Moisture-resistant two-component adhesive composition

Abstract

A two-part adhesive composition comprising the reaction product of a polyol component comprising at least one hydrophobic polyol, polyphosphoric acid, and an isocyanate component comprising the reaction product of (I) an isocyanate compound and (II) a dimer acid polyester polyol.

Description

Technical Field

[0001] The present disclosure relates to an adhesive composition, and more specifically to a moisture-resistant two-component adhesive composition.

[0002] Introduction Mass production of battery packs in an economical way has achieved revolutionary developments in recent years, driving the adoption of electric vehicles (EVs) worldwide. From low cost, low volatility, high body strength, and toughness, polyurethane adhesives have become a common solution for battery pack assemblies where battery cells are joined onto cooling plates by polyurethane adhesives.

[0003] Bonding substrates for battery pack assemblies mainly include Al alloys, PET films, polycarbonates, etc., and the bonding of Al alloy - Al alloy is the most important. However, due to the high surface energy and the absence of organic chemical groups on the Al alloy surface, effective bonding between Al alloys is difficult. On the other hand, the moisture resistance of polyurethane components (including polyol and isocyanate parts) is another important industrial need. This is because both the polyol part and the isocyanate part can easily absorb moisture. For the isocyanate part, the absorbed moisture causes a decrease in the NCO content and the formation of a solid skin starting from the top of the component. As a result, the decrease in the NCO content makes the supply ratio between reactive groups inaccurate, and the thick skin usually blocks storage tanks and / or distribution tunnels, causing product defects and production interruptions respectively. For the polyol part, the absorbed moisture may bring numerous air bubbles to the cured adhesive after mixing and distributing the polyol part with the isocyanate part. Therefore, the higher the moisture resistance, the better its industrial use.

[0004] It is difficult for current two-component polyurethane adhesives to simultaneously meet these requirements.

[0005] Therefore, a polyurethane adhesive is needed that has strong bonding strength to the substrate, especially the Al alloy-Al alloy interface, and is inert to moisture absorption during adhesive application. [Overview of the project]

[0006] In the first aspect of this disclosure, this disclosure is, A) A polyol component comprising at least one hydrophobic polyol, B) Polyphosphate, and an isocyanate component comprising the reaction product of (I) an isocyanate compound and (II) a dimer acid polyester polyol, The present invention provides a two-component adhesive composition containing the reaction product of [the specified reaction].

[0007] In the second aspect of this disclosure, this disclosure is, The first substrate and A second substrate and An adhesive layer between the first substrate and the second substrate, the adhesive layer being formed from the two-component adhesive composition described herein, It provides a multilayer structure that includes [this component].

[0008] In a third aspect of this disclosure, the disclosure provides a method for forming a two-component adhesive composition, the method being: (i) To provide a polyol component A) comprising at least one hydrophobic polyol, (ii) Polyphosphate, and isocyanate component B) comprising the reaction product of (I) an isocyanate compound and (II) a dimer acid polyester polyol, (iii) Next, the isocyanate component B) is reacted with the polyol component A) to form the two-component adhesive composition described herein, Includes.

[0009] In a fourth aspect of the present disclosure, the present disclosure provides the use of a two-component adhesive composition in a battery pack.

[0010] Please understand that both the general description above and the detailed description below are illustrative and descriptive, and do not limit the claimed invention. [Modes for carrying out the invention]

[0011] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art to which this invention pertains. Furthermore, all publications, patent applications, patents, and other references referenced herein are incorporated by reference.

[0012] definition Numerical ranges disclosed herein include all values ​​from the lower limit to the upper limit (including the lower and upper limits). In the case of ranges that include explicit values ​​(e.g., ranges of 1, 2, 3-5, 6, or 7), any subrange between any two explicit values ​​is included (e.g., the above range 1-7 includes subranges 1-2, 2-6, 5-7, 3-7, 5-6, etc.).

[0013] Unless otherwise stated, implied in the context, or customary in the art, all parts and percentages are based on weight, and all test methods are current as of the filing date of this disclosure.

[0014] The term "composition" refers to a mixture of materials constituting the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0015] The terms “comprising,” “including,” and “having,” and their derivatives, are not intended to exclude the existence of any additional components, processes, or procedures, whether or not they are specifically disclosed herein. To avoid doubt, all compositions claimed through the use of the term “comprising” may include any additional additives, adjuvants, or compounds, whether polymers or otherwise, unless otherwise stated. In contrast, the term “essentially consisting of” excludes any other components, processes, or procedures from the scope of any subsequent description, except those not essential to operability. The term “consisting of” excludes any components, processes, or procedures not explicitly described or enumerated. The term “or” refers to the enumerated members individually and in any combination, unless otherwise specified. The use of the singular includes the use of the plural, and vice versa.

[0016] A "dicarboxylic acid" is a compound that contains two carboxyl (-COOH) groups.

[0017] An "isocyanate" is a chemical substance that contains at least one isocyanate group in its structure. The isocyanate group is represented by the formula -N=C=O. An isocyanate containing more than one or at least two isocyanate groups is a "polyisocyanate". An isocyanate having two isocyanate groups is a diisocyanate, an isocyanate having three isocyanate groups is a triisocyanate, and so on. Isocyanates may be aromatic or aliphatic.

[0018] A "polyol" is an organic compound containing multiple hydroxyl (-OH) groups. In other words, a polyol contains at least two hydroxyl groups. Non-limiting examples of suitable polyols include diols (containing two hydroxyl groups), triols (containing three hydroxyl groups), and polyhydroxyl-containing polyols.

[0019] "Polyether" is a compound containing two or more ether linking groups in the same straight chain of atoms.

[0020] "Polyester" is a compound containing two or more ester linking groups in the same straight chain of atoms.

[0021] "Polyester polyol" is a compound that is a polyester and a polyol.

[0022] "Polymer" is a polymeric compound prepared by polymerizing the same type or different types of monomers. Thus, the general term "polymer" encompasses the term "homopolymer" (used to refer to a polymer prepared from only one type of monomer, with the understanding that trace amounts of impurities may be incorporated into the polymer structure), and the term "interpolymer" (used with the same meaning as the term "copolymer") includes bipolymers (used to refer to polymers prepared from two different types of monomers), terpolymers (used to refer to polymers prepared from three different types of monomers), and polymers prepared from four or more different types of monomers. Trace amounts of impurities, such as catalyst residues, may be incorporated into and / or within the polymer. It also encompasses all forms of copolymers, such as random, block, etc. Polymers are often referred to as being "made from", "based on", "containing" one or more specific monomers, etc., but in this context, it should be noted that the term "monomer" is understood to refer to the polymerized residues of the specific monomer and not to the unpolymerized species. Generally, polymers herein are referred to as being based on "units" that are the polymerized form of the corresponding monomer.

[0023] A. Polyol Component The two-component adhesive composition contains a reaction product of A) a polyol component and B) an isocyanate component. The polyol component A) contains at least one hydrophobic polyol. The polyol component A) may optionally contain at least one selected from polyether polyols, polyester polyols, polyether ester polyols, polycarbonate polyols, polyurethane polyols, or combinations thereof. The polyol component A) may optionally contain a chain extender.

[0024] Hydrophobic polyol The hydrophobic polyol refers to a hydrophobic polyol having at least two hydroxyl groups.

[0025] In an embodiment, the hydrophobic polyol is selected from vegetable oils, hydrophobic polyols derived from vegetable oils, or mixtures thereof. The vegetable oil may be castor oil, soybean oil, etc.

