Sulfone resin containing gas barrier adhesive

Abstract

The present invention relates to compositions comprising a resin and optionally a curing agent containing sulfonic groups obtained by reacting a polyamine containing at least one sulfonic group with a polyepoxide, as well as adhesive and coating compositions comprising said compositions having gas barrier properties, a method for bonding substrates using said adhesive and the articles so obtained, and the use of the compositions described herein as adhesives or coatings having gas barrier properties.

Description

[Technical field]

[0001] The present invention relates to compositions comprising a resin containing sulfonic groups, obtainable by reaction of a polyamine containing at least one sulfonic group with a polyepoxide, and optionally a hardener, as well as adhesive and coating compositions comprising said compositions having gas barrier properties, a method for bonding substrates using said adhesive and the articles so obtained, and the use of the compositions described herein as adhesives or coatings having gas barrier properties. [Background technology]

[0002] Gas barrier materials are known to have advantages in the preparation of packaging materials for food, pet food and medical materials and devices, since the exclusion of gases, especially oxygen, has a positive effect on the shelf life and / or quality of the contents. If the laminating adhesive used to laminate different packaging materials already features gas barrier properties, the complexity of the laminate structure can be reduced, since no separate material layer, such as a special barrier film or aluminum foil, is required.

[0003] However, previously known curable gas barrier formulations are typically too rigid and brittle and, as a result, lack suitability as adhesives because they have poor adhesion performance and undergo rapid degradation, especially when exposed to humidity and / or high temperatures.

[0004] Traditionally, these shortcomings have been addressed by concepts such as incorporating phyllosilicates into curable adhesive formulations to provide desired gas barrier properties. Such approaches are described, for example, in International Patent Publications WO2017 / 218500, WO2013 / 097057 and WO02 / 24756. However, the use of such minerals often results in a significant reduction or even loss of adhesion. Furthermore, many of the clay minerals require lengthy treatments to adequately release the material.

[0005] Other approaches use highly crystalline polyesters based on aromatic carboxylic acids, as described, for example, in International Patent Publication WO2015 / 057444, but these suffer from hydrolytic degradation when exposed to humidity, resulting in loss of bonding and release of aromatic acids such as phthalates, which are problematic for toxicological reasons.

[0006] Yet another approach relies on specific polymer classes such as special polyurethanes or special epoxy resins, such as those described in WO2015 / 079924, WO2011 / 115020 and EP2897999. Such polymers often have a trade-off between good adhesive performance and gas barrier function. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] International Publication No. 2017 / 218500 [Patent Document 2] International Publication No. 2013 / 097057 [Patent Document 3] WO 02 / 24756 [Patent Document 4] International Publication No. 2015 / 057444 [Patent Document 5] International Publication No. 2015 / 079924 [Patent Document 6] International Publication No. 2011 / 115020 [Patent Document 7] European Patent No. 2897999 Summary of the Invention [Problem to be solved by the invention]

[0008] Thus, there remains a need in the art for alternative solutions that provide laminating adhesives with gas barrier properties that overcome some or all of the above-mentioned shortcomings of existing formulations.

[0009] The inventors have now surprisingly found that this need can be met by a new class of adhesives based on sulfone resins obtained by reacting amino-substituted sulfones with epoxides. Formulations containing such resins provide good adhesive performance while at the same time having excellent gas barrier properties, especially oxygen barrier properties. [Means for solving the problem]

[0010] Thus, in a first aspect, the present invention provides a method for producing a method for treating a cancer cell comprising the steps of: (A) (A1) a polyamine containing at least one sulfonic acid group; (A2) at least one polyepoxide; a resin component comprising an oligosulfone prepolymer obtained by reacting (B) Optionally, a hardener component, preferably comprising at least one polyisocyanate (B1), at least one polyepoxide (B2) and / or at least one polyamine (B3). A composition comprising: The molar ratio of primary amino groups in component A1 to epoxy groups in component A2 ranges from 0.5:1 to 1:0.5.

[0011] In another aspect, the invention also includes laminating adhesives having gas barrier properties, preferably for bonding films and papers, comprising the compositions described herein.

[0012] Also contemplated are coatings having gas barrier properties, preferably for coating films and papers, comprising the compositions described herein.

[0013] Another embodiment relates to a method for bonding two substrates, comprising applying a composition as described herein or a laminating adhesive of the present invention to at least one surface of at least one substrate, and contacting the substrate surface having the adhesive applied thereon with the substrate surface to be bonded. The substrate may comprise a film, foil or paper. Bonded articles, especially packaging materials, obtained by these methods are also included within the scope of the present invention.

[0014] Yet another aspect is directed to the use of the compositions described herein as adhesives or coatings on film substrates for food packaging or packaging for pharmaceutical or medical products, or as adhesives for industrial grade laminates. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] Other features and aspects of the subject matter are described in detail below.

[0016] As used herein, "one or more" refers to at least one, including one, two, three, four, five, six, seven, eight, nine, or more of the referenced species. Similarly, "at least one" means one or more, i.e., one, two, three, four, five, six, seven, eight, nine, or more. As used herein with respect to any component, "at least one" refers to the number of chemically distinct molecules, i.e., the number of different species in the referenced species, but not the total number of molecules. For example, "at least one epoxide" means that at least one type of molecule that fits the definition of an epoxide is used, but also means that there can be two or more different types of molecules that fit this definition, and does not mean that there is only one molecule of the epoxide.

