Aqueous Coating Composition

Abstract

An aqueous coating composition is provided that includes (a) a first polyurethane dispersion comprising a first polyurethane having a Tg of 5° C. to 20° C., (b) a second polyurethane dispersion comprising a second polyurethane having a Tg of −40° C. to −60° C., and (c) a polyacrylic emulsion comprising an acrylic (co)polymer having a Tg of −40° C. to −20° C. Also provided are methods for preparing a laminated material using the aqueous coating composition, and laminated materials prepared therefrom.

Description

[Technical Field]

[0001] The present disclosure relates to the technical field of coating materials, and in particular to an aqueous coating composition comprising a polyacrylic emulsion and two different polyurethane dispersions. [Background technology]

[0002] Press-through packaging (PTP) sheets are one of the most common packaging materials for medical packs worldwide. The adhesives used to prepare PTPs are primarily solvent-based (SB), which has become undesirable in recent years due to the organic solvents released during manufacturing procedures, such as coating and curing, as well as subsequent storage, transportation, and use. Due to stricter VOC emission regulations issued in many countries in recent years, PTP sheet suppliers have been striving to develop environmentally friendly solutions to replace the organic solvent-based adhesives currently used to prepare PTP foils. Several waterborne (WB) coating materials for PTP applications have been reported, specifically formulated with several emulsions or dispersions of several different polymers. However, none of these WB coating materials have been able to achieve a combination of excellent performance properties, including VOC-freeness, economic viability, and excellent heat seal strength and blocking resistance that are better than or at least comparable to those of commercially available solvent-borne (SB) coating materials.

[0003] From the above, it will be appreciated that there remains a strong need for WB coating compositions that can be easily prepared at limited cost and that exhibit the excellent performance characteristics described above.

[0004] After sustained research, it has surprisingly been discovered that a WB polyurethane coating composition can achieve the above targets. Summary of the Invention

[0005] The present disclosure provides a unique aqueous coating composition for PTP foil applications, a method for preparing a laminate material by using the aqueous coating composition, and a laminate material prepared therewith.

[0006] In a first aspect of the present disclosure, the present disclosure provides an aqueous coating composition comprising: (a) a first polyurethane dispersion comprising a first polyurethane having a Tg of 5°C to 20°C; (b) a second polyurethane dispersion comprising a second polyurethane having a Tg of -40°C to -60°C; and (c) a polyacrylic emulsion comprising an acrylic (co)polymer having a Tg of -40°C to -20°C.

[0007] According to one embodiment of the present disclosure, the first polyurethane is derived from a first raw material comprising 15% to 45% by weight of at least one first monomeric diisocyanate, 40% to 75% by weight of at least one first polyol, and 2% to 15% by weight of at least one first internal emulsifier, based on the total dry weight of the first polyurethane dispersion. According to another embodiment of the present disclosure, the second polyurethane is derived from a second raw material comprising 20% ​​to 35% by weight of at least one second monomeric diisocyanate, 50% to 75% by weight of at least one second polyol, and 2% to 10% by weight of at least one second internal emulsifier, based on the total dry weight of the second polyurethane dispersion. According to another embodiment of the present disclosure, the acrylic (co)polymer is derived from a third feedstock comprising 60% to 90% by weight of at least one (meth)acrylic monomer and 10% to 40% by weight of at least one styrenic monomer.

[0008] According to another embodiment of the present disclosure, each of the first and second monomeric diisocyanates is independently selected from the group consisting of C2 to C616 Aliphatic diisocyanates, C6-C 16 Aromatic diisocyanates, C5-C 16 cycloaliphatic diisocyanates, and combinations thereof.

[0009] According to another embodiment of the present disclosure, each of the first polyol and the second polyol independently comprises a C2-C hydroxyl group containing at least two hydroxyl groups. 16 Aliphatic polyhydric alcohols, C6-C containing at least two hydroxyl groups 15 Alicyclic or aromatic polyhydric alcohols, C7-C containing at least two hydroxyl groups 15 Aromatic aliphatic polyhydric alcohols, poly(C4-C6) with an average molecular weight of 500 to 5,000 12 lactone) polyols, polycarbonate polyols having an average functionality of 2 to 5 and an average molecular weight of 400 to 5,000, polyether polyols having an average functionality of 2 to 5 and an average molecular weight of 400 to 12,000, polyester polyols having an average functionality of 2 to 5 and an average molecular weight of 500 to 5,000, and any combination thereof.

[0010] According to another embodiment of the present disclosure, the first polyol is a C4-C6 hydroxyl group-containing polyol. 16 a branched aliphatic polyol and a polycarbonate polyol having an average functionality of 2 to 5 and a molecular weight of 500 to 3,000, optionally including a poly(C4-C6) having an average molecular weight of 800 to 4,000; 12 lactone) polyol, polyether polyol having an average functionality of 2 to 5 and an average molecular weight of 800 to 5,000, and polyester polyol having an average functionality of 2 to 5 and a molecular weight of 800 to 4,000.

[0011] According to another embodiment of the present disclosure, the second polyol comprises a linear polyester polyol having an average functionality of 2 to 5 and a molecular weight of 800 to 5,000, and optionally a poly(C4-C6) having an average molecular weight of 500 to 5,000.12 lactone) polyol, and a polyether polyol having an average functionality of 2 to 5 and an average molecular weight of 400 to 12,000.

[0012] According to another embodiment of the present disclosure, the first polyol is (a) a blend of one polycarbonate polyol having an average functionality of 2 and a molecular weight of 1,000 to 3,000, one polylactone polyol having an average functionality of 2 and a molecular weight of 1,000 to 3,000, and one polyester polyol having an average functionality of 2 and a molecular weight of 1,000 to 3,000; and (b) a blend of trimethylpentanediol, one polyester polyol having an average functionality of 2 and a molecular weight of 1,000 to 3,000, and one polyether polyol having an average functionality of 2 and a molecular weight of 1,000 to 3,000;

[0013] According to another embodiment of the present disclosure, the second polyol is (c) one linear polyester polyol having an average functionality of 2 and a molecular weight of 1,000 to 3,000; and (d) one linear polyester polyol having an average functionality of 2 and a molecular weight of 1,000 to 3,000 and one poly(C4-C6) having an average functionality of 2 and an average molecular weight of 1,000 to 3,000. 12 lactone) polyols, and blends with at least one of polyether polyols having an average functionality of 2 and an average molecular weight of 1,000 to 3,000.

[0014] According to another embodiment of the present disclosure, each of the first internal emulsifier and the second internal emulsifier independently comprises a C2-C substituted with at least two hydroxyl or amino groups. 16 Fatty acids or their salts, C5-C substituted with at least two hydroxyl or amino groups 16 The acid is selected from the group consisting of an alicyclic acid or a salt thereof, and any combination thereof.

[0015] According to another embodiment of the present disclosure, the acrylic copolymer of the polyacrylic emulsion comprises 60% to 80% by weight of at least one C1-C acrylic copolymer, based on the total solids weight of the polyacrylic emulsion. 12 It is derived from a third material comprising an alkyl (meth)acrylate, 1% to 10% by weight of (meth)acrylic acid, and 10% to 30% by weight of styrene and / or C1 to C6 alkyl-substituted styrene.

[0016] According to another embodiment of the present disclosure, the weight ratio of the first polyurethane dispersion, the second polyurethane dispersion, and the polyacrylic emulsion is (10-15):(1-7):(1-8).

[0017] In a second aspect of the present disclosure, the present disclosure provides a method for producing a pharmaceutical composition comprising: (a) providing a metal foil and a substrate; (b) applying an aqueous coating composition of the present disclosure onto at least one surface of a metal foil to form a wet coating, and then curing and drying the wet coating to form a dry coating layer; (c) laminating a substrate onto the dried coating layer under pressure and elevated temperature to form the laminated material.

[0018] In a third aspect of the present disclosure, the present disclosure provides a laminated material comprising a metal foil, a substrate, and a tie layer sandwiched therebetween, wherein the tie layer is derived from the aqueous coating composition of the present disclosure.

[0019] In a fourth aspect of the present disclosure, the present disclosure provides the use of the aqueous coating composition of the present disclosure in the preparation of a PTP (press-through packaging) foil.

[0020] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed. DETAILED DESCRIPTION OF THE INVENTION

[0021] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Additionally, all publications, patent applications, patents, and other references mentioned herein are incorporated by reference.

[0022] As disclosed herein, "and / or" means "and, or alternatively." All ranges are inclusive of the endpoints unless otherwise indicated.

[0023] As disclosed herein, the terms "composition," "formulation," or "mixture" refer to a physical blend of different components obtained by simply mixing the different components by physical means. The term "dispersion" refers to a physical blend comprising a liquid continuous phase and at least one solid and / or liquid dispersed phase, preferably a solid dispersed phase, dispersed in the liquid continuous phase. "Dispersion" is a general concept that can include a solution (i.e., the dispersed phase is soluble in the continuous phase) or a suspension (i.e., the dispersed phase is at least partially insoluble in the continuous phase). According to preferred embodiments of the present disclosure, the solid dispersed phase is uniformly dispersed in the liquid continuous phase. The term "emulsion," as used herein, refers to an essentially stable physical mixture of a liquid continuous phase and at least one solid and / or liquid dispersed phase dispersed in the liquid continuous phase, where the dispersed phase is partially or substantially immiscible in the liquid continuous phase. The stability of an emulsion is preferably derived from electrostatic repulsion effects.

[0024] As disclosed herein, the term "glass transition temperature" or "Tg" is determined by differential scanning calorimetry (DSC).