[0026] In an embodiment, the hydrophobic polyol is castor oil, a hydrophobic polyol derived from castor oil, soybean oil, a hydrophobic polyol derived from soybean oil, or a mixture thereof.

[0027] The hydrophobic polyol derived from a vegetable oil refers to a hydrophobic polyol obtained by increasing the molecular weight of a vegetable oil by alkoxylation, esterification, or polyurethane reaction of the vegetable oil, and the hydrophobic polyol derived from a vegetable oil has two or more hydroxyl groups.

[0028] The hydrophobic polyol derived from a vegetable oil may be a polyurethane reaction product of a reaction mixture containing (i) an isocyanate compound, (ii) a polyol, and (iii) a vegetable oil. <# <#

[0029] <# An "isocyanate compound" is a molecule containing at least two isocyanate groups. Isocyanate compounds can be chemically bonded to polyols to form prepolymers. Non-limiting examples of suitable isocyanate compounds include aromatic isocyanates, aliphatic isocyanates, carbodiimide-modified isocyanate compounds, and combinations thereof.

[0030] An "aromatic isocyanate compound" is an isocyanate compound containing one or more aromatic rings. Non-limiting examples of suitable aromatic isocyanate compounds include isomers of methylene diphenyl diisocyanate (MDI), such as 4,4-MDI, 2,4-MDI, and 2,2'-MDI; modified MDI, such as carbodiimide-modified MDI or allophanate-modified MDI; isomers of toluene-diisocyanate (TDI), such as 2,4-TDI and 2,6-TDI; isomers of naphthalene-diisocyanate (NDI), such as 1,5-NDI; and combinations thereof.

[0031] An "aliphatic isocyanate compound" is an isocyanate compound in which the isocyanate moiety (-NCO) is not directly connected to an aromatic ring. Non-limiting examples of suitable aliphatic isocyanate compounds include isomers of hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), xylene diisocyanate (XDI), other alicyclic isocyanates such as methylene biscyclohexyl isocyanate (HMDI) and cyclohexane diisocyanate, and combinations thereof.

[0032] In the embodiments, the isocyanate compound is selected from monoisocyanate compounds, diisocyanate compounds, triisocyanate compounds, and combinations thereof. In further embodiments, the isocyanate compound is a diisocyanate compound.

[0033] In the embodiment, the isocyanate compound is a polyfunctional isocyanate compound having at least two isocyanate groups or at least three isocyanate groups.

[0034] In some embodiments, the isocyanate compound is selected from MDI, TDI, HDI, and combinations thereof. In further embodiments, the isocyanate compound is MDI.

[0035] In the embodiments, the isocyanate compound is selected from carbodiimide-modified MDI, carbodiimide-modified TDI, carbodiimide-modified HDI, and combinations thereof. In further embodiments, the isocyanate compound is a carbodiimide-modified MDI such as ISONATE 143L from The Dow Chemical Company.

[0036] The polyol used to prepare the polyurethane reaction product of a reaction mixture comprising (i) an isocyanate compound, (ii) a polyol, and (iii) a vegetable oil may be a polyester polyol, a polyether polyol, or a combination thereof, preferably a polyether polyol. A "polyether polyol" is a compound that is both a polyether and a polyol. Non-limiting examples of suitable polyether polyols include polyaddition products of ethylene oxide, propylene oxide, tetrahydrofuran, and butylene oxide, and their coaddition and graft products, polyether polyols obtained by condensation of polyhydric alcohols, and combinations thereof.

[0037] Non-limiting examples of suitable polyether polyols include polypropylene glycol (PPG), polyethylene glycol (PEG), polybutylene glycol, polytetramethylene ether glycol (PTMEG), and combinations thereof. In one embodiment, the polyether polyol is polypropylene glycol (PPG).

[0038] Non-limiting examples of suitable polyether polyols include VORANOL® P400, VORANOL® 1010 L, PPG, and VORANOL® CP450, and glycerol propoxylated polyether triols, all of which are available from Dow.

[0039] In the embodiment, the polyether polyol has a molecular weight (Mw) of 50 g / mol, 100 g / mol, 400 g / mol, 450 g / mol to 1,000 g / mol, 1,500 g / mol, 2,000 g / mol, 4,000 g / mol, or 5,000 g / mol.

[0040] In one embodiment, the polyether polyol has a hydroxyl value of 30 mg KOH / g, or 50 mg KOH / g, or 75 mg KOH / g, or 100 mg KOH / g to 115 mg KOH / g, or 125 mg KOH / g, or 150 mg KOH / g, or 200 mg KOH / g, or 300 mg KOH / g, or 350 mg KOH / g, or 400 mg KOH / g, or 450 mg KOH / g, or 500 mg KOH / g.

[0041] In the embodiment, the polyether polyol has one or both of the following properties: (i) a molecular weight of 50 g / mol to 5,000 g / mol, or 100 g / mol to 2,000 g / mol, or 400 g / mol to 1,500 g / mol, or 400 g / mol to 1,000 g / mol, and / or (ii) a hydroxyl value of 30 mg KOH / g to 500 mg KOH / g, or 100 mg KOH / g to 400 mg KOH / g, or 100 mg KOH / g to 150 mg KOH / g, or 350 mg KOH / g to 400 mg KOH / g.

[0042] Polyol component A) comprises 20 to 60% by weight, preferably 25 to 50% by weight, more preferably 26 to 45% by weight, and even more preferably 28 to 40% by weight of a hydrophobic polyol, preferably castor oil and / or a hydrophobic polyol derived from castor oil, based on the total weight of polyol component A).

[0043] Polyol component A) comprises 10 to 50% by weight, preferably 12 to 40% by weight, more preferably 15 to 25% by weight, and even more preferably 15 to 20% by weight of vegetable oil, preferably castor oil or soybean oil, based on the total weight of polyol component A).

[0044] Polyol component A) comprises a polyurethane reaction product of a reaction mixture containing 1 to 30% by weight, preferably 2 to 25% by weight, more preferably 5 to 20% by weight, and even more preferably 8 to 15% by weight of a hydrophobic polyol derived from vegetable oil, preferably (i) an isocyanate compound, (ii) a polyol, and (iii) vegetable oil, based on the total weight of polyol component A).

[0045] Polyether polyol Polyol component A) may further contain a polyether polyol. A "polyether polyol" is a compound that is both a polyether and a polyol. Non-limiting examples of suitable polyether polyols include polyaddition products of ethylene oxide, propylene oxide, tetrahydrofuran, and butylene oxide, and their coaddition and graft products, polyether polyols obtained by condensation of polyhydric alcohols, or mixtures thereof, and combinations thereof.

[0046] Non-limiting examples of suitable polyether polyols include polypropylene glycol (PPG), polyethylene glycol (PEG), polybutylene glycol, polytetramethylene ether glycol (PTMEG), and combinations thereof. In one embodiment, the polyether polyol is polypropylene glycol (PPG).

[0047] Non-limiting examples of suitable polyether polyols include VORANOL® 1010 L, PPG, and VORANOL® CP450, glycerol propoxylated polyether triols, all of which are available from Dow.

[0048] In the embodiment, the polyether polyol has a molecular weight of 50 g / mol, or 100 g / mol, or 400 g / mol, or 450 g / mol to 1,000 g / mol, or 1,500 g / mol, or 2,000 g / mol, or 4,000 g / mol, or 5,000 g / mol.