[0017] As used herein in relation to numerical values, "about" means ±10%, preferably ±5% of said value.

[0018] When reference is made herein to molecular weight, this refers to the number average molecular weight M, unless expressly stated otherwise. nThe number average molecular weight M of a polymer n can be calculated based on end group analysis (OH number according to DIN EN ISO 4629, NCO content according to EN ISO 11909) if the polymer has hydroxyl end groups or, preferably, determined by gel permeation chromatography according to DIN 55672, in particular DIN 55672-1 with THF as eluent. Unless otherwise stated, all given molecular weights are determined by gel permeation chromatography according to DIN 55672-1 with THF as eluent. The weight average molecular weight M w is M n The molecular weight can be determined by GPC as described above.

[0019] All percentages given herein in relation to compositions or formulations relate to weight % relative to the total weight of the respective composition or formulation, unless expressly stated otherwise.

[0020] The present invention is based on the discovery that a new class of polymers containing sulfonic groups provides adhesive compositions, particularly for lamination applications, which at the same time have good gas barrier properties.

[0021] The adhesive composition of the present invention therefore comprises a resin component (A) which comprises, consists essentially of or consists of an oligosulfone prepolymer obtained by reaction of a polyamine (A1) containing at least one sulfone group with at least one polyepoxide (A2).

[0022] As used herein, "consisting essentially of" means that the respective composition or material comprises at least 50% by weight of the component, preferably at least 60% by weight, more preferably at least 70% by weight, and most preferably at least 80% by weight.

[0023] The oligosulfone prepolymers may be epoxy or amine terminated. "Epoxy" as used herein refers to a cyclic ether group of the formula:

[0024] [ka]

[0025] As used herein, "amine" refers to a group of formula -NRR', where R and R' can be H or organic moieties such as alkyl groups. Preferably, the amine group is an amino group, i.e., R and R' are both H.

[0026] The type of end group of the oligosulfone prepolymer depends on the molar ratio of amino groups to epoxy groups in components (A1) and (A2). The molar ratio of primary amino groups in component A1 to epoxy groups in component A2 ranges from 0.5:1 to 1:0.5, preferably 0.75:1 to 1.25:1, more preferably 0.9:1 to 1:0.9, particularly preferably 0.95:1 to 1:0.95, and most preferably 1:1. It is understood that when the molar ratio of primary amino groups in component A1 to epoxy groups in component A2 is less than 1:1, the resulting polymer typically has epoxy ends, and when it is greater than 1:1, it has amino ends. Laminating adhesives containing oligosulfone prepolymers prepared with an amino to epoxy molar ratio in the range of 0.5:1 to 1:0.5 exhibit the desired gas barrier properties. By bringing the ratio closer to 1:1, the gas barrier properties can also be improved. Furthermore, the bonding properties are also increased at the same time.

[0027] In various embodiments, preferred are oligosulfone prepolymers containing epoxy groups, where the epoxy groups may be at the ends or in the middle of the backbone, which can improve the adhesive properties of lamination adhesives.

[0028] The polyamine (A1) containing sulfonic groups can be a monomeric or polymeric polyamine. In various embodiments, the polyamine (A1) is a diamine containing a sulfonic group -SO2-. Monomeric sulfonic group-containing polyamines, especially diamines, are preferred. In various embodiments, the polyamine containing at least one sulfonic group has the formula: H2N-R 1 -(SO2)-R 2 -NH2 diamine, where R 1 and R 2 are independently selected from divalent linear or branched (hetero)alkyl groups, (hetero)aryl groups, (hetero)alicyclic groups, or combinations thereof, such as aralkyl and alkylaryl groups. Preferred are alkyl, aryl and cycloalkyl groups and combinations thereof, especially those having up to 20 carbon atoms, preferably up to 12 carbon atoms, more preferably 1 to 6 carbon atoms.

[0029] As used herein, "(hetero)alkyl group" refers to an alkyl group that may be linear or branched, substituted or unsubstituted, and in particular has up to 20 carbon atoms, preferably 1-12 carbon atoms, more preferably 1-6 carbon atoms, in which one or more carbon atoms may be replaced with a heteroatom such as O, S or N, respectively, to form a heteroalkyl group. Exemplary alkyl groups include, but are not limited to, -(CH2) m When substituted, the substituents are hydroxyl, amino, thiol, carboxyl, acetyl, halogen, C 6~14 Aryl or C 5~14The alkyl group may contain a C-C double bond. Similarly, "(hetero)aryl group" and "(hetero)alicyclic group" as used herein may be substituted or unsubstituted and relate to aromatic or aliphatic cyclic groups, in particular aromatic or aliphatic cyclic groups having up to 20 carbon atoms, preferably 5 to 14 or 6 to 14 carbon atoms, more preferably 6 carbon atoms, in which one or more carbon atoms may be substituted with a heteroatom such as O, S or N to form the respective heteroaryl or heteroalicyclic group. Representative groups include phenyl, cyclohexyl, etc. When substituted, the substituents may be hydroxyl, amino, thiol, carboxyl, acetyl, halogen and C 1~12 Preferably, the alkyl group is selected from the group consisting of aryl, aryl, aryls ...

