E sure Color (Hue and ShadeJ-match Consistency

Background f¾O01J The se of natural dyes for the dyeing of natural yarns and fabrics has been known since the beginning of recorded history. Howeve , consistent, uniform hue and shade-matching of dyed materials from hstch-to~bateh has eluded even the most practiced artisan. Consistent hue and shade-matching is the most difficult to achieve both within a batch and between batches. Prior art attempts to solve this problem etwee batches have failed. The dyeing industry has turned to synthetic dyes because they afford greater control over the dyeing process and can achieve the desired hue and shade-match consistency. However, the production and use of synthetic dyes results In vast quantities of toxic waste materials that need to be managed. Stiff, even when faced with the waste problem caused by the use of synthetic dyes, the commercial dyeing industry has rejected the use of natural dyes because of the aforementioned

inconsistency in hue and shade-matching, among other challenges. Thus, what is needed are new compositions and methods for dyeing natural fibers with natural dyes that achieve hue and shade-matching on a commercial scale and result In fewe rejects and greatly reduced wast© when compared to synthetic dyeing processes.

Summary of the invention

[0002] The present invention provides compositions and methods for the dyeing of natural fibers (yarns, fabrics and garments) with natural dyes while providing for uniform hue and shade-match in the same hatch and between batches. While not wishing to be bound by theory, it is believed that the use of ferrous sulfate solution at the disclosed concentrations and processes, together with the use of loosely wound yarn packages, provides for enhanced dye penetration (take-up) by the yarn package enabling uniform package dyeing. The inclusion of the natural dyestuf solution spectrophotometer and the yam package spectrophotometer provides system inputs enabling precise hue and shade-matching between batches with minimal dye waste. 803J The pr s nt invention contemplates a process for dying yarn produced from a natural fiber using a natural dyestuff, the process comprising: providing a loosely wound yam ckage having a yam density of lass than about 0.S6 g cm ³ ; providing a natural dyestuff ^' solution; providing a ta k that ill accommodate the yarn package and an initial volume of the natural dyestuff solution; providing a yarn package spectrophotometer and a natural dyestuff solution spectrophotometer, contacting the yarn package and the Initial olume of natural dyestuff solution within the tank under conditions appropriate for uptake of the natural dyestuff by the yarn; monitoring absorbance of the yam package by the yam package spectrophotometer and the natural dyestuff solution by the natural dyestuff solution spectrophotometer, supplementing the Initial volume of natural dyestuff solution with an appropriate quantity of the natural dyestuff solution, as needed, to achieve a condition wherein the yarn package spectrophotometer detects absorbance at a desired wavelength and the natural dyestuff solution spectrophotometer detects absorbance consistent with a substantially depleted natural dyestuff solution; replacing the dyestuff solution with a solution comprising ferrous sulfate at a concentration of about 1% to 8% by weight of the dry weight of goods (WOG) to be dyed; and contacting the yam package wit the ferrous sulfate comprising solution for a period of time suftabte to fix the dyestuff to the fibers.

{ 004J The present invention further contemplates that the yam package is contacted with a mordant solution prior to being contacted with the dyestuff solution and wherein the mordant solution is em ed before the yam package is contacted with the dyestuff solution. The present invention further contemplates that the natural fiber is selected from the group consisting of wool or cotton. The present invention further contemplates that the natural dyestuff Is selected from the group consisting logwood, cochineal, madder, cutch, myrobalan, hemafine, pomegranate, and chestnut. The present invention further contemplates that the ferrous sulfate solution is at a concentration of about 2% to 8% by weight of the dry WOO to be dyed. The present invention further contemplates that the process comprises filtering the natural dyestuff solution prior to use. The present invention further contemplates that the natural dyestuff solution is filtered through a 100-1000 nm filter.

