Solvent-free composition

Abstract

SUMMARY OF THE DISCLOSURE Embodiments of the present disclosure are directed to solventless compositions comprising a reaction product formed by reacting a polyol and an aminopolycarboxylic acid compound.

Description

Technical Field

[0001] Embodiments of the present disclosure are directed to solventless compositions, and more specifically, embodiments are directed to solventless compositions comprising reaction products formed by reacting a polyol and an aminopolycarboxylic acid compound.

Background Art

[0002] Solventless compositions can include, among other possible components, a polyol and an isocyanate. When used, for example, in adhesive applications, the solventless composition can be brought into contact with two substrates such that the polyol and the isocyanate react with each other to form a cured product and form a bond between the two substrates. When used, for example, in coating applications, the solventless composition can be brought into contact with one substrate such that the polyol and the isocyanate can react with each other to form a cured product.

Summary of the Invention

[0003] The present disclosure provides a solventless composition comprising a reaction product produced by reacting a polyol and an aminopolycarboxylic acid compound, and an isocyanate.

[0004] The above summary of the present disclosure is not intended to describe each disclosed embodiment or every implementation of the present disclosure. The following description illustrates exemplary embodiments in more detail. Throughout this application, guidance is provided through lists of examples, which can be used in various combinations. In each case, the listed lists function only as representative groups and should not be construed as exclusive lists.

Modes for Carrying Out the Invention

[0005] Reaction products of polyols and aminopolycarboxylic acid compounds are disclosed herein. The reaction products can be utilized in solventless compositions that can desirably provide one or more improved properties. Solventless compositions may also be referred to as, for example, solventless adhesive compositions or solventless coating compositions.

[0006] For example, a solventless composition containing the reaction product can provide an improved, i.e., increased, T-peel bond strength at 7 days compared to other compositions containing a polyol similar to the polyol used to make the reaction product. The increase in T-peel bond strength at 7 days indicates a higher adhesive strength, which is desirable for many applications.

[0007] In addition, a solventless composition containing the reaction product can provide an improved, i.e., increased, boil-in-bag value compared to other compositions containing a polyol similar to the polyol used to make the reaction product. The improved boil-in-bag value can indicate a higher adhesive strength when packaging products made with the solventless compositions disclosed herein are utilized in combination with consumer products. Higher adhesive strength is desired in many applications.

[0008] As used herein, "solventless composition" refers to a composition having from 0 weight percent to 5 weight percent solvent, such as an organic solvent or water, based on the total weight of the composition. One or more embodiments provide that the solventless composition is free of solvent and / or is applied without solvent. In this specification, using from 0 weight percent to 5 weight percent solvent based on the total weight of the solventless composition is considered a very small amount of solvent and thus may be referred to as solventless.

[0009] As described above, reaction products of polyols and aminopolycarboxylic acid compounds are disclosed herein. As used herein, "aminopolycarboxylic acid compound" includes its derivatives and / or structural analogs. One or more embodiments provide that the aminopolycarboxylic acid compound is an ethylenediaminetetraacetic acid compound. Examples of aminopolycarboxylic acid compounds, derivatives, and / or structural analogs include ethylenediaminetetraacetic anhydride, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic dianhydride, 4,4'-(propane-1,2-diyl)bis(morpholine-2,6-dione), 4,4'-(propane-1,3-diyl)bis(morpholine-2,6-dione), and 4,4'-(oxybis(ethane-2,1-diyl))bis(morpholine-2,6-dione). One or more embodiments of the present disclosure provide that the ethylenediaminetetraacetic acid compound can be selected from ethylenediaminetetraacetic anhydride, ethylenediaminetetraacetic acid, and combinations thereof.

[0010] Ethylenediaminetetraacetic dianhydride can be represented by the following formula: [Chemical formula]

[0011] Embodiments of the present disclosure provide that the polyol reacting with the aminopolycarboxylic acid compound can be a polyether polyol, a polyester polyol, or a combination thereof.

[0012] The polyol can be prepared, for example, by known processes using known components, known equipment, and known reaction conditions. The polyol can be commercially available.

[0013] Examples of commercially available polyols include, but are not limited to, polyols sold under the trade names VORANOL™, TERCAROL™, MOR-FREE™, PRIPLAST™, and VORATEC™.

