Adhesive Composition

Abstract

1. A laminating adhesive composition for use in producing a laminate structure for retort applications, comprising a mixture of (A) at least one isocyanate component as Component A and (B) at least one isocyanate-reactive component as Component B, wherein the at least one isocyanate-reactive component of Component B comprises (Bi) at least one silyl polymer, and (Bii) at least one polyol compound, and a laminate structure made using the laminating adhesive composition.

Description

[Technical field]

[0001] The present invention relates to an adhesive composition comprising an isocyanate component and an isocyanate-reactive component, more specifically, the present invention relates to a solvent-based lamination adhesive composition, the isocyanate-reactive component comprising at least one silyl polymer and at least one polyol compound (a hydroxyl group-containing compound). The adhesive composition is particularly useful for retort applications. [Background technology]

[0002] To date, various two-component (2K) type polyurethane (PU) adhesive compositions have been produced for use in various applications. As known in the art, 2K PU compositions are based on a reaction mixture of an isocyanate component, such as a polyisocyanate compound, and an isocyanate-reactive component, such as a polyol compound, and such 2K PU compositions have long been used as adhesives for producing laminates. When the two components (e.g., polyisocyanate and polyol) are mixed, the polyisocyanate and polyol react to form a cured polyurethane adhesive, which can form a strong adhesive bond that bonds many types of films and substrates.

[0003] Solvent-based polyurethane adhesive compositions containing adhesion promoters are known to be useful as adhesive compositions for retort applications. Common adhesion promoters used in food packaging in "high performance" applications (e.g., retort applications) are based on epoxy silanes. Recent government announcements (e.g., from the EU Commission) have warned the adhesive industry that adhesion promoters based on epoxy silanes and / or similar derivatives are potentially mutagenic and that in the near future, this family of adhesion promoters may be banned or restricted by EU regulations. As a result, the prohibition of the use of epoxy silanes as adhesion promoters in adhesive compositions and the absence of epoxy silanes as adhesion promoters in adhesive compositions may cause problems for the adhesive composition to achieve the performance required by laminates made from such adhesive compositions, especially those required for use in high performance or retort applications. It is therefore desirable to provide alternative adhesive compositions and / or alternative adhesion promoters that can be used in high performance or retort applications and perform as well or better than known epoxy silane promoters.

[0004] Although some progress has been made in the art with respect to 2K polyurethane adhesive compositions for use in various applications, there is still room for development in the field of adhesives.In particular, it remains desirable to provide a lamination adhesive composition that exhibits improved properties, such as bond strength, moldability, and heat resistance, so that the adhesive composition can be appropriately used to produce foil-based composite laminate film structures and laminated articles or products, for example, for use in general flexible food packaging applications, but also in retort applications. Summary of the Invention

[0005] One of the objects of the present invention is to provide an adhesive composition designed for use in retort applications and other applications similar to retort applications.

[0006] The invention described herein relates to the preparation and use of adhesive compositions that are useful for preparing thin multi-layer film flexible laminates based on two or more films, such as polypropylene (PP), polyethylene (PE), or metal foil-based laminate structures with propylene or ethylene-based copolymers as sealant layers, and a four-layer structure with an outer layer of polyethylene terephthalate (PET), a first upper intermediate layer of metal foil, a second lower intermediate layer of nylon, and an inner layer of unoriented polypropylene (CPP). The laminate formed should be able to maintain performance properties that allow the film laminate to withstand retort processing conditions (e.g., 121°C for 1 hour to 2 hours, 132°C for 30 minutes to 45 minutes, and / or 135°C for 30 minutes to 45 minutes) while minimizing loss of bond strength performance. The adhesive compositions of the invention have utility for use in, for example, food pouches, ready-to-eat meals, can coatings, and the like.

[0007] In one embodiment, the present invention comprises a silane-modified polymer or silyl polymer based on the reaction product of (a) at least one polyol compound (e.g., at least one polyester polyol) and (b) at least one isosilane compound to form a "partial silyl polymer" (abbreviated herein as "PSP").

[0008] In another embodiment, the present invention comprises a silane-modified polymer or silyl polymer based on the reaction product of (i) the PSP described above and (ii) at least one aminosilane compound to form a "final silyl polymer" (abbreviated herein as "FSP").

[0009] In yet another embodiment, the present invention relates to a process comprising: (I) preforming a PSP in a first reaction step and then (II) reacting the PSP from the first step with an aminosilane, and / or a derivative thereof, in a second step.

[0010] In yet another embodiment, the present invention comprises an adhesive composition comprising a mixture of (A) at least one isocyanate component and (B) at least one isocyanate-reactive component, the at least one isocyanate-reactive component comprising (Bi) a silyl polymer, such as the PSP described above and / or the FSP described above, and (Bii) at least one polyol compound.

[0011] In still yet another embodiment, the invention includes a laminate comprising: (α) at ​​least one first layer (primary layer) of a film or substrate; (β) at least one second layer (secondary layer) of a film or substrate; and (γ) at least one layer of the adhesive composition described above for bonding the first and second layers together, wherein the adhesive composition is disposed on at least a portion of a surface on one side of (1) the first layer, (2) the second layer, or (3) both the first layer and the second layer.

[0012] In yet another embodiment, the present invention comprises a retortable article made from the laminate described above.

[0013] In a preferred embodiment, the present invention provides a process for producing a silyl polymer, comprising the steps of: (I) In a first step, (Ia) at least one polyol compound; (Ib) reacting at least one isosilane compound with a first reacting step (I) carried out at a first predetermined temperature and for a first predetermined time period at said first temperature to form a PSP; (II) In a second step, (IIa) PSP resulting from step (I); (IIb) reacting at least one aminosilane compound with a second reacting step (II) conducted at a second predetermined temperature and for a second predetermined time at said second temperature to form an FSP.

[0014] In yet other embodiments, the present invention includes the adhesive composition described above, and a process for making the laminate described above. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] As used herein, "retort conditions" refers to the sterilization of a food product after it has been sealed in a container by steam or other heating methods. Typically, sterilization temperatures vary from 230°F (110°C) to 275°F (135°C).

[0016] By "isosilane" herein is meant a compound having an isocyanate functional group and a silane functional group.

[0017] By "silyl polymer" herein is meant a silane-modified compound or polymer having at least one silane group.

[0018] By "partially silyl polymer" herein is meant a polymer formed by the reaction of (Ia) at least one polyol compound and (Ib) at least one isosilane compound.

[0019] By "final silyl polymer" herein is meant the polymer formed by the reaction of (IIa) the partial silyl polymer described above with (IIb) at least one aminosilane compound.

