Bactericidal adhesive composition

Abstract

A solvent-based polyurethane bactericidal adhesive system for producing laminates, comprising: (A) at least one isocyanate compound, component A, comprising: a blend of: (i) at least one aliphatic isocyanate and (ii) at least one aromatic isocyanate; and (B) at least one isocyanate-reactive component, component B, comprising: (i) at least one phosphate compound and (ii) at least one polyether polyol having an average molecular weight of less than 1,500 g mol; a method for producing the above adhesive; a multilayer laminate comprising the above adhesive; and a method for producing a laminate using the above adhesive.

Description

Technical Field

[0001] The present invention relates to a bactericidal adhesive composition suitable for use in a laminating process; and the preparation of such a bactericidal adhesive composition. More specifically, the present invention relates to a solvent-based bactericidal adhesive composition for use with a laminating film, the adhesive composition exhibiting regulatory compliance, fast curing, and good adhesion performance; and a method for making the same. Background Art

[0002] Adhesive compositions are suitable for a variety of purposes. For example, two or more film layers of a substrate are adhered together using some adhesives to form a composite film, that is, a laminate comprising two or more film layers. Examples of substrates generally include polyethylene, polypropylene, polyester, polyamide, metal, paper or cellophane, etc. The use of adhesives in different lamination end-use applications is generally known. For example, adhesives are generally applied between laminating films and can be used to manufacture films / films and film / foil laminates for packaging food, pharmaceuticals and industrial consumer products, especially food packaging in the flexible packaging industry. Laminating adhesives can generally be divided into three categories: (1) solvent-based laminating adhesives, (2) solvent-free laminating adhesives, and (3) water-based laminating adhesives. The performance of the adhesive varies depending on the category and application of the applied adhesive. In the category of solvent-based laminating adhesives, solvent-based polyurethanes have been widely used to achieve relatively good heat resistance, moisture resistance and chemical resistance.

[0003] In the category of solvent-based laminating adhesives, there are many types; and one particular type includes multi-component laminating adhesives based on polyurethane; and more specifically, two-component adhesives. Typically, a two-component laminating adhesive based on polyurethane includes a first component, which includes an isocyanate and / or a polyurethane prepolymer, and a second component including one or more polyols. The polyurethane prepolymer can be obtained by the reaction of a polyisocyanate with a polyether polyol and / or a polyester polyol. The second component includes a polyether polyol and / or a polyester polyol. Each component may optionally include one or more additives. Commonly used solvents in such systems include methyl ethyl ketone, ethyl acetate, toluene, etc., all of which must be free of moisture to prevent premature reaction of the isocyanate groups of the polyurethane.

[0004] The two components of the adhesive composition (i.e., the isocyanate and polyol components) are combined in a predetermined ratio to form an adhesive composition. The adhesive composition carried in a solvent is then applied to a film / foil substrate. The solvent evaporates from the applied adhesive composition. Another film / foil substrate is then contacted with another substrate to form a curable laminate structure. The laminate structure is then cured to bond the two substrates together.

[0005] Solvent-based adhesive compositions can be used in high-performance laminate applications (e.g., sterilization, hot filling, retort bags, etc.). For example, in sterilization flexible package applications, the sterilization flexible package provides several benefits, such as (1) consumer convenience, (2) longer shelf life of the food packaged in the package, and (3) retention of the original flavor of the packaged food. Sterilization flexible packages such as retort pouches are typically constructed with a multilayer laminate structure, such as a three-layer structure or a four-layer structure. The three-layer structure typically includes, for example, an outer layer of polyethylene terephthalate (PET), an intermediate layer of metal foil (e.g., aluminum), and an inner layer of cast polypropylene (CPP); and the three-layer structure is typically indicated as PET / / foil / / CPP. The four-layer structure typically includes, for example, an outer layer of PET, a first top intermediate layer of metal foil, a second bottom intermediate layer of nylon, and an inner layer of CPP; and the four-layer structure is typically indicated as PET / / foil / / nylon / / CPP. A laminating adhesive is applied to the structure to bond the different layers together. Laminating adhesives used in sterilizable flexible packaging applications must not only meet extreme performance requirements at high temperatures in the presence of highly acidic and fatty foods, such as 121 degrees Celsius (°C) for 1 hour (hr) or 132°C for 30 minutes (min); but they must also meet extremely stringent regulatory standards, such as those issued by the U.S. Federal Administration (FDA) and the European Union (EU).

[0006] There are essentially four known sterilizing adhesives. Two adhesives are based on aliphatic isocyanates, which meet regulatory compliance, but such aliphatic isocyanate adhesives cure extremely slowly and the adhesives have performance issues. The other two types of adhesives contain aromatic isocyanates; and such aromatic isocyanate adhesives cure quickly, but such adhesives do not meet regulatory compliance for sterilizing applications and the adhesives also have performance issues. The prior art does not disclose an "all-in-one" sterilizing adhesive that meets regulatory compliance, has fast curing properties, and has good adhesion properties for sterilizing applications.

[0007] For example, known laminating adhesives for sterile applications: (1) exhibit good adhesion to a wide range of sterile substrates and structures, and the adhesives are generally compliant with global food regulations for sterile applications; but the adhesives exhibit slow curing characteristics, such as being cured at above 40° C. for at least 10 days prior to encapsulating food using an encapsulation made using the known laminating adhesive; or (2) are generally compliant with global food regulations for sterile applications; but the adhesives exhibit slow curing characteristics, such as being cured at above 40° C. for at least 10 days prior to encapsulating food using an encapsulation made using the known laminating adhesive. (3) exhibit fast curing properties, such as curing under ambient conditions within 10 days or at an evaluation temperature (e.g., greater than or equal to (≥) 40°C) within five days; and the adhesive exhibits good adhesion to typical sterile substrates and structures; but the adhesive is generally not compliant with global food regulations for sterile applications, for example, the adhesive has issues complying with FDA and EU regulations. It is also known that aromatic-based adhesives do not exhibit good adhesion properties.

[0008] It is therefore desirable to provide a bactericidal adhesive that not only exhibits excellent adhesion, heat resistance, and chemical resistance; but also exhibits rapid curing characteristics under ambient curing conditions (i.e., a curing time of less than [<] eight days) and a curing time of < five days at an evaluation temperature (e.g., ≥40°C). At the same time, it is desirable to provide a bactericidal adhesive that meets regulatory compliance. For example, adhesives containing aromatic polyisocyanates (e.g., methylene diphenyl diisocyanate (MDI) and toluene diisocyanate (TDI)) can produce primary aromatic amines, such as methylene diphenyl diamine (MDA) and toluene diamine (TDA), which are undesirable and can potentially migrate from the adhesive to food. In general, in order to comply with typical government regulations, the regulations require that the total amount of aromatic amines that migrate to food encapsulated in a package using a bactericidal adhesive needs to be extremely low, such as in a parts per billion (ppb) content, to comply with FDA and EU food regulations after the adhesive is subjected to rigorous sterilization test conditions. Summary of the invention

[0009] In the present invention, a novel solvent-based adhesive is disclosed that exhibits desirable performance attributes and solves the problems of previously known adhesives for sterilization applications. In one embodiment, the present invention is directed to a multi-component (e.g., two-component), solvent-based polyurethane sterilization adhesive composition for producing a laminate, comprising an isocyanate component, component A, and an isocyanate group (NCO) reactive component, component B. In a preferred embodiment, the adhesive composition comprises, for example: (A) at least one isocyanate compound; wherein the at least one isocyanate compound, component A, comprises a blend of: (i) at least one aliphatic isocyanate and (ii) at least one aromatic isocyanate; and (B) at least one isocyanate group (NCO) reactive component; wherein the at least one isocyanate reactive component, component B, comprises: (i) at least one phosphate compound and (ii) at least one polyol comprising a polyether polyol having a suitable molecular weight distribution, such as an average molecular weight (Mw) <1,500 grams / mole (g / mol).

[0010] In other embodiments, the present invention includes methods for producing the above-described adhesives; multi-layer laminates including the above-described adhesives; and methods of producing laminates using the above-described adhesives. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Figure 1 Graph showing the attenuated total reflection (ATR) of the inventive sample and the comparative sample after curing at an elevated temperature of 50° C. for 3 days. DETAILED DESCRIPTION

[0012] The numerical range disclosed herein includes all values ​​from the lower limit and the upper limit, and includes the lower limit and the upper limit. For a range containing an exact value (e.g., a range of 1 or 2 or 3 to 5 or 6 or 7), any sub-range between any two exact values ​​is included (e.g., the above range 1 to 7 includes sub-ranges 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6; etc.).

