Isocyanate-free laminating adhesive

Abstract

To provide a non-isocyanate-based adhesive that can advantageously be used in combination with a one-shot method to overcome the problems of isocyanate-based adhesives regarding application viscosity and pot-life stability.SOLUTION: Provided are: an epoxy terminated polyester; an adhesive formulation including the epoxy terminated polyester and a curative composition; and a laminating adhesive prepared from the adhesive formulation.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to adhesive formulations and their preparation, as well as to methods of using such adhesive formulations. More specifically, the present invention relates to a method for making a laminate using an amine-based curing agent. Non-isocyanate solvent-free laminating adhesives, including solvent-free epoxy-terminated polyesters Regarding the adhesive formulation, the adhesive formulation is suitable for one-shot coating / lamination process. It is suitable for use in [Background technology]

[0002] Solvent-free polyurethane adhesives are well known. In general, such adhesives are preferred. In the presence of commonly used additives such as suitable catalysts and / or adhesion promoters, a polyol It is prepared by mixing reactive chemical components such as olefins and isocyanates. Polyurethane adhesives are a useful class of laminating adhesives. Such adhesives include: A liquid composition containing a polyol and an isocyanate component, such an adhesive is They are also called two-part curable adhesives. Two-part curable adhesives are used for a variety of purposes, such as: It is useful as an adhesive for bonding films together to form laminates. The adhesives are useful in the packaging industry, especially in making flexible food packages.

[0003] To date, solvent-free polyurethane adhesives have been used in traditional solvent-free coating and lamination applications. In such a conventional process, the polyol compound is The adhesive and the isocyanate compound constitute an adhesive system, formulation, or composition, which comprises Also called a two-part adhesive system. In the traditional process, polyol and isocyanate are mixed. The compounds are mixed together and applied to a primary web (first film), and then the primary web is laminated to a secondary web (second film). Thereafter, the combined adhesive / web structure is cured. Thus, for use in conventional solventless coating / lamination processes the mixed adhesive system must have (1) an appropriate application viscosity, and (2) appropriate pot life stability.

[0004] As used herein, "application viscosity" means the initial viscosity of the formulation immediately before applying the adhesive formulation as a coating onto a substrate at the application temperature. Generally, the application viscosity is typically in the range of about 1,000 millipascal seconds (mPa·s ) to 5,000 mPa·s or less (≦) at an application temperature of about 40 degrees Celsius (°C) to 60 °C. As used herein, "pot life stability" means that the initial viscosity of the adhesive formulation does not double (i.e., does not increase by a factor of two) in about 40 minutes (min) during the coating / lamination process.

[0005] Another solventless coating and lamination process known in the art is referred to as the "one-shot duplex coating / lamination process" (referred to herein as the "one-shot process"), and the adhesive systems used in such processes are also solventless isocyanate-based adhesive systems. Prior art teaching solventless isocyanate-based adhesive systems for use in the one-shot process includes, for example, WO20171996 (A 1). In the one-shot process, two components (part A and part B) of the base resin are applied independently to two separate films. That is, part A is applied to the primary web ​Part A is applied to the film (web), part B is applied to the secondary film (web), and then , the primary film and the secondary film are joined together during the nip step of the lamination process . The mixing of part A and part B occurs during the nip step. By applying the two components of the adhesive system separately and independently of each other without pre-mixing the two components, and generating the mixing in the nip step of the process, the constraints on the pot life stability and the need to finely tune the adhesive system to have the controlled mixed coating viscosity as described above are eliminated.

[0006] Alternatives to solventless isocyanate-based adhesive systems have been developed in recent years, which are solventless alternative curable (non-isocyanate) adhesive systems based on aliphatic or cycloaliphatic epoxy-terminated polyesters cured with amine-based hardeners as described in U.S. Patent Nos. 9,751,977, 9,752,066, 9,701,786, and 9,701,787. Advantages of solventless epoxy-terminated polyester-based adhesive systems (i.e., isocyanate-free adhesive systems) over solventless isocyanate-based adhesive systems (i.e., isocyanate-containing adhesive systems) include, for example, (1) since the epoxy-based system is isocyanate-free, the use of this adhesive system eliminates the possibility of operator / worker exposure to isocyanates, (2) the use of an adhesive system that does not contain aromatic isocyanates eliminates the possibility of generating potentially mutagenic or carcinogenic aromatic amines as hydrolysis products that could potentially migrate into the food contained in the package made using the adhesive system, and (3) the use of aliphatic or cycloaliphatic epoxides in the adhesive system potentially ​ undesirable aromatic epoxides such as bisphenol A-epoxy resin, an endocrine disruptor, are not introduced into packages used in the food industry, enabling a curing chemistry which is mentioned.

SUMMARY OF THE INVENTION

PROBLEMS TO BE SOLVED BY THE INVENTION

[0007] Advantageously used in combination with the one-shot method, it is possible to overcome the problems of prior art isocyanate adhesives regarding coating viscosity and pot life stability, and to provide a non-isocyanate adhesive, as well as an improved process for laminate production is desired.

[0008] A general embodiment of the present invention is directed to a novel epoxy-terminated polyester composition comprising an epoxy-terminated polyester having the following structure (I).

Chemical formula

[0009] In a preferred embodiment, the two -R 1 groups of the above structure (I) can be the same or different, and each R group can have the following structure (II). 1

Chemical formula

[0010] In another preferred embodiment, the group -R 2 - of the above structure (II) is a divalent organic group having less than 50 carbon atoms, and the group G- has the following structure

Chemical formula

[0011] Another embodiment of the present invention is directed to a process for producing the above epoxy - terminated polyester. object.

[0012] Still another embodiment of the present invention is directed to an adhesive formulation comprising (A) the above epoxy - terminated polyester and (B) a curing agent composition.

[0013] Still another embodiment of the present invention is directed to a process for producing the above adhesive formulation. object.

[0014] Yet another embodiment of the present invention is directed to an adhesive for laminates prepared from the above adhesive formulation. object.

[0015] Yet another embodiment of the present invention is directed to a process for producing a laminate, and this process comprises (I) providing an epoxy - terminated polyester; (II) providing a curing agent composition; (III) coating a first film substrate with the epoxy - terminated polyester; (IV) coating a second film substrate with the curing agent composition; (V) laminating the first film and the second film together, wherein (IV) coating a second film substrate with the curing agent composition; (V) laminating the first film and the second film together, wherein the epoxy - terminated polyester on the first film contacts the curing agent composition on the second film, and an in - situ reaction occurs between the epoxy - terminated polyester on the first film and the curing agent composition on the second film, resulting in a bond between the first film and the second film. the epoxy - terminated polyester on the first film contacts the curing agent composition on the second film, and an in - situ reaction occurs between the epoxy - terminated polyester on the first film and the curing agent composition on the second film, resulting in a bond between the first film and the second film. the epoxy - terminated polyester on the first film contacts the curing agent composition on the second film, and an in - situ reaction occurs between the epoxy - terminated polyester on the first film and the curing agent composition on the second film, resulting in a bond between the first film and the second film. the epoxy - terminated polyester on the first film contacts the curing agent composition on the second film, and an in - situ reaction occurs between the epoxy - terminated polyester on the first film and the curing agent composition on the second film, resulting in a bond between the first film and the second film. formed, having a bonding layer disposed between a first film and a second film, a first film and a second film are formed to form a bonded laminate structure, laminating steps, including.

[0016] Still other embodiments of the present invention are directed to laminates produced by the above process, and flexible packages prepared from such laminates.

[0017] In a preferred embodiment, the present invention is directed to a process for producing a laminate that utilizes a solventless alternative curing (non-isocyanate curing) adhesive system in combination with a one-shot method. subject.

