EP4308622A1 - Kaschierklebstoff - Google Patents

Kaschierklebstoff

Info

Publication number
EP4308622A1
EP4308622A1 EP22714498.7A EP22714498A EP4308622A1 EP 4308622 A1 EP4308622 A1 EP 4308622A1 EP 22714498 A EP22714498 A EP 22714498A EP 4308622 A1 EP4308622 A1 EP 4308622A1
Authority
EP
European Patent Office
Prior art keywords
nco
polyol
composition according
chosen
component
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
EP22714498.7A
Other languages
English (en)
French (fr)
Inventor
Francis PARDAL
Marion JARNOUX
Dimitri BAUGNON
Ludwig FAROUX
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bostik SA
Original Assignee
Bostik SA
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 Bostik SA filed Critical Bostik SA
Publication of EP4308622A1 publication Critical patent/EP4308622A1/de
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
    • C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
    • 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
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy 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
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
    • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
    • C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
    • C08G18/8029—Masked aromatic polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters

Definitions

  • the present invention relates to a solvent-based two-component adhesive composition of the polyurethane type.
  • the invention also relates to a multilayer (or complex) structure, usable in particular in the field of flexible packaging, which comprises at least two layers of material bonded together by a layer of the crosslinked composition according to the invention.
  • the present invention also relates to the use of said multilayer structure for the preparation of flexible packaging for agri-food products.
  • Flexible (or flexible) packaging intended, in particular, for the packaging of agrifood products generally consist of several thin layers (in the form of sheets or films) whose thickness is between 5 and 150 ⁇ m and which are made up of different materials such as paper, a metal (for example aluminum) or else by thermoplastic polymers.
  • the corresponding complex (or multilayer) film makes it possible to combine the properties of the different individual layers of material (also called “supports") and to thus offer the consumer a set of characteristics adapted to the final flexible packaging such as, for example, its visual appearance (in particular that of the printed elements presenting the information concerning the packaged product and intended for the consumer, or even its transparency), a barrier effect to light or to atmospheric humidity or to gases, in particular to oxygen, or alternatively an appropriate thermal resistance.
  • the various layers of materials that make up the multilayer film are typically combined or assembled by lamination, during industrial lamination (or even "lamination") processes. These methods use adhesives (or glues) and equipment (or machines) which are designed for this purpose and which operate continuously with generally very high line speeds, of the order of several hundred meters per minute.
  • the multilayer film thus obtained is often itself referred to by the term "laminate”.
  • These lamination processes firstly comprise a step of coating the adhesive on a first film of material, which consists of depositing a continuous layer of glue and of controlled thickness generally less than 10 ⁇ m, corresponding to a quantity of adhesive (or weight) generally not exceeding 10 g/m 2 .
  • This coating step is followed by a step of laminating a second film of material, identical to or different from the first, consisting of the application under pressure of this second film on the first film covered with the layer of adhesive.
  • Complex films are thus finally obtained in very large widths and are generally packaged by winding, in the form of large reels from 1 m to 1.50 m in diameter having, like the film they store, up to 2 m wide. .
  • These large coils can be stored and transported, with a view to their use either directly by the food industry, with a view to packaging their product, or by processors (or complexers, also referred to by the English term “converters” ).
  • the film is cut to reduce its width, and shaped to manufacture sachets, themselves intended for the packaging of a product, for example an agri-food product.
  • Two-component solvent-based polyurethane laminating adhesives are widely used as glue for the manufacture of multilayer systems intended for the field of flexible packaging.
  • the implementation of said solvent-based adhesives in the complexing process necessitates a step of evaporation of the organic solvent. This step is carried out before the laminating step by passing through an oven the first film covered with adhesive following the coating step.
  • Two-component polyurethane type laminating adhesives with solvent are supplied to the laminator in the form of 2 compositions (or components):
  • -NCO component comprising chemical entities bearing isocyanate -NCO end groups
  • the mixture of these 2 components can be carried out at room temperature by the operator of the complexing machine before starting it up, which allows it to operate correctly, thanks to an appropriate viscosity.
  • the isocyanate groups of the -NCO component react with the hydroxyl groups of the component -OH, according to a so-called crosslinking reaction, to form a polyurethane which is in the form of a three-dimensional network with urethane groups, ensuring the cohesion of the adhesive joint between the 2 thin laminated layers.
  • adhesive compositions with good chemical resistance are known to contain toxic raw materials or which should soon be banned for regulatory reasons, despite their positive impacts on adhesion performance. This is particularly the case with epoxies (resins) or bisphenol-A.
  • polyurethane-based adhesive compositions generally have the disadvantage of using a majority NCO-terminated NCO component comprising significant residual contents of diisocyanate monomers originating from the synthesis reaction of the NCO-terminated polyurethane prepolymer.
  • These residual quantities of low molecular mass (so-called free) diisocyanate monomers are likely to migrate through the multilayer film, after the implementation of the two-component adhesive, and therefore through the final flexible packaging.
  • said compounds are capable of forming by hydrolysis, in contact with water or moisture present in particular in packaged foods, primary aromatic amines (often designated by the English terms Primary Aromatic Amines or PAA), which are considered as very harmful to human health and the environment.
  • the present invention relates to a two-component solvent-based adhesive composition
  • a two-component solvent-based adhesive composition comprising an -OH component and an -NCO component, characterized in that:
  • the -OH component is a composition comprising at least one A1 polyol
  • the -NCO component is a composition comprising at least one polyurethane P2 obtained by a process comprising the following steps:
