Amorphous copolyester resin for use as a cold seal adhesive and coating composition.

Abstract

The present invention provides a method for bonding substrate surfaces together without the presence of heat, and a cold seal adhesive that is compostable and possesses cohesive force. [Solution] A method for bonding substrate surfaces together, comprising applying a copolyester resin mixture to the surfaces and bringing the surfaces into contact with each other in a non-heated state to form a cold seal. The copolyester resin is sulfonable and is a reaction product of at least two diols containing ethylene glycol in a mole fraction of at least about 0.25, and (b)(i) a sulfonomer in a mole fraction of at least 0.02, preferably at least 0.07; (ii) at least one aromatic diacid or diester; and (iii) at least three diacids or diesters, including at least one aliphatic diacid or diester.

Description

[Technical Field]

[0001] The present invention relates to a method for bonding substrate surfaces together without the presence of heat (i.e., using a cold seal adhesive). The present invention further relates to copolyester resins and coating compositions incorporating such copolyester resins for application to substrate surfaces and for bonding such substrate surfaces without the presence of heat. Such coating compositions are particularly suitable for use in bonding food packaging materials, consumer goods, and medical devices. [Background technology]

[0002] The circular economy is changing the direction of the future development and evolution of flexible packaging. Sustainability has become a key slogan within flexible packaging. There is growing interest in sustainable solutions, such as biodegradable, compostable, and recyclable packaging, within the flexible packaging industry. Various developments aim to improve one of these key factors and incorporate it into the final product. Monomaterial packaging is one direction the market is heading. This makes sorting and recycling, composting, or biodegradability easier. Within sustainability, polyester (PET) technology is a clear component for monomaterial packaging because it has several advantages, including providing good moisture barrier and gas barrier properties. Adhesives for PET films are gaining momentum due to this changing market scenario.

[0003] Adhesives suitable for use as sealants should possess sufficient cohesive energy between polymer chains. Therefore, medium to high molecular weight copolyesters would be a good choice for use as adhesives. Sealing can be carried out in two ways: (1) with heat, or (2) without heat. Heat-seal adhesives seal by applying heat, pressure, and residence time to a substrate to which the adhesive has been applied. Sealing can occur by the adhesive itself (self-sealing), or it can be bonded to another substrate, such as a tray stock. Cold-seal adhesives are self-sealing adhesives that, when pressure is applied, thereby forming a strong bond to the substrate to which it has been applied. Only mechanical energy is required to initiate sealing. No heat is required, and sealing is carried out with minimal strain. Cold seals are a type of pressure-sensitive adhesive that is soft enough to flow over the adherend (also called the substrate in this specification) and hard enough to resist flow when stress is applied.

[0004] Important commercial applications for cold seal adhesives include food packaging for heat-sensitive products such as candies, chocolates, and snack foods like potato chips. Another desirable application is the packaging of medical products, where the adhesive must provide a strong seal to maintain sterility, but at the same time, it must not be resealable. Any contamination of the flexible substrate containing the adhesive will affect the formation of the bond. Therefore, adhesives with low tackiness (or adhesives that can be used with an over-lacquer or release lacquer) are preferred.

[0005] Converted rolls of heat-seal or cold-seal adhesives must not be tacky or prone to tackiness, or they must be able to be mixed with an anti-tack agent. If tackiness occurs, the adhesive will adhere to the opposite side of the flexible substrate to which it is coated. Therefore, attention must be paid to the tackiness or tendency to tackiness of these adhesives. Under certain conditions, high tackiness exceeding 50 grams / linear inch (gli) is not ideal. If tackiness is minimal or nonexistent, flexible substrates with the coated adhesive on them can be ideally stored in roll form without sticking to each other, i.e., without tackling.

[0006] Conventional technology describes the use of natural rubber latex and acrylic resins as self-sealing adhesives that adhere only to themselves (i.e., as cold seals). These chemicals have been used for decades in the production of confectionery packaging. There is a desire to use alternative chemicals for cold seals that may be compostable. Such adhesives would preferably adhere very well to polar substrates as well.

[0007] U.S. Patent No. 6,221,448 discloses a cold seal composition comprising 10 to 100% by weight of at least one homogeneous ethylene / alpha-olefin interpolymer. This composition can be coated onto various substrates, is less tacky when supplied as a roll, and exhibits a wide range of bonding strengths.

[0008] U.S. Patent No. 4,902,370 discloses a synthetic-based cold seal adhesive prepared from an acrylic copolymer or styrene-butadiene rubber as the base polymer and a styrene-acrylic copolymer as the secondary polymer. The adhesive is non-tacky, can be stored for long periods, and can be used as a substitute for natural rubber-based cold seal adhesives.

[0009] International Publication No. 2017 / 042178 discloses a cold seal adhesive based on an aqueous polyurethane dispersion, prepared either without a catalyst or using a very small amount of an organic catalyst.

[0010] U.S. Patent No. 3,779,993 discloses water-dissipatable polyesters and polyamides made from monomers containing sulfonate groups in the form of metal salts. These polyesters and polyamides are useful as adhesives and can be dissolved, dispersed, or otherwise dissipated in cold water, hot water, or aqueous solutions. [Overview of the project] [Problems that the invention aims to solve]

[0011] To date, the only type of technology used for cold seal adhesives is not based on technology that is considered compostable, although in some cases it may be recyclable. As changes occur in the flexible packaging industry, there is a need to develop water-based cold seal adhesives that are performance-wise compostable to replace current technologies. Newly developed copolyester resins can enable compostable and cohesive cold seal adhesives. These copolyesters bond well to a variety of substrates, including polar substrates.

[0012] For the purpose of addressing at least some of the needs described herein and not met by various prior art documents, the present invention provides a method for bonding a first substrate surface to a second substrate surface, comprising the steps of: applying a copolyester resin mixture to the first substrate surface and the second substrate surface; and bringing the first substrate surface into contact with the second substrate surface to form a laminate, wherein the method is carried out at ambient temperature. [Means for solving the problem]

[0013] One embodiment of the present invention provides a composition comprising an amorphous copolyester resin comprising the reaction products of: (a) at least two diols comprising ethylene glycol in a mole fraction of at least about 0.25, preferably at least about 0.5, most preferably at least about 0.7, and at most about 0.97, preferably at most about 0.95, and most preferably at most about 0.92 mole fractions based on the total amount of diols; and (b) at least three diacids or diesters comprising: (i) at least one sulfomer comprising at least 0.02, preferably at least 0.03, more preferably at least 0.05, more preferably at least 0.07, preferably at least 0.08, most preferably at least 0.09, and (ii) at least one sulfomer, comprising in a mole fraction of at most 0.2, more preferably at most 0.15, and most preferably at most 0.12; (ii) at least one aromatic diacid or diester; and (iii) at least one aliphatic diacid or diester, wherein the ratio of aromatic diacid or diester to aliphatic diacid or diester is between about 75 / 25 and about 45 / 55, preferably between about 72 / 28 and about 48 / 52, more preferably between about 70 / 30 and about 50 / 50, and most preferably between about 68 / 32 and about 50 / 50, and the amorphous copolyester resin having a glass transition temperature between about -25°C and about 15°C, preferably between about -18°C and about 10°C, most preferably between about -10°C and about 5°C, or most preferably between about -20°C and about -5°C or between about -20°C and about -5°C. In a preferred embodiment, ethylene glycol is present in an amount of about 0.65 to 0.97, preferably about 0.75 to 0.95, and most preferably about 0.80 to 0.92 mole fractions based on the total amount of diols.

[0014] In one embodiment of the present invention, the composition comprises an amorphous copolyester resin comprising: (a) at least two diol residues comprising ethylene glycol, and (b) at least three diacid or diester residues comprising: (i) at least one sulfonomer; (ii) at least one aromatic diacid or diester; and (iii) at least one aliphatic diacid or diester, wherein: (1) the copolyester resin has a bound mole fraction of ethylene glycol residues between about 0.5 and about 0.9, most preferably at least about 0.65 and about 0.85, based on the diols; and (2) the bound mole ratio of aromatic diacid or diester / aliphatic diacid or diester residues (bound (3) The ratio is between about 75 / 25 and about 45 / 55, preferably between about 72 / 28 and about 48 / 52, more preferably between about 70 / 30 and about 50 / 50, and most preferably between about 68 / 32 and about 50 / 50; and (3) the amorphous copolyester resin has a glass transition temperature between about -25°C and about 15°C, preferably between about -18°C and about 10°C.

[0015] In yet another embodiment of the present invention, the composition comprises the amorphous copolyester resin described above and a solvent which can be selected from the group consisting of water, an organic solvent, or both. [Modes for carrying out the invention]

[0016] The present invention can be more easily understood by referring to a detailed description of certain embodiments and examples of the present invention.

[0017] The term "copolyester" should be understood to mean a synthetic polymer prepared by reacting one or more difunctional carboxylic acids or esters (i.e., diacids or diesters) with one or more difunctional hydroxyl compounds (i.e., diols).

[0018] In one embodiment of the present invention, a composition comprising an amorphous copolyester resin is provided. As used herein, the term “amorphous” means a substantially amorphous substance having a heat of fusion of, for example, less than 5 joules / gram, preferably less than 1 joule / gram, and most preferably substantially zero joules / gram. The heat of fusion values ​​presented herein were measured according to ASTM E793-01 “Standard Test Method for Enthalpies of Fusion and Crystallization by Differential Scanning Calorimetry”.

[0019] One embodiment of the present invention, which aims to provide a method for bonding the surface of a first substrate to the surface of a second substrate, includes the steps of: applying a copolyester resin mixture to the surface of the first substrate and the surface of the second substrate; and bringing the surface of the first substrate into contact with the surface of the second substrate to form a laminate, wherein the method is carried out at ambient temperature. In one embodiment, the substrate is a single substrate, and its first and second surfaces are different regions of the substrate. For example, the substrate may be a film used as packaging material for food, such as candy, or for consumer packaging products, such as soap, feminine care products, and diapers. The two surfaces may also be used as the mating surfaces of the film to form a seal of the packaging material, such as an edge seal. Alternatively, the first and second surfaces may be different substrates. The materials of these substrates can be varied over a wide range, and standard substrates include, for example, PET and metallized PET, as well as compostable or biodegradable substrates such as polylactic acid, polybutylene succinate (PBS), cellulose-based substrates, and polyhydroxyalkanoates (PHA). The substrate may also be roll material for making bags, pouches, or sachets. The machine used to produce the sealed packaging may be a variety of suitable machines or systems, such as a horizontal filling and sealing machine or a vertical filling and sealing machine. The master roll of packaging is manufactured at the first site and then shredded into child rolls for use by the copacker or brand owner. This is the final packaging, in which consumers will find ready-to-eat packaged food. In any case, an adhesive is applied to both surfaces, which functions as a cold-seal adhesive, i.e., an adhesive that joins itself using pressure without the presence of heat.