[0018] Among other objects of the present invention, a novel adhesive formulation is provided by introducing a novel monomer such as tetraethylene glycol into a polyester backbone, and the resulting adhesive formulation has an optimal coating viscosity. Also, as described in the following examples, the molecular weight of the polyester backbone of the adhesive, even if it is a high molecular weight, does not reduce the adhesive strength of the adhesive formulation on various laminate substrates, so it increases (in some cases, for example, the molecular weight doubles). The increase in the molecular weight of the polyester backbone of the adhesive formulation of the present invention does not impair the adhesive strength of the adhesive formulation of the present invention. Further, the adhesive formulations of the examples of the present invention have a lower mixing ratio of epoxy-terminated polyester to amine curing agent compared to the formulations of the comparative examples, and such a lower mixing ratio contributes to the higher adhesive strength of the adhesive formulations of the examples of the present invention for various laminate structures. (in some cases, for example, the molecular weight doubles). ) The increase in the molecular weight of the polyester backbone of the adhesive formulation of the present invention does not impair the adhesive strength of the adhesive formulation of the present invention. Further, the adhesive formulations of the examples of the present invention have a lower mixing ratio of epoxy-terminated polyester to amine curing agent compared to the formulations of the comparative examples, and such a lower mixing ratio contributes to the higher adhesive strength of the adhesive formulations of the examples of the present invention for various laminate structures. compared to the formulations of the comparative examples, and such a lower mixing ratio contributes to the higher adhesive strength of the adhesive formulations of the examples of the present invention for various laminate structures. such a lower mixing ratio contributes to the higher adhesive strength of the adhesive formulations of the examples of the present invention for various laminate structures. product.

DETAILED DESCRIPTION OF THE INVENTION

[0019] "Dicarboxylic acid" is a compound containing two carboxyl (-COOH) groups .

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

[0021] "Carboxylic acid-terminated polyester" is a compound that is a polyester and a dicarboxylic acid is. Non-limiting examples of suitable polyester polyols include diols, polyols (e.g., triols, tetrols), dicarboxylic acids, polycarboxylic acids (e.g., tri carboxylic acids, tetracarboxylic acids), hydroxycarboxylic acids, lactones, and polycondensates of combinations thereof. Carboxylic acid-terminated polyesters can also be derived from the corresponding polycarboxylic anhydrides or the corresponding polyester esters of lower alcohols instead of free polycarbox ylic acids.

[0022] "Ether group" is a moiety containing an oxygen atom bonded to two alkyl or aryl groups is.

[0023] "Substituted ether group" refers to an ether group in which one or more hydrogen atoms bonded to any carbon of an alkyl or aryl are substituted with another group such as phosphate, hydroxy, and combinations thereof

[0024] "Polyamine" is a compound having two or more amine groups, and the amine groups can be primary or secondary, or mixtures thereof

[0025] "Diamine" is a compound having exactly two amine groups, and the diamine is two primary ​​​​​a primary amine group, two secondary amine groups, or one primary amine group and one secondary amine group may have.

[0026] An "aliphatic group" is a chemical group containing only carbon atoms and hydrogen atoms and not containing an aromatic ring is.

[0027] An "alicyclic group" is an aliphatic group containing one or more cyclic structures.

[0028] An "alkyl group" is an aliphatic group having no double bond. Examples of the alkyl group include monovalent and divalent alkyl groups such as a methylene group, a methyl group, an ethylene group, an ethyl group, as well as larger alkylene and alkyl groups.

[0029] A "cycloalkyl group" is an alkyl group containing one or more cyclic structures.

[0030] An "aromatic group" is any group having an aromatic ring.

[0031] An "aliphatic amine" is an amine in which the nitrogen atom of each amine group is bonded to a carbon atom that is part of an aliphatic group is.

[0032] An "aromatic amine" is an amine in which the nitrogen atom of each amine group is bonded to a carbon atom that is part of an aromatic ring is.

[0033] When the ratio is referred to as "X:1 or more" in this specification, it means that the ratio is Y:1 where Y is equal to or greater than X. For example, when the ratio is referred to as 3:1 or more, the ratio can be 3:1 or 5:1 or 100:1, but cannot be 2:1. Similarly, when the ratio is referred to as "W:1 or less" in this specification, it means that the ratio is Z:1 where Z is equal to or less than W. The ratio is Z:1, where Z is less than or equal to W. For example, when the ratio is mentioned as being less than 15:1 it can be 15:1 or 10:1 or 0.1:1, but it cannot be 20:1.

[0034] A "solventless adhesive" is an adhesive composition that lacks a solvent or substantially lacks a solvent.

[0035] The acid value is a measure of the amount of carboxylic acid present in a component or composition. The acid value is the number of milligrams of potassium hydroxide required to neutralize the free carboxylic acid present in 1 gram (g) of a substance (e.g., a polyol). The acid value unit is milligrams of potassium hydroxide per gram (mg KOH / g). The acid value (AV) is measured according to ASTM D 1386 / 7.

[0036] The "epoxy equivalent weight (EEW)" is measured according to ASTM D 1652.

[0037] The "amine number" is measured according to ASTM D2074-07 for the test method of the total, primary, secondary, and tertiary amine values of fatty amines by an alternative indication method.

[0038] The "viscosity" is measured at 25 °C and 40 °C according to ASTM D2196. The viscosity is reported in the unit of mPa·s, which is equivalent to the unit of centipoise.

[0039] Size exclusion chromatography (SEC) analysis The weight average molecular weight (M w ) and the number average molecular weight (M n ) are measured using a gel permeation chromatography - (GPC) system. The "Z average molecular weight" (M z ​​​​​) is the third mo lar mass average. M z is also measured using a GPC system.

[0040] M n , M w , and M z are calculated according to the following formulas (I), (II), and (III ), respectively,

Chemical formula

Chemical formula

[0041] The content of species where the M w of the polyol is less than 500 grams per mole (g / mol) per mole, and M w is less than 1000 g / mol is measured using the "GPC One" software available from PolymerChar Inc. and using the following formula (V) , where Wf

Chemical formula

[0042] The composition of the present invention is an epoxy-terminated polyester having the following structure (I).

Chemical formula

[0043] In the above structure (I), the two -R 1 groups may be the same or different, each R 1 group has the following structure (II).

Chemical formula

[0044] In the above structure (II), the group -R 2- is a divalent organic group having less than 50 carbon atoms, and the group G- has the following structure,

Chemical formula

[0045] a divalent alkyl group. In addition to one or more compounds having structure (I), the composition of the present invention may also contain one or more compounds having the following structure (III),

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0046] In a preferred embodiment, the group -R of the above structure (III) 2 - is a group having the following structure (IV)

Chemical formula

[0047] In the above structure (IV), the number p is 0 to 20 in one embodiment, 0 to 10 in another embodiment, and 0 to 5 in yet another embodiment. Each -R -, each -R 3 -, each -R 4 - and each -R 5 - are independent of other divalent organic groups. Within a single -R 2 - group, when p is 2 or more, the various -R 3 - groups can be identical to each other or different from each other Within a single -R 2 - group, when p is 2 or more, the various -R 4 - groups can be identical to each other or different from each other.

[0048] In a preferred embodiment, -R 3 - is selected from one or more divalent aliphatic groups, one or more divalent aromatic hydrocarbon groups, or mixtures thereof. Among the aliphatic groups, -R 3 - is an alkyl group in one embodiment, -R 3 - is a straight-chain or branched-chain alkyl group in another embodiment, and -R 3 - is a straight-chain alkyl group in yet another embodiment. Among the aliphatic groups, -R 3 - is a group having one or more carbon atoms in one embodiment, -R 3 - ​​In another embodiment, it is a group having 2 or more carbon atoms, -R 3 - is, in yet another embodiment, a group having 3 or more carbon atoms. Among the aliphatic groups, -R - is, in one embodiment, a group having 12 or fewer carbon atoms, -R 3 - is, in one embodiment, a group having 8 or fewer carbon atoms, -R - is, in another embodiment, a group having 6 or fewer carbon atoms. Among the aliphatic groups, -R 3 - is, in another embodiment, a group having 8 or fewer carbon atoms, -R - is, in yet another embodiment, a group having 6 or fewer carbon atoms. Among the aliphatic groups, -R 3 - is, in yet another embodiment, a group having 6 or fewer carbon atoms. Among the aliphatic groups, -R - is, in a preferred embodiment, -CH2CH2CH2CH2- 3 - is, in a preferred embodiment, -CH2CH2CH2- H2CH2CH2-.

