Document 6wrpZ7Ye25VadgLgXeerG9ezR

INTERME DI AT E S information bulletin February 16, 1962 BIPHENYL The attached paper by A. F. Strobel, entitled "Improvement of Light fastness of Dyeings on Synthetic Fibers by Ultraviolet Absorbers", that appeared in the February 5, 1962, AMERICAN DYESTUFF REPORTER, describes the superior properties of Biphenyl as a dye carrier in comparison with ortho-Phenylphenol, where an ultraviolet light absorber is present in the polyester fiber dyed to prevent color fading. The conclusions of the author are as follows: "The effectiveness of UV absorbers in improving the fastness to light of level-dyeing dyes, such as the Celliton disperse and Genacryl basic types on Dacron, is distinctly increased using Biphenyl as carrier. On Nylon-, Biphenyl employed as carrier does not appreciably increase the effectiveness of UV absorbers in improving the lightfastness of Celliton and Genacryl dyes." These results are very interesting and should be an added incentive for your customers to use Biphenyl instead of ortho-Phenylphenol. The following are advantages of using Biphenyl over ortho-Phenylphenol. 1. The already established fact that for achieving the same color shade. Biphenyl is a much cheaper dye carrier than ortho-Phenyl phenol. Your customer can realize a savings of approximately 1/3 of the cost of the carrier by basing it on Biphenyl rather than ortho-Phenylphenol. 2. Any traces of Biphenyl left over in the fiber after dyeing, do not affect the color fastness of the fiber, in contrast to the fading of the fiber when ortho-Phenylphenol is used. 3. The trend is for more and more dye houses to use UV absorbers to prevent color fading. No doubt. Biphenyl is far superior to ortho-Phenylphenol, as was proved by the authors. Recently, we have been working with the Sonneborn Chemical Company on the evaluation of various emulsifiers for Biphenyl in the preparation of a suitable dye carrier. Their recommendation, based on dye house trials, indicated that a mixture of Biphenyl and Sonolene 3753 in the ratio of 2:1 by weight is a cheap carrier with excellent dyeing properties. You may pass this information on to your customers and request them to direct sample requests to the Sonneborn Chemical Company, Hancox Avenue, Belleville 9, New Jersey. ORGANIC CHEMICALS DIVISION BYA:bp B. Y. ABADIR SAINT LOUIS 66, MISSOURI PCB-ARCH-EXT0376000 PROCEEDINGS OF THE AMERICAN ASSOCIATION OF TEXTILE CHEMISTS AND COLORISTS 1961 Convention------1-- v'" .... . IMPROVEMENT OF UGHTFASTNESS OF' DYEINGS ON SYNTHETIC . FIBERS BY ULTRAVIOLET ABSORBERS Part II* ' - A F STROBEL Antara Chemicals, a Division of General Aniline & Film Corporation INTRODUCTION IN Part I (I) it was seen that well leveling dyes of the Cclliton dis perse and Genacryl basic types could be co-dyed with certain UV absorb ers to improve the lightfastness of the dyeings. The efficiency of exhaust of the absorbers was seen to be little The effectiveness of UV absorbers in Improving the fastness to light of level-dyeing dyes, such as the Celllton disperse and Genacryl basic types on' Dacron, is distinctly in creased' using biphenyl as carrier. On nylon, biphenyl employed as carrier does not appreciably increase the effectiveness of UV absorbers in improving the lightfastness of Cel- better than 50%. Since these com pounds arc relatively costly, it be came of practical importance to at tempt new means of getting improved liton and Genacryl dyes. Spun nylon challis--Test Fabrics #354A--showed better penetration of dyes than did nylon filament taffeta Test Fabrics #302A. A cor exhaust while also continuing the endeavor to develop new absorbers of intrinsically better exhaust and efficiency. . respond ingly greater improvement in llghtfastncss of certain wool colors resulted from employing UV absorbers on spun nylon over nylon taffeta. With other level-dyeing In this paper we shall be dealing principally with the relative