WO2010026002A1 - Procédé servant à coller des feuilles - Google Patents

Procédé servant à coller des feuilles Download PDF

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Publication number
WO2010026002A1
WO2010026002A1 PCT/EP2009/059919 EP2009059919W WO2010026002A1 WO 2010026002 A1 WO2010026002 A1 WO 2010026002A1 EP 2009059919 W EP2009059919 W EP 2009059919W WO 2010026002 A1 WO2010026002 A1 WO 2010026002A1
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WIPO (PCT)
Prior art keywords
adhesive
use according
tdi
molecular weight
diols
Prior art date
Application number
PCT/EP2009/059919
Other languages
German (de)
English (en)
Inventor
Guido Kollbach
Rene Sauer
Norbert Bialas
Christoph Lohr
Andreas Brenger
Patrik Matusik
Original Assignee
Henkel Ag & Co. Kgaa
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Application filed by Henkel Ag & Co. Kgaa filed Critical Henkel Ag & Co. Kgaa
Publication of WO2010026002A1 publication Critical patent/WO2010026002A1/fr

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/14—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose characterised by containing special compounding ingredients
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/14—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose characterised by containing special compounding ingredients
    • B32B23/16—Modifying agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/14—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose characterised by containing special compounding ingredients
    • B32B23/18—Fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B32B29/002—Layered products comprising a layer of paper or cardboard as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • 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
    • C08G18/36—Hydroxylated esters of higher fatty acids
    • 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
    • C08G18/70—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
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond

