WO2011000619A1 - 2-komponenten kaschierklebstoff - Google Patents

2-komponenten kaschierklebstoff Download PDF

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Publication number
WO2011000619A1
WO2011000619A1 PCT/EP2010/056310 EP2010056310W WO2011000619A1 WO 2011000619 A1 WO2011000619 A1 WO 2011000619A1 EP 2010056310 W EP2010056310 W EP 2010056310W WO 2011000619 A1 WO2011000619 A1 WO 2011000619A1
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WO
WIPO (PCT)
Prior art keywords
component
composition according
epoxide
groups
adhesive
Prior art date
Application number
PCT/EP2010/056310
Other languages
German (de)
English (en)
French (fr)
Inventor
Holger Eichelmann
Michael HÖLTGEN
Original Assignee
Henkel Ag & Co. Kgaa
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 Henkel Ag & Co. Kgaa filed Critical Henkel Ag & Co. Kgaa
Priority to BRPI1014251A priority Critical patent/BRPI1014251A2/pt
Priority to ES10722327.3T priority patent/ES2527817T3/es
Priority to CN2010800295953A priority patent/CN102471457A/zh
Priority to JP2012518839A priority patent/JP5651172B2/ja
Priority to EP10722327.3A priority patent/EP2448989B1/de
Publication of WO2011000619A1 publication Critical patent/WO2011000619A1/de
Priority to US13/325,143 priority patent/US20120156382A1/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/182Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents
    • C08G59/184Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents with amines
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22Di-epoxy compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22Di-epoxy compounds
    • C08G59/28Di-epoxy compounds containing acyclic nitrogen atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins

