of the polyisocyanates and the homogeneous mixture is obtained until a constant NCO content is obtained. Value is stirred.
  • the reaction temperature 4O 0 C to 180 0 C, preferably 50 0 C to 140 0 C is selected.
  • the preparation of the polyurethane prepolymers A) can also be carried out continuously leh in a stirred tank cascade or suitable mixing units, such as high-speed mixers according to the rotor-stator principle.
  • HDI 1,6-hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • XDI xylylene diisocyanate
  • H12- MDI
  • TDI 2,4- and 2,6-toluene diisocyanate
  • MDI diphenylmethane-2,2'-diisocyanate
  • MDI diphenylmethane-2,4'-diisocyanate
  • MDI diphenylmethane-4,4'-diisocyanate
  • MDI diphenylmethane-4,4'-diisocyanate
  • MDI diphenylmethane-4,4'-diisocyanate
  • Particularly preferred is a mixture of max. 1% by weight of diphenylmethane-2,2'-diisocyanate, 40 to 70% by weight of diphenylmethane-2,4'-diisocyanate and 28 to 60% by weight of diphenylmethane-4,4'-diisocyanate (MDI) for the preparation the component A) used.
  • MDI diphenylmethane-4,4'-diisocyanate
  • MDI diphenylmethane-4,4'-diisocyanate
  • polyether polyols suitable for preparing the isocyanate-terminated polyurethane prepolymer A) and the polyol formulation B) are known per se to those skilled in polyurethane chemistry. These are typically obtained starting from low molecular weight polyfunctional OH or NH-functional compounds as starters by reaction with cyclic ethers or mixtures of various cyclic ethers.
  • the catalysts used are bases such as KOH or double metal cyanide-based systems. Suitable manufacturing processes for this purpose are known per se to the person skilled in the art, for example, from US Pat. No. 6,486,361 or L.E.St. Pierre, Polyethers Part I, Polyalkylene Oxide and other Polyethers, Editor: Norman G. Gaylord; High Polymers Vol. Xm; Interscience Publishers; Newark 1963; P. 130 ff.
  • polyether polyols containing tertiary amino groups and suitable for use as polyol component ii) to prepare the isocyanate-terminated polyurethane prepolymer A) can be prepared from a variety of aliphatic and aromatic amines containing one or more primary or secondary amino groups.
  • Suitable initiators for the preparation of the polyethers containing tertiary amino groups are the following amino compounds or mixtures of these amino compounds: ammonia, methylamine, triethanolamine, N-methyldiethanolamine, N, N, -dimethylethanolamine, ethylenediamine, N, N-dimethylethylenediamine, N, N'-dimethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 2,4-toluenediamine, 2,6-tolylenediamine, aniline, diphenylmethane-2,2'-diamine, diphenylmethane-2, 4'-diamine, diphenylmethane-4,4'-diamine, 1-aminomethyl-3-amino-1, 5,5-trimethylcyclohexane (isophoronediamine), dicyclohexylmethane-4,4'-diamine and xylylene diamine.
  • the amines are particularly preferably ethylenediamine, N, N-dimethylethylenediamine, N, N'-dimethylethylenediamine, triethanolamine and N-methyldiethanolamine.
  • ethylenediamine is used.
  • Polyether polyols containing no tertiary amino groups and suitable for use as polyol component ii) to prepare the isocyanate-terminated polyurethane prepolymer A) or for use in the polyol formulation B) can be prepared from a variety of alcohols having one or more primary or secondary alcohol groups contain.
  • polyethers containing no tertiary amino groups for example, the following compounds or mixtures of these compounds: water, ethylene glycol, propylene glycol, glycerol, butanediol, butanetriol, trimethylolethane, pentaerythritol, hexanediol, 3-hydroxyphenol, hexanetriol, trimethylolpropane, octanediol, neopentyl glycol, 1,4-hydroxymethylcyclohexane, bis (4-hydroxyphenyl ) dimethylmethanes and sorbitol.
  • Suitable cyclic ethers for the preparation of the polyethers described above are alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, styrene oxide or tetrahydrofuran or mixtures of these alkylene oxides. Preference is given to using propylene oxide, ethylene oxide or tetrahydrofuran or mixtures of these. Particular preference is given to using propylene oxide or ethylene oxide or mixtures of these. Most preferably, propylene oxide is used.
