Isocyanate compound and adhesive composition containing same

Abstract

Provided is an isocyanate compound containing a phosphate functional group, obtainable or obtainable by reacting at least one selected from the group consisting of an isocyanate monomer, an isocyanate adduct, and a combination thereof with a phosphate-functional polyol. Also provided are adhesive compositions including the isocyanate compound, cured adhesive compositions, methods for producing cured laminates, cured laminates so produced, and uses of the isocyanate compound in two-component solvent-based adhesive compositions.

Description

[Technical Field]

[0001] The present disclosure relates to an isocyanate compound. More particularly, the present disclosure relates to a phosphate-functional isocyanate compound, an adhesive composition containing the same, an article prepared from the adhesive composition, and a method for producing the same. The phosphate-functional isocyanate compound provides an adhesive composition with improved performance, for example, in terms of one or more of adhesive strength, heat seal performance, and chemical resistance. [Background technology]

[0002] Adhesive compositions are useful for a wide variety of purposes. For example, adhesive compositions are used to bond substrates such as polyethylene, polypropylene, polyester, polyamide, metal, paper, or cellophane together to form composite films, i.e., laminates. The use of adhesives in a variety of lamination end uses is generally known. For example, adhesives can be used in the production of film / film and film / foil laminates used in the packaging industry, particularly for food packaging. Adhesives used in lamination applications, i.e., "laminating adhesives," can be generally classified into three categories: solvent-based, water-based, and solventless. Adhesive performance varies depending on the category and the application to which the adhesive is applied.

[0003] There are many types within the category of solvent-based lamination adhesives. One particular type is a two-component polyurethane-based lamination adhesive. Typically, two-component polyurethane-based lamination adhesives include a first component containing an isocyanate and / or polyurethane prepolymer and a second component containing one or more polyols. The two components are combined to form an adhesive composition. The solvent-borne adhesive composition is then applied to a substrate, such as a film / foil substrate. The solvent is allowed to evaporate from the applied adhesive composition. Another film / foil substrate is then contacted with the other substrate to form a curable laminate structure. The laminate structure is cured to bond the two substrates together.

[0004] However, most of the current two-component solvent-based laminating adhesives have been found to fail the boil-in-bag (BIB) test using Morton's soup, making them unsuitable for use in applications such as food packaging applications using typical foil-based structures of foil / PE and foil / RCPP. Therefore, it is desirable to develop two-component solvent-based adhesives for foil-based laminate structures that have improved performance, for example, with respect to one or more of adhesive strength, chemical resistance, and heat resistance. Summary of the Invention

[0005] In one aspect, the present disclosure provides an isocyanate compound containing a phosphate functionality obtainable or obtainable by reaction of at least one selected from the group consisting of an isocyanate monomer, an isocyanate adduct, and combinations thereof with a phosphate-functional polyol.

[0006] In a further aspect, the present disclosure provides a method for producing a medicament for a medicament comprising: (A) an isocyanate component comprising an isocyanate prepolymer comprising an isocyanate compound described herein; (B) a polyol component comprising at least one polyester polyol.

[0007] In a further aspect, the present disclosure provides cured adhesive compositions prepared from the adhesive compositions described herein, comprising the reaction product of a curable mixture of the polyol component and the isocyanate component of the adhesive composition.

[0008] In a further aspect, the present disclosure provides a method for producing a cured laminate by using the adhesive composition described herein, comprising: (a) providing an adhesive composition including an isocyanate component and a polyol component; (b) contacting an isocyanate component with a polyol component to form a curable mixture; (c) applying the curable mixture to a first portion of a surface of the substrate to form a layer of the curable mixture; (d) contacting a second portion of a surface of the same substrate or a different substrate with the layer of curable mixture such that the layer of curable mixture is sandwiched between the first portion and the second portion; (e) evaporating the solvent or allowing the solvent to evaporate; (f) curing the curable mixture or allowing the curable mixture to cure.

[0009] In a further aspect, the present disclosure provides a cured laminate prepared by using the above-described method.

[0010] In a further aspect, the present disclosure provides a cured laminate comprising a first portion on a surface of a substrate, a layer of the cured adhesive composition described herein, and a second portion on a surface of the same or a different substrate, wherein the layer of the cured adhesive composition is sandwiched between and in contact with the first and second portions.

[0011] In a further aspect, the present disclosure provides the use of an isocyanate compound described herein in a two-component solvent-based adhesive composition.

[0012] 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

[0013] 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.

[0014] As disclosed herein, "and / or" means "and, or alternatively." All ranges are inclusive of the endpoints unless otherwise indicated.

[0015] As disclosed herein, all percentages referred to herein are by weight and temperatures are in °C unless otherwise specified.

[0016] Isocyanate compounds Provided herein are isocyanate compounds that contain phosphate functionality, also referred to herein as phosphate-functional isocyanate compounds.

[0017] In some embodiments, the phosphate-functional isocyanate compounds of the present disclosure may be obtainable or obtainable by the reaction of at least one selected from the group consisting of an isocyanate monomer, an isocyanate adduct, and combinations thereof with a phosphate-functional polyol.

[0018] In some embodiments, the phosphate-functional isocyanate compound may be obtainable or obtainable by reaction of at least one selected from the group consisting of an isocyanate monomer, an isocyanate adduct, and combinations thereof with a phosphate-functional polyol in a solvent.

