Aqueous dispersions for producing coatings with improved MVTR barrier properties

Abstract

The present invention relates to an aqueous dispersion comprising or consisting of A) at least one cyclic olefin copolymer, B) at least one surfactant, optionally C) at least one adhesion promoter, optionally D) at least one film-forming resin, optionally at least one additive, and F) water. The present invention further relates to a method for producing the aqueous dispersion, an article comprising at least one substrate and at least one coating layer obtained from the aqueous dispersion, and the use of the aqueous dispersion to coat a substrate.

Description

[Technical Field]

[0001] The present invention relates to an aqueous dispersion comprising or consisting of A) at least one cyclic olefin copolymer, B) at least one surfactant, optionally C) at least one adhesion promoter, optionally D) at least one film-forming resin, optionally at least one additive, and F) water. The present invention further relates to a method for producing the aqueous dispersion, an article comprising at least one substrate and at least one coating layer obtained from the aqueous dispersion, and the use of the aqueous dispersion to coat a substrate. [Background technology]

[0002] Polymer-based packaging systems, such as polyolefin films, are widely used in the packaging industry. Packaging is used to protect food and other contents from environmental influences. A balance must be struck between migrating gases such as CO₂ and O₂, flavor compounds, and moisture, as these environmental compounds can alter the product's original properties before it reaches its final use. For example, dry contents need to be protected from moisture. From this perspective, packaging must provide moisture protection from the outside of the package and vice versa.

[0003] The industry uses several concepts to provide long-term barrier properties. For example, olefin films such as polyethylene terephthalate (PET), polyethylene (PE), or oriented polypropylene (OPP) are coated with polyvinylidene chloride (PVDC) to increase the gas barrier, especially against O2 and moisture. Due to the presence of chlorides, this technology is of concern for environmental reasons.

[0004] Another approach is to cast multilayer films, but cast multilayer film technology is complex and costly from the manufacturing side, and recycling the material can be difficult.

[0005] A further alternative is the deposition of barrier films by evaporation. However, the technique of physical vapor deposition is associated with complex manufacturing processes. Chemical vapor deposition coatings have good barrier properties but are sensitive to mechanical stress. Therefore, a protective coating must be applied, which also increases costs and introduces more time-consuming process steps. Furthermore, the coatings often do not meet the desired aesthetic requirements. For example, AlO x The coating is metallic rather than transparent.

[0006] Although numerous processes for coating substrates already exist, all of these processes have one or more drawbacks. Therefore, there is a need for improved, preferably transparent, packaging solutions with good gas and moisture barrier properties.

[0007] In general, aqueous dispersions of polymers and copolymers for coating applications are usually preferred because they are easier to handle, less flammable, and less harmful to health than organic solvent-based mixtures and the processes described above. Furthermore, when organic solvent-based mixtures are used, the solvent can undesirably affect the properties of the resulting coating.

[0008] DE 19859191 A1 discloses a method for preparing an aqueous polyalkenamer dispersion by ring-opening metathesis polymerization of a) at least one poorly water-soluble cyclic olefin, and optionally also b) cyclic and / or acyclic olefins, in the presence of c) at least one metathesis catalyst, and at least one surface-active substance d) and optionally e) further additives, characterized in that the dispersion is prepared by miniemulsion polymerization. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] DE 19859191 Summary of the Invention [Problem to be solved by the invention]

[0010] Although methods for making aqueous dispersions already exist, mixing homopolymers and copolymers with water to achieve a stable solution or dispersion is quite difficult, and new methods are needed for making aqueous dispersions of homopolymers or copolymers that provide clear coatings for packaging systems with excellent gas and moisture barrier properties without the use of metallocene catalysts or ring-opening polymerization, which would undesirably alter the structure of the polymer.

[0011] Surprisingly, the present inventors have found that this problem can be solved by a novel aqueous dispersion comprising at least one cyclic olefin copolymer, at least one surfactant, and water. This aqueous dispersion can be prepared without the use of a (metallocene) catalyst or ring-opening polymerization. Optionally, the aqueous dispersion comprises at least one adhesion promoter, at least one film-forming resin, and / or at least one additive. The at least one adhesion promoter can be, for example, a polyester resin. This further improves the adhesion and gas barrier properties of the resulting coating to polyolefin substrates without altering the moisture barrier properties, compared to a coating of a cyclic olefin copolymer applied without being dispersed in water. [Means for solving the problem]

[0012] Thus, in a first aspect, the present invention relates to an aqueous solution comprising or consisting of A) at least one cyclic olefin copolymer, B) at least one surfactant, optionally C) at least one adhesion promoter, optionally D) at least one film-forming resin, optionally E) at least one additive, and F) water.

[0013] In a second aspect, there is provided a method of making an aqueous dispersion, the method comprising: (i) A) dissolving at least one cyclic olefin copolymer in a suitable solvent and optionally adding B) at least one surfactant, and / or optionally C) at least one adhesion promoter, and / or optionally D) at least one film-forming resin, and / or optionally E) at least one additive; (ii) optionally mixing the aqueous phase with B) at least one surfactant, preferably an anionic surfactant and / or a nonionic surfactant, if B) has not been added in step (i); (iii) if B) has not been added in step (i), mixing the solution of step (i) with an aqueous phase optionally containing B) at least one surfactant; and (iv) a process step of concentrating said used solvent.

[0014] In a third aspect, there is provided a method of making an aqueous dispersion, the method comprising: (i) feeding to an extruder A) at least one cyclic olefin copolymer, optionally B) at least one surfactant, and / or optionally C) at least one adhesion promoter, and / or optionally D) at least one film-forming resin, and / or optionally E) at least one additive; (ii) adding water to said extruder, preferably in a high shear region of the extruder, preferably during the extrusion process, wherein the water is mixed with optionally B) at least one surfactant if B) was not added in step (i), and / or optionally C) at least one adhesion promoter if C) is present and not added in step (i), and / or optionally D) at least one film forming resin if D) is present and not added in step (i), and / or optionally E) at least one additive if E) is present and not added in step (i); (iii) transferring the aqueous dispersion obtained by step (ii) from said extruder.

[0015] In a fourth aspect, there is provided a method of making an aqueous dispersion, the method comprising: (i) melting A) at least one cyclic olefin copolymer, B) at least one surfactant, optionally C) said at least one adhesion promoter, and / or optionally D) at least one film-forming resin, and / or optionally E) at least one additive; (ii) transferring the mixture of step (i) in a reaction chamber; (iii) transferring water having a temperature above 100°C but preferably below 200°C in a reaction chamber simultaneously with step (ii); (iv) simultaneously transferring the mixture of step (ii) and the water of step (iii) into a carrier gas, such as N2, H2, or argon, in a reaction chamber; and (v) transferring the mixture obtained by step (iv) from said reaction chamber.

[0016] Furthermore, in a fifth aspect, there is provided an article comprising at least one substrate and at least one coating layer, which article can be obtained by applying the aqueous dispersion of the present invention onto the substrate and then drying the article by heating to obtain the coating layer.

[0017] Finally, in a sixth aspect there is provided the use of the aqueous dispersion of the invention for coating a substrate. DETAILED DESCRIPTION OF THE INVENTION

[0018] As used herein, "one or more" relates to "at least one" and includes 1, 2, 3, 4, 5, 6, 7, 8, 9, or more of the referenced species. Similarly, "at least one" means "one or more," i.e., 1, 2, 3, 4, 5, 6, 7, 8, 9, or more. "At least one," as used herein with respect to any component, refers to the number of chemically distinct molecules, i.e., the number of different types of the referenced species, but not the total number of molecules. For example, "at least one cyclic polyolefin copolymer" means that at least one type of copolymer within the definition can be part of the aqueous dispersion, but also that there can be two or more different copolymer types included in this definition.

[0019] Numerical values ​​stated without decimal points refer to the full value stated to one decimal point, e.g., "99%" means "99.0%" unless otherwise stated.