[0020] The step of applying the copolyester resin mixture to the first and second substrate surfaces may be carried out by various methods. For example, the copolyester resin mixture may be applied to the first and second substrate surfaces by various known methods, such as: dipping, roll coating, reverse roll coating, spraying, knife-over-roll coating, air knife coating, gravure printing, gravure printing pattern coating, or slot die process. Similarly, forming a laminate by bringing the first substrate surface into contact with the second substrate surface can be carried out by various known methods, such as applying pressure using serrated jaws in some cases. The contact step is preferably carried out with sufficient time and pressure to bond the first substrate surface to the second substrate surface. Preferably, the resulting bond has sufficient bond strength to achieve an average value higher than 300 grams / linear inch (gli), as measured by a bond strength test performed on an Instron 5543 tensile testing machine in accordance with ASTM D903, under ambient conditions (25°C, 50% RH) and a peel rate of 12 inches / min. The lower and upper limits of the usable range would be 200 to 500 grams / linear inch (gli), and the lower and upper limits of the preferred range would be 300 to 400 grams / linear inch (gli). To avoid misunderstanding, it should be added that in this test, both bond formation and peeling are performed under ambient conditions. In one embodiment of the present invention, the contact step time is about 0.1 seconds to about 20 seconds, preferably about 0.2 seconds to about 2 seconds, and the pressure of the contact step is about 40 psi to about 120 psi, preferably about 60 psi to about 100 psi. Both the coating step and the contact step are performed at ambient temperature. When used herein, the ambient temperature is approximately 25°C. As will be described in more detail below, the copolyester resin may be a single copolyester resin reaction product or a blend of two or more copolyester resin reaction products. In addition, the copolyester resin mixture may be a solution or a dispersion.

[0021] In one embodiment of the present invention, the copolyester resin is sulfonated. This means that the copolyester resin is a reaction product of a plurality of monomers including at least one sulfo monomer. The sulfo monomer is difunctional, and is preferably those dicarboxylic acids or esters containing a metal sulfonate group, or a glycol containing a metal sulfonate group, or a hydroxy acid containing a metal sulfonate group. The cation of the sulfonate salt may be NH4 or a metal ion such as Li + , Na + , K + , Mg ++ , Ca ++ , Cu ++ , Ni ++ , Fe ++ , Fe +++ . When stability in water is desired, monovalent cations such as NH4 + , Li + , Na + , and K + are preferred. Preferably, the sulfo monomer includes an -SO3M group bonded to an aromatic nucleus, wherein M is hydrogen, NH4, or a metal ion. The difunctional monomer component may be either a dicarboxylic acid or a diol adduct containing the -SO3M group. In a preferred embodiment, the sulfo monomer is the sodium salt of dimethyl 5-sulfoisophthalate or 5-sulfoisophthalic acid.

[0022] In one embodiment of the present invention, the composition is a mixture of a copolyester resin and a solvent, the solvent being selected from the group consisting of water, organic solvents, or both. The blend of the resin and solvent is also referred to herein as a coating composition. As used herein, the solvent may be a single solvent or a mixture of several solvents. The solvent used will depend on the solubility characteristics of the coating composition before solvation and the end use. Depending on these factors, a wide range of solvents can be used. The solvent or solvent mixture is preferably selected to give a coating composition with appropriate viscosity and to dissolve the copolyester resin with minimal heating and stirring. It is preferable that the solvent be selected from the group consisting of acetone, isopropyl alcohol, tetrahydrofuran, and 1,3-dioxolane, or mixtures thereof. In preferred embodiments, the solvent is water and an organic solvent, the organic solvent including water-soluble organic solvents such as acetone, isopropyl alcohol, or mixtures thereof. It has been found that acetone sufficiently reduces the viscosity of the coating composition. In a preferred embodiment, the solvent is present in an amount corresponding to approximately 20-40% solids by weight, and the weight ratio of water to organic solvent (preferably isopropyl alcohol) is approximately 80:20 to approximately 60:40. In another embodiment, the solvent consists of water.

[0023] In one embodiment of the present invention, the copolyester resin has an overall (average) glass transition temperature between about -25°C and about 15°C, preferably between about -18°C and about 10°C, most preferably between about -10°C and 5°C, or in other embodiments, most preferably between about -20°C and about -5°C. The glass transition temperatures described herein were measured using differential scanning calorimetry (DSC) in accordance with ASTM E-794-01, except that the test method was modified in that a scanning temperature of 15°C / min was used instead of 10°C / min. If the copolyester resin is a single copolyester resin reaction product (i.e., a copolyester resin formed by a single esterification or transesterification reaction scheme), then its overall (average) glass transition temperature is the glass transition temperature of that single copolyester resin reaction product. If the copolyester resin is a blend of two or more single copolyester resin reaction products, its overall (average) glass transition temperature is the weighted average of the glass transition temperatures of the copolyester resin reaction products used to form the blend. For example, a blend of 75% by weight of a first copolyester resin reaction product having a glass transition temperature of -20°C and 25% by weight of a second copolyester resin reaction product having a glass transition temperature of 20°C would have an overall (average) glass transition temperature of -10°C. This method also applies when determining all the properties of the copolyester resins used herein. Therefore, even if one of the copolyester resin reaction products used in a blended product has a value outside the desired range, if the blend, when combined with another copolyester resin reaction product, has an overall (average) value within the desired range, it can be a composition of the present invention.

[0024] As used herein, the term "reaction product" refers to various reaction products of esterification or transesterification of various monomers used to prepare the copolyester (i.e., monomers charged into the reaction), or monomers formed in situ during the reaction by the interaction of the used monomers (including oligomers or final copolyesters that are reacted for a certain acid value and / or viscosity).

[0025] One embodiment of the present invention provides a copolyester resin comprising the reaction products of: (a) at least two diols, each containing ethylene glycol in a mole fraction of at least about 0.25, preferably at least about 0.5, most preferably at least about 0.7, and at most about 0.97, preferably at most about 0.95, and most preferably at most about 0.92 mole fractions based on the total amount of diols; and (b) at least three diacids or diesters comprising the following: i) at least one sulfonomer comprising at least 0.02, preferably at least 0.03, more preferably at least 0.05, more preferably at least 0.07, more preferably at least 0.08, most preferably at least 0.09, and at most 0.2, more preferably at most 0.15, most preferably at most 0.12 mole fractions based on the diacid or diester; (ii) at least one aromatic diacid or diester; and (iii) at least one aliphatic diacid or diester. In other embodiments, the at least one sulfonomer is present in a mole fraction of at least 0.07, preferably at least 0.08, more preferably at least 0.09 mole fractions based on the diacid or diester.In other embodiments, the copolyester resin comprises the reaction products of: (a) at least two diols, each containing ethylene glycol in a mole fraction of at least about 0.5, preferably at least about 0.6, more preferably at least about 0.7, most preferably at least about 0.75 to at most about 0.95, more preferably at most about 0.9, based on the diol; and (b) at least three diacids or diesters, each containing: (i) at least one sulfomer, each containing in a mole fraction of at least 0.02, preferably at least 0.03, more preferably at least 0.05, more preferably at least 0.07, more preferably at least 0.08, most preferably at least 0.09, and at most 0.2, more preferably at most 0.15, most preferably at most 0.12, based on the diacid or diester; (ii) at least one aromatic diacid or diester; and (iii) at least one aliphatic diacid or diester. In preferred embodiments, the ratio of aromatic diacid or diester to aliphatic diacid or diester is between about 75 / 25 and about 45 / 55, preferably between about 72 / 28 and about 48 / 52, more preferably between about 70 / 30 and about 50 / 50, and most preferably between about 68 / 32 and about 50 / 50.

[0026] In a preferred embodiment, the monomers used may include the following: a. At least one sulfonomer selected from at least one of sodium dimethyl-5-sulfoisophagate (DMSIP) or 5-sulfoisofalic acid (SIPA), preferably DMSIP; b. At least one aliphatic diacid or diester selected from the group consisting of succinic acid, sebacic acid, azelaic acid, and adipic acid, preferably sebacic acid; c. At least one aromatic diacid or diester is selected from the group consisting of at least one of isophthalic acid, dimethyl terephthalate, terephthalic acid, and dimethyl isophthalate, preferably isophthalic acid and dimethyl terephthalate; and d. At least two diols, one of which is ethylene glycol, and a second diol selected from the group consisting of at least one of neopentyl glycol, diethylene glycol, trimethylolpropane, and cyclohexanedimethanol, preferably neopentyl glycol.

[0027] It has been found that such monomer combinations provide a balance of performance across a wide range required for some of the applications described herein. For use as a cold seal, the resin produced from these monomers provides the cohesive force described above. Furthermore, the copolyester resin solvates to water and organic solvents, such as isopropyl alcohol or acetone, up to a maximum solids content of 40%. In addition, its glass transition temperature is within a desirable range for use as a cold seal adhesive.

[0028] In a preferred embodiment, the monomer used as a charge in the reaction may contain the following in the following amounts: a. Dimethyl-5-sulfoisophthalate sodium in a mole fraction of about at least 0.02, preferably at least 0.03, more preferably at least 0.05, more preferably 0.07 to about 0.2, preferably about 0.08 to about 0.15, and most preferably about 0.09 to about 0.12, based on the total amount of diacids and diesters; b. Isophthalic acid is present in a mole fraction of about 0.02 to 0.2, preferably about 0.03 to about 0.15, and most preferably about 0.05 to about 0.1, based on the total amount of diacids and diesters; c. Dimethyl terephthalate is present in a mole fraction of about 0.25 to 0.55, preferably about 0.3 to about 0.5, and most preferably about 0.35 to about 0.45, based on the total amount of diacids and diesters; d. Sebacic acid is present in a mole fraction of about 0.18 to 0.4, preferably about 0.2 to 0.38, and most preferably about 0.25 to 0.35, based on the total amount of diacids and diesters; e. Ethylene glycol is present in an amount of about 0.65 to 0.97, preferably about 0.75 to about 0.95, most preferably about 0.80 to about 0.92 mole fractions based on the total amount of diols; and f. Neopentyl glycol is present in an amount of about 0.03 to 0.25, preferably about 0.05 to about 0.2, and most preferably about 0.08 to about 0.15 mole fractions based on the total amount of diols. g. In some cases, diethylene glycol is present in a mole fraction of about 0.01 to 0.2, preferably about 0.01 to 0.15, and most preferably about 0.05 to 0.12, based on the total amount of diols.