  • E1 the preparation of a polyurethane prepolymer P1 comprising at least two -NCO terminal functions by a polyaddition reaction: i) of at least one polyester polyol A2 having a number-average molecular mass (Mn) ranging from 8,000 to 12,000 g/mol; ii) at least one polyol A3 having a molar mass less than or equal to 200 g/mol, said polyol A3 comprising at least one secondary OH function; iii) at least one polyisocyanate; iv) an optional polyol A4; in amounts such that the NCO/OH molar ratio (r1) ranging from 1.7 to 2.2, preferably from 1.8 to 2.1; and
  • step E2) the reaction of the product formed at the end of step E1) with at least one aminosilane, in quantities such that the NCO/NH (r2) molar ratio ranges from 10 to 25, preferably from 15 to 21.
  • the -OH component is a composition comprising at least one A1 polyol.
  • Polyol A1 can be chosen from:
  • polyols having a number-average molecular mass greater than 200 g/mol chosen from polyester polyols, polyether polyols, polyene polyols, polycarbonate polyols, polymers with —OH endings, and mixtures thereof.
  • the hydroxyl functionality of polyol A1 can range from 2 to 6.
  • the hydroxyl functionality of polyol A1 is 2.
  • the hydroxyl functionality is the average number of hydroxyl function per mole of polyol.
  • the polyol A1 can be chosen from polyols having a number-average molecular mass greater than 200 g/mol and less than or equal to 3000 g/mol chosen from polyester polyols, polyether polyols, polyene polyols, polycarbonate polyols, -OH-terminated polymers, and mixtures thereof.
  • the polyester polyols A1 having a number-average molecular mass greater than 200 g/mol can be chosen from polyester diols and polyester triols.
  • polyester polyols mention may be made, for example:
  • polyester polyols of natural origin such as castor oil
  • aliphatic (linear, branched or cyclic) or aromatic polyols such as, for example, monoethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, butenediol, 1,6-hexanediol, cyclohexane dimethanol, tricyclodecane dimethanol, neopentyl glycol, cyclohexane dimethanol, glycerol, trimethylolpropane, 1,2,6-hexanetriol, sucrose, glucose, sorbitol, pentaerythritol, mannitol, N-methyldiethanolamine, triethanolamine, dimer fatty alcohol, trimer fatty alcohol and mixtures thereof, with
  • polycarboxylic acid or its ester or anhydride derivative such as 1,6-hexanedioic acid (adipic acid), dodecanedioic acid, azelaic acid, sebacic acid, adipic acid, 1,18-octadecanedioic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, a dimer fatty acid, a trimer fatty acid and mixtures of these acids, an unsaturated anhydride such as for example l maleic or phthalic anhydride, or a lactone such as for example caprolactone.
  • anhydride derivative such as 1,6-hexanedioic acid (adipic acid), dodecanedioic acid, azelaic acid, sebacic acid, adipic acid, 1,18-octadecanedioic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid,
  • estolides polyols resulting from the polycondensation of one or more hydroxy acids, such as ricinoleic acid, on a diol (one can for example mention “POLYCIN® D-1000” and “POLYCIN® D-2000” available from VERTELLUS ).
  • polyester polyols can be prepared conventionally, and are mostly commercially available.
  • polyester polyols having an Mn greater than 200 g/mol mention may be made, for example, of the following products with a hydroxyl functionality equal to 2: “TONE® 0240” (marketed by UNION CARBIDE) which is a polycaprolactone with an average molecular mass in number of around 2000 g/mol, and a melting point of around 50° C., or "DEKATOL® 3008” (marketed by the company BOSTIK) with a number-average molar mass Mn close to 1060 g/mol and whose The hydroxyl index ranges from 102 to 112mg KOH/g. It is a product resulting from the condensation of adipic acid, diethylene glycol and monoethylene glycol.
  • the polyester polyols preferably have a number-average molecular mass ranging from 1000 to 2000 g/mol.
  • the polyether polyols having a number-average molecular mass greater than 200 g/mol can be chosen from polyoxyalkylene polyols, the alkylene part of which, linear or branched, comprises from 1 to 4 carbon atoms, more preferentially from 2 to 3 carbon atoms. carbon.
  • polyoxyalkylene diols or triols By way of example of polyoxyalkylene diols or triols, mention may be made, for example:
  • polyoxypropylene diols or triols also designated by polypropylene glycol (PPG) diols or triols
  • PPG polypropylene glycol
  • Mn number-average molecular weight
  • polyoxyethylene diols or triols also designated by polyethylene glycol (PEG) diols or triols
  • Mn number-average molecular weight
  • polyether polyols can be prepared conventionally, and are widely available commercially. They can be obtained by polymerization of the corresponding alkylene oxide in the presence of a basic catalyst (for example potash) or a catalyst based on a double metal-cyanide complex.
  • a basic catalyst for example potash
  • a catalyst based on a double metal-cyanide complex for example
  • polyether diol As an example of a polyether diol, mention may be made of the polyoxypropylene diol marketed under the name "VORANOL® P 400" by the company DOW with a number-average molecular mass (Mn) close to 400 g/mol and whose hydroxyl index ranges from 250 to 270 mg KOH/g.
  • Mn number-average molecular mass
  • polyether triol As an example of a polyether triol, mention may be made of the polyoxypropylene triol marketed under the name “VORANOL® CP 450” by the company DOW, with a number-average molecular mass (Mn) close to 450 g/mol and whose index hydroxyl ranges from 370 to 396 mg KOH/g, or the polyoxypropylene triol marketed under the name “VORANOL® CP3355” by the company DOW, with a number-average molecular mass close to 3,554 g/mol.
  • Mn number-average molecular mass
  • the polyene polyols having a molecular mass greater than 200 g/mol can be chosen from polyenes comprising terminal hydroxyl groups, and their corresponding hydrogenated or epoxidized derivatives.
  • the polyene polyols can be chosen from polybutadienes comprising terminal hydroxyl groups, optionally hydrogenated or epoxidized.
  • the polyene polyol(s) that can be used according to the invention is (are) chosen from homopolymers and copolymers of butadiene comprising terminal hydroxyl groups, optionally hydrogenated or epoxidized.
  • terminal hydroxyl groups” of a polyene polyol means the hydroxyl groups located at the ends of the main chain of the polyene polyol.
  • the hydrogenated derivatives mentioned above can be obtained by total or partial hydrogenation of the double bonds of a polydiene comprising terminal hydroxyl groups, and are therefore saturated or unsaturated.
  • the epoxide derivatives mentioned above can be obtained by chemoselective epoxidation of the double bonds of the main chain of a polyene having terminal hydroxyl groups, and therefore have at least one epoxy group in its main chain.
  • polyene polyols mention may be made of butadiene homopolymers, saturated or unsaturated, comprising terminal hydroxyl groups, optionally epoxidized, such as for example those marketed under the name "POLY BD® or KRASOL®” by the company CRAY VALLEY.
  • the polycarbonate polyols can be chosen from polycarbonate diols or triols, having in particular a number-average molecular mass (M n ) ranging from 300 to 12,000 g/mol.