[0025] As disclosed herein, unless otherwise specified, all percentages referred to herein are by weight, temperatures are in °C, and average molecular weights refer to number average molecular weight (Mn).

[0026] As used herein, the term "(meth)acrylate" refers to an acrylate or methacrylate, the term "(meth)acrylic" refers to an acrylic or methacrylic, and the term "(co)polymer" refers to a polymer or copolymer.

[0027] According to one embodiment of the present disclosure, the aqueous coating composition is substantially free of any intentionally added organic solvent. For example, the total amount of organic solvent is less than 5 wt %, or less than 4 wt %, preferably less than 2 wt %, more preferably less than 1 wt %, more preferably less than 0.1 wt %, more preferably less than 0.01 wt %, more preferably less than 100 wt ppm, more preferably less than 50 wt ppm, more preferably less than 10 wt ppm, more preferably less than 1 wt ppm, more preferably less than 1 wt ppm, based on the total weight of the aqueous coating composition. As disclosed herein, the term "solvent" in "solvent-based" refers to an organic liquid that simply dissolves one or more solid, liquid, or gaseous materials without causing any chemical reaction. In other words, although some organic compounds generally considered "solvents" in polymerization technology, e.g., ethylene glycol, propylene glycol, and other polyols, may be used in the preparation of one or more polymer components such as polyurethanes, none of them belong to the category of "solvents" because they primarily function as isocyanate-reactive functional materials, adhesion promoters, chain extenders, modifiers, emulsifiers, etc. by causing a chemical reaction. According to preferred embodiments of the present disclosure, the aqueous coating composition contains only water as the solvent and does not contain any intentionally added organic solvents.

[0028] In the context of this disclosure, all ingredients used to prepare the first polyurethane will be described with the term "first," and ingredients for the second polyurethane will be described with the term "second" to clearly distinguish them from one another.

[0029] According to various embodiments of the present disclosure, the aqueous coating composition comprises (a) a first polyurethane dispersion, (b) a second polyurethane dispersion different from the first polyurethane dispersion, and (c) a polyacrylate emulsion, and the formulation design of each component is specifically introduced in the following paragraphs.

[0030] First Polyurethane Dispersion In one embodiment of the present disclosure, the first polyurethane dispersion comprises a first polyurethane dispersed in water, and the first polyurethane dispersion has a Tg of 5° C. to 20° C., for example, 10° C. to 15° C., or within a range obtained by combining any two of the following values: 5° C., 6° C., 7° C., 8° C., 9° C., 10° C., 11° C., 12° C., 13° C., 14° C., 15° C., 16° C., 17° C., 18° C., 19° C., and 20° C. According to one embodiment of the present disclosure, the solids content of the first polyurethane dispersion is 20 to 50 wt %, for example, 22 to 48 wt %, or 24 to 46 wt %, or 25 to 45 wt %, or 27 to 42 wt %, or 30 to 40 wt %, or 32 to 38 wt %, or 34 to 36 wt %, based on the total weight of the first polyurethane dispersion. Alternatively, the first polyurethane dispersion may have a solids content within a range obtained by combining any two of the following percentage values: 20% by weight, 21% by weight, 22% by weight, 23% by weight, 24% by weight, 25% by weight, 26% by weight, 27% by weight, 28% by weight, 29% by weight, 30% by weight, 31% by weight, 32% by weight, 33% by weight, 34% by weight, 35% by weight, 36% by weight, 37% by weight, 38% by weight, 39% by weight, 40% by weight, 41% by weight, 42% by weight, 43% by weight, 44% by weight, 45% by weight, 46% by weight, 47% by weight, 48% by weight, 49% by weight, and 50% by weight.

[0031] According to one embodiment of the present disclosure, the first polyurethane is in the form of microparticles. For example, the microparticles of the first polyurethane may have a particle size of 10 nm to 500 nm, or 20 nm to 450 nm, or 30 nm to 400 nm, or 50 nm to 350 nm, or 60 nm to 300 nm, or 80 nm to 250 nm, or 90 nm to 200 nm, or 100 nm to 180 nm, or 120 nm to 150 nm, or within a numerical range obtained by combining any two of the above endpoint values.

[0032] According to one embodiment of the present disclosure, a first polyurethane is prepared by reacting at least one first monomeric diisocyanate with at least one first polyol and at least one first internal emulsifier.

[0033] According to one embodiment of the present disclosure, the first monomeric diisocyanate is a C2 to C 16 Aliphatic diisocyanates, C6-C 16 Aromatic diisocyanates, C5-C 16The diisocyanate may be selected from the group consisting of cycloaliphatic diisocyanates, cycloaliphatic diisocyanates, and combinations thereof. Aliphatic diisocyanates include, but are not limited to, ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (HDI), etc. Cycloaliphatic diisocyanates include, but are not limited to, cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate (IPDI), and methylene-bis-(4-cyclohexylisocyanate) (HMDI). Preferred aromatic diisocyanates are selected from phenylene diisocyanate, methylene diphenyl diisocyanate (MDI), toluene diisocyanate (TDI), carbodiimide-modified MDI, naphthylene diisocyanate, and combinations thereof. TDI can generally be used in any commonly available isomer distribution. The most commonly available TDI has an isomer distribution of 80% 2,4-isomer and 20% 2,6-isomer. TDI with other isomer distributions can also be used. When MDI is used, pure 4,4'-MDI or any combination of MDI isomers is preferred. More preferably, it is pure 4,4'-MDI or any combination of 4,4'-MDI with other MDI isomers. When a combination of 4,4'-MDI and other MDI isomers is used, the preferred concentration of 4,4'-MDI is 25% to 75% of the total MDI isomers.According to alternative embodiments of the present disclosure, examples of aromatic diisocyanates include, but are not limited to, isomers of methylene diphenyl dipolyisocyanate ("MDI"), such as 4,4-MDI, 2,4-MDI, and 2,2'-MDI, or modified MDI, such as carbodiimide-modified MDI or allophanate-modified MDI; isomers of toluene-dipolyisocyanate ("TDI"), such as 2,4-TDI and 2,6-TDI; isomers of naphthalene-dipolyisocyanate ("NDI"), such as 1,5-NDI; and combinations thereof. In a more preferred embodiment of the present disclosure, the first monomeric diisocyanate may be selected from the group consisting of 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-diisocyanatodicyclohexylmethane, diisocyanatomethyl-cyclohexane, and any combination thereof.

[0034] The amount of the first monomeric diisocyanate can be from 15% to 45% by weight, based on the total solids weight of the first polyurethane contained in the first polyurethane dispersion, for example, within a range obtained by combining any two of the following endpoint values: 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, and 45% by weight.

[0035] According to one embodiment of the present disclosure, the monomeric diisocyanates preferably have a molecular weight Mn of less than 500 g / mol, preferably less than 300 g / mol, more preferably less than 275 g / mol.

[0036] The first polyol for preparing the first polyurethane is a C2-C6 polyol containing at least two hydroxyl groups. 16 Aliphatic polyhydric alcohols, C6-C containing at least two hydroxyl groups 15 Alicyclic or aromatic polyhydric alcohols, C7-C containing at least two hydroxyl groups 15 Aromatic aliphatic polyhydric alcohols, poly(C4-C6) with an average molecular weight of 500 to 8,000 12 lactone) polyols, polycarbonate polyols having an average functionality of 2 to 5 and an average molecular weight of 400 to 5,000, polyether polyols having an average functionality of 2 to 5 and an average molecular weight of 400 to 12,000, polyester polyols having an average functionality of 2 to 5 and an average molecular weight of 500 to 5,000, and any combination thereof.

[0037] According to one embodiment of the present disclosure, the first polyol is a C4-C6 polyol containing at least two hydroxyl groups. 16 at least one of a branched aliphatic polyhydric alcohol and a polycarbonate polyol having an average functionality of 2 to 5 and a molecular weight of 600 to 3,000, optionally including the following polyols: poly(C4-C6) having an average molecular weight of 800 to 4,000; 12 lactone) polyol, polyether polyol having an average functionality of 2 to 5 and an average molecular weight of 800 to 5,000, and polyester polyol having an average functionality of 2 to 5 and a molecular weight of 800 to 5,000.

[0038] As used herein, the term "branched aliphatic polyhydric alcohol containing at least two hydroxyl groups" refers to an aliphatic polyhydric alcohol having at least two hydroxyl groups and at least two "branching groups" selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, and hexyl. For example, a C2-C6 branched aliphatic polyhydric alcohol containing at least two hydroxyl groups. 16The aliphatic polyhydric alcohol may be ethylene glycol, propanediol, butanediol, pentanediol, or hexanediol substituted with 2, 3, 4, 5, or 6 "branching groups" selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, and hexyl. According to a preferred embodiment of the present application, the branched aliphatic polyhydric alcohol of the present disclosure is a trimethylpentane-diol, such as 2,2,4-trimethylpentane-1,3-diol (TMPD).

[0039] According to one embodiment of the present disclosure, the polycarbonate polyol has a hydroxyl functionality of 2 to 5, such as 2 to 4, or 2 to 3, or about 2. According to another embodiment of the present disclosure, the polycarbonate polyol has a hydroxyl functionality of 400 to 5,000, such as 800 to 4,500, or the following values: 400, 500, 600, 700, 800, 900, 1,000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700, 3800, 3900, 4000, 4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800, 4900, 5100, 5200, 5300, 5400, 5500, 5600, 5700, 5800, 5900, 6000, 6100, 6200, 6300, 6400, 6500, 6600, 6700, 6800, 6900, 7000, 7100, 7200, 7300, 4000, 4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800, 4900, and 5000 g / mol.

[0040] According to one embodiment of the present disclosure, the first polyol is the above-mentioned C4 to C 16 It includes either a branched aliphatic polyol or a polycarbonate polyol, or a combination thereof.