[0049] Among the aromatic groups, a preferred embodiment includes an aromatic group having the following structure,

Chemical formula

Chemical formula

[0050] In a preferred embodiment, the group suitable for -R 5 - in the above structure (IV) is the same group as the group suitable for -R 3 -. The group -R 5 - can be different from all -R 3 - groups, or the group -R 5 - can be the same as one or all of the -R 3 - groups.

[0051] In another preferred embodiment, the group -R 4 - is either an aliphatic group or an aliphatic ether group. The aliphatic ether group has the following structure (V), and has the following structure (V).

Chemical formula

[0052] In some embodiments (referred to herein as "mixed polyester" embodiments) p is greater than 1, and some of the -R 3 - groups are not the same as some of the other -R 3 - groups. In some mixed polyester embodiments, -R - has the following structure (VI) 2 and. and.

Chemical formula

[0053] The group -R 3 - and -R 4 - and -R 5 - are as defined above in this specification and q can be 0 or more in one embodiment, and q is 1 or more in another embodiment. Further in another embodiment, q is 0 to 9, and in yet another embodiment is 1 to 4. - R 6 - suitable groups are the same as those suitable for -R 4 -. The groups suitable for -R 7 - are the same as those suitable for -R 3 -. In some mixed polyester embodiments (referred to herein as "M P1" embodiments), -R 5 - is -R 3- is the same as, -R 6 - is -R 4 - is the same as, -R 7 - is, -R 3 - is different from. In some embodiments of MP1 , all -R 4 - groups are identical to each other, and in other embodiments of MP1, some - R 4 - groups are different from other -R 4 -s. In some embodiments of the mixed polyester (referred to herein as the "MP2" embodiments), -R 5 - is, -R 7 - is the same as, -R 6 - is, -R 4 - is the same as, -R 7 - is, -R 3 - is different from. In some embodiments of MP2 , all -R 4 - groups are identical to each other, and in other embodiments of MP2, some -R 4 - groups are different from other -R 4 -s.

[0054] Other preferred embodiments are as follows: (a) Embodiments where p = 0, (b) Embodiments where p is 1 or more and all -R 3 - groups are identical to each other, all -R 4 - groups are identical to each other, and -R 5 - is the same as -R 3 - in the embodiment, (c) Embodiments of MP1, and (d) can be selected from embodiments of MP2.

[0055] In structure (II), j is 1 or more in one embodiment. In structure (II) , j is 5 or less in another embodiment, 4 or less in yet another embodiment, and further In another embodiment, it is 3 or less, and in still another embodiment, it is 2 or less. Structure (II ) in which j is preferably 1 in a preferred embodiment.

[0056] In Structure (II), -R 21 - is, in a general embodiment, a divalent alkyl group There is. In a preferred embodiment, -R 21 - has 2 or more carbon atoms, and in another embodiment it has 3 or more carbon atoms. In still another embodiment, -R 21 - has 6 or fewer carbon atoms, and in still another embodiment it has 5 or fewer carbon atoms, and in still another embodiment it has 4 or fewer carbon atoms. In still another embodiment, -R 21 - is , having 3 carbon atoms. Among the embodiments where -R 21 - has 3 carbon atoms, in a preferred embodiment, -R 21- is selected from the following structures (VII), (VIII), and (I X).

Chemical formula

Chemical formula

Chemical formula

[0057] In some embodiments, one polyester has a -R - group having one group having structure (VII), (VIII), 21 or (IX), and a mixture of polyesters may exist, and the -R 21 - group has different structures having (VII), (VIII), or (IX) Another polyester, which is the base, may be present.

[0058] In structure (V), when j is 1 or more, -R 22 A suitable structure for - is -R 21 The same as the suitable structure for -. The group -R 22 - may be the same as -R 21 - or -R 21 - may be different from -R 22 When j is 2 or more, each -R 22 - - may be the same as all other -R 22 - groups, or some -R 22 - groups may be different from other -R - groups. In a preferred embodiment, all -R 22 - groups have the same number of 22 carbon atoms as all other -R - groups. In another preferred embodiment, -R 21 - has the same number of carbon atoms as all -R 22 - groups. In yet another preferred embodiment, all -R - groups have 22 - three carbon atoms. In yet another preferred embodiment, at least one -R - has structure (VIII) or structure (IX). 22

[0059] The epoxy-terminated polyester of the present invention has an EEW of 275 or more in one embodiment, 350 or more in another embodiment , 400 or more in yet another embodiment. The epoxy -terminated polyester of the present invention has an EEW of 3,500 or less in one embodiment, 2 ,500 or less in another embodiment, 2,000 or less in yet another embodiment. The number average molecular weight (M n) of the epoxy-terminated polyester of the present invention is 500 or more in one embodiment, n or In another embodiment, it is 1,000 or more. The M of the epoxy-terminated polyester of the present invention n is in one embodiment 8,000 or less, in another embodiment 6,000 or less, and in yet another embodiment 3,500 or less.

[0060] It is useful to characterize the level of species having a low number average molecular weight (e.g., 1,000 daltons [Da or less) present in the composition of the present invention. The level of species having a low number average molecular weight is defined as the weight percentage of species having a number average molecular weight of 1,000 Da or less, based on the total weight of the composition. The level of species having a low number average molecular weight is, in one embodiment, 55 percent (%) or less, in another embodiment 30% or less, and in yet another embodiment 2 5% or less. or less) present in the composition of the present invention. The level of species having a low number average molecular weight is 5% or less.

[0061] The composition of the present invention can be prepared by any conventional method known to those skilled in the art. Preferably in one embodiment, the method used to produce the composition involves reacting at least one diepoxide with at least one dicarboxylic acid. The diepoxide has the following structure (X). G-Q-G structure (X) G in structure (X) has the following structure,

Chemical formula

Chemical formula

[0062] group -R 2 - is as defined with respect to structure (IV). The reaction is structure (IV) A sufficient amount of the compound having structure (XI) is used to produce a compound having .

[0063] Generally, the compound of structure (XI) has an acid value of 110 or more in one embodiment, 1 20 or more, and in yet another embodiment 125 or more (which is measured as described below) . In other embodiments, the compound of structure (XI) has an acid value of 26 0 or less, 200 or less in another embodiment, and 175 or less in yet another embodiment. In a preferred embodiment, the compound of structure (XI) has a number average molecular weight of 430 or more in one embodiment, 560 or more in another embodiment, and 640 or more in yet another embodiment. In other preferred embodiments, the compound of structure (XI) has a number average molecular weight of 1,020 or less in one embodiment, 940 or less in another embodiment, and 900 or less in yet another embodiment. Mixtures of suitable compounds of structure (XI) can also be used.

[0064] In the reaction of at least one diepoxide with at least one dicarboxylic acid, the stoichiometric ratio of epoxy groups to carboxylic acid groups can be, for example, 3.1:1 or more in one embodiment, 2.9:1 or more in another embodiment, and 2.7:1 or more in yet another embodiment. In other embodiments, the stoichiometric ratio of epoxy groups to carboxylic acid groups can be, for example, 2:1 or less in one embodiment, 1.6:1 or less in another embodiment, and 1.3:1 or less in yet another embodiment.

[0065] The amount of the epoxy-terminated polyester composition used in the process of the present invention is, for example, 50 weight percent (wt%) to 95 wt% in one embodiment, 65 from 50 wt% to 85 wt%, and in yet another embodiment, it can be from 75 wt% to 80 wt%. At concentrations less than 50 wt% and greater than 95 wt%, the adhesive composition will not be able to cure completely to completion.