[0020] As used throughout this specification, the following abbreviations have the following meanings, unless the context clearly indicates otherwise: "=" means "equal to", @ means "at", "<" means "less than", ">" means "greater than", "eg" means "for example", g = grams, g / m 2 or "gsm" = grams per square meter, g / m 3= grams per cubic meter, mg = milligrams, kg = kilograms, Da = Daltons, L = liter, mL = milliliter, g / L = grams per liter, m = meter, μm = micron, mm = millimeter, cm = centimeter, min = minute, s = second, hr = hour, m / min = meters per minute, kW = kilowatts, mm / min = millimeters per minute, °C = degrees Celsius, mPa.s = millipascal-second, PSI = pounds per square inch, MPa = millipascal, mm 2 = millimeters squared, % = percent, eq% = equivalent percent, and wt% = weight percent.

[0021] Unless otherwise stated, all percentages, parts, ratios, and similar amounts are defined by weight. All percentages set forth herein are weight percent (wt %) unless otherwise indicated.

[0022] Temperatures are in degrees Celsius (° C.) and "ambient temperature" or "room temperature" means 20° C. to 25° C. unless otherwise specified.

[0023] In the adhesive art, making a two-part (two-component) adhesive system or adhesive composition involves providing a first part that includes an isocyanate component (herein "Component A"), providing a second part that includes an isocyanate-reactive component (herein "Component B"), and then combining or mixing Components A and B to form the two-part reaction mixture adhesive system or adhesive composition.

[0024] In one broad embodiment, the present invention relates to a solvent-based polyurethane retort adhesive composition for producing a laminate comprising an isocyanate component, component A, and an isocyanate-reactive component, component B, as described above. However, the present invention uses a novel component B comprising a combination of (Bi) at least one silyl polymer and (Bii) at least one polyol compound.

[0025] Partially silyl polymer In one embodiment, the partial silyl polymer (PSP) of the present invention is produced by reacting a polyol compound with an isosilane compound. The polyol compound reacts with the isosilane compound via the reaction of hydroxyl groups present on the polyol compound with the isocyanate functional groups of the isosilane compound to form a reaction product comprising a compound formulation or composition mixture. During the polyol / isosilane reaction, some, but not all, of the polyol functional groups of the polyol compound react with the isocyanate functional groups of the isosilane compound to form a composition mixture. Thus, the reaction product resulting from the polyol / isosilane reaction, i.e., the PSP, is a formulation or composition mixture comprising at least one silyl polymer (i.e., a compound comprising at least one silane functional group) and residual unreacted polyol compound and / or residual unreacted isosilane compound. The OH number of the PSP is generally 1-100 in one embodiment, 2-50 in another embodiment, and 2-30 in yet another embodiment.

[0026] Polyol compounds useful in preparing the PSPs of the present invention can include, for example, a single compound or a combination, blend, or mixture of two or more compounds. For example, the polyol compound is at least one compound selected from the group consisting of polyether polyols, polyester polyols, polyurethane polyester polyols, polycarbonate polyols, polyacrylate polyols, polycaprolactone polyols, natural oil polyols, and mixtures thereof.

[0027] The isosilane compound useful for preparing the PSP of the present invention can include, for example, isocyanato-ethoxy-silane, isocyanato-methoxy-silane, and mixtures thereof. In one preferred embodiment, the isosilane compound useful in the present invention is, for example, isocyanato-ethoxy-silane. In other embodiments, the isosilane compound can be used in combination with any additive as required.

[0028] In another preferred embodiment, the isosilane compound can include one or more commercially available compounds including, for example, SILQUEST™ A-LINK-25 (gamma-isocyanatopropyltri-ethoxysilane), SILQUEST™ A-LINK-35 (gamma-isocyanatopropyltrimethoxysilane), and mixtures thereof, both of which are available from Momentive Inc., SILQUEST™ A-LINK-25 having a molecular weight of 247.3 and SILQUEST™ A-LINK-35 having a molecular weight of 205.2.

[0029] In general, the process of forming the PSP of the present invention includes, for example, reacting (a) at least one polyol compound with (b) at least one isosilane compound. The concentration of the isosilane compound is 0.1% to 10% by weight in one embodiment, 0.1% to 5% by weight in another embodiment, and 0.1% to 3% by weight in yet another embodiment, based on the total components in the reaction mixture. Any other materials, additives, or agents may be added to components (a) and / or (b) above.

[0030] Final Silyl Polymer In one embodiment, the FSP comprises the reaction product of (i) the PSP described above and (ii) at least one aminosilane compound. The PSP of component (i) is described above. The at least one aminosilane compound (i.e., a compound containing both silane and NH groups) of component (ii) can comprise, for example, SILQUEST™ A1100, an aminosilane compound available from Momentive Company. The amount of aminosilane compound used in the reaction mixture can range from 0.1% to 5% by weight in one typical embodiment, from 0.1% to 3% by weight in another embodiment, and from 0.2% to 2% by weight in yet another embodiment, based on the total weight of the components in the reaction mixture.

[0031] The FSP of the present invention, i.e., the reaction product resulting from the PSP / aminosilane reaction described above, is a formulation or composition mixture that includes at least one silyl polymer (i.e., a compound that includes at least one silane functional group) and residual unreacted polyol compound and / or residual unreacted aminosilane compound. The OH number of the PSP is generally 1-100 in one embodiment, 2-50 in another embodiment, and 2-30 in yet another embodiment.

[0032] In one broad embodiment, the process for making the FSP of the present invention comprises first preparing a PSP, which is a preformed polymer or prepolymer having at least one end of the polymer terminated with a hydroxyl group, as described above, and then secondly reacting the PSP with an aminosilane compound, the first and second reactions being carried out at different temperatures and for different periods of time. In another embodiment, the process for forming the FSP of the present invention generally comprises reacting, for example, (i) the PSP described above, and optionally one or more other different polyol compounds in combination with the PSP, with (ii) at least one aminosilane compound to form the FSP. In a preferred embodiment, the aminosilane compound is blended into the PSP as an additional reactive additive.

[0033] For example, in another preferred embodiment, the process for making FSPs is the following two-step process: Step (I) In the first step, (Ia) at least one polyol compound (e.g., a hydroxyl compound such as a polyether polyol, a polyester polyol, or a blend thereof); and (Ib) reacting at least one isosilane compound with a first reacting step (I) carried out at a first predetermined temperature and for a first predetermined time period at said first temperature to form a PSP; Step (II) In the second step, (IIa) a PSP resulting from step (I) and optionally other different polyol compounds; (IIb) reacting at least one aminosilane compound, wherein the second reaction is carried out at a second predetermined temperature and for a second predetermined time at said second temperature to form an FSP comprising at least one compound representing the final hydroxyl compound in component B of the adhesive composition of the present invention.