[0041] According to another embodiment of the present disclosure, the first polyol is a C4 to C6 16 Poly(C4-C6) containing branched aliphatic polyhydric alcohols and having an average molecular weight (Mn) of 800 to 4,000 12According to another embodiment of the present disclosure, the first polyol further comprises one or more of the poly(C4-C6) polyol, a polyether polyol having an average functionality of 2 to 5 and an average molecular weight of 400 to 5,000, and a polyester polyol having an average functionality of 2 to 5 and a molecular weight of 800 to 4,000. According to another embodiment of the present disclosure, the first polyol comprises the polycarbonate polyol described above and further comprises one or more of the poly(C4-C6) polyol having an average molecular weight of 800 to 4,000. 12 lactone) polyol, polyether polyol having an average functionality of 2 to 5 and an average molecular weight of 400 to 5,000, and polyester polyol having an average functionality of 2 to 5 and a molecular weight of 800 to 4,000.

[0042] In the above embodiment, C4 to C 16 The amount of branched aliphatic polyol can be 2% to 30% by weight, for example, 3% to 20% by weight, or up to 15% by weight, or up to 10% by weight, or up to 5% by weight, of the total weight of the first polyol. In the above embodiment, the amount of the "polycarbonate polyol" can be 10% to 50% by weight, for example, 15% to 45% by weight, or 20% to 40% by weight, or 25% to 35% by weight, of the total weight of the first polyol.

[0043] The polyether polyols mentioned above are addition polymerization and grafting products of ethylene oxide, propylene oxide, tetrahydrofuran, and butylene oxide, condensation products of polyhydric alcohols, and any combination thereof. Suitable examples of polyether polyols include polypropylene glycol (PPG), polyethylene glycol (PEG), polybutylene glycol, polytetramethylene ether glycol (PTMEG), and any combination thereof. Preferably, the polyether polyol is a combination of PEG and at least one other polyether polyol selected from the above-mentioned addition polymerization and grafting products and condensation products. More preferably, the polyether polyol is a combination of PEG and at least one of PPG, polybutylene glycol, and PTMEG. According to one embodiment of the present disclosure, the polyether polyol has a viscosity of 400 to 12,000, such as 800 to 5,000, or the following values: 400, 500, 600, 700, 800, 900, 1,000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700, 2800, 2900, 3000, 3100, 3200, 3300 , 3400, 3500, 3600, 3700, 3800, 3900, 4000, 4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800, 4900, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, 10000, 10500, 11000, 11500, and 12000 g / mol. According to one embodiment of the present disclosure, the amount of the polyether polyol may be 0 to 50 wt%, or at most 40 wt%, or at most 30 wt%, or at most 20 wt%, or at most 10 wt% of the total weight of the first polyol.

[0044] Examples of the above-mentioned polyester polyols are condensation products of diols with dicarboxylic acids and their derivatives or their derivatives. Suitable examples of diols include polyalkylene glycols such as ethylene glycol, butylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, and 3-methyl-1,5-pentanediol, and any combination thereof. Triols and / or tetraols can also be used to achieve polyol functionality greater than 2. Suitable examples of such triols include trimethylolpropane and glycerol. Suitable examples of such tetraols include erythritol and pentaerythritol. The dicarboxylic acid is selected from aromatic acids, aliphatic acids, and combinations thereof. Suitable examples of aromatic acids are phthalic acid, isophthalic acid, and terephthalic acid, while suitable examples of aliphatic acids are adipic acid, azelaic acid, sebacic acid, glutaric acid, tetrachlorophthalic acid, maleic acid, fumaric acid, itaconic acid, malonic acid, suberic acid, 2-methylsuccinic acid, 3,3-diethylglutaric acid, and 2,2-dimethylsuccinic acid. The anhydrides of these acids can also be used. Therefore, for the purposes of the present invention, anhydrides are encompassed by the term "acid." Preferably, the aliphatic and aromatic acids are saturated, such as adipic acid and isophthalic acid, respectively. Monocarboxylic acids, such as benzoic acid and hexanecarboxylic acid, should be minimized or eliminated.According to one embodiment of the present disclosure, the polyether polyols described above have a viscosity of 500 to 5,000, such as 800 to 4,000, or the following values: 500, 600, 700, 800, 900, 1,000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600 , 2700, 2800, 2900, 3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700, 3800, 3900, 4000, 4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800, 4900, and 5000 g / mol. According to one embodiment of the present disclosure, the amount of the polyester polyol may be 0 to 55 wt % or 20 to 50 wt % of the total weight of the first polyol.

[0045] The polylactone polyols described above include at least one C4-C 12This refers to polymer polyols prepared by addition polymerization of lactones with diols, triols, and / or tetraols. Suitable examples of lactones include propiolactone, caprolactone, butyrolactone, and valerolactone, such as ε-caprolactone, β-propiolactone, γ-butyrolactone, methyl-ε-caprolactone, or mixtures thereof. Suitable examples of diols include polyalkylene glycols such as ethylene glycol, butylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and any combination thereof. Suitable examples of triols include trimethylolpropane and glycerol. Suitable examples of tetraols include erythritol and pentaerythritol. According to one embodiment of the present disclosure, the polylactone polyol has a viscosity of 500 to 5,000, such as 800 to 4,000, or the following values: 500, 600, 700, 800, 900, 1,000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600 , 2700, 2800, 2900, 3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700, 3800, 3900, 4000, 4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800, 4900, and 5000 g / mol. According to one embodiment of the present disclosure, the amount of the polylactone polyol may be 0 to 40 wt %, or 0 to 35 wt %, of the total weight of the first polyol.

[0046] The total amount of the first polyol can be 40% to 75% by weight, based on the total solids weight of the first polyurethane contained in the first polyurethane dispersion, for example, within a range obtained by combining any two of the following endpoint values: 40% by weight, 41% by weight, 42% by weight, 43% by weight, 44% by weight, 45% by weight, 46% by weight, 47% by weight, 48% by weight, 49% by weight, 50% by weight, 51% by weight, 52% by weight, 53% by weight, 54% by weight, 55% by weight, 56% by weight, 57% by weight, 58% by weight, 59% by weight, 60% by weight, 61% by weight, 62% by weight, 63% by weight, 64% by weight, 65% by weight, 66% by weight, 67% by weight, 68% by weight, 69% by weight, 70% by weight, 71% by weight, 72% by weight, 73% by weight, 74% by weight, and 75% by weight.

[0047] According to one preferred embodiment of the present disclosure, one polycarbonate polyol, one polylactone polyol, and one polyester polyol as described above are used in combination as a first polyol to prepare a first polyurethane. Preferably, the weight ratio among these polyols is polycarbonate polyol:polylactone polyol:polyester polyol=(0.3-3):(0.3-3):(0.3-3), for example, (0.7-1.5):(0.7-1.5):(0.7-1.5), or (0.75-1.4):(0.75-1.4):(0.75-1.4). According to one preferred embodiment, the first polyol is a blend of one polycarbonate polyol having an average functionality of 2 and a molecular weight of 1,000 to 3,000, one polylactone polyol having an average functionality of 2 and a molecular weight of 1,000 to 3,000, and one polyester polyol having an average functionality of 2 and a molecular weight of 1,000 to 3,000.

[0048] According to another preferred embodiment of the present disclosure, one of C4 to C 16A branched aliphatic polyhydric alcohol, one polyester polyol, and one polyether polyol are used in combination as the first polyol to prepare the first polyurethane. Preferably, the weight ratio between these polyols is C4 to C6. 16 The branched aliphatic polyhydric alcohol: polyester polyol: polyether polyol ratio may be (0.05-5): (5-20): (5-20), for example (0.08-3): (7-15): (7-15), or (0.9-1.5): (8-12): (8-12), or (0.95-1.1): (9-11): (9-11). According to one preferred embodiment, the first polyol is a blend of trimethylpentanediol, one polyester polyol having an average functionality of 2 and a molecular weight of 1,000-3,000, and one polyether polyol having an average functionality of 2 and a molecular weight of 1,000-3,000.

[0049] The first internal emulsifier used to prepare the first polyurethane is preferably anionic. Suitable examples of the first internal emulsifier include C2-C substituted with at least two hydroxyl or amino groups. 16 Aliphatic acids or their salts, C5-C substituted with at least two hydroxyl or amino groups 16 The first internal emulsifier is selected from the group consisting of alicyclic acids or salts thereof, sulfonates, phosphates, carboxylates, and any combination thereof. Preferably, the first internal emulsifier includes 2,2-dimethylolpropionic acid and its derivatives.

[0050] The amount of the first internal emulsifier may be from 1 wt.% to 15 wt.%, based on the total solids weight of the first polyurethane contained in the first polyurethane dispersion, for example, the following endpoint values: 1 wt.%, 1.2 wt.%, 1.4 wt.%, 1.5 wt.%, 1.8 wt.%, 2 wt.%, 2.2 wt.%, 2.4 wt.%, 2.5 wt.%, 2.8 wt.%, 3 wt.%, 3.2 wt.%, 3.4 wt.%, 3.5 wt.%, 3.6 wt.%, 3.8 wt.%, 4.0 wt.%, 4.2 wt.%, 4.5 wt.%, 4.8 wt.%, 5.0 wt.%, 5.2 wt.%, 5.5 wt.%, 5.8 wt.%, 6.0 wt.%, 6.2 wt.%, 6.5 wt.%, 6.8 wt.%, 7.0 wt.%, 7.2 wt.%, 7.5 wt.%, %, 7.8 weight%, 8.0 weight%, 8.2 weight%, 8.5 weight%, 8.8 weight%, 9.0 weight%, 9.2 weight%, 9.5 weight%, 9.8 weight%, 10.0 weight%, 10.5 weight%, 11 weight%, 11.2 weight%, 11.4 weight%, 11.5 weight%, 11.8 weight%, 12 weight%, 12.2 weight%, 12.4 weight%, 12.5 weight%, 12.8 weight%, 13 weight%, 13.2 weight%, 13.4 weight%, 13.5 weight%, 13.6 weight%, 13.8 weight%, 14.0 weight%, 14.2 weight%, 14.5 weight%, 14.8 weight%, and 15.0 weight%.

