Phosphorus-Containing Phenolic Curing Agent for Epoxy Resins

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Solution Overview

Problem

Current methods for producing phosphorus-containing phenolic compounds face challenges such as low reactivity between phosphorus-containing compounds and phenolic resins, leading to insufficient heat resistance and fire retardancy in cured products, particularly in printed wiring boards and semiconductor sealing materials, due to limited usable phenols and low cross-linking density.

Innovation Solution

A method involving the reaction of an aromatic aldehyde with an alkoxy group substituent and a phosphorus-containing compound, followed by reaction with a phenol, enhances reactivity and heat resistance, allowing for the production of a novel phosphorus-containing phenolic compound that serves as a curing agent for epoxy resins, resulting in improved fire retardancy and heat resistance in cured products.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If conventional methods are used to produce phosphorus-containing phenolic compounds by reacting HCA with formaldehyde or acetone and then with phenolic resin, then fire retardancy is achieved, but reactivity is low resulting in poor heat resistance and failure to pass thermal delamination tests

Engineering Contradiction:
Improvefire retardancyVSAvoidheat resistance
Core Design Contradiction:
ReliabilityVSTemperature

Solution Approach 1:

The invention changes the chemical parameters by selecting specific aromatic aldehydes with particular substituents (such as -OH, -OCH3, -OC2H5 groups at specific positions) and controlling the molar ratios of reactants. This optimization of chemical parameters significantly improves the reactivity between the phosphorus-containing compound and phenolic resin, enabling the cured product to achieve both fire retardancy and heat resistance exceeding 350°C, thus passing thermal delamination tests.

Inventive Principle:
Principle #35Parameter changes

2Reliability

If halogen fire retardants and antimony compounds are used to impart fire retardancy to epoxy resin compositions, then fire retardancy is achieved, but environmental safety and reliability at high temperature deteriorate due to dioxin emission and cancer risk

Engineering Contradiction:
Improvefire retardancyVSAvoidenvironmental safety
Core Design Contradiction:
ReliabilityVSObject-affected harmful factors

Solution Approach 1:

The invention replaces harmful halogen-based fire retardants with a phosphorus-containing phenolic compound derived from environmentally benign reactants. The phosphorus compound achieves effective fire retardancy through its chemical structure and curing mechanism, eliminating the emission of dioxins and other harmful substances while maintaining or improving fire safety performance.

Inventive Principle:
Principle #22Blessing in disguise (Convert harm into benefit)

3Quantity of substance

If HCA is allowed to react with formaldehyde or acetone to provide phosphorus compound with hydroxy group, then phosphorus-containing phenolic resin is obtained, but unreacted components remain due to low reactivity resulting in poor thermal decomposition property

Engineering Contradiction:
Improvephosphorus contentVSAvoidreaction completeness
Core Design Contradiction:
Quantity of substanceVSManufacturing precision

Solution Approach 1:

The invention optimizes reaction parameters by selecting specific aromatic aldehydes with reactive substituents and controlling the molar ratios of HCA to aldehyde and aldehyde to phenolic resin within specific ranges. This ensures high reaction completeness with minimal unreacted components, achieving both adequate phosphorus content for fire retardancy and high reaction efficiency.

Inventive Principle:
Principle #35Parameter changes

4Ease of manufacture

If the type of usable polyfunctional phenols is limited due to low reactivity, then production is simplified, but the range of designing phosphorus-containing phenolic resins is considerably limited

Engineering Contradiction:
Improveproduction simplicityVSAvoiddesign range
Core Design Contradiction:
Ease of manufactureVSAdaptability or versatility

Solution Approach 1:

The invention expands the range of usable phenolic compounds by identifying specific structural requirements (aromatic rings with particular hydroxyl group positions and substituents). This broadens the selection of available phenolic resins while maintaining high reactivity, thus increasing design flexibility without significantly complicating the manufacturing process.

Inventive Principle:
Principle #35Parameter changes

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 method significantly enhances the reactivity and heat resistance of phosphorus-containing phenolic compounds, enabling the production of curable resin compositions with excellent fire retardancy and heat resistance, suitable for advanced printed wiring board materials and semiconductor sealing applications.

Implementation Method 1

allowing an aromatic aldehyde (a1) having an alkoxy group as a substituent on an aromatic nucleus to react with an organic phosphorus compound (a2) intramolecularly having a P-H group or a P-OH group; and subsequently allowing the reaction product to react with a phenol (a3)

Methodology Applied
Scientific EffectChemical reaction: Chemical Bonding

Data Source

PatentEP2409979B1Process for production of phosphorus-atom-containing phenol, novel phosphorus-atom-containing phenol, curable resin composition, cured product thereof, printed circuit board, and semiconductor sealing material
Publication Date: 2019.06.26 DIC CORP
  • EP2409979B1 patent drawingFigure 1~3
  • EP2409979B1 patent drawingFigure 4~8
  • EP2409979B1 patent drawingFigure 9~13

AI summary

Provided are a method for producing a phosphorus-containing phenolic compound in which reactivity is considerably excellent in the reaction between a phosphorus-containing compound and an aromatic nucleus of a phenol; in the case of using a polyhydric phenol or a phenolic resin as the phenol, a novel phosphorus-containing phenolic compound that serves as a curing agent for an epoxy resin and imparts excellent heat resistance to a cured product; a curable resin composition containing the novel phosphorus-containing phenolic compound; a cured product of the curable resin composition; a printed wiring board; and a semiconductor sealing material. An aromatic aldehyde (a1) having an alkoxy group as a substituent on an aromatic nucleus is allowed to react with an organic phosphorus compound (a2) intramolecularly having a P-H group or a P-OH group. The resultant reaction product is then allowed to react with a phenol (a3).