[0034] The first step (I) of the above process of the present invention comprises a first predetermined temperature of 50° C. to 100° C. in one typical embodiment, 50° C. to 80° C. in another embodiment, and 50° C. to 70° C. The heating time, i.e., the first predetermined time in the first step of the above process of the present invention, is 2 hours to 10 hours in one typical embodiment, and 4 hours to 6 hours in another embodiment.

[0035] The second step (II) of the above process of the present invention comprises a second predetermined temperature, which in one typical embodiment is between 50° C. and 100° C., and in another embodiment is between 60° C. and 70° C. The heating time, i.e. the second predetermined time in the second step of the above process of the present invention, is in one typical embodiment between 1 hour and 10 hours, and in another embodiment between 2 hours and 6 hours.

[0036] The resulting FSP of the present invention prepared by the above two-step process has a controlled total solids content of 30% to 100% by weight in a typical embodiment, 40% to 80% in another embodiment, and 50% to 70% in yet another embodiment, based on the resin composition in the reactor, where the residual compound is at least one solvent.

[0037] The resulting FSP of the present invention has a controlled viscosity at 25° C. of from 1,000 mPa.s to 30,000 mPa.s in a typical embodiment, from 2,000 mPa.s to 10,000 mPa.s in another embodiment, and from 2,000 mPa.s to 6,000 mPa.s in yet another embodiment.

[0038] The use of aminosilane compounds in forming FSPs is advantageous because the aminosilane compounds can form complexes with reactive sites on metal films, metal oxide coated films, or polymeric films to improve adhesion.

[0039] As mentioned above, the process of preparing the FSP includes mixing and reacting (i) a combination of PSP and optionally another different polyol compound with (ii) an aminosilane compound. In one embodiment, components (i) and (ii) are contacted with each other and mixed together to form the FSP. The optional polyol compound combined with component (i), PSP, can be polyether polyol, polyester polyol, polyurethane polyester polyol, polycarbonate polyol, polyacrylate polyol, polycaprolactone polyol, natural oil polyol, and mixtures thereof.

[0040] After reaction of the polyol compound with the isosilane compound in the first reaction, and after reaction of the PSP with the aminosilane compound in the second reaction, the desired OH number of the resulting FSP reaction product (used as component B of the adhesive composition) is in one embodiment 1-100, in another embodiment 1-50, in yet another embodiment 1-30, and in yet another embodiment 1-20.

[0041] Generally, the FSP has a molecular weight of 200 Da to 50,000 Da in one embodiment, and 10,000 Da to 30,000 Da in another embodiment. If a high molecular weight (e.g., >50,000 Da) FSP is used, the FSP cold will be too viscous to function, and if a low molecular weight (e.g., <200 Da) FSP is used, the final cured adhesive will not have the final performance desired or required by EU regulations.

[0042] Advantageously, the use of an isosilane compound in the first reaction and an aminosilane compound in the second reaction results in a reaction product mixture containing at least one silyl polymer, such as PSP and / or FSP. The silyl polymer in combination with a polyol compound can be used as component B of an adhesive composition, which, when used in an adhesive composition, produces an adhesive composition with the same or similar performance as adhesive compositions prepared using epoxy silane accelerators previously used in retort applications. Isosilane compounds are not commonly used as adhesion promoters in flexible food packaging because they are not approved for food contact. However, the synthesis procedure for the PSP and FSP used in the present invention links the adhesion promoter (silane group) to the backbone of the polyester resin used. Thus, extraction tests with isooctane show levels of free isosilane below the 10 ppb limit, which is the limit imposed by EU regulations for molecules not listed for food contact. Advantageously, the silane modified adhesion promoter of the present invention complies with EU regulations and the necessary limits mentioned above.

[0043] Adhesive Composition In one typical embodiment, the adhesive formulation or adhesive composition of the present invention comprises a two-part polyurethane adhesive composition (2K PU adhesive composition) useful for retort applications. For example, the adhesive composition comprises (A) at least one isocyanate component as a first part or component A, and (B) at least one isocyanate-reactive component as a second part or component B. The at least one isocyanate-reactive component, component B, comprises (Bi) a silyl polymer, such as the PSP described above and / or the FSP described above, and (Bii) at least one polyol compound.

[0044] The isocyanate component (NCO component), Component A of the present invention, includes any of the conventional isocyanate compounds known in the art for forming polyurethane adhesive compositions including, for example, aromatic isocyanate compounds, aliphatic isocyanate compounds, blends of aromatic and aliphatic isocyanate compounds, prepolymeric isocyanate derivatives, and mixtures thereof.

[0045] The isocyanate-reactive component, Component B of the present invention, can comprise, for example, (Bi) a mixture or blend of the PSPs and / or FSPs described above in combination with (Bii) at least one polyol compound (i.e., a hydroxyl group-containing compound), where the polyol compound, component (Bii), can comprise one or more different conventional polyol compounds.

[0046] In a preferred embodiment, the present invention comprises a solvent-based 2K PU adhesive composition comprising as component A an isocyanate component (e.g., an aromatic and / or aliphatic compound) and as component B an isocyanate-reactive component, e.g., a mixture of the above PSP, the above FSP, and a polyol compound, where component B has at least one compound having reactive groups, such as hydroxyl-terminated polyol groups (OH groups), that react with the isocyanate of component A. The solvent used in the above adhesive composition can be, for example, ethyl acetate, methyl ethyl ketone, methyl acetate, cyclohexane, propyl acetate, or other suitable solvents or solvent mixtures.

[0047] In a preferred embodiment, the polyol compound used in component B, component (Bii), can include one or more commercially available compounds including, for example, ADCOTE™ 810A EA, a polyol compound available from The Dow Chemical Company.

[0048] The amount of the isocyanate-reactive component, component B, of the adhesive composition can generally range from 5% to 99.5% by weight in one embodiment, from 30% to 98% by weight in another embodiment, and from 50% to 97% by weight in yet another embodiment, based on the total weight of the components in the adhesive composition.

[0049] Although the present invention relates to a two-part system, the adhesive composition of the present invention may be formulated with a wide variety of optional additives that allow the performance of the specific functions of the optional additives while maintaining the excellent advantages / properties of the adhesive composition. Optional components, compounds, agents or additives that can be added to the 2K PU adhesive composition can be added to component A, component B, or a blend of components A and B. For example, in one embodiment, optional additives useful in the adhesive composition may include additional adhesion promoters such as gas and water scavengers, compatibilizers, chemical rheology modifiers, fillers, polymer resins, chain extenders, catalysts, etc.