  • polyester polyols suitable for the preparation of the isocyanate-terminated polyurethane prepolymer A) and the polyol formulation B) are known per se to those skilled in polyurethane chemistry.
  • polyester polyols can be prepared which are formed by reacting low molecular weight alcohols, in particular ethylene glycol, diethylene glycol, neopentyl glycol, hexanediol, butanediol, propylene glycol, glycerol or trimethylolpropane with caprolactone.
  • low molecular weight alcohols in particular ethylene glycol, diethylene glycol, neopentyl glycol, hexanediol, butanediol, propylene glycol, glycerol or trimethylolpropane with caprolactone.
  • polyfunctional alcohols for the preparation of polyester polyols are 1, 4-hydroxymethylcyclohexane, 2-methyl-l, 3-propanediol, 1,2-butanetriol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol and polybutylene.
  • polyester polyols can be prepared by polycondensation.
  • difunctional and / or trifunctional alcohols with a deficit of dicarboxylic acids or tricarboxylic acids or mixtures of dicarboxylic acids or tricarboxylic acids, or their reactive derivatives, can be condensed to polyester polyols.
  • Suitable dicarboxylic acids are, for example, adipic acid or succinic acid and their higher homologues having up to 16 carbon atoms, furthermore unsaturated dicarboxylic acids such as maleic acid or fumaric acid and aromatic dicarboxylic acids, in particular the isomeric phthalic acids such as phthalic acid, isophthalic acid or terephthalic acid.
  • tricarboxylic acids for example, citric acid or trimellitic acid are suitable.
  • the acids mentioned can be used individually or as mixtures of two or more thereof.
  • Particularly suitable alcohols are hexanediol, butanediol, ethylene glycol, diethylene glycol, neopentyl glycol, 3-hydroxy-2,2-dimethylpropyl-3-hydroxy-2,2-dimethylpropanoate or trimethylolpropane or mixtures of two or more thereof.
  • Particularly suitable sow Ren are phthalic acid, isophthalic acid, terephthalic acid, adipic acid or dodecanedioic acid or mixtures thereof.
  • High molecular weight polyester polyols include, for example, the reaction products of polyfunctional, preferably difunctional, alcohols (optionally together with minor amounts of trifunctional alcohols) and polyfunctional, preferably difunctional, carboxylic acids.
  • polyfunctional, preferably difunctional, alcohols instead of free polycarboxylic acids (if possible), the corresponding polycarboxylic anhydrides or corresponding polycarboxylic acid esters can be used with alcohols having preferably 1 to 3 carbon atoms.
  • the polycarboxylic acids may be aliphatic, cycloaliphatic, aromatic or heterocyclic or both. They may optionally be substituted, for example by alkyl groups, alkenyl groups, ether groups or halogens.
  • polycarboxylic acids examples include succinic acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dimer fatty acid or Trimer fatty acid or mixtures of two or more thereof.
  • Lactones for example based on ⁇ -caprolactone, also called “polycaprolactones", or hydroxycarboxylic acids, for example ⁇ -hydroxycaproic acid, available polyesters, can also be used.
  • polyester polyols of oleochemical origin can be obtained, for example, by complete ring opening of epoxidized triglycerides of an at least partially olefinically unsaturated fatty acid-containing fatty mixture with one or more alcohols having 1 to 12 carbon atoms and subsequent partial transesterification of the triglyceride derivatives to alkylester polyols having 1 to 12 carbon atoms in the alkyl radical getting produced.
  • polycarbonate polyols suitable for preparing the isocyanate-terminated polyurethane prepolymer A) and the polyol formulation B) are known per se to those skilled in polyurethane chemistry.
  • polycarbonate polyols can be prepared by the reaction of diols, such as propylene glycol, 1,4-butanediol or 1,6-hexanediol, diethylene glycol, triethylene glycol or tetraethylene glycol or mixtures of these diols with diaryl carbonates, for example diphenyl carbonates, or phosgene ,
  • the adhesive formulation may additionally contain additives C) known from adhesive technology as formulation auxiliaries contain.