[0051] According to one embodiment of the present disclosure, at least one chain extender or crosslinker may be present in the reactants used to prepare the first polyurethane dispersion. The chain extender may be a chemical having two isocyanate-reactive groups per molecule and an equivalent weight per isocyanate-reactive group of less than 300, preferably less than 200, and particularly 31 to 125. The isocyanate-reactive groups are preferably hydroxyl, primary aliphatic or aromatic hydroxyl / amino, or secondary aliphatic or aromatic amino groups. Representative chain extenders or crosslinkers include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, cyclohexanedimethanol, ethylenediamine, phenylenediamine, bis(3-chloro-4-aminophenyl)methane, dimethylthio-toluenediamine, and diethyltoluenediamine.

[0052] According to one embodiment of the present disclosure, the content of the chain extender or crosslinker is 2 wt.% to 12 wt.%, based on the total solid weight of the first polyurethane contained in the first polyurethane dispersion, for example, the following endpoint values: 2 wt.%, 2.2 wt.%, 2.4 wt.%, 2.5 wt.%, 2.8 wt.%, 3 wt.%, 3.2 wt.%, 3.4 wt.%, 3.5 wt.%, 3.6 wt.%, 3.8 wt.%, 4.0 wt.%, 4.2 wt.%, 4.5 wt.%, 4.8 wt.%, 5.0 wt.%, 5.2 wt.%, 5.5 wt.%, 5.8 wt.%, It may be within a numerical range obtained by combining any two of 6.0 wt%, 6.2 wt%, 6.5 wt%, 6.8 wt%, 7.0 wt%, 7.2 wt%, 7.5 wt%, 7.8 wt%, 8.0 wt%, 8.2 wt%, 8.5 wt%, 8.8 wt%, 9.0 wt%, 9.2 wt%, 9.5 wt%, 9.8 wt%, 10.0 wt%, 10.2 wt%, 10.5 wt%, 10.8 wt%, 11.0 wt%, 11.2 wt%, 11.5 wt%, 11.8 wt%, and 12.0 wt%.

[0053] The pH of the reaction mixture can be adjusted by adding an acid or base during the preparation of the first polyurethane dispersion. Examples of bases include, but are not limited to, ammonia, diethylamine, triethylamine, dimethylethanolamine, triethanolamine, sodium hydroxide, potassium hydroxide, and sodium acetate. Examples of acids include, but are not limited to, acetic acid, formic acid, hydrochloric acid, nitric acid, and toluenesulfonic acid.

[0054] The first polyurethane of the first polyurethane dispersion has a glass transition temperature (Tg) of 5 to 20°C, for example, within the range obtained by combining any two of the following endpoint values: 5°C, or 6°C, or 7°C, or 8°C, or 9°C, or 10°C, or 11°C, or 12°C, or 13°C, or 14°C, or 15°C, or 16°C, or 17°C, or 18°C, or 19°C, or 20°C.

[0055] Second Polyurethane Dispersion In one embodiment of the present disclosure, the second polyurethane dispersion comprises a second polyurethane dispersed in water, and the solids content of the second polyurethane is 30 to 50 wt %, for example, 32 to 49 wt %, or 34 to 48 wt %, or 35 to 47 wt %, or 37 to 46 wt %, or 38 to 45 wt %, or 40 to 44 wt %, or 42 to 43 wt %, based on the total weight of the second polyurethane dispersion. Alternatively, the second polyurethane dispersion may have a solids content within a numerical range obtained by combining any two of the following percentage values: 30% by weight, 31% by weight, 32% by weight, 33% by weight, 34% by weight, 35% by weight, 36% by weight, 37% by weight, 38% by weight, 39% by weight, 40% by weight, 41% by weight, 42% by weight, 43% by weight, 44% by weight, 45% by weight, 46% by weight, 47% by weight, 48% by weight, 49% by weight, and 50% by weight.

[0056] According to one embodiment of the present disclosure, the second polyurethane is in the form of microparticles. For example, the microparticles of the second polyurethane may have a particle size of 15 nm to 600 nm, or 20 nm to 500 nm, or 30 nm to 450 nm, or 50 nm to 400 nm, or 60 nm to 350 nm, or 80 nm to 300 nm, or 90 nm to 250 nm, or 100 nm to 200 nm, or 120 nm to 150 nm, or within a numerical range obtained by combining any two of the above endpoint values.

[0057] According to one embodiment of the present disclosure, the second polyurethane is prepared by reacting at least one second monomeric diisocyanate with at least one second polyol and at least one second internal emulsifier.

[0058] According to one embodiment of the present disclosure, the second monomeric diisocyanate is a C2 to C 16 Aliphatic diisocyanates, C6-C 16 Aromatic diisocyanates, C5-C 16The diisocyanate may be selected from the group consisting of cycloaliphatic diisocyanates, cycloaliphatic diisocyanates, and combinations thereof. Aliphatic diisocyanates include, but are not limited to, ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (HDI), and the like. Cycloaliphatic diisocyanates include, but are not limited to, cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate (IPDI), and methylene-bis-(4-cyclohexylisocyanate) (HMDI). Preferred aromatic diisocyanates are selected from phenylene diisocyanate, methylene diphenyl diisocyanate (MDI), toluene diisocyanate (TDI), carbodiimide-modified MDI, naphthylene diisocyanate, and combinations thereof. TDI can generally be used in any commonly available isomer distribution. The most commonly available TDI has an isomer distribution of 80% 2,4-isomer and 20% 2,6-isomer. TDI with other isomer distributions can also be used. When MDI is used, pure 4,4'-MDI or any combination of MDI isomers is preferred. More preferably, it is pure 4,4'-MDI and any combination of 4,4'-MDI with other MDI isomers. When using a combination of 4,4'-MDI with other MDI isomers, the preferred concentration of 4,4'-MDI is 25% to 75% of the total MDI isomers. According to alternative embodiments of the present disclosure, examples of aromatic diisocyanates include, but are not limited to, isomers of methylene diphenyl dipolyisocyanate ("MDI"), such as 4,4-MDI, 2,4-MDI, and 2,2'-MDI, or modified MDI, such as carbodiimide-modified MDI or allophanate-modified MDI; isomers of toluene-dipolyisocyanate ("TDI"), such as 2,4-TDI and 2,6-TDI; isomers of naphthalene-dipolyisocyanate ("NDI"), such as 1,5-NDI; and combinations thereof.In a more preferred embodiment of the present disclosure, the second monomeric diisocyanate may be selected from the group consisting of 1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-diisocyanatodicyclohexylmethane, diisocyanatomethyl-cyclohexane, and any combination thereof.

[0059] The amount of the second monomeric diisocyanate can be from 10% to 35% by weight, based on the total solids weight of the second polyurethane contained in the second polyurethane dispersion, for example, within a range obtained by combining any two of the following endpoint values: 10% by weight, 11% by weight, 12% by weight, 13% by weight, 14% by weight, 15% by weight, 16% by weight, 17% by weight, 18% by weight, 19% by weight, 20% by weight, 21% by weight, 22% by weight, 23% by weight, 24% by weight, 25% by weight, 26% by weight, 27% by weight, 28% by weight, 29% by weight, 30% by weight, 31% by weight, 32% by weight, 33% by weight, 34% by weight, and 35% by weight.

[0060] According to one embodiment of the present disclosure, the second monomeric diisocyanate preferably has a molecular weight Mn of less than 500 g / mol, preferably less than 300 g / mol, more preferably less than 275 g / mol.

[0061] According to one embodiment of the present disclosure, the second polyol for preparing the second polyurethane comprises a polyester polyol having an average functionality of 2 to 5 and a molecular weight of 600 to 6,000, and optionally a poly(C4-C6) having an average molecular weight of 500 to 8,000. 12The polyester polyol further comprises one or both of a lactone polyol and a polyether polyol having an average functionality of 2 to 5 and an average molecular weight of 400 to 12,000. According to a preferred embodiment of the present disclosure, the polyester polyol is prepared by using adipic acid (ADA) and one or both of hexane diol (HDO, more preferably 1,6-hexane diol) and butane diol (BDO, more preferably 1,4-butane diol).

[0062] According to one embodiment of the present disclosure, the polyester polyol has a hydroxyl functionality of 2 to 5, for example, 2 to 4, or 2 to 3, or about 2. According to another embodiment of the present disclosure, the polyester polyol has a hydroxyl functionality of 800 to 5,000, such as 1,000 to 4,500, or the following values: 800, 900, 1,000, 1100, 1200, 1300, 1400, 1500, 1600, 1700, 1800, 1900, 2000, 2100, 2200, 2300, 2400, 2500, 2600, 2700 , 2800, 2900, 3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700, 3800, 3900, 4000, 4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800, 4900, 5000 g / mol.