[0013] The term "composition" refers to a mixture of materials comprising the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0014] The terms "comprising", "including", "having" and their derivatives are not intended to exclude the presence of any additional components, steps or procedures, whether or not specifically disclosed. For the avoidance of any doubt, unless stated to the contrary, all compositions claimed by using the term "comprising" may include any additional additives, adjuvants or compounds, whether polymeric or otherwise. In contrast, the term "consisting essentially of excludes any other components, steps or procedures from any subsequently listed scope, except those that are not essential to operability. The term "consisting of" excludes any components, steps or procedures that are not specifically described or listed. Unless otherwise stated, the term "or" refers to the listed members individually and in any combination. The use of the singular includes the use of the plural, and vice versa.

[0015] An "isocyanate" is a chemical substance that contains at least one isocyanate group in its structure. An isocyanate group is represented by the formula: -N=C=O or abbreviated as "NCO". Isocyanates containing more than one or at least two isocyanate groups are "polyisocyanates". An isocyanate with two isocyanate groups is a diisocyanate, and an isocyanate with three isocyanate groups is a triisocyanate, etc. Isocyanates can be aromatic or aliphatic.

[0016] A "polyisocyanate" is a molecule containing at least two isocyanate groups.

[0017] "Polyethers" are chemical compounds containing two or more ether linkages in a linear chain of the same atoms.

[0018] "Polyester" is a chemical compound containing two or more ester bonds in a linear chain of the same atoms.

[0019] "Polyol" is an organic compound containing multiple hydroxyl (OH) groups. In other words, a polyol contains at least two OH groups. Non-limiting examples of suitable polyols include diols having two OH groups, triols having three OH groups, and tetraols having four OH groups.

[0020] "Polyester polyol" is a compound containing polyester and polyol in the main chain structure of the compound.

[0021] The "polyether polyol" is a compound containing a polyether and a polyol in the main chain structure of the compound.

[0022] Unless thickness is specifically specified, "film" (including when referring to a "film layer" in the context of a thicker article) includes any thin, flat extruded or cast thermoplastic article having a generally consistent and uniform thickness in one dimension of about 0.5 millimeters (mm) (20 mils) or less.

[0023] A "polymer film" is a film made from a polymer or a mixture of polymers. The composition of a polymer film is typically 80 weight percent (wt%) of one or more polymers.

[0024] "Polymer" is a polymeric compound prepared by polymerizing monomers of the same or different types. Therefore, the general term polymer encompasses the term "homopolymer" (used to refer to polymers prepared from only one type of monomer, with the understanding that trace amounts of impurities can be incorporated into the polymer structure), and the term "interpolymer", which includes copolymers (used to refer to polymers prepared from two different types of monomers), terpolymers (used to refer to polymers prepared from three different types of monomers), and polymers prepared from more than three different types of monomers. Trace impurities, such as catalyst residues, may be incorporated into and / or within the polymer. It also encompasses all forms of copolymers, such as random, block, etc. It should be noted that although polymers are often referred to as "made from" one or more specified monomers, "based on" a specific monomer or monomer type, "containing" a specific monomer content, or similar statements, in this case, the term "monomer" should be understood to refer to the polymerized residue of a specific monomer and not to refer to unpolymerized species. In general, polymers herein are referred to as "units" based on the polymerized form of the corresponding monomer.

[0025] It is well recognized in the adhesive art that making a two-part adhesive system includes: providing a first part (herein, component A) comprising an isocyanate-containing component; providing a second part comprising an NCO-reactive component, such as a polyol component (herein, component B); and then combining or mixing component A and component B to form a two-part adhesive system or composition.

[0026] In a broad embodiment, the present invention relates to at least one solvent-based polyurethane bactericidal adhesive for producing a laminate, the adhesive comprising component A, which comprises at least one isocyanate-containing compound; and component B, which comprises at least one NCO-reactive component; wherein the at least one NCO-reactive component contains (i) at least one phosphate compound and (ii) at least one polyol, which comprises a polyether polyol having an average Mw<1,500 g / mol. In one embodiment, the phosphate polyol in the at least one NCO-reactive component can be present at a concentration of, for example, 0.1 wt% to 30 wt%. In a first preferred embodiment, the at least one isocyanate compound of the adhesive is, for example, at least one aliphatic isocyanate. In a second preferred embodiment, the at least one isocyanate compound is a blend of (i) at least one aromatic isocyanate and (ii) at least one aliphatic isocyanate. In a second preferred embodiment, the at least one aromatic isocyanate can be an isocyanate prepolymer comprising the reaction product of: (i) at least one polyisocyanate and (ii) at least one polyether polyol having a Mw>1,500 g / mol.

[0027] The unique adhesive of the present invention has several advantages over heretofore known solvent-based polyurethane bactericidal adhesive systems, including, for example, (1) good adhesion properties; (2) fast curing characteristics; and (3) (a) no aromatic amine migration or (b) very low aromatic amine migration. The unique solvent-based polyurethane bactericidal adhesive system is then suitable for use in a method of making a laminate having good heat resistance and good chemical resistance, which is used to make a sterile packaging article.

[0028] As mentioned above, in another embodiment, at least one isocyanate-containing compound used to prepare the solvent-based polyurethane bactericidal adhesive of the present invention, component A is, for example, a blend of the following substances: (i) at least one aliphatic isocyanate and (ii) at least one aromatic isocyanate. The isocyanate-containing compound suitable for the present invention can be selected from, for example, the group consisting of: isocyanate monomers, polyisocyanates (e.g., dimers, trimers, etc.), isocyanate prepolymers, and mixtures of two or more thereof. As used herein, "polyisocyanate" is any compound containing two or more isocyanate groups.

[0029] In addition, the isocyanate-containing compound can be selected from the group consisting of aliphatic polyisocyanates, cycloaliphatic polyisocyanates, aromatic polyisocyanates, and combinations of two or more thereof. "Aliphatic polyisocyanates" are polyisocyanates that do not contain aromatic rings. "Cycloaliphatic polyisocyanates" are a subgroup of aliphatic polyisocyanates in which the chemical chain is a cyclic structure. "Aromatic polyisocyanates" are polyisocyanates that contain one or more aromatic rings.

[0030] Aliphatic isocyanate components suitable for use in the present invention, component (i) of component A may include one or more compounds, including, for example, aliphatic polyisocyanates having, in one embodiment, 3 carbon atoms (C) to 16 C and in another embodiment, 4 C to 12 C in the linear or branched alkylene residue. Cycloaliphatic polyisocyanates are also suitable for use in the present invention, including, for example, cycloaliphatic polyisocyanates having, in one embodiment, 4 C to 18 C and in another embodiment, 6 C to 15 C in the cycloalkylene residue. Cycloaliphatic diisocyanates refer to NCO groups bonded in a ring to an aliphatic manner, such as isophorone diisocyanate and diisocyanatodicyclohexylmethane (HDI). 12 MDI).

[0031] Examples of suitable aliphatic and cycloaliphatic polyisocyanates for use in the present invention include, but are not limited to, cyclohexane diisocyanate, methyl cyclohexane diisocyanate, ethyl cyclohexane diisocyanate, propyl cyclohexane diisocyanate, methyl diethyl cyclohexane diisocyanate, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate, heptane diisocyanate, octane diisocyanate, nonane diisocyanate, nonane triisocyanate such as 4-isocyanatomethyl-1,8-octane diisocyanate (TIN), decane diisocyanate and triisocyanate, undecane diisocyanate and triisocyanate, and dodecane diisocyanate and triisocyanate, hexamethylene diisocyanate (HDI), diisocyanatodicyclohexylmethane (DICH), and the like. 12 MDI), 2-methylpentane diisocyanate (MPDI), 2,2,4-trimethylhexamethylene diisocyanate / 2,4,4-trimethylhexamethylene diisocyanate (TMDI), norbornane diisocyanate (NBDI), xylene diisocyanate (XDI), 1,4- or 1,3-bis(isocyanatomethyl)cyclohexane (H6XDI), tetramethylxylene diisocyanate and dimers, trimers, derivatives and mixtures thereof of two or more. Suitable aliphatic polyisocyanates and cycloaliphatic polyisocyanates suitable for the present invention also include, for example, polyisocyanates based on XDI, polyisocyanates based on H6XDI, XDI isocyanurates, polyisocyanates based on HDI, polyisocyanates based on H 12 Polyisocyanates of MDI, polyisocyanates of HDI, and mixtures of two or more thereof.