[0019] In some embodiments, the phosphate-functional polyol can be a phosphate ester polyol. In some embodiments, the phosphate-functional polyol can have a structure represented by formula (I):

[0020] [ka] In the formula, R 1 , R 2 and R 3 each independently represents hydrogen or an organic group, with the proviso that R 1 , R 2 and R 3At least one of R represents an organic group; 1 , R 2 and R 3 together contain at least two hydroxyl groups.

[0021] As used herein, the term "organic group" refers to any group containing at least one carbon-carbon bond and / or carbon-hydrogen bond. In some embodiments of Formula (I), the organic group can be any organic group. Examples of suitable organic groups can include, but are not limited to, alkyl-containing groups, alkenyl-containing groups, cycloalkyl-containing groups, aryl-containing groups, alkoxy-containing groups, ester-containing groups, ether-containing groups, polyester-containing groups, polyether-containing groups, and combinations thereof.

[0022] In some embodiments, R 1 , R 2 and R 3 At least two of the hydroxyl groups in are preferably primary hydroxyl groups. As used herein, the term "primary hydroxyl" refers to a hydroxyl group (-OH) on a carbon atom that has only one other carbon atom bonded to it (preferably, in addition to any single carbon atom, has only hydrogen atoms bonded to it).

[0023] In some embodiments of Formula (I), R 1 , R 2 and R 3 One of R represents an organic group and contains at least two hydroxyl groups (e.g., primary hydroxyl groups). In some embodiments, R 1 , R 2 and R 3 two of each independently represent an organic group and together comprise at least two hydroxyl groups (e.g., primary hydroxyl groups). In some embodiments, R 1 , R 2 and R 3 each independently represent an organic group, and together contain at least two hydroxyl groups (e.g., primary hydroxyl groups).

[0024] As used herein, the term "isocyanate monomer" refers to any compound containing two or more isocyanate groups. An "aromatic isocyanate" is an isocyanate that contains one or more aromatic rings. An "aliphatic isocyanate" does not contain an aromatic ring.

[0025] Suitable isocyanate monomers for use in accordance with the present disclosure may be selected from the group consisting of aromatic isocyanates, aliphatic isocyanates, carbodiimide-modified isocyanates, and combinations thereof. Examples of aromatic isocyanates suitable for use in accordance with the present disclosure include, but are not limited to, isomers of methylenediphenyldipolyisocyanate ("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. Examples of aliphatic polyisocyanates suitable for use according to the present disclosure include, but are not limited to, isomers of hexamethylene dipolyisocyanate ("HDI"), isomeric isophorone dipolyisocyanate ("IPDI"), isomeric xylene dipolyisocyanate ("XDI"), methylene-bis-(4-cyclohexylisocyanate) ("HMDI"), and combinations thereof. In some embodiments, the isocyanate monomer comprises a diisocyanate monomer selected from the group consisting of isophorone diisocyanate (IPDI), methylene-bis-(4-cyclohexylisocyanate) (HMDI), hexamethylene diisocyanate (HDI), methylene diphenyl diisocyanate (MDI), toluene diisocyanate (TDI), and combinations thereof.

[0026] As used herein, an "isocyanate adduct" can be a polyisocyanate adduct prepared by reacting an excess amount of an isocyanate (e.g., an aromatic diisocyanate) with a low molecular weight glycol and polyol having a molecular weight of less than 400. Suitable examples of glycols and polyols having a molecular weight of less than 400 include, but are not limited to, diethylene glycol, ethylene glycol, triethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol, trimethylpropane (TMP), glycerol, and pentaerythritol. In some embodiments, the isocyanate adduct can contain two or more isocyanate groups.

[0027] In some examples, the solvent can be an organic solvent. Common organic solvents used in such systems include methyl ethyl ketone, ethyl acetate, toluene, etc., all of which must be moisture-free to prevent premature reaction of the isocyanate groups of the polyurethane. In some embodiments, the solvent can be selected from the group consisting of methyl ethyl ketone, ethyl acetate, toluene, and combinations thereof.

[0028] In some embodiments, at least one selected from the group consisting of isocyanate monomers, isocyanate adducts, and combinations thereof is reacted with a phosphate-functional polyol in excess, and the weight ratio between the at least one selected from the group consisting of isocyanate monomers, isocyanate adducts, and combinations thereof and the phosphate-functional polyol in the reaction can be in the range of, for example, 1:1 to 20:1, 1.2:1 to 18:1, or 1.5:1 to 15:1.

[0029] In some embodiments, the phosphate-functional isocyanate compound according to the present disclosure can be a phosphate ester (e.g., a phosphate monoester, or a phosphate diester, a phosphate triester) having at least one, or at least two, or three terminal isocyanate groups.

[0030] adhesive composition The two-component adhesive composition according to the present disclosure includes (A) an isocynate component and (B) a polyol component.

[0031] In some embodiments, adhesive compositions according to the present disclosure can be two-component adhesive compositions. In some embodiments, adhesive compositions according to the present disclosure can be solvent-based.

[0032] As used herein, the term "two-component" means that the adhesive composition is provided in separate parts prior to use. Typically, compositions according to the present disclosure include at least a first component (also referred to herein as the "isocyanate component" or "NCO component") comprising an isocyanate-containing prepolymer and a second component (also referred to herein as the "polyol component" or "OH component") comprising one or more polyols. In exemplary embodiments of the present disclosure, the isocyanate component and the polyol component are prepared, stored, transported, and supplied separately, and then combined, for example, immediately prior to application to the surface of a substrate.