|O005¾ The present Invention contemplates a rocess for dying fabric produced from a natural fiber using a natural dyestuff , the process comprising; providing a natural ddyyeessttuuffff ssoolluuttiioonn;; pprroovviiddiinngg aa ttaannkk tthhaatt wwiillll accccoommmmooddaatete tthhee ffaabbriricc aanndd aann i Inniittiiaall vvoolluummee o off t thhee n naattuurraall ddyyeessttuuffff ssoolluuttiioonn;; p prorovviiddiinngg aa ffaabbrriicc s sppeeccttrroopphhoottoommeetteerr aanndd aa n naattuurrea!l ddyyeessftuuffff ssoolluuttiioonn s sppeeccttrroopphhoottoommeetteerr;; ccoonnttaaccttiinngg tthhee ffaabbrriicc aanndd tthhee iinniittiiaall v voolluummee o off n naattuurraall ddyyeessttuuffff ssoolluuttiioonn wwiitthhiinn t thhee ttaannkk uunnddeerr c coonnddiittiioonnss aapppprroopprriiaattee f foor uuppttaakkee ooff tthhee n naattuurraall ddyyeessftuuffff bbyy tthhee yyaarrnn;; mmoonniittoorriinngg aabbssoorrbbaannccee ooff tthhee f faabbrriicc b byy tthhee ffaabbrriicc s sppeeccttrroopphhoottoommeetteer aanndd tthhee nnaattuurraall ddyyeessttuuffff ssoolluuttiioonn bbyy tthhee nnaattuurraall ddyyeessttuuffff s soolluuttiioonn ssppeeccttrroopphhoottoommeetteerr;; ssuupppplleemmeennttiinngg tthhee iinniittiiaall vvoolluummee ooff nnaattuurraall ddyyeessttuuffff ssoolluuttiioonn w wiitthh aann aapppprroopprriiaattee qquuaannttiittyy ooff tthhee n naattuurraall ddyyeessffuuffff ssoolluuttiioonn,, aass n neeeeddeedd,, ttoo aacchhiieevvee aa ccoonnddiittiioonn wwhheerreeiinn tthhee ffaabbrriicc ssppeeccttrroopphhoottoommeetteerr ddeetteeccttss aabbssoorrbbaannccee aatt aa ddeessiirreedd wwaavveelleennggtthh aanndd tthhee n naattuurraall ddyyeessttuuffff ssoolluuttiioonn ssppeeccttrroopphhoottoommeetteerr ddeefteeccttss aabbssoorrbbaannccee ccoonnssiisstteenntt wwiin aa s suubbssttaannttiiaallllyy d deepplleetteedd nnaattuurraall ddyyeessttuuffff ssoolluuttiioonn;; rreeppllaacciinngg tthhee ddyyeessttuuffff ssoolluuttiioon wwiitthh a a ssoolluuttiioonn ccoommpprriissiinngg ffeerrrroouuss ssuullffaattee aatt aa ccoonncceennttrraattiioonn ooff aabboouutt 11%% ttoo 88%% bbyy w weeiigghhtt ooff tthhee ddrryy weiigghhtt ooff ggooooddss ((WOOGG)) ttoo bbee ddyyeedd;; aanndd c coonnttaaccttiinngg tthhee f faabbrriicc wwiitthh tthhee ffeerrrroouuss ssuullffaattee c coommpprriissiinngg s soolluuttiioonn ffoorr aa ppeerriioodd ooff ttiimmee ssuuiittaabbllee ttoo ffiixx tthhee ddyyeessttuuffff ttoo tthhee ffiibbeerrss..