[0032] In a preferred embodiment, the aliphatic components suitable for use in the present invention include, for example, XDI-based polyisocyanates, HDI-based polyisocyanates, and mixtures thereof.

[0033] Some of the exemplary commercial products of aliphatic components suitable for use in the present invention include, for example, TAKENATE D-110N and TAKENATE D-120N available from Mitsui Chemical; Desmodur N 3200 and Desmodur Quix 175 available from Coverstro Company; and mixtures thereof.

[0034] Additional isocyanate-containing compounds suitable for use in accordance with the present disclosure include, but are not limited to, 4-methyl-cyclohexane 1,3-diisocyanate, 2-butyl-2-ethylpentamethylene diisocyanate, 3(4)-isocyanatomethyl-1-methylcyclohexyl isocyanate, 2-isocyanatopropylcyclohexyl isocyanate, 2,4'-methylenebis(cyclohexyl) diisocyanate, 1,4-diisocyanato-4-methyl-pentane, and mixtures of two or more thereof.

[0035] In addition, isocyanate-containing compounds suitable for use as component (i) of component A according to the present disclosure include, for example, isocyanate prepolymers. "Isocyanate prepolymers" are the reaction products of polyisocyanates and isocyanate-reactive components, and their stoichiometric ratio (NCO / OH) is greater than (>) 2.0 in one embodiment, 3.0 to 10.0 in another embodiment, and 4.0 to 7.0 in yet another embodiment. As described above, polyisocyanates are selected from, for example, aromatic polyisocyanates, aliphatic polyisocyanates, cycloaliphatic polyisocyanates, and mixtures thereof. Suitable isocyanate-reactive components that can react with polyisocyanates to form isocyanate prepolymers (also referred to as "polyurethane prepolymers") include, for example, compounds having hydroxyl groups, amino groups, and thio groups. Isocyanate-reactive components that can react with polyisocyanates to form isocyanate prepolymers suitable for use in the present invention include, for example, polyether polyols, polyester polyols, polycaprolactone polyols, polyacrylates, polycarbonate polyols, natural oil-based polyols, and mixtures of two or more thereof.

[0036] Isocyanate reactive components that can react with polyisocyanates to form isocyanate prepolymers suitable for use in the present invention can also be characterized by the hydroxyl number of the isocyanate reactive component and its hydroxyl functionality. "Hydroxyl number" or "hydroxyl value" is a measure of the free hydroxyl content in a chemical substance. The hydroxyl number is the milligrams of potassium hydroxide (KOH) required to neutralize the acetic acid absorbed when acetylation is performed on one gram of a chemical substance containing free hydroxyl groups. The hydroxyl number (OHN) is usually expressed as milligrams of potassium hydroxide per gram of chemical substance (mg KOH / g). The hydroxyl number is determined according to DIN53240.

[0037] "Hydroxyl functionality" is the number of hydroxyl groups present in one molecule of a compound. Hydroxyl functionality is measured according to ASTM D4274-16, with results reported as integers of 1 or greater in one embodiment, and from 1 to 6 in another embodiment.

[0038] In some embodiments, the average hydroxyl number of the isocyanate reactive component can be, for example, 1 mg KOH / g to 2,000 mg KOH / g in one embodiment, 5 mg KOH / g to 2,000 mg KOH / g in another embodiment, 14 mg KOH / g to 850 mg KOH / g in yet another embodiment, 28 mg KOH / g to 500 mg KOH / g in yet another embodiment, and 35 mg KOH / g to 450 KOH / g in even yet another embodiment. In some embodiments, the average molar mass of the isocyanate reactive component is, for example, 62 g / mol to 20,000 g / mol in one embodiment, 250 g / mol to 12,000 g / mol in another embodiment, 500 g / mol to 6,000 g / mol in yet another embodiment, and 800 g / mol to 3,000 g / mol in yet another embodiment.

[0039] In some embodiments, the average hydroxyl functionality of the isocyanate reactive component can be, for example, 1.0 to 6.0 in one embodiment, 1.8 to 4.0 in another embodiment, and 2.0 to 3.0 in yet another embodiment. One of the advantageous properties exhibited by the aliphatic components of the present invention includes, for example, providing an adhesive that can comply with a wide range of government regulations.

[0040] Compounds having isocyanate groups are also characterized by the weight percent of isocyanate groups based on the total weight of the compound. The weight percent of isocyanate groups is referred to as "% NCO" and is measured according to ASTM D2572-97.

[0041] The amount of the aliphatic component used in the method of the present invention includes, for example, 30 wt % to 100 wt % in one embodiment, 40 wt % to 90 wt % in another embodiment, and 50 wt % to 80 wt % in yet another embodiment, based on the total amount of components in component A.

[0042] Aromatic isocyanate components suitable for use in the present invention, component (ii) of component A may include, for example, one or more polyisocyanate compounds, including, but not limited to, for example, 1,3- and 1,4-phenylene diisocyanates; 1,5-naphthylene diisocyanate; 2,6-toluene diisocyanate (2,6-TDI); 2,4-toluene diisocyanate (2,4-TDI); 2,4'-diphenylmethane diisocyanate (2,4'-MDI); 4,4'-diphenylmethane diisocyanate (4,4'-MDI); 3,3'-dimethyl-4,4'-biphenyl diisocyanate (TODI) and isomers thereof; polymeric isocyanates; and mixtures of two or more thereof.

[0043] Some of the exemplary commercial aromatic components suitable for use in the present invention may include, for example, Isonate 125M, ADCOTTE L76-204, Coreactant CT, and Catalyst F, available from The Dow Chemical Company; E 2200 / 76; and mixtures thereof. One of the advantageous properties exhibited by the aromatic components of the present invention includes, for example, providing an adhesive that cures rapidly.

[0044] The amount of the aromatic isocyanate component used in the method of the present invention is based on the total amount of the components in component A, for example, 5 wt % to 95 wt % in one embodiment, 20 wt % to 90 wt % in another embodiment, and 30 wt % to 90 wt % in yet another embodiment.

[0045] As mentioned above, at least one NCO reactive component for preparing the adhesive, component B is, for example, at least one NCO reactive component, which contains (i) at least one phosphate compound and (ii) at least one polyol, which contains a polyether polyol with an average Mw<1,500g / mol. As used herein, "polyol" refers to a compound having two or more hydroxyl groups (i.e., -OH) per molecule. As used herein, "ether" refers to a compound containing an ether bond. As used herein, "polyether" refers to a compound containing two or more ether bonds per molecule. Compounds that are both polyethers and polyols are referred to herein as "polyether polyols". "Aliphatic polyether polyols" are polyether polyols that do not contain aromatic rings in their molecules. "Aromatic polyether polyols" are polyether polyols that contain one or more aromatic rings in their molecules.

[0046] In one embodiment, the phosphate compound suitable for the present invention, component (i) of component B can be selected from, for example, a phosphate compound having the following chemical structure (I):

[0047]

[0048] Where R 1 In addition to the side groups shown in structure (I), R 1 may or may not have one or more additional pendant -OH groups, and R 1 There may or may not be one or more additional side groups of structure (I). Any two or more of the -OH group and one or more groups of structure (I) may or may not be attached to R 1 In a preferred embodiment, each -OH group and each group of structure (I) are connected to R 1 of individual atoms.

[0049] Characterization R 1 A suitable way to describe is to describe a compound having the following structure (II):

[0050]

[0051] Where R 1 Same as in structure (I). The compound having structure (II) is referred to herein as a "precursor polyol".

[0052] In some embodiments, the number average Mw of suitable precursor polyols is 90 g / mol or higher in one embodiment, 200 g / mol or higher in another embodiment, and 400 g / mol or higher in another embodiment. In some embodiments, the number average Mw of suitable precursor polyols is 4,000 g / mol or lower in one embodiment, 2,000 g / mol or lower in another embodiment, 1,200 g / mol or lower in another embodiment, 900 g / mol or lower in another embodiment, and 500 g / mol or lower in even another embodiment. In some embodiments, the number average Mw of suitable precursor polyols is 200 g / mol to 4,000 g / mol in one embodiment, 400 g / mol to 2,000 g / mol in another embodiment, 400 g / mol to 1,200 g / mol in another embodiment, and 400 g / mol to 900 g / mol in another embodiment.