[0020] The term "approximately" or "about" in conjunction with a numerical value, unless otherwise specified, refers to a variation of ±10%, preferably ±5%, and more preferably ±1% from the given numerical value.

[0021] All percentages given herein with respect to aqueous dispersions or the solids content of aqueous dispersions relate to weight percent (wt %) of the total weight of the respective aqueous dispersion or solids content of the aqueous dispersion, unless otherwise specified.

[0022] As used herein, the term "homopolymer" means a polymer prepared from a single monomeric species. The term "copolymer" means a polymer prepared from at least two monomeric species.

[0023] The terms "surfactant," "emulsifier," and "emulsifying agent" are used interchangeably in this application.

[0024] The term "additive" may be any common ingredient or compound added to an aqueous solution by a person skilled in the art of aqueous dispersions to achieve specific properties of the aqueous dispersion. Furthermore, according to the present invention, this term encompasses any impurities and / or reaction products or by-products that may form in small amounts, preferably less than 1% by weight, more preferably less than 0.1% by weight, and most preferably less than 0.01% by weight, in the aqueous dispersion.

[0025] These and other aspects, features, and advantages of the present invention will become apparent to those skilled in the art in the following detailed description and claims. Each feature from one aspect of the present invention can be used with any other aspect of the invention. Furthermore, unless otherwise specified, each feature from one embodiment can be combined with all other features from other embodiments. Furthermore, the examples included herein are intended to explain and illustrate the invention, but not to limit it, and in particular the invention is not limited to these examples.

[0026] In accordance with the present invention, the aqueous dispersion comprises or consists of A) at least one cyclic olefin copolymer, B) at least one surfactant, optionally C) at least one adhesion promoter, optionally D) at least one film-forming resin, optionally E) at least one additive, and F) water.

[0027] In a preferred embodiment, the aqueous dispersion comprises A) at least one cyclic olefin copolymer, the at least one cyclic olefin copolymer comprising: i) obtained by copolymerizing a C5-C12 cycloalkene with at least one C2-C10 alkylene, preferably norbornene with at least one of ethylene, propylene, butylene, hexylene and octylene, more preferably norbornene with ethylene; and / or ii) a glass transition temperature Tg of 6 to 138°C, preferably 33 to 78°C, most preferably 65°C, measured according to DIN EN ISO 11357-1:2017-02, -2:2014-07, or -3:2018-07; and / or iii) 905-1200 kg / m, measured according to DIN EN ISO 1183-1:2013-04 3 Preferably 1000 to 1050 kg / m 3 and / or iv) a tensile modulus in the machine direction, measured according to DIN EN ISO 527-3:2003-07, of 1500 to 2500 MPa, preferably 1600 to 1800 MPa; and / or v) a breaking strength in the machine direction of 40 to 70 MPa, preferably 50 to 60 MPa, measured according to DIN EN ISO 527-3:2003-07; and / or vi) an elongation at break in the machine direction of 2.0 to 4.0%, preferably 2.3 to 3.6%, measured according to DIN EN ISO 527-3:2003-07; and / or vii) a melt flow rate at 230°C and 2.16 kg load of 0.5 to 15.0 g / 10 min, preferably 3.5 to 9.5 g / 10 min; and / or viii) present in an amount of 5 to 99% by weight, preferably 50 to 95% by weight, based on the solids content of the aqueous dispersion; and / or ix) In aqueous dispersion, it has an average particle size, as measured by dynamic light scattering, of 50 to 500 nm as a D50 value.

[0028] In a preferred embodiment, at least one cyclic olefin copolymer is obtained by copolymerizing a C5-C12 cycloalkene and at least one C2-C10 alkylene, preferably norbornene and at least one of ethylene, propylene, butylene, hexylene, and octylene, more preferably norbornene and ethylene, in the presence of at least one metallocene catalyst. The resulting copolymer is used in the present invention, which is essentially free of metallocene catalyst, preferably contains less than 0.001 wt. % metallocene catalyst based on the total weight of the copolymer, more preferably less than 0.000001 wt. % metallocene catalyst based on the total weight of the copolymer, and most preferably is free of metallocene catalyst.

[0029] In another preferred embodiment, at least one cyclic olefin copolymer is obtained by chain copolymerization of a C5-C12 cycloalkene with at least one C2-C10 alkylene, preferably norbornene with at least one of ethylene, propylene, butylene, hexylene, and octylene, more preferably norbornene with ethylene. The composition of the copolymer preferably depends on the relative concentrations of the single monomers in the copolymerization mixture.

[0030] By using a high norbornene content in the cyclic olefin copolymer, the heat resistance of the resulting coating layer is increased.

[0031] In a preferred embodiment, the aqueous dispersion is essentially free of metallocene and / or metathesis catalysts, preferably containing less than 0.0001 wt. %, more preferably less than 0.0000001 wt. %, and most preferably free of metallocene and / or metathesis catalysts based on the total weight of the aqueous dispersion.

[0032] The term "Tg" as used herein refers to the glass transition temperature. Tg can be determined according to DIN EN ISO 11357-1:2017-02, -2:2014-07, or -3:2018-07. The glass transition temperature Tg is preferably determined by differential scanning calorimetry (DSC). More common techniques for measuring Tg are thermomechanical analysis (TMA) or dynamic mechanical analysis (DMA).

[0033] The D50 value indicates that 50% by volume of the dispersed polymer components of the coating inside the can have a size smaller than a given value. Preferably, the D50 value can be determined from the volume-weighted cumulative particle size distribution. The particle size distribution curve can preferably be measured using similar dynamic light scattering methods well known to those skilled in the art. Preferably, in the context of the present invention, the particle size is measured directly in the aqueous dispersion of the present invention at a temperature of 20° C., provided that the solids content of the dispersion is adjusted to 1 g / kg with deionized water (κ<1 μS cm -1 ).

[0034] In a preferred embodiment, a colorless and / or transparent and / or translucent coating layer is obtained from the aqueous dispersion. Preferably, the transmittance of the colorless and / or transparent and / or translucent coating layer is >0.85 (>85%), more preferably >0.9 (>90%). The transmittance of the coating layer of the present invention is determined by applying the aqueous dispersion of the present invention to a reference material. The transmittance of the reference material alone, without the coating layer of the present invention, serves as a background control, and the determined transmittance value is subtracted from the transmittance of the coated reference material. Preferably, the transmittance is determined by UV-Vis spectrophotometry using a striped incident light angle of 0° and wavelengths of 390-700 nm. A transparent, twin-screw coextruded polyethylene terephthalate film can be used as the reference material, which is commercially available from Mitsubishi under the trade name "Hostaphan RNK."

[0035] The water vapor transmission rate (MVTR) is the amount of water vapor that passes through a material or coating layer, measured according to DIN EN ISO 15106-3:2005-05.

[0036] Preferably, the oxygen permeability of the coating layer obtained by the aqueous dispersion of the present invention is 150 to 300 cm3, measured according to ASTM D3985-17 at 23°C and 50% RH. 3 / (m 2 ·day·bar), more preferably 160~200cm 3 / (m 2 ·day·bar).

[0037] In a more preferred embodiment, (i) the coating thickness of the coating layer obtained from the aqueous dispersion of the present invention is 0.1 to 15 g / m 2 , preferably 5 to 10 g / m 2 , more preferably 7 to 9.5 g / m 2 and / or ii) The coating layer is 7 to 60 g / (m 2 ·day), preferably 12 to 50 g / (m 2 It has an MVTR of 1000 / day.

[0038] Suitable cyclic olefin copolymers are commercially available from TOPAS Advances Polymers GmbH (Frankfurt, Germany) under the tradenames TOPAS 9506F-500 (Tg 65°C), TOPAS 8007F-600 (Tg 780°C), TOPAS 7010F-600 (Tg 110°C), TOPAS 6013F-04 (Tg 138°C), TOPAS 9903D-10 (Tg 33°C), TOPAS 8007F-04 (Tg 78°C), TOPAS 5013F-04 (Tg 136°C), or TOPAS E-140 (Tg 6°C). Preferably, they are amorphous thermoplastics and / or their rigidity is maintained up to about 10°C below Tg.