[0033] It is contemplated that the isocyanate and polyol components of the adhesive compositions described herein can be made separately and, if desired, stored separately until it is desired to use the adhesive composition. When it is desired to use the adhesive composition, the isocyanate and polyol components are contacted and mixed together. It is contemplated that contacting these two components initiates a curing reaction in which the isocyanate groups react with the hydroxyl groups to form urethane bonds. The adhesive composition formed by contacting the two components can be referred to as a "curable mixture."

[0034] In various embodiments of the present disclosure, the isocyanate component can include an isocyanate prepolymer. The isocyanate prepolymer can include the reaction product of at least one isocyanate monomer with at least one polyol selected from the group consisting of polyester polyols, polyether polyols, and combinations thereof. In some embodiments, the isocyanate prepolymer can include a phosphate-functional isocyanate compound of the present disclosure, as described above.

[0035] In various embodiments of the present disclosure, the polyol component can include at least one polyol selected from the group consisting of polyester polyols, polyether polyols, and combinations thereof. In some embodiments, the polyol component can include one or more polyester polyols. In some embodiments, the polyol component can be substantially free of polyether polyols, or can include only an ineffective amount of polyether polyols, or can be free of polyether polyols.

[0036] As used herein, the term "substantially free" refers to an amount of material that is less than 1%, 0.5%, 0.25%, 0.1%, 0.05%, 0.01%, or 0.001% by weight of an ingredient, composition, or article. "Free" refers to the absence of detectable amounts of the recited substance or ingredient.

[0037] In some embodiments, the adhesive composition according to the present disclosure further comprises a solvent. In some embodiments, the solvent may be present in one or both of the polyol component and the isocyanate component. In some examples, the solvent may be an organic solvent. Typical organic solvents suitable for use in the polyol component may include methyl ethyl ketone, ethyl acetate, toluene, and the like.

[0038] In some embodiments, adhesive compositions according to the present disclosure are free of highly reactive amine-initiated polyols and phosphate ester polyols.

[0039] In some embodiments, the combined molar ratio of NCO groups to OH groups in the adhesive composition can be, for example, greater than 1:1, greater than 1.2:1, greater than 1.6:1, greater than 1.8:1, or greater than 2:1.

[0040] In some embodiments, the dry weight mix ratio of polyol component to isocyanate component in adhesive compositions according to the present disclosure can be within a numerical range obtained by combining any two of the endpoints 100:150, 100:140, 100:130, 100:120, 100:110, 100:100, 100:90, 100:80, 100:70, 100:60, 100:50, 100:40, 100:30, 100:25, 100:20, 100:15, 100:10, and 100:5. In some embodiments, the dry weight mix ratio of polyol component to isocyanate component in adhesive compositions according to the present disclosure can be within a range from 100:150 to 100:5, e.g., from 100:150 to 100:10, or from 100:150 to 100:15.

[0041] In some embodiments, the adhesive composition of the present disclosure can be a polyurethane-based adhesive composition. In some embodiments, the adhesive composition of the present disclosure can be a laminating adhesive composition.

[0042] In some embodiments, the adhesive composition may optionally include one or more additional adjuvants and / or additives for particular purposes.

[0043] In some embodiments, the adhesive composition may optionally include one or more adhesion promoters to improve adhesive strength. Examples of one or more adhesion promoters suitable for use in the adhesive composition include, but are not limited to, silanes, epoxies, and phenolics.

[0044] In further embodiments, the adhesive composition may optionally include one or more chain extenders. Examples of one or more chain extenders suitable for use in the adhesive composition include, but are not limited to, glycerin, trimethylolpropane, diethylene glycol, propanediol, and 2-methyl-1,3-propanediol.

[0045] In further embodiments, the adhesive composition may optionally include one or more catalysts. Examples of at least one catalyst suitable for use in the adhesive composition include, but are not limited to, dibutyltin dilaurate, zinc acetate, 2,2-dimorpholinodiethyl ether, and combinations thereof.

[0046] In some embodiments, the adhesive composition may further comprise one or more adjuvants and / or additives selected from the group consisting of other co-catalysts, surfactants, toughening agents, flow modifiers, diluents, stabilizers, plasticizers, catalyst deactivators, dispersants, colorants, and mixtures thereof.

[0047] In some embodiments, the adhesive composition does not include or is colorant-free, such as a pigment, dye, or mixtures thereof.

[0048] Polyol component The polyol component included in the adhesive composition according to the present disclosure may include at least one polyol and optionally a solvent.

[0049] In some embodiments, the polyol component included in the adhesive composition can include two or more polyols. Generally, the polyols can be selected from the group consisting of polyester polyols, polyether polyols, and combinations thereof.

[0050] As used herein, the term "polyol" refers to a compound having two or more hydroxyl groups. A polyol with exactly two hydroxyl groups is a "diol." A polyol with exactly three hydroxyl groups is a "triol." A polyol with exactly four hydroxyl groups is a "tetraol."

[0051] Compounds containing two or more ester bonds in the same linear chain of atoms are known herein as "polyesters." Compounds that are polyesters and polyols are known herein as "polyester polyols." In some embodiments, the polyester polyols may have a molecular weight not exceeding 10,000 g / mol. In some embodiments, the polyester polyols may have a hydroxyl group functionality of at least 1.5 (i.e., f≧1.5).