  • CONVERGE® POLYOL 212-10 and “CONVERGE® POLYOL 212-20” marketed by the company NOVOMER respectively with a number molecular mass (M n ) equal to 1 000 and 2000 g/mol whose hydroxyl indices are respectively 112 and 56 mg KOH/g,
  • the -OH-terminated polymers can be obtained by polyaddition reaction between one or more polyol(s), and one or more polyisocyanate(s), in quantities of polyisocyanate(s) and polyol(s) leading to a molar ratio NCO/OH strictly less than 1.
  • the reaction can be carried out in the presence of a catalyst.
  • the polyols and polyisocyanates that can be used can be those typically used for the preparation of polymers with —OH endings, such as for example those cited in the present application.
  • the polyol A1 is chosen from diols having a molar mass less than or equal to 200 g/mol, preferably less than or equal to 150 g/mol.
  • diols having a molar mass less than or equal to 200 g/mol mention may be made of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, propane-1,3-diol, butane-1, 4-diol, neopentyl glycol, 2-methyl-1,3-propanediol, hexane-1,6-diol or mixtures thereof.
  • polyol A1 is diethylene glycol.
  • the -OH component may include at least one additive selected from the group consisting of plasticizers, catalysts, rheological additives, solvents, pigments, adhesion promoters (such as, for example, aminosilanes), moisture absorbers, UV stabilizers (or antioxidants), colorants, fillers, and mixtures thereof.
  • the total content of these optional additives can be up to 5% by weight relative to the total weight of said -OH component.
  • the -OH component may comprise more than 80% by weight of polyol(s) A1, preferably more than 90% by weight, preferentially more than 95% by weight, and even more preferentially more than 99% by weight of polyol(s). ) A1 relative to the total weight of said OH component.
  • the -OH component can have a viscosity at 23°C ranging from 1 to 3000 mPa.s.
  • the viscosity measurement at 23°C can be done using a Brookfield viscometer according to the ISO 2555 standard published in 1999. Typically, the measurement carried out at 23°C can be done using a Brookfield viscometer RVT, with a needle adapted to the viscosity range and at a speed of rotation of 20 revolutions per minute (rpm).
  • the -NCO component is a composition comprising at least one polyurethane P2 obtained by a process comprising the following steps:
  • E1 the preparation of a polyurethane prepolymer P1 comprising at least two -NCO terminal functions by a polyaddition reaction: i) of at least one polyester polyol A2 having a number-average molecular mass (Mn) ranging from 8,000 to 12,000 g/mol; ii) at least one polyol A3 having a molar mass less than or equal to 200 g/mol, said polyol A3 comprising at least one secondary OH function; iii) at least one polyisocyanate; iv) an optional polyol A4; in amounts such that the NCO/OH molar ratio (r1) ranging from 1.7 to 2.2, preferably from 1.8 to 2.1; and
  • step E2) the reaction of the product formed at the end of step E1) with at least one aminosilane, in quantities such that the NCO/NH (r2) molar ratio ranges from 10 to 25, preferably from 15 to 21.
  • the polyester polyol A2 has a number-average molecular mass Mn greater than or equal to 8,500 g/mol, preferably greater than or equal to 9,000 g/mol, and even more preferably greater than or equal to 10,000 g/mol.
  • the polyester polyol A2 is preferably a copolyester obtained by a polycondensation reaction:
  • aromatic diacid chosen from terephthalic acid, isophthalic acid, phthalic acid and one of their diester or anhydride derivatives;
  • the number-average molecular mass Mn is measured by size exclusion chromatography (or SEC, acronym for "Size Exclusion Chromatography” in English) which is also referred to by the terms gel permeation chromatography (or by the corresponding English acronym GPC ).
  • the calibration implemented is usually a PEG (PolyEthylene Glycol) or PS (Polystyrene) calibration, preferably PS.
  • the hydroxyl index (denoted IOH) of the polyester polyol A2, and more generally of a polyol, (denoted IOH) represents the number of hydroxyl functions per gram of polyol and is expressed in the form of the equivalent number of milligrams of potash (KOH ) used in the determination of hydroxyl functions, determined by titrimetry according to standard ISO 14900:2017.
  • the IOH is related to the number-average molecular mass Mn by the relationship:
  • the aliphatic diol (i) can be linear or branched and is chosen from the group consisting of ethylene glycol (CAS: 107-21-1), diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2- propanediol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 1,6-hexanediol, 3-ethyl-2-methyl-1,5-pentanediol, 2-ethyl-3-propyl-1,5-pentanediol , 2,4-dimethyl-3-ethyl-1,5-pentanediol, 2-ethyl-4-methyl-3-propyl-1,5-pentadiol, 2,3-diethyl-4-methyl-1, 5-pentanediol, 3-ethyl-2,2,4-trimethyl-1,5-pentadiol, 2,2-dimethyl-4-ethyl-3
  • 1,11-undecanediol (CAS: 35449-37-7), 1-phenyl-1,11-undecanediol (CAS: 109217-58-5), 1,2-undecanediol (CAS: 13006-29-6), 1,2-dodecanediol (CAS: 1119-87-5),
  • the diol (i) is chosen from ethylene glycol, diethylene glycol, trimethylene glycol, hexamethylene glycol, propylene glycol (or propane-1,2-diol), propane-1,3- diol, butanediol (-1,4, -1,3 or -1,2), neopentyl glycol, 2-methyl-1,3-propane diol, hexane diol or even cyclohexanedimethanol.
  • propane-1,2-diol propane-1,3- diol
  • butanediol -1,4, -1,3 or -1,2
  • neopentyl glycol 2-methyl-1,3-propane diol
  • hexane diol or even cyclohexanedimethanol.
  • the diol (i) is chosen from ethylene glycol and diethylene glycol.
  • 2 diols (i) consisting respectively of ethylene glycol and diethylene glycol are used.
  • diester derivatives of terephthalic acid of isophthalic acid or of phthalic acid which can be used as monomers (ii)
  • an anhydride derivative of an aromatic diacid for the monomer (ii) mention may be made of phthalic anhydride.
  • 2 diacids (ii) are used consisting, respectively, of terephthalic acid and isophthalic acid.
  • the aliphatic diacid (iii) can be linear or branched and is for example chosen from adipic acid, azelaic acid, sebacic acid, cyclohexanedicarboxylic acid, dodecanedicarboxylic acid, 1,10-decanedicarboxylic acid and succinic acid.
  • adipic acid is used as the aliphatic diacid (iii).
  • the polyester polyol A2 is an amorphous polyester polyol.
  • amorphous polyester polyol means a polyester polyol whose analysis by differential scanning calorimetry (in English, Differential Scanning Calorimetry or DSC) shows that it does not present no melting point.
  • the polyester polyol A2 is obtained by polycondensation:
  • diacids (ii) consisting, respectively, of terephthalic acid and isophthalic acid
  • the monomers (ii) and optionally (iii) are diester derivatives, such as for example methyl or ethyl diester derivatives
  • said monomers are, in a 1st step, mixed with one or more diol monomers (i), said mixture being brought to a temperature which can range up to 190° C., so as to carry out, preferably in the presence of a catalyst based on titanium or zinc, a transesterification reaction and eliminate the methanol or ethanol formed.