[0039] In a preferred embodiment, TOPAS 9506F-500 (Tg 65° C.), a cyclic olefin copolymer copolymerized from norbornene and ethylene, is used to prepare the aqueous dispersions of the present invention.

[0040] According to the present invention, the at least one cyclic olefin copolymer A) is different from the compounds of component B) of the aqueous dispersion, as well as from the optional components C), D), and E).

[0041] The aqueous dispersion preferably further comprises B) at least one surfactant to stabilize the aqueous dispersion.

[0042] In a preferred embodiment, i) the at least one surfactant is an anionic or nonionic surfactant or a mixture thereof, and / or ii) the at least one surfactant comprises an alkyl sulfate, preferably a fatty alcohol alkyl sulfate, more preferably sodium lauryl sulfate; and / or iii) the at least one surfactant comprises a fatty alcohol alkoxylate, preferably a linear C12-18 fatty alcohol alkoxylate, more preferably a linear C16-18 alcohol ethoxylate having 10 to 15 ethoxy units; and / or iv) the at least one surfactant comprises a copolymer obtained by reacting at least one olefinic monomer, preferably selected from ethylene, propene, 1-butene, 2-butene, isobutene, 1,3-butadiene and 2-methylbuta-1,3-diene, with at least one comonomer selected from an α,β-unsaturated carboxylic acid, preferably cinnamic acid, crotonic acid, fumaric acid, itaconic acid, maleic acid, acrylic acid and methacrylic acid, the resulting copolymer preferably having an acid number of at least 60 mg KOH / g, more preferably less than 200 mg KOH / g, more preferably less than 100 mg KOH / g; and / or v) The at least one surfactant is present in an amount of 0.01 to 10% by weight, preferably 2 to 7% by weight, based on the solids content of the aqueous dispersion.

[0043] The acid number is an intrinsic value that must be experimentally determined according to the present invention and is a measure of the number of free acid groups in the copolymer or copolymer blend. Preferably, the acid number is determined by dissolving a weighed amount of the reference material in a 3:1 volumetric ratio of methanol and distilled water, followed by potentiometric titration with 0.05 mol / L KOH in methanol. Preferably, the potentiometric measurement is performed using a combination electrode (Metrohm's LL-Solvotrode®, reference electrolyte 0.4 mol / L tetraethylammonium bromide in ethylene glycol). The acid number described in this invention corresponds to the amount of milligrams of KOH added per gram of copolymer and / or copolymer blend at the turning point of the potentiometric titration curve.

[0044] The acid number of the at least one surfactant is preferably at least 60 mg KOH / g, which improves the surface activity of the aqueous dispersion. Furthermore, to improve compatibility with the cyclic olefin copolymer A), the acid number of the at least one surfactant is preferably less than 200 mg KOH / g, more preferably less than 100 mg KOH / g.

[0045] More preferred anionic surfactants can be selected from the group consisting of C8-18 alkylbenzene sulfonates, olefin sulfonates, C12-18 alkane sulfonates, sulfonate esters, alk(en)yl sulfates, fatty alcohol ether sulfates, and mixtures thereof. Preferably, the anionic surfactant is selected from at least one C8-18 alkylbenzene sulfonate.

[0046] The aqueous dispersion of the present invention is a compound represented by the formula (T1) [ka] [In the formula, R 1is a linear or branched, substituted or unsubstituted functional group selected from alkyl, aryl or alkylaryl functional groups, and the group -A- is a chemical bond or a functional group -(OZ) n O, where OZ is an ethylene oxide (EO) group or a propylene oxide (PO) group, n is an integer from 1 to 50, preferably from 1 to 20, more preferably from 2 to 10, in particular 2, 3, 4, 5, 6, 7 or 8, and Y + is the nth moiety of a monovalent cation or an n-valent cation. It is preferred that the composition contains at least one anionic surfactant represented by the formula:

[0047] Formula (T1-1): [ka] Alkyl ether sulfates of the formula (I) are preferred.

[0048] In this formula (T1-1), R 1 is a linear or branched, substituted or unsubstituted alkyl functional group, preferably a linear unsubstituted alkyl functional group, in particular a fatty alcohol functional group. 1 is selected from the group consisting of decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl functional groups, and from the abovementioned compounds, those with an even number of C atoms are preferred. Particularly preferred functional groups R 1 is derived from a C12-C18 fatty alcohol, such as coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or a C10-C18 oxo alcohol. + and n are as previously described in formula (T1).

[0049] In a further preferred embodiment of formula (T1-1), OZ is an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide group. The index n is an integer from 1 to 50, preferably from 1 to 20, in particular from 2 to 10. More preferably, n is 2, 3, 4, 5, 6, 7 or 8. According to formula (T1-1), Y + is the nth moiety of a monovalent cation or an n-valent cation, in this case Na + or K + Alkali metal ions including Na are preferred. + is particularly preferred. Further cations include NH4 + , 1 / 2Zn 2+ , 1 / 2Mg 2+ , 1 / 2Ca 2+ , 1 / 2Mn 2+ and mixtures thereof.

[0050] The aqueous dispersion has the formula (T1-2): [ka] [Wherein k=11 to 19, n=2, 3, 4, 5, 6, 7, or 8] The fatty alcohol ether sulfate may comprise at least one alkyl ether sulfate selected from fatty alcohol ether sulfates represented by the formula:

[0051] A more preferred representative example is a C12-14 fatty alcohol ether sulfate with two EOs (k=11-13, n=2). The indicated degree of ethoxylation represents a statistical average that can correspond to an integer or fraction for a particular product. Preferred alkoxylates / ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).

[0052] The aqueous dispersion of the present invention preferably comprises at least one compound of formula (T1-1), (T1-2), (T1-3), (T1-3a) or a mixture thereof.

[0053] Compound (T1-3) has the following formula: [ka] wherein R′ and R″ are independently H or alkyl and together contain 9 to 19, preferably 9 to 15, in particular 9 to 13, C atoms; Y + is a monovalent cation or the nth moiety of an n-valent cation, especially Na + indicates.]

[0054] A more preferred typical example is represented by formula (T1-3a). [ka]

[0055] In a preferred embodiment, the at least one surfactant comprises an anionic or nonionic surfactant or a mixture thereof, and / or The at least one surfactant comprises an alkyl sulfate, preferably a fatty alcohol alkyl sulfate, more preferably sodium lauryl sulfate. A suitable anionic surfactant is commercially available from BASF (Monheim, Germany) under the trade name Texapon K 12P (0.3 wt%).

[0056] The aqueous dispersion of the present invention can contain at least one nonionic surfactant as at least one surfactant.In a preferred embodiment, the aqueous dispersion of the present invention contains at least one nonionic surfactant in addition to an anionic surfactant.Suitable additional nonionic surfactants include alkoxylated fatty acid alkyl esters, alkoxylated fatty acid amides, hydroxylated alkyl glycol ethers, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl (poly)glucosides, and mixtures thereof.

[0057] Particularly preferably, the agent according to the invention comprises, as a nonionic surfactant, a compound of formula (T2): [ka] [During the ceremony, R2 is a linear or branched C8-C18 alkyl, aryl, or alkylaryl functional group; XO are, independently of one another, ethylene oxide (EO) or propylene oxide (PO) groups, m is an integer between 1 and 50. The compound includes at least one compound represented by the formula:

[0058] Preferably, the functional group R of formula (T2) 2 is derived from a C12-C18 fatty alcohol, such as coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or a C8-C18 oxo alcohol.

[0059] According to formula (T2), XO is preferably an ethylene oxide group.

[0060] According to formula (T2), the index m is preferably a number from 1 to 20, in particular from 2 to 10. Preferably, m is 2, 3, 4, 5, 6, 7 or 8.