[0063] According to one embodiment of the present disclosure, the polyester polyol is a condensation product of a diol with a dicarboxylic acid or its derivatives. Suitable examples of the diol include 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, and any combination thereof. The dicarboxylic acid is selected from aromatic acids, aliphatic acids, and combinations thereof. Suitable examples of aromatic acids include phthalic acid, isophthalic acid, and terephthalic acid, while suitable examples of aliphatic acids include adipic acid, azelaic acid, sebacic acid, glutaric acid, tetrachlorophthalic acid, maleic acid, fumaric acid, itaconic acid, malonic acid, suberic acid, 2-methylsuccinic acid, 3,3-diethylglutaric acid, and 2,2-dimethylsuccinic acid. Anhydrides of these acids can also be used. Therefore, for purposes of the present invention, anhydrides are encompassed within the term "acid." Preferably, the aliphatic acid and aromatic acid are saturated, such as adipic acid and isophthalic acid, respectively. Monocarboxylic acids such as benzoic acid and hexanecarboxylic acid should be minimized or eliminated. According to a preferred embodiment, the majority of the polyester polyol for the second polyol, for example, at least 90%, or at least 95%, or at least 99%, or all, has a "linear structure." As used herein, the term "linear polyester polyol" refers to a polyester polyol derived from a carboxylic acid and a diol that does not have any side chain or branched structure.

[0064] According to one embodiment of the present disclosure, the amount of polyester polyol can be 35% to 100% by weight of the total weight of the second polyol, for example, at least 40% by weight, or at least 50% by weight, or at least 60% by weight, or at least 70% by weight, or at least 80% by weight, or at least 85% by weight.

[0065] According to one embodiment of the present disclosure, polyether polyols and polylactone polyols can optionally be used for the second polyol. According to a preferred embodiment, a majority of the polyether polyols and polylactone polyols for the second polyol, for example, at least 90%, or at least 95%, or at least 99%, or all, have a "linear structure." As used herein, the terms "linear polyether polyol" and "linear polylactone polyol" refer to polyether polyols and polylactone polyols that do not contain any side chains or branched structures. Preferably, the second polyol is a polycarbonate polyol or a C2-C6 polyol. 16 Does not contain aliphatic polyhydric alcohols, especially C4-C 16 Does not contain branched aliphatic polyhydric alcohols.

[0066] According to one embodiment of the present disclosure, the amount of the optional polyether polyol described above can be 0 to 50 wt %, or up to 40 wt %, or up to 30 wt %, or up to 20 wt %, or up to 15 wt % of the total weight of the second polyol. According to another embodiment of the present disclosure, the amount of the polylactone polyol described above can be 0 to 40 wt %, or up to 40 wt %, or up to 30 wt %, or up to 20 wt %, or up to 15 wt % of the total weight of the second polyol. The polyether polyols and polylactone polyols described above for the first polyol can be used as optional components in the second polyol.

[0067] According to a preferred embodiment of the present disclosure, the total amount of the second polyol may be 50% to 75% by weight, based on the total solids weight of the second polyurethane contained in the second polyurethane dispersion, for example, within a numerical range obtained by combining any two of the following endpoint values: 50% by weight, 51% by weight, 52% by weight, 53% by weight, 54% by weight, 55% by weight, 56% by weight, 57% by weight, 58% by weight, 59% by weight, 60% by weight, 61% by weight, 62% by weight, 63% by weight, 64% by weight, 65% by weight, 66% by weight, 67% by weight, 68% by weight, 69% by weight, 70% by weight, 71% by weight, 72% by weight, 73% by weight, 74% by weight, and 75% by weight.

[0068] According to one preferred embodiment of the present disclosure, one polyester polyol as described above is used exclusively as the second polyol for preparing the second polyurethane. According to another preferred embodiment of the present disclosure, one polyester polyol as described above is used in combination with one polyether polyol as described above as the second polyol for preparing the second polyurethane.

[0069] The second internal emulsifier used to prepare the second polyurethane is preferably anionic. Suitable examples of the second internal emulsifier include C2-C substituted with at least two hydroxyl or amino groups. 16 Fatty acids or their salts, C5-C substituted with at least two hydroxyl or amino groups 16 The second internal emulsifier is selected from the group consisting of alicyclic acids or salts thereof, sulfonates, phosphates, carboxylates, and any combination thereof. Preferably, the second internal emulsifier comprises 2,2-dimethylolpropionic acid and its derivatives.

[0070] The amount of the second internal emulsifier may be from 2 wt.% to 10 wt.%, based on the total solids weight of the second polyurethane contained in the second polyurethane dispersion, for example, the following endpoint values: 2 wt.%, 2.2 wt.%, 2.4 wt.%, 2.5 wt.%, 2.8 wt.%, 3 wt.%, 3.2 wt.%, 3.4 wt.%, 3.5 wt.%, 3.6 wt.%, 3.8 wt.%, 4.0 wt.%, 4.2 wt.%, 4.5 wt.%, 4.8 wt.%, 5.0 wt.% , 5.2 wt%, 5.5 wt%, 5.8 wt%, 6.0 wt%, 6.2 wt%, 6.5 wt%, 6.8 wt%, 7.0 wt%, 7.2 wt%, 7.5 wt%, 7.8 wt%, 8.0 wt%, 8.2 wt%, 8.5 wt%, 8.8 wt%, 9.0 wt%, 9.2 wt%, 9.5 wt%, 9.8 wt%, and 10.0 wt%.

[0071] According to one embodiment of the present disclosure, at least one chain extender or crosslinker may be present in the reactants used to prepare the second polyurethane dispersion. The above categories and contents of chain extenders or crosslinkers for the first polyurethane also apply to those for the second polyurethane.

[0072] The pH of the reaction mixture can be adjusted by adding an acid or base during the preparation of the first polyurethane dispersion. Examples of bases include, but are not limited to, ammonia, diethylamine, triethylamine, dimethylethanolamine, triethanolamine, sodium hydroxide, potassium hydroxide, and sodium acetate. Examples of acids include, but are not limited to, acetic acid, formic acid, hydrochloric acid, nitric acid, and toluenesulfonic acid.

[0073] The second polyurethane of the second polyurethane dispersion has a glass transition temperature (Tg) of -40 to -60°C, for example, within the range obtained by combining any two of the following endpoint values: -60°C, or -58°C, or -56°C, or -55°C, or -54°C, or -53°C, or -52°C, or -51°C, or -50°C, or -49°C, or -48°C, or -47°C, or -46°C, or -45°C, or -44°C, or -43°C, or -42°C, or -41°C, or -40°C.

[0074] Acrylic emulsion An acrylic emulsion is a latex, which is an aqueous dispersion of particles of a copolymer derived from at least one (meth)acrylic monomer and at least one styrenic monomer. The copolymer may further contain additional comonomers other than the (meth)acrylic monomer and the styrenic monomer, such as vinyl (e.g., acetates such as vinyl acetate and ethylene vinyl acetate; alcohols; chlorides such as polyvinyl dichloride and polyvinyl chloride). The latex typically exhibits a viscosity at 25°C of about 10 to 1,000 cps, more preferably 20 to 500 cps. The acrylic emulsion may have a solids content in the range of 35 to 65% by weight, based on the total weight of the polyacrylic emulsion, for example, within the range obtained by combining any two of the following endpoint values ​​based on the total weight: 35%, 38%, 40%, 42%, 44%, 45%, 46%, 48%, 50%, 52%, 54%, 55%, 57%, 58%, 60%, 61%, 62%, 63%, 64%, and 65% by weight. In one embodiment, the copolymer in the polyacrylic emulsion may have a number average molecular weight of 5,000 to 2,000,000, more preferably 100,000 to 2,000,000.

[0075] According to one embodiment of the present disclosure, the copolymer may comprise 5% to 50% by weight of repeat units derived from at least one styrenic monomer, based on the total solids weight of the polyacrylic emulsion. Alternatively, the content of polymerized residues derived from the at least one styrenic monomer may be within a range obtained by combining any two of the following endpoint values, based on the total solids weight of the polyacrylic emulsion: 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 44%, 45%, 48%, and 50% by weight. The styrenic monomer may include styrene or a C1-C6 alkyl-substituted styrene, such as styrene or α-methylstyrene.

[0076] According to one preferred embodiment of the present disclosure, the copolymer comprises 50% to 90% by weight of at least one C1-C6 copolymer, based on the total solids weight of the polyacrylic emulsion. 20 It may contain polymerized residues derived from alkyl (meth)acrylate monomers and, optionally, 1% to 15% by weight of repeat units derived from at least one ethylenically unsaturated acid having at least one carboxylic acid group.

[0077] For example, at least one C1~C 20 The content of repeat units derived from alkyl (meth)acrylate monomers may be within a range obtained by combining any two of the following endpoint values: 50 wt%, 52 wt%, 55 wt%, 58 wt%, 60 wt%, 62 wt%, 65 wt%, 68 wt%, 70 wt%, 72 wt%, 75 wt%, 78 wt%, 80 wt%, 82 wt%, 85 wt%, 88 wt%, and 90 wt%, based on the total solids weight of the polyacrylic emulsion. 20Alkyl (meth)acrylate monomers include C4 to C6 alkyl methacrylates such as methyl methacrylate (MMA), ethyl methacrylate (EMA), butyl methacrylate (BMA), ethylhexyl methacrylate (EHMA), lauryl methacrylate (LMA), hydroxyethyl methacrylate (HEMA), methyl acrylate (MA), ethyl acrylate (EA), butyl acrylate (BA), isobutyl acrylate (IBA), ethylhexyl acrylate (EHA), and hydroxyethyl acrylate (HEA). 12 It can be an alkyl (meth)acrylate ester monomer.

[0078] The content of repeat units derived from at least one ethylenically unsaturated acid may be within a range obtained by combining any two of the following endpoint values: 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, and 15 wt%, based on the total solids weight of the polyacrylic emulsion. According to one embodiment of the present disclosure, the ethylenically unsaturated acid may be acrylic acid, methacrylic acid, itaconic acid, fumaric acid, or a combination thereof.