per formances of absorbers described as in Part I. As before, Absorbers A wool colors applied to nylon, how ever, no improvement in lightfast ness was obtained using UV absorb ers. The washfastness of the ultraviolet and C are new substituted acrylon itrile compounds synthesized at the Rensselaer. (New York), laboratories absorbers described is superior on Dacron 64 to their washfastness on nylon. of General Aniline & Film Corp, Absorber B is Uvinul D-49 of Gen eral Aniline Si Film Corp. nique of structural variation to Im prove exhaust later. The unsubsti There is especial Interest in cation ic (eg, Genacryl) dyes on the "60" series Dacron, which can be dyed with cationic dyes. The "50" series Dacron is not dyed by the cationics. Thus woven mixtures of the two types of Dacron give patterns from a single dyeing operation, the "60" series threads being dyed and the "50" threads being undyed by cat- ionics. The "50" and "60" series are both dyed by disperse (eg, Celllton) colors. tuted compounds are more econom ical to make than the long-chain sub stituted absorbers, so we attempted Improvement of exhaust of Absorb ers A and B using carriers. Disperse and cationic dyes are of ten applied to Dacron using carriers anyway: one commonly used carrier is o-phenylphenol. This carrier pro duces fair exhaust of absorber as well as dye. However, a great loss of lightfastness of the dyeing occurs when the o-phenylphenol is present This is illustrated In Exhibit 1. The dyeing at the right is a dyeing on Dacron 54 of Vi% Cl Disperse Blue 3 + y4% Absorber A + 5% ophenylphenol, exposed to FadeOmeter 20 hours in upper section.. At the left is the same dyeing heatset at 200C. This treatment removes the o-phenylphenol carrier. The dyeing then becomes fast to light Without absorber tho dyeing would look, much like the dyeing at the right after light exposure. EXPERIMENTAL USE OF CARRIERS-------- In Part I we had experimented with the use of carriers to possibly improve the dyeing of UV absorbers on synthetic fibers. We synthesized and compared on nylon- and Dacron a series of com pounds derived from Absorbers A, B, C, D, E. It was found by dyeing the exhaust liquor on a second piece of cloth that the hydrocarbon sub stituents do improve the exhaustion. More will be said about this tech- Prcscntcd September 27. 1961 during the AATCC Convention at Buffalo, NY Exhibit I February 5, 1962 American Dyestuff Reporter (P99) 35 PCB-ARCH-EXT0376001 PROCEEDINGS OF THE AMERICAN ASSOCIATION OF TEXTILE CHEMISTS AND COLORISTS In ah article on carrier dyeing, Friedman (2) describes the evalua tion of a number of organic materials as carriers. We experimented with the effects of a group of these or ganic materials, on their efficiency in transferring the absorber from an aqueous both to Dacron. Table I shows the order of effectiveness of a scries of organic carriers in trans ferring Uvinul D-49 and In transfer ring 2-hydroxy-5-methylphenylben/.otriazolc. No dye was used here. The most effective carrier was found to be biphenyl for each of these ab sorbers. The trade prefers to use ophcnylphenol over biphenyl because of easy dispersibility, solubility in caustic, and reliability which includes freedom from spotting of the Dacron by the dye. In Tublc II we have compared the relative clfcctivcncss of biphenyl and 2-hydroxybiphcnyl as carriers for applying Uvinul D-49 and Absorber A to Dacron 04, using no dye with the absorber. To understand the sig nificance of these figures let us look for a moment at the design of our UV reficctomctcr shown schemat ically in Figure 1. The UV light from tlie Hg tube, called "black light", is filtered free of visible light by F-3. The UV light goes through the Pyrex window and impinges on the white Carrara glass; it is reflected back to tlic photocell through filter F-l, which screens out any visible fluorescence. The photocell current is adjusted to read 100 mv on the