[0029] The mole fraction for each monomer is calculated by dividing the number of moles of monomer added to the reaction by the total number of moles of monomers of that class (diols on the one hand, and diacids and diesters on the other). In a preferred embodiment in which the six or seven monomers described above are the only monomers used, the combined mole fractions of ethylene glycol, diethylene glycol (if added), and neopentyl glycol are 1, and the combined mole fractions of dimethyl-5-sulfoisophthalate sodium salt, isophthalic acid, dimethyl terephthalate, and sebacic acid are 1. It is preferable that the monomers used include, substantially consist of, or consist of the six or seven monomers listed above. Unless otherwise specified herein, the mole fractions and ratios of monomers given herein are relative amounts of monomers charged into the reaction. In some cases, when ethylene glycol is used, some amount of diethylene glycol is formed. Such diethylene glycol will also react in situ with a diacid or diester so that diethylene glycol residues form part of the main chain of the copolyester. For example, in embodiments where a mole fraction of ethylene glycol between about 0.8 and about 0.92 is used, diethylene glycol will be produced in situ and form part of the main chain of the copolyester in an amount between about 0.07 and about 0.32, preferably between about 0.12 and about 0.25, and the amount of ethylene glycol will decrease accordingly. The amount of diethylene glycol formed depends on the presence and amount of a highly acidic acid, as well as the reaction conditions (i.e., generally, longer reaction times and higher reaction temperatures result in greater production of diethylene glycol). By intentionally adding diethylene glycol to the charge, the amount of diethylene glycol residues formed throughout the reaction can be controlled with greater precision.For example, in an embodiment in which ethylene glycol in a mole fraction between approximately 0.8 and 0.92 is used in combination with diethylene glycol in a mole fraction between 0.05 and 0.15, the diethylene glycol is formed in situ and preferably becomes part of the copolyester main chain as diethylene glycol residues in a bound mole fraction between approximately 0.12 and 0.25, and accordingly the amount of ethylene glycol decreases to, for example, ethylene glycol residues with a bound mole fraction of approximately 0.65 to approximately 0.87.

[0030] In one embodiment, almost, substantially all, or all of the diol used is aliphatic. In a preferred embodiment, the diol contains, substantially consists of, or consists of ethylene glycol and neopentyl glycol. Preferably, the molar ratio of ethylene glycol to neopentyl glycol is between about 3:1 and about 20:1, preferably between about 4:1 and about 15:1, more preferably between about 5:1 and about 12:1, and most preferably between about 7:1 and about 17:2. These ratios help the copolyester resin achieve the preferred glass transition temperature desired in the applications described herein.

[0031] In another embodiment in which diethylene glycol is further used as a monomer charged into the reaction, the diol comprises, substantially consists of, or consists of ethylene glycol, diethylene glycol, and neopentyl glycol. Preferably, the molar ratio of ethylene glycol:diethylene glycol:neopentyl glycol is between about 3:1:1 and about 20:1:1, preferably between about 4:1:1 and about 15:1:1, more preferably between about 5:1:1 and about 12:1:1, and most preferably between about 7:1:1 and about 17:2:2. These ratios help the copolyester resin achieve the preferred glass transition temperature desired for the applications described herein.

[0032] In one embodiment of the present invention, the diacid and diester components include both aliphatic monomers and aromatic monomers. As is known in the production of copolyesters, either an acid or an ester is used in combination with an alcohol to form a copolyester resin by an esterification reaction or a transesterification reaction, respectively. Preferably, the ratio of aromatic diacid or diester to aliphatic diacid or diester is between about 75 / 25 and about 45 / 55, more preferably between about 72 / 28 and about 48 / 52, more preferably between about 70 / 30 and about 50 / 50, and most preferably between about 68 / 32 and about 50 / 50. This ratio provides a copolyester resin that has sufficient adhesiveness without giving excessively high adhesive strength and cohesive force that would cause damage to the substrate or excessive stickiness.

[0033] One embodiment of the present invention provides a composition comprising: (a) at least two diols containing ethylene glycol in a mole fraction of at least about 0.25, preferably at least about 0.5, and most preferably at least about 0.7, based on the diol; and (b) at least three diacids or diesters, wherein the composition comprises: (i) at least one sulfomer containing at least 0.02, preferably at least 0.03, more preferably at least 0.05, more preferably at least 0.07, preferably at least 0.08, most preferably at least 0.09, and at most 0.2, more preferably at most 0.15, and most preferably at most 0.12, based on the diacid or diester; and at least one sulfomer. The composition comprises an amorphous copolyester resin comprising the reaction product of (ii) a fucomomer; (ii) at least one aromatic diacid or diester; and (iii) at least three diacids or diesters, including at least one aliphatic diacid or diester, wherein the ratio of aromatic diacid or diester to aliphatic diacid or diester is between about 75 / 25 and about 45 / 55, preferably between about 72 / 28 and about 48 / 52, more preferably between about 70 / 30 and about 50 / 50, and most preferably between about 68 / 32 and about 50 / 50, and the amorphous copolyester resin has a glass transition temperature between about -25°C and about 15°C, preferably between about -18°C and about 10°C, most preferably between about -10°C and about 5°C, or in other embodiments, most preferably between about -20°C and about -5°C. The composition further comprises a solvent, which preferably results in a mixture of the amorphous copolyester resin and the solvent. The mixture may be in the form of a solution or a dispersion. The solvent is preferably selected from the group consisting of water, an organic solvent (for example, acetone, isopropyl alcohol, tetrahydrofuran, and 1,3-dioxolane, or a mixture thereof), or both. In a preferred embodiment, the solvent is a solvent mixture of water and an organic solvent, and more preferably, the organic solvent is acetone, isopropyl alcohol, or a mixture thereof.It is even more preferable if the solvent mixture of water and acetone / isopropyl alcohol is present in an amount corresponding to about 20-40% solids by weight, and in a water:organic solvent weight ratio of about 80:20 to about 60:40. The present invention considers whether the composition is compostable, methods of using such a composition, and articles made from such a composition.

[0034] As stated above, unless otherwise specified, the mole fractions and ratios of monomers presented herein refer to the relative amounts of monomers charged into the reaction. Mole fractions or ratios described herein as bonded mole fractions or bonded ratios refer to the mole fractions or ratios of residues that are part of the copolyester backbone. Therefore, even if diethylene glycol is not present as a monomer charged into the reaction in a particular embodiment, if diethylene glycol is formed in situ and becomes part of the resulting copolyester resin, the copolyester resin may have a bonded mole fraction of diethylene glycol residues greater than zero, for example, between about 0.07 and about 0.32, most preferably between at least about 0.12 and about 0.25, relative to the diol.

[0035] Embodiments of the present invention are considered to be compostable. In the composting process, microorganisms such as bacteria or fungi are used to decompose organic matter, from which carbon dioxide, water, heat, and compost are produced. It is important that the microorganisms receive a continuous supply of organic matter, water, and oxygen.

[0036] Standard methods for testing compostability are EN 13432 for packaging and ASTM 6400 (which is a standard for compostable plastics). For a product to be considered compostable, it must meet the following three criteria: a. Degeneration: Starting with a 2 cm length section of the product, composting for 12 weeks under a laboratory-controlled composting composition requires that 90% of the product pass through a 2 mm sieve. b. Biodegradability: By the end of the test period, 60% of the organic carbon must have been converted to carbon dioxide compared to the positive control (cellulose). c. No adverse effects on compost quality: The germination rate and plant biomass of the sample compost should be 90% or higher, and the heavy metal levels should be below a certain standard (which is region-dependent).

[0037] To carry out this test, special conditions are required. First, a temperature-controlled incubator is used to maintain a temperature of 58°C, and the composting container (capacity, 7.5 liters) is divided into two sections using a porous pad. The bottom section is filled with 1 liter of water, and carbon dioxide is bubbled into this water to saturate it with gas.

[0038] Inoculation: Use compost from 3 months of age; sift it through a 9.5 mm sieve and mix. Add ammonium chloride to bring the C / N ratio to less than 15, and adjust the volume of water so that the water content is 50%.

[0039] Decay Test: A 200g, 2cm x 2cm square sample of the product is added to 1.2kg of compost and placed in a 7.5-liter container to begin the test. The mixture is composted for 12 weeks, during which time the container is shaken weekly to mix the sample and compost and prevent channeling. After 12 weeks, the substance is sieved through a 2mm sieve. Less than 10% of the original dry weight of the product should remain on the sieve.

[0040] Biodegradation test: This test will be conducted with four types of mixtures: sample (10g product and 600g compost), positive control (product replaced with cellulose), negative control (100g PET and 600g compost), and blank (600g compost only).

[0041] The water content of the mixture is adjusted to 50%. The composting container is placed in an incubator at 58°C ± 2°C. CO2-free air is then connected and the flow rate is adjusted to between 150 and 200 mL / min. The gas coming out of the test chamber is piped to a solenoid valve (plumbed), and the valve is controlled to divert the air for 2 minutes every 2 hours. The diverted gas is then flowed into a 1-liter adsorption unit containing a known volume of 1N sodium hydroxide to adsorb the carbon dioxide produced in the container (for the remainder of the 2 hours, the exhaust gas is simply vented into the room). The sodium hydroxide is titrated periodically to measure the amount of CO2 produced, with standard titration intervals being 3 days, 7 days, 14 days, and every 7 days thereafter. BaCl2 is added to precipitate the carbonate produced by CO2, and then the mixture is titrated with 0.5N HCl until the pH reaches 8.5. Add fresh 1N sodium hydroxide to the absorption unit and repeat the entire process. Continue the test for up to 180 days until CO2 emissions from both the sample and the positive control plateau.