[0030] In various embodiments, the polyamine (A1) has the formula R x -(-aryl-R y -NH2) a wherein R x is -SO2- or -(CH2) n -SO2-(CH2) n -, an organic moiety containing a sulfone group, such as R y is an alkyl, alkoxy, aryl, aryloxy group and / or absent, preferably R y does not exist, -(CH2) n - or aryloxy, in particular phenoxy, a is 2 or more, preferably 2 or 3, more preferably 2, and each n is 0 or an integer from 1 to 4. Preferably, the polyamine (A1) is of the formula R x -(-aryl-NH2) a , R x -(-aryl-(CH2) n -NH2) a or R x -(-aryl-O-aryl-NH2) a Preferably, aryl is phenyl.

[0031] In various embodiments, the polyamine is diphenylsulfone, where the phenyl group is substituted with at least one amino group or at least one amino-containing group, and optionally with one further substituent, such as those described above. In particular, (A1) is 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone (DDS) or 4,4'-bis(3-aminophenoxy)diphenylsulfone (BADS), particularly preferably 4,4'-diaminodiphenylsulfone (DDS) or 4,4'-bis(3-aminophenoxy)diphenylsulfone (BADS).

[0032] In various embodiments, the at least one polyepoxide (A2) can be very generally any epoxy compound having at least two 1,2-epoxy groups per molecule, preferably 2 to 4 1,2-epoxy groups per molecule. Such polyepoxides can be saturated, unsaturated, cyclic or acyclic, aliphatic, cycloaliphatic, aromatic or heterocyclic polyepoxide compounds. Examples of suitable polyepoxides include polyglycidyl ethers, such as those that can be prepared by reacting epichlorohydrin or epibromohydrin with a polyhydroxy compound in the presence of a base.

[0033] In one embodiment, at least one polyepoxide (A2) is a glycidyl ether of a polyol. The polyol may be selected from saturated, unsaturated, cyclic or acyclic, aliphatic, cycloaliphatic, aromatic or heterocyclic polyols having at least two, preferably from 2 to 6, hydroxyl groups per molecule. Suitable polyols may be selected from aliphatic diols such as propanediol, butanediol or hexanediol, aromatic diols such as resorcinol, pyrocatechol, hydroquinone, bisphenol A (2,2-bis(4-hydroxyphenyl)propane), bisphenol F (bis(4-hydroxyphenyl)methane), 1,1-bis(4-hydroxyphenyl)isobutane, 4,4-dihydroxybenzophenone, 1,1-bis(4-hydroxyphenyl)ethane and 1,5-hydroxynaphthalene, triols or tetraols such as pentaerythritol or sugars, for example sorbitol. Aliphatic diols are particularly preferred. These diols improve the bonding properties of the resulting laminating adhesive.

[0034] In another embodiment, the polyepoxide (A2) is a polyepoxide, preferably a diepoxide, which preferably further comprises at least one hydroxyl group. Such compounds may be obtained by reacting a polyepoxide with a polyhydroxy compound having three or more hydroxyl groups, in particular a diepoxide of a polyol having three or more hydroxyl groups, such as glycerol. Particularly preferred are polyglycidyl ethers, preferably diglycidyl ethers and triglycidyl ethers, more preferably diglycidyl ethers of polyols such as glycerol or sugars, such as sorbitol, in particular polyglycerol polyglycidyl ether, glycerol triglycidyl ether, glycerol diglycidyl ether and sorbitol tetraglycidyl ether.

[0035] Alternatively, the polyepoxide (A2) may be a polymer or oligomer based on polyesters, polyamides, poly(meth)acrylates, polyurethanes, polyureas, polyolefins, polycarbonates or aromatic and aliphatic polyepoxides containing two or more epoxy groups per molecule. If the polyepoxide is a polymer, the epoxy groups can be directly incorporated into the polymer synthesis via epoxy-functional starting compounds. Alternatively, it is also possible to convert these into epoxy groups in polymers with double bonds. Another possibility is to react a polymer with OH or isocyanate groups as the base polymer with a low-molecular epoxide compound, which further has groups that react with OH or isocyanate groups. Such reaction steps or similar reactions of polymers are well known to those skilled in the art. Particularly preferred are polymeric polyepoxides based on polyether polyols. The polyether polyols can be selected from polyethylene glycol, polypropylene glycol or polyglycerol. In particular, polyglycerol polyglycidyl ethers are preferred.

[0036] In certain embodiments, it is preferred that the polyepoxide is a monomeric compound.

[0037] In various embodiments, the oligosulfone prepolymers are obtained by reacting diphenylsulfones in which the phenyl group is substituted with at least one amino group and, optionally, another substituent, such as those mentioned above, in particular 4,4′-diaminodiphenylsulfone (DDS), with diglycidyl ethers of polyols, in particular glycerol diglycidyl ether.

[0038] In various embodiments, the oligosulfone prepolymer thus obtained contains 2 to 10, preferably 3 to 4 repeat units.

[0039] In a particular embodiment of the present invention, the oligosulfone prepolymer is a compound of formula (Ia) or (Ib), depending on the molar ratio of components (A1) and (A2):

[0040] [ka]

[0041] [ka]

[0042] In the formula, n is 2-8, preferably 2-6, and more preferably 2-4.