galvanometer. Then the white Da cron cloth treated with UV absorber is inserted over the Pyrex window, and the photocell current is again read. The mv reading with ,A% ab sorber on the cloth is, say, 23 mv. Thus 23% as much light is reflected back as with the Carrara glass. To find out what reading would be ob tained with total absorption at the window, a black can was mounted over the pyrex window (to give black body absorption). A read ing of 19 mv was obtained. Also, 19 mv was obtained with a black cloth mounted over the Pyrex win dow in a conical form. This 19 mv is then due to background rad iation reflected from the black walls of the box. (Black paper over the Pyrex window read 23 vs). 23 mv is also read on Vi% absorber on Dacron 64. Therefore, 23-19 = 4 mv is due to the cloth with Vn% ab sorber present The total mv read ing from the Carrara glass is 100--19 = 81 mv. The percentages given in Table II are the residual % reflect ances of the Dacron 64 using this Flguro I TABLE I Order of effectiveness of organic carriers Uvinul P--fO 2- // Yttroxy-1 -methylphe.nylltctiZilriajo/- 1) biphenyl 2) Trichlorobenzenc .1) Methyl Ucylnt* 4) Dichlombcnzenu 5) o-Rhcnylphcniol I) biphenyl 2) Methyl salicylate M Trich!nrol>euzem: 4) UichlorolH'tucciu: 5) et-lNienyl phenol . TABLE II Comparison of affinity of UV absorbers on Dacron 64 using carriers Reflectance* of UV light Absorber A [ 1/8% Absorber owf \ \ 1/4% Absorber owf .............. 5% Carrier envf ------------ tUphrnyt 2-itydroxybi phenyl % 11% 4% 6% f 1/8% Absorber owf Uvinul D-49 11/4% Absorber owf n% (>% n% % Reflectances here have been calibrated to eliminate extraneous reflectance from black walls of rcflcclomctcr. TABLE III Comparison of affinity of UV absorbers with and without carriers on Dacron 64 Reflectance* of UV light V*% Absorber Absorber A Uvinul D-49 Mo carrier 7% 7% S% Hi phenyl 04%% 5% 2-Uydruxybiphenyl 6"V%o 7% Reflectance here bus been calibrated to eliminate extraneous reflectance from black walii of reficctomctcr. . method of calculation. The conclusion from Table II is that of UV absorber can absorb 96% of the UV radiation which falls on the swatch. Further, biphenyl is a more effective carrier than 2-hy- droxybiphenyl, especially for Ab sorber A, less so for Uvinul D-49. In Table III we have compared the efficiencies of absorption of Ab sorber A, using no carrier, with its efficiency using 5% biphenyl. It is seen to reduce the UV emission to 4% from 7% without biphenyl. Notice that Absorber B (Uvinul D-49) is not helped much by bi- 36 (P100) American Dyestuff Reporter February 5, 1962 PCB-ARCH-EXT0376002 PROCEEDINGS OF THE AMERICAN ASSOCIATION OF TEXTILE-CHEMISTS AND COLORISTS Exhibit 2 phenyl, and not any more or less efficiently exhausted using 2-hy- droxybiphenyl than with no carrier. The high absorption of UV light brought about by lU% absorber ac counts for our previous observation that Vfc% absorber (or more) gave little improvement over V4%. One is approaching absorption of all UV light even at the level. It is true that Va% gives distinctly less pro tection than >/4%, but Vfe% does not improve a great deal over Vi%. Since biphenyl is cheap and avail able commercially, we then investi-' gated the co-dyeing of a group, of UV absorbers with dyes in the presence of biphenyl. With biphenyl as carr.'er it was found not necessary to heat-set the fabric to get good light- fastness, as had been found with 2hydroxybiphenyl. On Dacron 64, a spun .challls, dye ing Vi% absorber +. Vi% Genacryl dye together with 5% biphenyl, a definite improvement of lightfastness resulted using . carrier, over ' the re sults ^obtained using absorber and dye alone, as seen' in Table TV. The effectiveness of Absorber A is great er with biphenyl carrier than with out The effectiveness of Uvinul D one case, and not others. - This- agrees on white Dacron absorbers alone. shows the lightfastness . 