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Volume 24, Issue 9
Displaying 1-9 of 9 articles from this issue
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V. EFFECTS OF VARIOUS DISCOLORATION PROTECANTS ON THE COLORATION OF NON-WOVENHideo Nishimoto, Saburo Tsuji1968 Volume 24 Issue 9 Pages 403-410
Published: September 10, 1968
Released on J-STAGE: November 28, 2008
JOURNAL FREE ACCESSThe anti-coloration effects of the some kinds of suhstance for non-woven fabrics was investigated. Commercially available anti-oxidants used for anti-coloration of non-woven fabrics, ultra-violet absorbents and stearic acid metallic soaps, as well as stearic acid were selected. Coloration of the non-woven fabrics is due to the deterioration phenomenon of the polymer. It is presumed that coloration is caused by the carbonyl group formed in the decomposition of the hydroperoxide, which, in turn, was formed by the action of a trace amount of oxygen on the hydrocarbons in the binder resins radicalized by heat or light. Since the anti-oxidants and the ultra-violet absorbents themselves are transformed during the prevention of the coloration of resins, they require an induction period in the process of the oxidation. While, stearic acid and the metallic soap prevent the deterioration by blooming on the surface of resins and covering them, and they themselves are not transformed, they do not require the induction period. The metallic soap of zinc, tin, plumb and magnesium has the effects of the similar degree to that of stearic acid. The metallic soap of aluminium, manganess as well as cobalt have effects superior to that of stearic acid. The effect of calcium is inferior to that of stearic acid. The difference in the covering effects of various metals may have some relationships with the refractive index of the metallic soap.View full abstractDownload PDF (575K) -
Kiyoshi Hirabayashi, Tsunekatsu Seki, Hiroshi Ishikawa, Masao Kakudo, ...1968 Volume 24 Issue 9 Pages 411-414
Published: September 10, 1968
Released on J-STAGE: November 28, 2008
JOURNAL FREE ACCESSOn the formation of spherulites in silk fibroin gel obtained from fresh silk gland, the conditions for crystallization such as pH and temperature and the structure of the spherulites resulted under these conditions were examined.
1. Spherulites of silk fibroin were observed at temperatures lower than 50°C and the range of pH from 3.0 to 10 except in pH 5.0. This prohibition of spherulites formation at pH 5.0 may be consistent with the fact the pH is about 5.0 in the living silk gland where the crystallization is not permissible.
2. Silk fibroin spherulites is confirmed to be α-form structure by X-ray diffractometry.
Surface structure of spherulites is similar to that of many other linear polymers under electron microscope.
The needle crystals which are often found in silk fibroin film coincide with β-form structure of silk fibroin.View full abstractDownload PDF (1926K) -
Kunio Hata, Kingo Yokota1968 Volume 24 Issue 9 Pages 415-419
Published: September 10, 1968
Released on J-STAGE: November 28, 2008
JOURNAL FREE ACCESSIn the previous paper, it was reported on the preparation of cellulose liquid sulfur dioxide solution in the presence of secondary or tertiary amines. In the present work, cellulose is regenerated from cellulose-triethylamine-liquid sulfur dioxide solution in a form of the model filament under various conditions. Some properties of these filaments were investigated comparing with those of viscose model filaments.
Clear and uniform filament was obtained by dry spinning in cooled atmosphere or wet spinning using cooled methanol (-10°C) as coagulating and regenerating bath. Meanwhile, in the case of wet spinning using acetone or NaCl-HCl aqueous solution (-10°C), cellulose was regenerated as milky white and non-uniform filament. From the above observations, it is clear that phat physical conditions such as the elimination of sulfur dioxide in the coagulating bath have an extremely great effect on the characteristics of these filaments.
The characteristics of the fine structure of the model filaments were studied by X-ray diffraction water and Iodine sorption methods. From these examinations, it is recognized that the filament regenerated in methanol or acetone is highly accessible (crystallinity: 12_??_18%, accessibility: 89_??_93%. calculated from water sorption data), and the X-ray diffraction pattern is similar to that of amorphous cellulose, while the filament regenerated in water is less accessible than the filaments regenerated in methanol or acetone (crystallinity: about 26%, accessibility: about 86%). Therefore, it is confirmed that the regenerated cellulose from liquid sulfur dioxide solution is more amorphous comparing with viscose model filament (crystallinity: about 34%, accessibility: about 81%).