Definitions

  • the invention relates to a 2-component binder based on an epoxy component and an amine component which have a high proportion of aromatic constituents.
  • the invention further relates to a 2K laminating adhesive and a 2K coating agent containing this binder system.
  • US Pat. No. 7,258,543 is known. It describes an aqueous-based composition which contains a polyepoxide resin which has at least one tertiary amino group, where the amino group has one or two substituents each carrying an epoxy group.
  • crosslinkers aqueous polyamino compounds are described.
  • EP 1086 190 is known. This describes a reactive system for film substrates which comprises an epoxy resin based on bisphenol A, F, resorcinol or aliphatic polyols with epoxide groups, as well as a crosslinker based on amino or carboxyl group-containing compounds. Crosslinking agents containing aromatic groups are not described.
  • DE 4128487 is known. This describes epoxide dispersions which can crosslink via amine hardeners.
  • the epoxy binders are described as reaction products of aromatic polyols and polyepoxides. Amine-containing polyepoxides are not described, so no amines are described with aromatic nuclei and primary amino groups.
  • EP 1219656 is known. This claims a coating composition having gas barrier properties wherein one component is an epoxy resin having at least one epoxyamine moiety and being a derivative of mXDA, and the hardener is a compound by reacting XDA with Monocarboxylic acid and polyfunctional compounds, which then form an amide group.
  • EP 1437393 is known. This claims an adhesive with an epoxy resin component and a hardener for these epoxy resins, wherein the epoxy resin has at least 40% of XDA structures.
  • mXDA or pXDA are generally used as crosslinking agents. These are primary aromatic amines. Such amines can migrate into the film materials under various environmental conditions. Therefore, such amines should be contained in adhesives that can come into contact with food in the bonded product, if possible in a reduced amount.
  • Another object of the invention are 2K laminating adhesives or 2K coating compositions, based on the 2K composition.
  • Another object of the invention is the use of such coating compositions for the production of coated films which have only a low permeability to gaseous or diffusible substances, for example for oxygen or flavorings.
  • a further object of the invention is the provision of adhesives or coating compositions from corresponding the binders, which have a low processing viscosity without the addition of solvents.
  • the invention is achieved by a 2-component composition consisting of a component A comprising a polymer having a molecular weight of 250 to 10,000 g / mol, which has at least 2 epoxide groups per molecule, and a component B, containing at least one compound of the formula (I) (I) R 1 - phenyl - (- O - R 2 ) a
  • R 1 H, Ci to C 6 - alkyl
  • R 2 -O-CH 2 -CHOH-CH 2 -NH-CH 2 -phenyl- CH 2 - NH 2 ,
  • epoxide / amine ratio of components A and B is between 0.75: 1 to 1, 25: 1.
  • a component of the 2-component binder composition according to the invention consists of the component A, a polymer based on polyesters, polyamides, poly (meth) acrylates, polyurethanes, polyolefins or aromatic polyepoxides. It is necessary according to the invention that these polymers have at least two epoxide groups per molecule. In this case, the epoxide groups can be incorporated via epoxide-functional building blocks directly in the polymer synthesis; alternatively, it is possible for polymers having double bonds to be converted into epoxide groups. Another possibility is to react polymers with OH groups or with isocyanate groups with low molecular weight epoxy compounds, which additionally have a group reactive with the OH group or the isocyanate group.
  • Suitable base polymers are OH-functionalized polyolefins.
  • Polyolefins are known in the art and can be obtained in many molecular weights.
  • Such polyolefins based on ethylene, propylene or higher-chain ⁇ -olefins as homo- or copolymer can be functionalized either by copolymerization of monomers containing functional groups or by grafting reactions.
  • Another possibility is that these Base polymers are subsequently provided, for example, by oxidation with OH groups.
  • base polymers for the preparation of component (A) can be selected from the group of olefin (co) polymers, such as ethylene-acrylate, butyl rubber; Natural rubber; Styrene copolymers, individually or in mixture, wherein the copolymers are random, alternating, graft or block copolymers.
  • olefin (co) polymers such as ethylene-acrylate, butyl rubber; Natural rubber; Styrene copolymers, individually or in mixture, wherein the copolymers are random, alternating, graft or block copolymers.
  • thermoplastic elastomers which are known per se.
  • thermoplastic rubbers such thermoplastic elastomers are in particular selected from the group of styrene block polymers, for example styrene-diene copolymers (SBS, SIS) styrene-ethylene / butylene copolymers (SEBS) or styrene-ethylene / propylene-styrene copolymers (SEPS, SEP).
  • SBS styrene-diene copolymers
  • SEBS styrene-ethylene / butylene copolymers