  • additives C) include, for example, the customary plasticizers, fillers, pigments, drying agents, light stabilizers, antioxidants, thixotropic agents, adhesion promoters and optionally further auxiliaries and additives.
  • suitable fillers are carbon black, precipitated silicas, pyrogenic silicic acids, mineral chalks and precipitation precipitates.
  • Suitable plasticizers are, for example, phthalic acid esters, adipic acid esters, alkylsulfonic acid esters of phenol or phosphoric acid esters.
  • thixotropic agents which may be mentioned are pyrogenic silicic acids, polyamides, hydrogenated castor oil derived products or else polyvinyl chloride.
  • Suitable drying agents are, in particular, alkoxysilyl compounds, e.g.
  • CaO Calcium oxide
  • isocyanate group bearing compounds such as e.g. Tosylisocyanate.
  • adhesion promoters known functional silanes are used, such as aminosilanes of the type mentioned above, but also N-aminoethyl-3-aminopropyl-trimethoxysilane, N-aminoethyl-3-aminopropyl-methyl-dimethoxysilane, N-aminoethyl-3-aminopropyl-trimethoxysilane , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, mercaptosilanes, bis (3-triethoxysilylpropyl) amine, bis (3-trimethoxysilylpropyl) amine, oligoaminosilanes, 3-aminopropyhnethyldiethoxysilane, 3-aminopropyltriethoxysilane, triaminofunctional propyltrimethoxysilane, N- (n-butyl ) -3
  • the preparation of the adhesive formulation from the isocyanate-terminated and tertiary amino-containing polyurethane prepolymer A) and the polyol or the polyol mixture B) for producing a composite film is known to those skilled in polyurethane chemistry per se.
  • the additives C) can be added to the polyol or the polyol formulation B) or to the isocyanate-terminated and tertiary amino-containing polyurethane prepolymer A) or both.
  • the additives C) are preferably added to the polyol or the polyol formulation B).
  • the two components A) and B) of the adhesive formulation, to which the additives C) have already been added are mixed together immediately prior to the production of the film composite and introduced into the laminating machine or the commissioned work.
  • the mixing of the components A) and B), where appropriate the additives C) have already been added in the laminating machine itself directly before or in the commissioned work.
  • the adhesive formulation can be used as a 100% system, ie solvent-free, or in a suitable solvent or a suitable solvent mixture for the production of the film composite.
  • the so-called carrier film is coated with the adhesive formulation with an average dry coating weight of 1 to 9 g / m 2 and laminated by bringing into contact with a second film to form the resulting film composite.
  • suitable solvents or solvent mixtures are used, prior to contacting the carrier sheet with the second sheet, remove the solvents completely in a drying channel or other suitable apparatus.
  • the adhesive formulation is preferably used for bonding plastic films, aluminum foils, other metal foils, metal vapor-deposited plastic foils and metal oxide vapor-deposited plastic foils.
  • the percentages are by weight. Unless otherwise indicated, the viscosities were determined at a measuring temperature of 25 ° C. using the Viskotester VT 550 rotational viscometer from Thermo Haake, Düsseldorf, DE with the measuring cup SV and the measuring device SV DIN.
  • the NCO content of the prepolymers or reaction mixtures was determined according to DIN EN 1242.
  • the determination of the monomer migration of aromatic polyisocyanates is based on the method according to ⁇ 35 LMBG (primary aromatic amines are determined).
  • the film composite to be examined (polyethylene terephthalate / aluminum foil / polyethylene film) is used as a roll pattern in a climate chamber at 23 ° C and 50% rel. Moisture stored. After 1.3 and 7 days, 5 layers of film web are unwound and two test specimens each of about 120 mm ⁇ 220 mm are removed for the production of the test bags.
  • test bags (100 mm x 200 mm inside dimensions) with the polyethylene films to the bag interior are filled with 200 ml of 3% aqueous acetic acid solution as a food simulant, sealed and stored at 70 ° C for two hours. Immediately after storage, the bags are emptied and the food simulant solution cooled to room temperature.