  • the monomers (ii) and optionally (iii) which are diacids are added, mixed with one or more diol monomers (i), the reaction medium being brought to a temperature which can go up to 230° C, so as to carry out the esterification reaction and eliminate the water formed.
  • the pressure is lowered to a value below approximately 5 mbar, and the reaction medium is brought to a higher temperature, up to a value close to 250° C., in order to increase the length chains of the polyester polyol to reach a given IOH.
  • the polyester polyol A2 can be in dry form or in solvent form.
  • the solvent can for example be chosen from the group consisting of esters, ketones, aromatic compounds, and mixtures thereof.
  • the solvent can for example be chosen from ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, and mixtures thereof.
  • the number-average molar mass Mn of polyol A3 may be less than or equal to 150 g/mol.
  • the hydroxyl functionality of polyol A3 can range from 2 to 6.
  • the hydroxyl functionality of polyol A3 is 2.
  • the hydroxyl functionality is the average number of hydroxyl function per mole of polyol.
  • Polyol A3 can be chosen from the group consisting of 1,2-propanediol or monopropylene glycol (CAS: 57-55-6), dipropylene glycol (CAS: 25265-71-8), tripropylene glycol (CAS: 24800- 44-0), 2,2-dimethyl-1,3-pentanediol (CAS: 2157-31-5), 5-methyl-2-(1-methylethyl)-1,3-hexanediol (CAS: 80220- 07-1), 1,4-dimethyl-1,4-butanediol, 1,3-heptanediol (CAS: 23433-04-7), 1,2-octanediol (CAS: 1117-86-8), 1,3-octanediol (CAS: 23433-05-8), 1,7-octanediol (CAS: 3207-95-2), 1,2-nonanediol (CAS: 42789-13-9), 1 ,5-nonan
  • Polyol A3 is preferably chosen from monopropylene glycol, dipropylene glycol, and mixtures thereof.
  • the polyurethane prepolymer P1 obtained in step E1) can be prepared in the presence of a polyol A4 different from the polyols A2 and A3 mentioned above.
  • the hydroxyl functionality of polyol A4 is preferably 3.
  • the hydroxyl functionality is the average number of hydroxyl function per mole of polyol.
  • Polyol A4 can be chosen from glycerol, trifunctional polyether polyols (triols), trimethylolalkanes comprising an alkane comprising from 1 to 20 carbon atoms and 3 methylol groups.
  • the polyoxyalkylene triols the linear or branched alkylene part of which comprises from 1 to 4 carbon atoms, more preferably from 2 to 3 carbon atoms. They may, for example, be polyoxypropylene triols (also referred to as polypropylene glycol (PPG) triols) having a number-average molecular weight (Mn) ranging from 300 to 12,000 g/mol or even polyoxyethylene triols (also referred to as polyethylene glycol (PEG) triols) having a number average molecular weight (Mn) ranging from 300 to 12,000 g/mol.
  • PPG polypropylene glycol
  • PEG polyethylene glycol
  • Trifunctional polyether polyols can be prepared conventionally, and are widely available commercially. They can be obtained by polymerization of the corresponding alkylene oxide in the presence of a basic catalyst (for example potash) or a catalyst based on a double metal-cyanide complex.
  • a basic catalyst for example potash
  • a catalyst based on a double metal-cyanide complex for example
  • polyether triol As an example of a polyether triol, mention may be made of the polyoxypropylene triol marketed under the name “VORANOL® CP 450” by the company DOW, with a number-average molecular mass (Mn) close to 450 g/mol and whose index hydroxyl ranges from 370 to 396 mg KOH/g, or the polyoxypropylene triol marketed under the name “VORANOL® CP3355” by the company DOW, with a number-average molecular mass close to 3,554 g/mol, or “ACCLAIM ® 6300 which is a trifunctional PPG with a number-average molecular mass of approximately 5948 g/mol, and with a hydroxyl index IO H equal to 28.3 mg KOH/g.
  • Mn number-average molecular mass
  • ACCLAIM ® 6300 which is a trifunctional PPG with a number-average molecular mass of approximately 5948 g/mol, and with a
  • trimethylolalkanes comprising an alkane comprising from 1 to 20 carbon atoms and 3 methylol groups
  • trimethylolmethane trimethylolethane, trimethylolpropane, trimethyloln-butane, trimethylolisobutane, trimethylols-butane, trimethylolt-butane , trimethylolpentane, trimethylolhexane, trimethylolheptane, trimethyloloctane, trimethylolnonae, trimethyloldecane, trimethylolundecane and trimethyloldo-decane.
  • polyol A4 is chosen from trimethylolalkanes comprising an alkane comprising from 1 to 20 carbon atoms and 3 methylol groups, it is even more preferably trimethylolpropane.
  • the polyisocyanate can be chosen from diisocyanates, triisocyanates and mixtures thereof.
  • diisocyanates examples include isophorone diisocyanate (IPDI), pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), heptane diisocyanate, octane diisocyanate, nonane diisocyanate, decane diisocyanate, undecane diisocyanate, dodecane diisocyanate, 4,4'-methylenebis(cyclohexylisocyanate) (4,4'-HMDI), norbornane diisocyanate, norbornene diisocyanate, 1,4-cyclohexane diisocyanate (CHDI), methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclohexane diisocyanate,
  • IPDI isophorone diisocyanate
  • the diisocyanates are preferably aromatic diisocyanates, arylaliphatic or cycloaliphatic diisocyanates.
  • the diisocyanates are chosen from toluene diisocyanate (in particular 2,4-toluene diisocyanate (2,4-TDI) and/or 2,6-toluene diisocyanate (2,6-TDI)), diphenylmethane diisocyanate (especially 4,4'-diphenylmethane diisocyanate (4,4'-MDI) and/or 2,4'-diphenylmethane diisocyanate (2,4'-MDI)), isophorone diisocyanate (IPDI), xylylene -diisocyanate (XDI) (especially m-xylylene diisocyanate (m-XDI)) and allophanates of HDI or PDI.
  • triisocyanates mention may be made, for example, of isocyanurates, biurets, and adducts of diisocyanates and of triols.
  • the isocyanurates can be used in the form of a technical mixture of (poly)isocyanurate(s) with a purity greater than or equal to 70% by weight isocyanurate(s).
  • diisocyanate trimers mention may be made of: the isocyanurate trimer of hexamethylene diisocyanate (HDI): isophorone diisocyanate isocyanurate trimer (I PDI):
  • adducts of diisocyanates and triols which can be used according to the invention, mention may be made of the adduct of meta-xylylene diisocyanate and of trimethylolpropane, as represented below.
  • This adduct is marketed for example by the company MITSUI CHEMICALS, Inc under the name “TAKENATE® D-110N”:
  • Polyisocyanates are widely available commercially.
  • SCURANATE® TX marketed by the company VENCOREX, corresponding to a 2,4-TDI of purity of the order of 95%
  • SCURANATE® T100 marketed by the company VENCOREX
  • DESMODUR ® I marketed by COVESTRO, corresponding to an I PDI.
  • the polyisocyanate is a diisocyanate, and even more preferably it is diphenylmethane diisocyanate.
  • the diphenylmethane diisocyanate may comprise at least 90% by weight of the 4,4' isomer based on its total weight, preferably at least 95%.
  • the -NCO group percentage of this product (expressed by weight/weight) is equal to 33.6%.
  • the polyaddition reaction can be carried out at a temperature below 95°C, for example between 50°C and 80°C.
  • (r1) is the NCO/OH molar ratio corresponding to the molar ratio of the number of isocyanate groups (NCO) to the number of hydroxyl groups (OH) carried by all of the polyisocyanate(s) and polyol(s) present in the reaction medium of step E1).