  • SEPS styrene-ethylene / propylene-styrene copolymers
  • olefinic polymers which are suitable as base polymers for the preparation of component (A) are, for example, homo- or copolymers of 1,3-butadiene, 2-methyl-1,3-butadiene (isoprene), 2-methyl-1,3 hexadiene, 2-methyl-1, 3-cyclopentadiene and other copolymerizable monomers.
  • the above-mentioned olefinic base polymers may contain a plurality of unsaturated double bonds. These may be contained in the polymer main chain and / or they may be contained in side chains. In particular, vinylic functional group should be included. These double bonds can be reacted by known methods, so that the base polymers have epoxide groups.
  • the epoxy-containing polymers thus obtained are suitable as component (A) in the context of the invention.
  • Other suitable base polymers having a polyolefin structure may contain functional groups, for example OH groups. These can then be reacted by known processes with bifunctional compounds, these compounds having an epoxide group. should point. Suitable polymers for component (A) with epoxide groups are obtained.
  • polyester polyols are polyester polyols. These can be obtained by polycondensation of acid and alcohol components, in particular by polycondensation of a polycarboxylic acid or a mixture of two or more polycarboxylic acids and a polyol or a mixture of two or more polyols.
  • Suitable polycarboxylic acids are those having an aliphatic, cycloaliphatic, aromatic or heterocyclic basic body.
  • free carboxylic acids and their acid anhydrides or their esters with Ci -5 -monoalcohols can be used for polycondensation.
  • diols for the reaction with the polycarboxylic acids a large number of polyols can be used.
  • aliphatic polyols having 2 to 4 primary or secondary OH groups per molecule and 2 to 20 carbon atoms are suitable. It is also possible to use partially higher-functionality
  • polyether polyols can be used as the diol component.
  • Polyether polyols are preferably obtained by reacting low molecular weight polyols with alkylene oxides, for example the reaction products of ethylene glycol, propylene glycol or the isomeric butanediols with ethylene oxide, propylene oxide or butylene oxide. Methods for preparing such polyester polyols are known to those skilled in the art and these products are commercially available.
  • Another class of base polymers contains a polyamide backbone.
  • Polyamides are reaction products of diamines with di- or polycarboxylic acids. By targeted synthesis, it is possible to introduce terminal OH groups in polyamides.
  • polyols based on acrylates are polymers prepared by polymerization of (meth) acrylic esters, such as acrylic acid, methacrylic acid, crotonic acid or maleic acid esters.
  • Usual Ci are preferred to C 5 alkyl esters of (meth) acrylic acid polymehsiert. It may also contain OH-containing monomers. Optionally, other copolymerizable monomers may also be included.
  • Other suitable poly (meth) acrylates should have at least two OH groups. These may preferably be present terminally in the polymer.
  • Such OH-functional poly (meth) acrylates are known to the person skilled in the art. These can then be functionalized by known methods to epoxy groups. Another procedure results directly acrylate polymers with epoxy groups. It will be
  • the OH group of the base polymers can be prepared by known methods
  • low molecular weight compounds are reacted which contain an epoxide group and one reacting with the OH group.
  • groups are NCO groups, halogens, anhydrides or esters.
  • polymers are obtained which have epoxide groups and are suitable as component A.
  • polyurethanes are polyurethanes. These can be prepared by reacting polyols, in particular diols and / or triols with di- or th-isocyanate compounds. The proportions are chosen so that terminally NCO-functionalized prepolymers are obtained. In particular, the polymers should be linear, i. are produced predominantly from diols and diisocyanates. An additional use of small amounts of trifunctional monomers is possible.
  • polyols and polyisocyanates which can be used in the synthesis of the PU polymers are known to the person skilled in the art. These are the monomeric aliphatic, cycloaliphatic or aromatic polyisocyanates known for adhesive application, in particular di- or triisocyanates are used. It is also possible to use known oligomers, such as biurets or isocyanurates. These are reacted, for example, with those polyols which are also known as polyol for the synthesis of polyesters, in particular with diols. Processes for the preparation of the PU prepolymers are also known to the person skilled in the art.
  • the amount of isocyanates is chosen in such a stoichiometric excess that NCO-functional PU prepolymers are obtained.
  • NCO OH ratio
  • a molecular weight increase in the synthesis can be avoided.
  • asymmetric isocyanates the proportion of unreacted residual monomers in the prepolymer can be reduced.
  • Another method of preparation distills off an excess of unreacted isocyanates from the reaction mixture. Subsequently, the isocyanate groups can be reacted with epoxide group-containing alcohols.
  • Preferred polymers with epoxy groups are the known polyepoxide resins which carry at least two epoxide groups per molecule.