[0042] Certain preferred embodiments of the copolyester resins of the present invention relate to the properties of the copolyester resin formed. In one such embodiment, the amorphous copolyester resin has an acid value less than 10 mg KOH / g, preferably less than 7 mg KOH / g, but greater than 0.1 mg KOH / g, preferably greater than 1 mg KOH / g. The acid value, as used herein, is measured according to DIN EN ISO 2114. The sample to be measured is dissolved in a blend of dichloromethane and methanol (80:20 by volume) and titrated with a 0.1 N sodium hydroxide solution in the presence of phenolphthalein. The acid value is the amount of milligrams of potassium hydroxide required to neutralize the acid present in 1 gram of polymer. The acid value is an indicator of the progress of the copolyester resin formation reaction, decreasing as the reaction progresses.

[0043] The number-average molecular weight and weight-average molecular weight were also determined using size exclusion chromatography (SEC) with PMMA standards and DMSO as the solvent. The amorphous copolyester resin has a number-average molecular weight (Mn) between about 1,000 and 15,000 daltons, preferably between about 5,000 and 12,000 daltons, and a weight-average molecular weight (Mw) between about 7,000 and 45,000 daltons, preferably between about 15,000 and 40,000 daltons. In yet another embodiment of the present invention, the amorphous copolyester resin has a Brookfield Thermosel melt viscosity (215°C) between 5,000 and 150,000 cP, measured using a #27 spindle at a rotational speed between about 0.5 and 10 rpm. In yet another embodiment of the present invention, the intrinsic viscosity of the copolyester resin is between about 0.1 dL / g and about 0.7 dL / g, preferably between about 0.15 dL / g and about 0.55 dL / g. When used herein, the intrinsic viscosity is measured according to ASTM D5225-14. Both the molecular weight and viscosity of the copolyester resin increase as the reaction progresses.

[0044] The copolyesters used in the present invention can be produced by various conventional methods for producing copolyesters by transesterification or direct esterification. However, considering applications in food, the use of heavy metals or compounds that pose hygiene problems as catalysts and additives should be avoided or limited. The copolyesters used in the present invention can typically be prepared from diacids or diesters and diols, which react in substantially equal proportions and are incorporated into the copolyester as their corresponding residues. As is well known, diols are added in excess because unreacted diols evaporate more easily than unreacted diacids or diesters. Therefore, the copolyesters of the present invention can contain diacid or diester residues and diol residues in substantially equimolar proportions. Accordingly, the molar percentages provided in this disclosure may be based on the total moles of the diacid and diester components, or the total moles of the diol component, unless otherwise stated as the bonded mole fraction or bonded ratio.

[0045] Suitable methods include (but are not limited to) reacting one or more dicarboxylic acids with two or more diols at a temperature of 100°C to 315°C and a pressure of 0.1 to 760 mmHg for a time sufficient to form a polyester. U.S. Patent No. 3,772,405 (as incorporated herein by reference) describes a suitable method for producing copolyesters. One process for producing a copolyester resin includes the following steps: (I) heating a mixture containing selected monomers useful in any of the copolyesters of the present invention in the presence of a catalyst at a temperature of 150 to 240°C for a time sufficient to produce an initial polyester; (II) heating the initial polyester from step (I) at a temperature of 240 to 320°C for 1 to 4 hours; and (III) removing various unreacted glycols.

[0046] Suitable catalysts for use in this process include (but are not limited to): organic zinc, titanium, or tin compounds (however, organotin compounds are undesirable for food and beverage applications). The use of this type of catalyst is well known to those skilled in the art. Examples of catalysts useful in the present invention include (but are not limited to): zinc acetate dihydrate, butyltin tris-2-ethylhexanoate, dibutyltin diacetate, titanium(IV) 2-ethylhexyl oxide, titanium(IV) butoxide, and / or dibutyltin oxide. Other catalysts include (but are not limited to): manganese, lithium, germanium, and cobalt-based catalysts. The amount of catalyst can be 10 ppm to 20,000 ppm, or 10 to 10,000 ppm, or ~5,000 ppm, or 10 to 1,000 ppm, or 10 to 500 ppm, or 10 to 300 ppm, or 10 to 250 ppm, based on the weight of the catalyst metal and the final polymer. This process can be carried out in either a batch or continuous manner.

[0047] In one preferred embodiment of the present invention, the copolyester resin is a reaction product of the following seven monomers in the following molar ratios: 0.81 moles of ethylene glycol, 0.09 moles of diethylene glycol, and 0.10 moles of neopentyl glycol, based on the total amount of glycol; and 0.41 moles of sebacic acid, 0.39 moles of dimethyl terephthalate, 0.1 mole of DMSIP, and 0.1 mole of isophthalic acid, based on the total amount of diacids and diesters. In one embodiment, the copolyester resin is a resin produced from a single esterification / transesterification reaction scheme containing these monomers in their relative amounts. In another embodiment, the copolyester resin is a blend of two or more resins, each produced from its own esterification / transesterification reaction scheme, each having its own blend of monomers. In the blend embodiment, the two or more resins are selected such that a weighted average of properties and monomer amounts that would be achieved with a resin produced from a single esterification / transesterification reaction scheme is achieved. For example, the copolyester resin may be a blend of a first resin made in 35% by weight of the following monomers in the following mole fractions (based on the total moles of the diols, 0.67 moles of ethylene glycol and 0.33 moles of neopentyl glycol, and based on the total moles of the diols, 0.54 moles of dimethyl terephthalate, 0.08 moles of isophthalic acid, 0.29 moles of sebacic acid, and 0.1 mole of DMSIP), and a second resin made in 65% by weight of the following monomers in the following mole fractions (on the diol side, ethylene glycol only, and 0.31 moles of dimethyl terephthalate, 0.11 moles of isophthalic acid, 0.48 moles of sebacic acid, and 0.1 mole of DMSIP).

[0048] Certain preferred embodiments of this embodiment of the present invention relate to the monomers used and some monomers not used in the production of the copolyester resin. In one such embodiment, propanediol, butanediol, isopropyl alcohol, or any of these are not used to produce the copolyester resin of the present invention. In other embodiments, alcohols such as ethanol are not used in the solvent mixture. In one embodiment of the present invention, the copolyester resin is in the form of pellets (before solvation). Alternative forms include granules, cut rods, or powder.

[0049] The coating compositions of the present invention may further contain other optional components that do not adversely affect the coating composition or the cured coating composition obtained therefrom. Such optional components are typically incorporated into the coating composition to improve the appearance of the composition, facilitate the manufacture, processing, handling, and application of the composition, or further improve certain functional properties of the coating composition or the cured coating composition obtained therefrom.

[0050] Such optional components include, for example, dyes, pigments, toners, extenders, fillers, lubricants, corrosion inhibitors, flow regulators, thixotropes, dispersants, antioxidants, adhesion promoters, light stabilizers, and mixtures thereof. Insecticides may be added to prevent aqueous products from microbial attack. Surfactants may be used to improve dispersion and limit various phase separations. Defoamers and thickeners may also be used in known ways. Each optional component is included in an amount sufficient to serve its intended purpose, but in such an amount that it does not adversely affect the coating composition or the cured coating composition obtained therefrom.

[0051] Another useful optional component is a lubricant, such as a wax, which facilitates the creation of flexible metal substrates or metallized paper by providing lubrication to the coated metal substrate sheet. The lubricant is preferably present in the coating composition in an amount of about 0.01% to about 2%, preferably about 0.1% to about 2%, of the weight of the non-volatile substance. Preferred lubricants include, for example, carnauba wax and polyethylene-type lubricants.

[0052] In one preferred embodiment, the cold seal adhesive is compostable, and contains less than 1% by weight of optional components that are not compostable themselves. In adhesives that are still characterized as compostable, it is preferable that they contain more than 1% by weight of optional components that are compostable themselves.

[0053] The present invention further relates to manufactured articles. These articles include wrappers, packaging, and food containers that are sealed together with the cold-seal adhesives according to the present invention. The coating compositions described above are particularly well suited for use as cold-seal adhesive coatings for food packaging, for example, for candy.

[0054] In one embodiment of the present invention, the substrate comprises a film having an adhesive according to the present invention coated on a first surface and an adhesive coated on a second surface, wherein the surfaces are sealed to each other. Preferably, the surfaces form a seal of the film, such as an end seal or a longitudinal seal. The articles may contain two or more substrates.

[0055] A method to minimize tackiness is to impregnate the substrate with an over-lacquer or release lacquer on the side of the substrate opposite to the adhesive coating. This ensures that when the substrate is rolled, the over-lacquer or release lacquer comes into contact with the adhesive layer, thereby preventing tackiness. These over-lacquers or release lacquers may be any known type and can be applied in a conventional manner.

[0056] In another embodiment, the cold seal adhesive composition described herein may be bonded to a release liner as a pressure-sensitive adhesive and then applied to a substrate.

[0057] In embodiments where multiple ranges, or multiple lower and upper limits, are given as parameters, the present invention includes all ranges from various lower limits to various upper limits for those parameters.