[0053] In some embodiments, suitable precursor polyols are alkyl higher polyols, monosaccharides, disaccharides, and compounds having the following structure (III):

[0054]

[0055] Where R 2 , R 3, R 4 and R 5 Each of n1, n2 and n3 is independently an integer from 0 to 10. In addition to the side groups shown in structure (III), R 2 It may or may not have one or more additional side groups. It is further understood that any two or more of the side groups may or may not be attached to R 2 In some embodiments, there is a mixture of compounds of structure (III) wherein the values ​​of one or more of n1, n2, and n3 of the compounds of structure (III) are different from each other. Such mixtures are described herein by setting forth non-integer values ​​of the parameters n1, n2, or n3, wherein the non-integer values ​​represent the number average of the parameters. When it is necessary to assess the molecular weight of such mixtures, the number average molecular weight is used.

[0056] In the precursor polyol having structure (III), in a preferred embodiment, each side group is attached to R 2 In the precursor polyol having structure (III), in another preferred embodiment, R 3 , R 4 and R 5 One or more of is a hydrocarbon group having 1 C to 4 C in one embodiment, 2 C to 3 C in another embodiment, and 3 C in yet another embodiment. In the precursor polyol having structure (III), in yet another preferred embodiment, R 3 , R 4 and R 5 One or more of them is an alkyl group, which may be a linear or cyclic or branched chain or a combination thereof; in yet another preferred embodiment, R 3 , R 4 and R 5 One or more of is a straight chain or branched chain alkyl group; and in even another preferred embodiment, R 3 , R 4 and R 5 In yet another preferred embodiment, one or more of R is a branched alkyl group. 3 , R 4 and R 5 Same as each other.

[0057] In the precursor polyol having structure (III), in a preferred embodiment, one or more of n1, n2 and n3 is 0 to 8. In the precursor polyol having structure (III), in another preferred embodiment, one or more of n1, n2 and n3 is 1 or greater. In the precursor polyol having structure (III), in yet another preferred embodiment, one or more of n1, n2 and n3 is 6 or less. In the precursor polyol having structure (III), in yet another preferred embodiment, n1, n2 and n3 are the same as each other.

[0058] In one embodiment, the group of precursor polyols having structure (III) is wherein R 2 , R 3 , R 4 and R 5 Each of the precursor polyols is an alkyl compound; such precursor polyols are referred to herein as alkoxylated alkyl triols. In the triol, when at least one of n1, n2, and n3 is 1 or greater and R 2 When having the following structure (IV):

[0059]

[0060] The triols are known herein as alkoxylated glycerols. In the alkoxylated triols, when R 3 , R 4 and R 5 When each of R is a branched alkyl radical having exactly 3 C, the alkoxylated triol is known herein as a propoxylated triol. 2 having structure (IV)) are known herein as propoxylated glycerols.

[0061] Among the precursor polyols that are alkyl higher polyols, in one embodiment, are compounds with 10 C or less carbon atoms; in another embodiment, are compounds with 6 C or less carbon atoms; in yet another embodiment, are compounds with 3 or less carbon atoms; and in yet another embodiment, the compound is glycerol.

[0062] In yet another embodiment, the precursor polyol is an alkyl higher polyol and a compound having structure (III). It should be noted that if n1 is equal to (=) n2=n3=0, and if R 2 is an alkyl group or an alkyl group having a hydroxyl group, then the compound having structure (IV) is an alkyl higher polyol.

[0063] In one embodiment, the group of precursor polyols is alkyl triols and alkoxylated alkyl triols. Among these compounds, in one embodiment, it is glycerol and alkoxylated glycerol; and in another embodiment, it is alkoxylated glycerol. Among the alkoxylated glycerols, in a preferred embodiment, it is propoxylated glycerol.

[0064] Another category of suitable phosphate compounds suitable for the present invention includes compounds containing carbamate bonds. Phosphate compounds containing carbamate bonds are prepared by reacting one or more suitable phosphate functional polyols with one or more polyisocyanates, and in a preferred embodiment, one or more diisocyanates. In a preferred embodiment, the amount of polyisocyanate is kept low enough so that some or all of the reaction product is a phosphate functional polyol. Alternatively, the polyol may first react with the polyisocyanate to obtain an -OH terminated prepolymer that is subsequently reacted with polyphosphoric acid. Phosphate compounds with carbamate bonds include compounds with a number average Mw in a general embodiment ranging from 1,000 g / mol to 6,000 g / mol, in another embodiment ranging from 1,200 g / mol to 4,000 g / mol, and in yet another embodiment ranging from 1,400 g / mol to 3,000 g / mol.

[0065] In some embodiments, the phosphate ester compound is a reaction product of reactants including a precursor polyol and a phosphoric acid-type acid, and the resulting phosphate ester compound has a chemical structure of structure (I).

[0066] In a preferred embodiment, the amounts of phosphoric acid and precursor polyol are selected to determine M as follows: p :M x Ratio: M hy = the number of hydroxyl groups per molecule of the precursor polyol; N x =M hy -2;M x =(number of moles of precursor polyol)×(N x ); and M p = Number of moles of phosphorus atoms contained in phosphoric acid.

[0067] Generally speaking, M p :M x In one embodiment, the ratio of M is 0.1:1 or higher, in another embodiment, 0.2:1 or higher, in yet another embodiment, 0.5:1 or higher, and in yet another embodiment, 0.75:1 or higher. In some embodiments, M p :M x The ratio is 1.1:1 or lower.

[0068] Typically, the weight ratio of phosphoric acid to precursor polyol is 0.005:1 or higher in one embodiment, 0.01:1 or higher in another embodiment, and 0.02:1 or higher in yet another embodiment. In some embodiments, the weight ratio of phosphoric acid to precursor polyol is 0.3:1 or lower, or 0.2:1 or lower, or 0.12:1 or lower.

[0069] In some embodiments, the phosphoric acid contains polyphosphoric acid. And, generally speaking, the amount of polyphosphoric acid in the phosphoric acid is 75 wt% or more in one embodiment, 80 wt% or more in another embodiment, and 90 wt% or more in yet another embodiment, based on the weight of the phosphoric acid. Various grades of polyphosphoric acid are available; each grade is characterized by a percentage. To determine the grade, first recognize that for pure monomeric orthophosphoric acid, the content of phosphorus pentoxide is considered to be 72.4%. Any grade of polyphosphoric acid can also be analyzed to consider that one mole of polyphosphoric acid (molecular weight indicated as "Fppa") contains the number of moles of phosphorus pentoxide indicated as "Nppo", and the percentage of phosphorus pentoxide ("PCppo") is given by PCppo = (Nppo × 142) / Fppa, expressed as a percentage. The grade of polyphosphoric acid is then the ratio (expressed as a percentage): Grade = PCppo / 72.4.

[0070] In some embodiments, the polyphosphoric acid used has a level of 100% or more in one embodiment, and 110% or more in another embodiment. In some embodiments, the polyphosphoric acid used has a level of 150% or less in one embodiment, and 125% or less in another embodiment.

[0071] In some embodiments, the disclosed solvent-based adhesive compositions contain one or more phosphorus-free polyols in addition to one or more phosphate-functional polyols.

[0072] Additional information regarding suitable phosphate esters and the preparation of such suitable phosphate esters can be found, for example, in PCT Publication No. WO / 2015 / 168670.

[0073] Typically, the amount of component (i) of the phosphate compound, component B used in the present invention is based on the dry weight of the polyol component, component B, in one embodiment, 0.1 wt % to 80 wt %, in another embodiment, 1 wt % to 70 wt %, in yet another embodiment, 5 wt % to 60 wt %, in yet another embodiment, 10 wt % to 60 wt %, and in yet another embodiment, 20 wt % to 60 wt %.

[0074] The polyol component suitable for use in the present invention, component (ii) of component B comprises at least one polyether polyol. Generally, the molecular weight of the polyether polyol is <1,500 g / mol in one embodiment, <1,000 g / mol in another embodiment, and from 50 g / mol to 1,500 g / mol in yet another embodiment. In another embodiment, the polyether polyol incorporated into the polyol component (component B) of the present invention has a molecular weight of 150 g / mol to 1,500 g / mol and a functionality of 2.0 to 6.0.