13 4- %% Absorber A 4- 5%. .biphenyl .to. .be improved over Cl Basic Red 13 4- 5% biphenyl without absorber: on DacrOn 64. Exhibit 3 shows the lightfastness of Genacryl Blue 6G + '/t% Ab sorber A 4- 5% biphenyl to be im proved over Genacryl Blue 6G alone 4- 5% biphenyl, on Dacron 64. (See editor's note at end of article). Table V compares the stabilizing power of Vs% Absorber A, Va% Uvinul D-49, and Vfe% 2'-hydroxy5' - methylphenylbenzotriazole ab sorber using basic dyes on Dacron 64; with Absorber A being superior to Uvinul D-49' in this comparison, and the triazole absorber being in ferior to both; again 5% biphenyl is used; Figure 2 compares the UV absorption curves of Absorber A, Uvinul D-49, the triazole and the 2,2'dioxy-4-octyloxy absorber 2* in alcohol. tABLE IV Level-dyeing dyes on Dacron 64j % loss on light fading** (20 nrs Fade-Ometer) 0.25% dye and 0.25% UV absorber, owf Dyrsluf Cl liutfic Red 13 Genacryl Blue JG Cl lluitic Yellow IJ . Carrier 5% Biphenyl No carrier 5% Biphenyl No carrier 5% Biphenyl No carrier Wank* 70 yo 25 30 35 40 Absorber A 30 45 10 IS 10 15 Absorber & (Uvinul 2M0) 40 .50 15 15 IS 15 TABLE V level-dyeing dyes on Dacron 64/ % loss on light fading** (20 hrs Fade-Ometer) 0.25% dye and 0.125% absorber, owf liyestnjf Cl-Battle Red 13 Genacryl Blue 3G Cl Butte Yellow 13 Genacryl l<ed.4U Cl llu*ic Blue l Monk* KO : 25 20 AO a 6*J . . Absorber ti Absorber A (Uvinul 2>WV) 40 45 ' 10 . 15 , 10 10 40 45 20 30 2-Hydroxy* 5* methyl phenyl* be ntotrinsole ' ' 60 ' - 20 : IS " ' .. 60 40 Blank here refer* la u dyeing .tiding 0.25% dye, 5% biphenyl and no ab*orbcr> . All percentage fading* uf color* were vUually estimated in north light und therefore arc to be taken a* relative only. All KadcrOmctcr exposure* were made at the mime elevation with retpect to the arc. . February 5, 1962 -. American Dyestuff Reporter Figure 2 UV absorption curves , A- -- Abxorber A . , . B -- Uvinul D*40 ; XV-- 2-Hydroxy-S-methylphenylbenxotriaxole Y -- 2l2'Dloxy-4-octyUwiyb*n*ophenonc (PI 01) 37 PCB-ARCH-EXT0376003 PROCEEDINGS OF THE AMERICAN ASSOCIATION OF TEXTILE CHEMISTS AND COLORISTS TABLE VI Level-dyeing dyes on nylon 66; % loss on light fading** (20 hrs Fade-Ometer) ,0.25% dye and 0.25% UV absorber, owf Dyestuff Cl Dlsjrcrsc Blue 7 Cl Disperse Red l Cl Dlsircrsc Blue 3 Carrier 5% Biphenyl No carrier 5% Biphenyl No carrier 3% Biphenyl No carrier Blank* 30 25 60 55 60 50 Absorber A 15 10 40 50 30 IS A bsorber B (Uvinul D-49) 20 18 25 30 40 25 Blank here refer* lo a dyeing using 0.25% dye and no absorber. All pcrccntHKC fading* of colors were visually estimated in north light and therefore arc lo be taken an relative only. All Fade-Ometer exposures were made t the same elevation with respect to the arc, . TABLE VIII Level-dyeing dyes on Dacron 62; % loss on light fading** (20 hrs Fado-Ometer pink and yellow, 40 hrs on blue) 0.25% dye and 0.25% absorber, owf Dyestuff Blank* Cl Basic Kcd 1.1 70 Cl Basic Yellow 15 '40 dcnacryl Blue .10 40 Absorber A 40 15 15 Absorber D (Uvinul D-49) 5 8 25 Absorber C (Cf Port l) 50 10 30 Blank here refers to n dyeing Lisina 0.25% dye and no absorber. All perccnincc fadings of colors wore visually estimated in north light and therefore arc to be taken ns relative only. All Fade-Ometer exposures were made at the same elevation with rcstiecl to the arc. TABLE VII Level-dyeing dyes on spun nylon (#354A); % loss on light fading** (20 hrs Fade-Ometer) 0.25% dye and Dyestuff 0.25% UV absorber, owf Absorber B Blank* Absorber A (Ovinut D-40) 2,2' Dioxy-4- octyloxybentophenone Cl Diipcric Red I 70 IS 25 33 Cl Disperse Orange 3 40 15 35 --" Cl DlipcrcBlue 7 55 15 25 35 See footnote under Table IV. TABLE IX . Level-dyeing dyes on nylon taffeta; % loss on light exposure** (20 hrs Fade-Ometer) 0.25% dye and 0.25% UV absorber, owf Dyestuff Cl Disperse Blue 7 Cl Disperse Red 16 Before Washing Wash Test II Before Washing Wash Test II Blank* 70 80 Absorber A< 20 ` 40 20 10 Absorber B . (Uvinul D-49) 30 . 