[0061] The preferred nonionic surfactants are alkoxylated, more preferably ethoxylated, and particularly preferably primary alcohols having 8 to 18 carbon atoms and an average of 4 to 12 moles of ethylene oxide (EO) per mole of alcohol. The alcohol functionality can be linear or methyl-branched, preferably in the 2-position, or can contain a mixture of linear and methyl-branched functionalities, as is commonly found in oxoalcohol functional groups. However, alcohol ethoxylates with linear functionality of naturally occurring alcohols having 12 to 18 carbon atoms, such as coconut, palm, tallow fat, or oleyl alcohol, and an average of 4 to 8 EOs per mole of alcohol, are particularly preferred. Examples of preferred ethoxylated alcohols are C12-14 alcohols with 4 or 7 EOs, C9-11 alcohols with 7 EOs, C13-15 alcohols with 5, 7, or 8 EOs, C12-18 alcohols with 5 or 7 EOs, and mixtures thereof. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to or instead of these preferred nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohols with 14EO, 25EO, 30EO, or 40EO. Nonionic surfactants containing both EO and PO groups in the molecule can also be used according to the present invention. Furthermore, mixtures of (higher) branched and unbranched ethoxylated fatty alcohols are preferred, such as a mixture of a C16-18 fatty alcohol with 7EO and 2-propylheptanol with 7EO. In particular, the aqueous dispersions of the present invention preferably contain a C12-18 fatty alcohol with 7EO or a C13-15 oxoalcohol with 7EO as the nonionic surfactant.

[0062] Nonionic surfactants can also be represented by the formula R 1 R 2 R 3 and the amine oxide of NO, wherein R 1 , R 2 and R3 are, independently of each other, optionally substituted C-C 30 A particularly preferred amine oxide is R 1 C 12 -C 18 alkyl, and R 2 and R 3 are each independently C1-C4 alkyl, in particular C 12 -C 18 Representative examples of suitable amine oxides are N-coconut alkyl-N,N-dimethylamine oxide, N-tallow alkyl-N,N-dihydroxyethylamine oxide, myristyl / cetyl dimethylamine oxide or lauryl dimethylamine oxide.

[0063] The aqueous dispersions of the present invention comprise at least one surfactant, which is preferably an anionic or nonionic surfactant or a mixture thereof, and / or which comprises a fatty alcohol alkoxylate, preferably a linear C12-18 fatty alcohol alkoxylate, more preferably a linear C16-18 alcohol ethoxylate having 10 to 15 ethoxy units, most preferably ceteareth-12, and / or which is present in an amount of 0.01 to 10% by weight, preferably 2 to 7% by weight, based on the solids content of the aqueous dispersion.

[0064] A suitable nonionic surfactant is commercially available from BASF (Ludwigshafen, Germany) under the trade name Eumulgin® B1 (ceteareth-12), which has a hydroxyl number of 70-75.

[0065] According to the invention, the at least one surfactant B) is different from the compounds of component A) of the aqueous dispersion and from the optional components C), D) and E).

[0066] In addition to the cyclic olefin copolymer and surfactant, a co-resin may also be included in the aqueous dispersion of the present invention, preferably the co-resin is C) at least one adhesion promoter, more preferably the at least one adhesion promoter enhances the adhesion of the resulting coating layer, particularly to polyethylene terephthalate or polyolefin substrates.

[0067] In a preferred embodiment, the aqueous dispersion of the present invention comprises at least one adhesion promoter C), i) the at least one adhesion promoter has a hydroxyl number of 10 to 100 mg KOH / g, preferably 20 to 60 mg KOH / g, and / or ii) the at least one adhesion promoter is selected from resins containing hydroxyl, carboxylic, phosphonic and / or phosphoric acid groups, the sum of the acid number and the hydroxyl number preferably being greater than 20 mg KOH / g, more preferably greater than 60 mg KOH / g; and / or iii) the at least one adhesion promoter comprises at least one polyester resin having an acid number of 5 to 75 mg KOH / g, preferably 20 to 30 mg KOH / g, and / or iv) the at least one adhesion promoter comprises at least one polyester resin, which has a glass transition temperature Tg of 0 to 35°C, preferably 10 to 25°C, measured according to DIN EN ISO 11357-1:2017-02, -2:2014-07 or -3:2018-07, and / or v) At least one polyester resin is present in an amount of 0.5 to 20% by weight, preferably 1 to 7% by weight, based on the solids content of the aqueous dispersion.

[0068] The hydroxyl number as a measure of the number of free hydroxyl groups in each defined reference set, e.g., hydroxyl number per gram of resin, can be determined experimentally, preferably by potentiometric titration. For this purpose, preferably, a weighed amount of the reference substance is dissolved in a reaction solution of 0.1 mol / L phthalic anhydride in pyridine at 130°C for 45 minutes, and then diluted with 1.5 times the volume of the reaction solution of pyridine, followed by 1.5 times the initial volume of the reaction solution of deionized water (κ<μScm). -1 ) was added. Preferably, the amount of phthalic acid released in this mixture is titrated with 1 M sodium hydroxide solution. Preferably, the potentiometric measurement is carried out using a combination electrode (LL Solvotrode® the Fa. Metrohm, reference electrolyte: 0.4 mol / L tetraethylammonium bromide in ethylene glycol). The amount of NaOH added per gram reference amount at the inflection point of the potentiometric titration curve is preferably converted into the theoretical amount of KOH added, which directly corresponds to the hydroxyl number.

[0069] In a preferred embodiment, the adhesion promoter, preferably a polyester resin suitable for the present invention, is prepared by reacting a carboxylic acid (or anhydride thereof, or ester thereof), preferably having an effective acid functionality of at least 2, with a polyol, preferably having a hydroxy functionality of at least 2. The molar equivalent ratio of carboxylic acid groups to hydroxy groups of the reactants is selected so that the resulting polyester has hydroxyl functionality and the desired molecular weight. The polyester resin that can be included in the aqueous dispersion of the present invention can be prepared by reacting a cyclic carboxylic acid ester with a polyol, preferably having a hydroxy functionality of at least 2.

[0070] Examples of polyfunctional carboxylic acids useful in preparing adhesion promoters, preferably polyester resins, include, but are not limited to, benzene-1,2,4-tricarboxylic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, endobicyclo-2,2,1,5-heptene-2,3-dicarboxylic acid, tetrachlorophthalic acid, cyclohexanedioic acid, succinic acid, isophthalic acid, terephthalic acid, azelanic acid, maleic acid, trimesic acid, 3,6-dichlorophthalic acid, adipic acid, and sebacic acid.

[0071] Examples of polyols useful in preparing the adhesion promoter, preferably a polyester resin, include, but are not limited to, glycerin, trimethylolpropane, bistrimethylolpropane, trimethylolethane, bistrimethylolethane, trishydroxyethyl isocyanurate, pentaerythritol, bispentaerythritol, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-, 1,2-, and 1,4-butanediol, heptanediol, hexanediol, octanediol, 2,2-bis(4-cyclohexanol)propane, neopentyl glycol, 2,2,3-trimethylpentane-1,3-diol, 1,4-dimethylolcyclohexane, and 2,2,4-trimethylpentanediol.

[0072] The adhesion promoter is preferably an aliphatic polyester resin. The aliphatic polyester resin does not contain aromatic groups and may optionally contain carbon-carbon double bonds and / or carbon-carbon triple bonds. The aliphatic polyester resin is preferably prepared from monomers that do not contain aromatic groups and that are not subsequently modified to contain aromatic groups.

[0073] The adhesion promoter is preferably an aliphatic polyester and includes the residue of at least one polyol having at least two hydroxyl groups, such as at least one aliphatic polyol having at least two hydroxyl groups. Examples of aliphatic polyols having at least two hydroxyl groups from which polyesters can be prepared include, but are not limited to, glycerin, trimethylolpropane, bistrimethylolpropane, trimethylolethane, bistrimethylolethane, trishydroxyethyl isocyanurate, pentaerythritol, bispentaerythritol, ethylene glycol, propylene glycol, trimethylene glycol, 1,3-, 1,2-, and 1,4-butanediol, heptanediol, hexanediol, octanediol, 2,2-bis(4-cyclohexanol)propane, neopentyl glycol, 2,2,3-trimethylpentane-1,3-diol, 1,4-dimethylolcyclohexane, and 2,2,4-trimethylpentanediol.