[0075] Exemplary suitable polyether polyols useful in the present invention include, but are not limited to, for example, polypropylene glycol, polytetramethylene ether glycol, polybutylene oxide-based polyols, and copolymers thereof; and mixtures thereof.

[0076] Exemplary suitable polypropylene glycols for use in the present invention include, but are not limited to, polyols such as those based on propylene oxide, ethylene oxide, or mixtures thereof with initiators selected from the group consisting of propylene glycol, dipropylene glycol, sorbitol, sucrose, glycerol, and / or mixtures thereof. For example, the polypropylene glycol may include VORANOL TM ; PLURACOL available from BASF TM ; POLY-G available from Lonza TM POLY-L TM and POLY-Q TM ; and ACCLAIM available from Covestro TM In a preferred embodiment, polypropylene glycol having a functionality between 2 and 6 and a Mw of 250 g / mol to 1,500 g / mol is used.

[0077] Exemplary suitable polytetramethylene ether glycols suitable for use in the present invention include, but are not limited to, POLYTHF TM ; TERTHANE available from Invista TM ; PTMG available from Mitsubishi TM ; and PTG available from Dairen TM and mixtures thereof. In a preferred embodiment, polytetramethylene ether glycol having a functionality between 2 and 6 and a Mw of 250 g / mol to 1,500 g / mol is used.

[0078] Exemplary suitable polybutylene oxide based polyols suitable for use in the present invention include, but are not limited to, for example, polybutylene oxide homopolymer polyols, polybutylene oxide-polypropylene oxide copolymer polyols, and polybutylene oxide-polyethylene oxide copolymer polyols; and mixtures thereof. In a preferred embodiment, polybutylene oxide based polyols having a functionality of 2.0 to 4.0 and a Mw of 150 g / mol to 1,500 g / mol are used.

[0079] In other embodiments, polyether polyols suitable for use in the present invention include, but are not limited to, low molecular weight glycols, including, but not limited to, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, triisopropanolamine, neopentyl glycol; and mixtures thereof.

[0080] Typically, the amount of component (ii) of the component, polyether polyol, component B used in the present invention is based on the dry weight of the polyol component, component B, in one embodiment, 20 wt% to 99.9 wt%, in another embodiment, 30 wt% to 99 wt%, and in yet another embodiment, 40 wt% to 95 wt%.

[0081] In addition to the polyether polyol (component (ii) of component B), the polyol component B may optionally include (iii) at least one polyester polyol. Typically, when used, the polyester polyol (component (iii) of component B) has a molecular weight of <3,000 g / mol in one embodiment, <3,500 g / mol in another embodiment, and from 500 g / mol to 3,000 g / mol in yet another embodiment.

[0082] Suitable polyester polyols for use in the present invention include, but are not limited to, aliphatic polyester polyols; aromatic polyester polyols; copolymers of aliphatic polyester polyols and aromatic polyester polyols; polycarbonate polyols; polycaprolactone polyols; and mixtures thereof. These polyester polyols are: the reaction product of a polyacid and a polyol; or the reactant of phosgene or carbonate monomers and a polyol; or are produced through the ring-opening polymerization of a cyclic ester compound.

[0083] Exemplary suitable polyacids suitable for use in the present invention include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentane-dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalenedicarboxylic acid, diphthalic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid, and anhydride or ester-forming derivatives of these dicarboxylic acids; and p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid, and ester-forming derivatives or dimer acids of these dihydroxycarboxylic acids; and mixtures thereof. These polyacids may be used alone or in combination of two or more polyacids.

[0084] According to the present disclosure, any known polyol can be used. Non-limiting examples of suitable polyols suitable for the present invention include: glycols such as ethylene glycol, propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, methyl pentanediol, dimethyl butanediol, butyl ethyl propanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, triethylene glycol, polycaprolactone diol, dimer glycol, bisphenol A and hydrogenated bisphenol A; via cyclic ester compounds (such as propiolactone, butyrolactone Polyesters produced by ring-opening polymerization of ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran and cyclohexylene in a conventional manner with the aid of one or more compounds containing two active hydrogen atoms as an initiator; and polyethers produced by addition polymerization of one or more monomers in a conventional manner with the aid of one or more compounds containing two active hydrogen atoms as an initiator, the monomers including ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran and cyclohexylene, the one or more compounds being, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol and neopentyl glycol; and mixtures thereof. These polyols may be used alone or in combination of two or more polyols.

[0085] Typically, the amount of optional component (iii) of the polyester polyol, component B (which can be added to the polyol component, component B when used) can include, for example, based on the dry weight of the polyol component, component B, from 0 wt% to 20 wt% in one embodiment, from 0.01 wt% to 15 wt% in another embodiment, and from 0.1 wt% to 10 wt% in yet another embodiment.

[0086] Generally, the adhesive composition of the present invention includes (C) at least one solvent as component C. By way of example, but not limitation, the solvent may be selected from the group consisting of ethyl acetate, methyl ether ketone, toluene, and mixtures thereof.

[0087] The amount of the solvent, component C, used in the method of the present invention may be, for example, 20 wt % to 90 wt % in one embodiment, 30 wt % to 80 wt % in another embodiment, and 40 wt % to 70 wt % in yet another embodiment, based on the total amount of components in the adhesive composition.

[0088] In some embodiments, the adhesive composition of the present invention may include (D) one or more additional optional conventional ingredients or additives as component D, including, but not limited to, for example, catalysts, tackifiers, plasticizers, rheology modifiers, adhesion promoters, antioxidants, fillers, colorants, pigments, surfactants, solvents, polymers (including, for example, thermoplastic resins other than those discussed above), dehydrating agents (including, for example, silanes), benzoyl chloride, other polyols (including, for example, fatty polyols), ultraviolet indicators, and combinations of two or more thereof.

[0089] As an illustrative example, the adhesive composition may include, for example, an adhesion promoter. Non-limiting examples of suitable adhesion promoters include coupling agents such as silane coupling agents, titanate coupling agents, and aluminate coupling agents; epoxy resins; phosphoric acid; polyphosphoric acid and phosphate esters.

[0090] Examples of silane coupling agents suitable for use in the present invention include, but are not limited to, aminosilanes such as γ-aminopropyltriethoxysilane, γ-aminopropyl-trimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethyldimethoxysilane, and N-phenyl-γ-aminopropyltrimethoxysilane, epoxysilanes such as β-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane, γ-glycidoxypropyl-trimethoxysilane, and γ-glycidoxypropyltriethoxysilane; vinylsilanes such as vinyltri(β-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane; hexamethyldisilazane; γ-mercaptopropyl-trimethoxysilane; and mixtures thereof.

[0091] Examples of titanate coupling agents suitable for use in the present invention include, but are not limited to, tetraisopropoxytitanium, tetra-n-butoxytitanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctanediol titanate, titanium lactate, tetrastearyl titanium, and mixtures thereof.

[0092] Examples of epoxy resins include, but are not limited to, a variety of readily commercially available epoxy resins, such as bisphenol A-epichlorohydrin (epi-bis) type epoxy resins, novolac type epoxy resins, β-methylepichlorohydrin type epoxy resins, cyclic oxirane type epoxy resins, glycidyl ether type epoxy resins, glycidyl ester type epoxy resins, polyglycol ether type epoxy resins, glycol ether type epoxy resins, epoxidized fatty acid ester type epoxy resins, polycarboxylate type epoxy resins, aminoglycidyl type epoxy resins, resorcinol type epoxy resins; and mixtures thereof.

[0093] In some embodiments, the adhesion promoter may be a phosphate compound. In other embodiments, the adhesion promoter is epoxy silane ((3-glycidyloxypropyl)-trimethoxysilane). In some embodiments, phosphoric acid may be incorporated into the polyol component, and epoxy silane may be incorporated into the isocyanate component. In some embodiments, both epoxy silane and phosphoric acid are incorporated into the polyol component.

[0094] In some embodiments, the average functionality of the adhesive composition (ie, the isocyanate component and the polyol component together) excluding non-reactive components (eg, solvents) is from 2 to 2.5.

[0095] When used, the amount of optional component D can be, for example, 0 to 15 wt % in one embodiment, 0.01 to 10 wt % in another embodiment, and 0.1 to 5 wt % in yet another embodiment, based on the total amount of components in the adhesive composition.