Definitions

  • the invention relates to liquid one-component adhesives based on isocyanate-reactive prepolymers which are suitable as laminating adhesive for producing composite films.
  • Isocyanate-based laminating adhesives are well known as 1K or 2K adhesives. These adhesives are applied, the substrates glued, then the films are usually stored. This can also happen at elevated temperature. The reaction rate can be accelerated by using aromatic isocyanates. The storage is necessary to ensure sufficient curing of the reactive adhesive. In order for the isocyanates contained to react with polymeric fractions, so as not to produce migratory components. If such monomeric isocyanates react with water, primary aromatic amines are formed in the preferred aromatic isocyanates. These should not come into contact with living resources. Therefore, it is necessary to avoid the formation of these substances.
  • EP 1253159 is known.
  • the prepolymer is the reaction product of polyethers and diisocyanates, in a list including TDI is listed.
  • As a substrate steel aluminum, glass fiber reinforced polyester, PVC, polycarbonate wood or glass are enumerated.
  • a disadvantage of 2-component adhesives in principle the two components that always require a complex mixture. In addition, an exact mixing ratio must be maintained in order to ensure a good bond. Otherwise unreacted isocyanates may be present, which then react to desired impurities.
  • EP 0827995 The describes a solid hot melt adhesive containing a reaction product of polyester alcohols with TDI. This product should also contain only small amounts less than 2% of monomeric diisocyanates. As application temperature 80 0 C are given in the example. Such high temperatures are not suitable for many film materials, as they can be destroyed under the constitutional fact temperature increase. In addition, application in a thin layer by the higher viscosity of hot melt adhesives is difficult.
  • EP 0961493 is known. This describes the bonding of film substrates with 1K PU adhesives. Two different diisocyanates are used, TDI and MDI. Prepolymers with different isocyanate groups are formed. By the reaction, the content of monomeric isocyanates can be less than 1%, a distillation step is not described. Due to the different isocyanates is a uniform fast reaction during bonding and fast processing ability not given.
  • thin layers should be applied quickly.
  • the bonded substrates should cure quickly, so that in a short time the composite films can be further processed into packaging. Nevertheless, the requirements for low levels of migratory aromatic primary amines should be met.
  • the object is achieved by the use of a solvent-free, liquid at room temperature Einkomponentenklebstoffs for bonding composite films, wherein the adhesive comprises a reaction product prepared from low molecular weight polyether diols, polyester diols and / or polyalkylene diols having a molecular weight of 60 to 2000 g / mol, reacted with a high molar excess of TDI greater than 3: 1 and removing the unreacted monomeric TDI by distillation, which may additionally contain auxiliaries and additives.
  • the adhesive comprises a reaction product prepared from low molecular weight polyether diols, polyester diols and / or polyalkylene diols having a molecular weight of 60 to 2000 g / mol, reacted with a high molar excess of TDI greater than 3: 1 and removing the unreacted monomeric TDI by distillation, which may additionally contain auxiliaries and additives.
  • the adhesive suitable according to the invention is a one-component adhesive based on reactive polyurethanes. It should have only a low content of monomeric isocyanates and a low viscosity.
  • Suitable polyols for the preparation of the PU prepolymers are the known polyether diols, polyester diols, polyalkylene diols and / or oleochemical polyols. These should be thin-viscous.
  • polyester polyols examples include polyester polyols. These are preferably preparable by polycondensation.
  • Such polyester polyols include the reaction products of preferably low molecular weight difunctional alcohols and preferably difunctional and / or trifunctional carboxylic acids. Instead of free polycarboxylic acids, the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters with alcohols with preferential Wise 1 to 3 carbon atoms are used.
  • Aliphatic alcohols such as hexanediol, 1,4-hydroxymethylcyclohexane, 2-methyl-1,3-propanediol, polyethylene glycol, ethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, dibutylene glycol and polybutylene glycol are particularly suitable for the preparation of such polyester polyols.
  • the polycarboxylic acids may be aliphatic or cycloaliphatic. They may optionally be substituted, for example by alkyl groups, alkenyl groups or ether groups.
  • polycarboxylic acids examples include succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, dinnerfatty acid or tri-fatty acid or mixtures of two or more thereof.
  • the amounts are chosen so that terminally OH-functional polyester diols are obtained.
  • no aromatic carboxylic acids are included.
  • polyalkylenediols can be used.
  • these are aliphatic alcohols having 2 OH groups per molecule.
  • the OH groups can be both primary and secondary.
  • Suitable aliphatic alcohols include, for example, ethylene glycol, propylene glycol, butanediol-1, 4, pentanediol-1, 5, hexanediol-1, 6, heptanediol-1, 7, octanediol-1, 8 and their higher homologs or isomers, such as for the skilled person from a gradual extension of the hydrocarbon chain by one CH2 group or by introducing branches into the carbon chain.
  • These can also be used proportionally mixed with other polyols. For example, these may contain up to 30 carbon atoms.
  • reaction products of low molecular weight polyfunctional alcohols with alkylene oxides can be used as the polyol component.
  • the alkylene oxides preferably have 2 to 4 carbon atoms.
  • Suitable examples are the reaction products of ethylene glycol, propylene glycol, the isomeric butanediols or hexanediols with ethylene oxide, propylene oxide or butylene oxide, or mixtures of two or more thereof.
  • Suitable polyols are further obtained by polymerization of tetrahydrofuran.
  • polyether polyols are the reaction products of polyfunctional low molecular weight alcohols with propylene oxide under conditions where at least partially secondary hydroxyl groups formed, particularly suitable.
  • Particularly suitable are polyether polyols having a molecular weight of about 100 to about 2000, preferably from 200 to 1200 g / mol.
  • Oleochemical polyols can also be used.
  • Oleochemical polyols are understood to be polyols based on natural oils and fats, e.g. the reaction products of epoxidized fatty substances with mono-, di- or polyfunctional alcohols or glycerol esters of long-chain fatty acids which are at least partially substituted by hydroxyl groups.
  • oleochemical polyols are ring-opening and transesterification products of epoxidized fatty acid esters of lower alcohols, ie of epoxidized fatty acid methyl, ethyl, propyl or butyl esters.
  • the oleochemical polyols also include the reaction products of epoxidized fatty alcohols with C 2 -C 8 alcohols having the functionality 1 to 10, in particular 2 to 4, in the molar ratio of the epoxide groups to the hydroxyl groups of 1: 1 to 1:10.
  • castor oil or dimerdiols obtained by complete ring opening of epoxidized triglycerides of an at least partially olefinically unsaturated fatty acid-containing fat mixture with one or more alcohols having 1 to 12 carbon atoms and subsequent partial transesterification of the triglycephodehydes to alkylester polyols 1 to 12 C-atoms are prepared in the alkyl radical.
  • the oleochemical polyols may have hydroxyl numbers of 50 to 400 (mg KOH / g solids), preferably 100 to 300. These polyols can have a functionality between 2 and 3.