50 .10 60 Blank here refers to a dyeing using 0.25% dye and no absorber. All pcrccntngr.sfadlngs of colors were visually estimated in north light and therefore arc lo be taken as relative only. All Fadc-Ometer exposures were made at the same elevation with respect lo the arc. The dyeing methods used in this More recently we have studied the the blues. The disperse (Celliton) work were essentially the same as effects of absorbers on the lightfast dyes include azos among the oranges, In Part I: ness of spun nylon challis (Test . reds, and yellows and anthraquin- Dacron 64--spun challis--Test Fab Fabrics #354A), and on Dacron 62 ones among the blues. Thus, here we rics #758 was used. Liquor to cloth Twill (#72) the latter a material of are stabilizing a wide variety of dye ratio was 40:1, with additions of 4% considerably higher luster than the or chemical sti'uctures with these Na.SO*, 0.1% Emulphor ON-870 owf, Dacron 64 used in Part I. Some re absorbei-s. followed by 5% biphenyl owf, the sults illustrated in Table VII and Only a small change in color is biphenyl being first prepared as a subsequent Table VIII show compar imparted by these absorbers at 14% 5% solution in methanol. A mechan able protection by the absorbers on to these dyeings examined visually. ical stainless-steel agitator to which the new fiber modifications to the Little loss in brightness of dyeing the cloth was attached was em protection obtained previously. results, especially with Absorber A, ployed. After addition of a 1% ace In Table VII on spun nylon, Ab even though fluorescence disappears. tone solution containing Vs% ab sorber A improves lightfastness more Thus, fluorescence of the cationic sorber and Vi% dye, owf, the bath than does Uvinul D-49, which lxn- dyes is apparently not responsible for was brought to the boil and kept at proves more than the absorber 2,2' their brightness. 200-2]0F for one hour with agita dioxy-4-octyloxybenzo-phenone. One question that arises is how tion. The dyed cloth was removed, In Table VIII on Dacron 62, Ab permanent are the - absorbers to rinsed, and dried. . sorber D-49 improves lightfastness washing and drycleaning after be Since the absorbers did not ex more than Absorber A on the pink ing applied to the fiber by the co haust with much better than 50% and yellow, and less than A on the dyeing method. efficiency on nylon 66 taffeta (Test Blue 3G. The effect of washing by AATCC Fabrics # 302A), the effect of using Exhibit 5 illustrates dyeing of 14% Wash Test #2 df Dacron co-dyed biphenyl. with disperse dyes on ny of Genacryl Blue 3G + 14% Ab with absorber 4- Celliton (or Gen lon was tested. Some results are sorber A on Dacron 62 compared acryl) dye was good, showing about given in Table VI. The use of bi with Genacryl Blue 3G without ab 15% loss in effectiveness of absorber phenyl does not help these dyeings sorber. It is seen that the absorber after washing compared with before on nylon over the use of absorber again improves lightfastness on Da washing. However, on nylon taffeta alone. The biphenyl helps Dacron cron 62. (See Editor's, note). both Absorber A and Uvinul D-49 only. . Exhibit 6 shows the protection of a lose considerably in effectiveness as In Exhibit 4 we have a dyeing of disperse dye, Cl Disperse Red 1, bn light stablizers after AATCC Wash 14% Celliton Fast Blue Green BP Dacron 64 using Absorber A. Again Test #2, as shown in Table IX. It 14% Absorber A on nylon. No the dispex-se dye without absorber, responds to light as if about 50% biphenyl is used in this test All light mounted on the right has poorer were lost in Wash Test #2 on nylon. tests were carried out in the Fade- lightfastness than the dyeing on the In Table X, wash tests of dyeings of Ometer. (See Editor's note). left which employs 14% Absorber A. Vs% Absorber A and Uvinul D-49 The results in Part I refer to the The cationic (Genacryl) dyes in on two white nylon fibers and