[0050] In a broad embodiment, the process for making the lamination adhesive composition of the present invention comprises thoroughly mixing, admixing or blending (A) at least one isocyanate component as described above, (B) at least one PSP or at least one FSP, and optionally different polyol compounds, and (C) any components for forming an adhesive composition or adhesive mixture that can be processed via conventional mixing equipment and techniques used to make the mixture. Components (A), (B) and (C) must be mixed in a preferred specific mixing ratio of hydroxyl groups / isocyanate groups to obtain an adhesive composition with a suitable solids content and provide a cured adhesive with the desired performance. In one embodiment, such a mixing ratio of hydroxyl groups / isocyanate groups is 100 / 2 to 100 / 15, and in another embodiment, 100 / 2 to 100 / 30. Component A, the isocyanate component, and component B, the isocyanate-reactive component, are present, for example, in a typical embodiment, in a stoichiometric ratio (NCO to OH) of 1 to 5.

[0051] The order of mixing the components is not important, and two or more components can be mixed together before adding the remaining components. The order of mixing the components is not important, but a sufficient amount of solvent (e.g., ethyl acetate) is added to the mixture to provide the appropriate coating weight, solids, and viscosity. For example, Table A below represents a typical dilution table for preparing an adhesive composition. For example, Table A describes dilution with ethyl acetate at a mix ratio of 100 / 10 hydroxyl / isocyanate components for a specific % solids in an application. [Table 1]

[0052] Once the adhesive composition is made according to the above process, the resulting adhesive composition can be used to prepare a laminate, which is used to make a retort pouch. Some advantageous properties exhibited by the resulting adhesive composition produced according to the above process can include, for example, that the adhesive composition has strong bonding adhesion performance to film and aluminum foil. For example, in one embodiment, based on the isocyanate component used, the adhesive performance property of the adhesive composition can be 4N / 15mm to 10N / 15mm after the pouch is subjected to a retort process. The adhesive performance property of the adhesive composition can be measured using the procedure described in ASTM F904.

[0053] In a preferred embodiment, the present invention comprises a 2K PU adhesive composition, which comprises, for example, (A) an aromatic or aliphatic isocyanate compound (a compound having an NCO group) as component A, and (B) an isocyanate-reactive component having a reactive group, such as a hydroxyl-terminated polyol group (OH group), which reacts with an isocyanate as component B. The adhesive composition of the present invention used to make laminates, such as metal / polymer film laminates, can maintain performance properties that minimize loss of bond strength performance (e.g., the laminate maintains a bond strength of 4 N / 15 mm or more for 1 hour, measured at 134° C.), while allowing the film laminate to withstand retort processing conditions (e.g., 1 hour or 2 hours at 121° C., 30 minutes or 45 minutes at 132° C., and / or 30 minutes to 45 minutes at 135° C.).

[0054] In a broad embodiment, the laminate product of the present invention comprises a combination of at least two film or substrate layers bonded together by an adhesive layer formed from the adhesive composition of the present invention. For example, the laminate product comprises (α) a first film or substrate layer, (β) a second film or substrate layer, and (γ) a layer of the above-mentioned adhesive composition for bonding layers (α) and (β). If necessary, one or more other optional film or substrate layers can be used to produce a multi-layer laminate structure.

[0055] The first or primary layer (α) of the present invention can include, for example, one or more layers of plastic film, metallized film, metal substrate, and combinations thereof. In one embodiment, the first layer (primary film) can include, for example, polyester (PET) film, oriented polyamide (OPA) film, or combinations thereof. In other embodiments, the primary film useful in the present invention can include, for example, PET SIOX, PET AlOX, and combinations thereof. In a preferred embodiment, the first layer (primary film) can include, for example, at least one PET film, or a film that is a similar modified version of PET that has been chemically or coated.

[0056] The thickness of the first layer used to form the multi-layer laminate product of the present invention may be, for example, from 10 μm to 50 μm in one embodiment, and from 10 μm to 30 μm in another embodiment.

[0057] The second or secondary layer (β) of the present invention can include, for example, one or more layers of aluminum foil, non-oriented polypropylene (CPP), polyethylene (PE), and combinations thereof. In a preferred embodiment, the second layer (secondary layer) can include, for example, aluminum foil.

[0058] The thickness of the second layer used to form the multilayer laminate product of the present invention can be, for example, 5 μm to 150 μm in one embodiment, 5 μm to 100 μm in another embodiment, 5 μm to 20 μm in yet another embodiment, 5 μm to 15 μm in yet another embodiment, and 5 μm to 9 μm in still yet another embodiment.

[0059] The layers of adhesive composition (γ) used to bond the first layer (α) and the second layer (β), respectively, are described above. The thickness of the adhesive layer used to bond the first and second layers together to form the multi-layer laminate product of the present invention may be, for example, in one typical embodiment, 1 μm to 10 μm, or in terms of coating weight, 2 g / m 2 ~10g / m 2 It could be.

[0060] The laminated product of the present invention is produced by applying the above-mentioned adhesive composition to the surface of a first film or substrate to form an adhesive layer on the surface of the film or substrate. The application of the adhesive composition can be carried out by a common application system, such as reverse gravure, direct gravure, smooth roller system, and other conventional methods. For example, the adhesive composition can be applied using conventional equipment and processes, such as using a solvent-based lamination device.

[0061] In a typical embodiment, a process for producing a laminate product of the present invention may include, for example: (A') providing (α) at ​​least a first layer of film or substrate, (β) at least a second layer of film or substrate, and (γ) an adhesive composition as described above; (B') applying the adhesive composition (γ) of step (A') to at least a portion of a surface of one side of (1) a first layer of film or substrate, (2) a second layer of film or substrate, or (3) the first layer of film or substrate and the second layer of film or substrate to form an adhesive layer; (C') combining first and second films or substrates together with an adhesive layer sandwiched between the first and second layers sufficient to form a multi-layer laminate structure; (D') curing the multi-layer laminate structure to bond the first layer and the second layer to form a multi-layer laminate product.

[0062] In one embodiment, the maximum chemical and thermal properties of the cured laminate structure are achieved within a cure period of, for example, 2 to 14 days, and in another embodiment, 2 to 10 days, at ambient temperature.

[0063] In another embodiment, the curing process can be ramped up using a hot chamber, for example, fixed at a temperature of 30° C. to 60° C. in one embodiment, and 30° C. to 50° C. in another embodiment. The curing time at the above curing temperatures can be for a period of 1 day to 14 days in one embodiment, and 2 days to 10 days in another embodiment.