TThhee pprreesseenntt iinnvveennttiioonn f fuurrtthheerr c coonntteemmppllaatteess tthhaatt tthhee ffaabbrriicc iiss ccoonnttaacctteedd wwiitthh aa mmoorrddaanntt ssoolluuttiioonn pprriioorr ttoo bbeeiinngg ccoonnttaacctteedd w wiitthh tthhee ddyyeessttuuffff ssoolluuttiioonn aanndd wwhheerreeiinn tthhee mmoorrddaanntt ssoolluuttiioonn I Iss rreemmoovveedd bbeeffoorree tthhee ffaabbrriicc IIss ccoonnttaacctteedd wwiitthh tthhee ddyyeessttuuffff ssoolluuttiioonn.. TThhee p prreesseenntt iInnvveennttiioonn ffuurrtthheerr c coonntteemmppllaatteess tthhaatt tthhee nnaattuurraall f fiibbeerr IIs sseelleecctteedd ffrroomm tthhee ggrroouupp ccoonnssiissttiinngg ooff wwooooll oorr ccootttteerrss.. TThhee pprreesseenntt i innvveennttiioonn ff uurrtthheerr ccoonntteemmppllaatteess tthhaatt tthhee nnaattuurraall ddyyeesstfuuffff iiss sseelleecctteedd ffrroomm tthhee ggrroouupp ccoonnssiissttiinngg llooggwwoooodd,, ccoocchhiinneeaall,, m maaddddeerr,, ccuuttcchh,, m myyrroofobaalaann,, hheemmaattllnnee,, ppoommeeggrraannaattee,, aanndd cchheessttnnuutt TThhee pprreesseenn iinnvveennttiioonn ffuurrtthheerr ccoonntteemmppllaatteess tthhaatt tthhee ffeerrrroouuss ssuullffaattee ssoolluuttiioonn iiss aatt aa ccoonncceennttrraattiioonn ooff aabboouutt 22%% ttoo 00%% bbyy wweeiigghhtt ooff tthhee d drryy WWOOGG ttoo bbee ddyyeedd.. TThhee pprreesseenntt iinnvveennttiioonn ffuurrtthheer c coonntteemmppllaatteess f fiilltteerriinngg tthhee nnaattuurraall d dyyeessttuuffff ssoolluuttiioonn pprriioorr ttoo uussee.. TThhee pprreesseenntt iinnvveennttiioonn ffuurtrthhee ccoonntteemmppllaatteess tthhaatt tthhee nnaattuurraall ddyyeessttuuffff ssoolluuttiioonn iiss ffiilltteerreedd tthhrroouugghh aa 110000--11000000 n nmm ffiilltteerr.. TThhee pprreesseenntt iinnvveennttiioonn ffuurrtthheerr ccoonntteemmppllaatteess tthhaatt tthhee ffaabbrriicc iiss sseelleecctteedd ffrroomm aa g grroouupp ccoonnssiissttiinngg ooff wwoovveenn aanndd nnoorrss ^»» wwoovveenn ffaabbrriicc..

E$00?J Figure 1 shows a ^' schematic diagram of one embodiment of the de ise used in the dying of natural fibers with natural dyes by the methods of the present invention. Fsg m 2 s ows a dyed 1 pound cotton yam package died berry color. O ¾ The methods described herein enable natural dyeing of natural fibers, on a

commercial sca e, with the consistent and reproducible hue and shade-matching

regard to the rim ry' (red, blue and yellow), secondary {green, purple and orange) and tertiary colors. The term ^' 'shade ^* refers to how dark the color is. In yeing, colo is determined by the dye mix and shade is determined by the uptake of the dye info the fiber. The ability to shade-match the dyeing of natural fibers using natural dyes

consistently has been previously unachievable on any scale. For example, US Patent No. S,851,?9S describes the shade-matching problem in column 1 , lines stating It is almost impossible using known techniques to obtain the same dye shade twice in succession with natural dyes, even using the seme method." G¾10J The term "natural dying," as used herein, refers to th dying of natural fibers with nature! dyes. Natural fibers include, for example, protein fibers such as wool and cellulose fibers such as cotton. Wool is a textile fiber obtained, for example, from sheep and certain other animals, including cashmere from goats, mohair from goats, qlviut from muskoxen, angora from rabbits, other types of wool from oamelids, and others known in the art. Examples of cellulose fibers include, cotton from the cotton plant, linen from the flax plant, Jute, hemp, papaya, sisal (agave), milkweed and others known in the art. In the present specification, the terms fiber, yam, garment and fabric all refer to a natural fiber article (i.e., the materials}) being dyed and may be used interchangeably. The term fabric shall refer to woven and non-woven fabric as well as items made from fabric such as garments, bags, tarps, etc.

