In “Studies on New yellow azo pigments (I) and (II)”, authors synthesized new six acetoacetarylides containing carbonamide group or carbonanilide group at benzene ring and prepared six water-insoluble disazo pigments, six water-insoluble monoazo pigments and forty-eight yellow monoazo lake pigments. Upon testing the properties of these pigments, authors found that the pigment prepared from 1-acetoacetamino-2-methoxy benzene-5-carboramide had good resistance to light and organic solvents. Then, authors synthesized twelve water-insoluble manoazo pigments shown in the following formula X-N=N-CH-CO-CH3-CONH-CH3O-CONH2 wherein X represents methyl group, methoxy group, chlorine atom or nitro group substituted at ortho-, meta-and para-position. Authors obtained these pigments by coupling 1-acetoacetamino-2-methoxy benzene-5-carbonamide with ortho-, meta- and para-substituted isomers respectively of toluidine, anisidine, chloroaniline and nitroaniline. As a result of testing the effect of substituents on the properties of these pigments, the pigments containing nitro group gave generally reddish yellow shade and chlorine atom, methyl group or methoxy group gave greenish yellow shade. However, in these pigments no effect of substituent's position was recognized on the color shade. On the fastness to light, negative group such as chlorine atom or nitro group gave better effect than positive group such as methyl group or methoxy group. On the resistance to methanol and xylene, negative group gave more effective resistance than positive group. These pigments had good resistance to ethyl acetate, regardless of the kind and position of substituents. Above all, the pigments derived from o-chloro-aniline and o-nitroaniline had the best resistance to light and organic solvents
As unsubstituted phenol (C6H5OH)-formaldehyde resin has a strong polarity, it is insoluble in drying oil. On the contrary as para alkyl and aryl substituted phenols are two functional and cannot form crosslinked_or three-dimentional structure and the substituent group has the oil-soluble property, the substituted_phenol formaldehyde resins are oil soluble. The 100 % phenol resin varnishes are used widely as the insulation varnishes and alkali resistance coating because of the excelent drying property, hardness, humidity resistance and chemical resistance. The reactivity of phenol with formaldehyde and the physical and chemical properties of the oleoresinous, varnishes depend greatly upon the size, the sort, and the property of the substituent group and the phenol-formaldehyde mol ratio. Five kinds of the para alkyl and aryl substituted phenol-formaldehyde resins and four kinds of the octyl phenol formaldehyde resins varied in formaldehyde/phenol mol ratio (both series are novolac type resins). were synthesized and the oil solubility, the oil reactivity and the coating properties of oleoresinous, varnishes were studied. The dynamic elasticity (E') and tan δ of oxidative-polymerized films were measured by Vibron Type II from room temperature to 200°C, and the relation of the chemical structure and viscoelasticity was studied. The results are as follows. (1) The order of reactivity of substituted phenol with formaldehyde is as follows. ρ-cresol>ρ-tert butyl phenol>ρ-phenyl phenol>ρ-octyl phenol>ρ-nonyl phenol. This order depends on the inductive effect of substituents. (2) The longer the chain length of substituents of 100% phenol resin is, the better is the oil solubility. (3) The higher the phenyl nucleus concentration of phenol resin and the more formaldehyde/phenol mol ratio are, the weaker is the reactivity between phenol resin and oil (gel time). (4) The relation on the oleoresinous varnishes is as follows. The higher the phenyl nucleus concentration and formaldehyde/phenol mol ratio are, the better are the drying property and the hardness, and. the smaller are the solubility and the degree of swelling mineral spirits and aceton on its cured films, and the higher are the glass transition temperature (Tg) and the elasticity at high temperature (En'). When kinds of oil and oil length are the same, the degree of crosslinking should be chemically same. Whereas on the results of experiment Tg and En' varied because of the physical crosslinking. When the resin is rigid and the intermolecular cohesive force is stronger, the apparent degree of crosslinking becomes higher.
Epoxy resin from alkali condensation of diphenolic acid (4, 4'-bis (ρ-hydroxy phenyl) valeric acid) with epichlorohydrin has been referred as patent by A. R. Bader (U. S. Patent 2,933,472/1962) and by Ledoga, S. P. A. (Fr. Patent 1,299,801/1962), however, no commercially valuable resin was obtained from these patents. The authors investigated a method for obtaining 4, 4'-bis (ρ-(2, 3-epoxy propoxy) phenyl) pentanoic acid in a high yield. 1) One mol of diphenoric acid and 2 mols of epichlorohydrin were reacted in four-neck flask attaching with reflux condenser, thermometer, dropping funuel and stirrer, and 30 percent caustic soda solution was dropped there into until the reactants turn alkaline while keeping at 100°C. C under stirring, then this was heated and stirred for 1. 5 hours. Then after, the product was dissolved in excess quantity of hot water, then acidified with hydrochloric acid to separate out the resin. The separated resin was again alkalified and dissolved in excess water by adding caustic soda, then re-separated by acidifying with hydrochloric acid. This was purified after enough washing with water until the water reaches neutral. 2) The resin thus obtained was white powder of 74-104°C. C for the melting point, 144. 8 for the neutralization value, 0.75 for the epoxy value, soluble in alkaline water, dimethyl formamide, dioxan and in ethyl cellosolve acetate etc., but insoluble in other solvents. This was confirmed as 4. 4'-bis (ρ- (2, 3-epoxy propoxy) phenyl) pentanoic acid after various analyses, having following formula : CH2-CH-CH2-O-CH3-C-CH2-CH2-COOH-O-CH2-CH-CH2 3) Aqueous solution (15-20 percent) of this resin, after esterification with unsaturated fatty acid such as linolic acid by 1 : 1 mol ratio then controlled at pH 7-8 by adding triethanolamine, was quite useful as the resin for electrodeposition coating since this does not require another crosslinking resin, making quite easy for control of the solution of electro-deposition bath.