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21世纪的环氧胶粘剂

来源:林中祥胶粘剂技术信息网2010年12月02日

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Phenolic-Epoxy Adhesives in The 21st Century

Phenolic-epoxy adhesives have been known for over 50 years and were one of the first commercial high temperature adhesives. 1 However, despite their age, until recently these products have still faced a major problem due to their short shelf-lives. Now, researchers have discovered how to resolve this issue, without sacrificing the adhesives performance advantages or creating toxicity issues as some previous attempts have.

This problem is part of the same characteristic that is also considered a virtue of phenolic-epoxies, namely their low curing temperature requirements in comparison to other phenolic-based resins. Their reactivity at low temperatures limits long-term stability, meaning that they often need to be stored at temperatures as low as -18°C.

Once cured, phenolic-epoxy adhesives retain their adhesive properties over a large temperature range, have high shear strengths, and are resistant to weathering, oil, solvents, and moisture. Some studies have shown that phenolic-epoxies cured at 74-95°C can retain reasonably good strengths at 482°C. Higher cure temperatures, often around 165-175°C, can give these adhesives better structural properties, however.

The ability to resist high temperatures has long proved useful, in applications like aircraft engines. However, today the increasing amounts of heat that some electronic devices now produce also see them exploited in applications including insulating or anisotropically conductive adhesives in LCDs 2, circuit boards, flip chip, and other semiconductor devices.

Example12345
Bisphenol epoxy resin (%)62.6564.7577.979.879.8
Phenolic novolac resin (low MW) (%)26.8527.7517.115.2--
Phenolic novolac resin (high MW) (%)--------15.2
Surfactant (%)10.57.5555
Epoxy/Phenolic Ratio 0.46/10.46/10.9/11/11/1
Co-dispersion epoxy group content (mmol/kg)11381156174315161476
Solids content (%)4550.159.356.758.7
Viscosity at 25°C (mPas)5900182054005520980
Particle Size, Dv (by Coulter (microns)) 0.290.950.970.991.4
Particle Size, Dv90 INSERT INTO [lzx].[dbo].[tb_new]([id],[type],[title],[source],[personal],[image],[contents],[time],[number]) VALUES (20 Min Cure At 200°C And 0.5 Phr 2-methyl Imidazole)0.441.61.691.622.05
Tg (°C)--95106108116
Table 1: Example one-part aqueous phenol/epoxy adhesive formulations 3

Phenolic-epoxies are available commercially as either one-part or two-part adhesives in several forms, including pastes, solutions in organic solvents or water, and supported films. Of the three forms, the adhesive film generally provides better adhesive strength.4 These take advantage of the three stages of curing often seen in these adhesives. In the first stage, the adhesive is applied and solvents are dried off of at up to 90°C, and here it can be mounted onto a carrier film. The second step involves baking at around 0.07-0.40 MPa pressure and at temperatures up to around 165°C. A final structural enhancement can then be attained by post curing at elevated temperatures if necessary.

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