[0096] In a broad embodiment, the method for producing the adhesive composition includes mixing the isocyanate and polyol components described above to form a curable adhesive composition. It is expected that two parts, the isocyanate part and the polyol component part, are used in the present invention. It is also expected that the isocyanate component and the polyol component of the disclosed adhesive composition can be separately prepared and stored if necessary until the adhesive composition needs to be used. In certain embodiments, the isocyanate component and the polyol component are each liquid at 25°C. When it is necessary to use the adhesive composition, the isocyanate component and the polyol component are usually contacted with each other and mixed together in a stoichiometric ratio (NCO / OH) between 1 and 2.5. It is expected that when these two components are contacted, a curing reaction is started, wherein the isocyanate group reacts with the hydroxyl group to form a carbamate linkage. The adhesive composition formed by contacting the two components can be referred to as a "curable mixture".

[0097] To form the adhesive composition, the mixing of the two components can be carried out at any suitable time in the process of forming the adhesive composition and the adhesive is applied to the substrate, such as before, during or as a result of the application process. All steps of the present invention can be carried out under ambient room temperature conditions. Heating or cooling can be adopted as required. And mixing can be carried out using a suitable conventional mixer, such as using an electrically, pneumatically or otherwise powered mechanical mixer.

[0098] In a general embodiment, a method for preparing a solvent-based adhesive composition of the present invention includes, for example, the steps of (1) providing an isocyanate component; (2) providing a polyol component; (3) mixing the two components to form a resin mixture; (4) diluting the resin mixture in a solvent to form a diluted resin mixture having an applied solid content of 25 wt % to 55 wt % in one embodiment, 30 wt % to 45 wt % in another embodiment, and 35 wt % to 40 wt % in yet another embodiment, based on the total weight of the diluted resin mixture; and (5) removing the solvent from the composition to form an adhesive composition, which is then applied to a substrate and then cured.

[0099] Before curing the resin mixture, the mixing ratio of the isocyanate component to the polyol component is 100:1 to 100:12 in one embodiment, and 100:4 to 100:10 in another embodiment.

[0100] Some of the advantageous properties exhibited by the solvent-based adhesive compositions of the present invention include, for example, (1) good adhesion properties; (2) fast curing; and (3) (a) no, or (b) low levels of, undesirable aromatic amines (such as MDA and TDA) that migrate into a food packaged in a package using the adhesive.

[0101] For example, the dry bond of the adhesive prior to sterilization testing may be greater than 500 g / 25 mm in one embodiment, 500 g / 25 mm to 2,500 g / 25 mm in another embodiment, 700 g / 25 mm to 2000 g / 25 mm in yet another embodiment, and 800 g / 25 mm to 1,800 g / 25 mm in yet another embodiment.

[0102] For example, the bond of the adhesive after 1 hour sterilization testing at 121° C. may be greater than 200 g / 25 mm in one embodiment, 200 g / 25 mm to 2,500 g / 25 mm in another embodiment, and 300 g / 25 mm to 2,000 g / 25 mm in yet another embodiment. The bond may depend on the type of film substrate used, and in some embodiments, the film may bond when a failure mode occurs before bonding after testing the substrate.

[0103] The curing time of the adhesive may be from 1 day to 8 days in one embodiment, from 1 day to 7 days in another embodiment, and from 2 days to 7 days in yet another embodiment.

[0104] Also disclosed herein is a method of forming a laminate using the adhesive composition of the present invention. In some embodiments, the adhesive composition, such as the adhesive composition discussed above, is liquid at 25°C. Even if the composition is solid at 25°C, it is acceptable to heat the composition as needed to convert the composition into a liquid state. Solvent is added to the mixed adhesive composition until the desired solid content is reached. Generally speaking, a solid content of 50% or more is used in one embodiment.

[0105] The adhesive composition of the present invention is suitable for bonding substrates together; and the adhesive composition can be used on a wide variety of single suitable substrates or multiple suitable substrates. The substrate can be a similar material or a different material. For example, in some embodiments, the substrate can be selected from high, low or medium density plastics (e.g., selected from the following types: polystyrene, polyethylene, ABS, polyurethane, polyethylene terephthalate, polybutylene terephthalate, polypropylene, polyphenylene, polycarbonate, polyacrylate, polyvinyl chloride, polysulfone and mixtures thereof), paper, wood and recycled wood products, polymer-coated substrates, wax-coated paperboard, cardboard, particle board, textiles, leather and metals (e.g., aluminum, iron and other non-ferrous metals), metallized plastics (e.g., metallized plastic films), etc.

[0106] The wet and dry bonding lamination of multiple substrate layers is possible. Adhesive composition can be applied to required substrate using conventional application technology, such as rotogravure, elastic relief printing, conventional or airless spraying, roll coating, brush coating, wire rod coating, scraping coating or, such as curtain coating, flood coating (flood-coating), bell-coating (bell-coating), disc coating (disc-coating) and dip coating coating method. Applying substrate with adhesive composition can be carried out on the whole surface of substrate or on a part of the surface of substrate, such as along the edge or in a discontinuous position. After being applied to substrate, such as by applying heat and air stream, or for removing some other suitable conventional methods of all residual solvents present in adhesive composition to dry adhesive composition.

[0107] The laminate comprising the solvent-based adhesive composition of the present invention can be formed by applying the adhesive to at least one of two different substrates and combining the substrates together so that the adhesive is disposed between the surfaces of the two substrates; and then curing the adhesive to form a bond between the two substrates. The substrate may include, for example, two separate films; and each of the films may be made of different materials or the same material. In general, a layer of the adhesive composition is applied to the film surface. In one embodiment, the thickness of the layer of the curable adhesive composition mixture applied to the film surface is 1 micron (μm) to 5 μm. As used herein, "film" is 0.5 mm or less in one dimension of the structure; and any structure that is 1 centimeter (cm) or longer in the other two dimensions of the structure.

[0108] In certain embodiments, the surface of another film is contacted with the layer of curable mixture to form an uncured laminate. The curable mixture is then cured or cured. The uncured laminate may be subjected to pressure, such as by passing through a roller, which may or may not be heated. The uncured laminate may be heated to accelerate the curing reaction.

[0109] Suitable substrates for forming laminated structures include films, such as paper, woven and nonwoven fabrics, polymer films, metal foils, metal-coated (metallized) polymer films and combinations thereof. The substrate is layered to form a laminated structure, wherein one or more of the substrates are adhered together according to the adhesive composition of the present invention. The film may optionally have a surface on which an image is printed with ink. The ink may contact the adhesive composition. In certain embodiments, the film is a polymer film and a metal-coated polymer film, and in a preferred embodiment, the film is a polymer film. "Polymer film" is a film made of a mixture of polymers or polymers. The composition of the polymer film is generally 80wt% or more of one or more polymers.

[0110] Adhesive compositions are particularly attractive for packaging and sealing applications. For example, plastic films, metal films, or metallized plastic films can be laminated with the adhesive compositions of the present invention (e.g., over their entire surface or at least a portion of their surface, such as along their edges or at intermittent locations) to form a laminate. In a preferred embodiment, the laminate is used, for example, to form a pouch made of at least two layers of film, wherein the adhesive is bonded between the two film layers. In some embodiments, food can be packaged for retort pouch preparation, or the resulting laminate can be used to seal or package some other article.

[0111] Examples

[0112] The following examples are presented to further illustrate the present invention in detail but should not be construed as limiting the scope of the claims. Unless stated to the contrary, implied by the context, or customary in the art, all parts and percentages are by weight, and all test methods are current as of the filing date of this disclosure.

[0113] The various raw materials or components used in the examples of the present invention (Inv.Ex.) and the comparative examples (Comp.Ex.) are described in the following Table 1:

[0114] Table I - Raw Materials

[0115]

[0116] Examples 1 and 2 and Comparative Examples A and B - Adhesives

[0117] The ingredients of the adhesive formulations used in the examples are described in Table II; and the adhesive formulations were prepared according to the following procedure:

[0118] General Procedure for the Preparation of Phosphate Ester Compounds

[0119] A 1 liter (L) multi-neck round bottom flask was dried in an oven, flushed with dry nitrogen (N2) for 30 minutes, and then charged with 150 grams (g) of VORANOL TM CP 450 polyether polyol was placed under a N2 purge at 70 mL / min. A syringe was loaded with 4 g of 115% polyphosphoric acid 20 (PPA). PPA was added dropwise to the polyether polyol under vigorous agitation. Minimal temperature rise was observed. The reactor contents were heated to 100°C for 1 hour and then cooled to 45°C. Subsequently, 40 g of ethyl acetate was added to the reactor, followed by the slow addition of 50 g of ISONATE TM 125M diisocyanate. A significant exotherm was controlled by applying ice batches to keep the reaction pot below 75°C, and a change from yellow 25 to amber was observed. The reactor was then maintained at 65°C for 1 hour, at which time the contents were cooled and packaged. The product had the following properties: 76.0% solids, a hydroxyl number (OHN) of 112 mg KOH / g, an acid value (AV) of 19.0 mg KOH / g, and a viscosity of 1,665 millipascal-seconds (mPa·s) at 25°C.

