T‑224 SEN‑I GAKKAISHI(報 文) (94) Transaction (Received September 20, 1985) EFFECT OF SOLVENT ON THE DYEING RATE TREATMENT OF WOOL FIBER By Kyohei Joko *,Joichi Koga * * and Nobuhiko Kuroki * (Textile Research Institute of Osaka Prefecture, Asahi, Izumi-Otsu, Osaka 595, Japan.) ** (Department of Applied Chemistry, University of Osaka Prefecture, Mozu-Umemachi, Sakai, Osaka 591, Japan.) Abstract The dyeing methanol of wool in an the rates and fibers. acidic dyeing dyebath. apparent and act the dyeing rate ments Since root to to barrier (CMC) and modification and be of nearly Accordingly, surface with the effect an of increase bulk for the dye the same 2) as of of faster the structure rate dye that the relationship it diffusion the cleaned apparent dyeing of solvent dye that dye same treatment wool relative dye surface lipid-type apparent that penetration all for the all 73 < cleaned (t- wool uptake (Ct/C•‡,) < contaminants solvent treat bulk phase, the pretreated the Red observed: treated the within structure Acid was is for phase fine and the it wool fibers, solvent-extracted the wools wool. rate molecules surface 7 (scourd) the chloroform/ the area is attributable within for dye to the cell penetration 1) the reduction membrane caused of complex by the CMC. 1. INTRODUCTION Lindberg1) has shown that the ether- and then ethanol-extracted wool dyes faster than wool extracted with ether alone. Medley et al.') and Butcher et al.') have also found that pretreatment with a number of alcohols can sharply increase the rate of dye uptake by the wool. Extraction of wool (which has been freed from external wool grease) with ethanol and other alcohols liberates a mixture of compounds whose main constituents are lipids and lipoproteins'-0. Makinson") has shown that extraction with hot ethanol modifies considerably the form of the cell-membrane network. From a comparison of electron micrographs of untreated the Orange uncleaned seen bulk acid, in = chloroform/methanol the was the internal the Further, facilitate movement the be changes Acid between penetration. for by wool can to C.I. order; treated (t1/2 ), effective in dyeing following within the of formic reference using acid materials molecule increase and time protein dye the formic the t-butanol-n-heptane, with performed the From dyeing energy mechanism assumed the lipid activation diffusion < wool. interfering extract the of of in wool with investigated were increased treated factor pretreated were acceleration treated) square a fibers experiments An n-propanol as wool n-propanol The butanol-n-heptane aqueous of aqueous wool and wool extracted with formic acid, chloroform/methanol and aqueous n-propanol, Leeder et al,') have recently indicated that electron microscopic image has revealed a modification of the cell membrane complex (CMC) by extraction with solvents, and that materials are preferentially extracted from the region of the CMC. Similar effects are considered for the treatments with other polar organic solvents9 -12) Thus, the dyeing rate of solvent-extracted wool is likely to be related also with a modification of the dyeing process in the CMC network. This communication presents the results of a comprehensive study of the uptakes of acid dyes by wool pretreated with polar organic solvents. (95) Vol. 42, No.4 (1986) the 2. T-225 dye solution being concentration 2.1 MATERIALS WOOL be SAMPLES: Merino 64's diameter method) was washed A wool (average in the sample form "Uncleaned" the dried wool: top it in used as strictly wool: The anhydrous t-butanol and then 3 vacuum, conditioned at 50:1 The wool The liquor was dried rpm and . at for extracted and at dye the immediately and 60•Ž. 25% value time, temperature hr with the initial given rinsed room 4 its a removed, oven was of After The could dried Dye on aqueous the pyridine concentration was deter- spectrophotometrically. 