[0074] In a further embodiment, the adhesion promoter is an aliphatic polyester, each polyol residue of which has at least three hydroxyl groups, preferably an aliphatic polyester, each polyol residue of which is an aliphatic polyol residue having at least three hydroxyl groups. Examples of aliphatic polyols having at least three hydroxyl groups from which polyesters can be prepared include, but are not limited to, glycerin, trimethylolpropane, bistrimethylolpropane, trimethylolethane, bistrimethylolethane, trishydroxyethyl isocyanurate, pentaerythritol, and bispentaerythritol.

[0075] The adhesion promoter preferably comprises the residue of at least one cyclic carboxylic acid ester. The polyester is an aliphatic polyester and comprises the residue of at least one cyclic carboxylic acid ester, such as at least one aliphatic cyclic carboxylic acid ester.

[0076] In some embodiments, the cyclic carboxylic acid ester from which polyesters that can be added to the aqueous dispersions of the present invention can be prepared can be represented by the following formula (T-3): [ka]

[0077] With respect to formula (T-3), and according to some embodiments, R 3 is selected from a divalent linear or branched C2-C20 alkyl, or a divalent linear or branched C2-C10 alkyl, or a divalent linear or branched C2-C5 alkyl, each of which may optionally contain at least one substituent selected from hydroxyl, thiol, and halogen, such as F, Cl, Br, and I.

[0078] In a preferred embodiment, the adhesion promoter is an aliphatic polyester and is prepared from a cyclic carboxylic acid ester (correspondingly comprising at least one residue of a cyclic carboxylic acid ester), the cyclic carboxylic acid ester being selected from epsilon-caprolactone, delta-valerolactone, and combinations thereof.

[0079] In a further preferred embodiment, the adhesion promoter suitable for the aqueous dispersion of the present invention, preferably a polyester resin, comprises the residue of at least one polyol having three hydroxyl groups and the residue of at least one cyclic carboxylic acid ester. The polyester consists essentially of the residue of at least one polyol having three hydroxyl groups and the residue of at least one cyclic carboxylic acid ester. The polyester is preferably an aliphatic polyester and consists essentially of the residue of at least one aliphatic polyol having three hydroxyl groups and the residue of at least one aliphatic cyclic carboxylic acid ester. More preferably, the adhesion promoter is an aliphatic polyester and consists essentially of the residue of at least one aliphatic polyol having three hydroxyl groups and the residue of at least one aliphatic cyclic carboxylic acid ester, and / or comprises less than 1 wt. %, or less than 0.5 wt. %, or less than 0.1 wt. %, based on the total weight of the aliphatic polyester, of residues other than (i) the residue of at least one aliphatic polyol having three hydroxyl groups and (ii) the residue of at least one aliphatic cyclic carboxylic acid ester. In a further preferred embodiment, the polyester, preferably an aliphatic polyester, consists essentially of residues of at least one polyol having three hydroxyl groups and at least one cyclic carboxylic acid ester, and does not contain any residues other than (i) residues of at least one aliphatic polyol having three hydroxyl groups and (ii) residues of at least one aliphatic cyclic carboxylic acid ester.

[0080] A suitable commercially available adhesion promoter, preferably a polyester resin, is, for example, Tego AddBond LTW (5% by weight) from Evonik (Essen, Germany), which has a glass transition temperature of about 20°C according to DIN EN ISO 11357-2:2014-07, an acid number of 20 to 30 mg KOH / g according to DIN EN ISO 2114:2002-06, and a hydroxyl number of about 30 mg KOH / g according to DIN EN ISO 4629-1:2016-12 or -2:2016-12.

[0081] According to the invention, the at least one adhesion promoter C) is different from the compounds of components A) and B) and optional components D) and E) of the aqueous dispersion.

[0082] In a preferred embodiment, the aqueous dispersion comprises or consists of A) at least one cyclic olefin copolymer, B) at least one surfactant, C) at least one adhesion promoter, and F) water.

[0083] In another preferred embodiment, the aqueous dispersion comprises or consists of A) at least one cyclic olefin copolymer, B) at least one surfactant, C) at least one adhesion promoter, D) at least one film-forming resin, and F) water.

[0084] In another preferred embodiment, the aqueous dispersion comprises or consists of A) at least one cyclic olefin copolymer, B) at least one surfactant, D) at least one film-forming resin, and F) water.

[0085] In a preferred embodiment, the aqueous dispersion comprises at least one film-forming resin, i) said at least one film-forming resin forms a coherent film after application at a temperature below 100°C; and / or ii) the at least one film-forming resin has a glass transition temperature, measured according to DIN EN ISO 11357-1:2017-02, -2:2014- or -3:2018-07, of less than 138°C, preferably less than 78°C, most preferably less than 65°C; and / or iii) said at least one film-forming resin comprises homo- and copolymers obtained by polymerizing at least one olefinic monomer having up to 8 carbon atoms, preferably selected from ethylene, propylene, 1-butene, 2-butene, isobutene, 1,3-butadiene and 2-methylbuta-1,3-diene, preferably ethylene and / or propylene; and / or iv) said at least one film-forming resin comprises a copolymer obtained by polymerizing isobutylene with a conjugated diene, such as isoprene, preferably butyl rubber; and / or v) the at least one film-forming resin comprises a copolymer obtained by polymerizing at least one olefinic monomer, preferably an acyclic olefinic monomer having 5 or fewer carbon atoms, more preferably ethylene, propylene, 1-butene, 2-butene, isobutene, 1,3-butadiene, 2-methylbuta-1,3-diene, with at least one comonomer selected from α,β-unsaturated carboxylic acids, preferably cinnamic acid, crotonic acid, fumaric acid, itaconic acid, maleic acid, acrylic acid and methacrylic acid, which copolymer has an acid number of less than 60 mg KOH / g, preferably at least 5 mg KOH / g, more preferably at least 10 mg KOH / g, even more preferably at least 20 mg KOH / g; and / or vi) said at least one film-forming resin is present in an amount of 0.5 to 40% by weight, preferably 5 to 20% by weight, based on the solids content of the dispersion;

[0086] Preferably, the film-forming resin has an acid number of at least 5 mg KOH / g to ensure film formation with compound A. However, the film-forming resin preferably has an acid number of less than 60 mg KOH / g to maintain a stable dispersion of compound A.

[0087] According to the invention, the at least one film-forming resin D) is different from the compounds of components A) and B) and optional components C) and E) of the aqueous dispersion.

[0088] In a preferred embodiment, the aqueous dispersion comprises or consists of A) at least one cyclic olefin copolymer, B) at least one surfactant, C) at least one adhesion promoter, D) at least one film-forming resin, E) at least one additive, and F) water.

[0089] In another preferred embodiment, the aqueous dispersion comprises or consists of A) at least one cyclic olefin copolymer, B) at least one surfactant, D) at least one film-forming resin, E) at least one additive, and F) water.

[0090] In another preferred embodiment, the aqueous dispersion comprises or consists of A) at least one cyclic olefin copolymer, B) at least one surfactant, C) at least one adhesion promoter, E) at least one additive, and F) water.

[0091] In another preferred embodiment, the aqueous dispersion comprises or consists of A) at least one cyclic olefin copolymer, B) at least one surfactant, E) at least one additive, and F) water.

[0092] In a preferred embodiment, the aqueous dispersion comprises at least one additive, i) said at least one additive is selected from the group comprising biocides, organic solvents, plasticizers, slip agents, antiblocking agents, pH adjusters, dyes, pigments, natural oils, synthetic oils, waxes, and / or organic or inorganic fillers, preferably from biocides and / or organic solvents, and / or ii) The at least one additive is present in an amount of 0.0001 to 20% by weight, preferably 0.01 to 15% by weight, based on the total weight of the aqueous dispersion.

