巻号一覧
27 巻, 3 号
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福田 卓司, 大森 進1971 年 27 巻 3 号 p. 83-95
発行日: 1971/03/10
公開日: 2008/11/28
ジャーナル フリーRelations between viscoelastic properties and dyeabilities of disperse dyes in fibers and films of polyethyleneterephthalate and copolyester were investigated in order to study the structure of the fibers and the dyeability. It was shown that the dyeability DY could be well expressed both for homopolyester and copolyester as follows,
where k is proportional constant, (tan δ)c the calibrated loss factor and T0 the characteristic temperature determined by the dye and the condition of dyeing. In this equation the characteristic temperature T0 is increased with increase of the molecular weight of the dyes. On the other hand the dyeability DY can be expressed also by dynamic storage moduli E′ at 20°C and the characteristic temperature T0 as follows,
where k′ is proportional constant, E′20 and E′T0 the storage moduli respectively at 20°C and T0. These results suggest that the temperature dependence curve of loss factor tan δ can be treated roughly as the distribution curve of the highest order in the texture that can adsorb the dyes.抄録全体を表示PDF形式でダウンロード (1411K) -
高沢 弘明, 片山 明, 黒木 宣彦1971 年 27 巻 3 号 p. 96-101
発行日: 1971/03/10
公開日: 2008/11/28
ジャーナル フリーThe diffusion of an acid dye (Acid Red 18) into Nylon 6 film from an infinite dyebath at various pH's was studied by means of the film roll method. The dyeing mechanism of Nylon 6 film with the acid dye varied with the pH of the dyebath: at pH lower than about 3.0 the adsorption of dye anions took place both on charged end amino groups, and amide groups, simultaneously, in the pH range from about 3.5 to 5.0 only on charged amino groups and at pH higher than about 6.0 on non-ionic sites. From the distribution of the dye through the film, the diffusion coefficients of the dye in the film corresponding to the adsorption on amino-, amide groups or nonionic sites were calculated, respectively, using some appropriate assumptions. The main assumption is that α, the fraction of end amino groups occupied by dye anions on the film surface, is equal to unit. This assumption is reasonable in this experiment.
The results obtained in this paper are as follows:
(a) The diffusion coefficient of the dye adsorped on charged amino groups is influenced by the variation in pH of the dyebath, that is, it increases with decreasing pH.
(b) The diffusion coefficient of the dye adsorped on charged amide groups increases with decreasing pH. The dye anion interacting with charged amide groups can diffuse more quickly in the film than that interacting with charged amino groups.
(c) The diffusion coefficient of the dye adsorped on non-ionic site is independent of the pH of the dyebath. This diffusion can occur most quickly among the three.抄録全体を表示PDF形式でダウンロード (933K) -
Yasuji Kobayashi, Saburo Okajima, Koji Fukuda1971 年 27 巻 3 号 p. 102-107
発行日: 1971/03/10
公開日: 2008/11/28
ジャーナル フリーDye dichroism can be used to determine the mean amorphous orientation. For this purpose, absorbed dyes must be dispersed uniformly in a whole amorphous region. This uniform dispersion may not always occurs in all cases. When the oriented cellulose and polyvinyl alcohol films are dyed with direct dichroic dyes, small amounts of dye molecules are absorbed preferentially into the higher order region of the polymer chain. With an increase of amount, dye molecules disperse uniformly in the whole amorphous region and the obserbed dichroism approaches to the mean amorphous orientation. But, the dye molecule of longer length has a lower preferential absorption. The preferential absorption phenomena relates to the affinity of dye to polymer and to the steric hindrance of dye diffusion into the narrow gaps of the higher order polymer chains. The study of dichroism of polymer at low content values of the dichroic dye may be useful for obtaining information on the lateral order of amorphous polymer chains. Conversely, to determin the mean amorphous orientation, the lower concentration dyeing must be avoided.抄録全体を表示PDF形式でダウンロード (331K) -
須沢 利郎, 流田 和, 水弘 洋司1971 年 27 巻 3 号 p. 108-112
発行日: 1971/03/10
公開日: 2008/11/28
ジャーナル フリーIn order to investigate the surface dyeability of the nylon 6 fiber in acid dye solution, the ζ-potential, the surface dye adsorption and the total dye adsorption of the nylon 6 fiber (undrawn) in an acidic solution (pH 4.0) of monoazo acid dyes - Orange II, I and IV were determined. The isoelectric point of the fiber was pH 4.58. With increasing dye concentrations, the sign of the ζ-potential of the fiber in dye solution changes from positive to negative because of the electrostatic bonds between the NH3+ of the fiber and the dye anion, RSO3-. Then the ζ-potential approaches the saturated value. Both, the surface dye adsorption and the total dye adsortion and the total dye adsorption increase with increasing dye concentrations. These dye adsorptions became smaller in the order of Orange IV, I and II. This fact may be attributed to the formation of hydrogen bonds and to the van der Waals' forces between the fiber surface and the dye. Moreover, the surface dye adsorption vs. the total dye adsorption curve had a same linear relationship independent on the molecular structure of dyes. The surface area covered by the adsorbed dye molecules, which was calculated from the reciprocal of the slope of this straight line, 5.26×106cm2/g fiber.抄録全体を表示PDF形式でダウンロード (341K) -
森実 弘司, 須田 昌男, 代田 忠1971 年 27 巻 3 号 p. 113-119
発行日: 1971/03/10
公開日: 2008/11/28
ジャーナル フリーThe effect of draw ratio on the diffusion of Naphthalene Fast Orange 2GS in nylon 6 has been studied by means of microspectrophotometric (MSP) method.