[0049] In one embodiment, the polyether polyol has a hydroxyl value of 30 mg KOH / g, or 50 mg KOH / g, or 75 mg KOH / g, or 100 mg KOH / g to 115 mg KOH / g, or 125 mg KOH / g, or 150 mg KOH / g, or 200 mg KOH / g, or 300 mg KOH / g, or 350 mg KOH / g, or 400 mg KOH / g, or 450 mg KOH / g, or 500 mg KOH / g.

[0050] In the embodiment, the polyether polyol has one or both of the following properties: (i) a molecular weight of 50 g / mol to 5,000 g / mol, or 100 g / mol to 2,000 g / mol, or 400 g / mol to 1,500 g / mol, or 400 g / mol to 1,000 g / mol, and / or (ii) a hydroxyl value of 30 mg KOH / g to 500 mg KOH / g, or 100 mg KOH / g to 400 mg KOH / g, or 100 mg KOH / g to 150 mg KOH / g, or 350 mg KOH / g to 400 mg KOH / g.

[0051] Preferably, polyol component A) may contain 1 to 20% by weight, preferably 1.5 to 15% by weight, more preferably 2 to 12% by weight, and even more preferably 3 to 6% by weight of a polyether polyol, preferably a glycerol propoxylated polyether triol, based on the total weight of polyol component A).

[0052] Polyester polyol Suitable polyester polyols for use include, but are not limited to, diols, and optionally polyols (e.g., triols, tetraols), and dicarboxylic acids, and optionally polycarboxylic acids (e.g., tricarboxylic acids, tetracarboxylic acids), or polycondensates of hydroxycarboxylic acids, anhydrides, or lactones.

[0053] Preferably, polyol component A) may contain 0 to 20% by weight, preferably 1 to 15% by weight, more preferably 2 to 12% by weight, and even more preferably 3 to 6% by weight of polyester polyol, based on the total weight of polyol component A).

[0054] Polyurethane polyol Polyurethane polyols can be synthesized using isocyanates as chain extenders and hydroxyl groups as terminal groups, a process well known to engineers with a background in polyurethanes. Examples of polyurethane polyol synthesis can be found in the Examples section.

[0055] Preferably, polyol component A) may contain 0 to 20% by weight, preferably 1 to 15% by weight, more preferably 2 to 12% by weight, and even more preferably 3 to 6% by weight of polyurethane polyol, based on the total weight of polyol component A).

[0056] Chain extender Polyol component A) may optionally contain a chain extender. Non-limiting examples of suitable chain extenders include glycerin; trimethylolpropane; diethylene glycol; propanediol; 2-methyl-1,3-propanediol; 1,4-butanediol (BDO); ​​and combinations thereof, with 1,4-butanediol (BDO) being preferred.

[0057] Polyol component A) contains 0 to 10% by weight, preferably 0.5 to 9% by weight, more preferably 1 to 8% by weight, even more preferably 2 to 6% by weight, or 2 to 3% by weight of a chain extender, preferably 1,4-butanediol (BDO), based on the total weight of polyol component A).

[0058] Polyol component A) may optionally contain moisture scavengers, catalysts, flame retardants, rheological modifiers, fillers, etc.

[0059] Moisture scavengers absorb moisture from the environment before reacting with NCO-containing groups in the adhesive to avoid problems of bubble formation. An example of a moisture scavenger commonly used in polyurethane adhesives is molecular sieves. Polyol component A) contains 0 to 10% by weight, preferably 0.5 to 9% by weight, more preferably 1 to 8% by weight, and even more preferably 2 to 6% by weight of a moisture scavenger, preferably molecular sieves, based on the total weight of polyol component A).

[0060] The catalyst adjusts the reaction rate to meet process requirements. Loading more catalyst helps increase initial adhesion strength but shortens pot life. A balanced catalyst package is an organometallic catalyst containing Zn, Bi, and Sn. Polyol component A) contains 0 to 3% by weight, preferably 0.2 to 2.5% by weight, more preferably 0.5 to 2% by weight, and even more preferably 1 to 1.5% by weight of catalyst, based on the total weight of polyol component A).

[0061] Flame retardants such as isopropylated phenol phosphate improve fire resistance when battery cells are exposed to electrical short circuits. Polyol component A) contains 0 to 20% by weight, preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight, even more preferably 2 to 8% by weight, or 3 to 6% by weight of the flame retardant, based on the total weight of polyol component A).

[0062] Rheology modifiers are often included in either polyol component A) or isocyanate component B) of the adhesive composition, or both, to provide thixotropic properties to meet the needs of various applications. Polyol component A) contains 0 to 10% by weight, preferably 0.5 to 9% by weight, more preferably 1 to 8% by weight, and even more preferably 2 to 6% by weight of the rheology modifier, based on the total weight of polyol component A).

[0063] Conventional adhesion promoters such as epoxysilane or polyphosphate can also be used. Polyol component A) contains 0 to 10% by weight, preferably 0.5 to 9% by weight, more preferably 1 to 8% by weight, and even more preferably 2 to 6% by weight of a conventional adhesion promoter, based on the total weight of polyol component A). For example, polyol component A) may contain 0.05 to 5.0% by weight, preferably 0.08 to 3.0% by weight, more preferably 0.09 to 2.5% by weight, even more preferably 0.1 to 1.0% by weight, or 0.1 to 0.8% by weight of polyphosphate, based on the total weight of polyol component A). Fillers can be added to either polyol component A) or isocyanate component B) or both of the adhesive composition to improve mechanical strength and reduce costs. Fillers may be selected from silica, CaCO3, kaolin, talc, Al2O3, boron nitride, or aluminum hydroxide, etc. Polyol component A) contains 0 to 95% by weight, preferably 5 to 90% by weight, more preferably 10 to 80% by weight, even more preferably 40 to 70% by weight, or 50 to 60% by weight of filler, based on the total weight of polyol component A).

[0064] B. Isocyanate components The two-component adhesive composition contains a reaction product of A) a polyol component and B) an isocyanate component. The isocyanate compound B) contains polyphosphate and the reaction product of (I) an isocyanate compound and (II) a dimer acid polyester polyol which is an NCO-terminated prepolymer.

[0065] Isocyanate prepolymers are intermediates between monomers and the final polymer.

[0066] Isocyanate compounds Isocyanate component B) includes the reaction product of (i) an isocyanate compound and (ii) a dimer acid polyester polyol.

[0067] An "isocyanate compound" is a molecule containing at least two isocyanate groups. The isocyanate compound can be chemically bonded to a polyol to form a prepolymer. Non-limiting examples of preferred isocyanate compounds include aromatic isocyanates, aliphatic isocyanates, carbodiimide-modified isocyanate compounds, and combinations thereof. Carbodiimide-modified isocyanate compounds are preferred for use in this disclosure. An "aromatic isocyanate compound" is an isocyanate compound containing one or more aromatic rings. Non-limiting examples of suitable aromatic isocyanate compounds include isomers of methylenediphenyl diisocyanate (MDI), such as 4,4-MDI, 2,4-MDI, and 2,2'-MDI; modified MDI, such as carbodiimide-modified MDI or allophanate-modified MDI; isomers of toluene-diisocyanate (TDI), such as 2,4-TDI and 2,6-TDI; isomers of naphthalene diisocyanate (NDI), such as 1,5-NDI; and combinations thereof.