1 uptake at RESULTS shows against 50•Ž, AND plots of dyeing pH DISCUSSION the time dye for all (A. Orange the wool the A. 7) samples 4.2. under desiccator then well wool under a slow as for formic ex - agitation below. repeatedly 3 as was detailed rinsed conditioned 98-100% cleaned solvents, water and variation water Figure was deionized- 20•Ž, a silica-gel ratio, swelling deionized-distilled air-dried wool of at in wool: various 300 mol/l 10). "Extracted" with hr 2% quickly 3. (20•Ž, The changes 24 temperature tracted at 2 •~ 10-3 dyeing. distilled with n-heptane 1 day). several over and room (30•Ž, in water and was under successively day) t-butanol washed distilled extracted conditions (30•Ž, 1 day) wool dye vacuum mined "Cleaned" 1. the solution, received. at a fiber was within was with been combed. wool kept sample A- has of throughout JIS-L-1083 IWS; and The Australian dry-combed by by detergent, of of 23.9ƒÊm; supplied with agitated EXPERIMENTAL days. with It was then above8). acid-extracted for 1 hr at 20•Ž. 2. 3. 2:1 (v/v) 4 hr at 50% at chloroform/methanol-extracted aqueous DYESTUFF AND Acid Orange (A. Red 73) in a vacuum which revealed of hr by at dyes Acid Red recrystallizing water 60•Ž for by paper no colored analytical and three and 10 hr. then The grade . were Fig. same rate as were solution of perature prior bubbles Dyeing temperature of were reported left pH 4 to and was ml pretreated used It , The other is could clear that without then .2 overnight wet at the sample out -70•Ž by . The acetate the rate. the The rate wool to tem- completely in cleaned Orange effect of the data 7 effect of t-butanol-n-heptane . examined. in dyeing is acid = as order on Figure follows; chloroform/ in pretreatment the 1 were to dyeing analysed al.") cleaning on Figure rate formic et solvents apparent n-propanol. Medley the by the dyeing < the to pretreatment the aqueous detail, First, of < according remove the increase order < examine buffer dyeing out for system. the 2 shows the of fiber rate of surface with dyeing relationship was between in a vessel of pH solution 50 13) an experiments carried dye-buffer range in dyeing to obtained previously immersed rate wool remarkably methanol curves dyeing and uncleaned dyeing method Apparent purified METHODS samples 1. dried chromatography impurities , 73 purification. The 1000 4 The 7) checked DYEING air Orange purified oven were 2.2 for REAGENTS: (A. deionized-distilled dyes reagents 7 were from further n-propanol-extracted 70•Ž. C.I. times for 70•Ž. for the containing 4 .2 in the desired time the of , for relative dyeing uncleaned dye time uptake (the and Ct/C•‡ (time)1/2 cleaned and plots wool the for fibers, square dyeing where root rate) C, T‑226 SEN‑I GAKKAISHI(報 文) superficial The (96) cleaning, effects on the of Ct/C•‡ rate extracted interfere of of the dyeing against with It is are examined (Figure various solvents and noted from difference dye (time)1/2 chloroform/methanol significant the penetration solvent-extracting 3) such aqueous Figure in the 3 . treatment from the plots for the wool as formic acid, n-propanol. that negative there is no intercept Fig. 2. Rate of dyeing for A. Orange 7 and uncleaned and cleaned wools system. and C, represent the dye uptake at the dyeing time t and infinite, respectively. An initial upward curvature and a subsequent straight line are clearly seen for each wool. For the uncleaned wool, the intercept of -0.08 ex trapolated from the straight line suggests the presence of a very significant surface barrier effect","). On the other hand, the cleaned wool gives a less negative intercept without