[0011] Natural dyes are dyes obtained from natural source materials such as plants, invertebrates, minerals and animal products such as urine. The source material must be processed to isolate and concentrate the dye, Man examples of natural dyes are known in the art and are discussed below. Natural dyes, such as Indigo, from the Indigofera plant, and madder, from the madder mot, have been used since the beginning of recorded history. However, shading-matching on a commercial scale has been unattainable by those of skill In the- art. This is because, as one synthetic dye

manufacturer states, the color-giving molecules used for dyeing have not been

"specifically designed by nature" for transfer to a su strate _* Because of these problems, la ge scale dyeing (t.e„ commercial scale dyeing) as turned to the use of synthetic dyes,

[0012J The unexpected success of the present invention to provide for shade-matched dying of natural fibers with natural dyes is based on several inventive concepts. These Inventive concepts of the present Invention relate to both package or yam dyeing and fabric or piece dyeing. For package dyeing, a loose winding of the yam on the tube on which the yarn will be. dyed. The yam on the tube is referred to in the art as a "package." While not wishing to e bound by theory, ft Is- believed that loosely wound yarn allows the dye and dyestuff solution to reach and penetrate all fibers of the yarn. The looseness or tightness of the yarn in a package is measured In terms of "package density." A tighter wind has a higher package density. A looser wind has a lower package density. The yarn package of the present invention has a package density of less than about 1.5 g/cm ^s , less than about 0.05 g/cm ⁵ , lass than about 0.75 g/em ³ ₍ loss than 0.65 gfem ³ , less than 0.50 g/em ³ , to about 0,10 §/cm ³ , For piece dyeing, it Is critical that the liquor ratio be maintained from about 3:1 to about 10:1.

|0O 33 inventive concepts of the present invention also include the use of at least one and preferably two spectrophotometers to monitor the dyeing process, The first spectrophotometer (the yarn or fabric spectrophotometer) is positioned to monitor the yam or fabric color in t e dyeing vat for kier) or tank. Feedback from the first spectrophotometer is used to monitor the yarn or fabric color and thereby control the dying process. The second spectrophotometer (the dyestuff spectrophotometer) is positioned in the recharge kier or dye bath vat or tank and used to measure the concentration of dyestuff In the dyestuff solution returning from the dyeing kier and/or in the dye bath tank in the case of package dyeing and in the case of piece dyeing. For package dyeing the recharge kier is used to replenish the dyestuff solution as needed to ensure proper and consistent dying of the fibers on the package.

1001 ] in an alternative embodiment, either th first or the second spectrophotometers can be used independently, In a preferred embodiment of this embodiment the spectrophotometer In the d eing vat is used to monitor the color of the yam or fabric eing dyed. The yarn or fabric Is removed upon obtaining the desired shade and hue. Ho ever, if desired, the spectrophotometer in th recharge kier (tank) can be used independently to monitor the dyeing process via the depletion of the dye in the dye solution. This option may e preferred, for example, to ensure that the system is run to depletion prior to the use of a different dye solution,

|001 SJ These inventive concepts also Include the incorporation of a ferrous sulfate

solution at the disclosed concentrations Into the dyeing process. While not wishing to be bound by theory, it is believed that ferrous sulfate acts to tlx, secure, bind, set,