These fresh filaments are also anisotropical for the shrinkage (the degree of shrinkage to the cross direction for fibre axis: 50_??_60%, longitudinal direction: 26_??_37%). While cellulose is coagulated by the elimination of sulfur dioxide, the cellulose gel may shrink to the cross direction for fibre axis, and consequently these filaments may have the above anisotropical property.View full abstractDownload PDF (360K) -
Kunio Hata, Kingo Yokota1968 Volume 24 Issue 9 Pages 420-424
Published: September 10, 1968
Released on J-STAGE: November 28, 2008
JOURNAL FREE ACCESSProperties of amine sulfur dioxide solution under various thermal conditions were studied on its conductivity and reactivity.
In present work, triethylamine, diethylamine and piperidine were employed, and all of these amines exert a dissolving effects upon cellulose in liquid sulfur dioxide. The reactivity of the solutions was determined by a method of conductometric titration with alcohol such as n-propyl alcohol.
From these examinations, it was recognized that the reactivity for alcohol and the dissolving effects upon cellulose of these solutions decrease by allowing to stand at high temperature. Meanwhile, the specific conductivities of these solutions are increased irreversibly according to the increase of standing temperature. Triethylamine is more unstable in liquid sulfur dioxide than secondary amine such as diethylamine or piperidine. The value of specific conductivity of 0.4 M triethylamine solution was 13×10-5cm-1Ω-1 at-22°C (diethylamine solution: 8×10-5cm-1Ω-1, piperidine: 10×10-5cm-1Ω-1) and it was raised to 52×10-5cm-1Ω-1 after standing at 35°C for 24 hours (diethylamine: 14×10-5cm-1Ω-1, piperidine: 11×10-5cm-1Ω-1). Therefore amount of active amine for alcoholic-OH in the triethylamine solution decreases readily below 30% of initial value after standing under the above condition (diethylamine: about 92%, piperidine: about 99%).
It is well known that amines form the charge-transfer complex as R3N-SO2 in liquid sulfur dioxide. The complex may react with the hydroxyl groups of cellulose disperse into liquid sulfur dioxide. But from the above results, it is assumed that the amine-SO2 complex, especially triethylamine-SO2 one may be decomposed by the thermal effect in liquid sulfur dioxide and more complicated reactions such as radical reaction occur rapidly.View full abstractDownload PDF (354K) -
Kazuo Nakayama, Saburo Okajima, Yasuji Kobayashi1968 Volume 24 Issue 9 Pages 425-429
Published: September 10, 1968
Released on J-STAGE: November 28, 2008
JOURNAL FREE ACCESSThe visible dichroism (D) of poly (ethylene terephthalate) film dyed with C. I. Disperse Yellow 7 or C. I. Disperse Red 17 was measured at 20_??_180°C. and the temperature effect on D was investigated. For this purpose a spectrophotometer equipped with a specially designed heating cell was used. Dyed PET films were prepared in two ways: (A) Undrawn film was dyed (70°C., 20 hr.) and then drawn (68°C.), and (B) Undrawn film was drawn (57 or 68°C.), heat-treated (190°C.) and then dyed (130°C., 90 min.).
The results are following:
(1) The measurements of D at elevated temperatures could be carried out as accurately as in the usual measurement at room temperatures.
(2) D decreases linearly as the temperature is elevated. In the case of films which have never been heat-treated above 120°C., two inflection points appear on heating in the relation D vs temperature at 80°C. and 120°C., and the change of D with temperature is irreversible, whereas in the case of films previously subjected to heat-treatment above 120°C., D changes reversibly when the temperature of the film remains below the temperature of treatment and the inflection point at 80°C. can hardly be observable.
From this phenomenon it is concluded that D of the heat-treated or thermally contracted PET, measured even at room temperature, indicates correctly the degree of amorphous orientation of polymer changed through the treatment and the intrinsic dichroism of the dyed polymer remains constant. As to the 120°C. inflection point, it is attributed to another transition point of the amorphous region remaining in PET after the cold crystallization.View full abstractDownload PDF (314K) -
(2) RELATION BETWEEN THE DYEING PROPERTIES ON NYLON 6 FIBER AND THE CHEMICAL STRUCTURE OF ACID DYESHiroaki Takasawa, Nobuhiko Kuroki, Akira Katayama1968 Volume 24 Issue 9 Pages 430-435
Published: September 10, 1968
Released on J-STAGE: November 28, 2008
JOURNAL FREE ACCESSThe relationship between the adsorption of acid dyestuffs on nylon 6 fiber and the chemical structure was investigated by the use of following five kinds of dye; Dye (1) (C. I. Acid Orange 7), Dye (2) (Blue 45), Dye (3) (Blue 120), Dye (4) (Red 99), Dye (5) (Orange 45).
