PARTICULATE CURING COMPONENTS

Abstract

The invention relates to a particulate curing component for a thermosetting resin, the particulate curing component comprising particles of a solid resin, wherein a curative for the thermosetting resin is dispersed within the particles of solid resin. The invention also relates to methods of forming particulate curing components and compositions comprising particulate curing components.

Claims

1. A particulate curing component for a thermosetting resin, the particulate curing component comprising particles of a solid resin, wherein a curative for the thermosetting resin is dispersed within the particles of solid resin.

2. (canceled)

3. The particulate curing component according to claim 1, wherein the solid resin melts or becomes sufficiently permeable to allow the curative to diffuse at a temperature of from 40? C. to 80? C.

4. The particulate curing component according to claim 3, wherein the solid resin is a phenoxy resin or an epoxidised resin, preferably an epoxy resin, more preferably a bisphenol-diglycidylether epoxy resin, a phenol novolac resin, an epoxy cresol novolac resin, a CTBAN-epoxy resin adduct or mixtures thereof.

5. The particulate curing component according to claim 4, wherein the curative is a solid at 20? C.

6. The particulate curing component according to claim 5, wherein the curative is a urea based curative or an imidazole curative, preferably wherein the curative is an isomer of N,N-(methyl-m-phenylene)bis(N,N-dimethylurea).

7. The particulate curing agent according to claim 6, wherein the curative is present in the particles of solid resin at a concentration of from 20 to 30 wt %.

8. The particulate curing component according to claim 7, wherein the particles of solid resin have a D.sub.90 of 100 ?m and a D.sub.10 of 2 ?m.

9. (canceled)

10. (canceled)

11. (canceled)

12. A curable resin composition comprising a thermosetting resin and a particulate curing component comprising particles of a solid resin, wherein a curative for the thermosetting resin is dispersed within the particles of solid resin, wherein the curative dispersed in the particles of solid resin is suitable for curing the thermosetting resin.

13. The composition according to claim 12, wherein the thermosetting resin is a liquid or semi-solid at 20? C.

14. The composition according claim 13, wherein the thermosetting resin is a phenoxy resin or an epoxidised resin, preferably an epoxy resin, more preferably a bisphenol-diglycidylether epoxy resin, a phenol novolac resin, an epoxy cresol novolac resin, a CTBAN-epoxy resin adduct, or blends thereof.

15. The composition according to claim 14, wherein the thermosetting resin has a minimum curing temperature of from 70? C. to 100? C.

16. The composition according to claim 15, wherein the concentration of the particulate curing composition is from 10 to 30 wt %, based on the weight of the composition.

17. The composition according to claim 16, wherein the concentration of the curative is from 0.5 to 10 wt %, based on the weight of the composition.

18. The composition according to claim 17 having air outlife at 30? C. of at least 3 months.

Description

EXAMPLES

[0064] Embodiments of the inventions will now be described by way of example only and with reference to the following Examples and Figures, in which:

[0065] FIG. 1 is a graph comparing the aging over 8 weeks (expressed as cold Tg) of an example of a composition of the invention compared to a standard resin composition;

[0066] FIG. 2 is a comparing the aging over 8 weeks (expressed as cold Tg) of a further example of a composition of the invention compared to the standard resin composition;

[0067] FIG. 3 is a graph showing the outlife (expressed as cold Tg) and dynamic enthalpy of a standard resin over 40 days; and

[0068] FIG. 4 is a graph showing the outlife (expressed as cold Tg) and dynamic enthalpy of two further examples of compositions of the invention over 40 days.

EXAMPLE 1

[0069] 10 g of a solid bisphenol A diglycidyl ether (GT7071, available from Huntsman Advanced Materials) was dissolved in 20 ml acetone, and 2.5 g of a urea based curative (Dyhard UR500, available from Alzchem) was then mixed in. The acetone was evaporated using a rotary evaporator to leave a solid residue comprising 20 wt % UR500. This solid residue was further dried at room temperature and then passed through a 90 ?m sieve to yield the curative dispersed in particles of a solid resin in the form of a powder. This powder was then mixed into a 20:80 w/w blend of a liquid bisphenol A diglycidyl ether (LY1556, available from Huntsman Advanced Materials) and a semisolid bisphenol A diglycidyl ether (YD-136, available from KUKDO Chemicals) at a concentration of 15 wt %, such that the urone was present in the final composition at a concentration of 3% w/w.