Intercalate or otherwise hold the dye to the yam fibers. Herein we refer to the ferrous sulfate as a fixative. Whereas a mordant (see, below) acts to prepa e fibers for attachment of dye (much like a primer for paint) a fixative secures dye already loosely attached to the fiber thereby ensuring that It does no come off during wearing or washing, for example. In the present dyeing process, ferrous sulfate solution i used after the dyeing of the fibers and removal of the dyestuff solution. Ferrous sulfate is colorless or essentially colorless when dissolved in water. Ferrous sulfate treatment of the material causes a slight darkening of the color shade. The degree of darkening is consistent between batches or runs, The darkening of the color shade is figured into the final color shade achieved during the dyeing ste so that the desired color shade is obtained after the treatment of the material with ferrous sulfide. Ferrous sulfate is used in the present invention at from 1 % to 8 % weight of goods (WOG), 2 % ^» 8 % WOG, 23 % - 4 % WOG or about 3 % WOG, Weight of goods refers to the dry weight of material (for example, yarn, cloth or garment) to be dyed. The ferrous sulfate step of the present invention may also be referred to a the fixing or fixative step,

|0Ο1β] in some instances the dyeing process of the present Invention also Includes the use of a mordant, A mordant provides for enhanced dye penetration (take-up) by the yam package enabling uniform package dyeing, A mordant is a substance used to set dyes on fabrics by forming a coordination complex with the dye which then attaches to the fabric. Examples of mordants for natural dyes are alum (potassium aluminum sulfate), aluminum acetate (for use when dyeing cotton), chrome (potassium dichromate or potassium bichromate), blue vitriol (copper sulfate), ferrous sulfate, stannous chloride., sodium difhionife or sodium hydrosu!fte, ammonium hydroxide, cream of tartar

8 (potassium ifartrate), "Glauber's salt" (sodium sulfate}, lime, y (sodium hydroxide), oxalic acid,- tannic acid, urea, vinegar (acetic acid) and washing soda (sodium carbonate, also known as soda as ). The use of ferrous sulfate In the context of the present invention as a fkafive is different than the use of ferrous sulfate as a mordant in the prior art. Preferred mordants for use in the present invention for dyeing wools are aluminum sulfate (at about 10 5 - about to 28 %) and cream of tarter (at about 3 % to about 10 ), Preferred mordants for use In the present Invention for dyeing cottons (and other cellulose fibers) are aluminum acetate (at about 10 0 - about to 20 %) and cream of tartar (at about 3 % to about 0 %}, Some dyes, suc as indigo, do not typically require the use of a mordant, !>1ordant(s), if used, are used at about 160 to about 210 °F, about 1: 70 - about 206 °F, about 1 SO - about 200 °F or about 00 °F, Mordants used for about 15- 120 minutes, 30 - 90 minutes, - ?§ minutes or about 80 minutes. After mordan treatment and prior to dyeing the mordant solution I removed from the material to be dyed and the material is rinsed and dried prior to dyeing.

;0€H?J Another mordant procedure that is compatible with the present Invention is as follows. Preferably, this procedure is used with dyeing of cotton, especially, but no limited to, goldanrod, rock salt and black dyes, First, goods and/or yarn is scoured, If desired. Tannin is dissolved in boiling water. The dissolved tannin Is added slowly into the bath (tank) while bringing .bath temperature to 120 °F for 6 minutes for a final concentration of 2% tannin. Although the present Invention is not limited by theory, it Is believed thai tannin hel s with color fastness. Tannin may darken with higher temperatures affecting lighter colors. This is taken info account when dyeing. The batch is drained, the fabric/yam is rinsed and the lank is refilled with 8% aluminum acetate in hot water 100 °F for 80 minutes. The tank is drained and the fabrlo yam is processed with the procedures of the present invention for dyeing,