[0064] In one preferred embodiment, the process conditions used to make the laminated product can include, for example, the conditions set forth in Table B. [Table 2]

[0065] The adhesive composition of the present invention is useful for producing laminated products for retort applications, such as those described above. Some advantageous properties exhibited by the resulting laminated products produced according to the above process may include, for example, laminated products that provide superior performance solutions for many challenging structural packaging applications. These include ready-to-eat meals, freezer to microwave food requirements, and the stringent requirements associated with pharmaceutical applications. In addition, the adhesive composition of the present invention provides, for example, excellent adhesion to retortable transparent barrier films, improved product resistance, improved heat resistance, improved chemical resistance, and extended product life cycle reliability. The adhesive composition of the present invention is compliant with most U.S. FDA and European regulations related to food contactable materials. EXAMPLES

[0066] The following examples are presented to further illustrate the invention, but should not be construed as limiting the scope of the claims. Unless otherwise indicated, all parts and percentages are by weight.

[0067] Various terms and designations used in the following Inv. Ex. and Comp. Ex. examples are explained below. "PRELAM" stands for pre-lamination. "CPP" stands for plain polypropylene. "PET" stands for polyethylene terephthalate. "ALU" stands for aluminum, and more specifically, aluminum foil. "Foil" means aluminum foil. "AKG (trademark)" is a CPP and a trademark of Bipack (Company). "CO-REACTANT F™" means a co-reagent that is a trademark of The Dow Chemical Company. "CAT F" stands for CATALYST F (trademark). "AMI" stands for aminosilane. "ISO" stands for isocyanate. "ISO-PET" stands for isocyanate-polyester resin.

[0068] The various raw materials used in the inventive and comparative examples are described below.

[0069] The isocyanate compounds used in the examples are as follows: (1) “Isocyanate 1” is an aliphatic isocyanate compound (e.g., MOR-FREE™ 200C). (2) “Isocyanate 2” is an aliphatic isocyanate compound (e.g., CATALYST 9L10™ [“9L10”]). (3) “Isocyanate 3” is an aliphatic isocyanate compound (e.g., ADCOTE™ 811B). (4) "Isocyanate 4" is an aromatic isocyanate compound (e.g., CATALYST F (trademark)).

[0070] The polymer resins used in the examples are as follows: (1) "Polymer Resin 1" is a standard polyester polyol resin (e.g., ADCOTE™ 811A EA). (2) "Polymer Resin 2" is a polyester polyol resin (e.g., ADCOTE™ L810).

[0071] The adhesion promoters used in the examples are as follows: (1) “Additive 1” is 3-isocyanatopropyltriethoxysilane. (2) "Additive 2" is N-(2-aminoethyl)-3-aminopropyltriethoxysilane. (3) “Additive 3” is 3-aminopropyltriethoxysilane.

[0072] General Procedure for Preparing Silane-Functionalized Polyester Polyols General Process Step (1) – Formation of PSP The adhesion promoters described above were used to functionalize the backbone of the polyester polymer resins described above. For example, 5,925.4 g of a solvent-based polyester polyol resin, such as ADCOTE™ L810 (98.756% w / w) or polymer resin 2 in a solvent, such as ethyl acetate, was charged into a round flask (e.g., a 6.5 L glass reactor) equipped with an overhead stirrer and a thermometer under ambient conditions. The solution in the glass reactor was heated to about 60° C. with stirring in an oil bath, flushed with nitrogen, and gradually heated to 70° C. with overhead stirring. The solvent was refluxed into the reactor through a condenser maintained at a temperature below 0° C. After the temperature of the polymer resin 2 was stabilized at 70° C. for 30 to 45 minutes, a certain amount of adhesion promoter, such as 44.8 g of the isosilane compound SILQUEST™ A Link 25 (0.746% w / w) or additive 1 was quickly charged into the glass reactor.

[0073] A gradual increase in temperature due to the exothermic reaction of SILQUEST™ A Link 25 and ADCOTE™ L810 was observed. After such gradual increase in temperature, the temperature of the glass reactor was increased to 70° C. with an oil bath and the resulting reaction mixture was maintained at 70° C. The resulting mixture was reacted for various times, for example, different reaction time intervals used included 2 hours, 4 hours, 6 hours, and 8 hours. For example, the resulting reaction mixture was maintained at 70° C. for 6 hours. After 6 hours at 70° C., the presence of residual isocyanate groups (NCO) of SILQUEST™ A Link 25 (isosilane) in the reaction solution was controlled by infrared spectroscopy. Once the NCO peak present in the reaction solution was zero as measured by infrared spectroscopy, the product obtained from the reaction solution of this step (1) was cooled from 70° C. to a temperature of 60° C.

[0074] The reaction exotherm of the reaction mixture was controlled by monitoring the reactor temperature to ensure that the reactor temperature was maintained such that less than 3 °C temperature rise was observed. The loading levels and reaction times of additives 1-3 for preparing silane-functionalized polyester polyol compositions (e.g., ISO-PET-1-ISO-PET-6 and AMI) are listed in Table I. When the desired reaction time was reached, the resulting product, PSP, was cooled to room temperature, poured out of the reactor, packaged, and stored for later use.

[0075] General Process Step (2)-Formation of FSP Once the already formed product (e.g., PSP) described in step (1) above is cooled to 60°C, an aminosilane compound is rapidly added to the glass reactor and mixed with the already formed product in step (1) above to form a reaction mixture. For example, a charge of 29.9 g of SILQUEST™ A1100 (0.498% w / w) was added to the glass reactor. The resulting mixture was reacted for various times, for example, at time intervals of 2 hours, 4 hours, 6 hours, and 8 hours. For example, the resulting reaction mixture was maintained at 60°C for 2 hours with stirring. After 2 hours of reaction, the resulting product was cooled to about 30°C. The resulting product was then discharged from the glass reactor. The resulting product, FSP, prepared as described above, has a controlled total solids content of 58% to 62% by weight and a controlled viscosity of 6,000 to 7,000 at 25°C.

[0076] When aminosilane compounds (e.g., Additive 2 and AMI) were used, no chemical reaction occurred by compounding these compounds as described in step (1) above. The solvent-based polyester polyol was charged to a round-bottom flask under ambient conditions and slowly heated to 60° C. with overhead mixing under a nitrogen sweep. A predetermined amount of Additive 2 was then quickly charged to the 60° C. reactor and blended for 2 hours. After blending and heating for 2 hours, the resulting product was cooled to room temperature, poured out, packaged, and stored for later use. The charge levels of Additive 2 and blending times are listed in Table I.

[0077] Using the same procedure as above, ISO-PET6 was prepared by combining Additive 1 (70°C for 6 h) and Additive 3 (60°C for 2 h) (see Table I). [Table 3]

[0078] General Procedure for Preparing the Adhesive Composition Each of the various polyester polyol resins, i.e., silane-functionalized polyester polyol compositions (or silane-modified hydroxyl-terminated polymers or silyl polymers) described in Table I above, was mixed with an isocyanate compound (e.g., MOR-FREE™ 200C or 9L10) to form adhesive compositions, for example, as described in Tables II, III, and IV.