[0093] According to the present invention, any impurities and / or any reaction products or by-products that may be formed in the aqueous dispersion in small amounts, preferably less than 1% by weight, more preferably less than 0.1% by weight, more preferably less than 0.01% by weight, also fall under the term "additive".

[0094] Preferred biocidal compounds that can be added to the aqueous dispersion of the present invention include triclosan, heavy metal-based compounds, especially silver-based compounds, zeolites, hydroxyapatite, zinc oxide, titanium dioxide, zirconium phosphate, isothiazolones, benzisothiazolin-3-one derivatives, 10,10'-oxybisphenoxyarsine, isothiazolin, zinc pyrithione, and inorganic carriers such as folpet (trichloromethylthiophthalimide). The addition of biocides can improve the bactericidal activity of coating layers containing known biocidal compounds. It is anticipated that other biocidal compounds can also be effectively used in the aqueous dispersion of the present invention.

[0095] The term "biocide" refers to a compound that has biostatic activity, i.e., a compound in which the growth of microbial species is reduced or eliminated in addition to true bactericidal activity, in which microbial species are killed. In accordance with the present invention, the term also includes activity against fungi, bacteria, and other microbial species.

[0096] Suitable organic solvents that can be added to the aqueous dispersions of the present invention include aromatic solvents such as benzaldehyde, toluene, benzene, and chlorinated solvents, nonpolar organic solvents such as C5-C12 hydrocarbons such as pentane, hexane, and heptane, gasoline (petroleum ether), norbornene, oleic acid, and mixtures thereof. Suitable organic solvents also include mixtures of aromatic solvents and / or nonpolar organic solvents with polar organic solvents such as ethanol, methanol, butanol, isopropanol, acetone, and butanone. A preferred mixture is toluene and isopropanol, particularly in a 9:1 ratio.

[0097] According to the invention, the at least one additive E) is different from the compounds of components A) and B) and optional components C) and D) of the aqueous dispersion.

[0098] In a preferred embodiment, the aqueous dispersion has a solids content of 20 to 60% by weight, preferably 40 to 55% by weight, more preferably 45 to 50% by weight.

[0099] According to aspect 2, the present invention provides a method for manufacturing a semiconductor device comprising: (i) A) dissolving at least one cyclic olefin copolymer in a suitable solvent and optionally adding B) at least one surfactant, and / or optionally C) at least one adhesion promoter, and / or optionally D) at least one film-forming resin, and / or optionally E) at least one additive; (ii) if B) has not been added in step (i), optionally mixing the aqueous phase with B) at least one surfactant, preferably an anionic surfactant and / or a nonionic surfactant, under heating, preferably to a temperature of 50-100°C, more preferably 65-80°C, most preferably 70-75°C, (iii) if B) has not been added in step (i), mixing the solution of step (i) with an aqueous phase optionally comprising B) at least one surfactant under high shear, preferably in a new vessel, more preferably in a high shear mixer, for preferably 0.1 to 10 minutes, more preferably 0.5 to 5 minutes, most preferably 0.7 to 2 minutes; and (iv) concentrating the used solvent, preferably under vacuum, more preferably at 50-500 mbar, more preferably at 150-450 mbar, most preferably at 200-400 mbar; The present invention relates to a method for producing an aqueous dispersion comprising or consisting of the steps of:

[0100] Suitable solvents for the method of producing the aqueous dispersion according to the present invention include, but are not limited to, polar organic solvents, aromatic and / or non-polar organic solvents, preferably ethanol, methanol, butanol, isopropanol, acetone, butanone, benzaldehyde, toluene, benzene, chlorinated solvents, C5-C12 linear or branched hydrocarbons such as pentane, hexane, heptane, or octane, gasoline (petroleum ether), norbornene, oleic acid, and mixtures thereof. Aromatic and non-polar organic solvents are preferred.

[0101] In a preferred embodiment, the solvent is a mixture of toluene and isopropanol.

[0102] Preferably, the shearing in step (iii) is carried out in a high shear mixer, more preferably a batch high shear mixer or an in-line high shear mixer. In a preferred embodiment, the impeller speed of the high shear mixer is 100 to 1500 rpm, more preferably 200 to 1000 rpm.

[0103] In a preferred embodiment, if B) has not been added in step (i), the solution of step (i) and optionally the aqueous phase mixed with B) at least one surfactant are added simultaneously, preferably to a new vessel.

[0104] In another preferred embodiment, if B) is not added in step (i), the solution of step (i) is first added to a new reaction vessel, followed by the stepwise addition of B) an aqueous phase optionally mixed with at least one surfactant under high shear.

[0105] In another preferred embodiment, if B) is not added in step (i), the aqueous phase, optionally mixed with B) at least one surfactant, is first added to a new reaction vessel, followed by the step (i) solution being added stepwise under high shear.

[0106] A suitable high shear mixer is, for example, a Kady Mill LT2000 available from Kady International, Scarborough.

[0107] In a preferred embodiment, the solution of step (i), and optionally B) the aqueous phase mixed with at least one surfactant if B) has not been added in step (i), are preferably added automatically, preferably to a new reaction vessel in a continuous process, more preferably by using an in-line high shear mixer.

[0108] According to a third aspect, (i) feeding to an extruder A) at least one cyclic olefin copolymer, optionally B) at least one surfactant, and / or optionally C) at least one adhesion promoter, and / or optionally D) at least one film-forming resin, and / or optionally E) at least one additive; (ii) adding water to said extruder, preferably in a high shear region of the extruder, more preferably during the extrusion process, wherein the water is mixed with optionally B) at least one surfactant if B) was not added in step (i), and / or optionally C) at least one adhesion promoter if C) is present and not added in step (i), and / or optionally D) at least one film forming resin if D) is present and not added in step (i), and / or optionally E) at least one additive if E) is present and not added in step (i); (iii) transferring the aqueous dispersion obtained by step (ii) from the extruder; A method for producing the aqueous dispersion of the present invention is claimed comprising or consisting of the above steps.

[0109] In a preferred embodiment, the screw speed of the extruder is 100 to 1500 rpm, more preferably 200 to 1000 rpm.

[0110] In another preferred embodiment, the water or aqueous phase in step (ii) is added stepwise under high shear, preferably at 100-1500 rpm, more preferably 200-1000 rpm.

[0111] In a preferred embodiment, in step (i), an extruder is fed with A) at least one cyclic olefin copolymer and, optionally, B) at least one surfactant, preferably ethylene acrylic acid (EAA). Then, in step (ii), water is added to the extruder, where, if B) was not added in step (i), the water is mixed with B) at least one surfactant, preferably ethylene acrylic acid (EAA), and / or optionally C) at least one adhesion promoter, and / or optionally D) a film-forming resin, and / or E) at least one additive.

[0112] According to a fourth aspect, (i) melting A) at least one cyclic olefin copolymer, B) at least one surfactant, optionally C) at least one adhesion promoter, and / or optionally D) at least one film-forming resin, and / or optionally E) at least one additive, preferably under stirring or mixing; (ii) transferring the mixture of step (i) in a reaction chamber, preferably over an inlet, more preferably under high pressure of from 10 to 900 bar; (iii) simultaneously with step (ii) in the reaction chamber, transferring water having a temperature above 100°C but preferably below 200°C, preferably over a second inlet, more preferably under high pressure of between 10 and 900 bar; (iv) simultaneously transporting the mixture of step (ii) and the water of step (iii) in a carrier gas, such as N2, H2 or argon, in a reaction chamber, preferably at a jet velocity of up to 300 m / s, more preferably with a mixing time of less than 0.1 ms for the mixture of step (ii) and the water of step (iii); (v) transferring the mixture obtained by step (iv) from the reaction chamber; A method for producing the aqueous dispersion of the present invention is claimed comprising or consisting of the above steps.

[0113] In a preferred embodiment of aspect 4, the method is carried out in a microjet reactor (MJR). A suitable device is commercially available from Nanosaar (Sternberg, Germany).

[0114] In a preferred embodiment, the aqueous dispersion of the present invention is used to form a copolymer coating on a substrate.