a change of the slope of the straight line. However, this means that the cleaned wool still shows the presence of a surface barrier effect. According to a series of works by Leeder et al.6,8-11) and other researchers 3,7), scouring by the normal processing (uncleaned wool) does not liberate all the wool-wax and lipids from the wool and, even after a number of very severe washes, a mixture of compounds whose main constituents are lipids and lipoproteins can be extracted with suitable solvents. The t-butanol n-heptane treatment liberates wool-wax and lipid type of contaminants from the surface but not labile materials from the interior of the fiber without swelling of the fiber 6). Therefore, the result of Figure 2 suggests that the surface cleaning by t-butanol and n-heptane increases the apparent dyeing rate by the reduction of the surface barrier effect without a change in the rate of dye penetration in the bulk phase. Thus, this gives us an impression that wool-wax and lipid-type of contaminants, removable by the Fig. 3. Rate of dyeing cleaned for A, Orange 7 and and extracted wool system. Fig. 4. Rate of dyeing for A. Red 73 and cleaned and extracted wool system. at C97? Vol. 42, No.4 (1986) t=0 between the cleaned and solvent-extracted wools but considerable differences among the line slopes. A similar result is given for A. Red 73 in Figure4. It is indicated that an increase of the apparent dyeing rate by the solvent extraction is not ascribed to a reduction Af the barrier effect on the fiber surface. In case where the cleaned wool is subsequently treated with formic acid, chloroform/methanol and aqueous n-propanol, it is well known that smallamounts of the labile lipid-type of materials are removed and small amounts of the proteinace ous materials are extracted by formic acid and aqueous n-propanol, while the chloroform/metha nol treatment can not be expected to remove the proteinaceous material 6,8-10). Furthermore, Leederet al.') have assumed from comparison of transmissionelectron micrographs (TEM) of the cleaned wool and solvent-extracted wools that lipid-type materials removed have been preferen tially extracted from the CMC region, including mainly the intercellular cement but occasionally the 9-layers. The TEM image of all the three extractedwools,compared with that of the cleaned wool, has revealed a modification of the CMC structureby the extraction. Accordingly, it is reasonable to consider that the effect of solvent treatment on the observed acceleration of the dyeing rate arises from the structuralmodification in the interior of the wool fiber,as judged by the increment of the line slopes. We evaluated the dye diffusion characteristics in the bulk phase by the apparent diffusion coefficient and the apparent activation energy, respectively,the former being calculated from the line slopeusing Hill's equation, where C•‡ fiber at tively, D time, is and For region Ct the effect. Medley epicuticle time of the plots an adsorbed of , t in is a without to any Further, the layer, damage each gaps through to dyes for dye diffusion present diffusion the was equation as Before made Figure of Ct/C•‡ ethanol A. cant a surface cylinder barrier attributed et a1 .'1 in in a have taken into by setting up a model . It has by been a surface layer shown, case by Orange of 7. The the the present is available of dye Hill's coefficient, the present Red system. dependence and Here, the we size difference rate dyeing 73 molecular the dyeing concentration concentration the of use diffusion A. In rate the fiber"). its the done"'). the of wool the across fiber. of of the may ether used larger be the than more signifi dependence. the dyeing Fig. diffusion 5. Concentration Dyeing barrier account of acting