  • the polyaddition reaction of step E1) can be implemented in the presence or absence of at least one reaction catalyst.
  • the catalyst can be any catalyst known to those skilled in the art for catalyzing the formation of polyurethane by reaction of at least one polyisocyanate with at least one polyol.
  • a quantity ranging up to 0.3% by weight of catalyst(s) relative to the weight of the reaction medium of stage E1) can be used.
  • the reaction of step E1) can also be carried out in the presence of a solvent.
  • the solvent can be selected from the group consisting of esters, ketones, aromatic compounds, and mixtures thereof.
  • the solvent can be added during step E1) or can come from the starting reagents in solution in said solvent.
  • the solvent can for example be chosen from the group consisting of esters, ketones, aromatic compounds, and mixtures thereof.
  • the solvent can for example be chosen from ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, and mixtures thereof.
  • Polyurethane P1 may have a mass content of NCO groups ranging from 0.5% to 5% by weight, preferably from 1% to 3% by weight relative to the total weight of polyurethane P1.
  • All of the conditions for obtaining the polyurethane prepolymer P1 described above advantageously make it possible to obtain a concentration of unreacted diisocyanate monomer(s) sufficiently low at the end of the reaction so that the polyurethane prepolymer P1 can be used directly. after its synthesis in the preparation of the -NCO component, without it being necessary to treat it, for example by purification, distillation or selective extraction processes as employed in the prior art, to eliminate or reduce the excess unreacted diisocyanate monomer(s) present in the reaction product.
  • the -NCO component obtained may thus comprise a content of diisocyanate monomer(s) less than or equal to 3.5% by weight (preferably less than or equal to 3.0%) relative to the weight of the -NCO component ( dry extract).
  • Step E2) can be implemented at a temperature below 95°C, for example between 40°C and 80°C.
  • (r2) is the NCO/NH molar ratio corresponding to the molar ratio of the number of NCO isocyanate groups to the number of NH functions carried respectively by all the isocyanates (s' acting in particular polyurethane with NCO endings and optionally the unreacted polyisocyanate(s) at the end of step E1)), and aminosilanes (present in the middle of step E2).
  • the polyaddition reaction of step E2) can be implemented in the presence or absence of at least one reaction catalyst.
  • the catalyst can be any catalyst known to those skilled in the art.
  • a quantity ranging up to 0.3% by weight of catalyst(s) relative to the weight of the reaction medium of step E2) can be used.
  • the reaction of step E2) can also be carried out in the presence of a solvent.
  • the solvent can be selected from the group consisting of esters, ketones, aromatic compounds, and mixtures thereof.
  • the solvent can be added during step E1), during step E2) or can come from the starting reagents in solution in said solvent.
  • the solvent can for example be chosen from ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, and mixtures thereof.
  • the aminosilanes contain in particular an amine function as a reactive function with the -NCO function of the polyurethane prepolymer P1 obtained at the end of step E1).
  • the aminosilane preferably has the following formula (I):
  • R 3 identical or different, each represents a linear or branched monovalent hydrocarbon radical comprising from 1 to 10 carbon atoms;
  • R 4 identical or different, represents a linear or branched monovalent hydrocarbon radical comprising from 1 to 10 carbon atoms, or two R 4 groups can form a cycle;
  • - p is an integer equal to 0, 1 or 2, preferably equal to 0 or 1, and even more preferably equal to 0;
  • R 1 represents a divalent linear or branched alkylene radical comprising from 1 to 12 carbon atoms, preferably from 1 to 6 carbon atoms, R 3 preferably representing methylene or n-propylene, and
  • R 2 represents H, a linear or branched alkyl radical, an arylalkyl radical, a cyclic radical comprising from 1 to 20 carbon atoms, or a radical having the following formula (II): in which :
  • R 7 and R 8 are independently of each other, hydrogen or a radical chosen from the group consisting of -R 9 , -COOR 9 and -CN;
  • radical R 10 is hydrogen, or a radical chosen from the group consisting of - CH2-COOR 9 , -COOR 9 , -CONHR 9 , -CON(R 9 ) 2 , -CN;
  • radical R 9 being a hydrocarbon radical having from 1 to 20 carbon atoms optionally comprising at least one heteroatom.
  • radical of formula (II) can be chosen from one of the following radicals: NC-CH2-CH2-
  • the raminosilane of formula (I) is that in which:
  • R 3 identical or different, each represents a linear or branched alkyl group comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms;
  • R 4 identical or different, each represents a linear or branched alkyl comprising
  • - p is an integer equal to 0, 1 or 2, preferably p is 0;
  • R 1 represents a divalent linear or branched alkylene radical comprising from 1 to 12 carbon atoms, preferably from 1 to 6 carbon atoms, R 1 preferably representing n-propylene, and
  • aminosilanes of formula (I) above are preferably primary aminosilanes such as, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 3-aminopropyldimethoxymethylsilane; secondary aminosilanes such as for example N-butyl-3-aminopropyltrimethoxysilane, N-butyl-3-aminopropyltriethoxysilane,
  • primary aminosilanes such as for example 3-aminopropyltrimethoxysilane or 3-aminopropyldimethoxymethylsilane
  • Michael acceptors such as for example acrylonitrile, acrylic esters, acrylamides, maleic diesters, methylene malonate diesters, itaconic diesters.
  • the aminosilane is 3-aminopropyltriethoxysilane.
  • the aminosilanes may be commercially available such as, for example, Dynasylan® 1189 marketed by Evonik, or alternatively SILQUEST® A1100 marketed by Momentive.
  • the -NCO component may comprise from 20% to 100% by weight, preferably from 30% to 90% by weight, more preferably from 40% to 80% by weight of polyurethane(s) P2 (dry extract) relative to the weight total of said -NCO component.
  • Polyurethane P2 can be a single polymer or a mixture of polymers.
  • Polyurethane P2 may have a mass content of NCO groups ranging from 0.5% to 5% by weight, preferably from 0.8% to 3% by weight relative to the total weight of polyurethane P2.
  • Polyurethane P2 may comprise at least one isocyanate group and at least one silyl group derived from aminosilane. These groups can be at the ends of the main chain and/or as side groups along the main chain.
  • the polyurethane P2 comprises silyl groups derived from the aminosilane at one or both ends of the main chain, but not as side groups (functionality in silyl group less than or equal to 2).
  • the -NCO component (dry extract) can have a viscosity at 23°C ranging from 2000 mPa.s to 8000 mPa.s.
  • the -NCO component may include at least one additive selected from the group consisting of plasticizers, catalysts, rheological agents, solvents, pigments, adhesion promoters, moisture absorbers, UV stabilizers (or antioxidants) , colorants, fillers, and mixtures thereof.