[0115] Thus, in a fifth aspect, the present invention relates to an article comprising at least one substrate and at least one coating layer, which can be obtained by applying the aqueous dispersion of the present invention onto the substrate, preferably by means of a film coater, more preferably under vacuum, and then drying the article, preferably by heating, to obtain the coating layer.

[0116] In a preferred embodiment, i) the substrate is a polyethylene terephthalate or polyolefin substrate, preferably polyethylene terephthalate or oriented polypropylene, and / or ii) the substrate is a flexible substrate, preferably a film, and / or iii) The coating layer obtained has a thickness of 0.1 to 15 g / m 2 , preferably 5 to 10 g / m 2 , more preferably 7 to 9.5 g / m 2 and / or having a coating thickness of iv) The article has a moisture content of 7 to 60 g / (m 2 ·day), preferably 12 to 50 g / (m 2 -Has MVTR of 100,000 yen.

[0117] Preferably, the aqueous dispersion is coated onto the substrate by using an (automatic) film coater, more preferably in combination with a vacuum plate as support. A suitable automatic film coater is commercially available, for example, from Elcometer Limited under the trade name Elcometer 4340. Furthermore, the aqueous dispersion of the present invention can be applied to the substrate using a wire bar coater or doctor blade, for example, in a gravure printing or roll-to-roll process.

[0118] In a preferred embodiment, conventional drying methods such as heat radiation are applied, preferably in an oven, preferably at 50-200°C, for example at 140°C, preferably for 0.5 minutes to 120 minutes, more preferably 1 minute to 10 minutes, most preferably for 5 minutes.

[0119] Preferably, according to the present invention, the term "vacuum" is defined as an air pressure of less than 500 mbar, more preferably less than 450 mbar, more preferably less than 400 mbar, more preferably less than 300 mbar, more preferably less than 200 mbar, more preferably less than 100 mbar, and most preferably less than 50 mbar, unless otherwise specified.

[0120] In a sixth aspect, the present invention relates to the use of the aqueous dispersion of the present invention for coating a substrate, preferably a polyethylene terephthalate or polyolefin substrate. The polyethylene substrate preferably consists of polyethylene and / or polypropylene, such as its oriented and unoriented versions, and its chlorinated or fluorinated versions.

[0121] In a preferred embodiment, the aqueous dispersion is used to form a coating layer that is a thermoformed film or sheet suitable for food packaging, e.g., multilayer pouches, multilayer twist / fold wrapping films for candy, and PE-based forming webs, packaging, e.g., linear tear pouches, high performance multilayer polyolefin shrink films and bubble wrap films for protective packaging, zippers for food and consumer goods, or packaging for pharmaceuticals and devices, e.g., blister films, medical forming webs for medical devices, transdermal patches and medical trays.

[0122] In a further preferred embodiment, the aqueous dispersions of the present invention provide a coating on a substrate, preferably a polyethylene terephthalate or polyolefin substrate, more preferably a polyethylene terephthalate or polyolefin packaging. Preferably, the coating obtained from the aqueous dispersion of the present invention enhances the gas barrier properties of the substrate. Furthermore, the coating produced from the aqueous dispersion of the present invention preferably improves the adhesion of the coating to the substrate without altering the moisture barrier properties.

[0123] All features described for the aqueous solution of the present invention also apply to the claimed manufacturing method, the claimed article and the claimed use, and vice versa. [Example]

[0124] Example 1 <Preparation of Dispersion> The procedure consisted of three steps. In the first step, a cyclic olefin copolymer resin (Topas 9506F-04, Topas GmbH, 7 wt%) was added to a three-neck round-bottom glass along with a polyester resin (Tego AddBond LTW, Evonik, 5 wt%), followed by a solvent mixture (toluene:isopropanol, 9:1 ratio). The round-bottom glass was connected to a reflux system and heated under continuous stirring until boiling using a heating mantle. The reactants had to be added in stages to avoid possible swelling of the polyolefin and thus clogging of the stirring blade. The mixture was stirred until complete solubilization was achieved, yielding the crude product. The size of the round-bottom glass depended on the total volume of the preparation.

[0125] In the second step, an anionic surfactant (BASF's Texapon K 12 P, 0.3 wt%) was added to a beaker along with a nonionic emulsifier (BASF's Eumulgin B1, 0.5 wt%) and mixed with the corresponding amount of water to prepare the aqueous phase. The beaker was heated to 70–75 °C using a magnetic hotplate with continuous stirring.

[0126] In the third step, the lacquer phase was transferred to a high-shear mixer (Kady Mill LT2000), followed by the addition of the aqueous phase. Finally, the mixture was dispersed using high shear for 1 minute. Next, the crude material was transferred again to a round-bottom glass and attached to the distillation setup by connecting it to a Claisen bridge. The solvent was distilled under vacuum (200-400 mbar, depending on the degree of foaming).

[0127] <Coating Preparation> Once dispersion was complete, coatings were prepared from the dispersion using a film coater (Elcometer 4340) equipped with a vacuum plate. The desired substrate (polyethylene terephthalate (PET) or oriented polypropylene (OPP)) was placed on the plate using a vacuum to prevent wrinkles that may occur during coating application. The dispersion was then applied to the substrate using a wire bar coater or doctor blade to produce a uniform film. The coating thickness could be adjusted by appropriately selecting the size of the wire bar or doctor blade. Finally, the coating was heat-dried in an oven at 140°C for 5 minutes.

[0128] <Measurement of Water Vapor Transmission Rate (MVTR)> Once the film was dry, two pieces were cut to the appropriate shape and placed in a Mocon cell (Permatran-W3 / 34 from Mocon Inc.). The film was placed with the coating facing dry, and its MVTR was measured continuously at 38°C and 90% RH until a plateau was reached. Table 1 shows the results for the thickness and MVTR of the final coating on PET.

[0129] [Table 1]

Claims

1. A) 50 to 95% by weight based on the solids content of the aqueous dispersion, C ５ ~C １２ Cycloalkene and at least one C ２ ~C １０ at least one cyclic olefin copolymer obtained by copolymerization with alkylene and having a glass transition temperature Tg of 6 to 138°C, measured according to DIN EN ISO 11357-1:2017-02, -2:2014-07 or -3:2018-07, B) at least one surfactant comprising an alkyl sulfate; C) at least one adhesion promoter comprising at least one polyester resin having a glass transition temperature Tg of 10 to 25°C, measured according to DIN EN ISO 11357-1:2017-02, -2:2014-07 or -3:2018-07, wherein the at least one polyester resin is present in an amount of 0.5 to 20% by weight, based on the solids content of the aqueous dispersion; D) optionally at least one film-forming resin; E) optionally at least one additive, and F) Water 1. An aqueous dispersion comprising or consisting of:

2. the at least one cyclic olefin copolymer i) obtained by copolymerizing norbornene with at least one of ethylene, propylene, butylene, hexylene and octylene, more preferably norbornene with ethylene; and / or ii) has a glass transition temperature Tg of 33 to 78°C, preferably 65°C, measured according to DIN EN ISO 11357-1:2017-02, -2:2014-07, or -3:2018-07; and / or iii) 905 to 1200 kg / m, measured according to DIN EN ISO 1183-1:2013-04 ３ , preferably 1000 to 1050 kg / m ３ and / or having a density of iv) a tensile modulus in the machine direction, measured according to DIN EN ISO 527-3:2003-07, of 1500 to 2500 MPa, preferably 1600 to 1800 MPa; and / or v) a breaking strength in the machine direction of 40 to 70 MPa, preferably 50 to 60 MPa, measured according to DIN EN ISO 527-3:2003-07; and / or vi) an elongation at break in the machine direction of 2.0 to 4.0%, preferably 2.3 to 3.6%, measured according to DIN EN ISO 527-3:2003-07; and / or vii) a melt flow rate at 230°C and 2.16 kg load of 0.5 to 15.0 g / 10 min, preferably 3.5 to 9.5 g / 10 min; and / or viii) in aqueous dispersion, having an average particle size, as measured by dynamic light scattering, of 50 to 500 nm as a D50 value; The aqueous dispersion of claim 1.