[0058] Embodiments of the present invention [Aspect 1] A method for bonding the surface of a first substrate to the surface of a second substrate, Steps include applying a copolyester resin mixture to the surface of a first substrate and the surface of a second substrate; and The step of bringing the first substrate surface into contact with the second substrate surface to form a laminate. A method comprising, wherein the method is carried out at ambient temperature. [Aspect 2] The method according to embodiment 1, wherein the copolyester resin is sulfonated. [Aspect 3] The method according to embodiment 1 or 2, wherein the contact step is performed for a sufficient time and pressure to bond the first substrate surface to the second substrate surface. [Aspect 4] The method according to embodiment 3, wherein the time of the contact step is about 0.1 seconds to about 20 seconds, preferably about 0.2 seconds to about 2 seconds, and the pressure of the contact step is about 40 psi to about 120 psi, preferably about 60 psi to about 100 psi. [Aspect 5] The method according to any one of embodiments 1 to 4, wherein the composition is a mixture of the copolyester resin and a solvent, and the solvent is selected from the group consisting of water, an organic solvent, or both. [Aspect 6] The method according to embodiment 5, wherein the solvent is water and an organic solvent, and the organic solvent comprises acetone and isopropyl alcohol. [Aspect 7] The method according to embodiment 6, wherein the solvent is present in an amount corresponding to approximately 20-40% solid content by weight, and the weight ratio of water to organic solvent is approximately 80:20 to approximately 60:40. [Aspect 8] The method according to any one of embodiments 1 to 7, wherein the overall Tg of the copolyester resin is between about -25°C and about 15°C, preferably between about -18°C and about 10°C, most preferably between about -10°C and 5°C, or between about -20°C and about -5°C. [Aspect 9] The method according to any one of embodiments 1 to 8, wherein the copolyester resin comprises a reaction product of at least two diols, each containing ethylene glycol in a mole fraction of at least about 0.25, preferably at least about 0.5, and most preferably at least about 0.7, based on the diols; and at least three diacids or diesters, wherein (i) at least one sulfomer in a mole fraction of at least 0.02, preferably at least 0.03, more preferably at least 0.05, more preferably at least 0.07, more preferably at least 0.08, most preferably at least 0.09, and at most 0.2, more preferably at most 0.15, and most preferably at most 0.12, based on the diacid or diester; (ii) at least one aromatic diacid or diester; and (iii) at least three diacids or diesters, each containing at least one aliphatic diacid or diester. [Aspect 10] The method according to embodiment 9, wherein the ratio of aromatic diacid or diester to aliphatic diacid or diester is between about 75 / 25 and about 45 / 55, preferably between about 72 / 28 and about 48 / 52, more preferably between about 70 / 30 and about 50 / 50, and most preferably between about 68 / 32 and about 50 / 50. [Aspect 11] The at least one sulfomer is at least one of dimethyl-5-sulfoisophagate sodium salt (DIMSIP) or 5-sulfoisofalic acid (SIPA); The aforementioned at least one aliphatic diacid or diester is selected from the group consisting of sebaciic acid, azelaic acid, and adipic acid; The aforementioned at least one aromatic diacid or diester is selected from the group consisting of at least one of isophthalic acid, dimethyl terephthalate, terephthalic acid, and dimethyl isophthalate; and The at least two diols further comprise at least one of neopentyl glycol, diethylene glycol, trimethylolpropane, and cyclohexanedimethanol; The method according to aspect 9 or 10. [Aspect 12] The at least one sulfonomer is dimethyl-5-sulfoisophthalate sodium salt; The at least one aliphatic diacid or diester is sebaic acid; The above at least one aliphatic diacid or diester is isophthalic acid and dimethyl terephthalate; and The aforementioned at least two diols are ethylene glycol and neopentyl glycol; The method according to embodiment 11. [Aspect 13] Dimethyl-5-sulfoisophthalate sodium salt is present in a mole fraction of about 0.07 to 0.2, preferably about 0.08 to 0.15, and most preferably about 0.09 to 0.12, based on the total amount of the diacid and diester; Isophthalic acid is present in a mole fraction of about 0.02 to 0.2, preferably about 0.03 to about 0.15, and most preferably about 0.05 to about 0.1, based on the total amount of diacids and diesters; Dimethyl terephthalate is present in a mole fraction of about 0.25 to 0.55, preferably about 0.3 to about 0.5, and most preferably about 0.35 to about 0.45, based on the total amount of diacids and diesters; Sebacic acid is present in a mole fraction of about 0.18 to 0.4, preferably about 0.2 to 0.38, and most preferably about 0.25 to 0.35, based on the total amount of diacids and diesters; Ethylene glycol is present in a mole fraction of about 0.75 to 0.97, preferably about 0.8 to 0.95, most preferably about 0.85 to 0.92, based on the total amount of diols; and Neopetyl glycol is present in a mole fraction of approximately 0.03 to 0.25, preferably approximately 0.05 to approximately 0.2, and most preferably approximately 0.08 to approximately 0.15, based on the total amount of diols; The method described in Embodiment 12. [Aspect 14] The method according to any one of embodiments 9 to 13, wherein most, substantially all, or all of the diol is aliphatic. [Aspect 15] The method according to embodiment 12 or 13, wherein the molar ratio of (ethylene glycol:neopentyl glycol) is between about 3:1 and about 20:1, preferably between about 4:1 and about 15:1, more preferably between about 5:1 and about 12:1, and most preferably between about 7:1 and about 17:2. [Aspect 16] A composition comprising an amorphous copolyester resin, comprising: (a) at least two diols, each containing ethylene glycol in a mole fraction of at least about 0.25, preferably at least about 0.5, and most preferably at least about 0.7, based on the diols; and (b) at least three diacids or diesters, comprising (i) at least one sulfonomer, each containing at least 0.02, preferably at least 0.03, more preferably at least 0.05, more preferably at least 0.07, preferably at least 0.08, and most preferably at least 0.09, based on the diacids or diesters; and at least one sulfonomer. A composition comprising: (ii) at least one aromatic diacid or diester; and (iii) at least three diacids or diesters including at least one aliphatic diacid or diester, wherein the ratio of aromatic diacid or diester to aliphatic diacid or diester is between about 75 / 25 and about 45 / 55, preferably between about 72 / 28 and about 48 / 52, more preferably between about 70 / 30 and about 50 / 50, most preferably between about 68 / 32 and about 50 / 50, and the amorphous copolyester resin having a glass transition temperature between about -25°C and about 15°C, preferably between about -18°C and about 10°C, most preferably between about -10°C and about 5°C, or most preferably between about -20°C and about -5°C. [Aspect 17] The composition according to embodiment 16, further comprising a solvent. [Aspect 18] The composition according to embodiment 17, wherein the solvent is selected from the group consisting of water, an organic solvent, or both. [Aspect 19] The composition according to embodiment 18, wherein the solvent is water and an organic solvent, and the organic solvent comprises acetone and isopropyl alcohol. [Aspect 20] The composition according to embodiment 19, wherein the solvent is present in an amount corresponding to approximately 20-40% solid content by weight, and the weight ratio of water to organic solvent is approximately 80:20 to approximately 60:40. [Aspect 21] The at least one sulfomer is at least one of dimethyl-5-sulfoisophagate sodium salt (DMSIP) or 5-sulfoisofalic acid (SIPA); The aforementioned at least one aliphatic diacid or diester is selected from the group consisting of sebaciic acid, azelaic acid, and adipic acid; The aforementioned at least one aromatic diacid or diester is selected from the group consisting of at least one of isophthalic acid, dimethyl terephthalate, terephthalic acid, and dimethyl isophthalate; and The at least two diols further comprise at least one of neopentyl glycol, diethylene glycol, trimethylolpropane, and cyclohexanedimethanol; The composition according to any one of embodiments 16 to 20. [Aspect 22] The at least one sulfonomer is dimethyl-5-sulfoisophthalate sodium salt; The at least one aliphatic diacid or diester is sebaic acid; The above at least one aliphatic diacid or diester is isophthalic acid and dimethyl terephthalate; and The aforementioned at least two diols are ethylene glycol and neopentyl glycol; The composition according to embodiment 21. [Aspect 23] Dimethyl-5-sulfoisophthalate sodium is present in a mole fraction of at least 0.02, preferably at least 0.03, more preferably at least 0.05, more preferably at least about 0.07 to about 0.2, preferably about 0.08 to about 0.15, and most preferably about 0.09 to about 0.12, based on the total amount of diacids and diesters; Isophthalic acid is present in a mole fraction of about 0.02 to 0.2, preferably about 0.03 to about 0.15, and most preferably about 0.05 to about 0.1, based on the total amount of diacids and diesters; Dimethyl terephthalate is present in a mole fraction of about 0.25 to 0.55, preferably about 0.3 to about 0.5, and most preferably about 0.35 to about 0.45, based on the total amount of diacids and diesters; Sebacic acid is present in a mole fraction of about 0.18 to 0.4, preferably about 0.2 to 0.38, and most preferably about 0.25 to 0.35, based on the total amount of diacids and diesters; Ethylene glycol is present in an amount of about 0.75 to 0.97, preferably about 0.8 to 0.95, most preferably about 0.85 to 0.92 mole fractions, based on the total amount of diols; and Neopetyl glycol is present in an amount of approximately 0.03 to 0.25, preferably approximately 0.05 to approximately 0.2, and most preferably approximately 0.08 to approximately 0.15 mole fractions based on the total amount of diols; The composition according to embodiment 22. [Aspect 24] The composition according to any one of embodiments 16 to 23, wherein most, substantially all, or all of the diol is aliphatic. [Pattern 25] The composition according to either embodiment 22 or 23, wherein the molar ratio of ethylene glycol to neopentyl glycol is between about 3:1 and about 20:1, preferably between about 4:1 and about 15:1, more preferably between about 5:1 and about 12:1, and most preferably between about 7:1 and about 17:2. [Aspect 26] The composition according to any one of embodiments 16 to 24, wherein diethylene glycol is present in a mole fraction of about 0.01 to about 0.2, preferably about 0.01 to about 0.15, and most preferably about 0.05 to about 0.12, based on the total amount of diols. [Aspect 27] A laminate formed by the method described in Embodiment 1. [Aspect 28] An article comprising at least one substrate having a first surface and a second surface combined with each other, and each having a composition according to any one of embodiments 16 to 26 coated thereon. [Aspect 28] An article comprising a first substrate having a first surface and a second substrate having a second surface, wherein each of the first and second surfaces is combined with each other and each is coated thereon, the article having a composition according to any one of embodiments 16 to 26. [Aspect 29] A composition comprising an amorphous copolyester resin, comprising (a) at least two diol residues including ethylene glycol, and (b) at least three diol or diester residues including (i) at least one sulfonomer; (ii) at least one aromatic diacid or diester; and (iii) at least one aliphatic diacid or diester, wherein the copolyester resin has a bound mole fraction of ethylene glycol residues between about 0.5 and about 0.9, most preferably at least about 0.65 and about 0.85, based on the diol; The binding ratio of aromatic diacids or diesters to aliphatic diacids or diester residues is between about 75 / 25 and about 45 / 55, preferably between about 72 / 28 and about 48 / 52, more preferably between about 70 / 30 and about 50 / 50, and most preferably between about 68 / 32 and about 50 / 50; and The amorphous copolyester resin has a glass transition temperature between approximately -25°C and approximately 15°C, preferably between approximately -18°C and approximately 10°C. composition. [Aspect 30] The composition according to embodiment 29, wherein the copolyester resin has a bound mole fraction of diethylene glycol residues between about 0.07 and about 0.32, most preferably between at least about 0.12 and about 0.25, based on the diol. [Aspect 31] The composition according to embodiment 28 or 28, wherein the copolyester resin has a bonded mole fraction of at least one sulfonomer in an amount of at least 0.02, preferably at least 0.03, more preferably at least 0.05, more preferably at least about 0.07 to about 0.2, preferably about 0.08 to about 0.15, and most preferably about 0.09 to about 0.12, based on the total amount of diacid and diester. [Examples]

[0059] The following examples illustrate some aspects of certain preferred embodiments of the present invention, but these examples should not be construed as limiting the present invention.