three use of nylon filament taffeta (Test clude methine types from indole white Dacron fibers are illustrated. Fabrics #302A) and Dacron 64-- bases among the reds and yellows, The. loss on the nylons is definitely spun challis--Test Fabrics #758. and triphenylmethane dyes among greater than on the Dacron,, especially 38 (PI 02) American Dyestuff Reporter o February 5, 1962 PCB-ARCH-EXT0376004 PROCEEDINGS OF THE AMERICAN ASSOCIATION OF,TEXTILE CHEMISTS AND COLORISTS TABLE X Washfastness of UV absorbers on undyed doth !4% Absorber ' . /Wt.otrbm Nylon 200 Spun nylon I75K Dacron 54 Dacron 62 Dacron 04 '< + 44 - 48 44 - 48 47 - 4`> 47 -* 48 45 45 1/tinnl P-W 48 -- 5,1 47 55 46 -- 4<> 50 -- 51 44 -- 45 *fNlomstn0li2c.r)u rriircmint % reftecttiiKtt of IJV lig. ht from cloth. (AATCC Wash TABLE XI Drycleaningfastnajs of UY absorbers on undyed cloth Perchlorethylene--'/% Absorber ` Absorbers Nylon 7110 Spun nylon I75H Dacron 54 Dacron 62 Dacron 64 + ' 44-46 14-47 47-57 47-55 45-4V Uvinul D-49 48-55 47-54 46-51 511-5 V 44-46 H-NtiinlKTH firprcHcut % rultrcmncc of UV lidtil from cloth. Figuro 3 ^ 1 UV absorption of Celliton and Gcnacryl. dyoi Dacron 64. Here again the higher numbers indicate greater reflectance, therefore, less absorber present. The dryclcariing fastness, of the absorbers from perchloroethylene solvent is illustrated in Table XI. It is not very good for either ab sorber, but is better for Uvinul D-49. The absorbers themselves are. much less soluble in hydrocarbon solvents than In perchloroethylene, and their dryclcariing fastness' would be ex pected to be much better with Stod dard's solvent. Absorber A and Uvinul D-49 can be evenly applied to. Dacron 64 from perchloroethylene containing %%, for example, of Absorber A by padding prc-dyed Dacron 64 evapor ated to dryness. The. resultant ap plication of absorber gives more, lightfastness to the. dyeing than the same amount of absorber co-dyed on the fabric. However, at least half of the absorber applied to Dacron 64 by the drycleaning solvent padding method was lost in AATCC Wash Test #2, whereas only about 15% was lost after AATCC Wash Test #2 on co-dyed absorber. These data on dryclcnning solvent application refer to disperse and cationic dyes on Dacron, ' MECHANISM OF THE EFFECT In Figure 3 the UV absorption curves of several of the dyes are given. In Table XIII are compared the total UV absorption (by measuring the area under the curve) between 310 m/i and 400 m/i of a number of disperse and basic dyes under discussion. It is seen that the total absorption varies over a range of ap proximately eightfold. It was seen from the stabilization afforded by the UV absorbers that the Cl Basic Red 13 and Genacryl Blue 3G, as well ns the Cl Disperse Blue 3, all of which have low UV absorption, were in most cases stabilized just as'much as the others with much higher absorption! Thus there appears to be no corre lation between large UV absorption of the dye and large stabilization by the absorber. It appears then, rather remarkably, that the dye is not di rectly activated and destroyed by the UV. Since UV light does play a large part In breaking down these cationic arid disperse dyes, we sug gest that the UV light is initiating some, other reaction, forming a rad ical which attacks the dye and de composes it Thus, it may be a rad ical from the polyper itself, or from impurities in the polymer, or it might be an attack on the dye by a UVactivated oxygen radical! As far as sensitization of dyes, by UV absorbers is concerned, we would like to describe . an experiment wherein we were trying to determine the protection afforded Scotch tape by UV absorbers: on top of the Scotch tape was placed a series of filters of cellulose acetate side by side. The first filter had no absorber, the second had Absorber A, the third Absorber B, the fourth had Absorber C, the fifth D and the sixth E. The most decomposed in 50 hours of Fade-Ometer