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WO2025029423A1 - Composition adhésive à base de polycarbodiimide - Google Patents

Composition adhésive à base de polycarbodiimide Download PDF

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Publication number
WO2025029423A1
WO2025029423A1 PCT/US2024/036355 US2024036355W WO2025029423A1 WO 2025029423 A1 WO2025029423 A1 WO 2025029423A1 US 2024036355 W US2024036355 W US 2024036355W WO 2025029423 A1 WO2025029423 A1 WO 2025029423A1
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WO
WIPO (PCT)
Prior art keywords
adhesive composition
cdi
component
substrate
isocyanate
Prior art date
Application number
PCT/US2024/036355
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English (en)
Inventor
James M. CABRERA
Manesh Nadupparambil Sekharan
Nolan T. MCDOUGAL
Yinzhong Guo
Original Assignee
Dow Global Technologies Llc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Global Technologies Llc filed Critical Dow Global Technologies Llc
Publication of WO2025029423A1 publication Critical patent/WO2025029423A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/341—Dicarboxylic acids, esters of polycarboxylic acids containing two carboxylic acid groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/797—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing carbodiimide and/or uretone-imine groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group

Definitions

  • the adhesive composition includes a reaction product formed from (A) a carbodiimide (CDI) component and (B) a CDI reactive component (r-CDI) selected from the group consisting of (i) a polycarboxylic acid functional polyester resin, and (ii) an amine functional resin.
  • CDI carbodiimide
  • r-CDI CDI reactive component
  • the present disclosure also provides a laminate.
  • the laminate includes a first substrate, a second substrate, and an adhesive composition disposed between the first substrate and the second substrate.
  • the adhesive composition includes a reaction product formed from (A) a carbodiimide (CDI), and (B) a CDI reactive component (r-CDI) selected from the group consisting of (i) a polycarboxylic acid functional polyester resin and (ii) an amine functional resin.
  • FIG. 1A is an infrared (IR) spectrograph of an NCO-terminated prepolymer used for preparing a carbodiimide component in accordance with an embodiment of the present disclosure (CDI-1).
  • IR infrared
  • FIG. IB is an IR spectrograph of a carbodiimide formed from the NCO-terminated prepolymer of FIG. 1A, in accordance with an embodiment of the present disclosure (CDI-1).
  • FIG. 2B is an IR spectrograph of a carbodiimide formed from the NCO-terminated prepolymer of FIG. 1A, in accordance with an embodiment of the present disclosure (CDI-2).
  • An "amine” refers to a compound containing: NR1R2R3, where each of Ri, R2 and R3 is independently selected from hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl (including pyridines), substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, silyl, and combinations thereof.
  • aryl refers to an aromatic substituent which may be a single aromatic ring or multiple aromatic rings which are fused together, linked covalently, or linked to a common group such as a methylene or ethylene moiety.
  • the aromatic ring(s) may include phenyl, naphthyl, anthracenyl, and biphenyl, among others.
  • aryls have from 1 to 200 carbon atoms, or from 1 to 50 carbon atoms, or from 1 to 20 carbon atoms.
  • composition refers to a mixture of materials which comprise the composition, as well as reaction products and decomposition products formed from the materials of the composition.
  • ether group is a moiety containing an oxygen atom bonded to two alkyl or aryl groups.
  • substituted ether group refers to an ether in which one or more hydrogen atom bound to any carbon of the alkyl or aryl is replaced by another group such as a phosphate, a hydroxy, and combinations thereof.
  • hydrocarbon is a compound that contains only hydrogen and carbon atoms.
  • the hydrocarbon can be (i) branched or unbranched, (ii) saturated or unsaturated, (iii) cyclic or acyclic, and (iv) any combination of (i)-(iii)-
  • Nonlimiting examples of hydrocarbons include alkyls, aryls, alkanes, alkenes, and alkynes.
  • An "isocyanate” is a compound that contains at least one isocyanate group in its structure.
  • a "polyisocyanate” (or “multifunctional isocyanate”) is an isocyanate containing more than one, or at least two, isocyanate groups.
  • a polyisocyanate having two isocyanate groups is a diisocyanate and an isocyanate having three isocyanate groups is a triisocyanate, etc.
  • Isocyanates include aromatic isocyanates, aromatic polyisocyanates, aliphatic isocyanates and aliphatic polyisocyanates.