[0014] One or more embodiments of the present disclosure provide that the polyol may include a polyether polyol. The polyether polyol can be prepared by known processes. For example, the polyether polyol can be prepared by alkoxylation of a starting compound. The alkoxylation is an anionic polyaddition of at least one alkylene oxide, such as ethylene oxide, 1,2-propylene oxide, or 1,2-butylene oxide. The starting compound is any organic compound that is alkoxylated in a polymerization reaction. The initiator may contain two or more hydroxyl and / or amine groups. A mixture of the starting compound / initiator may be used. Examples of initiator compounds include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, cyclohexanedimethanol, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, sorbitol, sucrose, and alkoxylates (particularly ethoxylates and / or propoxylates) of any of these, polyamines, and di- or trialkanolamines, but are not limited thereto. When several epoxides are used in the synthesis of the polyether polyol, the latter can have any arrangement of the desired oxyalkylene moieties. They can be homopolymers (when only one epoxide is used), copolymers, random copolymers, capped polymers, or polymers synthesized from a mixture of different epoxides to achieve the desired content of primary hydroxyl groups.

[0015] One or more embodiments of the present disclosure provide that the polyol may include a polyester polyol. The polyester-polyol may be prepared, for example, from an organic dicarboxylic acid having 2 to 12 carbon atoms, including an aromatic dicarboxylic acid having 8 to 12 carbon atoms, and a polyhydric alcohol including a diol having 2 to 12 carbon atoms. Examples of suitable dicarboxylic acids are succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, and isomeric naphthalenedicarboxylic acids. The dicarboxylic acids may be used alone or mixed with each other. The free dicarboxylic acid may be replaced with a corresponding dicarboxylic acid derivative, for example, a dicarboxylic acid ester of an alcohol having 1 to 4 carbon atoms or a dicarboxylic acid anhydride. Some specific examples may utilize a dicarboxylic acid mixture including succinic acid, glutaric acid, and adipic acid, for example, in a ratio of 20 to 35:35 to 50:20 to 32 parts by weight, adipic acid, and a mixture of phthalic acid and / or phthalic anhydride and adipic acid, phthalic acid or phthalic anhydride, a mixture of isophthalic acid and adipic acid or a dicarboxylic acid, a mixture of succinic acid, glutaric acid, and adipic acid, a mixture of terephthalic acid and adipic acid or a dicarboxylic acid, and a mixture of succinic acid, glutaric acid, and adipic acid. Examples of dihydric and polyhydric alcohols are, inter alia, ethanediol, diethylene glycol, 1,2- and 1,3-propanediol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, glycerol, trimethylolpropane. Some specific examples provide ethanediol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, or a mixture of at least two of the above diols, particularly a mixture of 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. Furthermore, polyester-polyols made from lactones, for example ε-caprolactone, or hydroxycarboxylic acids, for example ω-hydroxycaproic acid and hydroxybenzoic acid, may also be used.

[0016] The polyester-polyol can be prepared by polycondensing an organic polycarboxylic acid and / or its derivative with a polyhydric alcohol at a molar ratio of, for example, 1:1 to 1:1.8, for example 1:1.05 to 1:1.2.

[0017] The polyol used to produce the reaction product disclosed herein can have a weight average molecular weight of 300 to 12,000 g / mol. All individual values and subranges of 300 to 12,000 g / mol are included. For example, the polyol can have a weight average molecular weight of 300, 400, 500, 750, or 1000 g / mol (lower limit) to 12,000, 10,000, 8000, 5000, or 3000 g / mol (upper limit).

[0018] The polyol used to produce the reaction product disclosed herein can have an average functionality number, i.e., a hydroxyl functionality number, of 1.5 to 5.0. All individual values and subranges of 1.5 to 5.0 are included. For example, the polyol can have an average functionality number of 1.5, 1.7, or 2.0 (lower limit) to 5.0, 4.0, or 3.0 (upper limit).

[0019] The reaction product of a polyol and an aminopolycarboxylic acid compound can be prepared by reacting the polyol and the aminopolycarboxylic acid compound at a molar ratio of the moles of the hydroxyl groups of the polyol to the moles of the functional groups of the aminopolycarboxylic acid compound of 100:0.5 to 100:10. All individual values and subranges of the molar ratio of the moles of the hydroxyl groups of the polyol to the moles of the functional groups of the aminopolycarboxylic acid compound of 100:0.5 to 100:10 are included. For example, the polyol can react with an ethylenediaminetetraacetic acid compound at a molar ratio of the moles of the hydroxyl groups of the polyol to the moles of the functional groups of the aminopolycarboxylic acid compound of 100:0.5, 100:1, 100:2, 100:3, 100:4, 100:5, 100:6, 100:7, 100:8, 100:9, or 100:10. The functional groups of the aminopolycarboxylic acid compound include dianhydrides, monoanhydride diacids, tetraacids, and combinations thereof.

