Amine-catalyzed thiol-curing of epoxide resins

Patent metadata

Field	Value
Publication number	US-10179831-B2
Application number	US-201515118339-A
Country	US
Kind code	B2
Filing date	Feb 12, 2015
Priority date	Feb 13, 2014
Publication date	Jan 15, 2019
Grant date	Jan 15, 2019

Abstract

A composition containing an epoxide compound with two or more epoxide groups, a thiol ester with two or more ester groups and two or more thiol groups and/or a thiol ether with two or more thiol groups, and 0.005-2 wt. %, based on the total weight of the composition, of a tertiary amine which has a 5- or 6-membered aliphatic nitrogen heterocycle, said composition containing less than 1 wt. % of a primary amine. The composition can be used as, an embedding medium for microscopy and as an adhesive and to an optical element which comprises the composition.

First claim

The invention claimed is:

1. A composition comprising:
(A) an epoxy compound with two or more epoxy groups,
(B) a thiol ester with two or more ester groups and two or more thiol groups and/or a thioether with two or more thiol groups,
(C) 0.005-2 wt.-%, based on the total weight of the composition, of a tertiary amine which comprises a 5- or 6-membered aliphatic nitrogen heterocycle,
(D) 0.5-2 wt.-% of a photolatent base, selected from the group consisting of substituted 5-(carbonylarylmethyl)-1,5-diazabicyclo[4.3.0]nonane and optionally substituted 8-(carbonylarylmethyl)-1,8-diazabicyclo[5.4.0]undecane, and
(E) a photoinitiator,
wherein the composition contains less than 1 wt.-%, based on the total weight of the composition, of a primary amine.

2. The composition of claim 1 , wherein component (B) of the composition comprises the thiol ester with two or more ester groups and two or more thiol groups.

3. The composition of claim 1 , wherein the tertiary amine is selected from the group consisting of 1-(2-hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)pyrrolidone, 1-(2-hydroxyethyl)piperidine, 1-ethyl piperazine, 1-(2-hydroxyethyl)piperazine, 1,4-bis-(2-hydroxyethyl)piperazine, 1-methylimidazole, 4-(2-hydroxyethyl)morpholine, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

4. The composition of claim 1 , wherein the component (B) is an oligomeric thiourethane.

5. The composition of claim 1 , wherein component (B) is a mixture of two or more oligomeric thiourethanes.

6. The composition of claim 4 , wherein an average number of the monomers contained in the oligomeric thiourethane is between 5-25 and a proportion of the oligomeric thiourethane or of the oligomeric thiourethanes, based on the total weight of the composition, is 10-50 wt.-%.

7. The composition of claim 1 , wherein the thiol ester is selected from the group consisting of pentaerythritol tetra(3-mercaptopropionate), trimethylolpropane tri(3-mercaptopropionate), ethylene glycol di(3-mercaptopropionate), pentaerythritol tetra(mercaptoacetate), trimethylolpropane tri(mercaptoacetate), ethylene glycol di(mercaptoacetate), tris[2-(3-mercaptopropionyloxy)ethyl] isocyanurate, tris-[2-(2-mercaptopropionyloxy)ethyl] isocyanurate or a mixture thereof.

8. The composition of claim 1 , wherein component (A) comprises bisphenol A diglycidyl ether and/or bisphenol F diglycidyl ether, component (B) comprises 10-50 wt. % based on the total weight of the composition, of a thiol ester in the form of one or more oligomeric thiourethanes, which can be obtained in each case from pentaerythritol tetra(3-mercaptopropionate) (PTMP) and/or trimethylolpropane tri(3-mercaptopropionate) (TPMP) with xylylene diisocyanate (XDI), norbornyl diisocyanate (NBDI) and/or isophorone diisocyanate (IPDI), wherein each oligomeric thiourethane comprises two or more free thiol groups, and component (C) comprises 0.005-0.3 wt.-%, based on the total weight of the composition, one or more tertiary amines, selected from the group consisting of 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and 1,4-diazabicyclo[2.2.2]octane (DABCO) or 0.3-2 wt.-%, based on the total weight of the composition, one or more tertiary amines, selected from the group consisting of 1-(2-hydroxyethyl)pyrrolidine, 1-(2-hydroxyethyl)pyrrolidone, 1-(2-hydroxyethyl)piperidine, 1-ethylpiperazine, 1-(2-hydroxyethyl)piperazine, 1,4-bis-(2-hydroxyethyl)piperazine, 1-methylimidazole and 4-(2-hydroxyethyl)morpholine.

9. The composition of claim 1 , wherein the photolatent base is substituted 5-(carbonylarylmethyl)-1,5-diazabicyclo[4.3.0]nonane.

10. An adhesive comprising the composition according to claim 1 .

11. A cement comprising the adhesive according to claim 10 .

12. An optical element for a display device that can be fitted on the head of a user and generates an image, the optical element comprising
a front side and a rear side,
a coupling-in section and a coupling-out section spaced apart from the coupling-in section, and
a light guiding channel which is suitable for guiding light bundles of pixels of the generated image, which are coupled into the optical element via the coupling-in section of the optical element, in the optical element to the coupling-out section, by which they are coupled out of the optical element,
wherein the optical element comprises a plurality of joined to each other with a composition according to claim 1 .

13. A display device having a holder that can be fitted on the head of a user, an image-generating module secured to the holder, which generates an image, and an imaging optical system secured to the holder, which comprises an optical element according to claim 12 and which, when the holder is fitted on the user's head, images the generated image such that the user can perceive it as a virtual image.

14. The composition of claim 4 , wherein the oligomeric thiourethane is obtained by reacting at least one thiol ester that comprises two or more ester groups and two or more thiol groups and/or at least one thioether that comprises two or more thiol groups, with at least one di- or polyisocyanate, wherein the oligomeric thiourethane comprises two or more free thiol groups.

15. The composition of claim 5 , wherein the oligomeric thiourethanes is obtained by reacting at least one thiol ester that comprises two or more ester groups and two or more thiol groups and/or a thioether that comprises two or more thiol groups, with at least one di- or polyisocyanate, wherein each oligomeric thiourethane comprises two or more free thiol groups.

16. The composition of claim 5 , wherein an average number of the monomers contained in the oligomeric thiourethane is between 5-25 and a proportion of the oligomeric thiourethane or of the oligomeric thiourethanes, based on the total weight of the composition, is 10-50 wt.-%.

17. The composition of claim 1 , wherein the thioether is 2,3-bis(2-mercaptoethylsulfanyl)propane-1-thiol.

Assignees

• Carl Zeiss Smart Optics Gmbh
• tooz technologies GmbH

Inventors

• Weippert Hans-Joachim

Classifications

• G02B27/0172

  characterised by optical features · CPC title

• C08K5/3462

  Six-membered rings · CPC title

• C08K5/54

  Silicon-containing compounds {(C08K5/0091 takes precedence)} · CPC title

• C08K5/37

  Thiols · CPC title

• G01N2001/364

  using resins, epoxy · CPC title