[0068] An "aliphatic isocyanate compound" is an isocyanate compound in which the isocyanate moiety (-NCO) is not directly connected to an aromatic ring. Non-limiting examples of suitable aliphatic isocyanate compounds include isomers of hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), xylene diisocyanate (XDI), other alicyclic isocyanates such as methylene biscyclohexyl isocyanate (hydrogenated MDI) (HMDI) and cyclohexane diisocyanate, and combinations thereof.

[0069] In the embodiments, the isocyanate compound is selected from monoisocyanate compounds, diisocyanate compounds, triisocyanate compounds, and combinations thereof. In further embodiments, the isocyanate compound is a diisocyanate compound.

[0070] In the embodiment, the isocyanate compound is a polyfunctional isocyanate compound having at least two isocyanate groups or at least three isocyanate groups.

[0071] In some embodiments, the isocyanate compound is selected from MDI, TDI, HDI, and combinations thereof. In further embodiments, the isocyanate compound is MDI.

[0072] In the embodiments, the isocyanate compound is selected from carbodiimide-modified MDI, carbodiimide-modified TDI, carbodiimide-modified HDI, and combinations thereof. In further embodiments, the isocyanate compound is carbodiimide-modified MDI.

[0073] In the embodiment, the isocyanate compound has an NCO content of 20% or more, preferably 25% or more, and preferably 28% or more.

[0074] Dimer acid polyester polyol Isocyanate component B) comprises the reaction product of (i) an isocyanate compound and (ii) a dimer acid polyester polyol. "Dimer acid polyester polyol" (or "DAPP" or dimer acid-based polyester polyol) is a polyester polyol containing units derived from dimer acid. In embodiments, DAPP is the reaction product of (i) a dimer acid, (ii) at least one polyol, and (iii) optionally another carbonyl-containing compound such as a dicarboxylic acid, an anhydride, or caprolactone.

[0075] i. Dimer acid In the embodiment, DAPP is a reaction product of a reaction mixture comprising (i) a dimer acid, (ii) at least one polyol, and (iii) optionally another carbonyl-containing compound such as a dicarboxylic acid, an anhydride, or caprolactone.

[0076] A "dimer acid" is a dicarboxylic acid compound obtained by reacting a fatty acid having 2 to 4 ethylenically double bonds and 14 to 22 carbon atoms (hereinafter referred to as "unsaturated fatty acid A") with a fatty acid having 1 to 4 ethylenically double bonds and 14 to 22 carbon atoms (hereinafter referred to as "unsaturated fatty acid B") at the double bonds in a dimerization reaction. In one embodiment, unsaturated fatty acid A has two ethylenically double bonds and 14 to 22 carbon atoms, and unsaturated fatty acid B has one or two ethylenically double bonds and 14 to 22 carbon atoms. Non-limiting examples of suitable unsaturated fatty acid A include tetradecadienoic acid, hexadecadienoic acid, octadecadienoic acid (such as linoleic acid), eicosadienoic acid, docosadienoic acid, octadecatrienoic acid (such as linolenic acid), eicosatetraenoic acid (such as arachidonic acid), and combinations thereof. Non-limiting examples of suitable unsaturated fatty acids B, in addition to those mentioned above, include tetradecenoic acid (tuzic acid, ficeteric acid, myristoleic acid), hexadecenoic acid (palmitolic acid, etc.), octadecenoic acid (oleic acid, elaidic acid, vaccenic acid, etc.), eicosenoic acid (gadoleic acid, etc.), and docosenoic acid (erucic acid, cetoleic acid, brassic acid, etc.), as well as combinations thereof.

[0077] The resulting dimer acid is a mixture of dimer acids with different structures depending on the double bond site or isomerization. Non-limiting examples of suitable dimer acid structures are the following structures (A), (B), (C), (D), or (E): [ka]

[0078] In one embodiment, the dimer acid is a C36 dimer acid. In a further embodiment, the C36 dimer acid has structure (A).

[0079] In one embodiment, the resulting dimer acid contains 0% to 2% by weight, or 4% by weight, or 6% by weight of monomeric acid, and / or 0% to 2% by weight, or 4% by weight, or 6% by weight of polymeric acid, and has a degree of polymerization equal to or greater than that of the trimer acid.

[0080] In one embodiment, the dimer acid is unsaturated. An "unsaturated dimer acid" contains at least one carbon-carbon double bond. Structure (A) is an unsaturated dimer acid. A non-limiting example of a preferred dimer acid is ATUREX™ 1001 (CAS 61788-89-4), available from Jiangxi Aturex Co., Ltd.

[0081] In one embodiment, the dimer acid has an acid value of 150 mg KOH / g, or 160 mg KOH / g, or 170 mg KOH / g, or 180 mg KOH / g, or 190 mg KOH / g, or 194 mg KOH / g to 200 mg KOH / g, or 210 mg KOH / g, or 220 mg KOH / g, or 230 mg KOH / g, or 240 mg KOH / g, or 250 mg KOH / g. In another embodiment, the dimer acid has an acid value of 150 mg KOH / g to 250 mg KOH / g, or 180 mg KOH / g to 220 mg KOH / g, or 190 mg KOH / g to 200 mg KOH / g.

[0082] In one embodiment, the dimer acid has structure (A) and an acid value of 150 mg KOH / g to 250 mg KOH / g, or 180 mg KOH / g to 220 mg KOH / g, or 190 mg KOH / g to 200 mg KOH / g. In a further embodiment, the dimer acid is ATUREX™ 1001 (CAS 61788-89-4), available from Jiangxi Aturex Co., Ltd.

[0083] Dimer acids may include two or more embodiments disclosed herein.

[0084] ii. Polyols In the embodiment, DAPP is a reaction product of a reaction mixture comprising (i) a dimer acid, (ii) at least one polyol, and (iii) optionally another carbonyl-containing compound such as a dicarboxylic acid, an anhydride, or caprolactone.

[0085] Non-limiting examples of suitable polyols include diols (containing two hydroxyl groups), triols (containing three hydroxyl groups), and combinations thereof. In one embodiment, the polyol includes diols and triols.

[0086] Non-limiting examples of suitable diols include 3-methyl-1,5-pentanediol (MPD), 2-methyl-1,3-propanediol (MPG), polyalkylene glycols such as ethylene glycol, butylene glycol, diethylene glycol (DEG), triethylene glycol, polyethylene glycol, and polypropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol (NPG).

[0087] A non-limiting example of a suitable triol is trimethylolpropane (TMP).

[0088] In one embodiment, the polyol is a diol. In a further embodiment, the diol is an MPD.

[0089] The polyol may include two or more embodiments disclosed herein.

[0090] iii. An optional carbonyl-containing compound, e.g., a dicarboxylic acid, an anhydride, or caprolactone. In embodiments, DAPP is a reaction product of a reaction mixture comprising (i) a dimer acid, (ii) at least one polyol, and (iii) optionally another carbonyl-containing compound such as a dicarboxylic acid, an anhydride, or caprolactone.

[0091] The optional carbonyl-containing compound may be, for example, a dicarboxylic acid, an anhydride, or caprolactone. (iii) The dicarboxylic acid is not a dimer acid. In other words, (iii) the dicarboxylic acid is structurally and / or compositionally different from (i) the dimer acid in the reaction mixture.