[0020] The reaction product can be formed using known apparatus and reaction conditions. For example, the reactants, namely the polyol and the aminopolycarboxylic acid compound, can be heated to any desired temperature for a specific time sufficient to achieve the desired chemical / physical transformation. As an example, the reaction product can be formed at a temperature of 50°C to 200°C. The reaction can occur, for example, by being maintained for about 5 minutes to about 48 hours. Also, the reaction can occur in an inert environment such as a nitrogen environment. The reaction product can optionally be formed using a catalyst.

[0021] The reaction product of the polyol and the aminopolycarboxylic acid compound can have units derived from the aminopolycarboxylic acid compound that are from 0.03 to 10.0 weight percent based on the total weight of the reaction product. All individual values and subranges of units derived from the aminopolycarboxylic acid compound of 0.03 weight percent to 10.0 weight percent are included. For example, the reaction product can have units derived from the aminopolycarboxylic acid compound that are 0.03, 0.05, 0.08, or 1.0 weight percent (lower limit) to 10.0, 8.0, 6.0, or 5.0 weight percent (upper limit) based on the total weight of the reaction product.

[0022] Embodiments of the present disclosure provide a solvent-free composition comprising a reaction product of a polyol and an aminopolycarboxylic acid compound and an isocyanate. The solvent-free composition can be prepared by mixing using known conditions and known equipment, which may vary depending on different applications, for example.

[0023] The isocyanate may be a polyisocyanate. As used herein, "polyisocyanate" refers to a molecule having an average of more than 1.0 isocyanate groups / molecule, for example, an average functionality of more than 1.0.

[0024] The isocyanate can be, for example, an aliphatic polyisocyanate, an alicyclic polyisocyanate, an arylaliphatic polyisocyanate, an aromatic polyisocyanate, or a combination thereof. Examples of isocyanates include, inter alia, toluene 2,4- / 2,6-diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), polymeric MDI, triisocyanatononane (TIN), naphthyldiisocyanate (NDI), 4,4'-diisocyanatodicyclohexylmethane, 3-isocyanatomethyl-3,3,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate IPDI), tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate (THDI), dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 4,4'-diisocyanato-3,3'-dimethyldicyclohexylmethane, 4,4'-diisocyanato-2,2-dicyclohexylpropane, 3-isocyanatomethyl-1-methyl-1-isocyanatocyclohexane (MCI), 1,3-diisocyanato-4-methylcyclohexane, 1,3-diisocyanato-2-methylcyclohexane, and combinations thereof, but are not limited thereto. Similar to the above isocyanates, partially modified polyisocyanates including, inter alia, uretdione, isocyanurate, carbodiimide, uretonimine, allophanate, or biuret structures, and combinations thereof may also be used.

[0025] The isocyanate can be polymeric. As used herein, "polymer" refers to higher molecular weight homologs and / or isomers in the context of the description of isocyanates. For example, polymeric methylene diphenyl isocyanate refers to higher molecular weight homologs and / or isomers of methylene diphenyl isocyanate.

[0026] The isocyanate can be a prepolymer. For example, the isocyanate can be an isocyanate-terminated prepolymer, such as an isocyanate-terminated polyurethane prepolymer. The prepolymer can be prepared by reacting an isocyanate and a polyol.

[0027] As described above, the isocyanate can have an average functionality number of more than 1.0 isocyanate groups / molecule. For example, the isocyanate can have an average functionality number of 1.75 to 3.50. All individual values and sub-ranges from 1.75 to 3.50 are included. For example, the isocyanate can have an average functionality number of 1.75, 1.85, or 1.95 (lower limit) to 3.50, 3.40, or 3.30 (upper limit).

[0028] The isocyanate can have an isocyanate equivalent weight of 125 g / eq to 300 g / eq. All individual values and sub-ranges from 125 to 300 g / eq are included. For example, the isocyanate can have an isocyanate equivalent weight of 125, 135, or 145 (lower limit) to 300, 290, or 280 g / eq (upper limit).