however, dependence was 60•Ž surrounded wool have the confirmed and occupied carried pH (0 out 4.2. The of using dyeing A. fraction ): ƒÆ=C•‡/S, rate. Red 73 of where C•‡ S saturated an equilibrium infinite al. 5 is shown because for for dependence purified At expression briefly et calculating be In without diffusion evaluation Peters concentration should exact Thus, membrane, penetrate process study, cell. surface barrier. no 16) surface cuticle trans-cellular surface therefore, cells conclusively continuous the can involve cuticle-cell time, a effect cuticle proved not dye barrier surface in the the individual exist which necessity the al. 171 have is covers intercellular accelerates of of et epicuticle but the fiber diminution Leeder that dye wool a non-linear the is layer to of due fiber. initial term drawing uptake respec cylindrical the additional on dyeing, coefficient radius (time)',' which dye short diffusion r is the the represent and suggests equation, the and infinite that T-227 as dye dye uptake. ƒÆ=0.45 and 0.19 (-•£-). uptake (-•›-), and 0.30 (-•~-) at dye is T‑228 It SEN‑IGAKKAISHI(報 can be (time) are on a apparent of single dye the The tion Ct/C•‡, line. Therefore, will (0) be dye the independent that by against concentrations provided occupied for diffusion dyeing the fraction anion does dye concentra are activation also The not among in the treated of diffusion wools, is not worth for structural suggests that within wools the the microfibril/matrix the treatment This results studied the texture after Table the particular, energy the is little for the that affected used with al.8) dye solvent that concluded is consistent unaffected fact the as solvents et the This of all same does reflect 16) therefore, Leeder 1 energies In should for the texture of dye. cortex cortex Table differently mechanism conclusion presence the activation organic by and differences activation which the is, with the 6) from for the the diffusion It of absolute (Figure noted each 73 is nearly wool. work. for within the extracted be of Red changes plot considerable that A. molecule cleaned to same noting change The diffusion reciprocal bath the values approximately 1. dye Arrhenius coefficients the Table 1. point spite obtained the the dyeing Table significant that, the the in in for against of summarized a shown from coefficient temperature at energy calculated diffusion coefficients experiments 0=0.45 apparent it straight coefficient apparent the are of dye (98) 0.45. from is plots various concentration sites exceed is that at diffusion the of seen obtained 文) by in the which this TEM showed microfibril/matrix solvent-extraction. 1. Fig. 6. Arrhenius plot of diffusion coefficients of A. Orange 7 and A. Red 73 in cleaned wool and in aqueous n-propanol treated wool. According that mainly related structure. 3olo of these the to the However, the whole of the the increase modified modification as the dyeing Hence, that an increase of the area for the modification activation dye fiber rate may not be explained effective penetration energy is only mass, the observed it should of the CMC of the CMC CMC content of diffusion CMC. it may be con in the rate of dyeing is wool only by arguments, increase increase Apparent diffusion coefficient and apparent dyes and various treated wools. * the apparent diffusion coefficient (m2/min) ** the apparent activation energy (kcal/mol) to cluded rate within the be considered internal surface caused by the leads to an increase of for the systems of (99) the Vol. 42, No.4 (1986) dyeing REFERENCES rate. Furthermore, the although dyeing are also rates of to TEM detailed to the CMC images of and could not The dyeing in conclusion 1. acid from wool here nants 3. The type of solvent wool