Radiation sensitivity methacrylate

During mutual graft copolymerization, homopolymerization always occurs. This is one of the most important problems associated with this technique. When this technique is applied to radiation-sensitive monomers such as acrylic acid, methacrylic acid, polyfunctional acrylates, and their esters, homopolymer is formed more rapidly than the graft. With the low-molecular weight acrylate esters, particularly ethyl acrylate, the homopolymer problem is evidenced not so much by high yields as by erratic and irreproducible grafting. 

The intent of our investigations is to study the effects of spincasting on polymers at a molecular level. The polymers may be radiation sensitive materials such as poly(methyl methacrylate)... 

Poly(methyl methacrylate) (PMMA) is a classical one-component, positive resist system. PMMA is a single, homogeneous material that combines the properties of excellent film-forming characteristics, resistance to chemical etchants and intrinsic radiation sensitivity. 

To study the structural sensitivity of poly silanes to ionizing radiation, a number of samples were irradiated with a calibrated Co source, and the degraded materials were analyzed by GPC in a manner similar to that described for the determination of photochemical quantum yields (59). In radiation processes, the slopes of the plots of molecular weight versus absorbed dose yield the G values for scissioning, G(s), and cross-linking, G(x), rather than the respective quantum yields. These values, which represent the number of chain breaks or cross-links per 100 eV of absorbed dose, are indicative of the relative radiation sensitivity of the material. The data for a number of polysilanes are given in Table IV. Also included in Table IV for comparison is the value for a commercial sample of poly(methyl methacrylate) run under the same conditions. The G(s) value of this sample compares favorably with that reported in the literature (83). 

Haller, R. Feder, M. Hatzakis, and E. Spiller, Copolymers of methyl methacrylate and methacryhc acid and their metal salts as radiation sensitive resists, 7. Electrochem. Soc., 126,154 (1979) M. Hatzakis, PMMA copolymers as high sensitivity electron resists, J. Vac. Sci. Technol. 16,1984 (1979). 

In general, the lower the carbon contents in the polymer, the stronger its radiation sensitivity. Radiation sensitivity increases in the order polystyrene, polyethylene, polycarbonate, polymethyl methacrylate, polyvinyl chloride, polytetrafluoroethylene... 

The interaction volume of 20 kV electrons in poly(methyl methacrylate) (PMMA) has been shown directly by using its radiation sensitivity [39]. After exposure to a beam of electrons, the material was cross sectioned, polished, and etched. Pear-shaped holes up to 10/rm deep appear (Fig. 2.5) showing where the beam interacted with the PMMA (and reduced its molecular weight) [39]. Calculation of the interaction... 

The theory of radiation-induced grafting has received extensive treatment. The direct effect of ionizing radiation in material is to produce active radical sites. A material s sensitivity to radiation ionization is reflected in its G value, which represents the number of radicals in a specific type (e.g., peroxy or allyl) produced in the material per 100 eV of energy absorbed. For example, the G value of poly(vinyl chloride) is 10-15, of PE is 6-8, and of polystyrene is 1.5-3. Regarding monomers, the G value of methyl methacrylate is 11.5, of acrylonitrile is 5.6, and of styrene is >0.69. 

NR, styrene-butadiene mbber (SBR), polybutadiene rubber, nitrile mbber, acrylic copolymer, ethylene-vinyl acetate (EVA) copolymer, and A-B-A type block copolymer with conjugated dienes have been used to prepare pressure-sensitive adhesives by EB radiation [116-126]. It is not necessary to heat up the sample to join the elastomeric joints. This has only been possible due to cross-linking procedure by EB irradiation [127]. Polyfunctional acrylates, tackifier resin, and other additives have also been used to improve adhesive properties. Sasaki et al. [128] have studied the EB radiation-curable pressure-sensitive adhesives from dimer acid-based polyester urethane diacrylate with various methacrylate monomers. Acrylamide has been polymerized in the intercalation space of montmorillonite using an EB. The polymerization condition has been studied using a statistical method. The product shows a good water adsorption and retention capacity [129]. 

For extensive studies of the effects of 254 nm radiation on acrylates and methacrylates, the reader is referred to the work of Morimoto and Suzuki(14) and of Grassie (15,16). In 1964, Oster reported on the crosslinking of these and other polymers by the near ultraviolet, sensitized by the presence of 2-methylanthraquinone (17). 

C The Epoxy Resists. The first negative tone electron beam resist materials with useful sensitivity were based on utilizing the radiation chemistry of the oxirane or epoxy moiety. The most widely used of these materials, COP (Figure 32) is a copolymer of glycidyl methacrylate and ethyl acrylate and was developed at Bell Laboratories (43,44). COP has found wide applicability in the manufacturing of photomasks. The active element... 

Figure 41. A plot of sensitivity to Mo (5.4k) x-ray radiation and 20 kV electron beam radiation for several resists. EPB is epoxidized polybutadiene, P(GMA-EA) is a copolymer of glycidyl methacrylate and ethyl acrylate (COP), PGMA is poly (glycidyl methacrylate), PBS is poly (butene-1 -sulfone), FBM-1 is poly (2,2,3,3-tetrafluoropropyl methacrylate), P(MMA-MA) is a copolymer of methyl methacrylate and methacrylic acid, PMMA is poly (methyl methacrylate). (Reproduced with permission from Ref. 56J...

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