  • the migrated polyisocyanates are detected by diazotization of the primary aromatic amines formed in the aqueous food simulant from the aromatic polyisocyanates and subsequent coupling with N- (1-naphthyl) ethylenediamine.
  • the extinction values of the coupling component are measured against the respective zero sample, and the values are converted to a calibration curve in ⁇ g anilinium hydrochloride / 100 ml test food.
  • VH Composite adhesion [N / 1 5 mm] between the aluminum and the polyethylene layer in the following composite 12 ⁇ m polyethylene terephthalate / 9 ⁇ m aluminum foil / 60 ⁇ m polyethylene film
  • MIG migrated polyisocyanates converted into ⁇ g anilinium hydrochloride / 100 ml test food [ ⁇ g anilinium hydrochloride / 100 ml test food]
  • P 1 Polypropylene ether glycol, prepared by means of KOH catalysis, OHZ 112
  • P3 polyester polyol as reaction product of adipic acid and diethylene glycol, OHZ 112, SZ ⁇ 1.3
  • P4 polyesterpolyol as the reaction product of adipic acid and diethylene glycol, OHZ 43, SZ ⁇ 1.5
  • polyester polyol as the reaction product of adipic acid as the acid component and from a mixture of 1 part by weight of trimethylolpropane and 12.8 parts by weight of diethylene glycol as the alcohol component, OHZ 60, SZ ⁇ 2
  • PI 1 polypropylene ether triol prepared by KOH catalysis, OHZ 232 polyisocyanates:
  • NCOl A mixture of 0.1% diphenylmethane-2,2'-diisocyanate, 50.8% diphenylmethane-2,4'-diisocyanate, 49.1% diphenylmethane-4,4'-diisocyanate
  • a polyol mixture of 1102 g Pl and 1102 g P2 is stirred for dehydration for 1 hour at 120 ° C under a vacuum of 20 mbar. It is then cooled to 70 ° C. The resulting polyol mixture is added within about 30 minutes to 2797 g of NCOl. Then, taking advantage of a possibly occurring exothermic reaction is heated to 80 0 C and stirred for 2h. It is stirred at 80 0 C until the isocyanate content is constant. The result is an isocyanate-terminated polyurethane prepolymer with 15.2% NCO and a viscosity of 1630 mPas (25 ° C).
  • Non-inventive tertiary amino-free prepolymer
  • a polyol mixture of 3648 g P9, 486 g PlO and 849 g Pl 1 is stirred for 1 hour at 120 ° C under a vacuum of 20 mbar. It is then cooled to 70 ° C. The resulting polyol mixture is metered in within about 30 minutes to 6017 g of NCOl. Then, using a possibly occurring exothermic reaction is heated to 80 ° C and stirred for 2h. It is stirred at 80 ° C until the isocyanate content is constant. The result is an isocyanate-terminated polyurethane prepolymer with 14.8% NCO and a viscosity of 2140 mPas (25 ° C).
  • the adhesive formulation is prepared by intimately blending the polyol component and the polyisocyanate component.
  • the mixture is prepared with a 1.4-fold molar excess of isocyanate groups and processed immediately.
  • the film composites are produced by a "Polytest 440" solvent-free laminating system from Polytype in Freiburg, Switzerland.
  • the film composites are made of a polyethylene terephthalate / aluminum precompound and a polyethylene film.
  • the aluminum side of the pre-bond is coated with the adhesive formulation, glued to the polyethylene film and then wound up on a roll core.
  • the length of the film composite produced with the adhesive formulation is at least 20 m.
  • the dry application rate of the adhesive formulation is between 1.9 g and 2.8 g and the roller temperature of the commissioned work at 30-40 ° C.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Surgery (AREA)
  • Hematology (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L’invention concerne l’utilisation de prépolymères de polyuréthanne à terminaison isocyanate spéciaux dans des formulations d’adhésifs. Ces formulations d’adhésifs peuvent être utilisées dans des applications où, lors d’un contact direct ou indirect de la couche d’adhésif avec des substrats sensibles à celle-ci, des migrations doivent être évitées ou minimisées.
EP09709573A 2008-02-15 2009-02-06 Adhésif Withdrawn EP2245080A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008009407A DE102008009407A1 (de) 2008-02-15 2008-02-15 Klebstoff
PCT/EP2009/000818 WO2009100853A1 (fr) 2008-02-15 2009-02-06 Adhésif