[0066] The viscosity of the epoxy-terminated polyester composition is generally, in one embodiment, from 1,0 00 mPa·s to 10,000 mPa·s at 75°C, and in another embodiment, from 10,000 mP a·s to 150,000 mPa·s at 25°C. The weight fraction less than 500 g / mol is, in one embodiment, less than 20%, in another embodiment, less than 10%, and in yet another embodiment, 5% or less. The weight fraction less than 1,000 g / mol is, in one embodiment, 30 % or less, in another embodiment, 20% or less, and in yet another embodiment, 10% or less must be.

[0067] Hardener compounds useful in the present invention include compounds having two or more groups capable of reacting with epoxy groups. Examples of hardener compounds include amino compounds . In a preferred embodiment, the amino compound is phenalkamine, phenalk amide, and amine-terminated amide resin. The amine-terminated amide resin is a reaction product of a dicarboxylic acid and di amine. Examples of dicarboxylic acids useful for forming the amine-terminated amide resin include dimer acids, which are reaction products of two molecules of unsaturated fatty acids . The unsaturated fatty acid has the structure R -COOH, where R 19 - is an aliphatic group having 8 or more carbon atoms 19 . Further, the aliphatic group can contain one or more carbon-carbon double bonds .

[0068] ​ Examples of diamines useful for forming amine-terminated amide resins include, for example, ethylenediamine, diethylenetriamine, triethylenetriamine, tetraethylenepentamine, piperazine, aminoethylpiperazine, isophoronediamine, xylylenediamine, and mixtures thereof. The curing agent useful in the present invention has at least 150 in one embodiment, at least 160 in another embodiment, and at least 170 amine numbers in yet another embodiment. In some embodiments, the curing agent component useful in the present invention has, for example, no more than 420 in one embodiment, no more than 380 in another embodiment, and no more than 360 amine numbers in yet another embodiment.

[0069] The viscosity of the curing agent compound is, in one embodiment, in the range of 1,000 mPa·s to 10,000 mPa·s at 75 °C, and in another embodiment, in the range of 50,000 mPa·s to 100,000 mPa·s at 25 °C.

[0070] The amount of the curing agent compound used in the process of the present invention can be, for example, 5 wt% to 50 wt% in one embodiment, 15 wt% to 35 wt% in another embodiment, and 20 wt% to 25 wt% in yet another embodiment. Concentrations less than 5 wt% and greater than 50 wt% will result in an adhesive composition that may not cure completely.

[0071] In some embodiments, optionally, additives may be included in the adhesive composition. Examples of such additives include tackifiers, plasticizers, rheology modifiers, adhesion promoters, antioxidants, fillers, colorants, surfactants, solvents, and combinations of two or more thereof, but are not limited thereto. ​​​​​​​​​​

[0072] Generally, the solventless adhesive composition of the present invention comprises (a) an epoxy-terminated polyester composition, (b) a curing agent composition, and (c) any desired optional components, which are mixed together and reacted to form an adhesive bond when formulated. However, in a typical embodiment, the epoxy-terminated polyester of the solventless adhesive composition of the present invention, component (a), and the amine curing agent, component (b), are formulated and stored separately until it is desired to form a laminate structure. In a preferred embodiment, the epoxy-terminated polyester component and the amine curing agent component are in a liquid state at 25°C. If the components are solid at 25°C, the components can be heated as necessary to form them into a liquid state before use. The pot life of the adhesive composition is decoupled from the curing process, and the components can be stored indefinitely. Some examples of the process advantages of the adhesive formulations of the present invention include, for example, (1) the adhesive formulation having a good application viscosity, (2) the adhesive formulation having good pot life stability, and (3) the two reactive components that make up the adhesive formulation can be separated without concern for the pot life of the two components. For example, the application viscosity of the adhesive formulation can be, for example, 1,000 mPa·s to 5,000 mPa·s or less at an application temperature of 40°C to 60°C in one embodiment, and 1,200 mPa·s to 2,500 mPa·s at an application temperature of 40 °C to 60°C in another embodiment.

[0073] Some examples of the process advantages of the adhesive formulations of the present invention include, for example, (1) the adhesive formulation having a good application viscosity, (2) the adhesive formulation having good pot life stability, and (3) the two reactive components that make up the adhesive formulation can be separated without concern for the pot life of the two components.

[0074] For example, the application viscosity of the adhesive formulation can be, for example, 1,000 mPa·s to 5,000 mPa·s or less at an application temperature of 40°C to 60°C in one embodiment, and 1,200 mPa·s to 2,500 mPa·s at an application temperature of 40 °C to 60°C in another embodiment.

[0075] For example, as the pot life of the adhesive formulation, in one embodiment, for example, the viscosity of the adhesive formulation does not double or increase by more than double in 40 minutes. In another embodiment, the pot life is such that the viscosity of the adhesive formulation does not increase by 20% to 80% in 40 minutes. Examples thereof include those where the viscosity of the adhesive formulation does not double or increase by more than double in 40 minutes, or in another embodiment, the viscosity of the adhesive formulation does not increase by 20% to 80% in 40 minutes. Examples thereof include those where the viscosity of the adhesive formulation does not double or increase by more than double in 40 minutes, or in another embodiment, the viscosity of the adhesive formulation does not increase by 20% to 80% in 40 minutes. can be mentioned.

[0076] Examples of the operational advantages of the adhesive formulation of the present invention can include, for example, that the adhesive formulation does not cause exposure to toxic isocyanate compounds. Examples of the operational advantages of the adhesive formulation of the present invention can include, for example, that the adhesive formulation does not cause exposure to toxic isocyanate compounds.

[0077] Some examples of the performance advantages of the adhesive formulation of the present invention include, for example, (1 ) good adhesive strength to various types of films, and (2) the adhesive formulation is useful in all typical structures used in general and media performance applications. can be mentioned.

[0078] For example, as the adhesive strength of the adhesive formulation (fully cured after 14 days), in one embodiment, for example, it is 0.5 Newton per 15 millimeters (N / 15mm) to 4 N / 15mm per 15 millimeters, and in another embodiment, the adhesive strength is 0.7 N / 15mm to 3.5 N / 15mm. Examples of the adhesive strength include those where it is 0.5 Newton per 15 millimeters (N / 15mm) to 4 N / 15mm in one embodiment, and 0.7 N / 15mm to 3.5 N / 15mm in another embodiment.

[0079] A laminate containing the solventless adhesive composition of the present invention can be formed by first separately applying an epoxy - terminated polyester component to one of two different substrates, for example, two separate films, and an amine curing agent component to the other film. As used herein, a "film" has one dimension of the structure of 0.5 millimeters (mm) or less and the other two dimensions of the structure are both 1 centimeter (cm). A laminate containing the solventless adhesive composition of the present invention can be formed by first separately applying an epoxy - terminated polyester component to one of two different substrates, for example, two separate films, and an amine curing agent component to the other film. As used herein, a "film" has one dimension of the structure of 0.5 millimeters (mm) or less and the other two dimensions of the structure are both 1 centimeter (cm). A laminate containing the solventless adhesive composition of the present invention can be formed by first separately applying an epoxy - terminated polyester component to one of two different substrates, for example, two separate films, and an amine curing agent component to the other film. As used herein, a "film" has one dimension of the structure of 0.5 millimeters (mm) or less and the other two dimensions of the structure are both 1 centimeter (cm). A laminate containing the solventless adhesive composition of the present invention can be formed by first separately applying an epoxy - terminated polyester component to one of two different substrates, for example, two separate films, and an amine curing agent component to the other film. As used herein, a "film" has one dimension of the structure of 0.5 millimeters (mm) or less and the other two dimensions of the structure are both 1 centimeter (cm). or less, and the other two dimensions of the structure are both 1 centimeter (cm). The above is of any structure. The "polymer film" is a film made from a polymer or a mixture of polymers. The composition of the polymer film typically consists of one or more polymers in an amount of 80 weight percent or more.