[0052] Polyester polyols suitable for use in accordance with the present disclosure include, but are not limited to, polycondensates of diols, and optionally polyols (e.g., triols, tetraols), polycondensates of dicarboxylic acids, and optionally polycarboxylic acids (e.g., tricarboxylic acids, tetracarboxylic acids), or hydroxycarboxylic acids or lactones. Polyester polyols can also be derived from the corresponding polycarboxylic acid anhydrides, or corresponding polycarboxylic acid esters of lower alcohols, instead of the free polycarboxylic acids.

[0053] Suitable diols include, but are not limited to, polyalkylene glycols such as ethylene glycol, butylene glycol, diethylene glycol, triethylene glycol, pentylene glycol, hexalene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, and neopentyl glycol. Optionally, to achieve a polyester polyol functionality greater than 2, a polyol having a functionality of 3 (e.g., trimethylolpropane, glycerol, erythritol, pentaerythritol, trimethylolbenzene, or trishydroxyethyl isocyanurate) can be included in the adhesive composition.

[0054] Suitable dicarboxylic acids include, but are not limited to, fatty acids, aromatic acids, and combinations thereof. Examples of suitable aromatic acids include phthalic acid, isophthalic acid, terephthalic acid, and tetrahydrophthalic acid. Examples of suitable aliphatic acids include hexahydrophthalic acid, cyclohexanedicarboxylic acid, 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, 2,2-dimethylsuccinic acid, and trimellitic acid. As used herein, the term "acid" also includes any anhydrides of the acid. Furthermore, monocarboxylic acids such as benzoic acid and hexanecarboxylic acid should be minimized or eliminated from the disclosed compositions. Saturated aliphatic and / or aromatic acids such as adipic acid or isophthalic acid are also suitable for use in accordance with the present disclosure.

[0055] In some embodiments, the polyol component can include one or more polyester polyols.

[0056] In some embodiments, for example, the amount of polyester polyol in the polyol component can be at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt%, at least 45 wt%, at least 50 wt%, at least 55 wt%, at least 60 wt%, at least 65 wt%, at least 70 wt%, at least 75 wt%, at least 80 wt%, or at least 85 wt%, based on the weight of the polyol component.

[0057] In some embodiments, the amount of polyol(s) in the adhesive composition can be at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, or at least 45% by weight based on the weight of the adhesive composition, hi some embodiments, the amount of polyol(s) in the adhesive composition can be at most 70%, at most 60%, at most 55%, or at most 50% by weight based on the weight of the adhesive composition.

[0058] In some embodiments, the amount of polyester polyol(s) in the adhesive composition can be at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, or at least 45% by weight based on the weight of the adhesive composition. In some embodiments, the amount of polyester polyol(s) in the adhesive composition can be at most 70%, at most 60%, at most 55%, or at most 50% by weight based on the weight of the adhesive composition.

[0059] There is no particular limitation on the average molecular weight of the polyol applied to the adhesive composition according to the present disclosure. In one embodiment of the present disclosure, the polyester polyol can have a molecular weight within a numerical range obtained by combining any two of the endpoints 120, 200, 500, 800, 900, 1000, 1200, 1500, 1800, 2000, 2200, 2500, 2800, 3000, 3200, 3500, 3800, 4000, 4200, 4500, 4800, 5000, 5200, 5500, 5800, 6000, 6200, 6500, 6800, 7000, 7200, 7500, 7800, 8000, 8200, 8500, 8800, 9000, 9200, 9500, 9800, and 10,000 g / mol.

[0060] There is no particular limitation on the average functionality of the polyol applied in the adhesive composition according to the present disclosure.

[0061] In some embodiments, the polyol component may be substantially free of polyether polyols, or may include only an ineffective amount of polyether polyols, or may be polyether polyol-free.

[0062] A compound containing two or more ether linkages in the same linear chain of atoms is known herein as a "polyether." A compound that is a polyether and a polyol is a "polyether polyol." In some embodiments, the polyether polyol may have a molecular weight not exceeding 10,000 g / mol. In some embodiments, the polyether polyol may have a hydroxyl group functionality of at least 1.5 (i.e., f≧1.5).

[0063] In some embodiments, the polyol component may be substantially free of phosphate-functional polyols, such as those described above, or may include only an ineffective amount of a phosphate-functional polyol, or may be free of phosphate-functional polyols.

[0064] As used herein, the term "solvent" refers to organic and inorganic liquids that simply dissolve one or more solid, liquid, or gaseous materials without causing any chemical reaction. The solvent used in the polyol component can be any solvent suitable for dissolving one or more materials contained in the component without causing any chemical reaction. In some examples, the solvent can be an organic solvent. Typical organic solvents suitable for use in the polyol component can include methyl ethyl ketone, ethyl acetate, toluene, etc., all of which must be moisture-free to prevent premature reaction of the isocyanate groups of the polyurethane.

[0065] There is no particular limitation on the amount of solvent in the polyol component. In some embodiments, for example, the amount of solvent in the polyol component can be at least 5 wt%, at least 10 wt%, at least 15 wt%, at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt%, at least 45 wt%, at least 50 wt%, at least 55 wt%, at least 60 wt%, at least 65 wt%, at least 70 wt%, or at least 75 wt%, based on the weight of the polyol component.