[0043] In various embodiments, a polyamine (A1) containing at least one sulfonic group is reacted with at least two polyepoxides (A2), preferably two monomeric polyepoxides, selected from those mentioned above. In another embodiment, a polyamine (A1) containing at least two sulfonic groups is reacted with at least one polyepoxide (A2), preferably at least two polyepoxides (A2). In another embodiment, a polyamine (A1) containing at least one sulfonic group is reacted with at least one polyepoxide (A2) containing a polyepoxide having at least three 1,2-epoxy groups per molecule, preferably 3 to 4 1,2-epoxy groups per molecule. The use of a polyepoxide having three or more epoxy groups can result in a branched prepolymer, which can enhance the performance of the adhesive and its laminate.

[0044] To obtain the resin (A), the polyamine (A1), containing at least one sulfonic group, is reacted with at least one polyepoxide (A2) under suitable conditions to form the desired polymeric resin, which are known to those skilled in the art. In various embodiments, these conditions may involve reaction at elevated temperatures, preferably in the range of about 40 to about 90° C., preferably about 40 to about 70° C., and / or for a period of 0.5 hours to 6 weeks, preferably 1 to 3 weeks, and / or in the presence of an organic solvent, such as methyl ethyl ketone (MEK, the polymers of formula Ia and Ib may be obtained, for example, by reacting the extract, DDS and glycerol diglycidyl ether in MEK at 65° C. for 3 weeks). In certain other preferred embodiments, the temperature is in the range of 70° C. to 90° C., and / or for a period of 0.5 to 72 hours.

[0045] In certain other preferred embodiments, it is preferred to react components (A1) and (A2) in the presence of a catalyst to obtain resin (A). Suitable catalysts are known catalysts for the reaction of epoxyamines. Preferred catalysts are selected from organic bases, preferably containing nitrogen, in particular containing at least one tertiary nitrogen atom and / or imine nitrogen atom. The term "tertiary" as used herein indicates that three organic residues are covalently bonded to the nitrogen atom via single bonds. The term "imine" as used herein relates to a known class of substances and indicates that the nitrogen atom has a covalent double bond to an organic residue and a covalent single bond to a further organic residue. Preferred tertiary amine or imine bases are cyclic compounds containing at least two nitrogen atoms. In different embodiments, the base is, for example, an imidazole derivative, such as, for example, 1-alkyl-imidazole or 2,4-dialkylimidazole, an amidine derivative, such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), or a bicyclic tertiary amine, such as 1,4-diazabicyclo[2.2.2]octane (DABCO; triethylenediamine). Particularly preferred as catalyst is 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), in particular 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

[0046] In one embodiment, both components A1 and A2 are flowable. The viscosity may be less than 20,000 mPas (25° C., ISO 2555, Brookfield LVT). In another embodiment, an organic solvent is present in at least one component, so that these may be liquid components.

[0047] Although not necessary for curing, in various embodiments the compositions of the present invention may include a curing agent component, which preferably comprises, consists essentially of, or consists of at least one polyisocyanate (B1), at least one polyepoxide (B2) and / or at least one polyamine (B3).

[0048] The type of curing agent used depends on whether the resin (A) is epoxy- or amino-terminated. When the resin (A) is amino-terminated, polyisocyanate and polyepoxide curing agents are preferred. When the resin is epoxy-terminated, polyisocyanate and polyamine curing agents, especially polyisocyanate curing agents, are preferred. The use of polyisocyanate curing agents in the compositions of the present invention can further enhance the gas barrier properties.

[0049] The polyisocyanate (B1) used as the curing agent may be selected from monomeric or oligomeric polyisocyanates and NCO-terminated (pre)polymers, the former being preferred. Any suitable compound containing two or more isocyanate groups may be used in the curing agent of the present invention. Organic polyisocyanates that may be used to practice the present invention include alkylene diisocyanates, cycloalkylene diisocyanates, aromatic diisocyanates and aliphatic-aromatic diisocyanates. Specific examples of suitable isocyanate-containing compounds include ethylene diisocyanate, ethylidene diisocyanate, propylene diisocyanate, butylene diisocyanate, trimethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, cyclopentylene-1,3-diisocyanate, cyclohexylene-1,4-diisocyanate, cyclohexylene-1,2-diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,2-diphenylpropane-4,4'-diisocyanate, xylylene diisocyanate, 1,4-naphthylene diisocyanate, 1,5-naphthylene diisocyanate, m-phenylene diisocyanate, 1,6-diisocyanate, 1,7-diisocyanate, 1,8-diisocyanate, 1,9-diisocyanate, 2,10-diisocyanate, 2,11-diisocyanate, 2,12-diisocyanate, 2,13-diisocyanate, 2,14-diisocyanate, 2,15-diisocyanate, 2,16-diisocyanate, 2,17-diisocyanate, 2,18-diisocyanate, 2,19-diisocyanate, 2,20-diisocyanate, 2,21-diisocyanate, 2,22-diisocyanate, 2,23-diisocyanate, 2,24-diisocyanate, 2,25-diisocyanate, 2,26-diisocyanate, 2,27-diisocyanate, 2,28-diisocyanate, 2,29-diisocyanate, 2,30-diisocyanate, 2,31-diisocyanate Examples of suitable isocyanates include, but are not limited to, 4,4',4''-triisocyanatotriphenylmethane, 1,3,5-triisocyanato-benzene, 2,4,6-triisocyanato-toluene, 4,4'-dimethyldiphenyl-methane-2,2',5,5-tetraisocyanate, and the like. Although such compounds are commercially available, methods for synthesizing such compounds are well known in the art.Preferred isocyanate-containing compounds are methylene bisphenyl diisocyanate (MDI) and their polymeric analogs described in "The Book of Polyurethanes", edited by D. Randall and S. Lee, John Wiley & Sons, 2002, p. 84, isophorone diisocyanate (IPDI), hydrogenated methylene bisphenyl diisocyanate (HMDI) and toluene diisocyanate (TDI), as well as their oligomeric adducts, such as the reaction product of trimethylolpropane with TDI, commercially available under the trade name Desmodur® L-75 from Covestro.