  • a "polyester” is a compound containing two or more ester linkages in the same linear chain of atoms.
  • a "polyester polyol” is a compound that is a polyester and a polyol.
  • suitable polyester polyols include polycondensates of diols, polyols (e.g., triols, tetraols), dicarboxylic acids, polycarboxylic acids (e.g., tricarboxylic acids, tetracarboxylic acids), hydroxycarboxylic acids, lactones, and combinations thereof.
  • the polyester polyols can also be derived from, instead of the free polycarboxylic acids, the corresponding polycarboxylic anhydrides, or corresponding polycarboxylic esters of lower alcohols.
  • a "polymer” is a polymeric compound prepared by polymerizing monomers, whether of the same or a different type.
  • the generic term polymer thus embraces the term “homopolymer” (employed to refer to polymers prepared from only one type of monomer, with the understanding that trace amounts of impurities can be incorporated into the polymer structure), and the term “interpolymer,” which includes copolymers (employed to refer to polymers prepared from two different types of monomers), terpolymers (employed to refer to polymers prepared from three different types of monomers), and polymers prepared from more than three different types of monomers. Trace amounts of impurities, for example, catalyst residues, may be incorporated into and/or within the polymer.
  • a "polyol” is an organic compound containing multiple hydroxyl (—OH) groups.
  • a polyol contains at least two hydroxyl groups.
  • suitable polyols include diols (which contain two hydroxyl groups) and triols (which contain three hydroxyl groups).
  • the NCO-terminated prepolymer is an aliphatic isocyanate.
  • An "aliphatic isocyanate” is an isocyanate that is void of, or contains no, aromatic rings.
  • Aliphatic isocyanates include cycloaliphatic isocyanate, in which the chemical chain is ring-structured.
  • the aliphatic isocyanate contains from 3, or 4, or 5, or 6 to 7, or 8, 10, 12, or 13, or 14, or 15, or 16 carbon atoms in the linear, branched, or cyclic alkylene residue.
  • Nonlimiting examples of suitable aliphatic isocyanates include cyclohexane diisocyanate; methylcyclohexane diisocyanate; ethylcyclohexane diisocyanate; propylcyclohexane diisocyanate; methyldiethylcyclohexane diisocyanate; propane diisocyanate; butane diisocyanate; pentane diisocyanate; hexane diisocyanate; heptane diisocyanate; octane diisocyanate; nonane diisocyanate; nonane triisocyanate; decane di- and tri-isocyanate; undecane di- and tri-isocyanate; dodecane di- and tri-isocyanate; isophorone diisocyanate; hexamethylene diisocyanate; diisocyanatodicyclohexylmethane; 2-methylpentane di
  • the GDI component is formed by converting the isocyanate groups of the NCO-terminated prepolymer into carbodiimide groups using a catalyst.
  • the catalyst is a cyclic phosphorous compound, e.g., substituted phospholene-l-oxide, phosphetane 4-oxide, 1,3-diazaphospholidine oxide, 1,3-dimethylphospholine-l-oxide, 1- ethyl-3-methylphospholine-l-oxide, l-phenyl-3-methylphospholine-l-oxide, 1- phenylphospholene-l-oxide, l,3,2-diazaphospholidine-2-oxide, 3-methyl-l-phenyl-2- phospholene-l-oxide, and combinations thereof.
  • the catalyst is 3- methyl-phenyl-2-phospholene-l-oxide.
  • the conversion of the isocyanate groups to carbodiimide groups lowers the weight percent of the isocyanate in the prepolymer from an initial range from 5 wt% to 20 wt% of isocyanate groups to a final range of isocyanate groups in the CDI component to less than 1 wt%.
  • the CDI component has less than 1 wt% isocyanate, or 0 wt% or from greater than 0 wt% to 0.5 wt%, or 0 wt% or from greater than 0 wt% to 0.3 wt%, or 0 wt% or from greater than 0 wt% to 0.1 wt% isocyanate content.
  • Weight percent is based on total weight of the CDI component.
  • the CDI component is formed from an NCO-terminated prepolymer and has one, some, or all of the following properties:
  • the adhesive composition contains (B) the carbodiimide reactive component (or "r-CDI").