facilitation is considered effective internal rates of achieved CMC A (time)1/2 contami interfering wool, in not or a part part of this Wool 1985, of dye of the confirmed, of advances the penetration CMC. that improves dye which increase suggests successful of for lipid interior by been an modification reagents the the penetration has involve preferable the from mechanism surface-area chemical extract The conclusion International Tokyo, to the above of vs surface proteins the phase. occurs accompanying use n-propanol. C1/C•‡. to the facilitate this the in < formic as a factor treatments bulk but The study rate cleaned aqueous the act follows. this dyeing of that and fiber the as The penetration. of materials within < to fiber. in < curvature with reference wool apparent wool-wax dye pretreated of uncleaned indicates the rate study. is summarized the initial including with of present examined order; relationship in the dyeing with structure increase The the fibers = chloroform/methanol 2. each seen modification the investigated fine following of be wools8). the pretreatments remarkably the of obtained The action can CONCLUSION was the of as in yet rate solvents changes mode improvement 4. organic the 1) J. Lindberg; Textile Res. J., 23, 573 (1953). 2) J. A. Medley and M. W. Adrews; Textile Res. J., 30, 855 (1960). 3) B. H. Butcher and B. L. Cussler; J.S.D.C., 88, 398 (1972). 4) J. P. E. Human and J. B. Soeskman; J. Textile Inst., 45, T 162 (1954). 5) T. Green, R. P. Harker and F. O. Howitt; J. Textile Inst., 47, T 110 (1956). 6) C. A. Andson and J. D. Leeder; Textile Res. J., 34, 416 (1965). 7) K. R. Makinson; Textile Res. J., 46, 360 (1976). 8) J. D. Leeder, D. G. Bishop and L. N. Jones; Textile Res. J., 53, 402 (1983). 9) J. H. Bradbury, J. D. Leeder and I. C. Watt; Appl. Polymer Symp., No.18, 227 (1971). 10) J. D. Leeder and R. C. Marshall; Textile Res. J., 52, 245 (1982). 11) H. D. Feldman and J. D. Leeder; Textile Res. J., 54, 26 (1984). 12) H. M. Appleyard and C. M. Dymoke; J. Textile Inst., 45, T 480 (1954). 13) J. Koga, K. Joko, Y. J. Lim and N. Kuroki; Proc. Korea-Japan Joint Meeting on Text. Sci. Technol., p454 (1983). 14) J. A. Medley and M.W. Andrews; Textile Res. J., 29, 398 (1959). 15) G. M. Hampton and I. D. Rattee; J.S.D.C., 95, 396 (1979). 16) J. Koga, N. Kuroki and K. Joko; Proc. 7th Int. Wool Textile Research Conf., Tokyo, Vol.5, p14 (1985). 17) J. D. Leeder and J. H. Bradbury; Nature, 218, 694 (1968). J. D. Leeder and J. A. Rippon; Proc. Inter. Symp. Fiber Sci. Tech., Hakone, p. 203 (1985). 18) L. Peters and G. H. Lister; Dis. Faraday Soc., 16, 24 (1954). 19) K. Joko, J. Koga, Y. J. Lim and N. Kuroki; Sen-i Gakkaishi, 39, T-198 (1983). wools solvent-extracted clarified among solvent-extracted between the be differences structure relationship CMC the three attributable solvent T-229 although the dyeing should modification be of the the 7th it. study Textile was presented Research at Conference , T-230 SEN-I GAKKAISHI (•ñ•¶) (100) 羊 毛 の 染 色 速 度 に お け る溶 剤 に よ る 前 処 理 の 効 果 大阪 府立繊維技術研究所 大阪府立大学工学部 上甲恭平 古賀城一.黒 木宣彦 t一ブ タノー ル/n‑ヘ プ タ ン,ギ 酸,ク ロ ロホル ム/メ タ ノ ール お よびn‑プ ロパ ノール水 溶液 で前処 理 した羊 毛 を促 進す る ことが 明 らか に な った 。 また,染 料の内部層 繊 維 への 酸性 染料 の 染色速 度 を検 討 した。 溶剤処 理 に よ っ てみか けの 染色 速度 は次 の 順序で 増 大 した。 処 理 羊毛 間 で ほ とん ど差異 が 見 られ なか った。このこと 精練 羊毛<表 面洗 浄 羊毛<ギ 酸処 理 羊毛=ク ロロホ ル ム/メ タ ノール処 理 羊毛<n‑プ ロパ ノール水 溶 液処 理 羊 で のみ か けの拡 散 の活 性 化 エ ネルギ ーを求 めた ところ, か ら,そ れ ぞれ の処 理 羊毛 の 繊維 内部(特 にコルテック ス層)に お け る染料 の拡 散 機構 はほ ぼ同 じで あると推論 した。 したが って,溶 剤処 理1ζよ るみかけの染色速度の 毛 。 染色 速度 を相 対染 着量 と〓 との 関係 で示 し,得 ら れた 染色速 度 曲線 の比 較か ら,繊 維 表面 に存 在 す る脂質 増 大 は,1)表 面障 害 効果 の減 少,2)細 胞膜錯合体の 構 造変 化 に と もな う繊維 内 部 表面積 の増 大 による染籾染 類 は染 料 の浸透 に対 す る障害 と して 働 き,繊 維 内部 か ら の脂質 お よび タ ンパ ク質の 抽 出は,繊 維 内部 の 染料 染着 着 の増 大 が寄与 して い る もの と考 えた 。