exposure was Absorber A, flic least decomposed was blnnk containing no absorber, the others being intermediate and more decom posed tlie more the absorption. If the absorber had. been-in the Scotch tape resin, one would have bceri inclined to say the resin was "sensitized" by the absorber. Since the absorber was placed in n separate film above the resin, a simple explanation is that the acetate sheet containing the absorher has absorbed more energy from the light source than blank, thus the temperature of the Scotch tape has been higher and, therefore, more subject to light degradation' at this temperature. Absorber E is ac tually a sensitizer for some dyes. WOOL COLORS ON NYLON AND WOOL As to other dyes, besides the cationics and disperse colors which we have been considering to this point, we will take up the effect of UV ab sorbers on wool colors on nylon. In *he first paper it was reported that a number of classes of wool dyes:, premetallized (Supralan), acid dyes such as Cl Acid Red 4, Cl Acid Blue 90--all of which gave relatively unlevel (c.ompared with Cellitons) dyeings on nylon 66 taffeta.(#302A), also were not improved in lightfast ness by co-dyeing with UV absorb ers. It appeared of interest to deter mine whether use of a more easily dyed nylon would show any im provement. In Table XII appears the largest improvement in lightfastness we February 5, 1962 American Dyestuff Reporter (P103) 3? PCB-ARCH-EXT0376005 PROCEEDINGS OF THE AMERICAN'ASSOCIATlON OF TEXTILE CHEMISTS AND COLORISTS TABLE XII Wool colors on spun nylon (#758)) % loss on light fading** (20 hrs Fade-Ometer) 0.25% dye and 0.25% UV absorber, owf Dyestuff Wank* , ' Absorber It Absorb** A {Uvinul P-tO) 2-11 ytlroxy*!' methylphenyl- bruzoiriozolr Cl Add Green 41 25 . 15 10 15 Cl Acid Mine 78 JO 10 20 20 Cl Arid Red 7J 60 40 45 40 Bleak lrrc refer* to a dyeing lining 0.25% dvr and no nb*ori>er. **A1I pcivrningc fading* of colors wore visually estimated in north light and therefore arc to hr taken as relative only. Al! Kndc-Omclcr exposures were innflu at the same elevation with reajtcci to t lie arc. TABLE. XIII UV Absorption of disperse and basic dyes Relative values Cl Diijicrtc Orange J Cl Disperse Blue 7 Cl DisiKm' IMnr J Cl Basic Yellow 1J Cl Bitpic Blue l ' Genacryl Red 4M Cl Basle Red M Total fibre* 5.2 5.2 1.4 6.5 5.5 2.1 1.2 .75 have found aflorded by UV absorbers absorbers. Cl Acid Red 97 gave a on acid colors on spun nylon (#758). rather unlevel dyeing at Vei% bn spun It is seen that Cl Acid Green 41 nylon, but its lightfastness was a Is definitely improved in lightfastness trace improved using 2'-hydroxy-5'- by absorbers, Cl Acid Blue 78 is methylphenylbenzotriazole. Cl Acid markedly improved ,also, while Cl Yellow 25 gave a very level dyeing Acid Red 73 is little improved. From on spun nylon, and the lightfastness Table XII it is seen that the triazole of this dye was very much improved absorber is relatively a better stab using UV absorbers, especially Uvi ilizer with these wool colors than it nul D-50. Again Cl Acid Violet 11 was with the Cclliton colors. was level dyeing and only slightly The lightfastness of the dyes shown improved in lightfastness by Uvinul in Table XII was not improved using D-50. Brilliant Indocyanine G was nylon taffeta (Test Fabrics #302A). rather unlevel on spun nylon, and The dyes are distinctly better pen not improved by UV absorbers. etrated and stronger on the spun It was found in several instances nylon than on nylon tafTeta. This to be effective in stabilizing color suggests that sufficient penetration of ings. However, it is sensitive to basic the fiber by the dye is a prerequisite media, changing color and losing to satisfactory stabilization of dyes strength. Absorber A and Uvinul by UV nhsorbers. D-49 have considerably better fast The method, of applying the wool ness to washing by AATCC Wash colors which are not premetallized Test #2. . , types was to dye in the presence of No Supralan (premetallized) dye 1% owf Igcpon T-51 and 2%, owf, was improved in lightfastness by UV sodium, sulfate, dyeing temperature absorbers/ on spun nylon: in fact 200F, one hour. Liquor to cloth Supralan'. Orange NR and Supralan ratio 40:1. The premetallized dyes Red NR were poorer in lightfastness were applied to nylon using 5%, owf, with UV absorbers present than in ammonium acetate and 2%, owf, . 