  • the r-CDI is a carboxyl functional polyester resin, an amine functional resin polyol component, and combinations thereof.
  • the r-CDI component is the polycarboxylic acid functional polyester resin ("PAFP").
  • the polycarboxylic acid functional polyester resin was synthesized by polyesterification of two or more diols with two or more dicarboxylic acids with excess mol% of the dicarboxylic acids.
  • the PAFP is a polyester with terminal carboxylic acid functional groups at each chain-end.
  • the PAFP resin has one, some, or all of the following properties:
  • a weight average molecular weight, Mw from 400 g/mol to 3000 g/mol; or from 500g/mol to 2000g/mol; and/or
  • the r-CDI component is the amine functional resin.
  • the amine functional resin has a terminal amine functional group at each chain-end.
  • the terminal amine can be a primary amine or a secondary amine.
  • the amine functional resin is a polyetheramine having a terminal amine functional group at each chain-end.
  • the adhesive composition is prepared by adding the CDI component (A) and the r-CDI component (B) to a polar solvent and mixing to obtain a homogeneous solution.
  • a "polar solvent” is a substance capable of dissolving another substance (solute) to form a uniformly dispersed mixture (solution) at the molecular or ionic level; the solvent composed of molecules in which positive and negative electrical charges are permanently separated, as opposed to nonpolar molecules in which the charges coincide.
  • polar solvents include alcohols, ketones and esters.
  • the polar solvent is an ester.
  • suitable esters include butyl acetate and ethyl acetate.
  • the solvent is ethyl acetate.
  • the CDI component (A) and the r-CDI component (B) are completely dissolved, or substantially dissolved, and are combined, or otherwise mixed, in the solvent at a temperature from 15°C to 45°C, or from 20°C to 25°C for a period from 10 minutes to 30 minutes.
  • the GDI component (A) and the r-CDI component react in the polar solvent; the adhesive composition is the reaction product of (A) the CDI component; (B) the r-CDI component.
  • the adhesive composition has a solids content from 20 wt% to 45 wt%, or from 30 wt% to 40 wt%, or 35 wt%, based on the total weight of the adhesive composition and the solvent.
  • the adhesive composition includes
  • the adhesive composition includes
  • the present disclosure provides a laminate.
  • the laminate includes a first substrate, a second substrate, and an adhesive layer between the first substrate and the second substrate.
  • the adhesive layer is formed from the present adhesive composition.
  • the adhesive composition may be any adhesive composition with the CDI component (A) and the r-CDI component (B) as disclosed herein.
  • the laminate includes a first substrate and a second substrate.
  • the first substrate and the second substrate may be the same or different.
  • the first substrate and the second substrate are the same, such that they have the identical compositions and identical structures.
  • the first substrate and the second substrate are compositionally distinct and/or structurally distinct from one another.
  • substrate refers to the first substrate and the second substrate, individually and/or collectively.
  • a nonlimiting example of a suitable substrate is a film.
  • the film may be a monolayer film or a multilayer film.
  • the multilayer film contains two layers, or more than two layers.
  • the multilayer film can have two, three, four, five, six, seven, eight, nine, ten, eleven, or more layers.
  • the multilayer film contains only two layers, or only three layers.
  • the film is a monolayer film with one, and only one, layer.
  • the film includes a layer containing a component selected from ethylene-based polymer, propylene-based polymer (PP), polyamide (such as nylon), polyester, ethylene vinyl alcohol (EVOH) copolymer, polyethylene terephthalate (PET), ethylene vinyl acrylate (EVA) copolymer, ethylene methyl acrylate copolymer, ethylene ethyl acrylate copolymer, ethylene butyl acrylate copolymer, ethylene acrylic acid copolymer, ethylene methacrylic acid copolymer, an ionomer of ethylene acrylic acid, an ionomer of methacylic acid, maleic anhydride grafted ethylene-based polymer, a polylactic acid (PLA), a polystyrene, a metal foil, a cellulose, cellophane, nonwoven fabric, and combinations thereof.
  • a nonlimiting example of a suitable metal foil is aluminum foil.
  • the film includes a layer containing metal foil.
  • the film is a monolayer film having a single layer that is an ethylenebased polymer layer. In a further embodiment, the film is a monolayer film having a single layer that is a polyethylene layer.
  • the substrate, and further the film, is a continuous structure with two opposing surfaces.