[0029] The isocyanate may be prepared by known processes. For example, the isocyanate can be provided by phosgenating the corresponding polyamine, involving the formation of polycarbamoyl chloride and its thermal decomposition, to provide the isocyanate and hydrogen chloride, or by a phosgene-free process. For example, the corresponding polyamine can be reacted with urea and alcohol to obtain a polycarbamate, and by its thermal decomposition, for example, the isocyanate and alcohol can be obtained.

[0030] Isocyanates are commercially available. Examples of commercially available isocyanates and / or NCO-terminated prepolymers include, among other commercially available isocyanates, the isocyanates of the trade names MOR-FREE™, VORANATE™, and PAPI™ available from The Dow Chemical Company, but are not limited thereto.

[0031] Isocyanates can be utilized such that the solvent-free composition has an isocyanate index in the range of 1.0 to 1.6. The isocyanate index can be determined by dividing the equivalent weight of the isocyanate by the total equivalent weight of the isocyanate-reactive components of the solvent-free composition, e.g., the total equivalent weight of isocyanate-reactive hydrogen, and multiplying. In other words, the isocyanate index can be determined as the ratio of isocyanate groups to isocyanate-reactive hydrogen. All individual values and subranges from 1.0 to 1.6 are included, e.g., the solvent-free composition can have an isocyanate index of 1.0, 1.05, or 1.1 (lower limit) to 1.6, 1.5, or 1.45 (upper limit).

[0032] The solvent-free composition can include a catalyst, e.g., known catalysts utilized in the formation of polyurethanes. Examples of catalysts include aluminum catalysts, bismuth catalysts, tin catalysts, vanadium catalysts, zinc catalysts, zirconium catalysts, titanium catalysts, amine catalysts, and combinations thereof. One or more embodiments provide that the catalyst is selected from dibutyltin diacetate, dibutyltin dilaurate, dibutyltin diacetylacetonate, dibutyltin dimercaptide, dibutyltin dioctoate, dibutyltin dimaleate, dibutyltin acetonylacetonate, dibutyltin oxide, and combinations thereof. When used, the catalyst can be from 0.001 parts per million (ppm) to 100 ppm based on the total weight of the solvent-free composition. For example, the catalyst can be from 0.005 ppm to 10 ppm based on the total weight of the solvent-free composition.

[0033] Solventless compositions are known in the art and can be used in many applications, for example, as adhesives such as laminate adhesives or as coatings. Embodiments of the present disclosure provide that the solventless composition can include one or more additional components, such as known components used with adhesive compositions and / or known components used with coating compositions. Different additional components and / or different amounts of additional components can be used for various applications. Examples of additional components include polyols, surfactants, chelating agents, crosslinking agents, chain extenders, antioxidants, and combinations thereof, among other known components.

[0034] Advantageously, the solventless composition can be applied to materials. For example, the solventless composition can be applied to a first material, and a second material may be contacted with the solventless composition. Thereafter, the solventless composition can be cured to form a laminate. Also, the solventless composition can be applied to a first material, and then the composition can be cured to form a coating. The solventless composition can be applied by known processes, such as known components, known apparatuses, and known application conditions such as gravure lamination, flexographic lamination. In addition, the solventless composition and isocyanate can be applied on different substrates and then laminated together.

[0035] The solventless compositions disclosed herein can be cured. For example, the reaction products of polyols and aminopolycarboxylic acid compounds and isocyanates can react with each other to form a cured product. Known curing conditions such as temperature, humidity, and duration can be utilized to cure the solventless compositions disclosed herein.

[0036] Advantageously, the solventless compositions disclosed herein can provide improved T-peel bond strength at 7 days, for example, when cured, compared to other compositions containing a polyol similar to the polyol used to make the reaction product. As described above, an increase in T-peel bond strength at 7 days indicates higher adhesion strength. This higher adhesion strength may desirably help to provide a greater seal with products made using the solventless compositions disclosed herein.

[0037] Advantageously, the solventless compositions disclosed herein can provide improved boil-in-bag values, for example, when cured, compared to other compositions containing a polyol similar to the polyol used to make the reaction product. The improved boil-in-bag values indicate higher adhesion strength when packaging products made using the solventless compositions disclosed herein are used, especially in combination with consumer products such as sources. In other words, the improved boil-in-bag values may indicate that the resistance of the consumer product to package breakage is desirably improved.

