Use of toughness improvers for increasing the maximum linear expansion of single-component heat-curing epoxy resin compositions

Patent metadata

Field	Value
Publication number	US-11624013-B2
Application number	US-201816771748-A
Country	US
Kind code	B2
Filing date	Dec 18, 2018
Priority date	Dec 19, 2017
Publication date	Apr 11, 2023
Grant date	Apr 11, 2023

Abstract

Methods in which toughness improvers based on terminally blocked polyurethane prepolymers are used to increase the maximum linear expansion of single component heat-curing epoxy resin compositions, in particular for joining substrates having different thermal expansion coefficients, in particular in the framework of transport agents or white goods.

First claim

The invention claimed is:

1. A method comprising:
adding at least one toughness improver D to a one-component thermosetting epoxy resin composition in an amount effective to increase the maximum linear expansion Max. elongation of the one-component thermosetting epoxy resin composition, wherein
the one-component thermosetting epoxy resin composition comprises:
a) at least one epoxy resin A having an average of more than one epoxy group per molecule, and
b) at least one latent curing agent for epoxy resins B;

where the weight ratio of all epoxy resin(s) A having an average of more than one epoxy group per molecule to the at least one toughness improver D is 0.3-2.2;
the toughness improver D is a terminally blocked polyurethane prepolymer of the formula (I):

where
R 1 is a p-valent radical of a linear or branched polyurethane prepolymer terminated by isocyanate groups after the removal of the terminal isocyanate groups,
p has a value of 2 to 8, and
R 2 is a blocking group which is detached at a temperature above 100° C., where R 2 is not a substituent selected from the group consisting of

where
R 12 is an alkylene group which has 2 to 5 carbon atoms and optionally has double bonds or is substituted, or is a phenylene group or a hydrogenated phenylene group, especially ε-caprolactam after removal of the NH proton, and
R 19 represents bisphenols, after removal of a hydroxyl group;

the maximum linear expansion Max. elongation is determined in a lap shear test during the cooling of a heated cured lap shear specimen, and
wherein the maximum linear expansion Max. elongation is ≥2.1 mm.

2. The method of claim 1 , wherein
R 2 is independently a substituent selected from the group consisting of

where
R 5 , R 6 , R 7 and R 8 are each independently an alkyl or cycloalkyl or aralkyl or arylalkyl group, or R 5 together with R 6 , or R 7 together with R 8 , form part of a 4- to 7-membered, optionally substituted ring;
R 9 , R 9′ and R 10 are each independently an alkyl or aralkyl or arylalkyl group or an alkyloxy or aryloxy or aralkyloxy group;
R 11 is an alkyl group;
R 13 and R 14 are each independently an alkylene group which has 2 to 5 carbon atoms and optionally has double bonds or is substituted, or a phenylene group or a hydrogenated phenylene group;
R 15 , R 16 and R 17 are each independently H or an alkyl group or an aryl group or an aralkyl group;
R 18 is an aralkyl group or is a mono- or polycyclic, substituted or unsubstituted aromatic group optionally having aromatic hydroxyl groups;
R 4 is a radical of an aliphatic, cycloaliphatic, aromatic or araliphatic epoxide containing a primary or secondary hydroxyl group after the removal of the hydroxyl and epoxy groups; and
m has a value of 1, 2 or 3.

3. The method of claim 1 , wherein
R 2 is independently a substituent selected from the group consisting of

where
R 5 , R 6 , R 7 and R 8 are each independently an alkyl or cycloalkyl or aralkyl or arylalkyl group, or R 5 together with R 6 , or R 7 together with R 8 , form part of a 4- to 7-membered, optionally substituted ring;
R 15 , R 16 and R 17 are each independently H or an alkyl group or an aryl group or an aralkyl group; and
R 18 is an aralkyl group or is a mono- or polycyclic, substituted or unsubstituted aromatic group optionally having aromatic hydroxyl groups.