[0060] Example 1 Dimethyl terephthalate (403.67 g), ethylene glycol (469.50 g), and zinc acetate dihydrate (0.588 g) were added to a 2-liter glass flask. The reaction mixture was stirred and heated under a gentle nitrogen purge to 204°C. After reaching 204°C, the reaction mixture was stirred for approximately 1.5 hours using a gentle nitrogen purge until the distillation temperature at the top of the column dropped to below 60°C. Approximately 100 g of colorless distillate was collected throughout this heating cycle. At this point, isophthalic acid (118.82 g), ethylene glycol (153.26 g), 5-sodioisophthalic acid (179.25 g), sebacic acid (651.59 g), and germanium dioxide (0.279 g) were added to the flask. The reaction mixture was then heated over 0.4 hours under a gentle nitrogen purge with stirring to 200°C. The reaction mixture obtained in this manner was held at 200°C under a gentle nitrogen purge for approximately 2 hours, or until the distillation temperature at the top of the column dropped to below 90°C. The reaction mixture was then heated under a gentle nitrogen purge with stirring over 1.5 hours to 255°C. Approximately 120 grams of colorless distillate were collected throughout this heating cycle. At this point, ethylene glycol (124.85 grams) and p-toluenesulfonic acid (0.01 grams) were added to the flask and stirred for 30 minutes. The reaction mixture was then placed under full vacuum at 255°C with stirring. The resulting reaction mixture was stirred under full vacuum (pressure less than 5 Torre) for 2 hours. The vacuum was then broken using nitrogen, and the reactants were transferred to a PTFE tray and allowed to cool to room temperature. An additional 250 grams of distillate were recovered, and 1.35 kilograms of solid reaction product were recovered. Calculations of the reaction product sample revealed an inherent viscosity (IV) of 0.53 dL / g. The sample was further subjected to differential scanning calorimetry (DSC) analysis. A glass transition temperature (Tg) was observed at -22.83°C.

[0061] Example 2 Dimethyl terephthalate (403.67 g), sodium dimethyl-5-sulfoisophthalate (198.00 g), ethylene glycol (469.50 g), and zinc acetate dihydrate (0.588 g) were added to a 2-liter glass flask. The reaction mixture was stirred and heated under a gentle nitrogen purge to 204°C. After reaching 204°C, the reaction mixture was stirred for approximately 1.5 hours using a gentle nitrogen purge until the distillation temperature at the top of the column dropped to below 60°C. Approximately 140 g of colorless distillate was collected throughout this heating cycle. At this point, isophthalic acid (118.82 g), ethylene glycol (153.26 g), sebacic acid (651.59 g), and germanium dioxide (0.279 g) were added to the flask. The reaction mixture was then heated over 0.4 hours under a gentle nitrogen purge with stirring to 200°C. The reaction mixture obtained in this manner was held at 200°C under a gentle nitrogen purge for approximately 2 hours, or until the distillation temperature at the top of the column dropped to below 90°C. The reaction mixture was then heated under a gentle nitrogen purge with stirring over 1.5 hours to 255°C. Approximately 120 grams of colorless distillate were collected throughout this heating cycle. At this point, ethylene glycol (124.85 grams) and p-toluenesulfonic acid (0.01 grams) were added to the flask and stirred for 30 minutes. The reaction mixture was then placed under full vacuum at 255°C with stirring. The resulting reaction mixture was stirred under full vacuum (pressure less than 20 Torre) for 2.5 hours. The vacuum was then broken using nitrogen, and the reactants were transferred to a PTFE tray and allowed to cool to room temperature. An additional 285 grams of distillate were recovered, and 1.30 kilograms of solid reaction product were recovered. Calculations of the reaction product sample revealed an inherent viscosity (IV) of 0.44 dL / g. The sample was further subjected to differential scanning calorimetry (DSC) analysis. A glass transition temperature (Tg) was observed at -23.09°C.

[0062] Example 3 Dimethyl terephthalate (300.60 g), sodium dimethyl-5-sulfoisophthalate (195.97 g), ethylene glycol (464.67 g), and zinc acetate dihydrate (0.588 g) were added to a 2-liter glass flask. The reaction mixture was stirred and heated under a gentle nitrogen purge to 204°C. After reaching 204°C, the reaction mixture was stirred for approximately 1.5 hours using a gentle nitrogen purge until the distillation temperature at the top of the column dropped to below 60°C. Approximately 110 g of colorless distillate was collected throughout this heating cycle. At this point, isophthalic acid (117.60 g), ethylene glycol (151.69 g), sebacic acid (743.90 g), and germanium dioxide (0.279 g) were added to the flask. The reaction mixture was then heated over 0.4 hours under a gentle nitrogen purge with stirring to 200°C. The reaction mixture obtained in this manner was held at 200°C under a gentle nitrogen purge for approximately 2 hours, or until the distillation temperature at the top of the column dropped below 90°C. The reaction mixture was then heated under a gentle nitrogen purge with stirring over 1.5 hours to 255°C. Approximately 130 grams of colorless distillate were collected throughout this heating cycle. At this point, ethylene glycol (123.57 grams) and p-toluenesulfonic acid (0.01 grams) were added to the flask and stirred for 30 minutes. The reaction mixture was then placed under full vacuum at 255°C with stirring. The resulting reaction mixture was stirred under full vacuum (pressure less than 20 Torre) for 2.5 hours. The vacuum was then broken using nitrogen, and the reactants were transferred to a PTFE tray and allowed to cool to room temperature. An additional 280 grams of distillate were recovered, and 1.27 kilograms of solid reaction product were recovered. Calculations of the reaction product sample revealed an inherent viscosity (IV) of 0.35 dL / g. The sample was further subjected to differential scanning calorimetry (DSC) analysis. A glass transition temperature (Tg) of -34.7°C and a melt transition temperature (Tm) of 94.5°C were observed.

[0063] Example 4 Dimethyl terephthalate (674.14 g), sodium dimethyl-5-sulfoisophthalate (191.86 g), ethylene glycol (307.26 g), neoptentyl glycol (249.37 g), germanium dioxide (0.28 g), Irganox 1010 (5.20 g), and zinc acetate dihydrate (0.56 g) were added to a 2-liter glass flask. The reaction mixture was stirred and heated to 204°C under a gentle nitrogen purge. After reaching 204°C, the reaction mixture was stirred for approximately 1.5 hours using a gentle nitrogen purge until the distillation temperature at the top of the column dropped to below 60°C. Approximately 230 g of colorless distillate was collected throughout this heating cycle. At this point, isophthalic acid (89.93 g), ethylene glycol (131.68 g), sebacic acid (374.64 g), and neopentyl glycol (106.87 g) were added to the flask. The reaction mixture was then heated to 200°C over 0.4 hours with stirring under a gentle nitrogen purge. The resulting reaction mixture was then held at 200°C under a gentle nitrogen purge for approximately 2 hours, or until the distillation temperature at the top of the column dropped below 90°C. The reaction mixture was then heated to 255°C over 1.5 hours with stirring under a gentle nitrogen purge. Approximately 70 g of colorless distillate was collected throughout this heating cycle. The reaction mixture was then placed under full vacuum at 255°C with stirring. The resulting reaction mixture was then stirred under full vacuum (pressure less than 20 Torre) for 2.5 hours. The vacuum was then broken using nitrogen, the reactants were transferred to a PTFE tray, and allowed to cool to room temperature. An additional 275 grams of distillate were recovered, and 1.31 kilograms of solid reaction products were recovered. Calculations of the reaction product sample revealed an inherent viscosity (IV) of 0.30 dL / g. The sample was further subjected to differential scanning calorimetry (DSC) analysis. A glass transition temperature (Tg) was observed at 20.36°C.

[0064] Example 5 Dimethyl terephthalate (686.32 g), sodium dimethyl-5-sulfoisophthalate (195.33 g), ethylene glycol (312.82 g), neoptentyl glycol (253.88 g), germanium dioxide (0.28 g), Irganox 1010 (5.20 g), and zinc acetate dihydrate (0.56 g) were added to a 2-liter glass flask. The reaction mixture was stirred and heated to 204°C under a gentle nitrogen purge. After reaching 204°C, the reaction mixture was stirred for approximately 1.5 hours using a gentle nitrogen purge until the distillation temperature at the top of the column dropped to below 60°C. Approximately 230 g of colorless distillate was collected throughout this heating cycle. At this point, isophthalic acid (85.45 g), ethylene glycol (134.06 g), azelaic acid (354.95 g), and neopentyl glycol (108.80 g) were added to the flask. The reaction mixture was then heated to 200°C over 0.4 hours with stirring under a gentle nitrogen purge. The resulting reaction mixture was then held at 200°C under a gentle nitrogen purge for approximately 2 hours, or until the distillation temperature at the top of the column dropped below 90°C. The reaction mixture was then heated to 255°C over 1.5 hours with stirring under a gentle nitrogen purge. Approximately 70 g of colorless distillate was collected throughout this heating cycle. The reaction mixture was then placed under full vacuum at 255°C with stirring. The resulting reaction mixture was then stirred under full vacuum (pressure less than 20 Torre) for 2.25 hours. Next, the vacuum was broken using nitrogen, the reactants were transferred to a PTFE tray, and allowed to cool to room temperature. An additional 285 grams of distillate were recovered, and 1.30 kilograms of solid reaction products were recovered. Calculations of the reaction product sample revealed an inherent viscosity (IV) of 0.30 dL / g. The sample was further subjected to differential scanning calorimetry (DSC) analysis. A glass transition temperature (Tg) was observed at 18.38°C.