[0038] In addition, the solventless compositions containing the reaction product can provide improved, i.e., faster, curing compared to other compositions containing a polyol similar to the polyol used to make the reaction product. Advantageously, the relatively fast curing can help to provide a faster breakdown of primary aromatic amine (PAA). The faster decay of the primary aromatic amine may be desirable for many applications, such as those related to food regulatory compliance. Further, the solventless compositions containing the reaction product can provide improved, for example, extended pot life, compared to other compositions containing a polyol similar to the polyol used to make the reaction product.

[0039] As used herein, a polyol similar to the polyol used to make the reaction product refers to the same polyol as the polyol used to make the reaction product, or a polyol having a weight average molecular weight that is +10% and an average hydroxyl functionality that is +10% compared to the polyol utilized to make the reaction product.

[0040] Embodiments provide that the solventless composition can be utilized with various materials, such as substrates. Examples of materials that can be utilized with the solventless compositions disclosed herein include polymeric materials such as polyethylene terephthalate, polyethylene, polypropylene, and combinations thereof. The polymeric materials can be, for example, films. Embodiments provide that the materials that can be utilized with the solventless composition can include metals, such as foils or metallized films. Foils and metallized films are well known. For example, the polymeric materials can be pretreated, such as by corona treatment and plasma treatment, prior to metallization. Next, the metallization can be carried out by a physical vapor deposition process. In such a process, the metal is heated and evaporated under vacuum. Next, the metal condenses on the polymeric material to form a metallized film. Examples of suitable metals include, but are not limited to, aluminum, nickel, chromium, and combinations thereof. Embodiments provide that the adhesive composition can be utilized, for example, in laminating films to each other and laminating films to foils.

Examples

[0041] In this example, various terms and names related to materials are used, including, for example, the following.

[0042] Aminopolycarboxylic acid compound (ethylenediaminetetraacetic dianhydride, obtained from Aldrich);

[0043] Polyol #1 (polyol; 70 wt% polyether polyol / 30 wt% castor oil blend; the average functionality of the polyether polyol is 2.0 - 3.0, and the weight average equivalent is 1280 g / mol).

[0044] Polyol #2 (63 wt% polyol / 27 wt% castor oil / 10 wt% silane blend; the average functionality of the polyol is 2.0 - 3.0, and the weight average equivalent is 1200 g / mol);

[0045] PACACEL L-75-191 (NCO-terminated solventless polyurethane adhesive; obtained from The Dow Chemical Company);

[0046] Metallized PET film (48 g metallized PET film; obtained from Filmquest Group); PET film (48 LBT; polyester film [poly(ethylene glycol - terephthalate)]; obtained from DuPont); PET / foil laminated film (PET Al foil film; obtained from FILM TECH Inc.); low-density polyethylene film (GF-19 film); high-slip low-density film; thickness 1.5 mil; obtained from Berry Plastics Corp).

[0047] Example 1, the reaction product of polyol and ethylenediaminetetraacetic dianhydride was prepared as follows. Polyol #1 (99.5 grams) was added to a container and dried under nitrogen at about 120 °C for 60 minutes. Then, the contents of the container were cooled to about 80 °C, and ethylenediaminetetraacetic dianhydride (0.5 grams) was added to the container. The contents of the container were slowly heated to 150 °C and maintained at that temperature for about 1 hour. Then, the contents of the container were slowly heated to 160 °C and maintained at that temperature for about 1 hour. Then, the contents of the container were slowly heated to 180 °C and maintained at that temperature for about 3 hours. Next, the contents of the container were cooled to about 60 °C and filtered to obtain Example 1. In Example 1, the units derived from ethylenediaminetetraacetic dianhydride were 0.5 weight percent based on the total weight of Example 1.

[0048] Example 2. A reaction product of a polyol and ethylenediaminetetraacetic dianhydride was prepared as in Example 1 with the modification that polyol #1 (99 grams) was utilized. Example 2 contained units derived from ethylenediaminetetraacetic dianhydride at 1.0 weight percent based on the total weight of Example 2.