The diffusion coefficient D (c) of the dye in nylon 6 was found to be strongly dependent on dye concentration in the substrate. This concentration dependence of D (c) decreases with a minimum at the draw ratio of 2, and then increases with the increase of draw ratio.
The diffusion coefficient at zero concentration of dye Do, the apparent diffusion coefficient by Krämer's method _??_ and the amount of dye adsorbed at equilibrium pass through a maximum at the same draw ratio.
The amount of the amino end groups does not change appreciably with drawing.
These results are explained by changes, accompanied by drawing of, the fine structure of nylon 6 and the contribution of non-ionic adsorption in dyeing mechanism.抄録全体を表示PDF形式でダウンロード (482K) -
森実 弘司, 須田 昌男, 中島 冨士雄1971 年 27 巻 3 号 p. 120-126
発行日: 1971/03/10
公開日: 2008/11/28
ジャーナル フリーThe effect of heat-treatment on diffusion of Naphthalene Fast Orange 2 GS in nylon 6 has been studied by means of microspectrophotometric (MSP) method,
While the apparent diffusion coefficient by Krämer's method _??_ exhibits a minimum at 170°C, the concentration dependence of diffusion coefficient D (c) decreases with rising temperature of dryheat-treatment.
Dry-heat-treated nylon 6 adsorbs less dyes at equilibrium in the middle region of pH than untreated one does, corresponding with the change of the amount of amino end groups, but the amount of adsorption in the higher pH increases by treatment.
In the steam-heat treatment, both the _??_ and the D (c) increase, but the concentration dependence decreases. The higher the treating temperature becomes, the more remarkable these tendencies become.
The amount of the amino end groups does not change regardless of steam-heating, A possible explanation on these results is discussed.抄録全体を表示PDF形式でダウンロード (498K) -
柴田 勝喜, 小川 利彦, 高瀬 福巳1971 年 27 巻 3 号 p. 127-131
発行日: 1971/03/10
公開日: 2008/11/28
ジャーナル フリーThe behavior of aromatic sulfonic acids in the aqueous solution was studied in relation to the molecular structure.
The mobilities of the aromatic sulfonate ions were measured by the Tiselius electrophoretic apparatus.
The mobilities of the disulfonate ions were found to be much larger than that of the monosulfonate ions. This may be due to the larger charge quantity as well as the larger disturbance of arrangement of surrounding water of aromatic rings of disulonic acid than those in the monosulfonate. But the rate of increment of mobilities with the increase of concentration of disulfonate ions were equal or less than that of monosulfonate ions in spite of the larger reduction of ionic atmosphere. This difference may be ascribed to the repulsion of sulfonate ions themselves. The larger the concentration of the sulfonate ion in the aqueous solution of sodium chloride of definite amount, the larger the mobility of the respective ion. A factor explaining this phenomenon may be the increase in effective charge induced by the decrease of ratios of sulfonate and sodium chloride. When the groups such as NH2 or OH are introduced into aromatic ring, the ratio of increment of the mobility increased. For this observation a rationale is advanced in which the disturbance of arrangement of surrounding water of aromatic ring by these groups causes the increase of mobility. The mobility of benzidine systems as well as aniline systems coupled with the same aromatic sulfonic acid in addition to the aromatic sulfonic acid itself were compared and the results are obtained in which the ratio of increment of mobilities increase in the order of; aromatic sulfonic acid, aniline systems, benzidine systems.抄録全体を表示PDF形式でダウンロード (358K) -
柴田 勝喜, 小川 利彦, 高瀬 福巳1971 年 27 巻 3 号 p. 132-137
発行日: 1971/03/10
公開日: 2008/11/28
ジャーナル フリーThe interaction between water-soluble basic vinyl copolymer and acid dyes was studied by the methods of spectrophotometry and dialysis equilibrium.