[0120] General Procedure for Preparing the Isocyanate Component (Component A)

[0121] The relevant ingredients used to prepare the isocyanate reactive components of Inventive Example 1 and Inventive Example 2 are described in Table II. Using the isocyanate component of Inventive Example 1 as a typical example of sample preparation, about 450 g of ADCOTE TM577 and about 50g MOR-FREE TM C33 was fed into a glass reactor. The reactor was heated to about 40° C. and the resulting mixture was stirred at 40° C. for about 30 minutes. Subsequently, the resulting sample mixture was packaged and placed in a storage container for subsequent use.

[0122] General Procedure for Preparing the Isocyanate Reactive Component (Component B)

[0123] The relevant ingredients used to prepare the isocyanate reactive components of Inventive Example 1 and Inventive Example 2 are described in Table II. Using the isocyanate reactive components of Example 1 as a typical example of sample preparation, about 400 g of VORANOL TM CP450, about 40g POLYG TM 30-112 and about 360 g of a phosphate compound were fed into a glass reactor. The reactor was heated to about 40° C. and the resulting mixture was stirred at 40° C. for about 30 minutes. Subsequently, the resulting sample mixture was packaged and placed in a storage container for subsequent use.

[0124] General Procedure for Preparing Adhesive Formulations

[0125] The relevant ingredients for preparing the adhesive formulation including the isocyanate reactive component, the isocyanate component and the solvent are described in Table II. Using the adhesive of Example 1 of the present invention as a typical example of the preparation of the adhesive formulation sample, about 1,000 g of the isocyanate component (component A), about 160 g of the isocyanate reactive component (component B) and about 1,460 g of ethyl acetate were loaded into a plastic container. The materials were mixed for 30 minutes at room temperature (about 25° C.) using a mechanical mixer to obtain the formulated adhesive of Example 1 of the present invention.

[0126] Table II - Adhesive Formulations

[0127]

[0128] *“Ad” stands for “Adhesive”.

[0129] Examples 3 and 4 and Comparative Examples C and D - Laminates

[0130] General Procedure for Preparing Laminates

[0131] Table III describes various films used in the examples to prepare laminates and laminate samples using the adhesives described in Table II above. Laminates based on solvent-based adhesives were produced at room temperature (about 25° C.) via a Nordmeccanica Labo Combi 400 pilot coater. The polymer films were corona treated prior to lamination, and aluminum (Al) foil was used without corona treatment. The coating weight of each laminate was maintained at about 4.9 grams per square meter (g / m 2 The prepared laminate is then cured in a controlled environment (eg at 50° C. at 25° C. and 50% relative humidity).

[0132] Each example was prepared using films including "Prelam", which is a 12 μm (48 gauge) polyester ("PET") film at 3.26 g / m 2 (2.00 lbs / ream) laminated to TM / 0.00035 mil Al foil of co-reactant F, available from the Dow Chemical Company; and a cast polypropylene ("CPP") film having a thickness of 3 mil (75 μm).

[0133] Table III - Film Laminates

[0134]

[0135] *“Ad” stands for “Adhesive”.

[0136] Membrane testing and measurement methods

[0137] Bond strength measurement

[0138] 90° T peel tests were performed on laminate samples cut into 15 mm wide and 1 inch (25.4 mm) long strips and were tested on a Thwing Albert equipped with a 50 Newton (N) loading cell. TM Pull at a rate of 4 inches / minute (101.6 mm / min) on a 1 inch (25.4 mm) strip on a QC-3A peel tester. Test three individual sample strips and average the result values ​​for the three strips. When the two films in the laminate are separated (peeled off), the average value of the force during the pull is recorded. If one of the films stretches or breaks, the maximum force or force at break is recorded. Failure mode (FM) or mode of failure (MOF) is recorded according to the following names:

[0139] "FS" stands for "Film Stretched".

[0140] "FT" means "film tear" (or rupture).

[0141] "DL" stands for "debonding," which means that the secondary film is separated from the primary film.

[0142] "AT" stands for "Adhesive Transfer," which means that the adhesive failed to adhere to the primary film and transferred to the secondary film.

[0143] "AS" stands for adhesive separation (or cohesive failure), which means that adhesive was found on both the primary and secondary films.

[0144] "MT" stands for "metal transfer," which indicates that metal transfer occurs from the metallized film to the secondary film.

[0145] "PMT" stands for "partial metal transfer".

[0146] Initial or "wet" adhesion was tested as soon as possible after the laminate was made. Additional T-peel tests were conducted at the time intervals indicated below.

[0147] Curing time

[0148] ATR was used to monitor the cure of the inventive and comparative adhesives in the foil / / CPP structure and the cure time for each adhesive used was determined when the isocyanate peak disappeared from the ATR spectrum.

[0149] General procedure for preparing sachets

[0150] The laminate was made from Prelam / / CPP as described above. One of the 9-inch by 12-inch (23 cm by 30.5 cm) sheets of the laminate was folded to obtain a double layer of about 9 inches by 6 inches (23 cm by 15.3 cm) so that the CPP film of one layer was in contact with the CPP film of the other layer. The edges of the folded laminate were trimmed on a paper cutter to obtain a folded sheet of about 5 inches by 7 inches (12.7 cm by 17.8 cm). The two long sides and one short side of the folded sheet were heat sealed at the edges to obtain a finished pouch with an inner dimension of 4 inches by 6 inches (10.2 cm by 15.2 cm). The heat seal was performed at 400°F (204°C) under a hydraulic pressure of 40 pounds per square inch (psi) (276 kilopascals [kPa]) for 1 second (s). Two or three pouches were made for each test.

[0151] Test and measurement methods for pouches

[0152] Sterilization performance test

[0153] The pouches prepared as described above were filled with 100 milliliters (mL) ± 5 mL of distilled water (DI water) or 1:1:1 sauce (a blend of equal weight parts of ketchup, vinegar, and vegetable oil) via the edge of the opening. Avoid splashing the filler into the heat seal area, as this may cause the heat seal to fail during the test. After filling, the pouch top was sealed in a manner that minimizes air trapped inside the pouch. The seal integrity on all four sides of the pouch was checked to ensure that there were no defects in the seal that would cause the pouch to leak during the test. Any defective pouches were discarded and replaced. In some cases, defects in the laminate were marked to identify whether new additional defects would be generated during the test.

[0154] The pouches containing the 1:1:1 sauce were then placed in a STERIS autoclave set at 121°C for 1 hour. The pouches were removed after sterilization and the extent of opening, blistering, delamination or leakage was compared with any of the previously marked defects. Observations were recorded. The pouches were cut open, emptied, and rinsed with soap and water. One or more one-inch (2.54 cm) strips were cut from the pouches and laminate bond strength was measured according to the standard bond strength test described above. This was done as soon as possible after removing the pouch contents. Visually inspect the interior of the pouches and record any visible defects.

[0155] Sterilization Regulatory Sample Preparation

[0156] 30.8 square inches (in 2 )(198.7 square centimeters (cm 2 ) laminate was each filled with 100 mL of 3% acetic acid per sample. The pouches were then transferred to a retort chamber where they were stored at 121° C. for 2 hours. After testing and after cooling to ambient temperature, the acetic acid was transferred to a polyethylene bottle.

[0157] Acetic acid samples were extracted and prepared for analysis within days of preparation and analyzed via liquid chromatography / mass spectrometry (LC / MS) within 24 hours of preparation.

[0158] The above testing and measurement procedures were performed on various samples prepared as described above. Table IV describes the properties of such samples.

[0159] Table IV - Properties of Film Samples

[0160]

[0161] *“Ad” stands for “Adhesive”.