[0092] Non-limiting examples of suitable dicarboxylic acids include fatty acids, aromatic acids, and combinations thereof. Non-limiting examples of suitable aromatic dicarboxylic acids include phthalic acid, isophthalic acid, and terephthalic acid. Non-limiting examples of suitable aliphatic dicarboxylic acids include cyclohexanedicarboxylic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, maleic acid, fumaric acid, itaconic acid, malonic acid, suberic acid, 2-methylsuccinic acid, 3,3-diethylglutaric acid, 2,2-dimethylsuccinic acid, and trimellitic acid. As used herein, the term “acid” also includes any anhydride of the acid. Saturated aliphatic acids and / or aromatic acids, such as adipic acid or isophthalic acid, are also suitable.

[0093] In one embodiment, the dicarboxylic acid has 4, 5, 6-7, 8, 9, or 10 carbon atoms. In another embodiment, the dicarboxylic acid has 4-10 carbon atoms or 6-8 carbon atoms. In a further embodiment, the dicarboxylic acid has 8 carbon atoms.

[0094] In one embodiment, the dicarboxylic acid is selected from phthalic acid, isophthalic acid, terephthalic acid, and combinations thereof.

[0095] The dicarboxylic acid may comprise two or more embodiments disclosed herein.

[0096] iv. Any additives In the embodiment, DAPP is a reaction product of a reaction mixture comprising (i) a dimer acid, (ii) at least one polyol, (iii) optionally another carbonyl-containing compound such as a dicarboxylic acid, an anhydride, or caprolactone, and (iv) optionally an additive.

[0097] Non-limiting examples of suitable additives include adhesion promoters, chain extenders, catalysts, and combinations thereof.

[0098] A non-limiting example of a suitable adhesion promoter is aminosilane.

[0099] Non-limiting examples of suitable chain extenders include glycerin, trimethylolpropane, diethylene glycol, propanediol, 2-methyl-1,3-propanediol, and combinations thereof.

[0100] Non-limiting examples of suitable catalysts include tetra-n-butyl titanate, zinc sulfate, organotin catalysts, and combinations thereof.

[0101] In one embodiment, the reaction mixture excludes the chain extender.

[0102] Any additive may include two or more embodiments disclosed herein.

[0103] The isocyanate component B) may contain, based on the total weight of the isocyanate component B), 5 to 99.95% by weight, preferably 10 to 95% by weight, more preferably 20 to 90% by weight, even more preferably 25 to 80% by weight, or 30 to 60% by weight, or 35 to 50% by weight of the reaction product of (i) an isocyanate compound and (ii) a dimer acid polyester polyol.

[0104] Isocyanate component B) also contains polyphosphate. Polyphosphate is HO[P(OH)(O)O] n The formula has the following characteristics: H, where n represents the degree of polymerization of the repeating unit.

[0105] The isocyanate component B) contains 0.05 to 5.0% by weight, preferably 0.08 to 3.0% by weight, more preferably 0.09 to 2.5% by weight, and even more preferably 0.1 to 1.0% by weight or 0.1 to 0.8% by weight of polyphosphate, based on the total weight of the isocyanate component B).

[0106] The isocyanate component B) may optionally include plasticizers, flame retardants, adhesion promoters, rheology modifiers, fillers, and the like.

[0107] Plasticizers such as diisononyl phthalate help reduce skinning that accumulates during application of isocyanate component B). Isocyanate component B) contains 0 to 20% by weight, preferably 0.1 to 15% by weight, more preferably 0.2 to 10% by weight, even more preferably 0.3 to 8% by weight, or 0.5 to 6% by weight of plasticizer, based on the total weight of isocyanate component B).

[0108] Flame retardants such as isopropylated phenol phosphate improve fire resistance when battery cells are exposed to electrical short circuits. Isocyanate component B) contains 0 to 20% by weight, preferably 0.1 to 15% by weight, more preferably 0.2 to 10% by weight, even more preferably 0.3 to 8% by weight, or 0.5 to 6% by weight of the flame retardant, based on the total weight of isocyanate component B).

[0109] Other conventional adhesion promoters, such as epoxysilanes, may also be used. The isocyanate component B) comprises 0 to 10% by weight, preferably 0.5 to 9% by weight, more preferably 0.6 to 8% by weight, and even more preferably 0.8 to 6% by weight of other conventional adhesion promoters, based on the total weight of the isocyanate component B).

[0110] Rheology modifiers such as fumed silica are often included in adhesive compositions to provide thixotropic properties to meet the needs of various applications. In isocyanate component B), hydrophobic surface-treated fumed silica is often used as the rheology modifier. Isocyanate component B) contains 0 to 10% by weight, preferably 0.5 to 9% by weight, more preferably 0.6 to 8% by weight, and even more preferably 0.8 to 6% by weight of the rheology modifier, based on the total weight of isocyanate component B).

[0111] To improve mechanical strength and reduce costs, fillers are added to the adhesive composition. The fillers may be selected from silica, CaCO3, kaolin, talc, Al2O3, boron nitride, or aluminum hydroxide, etc. The isocyanate component B) contains 0 to 95% by weight, preferably 5 to 90% by weight, more preferably 10 to 80% by weight, and even more preferably 40 to 70% by weight of the filler, based on the total weight of the isocyanate component B).

[0112] A mixture for preparing the reaction product of (i) an isocyanate compound and (ii) a dimer acid polyester polyol (also called an NCO-terminated prepolymer) typically comprises 60-95% by weight, preferably 65-85% by weight, more preferably 70-80% by weight of an aromatic isocyanate and 5-40% by weight, preferably 15-35% by weight, more preferably 20-30% by weight of a dimer acid polyester polyol, based on the total weight of the mixture for preparing the reaction product of (i) an isocyanate compound and (ii) a dimer acid polyester polyol.

[0113] The isocyanate component B) is typically a reaction product of (i) an isocyanate compound and (ii) a dimer acid polyester polyol in 30-100% by weight, preferably 35-95% by weight, more preferably 38-90% by weight, even more preferably 40-80% by weight, or 50-75% by weight, or 60-70% by weight, based on the total weight of the isocyanate component B), optionally 0-20% by weight, preferably 0.1-15% by weight, more preferably 0.2-10% by weight, even more preferably 0.3-8% by weight, or 0.5-6% by weight of a plasticizer, and 0-20% by weight, preferably 0.1-1 The material comprises 5% by weight, more preferably 0.2 to 10% by weight, even more preferably 0.3 to 8% by weight, or 0.5 to 6% by weight of a flame retardant; 0 to 10% by weight, preferably 0.5 to 9% by weight, more preferably 0.6 to 8% by weight, even more preferably 0.8 to 6% by weight of another conventional adhesion promoter; 0 to 10% by weight, preferably 0.5 to 9% by weight, more preferably 0.6 to 8% by weight, even more preferably 0.8 to 6% by weight of a rheology modifier; and 0 to 95% by weight, preferably 5 to 90% by weight, more preferably 10 to 80% by weight, even more preferably 40 to 70% by weight of a filler.

[0114] C. Two-component adhesive composition Two-component adhesive compositions contain no solvent, or substantially no solvent.

[0115] In one embodiment, the two-component adhesive composition includes any conventional additives. The additives may be any of those disclosed herein, such as plasticizers, chain extenders, flame retardants, adhesion promoters, rheology modifiers, fillers, moisture scavengers, and catalysts.

[0116] The two-component adhesive composition is formed by mixing polyol component A) and isocyanate component B) under conditions suitable for reacting the -NCO group of the isocyanate component with the hydroxyl group of the polyol component. In one embodiment, polyol component A) and isocyanate component B) are mixed via a static or dynamic mixing device (such as a meter mix dispenser) at a temperature of 15°C, 20°C, 25°C, 30°C, 35°C, 40°C-45°C, 50°C, or 55°C.