[0050] In various embodiments, component B1 is a di- or triisocyanate and / or an aromatic polyisocyanate, preferably a reaction product of an aromatic diisocyanate with a polyol, more preferably a reaction product of TDI with trimethylolpropane having three isocyanate groups.

[0051] The polyepoxide (B2) and polyamine (B3) may also be selected from monomeric, oligomeric or polymeric compounds. As polyepoxide (B2), the same compounds as those described herein as component A2 are suitable. In various embodiments, component B2 is thus selected from monomeric epoxides, preferably diepoxides, more preferably diglycidyl ethers of polyhydroxy compounds, most preferably diglycidyl ethers of polyols, oligomeric or polymeric epoxides selected from epoxy resins and prepolymers containing at least two epoxy groups selected from the group consisting of poly(meth)acrylates, polyolefins, polybutadienes, polyesters, polyamides, polyurethanes, and aliphatic and / or aromatic polyepoxide resins.

[0052] In some embodiments, the at least one polyamine (B3) is selected from monomeric polyamines, preferably diamines, more preferably aliphatic diamines, or oligomeric or polymeric polyamines selected from polyamine resins and prepolymers containing primary amine groups.

[0053] The hardener may be used in an amount suitable to achieve the desired hardness. When a hardener is used, the composition is typically a two-component composition, the two components being mixed just prior to or during application.

[0054] The compositions described herein may be used as adhesive compositions or more preferably to manufacture such adhesive compositions, particularly adhesives for lamination applications, such as packaging, for example for bonding films and papers. The invention thus features adhesive compositions, particularly lamination / laminating adhesives, comprising the compositions described herein. In these adhesives, it may be advantageous to add additional ingredients, such as, for example, solvents, plasticizers, catalysts, stabilizers, adhesion promoters, pigments and / or fillers.

[0055] Thus, in one embodiment, the adhesive composition contains at least one tackifying resin. In principle, all resins that are compatible and form a homogeneous mixture may be used. For example, aromatic, aliphatic or cycloaliphatic hydrocarbon resins may be used, as well as modified or hydrogenated versions thereof. The resins may be used in an amount of 0 to 50% by weight, preferably up to 20% by weight, based on the composition.

[0056] Additional soluble polymers may be included in the adhesive composition, such as polymers with gas or fragrance barrier properties, examples of which include polysaccharides, such as cellulose ethers or esters.

[0057] Additionally, plasticizers may be present, such as white oils, naphthenic mineral oils, paraffinic hydrocarbon oils, adipates, benzoates, vegetable or animal oils and their derivatives. In particular, food-safe plasticizers, such as citrate esters or short chain triglycerides, are suitable.

[0058] Phenols, high molecular weight sterically hindered phenols, polyfunctional phenols, and sulfur- and phosphorus-containing phenols or amines are suitable as optional stabilizers or antioxidants.

[0059] Silane compounds can also be added to the composition as adhesion promoters. Adhesion promoters that can be used include known organofunctional silanes, such as (meth)acryloxy-functional, epoxy-functional, amine-functional silanes or non-reactive substituted silanes. In a preferred embodiment, 0.1 to 5% by weight of these silanes are added to the adhesive. Depending on the choice of silane, it is advantageous to mix the silane into only one component, either the resin or the hardener. This can prevent premature reaction and loss of storage stability.

[0060] The adhesive composition may also contain a catalyst as an optional additional additive. The catalysts used may include all known compounds capable of catalyzing the reaction of amino / epoxy groups and isocyanate / epoxy / amino / hydroxyl groups. Examples include metal compounds such as titanates, bismuth compounds, tin or zirconium carboxylates, or amine compounds such as non-volatile alkylamines, aminoalkanols, morpholine and their derivatives or carboxylic acids and their salts, polyamines such as triethylenetetramine, guanidine or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). The catalyst may be used in an amount of 0 to about 5% by weight, preferably 0.1 to 1% by weight, of catalyst, based on the total weight of the adhesive.

[0061] Special embodiments of the present invention may also contain pigments or fillers in the composition. These are finely divided pigments, for example with a particle size of less than 5 μm. Some embodiments of the present invention involve flake-like pigments that can be dispersed in the binder components. Another procedure uses nanoparticles, usually with a particle size of less than 500 nm, in particular less than 100 nm. Those skilled in the art are familiar with such pigments or fillers and can select them according to conventional considerations and incorporate them into one or both binder components using known methods.