  • the substrate has a thickness from 5 pm, or 10 pm, or 15 pm, or 20 pm to 25 pm, or 30 pm, or 40 pm, or 50 pm, or 100 pm, or 200 pm, or 300 pm, , or 400 pm, or 500 pm.
  • the first substrate is a film having a layer that is a metal foil layer; and the second substrate is a monolayer film having a single layer that is an ethylene-based polymer layer (such as low density polyethylene (LDPE)) or a propylene-based polymer layer (such as polypropylene).
  • LDPE low density polyethylene
  • propylene-based polymer layer such as polypropylene
  • the first substrate may comprise two or more embodiments disclosed herein.
  • the second substrate may comprise two or more embodiments disclosed herein.
  • the adhesive composition is applied between the first substrate and the second substrate, such as with a Nordmeccanica Labo Combi laminator, for example.
  • Nonlimiting examples of suitable application methods include brushing, pouring, spraying, coating, rolling, spreading, and injecting.
  • the adhesive composition is applied between the first substrate and the second substrate at a coat weight from 0.5 grams per square meter (g/m 2 ) to 5.0 g/m 2 .
  • the adhesive composition is uniformly applied on the first substrate, on the second substrate, or on both first and second substrates, the solvent is evaporated to form an adhesive layer, and then the adhesive layer is brought into contact with the second substrate.
  • a "uniform application” is a layer of the composition that is continuous (not intermittent) across a surface of the substrate, and of the same, or substantially the same, thickness across the surface of the substrate. In other words, a composition that is uniformly applied to a substrate directly contacts the substrate surface, and the composition is coextensive with the substrate surface.
  • the adhesive composition and the first substrate are in direct contact with each other.
  • the term "directly contacts,” as used herein, is a layer configuration whereby a substrate is located immediately adjacent to a two-component solvent-based adhesive composition, or an adhesive layer and no intervening layers, or no intervening structures, are present between the substrate and the two-component solvent-based adhesive composition, or the adhesive layer.
  • the adhesive composition directly contacts a surface of the first substrate.
  • the structure containing the first substrate and the adhesive composition has the following Structure (D):
  • the Structure (D) is dried to form an adhesive layer in direct contact with the first substrate.
  • the Structure (D) is dried by passing it through an oven at a temperature sufficient to evaporate all, or substantially all, of the solvent from the adhesive composition. Then, the adhesive layer is contacted with the second substrate to form a laminate.
  • the first substrate is in direct contact with the adhesive layer and the second substrate is in direct contact with the adhesive layer and the laminate has the following Structure (E): First Substrate / Adhesive Layer I Second Substrate Structure (E).
  • the adhesive layer and the second substrate are in direct contact with each other.
  • the adhesive layer directly contacts a surface of the second substrate.
  • the adhesive layer of Structure (E) is formed from curing, or drying the adhesive composition.
  • the adhesive composition is formed from mixing and reacting the (A) CDI component and the (B) r-CDI component in the presence of (C) the polar solvent (and subsequent removal of the solvent), as disclosed above.
  • the laminate includes the first substrate in direct contact with the adhesive layer, and the second substrate in direct contact with the adhesive layer.
  • the present disclosure also provides an article containing the laminate.
  • suitable articles include packages, bags, pouches, deep-drawn cans, and containers.
  • the laminate contacts a comestible.
  • a "comestible" is an edible food item.
  • FT-IR in FIGS. 1A-1B confirmed the loss of the isocyanate peak (2257 cm -1 ) in FIG. 1A and increase of the carbodiimide peak (2106, 2132 cm' 1 ) in FIG IB. After completion of the reaction, the mixture was cooled to room temperature and stored in the glovebox.
  • NCN carbodiimide
  • Moles of CO 2 formed (Moles of NCN) x MW (CO 2 )
  • ISONATETM 125M was added, previously melted in a water-bath.
  • a polyether polyol (Voranol PUP 2025) was pre-heated to 50°C and added to the heated ISONATETM 125M to form a reaction mixture.
  • reaction mixture was stirred, until exothermic phenomena were completed. Then, the reaction mixture was heated to 80-85°C. The reaction mixture was maintained under constant stirring at 80°C for 1.5 hours. Residual %NCO was determined via titration. The reaction mixture was cooled to 40-50°C and transferred to metallic cans. The metallic cans were filled with nitrogen to prevent reaction with moisture and stored in a freezer until the stripping step.