'their absence. Supralan Blue NB and Dinzopon SS-837. ' Red NB showed no Improvement The results obtained are erratic' ..With UV absorbers. and difficult to' put In table form, It is interesting that Absorber A but include the following observa and. Uvinul D-49 can be dyed on tions: Wool with exhaust of 40% to 50%. Cl Acid Yellow 7 V5i%, owf, ap However, Cl Acid Yellow 36 at %% plied to spun nylon gave a very level gave a level dyeing on wool which dyeing. Co-dyeing with Vi% Ab was not improved in lightfastness by sorber A, as well as with XU% Uvi- any UV absorber. On the other nul D-49, gave a slight improve- hand, Cl Acid Red 4 at xk%, owf, ment in lightfastness; however, a also dyed level on wool and did show definite color change toward brown improved lightfastness in the pre occurred on exposure to light. Cl sence of Absorber A. Acid Blue 11.8 dyed unlevel on ny It is seen from the above that wool lon taffeta, but a slight improvement dyes oh nylon and on wool respond in lightfastness resulted from Ab quite differently to UV absorbers sorber A. Wool Fast Blue BA gave a than Celliton and Genacryl dyes on level dyeing on spun nylon: its light synthetic fibers. ' fastness was only slightly Improved Absorber A has been sampled in by Uvinul D-50f and not by other the field and we have received re ports from outside laboratories of tUvimil D*50 it 2,2',4.4'-lcirnltydroxybcnx6|)hcnonr! its superior performance to other OH O HO absorbers. 1 This- experimental pro HO-r o 1 <z>- duct Is still under process develop ment before manufacture. ACKNOWLEDGMENT The experiments described in this paper are the results of a team effort on the part of S C Catino, R Rounds, and the author, at the Rensselaer, NY, laboratories of General Aniline & Film Corporation. FUTURE WORK Future work in this field will in clude evaluation of light protection afforded dyes by UV absorbers in resin finishes on natural.: and syn thetic fibers, as well ns study of per formance of absorbers in Dacron/ cotton and Orion/wool blends. In a resin finish the UV absorber will be where it can do the most good: that is between the dye and the light. Further in resin finish the dryclean ing fastness of the absorbers should be improved. LITERATURE CITED (2) Strobel, A F, .'`Improvement of Light fastness of Dyeings of Synthetic Fibers by Ultrnviolet Absorbers, Port I." Am Dyestuff RepIr 50, No. 1G, 583-8 (19GU. (2) Friedman, H M. "Some Aspects of Carrier Dyeing", ibid 40, 946-51 (I960). (3) Coleman, R A. and, Pcneock. W H, "Ultra violet Absorbers", Textile Research J 28, 784 (1958). TRADEMARKS The following trademarks have been used in this paper: . Carolld--Tonntcx Chemical Coni . Celliton--General Aniline & Film Corp Dacron--E I. duPont dc' Nemours & Co, Inc Diazopon--General Aniline & Film Corp Emulphor--General Aniline & Film Corp Fadc-Ometer--Atlas Electric Devices Co Genacryl--General Aniline & Film Corp Igepon--General Aniline Film Corp Orion--E I duPont dc Nemours A. Co, Inc Pyrex--Corning Glass Sulphon--General Aniline & Film Corp Supralan--General Anilino & Film Corp Supramine--General Aniline & Film Corp Tannvol--Tnnatex Chemical Corp Uvinul--General Aniline & Film Corp . EDITOR'S NOTE Exhibits 1 through 6 referred to in this paper were shown as colored slides, Fading appears mainly in the blue element. As this does not show up sufficiently in black-and-white illustrations, we have shown only two examples to point up the effect. 40 (PI 04) American Dyestuff Reporter ,February 5, 1962 PCB-ARCH-