[0062] In some embodiments, the adhesive composition may also contain a solvent. These are conventional solvents that can evaporate at temperatures up to 120° C. The solvent may be selected from the group consisting of aliphatic hydrocarbons, aromatic aliphatic hydrocarbons, ketones, in particular C1-C4 alcohols, ketones or water. In some embodiments, the two-component composition contains such a solvent.

[0063] Together with additives, (two-component) adhesives or two-component coatings can be produced from the compositions.

[0064] The adhesive should have a low viscosity at application temperatures of about 20° C. to 90° C., since it is particularly suitable for coating large surface areas. The viscosity of the adhesive according to the invention, measured after mixing the components, should be between 200 and 5000 mPas at the application temperature, preferably 300 to 3000 mPas (in a Brookfield viscometer LVT according to EN ISO 2555) in particular at 20° to 60° C.

[0065] Known auxiliary substances and additives may be added to either component A or component B in the two-component adhesive, as long as they do not react with the additives. Solvents may be included and in a preferred embodiment are used in the composition.

[0066] The adhesive of the present invention may in particular be used as a laminating adhesive. The adhesive is applied in a thin layer to a substrate such as a film. Any solvent optionally present should then be allowed to evaporate immediately. A second substrate, such as a second film, is then contacted / applied to the adhesive layer and, if necessary, the resulting laminate is pressed under pressure.

[0067] Thus, the present invention also includes a method of joining two substrates which comprises applying a composition or laminating adhesive according to the present invention to at least one surface of at least one substrate and contacting the substrate surface bearing the adhesive with the substrate surface to be joined.

[0068] As substrates, i.e. film materials, for producing multilayer films, known flexible films may be used. These are substrates of thermoplastic materials in film form, for example polyolefins such as polyethylene (PE) or polypropylene (PP, CPP, OPP), polyvinyl chloride (PVC), polystyrene (PS), polyesters such as PET, polyamides, organic polymers such as cellophane; furthermore, metallized films, films coated with SiO2 or Al2O3, metal foils or paper are also possible as substrates. The film materials may also be modified, for example by modifying the polymer with functional groups, or additional components may be included in the film, for example pigments, dyes or foam layers. Colored, printed, colorless or transparent films may also be used.

[0069] Another embodiment of the present invention uses compositions for (two-component) coatings. These coatings can in principle contain the same ingredients as those described for laminating adhesives. However, when selecting, it is important to ensure that the coating has a smooth, non-sticky surface after crosslinking. Adhesion is only good to substrates to which the coating is applied in liquid form. Those skilled in the art are familiar with such ingredients, which should only be used in small amounts by weight or should be avoided in the production of non-stick surfaces.

[0070] The subject of the present invention also relates to a bonded article obtained by using the adhesive of the present invention to bond two substrates. In various embodiments, the bonded article is a multilayer film bonded using a laminating adhesive comprising a composition according to the present invention; a known plastic film can be used as substrate. A continuous layer is produced on this film using the adhesive of the present invention, which is bonded immediately after application to a second film of the same or different type. In addition to two-layer films, multilayer films can also be produced with additional work steps. Certain embodiments according to the present invention work on transparent films, which are advantageous when the adhesive according to the present invention is likewise transparent and does not discolor. In principle, other non-plastic films, such as paper or metal foils, can also be used for the multilayer film.

[0071] The adhesive of the present invention shows good adhesion between different layers. It does not show any air bubbles or defects in the adhesive layer. The resulting composite substrate is flexible. It can prevent cracking and delamination, and the additional production step of packaging is not a problem.

[0072] The subject of the present invention further relates to the use of the composition according to the invention for producing a coating on a flexible composite substrate. The above-mentioned additives and auxiliary substances may be contained in the coating agent. The coating agent may be liquid or applied in a flowable form by heating to 90°C. These coatings are flexible after crosslinking and may therefore be used in particular for flexible multilayer films. In a preferred embodiment, the coating agent according to the present invention is applied at an application temperature between 20°C and 60°C.

[0073] After crosslinking, a tack-free layer is obtained on the surface. Such a film can then be further processed in known manner, either applied as an additional lamination layer or finished.

[0074] The composite films produced according to the invention have high flexibility. They may be transparent, i.e. contain only nanoparticles as fillers, or may contain no fillers or only small amounts of conventional fillers, so that the adhesive layer does not have an excessively cloudy appearance in the composite. However, they may also be dye or pigment layers.

[0075] The layers according to the invention have the particularly advantageous property of providing a gas barrier effect: compared to conventional adhesive bonding films, the materials according to the invention have been shown to exhibit an improved barrier effect against the diffusion of gases such as oxygen or water vapor.

[0076] The composition of the present invention can be further processed to form a two-component coating or adhesive in a simple manner.These adhesives or coatings can be used on film substrates to obtain composite films with high barrier properties.Barrier properties can be based on various factors; for example, they can reduce the diffusion of oxygen.Another embodiment reduces the diffusion of water.Furthermore, they can reduce the diffusion of, for example, perfume materials from or into the package.