A copolymer of 2-vinylpyridine and 1-vinyl-2-pyrrolidone (I) was chosen as a water-soluble basic vinyl copolymer. As acid dyes were used C. I. Acid Orange 7 (II a), C. I. Food Yellow 3 (II b) and C. I. Acid Red 88 (II c). As the quantity of I added to the aqueous solution of II in a given concentration increased, the molar extinction coefficient of II decreased, reached the minimum at a certain quantity of I, and then began to increase. The lower acidity of the aqueous solution of II, the more quantity of I was required to reach the minimum of molar extinction coefficient. No change of the spectrum was observed even by the addition of poly-l-vinyl-2-pyrrolidone. The saturated binding quantities of acid dyes to copolymers were obtained by dialysis equilibrium. Their caluculated values were higher than those determined from the degree of dissociation by potentiometric titration, and hence the significant amount of dyes were absorbed to copolymerwith mechanism other than ionic bonding.
These observations indicate that the bonding between I and II is principally ionic in character, although to some extent II is aggregated around I by absorption.抄録全体を表示PDF形式でダウンロード (416K) -
川井 收治, 狩野 文男, 五十嵐 良一, 中保 治郎1971 年 27 巻 3 号 p. 138-143
発行日: 1971/03/10
公開日: 2008/11/28
ジャーナル フリーDiffusion behavior of dye particles into various polymer films was investigated comparing the degree of coloring with the dynamic mechanical properties of dyed films.
The polymers used in this work were polystylene (PST), polymethyl methacrylate (PMMA), polyethylene (PE), polyethylene terephthalate (PET) and polyvinyl alcohol (PVA).
Dynamic mechanical properties were measured by free vibration technique holding the polymer film samples in dyeing solutions. As a measure of the degree of coloring, optical densities at 608mμ and 640mμ in spectroscopy were used. Data were taken mainly in the temperature rang where the mechanical dispersion based on the onset of microbrownian motion of polymer chains, was observed.
As the results:
(1) For the polymers used in this work, the dyeing begins at the temperature where the loss modulus G″ begins to increase in the log G″ vs. temperature curve. The dispersion is refered to α mechanism for PST, PMMA and PET, to mechanism I for PE and to mechanism 2 for PVA.
(2) For high density polyethylene, the TG″max belongs to mechanism I, The activation energy calculated from the shift factors for mechanism I was close to that for diffusion of low molecular weight substances into polymer films. The results of dyeing of single crystal mats of big density polyethylene showed that no dye particle disperses into crystallites.
(3) PVA films is not dyed below 120°C in the case of dyeing in non-aqueous dispersion medium for dyes. The dispersion around 120°C belongs to mechanism 2. The activation energy calculated from shift factors for mechanism 2 ws close to that for diffusion of dye into polymer films.
Thus the molecular motion associated with this dispersion is considered to have a close relation to the diffusion of dye particles.
It is noted that abrupt changes in the temperature dependence of specific volume, IR spectra and spacings in X-ray diffraction were observed at around 120°C and that this dispersion is concidered as due to the crystalline region.
The results in this report suggest that the change of the crystalline region seems to affect the motion of amorphous chainsegments.
Thus released molecular motions may be available to make the holes which are large enough for dye particles to diffuse into polymer films.抄録全体を表示PDF形式でダウンロード (452K) -
甫天 正靖1971 年 27 巻 3 号 p. 144-151
発行日: 1971/03/10
公開日: 2008/11/28
ジャーナル フリーThe effects of steam-heat-treatment of acrylic fiber, in manufacturing process in particular, on dyeability were investigated, and were discussed regarding the changes of fine structure of the heat-treated fiber.
Studies on equilibrium dyeing and dyeing kinetics of the steam-heat-treated fiber with cationic and disperse dyes were carried out to determine partition coefficients of disperse dyes, saturation values of cationic dyes, apparent diffusion coefficients at various temperatures and activation energies of the diffusion.
The results obtained were as follows:
As the temperature in steam-heating of the fiber gets higher,
1) Partition coefficients of disperse dyes in fiber become higher due to the increase of dyeing effective volume.
2) Saturation values of cationic dyes show a slight decrease, indicating some loss of dye sites during the heat-treatment.
3) Apparent diffusion coefficients of both cationic and disperse dyes into the fiber increase, and activation energy of the diffusion decreases.
The changes in the dyeability of the steam-heated fibers depend upon the maximum steam temperature throughout the processes the fiber has been exposed.
The change of the dyeability in the steam-heating is largely related to that of the orientation function determined with Congo Red, FCR, which represents the degree of orientation of amorphous region in fiber.
Steam-heating of acrylic fiber seems to deteriorate the orientation of molecular chains in the amorphous region, consequently to loosen the structure of the molecular chain net-work through which dye molecules penetrate, resulting in higher dye diffusion into fiber or expansion of effective volume in dyeing with disperse dyes.抄録全体を表示PDF形式でダウンロード (613K)
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