It is well known that as the water-insoluble yellow monoazo pigments, the “Fast yellow” or “Hansa yellow” pigments have been used for printing ink, paint, etc. Those pigments lack the resistance to organic solvents, therefore, few yellow monoazo lake pigments have been prepared to increase the resistance to organic solvents. As regards the coupling component authors found in Russian Patent a few studies on yellow monoazo pigments using acetoacetanylides substituted with p-carbonamide or p-carbonanilide group in the benzene ring of them. But the authors couldn't find the datum on yellow monoazo lake pigments containing carbonamide or carbonanilide group in benzene ring of acetoacetarylides. Authors tested the properties of new water-insoluble monoazo pigments or monoazo lake pigments containing m-carbonamide or m-carbonanilide group in benzene ring of acetoacetarylides. Authors synthesized six acetoacetarylides (as reported in “Studies on New yellow azo pigments [I]”) and prepared six water-insoluble monoazo pigments (I) by coupling with diazotised o-nitro-p-chloro-aniline and forty-eight yellow monoazo lake pigments (II) by coupling with diazotised 2-chloro-p-toluidine-5-sulfonic acid and by laking with Ba, Sr, Ca and Mn. Cl-NO2-N=N-CH-CO-CH3-CONH-X-CONH.Y (I) [CH3-Cl-SO3-N=N-CH-CO-CH3-CONH-X- -CONH.Y] 2M++ (II) In the above formula X represents hydrogen atom, chlorine atom or methoxy group, Y is hydrogen atom or phenyl group, M++ is Calcium, Stronthium, Barium or Manganese ion. In the new synthesized water-insoluble monoazo pigments, the pigments obtained from 1-acetoacet-amino-2-chlorobenzene-5-carbonamide or carbonanilide gave greenish yellow shade and ones obtained from 1-acetoacetamino-2-methoxybenzene-5-carbonamide or carbonanilide gave reddish yellow shade. The latter pigments gave better resistance to organic solvents than the former. The hue and resistance to light of the new synthesized monoazo lake pigments were considerably different by the variation of coupling component, laking metal ion or by laking temperature, and these pigments generally gave the good resistance to organic solvents.
On the drying oil-modified alkydr esin, the residual radical of polyol constitutes the branch unit, and the cross-linking reaction takes place by the unsaturated bond of side chain fatty acid. The networks thus built up exhibit rubber-elasticity at temperature more than the glass-transition temperature in the case of the cross linking density is comparatively low, and the elasticity increases with increase in temperature indicating well agreement with theory. This experiment was carried out in order to obtain clarified relationship between the composition of alkyd resin and the networks of cured film by applying the rubber elasticity theory. Author synthesized a series of pentaerythritol alkyd resins containing 60 percent fatty acids of which the degree of unsaturation was varied by changing the ratio of linseed oil fatty acid to oleic acid. of these cured resin films, the author measured the temperature-dependency of rigidity and of logarithmic decrement by means of tortional oscillation method. Similar measurements were also made and were analyzed for various resin films, already published as references, including; alkyd resin of 50 percent oil length, polymerized linseed oil, urethanated aklyd resin of different molecular weight, tall oil fatty acid-modified and dehydrated castor oil fatty acid-modified epoxy ester resins. In order to find the necessary number (n) of double bond for making one bridge, the author derived the following equation wherein F is the concentration of functional group, Mc is the molecular weight between crosslinks, and Mn is the number average molecular weight of prepolymer. Mc=n.Mn/ (F. Mn-n) (1) From the statistical theosy of rubber-elasticity, Mc can be also expressed by the following equation; Mc=ρ.R. T/Gh (2) where Gh is the rigidity at high temperature, ρ is the density, R is the gas constant and T is the absolute temperature. Mc found in the equation (2) was substituted into eqution (1) to calculate n, and therewith the author analyzed the cured condition of various oil-modified resins, obtaining the following results : 1) In the same oil length, the higher concentration of functional group in the alkyd resin gives a film having decreased Mc and more compact network, and the glass-transition temperature (Tg) is high. In accordance with increase in the oil length, the concentration of functional group increases, indicating similar tendency with the above. The Tg of pentaerythritol alkyd resin of 60 percent oil length ranges between 65 and 80°C. 2) The n varies with the degree of branching, accordingly n=2.0-2.5 for the alkyd resin of glycerin type and n=1.1-1.5 for that of pentaerythritol type. 3) On the urethanated alkyd resin, n increases according with increase in the TDI content of the resin, with parallel increase in cross linkage which is effectless on rubber-elasticity. 4) On epoxy ester resins, n is nearly constant for the variation in the oil length and in molecular weight of epoxy resin used, this is also held in case p-tert-butyl benzoic acid is concurrently used. Cross linking effect is higher for the dehydrated castor oil fatty acid containing conjugated double bond, as compared with tall oil fatty acid. The epoxy ester resin of the former acid indicates n=1.2-1.5 while that of the latter acid indicates n=1.7-2.3. 5) Polymerized linseed oil, being n=4. 64, is presumed as that there occurred uneffective of cross linkage which comes from steric hindrance and or innermolecular cyclization, etc, at time of the resin synthesis and the film formations.
The varnish of thermosetting type prepared from drying oil and various alkyl phenol resins blended therewith has been widely used as vehicle of industrial paints and as varnishes for insulation because of its superiority in physical and chemical properties, while there is a few composite data studied on the property of the material. In this paper authors investigated the temperature-dependency on viscoelasticity of tung oil-modified xylene resin film to be obtained by the reaction of Chinese tung oil with p-tert-butyl phenol-modified xylene resin (hereinafter this is called as xylene resin), by means of free tortional oscillation method placing the authors' view onto the transition temperature (Tg) and the cross linking density (ρ) which should indicate the effect of xylene resin affecting viscoelasticity of the resin film. From experiments carried out on various xylene resin samples prepared in different number average molecular weight (MN) and different weight fraction rate (WR), the authors could confirm the following relationship between Tg and ρ ; Tg=K 1n (ρ/ρ0) +Tg0 where, Tg0 and ρ0 are constants. The parameter K could be expressed in a form of ; K=k/ (1-WR) 2and the value was independent with MN and the value clearly reflected the contribution of resin component. With this K, the authors also attempted an application of Iso-free volume theory fo K1=a/αa-αb (1-β) which is applicable in high molecule of bridge structure, proposed by Shibayama (K. Shibayama : Chemistry of High Polymer., 19,219, (1962)), and the authors could recognize the possibility of similar handling in the physical conception involved therein. Authors could obtain another finding on the relationship Tg v. s. ρ, being restricted by WR, which converged at a point. This fact was presumed, from investigation on the bridge effect affecting relationship Tg v. s. ρ, as that the effect affecting relationship Tg v. s. ρ may be disappeared at this convergent point, resulting that it becomes to depend solely upon loose bridge structure existing in the tung oil molecule. Viewed from the above, the convergent point is believd as standard point in the viscoelastic behavior of resin film.