3. i) the at least one surfactant further comprises a non-ionic surfactant; and / or ii) the alkyl sulfate comprises a fatty alcohol alkyl sulfate, preferably sodium lauryl sulfate; and / or iii) the at least one surfactant comprises a fatty alcohol alkoxylate, preferably a linear C12-18 fatty alcohol alkoxylate, more preferably a linear C16-18 alcohol ethoxylate having 10 to 15 ethoxy units; and / or iv) the at least one surfactant comprises a copolymer obtained by reacting at least one olefin monomer, preferably selected from ethylene, propene, 1-butene, 2-butene, isobutene, 1,3-butadiene and 2-methylbuta-1,3-diene, with at least one comonomer selected from an α,β-unsaturated carboxylic acid, preferably cinnamic acid, crotonic acid, fumaric acid, itaconic acid, maleic acid, acrylic acid and methacrylic acid, wherein the obtained copolymer preferably has an acid number of at least 60 mg KOH / g, more preferably less than 200 mg KOH / g, more preferably less than 100 mg KOH / g; and / or v) the at least one surfactant is present in an amount of 0.01 to 10% by weight, preferably 2 to 7% by weight, based on the solids content of the aqueous dispersion; 3. The aqueous dispersion according to claim 1 or 2.

4. i) the at least one adhesion promoter has a hydroxyl number of 10 to 100 mg KOH / g, preferably 20 to 60 mg KOH / g, and / or ii) the at least one adhesion promoter is selected from resins containing hydroxyl, carboxylic, phosphonic and / or phosphoric acid groups, preferably having an acid number and a hydroxyl number sum of more than 20 mg KOH / g, more preferably more than 60 mg KOH / g; and / or iii) the at least one polyester resin contained in the adhesion promoter has an acid number of 5 to 75 mg KOH / g, preferably 20 to 30 mg KOH / g; and / or iv) the at least one polyester resin is present at 1 to 7 wt. %, based on the solids content of the aqueous dispersion; The aqueous dispersion according to any one of claims 1 to 3.

5. i) the at least one film-forming resin, after application, forms a coherent film at a temperature below 100°C; and / or ii) the at least one film-forming resin has a glass transition temperature, measured according to DIN EN ISO 11357-1:2017-02, -2:2014-07, or -3:2018-07, of less than 138°C, preferably less than 78°C, and most preferably less than 65°C; and / or iii) the at least one film-forming resin comprises homopolymers and copolymers obtained by polymerizing at least one olefinic monomer having 8 or fewer carbon atoms, preferably selected from ethylene, propylene, 1-butene, 2-butene, isobutene, 1,3-butadiene and 2-methylbuta-1,3-diene, preferably ethylene and / or propylene; and / or iv) the at least one film-forming resin comprises a copolymer obtained by polymerizing isobutylene with a conjugated diene, such as isoprene, preferably butyl rubber; and / or v) said at least one film-forming resin comprises a copolymer obtained by polymerizing at least one olefinic monomer, preferably an acyclic olefinic monomer having not more than 5 carbon atoms, more preferably ethylene, propylene, 1-butene, 2-butene, isobutene, 1,3-butadiene and 2-methylbuta-1,3-diene, with at least one comonomer selected from α,β-unsaturated carboxylic acids, preferably cinnamic acid, crotonic acid, fumaric acid, itaconic acid, maleic acid, acrylic acid and methacrylic acid, wherein the comonomer has an acid number of less than 60 mg KOH / g, preferably at least 5 mg KOH / g, more preferably at least 10 mg KOH / g and even more preferably at least 20 mg KOH / g; and / or vi) said at least one film-forming resin is present in an amount of 0.5 to 40% by weight, preferably 5 to 20% by weight, based on the solids content of the dispersion; The aqueous dispersion according to any one of claims 1 to 4.

6. i) the at least one additive is selected from the group comprising biocides, organic solvents, plasticizers, slip agents, antiblocking agents, pH adjusters, dyes, pigments, natural oils, synthetic oils, waxes, and / or organic or inorganic fillers, preferably from biocides and / or organic solvents; and / or ii) the at least one additive is present in an amount of 0.0001 to 20% by weight, preferably 0.01 to 15% by weight, based on the total weight of the aqueous dispersion; The aqueous dispersion according to any one of claims 1 to 5.

7. the aqueous dispersion has a solids content of 20 to 60% by weight, preferably 40 to 55% by weight; The aqueous dispersion according to any one of claims 1 to 6.

8. (i) dissolving A) at least one cyclic olefin copolymer and C) at least one adhesion promoter in a suitable solvent, and optionally adding B) at least one surfactant, and / or optionally D) at least one film-forming resin, and / or optionally E) at least one additive to obtain a solution; (ii) if B) has not been added in step (i), mixing B) at least one surfactant with the aqueous phase under heating at a temperature of 50-100°C; (iii) mixing under shear the solution of step (i) with an aqueous phase or, if B) is not added in step (i), with an aqueous phase containing B) at least one surfactant; and, (iv) concentrating the spent solution under vacuum; A method for producing the aqueous dispersion according to any one of claims 1 to 7, comprising or consisting of the steps:

9. (i) feeding to an extruder A) at least one cyclic olefin copolymer, optionally B) at least one surfactant, and / or optionally C) at least one adhesion promoter, and / or optionally D) at least one film-forming resin, and / or optionally E) at least one additive; (ii) adding water to said extruder, preferably in a high shear region of the extruder, more preferably during the extrusion process, wherein the water is mixed with B) at least one surfactant if B) was not added in step (i), and / or C) at least one adhesion promoter if C) was not added in step (i), and / or optionally D) at least one film forming resin if D) is present and not added in step (i), and / or optionally E) at least one additive if E) is present and not added in step (i); (iii) transferring the aqueous dispersion obtained by step (ii) from the extruder; A method for producing the aqueous dispersion according to any one of claims 1 to 7, comprising or consisting of the steps:

10. (i) melting A) at least one cyclic olefin copolymer, B) at least one surfactant, C) at least one adhesion promoter, and / or, optionally, D) at least one film-forming resin, and / or, optionally, E) at least one additive, preferably under stirring or mixing; (ii) transferring the mixture of step (i) in a reaction chamber, preferably over an inlet, more preferably under high pressure of 10 to 900 bar; (iii) simultaneously with step (ii) in the reaction chamber, transferring water having a temperature above 100°C but preferably below 200°C, preferably over a second inlet, more preferably under high pressure of between 10 and 900 bar; (iv) In a reaction chamber, the mixture of step (ii) and the water of step (iii) are simultaneously mixed with a carrier gas, e.g., N ２ , H ２ or argon, preferably at a jet velocity of up to 300 m / s, more preferably for a mixing time of less than 0.1 ms between the mixture of step (ii) and the water of step (iii); (v) transferring the mixture obtained by step (iv) from the reaction chamber; A method for producing the aqueous dispersion according to any one of claims 1 to 7, comprising or consisting of the steps:

11. An article comprising at least one substrate and at least one coating layer, applying the aqueous dispersion according to any one of claims 1 to 7 onto a substrate, preferably by means of a film coater, more preferably under vacuum; and The resulting article is then dried, preferably by heating, thereby obtaining a coating layer. An item obtained by

12. i) the substrate is a polyethylene terephthalate or polyolefin substrate, preferably polyethylene terephthalate or oriented polypropylene, and / or ii) the substrate is a flexible substrate, preferably a film, and / or iii) The resulting coating layer has a coating weight of 0.1 to 15 g / m ２ , preferably 5 to 10 g / m ２ , more preferably 7 to 9.5 g / m ２ and / or having a coating thickness of iv) The article has a moisture content of 7 to 60 g / (m ２ ・day), preferably 12 to 50 g / (m ２ -Having MVTR of Japan The article of claim 11.

13. Use of an aqueous dispersion according to any of claims 1 to 7 for coating a substrate, preferably a polyethylene terephthalate or polyolefin substrate.

Images