Publications (1)

Publication Number Publication Date
EP2245080A1 true EP2245080A1 (fr) 2010-11-03

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EP09709573A Withdrawn EP2245080A1 (fr) 2008-02-15 2009-02-06 Adhésif

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US (1) US20110004241A1 (fr)
EP (1) EP2245080A1 (fr)
JP (1) JP2011512434A (fr)
CN (1) CN101945909B (fr)
DE (1) DE102008009407A1 (fr)
WO (1) WO2009100853A1 (fr)

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JP5172861B2 (ja) * 2007-01-30 2013-03-27 ダウ グローバル テクノロジーズ エルエルシー アミン開始ポリオール及びアミン開始ポリオールから作製される硬質ポリウレタンフォーム
DE102009008867A1 (de) 2009-02-13 2010-08-19 Bayer Materialscience Ag Klebstoff
JP6068440B2 (ja) 2011-04-15 2017-01-25 エイチ．ビー．フラー カンパニー 修飾ジフェニルメタンジイソシアネート系接着剤
CA2840641A1 (fr) 2011-06-30 2013-01-03 The Procter & Gamble Company Structure absorbante comprenant un composant eliminateur d'huile
US9315616B2 (en) 2011-07-26 2016-04-19 Dow Global Technologies Llc Blocked prepolymers and acrylic plastisol compositions comprising the blocked prepolymers
CN104044306A (zh) * 2013-03-14 2014-09-17 上海昊海化工有限公司 一种提高了面层粘接强度的连续法制备的酚醛泡沫复合保温板材
JP6634027B2 (ja) * 2014-05-08 2020-01-22 ダウ グローバル テクノロジーズ エルエルシー ガラスを接合するのに有用な水分硬化性ポリウレタン接着剤組成物の硬化の促進
EP3067377B1 (fr) * 2015-03-12 2023-01-18 Henkel AG & Co. KGaA Polyuréthanes à très faible teneur en monomère
DE102015207792A1 (de) * 2015-04-28 2016-11-03 Henkel Ag & Co. Kgaa Polyurethan-basiertes Bindemittel-System
CN107583100B (zh) * 2017-09-26 2019-08-20 华南理工大学 一种Si基聚氨酯医用胶黏剂的制备方法与应用
EP4259685A1 (fr) 2020-12-10 2023-10-18 Covestro Deutschland AG Procédé de préparation d`un polyisocyanate, polyisocyanate, son utilisation et produits de polyaddition préparés à partir de ce dernier

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DE102004018048A1 (de) * 2004-04-08 2005-11-10 Henkel Kgaa Verfahren zur Herstellung von Polyurethan-Prepolymeren

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DE4136490C2 (de) 1991-11-06 2003-04-30 Bayer Ag Lösungsmittelfreie Beschichtungssysteme
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DE102004018048A1 (de) * 2004-04-08 2005-11-10 Henkel Kgaa Verfahren zur Herstellung von Polyurethan-Prepolymeren

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Also Published As

Publication number Publication date
US20110004241A1 (en) 2011-01-06
WO2009100853A1 (fr) 2009-08-20
DE102008009407A1 (de) 2009-08-20
CN101945909B (zh) 2015-04-01
CN101945909A (zh) 2011-01-12
JP2011512434A (ja) 2011-04-21

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