[0080] In one embodiment, for example, the layer of component (a), which is an epoxy-terminated polyester, is applied to the surface of the first substrate. The thickness of the layer of the epoxy-terminated polyester component on the first substrate is generally, in a preferred embodiment, from 0.5 micrometers (μm) to 2.5 μm. The layer of component (b), which is an amine curing agent, is applied to the surface of the second substrate. The thickness of the layer of the amine curing agent component on the second substrate is generally, in a preferred embodiment, from 0.5 μm to 2.5 μm. By controlling the thickness of the layers applied to each substrate, the ratio of the two components can be controlled. In some embodiments, the mixing ratio of the epoxy-terminated polyester component to the amine curing agent component in the final adhesive composition can be 100:15 in one embodiment, 100:21 in another embodiment, and 100:40 in yet another embodiment. The adhesive composition of the present invention is more tolerant than conventional adhesives and can accommodate some coating weight errors (e.g., a coating weight error of up to about 10%).

[0081] Subsequently, the first and second substrates are passed through a vice, such as a nip roller, for applying external pressure to the first and second substrates. The supply of the first and second substrates to the nip roller is such that the surface of the first substrate containing the layer of the epoxy-terminated polyester component faces the surface of the second substrate containing the layer of the amine curing agent component, and the two components pass through the nip roller. ​​​​​​​​​​​​​​They are then brought into contact with each other. By combining the epoxy-terminated polyester component and the amine curing agent component together, a curable adhesive mixture layer is formed. When the surfaces of the first and second substrates are brought together, the thickness of the resulting curable adhesive mixture layer is generally, in one embodiment state, from 1 μm to 5 μm. The epoxy-terminated polyester component and the amine curing agent component are such that when the first and second substrates are brought together and the components come into contact with each other, they mix and begin to react with each other. The two substrates that are integrally in contact with each other indicate the start of the curing process of the solventless adhesive composition of the present invention.

[0082] Further mixing and reaction of the two components of the adhesive composition, namely the epoxy-terminated polyester component and the amine curing agent component, are achieved when the first and second substrates pass through various other rollers and finally when the first and second materials are fed to the rewinding roller. Since each of the substrates takes a longer or shorter path across each roller than the other substrate, further mixing and reaction occur when the first and second substrates pass through the rollers. In this way the two substrates move relative to each other and mix the components on each substrate. Such an arrangement of rollers in a coating apparatus is widely known in the art. Next the curable mixture is cured or becomes capable of being cured. Suitable substrates in the laminate structure include papers, woven and non-woven fabrics, polymer films

[0083] , metal foils, metal-coated (metallized) polymer films, and films such as combinations thereof . Some films may optionally have an adhesive coating. It has a surface on which an image is printed with ink that can come into contact with the composition. The substrate is laminated to form a laminate structure, and the adhesive composition according to the present invention adheres one or more of the substrates together .

[0084] After the lamination step, the laminated material is, in one embodiment, at ambient conditions ( 25 °C, 50% relative humidity), and cured from ambient conditions to high temperature conditions (up to 50 °C, 5 0% relative humidity). During the curing process, the laminated material is, in one embodiment, 0.1 4 megapascals (MPa) to 0.24 MPa, and in another embodiment, 0.17 MPa to 0.2 1 MPa of unwind pressure must be maintained.

[0085] In one embodiment, the lamination is used in flexible packaging applications. A package made using the laminate exhibits several advantageous properties. For example, due to the high green bond of these adhesive formulations compared to conventional solventless lamination adhesives, the package can be further processed (slit) within a shorter waiting time. These laminations adhere well to various types of barrier films, such as nylon, metallized films, etc., and thus the lamination can have a wide range of applications. For example, the solventless epoxy - terminated polyester adhesive system according to the present invention can be used in general - to - high - end

[0086] media performance applications that cover the range of common dry food packages for hot filling and retort applications. These applications are generally recognized by the US Food and Drug Administration (FDA) as uses from "FDA Condition B" to "FDA Condition H". ​​It is also stated that the adhesive formulation of the present invention complies with the safety regulations of the FDA and contains components recognized by the FDA.

Examples

[0087] The following examples are presented to explain the present invention in more detail, but should not be construed as limiting the scope of the claims. Unless otherwise indicated, all parts and percentages are by weight.

[0088] The various raw materials or components used in the examples (Inv.Ex.) and comparative examples (Comp.Ex.) of the present invention are described in Table I as follows.

Table 1

[0089] The various films used in the examples to prepare the laminate are described in Table II as follows.

Table 2

[0090] Preparation of Components for the Adhesive Formulation Synthesis Example 1 - Preparation of Carboxylic Acid-Terminated Polyester (Acid-PE-1) In this Synthesis Example 1, the carboxylic acid-terminated polyester (Acid-PE-1) is prepared using the components described in Table III. The polyester prepared in this Synthesis Example 1 is a precursor component used to produce the adhesive formulation of the present invention.

Table 3

[0091] ​​​​​​​Charge items 1 to 4 described in Table III above into the reactor at ambient temperature (about 25°C to 30°C). The reaction mixture is slowly heated to 100°C while stirring under nitrogen (N2). Next, raise the reaction temperature to 225°C and hold at 225°C. Monitor the AV and in-process viscosity when about 50% of the theoretical water has been generated. As used herein, the term "in-process viscosity" means the viscosity tested during the condensation reaction. Maintain the reactor at 225°C until the AV is less than about 80. Then cool the resin to below 125°C. After cooling the resin, add item 5 to the resin and maintain the resulting resin mixture at 125°C to 130°C for 0.50 hour (h). Then slowly raise the temperature of the reactor to 225°C, hold at 225°C, and apply a vacuum at about 435 millimeters of mercury (mm Hg) as needed to reduce the AV to the final target property. Monitor the AV and in-process viscosity and maintain the reaction at 225°C until the AV is less than 160. Then cool the resin to about 150°C, filter, and package.

[0092] The resulting product had the following final properties: AV 158.2, number average molecular weight (M n ) 550 g / mol, weight average molecular weight (M w ) 1,150 g / mol, Z average molecular weight (M z ) 1,850 g / mol, weight fraction below 500 Da 26.0%, weight fraction below 1,000 Da 55.1%, viscosity at 25°C 209,000 mPa·s.

[0093] Synthesis Example 2 - Polyester Carboxylic Acid-Terminated Polyester (Acid-PE-2) Carboxylic acid-terminated polyester (Acid-PE-2) was prepared from carboxylic acid-terminated polyester ​​​​​​​​Use the same procedure as described in Synthesis Example 1 for preparing Lu (Acid-PE-1), provided that in this Synthesis Example 2, the components described in Table IV are used and the AV before adding adipic acid is about 131. Prepare it, but in this Synthesis Example 2, use the components described in Table IV and the AV before adding adipic acid is about 131. is about 131. [Table 4]