[0079] According to one embodiment of the present disclosure, the copolymer in the polyacrylic emulsion contains less than 0.5% residues of hydroxyl-containing monomers. Preferably, the polymer has less than 0.3% of such residues, more preferably less than 0.2%, and most preferably, the polymer is substantially free of residues of hydroxyl-containing monomers. Examples of hydroxyl-containing monomers include, for example, HEMA, HEA, vinyl alcohol, hydroxypropyl methacrylate (HPMA), and hydroxypropyl acrylate. Preferably, the polymer is substantially free of amino-containing monomers. Preferably, the polymer has less than 0.5% isocyanate-reactive groups other than carboxylic acid groups, more preferably less than 0.2%, and most preferably, is substantially free of isocyanate-reactive groups other than carboxylic acid groups.

[0080] Conventional processing agents such as surfactants and initiators can be used in the preparation of polyacrylic emulsions. For example, surfactants can be used during the preparation of polyacrylic emulsions to provide stability and control particle size. Conventional surfactants include anionic or nonionic emulsifiers or combinations thereof. Typical anionic emulsifiers include, but are not limited to, alkali or ammonium alkyl sulfates, alkali or ammonium alkyl ether sulfates, alkali or ammonium alkyl aryl ether sulfates, alkyl sulfonates, salts of fatty acids, esters of sulfosuccinates, alkyl diphenyl ether disulfonates, and salts or free acids of complex organic phosphate esters. Typical nonionic emulsifiers include, but are not limited to, polyethers such as propylene oxide ethylene and propylene oxide condensates, including linear and branched alkyl and alkylaryl polyethylene glycols and polypropylene glycol ethers and thioethers, alkylphenoxypoly(ethyleneoxy)ethanols having alkyl groups containing from about 7 to about 18 carbon atoms and from about 4 to about 100 ethyleneoxy units, and polyoxyalkylene derivatives of hexitols, including sorbitan, sorbide, mannitan, and mannide. Surfactants may be used at levels of 0.1 to 5% by weight, based on the total weight of the resulting polyacrylic emulsion.

[0081] According to one embodiment of the present disclosure, the acrylic emulsion has a Tg of -40°C to -20°C, for example, within a range obtained by combining any two of the following endpoint values: -40°C, or -39°C, or -38°C, or -37°C, or -36°C, or -35°C, or -34°C, or -33°C, or -32°C, or -31°C, or -30°C, or -29°C, or -28°C, or -27°C, or -26°C, or -25°C, or -24°C, or -23°C, or -22°C, or -21°C, or -20°C.

[0082] Other additives To prepare the first and second polyurethane dispersions, one or more catalysts can optionally be used to promote or accelerate the polymerization reaction described above. Catalysts can include any substance capable of promoting the reaction between isocyanate groups and hydroxyl groups. Without being limited by theory, catalysts include, for example, glycine salts; tertiary amines; tertiary phosphines, such as trialkylphosphines and dialkylbenzylphosphines; morpholine derivatives; piperazine derivatives; chelates of various metals, such as Be, Mg, Zn, Cd, Pd, Ti, Zr, Sn, As, Bi, Cr, Mo, Mn, Fe, Co, and Ni, with acetylacetone, benzoylacetone, trifluoroacetylacetone, ethyl acetoacetate, and the like; acidic metal salts of strong acids, such as ferric chloride and stannic chloride; alkali metals, alkaline earth metals, such as Al, Sn, Pb, Mn, Co, Ni, and Cu. Examples of suitable catalysts include organic tin compounds such as tin(II) salts of organic carboxylic acids containing various metals, such as tin(II) diacetate, tin(II) dioctanoate, tin(II) diethylhexanoate, and tin(II) dilaurate, and dialkyltin(IV) salts of organic carboxylic acids, such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, and dioctyltin diacetate; bismuth salts of organic carboxylic acids, such as bismuth octoate; organometallic derivatives of trivalent and pentavalent As, Sb, and Bi, and metal carbonyls of iron and cobalt; or mixtures thereof. Generally, the catalyst content used herein is greater than zero and is up to 1.0 wt %, preferably up to 0.5 wt %, and more preferably up to 0.05 wt %, based on the total weight of all reactants. According to another embodiment of the present disclosure, either or both of the first and second polyurethane dispersions are prepared without the use of a catalyst.

[0083] The coating composition of the present disclosure may optionally contain any additional adjuvants and / or additives for specific purposes. In one embodiment of the present disclosure, the adjuvants and / or additives are selected from the group consisting of tackifiers, plasticizers, rheology modifiers, antioxidants, fillers, colorants, pigments, water scavengers, surfactants, solvents, diluents, flame retardants, anti-slip agents, antistatic agents, preservatives, biocides, antioxidants, and combinations of two or more thereof.

[0084] Aqueous Coating Composition According to an embodiment of the present application, the weight ratio of the first polyurethane dispersion, the second polyurethane dispersion and the polyacrylic emulsion may be (10-15):(1-7):(1-8).

[0085] According to one embodiment of the present disclosure, the relative content of the first polyurethane dispersion can be 50 to 75 parts by weight, for example, within a numerical range obtained by any two of the following endpoint values: 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, and 75 parts by weight.

[0086] According to another embodiment of the present disclosure, the relative content of the second polyurethane dispersion can be 10 to 25 parts by weight, for example, within a numerical range obtained by any two of the following endpoint values: 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, and 25 parts by weight.

[0087] According to another embodiment of the present disclosure, the polyacrylic emulsion can be 5 to 40 parts by weight, for example, within a numerical range obtained by any two of the following endpoint values: 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, and 40 parts by weight.

[0088] It should be understood that the above contents of the first polyurethane dispersion, the second polyurethane dispersion and the polyacrylic emulsion are calculated in parts by weight instead of percent by weight, and therefore the contents of these three components do not necessarily add up to 100.

[0089] Press-through-pack sheet According to one embodiment of the present disclosure, the aqueous coating composition of the present disclosure can be used to bond at least two different layers together to form a laminated material, such as a PTP (press-through packaging) sheet for medical packs. According to an example of the present disclosure, the PTP sheet includes a container film having a pocket portion into which contents such as tablets are filled, and a cover film attached to the container film so as to seal the opening of the pocket portion. The container film can be made of different polymers such as polymethyl methacrylate, polypropylene carbonate, polybutene carbonate, polystyrene, acrylonitrile-butadiene-styrene resin, acrylic resin, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polyethylene terephthalate, polyurethane, polyimide, and copolymers thereof, and is preferably a transparent resin material. The cover film can be made of a metal foil such as aluminum foil or aluminum alloy foil.

[0090] The aqueous coating composition of the present disclosure can be applied onto the surface of a cover film, followed by drying and / or curing to form a tie layer, and then the container film is compressed onto the exposed surface of the tie layer under high temperature and pressure to form a PTP sheet, thus enclosing the drug (e.g., tablet) within the pocket portion. [Example]

[0091] Next, some embodiments of the present invention will be described in the following examples, in which all parts and percentages are by weight unless otherwise specified. However, the scope of the present disclosure is not limited to the formulations shown in these examples. Rather, the examples simply relate to the invention of the present disclosure.

[0092] [Table 1]

[0093] Preparation Example 1: Preparation of first polyurethane dispersion (PUD-1) 11 g of Desmodur W was added to a mixture of 7 g of Capa 220, 6 g of Eternacoll UP-100, 2.0 g of Bis-MPA, and 8 g of Bester 127. The contents of the mixture were then reacted at 75°C for 4.5 hours with stirring to form a prepolymer. The prepolymer was then transferred to a plastic jar, and TEA was added to the jar with high-speed (2500 rpm) stirring for 2 minutes, thereby neutralizing the contents of the jar to a pH of approximately 7. 66 g of cold DI water (5°C) was added to the jar with high-speed stirring to form a uniform oil-in-water dispersion, to which 3 g of an aqueous EDA solution (20%) was slowly added with stirring at 1200 rpm for 20 minutes. The resulting dispersion was designated PUD-1 and exhibited a Tg value of 10°C.

[0094] Preparation Example 2: Preparation of First Polyurethane Dispersion (PUD-2) 12.5 g of Desmodur W was added to a mixture of 10.0 g of PTMEG2000, 10.5 g of Bester127, 1.0 g of TMPD, and 3 g of Bis-MPA. The mixed contents were then reacted at 80°C for 4 hours to form a prepolymer. The prepolymer was then transferred to a plastic jar, and TEA was added to the jar while stirring at high speed (2500 rpm) for 2 minutes, thereby neutralizing the contents of the plastic jar to a pH of approximately 7. 64.5 g of cold DI water (5°C) was added to the jar under high-speed stirring to form a uniform oil-in-water dispersion, and 4.5 g of an aqueous EDA solution (20%) was slowly added to the dispersion while stirring at 1200 rpm for 20 minutes. The resulting dispersion was marked PUD-2 and exhibited a Tg value of 15°C.

[0095] Preparation Example 3: Preparation of a second polyurethane dispersion (PUD-3) 13 g of Vestanat IPDI was added to a mixture of 33.5 g of Bester 80 and 2.5 g of Bis-MPA. The mixture was then reacted at 70°C for 4.5 hours to form a prepolymer. The prepolymer was then transferred to a plastic jar, and TEA was added to the jar while stirring at high speed (2500 rpm) for 2 minutes, thereby neutralizing the contents of the jar to a pH of approximately 7. 51 g of cold DI water (5°C) was added to the jar with high speed stirring to form a uniform oil-in-water dispersion, and 4.8 g of an aqueous solution of EDA (20%) was slowly added to the dispersion while stirring at 1200 rpm for 20 minutes. The resulting dispersion was designated PUD-3 and exhibited a Tg value of -47°C.