[0117] The isocyanate index ("NCO index") is the molar ratio of isocyanate groups in the isocyanate component to the amount of hydroxyl groups in the polyol component. The NCO index is calculated according to the following formula (1):

[0118]

number

[0119] In one embodiment, the two-component adhesive composition has an NCO index of 1.05, 1.10, 1.15-1.85, 1.80, 1.70, 1.60, 1.50, 1.40, 1.30, or 1.25. In another embodiment, the two-component adhesive composition has an NCO index of 1.05-1.85, 1.05-1.80, 1.10-1.60, or 1.15-1.25.

[0120] In one embodiment, the two-component adhesive composition contains polyol component A) and isocyanate component B) in a volume ratio of isocyanate component B):polyol component A) of 120:100 to 80:100, or 115:100 to 90:100, or 110:100 to 95:100, or 105:100 to 98:100.

[0121] The two-component adhesive composition may include two or more embodiments disclosed herein.

[0122] D.Multilayer structure This disclosure provides a multilayer structure comprising a first substrate, a second substrate, and an adhesive layer between the first and second substrates. The adhesive layer is formed from a two-component adhesive composition.

[0123] The two-component adhesive composition may be any of the two-component adhesive compositions disclosed herein.

[0124] First substrate and second substrate The multilayer structure includes a first substrate and a second substrate.

[0125] The first substrate and the second substrate may be the same or different. In one embodiment, the first substrate and the second substrate are the same, and therefore they have the same composition and the same structure.

[0126] In one embodiment, the first substrate and the second substrate differ from each other in terms of composition and / or structure.

[0127] In the following description referring to "substrate," it is understood that the first substrate and the second substrate refer to them individually and / or collectively.

[0128] A non-limiting example of a suitable substrate is a film. The film may be a single-layer film or a multilayer film. A multilayer film may contain two or more layers. For example, a multilayer film may have two, three, four, five, six, seven, eight, nine, ten, eleven, or more layers. In one embodiment, the multilayer film may contain only two or only three layers.

[0129] In one embodiment, the film is a single-layer film having only one layer.

[0130] In one embodiment, the film comprises layers containing components selected from ethylene-based polymers (PE), propylene-based polymers (PP), polyamides (such as nylon), polyesters, ethylene vinyl alcohol (EVOH) copolymers, polyethylene terephthalate (PET), ethylene vinyl acrylate (EVA) copolymers, ethylene methyl acrylate copolymers, ethylene ethyl acrylate copolymers, ethylene butyl acrylate copolymers, ethylene acrylic acid copolymers, ethylene methacrylic acid copolymers, ethylene acrylic acid ionomers, methacrylic acid ionomers, maleic anhydride grafted ethylene-based polymers, polylactic acid (PLA), polystyrene, metal foils, cellulose, cellophane, nonwoven fabrics, and combinations thereof. A non-limiting example of a suitable metal foil is aluminum foil. Each layer of the multilayer film may be formed from the same components or from different components.

[0131] In one embodiment, the film includes a layer containing metal foil.

[0132] In one embodiment, the film is a single-layer film having a single layer that is an ethylene-based polymer layer. In a further embodiment, the film is a single-layer film having a single layer that is a polyethylene layer.

[0133] The substrate and the film have a continuous structure with two opposing surfaces.

[0134] In one embodiment, the substrate has a thickness of 5 μm, or 10 μm, or 12 μm, or 15 μm, or 20 μm, or 21 μm to 23 μm, or 24 μm, or 25 μm, or 30 μm, or 35 μm, or 40 μm, or 45 μm, or 50 μm, or 100 μm, or 150 μm, or 200 μm, or 250 μm, or 300 μm, or 350 μm, or 400 μm, or 450 μm, or 500 μm.

[0135] In one embodiment, the substrate excludes cellulose-based substrates such as paper and wood.

[0136] In one embodiment, the first substrate is a single-layer film having a single layer which is a PE layer, and the second substrate is a film having a layer which is a metal foil layer.

[0137] The film may include two or more embodiments disclosed herein.

[0138] The first substrate may include two or more embodiments disclosed herein.

[0139] The second substrate may include two or more embodiments disclosed herein.

[0140] The two-component adhesive composition is applied between the first substrate and the second substrate, for example, using a Nordmeccanica Labo Combi 400 laminator. In one embodiment, the two-component adhesive composition is applied between the first substrate and the second substrate at a temperature of 20°C, 30°C, 40°C to 50°C, 60°C, 70°C, 80°C, or 90°C.

[0141] Non-limiting examples of preferred application methods include brushing, pouring, spraying, coating, rolling, scattering, and injecting.

[0142] In one embodiment, a two-component adhesive composition is applied between a first substrate and a second substrate by a conventional coating method.

[0143] In one embodiment, a two-component adhesive composition is uniformly applied between a first substrate and a second substrate. "Uniform application" means a continuous (not discontinuous) layer of the composition across the surface of the substrates, with the same or substantially the same thickness across the surface of the substrates. In other words, a composition uniformly applied to the substrates is in direct contact with the substrate surface, and the composition has the same extent as the substrate surface.

[0144] The two-component adhesive composition and the first substrate are in direct contact with each other. As used herein, the term "direct contact" means a layer configuration in which the substrate is located directly adjacent to the two-component adhesive composition or adhesive layer, and there is no intervening layer or structure between the substrate and the two-component adhesive composition or adhesive layer. The two-component adhesive composition is in direct contact with the surface of the first substrate.

[0145] The two-component adhesive composition and the second substrate are in direct contact with each other. The two-component adhesive composition is in direct contact with the surface of the second substrate.

[0146] The structure comprising a first substrate, a second substrate, and a two-component adhesive composition has the following structure (P): First substrate / two-component adhesive composition / second substrate structure (P).

[0147] The adhesive layer of structure (P) is formed by curing a two-component adhesive composition. The two-component adhesive composition is formed by mixing and reacting polyol component A) and isocyanate component B).

[0148] In one embodiment, the two-component adhesive composition is cured in an oven at a temperature of 10°C, 20°C, 35°C to 40°C, 45°C, or 50°C.

[0149] In one embodiment, the two-component adhesive composition is cured at a temperature of 20°C to 30°C, preferably 25°C, for 1 to 2 days, or 4 days, or 7 days, or 10 days.

[0150] In one embodiment, the two-component adhesive composition is cured in the absence or substantially absence of a photoinitiator.

[0151] In one embodiment, the two-component adhesive composition is cured in the absence or substantially absence of water.

[0152] In one embodiment, structure (P) is cured to form an adhesive layer between the first substrate and the second substrate, thereby forming a multilayer structure. The multilayer structure has the following structure (Q): First substrate / adhesive layer / second substrate structure (Q).

[0153] The multilayer structure includes a first substrate that is in direct contact with the adhesive layer and a second substrate that is in direct contact with the adhesive layer.

[0154] A multilayer structure includes alternating substrate layers and adhesive layers. A multilayer structure includes a total of at least three layers, including substrate layers and adhesive layers. In one embodiment, a multilayer structure includes a total of 3 to 4 layers, or 5 layers, or 6 layers, or 7 layers, or 8 layers, or 9 layers, or 10 layers.