[0094] Items 1 to 4 described in the above Table IV were charged into the reactor at ambient temperature. The reaction mixture was slowly heated to 100 °C while stirring under N2. Then, the reaction temperature was raised to 220 °C and maintained at 220 °C, and the AV and in-process viscosity were monitored when about 50% of the theoretical water was generated. The reactor was maintained at 220 °C until the AV was less than about 20. Then, the resin was cooled to less than 125 °C. After the resin was cooled, Item 5 was added to the resin and the resin mixture was maintained at 125 °C to 130 °C for 0.50 hour. Then, the temperature of the reactor was slowly raised to 225 °C and maintained at 225 °C to reduce the AV to the final target property. The AV and in-process viscosity were monitored and the reaction was maintained at 225 °C until the AV was less than 135. Then, the resin was cooled to about 150 °C, filtered, and packaged. and slowly heated to 100 °C while stirring under N2. Then, the reaction temperature was raised to 220 °C and maintained at 220 °C, and the AV and in-process viscosity were monitored when about 50% of the theoretical water was generated. The reactor was maintained at 220 °C until the AV was less than about 20. Then, the resin was cooled to less than 125 °C. After the resin was cooled, Item 5 was added to the resin and the resin mixture was maintained at 125 °C to 130 °C for 0.50 hour. Then, the temperature of the reactor was slowly raised to 225 °C and maintained at 225 °C to reduce the AV to the final target property. The AV and in-process viscosity were monitored and the reaction was maintained at 225 °C until the AV was less than 135. Then, the resin was cooled to about 150 °C, filtered, and packaged. and the AV and in-process viscosity were monitored when about 50% of the theoretical water was generated. The reactor was maintained at 220 °C until the AV was less than about 20. Then, the resin was cooled to less than 125 °C. After the resin was cooled, Item 5 was added to the resin and the resin mixture was maintained at 125 °C to 130 °C for 0.50 hour. Then, the temperature of the reactor was slowly raised to 225 °C and maintained at 225 °C to reduce the AV to the final target property. The AV and in-process viscosity were monitored and the reaction was maintained at 225 °C until the AV was less than 135. Then, the resin was cooled to about 150 °C, filtered, and packaged. The reactor was maintained at 220 °C until the AV was less than about 20. Then, the resin was cooled to less than 125 °C. After the resin was cooled, Item 5 was added to the resin and the resin mixture was maintained at 125 °C to 130 °C for 0.50 hour. Then, the temperature of the reactor was slowly raised to 225 °C and maintained at 225 °C to reduce the AV to the final target property. The AV and in-process viscosity were monitored and the reaction was maintained at 225 °C until the AV was less than 135. Then, the resin was cooled to about 150 °C, filtered, and packaged. Then, the resin was cooled to less than 125 °C. After the resin was cooled, Item 5 was added to the resin and the resin mixture was maintained at 125 °C to 130 °C for 0.50 hour. Then, the temperature of the reactor was slowly raised to 225 °C and maintained at 225 °C to reduce the AV to the final target property. The AV and in-process viscosity were monitored and the reaction was maintained at 225 °C until the AV was less than 135. Then, the resin was cooled to about 150 °C, filtered, and packaged. and the resin mixture was maintained at 125 °C to 130 °C for 0.50 hour. Then, the temperature of the reactor was slowly raised to 225 °C and maintained at 225 °C to reduce the AV to the final target property. The AV and in-process viscosity were monitored and the reaction was maintained at 225 °C until the AV was less than 135. Then, the resin was cooled to about 150 °C, filtered, and packaged. The temperature of the reactor was slowly raised to 225 °C and maintained at 225 °C to reduce the AV to the final target property. The AV and in-process viscosity were monitored and the reaction was maintained at 225 °C until the AV was less than 135. Then, the resin was cooled to about 150 °C, filtered, and packaged. The AV and in-process viscosity were monitored and the reaction was maintained at 225 °C until the AV was less than 135. Then, the resin was cooled to about 150 °C, filtered, and packaged. Then, the resin was cooled to about 150 °C, filtered, and packaged.

[0095] The resulting product had the following final properties: AV 131, and viscosity at 25 °C 237,300 mPa·s.

[0096] Synthesis Example 3 - Preparation of Carboxylic Acid-Terminated Polyester (Acid-PE-3) The carboxylic acid-terminated polyester (Acid-PE-3) was prepared using the same procedure as described in Synthesis Example 1 for preparing the carboxylic acid-terminated polyester (Acid-PE-1). Use the same procedure as described in Synthesis Example 1 for preparing Lu (Acid-PE-1), provided that in this Synthesis Example 2, the components described in Table IV are used and the AV before adding adipic acid is about 131. It is prepared, provided that in this Synthesis Example 3, the components described in Table V are used, and the AV before adding adipic acid is about 153. The AV before addition is about 153. [Table 5]

[0097] Items 1 to 4 described in Table V above were charged into the reactor at ambient temperature. The reaction mixture was slowly heated to 100 °C while stirring under N 2. Then, the reaction temperature was raised to 220 °C and maintained at 220 °C. When about 50% of the theoretically generated water had occurred, the AV and the in-process viscosity were monitored. The reactor was maintained at 220 °C until the AV was less than about 60. The resin was cooled to less than 125 °C, then Item 5 was added, and the resin mixture was maintained at 125 °C to 13 0 °C for 0.50 h. The temperature of the reactor was slowly raised to 225 °C and then maintained at 2 25 °C to lower the AV to the final target properties. The AV and the in-process viscosity were monitored, and the reaction was maintained at 225 °C until the AV was less than 160. The resin was cooled to about 150 °C, filtered, and packaged.

[0098] The resulting product had the following final properties: AV 153, M n 939 g / mol 、M w 1,707 g / mol, polydispersity 1.82, weight fraction 1 3.0% below 500 g / mol, weight fraction 33.7% below 1,000 g / mol, viscosity at 60 °C 1,440 mPa·s.

[0099] Preparation of Synthesis Example 4 - Carboxylic Acid-Terminated Polyester (Acid-PE-4) The carboxylic acid-terminated polyester (Acid-PE-4) was prepared from the carboxylic acid-terminated polyester Use the same procedure as described in Synthesis Example 1 for preparing Lu (Acid-PE-1), provided that in this Synthesis Example 4, the components described in Table VI are used and the AV before adding adipic acid is about 149. Prepare in the same way, except that in this Synthesis Example 4, the components described in Table VI are used and the AV before adding adipic acid is about 149. is about 149. [Table 6]

[0100] Items 1 to 3 described in Table VI above were charged into the reactor at ambient temperature. The reaction mixture was slowly heated to 100 °C while stirring under N2. Then, the reaction temperature was raised to 220 °C and maintained at 220 °C. When about 50% of the theoretical water was generated, the AV and the in-process viscosity were monitored. The reactor was maintained at 220 °C until the AV was less than about 60. The resin was cooled to less than 125 °C, then Item 4 was added, and the resin mixture was maintained at 125 °C to 130 °C for 0.50 hour. The temperature of the reactor was slowly raised to 225 °C and then maintained at 225 °C to reduce the AV to the final target properties. The AV and the in-process viscosity were monitored, and the reaction was maintained at 225 °C until the AV was less than about 160. The resin was cooled to about 150 °C, filtered, and packaged. The reaction mixture was slowly heated to 100 °C while stirring under N2. Then, the reaction temperature was raised to 220 °C and maintained at 220 °C. When about 50% of the theoretical water was generated, the AV and the in-process viscosity were monitored. The reactor was maintained at 220 °C until the AV was less than about 60. The resin was cooled to less than 125 °C, then Item 4 was added, and the resin mixture was maintained at 125 °C to 130 °C for 0.50 hour. The temperature of the reactor was slowly raised to 225 °C and then maintained at 225 °C to reduce the AV to the final target properties. The AV and the in-process viscosity were monitored, and the reaction was maintained at 225 °C until the AV was less than about 160. The resin was cooled to about 150 °C, filtered, and packaged. raised and maintained at 220 °C until about 50% of the theoretical water was generated, and the AV and the in-process viscosity were monitored. The reactor was maintained at 220 °C until the AV was less than about 60. The resin was cooled to less than 125 °C, then Item 4 was added, and the resin mixture was maintained at 125 °C to 130 °C for 0.50 hour. The temperature of the reactor was slowly raised to 225 °C and then maintained at 225 °C to reduce the AV to the final target properties. The AV and the in-process viscosity were monitored, and the reaction was maintained at 225 °C until the AV was less than about 160. The resin was cooled to about 150 °C, filtered, and packaged. The reactor was maintained at 220 °C until the AV was less than about 60. The resin was cooled to less than 125 °C, then Item 4 was added, and the resin mixture was maintained at 125 °C to 130 °C for 0.50 hour. The temperature of the reactor was slowly raised to 225 °C and then maintained at 225 °C to reduce the AV to the final target properties. The AV and the in-process viscosity were monitored, and the reaction was maintained at 225 °C until the AV was less than about 160. The resin was cooled to about 150 °C, filtered, and packaged. The obtained product had the following final properties: AV 149, M

[0101] The obtained product had the following final properties: AV 149, M n 994 g / mol , M w 1,888 g / mol, polydispersity 1.90, weight fraction 1 below 500 g / mol 1.3%, weight fraction 2 below 1,000 g / mol 27.4%, viscosity at 60 °C 1,052 mPa·s.