[0079] Examples 1-7 - Preparation of Adhesive Various polyols (e.g., ISO-PET-1 through ISO-PET-5 and AMI) listed in Table II were mixed with an isocyanate compound (e.g., MOR-FREE™ 200C or Isocyanate 1) in the ratios specified in the examples (see Table II) to form adhesive compositions of Inventive Examples 1 through 7. The adhesive compositions cured with MOR-FREE™ 200C are listed in Table II. [Table 4]

[0080] Examples 8-12 - Preparation of Adhesives Various polyols (e.g., ISO-PET-2 through ISO-PET-5 and AMI) set forth in Table III were mixed with an isocyanate compound (e.g., 9L10 or Isocyanate 2) in the ratios specified in the examples (see Table III) to form adhesive compositions of Inventive Examples 8 through 12. The adhesive compositions cured with 9L10 are set forth in Table III. [Table 5]

[0081] Comparative Examples A-C - Preparation of Adhesive For comparison purposes, various adhesive compositions set forth in Table IV were prepared in the proportions specified in the Examples (see Table IV) to form Comparative Adhesive Compositions A through C. Comparative adhesive compositions cured with MOR-FREE™ 200C or 9L10 are set forth in Table IV. [Table 6]

[0082] Examples 13-16 - Preparation of Adhesive The polyols listed in Table V (e.g., ISO-PET-6) were mixed with the isocyanate compounds (e.g., MOR-FREE™ 200C and / or 9L10) in the ratios specified in the examples (see Table V) to form the adhesive compositions of Inventive Examples 13-16. A Labo Combi machine was used in the examples. The adhesive compositions are listed in Table V. [Table 7]

[0083] Comparative Examples D-G - Preparation of Adhesive A polyol as set forth in Table VI (e.g., ADCOTE™ 811A EA or Polymer Resin 1) was mixed with an isocyanate compound (e.g., MOR-FREE™ 200C and / or 9L10) in the ratios specified in the examples (see Table VI) to form the adhesive compositions of Comparative Examples D through G. A Labo Combi machine was used in the examples. The adhesive compositions are set forth in Table VI. [Table 8]

[0084] General procedure for preparing films Using a manual layup procedure, 2.0 lb / ream (3.26 g / m 2 ) ~2.3 lbs / ream (3.26 g / m 2Each of the adhesive composition mixtures was applied to the primary film (back foil) using a Meyer rod #3, which gave a consistent adhesive composition coating weight in the range of 1000g / g. The adhesive composition coatings were then dried in a 90°C convection oven for 1 minute.

[0085] General procedure for preparing laminates After drying the adhesive composition coating as described above, the coating was laminated with a secondary film (CPP) using a manual lamination device with a nip roll temperature of 65°C and a nip pressure of 20 PSI (0.14 MPa). For all adhesive compositions, the solids content was maintained between 30% and 32% by weight during molding. The bond strength between the two films was measured at various time intervals after lamination (e.g., 1 day, 3 days, and 7 days after lamination and after storage in a hot room at 45°C for 7 days) using the 90°T peel test described below.

[0086] The laminates made in the examples using the above procedure were multi-layer laminates made according to the machine parameters set out in Table VII below. [Table 9]

[0087] The laminates of Examples 17-32 and Comparative Examples H-N below include layers of a polyol compound, ISO-PET6, mixed with an isocyanate compound (e.g., MOR-FREE™ 200C, 9L10, ADCOTE™ 811B [isocyanate 3] and CAT F [isocyanate 4]). The resulting laminates were compared to standard ADCOTE™ 811A EA mixed with the same isocyanate compounds.

[0088] PET / ALU / CPP laminates were prepared by applying 4 gsm to 4.5 gsm of adhesive composition between each layer using a Labo Combi 400 machine. After the above laminates were cured, they were retort tested and the thermal cycle of the retort test is shown in Table X.

[0089] Preparation of laminates of Examples 17 to 32 and Comparative Examples H to N Inventive Examples 17-32, PET / ALU / CPP laminate structures were made using the PRELAM structure (available from The Dow Chemical Company). PRELAM is a multi-layer structure that includes a 12 μm (48 gauge) polyester (PET) film laminated onto 0.00035 mil aluminum foil using ADCOTE™ 577 / CO-REACTANT F™. The laminate was made using a 3.26 g / m 2 (2.0 lbs / ream). In addition to the PRELAM mentioned above, a 3 mil thick CPP was used. 1.5 gauge aluminum foil was also used to prepare the laminate structure.

[0090] In Comparative Examples H to N, a PET / ALU / CPP laminate structure was fabricated using a 12 μm-thick PET layer that had been pretreated by corona treatment, a 9 μm-thick ALU layer, and a CPP layer with an AKG of 65 μm.

[0091] Using the general procedure above, various laminates were prepared and tested. The film test results are listed in Tables VIII, IX and X.

[0092] General Procedure for Preparing Pouches After the laminate was cured at 45°C and 30% relative humidity for 7 days, the laminate structure was used to make pouches. The laminates were made from PRELAM / CPP and PET / ALU / CPP as described above. One of the 9" x 12" (23 cm x 30.5 cm) sheets of the laminate was folded over with the polymer film of one layer in contact with the polymer film of the other layer to obtain a bilayer of approximately 9" x 6" (23 cm x 15.3 cm). Both ends of the film were trimmed with a paper cutter to obtain a folded piece of approximately 5" x 7" (12.7 x 17.8 cm) size. The two long sides of the film and one short side of the film were heat sealed at the edges to obtain a finished pouch with an internal size of 4" x 6" (10.2 cm x 15.2 cm). The film was heat sealed at 420°F (216°C) for 1 second with 40 PSI (276 kPa) water pressure.

[0093] For each test, two or three pouches were made. The open end of the pouch was filled with 100±5 mL of deionized (DI) water. The heat-sealed area was prevented from contacting the fill, as this could cause heat-seal failure during testing. After filling, the top of the pouch was sealed in a manner that minimized air entrapment inside the pouch. The seal integrity of all four sides of the pouch was inspected to ensure there were no flaws in the seal that would cause the pouch to leak during testing. Any pouches with any flaws were discarded and replaced with flawless pouches. In some cases, flaws in the laminate were marked to identify if additional flaws occurred during testing. After sealing the pouch filled with DI water, the pouch was subjected to the retort test described below.