[0066] The polyol component may optionally contain one or more additional adjuvants and / or additives for specific purposes.

[0067] In some embodiments, the polyol component may optionally include one or more adhesion promoters to improve adhesive strength. Examples of one or more adhesion promoters suitable for use in the polyol component include, but are not limited to, silanes, epoxies, and phenolics.

[0068] In further embodiments, the polyol component may optionally include one or more chain extenders. Examples of one or more chain extenders suitable for use in the polyol component include, but are not limited to, glycerin, trimethylolpropane, diethylene glycol, propanediol, and 2-methyl-1,3-propanediol.

[0069] In further embodiments, the polyol component may optionally include one or more catalysts. Examples of at least one catalyst suitable for use in the polyol component include, but are not limited to, dibutyltin dilaurate, zinc acetate, 2,2-dimorpholinodiethyl ether, and combinations thereof.

[0070] In some embodiments, the polyol component may further comprise one or more adjuvants and / or additives selected from the group consisting of other cocatalysts, surfactants, toughening agents, flow modifiers, diluents, stabilizers, plasticizers, catalyst deactivators, dispersants, colorants, and mixtures thereof.

[0071] Isocyanate component The isocyanate component included in the adhesive composition according to the present disclosure may include an isocyanate prepolymer and optionally a solvent.

[0072] In some embodiments, the isocyanate prepolymer may comprise a product obtainable or obtained by the reaction of at least one selected from the group consisting of an isocyanate monomer, an isocyanate adduct, and combinations thereof with a phosphate-functional polyol in a solvent.

[0073] In some embodiments, the isocyanate prepolymer may include a phosphate-functional isocyanate compound as described herein. When included in an adhesive composition according to the present disclosure, the phosphate-functional isocyanate compound may also be referred to as a "phosphate-functional isocyanate curing agent."

[0074] In some embodiments, the amount of phosphate-functional isocyanate compound in the isocyanate component is not particularly limited. In some embodiments, for example, the amount of isocyanate prepolymer in the isocyanate component can be at least 30 wt%, at least 35 wt%, at least 40 wt%, at least 45 wt%, at least 50 wt%, at least 55 wt%, at least 60 wt%, at least 65 wt%, at least 70 wt%, at least 75 wt%, at least 80 wt%, at least 85 wt%, at least 80 wt%, or at least 90 wt%, based on the weight of the isocyanate component.

[0075] In some embodiments, the amount of isocyanate prepolymer in the described adhesive compositions can be at least 1 wt%, at least 3 wt%, at least 5 wt%, at least 8 wt%, at least 10 wt%, at least 11 wt%, or at least 12 wt%, based on the weight of the adhesive composition. In some embodiments, the amount of isocyanate prepolymer in the described adhesive compositions can be at most 40 wt%, at most 30 wt%, at most 25 wt%, at most 20 wt%, at most 18 wt%, at most 17 wt%, or at most 16 wt%, based on the weight of the adhesive composition.

[0076] In some embodiments, the amount of phosphate-functional isocyanate prepolymer in the adhesive composition can be at least 1 wt%, at least 3 wt%, at least 5 wt%, at least 8 wt%, at least 10 wt%, at least 11 wt%, or at least 12 wt%, based on the weight of the adhesive composition. In some embodiments, the phosphate-functional isocyanate prepolymer can comprise at most 40 wt%, at most 30 wt%, at most 25 wt%, at most 20 wt%, at most 18 wt%, at most 17 wt%, or at most 16 wt%, based on the weight of the adhesive composition.

[0077] In some embodiments, the isocyanate prepolymer may comprise a product obtainable or obtained by the reaction of at least one isocyanate monomer with at least one polyol selected from the group consisting of polyester polyols, polyether polyols, and combinations thereof.

[0078] Suitable examples of the isocyanate monomer are as described above in the "Isocyanate Compound" section.

[0079] Suitable examples of polyester polyols are as described above in the "Polyol Component" section.

[0080] The polyether polyol may be a polyether polyol obtained by polyaddition of ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide, and their co-addition and grafting products, and condensation of polyhydric alcohols, or a mixture thereof. Examples of polyether polyols may include, but are not limited to, polypropylene glycol ("PPG"), polyethylene glycol ("PEG"), polybutylene glycol, and polytetramethylene ether glycol ("PTMEG").

[0081] In one embodiment of the present disclosure, the polyether polyol can have a molecular weight within a numerical range obtained by combining any two of the endpoints 120, 200, 500, 800, 900, 1000, 1200, 1500, 1800, 2000, 2200, 2500, 2800, 3000, 3200, 3500, 3800, 4000, 4200, 4500, 4800, 5000, 5200, 5500, 5800, 6000, 6200, 6500, 6800, 7000, 7200, 7500, 7800, 8000, 8200, 8500, 8800, 9000, 9200, 9500, 9800, and 10,000 g / mol.

[0082] In some embodiments, the isocyanate component does not include a polyether polyol.

[0083] Compounds having isocyanate groups, such as isocyanate prepolymers of an isocyanate component, can be characterized by the parameter "%NCO," which is the amount of isocyanate groups by weight based on the weight of the compound. The parameter %NCO is measured by the method of ASTM D2572-97(2010). The disclosed isocyanate component can have a %NCO of at least 3% by weight, or at least 5% by weight, or at least 7% by weight. In some embodiments, the isocyanate component can have a %NCO of no more than 30% by weight, or 25% by weight, or 22% by weight, or 20% by weight.