[0049] Some properties. Examples 1 - 2 and polyol #1. The OH number was determined according to ASTM E1899 - 08. The acid number was determined according to ASTM D4274 - 16. The number average molecular weight (M n ) and weight average molecular weight (M w ) were by SEC analysis as described below. Each sample (0.01 gram) was dissolved in tetrahydrofuran (4.0 mL) to obtain a sample concentration (2.5 mg / mL). Separation module: Waters e2695; Columns: Polymer Labs PLGel Mixed - E columns × 2, 3 μm particle size and Mixed - C column × 1, 5 μm particle size; Column temperature: 40 °C; Eluent: Tetrahydrofuran (stabilized); Flow rate: 1 mL / min; Injection volume: 50 μL; Analysis time: 40 min; Detector: Waters 2414 refractive index detector (40 °C); Calibration: Agilent Technologies Polystyrene (PS) - Medium EasiVials, batch number 0006386106; Software: Agilent OpenLAB CDS (EZChrome Edition) Version A.04.06.

[0050] The results are reported in Table 1.

Table 1

[0051] The data in Table 1 show that for Examples 1 - 2, reaction products of a polyol and ethylenediaminetetraacetic dianhydride were prepared.

[0052] The solvent-free composition of Example 3 was formed as follows. Example 1 and PACACEL L75-191 were mixed with an isocyanate index of 1.3 for 10 minutes using a roller mixer to obtain Example 3.

[0053] The solvent-free composition of Example 4 was formed as follows. Example 2 and PACACEL L75-191 were mixed with an isocyanate index of 1.3 for 10 minutes using a roller mixer to obtain Example 4.

[0054] A laminate was prepared using Example 3 as follows. An oil-heated roll handler laminator (nip temperature 150°F; running speed 20 feet / minute) and a coating weight of about 1.05 pounds / ream were used. The laminate was prepared for each sheet having a coating area of about 12 inches × 10 inches. Example 3 was formulated as a 35 weight percent solids in ethyl acetate and then coated onto a primary film. The coated primary film was oven dried (90°C, about 1 minute). Next, the coated primary film was laminated to a secondary film using an oil-heated roll handler laminator (about 40 psi). Next, the laminate was cured at about 20°C for 7 days.

[0055] The laminate was prepared to obtain an isocyanate index of 1.3 using Comparative Example A consisting of polyol #1 and PACACEL L75-191 as described above.

[0056] A T-peel bond strength test and a boil-in-bag test were performed on the laminate. The results are reported in Table 2.

[0057] The T-peel bond strength was measured on a 1-inch strip at a speed of 10 inches / minute using an Instron tensile tester equipped with a 50 N load cell. Three strips were tested for each laminate, and the high strength and average strength were recorded together in the failure mode. For film tear and film elongation, the high value was reported, and for other failure modes, the average T-peel bond strength was reported.

[0058] The boil-in-bag test of the laminate was carried out as follows. The cured laminate (9 inches × 11 inches) was folded to form a double layer such that the PE film of one layer contacted the PE film of the other layer. Next, the edges were trimmed with a paper cutter to obtain a folded portion (about 5 inches × 7 inches). Next, the edges were heat-sealed to form a pouch with an internal size of 4 inches × 6 inches. Then, 100 mL of an equal weight part source blend of ketchup, vinegar, and vegetable oil was filled into the pouch from the open edge. After filling, the pouch was sealed while minimizing the entrapment of air inside the pouch. Next, the filled pouch was carefully placed in boiling water and immersed in water for 30 minutes or 60 minutes. When completed, the degree of tunneling, delamination, and / or leakage was compared with the marked existing defects.

Table 2

[0059] The data in Table 2 indicate that Example 3 had advantageously improved T-peel bond strength at 7 days compared to Comparative Example A for both laminates containing metallized films.

[0060] In addition, the data in Table 2 indicate that Example 3 had advantageously improved boil-in-bag values at 30 minutes compared to Comparative Example A for the laminate containing metallized film. The improved boil-in-bag values advantageously indicated higher adhesion strength to the test source blend.

[0061] The laminate was prepared using Example 4 as described above. The laminate was prepared to obtain an isocyanate index of 1.3 using Comparative Example B consisting of polyol #2 and PACACEL L75-191 as described above. As described above, the T-peel bond strength test and the boil-in-bag test were performed on the laminate. The results are reported in Table 3.

Table 3

[0062] The data in Table 3 indicate that Example 4 advantageously had improved 7-day T-peel bond strength for both laminates containing the metallized film, as compared to Comparative Example B.

[0063] In addition, the data in Table 3 indicate that Example 4 advantageously had improved 30-minute boil-in-bag values for the laminate containing the metallized film, as compared to Comparative Example B. The improved boil-in-bag values advantageously indicated higher adhesion strength to the test source blend.