[0077] The adhesion with various substrate materials is good. When the composite material, for example the adhesive bonded film, is subjected to mechanical load, no separation between the adhesive bonded surfaces is observed. For example, packaging can be produced from the composite material of the invention. Due to the barrier effect, such packaging is suitable for delicate articles such as food or medical products. Another application area is industrial laminating adhesives, for example adhesive bonds for flexible circuits or similar objects.

[0078] Thus, the present invention also relates to the use of the compositions described herein as adhesives or coatings on film substrates for food packaging or packaging for pharmaceutical or medical products, or as adhesives for industrial grade laminates.

[0079] It is understood that all embodiments disclosed herein with respect to the compositions of the present invention are equally applicable to the adhesives and coatings, methods, bonded articles and uses, to the extent applicable, and vice versa.

[0080] The following examples are given to illustrate the present invention, but the present invention should not be considered as being limited thereto, as these examples are given for illustrative purposes only. EXAMPLES

[0081] <Example 1> Laminates were prepared on PET (12 μm) and crystalline PP (cPP; 40 μm). The PET film (dry: 3.5 g / m 2 After applying a solvent-based adhesive formulation onto the PET film, the solvent was allowed to dry and then a second film (cPP) was laminated on top. After the adhesive was cured, it was subjected to an oxygen barrier test (OTR; cm at 75% relative humidity). 3 / (m 2 The peel strength (in N / 15 mm after 3 weeks) and the adhesion strength (measured twice) were measured under the same conditions (-24h-ND). As a control, a laminate with a standard laminating adhesive was prepared under the same conditions.

[0082] The following adhesive compositions were tested: Base polymer: a polymer of formula Ia having n to 3; Hardeners: none, adduct of TDI and trimethylolpropane (Desmodur(R) L-75; 6.1% by weight based on solids of the adhesive composition), glycerol diglycidyl ether (GDGE) (11.3 and 20.3% by weight of the adhesive composition).

[0083] [Table 1]

[0084] The results in Table 1 show that in all cases, even in the absence of a hardener, outstanding oxygen barrier can be achieved while maintaining outstanding peel strength.

[0085] The experiment was repeated using different amounts of isocyanate hardener (Desmodur® L-75) and two different base polymers. Peel strength was tested after 1 week (1w) and 5 weeks (5w).

[0086] The following adhesive compositions were tested: Base polymer: Polymer of formula Ia having n to 3 and polymer of formula Ib having n to 3 Curing agent: adduct of TDI and trimethylolpropane (Desmodur(R) L-75; weight % based on solids in adhesive composition).

[0087] [Table 2]

[0088] Again, significant oxygen barrier properties were found, the peel strength was even higher than in the first experiment, and the bond strength can be seen to increase with time.

[0089] In the next experiments, the base polymer of formula Ib(n-3) was combined with an isocyanate curing agent (Desmodur® L-75; Formulation 11) and a linear prepolymer curing agent (Liofol LA7777, Henkel; Formulations 12-14). Peel strength was measured after 7 and 28 days. OTR was measured after 16 and 35 hours.

[0090] [Table 3]

[0091] Significant oxygen barrier properties could be demonstrated. The OTR as well as the peel strength increased over time. The oxygen barrier properties were measured at relatively high humidity and still showed a significant barrier effect, meaning that the cured adhesive is relatively insensitive to moisture.

[0092] In addition, adhesive compositions containing reaction products of glycerol diglycidyl ether or glycerol triglycidyl ether with DDS having a molar ratio of amino groups to epoxy groups of 1:1 as the base polymer together with an adduct of TDI and trimethylolpropane (Desmodur(R) L-75; weight % based on solids in the adhesive composition) as the curing agent were tested.

[0093] [Table 4]

[0094] As a comparative example, an adhesive composition was tested containing as the base polymer the reaction product of glycerol diglycidyl ether and DDS, with an epoxy to amino molar ratio of 1:2.5. The use of such an adhesive composition resulted in a laminate with no bond immediately after lamination, and after a few days a peel strength of 0 N / 15 mm. The measured OTR was 84.2 cm 3 / (dm 2 ), indicating that such adhesive compositions result in laminates with poor gas barrier properties.

[0095] [Measurement method] <Peel strength> Peel strength was measured on 15 mm wide laminate stripes with a peel tester (e.g. from Instron or Zwick) with a force of 0 to 20 N. The laminate stripes were partially cut apart on one side, mounted in the peel tester and pulled apart at an angle of 90° at 100 mm / min. The results shown above are the average values ​​based on three measurements.