[0102] Synthesis Example 5 - Preparation of Epoxy-Terminated Polyester (ET-PE-1) In this Synthesis Example 5, D.E.R. (trademark) 731 epoxy diluent (1,4-butanedi ol diglycidyl ether), the acid-terminated polyester of Synthesis Example 1 (Acid-PE-1 ), and the catalyst described in Table VII are charged into the reactor at ambient temperature to prepare an epoxy-terminated polyester (ET-PE-1).

Table 7

[0103] The reactor was subjected to 4 N2 purge / vacuum cycles and maintained under a stable N2 flow. The resin mixture was slowly heated to a temperature of 135°C to 140°C. The reaction was maintained at 135°C to 140°C for about 0.50 h, then heated to 150°C to 155°C and maintained at 150°C to 155°C for about 1.5 h to 2 h, and then the AV and in-process viscosity were monitored. The reaction was maintained at 150°C to 155°C, and the AV and in-process viscosity were monitored until the AV was less than 1.0. Thereafter, when the AV was less than 1.0, the resin was transferred and packaged.

[0104] The resulting product had the following final properties: AV 0.19, EEW 487 g / mol, and viscosity at 25°C of 13,130 mPa·s. Under SEC analysis, the product had the following properties: M n 1,340 g / mol, M w 6,322 g / mol, polydispersity 4.72, weight fraction less than 500 g / mol 5.6%, and weight fraction less than 1,000 g / mol 19.2%.

[0105] Synthesis Example 6 - Preparation of Epoxy-Terminated Polyester (ET-PE-2) ​In this Synthesis Example 6, the D.E.R. (trademark) 731 epoxy diluent (1,4-butanedi ol diglycidyl ether), the acid-terminated polyester of Synthesis Example 2 (Acid-PE-2 ), and the catalyst described in Table VIII are charged into the reactor at ambient temperature to prepare an epoxy -terminated polyester (ET-PE-2).

Table 8

[0106] The reactor was subjected to 4 N2 purge / vacuum cycles and maintained under a stable N2 flow. The resin mixture was slowly heated to 135 °C to 140 °C. The reaction was maintained at 135 °C to 140 °C for about 0 .50 hours, then heated to 150 °C to 155 °C and maintained at 150 °C to 155 °C for about 1.5 to 2 hours, and then the AV and in-process viscosity were monitored. The reaction was maintained at 15 0 °C to 155 °C, and the AV and in-process viscosity were monitored until the AV was less than 1.0 . When the AV was less than 1.0, the resin was transferred and packaged.

[0107] The resulting product had the following final properties: AV 0.5, EEW 941.1 g / mol, and a viscosity of 112,400 mPa·s at 25 °C. Under SEC analysis, the product had the following properties: M n 2,787 g / mol, M w 13,028 g / mol, M z 38,951 g / mol, polydispersity 4.67, weight fraction less than 500 g / mol 1. 1%, and weight fraction less than 1,000 g / mol 7.8%.

[0108] Preparation of Synthesis Example 7 - Epoxy-Terminated Polyester (ET-PE-3) In this Synthesis Example 7, D.E.R. (trademark) 731 epoxy diluent (1,4-butanedi ol diglycidyl ether), the acid-terminated polyester of Synthesis Example 3 (Acid-PE-3 ), and the catalyst described in Table IX are charged into the reactor at ambient temperature to prepare an epoxy-terminated polyester (ET-PE-3).

Table 9

[0109] The reactor was subjected to 4 N2 purge / vacuum cycles and maintained under a stable N2 flow. The resin mixture was slowly heated to 135°C to 140°C. The reaction was maintained at 135°C to 140°C for about 0 .50 hours, then heated to 150°C to 155°C and maintained at 150°C to 155°C for about 1.5 hours to 2 hours, and then the AV and in-process viscosity were monitored. The reaction was maintained at 15 0°C to 155°C, and the AV and in-process viscosity were monitored until the AV was less than 1.0 . When the AV was less than 1.0, the resin was transferred and packaged.

[0110] The resulting product had the following final properties: AV 0.27, EEW 909.5 g / mol, and a viscosity of 1,434 mPa·s at 75°C. Under SEC analysis, the product had the following properties: M n 1,571 g / mol, M w 10,817 g / mol, polydispersity 6.81, a weight fraction of less than 500 g / mol of 8.9%, and a weight fraction of less than 1,000 g / mol of 16.5%.

[0111] Preparation of Synthesis Example 8 - Epoxy-Terminated Polyester (ET-PE-4) In this Synthesis Example 8, D.E.R. (trademark) 731 epoxy diluent (1,4-butanedi ​All of diglycidyl ether), the acid-terminated polyester of Synthesis Example 4 (Acid-PE-4 ), and the catalyst described in Table X are charged into the reactor at ambient temperature to prepare an epoxy-terminated poly ester (ET-PE-4).

Table 10

[0112] The reactor was subjected to 4 N2 purge / vacuum cycles and maintained under a stable N2 flow. The resin mixture was slowly heated to 135 °C to 140 °C. The reaction was maintained at 135 °C to 140 °C for about 0 .50 hours, then heated to 150 °C to 155 °C and maintained at 150 °C to 155 °C for about 1.5 hours to 2 hours, and then the AV and in-process viscosity were monitored. The reaction was maintained at 15 0 to 155 °C, and the AV and in-process viscosity were monitored until the AV was less than 1.0 ring. When the AV was less than 1.0, the resin was transferred and packaged.

[0113] The resulting product had the following final properties: AV 0.90, EEW 869.5 g / mol, and viscosity at 75 °C of 1,133 mPa·s. Under SEC analysis, the product had the following properties: M n 1,571 g / mol, M w 10,541 g / mol, polydispersity 6.72, weight fraction less than 500 g / mol of 8.9%, and weight fraction less than 1,000 g / mol of 15.1%.

[0114] Preparation of Synthesis Example 9 - Amine Hardener (AC-1) In this Synthesis Example 9, Unidyme (trademark) 22 dimer acid (AV = 192.9) and triethylenetetramine described in Table XI are charged into the reactor at ambient temperature to prepare an Prepare the amine curing agent (AC-1).

Table 11

[0115] The reactor was subjected to 4 N2 purge / vacuum cycles and maintained under a stable N2 flow. The resin mixture was slowly heated to 150 °C. The reaction was maintained at 150 °C to 155 °C for about 0.50 h and then heated to 200 °C to 205 °C and maintained at 200 °C to 205 °C for about 1.5 h to 2 h and then the generation of water was monitored. The reaction was maintained at 200 °C to 205 °C until no more water was distilled from the reactor. The resin was transferred and packaged at 150 °C.

[0116] The resulting product had the following final properties: amine number 169.64 (IPA titration) , viscosity at 25 °C 54,625 mPa·s, and viscosity at 40 °C 12,975 mPa· s.

[0117] Synthesis Example 10 - Preparation of Amine Curing Agent (AC-2) In this Synthesis Example 10, the amine curing agent (AC-2) is prepared by filling the reactor with PRIPOL™ 1017 dimer acid and the triethylenetetramine described in Table XII at ambient temperature.

Table 12

[0118] The reactor was subjected to 4 N2 purge / vacuum cycles and maintained under a stable N2 flow. The resin mixture was slowly heated to 150 °C. The reaction was maintained at 150 °C to 155 °C for about 0.50 h and then heated to 200 °C to 205 °C and maintained at 200 °C to 205 °C for about 1.5 h to 2 h The reaction was continued for 10 minutes, and then the evolution of water was monitored until no more water was distilled from the reactor. The reaction was maintained at 200° C.-205° C. The resin was transferred and packaged at 150° C.

[0119] The resulting product had the following final properties: Amine Number 352.3 (IPA titration); and viscosity at 75°C of 1,417 mPa·s. Under SEC analysis, the product had the following characteristics: Did:M n 567g / mol, M w 1,248g / mol, polydispersity 2.20, 50 29.2% weight fraction less than 0 g / mol, and 4% weight fraction less than 1,000 g / mol 8.8%.

