Fluorinated Copolymer Salt Composition for Water-Oil Resistance

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Solution Overview

Problem

Conventional water/oil resistant compositions using fluorinated copolymers with perfluoroalkyl groups having at least 8 carbon atoms face issues with agglomeration, pH sensitivity, and odor, while those with fewer than 6 carbon atoms or perfluoropolyether offer inadequate water/oil resistance and environmental concerns.

Innovation Solution

A water/oil resistant composition is developed using a fluorinated copolymer with structural units based on specific monomers, converted to a salt with an organic acid having a pKa of 2.0 to 4.0, such as lactic acid, citric acid, or malic acid, and optionally including adjuvants like anionic paper strength enhancing agents, to achieve improved water/oil resistance and reduced environmental impact.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If a fluorinated copolymer with perfluoroalkyl groups having at least 8 carbon atoms is used to achieve adequate water/oil resistance, then water/oil resistance is improved, but agglomerates are likely to be formed and operational trouble occurs

Engineering Contradiction:
Improvewater/oil resistanceVSAvoidoperational smoothness
Core Design Contradiction:
ReliabilityVSEase of operation

Solution Approach 1:

The patent changes the carbon atom count parameter of perfluoroalkyl groups from ≥8 to 6-7 carbon atoms, and specifies a particular structural formula with n=1 or 2 and specific Z and R group configurations. This parameter optimization maintains water/oil resistance while preventing agglomeration and operational issues.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent uses a copolymer composed of multiple monomer units including perfluoroalkylethyl methacrylate, (meth)acrylate, and vinyl chloride or vinylidene chloride. This composite structure combines the benefits of fluorinated groups for water/oil resistance with other monomers that prevent agglomeration and improve operational stability.

Inventive Principle:
Principle #40Composite materials

2Ease of manufacture

If acetic acid is used to convert amino groups to form a salt in the fluorinated copolymer, then cost and safety are improved, but the composition becomes sensitive to pH and adjuvants causing agglomeration and loss of water/oil resistance

Engineering Contradiction:
Improvemanufacturing cost and safetyVSAvoidwater/oil resistance stability
Core Design Contradiction:
Ease of manufactureVSReliability

Solution Approach 1:

The patent changes the pKa parameter of the organic acid from acetic acid (pKa 4.76) to acids with pKa of 2.0-4.0, such as formic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, or their mixtures. This parameter change reduces pH sensitivity and prevents agglomeration while maintaining water/oil resistance stability.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent introduces a specific organic acid as an intermediary substance that mediates between the amino groups of the copolymer and the environment. These acids with pKa 2.0-4.0 provide stable salt formation that is less sensitive to pH changes and anionic adjuvants, preventing agglomeration.

Inventive Principle:
Principle #24Intermediary (Mediator)

3Object-affected harmful factors

If perfluoropolyether is used as a substitute for longer perfluoroalkyl chains to reduce environmental concerns, then environmental impact is reduced, but water/oil resistance becomes inadequate

Engineering Contradiction:
Improveenvironmental impactVSAvoidwater/oil resistance
Core Design Contradiction:
Object-affected harmful factorsVSReliability

Solution Approach 1:

The patent optimizes the perfluoroalkyl chain length parameter to 6-7 carbon atoms (specifically perfluoroalkylethyl groups with n=1 or 2), which is shorter than conventional ≥8 carbon chains but longer than perfluoropolyether. This intermediate length provides adequate water/oil resistance while reducing environmental persistence and bioaccumulation concerns.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent combines perfluoroalkylethyl methacrylate units with other monomer units including (meth)acrylate and vinyl chloride or vinylidene chloride. This composite structure achieves adequate water/oil resistance through the synergistic effect of fluorinated groups and other hydrophobic monomers, allowing the use of shorter, more environmentally friendly perfluoroalkyl chains.

Inventive Principle:
Principle #40Composite 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 composition provides sufficient water/oil resistance to base materials, is less influenced by pH and adjuvants, and has minimal odor, while reducing environmental concerns associated with longer perfluoroalkyl chains.

Implementation Method 1

converted to a salt with an organic acid having a pKa of 2.0 to 4.0

Methodology Applied
Scientific EffectSalt formation: Chemical Bonding

Implementation Method 2

fluorinated copolymer having structural units based on specific monomers... converted to a salt... to achieve improved water/oil resistance

Methodology Applied
Scientific EffectHydrophobic effect: Hydrophobe

Data Source

PatentEP2500394B1Water-resistant/oil-resistant agent composition, article treated with the composition, and processes for production of the composition and the article
Publication Date: 2016.09.28 AGC INC

AI summary

To provide a water/oil resistant composition which can impart a sufficient water/oil resistance to a base material even though a fluorinated copolymer having an Rf group with at most 6 carbon atoms is used, said water/oil resistance being not substantially influenced by an adjuvant or the pH of dilution water, and which has little odor; an article treated therewith; and processes for their production. A water/oil resistant composition having a fluorinated copolymer dispersed or dissolved in a medium, wherein the fluorinated copolymer is one having one, some or all of amino groups in a fluorinated copolymer comprising structural units based on a monomer (a) having a C1-6 Rf group and structural units based on a monomer (b) having an amino group, converted to form a salt with an organic acid comprising an organic acid having a pKa of from 2.0 to 4.0.