  • the polyols can be used individually or in a mixture. They should have a molecular weight of 60 to 2000 g / mol, in particular from 200 to 1200 g / mol. It should preferably be at temperatures up to 30 0 C liquid polyols. Particularly preferred are polyether polyols, optionally also in a mixture with oleochemical polyols (number average molecular weight, M N , as determined by GPC). The polyols can be mixed and reacted together with the isocyanates, but no other procedure, the polyols converts separately, wherein in a later step, the two prepolymers are mixed.
  • the isocyanate used to prepare the prepolymers are toluene diisocyanate (TDI), its isomers or oligomers. If appropriate, proportions of other diisocyanates may also be added, for example the aromatic polyisocyanates known in urethane chemistry, such as MDI. Preference is given to using technical mixtures of TDI.
  • TDI toluene diisocyanate
  • MDI urethane chemistry
  • a further embodiment converts the above-mentioned polyol separately with the other aromatic isocyanates, in particular MDI, to polymers, which are then reduced by distillation in the monomer content.
  • the prepolymers are then mixed later, but the amounts should be below 25 wt .-% based on the amount of TDI polymer.
  • the prepolymers are prepared by methods known per se.
  • the isocyanates and the polyols are mixed and reacted. If necessary, the reaction can be accelerated by heating.
  • the amount of isocyanates is chosen so that a molar excess of diisocyanate is used.
  • the ratio NCO: OH should be more than 3: 1 to 10: 1, in particular up to 5: 1.
  • the purification step can be carried out by processes known per se, such as extraction, chromatography or crystallization processes individually or, if appropriate, in combination of the processes listed.
  • the concentration of the monomeric isocyanates should be below 0.1 wt .-%, preferably below 0.05 wt .-%, based on the prepolymer.
  • additives and auxiliaries may also be added to the prepolymer for formulating the adhesive.
  • additives and auxiliaries may be, for example, plasticizers, stabilizers, antioxidants, adhesion promoters, resins, polymers, dyes or fillers.
  • the adhesive useful in this invention contains at least one tackifying resin.
  • the resin causes additional stickiness.
  • all resins can be used that are compatible, i. form a largely homogeneous mixture.
  • resins which have a low softening point below 100 ° C. are, for example, aromatic, aliphatic or cycloaliphatic hydrocarbon resins, as well as modified or hydrogenated versions thereof.
  • the resins generally have a low molecular weight below 1500 g / mol, in particular below 1000 g / mol. They should be chemically inert so that any functional groups present do not react with the PU prepolymer. Preference is also given to using liquid resins.
  • the resin can be used in an amount of 0 to 50 wt .-%, preferably up to 25 wt .-% based on the adhesive.
  • plasticizers for example, medicinal white oils, naphthenic mineral oils, paraffinic hydrocarbon oils, polypropylene, polybutene, polyisoprene oligomers, hydrogenated polyisoprene and / or polybutadiene oligomers, phthalates, adipates, benzoate esters, vegetable or animal oils and derivatives thereof can be used .
  • Suitable stabilizers or antioxidants which can be used are phenols, high molecular weight, hindered phenols, polyfunctional phenols, sulfur and phosphorus phenols or amines.
  • adhesion promoters are preferably organofunctional silanes, such as hydroxyfunctional, (meth) acryloxyfunctional, mercapto-functional, amino-functional or epoxy-functional silanes.
  • NCO groups may have reactive groups with NCO groups, or they may not react with isocyanates. It may be dialkoxy or Thal koxysilane, in particular with methoxy, ethoxy, propoxy or butoxy. Particularly suitable are amino or epoxy silanes. In a preferred embodiment, 0.1 to 3 wt .-% of such silanes are added to the adhesive.
  • a suitable adhesive according to the invention may also contain catalysts.
  • catalysts are organometallic compounds, such as iron or tin compounds, for example, 1, 3-dicarbonyl compounds of iron or tin, or tin (II) carboxylates or dialkyltin (4) dicarboxylates.
  • organometallic compounds such as iron or tin compounds, for example, 1, 3-dicarbonyl compounds of iron or tin, or tin (II) carboxylates or dialkyltin (4) dicarboxylates.
  • DABCO 1,4-diazabicyclo [2.2] octane
  • DBU 1,8-diazabic
  • the amount of catalysts may be between 0.01 to 1 wt .-%, another embodiment operates without a catalyst.
  • the viscosity of these suitable laminating adhesives should be between 200 to 5000 mPa.s at application temperature, preferably 500 to 3000 mPas, in particular at 20 to 5O 0 C (measured Brookfield viscometer, according to ISO 2555). Since rapid further processing is necessary, the adhesives should be solvent-free.
  • the known flexible films can be used as film materials for producing the multilayer films.
  • substrates of thermoplastic plastics in film form for example polyolefins, such as polyethylene (PE) or polypropylene (PP, CPP, OPP), polyvinyl chloride (PVC), polystyrene (PS), polyesters, such as PET, polyamide, organic Polymers such as cellophane, metal foils or paper as substrates are possible.
  • the film matehals may also be modified, e.g. by modifying the polymers having functional groups, or additional components, for example, pigments, dyes, or foamed layers may be included in the film. It may be colored, printed, colorless or transparent films.
  • the procedure according to the invention glues two or more, identical or in particular different films together.
  • the outer film may already be printed in color prior to application of the laminating adhesive.
  • a liquid Kaschierklebstoff suitable according to the invention is then applied. This can be achieved by printing methods known per se, for. For example, with anilox rollers, burnishing, done, the adhesive is sprayed on nozzles, or the adhesive is applied via slot dies.
  • the application method should be selected depending on the viscosity of the adhesive.
  • the adhesive according to the invention has a low viscosity, des- because of an order in a thin layer thickness of 1 to 25 .mu.m, in particular from 2 to 15 microns possible.
  • the multilayer film is produced by joining together an outer layer coated with the adhesive and a second film.
  • the bonding can be done under pressure and elevated temperature.
  • several films can be glued together.
  • Such laminating methods are known to the person skilled in the art.
  • the multilayer films can be wound up and stored immediately. In this case, a good bond is achieved. Furthermore, a complete reaction of individual residual reactive groups should be done quickly. This can be achieved by increased temperature, increased humidity or catalysis of the isocyanate groups. Usually after 48 hours, especially after 24 hours, the films can be processed further. Then also the levels of migratory constituents of the adhesive, e.g. Isocyanates or reaction products of the adhesive, such as primary aromatic amines lowered so far that the requirements for the content of such components are met.
  • migratory constituents of the adhesive e.g. Isocyanates or reaction products of the adhesive, such as primary aromatic amines
  • the polyols from non-aromatic polyols, a high flexibility of the composite film is achieved.
  • the adhesion to the various film substrates is very good. This is also evident in the mechanical stability of the laminating-bonded substrates.
  • the prepolymer has a viscosity of 2120 mPas at 60 ° C.
  • Example 2 are mixed and 0.5 part of UL 28 (catalyst) under rapid
  • the films are stored for 48 hours, after which a packaging can be produced.
  • a correspondingly stored film is extracted according to RiLi 2002/72 EC and investigated for primary aromatic amines.
  • CPP film Casted polypropylene (Nordenia), type PP0946.080 (thickness 50 ⁇ m) PE-FoNe polyethylene film (thickness 12 ⁇ m).