[0065] Example 6 Dimethyl terephthalate (725.652 g), sodium dimethyl-5-sulfoisophthalate (206.52 g), ethylene glycol (330.74 g), neoptentyl glycol (268.43 g), germanium dioxide (0.28 g), Irganox 1010 (5.20 g), and zinc acetate dihydrate (0.56 g) were added to a 2-liter glass flask. The reaction mixture was stirred and heated to 204°C under a gentle nitrogen purge. After reaching 204°C, the reaction mixture was stirred for approximately 1.5 hours using a gentle nitrogen purge until the distillation temperature at the top of the column dropped to below 60°C. Approximately 240 g of colorless distillate was collected throughout this heating cycle. At this point, isophthalic acid (138.82 g), ethylene glycol (141.75 g), adipic acid (291.39 g), and neopentyl glycol (115.04 g) were added to the flask. The reaction mixture was then heated to 200°C over 0.4 hours with stirring under a gentle nitrogen purge. The resulting reaction mixture was then held at 200°C under a gentle nitrogen purge for approximately 2 hours, or until the distillation temperature at the top of the column dropped below 90°C. The reaction mixture was then heated to 255°C over 1.5 hours with stirring under a gentle nitrogen purge. Approximately 80 g of colorless distillate was collected throughout this heating cycle. The reaction mixture was then placed under full vacuum at 255°C with stirring. The resulting reaction mixture was then stirred under full vacuum (pressure less than 20 Torre) for 2 hours. The vacuum was then broken using nitrogen, and the reactants were transferred to a PTFE tray and allowed to cool to room temperature. An additional 290 grams of distillate was recovered, and 1.29 kilograms of solid reaction products were recovered. Calculations of the reaction product sample revealed an inherent viscosity (IV) of 0.27 dL / g. The sample was further subjected to differential scanning calorimetry (DSC) analysis. A glass transition temperature (Tg) was observed at 13.61°C.

[0066] Example 7 Dimethyl terephthalate (499.57 g), sodium dimethyl-5-sulfoisophthalate (195.41 g), ethylene glycol (441.85 g), neoptentyl glycol (95.39 g), Irganox 1010 (5.20 g), and zinc acetate dihydrate (0.56 g) were added to a 2-liter glass flask. The reaction mixture was stirred and heated to 204°C under a gentle nitrogen purge. After reaching 204°C, the reaction mixture was stirred for approximately 1.5 hours using a gentle nitrogen purge until the distillation temperature at the top of the column dropped to below 60°C. Approximately 180 g of colorless distillate was collected throughout this heating cycle. At this point, isophthalic acid (106.31 g), ethylene glycol (189.36 g), sebacic acid (550.99 g), neopentyl glycol (40.88 g), and germanium dioxide (0.28 g) were added to the flask. The reaction mixture was then heated to 200°C over 0.4 hours with stirring under a gentle nitrogen purge. The resulting reaction mixture was then held at 200°C under a gentle nitrogen purge for approximately 2 hours, or until the distillation temperature at the top of the column dropped to below 90°C. The reaction mixture was then heated to 255°C over 1.5 hours with stirring under a gentle nitrogen purge. Approximately 110 g of colorless distillate was collected during this entire heating cycle. The reaction mixture was then placed under full vacuum at 255°C with stirring. The resulting reaction mixture was then stirred under full vacuum (pressure less than 5 Torre) for 3 hours. Next, the vacuum was broken using nitrogen, the reactants were transferred to a PTFE tray, and allowed to cool to room temperature. An additional 275 grams of distillate were recovered, and 1.34 kilograms of solid reaction products were recovered. Calculations of the reaction product sample revealed an inherent viscosity (IV) of 0.44 dL / g. The sample was further subjected to differential scanning calorimetry (DSC) analysis. A glass transition temperature (Tg) was observed at -18.1°C.

[0067] Example 8 Dimethyl terephthalate (441.92 g), sodium dimethyl-5-sulfoisophthalate (195.44 g), ethylene glycol (441.92 g), neoptentyl glycol (95.41 g), Irganox 1010 (5.20 g), and zinc acetate dihydrate (0.60 g) were added to a 2-liter glass flask. The reaction mixture was stirred and heated to 204°C under a gentle nitrogen purge. After reaching 204°C, the reaction mixture was stirred for approximately 1.5 hours using a gentle nitrogen purge until the distillation temperature at the top of the column dropped to below 60°C. Approximately 170 g of colorless distillate was collected throughout this heating cycle. At this point, isophthalic acid (106.32 g), ethylene glycol (189.39 g), sebacic acid (551.08 g), and neopentyl glycol (40.88 g) were added to the flask. The reaction mixture was then heated to 200°C over 0.4 hours with stirring under a gentle nitrogen purge. The resulting reaction mixture was then held at 200°C under a gentle nitrogen purge for approximately 2 hours, or until the distillation temperature at the top of the column dropped below 90°C. The reaction mixture was then heated to 255°C over 1.5 hours with stirring under a gentle nitrogen purge. Approximately 105 g of colorless distillate was collected throughout this heating cycle. The reaction mixture was then placed under full vacuum at 255°C with stirring. The resulting reaction mixture was then stirred under full vacuum (pressure less than 5 Torre) for 2.5 hours. The vacuum was then broken using nitrogen, and the reactants were transferred to a PTFE tray and allowed to cool to room temperature. An additional 300 grams of distillate were recovered, and 1.34 kilograms of solid reaction products were recovered. Calculations of the reaction product sample revealed an inherent viscosity (IV) of 0.41 dL / g. The sample was further subjected to differential scanning calorimetry (DSC) analysis. A glass transition temperature (Tg) was observed at -18.3°C.

[0068] Example 9 Dimethyl terephthalate (662.73 g), sodium dimethyl-5-sulfoisophthalate (198.23 g), ethylene glycol (360.39 g), neoptentyl glycol (432.43 g), Irganox 1010 (1.47 g), tetra-n-butyl titanate (0.264 g), and zinc acetate dihydrate (0.499 g) were added to a 2-liter glass flask. The reaction mixture was stirred and heated to 204°C under a gentle nitrogen purge. After reaching 204°C, the reaction mixture was stirred for approximately 1.5 hours using a gentle nitrogen purge until the distillation temperature at the top of the column dropped to below 60°C. Approximately 230 g of colorless distillate was collected throughout this heating cycle. At this point, isophthalic acid (433.59 g), ethylene glycol (90.10 g), and neopentyl glycol (114.95 g) were added to the flask. The reaction mixture was then heated to 200°C over 0.4 hours with stirring under a gentle nitrogen purge. The resulting reaction mixture was then held at 200°C under a gentle nitrogen purge for approximately 2 hours, or until the distillation temperature at the top of the column dropped below 90°C. The reaction mixture was then heated to 255°C over 1.5 hours with stirring under a gentle nitrogen purge. Approximately 80 g of colorless distillate was collected throughout this heating cycle. The reaction mixture was then placed under full vacuum at 255°C with stirring. The resulting reaction mixture was then stirred under full vacuum (pressure less than 5 Torre) for 2 hours. The vacuum was then broken using nitrogen, and the reactants were transferred to a PTFE tray and allowed to cool to room temperature. An additional 380 grams of distillate were recovered, and 1.29 kilograms of solid reaction products were recovered. Calculations of the reaction product sample revealed an inherent viscosity (IV) of 0.25 dL / g. The sample was further subjected to differential scanning calorimetry (DSC) analysis. A glass transition temperature (Tg) was observed at 56.1°C.

[0069] Example 10 Dimethyl terephthalate (647.66 g), sodium dimethyl-5-sulfoisophthalate (290.58 g), ethylene glycol (352.20 g), neopentyl glycol (422.60 g), Irganox 1010 (1.47 g), tetra-n-butyl titanate (0.264 g), and zinc acetate dihydrate (0.499 g) were added to a 2-liter glass flask. The reaction mixture was stirred and heated to 204°C under a gentle nitrogen purge. After reaching 204°C, the reaction mixture was stirred for approximately 1.5 hours using a gentle nitrogen purge until the distillation temperature at the top of the column dropped to below 60°C. Approximately 245 g of colorless distillate was collected throughout this heating cycle. At this point, isophthalic acid (369.41 g), ethylene glycol (88.05 g), and neopentyl glycol (112.34 g) were added to the flask. The reaction mixture was then heated to 200°C over 0.4 hours with stirring under a gentle nitrogen purge. The resulting reaction mixture was then held at 200°C under a gentle nitrogen purge for approximately 2 hours, or until the distillation temperature at the top of the column dropped below 90°C. The reaction mixture was then heated to 255°C over 1.5 hours with stirring under a gentle nitrogen purge. Approximately 70 g of colorless distillate was collected throughout this heating cycle. The reaction mixture was then placed under full vacuum at 255°C with stirring. The resulting reaction mixture was then stirred under full vacuum (pressure less than 5 Torre) for 2 hours. The vacuum was then broken using nitrogen, and the reactants were transferred to a PTFE tray and allowed to cool to room temperature. An additional 380 grams of distillate were recovered, and 1.30 kilograms of solid reaction products were also recovered. Calculations of the reaction product sample revealed an inherent viscosity (IV) of 0.23 dL / g. The sample was further subjected to differential scanning calorimetry (DSC) analysis. A glass transition temperature (Tg) was observed at 58.1°C.

[0070] Example 11 Dimethyl terephthalate (476.62 g), sodium dimethyl-5-sulfoisophthalate (186.43 g), ethylene glycol (339.17 g), neopentyl glycol (73.23 g), diethylene glycol (93.50 g), Irganox 1010 (5.2 g), and zinc acetate dihydrate (0.56 g) were added to a 2-liter glass flask. The reaction mixture was stirred and heated to 204°C under a gentle nitrogen purge. After reaching 204°C, the reaction mixture was stirred for approximately 1.5 hours using a gentle nitrogen purge until the distillation temperature at the top of the column dropped to below 60°C. Approximately 145 g of colorless distillate was collected throughout this heating cycle. At this point, isophthalic acid (101.42 g), sebacic acid (525.68 g), ethylene glycol (145.36 g), neopentyl glycol (31.38 g), and germanium dioxide (0.28 g) were added to the flask. The reaction mixture was then heated to 200°C over 0.4 hours with stirring under a gentle nitrogen purge. The resulting reaction mixture was then held at 200°C under a gentle nitrogen purge for approximately 2 hours, or until the distillation temperature at the top of the column dropped below 90°C. The reaction mixture was then heated to 255°C over 1.5 hours with stirring under a gentle nitrogen purge. Approximately 135 g of colorless distillate was collected during this entire heating cycle. The reaction mixture was then placed under full vacuum at 255°C with stirring. The resulting reaction mixture was then stirred under full vacuum (pressure less than 5 Torre) for 2.25 hours. Next, the vacuum was broken using nitrogen, the reactants were transferred to a PTFE tray, and allowed to cool to room temperature. An additional 70 grams of distillate were recovered, and 1.30 kilograms of solid reaction products were recovered. Calculations of the reaction product sample revealed an inherent viscosity (IV) of 0.41 dL / g. The sample was further subjected to differential scanning calorimetry (DSC) analysis. A glass transition temperature (Tg) was observed at -15.49°C.