[0155] In the embodiment, the first substrate is a single-layer film having a single layer of metal foil, and the second substrate is a single-layer film having a single layer of metal foil. The multilayer structure has a lap shear strength of 7 MPa, 7.5 MPa, 8 MPa, 8.5 MPa to 15 MPa, 13 MPa, or 12 MPa, and / or a cross tensile strength of 12.5 MPa, 13.0 MPa, 13.5 MPa, 14 MPa to 30 MPa, 25 MPa, or 22 MPa.

[0156] E. Method for forming a two-component solvent-free adhesive composition This disclosure also provides a method for forming a two-component adhesive composition, the method being, i) To provide a polyol component A) comprising at least one hydrophobic polyol, ii) To provide (I) the reaction product of an isocyanate compound and (II) a dimer acid polyester polyol, and an isocyanate component B) containing polyphosphate, iii) reacting isocyanate component B) with polyol component A) to form a two-component adhesive composition.

[0157] The multilayer structure may be in the form of a jelly roll or a laminate, and is preferably located within a battery package.

[0158] This disclosure also provides articles including multilayer structures. Non-limiting examples of suitable articles include packages such as battery packages.

[0159] Rather than being limiting, some embodiments of the present disclosure are described in detail below in the following examples. [Examples]

[0160] The substances used in the examples are shown in Table 1 below.

[0161] [Table 1]

[0162] Synthesis of dimer acid-based polyester polyol-1: 100 g of 1,6-hexanediol and 353 g of ATUREX-1001 were placed in a 500 mL glass reactor and thoroughly mixed. The mixture was heated to 100°C. Stirring was started when the raw materials became liquid. The temperature was controlled to an appropriate level and monitored throughout the process. If the maximum temperature of the glass condenser exceeded 103°C, the reactor was cooled as quickly as possible. When the reaction temperature rose to 220°C and the maximum temperature fell below 100°C, vacuum was started and the pressure was slowly reduced to 30 mm Hg over 30 minutes. The acid value was checked every 30 minutes. A constant amount of catalyst Tyzor TBT was added until the acid value was less than 10. After adding the catalyst, the reaction system was maintained under a vacuum of 30 mm Hg for more than 1 hour until the OH value of the reaction system reached the theoretical value. The mixture was cooled to 60-70°C, and the final product was collected as dimer acid-based polyesterdiol-1.

[0163] Synthesis of dimer acid-based polyester polyol-2: 100 g of 2-methyl-1,3-propanediol and 467.5 g of ATUREX-1001 were placed in a 500 mL glass reactor and thoroughly mixed. The mixture was heated to 100°C. Stirring was started when the raw materials became liquid. The temperature was controlled to an appropriate level and monitored throughout the process. If the maximum temperature of the glass condenser exceeded 103°C, the reactor was cooled as quickly as possible. When the reaction temperature rose to 220°C and the maximum temperature fell below 100°C, vacuum was started and the pressure was slowly reduced to 30 mm Hg over 30 minutes. The acid value was checked every 30 minutes. A constant amount of catalyst Tyzor TBT was added until the acid value was less than 10. After adding the catalyst, the reaction system was maintained under a vacuum of 30 mm Hg for more than 1 hour until the OH value of the reaction system reached the theoretical value. The mixture was cooled to 60-70°C, and the final product was collected as dimer acid-based polyesterdiol-2.

[0164] Synthesis of polyurethane polyols (OH-terminated polyurethane prepolymers, i.e., castor oil derivatives): Polyurethane polyols were synthesized in a 1,000 mL glass reactor as part of a standard polyurethane prepolymer preparation process. 12 g of ISONATE OP 50 was added to the reactor and maintained at 60°C under nitrogen protection. Then, 44 g of castor oil and 44 g of VORANOL P 400 were added to the reactor and mixed with ISONATE OP 50. The temperature was slowly increased to 80°C and held for 2 hours. Finally, for further use, the polyurethane polyols were placed in a nitrogen-protected, well-sealed container.

[0165] Synthesis of NCO-terminated prepolymer-1: 75 g of ISONATE 143L was placed in a 1,000 mL glass reactor and maintained at 60°C under nitrogen protection. Then, 25 g of PTMEG2000 was added to the reactor and mixed with ISONATE 143L. The temperature was slowly increased to 80°C and maintained for 2-3 hours until the NCO content met the theoretical value. Finally, for further application, the prepolymer was placed in a nitrogen-protected, well-sealed container.

[0166] Synthesis of NCO-terminated prepolymer-2: 75 g of ISONATE 143L was placed in a 1,000 mL glass reactor and maintained at 60°C under nitrogen protection. Then, 25 g of dimer acid-based polyester diol-1 was added to the reactor and mixed with ISONATE 143L. The temperature was slowly increased to 80°C and maintained for 2-3 hours until the NCO content reached the theoretical value. Finally, for further application, the prepolymer was placed in a nitrogen-protected, well-sealed container.

[0167] Synthesis of NCO-terminated prepolymer-3: 75 g of ISONATE 143L was placed in a 1,000 mL glass reactor and maintained at 60°C under nitrogen protection. Then, 25 g of dimer acid-based polyester diol-2 was added to the reactor and mixed with ISONATE 143L. The temperature was slowly increased to 80°C and maintained for 2-3 hours until the NCO content reached the theoretical value. Finally, for further application, the prepolymer was placed in a nitrogen-protected, well-sealed container.

[0168] Table 2 summarizes the part B isocyanate portion that can meet the moisture resistance requirements. Table 3 summarizes adhesive formulations including parts A and B.

[0169] In samples E01 and E02, very short non-stick times were observed when the isocyanate was used as is. When comparing E03 with E07 or E10, the isocyanate based on the dimer acid polyester prepolymer showed a much longer non-stick time. Comparing E04 to E10, only the isocyanate portion containing a dimer acid-based prepolymer and with added phosphoric acid or polyphosphate showed a satisfactory non-stick time (≥11 hours). This significantly extended non-stick time must be due to the deactivation effect of the NCO group by protons.

[0170] [Table 2]

[0171] The adhesive formulations, along with details in Part A and corresponding examples in Part B, are summarized in Table 3. Adhesive dispensers are most commonly available at a volume mixing ratio of 1:1. Furthermore, to ensure complete curing of the adhesive, the stoichiometric ratio of the 2K polyurethane adhesive is typically set in the range of 1.05 to 1.85. Therefore, formulations were designed to meet these requirements. The volume mixing ratios and stoichiometric ratios were calculated and listed in Table 3.

[0172] Examples E01-E03 are comparative examples demonstrating the limited adhesion-promoting effects of phosphoric acid (containing 15% by weight of water in the product, which cannot be removed), triethyl phosphate (TEP), and tris(chloropropyl) phosphate (TCPP). In contrast, Examples 01-05 of the present invention, which include polyphosphate as an adhesion promoter, show significantly improved adhesion strength. Comparing Inv.01-03 or Inv.04-05, which contain gradually increasing amounts of polyphosphate, the adhesion-promoting effect was enhanced. Comparing Inv.01 and Inv.04, different adhesion strengths were achieved by changing the structure of the dimer acid polyester polyol. Comparing Inv.04-05, polyphosphate may be added to the polyol portion to achieve the adhesion-promoting effect.

[0173] [Table 3] * Com. - Comparative Example; Inv. - Example of the present invention. A lap shear strength of ≥ 8.5 MPa and a cross tensile strength of ≥ 12.5 MPa are preferred.