[0094] Test procedure Bond strength measurement Laminate samples cut into 15 mm wide strips were subjected to 90° T peel testing on a Thwing Albert™ QC-3A peel tester equipped with a 50 N load cell, pulling at a rate of 0.7 N / mm. The average force during the pull was recorded when the two films in the laminate separated (peeled). If one of the films stretched or broke, the maximum force or force at break was recorded. Values ​​were the average of three separate sample strips. The failure mode (FM) or mode of failure (MOF) was recorded as follows: "FS" refers to the film's elongation. "FT" refers to film rupture or break. "DL" refers to delamination (eg, the secondary film separates from the primary film). "AT" refers to adhesive migration (eg, the adhesive fails to adhere to the primary film and migrates to the secondary film). "AS" refers to adhesive splitting or cohesive failure (eg, adhesive found in both the primary and secondary films).

[0095] Retort Testing Procedure The DI water-containing pouches were placed in a retort chamber programmed to undergo a retort cycle including (1) a heat / pressurization stage, (2) an isothermal stage, and (3) a cooling / depressurization stage with the isothermal stage set at 121°C for 1 hour, 128°C for 1 hour, or 134°C for 1 hour. After retort testing, the pouches were removed and the extent of defects, whether tunneling, blistering, delamination, or leakage, was visually compared to any pre-existing flaws that were marked. Observations of defects were recorded according to the failure mode designation above. The pouches were cut open, emptied, and allowed to dry under ambient conditions. One or more 1-inch (15 mm) strips were cut from the pouches and the laminate bond strength was measured according to the standard bond strength test described above. The bond strength test was performed as soon as possible after the pouch contents were removed. The interior of the pouches was inspected and any other visual defects were noted.

[0096] Bond strength and retort performance data are listed in Tables VIII, IX, and X. For example, Table VIII lists the bond strength and retort performance results for foil / CPP laminate structures cured with MOR-FREE™ 200C. Table IX lists the bond strength and retort performance results for foil / CPP laminate structures cured with 9L10. Also, Table X lists the bond strength and retort performance results for PET / ALU / CPP laminate structures made with ADCOTE™ 811A EA and ISO-PET in combination with (MOR-FREE™ 200C, 9L10, CAT F, and ADCOTE™ 811B-Labo Combi results). [Table 10] [Table 11] [Table 12]

[0097] Discussion of results The results reported in the table above show bond strength values ​​measured after retort thermal cycling and are comparable to standard products based on epoxy silanes.

[0098] Lamination based on the adhesive composition of the present invention produced a final pouch that was able to resist, withstand and function in retort conditions.

[0099] The procedure for preparing the silyl polymers used in this process advantageously provides for the use of non-food approved silanes for food applications.

[0100] Other embodiments In one embodiment, the PSP of the present invention comprises at least one isosilane compound, component (b), where the isosilane compound comprises an isocyanato-ethoxy-silane, an isocyanato-ethoxy-silane, or a mixture thereof.

[0101] In another embodiment, the solvent-based retort adhesive composition of the present invention comprises a mixture of (A) at least one isocyanate component as component A, where the isocyanate component can be an aromatic isocyanate compound, an aliphatic isocyanate compound, and mixtures thereof, and (B) at least one isocyanate-reactive component as component B, where the at least one isocyanate-reactive component of component B comprises (Bi) at least one silyl polymer and (Bii) at least one polyol compound. The polyol compound can be an aromatic polyol compound, an aliphatic polyol compound, an aromatic prepolymer, an aliphatic prepolymer, and mixtures thereof.

[0102] In yet another embodiment, the laminate of the present invention comprises at least one first layer of a substrate such as an (α) film or polyester film.

[0103] In a preferred embodiment, the laminate of the present invention comprises (α) at ​​least one first layer of a film or substrate, comprising at least two layers comprising (1) a film, (2) a substrate, or (3) a combination of a film and substrate, and a layer of the adhesive composition of the present invention is disposed on a surface of at least one of layers (1), (2) or (3) to bond layers (1) and (2) together.

[0104] In yet another embodiment, the laminated product of the present invention is used to make a retort article. In a preferred embodiment, the retort article may be a pouch.

[0105] The process for producing the silyl polymer of the present invention comprises the following first and second steps: (I) in the first step, reacting (Ia) at least one polyol compound with (Ib) at least one isosilane compound, the first reaction step (I) being carried out at a first predetermined temperature of 50°C to 100°C and for a first predetermined time of 1 hour to 8 hours to form a partial silyl polymer; and (II) in the second step, reacting (IIa) the partial silyl polymer resulting from step (I) with (IIb) at least one aminosilane compound, the second reaction being carried out at a second predetermined temperature of 50°C to 70°C and for a second predetermined time of 1 hour to 4 hours to form a final silyl polymer.

[0106] The above process of the present invention includes a mixing step of mixing component A with component B, the mixing step being carried out at a temperature between 15°C and 60°C.

[0107] The process for producing the laminated product of the present invention includes using at least one first layer of a film or substrate made, for example, of a polyester resin.