  • the -NCO component may comprise phosphoric acid, for example in a content ranging from 0.001% to 1% by weight relative to the total weight of said -NCO component.
  • the phosphoric acid can be added during step E1, after step E1, during step E2 or after step E2.
  • the -NCO component may comprise at least one solvent, preferably in an amount ranging from 10% to 60% by weight, more preferably ranging from 15% to 50% by weight, and even more preferably from 20 to 45% by weight, relative to the total weight of the -NCO component.
  • the solvent can be chosen from organic and alcoholic solvents such as ethyl acetate, methyl ethyl ketone, xylene, ethanol, isopropanol, tetrahydrofuran, methyl-tetrahydrofuran, or else among G "ISANE®” (based on isoparaffins, available from the company TOTAL) or G “EXXOL® D80” (based on aliphatic hydrocarbons, available from the company EXXON MOBIL CHEMICAL).
  • organic and alcoholic solvents such as ethyl acetate, methyl ethyl ketone, xylene, ethanol, isopropanol, tetrahydrofuran, methyl-tetrahydrofuran, or else among G “ISANE®” (based on isoparaffins, available from the company TOTAL) or G “EXXOL® D80” (based on aliphatic hydrocarbons, available from the company EXXON MOB
  • the -NCO component comprises ethyl acetate.
  • the -NCO component may further comprise a polyisocyanate comprising three terminal NCO groups, preferably an adduct of diisocyanate and triol. Its content may be less than or equal to 10% by weight relative to the total weight of said -NCO component.
  • the -NCO component does not comprise an XDI-based triisocyanate, more particularly the -NCO component does not comprise a triisocyanate.
  • the -NCO component comprises: from 30% to 90% by weight, more preferentially from 40% to 80% by weight of polyurethane(s) P2 (dry extract); from 10% to 60% by weight, more preferably ranging from 15% to 50% by weight, and even more preferably from 20 to 45% by weight of solvent(s); from 0% to 1% by weight, preferably from 0.001% to 1% by weight of phosphoric acid; the percentages being percentages by weight relative to the total weight of said -NCO component.
  • the amounts of the -NCO and -OH components in said composition may be such that the -NCO/-OH molar equivalent ratio is within a range ranging from 1.7 to 3, preferably from 1.9 to 2.5, and even more preferably from 2 to 2.2.
  • molar equivalent ratio -NCO/-OH is meant the ratio of the equivalent number of -NCO groups (present in the -NCO component) to the equivalent number of -OH groups (present in the -OH component).
  • the mixture of the -NCO and -OH components, in the ratio indicated, can be carried out at 23°C by the operator of the complexing machine, prior to its start-up.
  • the viscosity of the adhesive composition thus obtained can be adjusted by simply adding solvent, resulting in a final quantity of dry extract of the adhesive composition which can vary in practice from 30 to 40% weight/weight.
  • the adhesive composition thus obtained can be adapted to its implementation in a complexing machine and to its correct operation.
  • the present invention also relates to a multilayer (complex) structure comprising at least two layers of material bonded together by an adhesive layer, characterized in that said adhesive layer consists of the composition according to the invention, in the crosslinked state. .
  • the adhesive layer preferably has a thickness ranging from 1.2 to 5 ⁇ m.
  • the adhesive layer can be obtained by crosslinking the composition according to the invention, in an amount preferably ranging from 0.5 to 5 g/m 2 .
  • the materials of which the layers of material surrounding the adhesive layer are made are generally chosen from paper, a metal, such as for example aluminum or thermoplastic polymers such as:
  • PE polyethylene
  • PET polyethylene terephthalate
  • a copolymer based on ethylene such as for example a maleic anhydride graft copolymer, a copolymer of ethylene and vinyl acetate (EVA), a copolymer of ethylene and vinyl alcohol (EVOH), a copolymer of ethylene and an alkyl acrylate such as methyl acrylate (EMA) or butyl acrylate (EBA),
  • PVDF polyvinylidene fluoride
  • PLA lactic acid
  • PHA polyhydroxyalkanoate
  • An individual layer of material may itself consist of several materials. It can be for example a layer of thermoplastic polymers obtained by coextrusion of two polymers (there is then no glue between the coextruded layers), the individual layers of thermoplastic polymer can also be coated with a substance (for example based on aluminum oxide or silicon oxide) or metallized (case of PET metallized with aluminum particles) to add an additional barrier effect.
  • a substance for example based on aluminum oxide or silicon oxide
  • metallized case of PET metallized with aluminum particles
  • the thickness of the 2 layers of material adjacent to the adhesive layer and of the other layers of material implemented in the multilayer structure according to the invention may be capable of varying within a wide range ranging for example from 5 to 150 ⁇ m.
  • the total thickness of said structure may also vary within a wide range ranging for example from 20 to 400 ⁇ m.
  • the multilayer structure is in the form of a multilayer film.
  • the film comprises 2 to 4 thin layers of materials, said film then being called respectively duplex, triplex or quatruplex.
  • said film is a triplex film: PET/ALU/PE (bi-oriented polyester).
  • the invention also relates to a method for manufacturing the (complex) multilayer structure according to the invention comprising the following steps:
  • the step of mixing the -NCO and -OH components can be carried out at room temperature (23°C) or hot, before coating.
  • the mixture is carried out at a temperature below the degradation temperature of the ingredients included in one or other of the -NCO and -OH components.
  • the mixture is carried out at a temperature below 95° C., preferably ranging from 15 to 80° C., more preferably ranging from 25° C. to 50° C., in order to avoid any thermal degradation.
  • the coating of said mixture can be carried out on all or part of the surface of a material.
  • the coating of said mixture can be carried out in the form of a layer with a thickness ranging from 1.5 to 5 ⁇ m.
  • the coating is preferably carried out continuously or substantially continuously.
  • the crosslinking of said mixture on the surface of the material can be accelerated by heating the coated material(s) to a temperature less than or equal to 70°C.
  • the time required to complete this crosslinking reaction and thus ensure the required level of cohesion is generally of the order of 0.5 to 24 hours.
  • the coating and the lamination of the second material are generally carried out in a time interval compatible with the coating process, as is well known to those skilled in the art, that is to say before the layer of adhesive loses its ability to bond the two materials together.
  • the crosslinking of said mixture on the surface of the material can be accelerated by heating the coated material(s) to a temperature less than or equal to 70°C.
  • the time required to complete this crosslinking reaction and thus ensure the required level of cohesion is generally of the order of 0.5 to 24 hours.