[0174] The isocyanate prepolymer of Part B was prepared according to the following procedure. Step 1: The NCO-terminated prepolymer is placed in a container, and then other liquid components (DINP, IPPP, Z-6040, etc.) are added. Step 2: Apply vacuum and mix at medium speed for 30 minutes. Step 3: Place the alumina into the container, add the powder, then apply a vacuum and mix at high speed for 30 minutes. Step 4: Place the fumed silica into the container, add the powder, then apply a vacuum and mix at high speed for 1 hour. Step 5: Set the bath temperature to 80°C and continue stirring at medium to low speed for 30 minutes to maintain the temperature. Step 6: Set the temperature bath to 20°C and cool it down to below 40°C.

[0175] The non-stick time was tested according to the following procedure. Place 10g of Part B into a 50mL plastic beaker and place the beaker in an oven at 45% humidity and 23°C. Begin recording time. Periodically remove the beaker and lightly touch the surface of Part B with a plastic rod. As the reaction between Part B and moisture progresses, the surface viscosity will increase. Stop recording time when the surface of Part B is no longer sticky. Record this period as the non-stick time of Part B.

[0176] Prepare the polyol mixture for Part A by following the steps below. Step 1: Add castor oil, polyurethane polyol, CP450, and BDO to a container. Step 2: Heat to 80°C, apply vacuum, and mix with medium-speed stirring for 1 hour to degas. Step 3: Add ATH to the container, then add the powder, apply a vacuum, and mix at high speed for 15 minutes. Step 4: Place the molecular sieve 3A into the container, add the powder, then apply a vacuum and mix at high speed for 15 minutes. Step 5: Place H-18 into the container, add the powder, then apply a vacuum and mix at high speed for 1 hour. Step 6: Cool to below 40°C.

[0177] Test method: The lap joint test coupon was prepared using the following procedure. 1. A base material was fabricated from 3003 aluminum alloy with dimensions of 25mm x 12.5mm. 2. Clean the surface of the substrate by wiping it with ethanol. 3. Use pressure-sensitive tape to mask the adhesive area, which should be 25mm x 12mm. 4. Mix parts A and B of the adhesive together and place in a 1000 rpm speed mixer for 1 minute to ensure they are thoroughly mixed. 5. Apply 0.5g to 1.5g of adhesive to the bonding area of ​​the substrate. Insert two 0.2mm diameter copper wires to adjust the thickness of the adhesive. 6. Stack another masked substrate along the length, ensuring the same bonding area is in contact head to head. Place two clippers side by side and press the bonding surface to secure it. 7. Allow the adhesive to cure at 25°C for 7 days.

[0178] The butt joint test coupon was prepared using the following procedure. 1. A base material was fabricated from 3003 aluminum alloy with dimensions of 60 mm in height and 15 mm in diameter. 2. Clean the surface of the substrate by wiping it with ethanol. 3. Mix parts A and B of the adhesive together and place in a 1000 rpm speed mixer for 1 minute to ensure thorough mixing. 4. Apply 0.5g to 1g of adhesive to the flat surface of the substrate. Insert two 0.25mm diameter copper wires to control the thickness of the adhesive. 5. Stack the other cleaned substrates with their flat surfaces joined together. Keep the stacked substrates vertical so that the joined surfaces remain fixed in place by gravity. 6. Allow the adhesive to cure at 25°C for 7 days.

[0179] The test coupons were assembled on the fixtures of an Instron testing machine (model: Instron 5566), and the shear strength of the lap joint and the tensile strength of the butt joint were tested at a strain rate of 5 mm / min.

Claims

1. Polyol component A) containing at least one hydrophobic polyol, Polyphosphate, and isocyanate component B) comprising the reaction product of (I) an isocyanate compound and (II) a dimer acid polyester polyol, A two-component adhesive composition comprising the reaction product of, The amount of the hydrophobic polyol is 20 to 60% by weight, based on the total weight of the polyol component A. The hydrophobic polyol is selected from vegetable oil, hydrophobic polyol derived from vegetable oil, or a mixture thereof. A two-component adhesive composition wherein the amount of the reaction product of (I) the isocyanate compound and (II) the dimer acid polyester polyol is 25 to 80% by weight, based on the total weight of the isocyanate component B).

2. The two-component adhesive composition according to claim 1, wherein the hydrophobic polyol is selected from castor oil, a hydrophobic polyol derived from castor oil, soybean oil, a hydrophobic polyol derived from soybean oil, or a mixture thereof.

3. The aforementioned dimer acid polyester polyol a) Dimer acid and, b) at least one polyol, The two-component adhesive composition according to claim 1, comprising a reaction product of a reaction mixture containing the following.

4. The aforementioned dimer acid polyester polyol a) Dimer acid and, b) at least one polyol, c) With other carbonyl-containing compounds, The two-component adhesive composition according to claim 1, comprising a reaction product of a reaction mixture containing the following.

5. The two-component adhesive composition according to claim 1, wherein the isocyanate component B) contains 0.05 to 5.0% by weight of the polyphosphate based on the total weight of the isocyanate component B).

6. The two-component adhesive composition according to claim 1, wherein the polyol component A) contains 0.05 to 5.0% by weight of polyphosphate based on the total weight of the polyol component A).

7. The two-component adhesive composition according to claim 1, wherein the NCO index is 1.05 to 1.

85.

8. The dimer acid is one of the following structures: (A), (B), (C), (D), or (E): 【Chemistry 1】 【Chemistry 2】 A two-component adhesive composition according to claim 3, having the following characteristics.

9. It has a multilayer structure, The first substrate and A second substrate and An adhesive layer located between the first substrate and the second substrate, formed from the two-component adhesive composition described in claim 1, A multilayer structure including a multilayer structure.

10. The multilayer structure according to claim 9, wherein the first substrate and the second substrate are films comprising layers containing components selected from ethylene polymers (PE), propylene polymers (PP), polyamides, polyesters, ethylene vinyl alcohol (EVOH) copolymers, polyethylene terephthalate (PET), ethylene vinyl acrylate (EVA) copolymers, ethylene methyl acrylate copolymers, ethylene ethyl acrylate copolymers, ethylene butyl acrylate copolymers, ethylene acrylic acid copolymers, ethylene methacrylic acid copolymers, ethylene acrylic acid ionomers, methacrylic acid ionomers, maleic anhydride grafted ethylene polymers, polylactic acid (PLA), polystyrene, metal foils, cellulose, cellophane, nonwoven fabrics, and combinations thereof.

11. The multilayer structure according to claim 9, wherein the first substrate is a single-layer film having a single layer of metal foil, and the second substrate is a single-layer film having a single layer of metal foil.

12. A method for forming the two-component adhesive composition described in claim 1, i) To provide a polyol component A) comprising at least one hydrophobic polyol, ii) to provide polyphosphate and isocyanate component B) comprising the reaction product of (I) an isocyanate compound and (II) a dimer acid polyester polyol, iii) Next, the isocyanate component B) is reacted with the polyol component A) to form a two-component adhesive composition, Includes, The amount of the hydrophobic polyol is 20 to 60% by weight, based on the total weight of the polyol component A. The hydrophobic polyol is selected from vegetable oil, hydrophobic polyol derived from vegetable oil, or a mixture thereof. A method wherein the amount of the reaction product of (I) the isocyanate compound and (II) the dimer acid polyester polyol is 25 to 80% by weight, based on the total weight of the isocyanate component B).

13. Use of the two-component adhesive composition according to claim 1 in a battery pack.

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