[0071] ¹H NMR spectroscopy was performed on the copolyester resins formed in some of the aforementioned examples, and the recorded diol residues obtained in this manner are shown in Table 1 below. Since the ¹H NMR was performed in CDCl3, accurate results for the diacid content could not be obtained.

[0072] [Table 1]

[0073] As described above, some of the copolyester resins formed in each example had glass transition temperatures outside the optimal range. However, it is readily apparent that by combining two or more such resins, it is possible to form a blend with an overall (average) glass transition temperature within the optimal range. For example, a blend of 65% by weight of the resin from Example 1 and 35% by weight of the resin from Example 4 would have an overall (average) Tg of approximately -8°C.

[0074] The composition of Example 8 was dispersed in water at 97°C to a 30% solids content, then cooled to room temperature and applied to two surfaces of two different substrates (92 gauge PET or metallized PLA). The surfaces of each substrate were bonded under the following conditions to form PET-cold-seal-PET laminates and PLA-cold-seal-PLA laminates (80 psi, 0.5 sec, 72°F, 50% RH, and sawtooth gripping). Bond strength was determined by a bond strength test conducted according to ASTM D903 using an Instron 5543 tensile testing machine under ambient conditions (25°C, 50% RH) and a peel rate of 12 inches / min. The results were 614 gli for the standard 92 gauge PET laminate and 536 gli for the PLA laminate.

Claims

1. A method for bonding the surface of a first substrate to the surface of a second substrate, The steps of applying a copolyester resin mixture to the surface of a first substrate and the surface of a second substrate; and The step of bringing the first substrate surface into contact with the second substrate surface to form a laminate. A method comprising, wherein the method is carried out at ambient temperature.

2. The method according to claim 1, wherein the copolyester resin is sulfonated.

3. The method according to claim 1, wherein the contact step is performed for a time and pressure sufficient to bond the first substrate surface to the second substrate surface.

4. The method according to claim 3, wherein the time of the contact step is about 0.1 seconds to about 20 seconds, preferably about 0.2 seconds to about 2 seconds, and the pressure of the contact step is about 40 psi to about 120 psi, preferably about 60 psi to about 100 psi.

5. The method according to claim 1, wherein the composition is a mixture of the copolyester resin and a solvent, and the solvent is selected from the group consisting of water, an organic solvent, or both.

6. The method according to claim 5, wherein the solvent is water and an organic solvent, and the organic solvent comprises acetone and isopropyl alcohol.

7. The method according to claim 6, wherein the solvent is present in an amount corresponding to about 20-40% solids by weight, and the weight ratio of water to organic solvent is about 80:20 to about 60:

40.

8. The method according to claim 1, wherein the overall Tg of the copolyester resin is between about -25°C and about 15°C, preferably between about -18°C and about 10°C, most preferably between about -10°C and about 5°C, or between about -20°C and about -5°C.

9. The method according to claim 1, wherein the copolyester resin comprises a reaction product of at least two diols, each containing ethylene glycol in a mole fraction of at least about 0.25, preferably at least about 0.5, and most preferably at least about 0.7, based on the diols; and at least three diacids or diesters, wherein (i) at least one sulfonomer in a mole fraction of at least 0.02, preferably at least 0.03, more preferably at least 0.05, more preferably at least 0.07, more preferably at least 0.08, most preferably at least 0.09, and at most 0.2, more preferably at most 0.15, and most preferably at most 0.12, based on the diacid or diester; (ii) at least one aromatic diacid or diester; and (iii) at least three diacids or diesters, each containing at least one aliphatic diacid or diester.

10. The method according to claim 9, wherein the ratio of aromatic diacid or diester to aliphatic diacid or diester is between about 75 / 25 and about 45 / 55, preferably between about 72 / 28 and about 48 / 52, more preferably between about 70 / 30 and about 50 / 50, and most preferably between about 68 / 32 and about 50 / 50.

11. The at least one sulfomer is at least one of dimethyl-5-sulfoisophagate sodium salt (DMSIP) or 5-sulfoisofalic acid (SIPA); The aforementioned at least one aliphatic diacid or diester is selected from the group consisting of sebaciic acid, azelaic acid, and adipic acid; The at least one aromatic diacid or diester is selected from the group consisting of at least one of isophthalic acid, dimethyl terephthalate, terephthalic acid, and dimethyl isophthalate; and The at least two diols further comprise at least one of neopentyl glycol, diethylene glycol, trimethylolpropane, and cyclohexanedimethanol; The method according to claim 9.

12. The at least one sulfomer is dimethyl-5-sulfoisophthalate sodium salt; The at least one aliphatic diacid or diester is sebaic acid; The above at least one aliphatic diacid or diester is isophthalic acid and dimethyl terephthalate; and The at least two diols mentioned above are ethylene glycol and neopentyl glycol; The method according to claim 11.

13. Dimethyl-5-sulfoisophthalate sodium is present in a mole fraction of about 0.07 to 0.2, preferably about 0.08 to about 0.15, and most preferably about 0.09 to about 0.12, based on the total amount of diacids and diesters; Isophthalic acid is present in a mole fraction of about 0.02 to 0.2, preferably about 0.03 to about 0.15, and most preferably about 0.05 to about 0.1, based on the total amount of diacids and diesters; Dimethyl terephthalate is present in a mole fraction of about 0.25 to 0.55, preferably about 0.3 to about 0.5, and most preferably about 0.35 to about 0.45, based on the total amount of the diacitor and diester; Sebacic acid is present in a mole fraction of about 0.18 to 0.4, preferably about 0.2 to about 0.38, and most preferably about 0.25 to about 0.35, based on the total amount of diacids and diesters; Ethylene glycol is present in a mole fraction of about 0.75 to 0.97, preferably about 0.8 to about 0.95, most preferably about 0.85 to about 0.92, based on the total amount of diols; and Neopetyl glycol is present in a mole fraction of about 0.03 to 0.25, preferably about 0.05 to about 0.2, and most preferably about 0.08 to about 0.15, based on the total amount of diols. The method according to claim 12.

14. The method according to claim 9, wherein most, substantially all, or all of the diol is aliphatic.

15. The method according to claim 12, wherein the molar ratio of ethylene glycol to neopentyl glycol is between about 3:1 and about 20:1, preferably between about 4:1 and about 15:1, more preferably between about 5:1 and about 12:1, and most preferably between about 7:1 and about 17:

2.

16. A composition comprising an amorphous copolyester resin, wherein (a) at least two diols, each containing ethylene glycol in a mole fraction of at least about 0.25, preferably at least about 0.5, and most preferably at least about 0.7, based on the diols, and (b) at least three diacids or diesters, and (i) at least one sulfonomer, each containing at least one sulfonomer in a mole fraction of at least 0.02, preferably at least 0.03, more preferably at least 0.05, more preferably at least 0.07, preferably at least 0.08, and most preferably at least 0.09, based on the diacids or diesters. A composition comprising: (ii) at least one aromatic diacid or diester; and (iii) a reaction product with at least three diacids or diesters, wherein the ratio of aromatic diacid or diester to aliphatic diacid or diester is between about 75 / 25 and about 45 / 55, preferably between about 72 / 28 and about 48 / 52, more preferably between about 70 / 30 and about 50 / 50, most preferably between about 68 / 32 and about 50 / 50, and the amorphous copolyester resin having a glass transition temperature between about -25°C and about 15°C, preferably between about -18°C and about 10°C, most preferably between about -10°C and about 5°C, or between about -20°C and about -5°C.

17. The composition according to claim 16, further comprising a solvent.

18. The composition according to claim 17, wherein the solvent is selected from the group consisting of water, an organic solvent, or both.

19. The composition according to claim 18, wherein the solvent is water and an organic solvent, and the organic solvent comprises acetone and isopropyl alcohol.

20. The composition according to claim 19, wherein the solvent is present in an amount corresponding to about 20-40% of the solid content by weight, and the weight ratio of water to organic solvent is about 80:20 to about 60:

40.

21. The composition according to claim 13, wherein diethylene glycol is present in a mole fraction of about 0.01 to about 0.2, preferably about 0.01 to about 0.15, and most preferably about 0.05 to about 0.12, based on the total amount of diols.

22. A laminate formed by the method described in claim 1.

23. An article comprising at least one substrate having the composition according to claim 16, each having a first surface and a second surface that are combined with each other, and each of which is coated thereon.

24. A composition comprising an amorphous copolyester resin, (a) a residue of at least two diols containing ethylene glycol, and (b) a residue of at least three diacids or diesters, including (i) at least one sulfonomer; (ii) at least one aromatic diacid or diester; and (iii) at least one aliphatic diacid or diester, wherein The copolyester resin has a binding mole fraction of ethylene glycol residues between about 0.5 and about 0.9, most preferably at least between about 0.65 and about 0.85, based on the diol; The binding ratio of aromatic diacid or diester / aliphatic diacid or diester residues is between about 75 / 25 and about 45 / 55, preferably between about 72 / 28 and about 48 / 52, more preferably between about 70 / 30 and about 50 / 50, and most preferably between about 68 / 32 and about 50 / 50; and The amorphous copolyester resin has a glass transition temperature between approximately -25°C and approximately 15°C, preferably between approximately -18°C and approximately 10°C; composition.

25. The composition according to claim 24, wherein the copolyester resin has a bound mole fraction of diethylene glycol residues between about 0.07 and about 0.32, most preferably between at least about 0.12 and about 0.25, based on the diol.

26. The composition according to claim 24, wherein the copolyester resin has a bound mole fraction of at least one sulfonomer in an amount of at least 0.02, preferably at least 0.03, more preferably at least 0.05, more preferably at least about 0.07 to 0.2, preferably about 0.08 to about 0.15, and most preferably about 0.09 to about 0.12, based on the total amount of diacid and diester.

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