[0162] For solvent-based adhesives, Inv.Ex.1 and Inv.Ex.2 exhibit good chemical resistance and temperature resistance. In addition, Inv.Ex.1 and Inv.Ex.2 exhibit fast curing characteristics (e.g., 3 days to cure at 50°C). Inv.Ex.1 and Inv.Ex.2 also exhibit low MDA content (e.g., <20 ppb after only 3 days of curing at 50°C).

[0163] Other embodiments

[0164] In one embodiment, the present invention includes a solvent-based biocide adhesive composition comprising: (A) at least one isocyanate compound, component A, wherein the at least one isocyanate compound, component A comprises: a blend of: (i) at least one aliphatic isocyanate and (ii) at least one aromatic isocyanate; and (B) at least one isocyanate-reactive component, component B, wherein the at least one isocyanate-reactive component, component B comprises: (i) at least one phosphate compound and (ii) at least one polyether polyol having an average molecular weight of less than 1,500 g / mol.

[0165] In another embodiment, at least one aliphatic isocyanate, component (i) of component A of the adhesive is selected from the group consisting of: polyisocyanates based on xylene diisocyanate, polyisocyanates based on 1,4- or 1,3-bis(isocyanatomethyl)cyclohexane, xylene diisocyanate isocyanurate, polyisocyanates based on hexamethylene diisocyanate, polyisocyanates based on diisocyanatodicyclohexylmethane, hexamethylene diisocyanate isocyanurate and mixtures thereof.

[0166] In another embodiment, at least one aromatic isocyanate, component (ii) of component A of the adhesive is selected from the group consisting of 1,3- and 1,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, polymeric isocyanates, and mixtures thereof.

[0167] In another embodiment, at least one aromatic isocyanate, component (ii) of component A of the adhesive is an isocyanate prepolymer comprising the reaction product of (α) at ​​least one isocyanate compound and (β) at least one polyol compound. And in another embodiment, at least one isocyanate compound, component (α) is selected from the group consisting of: aromatic polyisocyanates, aliphatic polyisocyanates, cycloaliphatic polyisocyanates, and mixtures thereof. And in another embodiment, the polyol compound, component (β) is selected from the group consisting of: polyether polyols, polyester polyols, polycaprolactone polyols, polyacrylates, polycarbonate polyols, natural oil-based polyols, and mixtures thereof.

[0168] In another embodiment, the molecular weight of the polyether polyol, component (β) is less than 5,000 g / mol. And in another embodiment, the molecular weight of the polyester polyol, component (β) is greater than 1,500 g / mol.

[0169] In another embodiment, the at least one isocyanate compound is free of solvent and the isocyanate content of component A is from 1 wt % to 25 wt %.

[0170] In another embodiment, at least one phosphate compound, component (i) of component B of the adhesive is selected from the group consisting of a phosphate compound having the following structure (I):

[0171]

[0172] Where R 1 is an organic group, where R 1 may or may not have one or more additional pendant -OH groups, wherein R 1 may or may not have one or more additional side groups of structure (I), and wherein the -OH group and two or more of the one or more groups of structure (I) may or may not be attached to R 1 a phosphate compound containing a carbamate bond; and mixtures thereof. And in another embodiment, at least one phosphate compound, component (i) of component B of the adhesive has a content of 0.1 wt % to 30 wt %.

[0173] In another embodiment, the at least one polyether polyol, component (ii) of component B of the adhesive is selected from the group consisting of polypropylene glycol, polytetramethylene ether glycol, polybutylene oxide-based polyols, mixtures thereof, and copolymers thereof.

[0174] In another embodiment, the at least one isocyanate-reactive component, Component B of the adhesive further comprises (iii) at least one polyester polyol having an average molecular weight of less than 1,500 g / mol.

[0175] In another embodiment, the at least one polyester polyol, component (iii) of component B of the adhesive is selected from the group consisting of aliphatic polyester polyols, aromatic polyester polyols, copolymers of aliphatic polyester polyols and aromatic polyester polyols, polycarbonate polyols, polycaprolactone polyols, and mixtures thereof.

[0176] In another embodiment, at least one polyester polyol, component (iii) of component B of the adhesive is: (1) a reaction product of a polyacid and a polyol, (2) a reaction product of phosgene or a carbonate monomer and a polyol; or (3) produced by ring-opening polymerization of a cyclic ester compound.

[0177] In another embodiment, the adhesive of the present invention further comprises: (C) a solvent selected from the group consisting of ethyl acetate, methyl ether ketone, toluene and a mixture thereof.

[0178] In another embodiment, the adhesive of the present invention further comprises: (D) an additive selected from the group consisting of a catalyst, a surfactant, a leveling agent, a defoaming agent, a rheology modifier, a color pigment, and a mixture thereof.

Claims

1. A solvent-based bactericidal adhesive composition comprising: (A) at least one isocyanate compound, component A, comprising: a blend of: (i) at least one aliphatic isocyanate selected from: polyisocyanates based on xylene diisocyanate, polyisocyanates based on 1,4- or 1,3-bis(isocyanatomethyl)cyclohexane, xylene diisocyanate isocyanurate, polyisocyanates based on hexamethylene diisocyanate, polyisocyanates based on diisocyanatodicyclohexylmethane, hexamethylene diisocyanate isocyanurate and mixtures thereof, and (ii) at least one aromatic isocyanate, which is an isocyanate prepolymer comprising the reaction product of: (α) at ​​least one isocyanate compound and (β) at least one polyol compound; and (B) at least one isocyanate-reactive component, component B, comprising: (i) at least one phosphate compound and (ii) at least one polyether polyol having an average molecular weight of less than 1,500 g / mol.

2. The adhesive composition according to claim 1, wherein the at least one phosphate compound, component (i) of component B is selected from the group consisting of: a phosphate compound having the following structure (I): Where R 1 is an organic group, where R 1 may or may not have one or more additional pendant -OH groups, wherein R 1 may or may not have one or more additional side groups of structure (I), and wherein the -OH group and two or more of the one or more groups of structure (I) may or may not be attached to R 1 the same atom of ; a phosphate compound containing a carbamate bond; and a mixture thereof.

3. The adhesive composition of claim 1, wherein the at least one polyether polyol, component (ii) of component B, is selected from the group consisting of polypropylene glycol, polytetramethylene ether glycol, polybutylene oxide-based polyols, mixtures thereof, and copolymers thereof.

4. The adhesive composition of claim 1, wherein the at least one isocyanate-reactive component, Component B, further comprises (iii) at least one polyester polyol having an average molecular weight of less than 1,500 g / mol.

5. The adhesive composition of claim 1, wherein the at least one polyester polyol, component (iii) of component B, is selected from the group consisting of aliphatic polyester polyols, aromatic polyester polyols, copolymers of aliphatic polyester polyols and aromatic polyester polyols, polycarbonate polyols, polycaprolactone polyols, and mixtures thereof.

6. A method for producing a solvent-based polyurethane bactericidal adhesive composition for use in producing laminates, comprising admixing: (A) at least one isocyanate compound; Component A comprising: a blend of: (i) at least one aliphatic isocyanate selected from: polyisocyanates based on xylene diisocyanate, polyisocyanates based on 1,4- or 1,3-bis(isocyanatomethyl)cyclohexane, xylene diisocyanate isocyanurate, polyisocyanates based on hexamethylene diisocyanate, polyisocyanates based on diisocyanatodicyclohexylmethane, hexamethylene diisocyanate isocyanurate and mixtures thereof, and (ii) at least one aromatic isocyanate, which is an isocyanate prepolymer comprising the reaction product of: (α) at ​​least one isocyanate compound and (β) at least one polyol compound; and (B) at least one isocyanate-reactive component, component B, comprising: (i) at least one phosphate compound and (ii) at least one polyol comprising at least one polyether polyol having an average molecular weight of less than 1,500 g / mol.

7. A multilayer laminate comprising: (a) at least the first layer; (b) at least a second layer; and (c) a bactericidal adhesive composition according to claim 1 disposed between the first layer and the second layer; wherein the adhesive is cured to bond the first layer to the second layer.

8. A method for producing a laminate comprising the steps of: (I) applying the bactericidal adhesive composition according to claim 1 to at least a portion of the surface of the first layer and / or the second layer; (II) contacting the first layer and the second layer such that the adhesive is disposed between the first layer and the second layer; and (III) curing the adhesive to form a laminate comprising the first layer bonded to the second layer via the cured adhesive.

9. A container for sterilization packaging, comprising the laminate according to claim 7.

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