[0108] In yet another embodiment, a process for producing a laminated product of the present invention comprises the steps of: (i) providing (a) a first layer of film or substrate; (b) a second layer of film or substrate; and (c) a lamination adhesive composition of the present invention; (ii) applying the adhesive composition from step (i) to at least a portion of a surface of at least one of the first or second layers of step (i) to form an adhesive layer; (iii) combining the first and second layers with a sufficient adhesive layer to form a laminate structure; (iv) curing the laminate structure of step (iii) to form a multi-layer laminate product. It should be noted that the present invention includes the following aspects. [Aspect 1] A partially silyl polymer, (a) at least one polyol compound; (b) a reaction product of at least one isosilane compound to form a partially silyl polymer. [Aspect 2] 2. The partially silyl polymer of embodiment 1, wherein the at least one polyol compound is at least one compound selected from the group consisting of polyether polyols, polyester polyols, polyurethane polyester polyols, polycarbonate polyols, polyacrylate polyols, polycaprolactone polyols, natural oil polyols, and mixtures thereof. [Aspect 3] A final silyl polymer comprising: (i) a partially silyl polymer according to embodiment 1; (ii) a final silyl polymer comprising the reaction product of with at least one aminosilane compound to form the final silyl polymer. [Aspect 4] 1. A process for producing a silyl polymer comprising the steps of: (I): In the first step, (Ia) at least one polyol compound; (Ib) reacting at least one isosilane compound, wherein said first reacting step (I) is carried out at a first predetermined temperature and for a first predetermined time period at said first temperature to form a partial silyl polymer; (II) in the second step, (IIa) the partially silyl polymer resulting from step (I); (IIb) reacting with at least one aminosilane compound, wherein a second reaction is carried out at a second predetermined temperature and for a second predetermined period of time at said second temperature to form a final silyl polymer. [Aspect 5] 1. A solvent-based retort adhesive composition comprising: (A) at least one isocyanate component as component A; (B) at least one isocyanate-reactive component as component B, wherein the at least one isocyanate-reactive component as component B comprises a mixture of: (Bi) at least one silyl polymer according to embodiment 1 or embodiment 3; (Bii) at least one polyol compound. [Aspect 6] The adhesive composition of embodiment 5, wherein the at least one isocyanate component, Component A, is at least one aliphatic isocyanate compound, or the at least one isocyanate component, Component A, is a blend of (1) at least one aliphatic isocyanate compound and (2) at least one aromatic isocyanate compound. [Aspect 7] 6. The adhesive composition of claim 5, wherein Component A, the at least one isocyanate component, is an isocyanate prepolymer comprising the reaction product of (1) at least one isocyanate compound and (2) at least one polyol compound. [Aspect 8] 6. The adhesive composition of claim 5, wherein the at least one polyol compound, component (Bii), is selected from the group consisting of polyether polyols, polyester polyols, polyurethane polyester polyols, polycarbonate polyols, polyacrylate polyols, polycaprolactone polyols, natural oil polyols, and blends thereof. [Aspect 9] 6. The adhesive composition of embodiment 5, further comprising a solvent selected from the group consisting of ethyl acetate, methyl ether ketone, toluene, and mixtures of two or more of the foregoing. [Aspect 10] 6. The adhesive composition of embodiment 5, further comprising an additive selected from the group consisting of catalysts, surfactants, leveling agents, defoamers, fillers, rheology modifiers, color pigments, and mixtures of two or more of the foregoing. [Aspect 11] 1. A process for producing a solvent-based polyurethane retort adhesive composition for producing a laminate, comprising: (A) at least one isocyanate component as component A; (B) at least one isocyanate-reactive component as component B, wherein the at least one isocyanate-reactive component as component B is a mixture of (Bi) at least one silyl polymer according to embodiment 1 or embodiment 3; (Bii) at least one polyol compound. [Aspect 12] A laminate comprising: (α) at ​​least one first layer of a film or substrate; (β) at least a second layer of film or substrate; and (γ) (1) the at least one first layer (α), (2) the at least one second layer (β), or (3) at least one layer of the adhesive composition according to embodiment 5 disposed on at least a portion of one side surface of both the at least one first layer (α) and the at least one second layer (β). [Aspect 13] 13. A retortable article made from the laminate of embodiment 12. [Aspect 14] A process for producing a laminate comprising the steps of: (A') providing (α) at ​​least one first layer of a film or substrate, (β) at least one second layer of a film or substrate, and (γ) an adhesive composition according to embodiment 5; (B') applying the adhesive composition (γ) of step (A') to at least a portion of a surface of one side of (1) the at least one first layer (α), (2) the at least one second layer (β), or (3) the at least one first layer (α) and the at least one second layer (β), wherein the adhesive composition forms an adhesive layer; (C') combining the first and second layers with the adhesive layer of step (B') sandwiched between sufficient of the first and second layers to form a multi-layer laminate structure; (D') curing the multi-layer laminate structure of step (C') to bond the first and second layers together to form a cured multi-layer laminate product.

Claims

1. 1. A solvent-based retort adhesive composition comprising: (A) at least one isocyanate component as component A; (B) at least one isocyanate-reactive component as component B; A mixture of said at least one isocyanate-reactive component being component B; (Bi) at least one silyl polymer; (Bii) at least one polyol compound; Including, The silyl polymer is (i) a partial silyl polymer comprising the reaction product of (a) at least one polyol compound and (b) at least one isosilane compound having an isocyanate functional group and a silane functional group; (ii) at least one aminosilane compound; The adhesive composition is a final silyl polymer comprising the reaction product of:

2. 2. The adhesive composition of claim 1, wherein the at least one isocyanate component, Component A, is at least one aliphatic isocyanate compound, or the at least one isocyanate component, Component A, is a blend of (1) at least one aliphatic isocyanate compound and (2) at least one aromatic isocyanate compound.

3. 2. The adhesive composition of claim 1, wherein the at least one isocyanate component, component A, is an isocyanate prepolymer comprising the reaction product of (1) at least one isocyanate compound and (2) at least one polyol compound.

4. 2. The adhesive composition of claim 1, wherein the at least one polyol compound, component (Bii), is selected from the group consisting of polyether polyols, polyester polyols, polyurethane polyester polyols, polycarbonate polyols, polyacrylate polyols, polycaprolactone polyols, natural oil polyols, and blends thereof.

5. 10. The adhesive composition of claim 1, further comprising a solvent selected from the group consisting of ethyl acetate, methyl ether ketone, toluene, and mixtures of two or more thereof.

6. 10. The adhesive composition of claim 1 further comprising an additive selected from the group consisting of catalysts, surfactants, leveling agents, defoamers, fillers, rheology modifiers, color pigments, and mixtures of two or more thereof.

7. 1. A process for producing a solvent-based polyurethane retort adhesive composition for producing a laminate, comprising: (A) at least one isocyanate component as component A; (B) at least one isocyanate-reactive component as component B; mixing the said at least one isocyanate-reactive component being component B; (Bi) at least one silyl polymer; (Bii) at least one polyol compound; Including, The silyl polymer is (i) a partial silyl polymer comprising the reaction product of (a) at least one polyol compound and (b) at least one isosilane compound; (ii) at least one aminosilane compound; wherein the final silyl polymer comprises the reaction product of

8. A laminate comprising: (α) at ​​least one first layer of a film or substrate; (β) at least a second layer of film or substrate; and (γ) at least one layer of the adhesive composition according to claim 1 disposed on at least a portion of one surface of (1) the at least one first layer (α), (2) the at least one second layer (β), or (3) both the at least one first layer (α) and the at least one second layer (β); Including, laminated.

9. 10. A retortable article made from the laminate of claim 8.

10. A process for producing a laminate comprising the steps of: (A') providing (α) at ​​least one first layer of a film or substrate, (β) at least one second layer of a film or substrate, and (γ) an adhesive composition according to claim 1; (B') applying the adhesive composition (γ) of step (A') to at least a portion of a surface of one side of (1) the at least one first layer (α), (2) the at least one second layer (β), or (3) the at least one first layer (α) and the at least one second layer (β), wherein the adhesive composition forms an adhesive layer; (C') combining the first and second layers with the adhesive layer of step (B') sandwiched between sufficient of the first and second layers to form a multi-layer laminate structure; (D') curing the multi-layer laminate structure of step (C') to bond the first and second layers together to form a cured multi-layer laminate product.

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