[0096] Preparation Example 4: Preparation of a second polyurethane dispersion (PUD-4) 12.0 g of Desmodur W was added to a mixture of 30 g of Bester 121, 1.0 g of Bis-MPA, and 5.0 g of Voranol™ PEG 1000. The mixed contents were then reacted at 85°C for 4 hours to form a prepolymer. The prepolymer was then transferred to a plastic jar, and TEA was added to the plastic jar while stirring at high speed (2500 rpm) for 2 minutes, thereby neutralizing the contents of the plastic jar to a pH of approximately 7. 52 g of cold DI water (5°C) was added to the plastic jar under high-speed stirring to form a uniform oil-in-water dispersion, to which 4.0 g of an aqueous EDA solution (20%) was slowly added while stirring at 1300 rpm for 20 minutes. The resulting dispersion was marked PUD-4 and exhibited a Tg value of -55°C.

[0097] Preparation Example 5: Preparation of a second polyurethane dispersion (PUD-5) 10 g of Vestanat IPDI was added to a mixture of 28 g of Bester 121 and 2.0 g of Bis-MPA. The mixture was then reacted at 70°C for 4.5 hours to form a prepolymer. The prepolymer was then transferred to a plastic jar, and TEA was added to the jar while stirring at high speed (2600 rpm) for 2 minutes, thereby neutralizing the contents of the jar to a pH of approximately 7. 60 g of cold DI water (5°C) was added to the jar under high-speed stirring to form a uniform oil-in-water dispersion. 4.0 g of an aqueous EDA solution (20%) was slowly added to the dispersion while stirring at 1400 rpm for 25 minutes. The resulting dispersion was marked PUD-5 and exhibited a Tg value of -52°C.

[0098] Preparation Example 6: Preparation of polyacrylic emulsion (PAC-1) 2.38 g of DS-4 was dissolved in 315 g of deionized water (DI water) to form a solution, to which 31.9 g of AA, 692.7 g of BA, and 173.2 g of Sty were slowly added under stirring to form an emulsified monomer mixture.

[0099] A solution containing 5.62 g of DS4 and 300 g of deionized water was placed in a five-neck, 3-liter round-bottom flask equipped with a thermocouple, cooling condenser, and stirrer and heated to 84°C under nitrogen. A solution of 13.7 g of itaconic acid (IA) dissolved in 180 g of DI water at 60°C was added to the flask, followed by 52.5 g of the above monomer emulsion. A solution of 2.74 g of ammonium persulfate (APS) in 20 g of DI water was then added to the flask to initiate the reaction. As the exothermic reaction progressed, the temperature increased. When the temperature reached a peak of 84°C, the remaining monomer emulsion and APS solution (1.18 g in 44 g of DI water) were gradually added over a 150-minute period, while maintaining the temperature at a level of 83-85°C. After the addition was complete, the monomer emulsion container and the feed line leading to the flask were rinsed with 35 g of DI water, and the rinse was also added to the flask. The flask was held at 84°C for an additional 15 minutes, then cooled to 75°C. A solution of 3.58 g of tert-butyl hydrogen peroxide in 40 g of DI water and 2.29 g of isoascorbic acid in 47 g of DI water was slowly fed into the flask over 30 minutes, and the reaction mixture was then cooled to room temperature. 19.5 g of 25% aqueous ammonia was added to the flask to adjust the pH to 6.5-7.5. The contents of the flask were then diluted with DI water to 46% solids and exhibited a Tg of -30°C.

[0100] Preparation Example 7: Preparation of polyacrylic emulsion (PAC-2) 2.99 g of sodium carbonate, 4.03 g of DS-4, and 3.19 g of A-102 were dissolved in 249 g of deionized water to form a solution, into which 41.8 g of AA, 968.3 g of BA, and 167.3 g of Sty were slowly added under stirring to form an emulsified monomer mixture.

[0101] A solution containing 2.02 g of DS4 and 224 g of deionized water was placed in a five-neck, 3-liter round-bottom flask equipped with a thermocouple, cooling condenser, and stirrer and heated to 84°C under nitrogen. A solution of 18 g of itaconic acid dissolved in 69 g of DI water at 60°C was added to the flask, followed by 20.1 g of the above monomer emulsion. A solution of 3.6 g of ammonium persulfate (APS) in 15 g of DI water was then added to the flask to initiate the reaction. As the exothermic reaction progressed, the temperature increased. When the temperature reached a peak of 84°C, the remaining monomer emulsion and APS solution (1.18 g in 44 g of DI water) were gradually added over a 150-minute period, while maintaining the temperature at a level of 83–85°C. At 96.7 minutes, a solution of 16.11 g of DS4 in 13 g of DI water also began to be added to the flask. After the addition was complete, the vessel containing the monomer emulsion and the feed line leading to the flask were rinsed with 50 g of DI water, and the rinse was returned to the flask. The flask was held at 84°C for an additional 15 minutes, then cooled to 75°C. A solution of 5.16 g of tert-butyl hydrogen peroxide in 40 g of DI water and a solution of 4.4 g of FF6 in 40 g of DI water were slowly fed into the flask over 30 minutes, and the flask was then cooled to room temperature. 18.7 g of 25% aqueous ammonia was added to the flask to adjust the pH to 6.5-7.5. The contents of the flask were then diluted with DI water to 57.5% solids and exhibited a Tg of -25°C.

[0102] Examples 1 to 7 of the present invention and Comparative Examples 1 to 7: Preparation of coating compositions The PUD and PAC prepared above were combined together according to the relative amounts listed in Table 2 below to form the coating compositions of Inventive Examples (IE) 1-7 and Comparative Examples (CE) 1-7.

[0103] [Table 2]

[0104] Each of the above coating compositions was used to produce a laminate of aluminum foil and PVC plate and subjected to characterization of performance properties, the characterization results of which are summarized in Table 3 below.

[0105] [Table 3] HSS: heat seal strength; aging conditions: temperature 85°C and humidity 85%

[0106] From Table 3, it can be seen that the inventive examples (IE.1-7) containing two PUDs and one polyacrylic emulsion can still exhibit good heat seal strength and also achieve good blocking resistance after aging at 85°C and 85% humidity for 3 days, while the comparative examples (CE.1-7) showed very poor performance.

[0107] Test Method Heat Seal Strength (HS) The above formulated coating composition was coated onto one surface of an aluminum foil (100 mm x 100 mm) at a dry coating weight of 3.2 gsm, and the coated aluminum foil was heated in an oven at 150°C for 30 seconds, then removed from the oven and allowed to cool.

[0108] The coated foil was laminated to one PVC plate (100 mm × 100 mm) with the exposed surface of the coating layer facing the PVC plate, and the laminate was heat-compressed in a heat-sealing machine under the conditions of a sealing temperature of 150°C and a compression pressure of 0.2 MPa for a dwell time of 1 second, after which the sample was removed from the machine and cooled at ambient temperature for at least 2 hours.

[0109] Each sample was then cut into strips with a width of 15 mm, which were subjected to a heat seal strength test on a tensile tester. The test was repeated three times for each sample, and the average value of the three tests was reported as the final result. Specifically, a PVC plate was clipped to the upper clamp, and an aluminum foil was clipped to the lower clamp. When the test began, the tensile strength machine was turned on, and the two clamps began to move in opposite directions at a speed of 200 mm / min ± 20 mm / min to perform a 180° peel movement. Simultaneously, the heat seal strength value was recorded in real time on a computer. A higher value indicates better heat seal strength.

[0110] Blocking resistance test: The above formulated coating composition was coated onto one surface of an aluminum foil (100 mm x 100 mm) at a dry coating weight of 3.2 gsm, and the coated aluminum foil was heated in an oven at 150°C for 30 seconds, then removed from the oven and allowed to cool.

[0111] Four pieces of the coated foil prepared above were stacked on top of each other, with the coated surface of each piece in contact with the uncoated surface of another piece. The four-ply laminate was placed on a flat surface and a 1.0 kg weight was placed on top of it. The entire sample was heated in a 40°C oven for 2 hours and then removed to observe the blocking condition.

[0112] Aging test: The heat-sealed laminates were kept in a conditioned chamber at 85°C and 85% relative humidity for 3 days and removed and monitored daily for heat seal strength.