[0064] In addition, the data in Table 3 indicate that Example 4 advantageously had improved 60-minute boil-in-bag values for the laminate containing the metallized film, as compared to Comparative Example B. The improved boil-in-bag values advantageously indicated higher adhesion strength to the test source blend.

[0065] The breakdown of the primary aromatic amine ("PAA") was determined as follows. Samples were cured at 25 °C and 50% relative humidity for 2 days. Next, the cured laminate structure was folded to form a bilayer such that the polyethylene film of one layer contacted the polyethylene film of the other layer. Next, the edges were trimmed with a paper cutter to obtain a folded portion (approximately 6.5 inches × 7 inches). Next, the edges were heat-sealed to form a pouch with an internal size of 5.5 inches × 5.6 inches. Next, the pouch was filled with 100 mL of a 3 weight percent acetic acid solution. The pouch was extracted in an air-circulation oven at 70 °C for 2 hours, then quenched with cold tap water to equilibrate the test solution at room temperature, and 100 ml of the test solution was transferred to a beaker. The amount of primary aromatic amine extracted into the 3 weight percent acetic acid solution was determined by colorimetry. The results are reported in Table 4.

Table 4

[0066] The data in Table 4 indicate that the primary aromatic amine decay in Example 4 was advantageously improved, i.e., decreased, compared to Comparative Example A.

[0067] Furthermore, the data in Table 4 show that, in contrast to Comparative Example A, Example 4 advantageously had a primary aromatic amine concentration of less than 2.0 ppb. The Position Paper of the German Federal Institute for Risk Assessment (BfR) recommends a primary aromatic amine concentration of less than 2.0 ppb. The invention described in the original claims of the present application is appended below. [1] A solvent-free composition comprising: a reaction product produced by reacting a polyol and an aminopolycarboxylic acid compound; and an isocyanate. [2] The solvent-free composition according to [1], wherein the aminopolycarboxylic acid compound is an ethylenediaminetetraacetic acid compound. [3] The solvent-free composition according to [1] or [2], wherein the aminopolycarboxylic acid compound is selected from ethylenediaminetetraacetic anhydride, ethylenediaminetetraacetic acid, and combinations thereof. [4] The solvent-free composition according to any one of [1] to [3], wherein the unit derived from the aminopolycarboxylic acid compound is 0.03 to 10.0% by weight based on the total weight of the reaction product. [5] The solvent-free composition according to any one of [1] to [4], wherein the polyol has a weight average molecular weight of 300 to 12,000 g / mol. [6] The solvent-free composition according to any one of [1] to [5], wherein the polyol has an average functionality of 1.5 to 5.0. [7] The solvent-free composition according to any one of [1] to [6], wherein the polyol and the aminopolycarboxylic acid compound are reacted at a molar ratio of the hydroxyl groups of the polyol to the functional groups of the aminopolycarboxylic acid compound of 100:0.5 to 100:10. [8] The solvent-free composition according to any one of [1] to [7], wherein the solvent-free composition has an isocyanate index in the range of 1.0 to 1.6. [9] A laminate formed from the solvent-free composition according to any one of [1] to [8].

Claims

1. A solvent-free composition comprising: a reaction product produced by reacting a polyol and an aminopolycarboxylic acid compound, and an isocyanate, wherein the aminopolycarboxylic acid compound is ethylenediaminetetraacetic anhydride, and the unit derived from the aminopolycarboxylic acid compound in the reaction product is 0.03 to 10.0% by weight based on the total weight of the reaction product. A solvent-free composition.

2. The solvent-free composition according to claim 1, wherein the polyol has a weight average molecular weight of 300 to 12,000 g / mol.

3. The solvent-free composition according to claim 1 or 2, wherein the polyol has an average functionality of 1.5 to 5.

0.

4. The solvent-free composition according to any one of claims 1 to 3, wherein the polyol and the aminopolycarboxylic acid compound are reacted at a molar ratio of the hydroxyl group of the polyol to the functional group of the aminopolycarboxylic acid compound of 100:0.5 to 100:

5.

5. The solvent-free composition according to any one of claims 1 to 4, wherein the solvent-free composition has an isocyanate index in the range of 1.0 to 1.

6.

6. A laminate formed from the solvent-free composition according to any one of claims 1 to 5.

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