[0018 In one embodiment of the methods of the present invention, for package dyeing, the dyesfuff solution Is pumped from the recharge kier into the dyeing kier. The yarn package comprises the yarn wound loosely around a center tube (the tube). The tube Is porous (perforated) to permit fluid flow ¹ through the tube and then through the yarn. The dyesf yf solution is pumped In to the center of the package tube and the dyesfuff flows through the tube pores and into and ove the yarn. Once the dye stuff solution passes through the yarn package, the used dyesfuff solution flows back Into the recharg kier for recharging. The pr cess is continued until the yarn has obtained t e desired ooior (hue and shade). With the use of two spectrophotometers, the first spectrophotometer provides feedback for the yam color white the second spectrophotometer is used to regulate the concentration of dye in the dyestoff flowing from the recharge kier into the dyeing kier. Thus, the process can be controlled in such a way that the dyestuff solution is depleted of d esfuff as the yarn reaches the desired color (hue and shade). Irs this manner, waste is minimized and over or under dyeing of the yam is prevented. In one embodiment th temperature of the dyestur! is from about 180 to about 210 °F _S about 170 - about 205 °F, about 180 - about 200 °f or about 190 ⁰ F. The dye stuff is used for about 15 - 120 minutes, 30™ 90 minutes, 43 - 75 minutes or about 60 minutes. 0O1S| After dyeing, th« dyesiuff solution is removed and the yarn is contacted with the ferrous sulfate solution disclosed above. The ferrous sulfate solution is used at about 160 to about 21 °F, about 170™ about 20S °F, about 180 ~ about 200 °F or about 190 °F, The ferrous sulfate solution Is used to fix the dye t the yam for about 16— 120 minutes, 30 - SO minutes, 43™ 75 minutes or about 00 minutes. After fixation, the ferrous sulfate solution is removed. 2©3 After fixatio with the ferrous sulfate solution, the yarn fibers may be measured to confirm color shade match, washed, dried and inspected. A final color shade check can be performed if desired,

10821] In some embodiments, the flow of the mordant solution, dyestuff solution or ferrous sulfate solution can bo reversed. Although not necessa y, reverse flow can help ensure even preparation of the fibers, dyeing of the fiber s and/or fixing of the dye to the fibers by having the desired solutions flow over and Into the yam fibers from the opposite direction. Further, the flo may be run In forward or reverse to provide for rinsing of dyed yam after the dyeing process is complete. 02¾l Fo piece dyeing {e.g.., fabrics and garments) the dyestuff solution is pumped from the charge/recharge tank into the dyeing tank. The fabric comprises the knitted or woven fibers (either tubular o open width). The fabric is inserted into a Jet machine via the venturl with the ends sewn together to create a full loop so that t e entire length can he run through the dye bath tank up to about 1 yards per minute. One of ordinary skill i tlie art will be abfe to determ ne the appropriate spaed to ensure desired dyeing result without undu experimentation, A Jet machine is a dyeing machine known to those of ordinary sk in the art for dyeing piece material { .e,, fabrics and the like). Th dyeing process Is continued as established by the procedure (typically 4S to 80 minutes at temperature or until the fabric has obtained the desired color (hue and shade)}. With the use of two spectrophotometers, the first spectrophotometer provides feedback for the fabric color while the second spectrophotometer Is used to regulate the concentration of dye in the dye bath, Thus, the process can be controlled in such a way that the dyestuf solution is depleted of dyestuff as the fabric reaches the desired color (hue and shade), in this .manner, waste is minimized ami over or under dyeing of the piece is prevented. In one embodiment,, the temperature of the dyestuff is from about 160 to about 210 °F, about 170 - about 205 °F, about 180 - about 200 °F or about 100 °F. The dye stuff is used for about 15 - 120 minutes, 30 -.80 minutes, 45 - 75 minutes or about 80 minutes. Alternatively, piece dyeing can be performed with the process described above, using a dyeing vat end a recharge vat.

[00231 After dyeing., the dye bath solution i removed and the yarn is contacted with the ferrous sulfate solution disclosed above. The ferrous sulfate solution is used at about 160 to aiaoui 210 °F, about 170 - about 205 °F« about 180 - about 200 °F or about 190 °F. The ferrous sulfate solution Is used to fix the dye to the yam for about 1S ~ 120 minutes, 30 - 90 minutes, 45 - 75 minutes or about SO minutes. After fixation, the ferrous sulfate solution is removed.

|0024] After fixation with the ferrous sulfate solution, the fabric may be measured to confirm color shad match, washed, dried and Inspected. A final color shade check can be performed If desired.

