Modified EVOH Resin Adhesion and Flexibility

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Solution Overview

Problem

Existing resin compositions containing ethylene-vinyl alcohol copolymers (EVOH) face challenges in achieving improved adhesion to other resins, secondary processability, and flexibility while maintaining gas barrier properties, transparency, flavor retention, and oil resistance.

Innovation Solution

A resin composition comprising a modified EVOH with specific monomer content and degree of saponification, combined with inorganic oxide particles, enhances adhesion and flexibility without compromising gas barrier properties, suitable for various applications including molded articles, films, and containers.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Strength

If modified EVOH is used to improve adhesion to other resins, then interlayer adhesion is improved, but gas barrier properties decrease

Engineering Contradiction:
Improveinterlayer adhesionVSAvoidgas barrier properties
Core Design Contradiction:
StrengthVSReliability

Solution Approach 1:

The invention changes the chemical structure parameters of EVOH by copolymerizing ethylene, vinyl alcohol, and 1,3-propanediol units with specific compositional ratios (a: 10-50 mol%, b: 40-85 mol%, c: 5-20 mol%). This parameter optimization allows achieving both improved adhesion and maintained gas barrier properties, resolving the contradiction between modification level and barrier performance.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The invention creates a composite resin system by combining modified EVOH with specific polyolefin resins (polyethylene or polypropylene) in controlled ratios. This composite approach enables the synergistic combination of EVOH's gas barrier properties with polyolefin's adhesion and flexibility, while the controlled modification level prevents excessive loss of barrier performance.

Inventive Principle:
Principle #40Composite materials

2Reliability

If EVOH is used for high gas barrier properties, then gas barrier properties are improved, but flexibility decreases

Engineering Contradiction:
Improvegas barrier propertiesVSAvoidflexibility
Core Design Contradiction:
ReliabilityVSEase of operation

Solution Approach 1:

The invention modifies the physical and chemical parameters of EVOH by incorporating 1,3-propanediol units (c: 5-20 mol%) which introduce flexibility to the polymer chain. Simultaneously, the vinyl alcohol units (b: 40-85 mol%) maintain hydrogen bonding for gas barrier properties. This parameter balancing resolves the contradiction between flexibility and gas barrier performance.

Inventive Principle:
Principle #35Parameter changes

3Reliability

If EVOH is used for high gas barrier properties, then gas barrier properties are improved, but secondary processability decreases

Engineering Contradiction:
Improvegas barrier propertiesVSAvoidsecondary processability
Core Design Contradiction:
ReliabilityVSEase of manufacture

Solution Approach 1:

The invention changes the thermal and rheological parameters of EVOH by controlling the copolymer composition, particularly the ethylene units (a: 10-50 mol%) which improve melt flow characteristics. This enables better secondary processability through stretching and thermoforming while the vinyl alcohol units (b: 40-85 mol%) preserve gas barrier properties through hydrogen bonding.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The invention combines modified EVOH with polyolefin resins to create a composite material that exhibits improved secondary processability. The polyolefin component facilitates stretching and forming operations, while the modified EVOH maintains gas barrier properties, resolving the contradiction between processability and performance.

Inventive Principle:
Principle #40Composite materials

4Strength

If adhesive resin is used to improve adhesion between thermoplastic resins and EVOH, then interlayer adhesion is improved, but delamination still occurs

Engineering Contradiction:
Improveinterlayer adhesionVSAvoiddelamination resistance
Core Design Contradiction:
StrengthVSReliability

Solution Approach 1:

The invention extracts and eliminates the adhesive resin layer from the multilayer structure by directly incorporating adhesion-promoting functional groups into the EVOH polymer chain itself through copolymerization. This eliminates the intermediate adhesive layer that is prone to failure, achieving direct bonding between thermoplastic resins and EVOH while maintaining delamination resistance.

Inventive Principle:
Principle #2Taking out (Extraction)

Solution Approach 2:

The 1,3-propanediol units in the modified EVOH act as an intrinsic intermediary that facilitates adhesion between thermoplastic resins and EVOH. These units provide hydroxyl groups that form hydrogen bonds with thermoplastic resin chains, enabling direct adhesion without requiring a separate adhesive layer, thus improving both adhesion strength and delamination resistance.

Inventive Principle:
Principle #24Intermediary (Mediator)

Data Source

PatentEP3564307B1Resin composition and use of same
Publication Date: 2023.07.05 KURARAY CO LTD
  • EP3564307B1 patent drawingFigure 1
  • EP3564307B1 patent drawingFigure 2~3
  • EP3564307B1 patent drawingFigure 4

AI summary

A resin composition comprises: a modified EVOH (A) that is represented by a following formula (I), has contents (mol%) of a, b, and c based on the total monomer units satisfying following formulae (1) through (3), and has a degree of saponification (DS) defined by a following formula (4) of 90 mol% or more; and inorganic oxide particles (B), wherein a content of the inorganic oxide particles (B) is from 5 to 5000 ppm. Such a resin composition is improved in adhesion to a resin other than EVOH, secondary processability, and flexibility without decreasing the performances originally possessed by EVOH, such as gas barrier properties, transparency, flavor retention, solvent resistance, and oil resistance. Accordingly, the resin is preferably used as a molded article, a film, a sheet, a heat shrinkable film, a thermoformed article, a multilayer structure, a coinjection stretch blow molded container, a fuel container, and the like. 18≤a≤55 0.01≤c≤20 100−a+c×0.9≤b≤100−a+c DS=TotalNumberofMolesofHydrogenAtomsinX,Y,andZ/TotalNumberofMolesofX,Y,andZ×100