[0084] The isocyanate component may optionally include one or more additional adjuvants and / or additives for specific purposes.

[0085] In some embodiments, the isocyanate component may optionally include one or more adhesion promoters to improve adhesive strength. Examples of one or more adhesion promoters suitable for use with the isocyanate component include, but are not limited to, silanes, epoxies, and phenolics.

[0086] In further embodiments, the isocyanate component may optionally include one or more chain extenders. Examples of one or more chain extenders suitable for use with the isocyanate component include, but are not limited to, glycerin, trimethylolpropane, diethylene glycol, propanediol, and 2-methyl-1,3-propanediol.

[0087] In further embodiments, the isocyanate component may optionally include one or more catalysts. Examples of at least one catalyst suitable for use in the isocyanate component include, but are not limited to, dibutyltin dilaurate, zinc acetate, 2,2-dimorpholinodiethyl ether, and combinations thereof.

[0088] In some embodiments, the isocyanate component may further comprise one or more adjuvants and / or additives selected from the group consisting of other cocatalysts, surfactants, toughening agents, flow modifiers, diluents, stabilizers, plasticizers, catalyst deactivators, dispersants, colorants, and mixtures thereof.

[0089] Application of the adhesive composition In a further aspect, the present disclosure provides a cured adhesive composition.

[0090] In some embodiments, a cured adhesive composition can be prepared from the adhesive composition described herein. In some embodiments, the cured adhesive composition can comprise the reaction product of a curable mixture of a polyol component and an isocyanate component described herein. In some embodiments, the cured adhesive composition can be prepared by contacting the isocyanate component and the polyol component of the adhesive composition described herein to form a curable mixture and curing the curable mixture. In some embodiments, the cured adhesive composition can be in the form of a layer. In some embodiments, the cured adhesive composition can be included within a laminate.

[0091] In a further aspect, the present disclosure provides methods for producing cured laminates by using the adhesive compositions described herein.

[0092] In some embodiments, the method can include providing an adhesive composition comprising an isocyanate component and a polyol component as described. In some embodiments, each of the isocyanate component and the polyol component can be present in a liquid or solid-liquid mixture.

[0093] In some embodiments, the method can include contacting an isocyanate component with a polyol component to form a curable mixture. In some embodiments, nitrogen is applied during mixing to prevent moisture contamination. In some embodiments, the moisture content of all ingredients is controlled to less than 500 ppm.

[0094] In some embodiments, the method can include applying the curable mixture onto a first portion of a surface of a substrate (e.g., a film) to form a layer of the curable mixture. As used herein, "a first portion of a surface of a substrate" can refer to a portion or the entire surface. In some embodiments, the first portion of the surface can be a portion or the entire surface. In some embodiments, the dry coating weight of the curable mixture is 1.0 to 5.0 g / m 2 , 1.5 to 5.0 g / m 2 , 2.0~5.0g / m 2 , 2.0~4.0g / m 2 , 2.5 to 4.5 g / m 2 , 2.5~3.5g / m 2 , or 3.0 to 4.0 g / m 2 In some embodiments, the substrate may be made of a material selected from the group consisting of polyethylene, polypropylene, polyester, polyamide, metal, paper, cellophane, and combinations thereof. In some embodiments, the substrate may be in the form of a film.

[0095] A "film" may refer to a layer of material having a thickness of 0.5 mm or less. In some embodiments, a film may be a structure having one dimension of 0.5 mm or less and two other dimensions of 1 cm or more. In some embodiments, the polymer film is a film made from a polymer or a mixture of polymers. In some embodiments, the layer of curable mixture applied to the film has a thickness of 1 to 5 μm. Examples of films may include paper, woven and nonwoven fabrics, metal foils, polymers, and metal-coated polymers. The film optionally has a surface on which an image is printed with ink. The ink may be in contact with the adhesive composition. In some embodiments, the film is a polymer film or a metal-coated polymer film, more preferably a polymer film.

[0096] In some embodiments, the method can include contacting a second portion of a surface of a substrate (e.g., a film) with the layer of curable mixture such that the layer of curable mixture is sandwiched between the first and second portions to form an uncured laminate. As used herein, a "second portion of a surface of a substrate" can refer to a portion or the entire surface. Generally, the second portion is different from the first portion, as described above. In some embodiments, the first and second portions can be portions on the same or different surfaces. In some embodiments, the first and second portions can be portions of the same or different surfaces of the same or different substrates. In some embodiments, the first portion of the surface can be a portion of the surface or the entire surface. In some embodiments, the second portion of the surface can be a portion of the surface or the entire surface.

[0097] In some embodiments, uncured laminates can be made when the amount of unreacted polyisocyanate groups present in the adhesive composition is at least 50%, or at least 75%, or at least 90%, on a molar basis, compared to the amount of polyisocyanate groups present in the isocyanate component prior to contact with the polyol component. Uncured laminates can also be made when the amount of unreacted polyisocyanate groups present in the curable mixture is less than 100%, or less than 97%, or less than 95%.

[0098] In some embodiments, the method may include evaporating the solvent or allowing the solvent to evaporate.