[0070] The composition was stored at 30? C. for 8 weeks, and the cold Tg was measured at various intervals by Differential Scanning calorimetry (DSC) using a TA Instruments DSC Q100 and MT DSC 1 in order to determine the aging/outlife of the composition. This was compared to a standard resin (Standard 1) comprising a blend of liquid and semisolid bisphenol A type epoxy resins and neat UR500 curative in mixing ratios and concentrations equivalent to those used in Example 1. The results are shown in FIG. 1, which shows that the material of Example 1 had reduced aging over a 6 week period at 30? C.

[0071] A sample of the composition of Example 1 was taken after 4 weeks and was cured for 6 hours at 80? C., and found to have a cured Tg, measured by Dynamic Mechanical Analysis (DMA) of 91? C., demonstrating acceptable cure.

EXAMPLE 2

[0072] The curative powder prepared in Example 1 was mixed into a liquid bisphenol A diglycidyl ether (LY1556, available from Huntsman Advanced Materials) in the presence of less than 10 wt % isophorone diamine (IPDA), available from BASF, which acted as a room temperature B-stager to increase the overall molecular weight and uncured Tg of the main epoxy component of the formulation.

[0073] The formulation of Example 2 was stored at 30? C. for 8 weeks and the uncured Tg was measured at various intervals by DSC, as described for Example 1, to determine the aging/outlife of the composition compared to the standard resin (Standard 1) also described in Example 1. The results are shown in FIG. 2, which shows that although the material of Example 2 starts at a higher cold Tg at day 0 due to the amount of IPDA added (this could be tailored to better match the starting cold Tg of Standard 1), the change in cold Tg over the storage period was substantially smaller than that of Standard 1, indicating a reduced rate of aging of the liquid resin composition.

[0074] A sample of the composition of Example 2 was taken after 4 weeks and was cured for 6 hours at 80? C., and was found to have a cured Tg of 89? C., demonstrating acceptable cure.

EXAMPLE 3

[0075] 16 g of a solid bisphenol A diglycidyl ether (GT6099, available from Huntsman Advanced Materials) was dissolved in 400 ml methyl-ethyl-ketone, and 4 g of a urea based curative (Dyhard UR500, available from Alzchem) was then mixed in. The solvent was evaporated using a rotary evaporator to leave a solid residue. This solid residue was further dried in a vacuum oven and then passed through a 90 ?m sieve to yield the curative dispersed in particles of a solid resin in the form of a powder comprising 20 wt % UR500. This powder was then mixed into a 30:70 w/w blend of a liquid bisphenol A diglycidyl ether (LY1556, available from Huntsman Advanced Materials) and a semisolid bisphenol A diglycidyl ether (YD-136, available from KUKDO Chemicals) at a concentration of 15 wt %, such that the urone was present in the final composition at a concentration of 3% w/w.

EXAMPLE 4

[0076] 24 g of a solid bisphenol A diglycidyl ether (GT6099, available from Huntsman Advanced Materials) was dissolved in 400 ml methyl-ethyl-ketone, and 4 g of a urea based curative (Dyhard UR500, available from Alzchem) was then mixed in. The solvent was evaporated using a rotary evaporator to leave a solid residue. This solid residue was further dried in a vacuum oven and then passed through a 90 ?m sieve to yield the curative dispersed in particles of a solid resin in the form of a powder comprising 14.3 wt % UR500. This powder was then mixed into a 30:70 w/w blend of a liquid bisphenol A diglycidyl ether (LY1556, available from Huntsman Advanced Materials) and a semisolid bisphenol A diglycidyl ether (YD-136, available from KUKDO Chemicals) at a concentration of 21 wt %, such that the urone was present in the final composition at a concentration of 3% w/w.

[0077] The compositions of Example 3 and Example 4 were stored at 30? C. for 40 days, and the cold Tg was measured at various intervals by Differential Scanning calorimetry (DSC) using a TA Instruments DSC Q100 and MT DSC 1 in order to determine the aging/outlife of the compositions. This was compared to a standard resin (Standard 1, as described in Example 1). The results are shown in FIGS. 3 and 4, which show that the materials of Examples 3 and 4 had a smaller increase in cold Tg over a 6 week period at 30? C. compared to the material of Standard 1, indicating a reduced rate of aging.

[0078] Dynamic exotherm measurements were also made at various intervals for both the materials of Examples 3 and 4 and Standard 1 by DSC, and the results are also shown in FIGS. 3 and 4. These show that the dynamic enthalpy values remained generally similar during storage, suggesting that the curing ability of the materials of Examples 3 and 4 was generally unaffected.