  • reaction product mixture (RPA) was then subjected to distillation without solvent as follows: evaporator temperature of 175°C, condenser temperature of 45°C, pressure of 0.04 mbar, feed rate of 0.6 to 1.2 kg/hour, wiper speed of 360 U/minute, using a laboratory-scale UIC KDL 5 distillation device, using a single pass, thereby forming the NCO-terminated prepolymer.
  • the properties of the NCO-terminated prepolymer are shown in Table B below.
  • Table B NCO-terminated prepolymer properties (weight percent based on total weight of NCO-terminated prepolymer).
  • the NCO-terminated prepolymer is substantially void of free isocyanate monomer (less than 0.15 wt% free MDI, or 0.13 wt% free MDI) as shown in Table B below.
  • FT-IR in FIGS. 2A-2B confirmed formation of CDI-2 by the loss of the isocyanate peak (2261 cm' 1 ) in FIG. 2A and increase of the carbodiimide peak (2111, 2137 cm' 1 ) in FIG 2B. After completion of the reaction, the mixture was cooled to room temperature and stored in the glovebox.
  • the PAFP resin was synthesized by polyesterification of diols (neopentyl glycol and 1,6 hexane diol) with dicarboxylic acids (isophthalic acid and adipic acid) with excess mol% of the dicarboxylic acids.
  • the raw materials in Table 2 below were combined and were heated to 150°C gradually, then the temperature was gradually increased and water is removed. After most of the water was removed, a vacuum was applied to the reaction system to continually remove the reacting water while gradually increasing the reaction temperature to 220°C and increasing the vacuum pressure to 20mm Hg.
  • the final acid value of the resin was determined to be 153 mg KOH/gm of resin.
  • composition of the PAFP resin is provided in Table 2 below.
  • Laminated samples were prepared using a heated-roll hand laminator.
  • the adhesive composition was first coated onto a polyester film using a Meyer bar #2 to achieve dry adhesive coat weight in the range of 1.0-1.1 Ib/ream.
  • the primary substrate was then dried in a 90 °C oven for 2 minutes to remove the solvent (ethyl acetate) before it was laminated to a polyethylene sealant film with nip temperature at 150 °F and pressure at 40 psi.
  • the formed laminates were placed under 2 lb weight to cure at room temperature for 7 days. Bond strengths were tested after 1 day of curing.
  • Adhesive compositionlA Adhesive compositionlB
  • Adhesive composition2A Adhesive composition2B each is suitable as a laminating adhesive.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
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Abstract

La présente divulgation concerne une composition adhésive. Dans un mode de réalisation, la composition adhésive comprend un produit de réaction formé à partir de (A) un composant carbodiimide (CDI) et (B) un composant réactif CD I (r-CDI) choisi dans le groupe constitué par (i) une résine polyester fonctionnelle acide polycarboxylique, et (ii) une résine fonctionnelle amine. La présente divulgation concerne également un stratifié avec la présente composition adhésive disposée entre un premier substrat et un second substrat.
PCT/US2024/036355 2023-07-31 2024-07-01 Composition adhésive à base de polycarbodiimide WO2025029423A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5856014A (en) * 1996-02-29 1999-01-05 Nisshinbo Industries, Inc. Aqueous coating composition for the manufacture of precoated metal
JP2014156553A (ja) * 2013-02-15 2014-08-28 Fujifilm Corp ポリエステルフィルム、太陽電池用モジュール用バックシートおよび太陽電池用モジュール
US20150203728A1 (en) * 2012-09-11 2015-07-23 Sika Technology Ag Structural polyurethane adhesive having a low glass transition temperature

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5856014A (en) * 1996-02-29 1999-01-05 Nisshinbo Industries, Inc. Aqueous coating composition for the manufacture of precoated metal
US20150203728A1 (en) * 2012-09-11 2015-07-23 Sika Technology Ag Structural polyurethane adhesive having a low glass transition temperature
JP2014156553A (ja) * 2013-02-15 2014-08-28 Fujifilm Corp ポリエステルフィルム、太陽電池用モジュール用バックシートおよび太陽電池用モジュール

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Periodic Table of Elements", 1990, CRC PRESS, INC.

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