  • the epoxide equivalent of these polyepoxides can be selected within wide limits, for example between 50 and 1000 g / mol of epoxide.
  • the polyepoxides may in principle be saturated, unsaturated, cyclic or acyclic, aliphatic, alicyclic, aromatic or heterocyclic polyepoxide compounds.
  • suitable polyepoxides include the known polyglycidyl ethers prepared by reaction of epichlorohydrin with a polyphenol in the presence of alkali.
  • Suitable polyphenols for this purpose are, for example, resorcinol, pyrocatechol, hydroquinone, bisphenol A (bis (4-hydroxyphenyl) -2,2-propane), bisphenol F (bis (4-hydroxyphenyl) methane), bis (4-hydroxyphenyl) - 1, 1 -isobutane, 4,4'-dihydroxybenzophenone, bis (4-hydroxyphenyl) -1, 1-ethane or 1, 5-hydroxynaphthalene. It is also possible to react corresponding amino compounds to form epoxy resins. Likewise, hydroxyalkyl or aminoalkylaromatics can be reacted. In particular, at room temperature flowable epoxy resins are used, which generally have an epoxide equivalent weight of 50 to about 300 g / mol of epoxide,
  • component A is epoxy compounds of the formula (II) which have an aromatic nucleus.
  • (II) R 3 ring - (- CH 2 -N (R 4 ) b ) c
  • R 4 C 3 to Cs-alkyl with an epoxide group
  • Ring phenyl, diphenyl, naphthyl,
  • This aromatic nucleus may comprise, for example, phenyl, diphenyl, naphthyl units, which may optionally also carry alkyl substituents.
  • these are building blocks which are not substituted in the para position with the functional radicals.
  • Suitable examples of such aromatic building blocks are 1, 3 substituted phenyls, 2,2 'or 2,4' substituted biphenyls, 2,4 'substituted methylene diphenyl structures.
  • Particularly suitable are epoxy group-substituted derivatives of m-xylylenediamine, m-xylylene diisocyanate or resorcinol.
  • the polyepoxide compounds of component A which are suitable according to the invention should have from 2 to 10 epoxide groups, in particular 2, 4 or 6, per molecule.
  • a particular embodiment of the polyepoxide compound has the epoxide groups at the chain end or as the side chain end of a compound.
  • the polyepoxide compounds can be present individually or as a mixture with different structures.
  • the molecular weight (number average molecular weight, M N , as determinable via GPC) should be between 200 to 10,000 g / mol, preferably 250 to 5,000 g / mol, in particular 250 to 2,500 g / mol. Low molecular weights are preferred for solvent-free adhesives, and higher molecular weights can be selected for solvent-borne systems.
  • the binder system according to the invention contains aromatic compounds which must have primary amino groups. These are compounds of the formula
  • R 1 H, Ci to C 6 - alkyl
  • R 2 -O-CH 2 -CHOH-CH 2 -NH -CH 2 -phenyl- CH 2 - NH 2
  • di- or triepoxides with aromatic nuclei are the reaction products of catechol, resorcinol, hydroquinone, pyrogallol, phioroglucinol, 2,4-hydroxytoluene, and optionally also 1, 3 or 1, 5 or 1, 6-di - naphthol suitable. These can be reacted with, for example, epichlorohydrin or analogous compounds to di- or th-epoxide substituted compounds.
  • aromatic diamine for further reaction in particular the xylylenediamine (XDA) is suitable as the amine component, in particular the mXDA.
  • the quantitative ratio of amino groups of the diamine, such as XDA, to the glycidyl groups should be selected so that an excess of amino groups is present and all epoxide groups are reacted.
  • an epoxide-free component B is formed.
  • the epoxide / N H ratio should be 0.9: 4 to 1.1: 4 (calculated as H-acidic NH groups).
  • Another embodiment selects the amount of epoxide groups to the amount of NH functionality such that there is an excess of unreacted XDA.
  • component B is a mixture of XDA and a compound of formula (I).
  • the starting materials should be selected so that at most 50% by weight, based on the component A, of unreacted diamine are present.
  • Another embodiment selects the quantitative ratios for the preparation of component B such that a molecular weight build-up is achieved. occurs.
  • the epoxide / NH ratio for example, from 1, 1: 4 to 1, 6: 4.
  • suitable hardener component B is known.
  • the suitable di- or tri-epoxide compounds are mixed together with the appropriate amount of the XDA, in particular mXDA, and if appropriate reacted with slight heating. This can optionally also be carried out in solvents. These can be removed by distillation after the reaction if necessary.
  • the compounds suitable according to the invention as component B have primary amino groups. Furthermore, they contain secondary amino groups and in addition OH groups.
  • the molecular weight of these compounds can be between about 450 to 2500 g / mol, in particular up to about 1500 g / mol.
  • the suitable epoxy resins as component A and the polyamino compounds of component B are 2K compositions according to the invention.
  • the two components are mixed in the liquid state, wherein the ratio of amino groups (as NH group) to epoxy groups should be approximately equimolar. In particular, the ratio is about 0.75: 1 to 1.25: 1, in particular 0.95: 1 to 1:05: 1, in order to avoid an excess of unreacted amino groups.