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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 l'utilisation d'un adhésif monoconstituant sans solvant et liquide à la température ambiante afin de coller des feuilles composées, cet adhésif comprenant un produit de transformation de polyéther diols de faible poids moléculaire, de polyester diols et/ou polyalkyl diols possédant un poids moléculaire entre 60 et 2000 g/mol, transformé avec un excédent molaire élevé de TDI, le TDI monomère non transformé étant supprimé par distillation. L'invention concerne également des produits adjuvants et des produits d'addition.
PCT/EP2009/059919 2008-08-26 2009-07-31 Procédé servant à coller des feuilles WO2010026002A1 (fr)

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DE102008039679A DE102008039679A1 (de) 2008-08-26 2008-08-26 Verfahren zum Kaschieren von Folien
DE102008039679.6 2008-08-26

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WO2017127559A1 (fr) * 2016-01-19 2017-07-27 H.B. Fuller Company Composition de polyuréthane adhésive à un composant, procédé de fabrication d'un stratifié et stratifié

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ITUB20156312A1 (it) * 2015-12-04 2017-06-04 Soc Azionaria Per Lindustria Chimica Italiana S A P I C I S P A Adesivi poliuretanici monocomponenti e senza solvente per laminazione

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WO2002048227A2 (fr) * 2000-12-15 2002-06-20 Henkel Kommanditgesellschaft Auf Aktien Prepolymeres polyurethane comprenant des groupes nco et une faible teneur en polyisocyanate monomere

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JPH11341477A (ja) 1998-05-25 1999-12-10 Niles Parts Co Ltd 画像記憶処理装置
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WO2002034858A1 (fr) * 2000-10-23 2002-05-02 Henkel Kommanditgesellschaft Auf Aktien Adhesif reactif pauvre en monomeres, a durcissement etage
WO2002048227A2 (fr) * 2000-12-15 2002-06-20 Henkel Kommanditgesellschaft Auf Aktien Prepolymeres polyurethane comprenant des groupes nco et une faible teneur en polyisocyanate monomere

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Publication number Priority date Publication date Assignee Title
WO2017127559A1 (fr) * 2016-01-19 2017-07-27 H.B. Fuller Company Composition de polyuréthane adhésive à un composant, procédé de fabrication d'un stratifié et stratifié
US10836939B2 (en) 2016-01-19 2020-11-17 H.B. Fuller Company One-part polyurethane adhesive composition, method of making a laminate, and laminate

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