Phosphate-Free Detergent Composition with Stabilized Protease

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Solution Overview

Problem

Existing automatic dishwashing compositions face challenges in providing effective cleaning, especially in hard water conditions and under stressful washing cycles, due to the negative impact of strong complexing agents on enzymes like proteases.

Innovation Solution

A phosphate-free automatic dishwashing cleaning composition comprising 10-50% by weight of an organic complexing agent system with at least 15% methyl glycine diacetic acid, combined with a specific variant protease having mutations S039E-S099R-S126A-D127E-F128G, and an amylase, which enhances cleaning performance even in hard water and under hot, long cycles.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Object-affected harmful factors

If strong complexing agents are used to replace phosphates in phosphate-free compositions, then environmental profile is improved, but enzyme performance deteriorates due to extraction of structural calcium metal ions from proteases

Engineering Contradiction:
Improveenvironmental profileVSAvoidenzyme performance
Core Design Contradiction:
Object-affected harmful factorsVSReliability

Solution Approach 1:

The patent modifies the chemical parameters of the complexing agent system by selecting specific agents (MGDA, GLDA, IDS) with controlled stability constants and molecular structures that bind calcium less strongly than phosphates but sufficiently to maintain water softening. This parameter optimization allows environmental benefits to be achieved while preserving protease structural integrity and catalytic activity.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The invention employs a composite complexing agent system comprising multiple agents (MGDA, GLDA, and/or IDS) in specific ratios rather than a single strong complexing agent. This composite approach creates a synergistic effect where the combined system provides adequate water softening while individual agents at optimized concentrations minimize protease deactivation, thus resolving the contradiction between environmental performance and enzyme stability.

Inventive Principle:
Principle #40Composite materials

2Productivity

If hot and long washing cycles are used to improve cleaning of tough items, then cleaning performance is improved, but enzyme stability deteriorates under the stresses created by these cycles

Engineering Contradiction:
Improvecleaning performanceVSAvoidenzyme stability
Core Design Contradiction:
ProductivityVSStability of the object's composition

Solution Approach 1:

The patent incorporates stabilizers (sugars, polyols, amino acids, or their derivatives) into the detergent composition before use to preemptively protect proteases from thermal and chemical denaturation. These stabilizers pre-bind to the enzyme structure, forming a protective complex that maintains enzyme conformation and activity even under the extreme conditions of hot and long washing cycles, thus enabling both high cleaning performance and enzyme stability.

Inventive Principle:
Principle #10Preliminary action

3Productivity

If high levels of bleach are used to improve cleaning, then cleaning performance is improved, but enzyme performance deteriorates due to oxidative damage

Engineering Contradiction:
Improvecleaning performanceVSAvoidenzyme performance
Core Design Contradiction:
ProductivityVSReliability

Solution Approach 1:

The patent introduces enzyme stabilizers and protectants as intermediary substances that act as a buffer between the proteases and oxidative bleach agents. These intermediaries preferentially react with or sequester oxidative species, reducing their availability to damage enzyme structures. This mediator approach allows high bleach levels to be used for superior cleaning while the intermediaries shield the proteases from oxidative degradation, maintaining enzyme performance.

Inventive Principle:
Principle #24Intermediary (Mediator)

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 achieves excellent shine and effective removal of protein and starch-based soils, even under stressful washing conditions, while maintaining stability and performance in both hard and soft water.

Implementation Method 1

an organic complexing agent system comprising at least 15% by weight of the composition of methyl glycine diacetic acid

Methodology Applied
Scientific EffectComplexing: Solvation

Implementation Method 2

a protease wherein the protease is a variant having at least 90% identity with the amino acid sequence of SEQ ID NO:1 and comprising mutations S039E-S099R-S126A-D127E-F128G

Methodology Applied
Scientific EffectEnzymatic hydrolysis: Hydrolysis

Implementation Method 3

a protease wherein the protease is a variant having at least 90% identity with the amino acid sequence of SEQ ID NO:1

Methodology Applied
Scientific EffectEnzyme catalysis: Enzyme

Implementation Method 4

an amylase

Methodology Applied
Scientific EffectEnzymatic hydrolysis: Hydrolysis

Implementation Method 5

an amylase

Methodology Applied
Scientific EffectEnzyme catalysis: Enzyme

Data Source

PatentEP3502244B1Automatic dishwashing detergent composition
Publication Date: 2025.03.05 PROCTER & GAMBLE CO
  • EP3502244B1 patent drawing
  • EP3502244B1 patent drawing
  • EP3502244B1 patent drawing

AI summary

A phosphate-free automatic dishwashing cleaning composition comprising: a) from 10% to 50% by weight of the composition of an organic complexing agent system comprising at least 10% by weight of the composition of methyl glycine diacetic acid; b) an amylase; and c) a protease wherein the protease is a variant having at least 90% identity with the amino acid sequence of SEQ ID NO: 1 and comprising at least one amino acid substitution (using the SEQ ID NO:1 numbering) selected from the group consisting of S39E, S99R, S126A-D127E-F128G, N242D and mixtures thereof; or d)a protease wherein the protease is a variant having at least 90% identity with the amino acid sequence of SEQ ID NO:2 and comprising at least one amino acid substitution (using the SEQ ID NO:2 numbering) selected from the group consisting of X39E, X126A-X127E-X128G, X242D and mixtures thereof.