  • the two components are stored separately and mixed before processing. Thereafter, the components crosslink.
  • 2K laminating adhesives can be made from the compositions described above.
  • additional ingredients such as solvents, plasticizers, catalysts, stabilizers, adhesion promoters, pigments or fillers.
  • the adhesive useful in this invention contains at least one tackifying resin.
  • the resin causes additional stickiness.
  • all resins can be used which are compatible, ie form a substantially homogeneous mixture.
  • the resins generally have a low molecular weight below 1500 g / mol, in particular below 1000 g / mol.
  • the resin can be used in an amount of 0 to 50 wt .-%, preferably up to 20 wt .-% based on the adhesive.
  • plasticizers may also be present, such as 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 their derivatives are used.
  • plasticizers are suitable which are harmless under food law.
  • Suitable stabilizers or antioxidants which may be used are phenols, sterically hindered phenols of high molecular weight, polyfunctional phenols, sulfur and phosphorus-containing phenols or amines.
  • silane compounds as adhesives to the adhesive.
  • adhesion promoters it is possible to add the known organofunctional silanes, such as (meth) acryloxy-functional, epoxide-functional, amine-functional or non-reactively substituted silanes.
  • Examples of these are vinyltrialkoxysilane, alkyltrialkoxysilane, tetraalkoxysilanes, 3-acryloxypropyltrialkoxysilane, 3-methacryloxypropylthalkoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylthmethoxysilane, 3-glycidyloxymethyltrimethoxysilane, 3-glycidyloxy - Methyltriethoxysilane, 2-Glycidyloxyethylthmethoxysilan, or corresponding Di alkoxydehvate, preferably butoxy, propoxy, especially methoxy or ethoxy groups are suitable.
  • an adhesive according to the invention may also contain catalysts.
  • catalysts it is possible to use all known compounds which can catalyze the reaction of amino group and epoxide group.
  • titanates such as tetrabutyltitanate or titanium tetraacetylacetonate
  • Bismuth compounds such as bismuth tris-2-ethylhexanoate
  • Tin carboxylates such as dibutyltin dilaurate (DBTL), dibutyltin diacetate or dibutyltin diethylhexanoate
  • Tin oxides such as dibutyltin oxide and dioctyltin oxide
  • Organoaluminum compounds such as aluminum thiosacetylacetonate
  • Latex compounds such as zirconium tetraacetylacetonate
  • Amine compounds or their salts with carboxylic acids such as octylamine, cyclohexylamine, benzylamine, dibutylamine, monoethanolamine, triethanolamine, diethylenetriamine, thethylenetetramine, triethylenediamine, guanidine, morpholine, N-
  • a particular embodiment of the invention still uses pigments for the coating compositions. These are finely divided pigments, for example having a particle size ⁇ 5 microns.
  • One embodiment of the invention uses platelet-shaped pigments which can be dispersed in a component of the binder. They are then present in finely divided form, ie the pigments or fillers are dispersed in the form of platelets, ie they have only a small thickness.
  • Such pigments are known to the person skilled in the art, for example phyllosilicates of different composition.
  • Another way of working uses nanoparticles. These usually have a particle size ⁇ 500 nm, in particular less than 100 nm.
  • Such nanopigments may, for example, be those based on TiO 2, SiO 2, F 2 O 3 or similar oxides or ox hydrates. Those skilled in the art are familiar with such pigments. He can select them according to usual criteria and finely dispersed by means of known methods in one or both binder components.
  • the adhesives may also contain solvents. These are the usual solvents that can evaporate at temperatures up to 120 0 C. The solvent can be selected from the Grupppe the tables aliphatic hydrocarbons, aromatic hydrocarbons, ketones, in particular dC 4 -alcohols or water.
  • the 2K adhesive is solvent-free.
  • the adhesives are particularly suitable for coating large areas, they should have a low viscosity at application temperature of about 20 to 9O 0 C.
  • the viscosity of the lamination adhesives according to the invention, measured immediately after mixing the ingredients, is to be between 200 to 5000 mPa.s at application temperature, preferably 300 to 3000 mPas (at 20 to 6O 0 C, Brookfield viscometer, according to EN ISO 2555).
  • the known flexible films can be used as sheet materials for producing 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 known adjuvants and additives may be added to component A or to component B as long as they do not react with the additives. It may contain solvents, a particular embodiment of the invention, however, operates solvent-free. In particular, by selecting component A and component B, be ensured that at room temperature such as 25 0 C, a low-viscosity mixture of component A and B is obtained.
  • the adhesive according to the invention can be used in particular as a laminating adhesive.
  • the adhesives are applied in a thin layer and a film.
  • the optionally contained solvents should evaporate, then a second film is applied to the adhesive layer and pressed with pressure.
  • the inventive selection with low viscosity and solvents can be avoided.