[0099] In some embodiments, the method can include curing the curable mixture or allowing the curable mixture to cure. In some embodiments, the uncured laminate can be cured at a suitable curing temperature of 25°C to 60°C. In some embodiments, the uncured laminate can be heated to accelerate the curing reaction. In some embodiments, the uncured laminate can be pressed, for example, by passing it through nip rollers, which may or may not be heated.

[0100] In a further aspect, the present disclosure provides a cured laminate prepared by using the above-described method.

[0101] In a further aspect, the present disclosure provides a cured laminate comprising a first portion on a surface of a substrate, a layer of a cured adhesive composition prepared from the cured adhesive composition described herein, and a second portion on a surface of the same or a different substrate, wherein the layer of cured adhesive composition is sandwiched between and in contact with the first and second portions.

[0102] In some embodiments, the substrate may be in the form of a film. In some embodiments, the cured laminate may be prepared by using the methods for making a cured laminate described above.

[0103] In a further aspect, the present disclosure provides the use of a phosphate-functional isocyanate compound according to the present disclosure in a two-component polyurethane adhesive composition. In some embodiments, the adhesive composition can be solvent-based. In some embodiments, the phosphate-functional isocyanate compound can be included in the isocyanate component of the adhesive composition. [Example]

[0104] Next, some embodiments of the present disclosure 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.

[0105] 1.Raw materials Information on the raw materials used in the examples is shown in Table 1 below:

[0106] [Table 1]

[0107] 2. Synthesis Procedure and Sample Preparation The phosphate-functional isocyanate compounds of the present invention were synthesized according to the formulations listed in Table 2. Desmodur 2460M and Mor-free 88-138 were charged into a 1000 mL glass reactor and carefully mixed according to the formulation shown in Table 2. After all raw materials were added, heating was initiated. When the temperature of the raw material mixture reached approximately 60°C, the rotation speed was increased to 50 RM. Nitrogen was applied throughout the entire process to protect the system from moisture. When the reaction temperature reached approximately 80°C-85°C, the cooling process was initiated, and the reaction was maintained at 80°C-85°C for 2 hours. When the NCO value reached the theoretical value, the reactor was cooled as quickly as possible. The system was cooled to 60°C-70°C, and ethyl acetate was charged into the glass reactor. The rotation speed was maintained at 50 RM for 20 minutes. The final product was then placed in a tightly sealed steel bottle protected with nitrogen.

[0108] [Table 2]

[0109] The NCO components and OH components used in the examples are as follows: NCO Component: The phosphate-functional isocyanate SR-F1 (SR-F2 or SR-F3) and Dow's currently commercially available co-reactant Catalyst F were selected as the NCO component for testing. OH Component: Dow's current GP solvent-based laminating adhesive Adcote 545 and local vendor Huide's polyester solution in ethyl acetate 8302-3 were used as the OH component.

[0110] Adhesive compositions of the inventive examples and comparative examples were prepared according to the formulations listed in Table 3.

[0111] Before application, the NCO and OH components were mixed together. Nitrogen was applied to protect the system from moisture during the entire mixing process. The moisture content of all raw materials should be less than 500 ppm.

[0112] [Table 3]

[0113] Coating and lamination processes: The coating and lamination process was carried out on an SDC Labo-Combi 400 machine. The nip temperature was maintained at 70°C during the entire lamination process at a speed of 100 m / min. The dry coating weight was 3-3.5 g / m 2 The laminated film was then cured at room temperature (23°C to 25°C) or in an oven, and then tested for one week.

[0114] 3. Testing method: T-peel (90°) adhesive strength (hand-assisted T-peel) After curing, the laminated films were cut into 15 mm wide strips for T-peel testing on an Instron 5943 machine at a crosshead speed of 250 mm / min. Three strips were tested and an average value was obtained. During the test, the tail of the strip was pulled slightly with a finger to ensure that the tail remained at 90° to the peel direction.

[0115] Heat seal strength: The laminates were heat-sealed for 1 second in an HSG-C Heat-Sealing Machine available from Brugger Company at a sealing temperature of 140°C and a pressure of 300 N, then cooled and cut into 15 mm wide strips for heat seal strength testing using a 5940 Series Single Column Table Top System available from Instron Corporation at a crosshead speed of 250 mm / min. Three strips of each sample were tested and the average value was calculated. Results were reported in N / 15 mm.

[0116] Chemical resistance (boil-in bag filled with Morton's soup): The cured laminated film was cut into 8x12 inch pieces, then folded and heat-sealed at the bottom and sides of the larger rectangle at 140°C and 300N / 15mm for 1 second. The pouches were then filled approximately two-thirds full with Morton's Soup, and the tops were carefully sealed to minimize air entrapment. Morton's Soup can generally be described as a 1:1:1 mixture of soybean oil, ketchup, and vinegar. Water was prevented from getting into the heat-sealed area to prevent damage to the heat seal. Any significant pre-existing defects in the heat-sealed or laminated areas were marked with an indelible marker. The pouches were then carefully placed in boiling water and held there for 30 minutes. Ensure the pouches remained submerged during the entire boiling process. Upon completion, the extent of tunneling, delamination, and / or leakage was recorded relative to any existing defects. Samples that showed no evidence of tunneling, delamination, or leakage beyond any pre-existing heat seal or stacking faults were recorded as "passes." The pouches were opened, emptied, cooled, and then cut into 15 mm wide strips and tested for their T-peel bond strength and heat seal strength in an Instron 5943 machine.