[0096] <Oxygen permeability (Oxygen transmission rate (OTR)):> The oxygen permeability was measured using an OX-TRAN 2 / 21 H measuring device from MOCON. The test cell of the measuring device consists of two parts. The film was mounted between the two half-cells. Oxygen was passed through the outer half-cell as the test gas. A carrier gas, a mixture of 95% nitrogen and 5% hydrogen (essentially forming gas), flowed through the inner half-cell. Oxygen that permeated through the membrane was captured by the carrier gas and sent to a detector. The oxygen sensor generates a current in the presence of oxygen, which is proportional to the amount of oxygen that reaches it. Preferred aspects of the present invention include the following. [1] (A) (A1) a polyamine containing at least one sulfonic acid group; (A2) at least one polyepoxide; a resin component comprising an oligosulfone prepolymer obtained by reacting (B) Optionally, a hardener component, preferably comprising at least one polyisocyanate (B1), at least one polyepoxide (B2) and / or at least one polyamine (B3). A composition comprising: A composition, wherein the molar ratio of primary amino groups in component A1 to epoxy groups in component A2 ranges from 0.5:1 to 1:0.5. [2] The composition according to [1], wherein the oligosulfone prepolymer is an epoxy or amine terminated prepolymer. [3] The composition according to [1] or [2], wherein components (A1) and (A2) are mixed in a molar ratio of primary amino groups in component A1 to epoxy groups in component A2 of 0.75:1 to 1.25:1. [4] The polyamine containing at least one sulfonic group is a diamine, preferably Formula:H 2 NR 1 -(SO 2 )-R 2 -NH 2 (In the formula, R 1 and R 2 are independently selected from divalent linear or branched (hetero)alkyl groups, (hetero)aryl groups, (hetero)alicyclic groups, or combinations thereof; The composition according to any one of [1] to [3], [5] The composition according to any one of [1] to [4], wherein at least one polyepoxide (A2) is a glycidyl ether of a polyol, preferably a diglycidyl ether of a polyol. [6] The composition described in [5], wherein the polyepoxide further contains at least one hydroxyl group. [7] The composition according to any one of [1] to [6], wherein the oligosulfone prepolymer is a compound of formula (Ia) or (Ib).

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[10] The composition according to any one of [1] to [9], wherein the adhesive composition has a gas barrier function, preferably an oxygen barrier function.

[11] The composition according to any one of [1] to

[10] , further comprising an organic solvent.

[12] A laminating adhesive having gas barrier properties, preferably for bonding films and papers, comprising the composition according to any one of [1] to

[11] .

[13] A method for bonding two substrates, comprising applying the composition according to any one of [1] to

[11] or the laminating adhesive according to

[12] to at least one surface of at least one substrate, and contacting the substrate surface bearing the adhesive with the substrate surfaces to be bonded.

[14] A bonded article obtained by the method according to

[13] .

[14] Use of the composition according to any one of [1] to

[11] as an adhesive or coating for film substrates for food packaging or packaging for pharmaceutical or medical products, or as an adhesive for industrial grade laminates.

Claims

1. (A) (A1) a polyamine containing at least one sulfonic acid group; (A2) at least one polyepoxide; A resin component comprising an oligosulfone prepolymer obtained by reacting (B) Optionally, a hardener component comprising at least one polyisocyanate (B1), at least one polyepoxide (B2) and / or at least one polyamine (B3). A composition comprising: A composition, wherein the molar ratio of primary amino groups in component A1 to epoxy groups in component A2 ranges from 0.75:1 to 1.25:1, and said at least one polyepoxide (A2) is a glycidyl ether of a polyol, and said at least one polyepoxide (A2) contains at least one hydroxyl group.

2. 10. The composition of claim 1, wherein the oligosulfone prepolymer is an epoxy or amine terminated prepolymer.

3. 3. The composition of claim 1 or 2, wherein the polyamine containing at least one sulfone group is a diamine.

4. 4. The composition according to claim 1, wherein at least one polyepoxide (A2) is a diglycidyl ether of a polyol.

5. The composition according to any one of claims 1 to 4, wherein the oligosulfone prepolymer is a compound of formula (Ia) or (Ib). 【Chemistry 1】 【Chemistry 2】 (In the formula, n is 2 to 8.)

6. The at least one sulfonic acid group-containing polyamine (A1) is reacted with the at least one polyepoxide (A2). (i) in the range of 40 to 90° C., and / or (ii) 0.5 hours to 6 weeks, and / or (iii) In an organic solvent The composition according to any one of claims 1 to 5, which reacts with

7. (1) the at least one polyisocyanate (B1) is a di- or triisocyanate and / or an aromatic polyisocyanate, and / or (2) said at least one polyepoxide (B2) (i) a monomeric epoxide, or (ii) oligomeric or polymeric epoxides selected from epoxy resins and prepolymers containing epoxy groups selected from the group consisting of poly(meth)acrylates, polyolefins, polybutadienes, polyesters, polyamides, polyurethanes, and aliphatic and / or aromatic polyepoxide resins; and / or (3) The at least one polyamine (B3) (i) a monomeric polyamine, or (ii) oligomeric or polymeric polyamines selected from polyamine resins and prepolymers containing primary amine groups; The composition according to any one of claims 1 to 6, selected from:

8. The composition according to any one of claims 1 to 7, which has a gas barrier function.

9. The composition of any one of claims 1 to 8, wherein the composition further comprises an organic solvent.

10. A laminating adhesive having gas barrier properties comprising the composition according to any one of claims 1 to 9.

11. 11. A method of joining two substrates comprising applying a composition according to any one of claims 1 to 9 or a laminating adhesive according to claim 10 to at least one surface of at least one substrate and contacting the substrate surface carrying the adhesive with the substrate surface to be joined.

12. A bonded article obtainable by the method according to claim 11.

13. Use of the composition according to any one of claims 1 to 9 as an adhesive or coating on film substrates for food packaging or packaging for pharmaceutical or medical products, or as an adhesive for industrial grade laminates.

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