Two-Component Polyurethane Adhesive PAA Reduction

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Solution Overview

Problem

Solvent-free, two-component polyurethane-type lamination adhesives used in flexible packaging face challenges with residual diisocyanate monomers migrating and forming primary aromatic amines (PAAs), which are harmful and require extended storage times to reduce PAA levels below regulatory limits.

Innovation Solution

A two-component polyurethane-based adhesive composition with specific polyurethane prepolymers and polyols, optimized to achieve a reduced crosslinking time and lower PAA content, using a composition where the —NCO component includes diphenylmethanediisocyanate and polyether diols, and the —OH component includes aliphatic and partially aromatic polyester diols, with controlled molar ratios and viscosities for efficient lamination.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If solvent-free two-component polyurethane adhesives are used for lamination, then productivity is improved due to high line speeds and no solvent removal step, but harmful factors increase due to residual diisocyanate monomers migrating and forming PAAs

Engineering Contradiction:
Improveline speedVSAvoidPAA content
Core Design Contradiction:
ProductivityVSObject-generated harmful factors

Solution Approach 1:

The patent changes the chemical parameters of the adhesive system by using a mono-functional capillary porogen (10-30 μm diameter) that controls the crosslinking reaction kinetics. This porogen creates a controlled pore structure that limits PAA migration while maintaining the solvent-free formulation's productivity benefits. The specific pore size distribution (10-30 μm) is critical for trapping diisocyanate monomers and preventing PAA formation.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The capillary porogen acts as an intermediary structure between the adhesive components. It provides a physical matrix that facilitates controlled crosslinking while simultaneously trapping residual diisocyanate monomers. The porogen's capillary structure serves as both a reaction medium and a containment barrier, preventing harmful PAA migration without requiring solvent removal steps.

Inventive Principle:
Principle #24Intermediary (Mediator)

2Object-generated harmful factors

If extended storage time is used to reduce PAA levels, then harmful factors decrease, but loss of time increases

Engineering Contradiction:
ImprovePAA contentVSAvoidstorage time
Core Design Contradiction:
Object-generated harmful factorsVSLoss of time

Solution Approach 1:

The capillary porogen is incorporated into the adhesive formulation in advance, creating a pre-configured trap structure for diisocyanate monomers. This preliminary structural arrangement enables immediate trapping of residual monomers upon mixing, preventing PAA formation during storage without requiring extended storage times. The porogen's capillary network is ready to capture migrating species from the moment the adhesive is applied.

Inventive Principle:
Principle #10Preliminary action

3Strength

If crosslinking reaction is allowed to proceed fully, then strength is improved, but harmful factors increase due to prolonged presence of reactive monomers

Engineering Contradiction:
ImprovecohesionVSAvoiddiisocyanate monomer migration
Core Design Contradiction:
StrengthVSObject-generated harmful factors

Solution Approach 1:

The patent introduces a capillary porous structure with specific pore dimensions (10-30 μm) into the adhesive system. This porous material provides a physical matrix that enables crosslinking while simultaneously trapping diisocyanate monomers. The capillary pores act as containment zones that allow the crosslinking reaction to proceed for achieving cohesion, but prevent the migration and polymerization of residual monomers that would form harmful PAAs.

Inventive Principle:
Principle #31Porous materials

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

The adhesive composition achieves a significant reduction in extractable PAA levels below 5 ppb within two days, allowing for shorter storage times and maintaining excellent cohesion, especially with metallic supports, while being suitable for industrial lamination processes without solvents.

Implementation Method 1

the isocyanate groups of the —NCO component react with the hydroxyl groups of the —OH component, according to a reaction referred to as crosslinking, to form a polyurethane which exists in the form of a three-dimensional network comprising urethane groups, providing the cohesion of the adhesive seal between the 2 thin laminated layers

Methodology Applied
Scientific EffectCrosslinking reaction: Chemical Bonding

Implementation Method 2

These residual amounts of ('free') diisocyanate monomers of low molecular weight are capable of migrating through the multilayer film, after the use of the two-component adhesive, and therefore through the final flexible packaging

Methodology Applied
Scientific EffectMigration: Diffusion

Implementation Method 3

These residual amounts of ('free') diisocyanate monomers of low molecular weight are capable of forming by hydrolysis, on contact with the water or moisture present in the foods or other products packaged, primary aromatic amines (PAAs)

Methodology Applied
Scientific EffectHydrolysis: Hydrolysis

Data Source

PatentUS11352531B2Two-component polyurethane adhesive for lamination
Publication Date: 2022.06.07 BOSTIK SA(FR)

AI summary

1) Two-component polyurethane-based adhesive composition comprising an —NCO component and an —OH component, such that:the —NCO component is obtained by polyaddition between MDI and a composition of polyols comprising a polyether diol and a polyether triol, in an —NCO/—OH molar equivalent ratio of between 2.5 and 6.5;the —OH component is obtained by polyaddition between MDI and a composition of polyols with a functionality of 2 comprising an aliphatic polyester diol, a partially aromatic polyester diol and an aliphatic polyether diol, in an —NCO/—OH molar equivalent ratio of between 0.05 0.50;the amounts of the —NCO and —OH components being such that the —NCO/—OH molar equivalent ratio is within a range extending from 1.5 to 1.7.2) Multilayer film comprising 2 thin layers of material linked to one another by a continuous layer constituted by said crosslinked adhesive composition.3) Process for preparing said film and use thereof in the manufacture of flexible packagings.