# US 11,306,178 B2 · Epoxy resin composition and cured product

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- Number: US 11,306,178 B2
- Document ID: US11306178B2
- Status: Granted
- Kind: B2
- Application number: 17/042,629
- Filed: 2019-03-15
- Published: 2021-02-04
- Granted: 2022-04-19
- Earliest claimed: 2018-03-30
- Assignees: Nippon Steel Chemical & Material Co., Ltd.
- Applicants: Nippon Steel Chemical & Material Co., Ltd.
- Inventors: Koichi Hattori; Naoki Yokoyama
- Web page: https://patentgrep.com/patent/US11306178B2

## CPC

- C08G 59/1477: {containing nitrogen}
- C08G 59/4021: {Ureas; Thioureas; Guanidines; Dicyandiamides}
- C08G 18/12: using two or more compounds having active hydrogen in the first polymerisation step
- C08G 18/3206: {aliphatic}
- C08G 18/4825: {Polyethers containing two hydroxy groups (C08G18/4833 - C08G18/5096 take precedence)}
- C08G 18/58: Epoxy resins {(C08G18/42, C08G18/48 take precedence; reaction products of epoxy resins with at least equivalent amounts of compounds containing active hydrogen C08G18/6407, with at least equivalent amounts of amines C08G18/6415; polymeric products of isocyanates or isothiocyanates with epoxy compounds having no active hydrogen C08G18/003)}
- C08G 18/7671: {containing only one alkylene bisphenyl group}
- C08G 59/06: of polyhydric phenols
- C08G 59/226: {Mixtures of di-epoxy compounds}
- C08G 59/44: Amides
- C09D 175/08: from polyethers
- C09J 175/08: from polyethers
- C08L 2205/025: containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
- C08L 2205/03: containing three or more polymers in a blend
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- C09J: ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES (preparation of glue or gelatine C09H)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)

## Abstract

Provided is a polyurethane-modified epoxy resin composition having satisfactory operability of processing, such as casting or impregnation, in a composition state. The epoxy resin composition includes, as essential components, the following components (A) to (D): (A) a low-concentration polyurethane-modified epoxy resin containing a polyurethane having an epoxy resin added to each of both terminals thereof and/or one terminal thereof; (B) a polyurethane-unmodified epoxy resin that is liquid at 30° C.; (C) a solid epoxy resin having a bisphenol structure, the resin having a glass transition temperature or a melting point of 50° C. or more; and (D) an amine-based curing agent that is dicyandiamide or a derivative thereof, wherein the epoxy resin composition includes the component (A) at from 3.0 wt % to 30.0 wt %, and the component (C) at from 0.1 wt % to 40.0 wt % with respect to the total of the components (A) to (D).

## Claims

### Claim 1

An epoxy resin composition, comprising, as essential components, the following components (A) to (D):
(A) a low-concentration polyurethane-modified epoxy resin, which contains a polyurethane having an epoxy resin added to each of both terminals thereof and/or one terminal thereof, and in which a weight concentration of polyurethane constituent components is from 1.0 wt % to 15.0 wt %;
(B) a polyurethane-unmodified epoxy resin that is liquid at 30° C.;
(C) a solid epoxy resin having a bisphenol structure, the resin having a glass transition temperature or a melting point of 50° C. or more; and
(D) an amine-based curing agent that is dicyandiamide or a derivative thereof,
wherein the epoxy resin composition comprises the component (A) at from 3.0 wt % to 30.0 wt %, and the component (C) at from 0.1 wt % to 40.0 wt % with respect to a total of the components (A) to (D).

### Claim 2 (depends on 1)

The epoxy resin composition according to claim 1, wherein the epoxy resin composition has an initial viscosity of from 100 Pa·s to 2,000 Pa·s.