  • a particular embodiment of the invention is the provision of a water-soluble 2K adhesive. It is advantageous if the components have an increased number of polar groups in order to have improved water solubility or water miscibility. In this case, it is additionally advantageous to use emulsifiers or dispersing aids as further constituents. These also support the dispersibility of the components in water in small quantities.
  • the emulsifiers should be mixed in amounts of 0.1 to 5 wt .-% based on the composition. After mixing the two components and crosslinking, a network is formed. This is no longer soluble in water, but still has good barrier properties.
  • Another embodiment of the invention employs 2K compositions for 2K coating agents.
  • These coating compositions may in principle contain the same constituents as described for the laminating adhesives. However, care must be taken when selecting that the coating compositions after crosslinking have a smooth, non-sticky surface. Good adhesion should only exist to the substrate on which the coating agent is applied in liquid form.
  • the invention likewise relates to a multilayer film which is adhesively bonded to a laminating adhesive which is suitable according to the invention;
  • the known plastic films can be used as substrates, for example polypropylene, polyethylene, polyester, PVC, polyamide or others.
  • Onto this film a continuous layer is produced with an adhesive according to the invention, which is bonded immediately after application with a second identical or different film.
  • An embodiment of the invention works with transparent films, it is expedient if the adhesive according to the invention is also transparent and not discolored. It may be contained in these multilayer films and other non-plastic films, such as paper or metal foils.
  • a particularly advantageous property of the adhesive layers according to the invention is an increased barrier effect of the layer. It has been found that flavoring substances can penetrate such multilayer films less than conventionally bonded films. Also, an improved stability against diffusion of gases, such as oxygen, or water vapor is noted.
  • the adhesive according to the invention shows a good adhesion between the different layers. It shows no bubbles or imperfections in the adhesive layer.
  • Another object of the invention is the use of the composition according to the invention for producing coatings on flexible composite substrates.
  • the additives and auxiliaries mentioned above may be contained in the coating composition.
  • the coating compositions are liquid or can be applied by heating up to 90 0 C flowable. These coatings are flexible after crosslinking and can therefore be used especially for flexible multilayer films.
  • the suitable binders can be further processed in a simple manner into 2-component coating compositions or 2-component adhesives.
  • these adhesives or coating agents on film substrates composite films are obtained which have high barrier properties.
  • the barrier properties can be related to various components, for example, the diffusion of oxygen can be reduced. Another embodiment reduces the diffusion of water. Furthermore, it is possible to reduce the diffusion of flavorings.
  • the composite films produced according to the invention have a high flexibility. They may be transparent, i. they contain only nanoparticles as fillers or no fillers, but they can also be colored or pigmented layers.
  • the adhesion to the different substrate materials is good. Even with mechanical loading of composite materials, such as the bonded films, no separation between bonded surfaces is observed.
  • packaging can be produced. Due to the barrier effect, such packages are suitable for sensitive articles, for example for food or pharmaceutical goods.
  • Component A tetraglycidyl-m-xylylenediamine
  • Epoxide equivalent weight about 102 g / mol epoxide
  • Component B m-resorcinol diglycidyl ether is reacted with m-xylylenediamine in a molar ratio of 1: 3 (amine equivalent weight about 55 g / mol of NH).
  • the 2K adhesive (example 1 and example 2) has a viscosity of 1000 mPas at 40 0 C.
  • a commercially available polyurethane lamination adhesive from Henkel (trade name UR 7782 with UR 6083) is mixed.
  • the one component consists of an OH-containing polyester binder, molecular weight about 2200 g / mol and the crosslinker component of aromatic isocyanate prepolymers based on TDI reaction products.
  • the two components are mixed in the NCO: OH ratio of about 1: 1 and used as Kaschierklebstoff.
  • PET polyethylene terephthalate
  • PE polyethylene
  • OPP oriented polypropylene
  • SiOx-PET siloxane-coated polyethylene terephthalate
  • Thin layers of the adhesive are applied from the adhesives 1, 2 and 8 to the film substrates with a laminate coater (2 g / m 2 ) and bonded immediately afterwards with a second film. After 48 hours of storage at RT (25 ° C), the permeability is determined.
  • the barrier effect of the adhesive according to the invention is better than that of PU adhesives.
  • test bonds are made as indicated above.
  • the adhesion is better than that of the comparative adhesive.