  • the invention also relates to the use of the (complex) multilayer structure according to the invention for the manufacture of flexible packaging.
  • the complexes according to the invention can in fact be used for the manufacture of the most diverse flexible packaging, which is shaped and then closed (after the step of packaging the product intended for the consumer) by heat-sealing (or heat-sealing) techniques. .
  • the complex according to the invention can be used in food packaging, without risk of toxicity.
  • Food packaging can be heat treated at temperatures ranging from 90°C to 135°C before use.
  • the multilayer structure is advantageously adapted to the manufacture of flexible packaging intended for the packaging of food products.
  • the adhesive composition according to the invention advantageously leads, after crosslinking, to a multilayer structure having good chemical resistance for different types of ingredients to be packaged.
  • PAA aromatic amines
  • the adhesive composition according to the invention advantageously leads to a good compromise between: good chemical resistance of the multilayer structure to many aggressive ingredients (after crosslinking), low toxicity, and good adhesive properties.
  • between x and y or “ranging from x to y”, is meant an interval in which the limits x and y are included.
  • the range “between 0% and 25%” includes the values 0% and 25% in particular.
  • TMP Trimethylolpropane
  • the following are introduced into the reactor: 76.190 g of adipic acid, 170.035 g of isophthalic acid, 64.165 g of terephthalic acid and 0.035 g of a catalyst based on a chelate titanium (TYZOR ® LA from DuPont). Then a temperature ramp is programmed in order to reach a temperature of 230°C in 3 hours. The acid value ( la ) is then measured. The reaction is stopped when the acid number l a is less than 25 mg KOH/g.
  • a titanium-based catalyst (of formula (nBuO)4II, TYZOR ® TnBT from DuPont) is then introduced, then the reactor is placed under vacuum (15 mbar is reached in 2 hours) and the reaction mixture is heated to 240°C.
  • polyester polyol obtained is then cooled to 200° C. and then poured slowly into ethyl acetate at ambient temperature with stirring, to form a 59.47% weight/weight solution.
  • the IOH of the polyester polyol thus obtained was measured according to the ISO 14900:2017 standard and is equal to 10 mg KOH/g, corresponding to an Mn of 11220 g/mole.
  • Example 2 Component -NCO (2A, 2B, 2C)
  • the polyisocyanate (except DESMODUR® L75) and the polyols are mixed in a reactor kept under constant stirring and under nitrogen, at a temperature ranging from 75° C. to 77° C. in the quantities mentioned in table 1. The whole is maintained in a mixture at this temperature until the complete consumption of the hydroxyl functions of the polyols.
  • the progress rate of the reaction is checked by measuring the NCO group content by dosing dibutylamine in return, using hydrochloric acid according to standard NF T52-132.
  • the measured NCO group content is approximately equal to the desired NCO group content
  • phosphoric acid is added to the reaction mixture (at a temperature below 70° C.) which is then mixed for 30 minutes to homogenize the reaction medium.
  • Silquest® A1100 is added (at a temperature below 70°C).
  • the reaction mixture is stirred for 30 minutes before introducing the DESMODUR® L75.
  • Desmodur®75 acts as a thinner and does not participate in any chemical reaction. After homogenization of the mixture (30 minutes) maintained between 60-70° C., the Brookfield viscosity at 23° C. and the dry extract are measured.
  • the diisocyanate(s) and the polyols are mixed in a reactor kept under constant stirring and under nitrogen, at a temperature ranging from 75° C. to 77° C. in the quantities mentioned in Table 1. The whole is kept in a mixture at this temperature until the complete consumption of the hydroxyl functions of the polyols.
  • the progress rate of the reaction is checked by measuring the NCO group content by dosing dibutylamine in return, using hydrochloric acid according to standard NF T52-132. When the measured NCO group content is approximately equal to the desired NCO group content, phosphoric acid is added to the reaction mixture (at a temperature below 70° C.) which is then mixed for 30 minutes to homogenize the reaction medium. . Then Silquest® A1100 is added (at a temperature below 70°C).
  • Example 4 Two-component adhesive compositions An -OH component is mixed with the -NCO component of Example 2 (2A, 2B or 2C) or of Example 3 (3A) with solvent to thin the adhesive mixture, then introduced between the complexing dosing rollers at ambient temperature (23° C.) according to a given weight ratio making it possible to reach a given NCO/OH molar ratio.
  • a triplex film consisting of a first PET film, a second aluminum film and a third PE film is prepared.
  • PET PolyEthylene Terephthalate
  • ALU aluminum film
  • PE bi-oriented Polyester
  • This triplex film is obtained according to a sequential process by supplying the tank of a laminating machine of the Nordmeccanica type with the two-component adhesive composition, for each of Examples 1/2 to 1/6.
  • Said laminating machine is provided with a roller-type coating device with an open tray, operating at ambient temperature and at a running speed of 50 m/minute.
  • the adhesive layer linking the 3 films at each PET/ALU and ALU/PE interface has a thickness of approximately 2 ⁇ m.
  • This triplex film is subjected to the following tests:
  • the cohesion of the three-layer film is evaluated by a peel test at 180°C.
  • the 180° peel test is as described in the French standard NF T 54-122.
  • the principle of this test consists in determining the force necessary for the separation (or peeling) of 2 individual layers of films bonded by the two-component adhesive (OH component/NCO component).
  • the triplex film is stored at room temperature (23°C) and under an atmosphere of 50% relative humidity (RH). A sample is taken and subjected to the peel test at 180°C.
  • a rectangular shaped specimen 15 mm wide and about 10 cm long is cut from the triplex film. Manually peel off from the end of this specimen, and over approximately 2 cm, 2 individual layers (between the PET/ALU and the PE) of film included in this strip and the 2 free ends thus obtained are fixed on two devices attachment connected, respectively, to a fixed part and a movable part of a traction device which are located on a vertical axis.
  • Sachets are fashioned from the PET/ALU/PE three-layer complex of Example 8 (cutting template 12.2 ⁇ 10.2 cm; surface in contact with the simulant 240 cm 2 ).
  • the sachets are filled with 20 g of simulant (the orange juice is introduced at 85° C., the other simulants are introduced at 23° C.).
  • the bags are placed in a climatic chamber maintained at a temperature of 40°C for 25 days
  • the peel forces are measured before and after aging (kinetic monitoring).
  • the peel strength after aging should not be less than 40% of the initial value
  • the peel values obtained between aluminum and polyethylene are greater than 4N/15 mm and quite satisfactory given the aggressiveness of the various simulants tested (alcohol, acid, introduction at high temperature).