[G 25J The various dyes used In the present invention are known to one of ordinary skill in the art. They include, for example, indigo, madder, cochineal, outers, osage, logwood, myrobalan, hematine, pomegranate and chestnut. Powdered and/or liquid dyes are available from suppliers known In th art (for example, Botanical Colors _s Seattle WA.; Couieurs de f¾ntes, Rochefort, France). Powdered dyes require solubilization before use. Vigorous mixing may he required to dissolve the powdered dye into solution, liquid dyes may be provided as a concentrate. Liquid dyes and solubfeed powdered dyes may iwd. to fee adjusted to a desired concentration prior to use fey adding water or by concentrating by methods known in the erf . Other ingredients may fee re ui ed as components of the dyestuff solution prior to use. Other ingredients may include, for example, surfactants, calcium carbonate, ate. The present invention is not limited by the nature of other ingredients that may be used in the mordant, dyeing or fixi g steps disclosed herein. In other embodiments, the mordant, dye and fixative (ferrous sulfate) compositions given herein may be interpreted as "comprising "c nsist ng essentially of or "consisting of the ingredients as listed, O ] Filtration of the natural dyestuff solution may be required. Dyes may need to be filtered to remove imparities and an undissolved dye particles. Filtering can be

performed ffh filter materials having between 100 and 1000 nm (nanometer) porosity, 250 - 750 nm porosity, and 350 - 650 nm porosity . One of skill in the art can determine If filtering is necessary by, for example, checking for sediment in the dyestuff solution o by filtering samples of the dyestuff solution to check for Impurities. 0 ?] The use of spectrophotometry enables the accurate measurement of the

reflectivity of the material being dyed. The results are compared to one of several standards for such measurement The standard called CLE.. La (CLE. Lab [CIELAS] is a color space standard established by the Internationa! Commission on illumination} Is fha most common and the one used herein. An initial measurement of the desired color material is made and called the 'Aim' or Target ¹ Dyed samples of materials are measured to determine how near to the target the are. 028] In the process defined herein the measurements of both the dye bath and the yarn or fabric are recorded continually. The results are converted with a formula to provide what is called a ά (delta Έ) which Indicates how far from the aim that the result is. A process limit is set to result in < 1 ,5 &E (for reference, a result of <1 ΔΕ is not perceivable by most humans, while a result of 1.6 ΔΕ is considered barely perceptible). 02Sj The dyeing process will now be explained as illustrated in Figure 1 , Figure 1 represents only one of many possible configurations of the dyeing apparatus suitable for use with the present invention, others of which will be evident to one of skill in the ad based on the teachings of this specification. 03©1 Now, turning to Figure 1 , two vats, tanks or klers re shown. The right hand kler Is the recharge kier, The recharge kier has a viewing par a spectrophotometer (the second spectrophotometer), a drain at the bottom of the kier and an inlet from the dye kier located about two-thirds of the way up on the side. The top Is -hinged and secured by, for example, one or more nuts, latches or other suitable securing device. 031| The dyestuff solution (bath) leaves the recharge kler by the drain and enters th dyemg kier (the left Hand kler in the figure) through the c nter perforated] tube. The dyestuff flows through the perforations in the perforated tube and through the yam package. Both the color and shade of the yarn is monitored with the

spectrophotometer for riieasafiftfj yarn color (the first spectrophotometer). The dyestuff solution s then circulated back to the recharge kier where if will be recharged or allowed to run to dye depletion depending on the readings from the first and second spectrophotometers. The top of the dyeing kier Is also hinged and secured similarly to the top of the recharge kier,

| δ32| Hot seen in the figure are 1} holding containers and associated plumbing for compositions necessary to recharge the dyesiuff (e.g., dyesiuff solution or concentrate), if needed, 2) a computer for analyzing data received from the first end the second spectrophotometers to efficiently monitor and control the dyeing process, 3) plumbing between the two tanks, 4) an apparatus for installing and removing th yarn package from the dyeing kler; 5) pumps, etc,

PG33J All ranges given herein are Inclusive of all values within the given range. For example, the range of IS™ 120 minutes includes all values from 15 to 120, inclusive. Thus, for example, the value 36 minutes finds support In the present specification even though it is net specifically mentioned,

Exempllfisafioir

|B834| Example 1 - Dyeing Chocolate f rown) color

OSSJ This example provides one specific procedure used to mordant and dye wool yarn. One of ordinary skill in the art, when provided with the teachings of this specification, will be able to modify the procedure th regard to other d e colors and fibers (materials)..