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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)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Epoxy Resins (AREA)
  • Paints Or Removers (AREA)
PCT/EP2010/056310 2009-06-30 2010-05-10 2-komponenten kaschierklebstoff WO2011000619A1 (de)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BRPI1014251A BRPI1014251A2 (pt) 2009-06-30 2010-05-10 adesivo para laminação de dois componentes
ES10722327.3T ES2527817T3 (es) 2009-06-30 2010-05-10 Adhesivo de revestimiento de 2 componentes
CN2010800295953A CN102471457A (zh) 2009-06-30 2010-05-10 双-组份层合粘合剂
JP2012518839A JP5651172B2 (ja) 2009-06-30 2010-05-10 2成分貼合せ用接着剤
EP10722327.3A EP2448989B1 (de) 2009-06-30 2010-05-10 2-komponenten kaschierklebstoff
US13/325,143 US20120156382A1 (en) 2009-06-30 2011-12-14 2-component laminating adhesive

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009027329A DE102009027329A1 (de) 2009-06-30 2009-06-30 2-Komponenten Kaschierklebstoff
DE102009027329.8 2009-06-30

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US13/325,143 Continuation US20120156382A1 (en) 2009-06-30 2011-12-14 2-component laminating adhesive

Publications (1)

Publication Number Publication Date
WO2011000619A1 true WO2011000619A1 (de) 2011-01-06

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PCT/EP2010/056310 WO2011000619A1 (de) 2009-06-30 2010-05-10 2-komponenten kaschierklebstoff

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EP (1) EP2448989B1 (US20080242721A1-20081002-C00053.png)
JP (1) JP5651172B2 (US20080242721A1-20081002-C00053.png)
KR (1) KR20120111953A (US20080242721A1-20081002-C00053.png)
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DE (1) DE102009027329A1 (US20080242721A1-20081002-C00053.png)
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WO2014029606A2 (de) * 2012-08-23 2014-02-27 Henkel Ag & Co. Kgaa 2-k-kaschierklebstoff
WO2021032524A1 (en) * 2019-08-21 2021-02-25 Basf Se Method of making film laminates using amine-reactive acrylic lamination adhesives

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KR101293391B1 (ko) 2012-05-10 2013-08-12 주식회사 해광 에폭시수지 접착제 조성물 및 그를 갖는 클린룸용 퍼포레이트 플로어 패널
AU2013298716B2 (en) * 2012-07-31 2016-09-29 Henkel Ag & Co. Kgaa Adhesion method using thin adhesive layers
EP2826797A1 (de) 2013-07-18 2015-01-21 HILTI Aktiengesellschaft Härterkomponente, diese enthaltende Mörtelmasse und deren Verwendung
EP3045312B1 (en) * 2013-09-10 2020-04-15 DIC Corporation Barrier laminate and packaging material using same
CN106164187A (zh) 2014-04-10 2016-11-23 3M创新有限公司 增粘和/或抑尘涂层
JP6641912B2 (ja) * 2015-11-16 2020-02-05 王子ホールディングス株式会社 積層体及び積層体の製造方法
CN109306223A (zh) * 2017-07-28 2019-02-05 中国涂料株式会社 涂料组合物、涂膜、附有涂膜的基材和附有涂膜的基材的制造方法
US11926767B2 (en) 2020-02-12 2024-03-12 Dic Corporation Adhesive composition, laminate, and package
US20230104876A1 (en) 2020-03-27 2023-04-06 Dic Corporation Lamination method and lamination device

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WO2014029606A2 (de) * 2012-08-23 2014-02-27 Henkel Ag & Co. Kgaa 2-k-kaschierklebstoff
WO2014029606A3 (de) * 2012-08-23 2014-07-31 Henkel Ag & Co. Kgaa 2-k-kaschierklebstoff
JP2015533862A (ja) * 2012-08-23 2015-11-26 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンHenkel AG & Co.KGaA 2成分(2k)貼り合わせ用接着剤
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Also Published As

Publication number Publication date
DE102009027329A1 (de) 2011-01-05
ES2527817T3 (es) 2015-01-30
EP2448989A1 (de) 2012-05-09
JP2012531508A (ja) 2012-12-10
EP2448989B1 (de) 2014-10-22
CN102471457A (zh) 2012-05-23
US20120156382A1 (en) 2012-06-21
JP5651172B2 (ja) 2015-01-07
BRPI1014251A2 (pt) 2016-04-12
KR20120111953A (ko) 2012-10-11

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