[0113] Glass transition temperature (Tg) The PUD or PAC samples were heated to dryness and then transferred to aluminum crucibles and tested using a TA Instruments DSC Q2000 instrument with the following program: 1. Increase the temperature from -80°C to 120°C at a ramp rate of 20°C / min to erase the thermal history. 2. Cool the sample to -80°C. 3. Characterize the DSC plot by increasing the temperature from -80°C to 120°C at a ramp rate of 10°C / min. 4. The point at half height of the transition on the DSC plot is chosen as the glass transition temperature (Tg). The present specification includes the following inventions. Section 1. 1. An aqueous coating composition comprising: (a) a first polyurethane dispersion containing a first polyurethane having a Tg of 5°C to 20°C; (b) a second polyurethane dispersion comprising a second polyurethane having a Tg of −40° C. to −60° C.; (c) a polyacrylic emulsion containing an acrylic (co)polymer having a Tg of -40°C to -20°C. Section 2. the first polyurethane is derived from a first raw material comprising, by weight, 15% to 45% of at least one first monomeric diisocyanate, 40% to 75% of at least one first polyol, and 2% to 15% of at least one first internal emulsifier, based on the total dry weight of the first polyurethane dispersion; the second polyurethane is derived from a second raw material comprising, by weight, based on the total dry weight of the second polyurethane dispersion, 10% to 35% by weight of at least one second monomeric diisocyanate, 50% to 75% by weight of at least one second polyol, and 2% to 15% by weight of at least one second internal emulsifier; Item 1, wherein the acrylic (co)polymer is derived from a third raw material comprising 60% to 90% by weight of at least one (meth)acrylic monomer and 10% to 40% by weight of at least one styrenic monomer. The aqueous coating composition according to item 1. Section 3. The first monomeric diisocyanate and the second monomeric diisocyanate each independently contain a C2 to C 16 Aliphatic diisocyanates, C6-C 16Aromatic diisocyanates, C5-C 16 Item 1, the aqueous coating composition according to item 1, wherein the diisocyanate is selected from the group consisting of cycloaliphatic diisocyanates, ... and combinations thereof. Section 4. The first polyol is a C4-C hydroxyl group-containing polyol. 16 a branched aliphatic polyol and a polycarbonate polyol having an average functionality of 2 to 5 and an average molecular weight of 500 to 3,000, optionally including a poly(C4-C6) having an average functionality of 2 to 5 and an average molecular weight of 800 to 4,000; 12 lactone) polyol, a polyether polyol having an average functionality of 2 to 5 and an average molecular weight of 800 to 5,000, and a polyester polyol having an average functionality of 2 to 5 and a molecular weight of 800 to 5,000; The second polyol comprises a polyester polyol having an average functionality of 2 to 5 and a molecular weight of 800 to 5,000, and optionally a poly(C4-C6) having an average functionality of 2 to 5 and an average molecular weight of 500 to 8,000. 12 Item 1. The aqueous coating composition according to item 1, further comprising one or both of a lactone polyol and a polyether polyol having an average functionality of 2 to 5 and an average molecular weight of 400 to 12,000. Section 5. (A) the first polyol is selected from (a) a blend of one polycarbonate polyol having an average functionality of 2 and a molecular weight of 1,000 to 3,000, one polylactone polyol having an average functionality of 2 and a molecular weight of 1,000 to 3,000, and one polyester polyol having an average functionality of 2 and a molecular weight of 1,000 to 3,000, and (b) a blend of trimethylpentane-diol, one polyester polyol having an average functionality of 2 and a molecular weight of 1,000 to 3,000, and one polyether polyol having an average functionality of 2 and a molecular weight of 1,000 to 3,000; and / or (B) the second polyol is (c) one linear polyester polyol having an average functionality of 2 and a molecular weight of 1,000 to 3,000, and (d) one linear polyester polyol having an average functionality of 2 and a molecular weight of 1,000 to 3,000 and a poly(C4-C6) having an average functionality of 2 and an average molecular weight of 1,000 to 3,000. 12 Item 1, the aqueous coating composition according to item 1, wherein the polyol is selected from a blend of at least one of a lactone polyol and a polyether polyol having an average functionality of 2 and an average molecular weight of 1,000 to 3,000. Section 6. Each of the first internal emulsifier and the second internal emulsifier is independently a C2-C substituted with at least two hydroxyl or amino groups. 16 Fatty acids or their salts, C5-C substituted with at least two hydroxyl or amino groups 16 Item 1, the aqueous coating composition according to item 1, wherein the alicyclic acid or a salt thereof is selected from the group consisting of an alicyclic acid or a salt thereof, and any combination thereof. Section 7. The acrylic copolymer of the polyacrylic emulsion comprises 60% to 80% by weight of at least one of C1 to C6 based on the total solids weight of the polyacrylic emulsion. 12 Item 1. The aqueous coating composition according to item 1, derived from a third raw material comprising an alkyl (meth)acrylate, 1 wt% to 10 wt% of at least one ethylenically unsaturated acid, and 10 wt% to 40 wt% of styrene and / or C1 to C6 alkyl-substituted styrene. Section 8. Item 2. The aqueous coating composition according to Item 1, wherein the weight ratio of the first polyurethane dispersion, the second polyurethane dispersion, and the polyacrylic emulsion is (10 to 15):(1 to 7):(1 to 8). Section 9. 1. A method of producing a laminated material, comprising: (a) providing a metal foil and a substrate; (b) applying the aqueous coating composition according to any one of items 1 to 8 onto at least one surface of the metal foil to form a wet coating, and then curing and drying the wet coating to form a dry coating layer; (c) laminating said substrate onto said dried coating layer under pressure and elevated temperature to form said laminated material. Section 10. A laminated material comprising a metal foil, a substrate, and a coating layer sandwiched therebetween, wherein the coating layer is derived from the aqueous coating composition according to any one of items 1 to 8. A laminated material.

Claims

1. 1. An aqueous coating composition comprising: (a) a first polyurethane dispersion comprising a first polyurethane having a Tg of 5°C to 20°C; (b) a second polyurethane dispersion comprising a second polyurethane having a Tg of −40° C. to −60° C.; (c) a polyacrylic emulsion comprising an acrylic (co)polymer having a Tg of -40°C to -20°C.

2. the first polyurethane is derived from a first feedstock comprising, by weight, 15% to 45% of at least one first monomeric diisocyanate, 40% to 75% of at least one first polyol, and 2% to 15% of at least one first internal emulsifier, based on the total dry weight of the first polyurethane dispersion; the second polyurethane is derived from a second raw material comprising, by weight, based on the total dry weight of the second polyurethane dispersion, 10% to 35% by weight of at least one second monomeric diisocyanate, 50% to 75% by weight of at least one second polyol, and 2% to 15% by weight of at least one second internal emulsifier; 10. The aqueous coating composition of claim 1, wherein the acrylic (co)polymer is derived from a third source comprising 60% to 90% by weight of at least one (meth)acrylic monomer and 10% to 40% by weight of at least one styrenic monomer.

3. each of the first monomeric diisocyanate and the second monomeric diisocyanate independently comprises C ２ ~C １６ Aliphatic diisocyanate, C ６ ~C １６ Aromatic diisocyanate, C ５ ~C １６ 3. The aqueous coating composition of claim 2, wherein the diisocyanate is selected from the group consisting of cycloaliphatic diisocyanates, cycloaliphatic diisocyanates, and combinations thereof.

4. The first polyol is a C containing at least two hydroxyl groups. ４ ~C １６ a branched aliphatic polyol and a polycarbonate polyol having an average functionality of 2 to 5 and an average molecular weight of 500 to 3,000, optionally including a poly(C ４ ~C １２ lactone) polyol, a polyether polyol having an average functionality of 2 to 5 and an average molecular weight of 800 to 5,000, a polyester polyol having an average functionality of 2 to 5 and a molecular weight of 800 to 5,000; The second polyol comprises a polyester polyol having an average functionality of 2 to 5 and a molecular weight of 800 to 5,000, and optionally a poly(C ４ ~C １２ 3. The aqueous coating composition of claim 2, further comprising one or both of a polyol (lactone) and a polyether polyol having an average functionality of 2 to 5 and an average molecular weight of 400 to 12,000.

5. (A) the first polyol is selected from (a) a blend of one polycarbonate polyol having an average functionality of 2 and a molecular weight of 1,000 to 3,000, one polylactone polyol having an average functionality of 2 and a molecular weight of 1,000 to 3,000, and one polyester polyol having an average functionality of 2 and a molecular weight of 1,000 to 3,000, and (b) a blend of trimethylpentane-diol, one polyester polyol having an average functionality of 2 and a molecular weight of 1,000 to 3,000, and one polyether polyol having an average functionality of 2 and a molecular weight of 1,000 to 3,000; and / or (B) the second polyol is (c) one linear polyester polyol having an average functionality of 2 and a molecular weight of 1,000 to 3,000, and (d) one linear polyester polyol having an average functionality of 2 and a molecular weight of 1,000 to 3,000 and a poly(C ４ ~C １２ 3. The aqueous coating composition of claim 2, wherein the polyol is selected from a blend of at least one of a hydroxybenzoate (hydroxybenzoate) and a polyol having an average functionality of 2 and an average molecular weight of 1,000 to 3,000.

6. Each of the first internal emulsifier and the second internal emulsifier independently comprises a C substituted with at least two hydroxyl or amino groups. ２ ~C １６ Fatty acids or salts thereof, C substituted with at least two hydroxyl or amino groups ５ ~C １６ 3. The aqueous coating composition of claim 2, wherein the base is selected from the group consisting of an alicyclic acid or a salt thereof, and any combination thereof.

7. The acrylic (co)polymer of the polyacrylic emulsion comprises 60% to 80% by weight of at least one C based on the total solids weight of the polyacrylic emulsion. １ ~C １２ alkyl (meth)acrylate, 1% to 10% by weight of at least one ethylenically unsaturated acid, and 10% to 40% by weight of styrene and / or C １ ~C ６ 10. The aqueous coating composition of claim 1 derived from a third source comprising an alkyl-substituted styrene.

8. 2. The aqueous coating composition of claim 1, wherein the weight ratio of the first polyurethane dispersion, the second polyurethane dispersion, and the polyacrylic emulsion is (10-15):(1-7):(1-8).

9. 1. A method of producing a laminated material, comprising: (a) providing a metal foil and a substrate; (b) applying the aqueous coating composition of any one of claims 1 to 8 onto at least one surface of the metal foil to form a wet coating, and then curing and drying the wet coating to form a dry coating layer; (c) laminating said substrate onto said dried coating layer under pressure and elevated temperature to form said laminated material.

10. 9. A laminated material comprising a metal foil, a substrate, and a coating layer sandwiched therebetween, wherein the coating layer is derived from the aqueous coating composition of any one of claims 1 to 8.

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