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  • Polyurethanes Or Polyureas (AREA)
  • Adhesives Or Adhesive Processes (AREA)
EP22714498.7A 2021-03-18 2022-03-18 Kaschierklebstoff Pending EP4308622A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR2102702A FR3120870B1 (fr) 2021-03-18 2021-03-18 Adhesif de lamination
PCT/FR2022/050500 WO2022195235A1 (fr) 2021-03-18 2022-03-18 Adhesif de lamination

Publications (1)

Publication Number Publication Date
EP4308622A1 true EP4308622A1 (de) 2024-01-24

Family

ID=75746883

Family Applications (1)

Application Number Title Priority Date Filing Date
EP22714498.7A Pending EP4308622A1 (de) 2021-03-18 2022-03-18 Kaschierklebstoff

Country Status (6)

Country Link
US (1) US20240166928A1 (de)
EP (1) EP4308622A1 (de)
JP (1) JP2024512450A (de)
CN (1) CN117321112A (de)
FR (1) FR3120870B1 (de)
WO (1) WO2022195235A1 (de)

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8022164B1 (en) * 2010-03-04 2011-09-20 Microvast, Inc. Two-component solvent-free polyurethane adhesives
FR3053972B1 (fr) * 2016-07-12 2020-01-24 Bostik Sa Composition adhesive bicomposante a base de polyurethane

Also Published As

Publication number Publication date
FR3120870A1 (fr) 2022-09-23
WO2022195235A1 (fr) 2022-09-22
CN117321112A (zh) 2023-12-29
FR3120870B1 (fr) 2024-03-22
JP2024512450A (ja) 2024-03-19
US20240166928A1 (en) 2024-05-23

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