Three kinds of nylon 6 fiber which includes amino end group of 9.5×10-5, 5.4×10-4 or 2.5×10-5mol/g, were dyed at 90°C and at pH 3.5.
The result was as follows; the adsorption of Dye (1) which had small molecular weight and short molecular chain was completely equal to amino end-group content of the fiber.
The saturation of Dye (2) which had the same small molecular weight and short molecular chain as that of Dye (1), was 1/3-1/2 of amino end-group content of the fiber.
The saturation of Dye (3) and (5) which had large molecular weight and long molecular chain was lower than the end-group content.
The adsorption of Dye (4) which has large molecular weight and long chain showed H type curve.
Summary; it is confirmed that the adsorption of dyeson nylon 6 in equilibrium had no linear correlation with the molecular weight and chain length of dyes.View full abstractDownload PDF (362K) -
Takeo Sone, Takashi Yamazaki, Seigo Oya, Izumi Fumoto1968 Volume 24 Issue 9 Pages 436-441
Published: September 10, 1968
Released on J-STAGE: November 28, 2008
JOURNAL FREE ACCESSThe dyeing of synthetic fibers is generally diffcult especially vinylon.
Dyeing, of vinylon with cationic dyes, used widely in dyeing acrylic fibers, was experimented.
Vinylon acetalized with p-sulfobenzaldehyde was dyed with basic dyes. Excellent results were obtained for the vinylon acetalized by using hydrochloric acid as the catalyst, but not for the vinylon acetalized using sulfuric acid.
It seems that sulfuric acid as the catalyst is not so effective as hydrochloric acid in acetalizing vinylon with p-sulfobenzaldehyde, but it does react on vinylon, offering a high coloring property.
Good deep-dyeing was obtained with cationic dyes when the degree of acetalization is higher than a unity.View full abstractDownload PDF (360K) -
Takeo Sone, Takashi Yamazaki, Seigo Oya, Izumi Fumoto1968 Volume 24 Issue 9 Pages 442-448
Published: September 10, 1968
Released on J-STAGE: November 28, 2008
JOURNAL FREE ACCESSIn the previous study on sulfo-acetalization of vinylon and the dyeing of the acetalized vinylon, it was pointed out that vinylon treated with sulfuric acid was dyed with basic dyes. This effect may be due to the bonding sulfuric acid, for it has tendency to adhere to C-C double bond or carbonyl group in polyvinylalcohol. It was assumed from this that the addition of sodium bisulfite to the double bond or carbonyl group originated with oxidation of vinylon may be effective for introducing acid groups to polyvinylalcohol.
The treatment of oxidized vinylon with sodium bisulfite was found to be very practicable for dyeing with basic dyes. In the case of amino-group-introduced-vinylon the same circumstance was observed for dyeing with acid dyes.
Bromine or potassium bichromate is very effective as an oxidizing agent. The latter is less efficient in oxidizing than the former. Vinylon oxidized with bromine was treated with sodium bisulfite and then dyed with some basic dyes. The dyed goods have good fastness against light such as acrylic fiber. The vinylon oxidated with potassium bichromate was treated with ammonia or mono-ethanolamine and then dyed with metal-complex, sulfide or Indanthren dyes. The dyed goods have remarkable advantages in the high yields of colours and good washing fastness.
Foundamental formula of those reactions are as follows:View full abstractDownload PDF (382K) -
Kiyoshi Hirabayashi, Hiroshi Ishikawa1968 Volume 24 Issue 9 Pages 449-450
Published: September 10, 1968
Released on J-STAGE: November 28, 2008
JOURNAL FREE ACCESSSilk fibroin was regenerated from a concentrated lithium bromide solution. Conditions for the crystallization of the silk fibroin from its aqueous solution were investigated by means of optical rotatory dispersion and X-ray diffractometry.
The conformation of the silk fibroin was confirmed as coiled when regenerated at different temperatures (40_??_100°C). The silk fibroin showed the α-form structure when cast and dried at temperatures lower than 40°C, and the β-form structure when cast and dried at 40°C or over. No concentration (of silk fibroin) effect was observed.
By extruding very viscous solution of 15% fibroin through a tepered nozzle, a thread of silk fibroin was obtained. This, however, showed no birefringence, indicating an unoriented structure.View full abstractDownload PDF (109K)
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