* Prepare dyeing vat b¾? adding clean wafer at "190 ^a F

* Add mordant chemicals per formula based on % of WOG

o 15% Aluminum Sulfate

o $% cream of tartar

* Add material to fee dyed

* Contact material with mordant solution for -* 80 mm while mai tai temperature at o Drain mordant solution; keep material wet

* Add dye formula based on % of WOG

o 2.5% Logwood

o 10% Cutch

o 03% Madder

o 1% calcium carbonate

* Maintain temperature of -190 °F

o Run dyeing process until spectro hotometer readings Indicate target color and shade are obtained (apprax, 30 minutes),

o drain dye solution

* Add 3% solution of iron salts (ferrou sulfate) at ~190 °F

* Run process for ~30 min.

* Remove material, wash In warm water with soap and softener, dry,

* inspect

|063S] Example 2 - Othe D e Colors

|003?3 The general procedure outlined above In Example 1 can be used with minor modification with regard to other dye colors. One of ordinar skill in the art, provided with the teachings of this specification, will be able to adapt the procedure above without yndue experimentation. Dye formulations for numerous other colors are provided below. All percent are approximate within ± 20 % and may be modified by one of skill In the art as desired, for example, different lots of dye or dye from different suppliers may require minor adjustments in the amounts of dye used. All formulas are based OH percent of WOG (weight of goods) to be dyed unless otherwise noted, Mordant formulas are also noted below. Otter dye formyiations can be developed by one of ordinary skill in the art when provide with the teachings of this specification o 15% Aluminum Sulfate o §% Ci¾am es? Tartar

* Dye

o J % Hermatine HS or Logwood o 3.5 % Fustic or Osage

Frjne _. dder

* Mordant

o 15% Aluminum Sulfate

© 6% Cream of Tartar

* Dye

o 6 % French Madder or 15% India Madder adder Egd

* Mordant

o 20 % Aluminum Sulfate

ø S % Cream of Tartar

* Dye

o 7 % Madder Re or 30% India Madder o 4 % Calcium Carbonate

* Mordant

o 20 % Aluminum Sulfate

o 5 % Cream of Tartar

* Dye

© 0.8 % logwo d

o 0.25 % eoid n d

Plum

* Mordant

o 20 % Aluminum Sulfate

© S % Cream of Tartar

* Dye o 0 % Cochineal

BJSB

Far dyeing cotton

« Mordant

0 Aluminum Acetate

* Dye

o 7 % Cochineal ilisis

* Mordant

o 20 % Aluminum Sulfate o 5 % Cream of Tartar

* Dye

o 12 % logwood

o 7.5% .cutch

o 5% fustic

o 7% iron

Pewter

* Mordant

o 20 % Aluminum Sulfate o β % Cream of Tartar

* Dye

o 0.8 % tongwood or Hemailne o 0,25 % Chestnut

o 0.2 % Pomegranie

Gj fjirod

For dyeing cotton

* ordant

o 1 S % Aluminum Acetat

* Dye

© 10 % Go!denrod _* Mordant

o 20 % Aluminum Sulfate

S % Cream of Tartar

* D

o 10% Quebracho red Indigo does not generally require use of a mordant and the pH of the dye bath is about i 2 or greater. Use of the ferrou sulfate step Is optional

Dye - grams per gallon of dye bath

NaOH (Sodium hydroxide) 1.2 gams

HsS (Hydrogen sulfide) 8.0 gams

Indigo dye 11 grams