[0120] General Procedure for Adhesive Lamination The plastic film is heated at a low power of about 0.14 kilowatts (kW) before lamination. The epoxy-terminated polyester and amine hardener were first The solids content was determined (10% to 25%) and dissolved in methyl ethyl ketone (MEK). Two methods have been employed to prepare the esters: (I) the conventional standard method; and (II) one-shot method.

[0121] (I) Standard Method Standard procedures typically involve dissolving an epoxy-terminated polyester solution in a specified amount of amine curing agent. The mixture was then premixed with the agent solution (see Table XIII below) and then passed through a Mayer rod (# 0) was used to manually coat the primary film, and then the temperature was set at 80°C. The primary film was dried in an oven for 1 minute. The primary film was then dried in an oil-based The coating was laminated to the secondary film on a laminator. The coating weight was approximately 1.58 g / m2 ~1.63 g / m 2 was controlled. At least five laminates (20 .3 cm × 27.9 cm) were prepared for each formulation, and these laminates had joining strips within the laminate to facilitate the joining strength test. An equal pressure was applied to the entire laminate sample by placing the laminate under a weight of 0.45 kg to 0.9 kg, and the laminate was cured at room temperature (about 25 °C) for 2 weeks.

[0122] (II) One-shot method In the one-shot method, an epoxy-terminated polyester solution was manually coated onto a primary film, while an amine curing agent solution was manually coated onto a secondary film. After drying in an oven at 8 0 °C for 1 minute, the primary film and the secondary film were laminated together in the same manner as the standard method. The coating weight was controlled to 1.8 g / m 2 . The following curing protocol was the same as that of the standard method protocol.

[0123] Joining strength measurement A 90-degree T-peel test was performed on laminate samples cut into 1-inch (2.54 cm) wide strips, and the samples were pulled at a speed of 10 inches / min (25.4 cm / min) with a Thwing Albert (trademark) QC-3A peel tester equipped with a 50 N loading cell. The joining strength measurement value in g / lin (gram / linear inch) was converted to N / 15 mm by multiplying by a conversion factor of 0.0057915. When the two films in the laminate separated ( peeled), the average of the forces during the pull was recorded. When one of the films stretched or broke ​​​​​​​​It was average. The defect form (FM) or the form of the defect (MOF) was recorded as follows . "FS" represents the stretching of the film. "FT" represents a tear or break in the film. "DL" represents delamination where the secondary film separates from the primary film. "AT" represents the transfer of the adhesive (the adhesive fails to adhere to the primary film and is transferred to the secondary film). "AS" represents a tear in the adhesive or an adhesion defect (the adhesive is seen on both the primary film and the secondary film).

[0124] Examples comparing the conventional standard lamination process and the one-shot method result in equivalent or slightly better performance via the one-shot method.

[0125] Examples 1 to 5 and Comparative Examples A to E The following Tables XIII and XIV summarize the mixing ratios of the investigated adhesive compositions .

Table 13

Table 14

[0126] Note that epoxy-terminated polyester resins (ET-PE-3 and ET-PE-4) based on or partially based on tetraethylene glycol are comparative examples. The comparative examples are outside the scope of the present invention where the use of tetraethylene glycol and the comparative examples is compared to the epoxy-terminated polyester (ET-PE-1 and ET-PE-2) resins of the present invention, as well as those based on the resins of U.S. Patent Nos. 9,751,977 and 9,752,066 and are inferior. has demonstrated poor adhesion performance.

[0127] Tables XV - XVIII summarize the adhesion performance of different adhesive systems in different laminate structures evaluated using a standard lamination process. The laminate of Example 1 had a coating weight of 1.63 g / m 2 and laminates 3 - 10 had a coating weight of 1 .58 g / m 2 .

[0128] Table XV summarizes the adhesion performance of laminates with a structure based on PET / / PE(GF - 19) using a standard coating process.

Table 15

[0129] Table XVI summarizes the adhesion performance of laminates with a structure based on nylon / / PE(G - 19) using a standard coating process.

Table 16

[0130] Table XVII summarizes the adhesion performance of laminates with a structure based on PRELAM (foil backed with Al) / / PET and PRELAM (foil backed with Al) using a standard coating process.

Table 17

[0131] Table XVIII summarizes the adhesion performance of laminates with a structure The adhesion performance of laminates having a structure based on the foiled / / PE (G-19) is required.

Table 18

[0132] Tables XIX to XXII summarize the adhesion performance of different adhesive systems in different laminate structures evaluated using the one-shot method. The laminate of Example 2 was prepared by 2 coating the secondary film with an epoxy terminated polyester resin (ET-PE-1) at a coating weight of 1.22 g / m 2 and coating the primary film with an amine curing agent (AC-1) at a coating weight of about 0.41 g / m (the coating weight of ET-PE- 1 / AC-1 corresponds to an adhesive mixing ratio of 30.26:9.9 or 75.3 2 :24.7), resulting in a coating weight of 0.41 g / m in the final laminate. The epoxy-terminated polyesters (ET-PE-1, ET-PE-2, ET-PE-3 , or ET-PE-4) were coated on the primary film and the amine curing agent (AC-2 ) was coated on the secondary film to prepare the laminates of Examples 3 to 10 , obtaining an adhesive coating weight of 1.79 g / m 2 . The coatings of each component were adjusted to obtain an appropriate coating weight that matches the adhesive mixing ratio.

[0133] Table XIX summarizes the adhesion performance of laminates having a structure based on PET / / PE (G-19) evaluated using the one-shot method.

Table 19

[0134] Table XX summarizes the adhesion performance of laminates having a structure based on nylon / / PE(G-19) using the one-shot method.

Table 20

[0135] Table XXI summarizes the adhesion performance of laminates having a structure based on PRELAM (foil backed with Al) / / PET and PRELAM (foil backed with Al).

Table 21

[0136] Table XXII summarizes the adhesion performance of laminates having a structure based on PRELAM (foil backed with Al) / / PE(G-19) using the one-shot method.

Table 22

Claims

1. An epoxy-terminated polyester containing a polymer having the following structure, 【Chemical Formula 1】 In the formula, two -R １ groups are the same or different, and each R １ group has the following structure (I I) having, 【Chemical Formula 2】 In the formula, the group -R of the above structure (II) ２ - is a divalent organic group having less than 50 carbon atoms a machine group, and the group G− has the following structure, [Chemical Formula 3] The number j is from 0 to 5, and the group -R ２１ - is a divalent alkyl group, and the group -R ２２ - is , a divalent alkyl group, an epoxy-terminated polyester.

2. (A) The epoxy-terminated polyester according to claim 1, and (B) a curing agent composition, an adhesive formulation comprising.

3. The adhesive formulation has an application viscosity of about 1,000 mPa·s to 5, 000 mPa·s or less at an application temperature of 40°C to 60°C, and the adhesive formulation has the pot life stability such that the viscosity of the adhesive formulation does not double or increase by a factor of two in 40 minutes. The adhesive formulation according to claim 2, having.

4. A process for preparing an adhesive formulation, (A) The epoxy-terminated polyester according to claim 1, and (B) a curing agent composition, the process comprising mixing.

5. An adhesive for lamination prepared from the adhesive formulation according to claim 2.

6. A process for producing a laminate, (I) providing an epoxy-terminated polyester; (II) providing a curing agent composition; (III) coating a first film substrate with the epoxy-terminated polyester step; (IV) coating a second film substrate with the curing agent composition; (V) laminating the first film and the second film together, wherein the epoxy-terminated polyester on the first film contacts the curing agent composition on the second film, and an in-situ reaction occurs between the epoxy-terminated polyester on the first film and the curing agent composition on the second film to form a bond between the first film and the second film, and a laminated structure having a bonding layer of an adhesive for lamination disposed between the first film and the second film is formed, a step of laminating, comprising.

7. A laminate produced by the process according to claim 6.

8. A flexible package prepared from the laminate according to claim 7. ​ ​

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