[0117] 5.Performance Evaluation The bond strength (BS), heat seal strength (HS), and BIB properties are summarized in Table 4. The results show that the inclusion of phosphate-functional isocyanates can significantly improve the bond strength to foil, chemical resistance (good heat seal without tunneling after boil-in-bag testing with Morton's soup), and hydrolytic stability of two-component solvent-based adhesives.

[0118] [Table 4] The inventions described in the original claims of this application are set forth below. [1] An isocyanate compound containing a phosphate functional group, obtainable or obtainable by reacting at least one selected from the group consisting of an isocyanate monomer, an isocyanate adduct, and a combination thereof with a phosphate-functional polyol. [2] The phosphate-functional polyol has a structure represented by formula (I): [ka] In the formula, R 1 、R 2 and R 3 each independently represents hydrogen or an organic group, with the proviso that R 1 、R 2 and R 3 At least one of R represents an organic group; 1 、R 2 and R 3 The isocyanate compound according to [1], wherein the total of the hydroxyl groups is at least two. [3] R 1 、R 2 and R 3 The isocyanate compound according to [1], wherein the at least two hydroxyl groups are primary hydroxyl groups. [4] R 1 、R 2 and R 3 represents an organic group and contains at least two hydroxyl groups, or R 1 、R 2 and R 3 two of R each independently represent an organic group and together contain at least two hydroxyl groups; or 1 、R 2 and R 3 and each independently represent an organic group, and together they contain at least two hydroxyl groups. [5] The isocyanate compound according to [1], wherein the isocyanate monomer or the isocyanate adduct contains two or more isocyanate groups. [6] An adhesive composition comprising: (A) an isocyanate component containing an isocyanate prepolymer containing the isocyanate compound described in [1]; (B) a polyol component comprising at least one polyester polyol. [7] The adhesive composition according to [6], further comprising (C) a solvent. [8] The adhesive composition according to [6], wherein the dry weight mixing ratio of the polyol component to the isocyanate component is within the range of 100:150 to 100:5. [9] The adhesive composition according to [7], wherein the solvent is an organic solvent, and is preferably selected from the group consisting of methyl ethyl ketone, ethyl acetate, toluene, and combinations thereof.

[10] A cured adhesive composition prepared from the adhesive composition of [6], comprising a reaction product of a curable mixture of the polyol component and the isocyanate component of the adhesive composition.

[11] A method for producing a cured laminate by using the adhesive composition according to [6], (a) providing the adhesive composition comprising an isocyanate component and a polyol component; (b) contacting the isocyanate component with the polyol component to form a curable mixture; (c) applying the curable mixture to a first portion of a surface of a substrate to form a layer of the curable mixture; (d) contacting the second portion of the surface of the same or a different substrate with the layer of the curable mixture such that the layer of the curable mixture is sandwiched between the first and second portions; (e) evaporating the solvent or allowing the solvent to evaporate; (f) curing or allowing the curable mixture to cure.

[12] A cured laminate prepared by using the method for producing a cured laminate described in

[11] .

[13] A cured laminate comprising a first portion of a surface of a substrate, a layer of the cured adhesive composition of

[10] , and a second portion of a surface of the same or a different substrate, wherein the layer of cured adhesive composition is sandwiched between and in contact with the first and second portions.

[14] Use of the isocyanate compound according to [1] in a two-component solvent-based adhesive composition.

Claims

1. An adhesive composition comprising: (A) an isocyanate component consisting of an isocyanate prepolymer that is a reaction product of the following (i) and (ii): (i) an isocyanate monomer, an isocyanate adduct, or a combination thereof, wherein the isocyanate monomer or the isocyanate adduct contains two or more isocyanate groups; and (ii) phosphate polyol esters; (B) a polyol component comprising a polyester polyol.

2. The adhesive composition described in claim 1, further containing a solvent.

3. 2. The adhesive composition of claim 1, wherein the dry weight mix ratio of the polyol component to the isocyanate component is in the range of 100:150 to 100:

5.

4. The adhesive composition of claim 2 , wherein the solvent is an organic solvent selected from the group consisting of methyl ethyl ketone, ethyl acetate, toluene, and combinations thereof.

5. A cured adhesive composition prepared from the adhesive composition of claim 1 comprising the reaction product of a curable mixture of the polyol component and the isocyanate component of the adhesive composition.

6. 3. A method for producing a cured laminate by using the adhesive composition of claim 2, comprising: (a) providing the adhesive composition comprising an isocyanate component and a polyol component; (b) contacting the isocyanate component with the polyol component to form a curable mixture; (c) applying the curable mixture to a first portion of a surface of a substrate to form a layer of the curable mixture; (d) contacting the second portion of the surface of the same or a different substrate with the layer of the curable mixture such that the layer of the curable mixture is sandwiched between the first and second portions; (e) evaporating the solvent or allowing the solvent to evaporate; (f) curing or allowing the curable mixture to cure.

7. A cured laminate prepared by using the method of manufacturing a cured laminate of claim 6.

8. 10. A cured laminate comprising a first portion of a surface of a substrate, a layer of the cured adhesive composition of claim 5, and a second portion of a surface of the same or a different substrate, wherein the layer of cured adhesive composition is sandwiched between and in contact with the first and second portions.

9. The adhesive composition of claim 1 which is a two-component solvent-based adhesive composition.

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