4. The method of claim 1 , wherein the weight ratio of all epoxy resin A having an average of more than one epoxy group per molecule to the at least one toughness improver D is 0.4-2.0.

5. The method of claim 1 , wherein R 1 is a p-valent radical of a linear or branched polyurethane prepolymer terminated by isocyanate groups after the removal of the terminal isocyanate groups, and the polyurethane prepolymer is prepared from at least one diisocyanate or triisocyanate and from a polymer Q PM having terminal amino, thiol or hydroxyl groups.

6. The method of claim 5 , wherein the polymer Q PM having terminal amino, thiol or hydroxyl groups comprises polyols, each having an average molecular weight that is between 600 and 6000 daltons, the polyols being selected from the group consisting of polyethylene glycols, polypropylene glycols, polyethylene glycol-polypropylene glycol block polymers, polybutylene glycols, polytetramethylene ether glycols, hydroxyl-terminated polybutadienes, hydroxyl-terminated butadiene-acrylonitrile copolymers and mixtures thereof.

7. The method of claim 6 , wherein the polymer Q PM having terminal amino, thiol or hydroxyl groups comprises polyols, each having an average molecular weight that is between 600 and 6000 daltons, the polyols being selected from the group consisting of polytetramethylene ether glycols and hydroxyl-terminated polybutadienes, wherein the weight ratio of polytetramethylene ether glycol to hydroxyl-terminated polybutadiene is in the range from 100/0 to 70/30.

8. The method of claim 1 , wherein the maximum linear expansion Max. elongation is measured in a lap shear test at a strain rate V st of 0.52 mm/min.

9. The method of claim 1 , wherein a temperature of the lap shear specimen in the lap shear test is 190° C. at the start of the measurement and the lap shear specimen is cooled at the start of the measurement at a cooling rate of 40° C/min to a temperature of 25° C. and then left at that temperature.

10. The method of claim 1 , wherein the lap shear test is a lap shear test having lap shear test specimens having the following features:
steel sheets having the dimensions of 25 mm×100 mm×1.5 mm,
bonding area of the cured one-component thermosetting epoxy resin composition having the dimensions of 10 mm×25 mm with a thickness of 1.5 mm.

11. The method of claim 1 , wherein the maximum linear expansion Max. elongation is ≥2.145 mm.

12. The method of claim 1 , wherein a maximum force measured is ≤6000 N.

13. The method of claim 1 , wherein a force measured on attainment of the maximum linear expansion Max. elongation of 2.145 mm is ≤4000 N.

14. The method of claim 1 , wherein the latent curing agent for epoxy resins B is selected from the group consisting of dicyandiamide, guanidines, anhydrides of polybasic carboxylic acids, dihydrazides and aminoguanidines.

15. The method of claim 1 , wherein the one-component thermosetting epoxy resin composition is a thermosetting epoxy resin adhesive, and the method further comprises either
applying the thermosetting epoxy resin adhesive to at least one substrate to bond substrates of a motor vehicle construction, or
applying the thermosetting epoxy resin adhesive to at least one substrate to bond substrates of a sandwich panel construction.

16. The method of claim 1 , wherein the weight ratio of all epoxy resin(s) A having an average of more than one epoxy group per molecule to the at least one toughness improver D is 0.5-1.8.

17. The method of claim 1 , wherein the weight ratio of all epoxy resin(s) A having an average of more than one epoxy group per molecule to the at least one toughness improver D is 0.6-1.4.

Assignees

• Sika Tech Ag

Inventors

• Rheinegger Urs
• Jendoubi Elyes
• Gallo Dominique
• Krüger Christian

Classifications

• C08G59/4021

  Ureas; Thioureas; Guanidines; Dicyandiamides · CPC title

• C08G18/755

  and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate · CPC title

• C08G18/10 Primary

  Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step · CPC title

• C08G18/4845 Primary

  containing oxypropylene or higher oxyalkylene end groups · CPC title

• C08G18/12

  using two or more compounds having active hydrogen in the first polymerisation step · CPC title