### Claim 3 (depends on 2)

The epoxy resin composition according to claim 2,
wherein the component (A) is a low-concentration polyurethane-modified epoxy resin, which is obtained by modifying a bisphenol-based epoxy resin (a) represented by the following formula (1) having an epoxy equivalent of from 150 g/eq to 200 g/eq and a hydroxyl equivalent of from 2,000 g/eq to 2,600 g/eq with a medium to high molecular weight polyol compound (b) having a number-average molecular weight of 200 or more, a polyisocyanate compound (c), and a low molecular weight polyol compound (d) having a number-average molecular weight of less than 200 serving as a chain extender,
the low-concentration polyurethane-modified epoxy resin comprising a polyurethane having the epoxy resin (a) added to each of both terminals thereof and/or one terminal thereof, the polyurethane being obtained by:
producing a urethane prepolymer (P) by using the epoxy resin (a) in an amount of from 78 wt % to 92 wt % with respect to a total amount of the components (a), (b), (c), and (d), and causing the medium to high molecular weight polyol compound (b) and the polyisocyanate compound (c) to react with each other in the presence of the epoxy resin (a) while using the compounds in such amounts that a molar ratio between OH groups of the component (b) and NCO groups of the component (c) falls within a range of from 1:3 to 1:20; and
then subjecting the urethane prepolymer (P) to a polyurethanation reaction by adding the low molecular weight polyol compound (d) so that a molar ratio between NCO groups of the urethane prepolymer (P) and OH groups of the low molecular weight polyol compound (d) falls within a range of from 0.9:1 to 1:0.9:
where R and R1 each represent H or a methyl group, and “a” represents a number of from 0 to 10.

### Claim 4 (depends on 3)

An epoxy resin cured product, which is obtained by curing the epoxy resin composition of claim 3.

### Claim 5 (depends on 4)

The epoxy resin cured product according to claim 4, wherein the epoxy resin cured product has a glass transition temperature (Tg) of 110° C. or more, and an Izod impact value (unnotched) of 30 kJ/m2 or more measured in accordance with JIS K 7110.

### Claim 6 (depends on 2)

An epoxy resin cured product, which is obtained by curing the epoxy resin composition of claim 2.

### Claim 7 (depends on 6)

The epoxy resin cured product according to claim 6, wherein the epoxy resin cured product has a glass transition temperature (Tg) of 110° C. or more, and an Izod impact value (unnotched) of 30 kJ/m2 or more measured in accordance with JIS K 7110.

### Claim 8 (depends on 1)

The epoxy resin composition according to claim 1,
wherein the component (A) is a low-concentration polyurethane-modified epoxy resin, which is obtained by modifying a bisphenol-based epoxy resin (a) represented by the following formula (1) having an epoxy equivalent of from 150 g/eq to 200 g/eq and a hydroxyl equivalent of from 2,000 g/eq to 2,600 g/eq with a medium to high molecular weight polyol compound (b) having a number-average molecular weight of 200 or more, a polyisocyanate compound (c), and a low molecular weight polyol compound (d) having a number-average molecular weight of less than 200 serving as a chain extender,
the low-concentration polyurethane-modified epoxy resin comprising a polyurethane having the epoxy resin (a) added to each of both terminals thereof and/or one terminal thereof, the polyurethane being obtained by:
producing a urethane prepolymer (P) by using the epoxy resin (a) in an amount of from 78 wt % to 92 wt % with respect to a total amount of the components (a), (b), (c), and (d), and causing the medium to high molecular weight polyol compound (b) and the polyisocyanate compound (c) to react with each other in the presence of the epoxy resin (a) while using the compounds in such amounts that a molar ratio between OH groups of the component (b) and NCO groups of the component (c) falls within a range of from 1:3 to 1:20; and
then subjecting the urethane prepolymer (P) to a polyurethanation reaction by adding the low molecular weight polyol compound (d) so that a molar ratio between NCO groups of the urethane prepolymer (P) and OH groups of the low molecular weight polyol compound (d) falls within a range of from 0.9:1 to 1:0.9:
where R and R1 each represent H or a methyl group, and “a” represents a number of from 0 to 10.

### Claim 9 (depends on 8)

An epoxy resin cured product, which is obtained by curing the epoxy resin composition of claim 8.

### Claim 10 (depends on 9)

The epoxy resin cured product according to claim 9, wherein the epoxy resin cured product has a glass transition temperature (Tg) of 110° C. or more, and an Izod impact value (unnotched) of 30 kJ/m2 or more measured in accordance with JIS K 7110.

### Claim 11 (depends on 1)

An epoxy resin cured product, which is obtained by curing the epoxy resin composition of claim 1.

### Claim 12 (depends on 11)

The epoxy resin cured product according to claim 11, wherein the epoxy resin cured product has a glass transition temperature (Tg) of 110° C. or more, and an Izod impact value (unnotched) of 30 kJ/m2 or more measured in accordance with JIS K 7110.